Citation: Hanyu Xu, Xuedan Song, Qing Zhang, Chang Yu, Jieshan Qiu. Mechanistic Insights into Water-Mediated CO₂ Electrochemical Reduction Reactions on Cu@C₂N Catalysts: A Theoretical Study[J]. Acta Physico-Chimica Sinica, ;2024, 40(1): 230304. doi: 10.3866/PKU.WHXB202303040 shu

Mechanistic Insights into Water-Mediated CO₂ Electrochemical Reduction Reactions on Cu@C₂N Catalysts: A Theoretical Study

Hanyu Xu ¹ ,
Xuedan Song ^1,, ,
Qing Zhang ¹ ,
Chang Yu ¹ ,
Jieshan Qiu ^{1, 2,,}

1.
Liaoning Key Lab for Energy Materials and Chemical Engineering, State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning Province, China
2.
State Key Laboratory of Organic-Inorganic Composites, State Key Laboratory of Chemical Resource Engineering, College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Corresponding author: Xuedan Song, song@dlut.edu.cn Jieshan Qiu, jqiu@dlut.edu.cn
Received Date: 20 March 2023
Revised Date: 2 May 2023
Accepted Date: 8 May 2023
Available Online: 15 May 2023
Fund Project: the National Natural Science Foundation of China 22078052the Fundamental Research Funds for the Central Universities, China DUT22ZD207

CO₂ molecules can be converted into various fuels and industrial chemicals through electrochemical reduction, effectively addressing the problems of global warming, desertification, ocean acidification, and other adverse environmental changes and energy supply issues such as excessive utilization of nonrenewable fossil fuels. Generally, the pathway of the CO₂ reduction reaction (CO₂RR) involves multiple proton–electron pairs transferred to the reactants, resulting in the production of multiple reduction products. Here, protons are derived from water molecules under aqueous solvent conditions. Therefore, exploring the effect of water molecules on the proton–electron pair transfer process in CO₂RRs is essential. In this study, we developed a water-mediated hydrogen shuttle model (H-shuttling) as a hydrogenation model to investigate the effect of water molecules on the proton–electron pair transfer process in CO₂RRs and compared it with the widely used water-free direct hydrogenation model (H-transfer), wherein the hydrogen atom is used as a proton. Because copper is a metal electrode material capable of producing hydrocarbons from CO₂ electroreduction with a high faraday efficiency, and nitrogen-doped graphene (C₂N) exhibits excellent catalytic CO₂ activation, we selected a single copper atom-embedded C₂N (Cu@C₂N) as the catalyst. Furthermore, to study the effect of graphene on the CO₂RR activity of Cu@C₂N/G, we selected a graphene-loaded Cu@C₂N composite (Cu@C₂N/G) as the catalyst because graphene was utilized as a substrate to boost the conductivity of the catalyst. In the two hydrogenation models, we investigated the mechanisms of CO₂RRs on Cu@C₂N and Cu@C₂N/G catalysts through density functional theory calculations. Notably, in the H-shuttling model, the H atom combines with the water molecule to form H₃O, which transfers one of its own H atoms to a reactant on the catalyst surface, yielding a reaction intermediate. The H-shuttling model enhances the interaction between the catalyst and intermediate. Graphene, as a substrate, transfers electrons to the Cu@C₂N surface of the Cu@C₂N/G catalyst, which is demonstrated by calculations of the Bader charge transferred between the reaction intermediate and catalyst, as well as the Gibbs free energy of the CO₂ reduction elementary reaction. This effectively lowers the Gibbs free energy of the potential-determining step and enhances the CO₂RR catalytic activity of Cu@C₂N/G. Moreover the limiting potentials of the CO₂RR and hydrogen evolution reaction are determined to obtain the activity and selectivity of the Cu@C₂N and Cu@C₂N/G catalysts. The results indicate that CO₂ molecules on the Cu@C₂N and Cu@C₂N/G catalysts generate HCOOH at low applied potentials, and are able to produce CO, CH₃OH, CH₄, and H₂ as the applied potentials increases.
- CO₂ reduction reaction,
- Electrocatalysis,
- Nitrogen-doped graphene,
- Water-mediated hydrogen shuttle,
- Reaction mechanism,
- Density functional theory
1. [1]
  Dresselhaus, M. S.; Thomas, I. L. Nature 2001, 414, 332. doi: 10.1038/35104599 doi: 10.1038/35104599
2. [2]
  Chu, S.; Majumdar, A. Nature 2012, 488 (7411), 294. doi: 10.1038/nature11475 doi: 10.1038/nature11475
3. [3]
  Canadell, J. G.; Le Quéré, C.; Raupach, M. R.; Field, C. B.; Buitenhuis, E. T.; Ciais, P.; Conway, T. J.; Gillett, N. P.; Houghton, R. A.; Marland, G. Proc. Natl. Acad. Sci. U. S. A. 2007, 104, 18866. doi: 10.1073/pnas.0702737104 doi: 10.1073/pnas.0702737104
4. [4]
  Qiao, J.; Liu, Y.; Hong, F.; Zhang, J. Chem. Soc. Rev. 2014, 43 (2), 631. doi: 10.1039/c3cs60323g doi: 10.1039/c3cs60323g
5. [5]
  Jones, J. P.; Prakash, G. K. S.; Olah, G. A. Isr. J. Chem. 2014, 54 (10), 1451. doi: 10.1002/ijch.201400081 doi: 10.1002/ijch.201400081
6. [6]
  Whipple, D. T.; Kenis, P. J. A. J. Phys. Chem. Lett. 2010, 1 (24), 3451. doi: 10.1021/jz1012627 doi: 10.1021/jz1012627
7. [7]
  Hori, Y.; Kikuchi, K.; Suzuki, S. Chem. Lett. 1985, 14 (11), 1695. doi: 10.1246/cl.1985.1695 doi: 10.1246/cl.1985.1695
8. [8]
  Hinogami, R.; Yotsuhashi, S.; Deguchi, M.; Zenitani, Y.; Hashiba, H.; Yamada, Y. ECS Electrochem. Lett. 2012, 1 (4), H17. doi: 10.1149/2.001204eel doi: 10.1149/2.001204eel
9. [9]
  Li, C. W.; Kanan, M. W. J. Am. Chem. Soc. 2012, 134 (17), 7231. doi: 10.1021/ja3010978 doi: 10.1021/ja3010978
10. [10]
  Phillips, K. R.; Katayama, Y.; Hwang, J.; Shao-Horn, Y. J. Phys. Chem. Lett. 2018, 9 (15), 4407. doi: 10.1021/acs.jpclett.8b01601 doi: 10.1021/acs.jpclett.8b01601
11. [11]
  Yang, H.; Wu, Y.; Li, G.; Lin, Q.; Hu, Q.; Zhang, Q.; Liu, J.; He, C. J. Am. Chem. Soc. 2019, 141 (32), 12717. doi: 10.1021/jacs.9b04907 doi: 10.1021/jacs.9b04907
12. [12]
  Guan, A. X.; Chen, Z.; Quan, Y. L.; Peng, C.; Wang, Z. Q.; Sham, T. K.; Yang, C.; Ji, Y.; Qian, L. P.; Xu, X.; et al. ACS Energy Lett. 2020, 5 (4), 1044. doi: 10.1021/acsenergylett.0c00018 doi: 10.1021/acsenergylett.0c00018
13. [13]
  He, W.; Liberman, I.; Rozenberg, I.; Ifraemov, R.; Hod, I. Angew. Chem. Int. Ed. 2020, 59 (21), 8262. doi: 10.1002/anie.202000545 doi: 10.1002/anie.202000545
14. [14]
  Xu, C. C.; Zhi, X.; Vasileff, A.; Wang, D.; Jin, B.; Jiao, Y.; Zheng, Y.; Qiao, S. Z. Small Struct. 2020, 2 (1), 2000058. doi: 10.1002/sstr.202000058 doi: 10.1002/sstr.202000058
15. [15]
  Wang, G.; Chen, J.; Ding, Y.; Cai, P.; Yi, L.; Li, Y.; Tu, C.; Hou, Y.; Wen, Z.; Dai, L. Chem. Soc. Rev. 2021, 50 (8), 4993. doi: 10.1039/d0cs00071j doi: 10.1039/d0cs00071j
16. [16]
  Tan, L.; Nie, C.; Ao, Z.; Sun, H.; An, T.; Wang, S. J. Mater. Chem. A 2021, 9 (1), 17. doi: 10.1039/d0ta07437c doi: 10.1039/d0ta07437c
17. [17]
  Du, Y. D.; Meng, X. T.; Wang, Z.; Zhao, X.; Qiu, J. S. Acta Phys. -Chim. Sin. 2022, 38 (2), 2101009. doi: 10.3866/PKU.WHXB202101009
18. [18]
  Mahmood, J.; Lee, E. K.; Jung, M.; Shin, D.; Jeon, I. Y.; Jung, S. M.; Choi, H. J.; Seo, J. M.; Bae, S. Y.; Sohn, S. D.; et al. Nat. Commun. 2015, 6, 6486. doi: 10.1038/ncomms7486 doi: 10.1038/ncomms7486
19. [19]
  Ju, W.; Bagger, A.; Hao, G. P.; Varela, A. S.; Sinev, I.; Bon, V.; Cuenya, R. B.; Kaskel, S.; Rossmeisl, J.; Strasser, P. Nat. Commun. 2017, 8 (1), 944. doi: 10.1038/s41467-017-01035-z doi: 10.1038/s41467-017-01035-z
20. [20]
  Mahmood, J.; Li, F.; Kim, C.; Choi, H. J.; Gwon, O.; Jung, S. M.; Seo, J. M.; Cho, S. J.; Ju, Y. W.; Jeong, H. Y.; et al. Nano Energy 2018, 44, 304. doi: 10.1016/j.nanoen.2017.11.057 doi: 10.1016/j.nanoen.2017.11.057
21. [21]
  Sahoo, S. K.; Heske, J.; Antonietti, M.; Qin, Q.; Oschatz, M.; Kuhne, T. D. ACS Appl. Energy Mater. 2020, 3 (10), 10061. doi: 10.1021/acsaem.0c01740 doi: 10.1021/acsaem.0c01740
22. [22]
  Cui, X.; An, W.; Liu, X.; Wang, H.; Men, Y.; Wang, J. Nanoscale 2018, 10 (32), 15262. doi: 10.1039/c8nr04961k doi: 10.1039/c8nr04961k
23. [23]
  Ma, J.; Gong, H.; Zhang, T.; Yu, H.; Zhang, R.; Liu, Z.; Yang, G.; Sun, H.; Tang, S.; Qiu, Y. Appl. Surf. Sci. 2019, 488, 1. doi: 10.1016/j.apsusc.2019.03.187 doi: 10.1016/j.apsusc.2019.03.187
24. [24]
  Yuan, H.; Li, Z.; Zeng, X. C.; Yang, J. J. Phys. Chem. Lett. 2020, 11 (9), 3481. doi: 10.1021/acs.jpclett.0c00676 doi: 10.1021/acs.jpclett.0c00676
25. [25]
  Daté, M.; Haruta, M. J. Catal. 2001, 201 (2), 221. doi: 10.1006/jcat.2001.3254 doi: 10.1006/jcat.2001.3254
26. [26]
  Zhao, Y. F.; Yang, Y.; Mims, C.; Peden, C. H. F.; Li, J.; Mei, D. J. Catal. 2011, 281 (2), 199. doi: 10.1016/j.jcat.2011.04.012 doi: 10.1016/j.jcat.2011.04.012
27. [27]
  Nie, X.; Luo, W.; Janik, M. J.; Asthagiri, A. J. Catal. 2014, 312, 108. doi: 10.1016/j.jcat.2014.01.013 doi: 10.1016/j.jcat.2014.01.013
28. [28]
  Liu, S. P.; Zhao, M.; Zhu, Y. F.; Gao, W.; Jiang, Q. Appl. Catal. A- Gen. 2017, 547, 214. doi: 10.1016/j.apcata.2017.09.002 doi: 10.1016/j.apcata.2017.09.002
29. [29]
  Kresse, G.; Hafner, J. J. Non-Cryst. Solids 1993, 156–158, 956. doi: 10.1016/0022-3093(93)90104-6 doi: 10.1016/0022-3093(93)90104-6
30. [30]
  Kresse, G.; Hafner, J. Phys. Rev. B-Condens. Matter 1994, 49 (20), 14251. doi: 10.1103/physrevb.49.14251 doi: 10.1103/physrevb.49.14251
31. [31]
  Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi: 10.1103/PhysRevLett.77.3865 doi: 10.1103/PhysRevLett.77.3865
32. [32]
  Methfessel, M.; Paxton, A. T. Phys. Rev. B-Condens. Matter 1989, 40 (6), 3616. doi: 10.1103/physrevb.40.3616 doi: 10.1103/physrevb.40.3616
33. [33]
  Henkelman, G.; Uberuaga, B. P.; Jonsson, H. J. Chem. Phys. 2000, 113, 9901. doi: 10.1063/1.1329672 doi: 10.1063/1.1329672
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Mechanistic Insights into Water-Mediated CO2 Electrochemical Reduction Reactions on Cu@C2N Catalysts: A Theoretical Study

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Mechanistic Insights into Water-Mediated CO₂ Electrochemical Reduction Reactions on Cu@C₂N Catalysts: A Theoretical Study