Modulation of the superficial electronic structure via metal–support interaction for H(2) evolution over Pd catalysts

Electronic interactions can radically enhance the performance of supported metal catalysts and are critical for fundamentally understanding the nature of catalysts. However, at the microscopic level, the details of such interactions tuning the electronic properties of the sites on the metal particle's surface and metal–support interface remain obscure. Herein, we found polarized electronic metal–support interaction (pEMSI) in oxide-supported Pd nanoparticles (NPs) describing the enhanced accumulation of electrons at the surface of NPs (superficial Pd(δ−)) with positive Pd atoms distributed on the interface (interfacial Pd(δ+)). More superficial Pd(δ−) species mean stronger pEMSI resulting from the synergistic effect of moderate Pd–oxide interaction, high structural fluxionality and electron transport activity of Pd NPs. The surface Pd(δ−) species are responsible for improved catalytic performance for H(2) evolution from metal hydrides and formates. These extensive insights into the nature of supported-metal NPs may open new avenues for regulating a metal particle's electronic structure precisely and exploiting high-performance catalysts.