Photocatalytic co-production of high value-added multicarbon compounds and hydrogen from renewable bioethanol is an environmental and long-term approach to industrial activities and remains a great challenge because of the difficulty in bioethanol dehydrogenation. Guided by first-principle simulation, we first synthesized a partially reduced Pd–P₃ single atom (PdPSA) on CdS nanorods with an unoccupied hybrid state of Pd 4d and P 3p via both metal-support interaction effect and Pd–P coordination effect. This unique electronic structure of PdPSA is totally different from highly reduced S-coordinated Pd single atoms or nanoparticles and allows PdPSA-CdS to exhibit a visible-light photocatalytic activity of 35.1 mmol g⁻¹ h⁻¹ for the co-production of high-value-added 1,1-diethoxyethane and H₂ with a selectivity of 100%. Mechanism studies revealed that the unoccupied hybrid states of Pd 4d and P 3p in PdPSA not only greatly promoted the dehydrogenation of ethanol but also promised PdPSA with a high H₂-production activity.

从可再生生物乙醇中光催化联产高附加值的多碳化合物和氢是工业活动的一种环境和长期方法，由于生物乙醇脱氢的困难，它仍然是一个巨大的挑战。在第一性原理模拟的指导下，我们首先通过金属-载体相互作用效应和Pd-P配位效应，在CdS纳米棒上合成了部分还原的Pd-P ₃单原子（PdPSA），而其Pd 4d和P 3p的混合状态为空。PdPSA的这种独特的电子结构与高度还原的S配位的Pd单原子或纳米颗粒完全不同，并且使PdPSA-CdS表现出35.1 mmol g ^-1 h ^-1的可见光光催化活性。用于联产高附加值的1,1-二乙氧基乙烷和H ₂，选择性为100％。机理研究表明，PdPSA中Pd 4d和P 3p的未占杂状态不仅极大地促进了乙醇的脱氢作用，而且有望实现具有高H _2产生活性的PdPSA 。