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An iron-iron hydrogenase mimic with appended electron reservoir for efficient proton reduction in aqueous media

机译:具有附加电子存储库的铁-铁氢化酶模拟物可有效还原水性介质中的质子

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摘要

The transition from a fossil-based economy to a hydrogen-based economy requires cheap and abundant, yet stable and efficient, hydrogen production catalysts. Nature shows the potential of iron-based catalysts such as the iron-iron hydrogenase (H2ase) enzyme, which catalyzes hydrogen evolution at rates similar to platinum with low overpotential. However, existing synthetic H2ase mimics generally suffer from low efficiency and oxygen sensitivity and generally operate in organic solvents. We report on a synthetic H2ase mimic that contains a redox-active phosphole ligand as an electron reservoir, a feature that is also crucial for the working of the natural enzyme. Using a combination of (spectro)electrochemistry and time-resolved infrared spectroscopy, we elucidate the unique redox behavior of the catalyst. We find that the electron reservoir actively partakes in the reduction of protons and that its electron-rich redox states are stabilized through ligand protonation. In dilute sulfuric acid, the catalyst has a turnover frequency of 7.0 × 104 s−1 at an overpotential of 0.66 V. This catalyst is tolerant to the presence of oxygen, thereby paving the way for a new generation of synthetic H2ase mimics that combine the benefits of the enzyme with synthetic versatility and improved stability.
机译:从以化石为基础的经济向以氢为基础的经济过渡,需要廉价,丰富,稳定而高效的制氢催化剂。自然界显示出铁基催化剂的潜力,例如铁-铁氢化酶(H2ase)酶,其催化氢的逸出速率类似于低电位的铂。但是,现有的合成H2ase模拟物通常效率低,对氧气敏感,并且通常在有机溶剂中运行。我们报告了一个合成的H2ase模拟物,其中包含一个具有氧化还原活性的磷配体作为电子库,这一功能对于天然酶的工作也至关重要。结合(光谱)电化学和时间分辨红外光谱,我们阐明了催化剂的独特氧化还原行为。我们发现电子库积极参与质子的还原,并且其富电子的氧化还原态通过配体质子化得以稳定。在稀硫酸中,该催化剂在0.66 V的超电势下的周转频率为7.0×10 4 s -1 。该催化剂可耐受氧气的存在,从而为新一代合成H2ase模拟物铺平了道路,该模拟物将酶的优势与合成的多功能性和更高的稳定性相结合。

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