Herein, a fern-like p-n heterojunction by anchoring NiFe-LDH nanoplates onto CoO nanoneedles have been optionally constructed. Essentially, p-n heterojunction ensured to induce strong built-in electric field, and inherit interfacial electron redistribution. Based on their compatible and well-matched electronic band structures, a staggered type-II photo-generated electron/holes transfer pathway have been elaborated by density functional theory calculation (DFT), in situ irradiation X-ray photoelectron spectroscopy (XPS), and fluorescent decay. This band bending and charge migrating module conferred the architecture with strong redox ability, sufficient exciton dissociation, and admirable optoelectronic characteristics. Moreover, the heterostructure acquired broad absorption spectrum to exhibit outperforming photocatalytic effect. Totally, this electron redistribution at the hierarchical interface, a type-II scheme charge-transfer pathway and the oxygen defects would lead to high efficiency in solar light assisted N reduction. Typically, Co@NiFe-2 catalyst exhibited the highest NH production rate of 16.15 μg h mg and Faraday efficiency (FE) of 31.57% at −0.6 V vs. RHE in 0.1 M NaSO solution. Fortunately, with light exposure, the NH production rate and FE could increase by 27.9% and 18.1% than that under dark. This work would provide a plausible attitude towards the design of high efficient photocatalyst for artificial photosynthesis with multi-functionalized coupling effect.

中文翻译：

---

优化类蕨类Co3O4@Ni3Fe-LDH pn异质结的结构以促进光辅助电子N2还原为NH3和DFT计算

在此，通过将 NiFe-LDH 纳米板锚定到 CoO 纳米针上，可选地构建了蕨类 pn 异质结。从本质上讲，pn异质结确保产生强的内建电场，并继承界面电子重新分布。基于它们兼容且匹配良好的电子能带结构，通过密度泛函理论计算（DFT）、原位辐照X射线光电子能谱（XPS）和荧光衰减。这种能带弯曲和电荷迁移模块赋予了该结构强大的氧化还原能力、充分的激子解离和良好的光电特性。此外，异质结构获得了宽吸收光谱，表现出优异的光催化效果。总而言之，这种电子在分层界面上的重新分布、II型方案电荷转移途径和氧缺陷将导致太阳光辅助氮还原的高效率。通常，Co@NiFe-2 催化剂在 0.1 M NaSO 溶液中，在 -0.6 V vs. RHE 条件下表现出最高的 NH 产率（16.15 μg h mg）和法拉第效率（FE）为 31.57%。幸运的是，在光照条件下，NH 产率和 FE 比黑暗条件下提高了 27.9% 和 18.1%。这项工作将为具有多功能耦合效应的人工光合作用高效光催化剂的设计提供一种合理的态度。