Chen Kai-Hong, Wang Ning, Yang Zhi-Wen, Xia Shu-Mei, He Liang-Nian
State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, P. R. China.
ChemSusChem. 2020 Dec 7;13(23):6284-6289. doi: 10.1002/cssc.202000698. Epub 2020 May 15.
Developing an efficient and easy-to-handle strategy in designing catalysts for CO reduction into CO by harnessing sunlight is a promising project. Here, a facile strategy was developed to design a Re catalyst modified with an ionic secondary coordination sphere for photoreduction of CO to CO by visible light. By adding ionic liquids or tuning a different ionic secondary coordination sphere, it was discovered that an outstanding optical property, other than CO absorption ability or the ability to dissociation of chloride anion, is the prerequisite for catalyst design. Accordingly, a novel Re catalyst, {ReBpyMe(tris(2-hydroxyethyl)amine) Cl}Br (Re-THEA), was designed, screened, and resulted in a relative high quantum yield (up to 34 %) for visible-light-induced CO reduction with a single-molecule system. DFT calculations, combined with experimental outcomes, suggested the pendant ionic tris(2-hydroxyethyl)amino (THEA) group on Re-THEA can enhance visible-light absorption, stabilize reaction intermediates, and suppress the Re-Re dimer formation.
通过利用阳光开发一种高效且易于操作的策略来设计用于将二氧化碳还原为一氧化碳的催化剂是一个很有前景的项目。在此，我们开发了一种简便的策略来设计一种由离子二级配位球修饰的铼催化剂，用于通过可见光将二氧化碳光还原为一氧化碳。通过添加离子液体或调整不同的离子二级配位球，我们发现除了一氧化碳吸收能力或氯离子阴离子解离能力之外，出色的光学性质是催化剂设计的先决条件。因此，我们设计、筛选了一种新型铼催化剂{ReBpyMe(三(2-羟乙基)胺)Cl}Br（Re-THEA），并在单分子体系中实现了可见光诱导的二氧化碳还原的相对较高量子产率（高达34%）。密度泛函理论计算与实验结果相结合表明，Re-THEA上的悬挂离子三(2-羟乙基)氨基（THEA）基团可以增强可见光吸收、稳定反应中间体并抑制铼-铼二聚体的形成。
