Adsorption of formate on oxide surfaces plays a role in water-gas shift (WGS) and other reactions related to H2 production and CO2 utilization. CeO2 is of particular interest because its reducibility affects the redox of organic molecules. In this work, the adsorption and thermal evolution of formic acid and formate on highly ordered films of fully oxidized CeO2(111) and highly reduced CeOx(111) surfaces have been studied using reflection absorption infrared spectroscopy (RAIRS) under ultra-high vacuum conditions, and the experimental results are combined with density functional theory (DFT) calculations to probe the identity, symmetry, and bonding of the surface intermediates. Disordered ice, ordered α-polymorph and molecular formic acid bonded through the carbonyl are observed at low temperatures. By 250 K, desorption and deprotonation lead to formate coexisting with hydroxyl on CeO2(111), identified to be a bridging bidentate formate species that is coordinated to Ce cations in nearly C2v symmetry and interacting strongly with neighboring H. Changes in the spectra at higher temperatures are consistent with additional tilting of the formate, resulting in Cs(2) or lower symmetry. This change in bonding is caused primarily by interaction with oxygen vacancies introduced by water desorption at 300 K. On reduced CeOx, multiple low-symmetry formate states exist likewise due to interactions with oxygen vacancies. Isotopic studies demonstrate that the formyl hydrogen does not contribute to H incorporated in hydroxyl on the surface, and that both formate oxygen atoms may exchange with lattice oxygen at 400 K. The combined experimental and theoretical results thus provide important insights on the surface reaction pathways of formic acid on ceria.
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