碳修饰的铜催化剂实现安培级电流电化学还原CO<sub>2</sub>制C<sub>2+</sub>产物

引用本文: 董雪, 孙晓甫, 贾帅强, 韩世涛, 周达伟, 姚婷, 王敏, 方明慧, 吴海虹, 韩布兴. 碳修饰的铜催化剂实现安培级电流电化学还原CO₂制C₂₊产物[J]. 物理化学学报, 2025, 41(3): 240401. doi: 10.3866/PKU.WHXB202404012 shu

Citation: Xue Dong, Xiaofu Sun, Shuaiqiang Jia, Shitao Han, Dawei Zhou, Ting Yao, Min Wang, Minghui Fang, Haihong Wu, Buxing Han. Electrochemical CO₂ Reduction to C₂₊ Products with Ampere-Level Current on Carbon-Modified Copper Catalysts[J]. Acta Physico-Chimica Sinica, 2025, 41(3): 240401. doi: 10.3866/PKU.WHXB202404012 shu

碳修饰的铜催化剂实现安培级电流电化学还原CO₂制C₂₊产物

董雪 ^1, ,
孙晓甫 ^{2,
,} ,
贾帅强 ^1, ,
韩世涛 ^1, ,
周达伟 ^1, ,
姚婷 ^1, ,
王敏 ^1, ,
方明慧 ^1, ,
吴海虹 ^{1,
,} ,
韩布兴 ^{1, 2,
,}

1.
华东师范大学化学与分子工程学院, 上海市绿色化学与化工过程重点实验室, 上海 200062
2.
中国科学院化学研究所, 北京分子科学国家实验室, 中国科学院胶体、界面与化学热力学重点实验室, 中国科学院分子科学卓越研究/教育中心, 北京 100190

通讯作者: 孙晓甫, sunxiaofu@iccas.ac.cn; 吴海虹, hhwu@chem.ecnu.edu.cn; 韩布兴, hanbx@iccas.ac.cn

基金项目:
国家重点研发计划项目 2023YFA1507901

国家重点研发计划项目 2020YFA0710201

国家自然科学基金项目 22293015

国家自然科学基金项目 22121002

摘要: 铜基电催化剂在CO₂还原反应(CO₂RR)中产高附加值产物的潜力巨大，是实现碳负排放的一种很有前景的途径。同时，安培级电流是实现多碳(C₂₊)产业化的关键。然而，由于复杂的电子传递过程和不可避免的副反应，工业电流密度下的C₂₊选择性仍然不令人满意。在此，我们开发了一种碳修饰策略来优化局部环境并调节中间产物在Cu活性位点的吸附。结果表明，Cu-C_x催化剂(x为催化剂中C的原子百分数)能有效催化CO₂RR生成C₂₊产物。特别是在流动池中，Cu-C_6%在-0.72 V vs. RHE(相对可逆氢电极)条件下，电流密度可达1.25 A∙cm^-2, C₂H₄和C₂₊产物的法拉第效率(FE)分别可达54.4%和80.2%。原位光谱分析和密度泛函理论(DFT)计算表明，C的存在调节了^*CO在Cu表面的吸附，降低了C—C耦合的能垒，从而促进了C₂₊产物的生成。

关键词:

English

Electrochemical CO₂ Reduction to C₂₊ Products with Ampere-Level Current on Carbon-Modified Copper Catalysts

Xue Dong ^1, ,
Xiaofu Sun ^{2,
,} ,
Shuaiqiang Jia ^1, ,
Shitao Han ^1, ,
Dawei Zhou ^1, ,
Ting Yao ^1, ,
Min Wang ^1, ,
Minghui Fang ^1, ,
Haihong Wu ^{1,
,} ,
Buxing Han ^{1, 2,
,}

1.
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
2.
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Corresponding author: Email: sunxiaofu@iccas.ac.cn (X.F.)Tel.: +86-10-62562821 (X.F.); Email: hhwu@chem.ecnu.edu.cn (H.H.); Email: hanbx@iccas.ac.cn (B.X.)

Received Date: 08 April 2024
Accepted Date: 07 May 2024
Revised Date: 07 May 2024
Available Online: 15 March 2025
Fund Project:
the National Key Research and Development Program of China

the National Key Research and Development Program of China

National Natural Science Foundation of China

National Natural Science Foundation of China

Abstract: Copper-based electrocatalysts have great potential to produce high-value products in CO₂ reduction reaction (CO₂RR), offering a promising way to achieve negative carbon emissions. Additionally, achieving ampere-level currents is crucial for realizing the industrialization of multi-carbon (C₂₊) products. However, the C₂₊ selectivity at industrial current densities remains unsatisfactory due to complex electron transport processes and inevitable side reactions. Herein, we developed a carbon-modification strategy aimed at optimizing the local environment and regulating the adsorption of intermediates at Cu active sites. Our findings demonstrated the effectiveness of Cu-C_x catalysts (where 'x' denoted the atomic percentage of C in the catalysts) in facilitating CO₂RR for producing C₂₊ products. Especially, over Cu-C_6%, the current density could reach to 1.25 A∙cm^-2 at -0.72 V vs. RHE (versus reversible hydrogen electrode) in a flow cell, and the Faradaic efficiency (FE) of C₂H₄ and C₂₊ products could reach to 54.4% and 80.2%, respectively. In situ spectral analysis and density functional theory (DFT) calculations showed that the presence of C regulated the adsorption of ^*CO on Cu surface, reduced the energy barrier of C—C coupling, thus promoting the production of C₂₊ products.

Key words:

1. [1]
  Li, F.; Li, Y.; Wang, Z.; Li, J.; Nam, D. H.; Lum, Y.; Luo, M.; Wang, X.; Ozden, A.; Hung, S. F.; et al. Nat. Catal. 2020, 3, 75. doi: 10.1038/s41929-019-0383-7
2. [2]
  Liu, Z.; Yi, X.; Gao, F.; Xie, Z.; Han, B.; Sun, Y.; He, M.; Yang, J. Acta Phys. -Chim. Sin. 2023, 39, 2112029. doi: 10.3866/PKU.WHXB202112029
3. [3]
  De Luna, P.; Hahn, C.; Higgins, D.; Jaffer, S. A.; Jaramillo, T. F.; Sargent, E. H. Science 2019, 364, eaav3506. doi: 10.1126/science.aav3506
4. [4]
  Liu, H.; Jia, S.; Wu, L.; He, L.; Sun, X.; Han, B. Innovat. Mater. 2024, 2, 100058. doi: 10.59717/j.xinn-mater.2024.100058
5. [5]
  Li, X.; Chen, Y.; Zhan, X.; Xu, Y.; Hao, L.; Xu, L.; Li, X.; Umer, M.; Tan, X.; Han, B.; Robertson, A.W.; Sun, Z. Innovat. Mater. 2023, 1, 100014. doi: 10.59717/j.xinn-mater.2023.100014
6. [6]
  Yang, D.; Zhu, Q.; Han, B. Innovation 2020, 1. 100016. doi: 10.1016/j.xinn.2020.100016
7. [7]
  Peng, L.; Zhang, Y.; He, R.; Xu, N.; Qiao, J. Acta Phys. -Chim. Sin. 2023, 39, 2302037. doi: 10.3866/PKU.WHXB202302037
8. [8]
  Tan, X.; Sun, X.; Han, B. Natl. Sci. Rev. 2022, 9, nwab022. doi: 10.1093/nsr/nwab022
9. [9]
  Kibria, M. G.; Edwards, J. P.; Gabardo, C. M.; Dinh, C. T.; Seifitokaldani, A.; Sinton, D.; Sargent, E. H. Adv. Mater. 2019, 31, 1807166. doi: 10.1002/adma.201807166
10. [10]
  Jin, S.; Hao, Z.; Zhang, K.; Yan, Z.; Chen, J. Angew. Chem. Int. Ed. 2021, 133, 20795. doi: 10.1002/anie.202101818
11. [11]
  Zhu, S.; Delmo, E. P.; Li, T.; Qin, X.; Tian, J.; Zhang, L.; Shao, M. Adv. Mater. 2021, 33, 2005484. doi: 10.1002/adma.202005484
12. [12]
  Zou, Y.; Wang, S. Adv. Sci. 2021, 8, 2003579. doi: 10.1002/advs.202003579
13. [13]
  Gao, D.; Arán-Ais, R. M.; Jeon, H. S.; Roldan Cuenya, B. Nat. Catal. 2019, 2, 198. doi: 10.1038/s41929-019-0235-5
14. [14]
  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
15. [15]
  Xie, M.; Shen, Y.; Ma, W.; Wei, D.; Zhang, B.; Wang, Z.; Wang, Y.; Zhang, Q.; Xie, S.; Wang, C.; et al. Angew. Chem. Int. Ed. 2022, 61, e202213423. doi: 10.1002/anie.202213423
16. [16]
  Li, X.; Wu, X.; Lv, X.; Wang, J.; Wu, H. Chem. Catal. 2022, 2, 262. doi: 10.1016/j.checat.2021.10.015
17. [17]
  Rong, Y.; Sang, J.; Che, L.; Gao, D.; Wang, G. Acta Phys. -Chim. Sin. 2023, 39, 2212027. doi: 10.3866/PKU.WHXB202212027
18. [18]
  Lum, Y.; Cheng, T.; Goddard, W. A.; III; Ager, J. W. J. Am. Chem. Soc. 2018, 140, 9337. doi: 10.1021/jacs.8b03986
19. [19]
  Peng, C.; Yang, S.; Luo, G.; Yan, S.; Shakouri, M.; Zhang, J.; Chen, Y.; Li, W.; Wang, Z.; Sham, T. K.; et al. Adv. Mater. 2022, 34, 2204476. doi: 10.1002/adma.202204476
20. [20]
  Zhuang, T.; Liang, Z.; Seifitokaldani, A.; Li, Y.; De Luna, P.; Burdyny, T.; Che, F.; Meng, F.; Min, Y.; Quintero-Bermudez, R.; et al. Nat. Catal. 2018, 1, 421. doi: 10.1038/s41929-018-0084-7
21. [21]
  Kuang, S.; Su, Y.; Li, M.; Liu, H.; Chuai, H.; Chen, X.; Hensen, E. J.; Meyer, T. J.; Zhang, S.; Ma, X. Natl. Acad. Sci. USA 2023, 120, e2214175120. doi: 10.1073/pnas.2214175120
22. [22]
  Zhao, S.; Christensen, O.; Sun, Z.; Liang, H.; Bagger, A.; Torbensen, K.; Nazari, P.; Lauritsen, J. V.; Pedersen, S. U.; Rossmeisl, J.; et al. Nat. Commun. 2023, 14, 844. doi: 10.1038/s41467-023-36530-z
23. [23]
  Ge, W.; Chen, Y.; Fan, Y.; Zhu, Y.; Liu, H.; Song, L.; Liu, Z.; Lian, C.; Jiang, H.; Li, C. J. Am. Chem. Soc. 2022, 144, 6613. doi: 10.1021/jacs.2c02486
24. [24]
  Feng, J.; Wu, L.; Liu, S.; Xu, L.; Song, X.; Zhang, L.; Zhu, Q.; Kang, X.; Sun, X.; Han, B. J. Am. Chem. Soc. 2023, 145, 9857. doi: 10.1021/jacs.3c02428
25. [25]
  Liu, C.; Wang, M.; Ye, J.; Liu, L.; Li, L.; Li, Y.; Huang, X. Nano Lett. 2023, 23, 1474. doi: 10.1021/acs.nanolett.2c04911
26. [26]
  Zhou, Y.; Che, F.; Liu, M.; Zou, C.; Liang, Z.; De Luna, P.; Yuan, H.; Li, J.; Wang, Z.; Xie, H.; et al. Nat. Chem. 2018, 10, 974. doi: 10.1038/s41557-018-0092-x
27. [27]
  Guo, C.; Guo, Y.; Shi, Y.; Lan, X.; Wang, Y.; Yu, Y.; Zhang, B. Angew. Chem. Int. Ed. 2022, 134, e202205909. doi: 10.1002/anie.202205909
28. [28]
  Dinh, C.T.; Burdyny, T.; Kibria, M.G.; Sei, A. Science 2018, 360, 783. doi: 10.1126/science.aas9100
29. [29]
  Lv, J.; Jouny, M.; Luc, W.; Zhu, W.; Zhu, J.; Jiao, F. Adv. Mater. 2018, 30, 1803111. doi: 10.1002/adma.201803111
30. [30]
  Gao, D.; Scholten, F.; Roldan Cuenya, B. ACS Catal. 2017, 7, 5112. doi: 10.1021/acscatal.7b01416
31. [31]
  Chen, X.; Chen, J.; Alghoraibi, N. M.; Henckel, D. A.; Zhang, R.; Nwabara, U. O.; Madsen, K. E.; Kenis, P. J.; Zimmerman, S. C.; Gewirth, A. A. Nat. Catal. 2021, 4, 20. doi: 10.1038/s41929-020-00547-0
32. [32]
  Li, Y.; Wang, Z.; Yuan, T.; Nam, D. H.; Luo, M.; Wicks, J.; Chen, B.; Li, J.; Li, F.; De Arquer, F. P. G.; et al. J. Am. Chem. Soc. 2019, 141, 8584. doi: 10.1021/jacs.9b02945
33. [33]
  Li, F.; Thevenon, A.; Rosas-Hernández, A.; Wang, Z.; Li, Y.; Gabardo, C. M.; Ozden, A.; Dinh, C. T.; Li, J.; Wang, Y.; et al. Nature 2020, 577, 509. doi: 10.1038/s41586-019-1782-2
34. [34]
  Xue, L.; Gao, Z.; Ning, T.; Li, W.; Li, J.; Yin, J.; Xiao, L.; Wang, G.; Zhuang, L. Angew. Chem. Int. Ed. 2023, 135, e202309519. doi: 10.1002/anie.202309519
35. [35]
  Lim, C. Y. J.; Yilmaz, M.; Arce-Ramos, J. M.; Handoko, A. D.; Teh, W. J.; Zheng, Y.; Khoo, Z. H. J.; Lin, M.; Isaacs, M.; Tam, T. L. D.; et al. Nat. Commun. 2023, 14, 335. doi: 10.1038/s41467-023-35912-7
36. [36]
  Yu, S.; Jain, P. K. Nat. Commun. 2019, 10, 2022. doi: 10.1038/s41467-019-10084-5
37. [37]
  Zhao, K.; Liu, Y.; Quan, X.; Chen, S.; Yu, H. ACS Appl. Mater. Interfaces. 2017, 9, 5302. doi: 10.1021/acsami.6b15402
38. [38]
  Li, C. W.; Kanan, M. W. J. Am. Chem. Soc. 2012, 134, 7231. doi: 10.1021/ja3010978
39. [39]
  Kanda, S.; Shimizu, Y.; Ohno, Y.; Shirasaki, K.; Nagai, Y.; Kasu, M.; Shigekawa, N.; Liang, J. J. Appl. Phys. 2019, 59, SBBB03. doi: 10.7567/1347-4065/ab4f19
40. [40]
  Fallon, P. J.; Brown, L. M. Diam. Relat. Mater. 1993, 2, 1004. doi: 10.1016/0925-9635(93)90265-4
41. [41]
  Leapman, R. D.; Grunes, L. A.; Fejes, P. L. Phys. Rev. B 1982, 26, 614. doi: 10.1103/physrevb.26.614
42. [42]
  Feng, J.; Zhang, L.; Liu, S.; Xu, L.; Ma, X.; Tan, X.; Wu, L.; Qian, Q.; Wu, T.; Zhang, J.; et al. Nat. Commun. 2023, 14, 4615. doi: 10.1038/s41467-023-40412-9
43. [43]
  Yang, B.; Liu, K.; Li, H.; Liu, C.; Fu, J.; Li, H.; Huang, J. E.; Ou, P.; Alkayyali, T.; Cai, C.; et al. J. Am. Chem. Soc. 2022, 144, 3039. doi: 10.1021/jacs.1c11253
44. [44]
  Song, X.; Xu, L.; Sun, X.; Han, B. Sci. China Chem. 2023, 66, 315. doi: 10.1007/s11426-021-1463-6
45. [45]
  Zhu, S.; Jiang, B.; Cai, W. -B.; Shao, M. J. Am. Chem. Soc. 2017, 139, 15664. doi: 10.1021/jacs.7b10462
46. [46]
  Zhan, C.; Dattila, F.; Rettenmaier, C.; Bergmann, A.; Kühl, S.; García-Muelas, R.; López, N.; Cuenya, B. R. ACS Catal. 2021, 11, 7694. doi: 10.1021/acscatal.1c01478
47. [47]
  Calle-Vallejo, F.; Koper, M. T. M. Angew. Chem. Int. Ed. 2013, 52, 7282. doi: 10.1002/anie.201301470
48. [48]
  Kortlever, R.; Shen, J.; Schouten, K. J. P.; Calle-Vallejo, F.; Koper, M. T. M. J. Phys. Chem. Lett. 2015, 6, 4073. doi: 10.1021/acs.jpclett.5b01559
49. [49]
  Peng, C.; Yang, S.; Luo, G.; Yan, S.; Shakouri, M.; Zhang, J.; Chen, Y.; Wang, Z.; Wei, W.; Sham, T. K.; et al. Small 2023, 19, 2207374. doi: 10.1002/smll.202207374

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

碳修饰的铜催化剂实现安培级电流电化学还原CO₂制C₂₊产物

通讯作者: 孙晓甫, sunxiaofu@iccas.ac.cn; 吴海虹, hhwu@chem.ecnu.edu.cn; 韩布兴, hanbx@iccas.ac.cn

English

Electrochemical CO₂ Reduction to C₂₊ Products with Ampere-Level Current on Carbon-Modified Copper Catalysts

Corresponding author: Email: sunxiaofu@iccas.ac.cn (X.F.)Tel.: +86-10-62562821 (X.F.); Email: hhwu@chem.ecnu.edu.cn (H.H.); Email: hanbx@iccas.ac.cn (B.X.)

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通讯作者: 孙晓甫, sunxiaofu@iccas.ac.cn; 吴海虹, hhwu@chem.ecnu.edu.cn; 韩布兴, hanbx@iccas.ac.cn

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Corresponding author: Email: sunxiaofu@iccas.ac.cn (X.F.)Tel.: +86-10-62562821 (X.F.); Email: hhwu@chem.ecnu.edu.cn (H.H.); Email: hanbx@iccas.ac.cn (B.X.)

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