Accelerating C-C coupling in alkaline electrochemical CO2 reduction by optimized local water dissociation kinetics

doi:10.1016/S1872-2067(24)60243-3

Abstract

Abstract:

Electrochemical carbon dioxide reduction reaction (CO₂RR) produces valuable chemicals by consuming gaseous CO₂ as well as protons from the electrolyte. Protons, produced by water dissociation in alkaline electrolyte, are critical for the reaction kinetics which involves multiple proton coupled electron transfer steps. Herein, we demonstrate that the two key steps (CO₂-*COOH and *CO-*COH) efficiency can be precisely tuned by introducing proper amount of water dissociation center, i.e., Fe single atoms, locally surrounding the Cu catalysts. In alkaline electrolyte, the Faradaic efficiency (FE) of multi-carbon (C₂₊) products exhibited a volcano type plot depending on the density of water dissociation center. A maximum FE for C₂₊ products of 73.2% could be reached on Cu nanoparticles supported on N-doped Carbon nanofibers with moderate Fe single atom sites, at a current density of 300 mA cm^-2. Experimental and theoretical calculation results reveal that the Fe sites facilitate water dissociation kinetics, and the locally generated protons contribute significantly to the CO₂ activation and *CO protonation process. On the one hand, in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (in-situ ATR-SEIRAS) clearly shows that the *COOH intermediate can be observed at a lower potential. This phenomenon fully demonstrates that the optimized local water dissociation kinetics has a unique advantage in guiding the hydrogenation reaction pathway of CO₂ molecules and can effectively reduce the reaction energy barrier. On the other hand, abundant *CO and *COH intermediates create favorable conditions for the asymmetric *CO-*COH coupling, significantly increasing the selectivity of the reaction for C₂₊ products and providing strong support for the efficient conversion of related reactions to the target products. This work provides a promising strategy for the design of a dual sites catalyst to achieve high FE of C₂₊ products through the optimized local water dissociation kinetics.

Key words: CO₂ reduction, Proton, Microenvironment, Optimized local water dissociation kinetics, CO₂ activation, Asymmetric coupling

Qingfeng Hua, Hao Mei, Guang Feng, Lina Su, Yanan Yang, Qichang Li, Shaobo Li, Xiaoxia Chang, Zhiqi Huang. Accelerating C-C coupling in alkaline electrochemical CO₂ reduction by optimized local water dissociation kinetics[J]. Chinese Journal of Catalysis, 2025, 71: 128-137.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60243-3

https://www.cjcatal.com/EN/Y2025/V71/I4/128

Figures/Tables 4

Fig. 1. Characterizations of the Fe1/CuNP-NC catalyst. HRTEM image (a), STEM and EDS mapping (b) of Fe1/CuNP-NC-2, cyan, Cu; yellow, Fe; blue, N. (c) XRD patterns of Fe1/CuNP-NC-1, Fe1/CuNP-NC-2, Fe1/CuNP-NC-3 and CuNP-NC samples. (d) Normalized intensity of Fe K-edge XANES spectra for Fe foil, M-Fe1/CuNP-NC-2, FeO, Fe2O3 and Fe3O4 samples. (e) Fourier-transform k3-weighted EXAFS spectra in R space for Fe foil, Fe1/CuNP-NC-2 and FePc samples. (f) Wavelet transforms of Fe1/CuNP-NC-2.

Fig. 2. CO2RR performance of the Fe1/CuNP-NC catalyst. (a) The FE of C2+ and H2 products on the catalysts with different Fe mass loading at the current density of 300 mA cm-1 (0: CuNP-NC, 0.23: Fe1/CuNP-NC-1, 0.35: Fe1/CuNP-NC-2 and 0.68: Fe1/CuNP-NC-3). (b) FE values of various products on the Fe1/CuNP-NC-2 at different current densities in a flow cell. (c) The C2+: C1 FE ratio of different catalysts. (d) The FEC2+ change of the Fe1/CuNP-NC-2 catalyst at a current density of 300 mA cm-2 in a flow cell.

Fig. 3. KIE(a) and C2+ product selectivity (b) of different catalysts with or without t-BuOH addition at the potential of -1.2 V vs. RHE. In-situ ATR-FTIRS spectra recorded at different potentials for CuNP-NC (c) and Fe1/CuNP-NC-2 (d) catalyst.

Fig. 4. Model structures of CuNP-NC (a) and Fe1/CuNP-NC-2 (b) catalysts. (c) Calculated reaction energy for the H2O dissociation process of Cu sites and Fe sites. (d) Free energy diagram for the CO2RR to *OCCOH intermediates on CuNP-NC surface and Fe1/CuNP-NC-2 surface.

References

[1]	M. Jiang, H. Wang, M. Zhu, X. Luo, Y. He, M. Wang, C. Wu, L. Zhang, X. Li, X. Liao, Z. Jiang, Z. Jin, Chem. Soc. Rev., 2024, 53, 5149-5189.
[2]	D. Gao, R. M. Arán-Ais, H. S. Jeon, B. R. Cuenya, Nat. Catal., 2019, 2, 198-210.
[3]	X. Zeng, J. Shui, X. Liu, Q. Liu, Y. Li, J. Shang, L. Zheng, R. Yu, Adv. Energy Mater., 2018, 8, 1701345.
[4]	W. Zhu, S. Kattel, F. Jiao, J. G. Chen, Adv. Energy Mater., 2019, 9, 1802840.
[5]	T. Yan, X. Chen, L. Kumari, J. Lin, M. Li, Q. Fan, H. Chi, T. J. Meyer, S. Zhang, X. Ma, Chem. Rev., 2023, 123, 10530-10583.
[6]	L. Xie, Y. Jiang, W. Zhu, S. Ding, Y. Zhou, J.-J. Zhu, Chem. Sci., 2023, 14, 13629-13660.
[7]	J. Zhao, P. Zhang, T. Yuan, D. Cheng, S. Zhen, H. Gao, T. Wang, Z.-J. Zhao, J. Gong, J. Am. Chem. Soc., 2023, 145, 6622-6627.
[8]	C.-T. Dinh, T. Burdyny, M.G. Kibria, A. Seifitokaldani, C.M. Gabardo, F.P. García De Arquer, A. Kiani, J.P. Edwards, P. De Luna, O.S. Bushuyev, C. Zou, R. Quintero-Bermudez, Y. Pang, D. Sinton, E.H. Sargent, Science, 2018, 360, 783-787.
[9]	M. B. Ross, P. De Luna, Y. Li, C.-T. Dinh, D. Kim, P. Yang, E. H. Sargent, Nat. Catal., 2019, 2, 648-658.
[10]	L. Fan, C. Xia, F. Yang, J. Wang, H. Wang, Y. Lu, Sci. Adv., 2020, 6, eaay3111.
[11]	Z. Xing, L. Hu, D. S. Ripatti, X. Hu, X. Feng, Nat. Commun., 2021, 12, 136.
[12]	S. E. Weitzner, S. A. Akhade, J. B. Varley, B. C. Wood, M. Otani, S. E. Baker, E. B. Duoss, J. Phys. Chem. Lett., 2020, 11, 4113-4118.
[13]	P.-P. Yang, X.-L. Zhang, F.-Y. Gao, Y.-R. Zheng, Z.-Z. Niu, X. Yu, R. Liu, Z.-Z. Wu, S. Qin, L.-P. Chi, Y. Duan, T. Ma, X.-S. Zheng, J.-F. Zhu, H.-J. Wang, M.-R. Gao, S.-H. Yu, J. Am. Chem. Soc., 2020, 142, 6400-6408.
[14]	T.-T. Zhuang, Y. Pang, Z.-Q. Liang, Z. Wang, Y. Li, C.-S. Tan, J. Li, C.T. Dinh, P. De Luna, P.-L. Hsieh, T. Burdyny, H.-H. Li, M. Liu, Y. Wang, F. Li, A. Proppe, A. Johnston, D.-H. Nam, Z.-Y. Wu, Y.-R. Zheng, A.H. Ip, H. Tan, L.-J. Chen, S.-H. Yu, S.O. Kelley, D. Sinton, E. H. Sargent, Nat. Catal., 2018, 1, 946-951.
[15]	Y. Zhou, F. Che, M. Liu, C. Zou, Z. Liang, P. De Luna, H. Yuan, J. Li, Z. Wang, H. Xie, H. Li, P. Chen, E. Bladt, R. Quintero-Bermudez, T.-K. Sham, S. Bals, J. Hofkens, D. Sinton, G. Chen, E. H. Sargent, Nat. Chem., 2018, 10, 974-980.
[16]	Q. Chang, J. H. Lee, Y. Liu, Z. Xie, S. Hwang, N. S. Marinkovic, A.-H. A. Park, S. Kattel, J. G. Chen, JACS Au, 2022, 2, 214-222.
[17]	X. Zhou, H. Liu, B. Y. Xia, K. Ostrikov, Y. Zheng, S.-Z. Qiao, SmartMat., 2022, 3, 111-129.
[18]	C. Peng, G. Luo, J. Zhang, M. Chen, Z. Wang, T.-K. Sham, L. Zhang, Y. Li, G. Zheng, Nat. Commun., 2021, 12, 1580.
[19]	Q. Lei, H. Zhu, K. Song, N. Wei, L. Liu, D. Zhang, J. Yin, X. Dong, K. Yao, N. Wang, X. Li, B. Davaasuren, J. Wang, Y. Han, J. Am. Chem. Soc., 2020, 142, 4213-4222.
[20]	F. Li, A. Thevenon, A. Rosas-Hernández, Z. Wang, Y. Li, C.M. Gabardo, A. Ozden, C.T. Dinh, J. Li, Y. Wang, J.P. Edwards, Y. Xu, C. McCallum, L. Tao, Z.-Q. Liang, M. Luo, X. Wang, H. Li, C. P. O’Brien, C.-S. Tan, D.-H. Nam, R. Quintero-Bermudez, T.-T. Zhuang, Y. C. Li, Z. Han, R. D. Britt, D. Sinton, T. Agapie, J. C. Peters, E. H. Sargent, Nature, 2020, 577, 509-513.
[21]	Z. Xie, S. Hwang, J. G. Chen, SmartMat, 2023, 4, e1201.
[22]	Y. Y. Birdja, E. Pérez-Gallent, M. C. Figueiredo, A. J. Göttle, F. Calle-Vallejo, M. T. M. Koper, Nat. Energy, 2019, 4, 732-745.
[23]	A. J. Garza, A. T. Bell, M. Head-Gordon, ACS Catal., 2018, 8, 1490-1499.
[24]	D. Zhang, P. Ren, W. Liu, Y. Li, S. Salli, F. Han, W. Qiao, Y. Liu, Y. Fan, Y. Cui, Y. Shen, E. Richards, X. Wen, M. H. Rummeli, Y. Li, F. Besenbacher, H. Niemantsverdriet, T. Lim, R. Su, Angew. Chem., Int. Ed., 2022, 61, e202204256.
[25]	Z. Wang, L. Xu, Y. Zhou, Y. Liang, J. Yang, D. Wu, S. Zhang, X. Han, X. Shi, J. Li, Y. Yuan, P. Deng, X. Tian, Chem. Soc. Rev., 2024, 53, 6295-6321.
[26]	S. You, J. Xiao, S. Liang, W. Xie, T. Zhang, M. Li, Z. Zhong, Q. Wang, H. He, Energy Environ. Sci., 2024, 17, 5795-5818.
[27]	Y. Li, A. Xu, Y. Lum, X. Wang, S.-F. Hung, B. Chen, Z. Wang, Y. Xu, F. Li, J. Abed, J. E. Huang, A.S. Rasouli, J. Wicks, L. K. Sagar, T. Peng, A. H. Ip, D. Sinton, H. Jiang, C. Li, E. H. Sargent, Nat. Commun., 2020, 11, 6190.
[28]	L. Zhang, X.-X. Li, Z.-L. Lang, Y. Liu, J. Liu, L. Yuan, W.-Y. Lu, Y.-S. Xia, L.-Z. Dong, D.-Q. Yuan, Y.-Q. Lan, J. Am. Chem. Soc., 2021, 143, 3808-3816.
[29]	W. Ma, S. Xie, T. liu, Q. Fan, J. Ye, F. Sun, Z. Jiang, Q. Zhang, J. Cheng, Y. Wang, Nat. Catal., 2020, 3, 478-487.
[30]	Z.-Y. Du, S.-B. Li, G.-H. Liang, Y.-M. Xie, Y.-L. Zhang, H. Zhang, J.-H. Tian, S. Zheng, Q.-N. Zheng, Z. Chen, W. F. Ip, J. Liu, J.-F. Li, J. Am. Chem. Soc., 2024, 146, 32870-32879.
[31]	J. Feng, L. Zhang, S. Liu, L. Xu, X. Ma, X. Tan, L. Wu, Q. Qian, T. Wu, J. Zhang, X. Sun, B. Han, Nat. Commun., 2023, 14, 4615.
[32]	X. Chen, J. Chen, H. Chen, Q. Zhang, J. Li, J. Cui, Y. Sun, D. Wang, J. Ye, L. Liu, Nat. Commun., 2023, 14, 751.
[33]	X. He, L. Lin, X. Li, M. Zhu, Q. Zhang, S. Xie, B. Mei, F. Sun, Z. Jiang, J. Cheng, Y. Wang, Nat. Commun., 2024, 15, 9923.
[34]	J. Li, J. Dong, S. Liu, Y. Hua, X. Zhao, Z. Li, S. Zhao, S. Zang, R. Wang, Angew. Chem. Int. Ed., 2024, 63, e202412144.
[35]	F. Ma, P. Zhang, X. Zheng, L. Chen, Y. Li, Z. Zhuang, Y. Fan, P. Jiang, H. Zhao, J. Zhang, Y. Dong, Y. Zhu, D. Wang, Y. Wang, Angew. Chem. Int. Ed., 2024, 63, e202412785.
[36]	L. Liu, A. Corma, Chem. Rev., 2018, 118, 4981-5079.
[37]	Z. Li, S. Ji, Y. Liu, X. Cao, S. Tian, Y. Chen, Z. Niu, Y. Li, Chem. Rev., 2020, 120, 623-682.
[38]	A. Wang, J. Li, T. Zhang, Nat. Rev. Chem., 2018, 2, 65-81.
[39]	B. Wang, S. Chen, Z. Zhang, D. Wang, SmartMat, 2022, 3, 84-110.
[40]	G. Wang, J. Chen, Y. Ding, P. Cai, L. Yi, Y. Li, C. Tu, Y. Hou, Z. Wen, L. Dai, Chem. Soc. Rev., 2021, 50, 4993-5061.
[41]	B. Sun, H. Lv, Q. Xu, P. Tong, P. Qiao, H. Tian, H. Xia, Small, 2024, 20, 2400240.
[42]	Q. Chang, Y. Liu, J.-H. Lee, D. Ologunagba, S. Hwang, Z. Xie, S. Kattel, J. H. Lee, J. G. Chen, J. Am. Chem. Soc., 2022, 144, 16131-16138.
[43]	T. Zhang, B. Yuan, W. Wang, J. He, X. Xiang, Angew. Chem. Int. Ed., 2023, 62, e202302096.
[44]	Y.-J. Zhang, V. Sethuraman, R. Michalsky, A. A. Peterson, ACS Catal., 2014, 4, 3742-3748.
[45]	P. Wang, H. Yang, C. Tang, Y. Wu, Y. Zheng, T. Cheng, K. Davey, X. Huang, S.-Z. Qiao, Nat. Commun., 2022, 13, 3754.
[46]	R. Chen, J. Zhao, X. Zhang, Q. Zhao, Y. Li, Y. Cui, M. Zhong, J. Wang, X. Li, Y. Huang, B. Liu, J. Am. Chem. Soc., 2024, 146, 24368-24376.
[47]	M. Fan, G. F. S. Andrade, A. G. Brolo, Anal. Chim. Acta, 2011, 693, 7-25
[48]	E. L. Smith, M. D. Porter, J. Phys. Chem., 1993, 97, 8032-8038.

Accelerating C-C coupling in alkaline electrochemical CO₂ reduction by optimized local water dissociation kinetics

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