AAAS

Energy Material Advances

Volume 2021, Article ID 9761263, 12 pages
https://doi.org/10.34133/2021/9761263

Research Article
A Green Synthesis of Ru Modified g-C3N4 Nanosheets for
Enhanced Photocatalytic Ammonia Synthesis

Derek Hao ,1 Jiawei Ren ,1 Ying Wang ,2 Hamidreza Arandiyan ,3,4

Magnus Garbrecht ,5 Xiaojuan Bai ,6 Ho Kyong Shon,1 Wei Wei,1 and Bing-Jie Ni 1

1
Centre for Technology in Water and Wastewater (CTWW), School of Civil and Environmental Engineering, University of
Technology Sydney (UTS), Sydney, NSW 2007, Australia
2
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,
Changchun 130022, China

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3
Laboratory of Advanced Catalysis for Sustainability, School of Chemistry, The University of Sydney, Sydney 2006, Australia
4
Centre for Advanced Materials & Industrial Chemistry (CAMIC), School of Science, RMIT University, Melbourne,
VIC 3000, Australia
5
Australian Centre for Microscopy and Microanalysis, The University of Sydney, Sydney 2006, Australia
6
Beijing Engineering Research Center of Sustainable Urban Sewage System Construction and Risk Control, Beijing University of Civil
Engineering and Architecture, Beijing 102612, China

Correspondence should be addressed to Ying Wang; [email protected] and Bing-Jie Ni; [email protected]

Received 2 May 2021; Accepted 13 August 2021; Published 6 September 2021

Copyright © 2021 Derek Hao et al. Exclusive Licensee Beijing Institute of Technology Press. Distributed under a Creative
Commons Attribution License (CC BY 4.0).

Nitrate is a crucial environmental pollutant, and its risk on ecosystem keeps increasing. Photocatalytic conversion of nitrate to
ammonia can simultaneously achieve the commercialization of environmental hazards and recovery of valuable ammonia,
which is green and sustainable for the planet. However, due to the thermodynamic and kinetic energy barriers, photocatalytic
nitrate reduction usually involves a higher selectivity of the formation of nitrogen that largely limits the ammonia synthesis
activity. In this work, we reported a green and facile synthesis of novel metallic ruthenium particle modified graphitic carbon
nitride photocatalysts. Compare with bulk graphitic carbon nitride, the optimal sample had 2.93-fold photocatalytic nitrate
reduction to ammonia activity (2.627 mg/h/gcat), and the NH3 selectivity increased from 50.77% to 77.9%. According to the
experimental and calculated results, the enhanced photocatalytic performance is attributed to the stronger light absorption,
nitrate adsorption, and lower energy barrier for the generation of ammonia. This work may provide a facile way to prepare
metal modified photocatalysts to achieve highly efficient nitrate reduction to ammonia.

1. Introduction globin in the human body, causing the loss of oxygen

transportation. It can also react with secondary amine com-
Nitrate (NO3-) is a necessary nutrient for plants, whereas pounds to produce carcinogenic nitrosamines [9]. Therefore,
high-level of NO3- enters the food chain via water sources it is urgent to develop a novel strategy to remove NO3-
can be toxic and hazardous to the ecosystem [1–3]. The pollution with high efficiency and selectivity.
main culprits of NO3- pollution include agricultural runoff, Ammonia (NH3) is an important industrial ingredient
fertilizer abuse, septic systems, industrial plants, and irriga- widely used in fertilizers, pharmaceutical industries, and
tion systems [4]. Currently, NO3- contamination has been other areas [10–12]. More importantly, it is also an essential
a serious environmental concern as it can affect the quality energy source. The decomposition of ammonia is a low-cost
of groundwater and surface water, causing health problems and facile process; therefore, using ammonia as a hydrogen
to humans [5, 6]. In an oxygen-deficient environment, such carrier is able to solve the hydrogen storage problem to a
as in the digestive tract, NO3- can be reduced to more toxic certain extent [13, 14]. With the increase of the global pop-
nitrite [7, 8]. Nitrite can oxidize low ferritin into methemo- ulation, the demand for NH3 keeps increasing. Currently,
2 Energy Material Advances

NH3 is mainly produced via the Haber process, in which particle-based photocatalysts for highly efficient photocata-
gaseous nitrogen (N2) and water gas are converted to NH3 lytic NO3- reduction to synthesize NH3.
under high temperature and high pressure with the assist
of catalysts [15]. Every year, the synthesis of NH3 consumes 2. Experimental Section
about 2% of global energy, leading to serious carbon dioxide
emission [16–18]. Thus, it is urgent to develop a green syn- 2.1. Chemicals and Synthesis of Materials. All the used che-
thesis of NH3 under ambient conditions. micals including ruthenium trichloride (RuCl3), sodium
In recent years, photocatalytic synthesis of NH3 has nitrate (NaNO3), sodium sulfate (Na2SO4), dicyandiamide,
become a hot research frontier, where researchers are mainly sulfuric acid (H2SO4), formic acid, and dimethyl sulfoxide
focusing on the reduction of gaseous nitrogen [19–22]. (DMSO) are analytical reagent and used without further
However, the research is still limited in the laboratory, purification. These chemicals were purchased from Merck
because the strong bond energy of N ≡ N bonds and the poor Australia.
solubility of N2 make the catalytic NH3 yield efficiency low
[16]. Compared with N2, the required energy for the cleav- 2.2. Synthesis of g-C3N4 Nanosheets. g-C3N4 was prepared via
age of N=O is only 21.68% as that of N ≡ N bonds. In addi- the thermal polymerization of dicyandiamide. Firstly, 5 g of
tion, the solubility of NO3- is 40000 times higher than that of dicyandiamide was put in a 50 mL corundum crucible with-
N2 [23]. Therefore, if the waste NO3- can be converted to out the lid. Then, the crucible was transferred into the oven
NH3, the conversion of environmental hazards to valuable and heated from 25 to 540°C with the heating rate of
energy resources will be more sustainable for the planet. 4°C/min. After heating at 540°C for 4 h in air, the bulk
Graphitic carbon nitride (g-C3N4) is a metal-free photo- g-C3N4 was obtained. The g-C3N4 nanosheets were syn-
catalyst, which is a rising star in photocatalysis because it has thesized via the ultrasonic peeling of bulk g-C3N4 in water.

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the advantages of facile synthesis, wide sources, and good In details, 500 mg of bulk g-C3N4 was added in 800 mL
photocatalytic activity for redox reactions [24–26]. In recent water and put under ultrasonic bath for 24 h. Finally, the
years, several kinds of g-C3N4-based photocatalysts have ultrathin g-C3N4 nanosheets were successfully obtained
been prepared and applied in NO3- wastewater treat- and named as 2D-CN.
ment, such as TiO2/g-C3N4 [27], Mn2O3/g-C3N4 [28], and
g-C3N4@AgPd heterojunction [29]. However, the main aim 2.3. Synthesis of Ru/g-C3N4. Herein, we used waste green tea
is to convert NO3- to N2 to reduce environmental hazards. as the reduction regent to prepare Ru modified g-C3N4
Compared with the generation of N2, the reduction of NO3- (Scheme 1). To get simulated waste tea bags, 5 tea bags were
to NH3 is more challenging in terms of kinetics and thermo- put in boiled water for 20 min. Then, the 5 used tea bags
dynamics, as it is an eight-electron process with multiple were put in 500 mL and boiled for 30 min. After that, the
steps [30]. On the other hand, many ruthenium-containing tea water was gone through a filter for further use. A certain
compounds exhibit good catalytic properties because of their amount of RuCl3 and 0.5 g of g-C3N4 nanosheets was put
unique electronic structure [31–34]. Meanwhile, ruthenium into 150 mL prepared tea water and under magnetic stir
(Ru) can absorb the light in the visible spectrum, and it is for 24 h. Finally, the powder was washed by water and etha-
being actively researched for solar energy technologies nol for 5 times and then dried at 60°C for 4 h. The amounts
[35, 36]. Nevertheless, toxic reducing agents like ethylene of RuCl3 used were 0.005, 0.01 and 0.038 g, and the obtained
glycol are usually required to reduce Ru3+ to Ru0, making samples were named as CN-Ru-0.5, CN-Ru-1, and CN-Ru-3,
the synthesis complex, dangerous, and unecofriendly [37]. respectively.
Until now, Ru modified g-C3N4 photocatalysts for highly
efficient NO3- reduction to NH3 have never been reported, 2.4. Characterizations. The X-ray diffraction (XRD) patterns
and the reaction mechanism is not clear. of the samples were tested with a Bruker D8 Discover XRD
In this work, we report a green synthesis of Ru modified with intense Cu Kα radiation (40 kV and 40 mA, λ =
g-C3N4 nanosheets with significantly enhanced photocata- 1:5406 Å) at room temperature. The morphology observa-
lytic activity on the reduction of NO3- to NH3. Herein, waste tion on the materials was carried out using a Zeiss Supra
green tea bags were used to reduce the Ru3+, and the photo- 55VP scanning electron microscope (SEM), with an oper-
catalytic activity of the optimized sample was 2.93-fold as ating voltage of 5-15 kV. The images of SEM-energy-
that of bulk g-C3N4 under simulated sunlight irradiation. dispersive X-ray spectroscopy (EDS) for elemental mapping
The material preparation process was ecofriendly without were obtained with the Oxford Ultim Max. High-angle annu-
using strong reducing reagent. Based on experimental and lar dark-field scanning transmission electron microscopy
theoretical studies, the introduction of Ru to g-C3N4 can (HAADF-STEM) and EDS mapping were performed on a
not only boost the light absorption, the adsorption of double-corrected FEI Themis-Z 60-300 transmission elec-
NO3-, but also accelerate the separation of electron-hole tron microscopy (TEM) equipped with ChemiSTEM EDS
pairs. The thermodynamic energy barrier for the rate detector system for ultra-high count rates. The X-ray photo-
determining step in NO3- reduction to the NH3 process is electron spectra (XPS) of the samples were tested with a
calculated to be less than 0.75 eV, which is much lower than Thermo Fisher Scientific K-Alpha+X-ray photoelectron
the competing H2 generation (0.98 eV) and N2 formation spectroscopy. The UV-vis diffuse reflectance spectra (DRS)
(1.36 eV), leading to the preference of generating NH3. This of prepared samples were obtained from a Perkin Elmber
work provides a novel approach to synthesize metallic Lambda 950 UV/VIS/NIR spectrometer, using high-purity
Energy Material Advances 3

RuCl3

Green tea

Bulk CN g-C3N4 nanosheet

CN-Ru

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Polyphenols

Scheme 1: Schematic illustration of the preparation of Ru modified g-C3N4 nanosheets.

barium sulfate (BaSO4) as the blank reference. Photolumi- pressure integrated capillary anion chromatography (IC).
nescence (PL) spectra were obtained from a Shimadzu The exact details of Nessler’s reagent method, NMR, and
RF-6000 fluorescence spectrometer excited at 325 nm. The IC are shown in the supplementary materials (Figure S1-S4).
photocurrent, electrochemical impedance spectroscopy
(EIS) and Mott-Schottky curves of the samples were obtained 2.6. Density Functional Calculation. The calculations of
from an electrochemical working station (CHI-760E) in geometry structures and energies were carried out by density
0.1 M Na2SO4 solution (details shown in supplementary functional theory (DFT) with Vienna ab initio simulation
materials). package (VASP) [38–41]. The exact details are presented in
supplementary materials.

2.5. Photocatalytic Activity Testing. The photocatalytic 3. Results and Discussion

nitrate reduction performance was carried out with a self-
made quartz reactor under simulated sunlight irradiation. 3.1. Structure and Morphology. In the XRD patterns of g-
During the reaction process, the light intensity was C3N4 (Figure S5 in supporting information, SI), two
600 mW/cm2 (HSX-F300), and it was measured by a radi- distinct peaks at 13.1 and 27.1° can be assigned to the
ometer. The distance between the light and the reactor was (100) and (002) crystal plane diffraction (JCPDS 87-1526)
10 cm. Firstly, 20 mg of the samples was weighed and put [42]. After peeled off by ultrasonic powder, the peak
into the reactor. Then, 95 mL of NaNO3 (10 mg/L) solution intensity decreased, indicating the reduced crystallinity.
and 5 mL of formic acid (200 μL/L) were added. Before the Since the loaded amount of Ru is not high, it cannot be
reaction, argon was purged into the solution to remove air. detected by XRD. Then, HRTEM and SEM were used to
After 2 h strong stir to make the powder catalysts uniformly explore the morphology of the prepared samples. As
dispersed in the solution, the light was turned on and the shown in Figure 1(a), the g-C3N4 nanosheets showed an
light irradiation lasted 4 h. In each hour, 3 mL of liquid ultrathin film layer structure. The CN-Ru-1 sample had the
was sampled from the reactor. The concentration of ammo- same morphology as 2D-CN with Ru particles loaded on
nium was measured by UV-vis spectrometer using Nessler’s the g-C3N4 nanosheets (dark spots in Figure 1(b)). The
reagent method and was further verified by 1H-Nuclear size of the Ru particles was less than 5 nm. To further
magnetic resonance spectroscopy (NMR) analysis. The investigate the lattice, the Ru particles were zoomed in and
concentration of NO3- and NO2- was measured by a high- displayed in Figure 1(c). The lattice distance of 0.234 nm
4 Energy Material Advances

50 nm
10 nm

(a) (b) (c)

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200 nm 200 nm 200 nm

(d) (e) (f)

Figure 1: HRTEM image of g-C3N4 nanosheets (a), CN-Ru-1 (b) and the zoom-in part of the lattice (c), high-angle annular dark-field image
(d), energy dispersive spectroscopy for Ru element mapping (e), and SEM image of CN-Ru-1 (f).

can be indexed to the (100) of metallic Ru. Additionally, the 404.9, 400.1, and 398.6 eV, which was caused by the interac-
high-angle annular dark-field (HAADF) image and energy tion between 2D-CN and Ru [45].
dispersive spectroscopy (EDS) for Ru element mapping were Based on the XRD, SEM, TEM, and XPS results, it can be
obtained to further confirm the component of the CN-Ru concluded that metallic Ru particle modified g-C3N4 nano-
sample. As exhibited in Figures 1(d) and 1(e) and Figure S6, sheets were successfully fabricated.
Ru particles are uniformly distributed on g-C3N4 nanosheets.
SEM image was also employed to study the morphology of 3.2. Enhanced Photocatalytic NO3- Reduction to NH3.
CN-Ru-1 (Figure 1(f)). In the SEM image, we can only see Herein, we used photocatalytic NO3- reduction to NH3 to
the nanosheet structure of g-C3N4, since the size of Ru evaluate the catalytic activity of samples. After 4-hour
particles was too small to be observed by SEM. simulate sunlight irradiation, all the samples exhibited
Then, XPS was used to study the components of the apparent photocatalytic activity on the reduction of NO3-
prepared samples. Figures 2(a) and 2(b) are the narrow C to NH3 (Figure 3(a)). The NH3 yield rate of 2D-CN was
1 s spectra of 2D-CN and CN-Ru-1. The three peaks of 1.126 mg/h/gcat, and it was 1.26-fold as that of bulk g-
2D-CN at 293.6, 287.9, and 284.6 eV can be assigned to the C3N4. When metallic Ru was used to modify the 2D-CN,
conjugated π electrons and sp2-hybridized C and C–C bonds the photocatalytic activity increased remarkably. Among
[10]. Compared with 2D-CN, two new peaks appeared in the all the samples, CN-Ru-1 was the most active one
narrow XPS spectra of C of CN-Ru-1. The peak at 286.1 eV (2.627 mg/h/gcat), and its activity is 2.93 times higher than
was attributed to C–O which came from the green tea bulk g-C3N4. Cycle stability is crucial for the study and
(Figure 2(b)) [43]. The other new peak at 280.2 eV is associ- application of photocatalysts. After the fourth cycle, the
ated with Ru0 [44]. Both 2D-CN and CN-Ru-1 have 3 peaks NH3 yield of CN-Ru-1 was still 2.32 mg/h/gcat, which was
in the narrow N 1 s spectra. In Figure 2(c), the three peaks at 88.16% as the fresh catalyst, indicating good cycle stability
404.4, 400.0, and 398.4 eV of 2D-CN are attributed to the for reusage. The use of formic acid did not influence of
charging effect, tertiary nitrogen, and sp2-hybridized nitro- the detection by the accuracy of Nessler’s reagent method
gen. Notably, the three peaks of N of CN-Ru-1 shifted to (Figure S7).
Energy Material Advances 5

50000
287.9 eV 40000 288.1 eV

40000
286.1 eV
30000
30000 284.6 eV

Counts
Counts

284.6 eV
20000
20000
280.2 eV
10000 293.6 eV 10000

0
0
296 294 292 290 288 286 284 282 280 294 292 290 288 286 284 282 280
Binding energy (eV) Binding energy (eV)
(a) (b)

398.4 eV 60000
398.6 eV
80000

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50000

60000
40000
Counts

Counts

400.0 eV 400.1 eV
30000
40000

20000
404.4 eV 404.9 eV
20000
10000

408 406 404 402 400 398 396 394 408 406 404 402 400 398 396 394
Binding energy (eV) Binding energy (eV)
(c) (d)

Figure 2: Narrow C 1s and Ru 3d XPS spectra of 2D-CN (a) and CN-Ru-1 (b). Narrow N 1s XPS spectra of 2D-CN (c) and CN-Ru-1 (d).

To confirm the source of NH3 generated, we carried on both the NO3- conversion rate and NH3 selectivity were sig-
the 15N isotope experiment with Na15NO3. A series of nificantly increased by CN-Ru-1, compared with bulk CN.
15
NH4Cl solutions with different concentration were firstly In Table S1, we summarized several typical g-C3N4, TiO2,
used to generate a standard line, and then the concentration and other materials for photocatalytic NO3- reduction in
of photocatalytic reactions can be analyzed. As shown in literature for comparison. Many materials can achieve highly
Figure 3(c), the standard 1H-NMR spectrum of 15NH4+ efficient NO3- removal, whereas the ammonia selectivity is
had two peaks with a coupling constant of 73.14 Hz. In the quite low. Pd/TiO2 can get a high NH3 selectivity of 76.9%,
solution after photocatalytic reaction of CN-Ru-1 with but its catalytic activity is really poor [46]. Nevertheless, the
15
NO3-, two characteristic 15NH3 peaks were also found, CN-Ru-1 reported in this work can simultaneously realize
and the calculated concentration of NH3 was 2.05 mg/L, both high NO3- removal and high NH3 selectivity.
which well matched the results of UV-vis spectrophotome-
try. The NMR results can confirm that the formation of 3.3. Mechanism of the Enhanced Performance. Light absorp-
NH3 is attributed to the photocatalytic reduction of NO3-. tion is an essential step for photocatalytic reaction.
Besides NH3, there might be some other products of the Figure 4(a) shows the UV-vis DRS of bulk CN, 2D-CN,
NO3- reduction. Herein, we used ion chromatography to and CN-Ru samples. The absorption edge of bulk CN was
measure the concentration of NO3- and NO2-. After 4 h light at about 460 nm, indicating a bandgap of 2.70 eV. When
irradiation, bulk CN reduced 48.85% of the NO3- (10 mg/L), bulk CN was converted to 2D-CN, the absorption edge
50.77% of which was converted to NH3. Under the same had a blue shift to 430 nm, with a wider bandgap of
condition, CN-Ru-1 eliminated 92.85% of NO3-, and the 2.88 eV. When the 2D-CN was modified by metallic Ru
NH3 selectivity was 77.9%. The UV-vis spectrophotometry, particles, the absorption edge showed a redshift. Meanwhile,
1H-NMR, and ion chromatography results confirmed that the light absorption in the visible light region was also
6 Energy Material Advances

3.0 3.0 2.64

2.627
2.57
2.5 2.5 2.37 2.32
2.328

NH3 yield (mg/h/gcat)

NH3 yield (mg/h/gcat)

2.0 1.829 2.0

1.5 1.5
1.126
1.0 0.896 1.0

0.5 0.5

0.0 0.0
Bulk CN 2D-CN CN-Ru-0.5 CN-Ru-1 CN-Ru-3 1st 2nd 3rd 4th
(a) (b)
Bulk CN CN-Ru-1
51.15%
15.16%
15J = 73.14 Hz
N-H 5.36%
16.49%

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7.15%
7.56%
Intensity (a.u.)

24.8% 72.33%

15NH + NH3 Other NH3 Other

Standard curve 4 5 ppm
NO2– NO3– NO2– NO3–

(d) (e)

CN-Ru-1 Na15NO3 as N source 2.05 ppm Bulk CN CN-Ru-1

15.48%
33.76%
16.33%

6.7 6.8 6.9 7.0 7.1 5.77%

Chemical shift (ppm) 50.77% 77.9%

(c) NH3 NH3

NO2– NO2–
Other Other
(f) (g)

Figure 3: (a) Photocatalytic activity of bulk CN, 2D-CN, and CN-Ru samples and (b) cycle stability of CN-Ru-1. (c) The NMR spectra of
15
NH4Cl standard solution and the final photoreduction production of Na15NO3 by CN-Ru-1. The proportions of productions and NO3-
after photocatalytic reaction by (d) bulk CN and (e) CN-Ru-1. The selectivity of photocatalytic reduction of NO3- by (f) bulk CN and
(g) CN-Ru-1.

significantly enhanced. The increased light absorption trend as the photocatalytic activity, indicating that CN-Ru-
enabled to make the catalysts absorb more photons, boosting 1 had the fastest separation and transfer of electrons and
the solar energy utilization ratio. The density of states of holes. The photocurrent slightly decreased in 200 s, which
g-C3N4 and CN-Ru is calculated by DFT (Figure 4(b)). was caused by the decreased interaction between the powder
Compared with g-C3N4, the introduction of metallic Ru catalysts and the ITO glass [48]. It does not mean the photo-
can bring some metallicity to the composite catalysts, catalysts have poor stability. In the EIS Nyquist plot, the bulk
which is beneficial to the transfer and separation of photo- CN had the largest arc radius because of its poor conductiv-
catalytic generated electron-hole pairs [47]. ity. The 2D-CN got a smaller arc radius as it had better con-
In order to explore more direct evidence about the trans- ductivity than bulk CN. When the 2D-CN got modified by
fer and separation of photogenerated electron-hole pairs, the metallic Ru, the arc radius of the EIS Nyquist plot signifi-
photocurrent response, EIS, and PL spectra of bulk CN, 2D- cantly decreased, because Ru had strong conductivity. The
CN, and CN-Ru samples were tested. Figure 4(c) is the more metallic Ru loaded, the better conductivity the sample
photocurrent response image. All the tested samples had got. The PL spectra of bulk CN, 2D-CN, and CN-Ru samples
apparent and rapid photocurrent response under light irra- were displayed in Figures 4(e) and 4(f). Bulk CN showed a
diation. Among all the samples, the photocurrent intensity broad and strong emission spectrum with profiles slightly
of CN-Ru-1 was the strongest, which followed the same deviating from a perfect Guanine curve centered at about
Energy Material Advances 7

1.0 30 0.005
Light on Light off
CN-Ru-1
0.8 20
0.004

Photocurrent (𝜇A)
CN-Ru-3
10
Absorbance

0.6 0.003
CN-Ru-3 CN-Ru-0.5

DOS
0
CN-Ru-1
0.4 0.002
–10
Bulk CN CN-Ru-0.5
0.2 2D-CN
2D CN 0.001
–20
Bulk CN
0.0 –30 0.000
300 400 500 600 700 800 –8 –6 –4 –2 0 2 4 6 8 50 100 150 200
Wavelength (nm) Energy (eV) Time (s)

CN-Ru
g-C3N4
(a) (b) (c)

200000

150000
–Z″ (ohm)

Intensity

Intensity
100000

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50000

i n
om
0 Zo

0 20000 40000 60000 80000 100000 400 450 500 550 600 400 450 500 550 600
Z′ (ohm) Wavelength (nm) Wavelength (nm)

Bulk CN CN-Ru-1 Bulk CN CN-Ru-1 Bulk CN CN-Ru-1

2D-CN CN-Ru-3 2D-CN CN-Ru-3 2D-CN CN-Ru-3
CN-Ru-0.5 CN-Ru-0.5 CN-Ru-0.5

(d) (e) (f)

Figure 4: UV-vis DRS of bulk CN, 2D-CN, and CN-Ru samples (a). Density of states of g-C3N4 and CN-Ru (b). Photocurrent response (c),
EIS (d), and PL spectra (e, f) of bulk CN, 2D-CN and CN-Ru samples.

Spin density Charge differences

NO3– on g-C3N4 NO3– on CN-Ru

Mag = 4.48 𝜇B BRu = 1.13 |e|
Eads = –1.85 eV Eads = –3.75 eV
(a) (b) (c) (d)

Figure 5: Adsorption structures and calculated adsorption energies of NO3 adsorbed on g-C3N4 (a) and CN-Ru (b). Optimized spin density -

(c) and charge differences (d) of CN-Ru.

460 nm. Compared with bulk CN, the PL intensity of the other activity and selectivity of CN-Ru, the density functional
samples decreased significantly, which mean the recombina- theory calculation is performed. NO3- adsorption, the first
tion of photoinduced charge carriers was obstructed, and it step of NO3- reduction, was first calculated, and the opti-
is helpful for the enhanced photocatalytic activity [49]. mized adsorption structures, as well as the adsorption
Experimental studies on NO3- reduction have shown energies, are listed in Figures 5(a) and 5(b). The adsorp-
that Ru modified g-C3N4 plays an essential role in improving tion energy of NO3- on g-C3N4 was -1.85 eV, and it was
NH3 production compared with pure g-C3N4. To further -3.75 eV on CN-Ru. It is clearly seen that Ru modification
understand the reaction mechanism and the origin of high increased the NO3- stability by 2.03 times compared with
8 Energy Material Advances

2.5 N⁎ H2/N2
0.0

2.0

1.5
–0.5
ΔG (eV)

ΔG (eV)
0.98 eV
1.0 2.33 eV

0.5 H⁎
–1.0 1.36 eV
⁎
H2/N2
0.0 H
–0.08 eV N⁎

–0.5 –1.5
Reaction coordinate Reaction coordinate
(a) (b)

–2

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–4
ΔG (eV)

–6

0.75
–8
1.33
–10

–12

–14
NO3– NO3⁎ HNO3⁎ NO2⁎ HNO2⁎ NO NOH⁎ N⁎ NH⁎ NH2⁎ NH3⁎ NH3 (g)
Reaction coordinate
CN-Ru
g-C3N4
(c)

Figure 6: Calculated free energy differences between the formation of H2 and N2 on g-C3N4 (a) and CN-Ru (b). Calculated free energy
changes of NO3- reduction to NH3 on g-C3N4 and CN-Ru (c).

pristine g-C3N4, indicating the following NO3- reduction peting reactional products for the photocatalytic reduction
step proceeds more easily, consistent with the experimen- of NO3- including H2 and N2. For g-C3N4, it is very easy
tal observations. to take part in hydrogen generation reaction, while the for-
Furthermore, metallic Ru particles involve a high spin mation of N2 is very difficult because a higher thermody-
density on Ru cluster and positive Bader charge, as well as namic energy barrier of 2.33 eV should be overcome
a zero gap, which can enhance the electron transfer ability (Figure 6(a)). As for CN-Ru, the thermodynamic energy bar-
(Figures 5(c) and 5(d)). Since Ru cluster got a positive Bader riers of the formation of H2 and N2 are 0.98 and 1.36 eV
charge, the photocatalytic generated electrons for g-C3N4 (Figure 6(b)). All free energy curves are downhill from
can be accumulated on Ru, making it as the active sites. At NO3- to HNO2, and although the reaction pathway is differ-
the same time, the CN-Ru system got some magnetic prop- ent, the thermodynamic energy barrier for the rate deter-
erties, and the spin density is concentrated on Ru. All these mining step in this process is all calculated to be less than
electronic structure results are responsible for the improved 0.75 eV (Figure 6(c)), which is much lower than those of
photocatalytic activity of CN-Ru. 2H ⟶ H2 (0.98 eV) and 2 N ⟶ N2 (1.36 eV), suggesting
To further understand the role of metallic Ru particles in that induced Ru cluster played a key role in the enhance-
the NO3- reduction process, we calculated the free energy ment of the photocatalytic activity and selectivity for NO3-
diagrams of NO3- reduction on g-C3N4 and CN-Ru. Com- reduction to form NH3, in good agreement with the
pared with the generation of NH3, there are two main com- experimental observations.
Energy Material Advances 9

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Scheme 2: The scheme for the photocatalytic nitrate reduction to ammonia on the g-C3N4/Ru catalysts.

Based on the experimental and calculated results, the 4. Conclusion

mechanism for the enhanced photocatalytic NO3- reduction
to NH3 activity can be summarized as follows (Scheme 2). In summary, we used a facile and green approach to synthe-
Firstly, the introduction of metallic Ru caused a redshift of size novel metallic Ru modified g-C3N4 nanosheets as
the absorption edge as well as broad absorption in visible photocatalysts for enhanced NO3- reduction to NH3. The
light range, which boosted the absorption of photons and optimal sample (CN-Ru-1) had the highest NH3 yield rate
the utilization of solar light. Secondly, CN-Ru samples have of 2.627 mg/h/gcat, and it was 2.93 times as that of bulk
much better conductivity and higher separation efficiency of CN. After 4-hour light irradiation, CN-Ru-1 eliminated
photogenerated electron-hole pairs than g-C3N4. Thirdly, 92.85% of NO3-, and the NH3 selectivity was 77.9%. After
the high spin density of Ru cluster and its positive Bader four cycles, the sample still had good photocatalytic perfor-
charge can accumulate electrons, making the adsorption mance (88.16% as the fresh catalyst). NMR and 15N isotope
and cleavage of NO3- easier. More importantly, the thermo- labeling provided solid evidence that the N of NH3 was from
dynamic energy barrier for the rate determining step in this the reduction of NO3-. The g-C3N4 nanosheets modified by
process is all calculated to be less than 0.75 eV (Figure 6(c)), metallic Ru particles have stronger light absorption, better
which is much lower than the competing H2 generation conductivity, and more rapid separation of electron-hole
(0.98 eV) and N2 formation (1.36 eV), leading to the prefer- pairs. With the enhanced adsorption energy of NO3- and
ence of generating NH3 and higher activity. the low thermodynamic energy barriers, the photocatalytic
Using green tea as reducing reagent to prepare nano- activity and selectivity were increased significantly. The
materials is promising because it is cost-effective. More results and findings of this work may provide a new plat-
importantly, the operation and storage are much safer form for the facile and green synthesis of metal particle
than using strong reducing reagent like sodium borohy- modified photocatalysts for reducing NO3- to NH3 under
dride. The tea polyphenols of green tea are regarded as ambient conditions.
active ingredients to achieve reduction reactions [50, 51].
Meanwhile, the average reduction potential of green tea
is about 0.219 V, indicating that the approach reported in Data Availability
this work can be expanded to the synthesis of other
metal-based materials [52]. In Figure S8, we summarized The authors declare that the main data supporting the
the elements that can be reduced to zero valent theoretically, findings in this study are available within the article and its
including Tc, Ru, and Cu, which would potentially use the supplementary information. Additional data are available
proposed approach [53]. from the corresponding authors upon reasonable request.
10 Energy Material Advances

Conflicts of Interest [6] R. Kumar, F. Heße, P. S. C. Rao et al., “Strong hydroclimatic

controls on vulnerability to subsurface nitrate contamination
The authors declare no conflict of interest. across Europe,” Nature Communications, vol. 11, no. 1, article
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designed the experiment. D.H., J.R., and W.W. prepared the 2008.
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Council (ARC) Future Fellowship (FT160100195), the [10] D. Hao, C. Liu, X. Xu et al., “Surface defect-abundant one-
National Key Research and Development Program of dimensional graphitic carbon nitride nanorods boost photo-
China (2016YFA0602900), the National Natural Science catalytic nitrogen fixation,” New Journal of Chemistry,
Foundation of China (21673220), Department of Science

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vol. 44, no. 47, pp. 20651–20658, 2020.
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