%0 Journal Article
%T Halogen Tailoring of Platinum Electrocatalyst with High CO Tolerance for Methanol Oxidation Reaction.
%A Hui L
%A Yan D
%A Zhang X
%A Wu H
%A Li J
%A Li Y
%J Angew Chem Int Ed Engl
%V 0
%N 0
%D 2024 Jul 8
%M 38973379
%F 16.823
%R 10.1002/anie.202410413
%X 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.