Zhang Yong-Kang, Zhao Lan, Xie Wen-Jun, Li Hong-Ru, He Liang-Nian
State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin, 300071, P. R. China.
College of Pharmacy, Nankai University, Tianjin, 300350, P. R. China.
ChemSusChem. 2024 Jul 22;17(14):e202400090. doi: 10.1002/cssc.202400090. Epub 2024 Mar 18.
Designing earth-abundant metal complexes as efficient molecular photocatalysts for visible light-driven CO reduction is a key challenge in artificial photosynthesis. Here, we demonstrated the first example of a mononuclear iron pyridine-thiolate complex that functions both as a photosensitizer and catalyst for CO reduction. This single-component bifunctional molecular photocatalyst efficiently reduced CO to formate and CO with a total turnover number (TON) of 46 and turnover frequency (TOF) of 11.5 h in 4 h under visible light irradiation. Notably, the quantum yield was determined to be 8.4 % for the generation of formate and CO at 400 nm. Quenching experiments indicate that high photocatalytic activity is mainly attributed to the rapid intramolecular quenching protocol. The mechanism investigation by DFT calculation and electrochemical studies revealed that the protonation of Febpy(pyS) is indispensable step for photocatalytic CO reduction.
设计富含地球元素的金属配合物作为用于可见光驱动CO还原的高效分子光催化剂是人工光合作用中的一项关键挑战。在此，我们展示了首例单核吡啶硫醇铁配合物，它既作为光敏剂又作为CO还原催化剂。这种单组分双功能分子光催化剂在可见光照射下4小时内将CO高效还原为甲酸盐和CO，总周转数（TON）为46，周转频率（TOF）为11.5 h⁻¹。值得注意的是，在400 nm处甲酸盐和CO生成的量子产率测定为8.4%。猝灭实验表明高光催化活性主要归因于快速的分子内猝灭过程。通过DFT计算和电化学研究进行的机理研究表明，Febpy(pyS)的质子化是光催化CO还原不可或缺的步骤。
