Fuel 358 (2024) 130307

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

A critical review of the state-of-the-art green ammonia production

technologies- mechanism, advancement, challenges, and future potential
Joseph Sekhar S.a, Ahmed Said Ahmed Al-Shahri a, Godwin Glivin b, THT Le c, d,
Thangavel Mathimani c, d, *
a
Department of Engineering, University of Technology and Applied Sciences, Musandam, Oman
b
Department of Mechanical Engineering, Sree Chitra Thirunal College of Engineering, Pappanamcode, Thiruvananthapuram, Kerala 695018, India
c
Institute of Research and Development, Duy Tan University, Da Nang, Viet Nam
d
School of Engineering and Technology, Duy Tan University, Da Nang, Viet Nam

A R T I C L E I N F O A B S T R A C T

Keywords: Ammonia is significant in various industrial and transportation applications: carbon-free fuel, synthetic fertil­
Ammonia izers, mining, medicines, water treatment, polymers, and textiles. In recent times, the utilization of green
Green Ammonia ammonia as an environmentally sustainable fuel with zero carbon emissions has garnered significant attention.
Electrocatalysis
Electrocatalysis, photocatalysis, photoelectrocatalysis, and biocatalysis are the most common catalytic methods
Photocatalysis
Photoelectrocatalysis
in ammonia production. However, a substantial financial investment, lengthy time frame, eco-friendliness, en­
Biocatalysis ergy-intensiveness, and ammonia yield need to be considered, during long-term application within the ammonia
economy. Therefore, this review delivers insights into the comprehensive examination of existing scholarly
literature on ammonia characteristics and different methods of ammonia production. Specifically, principle,
strategies, reaction mechanism, catalysts engineering, and state-of-the-art photocatalysis, photoelectrocatalysis,
electrocatalysis, and biocatalysis methods in ammonia production has been extensively articulated in this review.
The challenges and advantages of each green ammonia production method have been highlighted. In the pho­
tocatalytic ammonia synthesis, comprehensive analysis and discussion of bismuth-based materials, Noble metal-
modified photocatalysts, Metal-free semiconductor photocatalysts, and Metal sulphide-based materials were
undertaken to lay a podium for green ammonia as promising material for various applications.

1. Introduction that RA will assume a prominent role in the entirety of the newly
established ammonia production capacity beyond the year 2025.
Ammonia, a key compound, is widely recognized for its significance Furthermore, by implementing appropriate policies, the manufacturing
in various industrial and agricultural applications. A diverse array of of RA has the potential to achieve widespread cost competitiveness
uses can be observed, encompassing synthetic fertilizers, refrigeration, commencing from the year 2030 [3].
mining, medicines, water treatment, polymers, and textiles [1]. By the year 2030, the projected manufacturing capacity of the
Emerging areas of investigation encompass the utilization of renewable renewable ammonia facilities that have been announced is estimated to
ammonia as an environmentally sustainable fuel with zero carbon be 15 million metric tonnes. Approximately 8 % of the existing ammonia
emissions, particularly within the maritime industry and for stationary market is distributed among 54 projects, with notable concentrations
power production purposes. Ammonia has been suggested as a potential observed in Australia, Mauritania, and Oman. There is a projected
medium for transporting hydrogen across large distances [2]. Renew­ pipeline of 71 MMT extending through the year 2040. However, it
able ammonia (RA) is derived from renewable hydrogen, which is should be noted that the majority of these projects are still awaiting
generated through the utilization of renewable electricity. Despite the investment choices. According to an estimate conducted by the Inter­
fact that renewable ammonia production began commercially in 1921, national Renewable Energy Agency (IRENA), it is projected that under a
the total output volume in 2021 was less than 0.02 million metric tonnes scenario where global temperatures rise by 1.5 ◦ C, the production ca­
(MMT), while total ammonia production was 182 MMT. It is anticipated pacity of renewable ammonia will need to reach 566 million metric

* Corresponding author.
E-mail address: [email protected] (T. Mathimani).

https://doi.org/10.1016/j.fuel.2023.130307
Received 7 September 2023; Received in revised form 17 October 2023; Accepted 2 November 2023
Available online 11 November 2023
0016-2361/© 2023 Elsevier Ltd. All rights reserved.
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

tonnes by the year 2050. The total capacity of the announced projects, Table 1
which amounts to 71 MMT, accounts for slightly more than 10 % of the Physical and chemical properties of ammonia.
required operational zero-carbon ammonia manufacturing capacity by Property Value Reference
the year 2050 [4]. There is a growing recognition that several regions,
Boiling temperature at 1 atm ( C)
◦
–33.4 [1]
including distant areas, possess abundant reserves of renewable energy, Condensation pressure at 25 ◦ C (atm) 9.90
and that the associated technology is progressively advancing at a Lower heating value, LHV (MJ/kg) 18.6
reduced expense. Consequently, the present dilemma revolves around Flammability limit (Equivalence ratio) 0.63–1.4
devising methods to effectively store and transport energy while Melting point (◦ C) − 77.7
Molecular weight 17.03
ensuring optimal efficiency and cost-effectiveness. This brings attention Colour Colourless
to the need for technologies that can produce liquid fuels with high Critical temperature (◦ C) 133.4 [8]
energy density, such as RA, in a manner that is both cost-effective and Vapor Density at 20 ◦C (kg/m3) 0.656
sustainable [5]. These substances can be utilized as fuels on-site or their liquid Density at 20 ◦C (kg/m3) 610
Adiabatic flame temperature (◦ C) 1800 [9]
carrier can be retrieved and reused. Consequently, the name “energy
Maximum laminar burning velocity (m/s) 0.07
carrier” is often favoured as it encompasses a wide array of potential Minimum auto ignition temperature (◦ C) 650
options. Liquid-state energy carriers are highly desirable due to their Flammability limits in air 16–25 %
ability to provide the energy density typically associated with condensed Solubility: Water at (0 ◦ C) 42.8 (w/w)
phases. Furthermore, they offer the advantages of easy generation and Solubility: Water at (25 ◦ C) 34 (w/w)
Odor threshold: Air 25 ppm (18 mg/m3)
dispatch that may be lacking in solids and gases [6]. Therefore, it is vital Odor threshold: Water 1.5 ppm
to conduct a comprehensive examination of the existing scholarly Specific gravity (25 ◦ C) 747 kg/m3
literature pertaining to the recent advancement in several methods for Vapor density 0.5967 (air = 1)
green ammonia synthesis for sustainability. Thus, this article imparts a Dielectric constant 22 at − 34 ◦ C [7]
Apparent activation energy for decomposition 25 – 220 kJ/mol [10]
critical analysis of the different methods throughout multiple sections
Explosive limits
such as Electrolytic ammonia synthesis, Photocatalytic ammonia syn­ NH3/oxygen (20 ◦C, 1 bar vol.% NH3) 5–79 [11]
thesis (strategies, metal-based and metal-free photocatalysts), Photo- NH3/air (20 ◦C, 1 bar vol.% NH3) 16–27
electrocatalytic ammonia synthesis, and Biocatalytic ammonia synthe­ NH3/air (100 ◦C, 1 bar vol.% NH3) 15.6–28
sis. Furthermore, the advantages and limitations of various current
technologies and practices are discussed along with the need for further
60.3 kg m-3, 651 ◦ C, 0.15 m s− 1, 22.5 MJ kg− 1, and 110–130 [14].
developments to meet the maturity of technologies for the effective
Regarding the effect of ammonia on humans, ammonia concentrations
implementation of green ammonia in various sectors.
of 400 ppm, 1700 ppm, and 2400 ppm cause throat irritation, coughing,
and a threat to life (30 min of exposure), respectively [1,9]. Therefore,
2. Ammonia characteristics
green ammonia is a reliable chemical for long-term energy storage and it
can be handled in liquid stage for transportation at low pressure and
Ammonia is a colourless gas that possesses a strong odour and is
high temperature as compared to hydrogen. However, appropriate
comprised of nitrogen and hydrogen. This chemical represents the most
technologies must be developed to overcome the safety issues.
basic and stable form of the aforementioned elements, and it functions as
a fundamental precursor for the synthesis of numerous nitrogen com­
3. Different methods for green ammonia production
pounds that hold significant commercial value. Ammonia has a trigonal
pyramidal molecular geometry, wherein the nitrogen atom is positioned
One of humanity’s greatest scientific-technological achievements is
at the apex and the three hydrogen atoms form a triangular base.
the synthesis of ammonia (NH3), which is a combination of N2 and H2.
Additionally, there exists a lone pair of electrons located above the ni­
The technology of ammonia synthesis was developed by Fritz Haber and
trogen atom. In the case of quaternary ammonium ions, the fourth
Robert Le Rossignol in the year 1909. Subsequently, Carl Bosch and his
substituent occupies this region. Its heat of vaporisation is 23.3 kJ mol− 1
colleagues at the German company BASF successfully implemented the
at its boiling point. Furthermore, this substance exhibits a notable ca­
method on a larger scale. The first commercial plant for ammonia syn­
pacity to undergo vaporisation. Consequently, it may be effectively
thesis was started in 1903 [15]. The manufacture of renewable ammonia
managed in liquid form within thermally insulated containers.
is dependent on the use of hydrogen, which is derived through the
Ammonia exhibits a comparatively lower dielectric constant in com­
process of water electrolysis, utilising electricity supplied from renew­
parison to water and hence it is a more favourable solvent for organic
able energy sources. From 1921 onwards RA emerged as a significant
substances (Table 1). Nevertheless, the solvating ability of ammonia
contributor to the attainment of national food security in several
remains sufficiently robust to enable it to function as a solvent with
countries till the latter half of the twentieth century. Due to economic
moderate ionization capabilities. Ammonia exhibits self-ionization to a
considerations, the production of renewable ammonia experienced a fall
lesser extent compared to water [7].
starting from the 1960s, as it was gradually replaced by the production
The decomposition of ammonia into nitrogen gas and hydrogen gas
of ammonia derived from fossil fuels. RA has recently had a resurgence
is an endothermic process, characterised by a standard enthalpy change
in popularity as a potential energy carrier. The increasing growth of the
(ΔH◦ ) of 92 kJ mol− 1. The efficiency of the conversion of ammonia to N2
hydrogen economy has made it a crucial element. During the 21st cen­
and H2 is expected to reach 99.99 % when conducted at a temperature of
tury, it is highly likely that ammonia from renewable sources will as­
400 ◦ C and 1.013 bar [10]. The high-pressure rate constant for ammonia
sume a substantial role in upholding both domestic and global energy as
recombination can be influenced by temperature, and it exhibits an in­
well as food security [16]. Major ammonia producers’ share of overall
crease from 1.7 × 1014 to 2.8 × 1014 cm3 mol− 1 s− 1 when the temper­
output over the previous 30 years was given in Fig. 1.
ature rises from 300 to 2500 K [12]. It is important to highlight that the
Three pathways such as generation 1 (G1), generation 2 (G2), and
utilization of ammonia in combustion processes has certain limitations
generation 3 (G3) are outlined in the generation of ammonia [6]. G1
attributable to its elevated ignition temperature, poor flame velocity,
entails the utilisation of carbon sequestration or offsets in order to
and retarded chemical kinetics [13]. The stored gaseous hydrogen at a
achieve a carbon–neutral outcome for ammonia production, which is
pressure of 240 bar has a density of 17.7 kg m− 3, an auto-ignition
sometimes denoted as blue ammonia. The incorporation of carbon
temperature of 571 ◦ C, a laminar flame speed of 3.51 m s− 1, a higher
sequestration into the manufacture of blue ammonia introduces addi­
heating value (HHV) of 142 MJ kg− 1, and an octane number of 130. The
tional expenses and increases the complexity of the existing H-B process.
ammonia at 10 bar storage pressure, has the respective properties of

2
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

Fig. 1. Major ammonia producers’ share of overall output over the previous 30 years [11,16,17].

Due to this rationale, it is probable that this solution will primarily serve such as solar, wind, and biomass, which are not available consistently
as a temporary measure, facilitating the development of a market for throughout the year [3]. Since the cost of batteries to store energy is
ammonia that extends beyond its traditional use in the fertilizer and high, hydrogen storage, whether in the form of liquid or compressed gas,
chemical sectors [18]. The scope of the G2 technologies exhibits sig­ seems to be the most favourable and effective alternative. In G3, the
nificant potential for long-term application within the ammonia econ­ ammonia synthesis process utilises air or nitrogen (N2) as the nitrogen
omy, with the establishment of new facilities requiring a substantial precursor and water (H2O) as the hydrogen precursor. The energy for
financial investment and a lengthy time frame. Presently, the estimated this process is supplied by electricity derived from renewable energy
cost for such equipment stands at around USD 1 million per megawatt sources and light energy harnessed from solar energy. Electrocatalysis,
(MW) of capacity [19]. One of the primary obstacles is the enhancement photocatalysis, photoelectrocatalysis, and biocatalysis are four distinct
of cellular and stack engineering in order to augment the area current catalytic processes and the most common methods that have garnered
density and reduce the device footprint. In contrast, the industry uses significant attention in the field of ammonia production. These processes
proton exchange membrane (PEM) technology primarily because of its involve the utilisation of different catalysts to facilitate chemical
capacity to produce higher current densities. Currently, there are reactions.
commercially accessible PEM water electrolysers with a heating value The REFUEL project [21] of the United States Department of Energy
efficiency of 75 % on the double-digit megawatt scale. The H-B plant’s has established realistic performance goals for G3 ammonia synthesis.
waste heat may be useful for high-temperature solid oxide electrolysis This includes a current density of 300 mA cm2, 90 % faradic efficiency
(SOE). The aforementioned procedure, with a projected aggregate en­ for ammonia, and 60 % energy efficiency. While some families of cat­
ergy efficiency of over 70 % for the manufacturing of ammonia, has the alysts and mediators may not be suited to this scenario, the G3 method
potential to produce pure nitrogen (N2) from atmospheric air at the gives more resistance to intermittency. Because the electrochemical
cathode. In addition to achieving a high efficiency of nearly 100 %, SOE process can in principle cycle down to zero current without damage at
systems have the potential to produce pure nitrogen (N2) from atmo­ ambient temperatures, as determined by the renewable energy source.
spheric air at the cathode. This substitution of traditional air separation In comparison to the H-B catalysts, which are harmed by as little as a few
units can significantly reduce the overall energy consumption associated parts per million (ppm) of O2 or H2O in the N2 feed supply [12]), they
with ammonia production [20]. may be less sensitive to N2 supply purity. In contrast to H-B procedures,
One of the challenges that remain to be addressed is the validation of the demand for N2 purity is less stringent in G3. Furthermore, in theory,
the durability of crucial components in electrolysers when subjected to G3 processes could achieve higher energy efficiency than Gen 2 pro­
extended periods of operation at temperatures ranging from 700 to cedures. Electro-reducing N2 to NH3 necessitates an overpotential of at
900 ◦ C. In addition, the effective functioning of high-temperature elec­ least 0.45 V, according to theory. This corresponds to a 0.4 V cathode
trolysers in intermittent conditions, fuelled by renewable sources, is a potential, relative to the reversible hydrogen electrode (RHE) [22]. It is
complex engineering challenge [16]. Indeed, the mitigation of inter­ interesting to note that at the level of fundamental electrochemistry,
mittency in the majority of renewable energy sources is a critically significantly more overpotential is often required for direct and medi­
significant element of the G2 methodology. The continuous operation of ated operations.
the H-B process poses challenges when integrating with energy sources

3
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

3.1. Electrolytic ammonia synthesis hydroxide (LiOH), direct nitridation of Li, and the liberation of ammonia
from lithium nitride (Li3N). This approach circumvents HER and has an
The Haber-Bosch (H-B) method, developed in the 20th century, had a initial current efficiency of 88.5 % [34].
significant societal influence by successfully enabling the artificial/
synthetic production of ammonia under conditions of elevated temper­ 3.1.2. Strategies for electrocatalysts selection and application
ature (500 ◦ C) and pressure (200–300 atm). It is worth noting that The investigation of electrocatalysts for electrochemical ammonia
approximately 1 to 2 % of the global energy utilised per year through synthesis is being investigated with a focus on various types of materials
this process, resulting in the emission of double the quantity of green­ such as metal oxides [35], metal nitrides, metal sulphides [36], and
house gases for every metric tonne of NH3 [23]. Henceforth, it is crucial transition metals [37]. and carbon materials [38]. Table 2 provides
to investigate and establish an environmentally-friendly approach for catalysts and electrolyte chemicals used for electrochemical ammonia
the synthesis of NH3 under favourable circumstances, preferably at low synthesis along with FE efficiency. These materials are considered
temperatures and minimal pressure. The catalytic mechanism discussed crucial for achieving efficient NH3 synthesis through electrochemical
here serves as a source of inspiration for the electrochemical synthesis of processes. Furthermore, the 2D material holds significant significance in
NH3 [23]. The synthesis relies on the utilisation of protons and elec­ the realm of catalysis owing to its enhanced structural and electronic
trons, which are supplied by renewable energy sources such as solar, benefits. Prominent examples of such materials include MXene [39],
biomass, hydro, geothermal, wind, and so on [24]. Since the 1960s, the phosphorene, bismuthine [40], and antimonene [41]. Several ap­
direct electrochemical reduction of nitrogen from N2 and H2O has been proaches have been devised to enhance the inherent catalytic activity
widely recognised as an advantageous pathway [25,26]. The field of and selectivity for NH3 production, including engineering grain
non-thermal reaction rates has achieved significant advancements in boundaries [42], alloying, heteroatom doping, and interface engineer­
recent years in the enhancement of Faradaic efficiency (FE) through the ing. Fig. 2 provides an overview of the notable characteristics of these
effective integration of theoretical and experimental investigations. This tactics implemented through various reaction pathways. In the subse­
successful approach has led to notable advances in the production of quent sections, a more detailed explanation of the methodologies
highly efficient catalysts, resulting in a remarkable increase in FE from employed to optimize the geometric and electrical structure in order to
less than 1 % to over 10 % [25–27]. Several routes are practiced for the enhance both the NH3 yield rate and FE was given. Various techniques,
electrochemical synthesis of ammonia. such as defect engineering, heteroatom doping, size effect, crystal-facet
design, alloying, and phase engineering, are employed to manipulate the
3.1.1. Routes for electrochemical ammonia synthesis geometric and electrical structures in order to enhance the rate of NH3
There are four main ways to make NH3 through electrochemistry: the production and improve the Faradaic efficiency. Defect engineering in
classic reaction mechanism, the Mars-van Krevelen (MvK) mechanism, materials science has been extensively investigated through experi­
the conversion of nitrate to NH3, and the metal-N2 battery [28]. Under mental and theoretical approaches. These studies have revealed that the
typical circumstances, the enzymatic conversion of nitrogen gas (N2) to removal of heteroatoms from the material’s surface leads to the for­
ammonia (NH3) occurs on the FeMo protein component of nitrogenase mation of defects, which can be effectively utilised in various electro­
enzymes. This is a standard classic reaction mechanism. In nature, the chemical reactions [43]. The defect’s existence will exert a significant
process of nitrogen reduction to ammonia is carried out by a group of influence on its chemical characteristics and electrical structure,
enzymes known as nitrogenases, presenting a contrasting scenario to the perhaps leading to an augmentation in the exposure of active sites
Haber-Bosch process. Irrespective of the specific operational mecha­ arising from surface cracking. The metal-based electrocatalysts were
nisms involved, it is evident that nitrogenase enzymes possess the able to produce an NRR rate of 8.09 mg h− 1 mg− 1 and a FE of 11.59 % at
capability to facilitate the synthesis of ammonia from atmospheric ni­ a potential of − 0.2 V [44].
trogen and water at ambient conditions, exhibiting remarkable energy The incorporation of heteroatoms has been extensively employed in
efficiency [29]. The primary objective of nitrogen reduction studies is to order to modify the physicochemical characteristics of catalyst mate­
replicate chemical processes in a manner that can be effectively imple­ rials. The catalytic characteristics of heteroatom-doped materials are
mented on an industrial scale. In the context of an electrochemical ni­ subject to alteration due to variations in their electronic structures,
trogen reduction reaction (NRR) system, the process of ammonia resulting in distinct adsorption energies, reaction thermodynamics, and
synthesis can be achieved by utilising N2, water, and electrical energy, activation barriers [45–47]. Heteroatom doping engineering is
all of which can be conducted under ambient circumstances. Therefore, commonly classified into two distinct categories: non-metal-atom
the H-B process can be effectively substituted by this energy system doping, encompassing materials doped with elements like nitrogen,
[28–30]. In addition to the associative and dissociative mechanisms, the boron, oxygen, sulphur, and phosphorus [48]; and metal-atom doping,
MvK mechanism involves the production of NH3 through the lattice N, involving materials doped with single atoms of palladium, gold, mo­
resulting in the formation of lattice vacancies. These vacancies are then lybdenum, iron, platinum), and cobalt [49–51]. Theoretical predictions
replaced by the introduction of gaseous N2. The given data consists of suggest that bi-atom catalysts (BACs) based on Co, Ni, and Cu exhibit
three numerical values [31]. Furthermore, the theoretical investigation significantly greater activity in O2 reduction compared to their single-
demonstrated that transition metal nitrides, such as VN and ZrN, possess atom counterparts. The catalytic activity of Mo and Mn was shown to
the capability to impede the hydrogen evolution reaction (HER) and be superior to that of the corresponding single-atom catalysts (SACs).
achieve the NRR at relatively low onset potentials. Nitrate reduction Crystal facet engineering is a viable approach for enhancing the elec­
reaction (NtrRR) has been proposed as an alternative approach, wherein trocatalytic activity associated with a given system [53]. Extensive
nitrate derived from various industrial waste sources is utilised to pro­ research has provided substantial evidence to support the notion that the
duce NH3 [32]. Cu-based nanomaterials have been extensively facet effect significantly contributes to the precise adjustment of the
employed in NtrRR due to their high FE of 97.0 %. The performance of physicochemical characteristics of a catalyst, including but not limited
the subject in question surpasses the electrochemical NRR by a factor of to the energy level and Fermi level [54]. Atomic-level engineering in­
two orders of magnitude. Metal-N2 batteries have garnered significant volves the precise manipulation of atomic arrangements and the coor­
attention from the scientific community and beyond. In addition to their dination of their interactions on active surfaces. This will enhance the
energy storage and release capabilities, these entities also possess the catalytic activity of the surface. The adsorption capacity of in­
ability to utilise nitrogen gas in order to synthesize chemically important termediates in the NRR process exhibits variation across different facets,
compounds [33]. The utilisation of electrochemical lithium cycling has as indicated by theoretical simulations [55]. The presence of a signifi­
been proposed as a potential method for the synthesis of ammonia. The cant quantity of surface atoms with unfulfilled valency can potentially
procedure consists of three distinct stages: electrolysis of lithium function as the active sites for the electrochemical NRR. Furthermore, it

4
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

Table 2 Table 2 (continued )

Catalysts and electrolyte chemical used for different category of electrochemical Category Catalyst Names Chemicals used Faraday
ammonia synthesis along with FE efficiency [69–71]. as electrolytes efficiency
Category Catalyst Names Chemicals used Faraday (%)
as electrolytes efficiency SnO2, Ti-doped SnO2,
(%) SnO2 (VO)_12
Nobel-metal- 20 % Pt-on-carbon cloth KOH, PBS, 2.3 to 60.9 NORR a-B2.6C@TiO2/Ti, Cu Na2SO4 + Fe2+- 45.46 to
based electrodes, Pt3Fe Na2SO4, electrocatalysts foam, NiO/TM, MoS2/ EDTA, HCl + 98.49
electrocatalysts nanocrystals, Pd/C, H2SO4, HCl, GF, Fe2O3/CP, Cu FeII-SB, NaOH,
PdH0.43 NRs, LiCl, K2SO4, PBS nanoparticle, Bi NDs, NaClO4, PBS,
PdNCs@CNFs, Pd/ Bi@C, MnO2–x NA, HCl
HsGDY, Pd3Bi, Pd3Cu, TiO2–x/TP, Ni2P/CP,
PdCu3, BCC PdCu, Au/ CoP/TM, FeP/CC, Fe1/
MBOP, AuSA/np-MoSe2, MoS2–x, Co1/MoS2,
Au25@S-G, Au–Fe3O4 CoS1–x/CP, HCNF/CP,
NPs, HT Au@MOF, g-C3N4 nanosheets
AgTPs, AgNPs, Ag NtrRR CuO NWAs, Co@TiO2/ Na2SO4 + 82–100
nanosheet, Ag2Au1 electrocatalysts TP, Co2AlO4/CC, NO3–, PBS +
nanotubes, Rh/CNT, B, Co@CC, Co-NCNT/CP, NO3− , NaOH +
S-mRh/NF, mAu3Rh/ Co@NC, PP-Co, NO3− , KOH +
NF, mRhRu/NF Co@JDC/GF, Vo- NO3−
Transition-metal- MoS2, DR MoS2 KOH, HCl, 1.7 to Co3O4/CC, vCo-Co3O4/
based nanoflower, MoS3, 1 T- Na2SO4, LiClO4, 87.64 CC, Fe-Co3O4 NA/TM,
electrocatalysts MoS2–Ni, MoS2, SVs(P- MH2SO4 Co3O4@TiO2/TP,
M1), 1D-MoS2-xOy, CoO@NCNT, CoP NA/
MoO3 nanosheets, TM, CoP NAs/CFC., CoP-
MoO2/NF, CNS, CoP/TiO2@TP,
MoO2@MoO3, NiCo2O4/CC, ZnCo2O4/
MoO3–CeOx, MoO2 + x, CC, FeCo2O4,
Fe(III) grafted MoO3, MnCo2O4/CC,
Mo/HNG, Mo2C Mn2CoO4/CC,
nanorod, Mo2C/NC, CoB@TiO2/TP, Co-P/
Mo2C/C nanosheets, B- TP, CoBx,
Mo2C/NC, Mo2N Co2B@Co3O4,
nanorod, MoN NA/CC, Cu@JDC, Cu@TiO2/TP,
Mo2N40/BN, Mo2N60/ Cu3P, NA/CF,
BN, Fe3O4-300, Zr/a- CF@Cu2O, Cu-N-C SAC,
FeOOH, FeTe2/RGO, Pt- Fe3O4/SS, FeOOH
FeP/C, FeS2@GO, nanorod, FeOOH NTA/
FeS2@GO, Vs-FePS3 CC, FeS2@TiO2, e2TiO5
NSs, FeWSx@FeWO4, nanofibers, NFP, Ni2P/
Fe–N/C–CNTs, NF, Ni@JBC,
TiO2–rGO, Li-TiO2(B), NiS2@TiO2, TiO2–x/CP,
d-TiO2/TM, Ti2O3, B- TiO2–x NBA/TP,
TiO1.8, NS-TiO2/C, 2.0 ITO@TiO2/TP, Anatase
%Cu/OV-TiO2, Fe-TiO2, TiO2–x, Fe-TiO2/TP, Co-
C-TiO2 nanoparticles, B- TiO2/TP, V-TiO2/TP,
TiO2, Mn-TiO2, La-TiO2, Ni-TiO2/TP, P-TiO2/TP
ReS2/TiO2, 5 %Pd-8 %
Co/TiO2-Vo, F-Fe: TiO2,
TiO2/Ti3C2Tx, was observed that when the operating temperature was raised from 20
MnO2–Ti3C2Tx, Bi2S3- to 50 ◦ C, the FE experienced a significant rise from 30.2 to 40.55 % and
x/Ti3C2Tx, MoO3-x/ this is due to the accelerated mass movement rate [56]. Alloying rep­
MXene, MnOx NA/TM,
Pd–MnO2-Ov/Ni foam
resents a potential approach that enables the manipulation of surface
Non-metal-based C-ZIF-1100–1 h, NPC- KOH, H2SO4, 1.42 to and electrical interactions. The field of alloying engineering offers a
electrocatalysts 750, NAC@NiO/GP, HCl, Na2SO4, 38.1 precise method for adjusting the binding strength of intermediates on
BC3, B4C nanosheets, LiClO4, K2SO4 the surface of a catalyst, hence leading to an enhancement in the specific
np-B13C2, B-BCN, O–G,
catalytic activity [57]. The manipulation of phases in a material has the
O-CNT, ERGO-0.4, S-G,
S-3DG, F-doped carbon, potential to alter its electronic state and enhance its catalytic charac­
P-CNTs, PG, S6.23- teristics. The effectiveness and widespread application of this phenom­
B8.09/CNFs, S/N-MPC, enon have been demonstrated in the context of the oxygen reduction
PN-C-ZIF-8, BNQDs/ reaction (ORR), oxygen evolution reaction (OER), and HER [58]. The
C3N4, NCNT@MIL-101
(Fe), CNT@MIL-101
utilization of amorphous gold nanoparticles bound to reduced graphene
(Fe), 2D C3N4-NV P-NV- oxide has been proposed as a potential method for nitrogen fixation
C3N4, RuAu3/0.3Zr- [59]. In contrast to the use of crystalline materials, amorphous materials
C3N4 exhibit higher levels of activity due to the bond variations. However,
main group Bi@C-900, Bi NPs, Bi Na2SO4, LiClO4, 3.67 to
these materials should be further studied for their technology maturity
metal-based nanosheets, Bi NS, Bi HCl, KOH, DPBS, 42.6
electrocatalysts NSs, Bi@Ti3C2, Xene, H2SO4, KHCO3, and economic feasibility.
Bi/NPC, NC/Bi SAs/TiN/ PBS
CC, BVC-A, Plasma R-O- 3.1.3. Reaction strategies for electrochemical ammonia synthesis
Bi, Sn D/SF, SnSC/C, Sn/ The back-to-back cell, the proton exchange membrane (PEM) cell,
SnS2, NPG@SnS2, F-
SnO2/CC, Fe-doped
the H-type cell, and the single-chamber cell are the four main types of
electrochemical reactors used in the NRR. The cathode and anode gas
diffusion electrodes are used in back-to-back cell design. N2 gas and

5
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

Fig. 2. An overview of the typical techniques for engineering nanomaterials via diverse reaction pathways.

water, respectively, are placed inside these electrodes. Either a proton utilisation of in situ analytical methodologies is vital in order to sub­
exchange membrane or an anion exchange membrane is used to create stantiate the occurrence of catalyst surface reconstruction and the im­
the separation between them. Due to the lack of direct electrolyte- mediate formation of crucial intermediates during reactions conducted
cathode contact, both the PEM cell and the back-to-back cell effec­ under real-time conditions. In order to enhance the electrocatalytic ni­
tively suppress the HER. Conversely, the efficiency of gas–solid in­ trogen reduction reaction process, it is imperative to meticulously
teractions within the cathode chamber is very low when operating under evaluate various catalyst design techniques and vacancy engineering
ambient circumstances. Typically, liquid electrolytes are employed to approaches. By employing suitable electrocatalysts in conjunction with
fill single-chamber and H-type cells. In the aforementioned scenario, it is effective methodologies, it becomes possible to concurrently activate N2
observed that the cathodic and anodic processes occur within the and inhibit HER. Therefore, increasing the likelihood of achieving
confinement of the same electrolyte medium. This proximity may give noteworthy NRR activity and selectivity, resulting in a high yield of
rise to a concurrent decomposition or oxidation of the cathodic product ammonia and FE. The determination of a precise reaction mechanism for
on the anode, hence causing a diminished output. The scarcity can be NRR in a given electrocatalytic process is a formidable task, necessi­
resolved by implementing a H-type cell, which is a commonly employed tating the acquisition of mechanistic insights through density functional
reactor design in situations of comparability. In this configuration, a theory (DFT) simulations. Alternatively, certain nitrogen-to-ammonia
membrane is employed to separate the anodic and cathodic reactions. fixation methodologies such as electrocatalytic reduction reactions of
Nevertheless, in both the single chamber cell and the H-type cell, the nitrate and nitrite have been suggested as a viable and environmentally
cathode’s interaction with the aqueous electrolyte might result in a friendly approach for electrochemical ammonia production. These
diminished FE of NH3 due to the simultaneous occurrence of the techniques enable the reduction of nitrate from wastewater into
competitive HER. ammonia, a valuable product, using water as the hydrogen source in
In order to optimise the performance of the cell, it is imperative to normal environmental circumstances. Additionally, they facilitate the
meticulously manage all of its parameters, including but not limited to conversion of NOx (NO, N2O) from air pollutants and greenhouse gases
temperature, flow rate, the volume of the electrolyte, and so on. Previ­ into ammonia, which is driven by renewable electricity [66–68]. Despite
ous research has indicated that the enhanced selectivity of the electro­ numerous attempts to achieve one-step electrochemical nitrogen
catalytic NRR could potentially be attributed to the electrolyte [62]. reduction in aqueous environments, several challenges persist. These
Nevertheless, it should be noted that within lithium-containing salt so­ challenges include the limited solubility of N2 in aqueous electrolytes,
lutions, there exists a minute quantity of nitrate and nitrite that has the low partial current density of ammonia production, unavoidable
potential to undergo reduction, resulting in the formation of N2 [63]. contamination from feed gases, catalysts, or electrolytes, and difficulties
Furthermore, it may be advantageous to consider the utilisation of polar in accurately quantifying ammonia levels.
solvents that exhibit enhanced miscibility with N2 and possess low H+
ions concentrations and this approach is more effective strategy for
3.2. Photocatalytic ammonia synthesis
optimising the electrolyte composition. Extensive research has been
conducted to investigate the advancements made in electrode materials
Two basic equations involved in the photocatalytic ammonia syn­
for NRR, including several categories such as precious metals, transition
thesis are;-.
metals (TMs), main group element-based materials, carbon-based ma­
N2(g) + 6H+ + 6e− ⇌ 2NH3(g), E0 = 0.092 V.
terials, and composites doped with heteroatoms. Despite prominent
2H2O(l) ⇌ O2(g) + 4H+ + 4e− , E0 = 1.229 V.
progress in optimising the reaction system for NH3 producing entailing
The utilisation of photocatalysts to produce renewable ammonia has
N2 and H2O as sources of H+ at ambient pressure and temperature, there
become increasingly appealing to reduce carbon emissions. In recent
is still a need for further enhancements in most electrochemical NRR
times, notable advancements have been achieved in comprehending,
methods. Despite the rapid evolution of electrolytic ammonia produc­
investigating, and devising effective photocatalysts. Moreover, the uti­
tion, researchers persist in the development and assessment of many
lisation of N2 and water as a hydrogen source for photochemical NH3
electrocatalysts and electrocatalytic systems for the purpose of sustain­
generation at ambient temperature can yield substantial environmental
able ammonia synthesis. Despite significant advancements in the
benefits [72]. The formation of NH3 in conjunction with water oxidation
research and development of superior electrode materials for NRR,
is a reaction that requires an input of external energy due to its ther­
comprehending the intricate interplay between the catalyst and elec­
modynamically uphill nature [73,74]. Significant progress has been
trolyte contact during the reaction remains a formidable task. The
made in the field of metal oxides, including TiO2 [12], WO3, and SrTiO3,

6
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

as well as bismuth oxyhalides and polymeric carbon nitride photo­ advancements in this field. This section provides a summary and anal­
catalysts. These advancements have generated considerable interest in ysis of current advancements in the development of photocatalytic
the exploration of photocatalysts and their potential uses in NH3 syn­ materials for ammonia synthesis.
thesis [72,75]. The primary issue in this method is the limited produc­
tion of ammonia, which has sparked a longstanding scholarly discourse 3.2.3. Materials based on titanium dioxide for ammonia production
over the feasibility of this reaction [76]. The attention given to photo­ Regarding semiconductor photocatalysts, titanium dioxide (TiO2) is
catalytic ammonia production has been inconsistent over the past few often viewed as the standard because it may exist in three different
decades, despite the numerous advantages associated with the photo­ polymorphic forms. Due to its outstanding chemical stability and
reduction of nitrogen. The major factor behind this may be due to its low affordability, the use of TiO2 photocatalysts in the process of ammonia
production rate and high production cost. production by N2 reduction has been done by many researchers [79].
Adding Fe species to TiO2 increased the separation of electron-hole pairs
3.2.1. Principle of photocatalytic ammonia production created during photochemical processes [80]. A wide range of alcohol-
The working principle of photocatalytic ammonia production given water concentrations were discovered to cause the creation of
in Fig. 3. In order to facilitate the overall synthesis of NH3, it is necessary ammonia, with a 75 percent alcohol concentration producing the most
to utilise photons with energy exceeding 1.137 eV. These photons are ammonia after 1.5 h of irradiation. The photocatalysts synthesised using
responsible for generating photoexcited electron-hole pairs. Therefore, Fe, Co, Ni, and Mo dopants exhibited superior catalytic performance for
an energy band gap (Eg = E (conduction band minimum) - E (valence NRR. This enhanced performance can be related to the prevalence of
band maximum)) that exceeds 1.137 eV is necessary. Furthermore, it is rutile phase TiO2 (10–95 %) in these particular samples. Subsequent
imperative for a photocatalyst to possess a conduction and valence band surveys revealed that the presence of surface oxygen defects led to the
alignment that is appropriate for facilitating two half-reactions through creation of Ti3+ sites, which in turn facilitated the effective conversion
the utilisation of photoexcited electrons (e-) and holes (h + ) when of N2 to NH3. A recent study successfully achieved accurate adjustment
exposed to solar irradiation [77]. When designing photocatalyst of the concentration of Vo in TiO2 nanosheets using a straightforward
ammonia synthesis systems, it is crucial to consider the key factors, such technique involving Cu2+ doping [81]. Yasushi and colleagues con­
as the process of photon absorption, the subsequent migration and ducted a study whereby they synthesised a range of semiconductor
separation of carriers, and the redox processes on the photocatalyst’s photocatalysts modified with Pt for the purpose of NRR. The photo­
surface. The prevailing energy distribution of photons derived from catalysts including Pt nanoparticles exhibited ammonia yields that were
sunshine falls within the wavelength range of 390–700 nm [72]. A 25–75 % greater compared to the photocatalysts without Pt nano­
photocatalyst that effectively increases the migration and separation of particles [82]. A comprehensive examination was conducted on four
electron-hole pairs in order to accelerate the photochemical NH3 pro­ esteemed noble metal co-catalysts, namely Ru, Rh, Pt, and Pd, in relation
duction needs to be developed [78]. In photocatalytic ammonia pro­ to their effectiveness in photocatalytic N2 reduction over TiO2. The
duction, two strategies, namely a. the development of catalysts and b. findings of this study revealed that the rates of ammonia production
improving the photocatalytic efficiency, are used to enhance the yield exhibited the following hierarchy: Ru > Rh > Pd > Pt. The use of
and reliability of green ammonia production. plasmonic metal is an additional approach to augment light absorption
and facilitate the process of photocatalytic ammonia synthesis [83–85].
3.2.2. Strategies to develop photocatalysts In addition, TiO2 can be utilised for the production of NH3 from nitrate.
Various materials exhibit distinct features and therefore, strategies Under UV irradiation, a TiO2 photocatalyst with surface modifications
for improving photocatalytic green ammonia synthesis based on mate­ demonstrated a high selectivity of 97 % for the transformation of nitrate
rials/photocatalysts/processes are given in Fig. 4. In recent times, to ammonia [86]. Upon doing more investigation, it was shown that
diverse materials have been engineered with the aim of enhancing the surfaces composed of TiO2, exhibiting a substantial concentration of Vo
effectiveness of artificial photochemical nitrogen fixation. These ideas [87] and a limited quantity of Lewis acid sites. This leads to the capa­
and strategies can potentially serve as sources of inspiration for future bility of producing ammonia with a notable level of selectivity. The

Fig. 3. Working principle of photocatalytic ammonia production.

7
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

Fig. 4. Strategies for enhancing the photocatalytic synthesis of green ammonia.

nitrate reduction pathway leading to the production of NH3 presents a grouping of photoexcited electrons and holes. Following this, the elec­
potentially advantageous approach for the transformation of ecologi­ trons in an excited state can be introduced into the unoccupied orbitals
cally detrimental nitrate into valuable ammonia. In brief, a significant of adsorbed N2 molecules in order to achieve the activation of N2. The
number of studies have been dedicated to the modification of TiO2 process of converting N2 to NH3 in the presence of Vo is considered a
photocatalysts, either in bulk or on the surface. The aim was to improve low-energy ammonia production method [92]. The studies on the mo­
their photocatalytic performance in the context of high ammonia pro­ lecular aspects underlying the impact of diverse semiconductor facets
duction. Nevertheless, photocatalysts based on TiO2 continue to have harbouring Vo on the process of N2 reduction provide a foundation for
challenges in achieving high conversion efficiencies from solar energy to future research endeavours focused on the photocatalysts advancement
chemical energy. Therefore, there is a need for more research and in enhanced ammonia yield [74]. Furthermore, the activation of N2 can
development in synthetic approaches to overcome this limitation. be enhanced through the engineering of bandgap structures, in addition
Moreover, there is a lack of certainty regarding the reaction process and to Vo. The catalytic activity of BiO quantum dots, which have an average
active sites on TiO2 in numerous instances. The utilisation of atomic- size ranging from 2 to 5 nm, was shown to be outstanding for NRR when
scale observations, in-situ experimental techniques, and density func­ exposed to simulated solar light [93]. The active sites responsible for N2
tional theory (DFT) computations presents an opportunity to get a activation were determined to be low-valence surface Bi(II) species.
molecular-level understanding of the process by which N2 is converted Furthermore, it has been demonstrated that Bi2MoO6 photocatalysts
into NH3. exhibit high efficiency in the process of ammonia production using
ambient air as the source [93,94]. It has been postulated that the ca­
3.2.4. Bismuth-based materials pacity of Bi2MoO6 crystals to catalyse the activation of N2 arises from the
In recent times, there has been a significant focus on bismuth-based presence of Mo atoms with unsatisfied coordination in the peripheries of
materials as an efficient photocatalyst in ammonia production owing to Mo-O polyhedral. This study involved the fabrication of a mesoporous
their remarkable optical characteristics, such as a narrow band gap that Bi2MoO6 framework by a solvothermal synthetic approach, which was
enables the absorption of a wide range of solar spectrum. Additionally, subsequently subjected to a hydrogenation treatment [92]. The uti­
these materials exhibit favourable photocatalytic performance in lisation of 2D bismuth oxyhalides and other bismuth-based photo­
various applications [88], including the decomposition of organic pol­ catalysts has been employed as a means to study the impact of Vo, facet
lutants, water splitting, and the conversion of nitrogen to ammonia. engineering, and bandgap structure management on the process of
These attributes have attracted considerable attention from researchers photocatalytic N2 reduction. These findings have served as a catalyst for
and scientists [89,90]. Bismuth oxyhalides are commonly classified as a the advancement of more efficient two-dimensional photocatalysts in
collection of ternary compound semiconductors. They exhibit a strati­ forthcoming research endeavours.
fied composition and present two intriguing characteristics that
contribute to the enhancement of photocatalytic processes [91]. These 3.2.5. Noble metal-modified photocatalysts for ammonia production
characteristics facilitate the highly effective production and segregation Photocatalysts modified using noble metals can be broadly catego­
of charge carriers synthesized from photosynthesis, as well as the acti­ rized into two groups: noble metal-based photocatalysts and noble
vation of reactants. Based on a series of conducted experiments, a pro­ metal-doped photocatalysts. Noble metals such as gold and silver, which
posed interfacial electron transfer mechanism suggests the presence of exhibit surface plasmon resonance, have the ability to introduce active
numerous oxygen vacancies (Vo) on the surface of BiOBr. This results in and high-energy electrons into the anti-bonding orbital of nitrogen
the formation of a defect state positioned between the conduction band molecules. The reduction in chemical bond energy of nitrogen molecules
(CB) and valence band (VB). Moreover, the defect state exhibits the facilitates the completion of the initial stage of hydrogenation. Plasma-
ability to effectively capture and confine excited electrons originating assisted noble metal-based photocatalysts offer a potential avenue for
from the CB of BiOBr. Consequently, this process hinders the direct overcoming the limitations imposed by conventional catalytic processes,

8
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

making them a highly intriguing area of investigation in the field of consisting of CdS and Pt were fabricated for photocatalytic reduction of
nitrogen reduction research. Gold nanocrystals were chosen as plas­ N2 to ammonia. The resulting yield of NH3 was found to be higher
monic nanostructures to achieve a broad spectrum of light absorption, compared to that of pure CdS, thus emphasising the significant contri­
which resulted in an ammonia output of 101.4 μmol g− 1h− 1 [95]. The bution of Pt co-catalysts in the process of NRR [82]. The Photocorrosion
gas-membrane solution interface, which is comprised of the film, has the of metal sulphides poses a significant challenge in the context of pho­
ability to facilitate efficient gas diffusion. Every individual Au nano­ tocatalytic ammonia production, despite their favourable visible light
particle is evenly distributed within the MOF matrix and serves the dual absorption properties. In order to sustain a heightened level of photo­
purpose of functioning as a photosensitizer [96]. The potential for catalytic activity, the utilisation of nickel phosphide (Ni2P) has been
developing noble metal photocatalysts with varying forms and array implemented as a co-catalyst for the purpose of capturing photoexcited
architectures, utilising the plasma amplification effect, remains signifi­ metal sulphide [105]. Metal sulphide photocatalysts with a significant
cant. Precious metal–semiconductor heterostructures have also been presence of sulphur vacancies (Vs) have been employed in the photo­
fabricated, comprising a combination of precious metals and semi­ catalytic generation of NH3, drawing inspiration from the advantageous
conductor materials. In a recent study, the immobilisation of gold properties exhibited by Vo in oxide photocatalysts for N2 reduction. The
nanoparticles onto titanium dioxide nanosheets has been used with the rate of NH3 generation exhibited a linear relationship with the con­
aim of enhancing the photocatalytic process of nitrogen fixation. Recent centration of Vs. The highest concentration of Vs demonstrated the
studies documented the synthesis of a heterojunction photocatalyst highest rate of NH3 production [106]. In the past few years, there has
consisting of Ru, RuO2, and g-C3N4 [97,98]. Upon exposure to light been significant attention in the field of catalysis towards certain tran­
irradiation, the holes undergo transfer to RuO2, leading to a reaction sition metal dichalcogenides, including MoS2, Ag2S, and WS2. This in­
with methanol present in the solution. This ultimately results in the terest stems from their two-dimensional structure and remarkable
production of ammonia at a rate of 13.3 μmol g− 1h− 1. Additionally, the electrical and optical properties [76].
presence of single-atom distributed platinum atoms facilitates the sep­ Green ammonia synthesis using a photocatalytic pathway is still in
aration of electron-hole pairs. Furthermore, a yield of 171.40 μmol its early stages but is garnering significant interest. Numerous unique
g− 1h− 1 of ammonia was attained in the absence of sacrificial agents. photocatalysts and strategies have been utilised in order to enhance the
While the surface plasmon resonance (SPR) of noble metals has been processes of nitrogen adsorption and activation [74,107]. In addition, it
shown to greatly enhance the activation of nitrogen molecules, their is worth considering that the use of morphological control or hetero­
cost-effectiveness remains a limiting factor for achieving large-scale junction construction may present a viable approach to enhance the
production. Efforts should be taken to devise strategies for the optimal efficiency of electron-hole separation [108,109]. In recent studies, it has
utilisation of noble metals in enhanced photocatalytic activity. been observed that the problem of electron-hole recombination can be
successfully mitigated in an environment with high temperatures
3.2.6. Metal-free semiconductor photocatalysts for ammonia synthesis (>270 ◦ C). Ammonia production can be enhanced with these new
Among the metal-free semiconductor photocatalysts, g-C3N4 is a technologies [110–112]. Nevertheless, there exist numerous significant
highly favoured photocatalysts that find extensive application in the obstacles that must be addressed prior to the commercialization of this
field of photocatalytic ammonia production. Nevertheless, the photo­ technology. The examination of the reaction mechanism, the effect of
catalytic ammonia synthesis performance of pure g-C3N4 is hindered due solution composition and additives on reaction performance [93,113],
to the significant combination of photogenerated carriers and the and the clarification of the relationship between surface flaws [114] and
restricted capacity for nitrogen adsorption and activation. Significant material activity are all included as challenges [115]. It is essential to
activities have been undertaken to address these challenges. The uti­ create an in-line in-operando technique for measuring ammonia in order
lisation of non-metallic dopants such as boron (B), phosphorus (P), to overcome the aforementioned issues and increase knowledge of the
sulphur (S), and iodine (I) has been demonstrated as a viable approach photocatalytic nitrogen reduction reaction (PNRR) mechanism. It is
to enhance the photocatalytic activity of g-C3N4 in the manufacture of crucial to design a standardised protocol for conducting research in
ammonia [99]. The utilisation of metallic doping with copper potas­ order to ensure replicability in view of the inadequate efficiency dis­
sium, cobalt, iron, and silver has been extensively employed to enhance played by the current PNRR. UV or full-spectrum light sources are used
the efficiency of photocatalytic ammonia photosynthesis. Since the ex­ in the bulk of photocatalytic research studies. However, this strategy
istence of defect sites can operate as active centres for ammonia pro­ may possibly result in the degradation of catalysts and materials when
duction, increasing the intrinsic activity, defect approaches offer a exposed to light. Consequently, this may lead to the contamination of
highly effective method for changing the properties of photocatalysts. ammonia or interfere with the accurate measurement of ammonia
Implementing coupling with other semiconductors is a good strategy for concentration.
improving carrier separation efficiency. The presence of nitrogen-
containing groups could potentially influence the outcomes of the 3.3. Photo-electrocatalytic ammonia synthesis
tests. Furthermore, the utilisation of ethanol and heavy metal ions
during the synthesis process of g-C3N4 has the potential to impact the The utilisation of photo electrocatalytic (PEC) processes for the
precision and reliability of the Nessler’s reagent approach [101,102]. synthesis of ammonia from nitrogen and water represents a highly
Moreover, ethanol is extensively employed as the sacrificial agent for promising strategy in the field of energy development, as well as in the
holes, so it serves as a confounding element that impacts the outcomes of pursuit of achieving N-neutralization objectives. This technique offers
detection [103]. Furthermore, a significant portion of the existing the advantage of operating under moderate conditions. Despite notable
literature pertaining to metal-free semiconductor photocatalysts is advancements in recent years, understanding the intricate mechanisms
centered around the investigation of g-C3N4. It is anticipated that the that drive the synergistic interplay between light and electricity remains
utilisation of alternative metal-free semiconductor photocatalysts, sur­ a formidable task. The electrocatalytic reduction of N2 in aqueous so­
passing g-C3N4, will effectively facilitate the manufacture of ammonia. lution entails the transport of electrons and protons, along with the
generation of distinct product distributions. The low yield and FE of
3.2.7. Metal sulphide-based materials electrocatalytic ammonia synthesis [116,117] can be attributed to the
Several transition metal sulphides exhibit narrow band gaps and presence of inadequate sites and the HER. Numerous investigations have
band edges that are ideal for NRR. Extensive study has been conducted demonstrated that Bi-based materials and layered double hydroxides
on the photocatalytic reduction of N2 using transition metal sulphides play a significant role in the activation of N2, facilitating rapid charge
due to their remarkable optical features, particularly their responsive­ separation, and promoting the creation of electrons through their
ness to visible light [104]. In the year 1980, composite materials notable reducibility. Currently, the integration of electrocatalysis with

9
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

photocatalysis is a promising approach for enhancing the efficiency and process of hydrogenation within the association mechanism can occur
specificity of NH3 production. The reason for this phenomenon is through two distinct paths, specifically the distal and alternate routes.
attributed to the inherent bias of electrocatalysis, whereas photo­ N2 facilitates hydrogenation on the nitrogen atom distal to the catalysts
catalysts possess a multitude of active sites [118]. The process of PEC N2 in the context of terminal coordination. The metal nitrogen unit com­
reduction involves the excitation of catalysts under irradiation, leading bines with H+ to produce an extra NH3 molecule, resulting in the gen­
to the generation of carriers. Subsequently, these carriers are separated eration of NH3 molecules [123]. In order to understand the underlying
into electrons and holes. In conclusion, the quick migration of electrons variables impacting selectivity, numerous computational models and
facilitates their active involvement in the reduction of N2 on the surface experimental investigations have been conducted. The main objective is
sites, which is further facilitated by the presence of a bias. Furthermore, to overcome the difficulty of establishing the selectivity of NH3 over N2
the phenomenon of photoelectric synergy is manifested through the and H2O in the presence of the HER. The impact of proton concentration
simultaneous occurrence of photochemical and electrochemical events. on the efficiency of the hydrogen evolution reaction has been addressed
Hence, the synthesis of PEC NH3 is regarded as a promising methodol­ using a variety of tactics. These methods include placing a hydrophobic
ogy. It combines the benefits of photocatalysis with electrocatalysis in shield over the catalyst, the use of aprotic solvents, and the synthesis of
order to achieve effective N2 conversion [119,120]. Various candidate photoelectrocatalysts [114,124]. Additionally, altering nitrogen and
photocathodes have been identified for use in photoelectrochemical hydrogen adsorption affinities toward catalytic sites has the ability to
cells. These include inorganic semiconductors with appropriate bandg­ change the selectivity of ammonia [76,125].
aps, such as g-C3N4, BiOI, TiO2, and Cu2O [121]. Furthermore, there
have been advancements in metal alterations, the development of 3.3.2. Coupling light and electricity
metal–organic frameworks with adjustable topologies, and the explo­ The development of PEC processes can be enhanced through the
ration of single atoms possessing exceptional active sites [118]. The low utilisation of co-operative effects between light and electricity, which
conduction band minimum and the increased electron reduction ca­ leverage the benefits of both photocatalysis and electrocatalysis. The
pacity are advantageous for NRR. Various approaches can be employed electro-coupled photocatalysis strategy is specifically designed to pre­
in the PEC strategy to enhance the ability of N2 reduction. These ap­ vent the oxidation of NH3, enhance the reduction capacity of electrons,
proaches include vacancy engineering, heteroatom doping, hetero­ and improve the separation of charge carriers. Additionally, photo-
structure construction, and single-atom synthesis. Moreover, they have assisted electrocatalysis exhibits superior performance compared to
shown promise in improving the efficiency of N2 reduction. Further­ single electrocatalysis, thereby facilitating the maintenance of electron
more, the possible use of expanded light response capacity in the near- distribution equilibrium under irradiation [126]. Furthermore, the
infrared region has been proposed as a viable concept for establishing manifestation of the synergistic effect is observed through the simulta­
a solar-based economy in the context of photoelectrochemical nitrogen neous occurrence of photochemical and electrochemical processes.
(PEC N2) reduction to produce green ammonia [122]. There are many Specifically, the electrocatalytic potential of electrons is influenced by
strategies followed to implement the PEC-based ammonia synthesis bias, while the photocatalytic reduction capability of photoelectrons is
from nitrogen (Fig. 5). contingent upon the minimum CB of semiconductors [73]. Typically, the
absorption of light in the PEC process initiates the catalytic reaction
3.3.1. Mechanisms directly. By effectively suppressing the recombination of photo­
Reduction of PEC N2 to ammonia on the surface of a heterogeneous generated holes in the valence band, controlling the concentration of H+
catalyst occurs through two distinct mechanisms, specifically the asso­ on the catalyst surface, and enhancing the accumulation of electrons at
ciative reaction and the dissociative reaction [118]. Upon the dissocia­ the catalytic site, a notable enhancement in the catalytic efficiency of
tion of the nitrogen-nitrogen link, the compound NH3 is liberated. The ammonia synthesis can be achieved [127,128]. Simultaneous

Fig. 5. Approaches for making ammonia from nitrogen using PEC.

10
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

occurrence of electrocatalysis increased by photo-excitation, and pho­ et al. successfully synthesised hydrogenated mesoporous SrTiO3 modi­
tocatalysis boosted by external bias is observed in the PEC ammonia fied with carbon quantum dots (CQDs/STO. The ammonia production
synthesis process. As a result, the catalytic efficiency is increased with rate of CQDs/STO is measured at 143 μmol g− 1h− 1, which is sevenfold
respect to individual electrocatalytic or photocatalytic nitrogen fixation higher compared to STO without the presence of a sacrificial agent
methods. Photocatalysts, including g-C3N4, TiO2, BiVO4, and others, [138]. Additional sophisticated catalysts and methodologies: The uti­
have suboptimal electrocatalytic efficiency as a result of their inade­ lisation of single-atomic alloy catalysts holds significant potential in the
quate conductivity. Recent research has demonstrated that the process field of electro-catalytic nitrogen reduction due to their exceptional
of PEC N2 fixation can be achieved without the use of electrochemical exposure to active sites. Nevertheless, there exists a scarcity of
equipment. Furthermore, it has been observed that the anode photo­ comprehensive experimental investigations and theoretical studies
voltage generated during this process plays a crucial role in facilitating pertaining to the conversion process of N2 into nitrogen-containing
the reduction of N2 by providing a compensatory negative potential compounds. Furthermore, the use of the Ru-Cu alloy demonstrated
[130]. The photovoltage generated by plasma-induced semiconductors that the incorporation of copper resulted in a 31 % enhancement in the
exhibits significant promise for enhancing the efficiency of ammonia faradaic efficiency of ammonia production in comparison to the uti­
production in PEC cells, hence eliminating the need for additional lisation of pure ruthenium (Ru) [138]. The features of the interface
equipment. produced by the imide-based lithium salt electrolytes were investigated.
The results show a significant NH3 yield of 150 ± 20 nmol s− 1 cm− 2,
3.3.3. Advanced catalysts synthesis and performance accompanied by a maximum Faradaic efficiency (FE) of 100 %.
Heteroatom doping, research on vacancy engineering, frustrated Furthermore, the production of ammonia using the phosphonium cation
Lewis pairs, heterojunction construction, and cocatalyst loading for and isopropanol is also possible [139]. Hence, the exploration and
photo-electrocatalyst ammonia synthesis is becoming popular, and the advancement of non-metallic materials exhibiting a notable capacity for
major PEC techniques for ammonia production from N2 are presented in nitrogen fixation has significant promise. In recent times, there has been
Fig. 5. Ammonia synthesis PEC performance improved considerably a growing body of evidence from experimental studies and theoretical
with vacancies and thus, oxygen vacancy (Ov) construction methods calculations indicating that conventional semiconductor materials hold
have been extensively investigated, improving nitrogen fixation effec­ significant potential as photoelectrocatalysts for the reduction of N2
tiveness. The addition of Ov increased the adsorption ability of R-BiOI to under ambient settings.
N2, resulting in a 1400 μmol m− 2h− 1 ammonia generation rate at 0.4 V. The foregoing results suggest that PEC N2 reduction is a potential
The BiOBr/TiO2 photoelectrode with Ovs yields 3.3 times more NH3 technique to attain the N-cycle target under environmental conditions,
than the photocathode without Ovs [132,133]. A simple pretreatment of and numerous catalytic solutions have been developed to improve NH3
ZnCr-LDH, ZnAl-LDH, and NiAl-LDH nanosheets with aqueous NaOH to yield and selectivity. PEC N2 reduction is more efficient than photo­
increase oxygen vacancies increased photocatalytic activity for N2 catalysis or electrocatalysis, but this collaborative technique hinders
reduction to NH3 [121]. mechanistic knowledge and photogenic/electrical effects. Most studies
Metal/non-metal ion doping can alter electrical structure, electron show that light irradiation increases electrocatalysis and bias accelerates
density, and surface defects followed by the improvement in NH3 gen­ photogenerated carrier separation, but few prove that photocatalysis
eration [134]. Iron ions with many empty 3D orbitals are the most and electrocatalysis coexist. Spectral analysis is flexible; however, pH,
researched metal doping for photocatalytic nitrogen fixation. Non- ionic strength, and sacrificial agents affect accuracy. Therefore, it must
metallic atoms like B, P, N, etc. are doped to improve NH3 production. be combined with other quantitative studies like ion chromatography
In photocatalysis and electrocatalysis, graphene is a growing class of and NMR to get correct NH3 concentrations. Reconstructing the surface
two-dimensional materials. Even while non-metallic catalysts doped structure, changing valence states, identifying reaction intermediates
with non-metallic elements function better, additional research is and active centres, and monitoring reaction processes in real time are
needed on their mechanism and stability because the added elements challenging to forecast. Based on calculation and experiment, PEC N2
could inhibit electrons and holes [135,136]. Unlike single-phase cata­ reduction outperforms photocatalysis and electrocatalysis and dura­
lysts, heterojunction materials regulate light absorption, accelerate bility testing is also necessary to prove its industrial applicability.
carrier separation, and passivate electron-hole recombination. The Cu-
MOF/Cu2O heterostructure enhances carrier density, charge separation 3.4. Biocatalytic ammonia synthesis
efficiency, and NH3 yield to 7.2 mmol m− 2h− 1. The phthalocyanine
copper/CeO2heterostructure exhibits a broad absorbance spectrum and Microorganisms present in nature possess have the ability to function
a maximum NH3 yield of 1.16 μmol h− 1 cm− 2. The LDH is useful in as catalysts, thus, facilitating the production of NH3 by utilising the
photocatalysis, electrocatalysis, and energy conversion because its nitrogen present in the atmosphere. Biocatalytic ammonia synthesis can
composition is easy to regulate, and it has many vacant oxygen sites. The occur under ambient atmospheric temperatures and pressures and it
innovative three-dimensional hollow hierarchical structure has several exhibits a higher nitrogen reduction capability compared to the Haber-
nitrogen adsorption and reduction sites to NH3 [137]. Bosch process. The process of biological nitrogen reduction can be
Noble metal catalysts possess several advantageous characteristics, categorized as biological nitrogen reduction bacteria and biomimetic
including enhanced catalytic activity, stability, and selectivity. In order chemical nitrogen reduction. The biomimetic chemical synthesis of
to optimise the usage of noble metals, it is imperative to incorporate ammonia through nitrogen fixation is a chemical approach aimed at
them onto the host matrix. An instance of this is when black silicon is emulating the nitrogenase function observed in biological organisms.
utilised to offer a substantial surface area for the loading of gold (Au). This method seeks to develop highly efficient chemical catalysts capable
The ammonia yield of Au-coated black silicon is more than that of black of producing ammonia at ambient temperature and pressure conditions.
silicon, with a value above 13 mg m− 2h− 1. The PEC method of nitrogen The fundamental concept of green ammonia synthesis within a bio­
conversion into ammonia was successfully achieved through the uti­ catalytic ammonia synthesis system is exemplified in Fig. 6.
lisation of black silicon to improve light absorption and silver as an Significant advancements have been achieved in recent years
active site. The process achieved a Faradaic efficiency of 55.05 % at a regarding the utilisation of nitrogenase for the synthesis of ammonia
potential of 0.1 V [119]. The enhanced transfer and separation of car­ through the utilisation of sustainable energy sources. Nitrogenases are a
riers can be ascribed to the robust interaction between SnO2 and MoS2, class of metalloenzymes consisting of two components. The initial
resulting in an NH3 yield of 19.6 μg h− 1 mg− 1 and a Faradaic efficiency component is referred to as the Fe-protein, an ATP-dependent enzyme
of 40.34 %. These values significantly surpass the NH3 production ca­ that comprises a Fe-S cluster and serves as an electron donor to the
pabilities of standalone SnO2 and MoS2 materials. In their study, Hu catalytic component [140,141]. The nitrogenase enzyme consists of

11
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

Fig. 6. The fundamental concept of green ammonia synthesis by the biocatalytic system.

several subunits, each of which plays a distinct role in the overall nitrogenase catalysis process. At the same time the catalytic interme­
functioning of the enzyme. The functions of these subunits are inter­ diate forms a complicated arrangement with the binding of nitrogen gas
connected, and the molecular mechanism behind their interactions is (N2). Hydrogen gas is generated during the conversion of nitrogen gas
intricate. Hence, the precise details of the reaction mechanism have yet (N2) into ammonia. According to the stoichiometric formula, 16 mole­
to be fully elucidated [142,143]. Efforts have been made to generate cules of MgATP must participate in the system and eight electrons must
ammonia by the utilisation of nitrogenase. These endeavours be transferred in total for the nitrogen-fixation reaction to occur.
commenced by establishing a heterologous expression system for the
nitrogenase subunits derived from Klebsiella oxytoca in Escherichia coli N2 + 8H++ 16MgATP + 8e~-→2NH3 + H2 + 16MgADP + 16Pi (9)
[144]. The nitrogenase enzyme in question utilises molybdenum as a where ADP is adenosine diphosphate and Pi is inorganic phosphate
cofactor. However, it is worth noting that Azotobacter vinelandii, a bac­ [149].
terium known for its nitrogen-fixing capabilities, possesses a distinct Nitrogenase allows for biological nitrogen fixation without the need
nitrogenase enzyme that employs vanadium and iron as cofactors. for direct light interaction. Nitrogen-fixing bacteria that live in symbi­
Several previous efforts have been undertaken, yielding some levels of otic partnerships with plants use photosynthesis as a source of energy for
achievement, in order to establish heterologous expression of the nitrogenase. The CdS-MoFe protein biohybrid’s rate of NH3 synthesis
nitrogenase gene cluster in both E. coli and yeast. These endeavours under visible light is 15 nmol/mg/min, which is comparable to nitro­
aimed to unravel the mechanism responsible for safeguarding the gene genase’s rate of NH3 synthesis in natural systems. A noteworthy benefit
cluster from oxygen and to enhance its overall activity [145]. of the nitrogenase ammonia synthesis method is the high electronic ef­
In recent times, there has been a growing interest among industrial ficiency and minimal energy consumption. However, the progress of this
entities, such Ginkgo Bioworks and Pivot Bio, Inc., in investigating the technology is hindered by the limitation of low reaction rates, which
prospective utilisation of nitrogen-fixing microorganisms for industrial restricts further enhancements. Furthermore, the issues associated with
uses. A study was conducted by Pivot Bio, Inc., wherein nitrogen-fixing the stability and recycling of the catalyst are particularly noteworthy.
bacteria belonging to the genus Enterobacter sp. were utilised through The primary challenge encountered in ammonia synthesis under
genetic engineering techniques. The insufficiency of glutamine in these ambient temperature and pressure conditions is the insufficient pro­
bacteria can be attributed to the diminished expression of the tran­ duction rate of NH3, which falls far below the established industrial
scription factor GlnR. Therefore, the bacteria exhibited an enhanced demands (9.3 × 10–7 mol cm− 2 s− 1). Moreover, using biocatalysts for
capacity to synthesise ammonia in the presence of increased intracel­ ammonia production presents numerous obstacles and potential.
lular glutamine. This action is evidenced by the upregulation of nitro­ Various techniques have been documented in the literature for synthe­
genase activity compared to the wild type of strain. Furthermore, the sizing ammonia from food waste and other forms of biomass. The
maize (Zea mays) seedlings were inoculated with these bacteria prior to genetically modified strains of E. coli and Bacillus were involved in this
planting and were supplied with a consistent source of nutrients process. An instance of the utilisation of Bacillus subtilis involves its
[140,146]. The production of a single molecule of ammonia necessitates application in the hydrolysis of protein biomass by the action of its
the use of eight molecules of ATP by nitrogenase, and its deactivation intrinsic protease, leading to the effective synthesis of amino acids.
can occur rapidly upon exposure to oxygen. The catalysts in question Furthermore, the employment of metabolic engineering techniques fa­
have a comparable catalytic effect to MoFe, but with a lower level of cilitates the substantial production of ammonia and alcohol from these
activity [147]. The process of converting N2 to NH3 frequently involves amino acids [151,152]. Several investigations have been conducted to
the production of H2 through the catalytic activity of nitrogenase and explore the heterologous production of nitrogenases in yeast. Cloning
the utilisation of energy derived from ATP hydrolysis. techniques, such as gene synthesis with codon optimisation, along with
The electron transfer pathways involved in the catalysis of N2 other tools in synthetic biology, such as metabolic engineering methods,
reduction by nitrogenase were thoroughly examined by Howard and enable the assembly of multi-protein pathways that incorporate proteins
Rees [148]. According to the study, they specifically looked at three from diverse sources. Hence, it is plausible that in the future, there may
different types of electron transport. The MoFe protein aids in the be potential for the development of functional nitrogenases within plant
reduction of protons to make molecular hydrogen (H2) during the cells. This can enable the creation of agriculturally viable crops capable

12
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

of autonomously fixing nitrogen [151,152]. The utilisation of ammonia [2] Salmon N, Bañares-Alcántara R. A global, spatially granular techno-economic
analysis of offshore green ammonia production. J Clean Prod 2022;367:133045.
derived from soybean residues has been employed in the process of yeast
https://doi.org/10.1016/j.jclepro.2022.133045.
cell surface engineering. The yeast demonstrated a notable proficiency [3] MacFarlane DR, Choi J, Suryanto BHR, Jalili R, Chatti M, Azofra LM, et al.
(83.2 %) and achieved a substantial concentration (3.34 g/L) of Liquefied Sunshine: Transforming Renewables into Fertilizers and Energy
ammonia when exposed to a glutamine solution [153]. Hence, the Carriers with Electromaterials. Adv Mater 2020;32:1–13. https://doi.org/
10.1002/adma.201904804.
efficient production of ammonia from food waste can be achieved [4] IRENA and AEA. Innovation Outlook: Renewable Ammonia. 2022.
through the utilisation of yeast that exhibits the enzyme HcLAAO. The [5] Wang Y, Zheng S, Chen J, Wang Z, He S. Ammonia (NH 3) Storage for Massive PV
expression of HcLAAO in Saccharomyces cerevisiae resulted in a signifi­ Electricity. Energy Procedia 2018;150:99–105. https://doi.org/10.1016/j.
egypro.2018.09.001.
cant increase in ammonia production efficiency, reaching approxi­ [6] Macfarlane DR, Cherepanov PV, Choi J, Suryanto BHR, Hodgetts RY, Bakker JM,
mately 88 %, when conducted under mild circumstances at 30 ◦ C. et al. A roadmap to the ammonia economy. Joule 2020;4:1186–205. https://doi.
Notably, there have been significant advancements in the development org/10.1016/j.joule.2020.04.004.
[7] Steven S. Zumdahl. ammonia. Britannica 2023.
of enzymes capable of converting 13 different amino acids into [8] Lemmon EW, Bell IH, Huber ML, McLinden MO. NIST Reference Fluid
ammonia. Hence, it is vital to contemplate the potential of a biocatalytic Thermodynamic and Transport Properties Database (REFPROP), Version 10.0;
system for social implementation in the forthcoming years [140,141]. Standard Reference Data; National Institute of Standards and Technology:
Gaithersburg, MD. NIST Stand Ref Databasev23 2018:288–90.
Based on the in-depth analysis of ammonia production, it is concluded [9] Agency for Toxic Substances and Disease Registry. Toxicological profile for
that the selection of a lucrative, energy-efficient, and environmentally ammonia. Fed Reg 2004;269.
benign catalytic system is essential to augment the green ammonia yield. [10] Lucentini I, Garcia X, Vendrell X, Llorca J. Review of the decomposition of
ammonia to generate hydrogen. Ind Eng Chem Res 2021;60:18560–611. https://
doi.org/10.1021/acs.iecr.1c00843.
4. Conclusion [11] Chehade G, Dincer I. Progress in green ammonia production as potential carbon-
free fuel. Fuel 2021;299:120845. https://doi.org/10.1016/j.fuel.2021.120845.
[12] Stagni A, Cavallotti C, Arunthanayothin S, Song Y, Herbinet O, Battin-Leclerc F,
Understanding the rudimentary mechanism and efficiency of the
et al. An experimental, theoretical and kinetic-modeling study of the gas-phase
technique is essential to ameliorate green ammonia production and also oxidation of ammonia. React Chem Eng 2020;5:696–711. https://doi.org/
project it as a commercially viable fuel/ material for the years to come. 10.1039/c9re00429g.
Therefore, this review extensively evaluated the principle, strategies, [13] Kobayashi H, Hayakawa A, Somarathne KDKA, Okafor EC. Science and
technology of ammonia combustion. Proc Combust Inst 2019;37:109–33. https://
reaction mechanism, catalysts engineering and state of the art of elec­ doi.org/10.1016/j.proci.2018.09.029.
trocatalysis, photocatalysis, photoelectrocatalysis, and biocatalysis [14] Herbinet O, Bartocci P, Grinberg DA. On the use of ammonia as a fuel – A
methods for green ammonia production. Of the most commonly used perspective. Fuel Commun 2022;11:100064. https://doi.org/10.1016/j.
jfueco.2022.100064.
methods electrocatalysis, photocatalysis, biocatalysis, and photo­ [15] Liu H. Ammonia synthesis catalyst 100 years: Practice, enlightenment and
electrocatalysis, water electrolysis using Haber-Bosch process is the challenge. Cuihua Xuebao/Chinese J Catal 2014;35:1619–40. https://doi.org/
widely adopted method. On the other hand, the microorganism-based 10.1016/S1872-2067(14)60118-2.
[16] Rouwenhorst KHR, Travis AS, Lefferts L. 1921–2021: A Century of Renewable
biocatalytic method exhibits a higher nitrogen reduction capability Ammonia Synthesis. Sustain Chem 2022;3:149–71. https://doi.org/10.3390/
and is deemed to be environmentally benign technique for green suschem3020011.
ammonia production. Further, exploration of novel and emerging metal [17] IEA (2021) Ammonia Technology Roadmap. Ammonia Technology Roadmap.
2021. Doi: 10.1787/f6daa4a0-en.
and non-metal-based photocatalysts can be a promising choice to [18] The Royal Society. AMMONIA: ZERO-CARBON FERTILISER, FUEL AND ENERGY
augment ammonia production in bulk quantity for various industrial STORE. 2020.
application. However, the cost of the process and ammonia yield must [19] Schmidt O, Gambhir A, Staffell I, Hawkes A, Nelson J, Few S. Future cost and
performance of water electrolysis: An expert elicitation study. Int J Hydrogen
be taken into account to ensure the economic feasibility of the process.
Energy 2017;42:30470–92. https://doi.org/10.1016/j.ijhydene.2017.10.045.
However, commercially viable green ammonia production is still at a [20] Buttler A, Splietho H. Current status of water electrolysis for energy storage, grid
primitive stage and therefore, the design of photocatalysts, and micro­ balancing and sector coupling via power-to-gas and power-to-liquids: A review.
bial catalysis requires R and D attempts to accelerate the ammonia yield Renew Sustain Energy Rev 2018;82:2440–54. https://doi.org/10.1016/j.
rser.2017.09.003.
with better reproducibility to propose ammonia as a carbon-free fuel for [21] Soloveichik G. Renewable Energy to Fuels Through Utilization of Energy- Dense
the future. Liquids (REFUEL) Program Overview. 2016.
[22] Skúlason E, Bligaard T, Gudmundsdóttir S, Studt F, Rossmeisl J, Abild-Pedersen F,
et al. A theoretical evaluation of possible transition metal electro-catalysts for N2
Credit authorship contribution statement reduction. PCCP 2012;14:1235–45. https://doi.org/10.1039/C1CP22271F.
[23] Chen JG, Crooks RM, Seefeldt LC, Bren KL, Morris Bullock R, Darensbourg MY,
Joseph Sekhar S.: Conceptualization, Methodology, Formal anal­ et al. Beyond fossil fuel–driven nitrogen transformations. Science 2018;80:360.
https://doi.org/10.1126/science.aar6611.
ysis, Data curation, Software, Writing – original draft; Writing – Review [24] Anderson JS, Rittle J, Peters JC. Catalytic conversion of nitrogen to ammonia by
& Editing. Ahmed Said Ahmed Al-Shahri: Writing – Review & Editing. an iron model complex. Nature 2013;501:84–7. https://doi.org/10.1038/
Godwin Glivin: Writing – Review & Editing. THT Le: Formal analysis, nature12435.
[25] Jeroh DM. Electrochemical synthesis of nanomaterials. Eng Mater 2022:1–9.
Writing – Review & Editing. Thangavel Mathimani: Conceptualization, https://doi.org/10.1007/978-3-030-85555-0_1.
Formal analysis, Data curation, Supervision, Writing – original draft, [26] Song Y, Johnson D, Peng R, Hensley DK, Bonnesen PV, Liang L, et al. A physical
Review & Editing. catalyst for the electrolysis of nitrogen to ammonia. Sci Adv 2018;4. https://doi.
org/10.1126/sciadv.1700336.
[27] Cao N, Zheng G. Aqueous electrocatalytic N2 reduction under ambient
Declaration of Competing Interest conditions. Nano Res 2018;11:2992–3008. https://doi.org/10.1007/s12274-018-
1987-y.
[28] Li Y, Zhang Q, Mei Z, Li S, Luo W, Pan F, et al. Recent advances and perspective
The authors declare that they have no known competing financial on electrochemical ammonia synthesis under ambient conditions. Small Methods
interests or personal relationships that could have appeared to influence 2021;5:2100460. https://doi.org/10.1002/smtd.202100460.
the work reported in this paper. [29] Yao Y, Wang H, Yuan X, Li H, Shao M. Electrochemical nitrogen reduction
reaction on ruthenium. ACS Energy Lett 2019;4:1336–41. https://doi.org/
10.1021/acsenergylett.9b00699.
Data availability [30] Shipman MA, Symes MD. Recent progress towards the electrosynthesis of
ammonia from sustainable resources. Catal Today 2017;286:57–68. https://doi.
org/10.1016/j.cattod.2016.05.008.
The data that has been used is confidential. [31] Higham MD, Zeinalipour-Yazdi CD, Hargreaves JSJ, Catlow CRA. Mechanism of
ammonia synthesis on Fe3Mo3N. Faraday Discuss 2022:77–96. https://doi.org/
References 10.1039/d2fd00148a.

[1] Ashrae. ASHRAE Position Document on Ammonia as refrigerant. 2014.

13
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

[32] van Langevelde PH, Katsounaros I, Koper MTM. Electrocatalytic nitrate reduction hydrogen evolution in an alkaline medium. Adv Mater 2016;28:7527–32. https://
for sustainable ammonia production. Joule 2021;5:290–4. https://doi.org/ doi.org/10.1002/adma.201601663.
10.1016/j.joule.2020.12.025. [59] Arabczyk W, Pelka R, Kocemba I, Brzoza-Kos A, Wyszkowski A, Lendzion-
[33] Wen J, Zuo L, Sun H, Wu X, Huang T, Liu Z, et al. Nanomaterials for the Bieluń Z. Study of phase transformation processes occurring in the
electrochemical nitrogen reduction reaction under ambient conditions. Nanoscale nanocrystalline iron/ammonia/hydrogen system by the magnetic permeability
Adv 2021;3:5525–41. https://doi.org/10.1039/d1na00426c. measurement method. J Phys Chem C 2022;126:7704–10. https://doi.org/
[34] Xu H, Ithisuphalap K, Li Y, Mukherjee S, Lattimer J, Soloveichik G, et al. 10.1021/acs.jpcc.2c00807.
Electrochemical ammonia synthesis through N2 and H2O under ambient [62] Singh AR, Rohr BA, Schwalbe JA, Cargnello M, Chan K, Jaramillo TF, et al.
conditions: Theory, practices, and challenges for catalysts and electrolytes. Nano Electrochemical Ammonia synthesis—the selectivity challenge. ACS Catal 2017;
Energy 2020;69:104469. https://doi.org/10.1016/j.nanoen.2020.104469. 7:706–9. https://doi.org/10.1021/acscatal.6b03035.
[35] Li B, Zhu Y, Guo W. Recent advances of metal oxide catalysts for electrochemical [63] Zhou F, Azofra LM, Ali M, Kar M, Simonov AN, McDonnell-Worth C, et al. Electro-
NH3 production from nitrogen-containing sources. Inorg Chem Front 2023: synthesis of ammonia from nitrogen at ambient temperature and pressure in ionic
5812–38. https://doi.org/10.1039/d3qi01448g. liquids. Energ Environ Sci 2017;10:2516–20. https://doi.org/10.1039/
[36] Wang H, Xiao X, Liu S, Chiang C-L, Kuai X, Peng C-K, et al. Structural and C7EE02716H.
electronic optimization of MoS2 edges for hydrogen evolution. J Am Chem Soc [66] Wang Y, Wang C, Li M, Yu Y, Zhang B. Nitrate electroreduction: mechanism
2019;141:18578–84. https://doi.org/10.1021/jacs.9b09932. insight, in situ characterization, performance evaluation, and challenges. Chem
[37] Wen Y, Liu J, Zhang F, Li Z, Wang P, Fang Z, et al. Mesoporous MnO2 nanosheets Soc Rev 2021;50:6720–33. https://doi.org/10.1039/D1CS00116G.
for efficient electrocatalytic nitrogen reduction via high spin polarization induced [67] Wang Y, Xu A, Wang Z, Huang L, Li J, Li F, et al. Enhanced nitrate-to-ammonia
by oxygen vacancy. Nano Res 2023;16:4664–70. https://doi.org/10.1007/ activity on copper-nickel alloys via tuning of intermediate adsorption. J Am Chem
s12274-022-5117-5. Soc 2020;142:5702–8. https://doi.org/10.1021/jacs.9b13347.
[38] Rogers JA. Integrated nanoelectronic-photonic devices and bioresorbable [68] Crawford J, Yin H, Du A, Mullane APO. Nitrate-to-Ammonia conversion at an
materials. Nano Res 2021;14:2885–7. https://doi.org/10.1007/s12274-021- insn-enriched liquid-metal electrode. Angew Chemie 2022;202201604:1–5.
3742-z. https://doi.org/10.1002/ange.202201604.
[39] Luo Y, Chen G-F, Ding L, Chen X, Ding L-X, Wang H. Efficient electrocatalytic N2 [69] Lv Zengxiang, Hao Leiduan, Yao Zhibo, Li Weixiang, Robertson Alex W, Sun Z,
fixation with MXene under ambient conditions. Joule 2019;3:279–89. https:// Rigorous Assessment of Cl− -Based Anolytes on Electrochemical Ammonia
doi.org/10.1016/j.joule.2018.09.011. Synthesis. Adv Sci 2022. https://doi.org/10.1002/advs.202204205.
[40] Sun Y, Deng Z, Song X-M, Li H, Huang Z, Zhao Q, et al. Bismuth-based free- [70] Huang Z, Rafiq M, Reda A, Tong Q, Astruc D, Hu L. Recent progress in
standing electrodes for ambient-condition ammonia production in neutral media. electrocatalytic nitrogen reduction to ammonia (NRR). Coord Chem Rev 2023;
Nano-Micro Lett 2020;12:133. https://doi.org/10.1007/s40820-020-00444-y. 478:214981. https://doi.org/10.1016/j.ccr.2022.214981.
[41] Li L, Tang C, Yao D, Zheng Y, Qiao S-Z. Electrochemical nitrogen reduction: [71] Ouyang L, Liang J, Luo Y, Zheng D, Sun S, Liu Q, et al. Recent advances in
identification and elimination of contamination in electrolyte. ACS Energy Lett electrocatalytic ammonia synthesis. Chinese J Catal 2023;50:6–44. https://doi.
2019;4:2111–6. https://doi.org/10.1021/acsenergylett.9b01573. org/10.1016/S1872-2067(23)64464-X.
[42] Zhong X, Yuan E, Yang F, Liu Y, Lu H, Yang J, et al. Optimizing oxygen vacancies [72] Wei Y, Jiang W, Liu Y, Bai X, Hao D, Ni BJ. Recent advances in photocatalytic
through grain boundary engineering to enhance electrocatalytic nitrogen nitrogen fixation and beyond. Nanoscale 2022;14:2990–7. https://doi.org/
reduction. Proc Natl Acad Sci 2023;120. https://doi.org/10.1073/ 10.1039/d2nr00198e.
pnas.2306673120. [73] Jang YJ, Lindberg AE, Lumley MA, Choi K-S. Photoelectrochemical nitrogen
[43] Wang Q, Lei Y, Wang D, Li Y. Defect engineering in earth-abundant reduction to ammonia on cupric and cuprous oxide photocathodes. ACS Energy
electrocatalysts for CO2 and N2 reduction. Energ Environ Sci 2019;12:1730–50. Lett 2020;5:1834–9. https://doi.org/10.1021/acsenergylett.0c00711.
https://doi.org/10.1039/C8EE03781G. [74] Ithisuphalap K, Zhang H, Guo L, Yang Q, Yang H, Wu G. Photocatalysis and
[44] Hubert Ronduda, a Magdalena Zybert, a Wojciech Patkowski, a Kamil Sobczak B, photoelectrocatalysis methods of nitrogen reduction for sustainable ammonia
Moszynski D, ́ c Aleksander Albrecht c AS and WR-,́ Pileck. On the effect of metal synthesis. Small Methods 2019;3:1800352. https://doi.org/10.1002/
loading on the performance oxides for ammonia synthesis †. RSC Adv Open 2022: smtd.201800352.
33876–88. Doi: 10.1039/d2ra06053a. [75] Wu F, Yu Y, Yang H, German LN, Li Z, Chen J, et al. Simultaneous enhancement of
[45] Gu H, Chen W, Li X. Atomically dispersed metal catalysts for the electrochemical charge separation and hole transportation in a TiO2–SrTiO3 core-shell nanowire
nitrogen reduction reaction. J Mater Chem A 2022;10:22331–53. https://doi.org/ photoelectrochemical system. Adv Mater 2017;29:1701432. https://doi.org/
10.1039/D2TA06187B. 10.1002/adma.201701432.
[46] Yang Y, Zhang L, Hu Z, Zheng Y, Tang C, Chen P, et al. The crucial role of charge [76] Huang PW, Hatzell MC. Prospects and good experimental practices for
accumulation and spin polarization in activating carbon-based catalysts for photocatalytic ammonia synthesis. Nat Commun 2022;13:1–7. https://doi.org/
electrocatalytic nitrogen reduction. Angew Chemie Int Ed 2020;59:4525–31. 10.1038/s41467-022-35489-7.
https://doi.org/10.1002/anie.201915001. [77] Schrauzer GN, Guth TD. Photolysis of water and photoreduction of nitrogen on
[47] Peng W, Luo M, Xu X, Jiang K, Peng M, Chen D, et al. Spontaneous atomic titanium dioxide. J Am Chem Soc 1977;99:7189–93. https://doi.org/10.1021/
ruthenium doping in Mo2CTX MXene defects enhances electrocatalytic activity ja00464a015.
for the nitrogen reduction reaction. Adv Energy Mater 2020;10:2001364. https:// [78] Lumley MA, Radmilovic A, Jang YJ, Lindberg AE, Choi K-S. Perspectives on the
doi.org/10.1002/aenm.202001364. development of oxide-based photocathodes for solar fuel production. J Am Chem
[48] Liu B, Zheng Y, Peng H-Q, Ji B, Yang Y, Tang Y, et al. Nanostructured and boron- Soc 2019;141:18358–69. https://doi.org/10.1021/jacs.9b07976.
doped diamond as an electrocatalyst for nitrogen fixation. ACS Energy Lett 2020; [79] Arun J, Nachiappan S, Rangarajan G, Alagappan RP, Gopinath KP, Lichtfouse E.
5:2590–6. https://doi.org/10.1021/acsenergylett.0c01317. Synthesis and application of titanium dioxide photocatalysis for energy,
[49] Zhang J, Liu J, Xi L, Yu Y, Chen N, Sun S, et al. Single-atom Au/NiFe layered decontamination and viral disinfection: a review. Environ Chem Lett 2023;21:
double hydroxide electrocatalyst: probing the origin of activity for oxygen 339–62. https://doi.org/10.1007/s10311-022-01503-z.
evolution reaction. J Am Chem Soc 2018;140:3876–9. https://doi.org/10.1021/ [80] Bouras P, Stathatos E, Lianos P. Pure versus metal-ion-doped nanocrystalline
jacs.8b00752. titania for photocatalysis. Appl Catal B Environ 2007;73:51–9. https://doi.org/
[50] Zhang H, Liu G, Shi L, Ye J. Single-atom catalysts: emerging multifunctional 10.1016/j.apcatb.2006.06.007.
materials in heterogeneous catalysis. Adv Energy Mater 2018;8:1701343. https:// [81] Zhao Y, Zhao Y, Shi R, Wang B, Waterhouse GIN, Wu L-Z, et al. Tuning oxygen
doi.org/10.1002/aenm.201701343. vacancies in ultrathin TiO2 nanosheets to boost photocatalytic nitrogen fixation
[51] Hao R, Sun W, Liu Q, Liu X, Chen J, Lv X, et al. Efficient electrochemical nitrogen up to 700 nm. Adv Mater 2019;31:1806482. https://doi.org/10.1002/
fixation over isolated Pt sites. Small 2020;16. https://doi.org/10.1002/ adma.201806482.
smll.202000015. [82] Miyama H, Fujii N, Nagae Y. Heterogeneous photocatalytic synthesis of ammonia
[53] Abghoui Y. Superiority of the (100) over the (111) facets of the nitrides for from water and nitrogen. Chem Phys Lett 1980;74:523–4. https://doi.org/
hydrogen evolution reaction. Top Catal 2022;65:262–9. https://doi.org/ 10.1016/0009-2614(80)85266-3.
10.1007/s11244-021-01474-5. [83] Ali M, Zhou F, Chen K, Kotzur C, Xiao C, Bourgeois L, et al. Nanostructured
[54] Gudmundsson M, Ellingsson V, Skúlason E, Abghoui Y. Optimizing nitrogen photoelectrochemical solar cell for nitrogen reduction using plasmon-enhanced
reduction reaction on nitrides: A computational study on crystallographic black silicon. Nat Commun 2016;7:11335. https://doi.org/10.1038/
orientation. Top Catal 2022;65:252–61. https://doi.org/10.1007/s11244-021- ncomms11335.
01485-2. [84] Zheng J, Lyu Y, Qiao M, Wang R, Zhou Y, Li H, et al. Photoelectrochemical
[55] Montoya JH, Tsai C, Vojvodic A, Nørskov JK. The challenge of electrochemical synthesis of ammonia on the aerophilic-hydrophilic heterostructure with 37.8%
ammonia synthesis: A new perspective on the role of nitrogen scaling relations. efficiency. Chem 2019;5:617–33. https://doi.org/10.1016/j.
ChemSusChem 2015;8:2180–6. https://doi.org/10.1002/cssc.201500322. chempr.2018.12.003.
[56] Ripepi D, Schreuders H, Mulder FM. Effect of temperature and H Flux on the NH3 [85] Zeng H, Terazono S, Tanuma T. A novel catalyst for ammonia synthesis at
synthesis via electrochemical hydrogen permeation. ChemSusChem 2023;16. ambient temperature and pressure: Visible light responsive photocatalyst using
https://doi.org/10.1002/cssc.202300460. localized surface plasmon resonance. Catal Commun 2015;59:40–4. https://doi.
[57] Asano M, Kawamura R, Sasakawa R, Todoroki N, Wadayama T. Oxygen reduction org/10.1016/j.catcom.2014.09.034.
reaction activity for strain-controlled Pt-based model alloy catalysts: surface [86] Hirakawa H, Hashimoto M, Shiraishi Y, Hirai T. Selective nitrate-to-ammonia
strains and direct electronic effects induced by alloying elements. ACS Catal transformation on surface defects of titanium dioxide photocatalysts. ACS Catal
2016;6:5285–9. https://doi.org/10.1021/acscatal.6b01466. 2017;7:3713–20. https://doi.org/10.1021/acscatal.7b00611.
[58] Chen P, Xu K, Tao S, Zhou T, Tong Y, Ding H, et al. Phase-transformation [87] Chen S, Xu Y-M, He J-N, Chen S-L, Wang A-J. Photon localization effect and
engineering in cobalt diselenide realizing enhanced catalytic activity for surface oxygen vacancy enhanced photocatalytic nitrogen fixation performance

14
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

for nanocrystalline titanium dioxide films. New J Chem 2023;47:14494–507. [114] Zuo C, Su Q. Advances in semiconductor-based nanocomposite photo(electro)
https://doi.org/10.1039/D3NJ02585C. catalysts for nitrogen reduction to ammonia. Molecules 2023:28. https://doi.org/
[88] Li H, Shang J, Ai Z, Zhang L. Efficient visible light nitrogen fixation with BiOBr 10.3390/molecules28062666.
nanosheets of oxygen vacancies on the exposed 001 facets. J Am Chem Soc 2015; [115] Zhao Z, Tan R, Kong Y, Zhang Z, Qiu S, Mu X, et al. Defect pyrochlore-type Mott-
137:6393–9. https://doi.org/10.1021/jacs.5b03105. Schottky photocatalysts for enhanced ammonia synthesis at low pressure. Angew
[89] Liu Y, Huang L, Fang Y, Zhu X, Dong S. Achieving ultrahigh electrocatalytic NH3 Chemie - Int Ed 2023:62. https://doi.org/10.1002/anie.202303629.
yield rate on Fe-doped Bi2WO6 electrocatalyst. Nano Res 2021;14:2711–6. [116] Niu Z-Y, Jiao L, Zhang T, Zhao X-M, Wang X-F, Tan Z, et al. Boosting
https://doi.org/10.1007/s12274-020-3276-9. electrocatalytic ammonia synthesis of bio-inspired porous mo-doped hematite via
[90] Li J, Niu A, Lu C-J, Zhang J-H, Junaid M, Strauss PR, et al. A novel forward nitrogen activation. ACS Appl Mater Interfaces 2022;14:55559–67. https://doi.
osmosis system in landfill leachate treatment for removing polycyclic aromatic org/10.1021/acsami.2c16081.
hydrocarbons and for direct fertigation. Chemosphere 2017;168:112–21. https:// [117] Xu X, Liu X, Zhao J, Wu D, Du Y, Yan T, et al. Interface engineering of MoS2@Fe
doi.org/10.1016/j.chemosphere.2016.10.048. (OH)3 nanoarray heterostucture: Electrodeposition of MoS2@Fe(OH)3 as N2 and
[91] Huang WL, Zhu Q. DFT calculations on the electronic structures of BiOX (X = F, H+ channels for artificial NH3 synthesis under mild conditions. J Colloid
Cl, Br, I) photocatalysts with and without semicore Bi 5d states. J Comput Chem Interface Sci 2022;606:1374–9. https://doi.org/10.1016/j.jcis.2021.08.099.
2009;30:183–90. https://doi.org/10.1002/jcc.21055. [118] Li P, Liu Y, Mushtaq MA, Yan D. Recent progress on ammonia synthesis based on
[92] Sun Y, Ahmadi Y, Kim KH, Lee J. The use of bismuth-based photocatalysts for the photoelectrocatalysis. Inorg Chem Front 2023:4650–67. https://doi.org/
production of ammonia through photocatalytic nitrogen fixation. Renew Sustain 10.1039/d3qi00683b.
Energy Rev 2022;170:112967. https://doi.org/10.1016/j.rser.2022.112967. [119] Wang B, Yao L, Xu G, Zhang X, Wang D, Shu X, et al. Highly efficient
[93] Sun S, An Q, Wang W, Zhang L, Liu J, Goddard III WA. Efficient photocatalytic photoelectrochemical synthesis of ammonia using plasmon-enhanced black
reduction of dinitrogen to ammonia on bismuth monoxide quantum dots. J Mater silicon under ambient conditions. ACS Appl Mater Interfaces 2020;12:20376–82.
Chem A 2017;5:201–9. https://doi.org/10.1039/C6TA09275F. https://doi.org/10.1021/acsami.0c00881.
[94] Feng Y, Zhang Z, Zhao K, Lin S, Li H, Gao X. Photocatalytic nitrogen fixation: [120] Niu X, Shi A, Sun D, Xiao S, Zhang T, Zhou Z, et al. Photocatalytic ammonia
Oxygen vacancy modified novel micro-nanosheet structure Bi(2)O(2)CO(3) with synthesis: mechanistic insights into N2 activation at oxygen vacancies under
band gap engineering. J Colloid Interface Sci 2021;583:499–509. https://doi.org/ visible light excitation. ACS Catal 2021;11:14058–66. https://doi.org/10.1021/
10.1016/j.jcis.2020.09.089. acscatal.1c03407.
[95] Gao X, Wen Y, Qu D, An L, Luan S, Jiang W, et al. Interference effect of alcohol on [121] Lin S, Chen Y, Fu J, Sun L, Jiang Q, Li J-F, et al. Photoelectrocatalytic nitrogen
Nessler’s reagent in photocatalytic nitrogen fixation. ACS Sustain Chem Eng fixation with Vo-BiOBr/TiO2 heterostructured photoelectrode as photocatalyst.
2018;6:5342–8. https://doi.org/10.1021/acssuschemeng.8b00110. Int J Hydrogen Energy 2022;47:41553–63. https://doi.org/10.1016/j.
[96] Banerjee A, Yuhas BD, Margulies EA, Zhang Y, Shim Y, Wasielewski MR, et al. ijhydene.2022.02.026.
Photochemical nitrogen conversion to ammonia in ambient conditions with [122] Liu Y-G, Tian M, Hou J, Jiang H-Y. Research progress and perspectives on active
FeMoS-chalcogels. J Am Chem Soc 2015;137:2030–4. https://doi.org/10.1021/ sites of photo- and electrocatalytic nitrogen reduction. Energy Fuel 2022;36:
ja512491v. 11323–58. https://doi.org/10.1021/acs.energyfuels.2c01390.
[97] Li C, Wang T, Zhao Z-J, Yang W, Li J-F, Li A, et al. Promoted fixation of molecular [123] Suryanto BHR, Kang CSM, Wang D, Xiao C, Zhou F, Azofra LM, et al. Rational
nitrogen with surface oxygen vacancies on plasmon-enhanced TiO(2) electrode-electrolyte design for efficient ammonia electrosynthesis under ambient
photoelectrodes. Angew Chem Int Ed Engl 2018;57:5278–82. https://doi.org/ conditions. ACS Energy Lett 2018;3:1219–24. https://doi.org/10.1021/
10.1002/anie.201713229. acsenergylett.8b00487.
[98] Hirakawa H, Hashimoto M, Shiraishi Y, Hirai T. Photocatalytic conversion of [124] Lee HK, Koh CSL, Lee YH, Liu C, Phang IY, Han X, et al. Favoring the unfavored:
nitrogen to ammonia with water on surface oxygen vacancies of titanium dioxide. Selective electrochemical nitrogen fixation using a reticular chemistry approach.
J Am Chem Soc 2017;139:10929–36. https://doi.org/10.1021/jacs.7b06634. Sci Adv 2018;4. https://doi.org/10.1126/sciadv.aar3208.
[99] Zhao Y, Zhao Y, Waterhouse GIN, Zheng L, Cao X, Teng F, et al. Layered-double- [125] Abghoui Y, Garden AL, Hlynsson VF, Björgvinsdóttir S, Ólafsdóttir H, Skúlason E.
hydroxide nanosheets as efficient visible-light-driven photocatalysts for Enabling electrochemical reduction of nitrogen to ammonia at ambient conditions
dinitrogen fixation. Adv Mater 2017:29. https://doi.org/10.1002/ through rational catalyst design. PCCP 2015;17:4909–18. https://doi.org/
adma.201703828. 10.1039/C4CP04838E.
[101] Jo YK, Lee JM, Son S, Hwang S-J. 2D inorganic nanosheet-based hybrid [126] Bharath G, Rambabu K, Hai A, Ponpandian N, Schmidt JE, Dionysiou DD, et al.
photocatalysts: Design, applications, and perspectives. J Photochem Photobiol Dual-functional paired photoelectrocatalytic system for the photocathodic
C: Photochem Rev 2019;40:150–90. https://doi.org/10.1016/j. reduction of CO2 to fuels and the anodic oxidation of furfural to value-added
jphotochemrev.2018.03.002. chemicals. Appl Catal B Environ 2021;298:120520. https://doi.org/10.1016/j.
[102] Wang Y, Cai J, Wu M, Chen J, Zhao W, Tian Y, et al. Rational construction of apcatb.2021.120520.
oxygen vacancies onto tungsten trioxide to improve visible light photocatalytic [127] Safaei J, Ullah H, Mohamed NA, Mohamad Noh MF, Soh MF, Tahir AA, et al.
water oxidation reaction. Appl Catal B Environ 2018;239:398–407. https://doi. Enhanced photoelectrochemical performance of Z-scheme g-C3N4/BiVO4
org/10.1016/j.apcatb.2018.08.029. photocatalyst. Appl Catal B Environ 2018;234:296–310. https://doi.org/
[103] Ou H, Lin L, Zheng Y, Yang P, Fang Y, Wang X. Tri-s-triazine-based crystalline 10.1016/j.apcatb.2018.04.056.
carbon nitride nanosheets for an improved hydrogen evolution. Adv Mater [128] Bai Y, Bai H, Fang Z, Li X, Fan W, Shi W. Understanding the Z-scheme
2017:29. https://doi.org/10.1002/adma.201700008. heterojunction of BiVO4/PANI for photoelectrochemical nitrogen reduction.
[104] Zong X, Yan H, Wu G, Ma G, Wen F, Wang L, et al. Enhancement of Chem Commun 2021;57:10568–71. https://doi.org/10.1039/D1CC03687D.
photocatalytic H2 evolution on CdS by loading MoS2 as cocatalyst under visible [130] Chae SY, Choi JY, Kim Y, Le Tri ND, Joo O-S. Photoelectrochemical CO2
light irradiation. J Am Chem Soc 2008;130:7176–7. https://doi.org/10.1021/ reduction with a rhenium organometallic redox mediator at semiconductor/
ja8007825. aqueous liquid junction interfaces. Angew Chemie Int Ed 2019;58:16395–9.
[105] Ye L, Han C, Ma Z, Leng Y, Li J, Ji X, et al. Ni2P loading on Cd0.5Zn0.5S solid https://doi.org/10.1002/anie.201908398.
solution for exceptional photocatalytic nitrogen fixation under visible light. [132] Xue X, Chen R, Chen H, Hu Y, Ding Q, Liu Z, et al. Oxygen vacancy engineering
Chem Eng J 2017;307:311–8. https://doi.org/10.1016/j.cej.2016.08.102. promoted photocatalytic ammonia synthesis on ultrathin two-dimensional
[106] Hu S, Chen X, Li Q, Zhao Y, Mao W. Effect of sulfur vacancies on the nitrogen bismuth oxybromide nanosheets. Nano Lett 2018;18:7372–7. https://doi.org/
photofixation performance of ternary metal sulfide photocatalysts. Cat Sci 10.1021/acs.nanolett.8b03655.
Technol 2016;6:5884–90. https://doi.org/10.1039/C6CY00622A. [133] Gao K, Zhang C, Zhang Y, Zhou X, Gu S, Zhang K, et al. Oxygen vacancy
[107] Shen H, Yang M, Hao L, Wang J, Strunk J, Sun Z. Photocatalytic nitrogen engineering of novel ultrathin Bi12O17Br 2 nanosheets for boosting
reduction to ammonia: Insights into the role of defect engineering in photocatalytic N2 reduction. J Colloid Interface Sci 2022;614:12–23. https://doi.
photocatalysts. Nano Res 2022;15. https://doi.org/10.1007/s12274-021-3725-0. org/10.1016/j.jcis.2022.01.084.
[108] Zhang G, Sewell CD, Zhang P, Mi H, Lin Z. Nanostructured photocatalysts for [134] Sun PX, Cao Z, Zeng YX, Xie WW, Li NW, Luan D, et al. Formation of super-
nitrogen fixation. Nano Energy 2020;71:104645. https://doi.org/10.1016/j. assembled TiOx/Zn/N-doped carbon inverse opal towards dendrite-free Zn
nanoen.2020.104645. anodes. Angew Chemie Int Ed 2022;61. https://doi.org/10.1002/
[109] Lee J, Tan L-L, Chai S-P. Heterojunction photocatalysts for artificial nitrogen anie.202115649.
fixation: fundamentals{,} latest advances and future perspectives. Nanoscale [135] Natarajan TS, Mozhiarasi V, Tayade RJ. Nitrogen doped titanium dioxide (N-
2021;13:7011–33. https://doi.org/10.1039/D1NR00783A. TiO2): synopsis of synthesis methodologies, doping mechanisms, property
[110] Zheng J, Lu L, Lebedev K, Wu S, Zhao P, McPherson IJ, et al. Fe on molecular- evaluation and visible light photocatalytic applications. Photochem 2021;1:
layer MoS2 as inorganic Fe-S2-Mo motifs for light-driven nitrogen fixation to 371–410. https://doi.org/10.3390/photochem1030024.
ammonia at elevated temperatures. Chem Catal 2021;1:162–82. https://doi.org/ [136] Nosaka Y, Matsushita M, Nishino J, Nosaka A. Nitrogen-doped titanium dioxide
10.1016/j.checat.2021.03.002. photocatalysts for visible response prepared by using organic compounds. Sci
[111] Tan J, Ren H, Zhao Z, Xin X, Shi Y, Yang D, et al. Ca2+ doped metal organic Technol Adv Mater 2005;6:143–8. https://doi.org/10.1016/j.stam.2004.11.006.
frameworks for enhanced photocatalytic ammonia synthesis. Chem Eng J 2023; [137] Arif M, Yasin G, Luo L, Ye W, Mushtaq MA, Fang X, et al. Hierarchical hollow
466:143259. https://doi.org/10.1016/j.cej.2023.143259. nanotubes of NiFeV-layered double hydroxides@CoVP heterostructures towards
[112] Ahmad N, Anae J, Khan MZ, Sabir S, Campo P, Coulon F. A novel CuBi2O4/ efficient, pH-universal electrocatalytical nitrogen reduction reaction to ammonia.
polyaniline composite as an efficient photocatalyst for ammonia degradation. Appl Catal B Environ 2020;265:118559. https://doi.org/10.1016/j.
Heliyon 2022;8. https://doi.org/10.1016/j.heliyon.2022.e10210. apcatb.2019.118559.
[113] Zhang H, Chen Y, Pan Y, Bao L, Ge JY. Multicomponent hydroxides supported Cu/ [138] Hu Y, Zhao ZL, Ahmad R, Harb M, Cavallo L, Azofra LM, et al. A bifunctional
Cu2O nanoparticles for high efficient photocatalytic ammonia synthesis. J Colloid catalyst based on a carbon quantum dots/mesoporous SrTiO3 heterostructure for
Interface Sci 2023;642:470–8. https://doi.org/10.1016/j.jcis.2023.03.187.

15
S. Joseph Sekhar et al. Fuel 358 (2024) 130307

cascade photoelectrochemical nitrogen reduction. J Mater Chem A 2022;10: [146] Davis WG, Bonini Pires CA, Ruiz Diaz DA, Roozeboom KL, Rice CW. Pivot bio
12713–21. https://doi.org/10.1039/D2TA02187K. proven inoculant as a source of nitrogen in corn. Kansas Agric Exp Stn Res Reports
[139] Du H-L, Matuszek K, Hodgetts RY, Ngoc Dinh K, Cherepanov PV, Bakker JM, et al. 2020:6. https://doi.org/10.4148/2378-5977.7975.
The chemistry of proton carriers in high-performance lithium-mediated ammonia [147] Hoffman BM, Lukoyanov D, Yang Z-Y, Dean DR, Seefeldt LC. Mechanism of
electrosynthesis. Energ Environ Sci 2023;16:1082–90. https://doi.org/10.1039/ nitrogen fixation by nitrogenase: the next stage. Chem Rev 2014;114:4041–62.
D2EE03901J. https://doi.org/10.1021/cr400641x.
[140] Watanabe Y, Aoki W, Ueda M. Ammonia production using bacteria and yeast [148] Howard JB, Rees DC. Structural basis of biological nitrogen fixation. Chem Rev
toward a sustainable society. Bioengineering 2023;10:20–4. https://doi.org/ 1996;96:2965–82. https://doi.org/10.1021/cr9500545.
10.3390/bioengineering10010082. [149] Rees DC, Akif Tezcan F, Haynes CA, Walton MY, Andrade S, Einsle O, et al.
[141] Wang B, Zhang Y, Minteer SD. Renewable electron-driven bioinorganic nitrogen Structural basis of biological nitrogen fixation. Philos Trans Ser A, Math Phys Eng
fixation: a superior route toward green ammonia? Energ Environ Sci 2022;16: Sci 2005;363:940–71. https://doi.org/10.1098/rsta.2004.1539.
404–20. https://doi.org/10.1039/d2ee03132a. [151] Tatemichi Y, Kuroda K, Nakahara T, Ueda M. Efficient ammonia production from
[142] Einsle O, Rees DC. Structural enzymology of nitrogenase enzymes. Chem Rev food by-products by engineered Escherichia coli. AMB Express 2020;10:150.
2020;120:4969–5004. https://doi.org/10.1021/acs.chemrev.0c00067. https://doi.org/10.1186/s13568-020-01083-7.
[143] Lindström K, Mousavi SA. Effectiveness of nitrogen fixation in rhizobia. [152] Huo Y-X, Cho KM, Rivera JGL, Monte E, Shen CR, Yan Y, et al. Conversion of
J Microbial Biotechnol 2020;13:1314–35. https://doi.org/10.1111/1751- proteins into biofuels by engineering nitrogen flux. Nat Biotechnol 2011;29:
7915.13517. 346–51. https://doi.org/10.1038/nbt.1789.
[144] Temme K, Zhao D, Voigt CA. Refactoring the nitrogen fixation gene cluster from [153] Watanabe Y, Kuroda K, Tatemichi Y, Nakahara T, Aoki W, Ueda M. Construction
Klebsiella oxytoca. Proc Nat Acad Sci USA 2012;109:7085–90. https://doi.org/ of engineered yeast producing ammonia from glutamine and soybean residues
10.1073/pnas.1120788109. (okara). AMB Express 2020;10:70. https://doi.org/10.1186/s13568-020-01011-
[145] López-Torrejón G, Burén S, Veldhuizen M, Rubio LM. Biosynthesis of cofactor- 9.
activatable iron-only nitrogenase in Saccharomyces cerevisiae. J Microbial
Biotechnol 2021;14:1073–83. https://doi.org/10.1111/1751-7915.13758.

16