Ren Fang-Yu, Chen Kaihong, Qiu Li-Qi, Chen Jin-Mei, Darensbourg Donald J, He Liang-Nian
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, P. R. China.
Department of Chemistry, Texas A&M University, College Station, Texas, TX 77843, USA.
Angew Chem Int Ed Engl. 2022 Jul 4;61(27):e202200751. doi: 10.1002/anie.202200751. Epub 2022 May 13.
A triblock amphiphilic polymer derived from the copolymerization of CO and epoxides containing a bipyridine rhenium complex in its backbone is shown to effectively catalyze the visible-light-driven reduction of CO to CO. This polymer provides uniformly spherical micelles in aqueous solution, where the metal catalyst is sequestered in the hydrophobic portion of the nanostructured micelle. CO to CO reduction occurs in an efficient visible-light-driven process in aqueous media with turnover numbers up to 110 (>99 % selectivity) in the absence of a photosensitizer, which is a 37-fold enhancement over the corresponding molecular rhenium catalyst in organic solvent. Notably, the amphiphilic polycarbonate micelle rhenium catalyst suppresses H generation, presumably by preventing deactivation of the active catalytic center by water.
一种由一氧化碳（CO）与环氧化物共聚得到的三嵌段两亲聚合物，其主链中含有联吡啶铼配合物，该聚合物被证明能有效催化可见光驱动的CO还原为CO。这种聚合物在水溶液中形成均匀的球形胶束，金属催化剂被隔离在纳米结构胶束的疏水部分。在没有光敏剂的情况下，CO还原为CO的过程在水性介质中通过高效的可见光驱动过程发生，周转数高达110（选择性>99%），这比相应的有机溶液中的分子铼催化剂提高了37倍。值得注意的是，两亲性聚碳酸酯胶束铼催化剂抑制了氢气的产生，推测是通过防止活性催化中心被水失活来实现的。
