Highly conjugated and chemically stable three-dimensional covalent organic frameworks for efficient photocatalytic CO2 reduction

doi:10.1016/S1872-2067(25)64717-6

Abstract

Abstract:

Covalent organic frameworks (COFs), as efficient photocatalysts, can convert CO₂ and H₂O into value-added fuel, thus improving the deteriorating ecological environment. However, achieving high photocatalytic efficiency and selectivity without relying on noble metals or sacrificial agents remains a significant challenge. Here, a highly conjugated three-dimensional (3D) COF 3D-COF-1 with imine linkage is constructed by the combination of two rigid and conjugated orthogonal building blocks (spirobifluorene and bicarbazole) with good photoactivites. Through a simple post-synthetic reduction, a chemically stable and amine-linked 3D-COF-2 which maintains excellent crystallinity and porosity can be obtained. Notably, the 3D-COF-2 exhibits excellent performance in CO₂ reduction and exceptional selectivity of CO due to the highly conjugated structure and abundant amine groups as chemisorption sites for selectively capturing CO₂. Under the irradiation of visible light and without noble metals and sacrificial agents, 3D-COF-2 produces 1070 μmol g^-1 of carbon monoxide in 4.5 h, and the selectivity is close to 100%.

Key words: Covalent organic frameworks, Three-dimensional structure, Photocatalytic CO₂ reduction, Metal-free catalysis, Chemically stable structure

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: 144-154.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64717-6

https://www.cjcatal.com/EN/Y2025/V74/I7/144

Figures/Tables 6

Fig. 1. (a) The synthesis of 3D-COF-1 and 3D-COF-2. (b) FT-IR spectra of 3D-COF-1, 3D-COF-2, compound A, and compound B and the enlarged portion within the green dashed box of the left image.

Fig. 2. Simulated and experimental powder X-ray diffraction patterns and difference curves of 3D-COF-1 (a) and 3D-COF-2 (b). N2 adsorption?desorption isotherms and pore size distribution profiles of 3D-COF-1 (c) and 3D-COF-2 (d).

Fig. 3. SEM (a, b) and TEM (c,d) images of 3D-COF-1. SEM (e,f) and TEM (g,h) images of 3D-COF-2.

Fig. 4. (a) CO2 adsorption-desorption isotherms at 25 and 0 °C of 3D-COF-1 and 3D-COF-2. (b) Photocatalytic CO yields of 3D-COF-1 and 3D-COF-2. (c) Recycling stability tests of 3D-COF-2.

Fig. 5. (a) Solid-state UV/vis absorption spectra of 3D-COF-1 and 3D-COF-2. (b) Band gaps of 3D-COF-1 and 3D-COF-2. (c) Mott-Schottky plot of 3D-COF-1. (d) Mott-Schottky plot of 3D-COF-2. (e) The band structure diagram of 3D-COF-1 and 3D-COF-2. (f) Transient photocurrent response of 3D-COF-1 and 3D-COF-2. (g) Electrochemical impedance spectroscopy of 3D-COF-1 and 3D-COF-2. (h) EPR spectra of 3D-COF-1 in the dark and under the light. (i) EPR spectra of 3D-COF-2 in the dark and under the light.

Fig. 6. (a) In situ DRIFTS of 3D-COF-2 in the dark (background) and under visible light irradiation for different durations. (b) In situ DRIFTS of 3D-COF-2 for *CO adsorption. (c) In situ DRIFTS of 3D-COF-2 for CO2 adsorption. (d) The possible reaction mechanism for photocatalytic CO2-to-CO reduction on the 3D-COF-2-based metal-free catalyst, along with the corresponding Gibbs free energy change (ΔG) values for each step. (e) Gibbs free energy plots for 3D-COF-2 in the process of CO2 reduction. Calculated ESP on the van der Waals surface of 3D-COF-1 (f) and 3D-COF-2 (g), with blue indicating more negative ESPs and red indicating more positive ESPs. The simulated structures and adsorption energies of CO2 adsorbed in 3D-COF-1 (h) and 3D-COF-2 (i).

References

[1]	E. Nikoloudakis, I. López-Duarte, G. Charalambidis, K. Ladomenou, M. Ince, A. G. Coutsolelos, Chem. Soc. Rev., 2022, 51, 6965-7045.
[2]	K. Rennert, F. Errickson, B. C. Prest, L. Rennels, R. G. Newell, W. Pizer, C. Kingdon, J. Wingenroth, R. Cooke, B. Parthum, D. Smith, K. Cromar, D. Diaz, F. C. Moore, U. K. Müller, R. J. Plevin, A. E. Raftery, H. Ševčíkov, H. Sheets, J. H. Stock, T. Tan, M. Watson, T. E. Wong, D. Anthoff, Nature, 2022, 610, 687-692.
[3]	J. Strefler, E. Kriegler, N. Bauer, G. Luderer, R. C. Pietzcker, A. Giannousakis, O. Edenhofer, Nat. Commun., 2021, 12, 2264.
[4]	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.
[5]	M. Zhang, J.-N. Chang, Y. Chen, M. Lu, T.-Y. Yu, C. Jiang, S.-L. Li, Y.-P. Cai, Y.-Q. Lan, Adv. Mater., 2021, 33, 2105002.
[6]	H. Wang, H. Wang, Z. Wang, L. Tang, G. Zeng, P. Xu, M. Chen, T. Xiong, C. Zhou, X. Li, D. Huang, Y. Zhu, Z. Wang, J. Tang, Chem. Soc. Rev., 2020, 49, 4135-4165.
[7]	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.
[8]	A. Wagner, C. D. Sahm, E. Reisner, Nat. Catal., 2020, 3, 775-786.
[9]	P. Prabhu, V. Jose, J.-M. Lee, Adv. Funct. Mater., 2020, 30, 1910768.
[10]	A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
[11]	L. Wang, J. Zhang, Y. Zhang, H. Yu, Y. Qu, J. Yu, Small, 2022, 18, 2104561.
[12]	Z. Cheng, W. Qi, C.-H. Pang, T. Thomas, T. Wu, S. Liu, M. Yang, Adv. Funct. Mater., 2021, 31, 2100553.
[13]	M. Liras, M. Barawi, V. A. de la Peña O’Shea, Chem. Soc. Rev., 2019, 48, 5454-5487.
[14]	J. Liu, H. Wang, M. Antonietti, Chem. Soc. Rev., 2016, 45, 2308-2326.
[15]	Y. Moriya, T. Takata, K. Domen, Coord. Chem. Rev., 2013, 257, 1957-1969.
[16]	H. Wang, L. Zhang, Z. Chen, J. Hu, S. Li, Z. Wang, J. Liu, X. Wang, Chem. Soc. Rev., 2014, 43, 5234.
[17]	C. Dai, B. Liu, Energy Environ. Sci., 2020, 13, 24-52.
[18]	J. Xiao, X. Liu, L. Pan, C. Shi, X. Zhang, J.-J. Zou, ACS Catal., 2020, 10, 12256-12283.
[19]	G. Cai, P. Yan, L. Zhang, H.-C. Zhou, H.-L. Jiang, Chem. Rev., 2021, 121, 12278-12326.
[20]	M. Ding, R. W. Flaig, H.-L. Jiang, O. M. Yaghi, Chem. Soc. Rev., 2019, 48, 2783-2828.
[21]	Y. Liu, D. Huang, M. Cheng, Z. Liu, C. Lai, C. Zhang, C. Zhou, W. Xiong, L. Qin, B. Shao, Q. Liang, Coord. Chem. Rev. 2020, 409, 213220.
[22]	J. Liang, H. Yu, J. Shi, B. Li, L. Wu, M. Wang, Adv. Mater. 2023, 35, 2209814.
[23]	X. Ma, H. Liu, W. Yang, G. Mao, L. Zheng, H.-L. Jiang, J. Am. Chem. Soc., 2021, 143, 12220-12229.
[24]	W. Zhao, L. Luo, M. Cong, X. Liu, Z. Zhang, M. Bahri, B. Li, J. Yang, M. Yu, L. Liu, Y. Xia, N. D. Browning, W.-H. Zhu, W. Zhang, A. I. Cooper, Nat. Commun., 2024, 15, 6482.
[25]	R. Liu, K.-T. Tan, Y. Gong, Y. Chen, Z. Li, S. Xie, T. He, Z. Lu, H. Yang, D. Jiang, Chem. Soc. Rev., 2021, 50, 120-242.
[26]	B. B. Rath, S. Krause, B. V. Lotsch, Adv. Funct. Mater., 2024, 34, 2470252.
[27]	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.
[28]	W. Lin, F. Lin, J. Lin, Z. Xiao, D. Yuan, Y. Wang, J. Am. Chem. Soc., 2024, 146, 16229-16236.
[29]	Y.-N. Gong, X. Guan, H.-L. Jiang, Coord. Chem. Rev., 2023, 475, 214889.
[30]	N.-Y. Huang, Y.-T. Zheng, D. Chen, Z.-Y. Chen, C.-Z. Huang, Q. Xu, Chem. Soc. Rev., 2023, 52, 7949-8004.
[31]	X. Qiu, Y. Zhang, Y. Zhu, C. Long, L. Su, S. Liu, Z. Tang, Adv. Mater., 2021, 33, 2001731.
[32]	S. Daliran, M. Blanco, A. Dhakshinamoorthy, A. R. Oveisi, J. Alem n, H. García, Adv. Funct. Mater., 2024, 34, 2312912.
[33]	K.-T. Tan, S. Ghosh, Z. Wang, F. Wen, D. Rodríguez-San-Miguel, J. Feng, N. Huang, W. Wang, F. Zamora, X. Feng, A. Thomas, D. Jiang, Nat. Rev. Meth. Primers, 2023, 3, 1.
[34]	Y. Li, W. Chen, G. Xing, D. Jiang, L. Chen, Chem. Soc. Rev., 2020, 49, 2852-2868.
[35]	M. Liu, Q. Xu, G. Zeng, Angew. Chem. Int. Ed., 2024, 63, e202404886.
[36]	H. Li, A. Dilipkumar, S. Abubakar, D. Zhao, Chem. Soc. Rev., 2023, 52, 6294-6329.
[37]	Y. Zeng, R. Zou, Y. Zhao, Adv. Mater., 2016, 28, 2855-2873.
[38]	H. Lyu, H. Li, N. Hanikel, K. Wang, O. M. Yaghi, J. Am. Chem. Soc., 2022, 144, 12989-12995.
[39]	X. Zhao, Q. Li, P. Pachfule, Z. Wang, S. Liu, W. Wu, M. Wu, A. Thomas, Small, 2023, 19, 2301200.
[40]	C. Yu, H. Li, Y. Wang, J. Suo, X. Guan, R. Wang, V. Valtchev, Y. Yan, S. Qiu, Q. Fang, Angew. Chem. Int. Ed., 2022, 61, e202117101.
[41]	Z. Wang, S. Zhang, Y. Chen, Z. Zhang, S. Ma, Chem. Soc. Rev., 2020, 49, 708-735.
[42]	Y.-Z. Cheng, W. Ji, P.-Y. Hao, X.-H. Qi, X. Wu, X.-M. Dou, X.-Y. Bian, D. Jiang, F.-T. Li, X.-F. Liu, D.-H. Yang, X. Ding, B.-H. Han, Angew. Chem. Int. Ed., 2023, 62, e202308523.
[43]	J. Ding, X. Guan, J. Lv, X. Chen, Y. Zhang, H. Li, D. Zhang, S. Qiu, H.-L. Jiang, Q. Fang, J. Am. Chem. Soc., 2023, 145, 3248-3254.
[44]	Y. Liu, H. Tan, J. Sun, Y. Wei, M. Liu, J. Hong, S. Shang, X. Wang, L. Li, Y. Gu, N. Ye, J. Chen, Y. Yang, S. Guo, Y. Liu,, Adv. Funct. Mater., 2023, 33, 2302874.
[45]	Y. Yang, X. Chu, H.-Y. Zhang, R. Zhang, Y.-H. Liu, F.-M. Zhang, M. Lu, Z.-D. Yang, Y.-Q. Lan, Nat. Commun., 2023, 14, 593.
[46]	J. Xu, C. Yang, S. Bi, W. Wang, Y. He, D. Wu, Q. Liang, X. Wang, F. Zhang, Angew. Chem. Int. Ed., 2020, 59, 23845-23853.
[47]	P. Li, X. Dong, Y. Zhang, X. Lang, C. Wang, Mater. Today Chem., 2022, 25, 100953.
[48]	Y. Meng, Y. Luo, J.-L. Shi, H. Ding, X. Lang, W. Chen, A. Zheng, J. Sun, C. Wang, Angew. Chem. Int. Ed., 2020, 59, 3624-3629.
[49]	S. Xue, X. Ma, Y. Wang, G. Duan, C. Zhang, K. Liu, S. Jiang, Coord. Chem. Rev., 2024, 504, 215659.
[50]	Z. a. Guo, Z. Zhang, J. Sun, Adv. Mater. 2024, 36, 2312889.
[51]	C. Wu, Y. Liu, H. Liu, C. Duan, Q. Pan, J. Zhu, F. Hu, X. Ma, T. Jiu, Z. Li, Y. Zhao, J. Am. Chem. Soc., 2018, 140, 10016-10024.
[52]	Y. Yin, Y. Zhang, X. Zhou, B. Gui, G. Cai, J. Sun, C. Wang, J. Am. Chem. Soc., 2023, 145, 22329-22334.
[53]	R. Bao, Z. Xiang, Z. Qiao, Y. Yang, Y. Zhang, D. Cao, S. Wang, Angew. Chem. Int. Ed., 2023, 62, e202216751.
[54]	S. Wang, L. Da, J. Hao, J. Li, M. Wang, Y. Huang, Z. Li, Z. Liu, D. Cao, Angew. Chem. Int. Ed., 2021, 60, 9321-9325.
[55]	M. Lu, S.-B. Zhang, R.-H. Li, L.-Z. Dong, M.-Y. Yang, P. Huang, Y.-F. Liu, Z.-H. Li, H. Zhang, M. Zhang, S.-L. Li, Y.-Q. Lan, J. Am. Chem. Soc., 2024, 146, 25832-25840.
[56]	F. Jin, E. Lin, T. Wang, D. Yan, Y. Yang, Y. Chen, P. Cheng, Z. Zhang, Chem, 2022, 8, 3064-3080.
[57]	Y. Yang, C. Schäfer, K. Börjesson, Chem 2022, 8, 2217-2227.
[58]	L. Zhang, D. Wang, M. Cong, X. Jia, Z. Liu, L. He, C. Li, Y. Zhao, Chem. Commun., 2023, 59, 4911-4914.
[59]	S. Biswas, A. Dey, F. A. Rahimi, S. Barman, T. K. Maji, ACS Catal., 2023, 13, 5926-5937.
[60]	K. Lei, D. Wang, L. Ye, M. Kou, Y. Deng, Z. Ma, L. Wang, Y. Kong, ChemSusChem, 2020, 13, 1725-1729.
[61]	L.-J. Wang, R.-L. Wang, X. Zhang, J.-L. Mu, Z.-Y. Zhou, Z.-M. Su, ChemSusChem, 2020, 13, 2973-2980.
[62]	J.-X. Cui, L.-J. Wang, L. Feng, B. Meng, Z.-Y. Zhou, Z.-M. Su, K. Wang, S. Liu, J. Mater. Chem. A, 2021, 9, 24895-24902.
[63]	X. Yu, K. Gong, S. Tian, G. Gao, J. Xie, X.-H. Jin, J. Mater. Chem. A, 2023, 11, 5627-5635.

Highly conjugated and chemically stable three-dimensional covalent organic frameworks for efficient photocatalytic CO₂ reduction

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]	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(7): 155-166.
[3]	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.
[4]	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.
[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]	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.
[7]	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.
[8]	Lingkun Yang, Zongjun Li, Xin Wang, Lingling Li, Zhe Chen. Facile electrospinning synthesis of S-scheme heterojunction CoTiO₃/g-C₃N₄ nanofiber with enhanced visible light photocatalytic activity [J]. Chinese Journal of Catalysis, 2024, 59(4): 237-249.
[9]	Yong Zhang, Junyi Qiu, Bicheng Zhu, Guotai Sun, Bei Cheng, Linxi Wang. Hollow spherical covalent organic framework supported gold nanoparticles for photocatalytic H₂O₂ production [J]. Chinese Journal of Catalysis, 2024, 57(2): 143-153.
[10]	Yucheng Jin, Xiaolin Liu, Chen Qu, Changjun Li, Hailong Wang, Xiaoning Zhan, Xinyi Cao, Xiaofeng Li, Baoqiu Yu, Qi Zhang, Dongdong Qi, Jianzhuang Jiang. Perylene diimide covalent organic frameworks super-reductant for visible light-driven reduction of aryl halides [J]. Chinese Journal of Catalysis, 2024, 57(2): 171-183.
[11]	Xiaotian Wang, Bo Hu, Yuan Li, Zhixiong Yang, Gaoke Zhang. Dipole moment regulation by Ni doping ultrathin Bi₄O₅Br₂ for enhancing internal electric field toward efficient photocatalytic conversion of CO₂ to CO [J]. Chinese Journal of Catalysis, 2024, 66(11): 257-267.
[12]	Mingming Song, Xianghai Song, Xin Liu, Weiqiang Zhou, Pengwei Huo. Enhancing photocatalytic CO₂ reduction activity of ZnIn₂S₄/MOF-808 microsphere with S-scheme heterojunction by in situ synthesis method [J]. Chinese Journal of Catalysis, 2023, 51(8): 180-192.
[13]	Zizi Li, Jia-Wei Wang, Yanjun Huang, Gangfeng Ouyang. Enhancing CO₂ photoreduction via the perfluorination of Co(II) phthalocyanine catalysts in a noble-metal-free system [J]. Chinese Journal of Catalysis, 2023, 49(6): 160-167.
[14]	Houwei He, Zhongliao Wang, Kai Dai, Suwen Li, Jinfeng Zhang. LSPR-enhanced carbon-coated In₂O₃/W₁₈O₄₉ S-scheme heterojunction for efficient CO₂ photoreduction [J]. Chinese Journal of Catalysis, 2023, 48(5): 267-278.
[15]	Chengcheng Chen, Fangting Liu, Qiaoyu Zhang, Zhengguo Zhang, Qiong Liu, Xiaoming Fang. Theoretical design and experimental study of pyridine-incorporated polymeric carbon nitride with an optimal structure for boosting photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2023, 46(3): 91-102.