Photocatalytic hydrogen production coupled with selective oxidation of organic substances is of significance and remains a grand challenge because of unsatisfied photocatalytic activity and unclear mechanism. Herein, we first design and synthesize atomically dispersed Pd on ZnIn₂S₄ (PdSA-ZIS) for simultaneously photocatalytic hydrogen production and oxidation of benzylamine. Based on systematic characterization with a combination of theoretical simulations, light irradiation-kelvin probe force microscopy (KPFM) and time-resolved photoluminescence spectrum etc, we demonstrate that Pd single atoms can modulate charge polarization as well as the active sites of ZnIn₂S₄ to promote spatial charge separation and decrease the energy barriers of reaction. The electrons are enriched around Pd single atoms-ZnS layer with lowest energy barriers of H₂ production, while more holes are accumulated on InS₂ layer for dehydrogenation of benzylamine. This enables PdSA-ZIS to exhibit remarkable photocatalytic performance for the co-production of N-benzylidenebenzylamine (10.2 mmol g⁻¹ h⁻¹) with selectivity of 100% and H₂ (11.1 mmol g⁻¹ h⁻¹) under visible irradiation. Furthermore, by means of controlled experiments, theoretical simulations and in situ electron spin resonance (ESR) spectroscopy, a synergetic photocatalytic redox mechanism on the Pd single atom-ZIS interface for dehydrogenation and coupling of benzylamine and H₂ production has been investigated in detail.

光催化制氢与有机物质的选择性氧化相结合具有重要意义，但由于光催化活性不令人满意且机理尚不清楚，因此仍然是一个巨大的挑战。在此，我们首先设计并合成了原子分散在 ZnIn ₂ S ₄上的 Pd (PdSA-ZIS)，用于同时光催化制氢和氧化苄胺。基于结合理论模拟、光辐照-开尔文探针力显微镜（KPFM）和时间分辨光致发光光谱等的系统表征，我们证明了Pd单原子可以调节电荷极化以及ZnIn ₂ S _{4的活性位点。}促进空间电荷分离并降低反应的能垒。电子富集在Pd单原子-ZnS层周围，产生H ₂的能垒最低，而更多的空穴聚集在InS ₂层上，用于苄胺的脱氢。这使得 PdSA-ZIS 表现出卓越的光催化性能，可用于联产 N-亚苄基苄胺 (10.2 mmol g ^-1 h ^-1 )，选择性为 100% 和 H ₂ (11.1 mmol g ^-1 h ^-1) 在可见光照射下。此外，通过受控实验、理论模拟和原位电子自旋共振 (ESR) 光谱，详细研究了 Pd 单原子-ZIS 界面上的协同光催化氧化还原机制，用于苄胺和 H ₂生产的脱氢和偶联。