Abstract：
The catalytic activity of platinum for CO oxidation depends on the interaction of electron donation and back-donation at the platinum center. Here we demonstrate that the platinum bromine nanoparticles with electron-rich properties on bromine bonded with sp-C in graphdiyne (PtBr NPs/Br-GDY), which is formed by bromine ligand and constitutes an electrocatalyst with a high CO-resistant for methanol oxidation reaction (MOR). The catalyst showed peak mass activity for MOR as high as 10.4 A mgPt -1, which is 20.8 times higher than the 20 % Pt/C. The catalyst also showed robust long-term stability with slight current density decay after 100 hours at 35 mA cm-2. Structural characterization, experimental, and theoretical studies show that the electron donation from bromine makes the surface of platinum catalysts highly electron-rich, and can strengthen the adsorption of CO as well as enhance π back-donation of Pt to weaken the C-O bond to facilitate CO electrooxidation and enhance catalytic performance during MOR. The results highlight the importance of electron-rich structure among active sites in Pt-halogen catalysts and provide detailed insights into the new mechanism of CO electrooxidation to overcome CO poisoning at the Pt center on an orbital level.
摘要：
铂对CO氧化的催化活性取决于铂中心的电子捐赠和回赠的相互作用。在这里，我们证明了在石墨炔（PtBrNP/Br-GDY）中与sp-C键合的溴上具有富电子性质的铂溴纳米颗粒，它由溴配体形成，并构成对甲醇氧化反应（MOR）具有高耐CO性的电催化剂。催化剂对MOR的峰质量活性高达10.4AmgPt-1，比20%Pt/C高20.8倍。催化剂还显示出稳健的长期稳定性,在35mAcm-2下100小时后具有轻微的电流密度衰减。结构表征,实验性的,理论研究表明，溴的电子提供使铂催化剂表面高度富电子，并可以增强CO的吸附，增强Pt的π回赠，削弱C-O键，促进CO电氧化，提高MOR过程中的催化性能。结果突出了Pt-卤素催化剂中活性位点中富电子结构的重要性，并为CO电氧化的新机制提供了详细的见解，以克服轨道水平上Pt中心的CO中毒。
