Developing durable Si-based photoelectrochemical hydrogen evolution reaction in alkaline media is attracting attention in device-level water splitting, but still faces a trade-off between the alkalic corrosion resistance and light transmission for Si photocathodes. Herein, a synergetic strategy is proposed to employ an anti-reflective Co-P film cocatalyst modulated via self-assembly of protective-layer WS_x onto Si photocathode. The controllable WS_x thin-film efficiently ensures the excellent anti-alkali corrosion of Si semiconductors, and serves as an appropriate nucleation base to modulate the structure of Co-P cocatalyst to possess anti-reflection. The optimal Co-P/WS_x/Si photocathode exhibits an onset potential of +0.47 V vs. reversible hydrogen electrode (V_RHE), a photocurrent density of −25.1 mA cm⁻² at 0 V_RHE, and superior durability of up to 300 h at 0 V_RHE in 1.0 M KOH electrolyte. These findings offer a facile and effective approach for the further development of durable Si-based photoelectrochemical devices.

在碱性介质中开发持久的 Si 基光电化学析氢反应在器件级水分解中引起了人们的关注，但仍然面临着 Si 光电阴极的耐碱性腐蚀性和透光性之间的权衡。在此，提出了一种协同策略，即采用通过保护层 WS _x自组装到 Si 光电阴极上调制的抗反射 Co-P 膜助催化剂。可控的WS _x薄膜有效地保证了Si半导体优异的抗碱腐蚀，并作为合适的成核基来调节Co-P助催化剂的结构以具有抗反射性。最佳 Co-P/WS _x /Si 光电阴极的起始电位为 +0.47 V 与可逆氢电极 (V _RHE )、0 V _{RHE 下}的光电流密度为 -25.1  mA  cm ^-2以及在 0 V _{RHE 下}在 1.0 M KOH 电解质中长达 300小时的卓越耐久性。这些发现为进一步开发耐用的硅基光电化学装置提供了一种简便有效的方法。