As an intriguing strategy for massive hydrogen production, photoelectrochemical (PEC) seawater splitting compels the anode to be highly hypochlorite-resistant. Inspired by algae, we designed a robust photoelectrocatalyst that WO3 nanorods (NRs) are covered by N/W co-doped (Co, Ni, W)OxNy nanosheets (NSs). The NSs expose (111) faces and are decorated by (Co, Ni)WO4 nanoparticles. DFT calculations reveal that Co and Ni atoms on the (111) surface of N/W co-doped NSs are more likely to adsorb OH-, while W atoms are more favorable to adsorb Cl-. Secondly, the lattice distortion and multi-crystal phases of NSs are triggered by doped W atoms, and the evacuation of 5d electrons makes W atoms as donor centers, leading to enhanced catalytic activity of CoNi atoms and corrosion resistance to Cl-. Furthermore, the N atoms expand the valence band of CoNiOx and elevate the conduction band of (Co, Ni)WO4, facilitating more electrons to participate in PEC reaction and the realization of seawater full-splitting. Resultantly, the N/W co-doped (Co, Ni, W)OxNy/WO3 hetero-NRs (HNRs) demonstrate a PEC current density about 0.35 mA/cm2 at 1.23 VRHE with durability over 100 hours in seawater. This work provides a practical strategy towards the durable PEC anode for seawater splitting.

中文翻译：

---

用于强力海水氧化的仿生 (Co, Ni, W)OxNy/WO3 光电催化剂


作为大规模制氢的一种有趣策略，光电化学（PEC）海水分解迫使阳极具有高度抗次氯酸盐的能力。受藻类的启发，我们设计了一种坚固的光电催化剂，WO3 纳米棒 (NR) 被 N/W 共掺杂 (Co, Ni, W)OxNy 纳米片 (NS) 覆盖。 NSs 暴露 (111) 面并由 (Co, Ni)WO4 纳米颗粒装饰。 DFT计算表明，N/W共掺杂NSs（111）表面的Co和Ni原子更有利于吸附OH-，而W原子更有利于吸附Cl-。其次，NSs的晶格畸变和多晶相是由掺杂W原子引发的，5d电子的疏散使W原子成为施主中心，从而增强了CoNi原子的催化活性和对Cl-的耐腐蚀性。此外，N原子扩大了CoNiOx的价带，提升了(Co,Ni)WO4的导带，有利于更多的电子参与PEC反应，实现海水全分裂。结果，N/W 共掺杂 (Co, Ni, W)OxNy/WO3 异质 NR (HNR) 在 1.23 VRHE 下表现出约 0.35 mA/cm2 的 PEC 电流密度，在海水中具有超过 100 小时的耐久性。这项工作为用于海水分解的耐用 PEC 阳极提供了实用策略。