In situ electrochemical surface-enhanced infrared absorption spectroscopy (EC-SEIRAS) together with a periodic density functional theory (DFT) calculation has been initially applied to investigate the mechanism of formic acid electro-oxidation on Sb-modified Pt (Sb/Pt) electrode. EC-SEIRAS measurement reveals that the main formic acid oxidation current on Sb/Pt electrode is ca. 10-fold enhanced as compared to that on clean Pt electrode, mirrored by nearly synchronous decrease of the CO and formate surface species, suggesting a “non-formate” oxidation as the main pathway on the Sb/Pt electrode. On the basis of the calculations from periodic DFT, the catalytic role of Sb adatoms can be rationalized as a promoter for the adsorption of the CH-down configuration but an inhibitor for the adsorption of the O-down configuration of formic acid, kinetically facilitating the complete oxidation of HCOOH into CO 2 . In addition, Sb modification lowers the CO adsorption energy on Pt, helps to mitigate the CO poisoning effect on Pt.
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Peng et al. (2010) studied this question.
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