Charged Macromolecular Rhenium Bipyridine Catalysts with Tunable CO2 Reduction Potentials,Chemistry - A European Journal

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Charged Macromolecular Rhenium Bipyridine Catalysts with Tunable CO2 Reduction Potentials
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2017-06-05 13:30:55 , DOI: 10.1002/chem.201701901
Swagat Sahu ₁ , Po Ling Cheung ₁ , Charles W. Machan ₁ , Steven A. Chabolla ₁ , Clifford P. Kubiak ₁ , Nathan C. Gianneschi _{1,

2}

Affiliation

A series of polymeric frameworks with functional assemblies were designed to alter the catalytic activity of covalently bound Re^I electrocatalysts. Norbornenyl polymers containing positively charged quaternary ammonium salts, neutral phenyl, or negatively charged trifluoroborate groups were end-labelled with a Re^I fac-tricarbonyl bipyridine electrocatalyst via cross metathesis. Electrochemical studies in acetonitrile under an inert atmosphere and with saturated CO₂ indicate that the quaternary ammonium polymers exhibit a significantly lower potential for CO₂ reduction to CO (ca. 300 mV), while neutral polymers behave consistently with what has been reported for the free, molecular catalyst. In contrast, the trifluoroborate polymers displayed a negative shift in potential and catalytic activity was not observed. It is demonstrated that a single catalytically active complex can be installed onto a charged polymeric framework, thereby achieving environmentally tuned reduction potentials for CO₂ reduction. These materials may be useful as polymer-based precursors for preparing catalytic and highly ordered structures such as thin films, porous catalytic membranes, or catalytic nanoparticles.

中文翻译：

具有可调的CO2还原潜力的带电大分子Bi联吡啶催化剂

设计了一系列具有功能组件的聚合物骨架，以改变共价键合的Re ^I电催化剂的催化活性。含有带正电荷的季铵盐，中性苯基，或带负电荷的三氟硼酸基降冰片烯基聚合物进行末端标记具有可重新^我 FAC三羰联吡啶电通过交叉复分解。在乙腈中在惰性气氛和饱和CO ₂下进行的电化学研究表明，季铵聚合物对CO _2的电势显着降低。降低至CO（约300 mV），而中性聚合物的性能与游离分子催化剂所报道的一致。相反，三氟硼酸酯聚合物显示出负的电位变化并且未观察到催化活性。已经证明，可以将单一的催化活性络合物安装在带电的聚合物骨架上，从而实现环境调整的CO ₂还原潜力。这些材料可用作基于聚合物的前体，用于制备催化和高度有序的结构，例如薄膜，多孔催化膜或催化纳米颗粒。

更新日期：2017-06-06

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