Asymmetric N-Ru-S dipole within covalent organic framework enhances internal electric field for efficient CO2 photoreduction

doi:10.1016/S1872-2067(26)65082-6

Abstract

Abstract:

Asymmetric electron distribution at single-atom centers offers a promising pathway to enhance photocatalytic CO₂-to-CO conversion; however, direct visualization of how such symmetry-breaking influences local electric fields and reaction coordinates remains elusive. Herein, an asymmetric N-Ru-S motif was constructed in a thiophene-based covalent organic framework (Ru/Py-bTDC) via post-synthetic metalation. Under visible light in a gas-solid system without sacrificial agents, Ru₁₀/Py-bTDC exhibited a CO production of 226.88 μmol·L^-1, representing a 13-fold increase over pristine Py-bTDC. In-situ Kelvin probe force microscopy revealed that the N-Ru-S unit acts as a directional nanoscale dipole, intensifying the internal electric field (IEF) by 6.15-fold and steering photogenerated electrons toward Ru sites to facilitate charge separation. In-situ Fourier transform infrared spectroscopy and theoretical calculations demonstrated that the enhanced IEF promotes CO₂ activation, lowering the energy barrier for *COOH formation from 2.63 to 0.40 eV and shifting the rate-determining step to *CO desorption. This work establishes a direct spatial correlation between atomic-scale asymmetry, IEF enhancement, and optimized reaction kinetics, offering a design strategy to overcome both charge separation and activation barriers in CO₂ photoreduction through symmetry-breaking coordination.

Key words: Asymmetric electron distribution, Covalent organic framework, Single-atom catalysts, Internal electric field, CO₂ photoreduction

Yueling Chen, Yuling Lin, Ziyan Chen, Xiangyu Kong, Jinhong Bi, Guocheng Huang, Ling Wu. Asymmetric N-Ru-S dipole within covalent organic framework enhances internal electric field for efficient CO₂ photoreduction[J]. Chinese Journal of Catalysis, 2026, 87: 59-69.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65082-6

https://www.cjcatal.com/EN/Y2026/V87/I8/59

Figures/Tables 5

Fig. 1. XRD patterns (a) and FTIR spectra (b) of Py-bTDC and Rux/Py-bTDC samples. SEM (c), TEM (d), HAADF-STEM (e) images and elemental distribution (f) of Ru10/Py-bTDC.

Fig. 2. High resolution N 1s (a) and S 2p (b) XPS spectrum of Py-bTDC and Ru10/Py-bTDC. The XANES spectra (c) and the Fourier transform of the corresponding EXAFS spectra (d) of Ru10/Py-bTDC, Ru-Foil, RuO2, and Ru2O3 on the K-edge of Ru. (e) The EXAFS fitting curve of Ru10/Py-bTDC. Wavelet transform diagrams of Ru-foil (f), Ru2O3 (g) and Ru10/Py-bTDC (h). (i) Schematic model of Ru10/Py-bTDC.

Fig. 3. (a) UV-vis DRS spectra of Py-bTDC and Ru10/Py-bTDC. Transient photocurrent curves (b) and EIS plots (c) of Py-bTDC and Rux/Py-bTDC. TRPL spectra (d) and KPFM images of Ru10/Py-bTDC under dark (e) and light (f). Surface potentials under dark conditions (g), surface charge densities (h), and the intensity of the IEF (i) of Py-bTDC and Ru10/Py-bTDC.

Fig. 4. (a) CO2 adsorption profiles of Ru10/Py-bTDC at 273 and 298 K. (b) CO2-TPD spectra of Ru10/Py-bTDC. (c) LSV curves of Py-bTDC and Ru10/Py-bTDC. (d) CO2 photoreduction performance of Py-bTDC and Rux/Py-bTDC (All experiments were conducted in triplicate). Control experiments (e) and isotope experiment (f) for photocatalytic CO2 reduction over Ru10/Py-bTDC.

Fig. 5. (a) In-situ FTIR spectra of photocatalytic reduction of CO2 on Ru10/Py-bTDC. Adsorption energies (b), charge density difference and bader charge change results (c) for CO2 adsorption on Py-bTDC and Ru10/Py-bTDC. (d) Gibbs free energy changes during CO2 reduction to CO on Py-bTDC and Ru10/Py-bTDC.

References

[1]	A. M. Sadanandan, J. H. Yang, V. Devtade, G. Singh, N. Panangattu Dharmarajan, M. Fawaz, J. Mee Lee, E. Tavakkoli, C. H. Jeon, P. Kumar, A. Vinu, Prog. Mater. Sci., 2024, 142, 101242.
[2]	M. Bonchio, J. Bonin, O. Ishitani, T. B. Lu, T. Morikawa, A. J. Morris, E. Reisner, D. Sarkar, F. M. Toma, M. Robert, Nat. Catal., 2023, 6, 657-665.
[3]	J. Lv, H. Chu, C. Shao, L. Sun, G. Dawson, K. Dai, Chin. J. Catal., 2025, 78, 75-99.
[4]	Y. Liu, C. Chen, G. Dawson, J. Zhang, C. Shao, K. Dai, J. Mater. Sci. Technol., 2025, 233, 10-37.
[5]	R. Bhimpuria, M. Tomar, A. Thapper, M. Ahlquist, K. E. Borbas, Chem, 2025, 11, 102450.
[6]	Z. Zhang, Y. Xia, C. Shao, L. Sun, G. Dawson, K. Dai, J. Mater. Sci. Technol., 2026, 252, 1-33.
[7]	C. Li, J. He, T. Cai, X. Chen, H. Tao, Y. Zhou, M. Zhu, Chin. J. Catal., 2025, 74, 130-143.
[8]	E. Nikoloudakis, I. López-Duarte, G. Charalambidis, K. Ladomenou, M. Ince, A. G. Coutsolelos, Chem. Soc. Rev., 2022, 51, 6965-7045.
[9]	T. Kong, Y. Jiang, Y. Xiong, Chem. Soc. Rev., 2020, 49, 6579-6591.
[10]	X. Wu, M. Sayed, G. Wang, W. Yu, B. Zhu, Adv. Mater., 2026, 38, e11322.
[11]	F. Cao, G. Liu, X. Wang, L. Tan, N. Tsubaki, EnergyChem, 2024, 6, 100141.
[12]	Y. H. Li, Y. Chen, J. Y. Guo, R. Wang, S. N. Zhao, G. Li, S. Q. Zang, Chin. J. Catal., 2025, 74, 155-166.
[13]	S. Wang, X. T. Min, B. Qiao, N. Yan, T. Zhang, Chin. J. Catal., 2023, 52, 1-13.
[14]	Z. Liu, J. Ma, Y. Guo, M. Hong, R. Sun, Appl. Catal. B, 2024, 342, 123429.
[15]	X. Li, M. Wang, R. Wang, Y. Wang, M. Zhu, L. Zhang, J. Shi, ACS Nano, 2024, 18, 5741-5751.
[16]	H. Ma, X. Zheng, H. Zhang, G. Ma, W. Zhang, Z. Jiang, D. Chen, Adv. Sci., 2023, 10, 2205635.
[17]	G. Jia, Y. Zhang, J. C. Yu, Z. Guo, Adv. Mater., 2024, 36, 2403153.
[18]	M. Ahmed, M. Tabish, M. Mubeen, A. Kumar, S. Ajmal, A. Abbas, M. M. Alam, M. Arif, A. G. Al-Sehemi, G. Yasin, Coord. Chem. Rev., 2026, 547, 217105.
[19]	Y. Q. Su, Y. Wang, J. X. Liu, I. A. W. Filot, K. Alexopoulos, L. Zhang, V. Muravev, B. Zijlstra, D. G. Vlachos, E. J. M. Hensen, ACS Catal., 2019, 9, 3289-3297.
[20]	S. Mohata, P. Majumder, R. Banerjee, Chem. Soc. Rev., 2025, 54, 6062-6087.
[21]	Z. Xue, B. Zhang, Q. Guo, Y. Wang, Q. Li, K. Yang, S. Qiao, Adv. Mater., 2025, 37, e10201.
[22]	L. Zhang, H. Zhang, J. Fang, J. Cui, J. Liu, H. Liu, L. Sun, Q. Sun, L. Dong, Y. Zhao, Chin. J. Catal., 2025, 74, 144-154.
[23]	D. Wu, H. Wang, Y. Nie, H. Wan, S. Liu, S. Yang, H. Li, H. Zhang, C. Zhu, T. Ma, Prog. Mater. Sci., 2026, 155, 101538.
[24]	L. Zhou, X. Jia, Y. Wang, K. Xiong, J. Yang, Y. Kong, M. Guo, X. Xu, S. Li, X. Ren, C. Cheng, Mater. Sci. Eng. R Rep., 2026, 167, 101117.
[25]	S. Li, Y. Liu, L. Li, C. Liu, J. Li, S. Ashraf, P. Li, B. Wang, ACS Appl. Mater. Interfaces, 2020, 12, 22910-22916.
[26]	Z. Gu, Z. Shan, Y. Wang, J. Wang, T. Liu, X. Li, Z. Yu, J. Su, G. Zhang, Chin. Chem. Lett., 2024, 35, 108356.
[27]	S. Y. Jiang, Z. B. Zhou, S. X. Gan, Y. Lu, C. Liu, Q. Y. Qi, J. Yao, X. Zhao, Nat. Commun., 2024, 15, 698.
[28]	C. Li, D. Li, W. Zhang, H. Li, G. Yu, Angew. Chem. Int. Ed., 2021, 60, 27135-27143.
[29]	L. Wang, L. Wang, Y. Xu, G. Sun, W. Nie, L. Liu, D. Kong, Y. Pan, Y. Zhang, H. Wang, Y. Huang, Z. Liu, H. Ren, T. Wei, Y. Himeda, Z. Fan, Adv. Mater., 2024, 36, 2309376.
[30]	H. Jia, N. Yao, Y. Jin, L. Wu, J. Zhu, W. Luo, Nat. Commun., 2024, 15, 5419.
[31]	C. Yang, J. Yue, G. Wang, W. Luo, Angew. Chem. Int. Ed., 2024, 63, e202401453.
[32]	H. Xu, G. Xin, W. Hu, Z. Zhang, C. Si, J. Chen, L. Lu, Y. Peng, X. Li, Appl. Catal. B, 2023, 339, 123157.
[33]	J. Qiu, Q. Chen, C. Liu, Y. Chen, J. Wu, K. Jing, J. C. Yu, L. Wu, X. Fu, Appl. Catal. B, 2025, 366, 125034.
[34]	B. Wang, L. Li, T. Zhang, J. Wu, J. Zhang, ACS Catal., 2025, 15, 3085-3095.
[35]	Y. Fan, H. Xu, G. Gao, M. Wang, W. Huang, L. Ma, Y. Yao, Z. Qu, P. Xie, B. Dai, N. Yan, Nat. Commun., 2024, 15, 6035.
[36]	W. Li, X. Zheng, B. B. Xu, Y. Yang, Y. Zhang, L. Cai, Z. J. Wang, Y. F. Yao, B. Nan, L. Li, X. L. Wang, X. Feng, M. Antonietti, Z. Chen, Angew. Chem. Int. Ed., 2024, 63, e202320014.
[37]	E. Gong, S. Ali, C. B. Hiragond, H. S. Kim, N. S. Powar, D. Kim, H. Kim, S. I. In, Energy Environ. Sci., 2022, 15, 880-937.
[38]	K. Wang, T. Yang, G. Dawson, J. Zhang, C. Shao, K. Dai, Chem. Res. Chin. Univ., 2025, 41, 716-725.
[39]	W. Zhong, A. Meng, X. Cai, Y. Gan, J. Wang, Y. Su, Chin. J. Catal., 2025, 76, 108-119.
[40]	J. Chen, L. Lin, P. Lin, L. Xiao, L. Zhang, Y. Lu, W. Su, Chin. J. Struct. Chem., 2023, 42, 100010.
[41]	B. Zhang, H. Li, Y. Kang, K. Yang, H. Liu, Y. Zhao, S. Qiao, Adv. Funct. Mater., 2025, 35, 2416958.
[42]	L. Fang, L. W. Bai, D. Wu, H. T. Che, Y. Jiang, Y. Wang, H. Dong, F. M. Zhang, Chem. Eng. J., 2025, 510, 161820.
[43]	W. Zhong, A. Meng, Y. Su, H. Yu, P. Han, J. Yu, Angew. Chem. Int. Ed., 2025, 64, e202425038.
[44]	Z. Liu, Y. Bian, G. Dawson, J. Zhu, K. Dai, Chin. Chem. Lett., 2025, 36, 111272.
[45]	W. Zhong, J. Wang, A. Meng, B. He, P. Han, Y. Su, Chem. Eng. J., 2025, 519, 164921.
[46]	Y. He, P. Hu, J. Zhang, G. Liang, J. Yu, F. Xu, ACS Catal., 2024, 14, 1951-1961.
[47]	J. Wang, C. S. Cao, Y. Zhang, L. Zhu, Appl. Catal. B, 2023, 336, 122899.
[48]	Y. Chen, T. Liang, Y. Lin, W. Peng, Z. Chen, W. Lin, Y.-T. Sham, M. Pan, Q. Chen, G. Huang, J. Bi, J. Colloid Interface Sci., 2026, 701, 138770.
[49]	M. Yu, W. Chen, Q. Lin, L. Li, Z. Liu, J. Bi, Y. Yu, Angew. Chem. Int. Ed., 2024, 64, e202418422.
[50]	X. Zhou, E. Song, Z. Kuang, Z. Gao, H. Zhao, J. Liu, S. Sun, C.-Y. Mou, H. Chen, Chem. Eng. J., 2022, 430, 133035.
[51]	B. Su, Y. Kong, S. Wang, S. Zuo, W. Lin, Y. Fang, Y. Hou, G. Zhang, H. Zhang, X. Wang, J. Am. Chem. Soc., 2023, 145, 27415-27423.
[52]	H. Han, L. Tang, K. Wei, S. Zhang, X. Ma, C. Ma, S. Feng, Sep. Purif. Technol., 2025, 356, 129800.
[53]	Y. Wang, J. Hu, T. Ge, F. Chen, Y. Lu, R. Chen, H. Zhang, B. Ye, S. Wang, Y. Zhang, T. Ma, H. Huang, Adv. Mater., 2023, 35, 2302538.
[54]	J. Ning, J. Huang, Y. Liu, Y. Chen, Q. Niu, Q. Lin, Y. He, Z. Liu, Y. Yu, L. Li, Chin. J. Struct. Chem., 2024, 43, 100453.
[55]	H. Dong, L. Fang, K. X. Chen, J. X. Wei, J. X. Li, X. Qiao, Y. Wang, F. M. Zhang, Y. Q. Lan, Angew. Chem. Int. Ed., 2025, 64, e202414287.
[56]	H. Fu, J. Tian, Q. Zhang, Z. Zheng, H. Cheng, Y. Liu, B. Huang, P. Wang, Chin. J. Catal., 2024, 64, 143-151.
[57]	Y. Bian, H. He, G. Dawson, J. Zhang, K. Dai, Sci. China Mater., 2024, 67, 514-523.
[58]	A. Meng, P. Yang, D. Fu, W. Peng, W. Zhong, Y. Su, J. Colloid Interface Sci., 2025, 684, 148-157.
[59]	J. Liang, H. Zhang, Q. Song, Z. Liu, J. Xia, B. Yan, X. Meng, Z. Jiang, X. W. D. Lou, C. S. Lee, Adv. Mater., 2024, 36, 2303287.
[60]	Z. Liu, L. Mao, Z. Liu, M. Zhou, H. Wang, J. Li, R. Zhang, K. Nie, B. Yan, H. Zhang, Z. Jiang, S. Song, W. Shi, Angew. Chem. Int. Ed., 2026, 65, e22838.
[61]	Y. Wang, Z. Fan, Y. Wan, M. Xu, J. Li, Y. Ling, Y. Xie, K. Yang, X. Li, Appl. Catal. B, 2025, 366, 125017.
[62]	F. Xie, C. Bie, J. Sun, Z. Zhang, B. Zhu, J. Mater. Sci. Technol., 2024, 170, 87-94.

Asymmetric N-Ru-S dipole within covalent organic framework enhances internal electric field for efficient CO₂ photoreduction

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