Mechanism of Protection of Catalysts Supported in Redox Hydrogel Films
Mechanism of Protection of Catalysts Supported in Redox Hydrogel Films
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DOI：
10.1021/jacs.5b01194
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发表时间：
2015-04-29
影响因子：
15
通讯作者：
Leger, Christophe
中科院分区：
文献类型：
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作者：
Fourmond, Vincent;Stapf, Stefanie;Leger, Christophe
使用合成的无机络合物作为负载型催化剂是能源生产和工业合成中的关键路线。然而，其固有的氧敏感性有时是一个问题。我们中的一些人最近已经证明，氢化酶，脆弱的，但非常有效的生物催化剂的H2氧化，可以保护O-2损伤后，整合到一个专门设计的氧化还原聚合物的膜。H-2的催化氧化产生电子，其还原膜/溶液界面附近的氧，从而提供自活化保护以免受氧的影响[Plumere等人，Nat Chem.2014，6，822-827]。在这里，我们合理化这种保护机制，通过检查的氢化酶/聚合物膜中的物种的时间依赖性分布，使用测量或估计值的所有相关参数和一个现实的反应扩散方案的数值和分析解决方案。我们的研究为优化氢化酶-聚合物膜的设计，并将此策略扩展到其他脆弱的催化剂奠定了基础。
The use of synthetic inorganic complexes as supported catalysts is a key route in energy production and in industrial synthesis. However, their intrinsic oxygen sensitivity is sometimes an issue. Some of us have recently demonstrated that hydrogenases, the fragile but very efficient biological catalysts of H2 oxidation, can be protected from O-2 damage upon integration into a film of a specifically designed redox polymer. Catalytic oxidation of H-2 produces electrons which reduce oxygen near the film/solution interface, thus providing a self-activated protection from oxygen [Plumere et al., Nat Chem. 2014, 6, 822-827]. Here, we rationalize this protection mechanism by examining the time-dependent distribution of species in the hydrogenase/polymer film, using measured or estimated values of all relevant parameters and the numerical and analytical solutions of a realistic reaction-diffusion scheme. Our investigation sets the stage for optimizing the design of hydrogenase-polymer films, and for expanding this strategy to other fragile catalysts.