Promoting dilute CO2 electrolysis with electron-withdrawing ligand modification

doi:10.1016/S1872-2067(26)65151-0

Abstract

Abstract:

The efficient production of valuable multicarbon (C₂₊) chemicals via direct electrolysis of dilute CO₂ derived from industrial flue gases is a promising route to close the carbon cycle, but is not yet practical owing to insufficient electrocatalytic performance limited by sluggish reaction kinetics at low CO₂ concentrations. Herein, we develop BDC-X (where BDC represents 1,4-benzenedicarboxylic acid and X represents H, F, and NH₂) ligand-modified Cu nanoparticle catalysts via in-situ electrochemical reconstruction of metal organic frameworks precursors, for dilute CO₂ electrolysis to C₂₊ products. The -X functional groups anchored on the BDC can be deemed as site-specific regulators for modulating the electronic structure of Cu nanoparticles. The BDC-F ligand with strong electron-withdrawing ability exhibits the most remarkable promoting effect, with an impressive C₂₊ Faradaic efficiency of 67.9% and a maximum C₂₊ partial current density of 130 mA cm⁻² under a 15% CO₂ feed at 0.4 MPa. Combined experimental and theoretical investigations indicate that the reduced electron density of Cu active sites induced by the electron-withdrawing -F group improves *CO adsorption and lowers energy barrier for C−C coupling, thus resulting in improved C₂₊ selectivity.

Key words: Dilute CO₂ electrolysis, Electron-withdrawing, Ligand modification, Selectivity, Multicarbon products

Xiaojuan Wen, Pengfei Wei, Yiyuan Jiang, Yanpeng Song, Hanyu Wang, Jing Xue, Tianfu Liu, Dunfeng Gao, Guoxiong Wang, Xinhe Bao. Promoting dilute CO₂ electrolysis with electron-withdrawing ligand modification[J]. Chinese Journal of Catalysis, 2026, 90: 210-219.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65151-0

https://www.cjcatal.com/EN/Y2026/V90/I11/210

Figures/Tables 4

Fig. 1. (a) Schematic illustration of the preparation of Cu-BDC-X MOFs. (b) SEM image of Cu-BDC. (c) FTIR spectra of Cu-BDC-X. C 1s (d) and Cu 2p (e) XPS spectra of Cu-BDC-X. Cu K-edge (f) XANES and (g) R-space EXAFS spectra for Cu-BDC-X, CuO, and Cu foil.

Fig. 2. FE and cell voltage as a function of applied current density over Cu-BDC (a), Cu-BDC-F (b), and Cu-BDC-NH2 (c) measured under high-purity CO2 feed. (d) Schematic of the production of chemicals and fuels via direct flue gas electrolysis. (e) C2+ FE on Cu-BDC-F at 150 mA cm-2 at different CO2 pressures. (f) FE and cell voltage as a function of applied current density over Cu-BDC-F measured under 0.4 MPa dilute CO2 (15%) feed. (g) C2+ FE as a function of applied current density over Cu-BDC, Cu-BDC-F, and Cu-BDC-NH2 measured under 0.4 MPa dilute CO2 (15%) feed. (h) Stability of Cu-BDC-F at 150 mA cm-2 under 0.4 MPa dilute CO2 (15%) feed.

Fig. 3. (a) FTIR spectra of Cu-BDC-X after CO2 electrolysis. (b) HRTEM image of the Cu-BDC-F electrode after CO2 electrolysis. (c) Quasi in-situ XPS spectra of Cu LMM of Cu-BDC-X after CO2 electrolysis at 250 mA cm-2. Operando Cu K-edge XANES (d) and EXAFS (e) spectra of Cu-BDC-F measured in a MEA cell. (f) Cu K-edge XANES spectra of Cu-BDC-X during CO2 electrolysis at 200 mA cm-2.

Fig. 4. Operando Raman spectra of Cu-BDC-F (a) and Cu-BDC (b) in a MEA cell at different applied current densities. (c) CO stripping experiments on Cu-BDC-X after CO2 electrolysis, with a scan rate of 50 mV s-1. (d) Gibbs free energy barriers for the formation of C2H4 on Cu-BDC-X during CO2 electrolysis, including the optimized structures of 2*CO, *COCOH, *COH-COH, *CCOH, *CHCOH, *CHCHOH, *CH2CHOH and *CH2CH on the Cu-BDC and Cu-BDC-F during CO2 electrolysis. Projected COHP (pCOHP) curves for the Cu-C1 (C1 originates from the carbon of the -CO fragment in *COCOH) and Cu-C2 (C2 originates from the carbon of the -COH fragment in *COCOH) interactions for the adsorbate carbon atoms in *COCOH and their coordinating Cu sites in Cu-BDC (e) and Cu-BDC-F (f).

References

[1]	D.-H. Nam, P. De Luna, A. Rosas-Hernández, A. Thevenon, F. Li, T. Agapie, J. C. Peters, O. Shekhah, M. Eddaoudi, E. H. Sargent, Nat. Mater., 2020, 19, 266-276.
[2]	S. Overa, B. H. Ko, Y. Zhao, F. Jiao, Acc. Chem. Res., 2022, 55, 638-648.
[3]	W. Gao, Y. Xu, L. Fu, X. Chang, B. Xu, Nat. Catal., 2023, 6, 885-894.
[4]	M. Wang, W. Fang, D. Zhu, C. Xia, W. Guo, B.-Y. Xia, Chin. J. Catal., 2025, 69, 1-16.
[5]	Y. Xie, Z. Xu, Q. Lu, Y. Wang, Chin. J. Catal., 2024, 59, 82-96.
[6]	Y.-B. Hua, B.-X. Ni, K. Jiang, J. Electrochem., 2025, 31, 2504082.
[7]	X. Dong, X. Sun, S. Jia, S. Han, D. Zhou, T. Yao, M. Wang, M. Fang, H. Wu, B. Han, Acta Phys.-Chim. Sin., 2025, 41, 100024.
[8]	X. Wang, S. Zhao, T. Guo, L. Yang, Q. Zhao, Y. Wu, Y. Chen, Trans. Tianjin Univ., 2024, 30, 117-129.
[9]	X. Wen, D. Gao, G. Wang, ChemSusChem, 2025, 18, e202402438.
[10]	D. Tian, Q. Wang, Z. Qu, H. Zhang, Nano Energy, 2025, 134, 110563.
[11]	M. Wang, A. Ozden, W. Tian, J. Chen, W. Chen, L. Wang, A. B. Wong, Y. Lum, Adv. Mater., 2025, 37, e09581.
[12]	Q. Xia, K. Zhang, T. Zheng, L. An, C. Xia, X. Zhang, ACS Energy Lett., 2023, 8, 2840-2857.
[13]	A. M. Appel, J. Y. Yang, ACS Energy Lett., 2024, 9, 768-770.
[14]	Y. Rong, C. Yan, X. Li, J. Liu, X. Su, G. Zhang, D. Gao, G. Wang, X. Bao, Angew. Chem. Int. Ed., 2026, 65, e23118.
[15]	J.-J. Li, X.-R. Qin, X.-R. Wang, L.-L. Wang, Z.-Y. Yu, T.-B. Lu, ACS Nano, 2025, 19, 10620-10629.
[16]	X.-R. Qin, J.-J. Li, L.-L. Wang, H. Liu, Z.-T. Yang, G.-J. Feng, X.-R. Wang, X.-X. Cheng, C. Zhang, Z.-Y. Yu, T.-B. Lu, Nat. Commun., 2025, 16, 4447.
[17]	J. Zhang, Y. Cao, P. Ou, G. Lee, Y. Zhao, S. Liu, E. Shirzadi, R. Dorakhan, K. Xie, C. Tian, Y. Chen, X. Li, Y. C. Xiao, A. Shayesteh Zeraati, R.-K. Miao, S. Park, C. P. O’Brien, J. Ge, X. Zhou, D. Sinton, E. H. Sargent, Nat. Commun., 2025, 16, 3553.
[18]	M. Sun, J. Cheng, M. Yamauchi, Nat. Commun., 2024, 15, 491.
[19]	W. Yang, Y. Zhao, Y. Chen, H. Ren, J. Sun, Z. Shi, X. Jin, Z. Zhang, X. Wang, Angew. Chem. Int. Ed., 2025, 64, e202422082.
[20]	Y.-Y. Liu, J.-R. Huang, H.-L. Zhu, P.-Q. Liao, X.-M. Chen, Angew. Chem. Int. Ed., 2023, 62, e202311265.
[21]	T. Yan, S. Liu, Z. Liu, J. Sun, P. Kang, Adv. Funct. Mater., 2024, 34, 2311733.
[22]	J.-W. Sun, T. Yu, H. Wu, M. Zhu, A. Chen, C. Lian, H.-G. Yang, P.-F. Liu, Chem Catal., 2024, 4, 100923.
[23]	X.-H. Li, B.-W. Zhang, W.-F. Xiong, Z. Li, X.-Y. Xiang, S.-Y. Zhang, D.-H. Si, H.-F. Li, R. Cao, Chin. J. Catal., 2025, 73, 196-204.
[24]	Y. Rong, T. Liu, J. Sang, R. Li, P. Wei, H. Li, A. Dong, L. Che, Q. Fu, D. Gao, G. Wang, Angew. Chem. Int. Ed., 2023, 62, e202309893.
[25]	W. Li, Z. Yin, Z. Gao, G. Wang, Z. Li, F. Wei, X. Wei, H. Peng, X. Hu, L. Xiao, J. Lu, L. Zhuang, Nat. Energy, 2022, 7, 835-843.
[26]	B. Chen, Y. Rong, X. Li, J. Sang, P. Wei, Q. An, D. Gao, G. Wang, ACS Energy Lett., 2024, 9, 911-918.
[27]	W. Liu, Z. Lv, X. Li, C. Wang, C. Tian, X. Feng, B. Wang, W. Yang, J. Am. Chem. Soc., 2025, 147, 24023-24031.
[28]	B. Wang, X. Wang, B. Wu, P. Li, S. Chen, R. Lu, W. Lai, Y. Shen, Z. Zhuang, J. Zhu, Z. Wang, D. Wang, Y. Lum, Angew. Chem. Int. Ed., 2025, 64, e202417196.
[29]	W. Zhang, M. Dai, Z. Zeng, Y. Wang, Y. Zhang, W. Ni, S. Wang, S. Zhang, Angew. Chem. Int. Ed., 2025, 64, e202424104.
[30]	G. Li, C. Zhang, Y. Liu, Y. Song, W. Guo, L. Huang, J. Su, Q. Zhang, Y. Xin, T. Feng, X. Cao, M. He, T. K. Kwok, J. W. Y. Lam, Z. Jin, B.-Z. Tang, Z. Wang, R. Ye, Adv. Mater., 2024, 36, 2409390.
[31]	J. Chen, T. Lu, X. Liao, S. Chen, Y. Li, Y. Wang, R. Lv, W. Cui, W. Lan, W. Wang, L. Cao, Z. Chen, Z. Zhao, J. Li, W. Shi, S. Zhang, H. Wang, Nat. Commun., 2025, 16, 7598.
[32]	Y. Zhang, Q. Yu, Z. Wang, W. Zhang, X. She, Q. Zhang, Y. Liu, H. Li, H. Xu, ACS Catal., 2025, 15, 7352-7360.
[33]	J. Wang, X. Jing, Y. Yang, B. Xu, R. Jia, C. Duan, J. Am. Chem. Soc., 2024, 146, 19951-19961.
[34]	P. Huang, Z. Yang, K. Zhai, B. Huang, J. Zhou, X. Sun, Y. Lin, J. Xu, C. Pan, Y. Dong, Y. Wang, Y. Zhang, Y. Lou, H. Huang, Y. Zhu, J. Zhang, J. Am. Chem. Soc., 2025, 147, 22062-22071.
[35]	J. S. Stanley, H. N. Pauker, E. Kuker, V. Dong, R. J. Nielsen, J. Y. Yang, J. Am. Chem. Soc., 2025, 147, 16099-16106.
[36]	L. Xie, Y. Cai, Y. Jiang, M. Shen, J. C. Lam, J.-J. Zhu, W. Zhu, Nat. Commun., 2024, 15, 10386.
[37]	M. Wang, B. Wang, J. Zhang, S. Xi, N. Ling, Z. Mi, Q. Yang, M. Zhang, W. R. Leow, J. Zhang, Y. Lum, Nat. Commun., 2024, 15, 1218.
[38]	A. Torrisi, C. Mellot-Draznieks, R. G. Bell, J. Chem. Phys., 2010, 132, 044705.
[39]	T. Di, Y. Yoshida, K.-I. Otake, S. Kitagawa, H. Kitagawa, Chem. Sci., 2024, 15, 9641-9648.
[40]	G. Lee, D. Choi, M. Oh, J. Am. Chem. Soc., 2025, 147, 12811-12820.
[41]	S. Sadjadi, F. Koohestani, J. Solid State Chem., 2022, 308, 122888.
[42]	M. Muttaqin, F. I. Hidayat, J. Nat., 2021, 21, 128-134.
[43]	R. Chen, L. Cheng, J. Liu, Y. Wang, W. Ge, C. Xiao, H. Jiang, Y. Li, C. Li, Small, 2022, 18, 2200720.
[44]	Q. Zhang, M. Chen, L. Zhong, Q. Ye, S. Jiang, Z. Huang, Molecules, 2018, 23, 2086.
[45]	B. C. E. Silva, K. Irikura, R. C. G. Frem, M. V. B. Zanoni, J. Electroanal. Chem., 2021, 880, 114856.
[46]	G. Zhan, L. Fan, F. Zhao, Z. Huang, B. Chen, X. Yang, S.-F. Zhou, Adv. Funct. Mater., 2019, 29, 1806720.
[47]	Y. Wang, W. C. Lee, K. K. Manga, P. K. Ang, J. Lu, Y.-P. Liu, C. T. Lim, K. P. Loh, Adv. Mater., 2012, 24, 4285-4290.
[48]	Q. Chen, D. H. Si, Q. J. Wu, R. Cao, Y. B. Huang, Adv. Funct. Mater., 2024, 34, 2315368.
[49]	N.-Y. Huang, H. He, S. Liu, H.-L. Zhu, Y.-J. Li, J. Xu, J.-R. Huang, X. Wang, P.-Q. Liao, X.-M. Chen, J. Am. Chem. Soc., 2021, 143, 17424-17430.
[50]	L. Majidi, A. Ahmadiparidari, N. Shan, S. N. Misal, K. Kumar, Z. Huang, S. Rastegar, Z. Hemmat, X. Zou, P. Zapol, J. Cabana, L. A. Curtiss, A. Salehi-Khojin, Adv. Mater., 2021, 33, 2004393.
[51]	Y. Zhang, W. Hu, D. Wang, B. J. Reinhart, J. Huang, J. Mater. Chem. A, 2021, 9, 6180-6187.
[52]	J. Zheng, J. Ye, M. A. Ortuño, J. L. Fulton, O. Y. Gutiérrez, D. M. Camaioni, R. K. Motkuri, Z. Li, T. E. Webber, B. L. Mehdi, N. D. Browning, R. L. Penn, O. K. Farha, J. T. Hupp, D. G. Truhlar, C. J. Cramer, J. A. Lercher, J. Am. Chem. Soc., 2019, 141, 9292-9304.
[53]	A. V. Rudnev, Y.-C. Fu, I. Gjuroski, F. Stricker, J. Furrer, N. Kovács, S. Vesztergom, P. Broekmann, ChemPhysChem, 2017, 18, 3153-3162.
[54]	M. A. Adnan, S. K. Nabil, K. Kannimuthu, M. G. Kibria, ChemSusChem, 2024, 17, e202301425.
[55]	H. Song, J. T. Song, B. Kim, Y.-C. Tan, J. Oh, Appl. Catal. B, 2020, 272, 119049.
[56]	D. Tian, Z. Qu, J. Zhang, Appl. Energy, 2023, 351, 121787.
[57]	H.-J. Zhu, D.-H. Si, H. Guo, Z. Chen, R. Cao, Y.-B. Huang, Nat. Commun., 2024, 15, 1479.
[58]	Y. Cheng, J. Hou, P. Kang, ACS Energy Lett., 2021, 6, 3352-3358.
[59]	H. Guo, D.-H. Si, H.-J. Zhu, Z.-A. Chen, R. Cao, Y.-B. Huang, Angew. Chem. Int. Ed., 2024, 63, e202319472.
[60]	M. Sassenburg, M. Kelly, S. Subramanian, W. A. Smith, T. Burdyny, ACS Energy Lett., 2023, 8, 321-331.
[61]	K. Yue, Y. Qin, H. Huang, Z. Lv, M. Cai, Y. Su, F. Huang, Y. Yan, Nat. Commun., 2024, 15, 7820.
[62]	Q. Li, M. Hu, C. Ge, Y. Yang, L. Xiao, L. Zhuang, H. D. Abruña, Chem. Sci., 2023, 14, 10429-10434.
[63]	S. Hu, J. Huang, M.-L. Gao, Z. Lin, Y. Qian, W. Yang, L. Jiao, H.-L. Jiang, Angew. Chem. Int. Ed., 2025, 64, e202415155.
[64]	Y. Shi, K. Zhang, C.-L. Dong, T. T. T. Nga, M. Wang, D. Wei, J. Wang, Y. Wang, S. Shen, Sci. Bull., 2024, 69, 2395-2404.
[65]	J. Sang, T. Liu, P. Wei, H. Li, C. Liu, Y. Wang, Y. Rong, Q. Wang, G. Wang, X. Bao, Energy Environ. Sci., 2024, 17, 3594-3603.
[66]	X. Zhi, Y. Jiao, Y. Zheng, S.-Z. Qiao, Chem. Commun., 2021, 57, 9526-9529.

Promoting dilute CO₂ electrolysis with electron-withdrawing ligand modification

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