In-situ Bi-modified Pt towards glycerol and formic acid electro-oxidation: Effects of catalyst structure and surface microenvironment on activity and selectivity

The performances of glycerol electro-oxidation reaction (GOR) and formic acid electro-oxidation reaction (FAOR) catalyzed by Pt catalyst were dramatically improved by adding Bi 3+ into the reaction solution. The dynamic structure and microenvironment of in-situ Bi-modified Pt and their impact on the catalytic performances were revealed. A strong correlation was established between the Bi coverage of Pt-based catalysts and their resistance to CO poisoning and performance in GOR and FAOR. When Bi 3+ increased to a certain amount, a Bi-shell containing hydroxides was formed on Pt surfaces except the formation of Pt-Bi ensemble. On Pt catalyst covered with 43.9 % Bi, the peak mass-specific activities of GOR and FAOR in forward scans were 4.2 and 34.7 times that of Pt/NCNTs, respectively. The peak electrochemical active surface area (ECSA)-specific activity of FAOR in forward scan for Pt with 52.6 % Bi coverage was 80.6 times that of Pt/NCNTs. The dehydrogenation process in FAOR and the 4-electron pathway in GOR were improved for Bi-modified Pt. The experimental results and DFT calculations indicated that the positively charged Bi and structure of Pt-Bi ensemble improved the adsorption and interaction of negatively charged intermediates, and the enhanced hydroxides facilitated the oxidation and removal of toxic intermediates, such as CO.