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CO2 and Formate Pathway of Methanol Electrooxidation at Rhodium Electrodes in Alkaline Media: An In Situ Electrochemical Attenuated Total Refection Surface-Enhanced Infrared Absorption Spectroscopy and Infrared Reflection Absorption Spectroscopy Investigation.

Rh catalysts exhibit unexpected high activity for the methanol oxidation reaction (MOR) in alkaline conditions, making them potential anodic catalysts for direct methanol fuel cells (DMFCs). Nevertheless, the MOR mechanism on Rh electrodes has not been clarified thus far, which impedes the development of high-efficiency Rh-based MOR catalysts. To investigate it, a combination of in situ electrochemical techniques called attenuated total refection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and infrared reflection absorption spectroscopy (IRAS) is used. Cyclic voltammograms of MOR at Rh electrodes show considerable activity in alkaline media rather than acidic media, although the real-time ATR-SEIRA spectral results demonstrate that methanol can rarely self-decompose on Rh at open-circuit conditions. Meanwhile, in combination of ATR-SEIRAS and IRAS results, CO2 and formate are thought to be MOR products, suggesting a dual-pathway mechanism ("CO2 pathway" and "formate pathway"). Specifically, COad species, which are the major intermediates in the CO2 pathway, can produce at lower potentials and be oxidized into CO2 at a potential of 0.5-0.75 V. Concurrently, the formate can be produced from 0.5 V and diffuse into the bulk electrolyte to become one of the MOR products, while the further electrochemical conversion of formate to CO2 is essentially negligible. More directly, the apparent selectivity (r) of the CO2 pathway is estimated to reach ca. 0.63 at 0.9 V, confirming the potential-dependent selectivity of MOR at Rh surfaces. This study might provide fresh insights into the design and fabrication of effective Rh-based catalysts for MOR.