Abstract：To realize the production of methyl formate from methanol self-coupling under mild conditions, photocatalytic oxidative dehydrogenation of methanol to methyl formate was investigated, and the mechanism was discussed. TiO2 catalysts loaded with different metals were prepared by photochemical reduction, and the photocatalytic performance of different catalysts was investigated. 0.5%Pd/TiO2 presented the best dehydrogenation activity. The distribution of Pd on the surface of TiO2 particles was characterized by X-ray diffraction (XRD), Raman spectroscopy, high resolution transmission electron microscope (HRTEM) and ultraviolet-visible diffuse-reflectance spectrum (UV-Vis DRS), and the effect of the surface morphology on the photocatalytic properties was investigated. To reveal the photocatalytic dehydrogenation mechanism, in-situ diffuse reflectance infrared spectroscopy (in-situ DRIFTS) analysis was conducted to analyze and characterize the intermediate products of photocatalytic dehydrogenation of methanol to methyl formate in oxygen atmosphere. It was found that methyl formate was derived from two pathways. One was the cross-coupling reaction between the intermediate of formaldehyde and the adsorbed methanol to generate methyl formate, and the other was the further esterification of the intermediate formate derived from the oxidation of HCHO with methanol to produce methyl formate. The present work provides theoretical and data support for the photocatalytic production of methyl formate.
WANG Bin,ZHONG Shan,TANG Siyang et al. Investigation on Photocatalytic Production of Methyl Formate by Oxidative Dehydrogenation of Methanol[J]. 化学反应工程与工艺, 2021, 37(1): 15-24.
