Control of the overpotential of a [FeFe] hydrogenase mimic by a synthetic second coordination sphere†,Chemical Communications

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Control of the overpotential of a [FeFe] hydrogenase mimic by a synthetic second coordination sphere†
Chemical Communications ( IF 4.3 ) Pub Date : 2019-02-13 00:00:00 , DOI: 10.1039/c9cc00901a
Sandra S. Nurttila _{1,

2,

3} , Riccardo Zaffaroni _{1,

2,

3} , Simon Mathew _{1,

2,

3} , Joost N. H. Reek _{1,

2,

3}

Affiliation

Hydrogen as a renewable fuel is viable when produced sustainably via proton reduction catalysis (PRC). Many homogeneous electrocatalysts perform PRC with high rates, but they all require a large overpotential to drive the reaction. Natural hydrogenase enzymes achieve reversible PRC with potentials close to the thermodynamic equilibrium through confinement of the active site in a well-defined protein pocket. Inspired by nature, we report a strategy that relies on the selective encapsulation of a synthetic hydrogenase mimic in a novel supramolecular cage. Catalyst confinement decreases the PRC overpotential by 150 mV, and is proposed to originate from the cationic cage stabilizing anionic reaction intermediates within the catalytic cycle.

中文翻译：

通过合成的第二配位球控制[FeFe]氢化酶模拟物的超电势†

当通过质子还原催化（PRC）可持续地产生氢时，作为可再生燃料的氢是可行的。许多均相电催化剂均以高速率执行PRC，但它们都需要很大的超电势来驱动反应。天然氢化酶通过将活性位点限制在明确定义的蛋白质囊中，从而实现了可逆的PRC，其电位接近热力学平衡。受自然界的启发，我们报告了一种策略，该策略依赖于在新型超分子笼中选择性封装合成氢酶模拟物。催化剂的限制使PRC过电势降低了150 mV，并且被认为是由催化循环内的阳离子笼稳定阴离子反应中间体引起的。

更新日期：2019-02-13

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