Porphyrin-based conjugated organic polymer with dual metal sites for highly active and selective visible-light-driven reduction of CO2 to CO

Jinyu Li; Yuxia Hou; Cheng-Xing Cui; Xiupeng Zhang; Ji-Chao Wang; Airong Wang; Zhipeng Chen; Mingchang Li; Tianjun Lou

doi:10.1039/d2dt02500k

Porphyrin-based conjugated organic polymer with dual metal sites for highly active and selective visible-light-driven reduction of CO₂ to CO

Dalton Trans. 2022 Oct 11;51(39):15022-15030. doi: 10.1039/d2dt02500k.

Authors

Jinyu Li¹, Yuxia Hou¹, Cheng-Xing Cui¹, Xiupeng Zhang¹, Ji-Chao Wang¹, Airong Wang¹, Zhipeng Chen¹, Mingchang Li¹, Tianjun Lou¹

Affiliation

¹ Department of Chemistry and Chemical Engineering, Henan Institute of Science and Technology, Xinxiang, 453003, China. yxhou@hist.edu.cn.

PMID: 36112028
DOI: 10.1039/d2dt02500k

Abstract

A porphyrin-based conjugated organic polymer (COP) was constructed from 5,10,15,20-tetrakis(4-bromophenyl)porphyrin copper (CuTBPP) and 5,5'-bis-ethynyl-2,2'-bipyridine (BPY) via Sonogashira coupling. Its complex Co/CuTBPP-BPY-COP (with dual metal sites composed of copper porphyrin and a cobalt BPY unit) was prepared by coordination with Co²⁺. All of the prepared CuTBPP-BPY-COP and Co/CuTBPP-BPY-COP compounds exhibited excellent photocatalytic performance toward CO₂ reduction under visible-light irradiation without another sacrificial reagent but only H₂O. Co/CuTBPP-BPY-COP (dual metal sites) exhibited better photocatalytic activity than CuTBPP-BPY-COP (a single metal site). Co/CuTBPP-BPY-COP retained a higher photocatalysis capacity for CO₂ reduction after 10 consecutive cycles. The total quantity of CO product was 263.2 μmol g^-1 after 10 h of irradiation. Theoretical studies indicate that introducing Co metal centers and nitro groups are more favorable for the photoreduction catalysis of CO₂ compared with that using CuTBPP-BPY-COP.