摘要：Heteroatom-doped Pt-based nanocrystals have generated considerable interest and hold great prospects in heterocatalysis. However, engineering the superficial atomic configurations of these nanocrystals via in situ surface doping remains exceedingly challenging. Herein, we propose a onepot, in situ surface doping chemical synthesis protocol to prepare quatermetallic Pt Ni Co Rh dendritic nanocrystals as versatile and active catalysts for the electrooxidation of C_(1) fuels. Leveraging the selective coordination effect between ascorbic acid and Rh^(3+)ions, the doping of trace Rh atoms can be guided specifically at the near-surface of Pt Ni Co Rh nanocatalysts. Electrocatalytic tests indicate that Pt_(67)Ni_(16)Co_(16)Rh_(1) nanocrystals with in situ trace Rh-doped surface exhibit substantially enhanced activity, durability, and CO tolerance for the electrooxidation of methanol, formaldehyde, and formic acid. In situ Fourier transform infrared spectroscopy provides molecular-level insight into the exceptional performance of these nanocatalysts. The surface incorporation of anticorrosive Rh atoms enables the transfer of CO intermediates from the atop Pt sites to the bridged Rh–Pt surface sites,thereby facilitating the elimination of these poisoning species from the catalyst surface. This study presents an effective in situ surface doping strategy which can enable the design of more atom-economic heterocatalysts.

摘要：综述近年来Cu基材料电催化CO_(2)还原(ECR)生成多碳产物的研究进展,着重介绍ECR反应机理、Cu基催化材料的各种设计策略及电解池系统优化,并展望未来该领域的发展方向.结果表明:Cu基催化剂的优化和设计能够有效降低*CO关键中间体产生及偶联的能垒,进而优化多碳产物的合成效率;原位检测技术时空分辨率的提升则有助于深入ECR认识反应机理,从而优化Cu基材料的设计合成.