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Modulating Hydrogen Adsorption via Charge Transfer at the Semiconductor-Metal Heterointerface for Highly Efficient Hydrogen Evolution Catalysis.

Yuhang LiuJie DingFuhua LiXiaozhi SuQitao ZhangGuangjian GuanFangxin HuJincheng ZhangQilun WangYucheng JiangBin LiuHong Bin Yang
Published in: Advanced materials (Deerfield Beach, Fla.) (2022)
Designing and synthesizing highly efficient and stable electrocatalysts for hydrogen evolution reaction (HER) is important for realizing the hydrogen economy. Tuning the electronic structure of the electrocatalysts is essential to achieve optimal HER activity, and interfacial engineering is an effective strategy to induce electron transfer in a heterostructure interface to optimize HER kinetics. In this study, ultrafine RhP 2 /Rh nanoparticles are synthesized with a well-defined semiconductor-metal heterointerface embedded in N,P co-doped graphene (RhP 2 /Rh@NPG) via a one-step pyrolysis. RhP 2 /Rh@NPG exhibits outstanding HER performances under all pH conditions. Electrochemical characterization and first principles density functional theory calculations reveal that the RhP 2 /Rh heterointerface induces electron transfer from metallic Rh to semiconductive RhP 2 , which increases the electron density on the Rh atoms in RhP 2 and weakens the hydrogen adsorption on RhP 2 , thereby accelerating the HER kinetics. Moreover, the interfacial electron transfer activates the dual-site synergistic effect of Rh and P of RhP 2 in neutral and alkaline environments, thereby promoting reorganization of interfacial water molecules for faster HER kinetics.
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