Hydrogenases (H₂ases) are benchmark electrocatalysts for H₂ production, both in biology and (photo)catalysis in vitro. We report the tailoring of a p‐type Si photocathode for optimal loading and wiring of H₂ase through the introduction of a hierarchical inverse opal (IO) TiO₂ interlayer. This proton‐reducing Si|IO‐TiO₂|H₂ase photocathode is capable of driving overall water splitting in combination with a photoanode. We demonstrate unassisted (bias‐free) water splitting by wiring Si|IO‐TiO₂|H₂ase to a modified BiVO₄ photoanode in a photoelectrochemical (PEC) cell during several hours of irradiation. Connecting the Si|IO‐TiO₂|H₂ase to a photosystem II (PSII) photoanode provides proof of concept for an engineered Z‐scheme that replaces the non‐complementary, natural light absorber photosystem I with a complementary abiotic silicon photocathode.

中文翻译：

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集成在光电化学串联电池中的加氢酶分解太阳能。

氢化酶（H ₂ ases）是生物学和体外（光）催化中H ₂产生的基准电催化剂。我们报告了通过引入分级反蛋白石（IO）TiO ₂中间层，对ap型Si光电阴极进行了定制，以实现H ₂酶的最佳负载和布线。这种减少质子的Si | IO-TiO ₂ | H ₂酶光电阴极能够与光电阳极一起驱动整体水分解。我们通过将Si | IO-TiO ₂ | H ₂酶连接到改性BiVO _4上，展示了无辅助的（无偏差）水分解辐照几个小时后，光电化学（PEC）电池中的光阳极。将Si | IO-TiO ₂ | H ₂酶连接至光系统II（PSII）光电阳极可为工程Z方案提供概念证明，该方案可通过互补的非生物硅光电阴极替代非互补的自然光吸收剂光系统I。