Abstract

AbstractThis work investigated the kinetics of formic acid (FA) disproportionation using an Ir complex immobilized on bipyridine‐periodic mesoporous organosilica (BPy‐PMO). The selectivity for methanol (MeOH) is increased using this catalyst compared to conventional homogeneous Ir complexes. This enhanced selectivity is attributed to the retention of H2 and CO2 generated by the competing FA dehydrogenation in PMO mesochannels having a high aspect ratio. However, no direct evidence for this process was previously obtained. The present work clarified the unique catalysis mechanism associated with a PMO catalyst exhibiting higher MeOH selectivity based on a hypothesis that the generation of MeOH via FA hydrogenation is promoted by the confinement of H2 in the PMO pores. The results obtained from the present kinetics study and data regarding H2 diffusion in the PMO pores strongly support this hypothesis.

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