Fe/Fe3C Boosts H2O2 Utilization for Methane Conversion Overwhelming O2 Generation

作者：Yicheng Xing, Zheng Yao, Wenyuan Li, Wenting Wu, Xiaoqing Lü, Jun Jie Tian, Zhongtao Li, Han Xiang Hu, Mingbo Wu · 发表于：Angewandte Chemie International Edition · 年份：2021 · DOI：10.1002/anie.202016888 · 被引用次数：141 · 研究领域：Catalytic Processes in Materials Science、Catalysis and Oxidation Reactions、Electrocatalysts for Energy Conversion

Abstract H2O2 as a well‐known efficient oxidant is widely used in the chemical industry mainly because of its homolytic cleavage into .OH (stronger oxidant), but this reaction always competes with O2 generation resulting in H2O2 waste. Here, we fabricate heterogeneous Fenton‐type Fe‐based catalysts containing Fe‐Nx sites and Fe/Fe3C nanoparticles as a model to study this competition. Fe‐Nx in the low spin state provides the active site for .OH generation. Fe/Fe3C, in particular Fe3C, promotes Fe‐Nx sites for the homolytic cleavages of H2O2 into .OH, but Fe/Fe3C nanoparticles (Fe0 as the main component) with more electrons are prone to the undesired O2 generation. With a catalyst benefiting from finely tuned active sites, 18 % conversion rate for the selective oxidation of methane was achieved with about 96 % selectivity for liquid oxygenates (formic acid selectivity over 90 %). Importantly, O2 generation was suppressed 68 %. This work provides guidance for the efficient utilization of H2O2 in the chemical industry.