Engineering coordination microenvironments of polypyridine Ni catalysts embedded in covalent organic frameworks for efficient CO2 photoreduction

doi:10.1016/S1872-2067(25)64666-3

Abstract

Abstract:

The coordination engineering of catalytic centers emerges as a pivotal strategy for precise electronic configuration modulation in photocatalytic CO₂ reduction. Herein, the electronic structure of active sites in polypyridine nickel catalysts is well modified through strategic ligand variation (bipyridine, terpyridine (TPY), 2,6-di(1-pyrazolyl)pyridine) and anion coordination (NO₃^-, Cl^-, and CH₃COO^-), achieving enhanced CO₂ performance. Crucially, covalent immobilization of these molecular catalysts within the COF-OH framework not only preserves their precisely defined and structurally adaptable characteristics but also demonstrates synergistic enhancement of CO₂ adsorption capacity and charge transfer kinetics, as verified by CO₂ adsorption isothermal analysis and ultrafast time-resolved transient absorption spectroscopy. Remarkably, COF-O-TPYNi(NO₃^-) catalyst exhibits a CO₂-to-CO reduction activity of 9006.0 μmol·g^-1·h^-1 with 95.9% selectivity, superior to its counterpart catalysts, directly validating the mechanistic significance of precisely tailored coordination microenvironments around Ni active sites. Mechanistic studies through in situ XAFS, in situ ATR-SEIRAS and theoretical calculations reveal that this performance improvement over COF-O-TPYNi(NO₃^-) is attributed to the reduced reaction energy barrier of *COOH generation. This work pioneers a coordination shell engineering paradigm for rational design of molecularly defined catalytic architectures.

Key words: Coordination number, Anion regulation, Covalent organic framework, Polypyridine nickel catalyst, Photocatalytic CO₂ reduction

Ya-Hui Li, Yu Chen, Jin-Yu Guo, Rui Wang, Shu-Na Zhao, Gang Li, Shuang-Quan Zang. Engineering coordination microenvironments of polypyridine Ni catalysts embedded in covalent organic frameworks for efficient CO₂ photoreduction[J]. Chinese Journal of Catalysis, 2025, 74: 155-166.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64666-3

https://www.cjcatal.com/EN/Y2025/V74/I7/155

Figures/Tables 6

Scheme 1. Design of high-efficiency photocatalysts. (a) Polypyridine nickel catalysts and photocatalytic process. (b) Integrating polypyridine nickel catalysts with COF-OH through a covalently linking strategy for enhanced photocatalytic CO2 reduction.

Fig. 1. (a) Synthetic scheme of COF-O-Ni samples. PXRD patterns (b), FT-IR spectra (c), N2 absorption-desorption isotherms at -196 °C (d) of COF-OH and COF-O-Ni samples.

Fig. 2. HR-TEM image (a), the AC-HAADF-STEM image (b), and the EDX elemental mapping (c) of COF-O-TPYNi(NO3-). (d) Normalized XANES spectra at the Ni K-edge of COF-O-Ni samples with Ni foil, NiO, and Cl-TPYNi as the reference. (e) FT-EXAFS spectra at the Ni K-edge of Cl-TPYNi and COF-O-Ni samples with Ni foil, NiO, and NiPc as the reference. (f-i) EXAFS fitting and structure of Cl-TPYNi and COF-O-Ni samples at R space.

Fig. 3. (a) CO and H2 evolution at 2 h catalyzed by COF-O-Ni samples. (b) Summary of Ni-based photocatalytic systems for reduction of CO2 to CO. (c) Control experiments of catalytic conditions. (d) Cycle test of COF-O-TPYNi(NO3-). (e) Transient photoresponsive current density analyst for TPYNi, COF-OH, and COF-O-Ni samples. (f) Nyquist plots of TPYNi, COF-OH, and COF-O-Ni based on EIS measurements.

Fig. 4. (a) In-situ XANES spectra at Ni K-edge of COF-O-TPYNi(NO3-) collected under Ar atmosphere, CO2 atmosphere, and CO2 atmosphere with light illumination. (b) CO2 sorption isotherms at -0.15 °C for COF-OH and COF-O-Ni samples. (c) The isosteric heats of adsorption (Qst) for COF-O-Ni samples. Pseudocolor plots (d,g) and ultrafast time-resolved TA spectra (e,h) of COF-O-TPYNi(NO3-) and the physical mixture of COF-OH and TPYNi. All the samples are tested under 330 nm. (f,i) TA decay curves at 400 and 520 nm of COF-O-TPYNi(NO3-) and the physical mixture of COF-OH and TPYNi.

Fig. 5. (a) ATR-SEIRAS of COF-O-TPYNi(NO3-). (b,c)PDOS of COF-OH and COF-O-TPYNi(NO3-). (d) TDOS of COF-OH and COF-O-TPYNi(NO3-). (e,f) The Gibbs free energy diagram of the CO2RR to CO photocatalytic reaction. (g) Proposed CO2 to CO photocatalytic pathway in the model of COF-O-TPYNi(NO3-).

References

[1]	M. Li, Z. Han, Q. Hu, W. Fan, Q. Hu, D. He, Q. Chen, X. Jiao, Y. Xie, Chem. Soc. Rev., 2024, 53, 9964-9975.
[2]	K. G. Liu, F. Bigdeli, A. Panjehpour, A. Larimi, A. Morsali, A. Dhakshinamoorthy, H. Garcia, Coord. Chem. Rev., 2023, 493, 215257.
[3]	H. Q. Yin, Z. M. Zhang, T. B. Lu, Acc. Chem. Res., 2023, 56, 2676-2687.
[4]	X. Li, J. Yu, M. Jaroniec, X. Chen, Chem. Rev., 2019, 119, 3962-4179.
[5]	W. Zhang, C.-C. Song, J.-W. Wang, S.-T. Cai, M.-Y. Gao, Y.-X. Feng, T.-B. Lu, Chin. J. Catal., 2023, 52, 176-186.
[6]	X. Meng, R. Li, J. Yang, S. Xu, C. Zhang, K. You, B. Ma, H. Guan, Y. Ding, Chin. J. Catal., 2022, 43, 2414-2424.
[7]	M. Reguero, C. Claver, R. M. B. Carrilho, A. M. Masdeu-Bultó, Adv. Sustainable Syst., 2022, 6, 2100493.
[8]	Y. Wei, L. Chen, H. Chen, L. Cai, G. Tan, Y. Qiu, Q. Xiang, G. Chen, T. C. Lau, M. Robert, Angew. Chem. Int. Ed., 2022, 61, e202116832.
[9]	C. Wei, Y. He, X. Shi, Z. Song, Coord. Chem. Rev., 2019, 385, 1-19.
[10]	X. Z. Wang, S. L. Meng, J. Y. Chen, H. X. Wang, Y. Wang, S. Zhou, X. B. Li, R. Z. Liao, C. H. Tung, L. Z. Wu, Angew. Chem. Int. Ed., 2021, 60, 26072-26079.
[11]	J.-H. Zhang, H.-J. Wang, W.-J. Shi, W. Yang, J.-H. Mei, Y.-C. Wang, T.-B. Lu, D.-C. Zhong, CCS Chem., 2024, 6, 2961-2970.
[12]	J. Joekel, E. B. Boydas, J. Wellauer, O. S. Wenger, M. Robert, M. Roemelt, U.-P. Apfel, Chem. Sci., 2023, 14, 12774-12783.
[13]	L. Q. Qiu, H. R. Li, L. N. He, Acc. Chem. Res., 2023, 56, 2225-2240.
[14]	P. M. Stanley, J. Haimerl, N. B. Shustova, R. A. Fischer, J. Warnan, Nat. Chem., 2022, 14, 1342-1356.
[15]	N. Elgrishi, M. B. Chambers, X. Wang, M. Fontecave, Chem. Soc. Rev., 2017, 46, 761-796.
[16]	J. Wang, K. Sun, D. Wang, X. Niu, Z. Lin, S. Wang, W. Yang, J. Huang, H.-L. Jiang, ACS Catal., 2023, 13, 8760-8769.
[17]	H. Liu, M. Cheng, Y. Liu, J. Wang, G. Zhang, L. Li, L. Du, G. Wang, S. Yang, X. Wang, Energy Environ. Sci., 2022, 15, 3722-3749.
[18]	H. X. Liu, D. H. Si, M. F. Smith, R. F. Li, X. Y. Li, L. Li, H. B. Huang, Z. B. Fang, H. C. Zhou, T. F. Liu, Aggregate, 2023, 4, e383.
[19]	G. Yang, D. N. Wang, Y. Wang, W. H. Hu, S. S. Hu, J. Jiang, J. E. Huang, H. L. Jiang, J. Am. Chem. Soc., 2024, 146, 10798-10805.
[20]	L. Yao, A. M. Putz, H. Vignolo-Gonzalez, B. V. Lotsch, J. Am. Chem. Soc., 2024, 146, 9479-9492.
[21]	J. Yang, Z. Chen, L. Zhang, Q. Zhang, ACS Nano, 2024, 18, 21804-21835.
[22]	X. A. Li, Z. Z. Liang, Y. C. Zhou, J. F. Huang, X. L. Wang, L. M. Xiao, J. M. Liu, Aggregate, 2024, 5, e442.
[23]	M. Dong, W. Li, J. Zhou, S.-Q. You, C.-Y. Sun, X.-H. Yao, C. Qin, X.-L. Wang, Z.-M. Su, Chin. J. Chem., 2022, 40, 2678-2684.
[24]	X. Yang, X. Lan, Y. Zhang, H. Li, G. Bai, Appl. Catal. B, 2023, 325, 122393
[25]	L. Zhang, H. Zhang, D. Zhu, Z. Fu, S. Dong, C. Lyu, Chin. J. Catal., 2024, 66, 181-194.
[26]	J. He, X. Wang, S. Jin, Z.-Q. Liu, M. Zhu, Chin. J. Catal., 2022, 43, 1306-1315.
[27]	D. Song, W. Xu, J. Li, J. Zhao, Q. Shi, F. Li, X. Sun, N. Wang, Chin. J. Catal., 2022, 43, 2425-2433.
[28]	L. Y. Qin, C. D. Ma, J. Zhang, T. H. Zhou, Adv. Funct. Mater., 2024, 34, 2401562.
[29]	W. Liu, Y. N. Zhang, J. Wang, X. B. Shang, C. X. Zhang, Q. L. Wang, Coord. Chem. Rev., 2024, 516, 215997.
[30]	S. P. Qi, R. T. Guo, Z. X. Bi, Z. R. Zhang, C. F. Li, W. G. Pan, Small, 2023, 19, 2303632.
[31]	Y. L. Li, A. J. Li, S. L. Huang, J. J. Vittal, G. Y. Yang, Chem. Soc. Rev., 2023, 52, 4725-4754.
[32]	X. Y. Dong, Y. N. Si, Q. Y. Wang, S. Wang, S. Q. Zang, Adv. Mater., 2021, 33, 2101568.
[33]	M. P. Kou, W. Liu, Y. Y. Wang, J. D. Huang, Y. L. Chen, Y. Zhou, Y. Chen, M. Z. Ma, K. Lei, H. Q. Xie, P. K. Wong, L. Q. Ye, Appl. Catal. B, 2021, 291, 120146.
[34]	S. S. Zhao, J. Liang, D.-H. Si, M.-J. Mao, Y. B. Huang, R. Cao, Appl. Catal. B, 2023, 333, 122782.
[35]	W. Zhou, X. Wang, W. Zhao, N. Lu, D. Cong, Z. Li, P. Han, G. Ren, L. Sun, C. Liu, W.-Q. Deng, Nat. Commun., 2023, 14, 6971.
[36]	S. Yang, W. Hu, X. Zhang, P. He, B. Pattengale, C. Liu, M. Cendejas, I. Hermans, X. Zhang, J. Zhang, J. Huang, J. Am. Chem. Soc., 2018, 140, 14614-14618.
[37]	T.-X. Luan, J.-R. Wang, K. Li, H. Li, F. Nan, W. W. Yu, P.-Z. Li, Small, 2023, 19, 2303324.
[38]	Y. Zhang, L. Cao, G. Bai, X. Lan, Small, 2023, 19, 2300035.
[39]	P. Fu, C. Chen, C. Wu, B. Meng, Q. Yue, T. Chen, W. Yin, X. Chi, X. Yu, R. Li, Y. Wang, Y. Zhang, W. Luo, X. Liu, Y. Han, J. Wang, S. Xi, Y. Zhou, Angew. Chem. Int. Ed., 2025, 64, e202415202.
[40]	C. Zhao, C. Yang, X. Lv, S. Wang, C. Hu, G. Zheng, Q. Han, Adv. Mater., 2024, 36, 2401004.
[41]	Y. Yang, H. Y. Zhang, Y. Wang, L. H. Shao, L. Fang, H. Dong, M. Lu, L. Z. Dong, Y. Q. Lan, F. M. Zhang, Adv. Mater., 2023, 35, 2304170.
[42]	Q. Guan, L.-L. Zhou, Y.-B. Dong, Chem. Soc. Rev., 2022, 51, 6307-6416.
[43]	B. Zhang, H. Li, Y. Kang, K. Yang, H. Liu, Y. Zhao, S. Qiao, Adv. Funct. Mater., 2024, 35, 2416958.
[44]	N. Dai, Y. Y. Qian, D. N. Wang, J. J. Huang, X. Y. Guan, Z. Y. Lin, W. J. Yang, R. Wang, J. E. Huang, S. Q. Zang, H, L. Jiang, Precis. Chem., 2024, 2, 600-609.
[45]	Y. Qian, H.-L. Jiang, Acc. Chem. Res., 2024, 57, 1214-1226.
[46]	B. B. Rath, S. Krause, B. V. Lotsch, Adv. Funct. Mater., 2024, 34, 2309060.
[47]	M. Lu, M. Zhang, J. Liu, T. Y. Yu, J. N. Chang, L. J. Shang, S. L. Li, Y. Q. Lan, J. Am. Chem. Soc., 2022, 144, 1861-1871.
[48]	T. Li, P. L. Zhang, L. Z. Dong, Y. Q. Lan, Angew. Chem. Int. Ed., 2024, 63, e202318180.
[49]	S. Liang, X. Zhong, Z. Zhong, H. Deng, W.-Y. Wong, Appl. Catal. B, 2023, 337, 122958.
[50]	Y. Xie, T. Pan, Q. Lei, C. Chen, X. Dong, Y. Yuan, J. Shen, Y. Cai, C. Zhou, I. Pinnau, Y. Han, Angew. Chem. Int. Ed., 2021, 60, 22432-22440.
[51]	M. Lu, Q. Li, J. Liu, F. M. Zhang, L. Zhang, J. L. Wang, Z. H. Kang, Y. Q. Lan, Appl. Catal. B, 2019, 254, 624-633.
[52]	M. Zhou, Z. Wang, A. Mei, Z. Yang, W. Chen, S. Ou, S. Wang, K. Chen, P. Reiss, K. Qi, J. Ma, Y. Liu, Nat. Commun., 2023, 14, 2473.
[53]	S. L. Yang, R. J. Sa, H. Zhong, H. W. Lv, D. Q. Yuan, R. H. Wang, Adv. Funct. Mater., 2022, 32, 2110694.
[54]	M. Yu, H. W. Chen, Q. Lin, L. Li, Z. Liu, J. Bi, Y. Yu, Angew. Chem. Int. Ed., 2025, 64, e202418422.
[55]	Y. He, Y. Zhao, X. Wang, Z. Liu, Y. Yu, L. Li, Angew. Chem. Int. Ed., 2023, 62, e202307160.
[56]	Y. Xiang, W. Dong, P. Wang, S. Wang, X. Ding, F. Ichihara, Z. Wang, Y. Wada, S. Jin, Y. Weng, H. Chen, J. Ye, Appl. Catal. B, 2020, 274, 119096.
[57]	D. Wu, H. Q. Yin, Z. Wang, M. Zhou, C. Yu, J. Wu, H. Miao, T. Yamamoto, W. Zhaxi, Z. Huang, L. Liu, W. Huang, W. Zhong, Y. Einaga, J. Jiang, Z. M. Zhang, Angew. Chem. Int. Ed., 2023, 62, e202301925.
[58]	P. M. Stanley, A. Y. Su, V. Ramm, P. Fink, C. Kimna, O. Lieleg, M. Elsner, J. A. Lercher, B. Rieger, J. Warnan, R. A. Fischer, Adv. Mater., 2023, 35, 2207380.
[59]	S. Monticelli, A. Talbot, P. Gotico, F. Caille, O. Loreau, A. Del Vecchio, A. Malandain, A. Sallustrau, W. Leibl, A. Aukauloo, F. Taran, Z. Halime, D. Audisio, Nat. Commun., 2023, 14, 4451.
[60]	J. W. Wang, F. Ma, T. Jin, P. He, Z. M. Luo, S. Kupfer, M. Karnahl, F. Zhao, Z. Xu, T. Jin, T. Lian, Y. L. Huang, L. Jiang, L. Z. Fu, G. Ouyang, X. Y. Yi, J. Am. Chem. Soc., 2023, 145, 676-688.
[61]	Q. Zhang, S. Gao, Y. Guo, H. Wang, J. Wei, X. Su, H. Zhang, Z. Liu, J. Wang, Nat. Commun., 2023, 14, 1147.
[62]	F. Q. Yan, X. Y. Dong, Y. M. Wang, Q. Y. Wang, S. Wang, S. Q. Zang, Adv. Sci., 2024, 11, 2401508.
[63]	J. Wang, W. B. Zhu, F. Y. Meng, G. Y. Bai, Q. F. Zhang, X. W. Lan, ACS Catal., 2023, 13, 4316-4329.
[64]	X. Yu, M. Sun, T. Yan, L. Jia, M. Chu, L. Zhang, W. Huang, B. Huang, Y. Li, Energy Environ. Sci., 2024, 17, 2260-2268.
[65]	A. Deng, E. Zhao, Q. Li, Y. Sun, Y. Liu, S. Yang, H. He, Y. Xu, W. Zhao, H. Song, Z. Xu, Z. Chen, ACS Nano, 2023, 17, 11869-11881.

Engineering coordination microenvironments of polypyridine Ni catalysts embedded in covalent organic frameworks for efficient CO₂ photoreduction

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 6

References

Related Articles 15

Recommended Articles

Metrics

[1]	Yunchao Zhang, Jinkang Pan, Xiang Ni, Feiqi Mo, Yuanguo Xu, Pengyu Dong. Revealing the dynamics of charge carriers in organic/inorganic hybrid FS-COF/WO₃ S-scheme heterojunction for boosted photocatalytic hydrogen evolution [J]. Chinese Journal of Catalysis, 2025, 74(7): 250-263.
[2]	Lin Zhang, Hui Zhang, Jinghong Fang, Jialin Cui, Jie Liu, Hui Liu, Lishui Sun, Qiong Sun, Lifeng Dong, Yingjie Zhao. Highly conjugated and chemically stable three-dimensional covalent organic frameworks for efficient photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2025, 74(7): 144-154.
[3]	Chang Shu, Xiaoju Yang, Peixuan Xie, Xuan Yang, Bien Tan, Xiaoyan Wang. Long-term photocatalytic hydrogen peroxide production by hydroquinone-buffered covalent organic frameworks [J]. Chinese Journal of Catalysis, 2025, 73(6): 300-310.
[4]	Rui Li, Pengfei Feng, Bonan Li, Jiayu Zhu, Yali Zhang, Ze Zhang, Jiangwei Zhang, Yong Ding. Photocatalytic reduction of CO₂ over porous ultrathin NiO nanosheets with oxygen vacancies [J]. Chinese Journal of Catalysis, 2025, 73(6): 242-251.
[5]	Xuemeng Sun, Jianan Liu, Qi Li, Cheng Wang, Baojiang Jiang. Schottky junction coupling with metal size effect for the enhancement of photocatalytic nitrate reduction [J]. Chinese Journal of Catalysis, 2025, 73(6): 358-367.
[6]	Hongjun Dong, Chunhong Qu, Chunmei Li, Bo Hu, Xin Li, Guijie Liang, Jizhou Jiang. Recent advances of covalent organic frameworks-based photocatalysts: Principles, designs, and applications [J]. Chinese Journal of Catalysis, 2025, 70(3): 142-206.
[7]	Mingyang Xu, Zhenzhen Li, Rongchen Shen, Xin Zhang, Zhihong Zhang, Peng Zhang, Xin Li. Constructing S-scheme heterojunction between porphyrinyl covalent organic frameworks and Nb₂C MXene for photocatalytic H₂O₂ production [J]. Chinese Journal of Catalysis, 2025, 70(3): 431-443.
[8]	Dongxiao Wen, Nan Wang, Jiahe Peng, Tetsuro Majima, Jizhou Jiang. Collaborative photocatalytic C-C coupling with Cu and P dual sites to produce C₂H₄ over Cu_xP/g-C₃N₄ heterojunction [J]. Chinese Journal of Catalysis, 2025, 69(2): 58-74.
[9]	Xiaoning Zhan, Yucheng Jin, Bin Han, Ziwen Zhou, Baotong Chen, Xu Ding, Fushun Li, Zhiru Suo, Rong Jiang, Dongdong Qi, Kang Wang, Jianzhuang Jiang. 2D Phthalocyanine-based covalent organic frameworks for infrared light-mediated photocatalysis [J]. Chinese Journal of Catalysis, 2025, 69(2): 271-281.
[10]	Zheng Lin, Wanting Xie, Mengjing Zhu, Changchun Wang, Jia Guo. Boosting photocatalytic hydrogen evolution enabled by SiO₂-supporting chiral covalent organic frameworks with parallel stacking sequence [J]. Chinese Journal of Catalysis, 2024, 64(9): 87-97.
[11]	Yanyan Zhao, Chunyan Yang, Shumin Zhang, Guotai Sun, Bicheng Zhu, Linxi Wang, Jianjun Zhang. Investigating the charge transfer mechanism of ZnSe QD/COF S-scheme photocatalyst for H₂O₂ production by using femtosecond transient absorption spectroscopy [J]. Chinese Journal of Catalysis, 2024, 63(8): 258-269.
[12]	Chao Li, Shuo Wang, Yuan Liu, Xihe Huang, Yan Zhuang, Shuhong Wu, Ying Wang, Na Wen, Kaifeng Wu, Zhengxin Ding, Jinlin Long. Superposition of dual electric fields in covalent organic frameworks for efficient photocatalytic hydrogen evolution [J]. Chinese Journal of Catalysis, 2024, 63(8): 164-175.
[13]	Gaoxiong Liu, Rundong Chen, Bingquan Xia, Zhen Wu, Shantang Liu, Amin Talebian-Kiakalaieh, Jingrun Ran. Synthesis of H₂O₂ and high-value chemicals by covalent organic framework-based photocatalysts [J]. Chinese Journal of Catalysis, 2024, 61(6): 97-110.
[14]	Haoming Huang, Qingqing Lin, Qing Niu, Jiangqi Ning, Liuyi Li, Jinhong Bi, Yan Yu. Metal-free photocatalytic reduction of CO₂ on a covalent organic framework-based heterostructure [J]. Chinese Journal of Catalysis, 2024, 60(5): 201-208.
[15]	Junxian Bai, Rongchen Shen, Guijie Liang, Chaochao Qin, Difa Xu, Haobin Hu, Xin Li. Topology-induced local electric polarization in 2D thiophene-based covalent organic frameworks for boosting photocatalytic H₂ evolution [J]. Chinese Journal of Catalysis, 2024, 59(4): 225-236.