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 PtNiCoRh dendritic nanocrystals as versatile and active catalysts for the electrooxidation of C₁ fuels. Leveraging the selective coordination effect between ascorbic acid and Rh³⁺ ions, the doping of trace Rh atoms can be guided specifically at the near-surface of PtNiCoRh nanocatalysts. Electrocatalytic tests indicate that Pt₆₇Ni₁₆Co₁₆Rh₁ 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.

杂原子掺杂的Pt基纳米晶体引起了人们的极大兴趣，并在异催化方面具有广阔的前景。然而，通过原位表面掺杂工程化这些纳米晶体的表面原子构型仍然极具挑战性。在这里，我们提出了一种单罐，原位表面掺杂化学合成方案，以制备季金属PtNiCoRh树突状纳米晶体，作为用于C ₁燃料电氧化的通用活性催化剂。利用抗坏血酸和Rh ³⁺离子之间的选择性配位作用，可以在PtNiCoRh纳米催化剂的近表面专门引导痕量Rh原子的掺杂。电催化测试表明Pt ₆₇ Ni ₁₆具有原位痕量Rh掺杂表面的Co ₁₆ Rh ₁纳米晶体对甲醇，甲醛和甲酸的电氧化具有显着增强的活性，耐久性和CO耐受性。原位傅立叶变换红外光谱提供了有关这些纳米催化剂优异性能的分子水平的见解。表面掺入防腐Rh原子可使CO中间体从顶部Pt位转移到桥接的Rh-Pt表面位，从而有助于从催化剂表面消除这些中毒物质。这项研究提出了一种有效的原位表面掺杂策略，该策略可以设计更多原子经济的杂催化剂。