Unveiling the catalytic active sites of iron-vanadium catalysts for the selective oxidation of methanol to formaldehyde

Iron-Vanadium (FeV) catalyst showed a unique catalytic activity for the selective oxidation of methanol to formaldehyde; however, due to its complex compositions, the identification of catalytic active sites still remains challenging, inhibiting the rational design of excellent FeV-based catalysts. Here, in this work, a series of FeV catalysts with various compositions, including FeVO4, isolated VOx, low-polymerized VnOx, and crystalline V2O5 were prepared by controlling the preparation conditions, and were applied to methanol oxidation to formaldehyde reaction. A FeV1.1 catalyst, which consisted of FeVO4 and low-polymerized VnOx species showed an excellent catalytic performance with a methanol conversion of 92.3% and a formaldehyde selectivity of 90.6%, which was comparable to that of conventional iron-molybdate catalyst. The results of CH3OH-IR, O2 pulse and control experiments revealed a crucial synergistic effect between FeVO4 and low-polymerized VnOx. It enhanced the oxygen supply capacity and suitable binding and adsorption strengths for formaldehyde intermediates, contributing to the high catalytic activity and formaldehyde selectivity. This study not only advances the understanding of FeV structure but also offers valuable guidelines for selective methanol oxidation to formaldehyde. (c) 2025, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.