Leung Jane J, Vigil Julian A, Warnan Julien, Edwardes Moore Esther, Reisner Erwin
Christian Doppler Laboratory for Sustainable SynGas Chemistry, Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, UK.
Angew Chem Int Ed Engl. 2019 Jun 3;58(23):7697-7701. doi: 10.1002/anie.201902218. Epub 2019 May 6.
A series of copolymers comprising a terpyridine ligand and various functional groups were synthesized toward integrating a Co-based molecular CO reduction catalyst. Using porous metal oxide electrodes designed to host macromolecules, the Co-coordinated polymers were readily immobilized via phosphonate anchoring groups. Within the polymeric matrix, the outer coordination sphere of the Co terpyridine catalyst was engineered using hydrophobic functional moieties to improve CO reduction selectivity in the presence of water. Electrochemical and photoelectrochemical CO reduction were demonstrated with the polymer-immobilized hybrid cathodes, with a CO:H product ratio of up to 6:1 compared to 2:1 for a corresponding "monomeric" Co terpyridine catalyst. This versatile platform of polymer design demonstrates promise in controlling the outer-sphere environment of synthetic molecular catalysts, analogous to CO reductases.
合成了一系列包含三联吡啶配体和各种官能团的共聚物，以整合基于钴的分子CO还原催化剂。使用设计用于容纳大分子的多孔金属氧化物电极，通过膦酸酯锚定基团可轻松固定钴配位聚合物。在聚合物基质中，利用疏水官能团对钴三联吡啶催化剂的外配位层进行了设计，以提高在有水存在时CO还原的选择性。聚合物固定化混合阴极实现了电化学和光电化学CO还原，与相应的“单体”钴三联吡啶催化剂相比，CO:H产物比高达6:1，而后者为2:1。这种通用的聚合物设计平台在控制合成分子催化剂的外层环境方面显示出前景，类似于CO还原酶。
