Journal of CO₂ Utilization 24 (2018) 34–39

Contents lists available at ScienceDirect

Journal of CO2 Utilization

journal homepage: www.elsevier.com/locate/jcou

Highly selective conversion of CO2 into ethanol on Cu/ZnO/Al2O3 catalyst T

with the assistance of plasma
⁎
Binran Zhaoa,b, Yajun Liua, Zijun Zhua, Huaizheng Guoa, Xiaoxun Maa,b,
a
School of Chemical Engineering, Northwest University, Xi’an, 710069, China
b
International Scientific & Technological Cooperation Base for Clean Utilization of Hydrocarbon Resources, Chemical Engineering Research Center of the Ministry of
Education for Advanced Use Technology of Shanbei Energy, Research Center of Engineering Technology for Clean Coal Conversion, Collaborative Innovation Center for
Development of Energy and Chemical Industry in Northern Shaanxi, Northwest University, Xi’an, 710069, China

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

Keywords: A novel and efficient way for conversion of CO2 and H2O into ethanol over a commercial Cu/ZnO/Al2O3 catalyst
Carbon dioxide with the assistance of negative corona discharge plasma was presented in this work. The low-temperature
Water production rate and selectivity of ethanol were effectively enhanced by combining catalyst with plasma. The
Ethanol production rate of ethanol increased with increasing of input power and water vapor content, while decreased
Plasma
with the increase of flow rate of CO2. XRD and XPS results revealed that metallic copper was partly or completely
Cu/ZnO/Al2O3
oxidized after reaction and FTIR results uncovered that on the oxidized copper CO2 adsorbed as carboxylate
(COO−) which finally hydrogenated to ethanol. The synergistic effect of partly oxidized copper combined with
plasma could promote the dissociation of methanol to form ethanol, which resulted in the high selectivity of
ethanol.

1. Introduction plasma could be generated under atmospheric pressure and low tem-
perature. And reactant molecules could be activated by the plasma with
Nowadays, the greenhouse effect caused by the emission of carbon low energy consumption. In our previous study, the reaction between
dioxide is one of the main challenges for human beings. Meanwhile, CO2 and water vapor, which was not thermodynamically feasible at
carbon dioxide is a ubiquitous and generally available C1 resource in ambience, was conducted under negative corona discharge plasma
the world. An alternative way to solve the problem is the utilization of [17]. The results proved that it was an efficient way for the synthesis of
carbon dioxide [1–5]. Ethanol is a potential product for CO2 utilization, ethanol at low temperature and pressure. However, a by-product, me-
since it is not merely an ideal clean fuel with high energy density, high thanol, formed accompanying ethanol synthesis when CO2 reacted with
octane rating, but also an excellent gasoline additive. Many researchers H2O in negative corona discharge plasma.
had attempted to promote the selectivity of ethanol for the hydro- Many reports indicated that the combination of plasma and catalyst
genation of carbon dioxide [6–8]. And conventional ways, thermal [18–22] was an alternative way as the combination could overcome the
conversion of carbon dioxide had been discussed [9–12]. Kangvansura drawbacks of plasma reaction and catalytic reaction: plasma might
et al. conducted CO2 hydrogenation at 250 °C and 2.5 MPa on iron restructure the active metals and supports which resulted in the pro-
based catalyst, found potassium as an electronic promoter together with motion of the catalytic performance. Meanwhile, the electron density
manganese as a structural promoter improved the selectivity of ethanol could be increased in presence of catalysts in the process of discharge
of iron-active phase [9]. Kurakata et al. reported that carbon dioxide [18,23,24]. Krawczyk et al. used a dielectric barrier discharge com-
and H2 converted into ethanol fast over [Rh10Se]/TiO2 catalyst at the bined with different catalysts for the carbon dioxide reforming of me-
pressure of 4.7 MPa from 250 to 450 °C, and the highest selectivity of thane, the results showed that the conversion of methane was promoted
ethanol was 83% [10]. and alcohols (methanol and ethanol) were detected [20]. Similar CO2
However, owing to the high operation temperature and pressure, conversion and methane selectivity were obtained using a dielectric
those processes consumed high energy with low energy efficiency. So in barrier discharge (DBD) plasma reactor packed with Ni-CexZr1-xO2
recent years, many surveys had focused on plasma methods for con- catalyst for the hydrogenation of carbon dioxide into methane at the
verting carbon dioxide to the high value-added products [13–16]. Cold atmospheric pressure and 90 °C, much lower than 300 °C for the same

⁎
Corresponding author at: School of Chemical Engineering, Northwest University, Xi’an, 710069, China.
E-mail address: [email protected] (X. Ma).

https://doi.org/10.1016/j.jcou.2017.10.013
Received 16 July 2017; Received in revised form 7 October 2017; Accepted 12 October 2017
2212-9820/ © 2017 Published by Elsevier Ltd.
B. Zhao et al. Journal of CO₂ Utilization 24 (2018) 34–39

catalyst in the absence of plasma with similar catalytic activity [21]. Rigaku D/Max-2500 diffractometer equipped with a Ni-filtered Cu Kα
It was well recognized that catalyst could improve the selectivity of radiation source (λ=1.54056 Å). The scanning speed was 8°/min over
reaction. Thus, in this work, we attempted to conduct the reaction of the 2θ range of 10−90°, the phase identification was made by com-
CO2 with water over a commercial Cu/ZnO/Al2O3 catalyst combined parison to the Joint Committee on Powder Diffraction Standards
with negative corona discharge plasma to improve the selectivity of (JCPDSs).
ethanol. The effects of input power, flow rate of CO2 and water vapor X-ray photoelectron spectroscopy (XPS) was applied to identify the
content on the production rate of ethanol were investigated. The fresh chemical nature of copper species by a K-Alpha spectrometer using a
and spent catalysts were characterized using X-ray diffraction and X-ray focused monochromatized Al-Kα radiation (1486.6 eV). The binding
photoelectron spectroscopy. Furthermore, the adsorbed species of CO2 energy was calibrated using C1 s peak (284.6 eV) as reference.
on the surface of catalyst were analyzed by FTIR. The preliminary The Fourier Transform Infrared Spectroscopy (FTIR) was used to
mechanism of CO2 reaction with H2O was also discussed. study the surface species of CO2 adsorbed on the reduced catalysts and
the reduced catalysts after exposing to plasma, and it was recorded by
2. Experimental the BRUKER X70 Fourier transform spectrometer with a spectral re-
solution of 4 cm−1. The samples were set in an IR cell with CaF2 win-
2.1. Reaction of CO2 with water dows and were purged by the flowing argon (20 ml/min) at 300 °C for
30 min. Then the samples were cooled down to 50 °C with Ar (20 ml/
A tubular quartz-glass reactor was applied for this experiment. The min). After that, the catalysts were heated from 50 °C to 250 °C at a
electrode contained twenty stainless steel pins was installed in the heating rate of 5 °C/min for the temperature-programmed adsorption of
middle of the reactor to generate plasma. An SJ-2000E negative power carbon dioxide (20 ml/min).
supply was used for the generation of plasma with the voltage range of
−15 kV to 15 kV. A half-wave rectifier unit was connected to the outlet 3. Results and discussions
of the power supply to generate stable DC negative high voltage.
Besides, the quartz reactor was set in the center of a furnace. A bubbling 3.1. Alcohols in the liquid products
device heated in a water bath was used to generate water vapor. The
gas circuit between the bubbling device and the reactor was entwined The alcohols in the liquid were analyzed by GC equipped with KB-
with heater band to make sure water was thoroughly gasified. And the WAX column. As shown in Table 1, both methanol and ethanol could be
reaction of CO2 with water was conducted as follows: N2 was firstly detected for CO2 reaction with H2O over catalyst alone or plasma alone.
used to sweep the system. Before reaction the catalyst was reduced as However, methanol disappeared and only ethanol was obtained when
the following procedure: the fresh catalysts were firstly heated in the CO2 reacted with H2O over the catalyst combined with negative corona
flowing of N2 at 30 ml/min with the temperature range from room discharge plasma. This indicated that the high selectivity of ethanol
temperature to 300 °C at a heating rate of 5 °C/min and then the cat- could be achieved with combining Cu/ZnO/Al2O3 catalyst and plasma.
alysts were reduced by H2 (30 ml/min) for 2 h. After reduction, the To be noted, the production rate of ethanol was significantly improved
catalysts were cooled down to desired temperature in the flowing of N2 in the presence of the plasma. it was about 15.60 μmol gcat−1 h−1 over
(30 ml/min). CO2 (99.99%) was fed through a mass flow meter, and catalyst with the assistance of plasma at 160 °C, which was much higher
carried water vapor to the reactor through the bubbling device. The than the sum of catalyst alone (3.02 μmol gcat−1 h−1) and plasma
liquid products were collected by a condenser and then analyzed by the alone (3.50 μmol h−1) at the same temperature. This data was also
gas chromatography (GC, FULI 9790) with a flame ionization detector higher than the highest production rate of ethanol (13.38 μmol g-
(FID) and a KB-WAX capillary column. The temperatures of injector and cat−1 h−1) when the reaction occurred over Cu/ZnO/Al2O3 catalyst
detector were both 230 °C. Gaseous products were also analyzed by the alone at 260 °C. As such, combining the catalyst with the negative
same GC with thermal conductivity detector (TCD) and GDX-02 corona discharge enhanced the selectivity and production rate of
column. The reaction of CO2 with water was conducted in three ways: ethanol at lower temperature for the reaction of CO2 with water. Fur-
negative corona discharge plasma alone, catalyst alone and catalyst ther analysis of the alcohols in the liquid products was conducted with
combined with negative corona discharge plasma. For the latter two GC equipped with flame ionization detector and HP Plot Q column. The
methods, a commercial Cu/ZnO/Al2O3 catalyst (0.5 g) was applied. The results presented in Fig. S1 further proved our conclusion above.
calculations of production rates for ethanol and methanol were defined
as follows: 3.2. Effects of parameters on production rate of ethanol
Methanol (μmol)
Production rate of ethanol (μmol gcat−1h−1) = The effect of input power on the production rate of ethanol was
time(h)⋅m catalyst (g) (1)
examined (Fig. 1). When CO2 reacted with H2O in negative corona
Mmethanol (μmol) discharge plasma alone, the production rates of alcohols (methanol
Production rate of methanol (μmol gcat−1h−1) =
time(h)⋅m catalyst (g) + ethanol) raised up with increasing the input power. When combining
(2) Cu/ZnO/Al2O3 catalyst with plasma, an enhancement of the production
rate of ethanol with increasing the input power was also observed, as
When the reaction occurred in plasma alone, the unit of production
rate was μmol h−1. Table 1
The producion rates for catalyst alone (μmol gcat−1 h−1), plasma alone (μmol h−1) and
2.2. Characterizations of the catalyst catalyst with the assistance of plasma (μmol gcat−1 h−1).

S1/T (°C) S2 S3
The reduced catalyst and the catalysts after reaction were collected
for further characterization. 160 180 200 220 240 260 280 300
The surface areas and pore structures of catalysts were studied by
nitrogen adsorption-desorption at −196 °C with the application of Ethanol 3.02 3.82 3.54 6.20 9.14 13.38 8.42 7.60 3.50 15.60
Methanol 2.42 1.56 2.44 2.76 5.90 4.46 7.96 8.66 1.53 0
Quantachrome Autosorb-1 analyzer. The surface areas were gained
through the BET method, while the pore volume and diameter were S1: catalyst alone, S2: plasma alone, S3: catalyst with the assistance of plasma. For S2 and
calculated by the BJH equation. S3, reaction temperature: 160 °C. For all the three methods, input power: 480 W, flow rate
X-ray diffraction (XRD) patterns of the catalysts were recorded on a of CO2: 30ml min−1, water vapor content: 63.12%.

35
B. Zhao et al. Journal of CO₂ Utilization 24 (2018) 34–39

Fig. 1. The effect of input power on the production rate of ethanol and methanol. S2:
Fig. 3. The effect of content of water vapor on the production rate of ethanol and me-
plasma alone, S3: catalyst with the assistance of plasma. Experiment condition: T: 160 °C,
thanol, S1: catalyst alone, S2: plasma alone, S3: catalyst with the assistance of plasma.
the flow rate of CO2: 30 ml/min and water vapor content: 63.12%.
Experiment condition: T: 160 °C, the flow rate of CO2: 30 ml/min and the input power:
480 W.
shown in Fig. 1. According to the literature, when the input power
increased, the quantities of electrons released from the discharge pins the production rate of ethanol was improved from 3.71 μmol h−1 to
were increased [17]. In addition, under negative corona discharge 5.03 μmol h−1 with increasing the water vapor content from 25.61% to
plasma, H2O and CO2 could capture an electron and convert into H2O− 63.12%. During the reaction of CO2 with water occurred on the Cu/
and CO2− anions, respectively. The anions were the active species for ZnO/Al2O3 catalyst in the presence of plasma, the production rate of
ethanol synthesis [17]. As such, increasing the input power of plasma ethanol was enhanced by about 200% by increasing the water vapor
led to more electrons, more H2O− and CO2− anions, thereby ethanol content from 25.61% to 63.12%. This might be related to generation of
production rate was enhanced. Unlike the trend in catalyst combined more H species supplied by H2O.
with plasma, the production rate of ethanol was irrelevant with the
input power from 192 to 480 W in plasma alone, indicating that Cu/
ZnO/Al2O3 catalyst was indispensable for the high selectivity of ethanol 3.3. Characterizations of the Cu/ZnO/Al2O3 catalyst
in plasma.
The effect of flow rate of CO2 on the production rate of alcohols was In order to explain the change of the catalyst and the reaction me-
further investigated. As presented in Fig. 2, when the temperature was chanism, Cu/ZnO/Al2O3 catalysts after reduction, after reaction with
remained at 160 °C and the input power was kept at 480 W, the pro- and without plasma were characterized by using N2 adsorption-deso-
duction rates of the ethanol reduced with increasing of the flow rate of rption, XRD, XPS and CO2-FTIR techniques. The BET surface areas of
CO2. Increasing the flow rate of the feedstock shortened the residence the Cu/ZnO/Al2O3 catalysts after reduction, after reaction in the ab-
time of CO2 and H2O in the reactor, lowered the possibility of inter- sence and in the presence of plasma were 49.6, 48.8 and 48.2 m2/g,
action for the reactants with the catalysts and plasma, thereby reduced respectively, and the average pore sizes were 19.9, 19.5 and 19.8 nm,
the production rate of ethanol. separately. As such, the surface areas and pore sizes of fresh and spent
The effect of the content of water vapor in the feedstock on the Cu/ZnO/Al2O3 catalysts were similar to each other, indicating that
production rates of alcohols was shown in Fig. 3. When the water vapor surface area and pore structure were not the main reason for the sig-
content increased from 25.61% to 63.12%, the production rate of the nificant difference in ethanol production.
ethanol remained almost unchanged during the reaction occurred on The XRD patterns of the Cu/ZnO/Al2O3 catalysts after reduction,
Cu/ZnO/Al2O3 catalyst without plasma. When the reaction of CO2 and after reaction with and without plasma were exhibited in Fig. 4. After
water occurred in zone of negative corona discharge without catalyst, reduction, peaks assigned to metal copper were observed. And the XRD
patterns had little change after reaction without plasma. However, the

Fig. 2. The effect of flow rate of CO2 on the production rate of ethanol and methanol, S1:
catalyst alone, S2: plasma alone, S3: catalyst with the assistance of plasma. Experiment Fig. 4. XRD patterns for the catalysts after reduction and the spent catalysts with and
condition: T: 160 °C, water vapor content: 63.12% and the input power: 480 W. without plasma.

36
B. Zhao et al. Journal of CO₂ Utilization 24 (2018) 34–39

Fig. 5. XPS spectra of Cu2p3/2 of the catalysts after reduction and the spent catalysts with
and without plasma.

catalyst after the reaction in the presence of plasma showed apparent

differences: besides the peaks to metal copper, peaks attributed to
CuxOy, Cu2O, CuO appeared. This indicated that the copper was par-
tially or completely oxidized during the reaction occurred in the pre-
sence of plasma.
Fig. 5 illustrated the Cu2p XPS spectra of the fresh and spent cata-
lyst. On the XPS spectrum of Cu/ZnO/Al2O3 catalyst after reduction,
the peaks at 952.4 and 932.4 eV attributed to the metallic copper
species were observed. The XPS spectrum of catalyst after reaction
without plasma was almost the same as that after reduction. While a
shoulder peak at 934.3 eV appeared over Cu/ZnO/Al2O3 catalyst after
reaction in the presence of plasma, which was associated with the
copper oxide, revealing the generation of the oxidized copper species
on Cu/ZnO/Al2O3 catalyst after reaction with the assistance of plasma. Fig. 6. FTIR spectra of carbon dioxide adsorption on (a) the catalysts after reduction and
The XRD and XPS results demonstrated that oxidized copper species (b) the reduced catalysts after exposure to plasma.
were formed in the presence of negative corona discharge plasma
during the reaction. As reported in our previous work, CO2 converted 3.4. The mechanism of ethanol formation from CO2 and H2O over Cu/
into CO2− anions by capturing electrons in plasma [25,26]. These an- ZnO/Al2O3 catalyst combined with negative corona discharge plasma
ions could be dissociated and generated O species. Besides, the de-
composition of H2O in plasma could also provide O species. Copper As demonstrated in literature, during the production of ethanol
could be oxidized into oxidation state by the O species. It had been from CO2 hydrogenation, methanol was the key intermediate [35].
shown that partially oxidized copper, the Cu0-Cu+ or Cuδ+ Here we proposed the synthesis of ethanol followed the methanol-
(0 < δ < 1), could be the active center for CO2 hydrogenation mediated path on the basis of the results from literature and our present
[27–31]. Therefore, the partially oxidized copper might be an origin for work.
the enhanced selectivity and low-temperature activity for ethanol To better understand the pathway for ethanol synthesis, gaseous
production in the presence of negative corona discharge plasma. components were analyzed and the results were presented in Fig. S2.
The plasma species was extremely short and could not remain after We could conclude that CO, O2, H2 existed in the exhaust gas except
exposure. And it was difficult to carry out the on-line measurement for CO2. There is no doubt that hydrogen species was from the decom-
adsorption species on catalyst when combined with plasma. So in this position of H2O. Cu catalyst was an excellent WGS catalyst, or its re-
work, we first exposed the reduced catalyst to plasma and then trans- verse reaction (RWGS), so CO and CO2 would interconvert during re-
ferred the catalyst to CO2 gas and studied the surface species of CO2 action which led to the debate of carbon source in the hydrogenation of
adsorbed on the catalysts using FTIR. For comparison, the adsorption CO/CO2 mixture gas [36–39]. Recent research found that methanol
species of CO2 on the surface of the reduced Cu/ZnO/Al2O3 catalyst was could be synthesized from either CO or CO2 hydrogenation using den-
also studied. As shown in Fig. 6, the adsorption species on the two sity functional theory (DFT) method [36,40]. Thus both CO and CO2
catalysts were different. On the reduced catalyst shown in Fig. 6(a), the were the carbon source for ethanol synthesis.
peak at 1323 cm−1 was ascribed to the CO2 molecule on surface of the For H2O decomposition, OH was a key intermediate species. There
metallic copper [32], the peak at 1430 cm−1 was assigned to the hy- were three possible channels: the first one was from the electron impact
drogencarbonate ions [33], and the peaks at 1630 and 1580 cm−1 dissociation of water molecules (Eq. (3)) [41–45]. Some authors also
[33,34] were due to carbonate structures. As presented in Fig. 6(b), on reported that electron dissociative recombination was an important
the FTIR spectra of Cu/ZnO/Al2O3 catalyst after exposing to plasma, reaction in gas-water plasma (Eq. (4)) [46–48]. In addition, O (which
peaks at 1530 and 1364 cm−1 appeared, and could be ascribed to can then produce O atoms) could affect OH generation through two
carboxylate species (COO−) [33]. As such, the catalyst exposed to reactions (Eqs. (5)-(6)) [40,41].
plasma would give priority to the formation of the carboxylate species.
e+ H2 O→ e+ H+ OH (3)

e+ H2 O+ → H+ OH (4)

37
B. Zhao et al. Journal of CO₂ Utilization 24 (2018) 34–39

Table 2
The production rates with different Cu species (μmol gcat−1 h−1).

Reaction Condition ethanol methanol

completely oxide copper 0 0

Partially oxide copper without plasma 3.42 2.56
Partially oxide copper with plasma 15.60 0

Reaction temperature: 160 °C, input power: 480 W, flow rate of CO2: 30 ml min−1, water
Fig. 7. The synthesis mechanism diagram of ethanol on Cu/ZnO/Al2O3 catalyst with the vapor content: 63.12%.
assistance of plasma.
(CuO) had no activity for CO2 hydrogenation with water in our ex-
O+ H2 → H+ OH (5) periments as shown in Table 2, which meant that the partially oxidized
copper was the active site. As such, the partially oxidized copper species
O+ H2 O→ OH + OH (6)
could be one reason for the enhanced selectivity of ethanol production
The observed gaseous products could be generated by the following in the presence of both catalyst and plasma. In addition, it had been
reactions (Eq. (7)–(9)): proved that plasma could cause partial decomposition of methanol
[53,54]. And both methanol (3.42 μmol gcat−1 h−1) and ethanol
H+ H→ H2 (7)
(2.56 μmol gcat−1 h−1) were synthesized over the catalyst when
OH + H→ O+ H2 (8) plasma was interrupted (Table 2), indicating high selectivity of ethanol
could not be obtained without plasma. Hence, the synergistic effect of
O+ O→ O2 (9) partially oxidized copper and plasma might promote the completely
Beside H2 and O2, these exited species would also be adsorbed on decomposition of methanol to form ethanol.
Cu/ZnO/Al2O3 catalyst to hydrogenate CO and CO2.
For CO2 hydrogenation, HCOO was the well-recognized inter- 4. Conclusion
mediate [36,40]. As mentioned above, the metallic copper on Cu/ZnO/
Al2O3 catalyst was oxidized after exposing to negative corona dis- CO2 conversion to ethanol with H2O on Cu/ZnO/Al2O3 catalyst in
charge, and the adsorption species formed on the oxidized copper were the presence of negative corona discharge plasma was conducted in
mainly carboxylates (COO−). The carboxylate species could be hydro- present work. Only ethanol produced for the alcohols in obtained liquid
genated to formate (HCOO−) species (Eq. (10)) with the presence of over catalyst with the assistance of plasma. By combining the catalyst
hydrogen atoms, and the following hydrogenation of formate (HCOO−) with negative corona discharge plasma, the production rate of ethanol
resulted in methanol (Eq. (11)). was also improved at lower temperature. The production rate of ethanol
increased with increasing of input power and water vapor content,
COO− (a) + (a) → HCOO− (a) (10) while decreased with the improvement of flow rate of CO2. Metal
HCOO− (a) + 3H (a) → CH3 OH (a) + O− (a) (11) copper was oxidized in the presence of plasma. The combination of
partially oxidized copper and plasma might be the main reason for the
the mechanism for CO hydrogenation were as follows (Eq. enhancement of selectivity for ethanol production. The present work
(11)–(14)) [36,40,49]: provided a novel and efficient way for highly selective conversion of
CO(a) + H(a) → HCO(a) (11) CO2 into ethanol.

HCO(a) + H(a) → H2 CO(a) (12) Acknowledgments

H2 CO(a) + H(a) → H3 CO(a) (13)

The supports from the National Natural Science Foundation of
H3 CO (a) + H (a) → CH3 OH (a) (14) China (No. 21406177), the Project Supported by Natural Science Basic
Research Plan in Shaanxi Province of China (Program No.
The ethanol formation could be described by Eq. (15), (16), (17) 2016JQ2007), Scientific Research Program Funded by Shaanxi
and (18). The dissociation of methanol led to the formation of CH3(a) Provincial Education Department (Program No. 14JK1749), the Science
and OH(a). The CH3(a) then reacted with CO to form CH3CO(a). Fi- Foundation of Northwest University (No. 13NW27) were greatly ap-
nally, ethanol was synthesized by the hydrogenation of CH3CO(a). The preciated.
synthesis mechanism diagram of ethanol from CO2 and H2O was pre-
sented in Fig. 7. Appendix A. Supplementary data
CH3 OH (a) → CH3 (a) + OH (a) (15)
Supplementary data associated with this article can be found, in the
CO 2−(a) → CO (g ) + O− (a) (16) online version, at https://doi.org/10.1016/j.jcou.2017.10.013.

CH3 (a) + CO (g) → CH3 CO (a) (17)

References
CH3 CO (a) + 3H (a) → CH3 CH2 OH (g) (18)
[1] V. Havra, M.P. Dudukovic, C.S. Lo, Conversion of methane and carbon dioxide to
Decomposition of methanol was a key step in the synthesis of higher value products, Ind. Eng. Chem. Res. 50 (2011) 7089–7100.
ethanol [35]. Lots of high-energy electrons existed in the negative [2] M. Aresta, A. Dibenedetto, A. Angelini, The changing paradigm in CO2 utilization, J.
CO2 Util. 3-4 (2013) 65–73.
corona plasma. Interaction of the electrons with the methanol produced [3] P. Markewitz, W. Kuckshinrichs, W. Leitner, J. Linssen, P. Zapp, R. Bongartz,
CH3OH− which could be absorbed on the catalyst and dissociated into A. Schreiber, T.E. Mueller, Worldwide innovations in the development of carbon
CH3(a) and OH(a). As reflected by the XRD and XPS results, the metallic capture technologies and the utilization of CO2, Energ. Environ. Sci. 5 (6) (2012)
7281–7305.
copper was oxidized in the presence of the negative corona discharge [4] P. Saikia, J. Saikia, S. Sarmah, N. Allou, R. Goswamee, Mesoporous oxidic holey
plasma. The oxidized copper species had been shown to be favorable for nanosheets from Zn-Cr LDH synthesized by soft chemical etching of Cr3+ and its
methanol dissociation [50–52] which was a key step in synthesizing application as CO2 hydrogenation catalyst, J. CO2 Util. 21 (2017) 40–51.
[5] O.Y. Abdelaziz, W.M. Hosny, M.A. Gadalla, F.H. Ashour, I.A. Ashour,
ethanol. While it was interesting that the completely oxidized copper

38
B. Zhao et al. Journal of CO₂ Utilization 24 (2018) 34–39

C.P. Hulteberg, Novel process technologies for conversion of carbon dioxide from catalysts, J. Chem. Soc. Faraday Trans. 88 (1992) 1477–1488.
industrial flue gas streams into methanol, J. CO2 Util. 21 (2017) 52–63. [33] G.J. Millar, C.H. Rochester, S. Bailey, K.C. Waugh, Combined temperature-pro-
[6] J. Yuan, X. Wang, F. Zhang, Communication-Potential pulsing photoelec- grammed desorption and fourier-transform infrared spectroscopy study of CO2, CO
trochemical reduction of carbon dioxide to ethanol, J. Electrochem. Soc. 163 (2016) and H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol
305–307. synthesis catalysts, J. Chem. Soc. Faraday Trans. 88 (1992) 2085–2093.
[7] S. Bai, Q. Shao, P. Wang, Q. Dai, X. Wang, X. Huang, Highly active and selective [34] T. Montanari, L. Castoldi, L. Lietti, G. Busca, Basic catalysis and catalysis assisted by
hydrogenation of CO2 to ethanol by ordered Pd-Cu nanoparticles, J. Am. Chem. Soc. basicity: FT-IR and TPD characterization of potassium-doped alumina, Appl. Catal.
139 (2017) 6827–6830. A. 400 (2011) 61–69.
[8] K. Atsonios, K.D. Panopoulos, E. Kakaras, Thermocatalytic CO2 hydrogenation for [35] Z. He, Q. Qian, J. Ma, Q. Meng, H. Zhou, J. Song, Z. Liu, B. Xing, Water-enhance
methanol and ethanol production: process improvements, Int. J. Hydrogen Energ. synthesis of higher alcohols from CO2 hydrogenation over a Pt/Co3O4 catalyst
41 (2016) 792–806. under milder conditions, Angew. Chem. Int. Ed 55 (2016) 727–741.
[9] P. Kangvansura, L.M. Chew, W. Saengsui, P. Santawaja, Y. Poo-arporn, M. Muhler, [36] L.C. Grabow, M. Mavrikakis, Mechanism of methanol synthesis on Cu through CO2
H. Schulz, A. Worayingyong, Product distribution of CO2 hydrogenation by K- and and CO hydrogenation, ACS Catal. 1 (2011) 365–384.
Mn-promoted Fe catalysts supported on N-functionalized carbon nanotubes, Catal. [37] Y. Yang, C.A. Mims, D.H. Mei, C.H.F. Peden, C.T. Campbell, Mechanistic studies of
Today 275 (2016) 59–65. methanol synthesis over Cu from CO/CO2/H2/H2O mixtures: the source of C in
[10] H. Kurakata, Y. Izumi, K. Aika, Ethanol synthesis from carbon dioxide on TiO2- methanol and the role of water, J. Catal. 298 (2013) 10–17.
supported [Rh10Se] catalyst, Chem. Commun. 3 (1996) 389–390. [38] F. Studt, M. Behrens, E.L. Kunkes, N. Thomas, S. Zander, A. Tarasov, J. Schumann,
[11] Q. Qian, M. Cui, Z. He, C. Wu, Q. Zhu, Z. Zhang, J. Ma, G. Yang, J. Zhang, B. Han, E. Frei, J.B. Varley, F. Abild-Pedersen, J.K. Nørskov, R. Schlögl, The mechanism of
Highly selective hydrogenation of CO2 into C2+ alcohols by homogeneous cata- CO and CO2 hydrogenation to methanol over Cu-Based Catalysts, ChemCatChem 7
lysis, Chem. Sci. 6 (2015) 5685–5689. (2015) 1105–1111.
[12] D. Wang, Q. Bi, G. Yin, W. Zhao, F. Huang, X. Xie, M. Jiang, Direct synthesis of [39] T. Kandemir, M. Friedrich, S.F. Parker, F. Studt, D. Lennon, R. Schlogl, M. Behrens,
ethanol via CO2 hydrogenation using supported gold catalysts, Chem. Commun. 52 Different routes to methanol: inelastic neutron scattering spectroscopy of ad-
(2016) 14226–14229. sorbates on supported copper catalysts, Phys. Chem. Chem. Phys. 18 (2016)
[13] S.U. Han, H.S. Kwak, Y.C. Hong, Carbon dioxide elimination and regeneration of 17253–17258.
resources in a microwave plasma torch, Environ. Pollut. 211 (2016) 191–197. [40] Y.M. Liu, J.T. Liu, S.Z. Liu, J. Li, Z.H. Gao, Z.J. Zuo, W. Huang, Reaction me-
[14] B. Zhu, X. Li, J. Liu, X. Zhu, A. Zhu, Kinetics study on carbon dioxide reforming of chanisms of methanol synthesis from CO/CO2 hydrogenation on Cu2O(111):
methane in kilohertz spark-discharge plasma, Chem. Eng. J. 264 (2015) 445–452. Comparison with Cu(111), J. CO2 Util. 20 (2017) 59–65.
[15] D. Yap, J.M. Tatibouët, C. Batiot-Dupeyrat, Carbon dioxide dissociation to carbon [41] R. Ono, T. Oda, OH radical measurement in a pulsed arc discharge plasma observed
monoxide by non-thermal plasma, J.CO2 Util. 12 (2015) 54–61. by a LIF method, IEEE Trans. Ind. Appl. 37 (2001) 709–714.
[16] J. Li, X. Zhang, J. Shen, T. Ran, P. Chen, Y. Yin, Dissociation of CO2 by thermal [42] N. Srivastava, C. Wang, Effects of water addition on OH radical generation and
plasma with contracting nozzle quenching, J.CO2 Util. 21 (2017) 72–76. plasma properties in an atmospheric argon microwave plasma jet, J. Appl. Phys.
[17] L. Guo, X. Ma, Y. Xia, X. Xiang, X. Wu, A novel method of production of ethanol by 110 (2011) 053304.
carbon dioxide with steam, Fuel 158 (2015) 843–847. [43] M. Sun, Y. Wu, J. Li, N.H. Wang, J. Wu, K.F. Shang, J.L. Zhang, Diagnosis of OH
[18] H.L. Chen, H.M. Lee, S.H. Chen, Y. Chao, M.B. Chang, Review of plasma catalysis on radical by optical emission spectroscopy in atmospheric pressure unsaturated
hydrocarbon reforming for hydrogen production − Interaction integration, and humid air corona discharge and its implication to desulphurization of flue gas,
prospects, Appl. Catal. B. 85 (2008) 1–9. Plasma Chem. Plasma Process. 25 (2005) 31–40.
[19] G. Chen, V. Georgieva, T. Godfroid, R. Snyders, M.P. delplancke-Ogletree. plasma [44] X. Yan, L. Sha, J. Bao, N. Zhang, B. Fan, R. Li, X. Liu, Y. Pan, Immobilization of
assisted catalytic decomposition of CO2, Appl. Catal.B. 190 (2006) 115–124. highly dispersed Ag nanoparticles on carbon nanotubes using electron-assisted re-
[20] K. Krawczyk, M. Młotek, B. Ulejczyk, K. Schmidt-Szałowski, Methane conversion duction for antibacterial performance, ACS Appl. Mater. Inter. 8 (2016)
with carbon dioxide in plasma-catalytic system, Fuel 117 (2014) 608–617. 17060–17067.
[21] M. Nizio, A. Albarazi, S. Cavadias, J. Amouroux, M.E. Galvez, P.D. Costa, Hybrid [45] X. Yan, B. Zhao, Y. Liu, Y. Li, Dielectric barrier discharge plasma for preparation of
plasma-catalytic methanation of CO2 at low temperature over ceria zirconia sup- Ni-based catalysts with enhanced coke resistance: current status and perspective,
ported Ni catalysts, Int. J. Hydrogen Energ. 41 (2016) 11584–11592. Catal. Today 256 (2015) 29–40.
[22] X. Zhu, S. Liu, Y. Cai, X. Gao, J. Zhou, C. Zheng, X. Tu, Post-plasma catalytic re- [46] P. Bruggeman, D.C. Schram, M.G. Kong, C. Leys, Is the rotational temperature of OH
moval of methanol over Mn-Ce catalysts in an atmospheric dielectric barrier dis- (A–X) for discharges in and in contact with liquids a good diagnostic for de-
charge, Appl. Catal. B. 183 (2016) 124–132. termining the gas temperature? Plasma Process. Polym. 6 (2009) 751–762.
[23] W.C. Chung, M.B. Chang, Review of catalysis and plasma performance on dry re- [47] P. Bruggeman, D.C. Schram, M.A. Gonzalez, R. Rego, M.G. Kong, C. Leys,
forming of CH4 and possible synergistic effects, Renew. Sust. Energ. Rev 62 (2016) Characterization of a direct dc-excited discharge in water by optical emission
13–31. spectroscopy, Plasma Sour. Sci. Technol 18 (2009) 25017.
[24] X. Tu, J.C. Whitehead, Plasma-catalytic dry reforming of methane in an atmo- [48] P. Bruggeman, F. Iza, P. Guns, D. Lauwers, M.G. Kong, Y.A. Gonzalvo, C. Leys,
spheric dielectric barrier discharge: understanding the synergistic effect at low D.C. Schram, Electronic quenching of OH (A) by water in atmospheric pressure
temperature, Appl. Catal. B. 125 (2012) 439–448. plasmas and its influence on the gas temperature determination by OH (A–X)
[25] X. Xiang, L. Guo, X. Wu, X. Ma, Y. Xia, Urea formation from carbon dioxide and emission, Plasma Sour. Sci. Technol 19 (2010) 15016.
ammonia at atmospheric pressure, Environ. Chem. Lett. 10 (2012) 295–300. [49] Y. Lu, R.G. Zhang, B.B. Cao, B.H. Ge, F.F. Tao, J.J. Shan, L. Nguyen, Z.H. Bao,
[26] X. Xiang, L. Guo, X. Wu, X. Ma, Y. Xia, Reduction of carbon dioxide into tetra- T.P. Wu, J.W. Pote, B.J. Wang, F. Yu, Elucidating the Copper-Hagg Iron carbide
iodomethane at 1 atm, Environ. Chem. Lett. 10 (2012) 413–418. synergistic interactions for selective CO hydrogenation to higher alcohols, ACS
[27] G.C. Chinchen, K.C. Waugh, D.A. Whan, The activity and state of the copper surface Catal. 7 (2017) 5500–5512.
in methanol synthesis catalysts, Appl. Catal. 25 (1986) 101–107. [50] M.B. Boucher, M.D. Marcinkowski, M.L. Liriano, C.J. Murphy, E.A. Lewis,
[28] S. Mehta, G.W. Simmons, K. Klier, R.G. Herman, Catalytic synthesis of methanol A.D. Jewell, M.F.G. Mattera, G. Kyriakou, M. Flytzani-Stephanopoulos,
from COH2: II. Electron microscopy (TEM, STEM, microdiffraction, and energy E.C.H. Sykes, Molecular-scale perspective of water-catalyzed methanol dehy-
dispersive analysis) of the CuZnO and Cu/ZnO/Cr2O3 catalysts, J. Catal. 57 (1979) drogenation to formaldehyde, Acs Nano 7 (2013) 6181–6187.
339–360. [51] P.R. Davies, M. Bowker, On the nature of the active site in catalysis: the reactivity of
[29] R. Burch, S.E. Golunski, M.S. Spencer, The role of hydrogen in methanol synthesis surface oxygen on Cu (110), Catal. Today 154 (2010) 31–37.
over copper catalysts, Catal. Lett. 5 (1990) 55–60. [52] J. Gong, H. Yue, Y. Zhao, S. Zhao, L. Zhao, J. Lv, S. Wang, X. Ma, Synthesis of
[30] S.P. Lau, L. Chen, J. Lin, C. Huan, Synergism between Cu and Zn sites in Cu/Zn ethanol via syngas on Cu/SiO2 catalysts with balanced Cu0-Cu+ sites, J. Am. Chem.
catalysts for methanol synthesis, Appl. Surf. Sci. 152 (1999) 193–199. Soc. 134 (2012) 13922–13925.
[31] Y. Okamoto, K. Fukino, T. Imanaka, S. Teranishi, Surface characterization of copper [53] J. Mizeraczyk, K. Urashima, K. Jasiński, M. Dors, Hydrogen production from gas-
(II) oxide-zinc oxide methanol-synthesis catalysts by x-ray photoelectron spectro- eous fuels by plasmas − A review, Int. J. Environ. Sci. 8 (2014) 89–97.
scopy. 1. Precursor and calcined catalysts, J. Phys. Chem. 87 (1983) 3740–3747. [54] H. Li, J. Zou, Y. Zhang, C. Liu, Novel plasma methanol decomposition to hydrogen
[32] G.J. Millar, C.H. Rochester, K.C. Waugh, Infrared study of CO, CO2, H2 and H2O using corona discharges, Chem. Lett. 33 (2004) 744–745.
interactions on potassium-promoted reduced and oxidized silica-supported copper

39