English

Designing Electrolyzers for Electrocatalytic CO₂ Reduction

• Gao Dunfeng ^{1, ,} ,
• Wei Pengfei ^1, ,
• Li Hefei ^1,2, ,
• Lin Long ^1,2, ,
• Wang Guoxiong ^{1,2, ,} ,
• Bao Xinhe ^1,

• 1.

  State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China

• 2.

  University of Chinese Academy of Sciences, Beijing 100049, China

Author Bio: Dunfeng Gao is currently an associate professor at the Dalian Institute of Chemical Physics, Chinese Academy of Sciences (DICP, CAS). He obtained B.Sc. degree from China University of Petroleum in 2009 and Ph.D. degree from the DICP in 2015. Then he worked as a postdoctoral researcher at the Ruhr University Bochum and the Fritz Haber Institute of the Max Planck Society in Germany (2015-2019). In 2019, he moved back to the DICP as an associate professor. His research focuses on electrocatalysis including CO₂ electroreduction, CH₄ electrooxidation and water electrolysis;Guoxiong Wang is currently a full professor at the Dalian Institute of Chemical Physics, Chinese Academy of Sciences (DICP, CAS). He obtained B.Sc. degree from Wuhan University in 2000 and Ph.D. degree from the DICP in 2006. After a one-year stay at the DICP as an assistant professor (2006-2007), he worked as a postdoctoral researcher at the Hokkaido University in Japan (2007-2010). In December 2010, he moved back to the DICP as an associate professor and promoted to a full professor in 2015. His research focuses on energy storage and conversion, electrocatalytic CO₂ reduction and fuel cell;

Corresponding author: Gao Dunfeng, dfgao@dicp.ac.cn Wang Guoxiong, wanggx@dicp.ac.cn

• Received Date: 04 September 2020
  Accepted Date: 24 September 2020
  Revised Date: 24 September 2020
  Available Online: 15 May 2021
• Fund Project:

  This project was supported by the National Key R & D Program of China (2016YFB0600901), the National Natural Science Foundation of China (21573222, 91545202, 22002155), Dalian National Laboratory for Clean Energy, China (DNL180404 and DNL201924), Dalian Institute of Chemical Physics, China (DICP DMTO201702), Dalian Outstanding Young Scientist Foundation, China (2017RJ03) and the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020200) and the CAS Youth Innovation Promotion (Y201938)

Abstract: The electrocatalytic CO₂ reduction reaction (CO₂RR) driven by renewable energy is an efficient approach to achieve the conversion and utilization of CO₂. In this context, CO₂RR has become an emerging research focus in the field of electrocatalysis over the past decade. While a large number of nanostructured catalysts have been developed to accelerate CO₂RR, the tradeoff between activity and selectivity usually renders the overall electrocatalytic performance very poor. Beyond catalyst design, rationally designing electrolyzers is also of substantial importance for improving the CO₂RR performance and achieving its scale-up for practical applications. To a large extent, the electrolyzer configuration determines the local reaction environment near an electrode by affecting the process conditions, thereby resulting in remarkably different electrocatalytic performances. To be techno-economically viable, the performance of CO₂ electrolyzers is expected to be at least comparable to that of the current state-of-the-art proton exchange membrane (PEM) water electrolyzers, with regard to their activity, selectivity, and stability. Researchers have made great progress in the development of CO₂ electrolyzers over the past few years, but they are also facing many issues and challenges. This review aims to provide an in-depth analysis of the research progress and status of current CO₂ electrolyzers including H-cell, flow-cell, and membrane electrode assembly cell (MEA-cell) electrolyzers. Herein, operation at industrial current densities (> 200 mA∙cm⁻²) is set as a basis when these electrolyzers are discussed and compared in terms of the four main figures of merit (current density, Faradic efficiency, energy efficiency and stability) that describe the CO₂RR performance of an electrolyzer. The advantages and drawbacks of each electrolyzer are discussed and highlighted with emphasis on the key achievements reported to date. Compared to conventional H-cell electrolyzers that work well in mechanistic studies, the newly developed electrolyzers using gas diffusion electrodes, both flow-cell and MEA-cell electrolyzers, are able to break the limitation of CO₂ solubility in water and acquire industrial current densities. Although flow-cell electrolyzers have achieved current densities exceeding 1 A∙cm⁻², they suffer from low energy efficiencies because of the significant iR drop and poor stability owing to the use of alkaline electrolytes. These issues can be overcome in the case of zero-gap MEA-cell electrolyzers with ion exchange membranes being as solid electrolytes. The anion exchange membrane (AEM)-based CO₂ electrolyzers are at the center of the current research, as they demonstrate promising activity and selectivity toward specific CO₂RR products and exhibit excellent stability for over thousands of hours in few cases. Meanwhile, the crossover of CO₂ and liquid products from the cathode to the anode through the membrane tends to lower the utilization efficiency of the CO₂ supplied to the AEM electrolyzers. MEA-cell electrolyzers using cation exchange membranes and bipolar membranes have also been explored; however, neither of them have shown satisfactory CO₂RR performance. The development of new polymer electrolyte membranes and ionomers would help address these problems. While issues and challenges still exist, MEA-cell electrolyzers hold the greatest promise for practical applications. As concluding remarks, research strategies and opportunities for the future have been proposed to accelerate the development of CO₂RR technology for practical applications and to deepen the mechanistic understanding behind improved performance. This review provides new insights into rational electrolyzer design and guidelines for researchers in this field.

Key words:
• CO₂ electrolyzers
•  /  Electrocatalytic reduction
•  /  Energy efficiency
•  /  Industrial current density
•  /  Flow cell
•  /  Membrane electrode assembly

• 1. [1]

     Artz, J.; Muller, T. E.; Thenert, K.; Kleinekorte, J.; Meys, R.; Sternberg, A.; Bardow, A.; Leitner, W. Chem. Rev. 2018, 118, 434. doi: 10.1021/acs.chemrev.7b00435

  2. [2]

     Tackett, B. M.; Gomez, E.; Chen, J. G. G. Nat. Catal. 2019, 2, 381. doi: 10.1038/s41929-019-0284-9

  3. [3]

     Yang, D. R.; Wang, G. X.; Wang, X. Sci. China Mater. 2019, 62, 1369. doi: 10.1007/s40843-019-9455-3

  4. [4]

     He, J.; Janaky, C. ACS Energy Lett. 2020, 5, 1996. doi: 10.1021/acsenergylett.0c00645

  5. [5]

     Zhang, F. T.; Zhang, H. Y.; Liu, Z. M. Curr. Opin. Green Sust. Chem. 2019, 16, 77. doi: 10.1016/j.cogsc.2019.02.006

  6. [6]

     谷雨星, 杨娟, 汪的华.物理化学学报, 2019, 35, 208. doi: 10.3866/PKU.WHXB201802121Gu, Y. X.; Yang, J.; Wang, D. H.Acta. Phys. -Chim. Sin. 2019, 35, 208. doi: 10.3866/PKU.WHXB201802121

  7. [7]

     刘艳芳, 胡兵, 尹雅芝, 刘国亮, 洪昕林.物理化学学报, 2019, 35, 223. doi: 10.3866/PKU.WHXB201802263Liu, Y. F.; Hu, B.; Yin, Y. Z.; Liu, G. L.; Hong, X. L. Acta. Phys. -Chim. Sin. 2019, 35, 223. doi: 10.3866/PKU.WHXB201802263

  8. [8]

     Bushuyev, O. S.; De Luna, P.; Dinh, C. T.; Tao, L.; Saur, G.; van de Lagemaat, J.; Kelley, S. O.; Sargent, E. H. Joule 2018, 2, 825. doi: 10.1016/j.joule.2017.09.003

  9. [9]

     Jouny, M.; Luc, W.; Jiao, F. Ind. Eng. Chem. Res. 2018, 57, 2165. doi: 10.1021/acs.iecr.7b03514

  10. [10]

      Spurgeon, J. M.; Kumar, B. Energy Environ. Sci. 2018, 11, 1536. doi: 10.1039/c8ee00097b

  11. [11]

      Verma, S.; Kim, B.; Jhong, H.; Ma, S. C.; Kenis, P. J. A. ChemSusChem 2016, 9, 1972. doi: 10.1002/cssc.201600394

  12. [12]

      Gao, D. F.; Cai, F.; Wang, G. X.; Bao, X. H. Curr. Opin. Green Sust. Chem. 2017, 3, 39. doi: 10.1016/j.cogsc.2016.10.004

  13. [13]

      杨艳, 张云, 胡劲松, 万立骏.物理化学学报, 2020, 36, 1906085. doi: 10.3866/PKU.WHXB201906085Yang, Y.; Zhang, Y.; Hu, J. S.; Wan, L. J. Acta. Phys. -Chim. Sin. 2020, 36, 1906085. doi: 10.3866/PKU.WHXB201906085

  14. [14]

      Yan, C. C.; Lin, L.; Wang, G. X.; Bao, X. H. Chin. J. Catal. 2019, 40, 23. doi: 10.1016/S1872-2067(18)63161-4

  15. [15]

      Jia, M. W.; Fan, Q.; Liu, S. Z.; Qiu, J. S.; Sun, Z. Y. Curr. Opin. Green. Sust. Chem. 2019, 16, 1. doi: 10.1016/j.cogsc.2018.11.002

  16. [16]

      Sun, X. T.; Wang, P.; Shao, Z. J.; Cao, X. M.; Hu, P. Sci. China Chem. 2019, 62, 1686. doi: 10.1007/s11426-019-9639-0

  17. [17]

      高敦峰, 阎程程, 汪国雄, 包信和.电化学, 2018, 24, 757. doi: 10.13208/j.electrochem.180845Gao, D. F.; Yan, C. C.; Wang, G. X.; Bao, X. H. J. Electrochem. 2018, 24, 757. doi: 10.13208/j.electrochem.180845

  18. [18]

      宁汇, 王文行, 毛勤虎, 郑诗瑞, 杨中学, 赵青山, 吴明铂.物理化学学报, 2018, 34, 938. doi: 10.3866/PKU.WHXB201801263Ning, H.; Wang, W. H.; Mao, Q. H.; Zheng, S. R.; Yang, Z. X.; Zhao, Q. S.; Wu, M. B. Acta. Phys. -Chim. Sin. 2018, 34, 938. doi: 10.3866/PKU.WHXB201801263

  19. [19]

      Hu, C. L.; Zhang, L.; Li, L. L.; Zhu, W. J.; Deng, W. Y.; Dong, H.; Zhao, Z. J.; Gong, J. L. Sci. China Chem. 2019, 62, 1030. doi: 10.1007/s11426-019-9474-0

  20. [20]

      Gao, D. F.; Aran-Ais, R. M.; Jeon, H. S.; Roldan Cuenya, B. Nat. Catal. 2019, 2, 198. doi: 10.1038/s41929-019-0235-5

  21. [21]

      Aran-Ais, R. M.; Gao, D. F.; Roldan Cuenya, B. Acc. Chem. Res. 2018, 51, 2906. doi: 10.1021/acs.accounts.8b00360

  22. [22]

      Weekes, D. M.; Salvatore, D. A.; Reyes, A.; Huang, A. X.; Berlinguette, C. P. Acc. Chem. Res. 2018, 51, 910. doi: 10.1021/acs.accounts.8b00010

  23. [23]

      Herranz, J.; Pătru, A.; Fabbri, E.; Schmidt, T. J. Curr. Opin. Electrochem. 2020, 23, 89. doi: 10.1016/j.coelec.2020.05.004

  24. [24]

      Lu, X.; Jiang, Z.; Yuan, X. L.; Wu, Y. S.; Malpass-Evans, R.; Zhong, Y. R.; Liang, Y. Y.; McKeown, N. B.; Wang, H. L. Sci. Bull. 2019, 64, 1890. doi: 10.1016/j.scib.2019.04.008

  25. [25]

      Jiang, X. L.; Li, H. F.; Yang, Y. Y.; Gao, D. F. J. Mater. Sci. 2020, 55, 13916. doi: 10.1007/s10853-020-04983-y

  26. [26]

      Gao, D. F.; Wang, J.; Wu, H. H.; Jiang, X. L.; Miao, S.; Wang, G. X.; Bao, X. H. Electrochem. Commun. 2015, 55, 1. doi: 10.1016/j.elecom.2015.03.008

  27. [27]

      Gao, D. F.; McCrum, I. T.; Deo, S.; Choi, Y. W.; Scholten, F.; Wan, W. M.; Chen, J. G. G.; Janik, M. J.; Roldan Cuenya, B. ACS Catal. 2018, 8, 10012. doi: 10.1021/acscatal.8b02587

  28. [28]

      Nwabara, U. O.; Cofell, E. R.; Verma, D. S.; Negro, E.; Kenis, P. J. A. ChemSusChem 2020, 13, 855. doi: 10.1002/cssc.201902933

  29. [29]

      范佳, 韩娜, 李彦光.电化学, 2020, 26, 510. doi: 10.13208/j.electrochem.200443Fan, J.; Han, N.; Li, Y. J. Electrochem. 2020, 26, 510. doi: 10.13208/j.electrochem.200443

  30. [30]

      Lin, R.; Guo, J. X.; Li, X. J.; Patel, P.; Seifitokaldani, A. Catalysts 2020, 10, 473. doi: 10.3390/catal10050473

  31. [31]

      Liang, S. Y.; Altaf, N.; Huang, L.; Gao, Y. S.; Wang, Q. J CO₂ Util. 2020, 35, 90. doi: 10.1016/j.jcou.2019.09.007

  32. [32]

      Li, J. C.; Kuang, Y.; Meng, Y. T.; Tian, X.; Hung, W. H.; Zhang, X.; Li, A. W.; Xu, M. Q.; Zhou, W.; Ku, C. S.; et al. J. Am. Chem. Soc. 2020, 142, 7276. doi: 10.1021/jacs.0c00122

  33. [33]

      Delacourt, C.; Ridgway, P. L.; Kerr, J. B.; Newman, J. J. Electrochem. Soc. 2008, 155, B42. doi: 10.1149/1.2801871

  34. [34]

      Ma, S.; Sadakiyo, M.; Heima, M.; Luo, R.; Haasch, R. T.; Gold, J. I.; Yamauchi, M.; Kenis, P. J. A. J. Am. Chem. Soc. 2017, 139, 47. doi: 10.1021/jacs.6b10740

  35. [35]

      Dinh, C. T.; Burdyny, T.; Kibria, M. G.; Seifitokaldani, A.; Gabardo, C. M.; de Arquer, F. P. G.; Kiani, A.; Edwards, J. P.; De Luna, P.; Bushuyev, O. S.; et al. Science2018, 360, 783. doi: 10.1126/science.aas9100

  36. [36]

      Lin, L.; Li, H. B.; Yan, C. C.; Li, H. F.; Si, R.; Li, M. R.; Xiao, J. P.; Wang, G. X.; Bao, X. H. Adv. Mater. 2019, 31, 1903470. doi: 10.1002/adma.201903470

  37. [37]

      Kutz, R. B.; Chen, Q. M.; Yang, H. Z.; Sajjad, S. D.; Liu, Z. C.; Masel, I. R. Energy Technol. 2017, 5, 929. doi: 10.1002/ente.201600636

  38. [38]

      Yin, Z. L.; Peng, H. Q.; Wei, X.; Zhou, H.; Gong, J.; Huai, M. M.; Xiao, L.; Wang, G. W.; Lu, J. T.; Zhuang, L. Energy Environ.Sci. 2019, 12, 2455. doi: 10.1039/c9ee01204d

  39. [39]

      Wei, P. F.; Li, H. F.; Lin, L.; Gao, D. F.; Zhang, X. M.; Gong, H. M.; Qing, G. Y.; Cai, R.; Wang, G. X.; Bao, X. H. Sci. China Chem. 2020, doi: 10.1007/s11426-020-9825-9

  40. [40]

      Gutierrez-Guerra, N.; Gonzalez, J. A.; Serrano-Ruiz, J. C.; Lopez-Fernandez, E.; Valverde, J. L.; de Lucas-Consuegra, A. J. Energy Chem. 2019, 31, 46. doi: 10.1016/j.jechem.2018.05.005

  41. [41]

      Patru, A.; Binninger, T.; Pribyl, B.; Schmidt, T. J. J. Electrochem. Soc. 2019, 166, F34. doi: 10.1149/2.1221816jes

  42. [42]

      Xia, C.; Zhu, P.; Jiang, Q.; Pan, Y.; Liang, W. T.; Stavitsk, E.; Alshareef, H. N.; Wang, H. T. Nat. Energy 2019, 4, 776. doi: 10.1038/s41560-019-0451-x

  43. [43]

      Jhong, H. R.; Ma, S. C.; Kenis, P. J. A. Curr. Opin. Chem. Eng. 2013, 2, 191. doi: 10.1016/j.coche.2013.03.005

  44. [44]

      Sanchez, O. G.; Birdja, Y. Y.; Bulut, M.; Vaes, J.; Breugelmans, T.; Pant, D. Curr. Opin. Green Sust. Chem. 2019, 16, 47. doi: 10.1016/j.cogsc.2019.01.005

  45. [45]

      Smith, W. A.; Burdyny, T.; Vermaas, D. A.; Geerlings, H. Joule 2019, 3, 1822. doi: 10.1016/j.joule.2019.07.009

  46. [46]

      Whipple, D. T.; Kenis, P. J. A. J. Phys. Chem. Lett. 2010, 1, 3451. doi: 10.1021/jz1012627

  47. [47]

      Carmo, M.; Fritz, D. L.; Merge, J.; Stolten, D. Int. J. Hydrogen Energy 2013, 38, 4901. doi: 10.1016/j.ijhydene.2013.01.151

  48. [48]

      Chen, J. G.; Jones, C. W.; Linic, S.; Stamenkovic, V. R. ACS Catal. 2017, 7, 6392. doi: 10.1021/acscatal.7b02839

  49. [49]

      Ma, W. C.; Xie, S. J.; Liu, T. T.; Fan, Q. Y.; Ye, J. Y.; Sun, F. F.; Jiang, Z.; Zhang, Q. H.; Cheng, J.; Wang, Y. Nat. Catal. 2020, 3, 478. doi: 10.1038/s41929-020-0450-0

  50. [50]

      De Arquer, F. P. G.; Dinh, C. T.; Ozden, A.; Wicks, J.; McCallum, C.; Kirmani, A. R.; Nam, D. H.; Gabardo, C.; Seifitokaldani, A.; Wang, X.; et al. Science 2020, 367, 661. doi: 10.1126/science.aay4217

  51. [51]

      Ebbesen, S. D.; Jensen, S. H.; Hauch, A.; Mogensen, M. B. Chem. Rev. 2014, 114, 10697. doi: 10.1021/cr5000865

  52. [52]

      Martin, A. J.; Larrazabal, G. O.; Perez-Ramirez, J. Green Chem. 2015, 17, 5114. doi: 10.1039/c5gc01893e

  53. [53]

      Scott, S. L.ACS Catal. 2018, 8, 8597. doi: 10.1021/acscatal.8b03199

  54. [54]

      Popovic, S.; Smiljanic, M.; Jovanovic, P.; Vavra, J.; Buonsanti, R.; Hodnik, N. Angew. Chem. Int. Ed. 2020, 59, 14736. doi: 10.1002/anie.202000617

  55. [55]

      Gao, D. F.; Zhou, H.; Cai, F.; Wang, D. N.; Hu, Y. F.; Jiang, B.; Cai, W. B.; Chen, X. Q.; Si, R.; Yang, F.; et al. Nano Res. 2017, 10, 2181. doi: 10.1007/s12274-017-1514-6

  56. [56]

      Singh, M. R.; Clark, E. L.; Bell, A. T. Phys. Chem. Chem. Phys. 2015, 17, 18924. doi: 10.1039/c5cp03283k

  57. [57]

      Weng, L. C.; Bell, A. T.; Weber, A. Z. Phys. Chem. Chem. Phys. 2018, 20, 16973. doi: 10.1039/c8cp01319e

  58. [58]

      Burdyny, T.; Smith, W. A. Energy Environ Sci. 2019, 12, 1442. doi: 10.1039/c8ee03134g

  59. [59]

      Xiao, L.; Zhang, S.; Pan, J.; Yang, C. X.; He, M. L.; Zhuang, L.; Lu, J. T. Energy Environ Sci. 2012, 5, 7869. doi: 10.1039/c2ee22146b

  60. [60]

      Zhang, H. W.; Shen, P. K. Chem. Rev. 2012, 112, 2780. doi: 10.1021/cr200035s

  61. [61]

      Noh, S.; Jeon, J. Y.; Adhikari, S.; Kim, Y. S.; Bae, C. Acc. Chem. Res. 2019, 52, 2745. doi: 10.1021/acs.accounts.9b00355

  62. [62]

      Kungas, R. J. Electrochem. Soc. 2020, 167, 044508. doi: 10.1149/1945-7111/ab7099

  63. [63]

      Song, Y. F.; Zhang, X. M.; Xie, K.; Wang, G. X.; Bao, X. H. Adv. Mater. 2019, 31, 1902033. doi: 10.1002/adma.201902033

  64. [64]

      Zhang, L. X.; Hu, S. Q.; Zhu, X. F.; Yang, W. S. J. Energy Chem. 2017, 26, 593. doi: 10.1016/j.jechem.2017.04.004

  65. [65]

      Hori, Y.; Kikuchi, K.; Suzuki, S. Chem. Lett. 1985, 14, 1695. doi: 10.1246/cl.1985.1695

  66. [66]

      Hori, Y.; Kikuchi, K.; Murata, A.; Suzuki, S. Chem. Lett. 1986, 15, 897. doi: 10.1246/cl.1986.897

  67. [67]

      Gao, D. F.; Sinev, I.; Scholten, F.; Aran-Ais, R. M.; Divins, N. J.; Kvashnina, K.; Timoshenko, J.; Roldan Cuenya, B. Angew. Chem. Int. Ed. 2019, 58, 17047. doi: 10.1002/anie.201910155

  68. [68]

      Zhang, B.; Zhang, J.; Hua, M.; Wan, Q.; Su, Z.; Tan, X.; Liu, L.; Zhang, F.; Chen, G.; Tan, D.; et al. J. Am. Chem. Soc. 2020, 142, 13606. doi: 10.1021/jacs.0c06420

  69. [69]

      Xu, H.; Rebollar, D.; He, H.; Chong, L.; Liu, Y.; Liu, C.; Sun, C.-J.; Li, T.; Muntean, J. V.; Winans, R. E.; et al. Nat. Energy 2020, 5, 623. doi: 10.1038/s41560-020-0666-x

  70. [70]

      Pupo, M. M. D.; Kortlever, R. ChemPhysChem 2019, 20, 2926. doi: 10.1002/cphc.201900680

  71. [71]

      Zhu, S. Q.; Jiang, B.; Cai, W. B.; Shao, M. H. J. Am. Chem. Soc. 2017, 139, 15664. doi: 10.1021/jacs.7b10462

  72. [72]

      Dunwell, M.; Lu, Q.; Heyes, J. M.; Rosen, J.; Chen, J. G. G.; Yan, Y. S.; Jiao, F.; Xu, B. J. J. Am. Chem. Soc. 2017, 139, 3774. doi: 10.1021/jacs.6b13287

  73. [73]

      Melchaeva, O.; Voyame, P.; Bassetto, V. C.; Prokein, M.; Renner, M.; Weidner, E.; Petermann, M.; Battistel, A. ChemSusChem 2017, 10, 3660. doi: 10.1002/cssc.201701205

  74. [74]

      Schouten, K. J. P.; Gallent, E. P.; Koper, M. T. M. J. Electroanal. Chem. 2014, 716, 53. doi: 10.1016/j.jelechem.2013.08.033

  75. [75]

      Jouny, M.; Luc, W.; Jiao, F. Nat. Catal. 2018, 1, 748. doi: 10.1038/s41929-018-0133-2

  76. [76]

      Bhargava, S. S.; Proietto, F.; Azmoodeh, D.; Cofell, E. R.; Henckel, D. A.; Verma, S.; Brooks, C. J.; Gewirth, A. A.; Kenis, P. J. A. ChemElectroChem 2020, 7, 2001. doi: 10.1002/celc.202000089

  77. [77]

      Whipple, D. T.; Finke, E. C.; Kenis, P. J. A. Electrochem. Solid State 2010, 13, D109. doi: 10.1149/1.3456590

  78. [78]

      Ma, S.; Luo, R.; Moniri, S.; Lan, Y. C.; Kenis, P. J. A. J. Electrochem. Soc. 2014, 161, F1124. doi: 10.1149/2.1201410jes

  79. [79]

      Verma, S.; Hamasaki, Y.; Kim, C.; Huang, W. X.; Lu, S.; Jhong, H. R. M.; Gewirth, A. A.; Fujigaya, T.; Nakashima, N.; Kenis, P. J. A. ACS Energy Lett. 2018, 3, 193. doi: 10.1021/acsenergylett.7b01096

  80. [80]

      Leonard, M. E.; Clarke, L. E.; Forner-Cuenca, A.; Brown, S. M.; Brushett, F. R. ChemSusChem2020, 13, 400. doi: 10.1002/cssc.201902547

  81. [81]

      Möller, T.; Scholten, F.; Thanh, T. N.; Sinev, I.; Timoshenko, J.; Wang, X.; Jovanov, Z.; Gliech, M.; Roldan Cuenya, B.; Sofia Varela, A.; et al. Angew. Chem. Int. Ed. 2020, 59, 17974. doi: 10.1002/anie.202007136

  82. [82]

      Moller, T.; Ju, W.; Bagger, A.; Wang, X. L.; Luo, F.; Thanh, T. N.; Varela, A. S.; Rossmeisl, J.; Strasser, P. Energy Environ. Sci. 2019, 12, 640. doi: 10.1039/c8ee02662a

  83. [83]

      Tan, Y. C.; Lee, K. B.; Song, H.; Oh, J. Joule 2020, 4, 1104. doi: 10.1016/j.joule.2020.03.013

  84. [84]

      Martić, N.; Reller, C.; Macauley, C.; Löffler, M.; Reichert, A. M.; Reichbauer, T.; Vetter, K. -M.; Schmid, B.; McLaughlin, D.; Leidinger, P.; et al. Energy Environ. Sci. 2020, 13, 2993. doi: 10.1039/d0ee01100b

  85. [85]

      Zhang, X.; Wang, Y.; Gu, M.; Wang, M.; Zhang, Z.; Pan, W.; Jiang, Z.; Zheng, H.; Lucero, M.; Wang, H.; et al. Nat. Energy 2020, 5, 684. doi: 10.1038/s41560-020-0667-9

  86. [86]

      Ye, K.; Zhou, Z. W.; Shao, J. Q.; Lin, L.; Gao, D. F.; Ta, N.; Si, R.; Wang, G. X.; Bao, X. H. Angew. Chem. Int. Ed. 2020, 59, 4814. doi: 10.1002/anie.201916538

  87. [87]

      Haas, T.; Krause, R.; Weber, R.; Demler, M.; Schmid, G. Nat. Catal. 2018, 1, 32. doi: 10.1038/s41929-017-0005-1

  88. [88]

      Genovese, C.; Ampelli, C.; Perathoner, S.; Centi, G. J. Energy Chem. 2013, 22, 202. doi: 10.1016/S2095-4956(13)60026-1

  89. [89]

      Gao, D. F.; Cai, F.; Xu, Q. Q.; Wang, G. X.; Pan, X. L.; Bao, X. H. J. Energy Chem. 2014, 23, 694. doi: 10.1016/S2095-4956(14)60201-1

  90. [90]

      Guterrez-Guerra, N.; Valverde, J. L.; Romero, A.; Serrano-Ruiz, J. C.; de Lucas-Consuegra, A. Electrochem. Commun. 2017, 81, 128. doi: 10.1016/j.elecom.2017.06.018

  91. [91]

      Lee, W.; Kim, Y. E.; Youn, M. H.; Jeong, S. K.; Park, K. T. Angew. Chem. Int. Ed. 2018, 57, 6883. doi: 10.1002/anie.201803501

  92. [92]

      Lee, S.; Ju, H.; Machunda, R.; Uhm, S.; Lee, J. K.; Lee, H. J.; Lee, J. J. Mater. Chem. A2015, 3, 3029. doi: 10.1039/c4ta03893b

  93. [93]

      Fujinuma, N.; Ikoma, A.; Lofland, S. E. Adv. Energy Mater. 2020, doi: 10.1002/aenm.202001645

  94. [94]

      毛庆, 李冰玉, 景维云, 赵健, 刘松, 黄延强, 杜兆龙.电化学, 2020, 26, 359. doi: 10.13208/j.electrochem.190305Mao, Q.; Li, B.; Jing, W.; Zhao, J.; Liu, S.; Huang, Y. Z.; Du, Z. L. J. Electrochem. 2020, 26, 359. doi: 10.13208/j.electrochem.190305

  95. [95]

      Gabardo, C. M.; O'Brien, C. P.; Edwards, J. P.; McCallum, C.; Xu, Y.; Dinh, C. T.; Li, J.; Sargent, E. H.; Sinton, D. Joule 2019, 3, 2777. doi: 10.1016/j.joule.2019.07.021

  96. [96]

      Ren, S. X.; Joulie, D.; Salvatore, D.; Torbensen, K.; Wang, M.; Robert, M.; Berlinguette, C. P. Science 2019, 365, 367. doi: 10.1126/science.aax4608

  97. [97]

      Li, F. W.; Thevenon, A.; Rosas-Hernandez, A.; Wang, Z. Y.; Li, Y. L.; Gabardo, C. M.; Ozden, A.; Dinh, C. T.; Li, J.; Wang, Y. H.; et al. Nature 2020, 577, 509. doi: 10.1038/s41586-019-1782-2

  98. [98]

      Lee, J.; Lim, J.; Roh, C. W.; Whang, H. S.; Lee, H. J. CO₂ Util. 2019, 31, 244. doi: 10.1016/j.jcou.2019.03.022

  99. [99]

      Liu, Z. C.; Yang, H. Z.; Kutz, R.; Masel, R. I. J. Electrochem. Soc. 2018, 165, J3371. doi: 10.1149/2.0501815jes

  100. [100]

       Reyes, A.; Jansonius, R. P.; Mowbray, B. A. W.; Cao, Y.; Wheeler, D. G.; Chau, J.; Dvorak, D. J.; Berlinguette, C. P. ACS Energy Lett. 2020, 5, 1612. doi: 10.1021/acsenergylett.0c00637

  101. [101]

       Lee, W. H.; Ko, Y. -J.; Choi, Y.; Lee, S. Y.; Choi, C. H.; Hwang, Y. J.; Min, B. K.; Strasser, P.; Oh, H. -S. Nano Energy 2020, 76, 105030. doi: 10.1016/j.nanoen.2020.105030

  102. [102]

       Ma, C.; Hou, P. F.; Wang, X. P.; Wang, Z.; Li, W. T.; Kang, P. Appl. Catal. B-Environ. 2019, 250, 347. doi: 10.1016/j.apcatb.2019.03.041

  103. [103]

       Hou, P. F.; Wang, X. P.; Wang, Z.; Kang, P. ACS Appl. Mater. Interfaces 2018, 10, 38024. doi: 10.1021/acsami.8b11942

  104. [104]

       Wang, G. L.; Pan, J.; Jiang, S. P.; Yang, H. J. CO₂ Util. 2018, 23, 152. doi: 10.1016/j.jcou.2017.11.010

  105. [105]

       Ozden, A.; Li, F.; de Arquer, P. G.; Rosas-Hernández, A.; Thevenon, A.; Wang, Y.; Hung, S. -F.; Wang, X.; Chen, B.; Li, J.; et al. ACS Energy Lett. 2020, 5, 2811. doi: 10.1021/acsenergylett.0c01266

  106. [106]

       Pavel, C. C.; Cecconi, F.; Emiliani, C.; Santiccioli, S.; Scaffidi, A.; Catanorchi, S.; Comotti, M. Angew. Chem. Int. Ed. 2014, 53, 1378. doi: 10.1002/anie.201308099

  107. [107]

       Endrodi, B.; Kecsenovity, E.; Samu, A.; Darvas, F.; Jones, R. V.; Torok, V.; Danyi, A.; Janaky, C. ACS Energy Lett. 2019, 4, 1770. doi: 10.1021/acsenergylett.9b01142

  108. [108]

       Ziv, N.; Mustain, W. E.; Dekel, D. R. ChemSusChem 2018, 11, 1136. doi: 10.1002/cssc.201702330

  109. [109]

       Larrazabal, G. O.; Strom-Hansen, P.; Heli, J. P.; Zeiter, K.; Therldldsen, K. T.; Chorkendorff, I.; Seger, B. ACS Appl. Mater. Interfaces 2019, 11, 41281. doi: 10.1021/acsami.9b13081

  110. [110]

       Ma, M.; Clark, E. L.; Therkildsen, K. T.; Dalsgaard, S.; Chorkendorff, I.; Seger, B. Energy Environ. Sci. 2020, 13, 977. doi: 10.1039/d0ee00047g

  111. [111]

       Oener, S. Z.; Foster, M. J.; Boettcher, S. W. Science 2020, 369, 1099. doi: 10.1126/science.aaz1487

  112. [112]

       Salvatore, D. A.; Weekes, D. M.; He, J. F.; Dettelbach, K. E.; Li, Y. G. C.; Mallouk, T. E.; Berlinguette, C. P. ACS Energy Lett. 2018, 3, 149. doi: 10.1021/acsenergylett.7b01017

  113. [113]

       Li, Y. G. C.; Zhou, D. K.; Yan, Z. F.; Goncalves, R. H.; Salvatore, D. A.; Berlinguette, C. P.; Mallouk, T. E. ACS Energy Lett. 2016, 1, 1149. doi: 10.1021/acsenergylett.6b00475

  114. [114]

       Vermaas, D. A.; Smith, W. A. ACS Energy Lett. 2016, 1, 1143. doi: 10.1021/acsenergylett.6b00557

  115. [115]

       Lin, M.; Han, L. H.; Singh, M. R.; Xiang, C. X. ACS Appl. Energy Mater. 2019, 2, 5843. doi: 10.1021/acsaem.9b00986

  116. [116]

       Ramdin, M.; Morrison, A. R. T.; de Groen, M.; van Haperen, R.; de Kler, R.; van den Broeke, L. J. P.; Trusler, J. P. M.; de Jong, W.; Vlugt, T. J. H. Ind. Eng. Chem. Res. 2019, 58, 1834. doi: 10.1021/acs.iecr.8b04944

  117. [117]

       Chen, Y. Y.; Vise, A.; Klein, W. E.; Cetinbas, F. C.; Myers, D. J.; Smith, W. A.; Deutsch, T. G.; Neyerlin, K. C. ACS Energy Lett. 2020, 5, 1825. doi: 10.1021/acsenergylett.0c00860

  118. [118]

       Zhang, J.; Luo, W.; Zuttel, A. J. Catal. 2020, 385, 140. doi: 10.1016/j.jcat.2020.03.013

  119. [119]

       Li, Y. G. C.; Yan, Z. F.; Hitt, J.; Wycisk, R.; Pintauro, P. N.; Mallouk, T. E. Adv. Sustain. Syst. 2018, 2, 1700187. doi: 10.1002/adsu.201700187

  120. [120]

       Endrodi, B.; Kecsenovity, E.; Samu, A.; HalmAgyi, T.; Rojas-Carbonell, S.; Wang, L.; Yan, Y.; Janaky, C. Energy Environ. Sci. 2020, doi: 10.1039/d0ee02589e

  121. [121]

       Gabardo, C. M.; Seifitokaldani, A.; Edwards, J. P.; Dinh, C. T.; Burdyny, T.; Kibria, M. G.; O'Brien, C. P.; Sargent, E. H.; Sinton, D. Energy Environ. Sci. 2018, 11, 2531. doi: 10.1039/c8ee01684d

  122. [122]

       Ripatti, D. S.; Veltman, T. R.; Kanan, M. W. Joule 2019, 3, 240. doi: 10.1016/j.joule.2018.10.007

  123. [123]

       Zhang, B. A.; Costentin, C.; Nocera, D. G. Joule 2019, 3, 1565. doi: 10.1016/j.joule.2019.05.017

  124. [124]

       Dinh, C. T.; Li, Y. G. C.; Sargent, E. H. Joule 2019, 3, 13. doi: 10.1016/j.joule.2018.10.021

  125. [125]

       Handoko, A. D.; Wei, F. X.; Jenndy; Yeo, B. S.; Seh, Z. W. Nat. Catal. 2018, 1, 922. doi: 10.1038/s41929-018-0182-6

  126. [126]

       Li, X. D.; Wang, S. M.; Li, L.; Sun, Y. F.; Xie, Y. J. Am. Chem. Soc. 2020, 142, 9567. doi: 10.1021/jacs.0c02973

  127. [127]

       Zhang, Z. S.; Melo, L.; Jansonius, R. P.; Habibzadeh, F.; Grant, E. R.; Berlinguette, C. P. ACS Energy Lett. 2020, 5, 3101. doi: 10.1021/acsenergylett.0c01606

  128. [128]

       Shi, R.; Guo, J. H.; Zhang, X. R.; Waterhouse, G. I. N.; Han, Z. J.; Zhao, Y. X.; Shang, L.; Zhou, C.; Jiang, L.; Zhang, T. R. Nat. Commun. 2020, 11, 3028. doi: 10.1038/s41467-020-16847-9

  129. [129]

       Arán-Ais, R. M.; Rizo, R.; Grosse, P.; Algara-Siller, G.; Dembele, K.; Plodinec, M.; Lunkenbein, T.; Chee, S. W.; Roldan Cuenya, B. Nat. Commun. 2020, 11, 3489. doi: 10.1038/s41467-020-17220-6

  130. [130]

       Salvatore, D.; Berlinguette, C. P. ACS Energy Lett. 2020, 5, 2150. doi: 10.1021/acsenergylett.9b02356

  131. [131]

       Verma, S.; Lu, S.; Kenis, P. J. A. Nat. Energy 2019, 4, 466. doi: 10.1038/s41560-019-0374-6

  132. [132]

       Song, Y. F.; Zhao, Y. H.; Nan, G. Z.; Chen, W.; Guo, Z. K.; Li, S. G.; Tang, Z. Y.; Wei, W.; Sun, Y. H. Appl. Catal. B-Environ. 2020, 270, 118888. doi: 10.1016/j.apcatb.2020.118888

  133. [133]

       Dresp, S.; Thanh, T. N.; Klingenhof, M.; Bruckner, S.; Hauke, P.; Strasser, P. Energy Environ. Sci. 2020, 13, 1725. doi: 10.1039/d0ee01125h

  134. [134]

       Vass, A.; Endrodi, B.; Janaky, C. Curr. Opin. Electrochem. 2020, doi: 10.1016/j.coelec.2020.08.003

  135. [135]

       Medvedeva, X. V.; Medvedev, J. J.; Tatarchuk, S. W.; Choueiri, R. M.; Klinkova, A. Green Chem. 2020, 22, 4456. doi: 10.1039/d0gc01754j

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