Construction of Modifiable Phthalocyanine-Based Covalent Organic Frameworks with Irreversible Linking for Efficient Photocatalytic CO_(2)ReductionOA
Covalent organic frameworks(COFs)are considered promising catalysts for photocatalytic CO_(2)reduction reaction(pCO_(2)RR)due to facilitated regulations.However,the instability of COFs with dynamic reversible covalent bonds and the limited modifiability of COFs with irreversible covalent bonds restricted the enhancement of the pCO_(2)RR performance.Herein,three phthalocyanine-based COFs with ether-linked,CoOP,CoPOP,and CoBOP,were successfully prepared via in situ polycondensation using modifiable bis-phthalonitrile.CoBOP achieved a record of syngas performance in pCO_(2)RR systems with photosensitizers and sacrificial agents(CO 83.7 mmol g^(-1)h^(-1)and H_254.7 mmol g^(-1)h^(-1)),surpassing most COF photocatalysts.Additionally,CoOP,CoPOP,and CoBOP exhibit stabilities in extreme environments owing to their irreversible covalent bonds.Experimental and density functional theory analyses confirm that the optimally matched the lowest unoccupied molecular orbital of the linking unit between the photosensitizer and active unit endowed Co BOP with the highest photoelectron transfer efficiency among the three catalysts,boosting its pCO_(2)RR activity.This work is highly instructive for designing COFs with structure-adjustable and irreversible covalent bonds.
Xuefei Zhou;Shaowei Yang;Zhengyang Hu;Zhanwei Chen;Ying Guo;Tianshuai Wang;Qiuyu Zhang;Hepeng Zhang
Xi’an Key Laboratory of Functional Organic Porous Materials,School of Chemistry and Chemical Engineering,Northwestern Polytechnical University,Xi’an 710129,People’s Republic of ChinaXi’an Key Laboratory of Functional Organic Porous Materials,School of Chemistry and Chemical Engineering,Northwestern Polytechnical University,Xi’an 710129,People’s Republic of ChinaXi’an Key Laboratory of Functional Organic Porous Materials,School of Chemistry and Chemical Engineering,Northwestern Polytechnical University,Xi’an 710129,People’s Republic of ChinaXi’an Key Laboratory of Functional Organic Porous Materials,School of Chemistry and Chemical Engineering,Northwestern Polytechnical University,Xi’an 710129,People’s Republic of ChinaXi’an Key Laboratory of Functional Organic Porous Materials,School of Chemistry and Chemical Engineering,Northwestern Polytechnical University,Xi’an 710129,People’s Republic of ChinaXi’an Key Laboratory of Functional Organic Porous Materials,School of Chemistry and Chemical Engineering,Northwestern Polytechnical University,Xi’an 710129,People’s Republic of ChinaXi’an Key Laboratory of Functional Organic Porous Materials,School of Chemistry and Chemical Engineering,Northwestern Polytechnical University,Xi’an 710129,People’s Republic of ChinaXi’an Key Laboratory of Functional Organic Porous Materials,School of Chemistry and Chemical Engineering,Northwestern Polytechnical University,Xi’an 710129,People’s Republic of China
化学化工
Photocatalytic CO_(2)RRPhthalocyanine-based COFIrreversible covalent bondElectronic property modulationPhotoelectron transfer
《Nano-Micro Letters》 2026 (4)
P.435-448,14
financially supported by the Innovation Capability Support Program of Shaanxi—Science and Technology Innovation Team Project(No.2025RS-CXTD-024)the Fundamental Research Foundation of SHCCIG New Materials Technology Research Institute Co.,Ltd(No.D5204230171)the Fundamental Research Funds for the Central Universities(G2025KY05240)the Natural Science Basic Research Program of Shaanxi(Program No.2024JC-YBQN-0073)the Fundamental Research Funds for the Central Universities(No.D5000250204)Young Talent Fund of Association for Science and Technology in Shaanxi(No.20230101)。
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