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Modulating Electronic Structure of PtCo-Ptrich Nanowires with Ru atoms for Boosted Hydrogen Evolution Catalysis
Xianjun Cao1, Li Gao1, Junpeng Qu1
1Joint International Laboratory on Environmental and Energy Frontier Materials, School of Environmental and Chemical Engineering, Shanghai University, Shanghai, 200444, P. R. China.
Abstract:
Rational design and development of highly efficient hydrogen evolution reaction (HER) electrocatalysts is of great significance for the development of green water electrolysis hydrogen production technology. Ru-engineered 1D PtCo-Ptrich nanowires (Ru-Ptrich Co NWs) are fabricated by a facile electrodeposition method. The rich Pt surface on 1D Pt3 Co contributes to the fully exposed active sites and enhanced intrinsic catalytic activity (co-engineered by Ru and Co atoms) for HER. The incorporation of Ru atoms can not only accelerate the water dissociation in alkaline condition to provide sufficient H* but also modulate the electronic structure of Pt to achieve optimized H* adsorption energy. As a result, Ru-Ptrich Co NWs have exhibited ultralow HER overpotentials (η) of 8 and 112 mV to achieve current densities of 10 and 100 mA cm-2 in 1 m KOH, respectively, which far exceed those of commercial Pt/C catalyst (η10 = 29 mV, η100 = 206 mV). Density functional theory (DFT) calculations further demonstrate that the incorporated Ru atoms possess strong water adsorption capacity (-0.52 vs -0.12 eV for Pt), facilitating water dissociation. The Pt atoms in the outermost Pt-rich skin of Ru-Ptrich Co NWs achieve optimized H* adsorption free energy (ΔGH* ) of -0.08 eV, boosting hydrogen generation.
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