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Abstract

The formic acid oxidation reaction (FAOR) is one of the key reactions that can be used at the anode of low-temperature liquid fuel cells. To allow the knowledge-driven development of improved catalysts, it is necessary to deeply understand the fundamental aspects of the FAOR, which can be ideally achieved by investigating highly active model catalysts. Here, we studied SnO₂-decorated Pd nanocubes (NCs) exhibiting excellent electrocatalytic performance for formic acid oxidation in acidic medium with a SnO₂ promotion that boosts the catalytic activity by a factor of 5.8, compared to pure Pd NCs, exhibiting values of 2.46 A mg^–1_Pd for SnO₂@Pd NCs versus 0.42 A mg^–1_Pd for the Pd NCs and a 100 mV lower peak potential. By using ex situ, quasi in situ, and operando spectroscopic and microscopic methods (namely, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray absorption fine-structure spectroscopy), we identified that the initially well-defined SnO₂-decorated Pd nanocubes maintain their structure and composition throughout FAOR. In situ Fourier-transformed infrared spectroscopy revealed a weaker CO adsorption site in the case of the SnO₂-decorated Pd NCs, compared to the monometallic Pd NCs, enabling a bifunctional reaction mechanism. Therein, SnO₂ provides oxygen species to the Pd surface at low overpotentials, promoting the oxidation of the poisoning CO intermediate and, thus, improving the catalytic performance of Pd. Our SnO_x-decorated Pd nanocubes allowed deeper insight into the mechanism of FAOR and hold promise for possible applications in direct formic acid fuel cells.