The exclusive surface and electronic effects of Ni on promoting the activity of Pt towards alkaline hydrogen oxidation

Ni modification is considered as an efficient strategy for boosting the performance of Pt towards alkaline hydrogen oxidation reaction(HOR),yet its specific role is largely undecoded.Here,ultrathin Pt nanowires(NWs)are selected as models for revealing the significance of Ni modification on HOR by precisely positioning Ni on distinct positions of Pt NWs.Ni solely influences the electronic properties of Pt and thus weakens*H adsorption when it is located in the core of PtNi alloyed NWs,leading to a moderate improvement of alkaline HOR activity.When Ni is distributed in both core and surface of PtNi alloyed NWs,Ni strongly weakens*H adsorption but strengthens*OH adsorption.On the other hand,the electronic properties of Pt are hardly influenced when Ni is deposited on the surface of Pt NWs,on which the strong*H and*OH adsorptions lead to the improved HOR activity.This work reveals the significance of Ni modification on HOR,but also promotes the fundamental researches on catalyst design for fuel cell reactions and beyond.

界面工程促进雪花状Ru/RuO_(2)纳米片氢气氧化性能

近年来,贵金属钌(Ru)因其具备与铂(Pt)媲美的氢吸附能以及比铂更低的价格被认为是很有前景的氢氧化反应(HOR)和析氢反应(HER)催化剂.然而,目前钌基催化剂在HOR和HER上的大规模应用依然受限于其活性低、稳定性不高等缺点.本文采用湿化学和热处理结合策略制备了具有Ru/RuO_(2)界面的二维雪花纳米片(Ru/RuO_(2) SNSs).表征和理论计算结果表明, Ru/RuO_(2) SNSs的界面结构与热处理温度密切相关.因此,可通过改变热处理温度调控界Ru/RuO_(2)界面相互作用,并进一步调控催化剂表面的氢结合能(HBE)和氢氧根结合能(OHBE),从而提高HOR和HER的催化性能.当Ru/RuO-12 SNSs用于催化碱性HOR时,在50 mV的过电位为下,其质量活性达到了9.13 A mgRu,分别是Ru SNSs(0.14 A mg^(-1)_(Ru))、RuO_(2) SNSs(0.03 A mg^(-1)_(Ru))和商用Pt/C(0.43 A mg^(-1)_(Ru))的65倍、304倍和21倍.此外, Ru/RuO_(2) SNSs还表现出优异的碱性HER性能.在1 mol L^(-1) KOH中,当电流密度达到10 mA cm^(-2)时,过电位低至20.2 mV.这项工作不仅开发了一种高效的HOR和HER催化剂,而且对开发新型高效催化剂也起到了重要的推动作用.

A top–down strategy to realize the synthesis of small-sized L10 - platinum-based intermetallic compounds for selective hydrogenation

The synthesis of Pt-based nanoparticles(NPs)with ultrasmall feature and tailored structure is of great importance for catalysis yet challenging.In this work,we demonstrate a facile top–down strategy for the fabrication of small-sized Pt-based intermetallic compounds(IMCs)with L10 structure through the evaporation of Cd under high temperature.Impressively,such thermal treatment can be used as a versatile strategy for creating binary,ternary,quaternary,quinary,and senary L10-Pt-based IMCs.Moreover,the small-sized Pt-based IMCs display high stability against high temperature of 700℃,which can serve as active and selective catalyst for the selective hydrogenation of 4-nitrophenylacetylene.This work may not only provide a versatile top–down strategy for fabricating highly stable small-sized Pt-based NPs with L10 structure,but also promote their extensive applications in catalysis and beyond.