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

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Porphyrin-based conjugated organic polymer with dual metal sites for highly active and selective visible-light-driven reduction of CO2 to CO
Dalton Transactions ( IF 3.5 ) Pub Date : 2022-09-16 , DOI: 10.1039/d2dt02500k
Jinyu Li ₁ , Yuxia Hou ₁ , Cheng-Xing Cui ₁ , Xiupeng Zhang ₁ , Ji-Chao Wang ₁ , Airong Wang ₁ , Zhipeng Chen ₁ , Mingchang Li ₁ , Tianjun Lou ₁

Affiliation

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.

中文翻译：

基于卟啉的具有双金属位点的共轭有机聚合物，用于高活性和选择性的可见光驱动将 CO2 还原为 CO

由 5,10,15,20-四(4-溴苯基)卟啉铜 (CuTBPP) 和 5,5'-bis-ethynyl-2,2'-bipyridine (BPY) 构建了一种基于卟啉的共轭有机聚合物 (COP) )通过Sonogashira 耦合。通过与Co ²⁺配位制备其复合物Co/CuTBPP-BPY-COP（具有由铜卟啉和钴BPY单元组成的双金属位点）。所有制备的 CuTBPP-BPY-COP 和 Co/CuTBPP-BPY-COP 化合物在可见光照射下对 CO _{2还原表现出优异的光催化性能，而无需其他牺牲试剂，但只有 H}₂O. Co/CuTBPP-BPY-COP（双金属位点）比CuTBPP-BPY-COP（单金属位点）表现出更好的光催化活性。Co/CuTBPP–BPY–COP 在连续 10 次循环后保持较高的 CO ₂还原光催化能力。辐照10小时后CO产物的总量为263.2 μmol g ^{-1 。}理论研究表明，与使用CuTBPP-BPY-COP相比，引入Co金属中心和硝基更有利于CO _{2的光还原催化。}

更新日期：2022-09-16

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