低碳化学与化工2026，Vol.51Issue(3)：1-11,77,12.DOI:10.12434/j.issn.2097-2547.20250191
ε-Keggin型类沸石八面体金属氧化物制备及其温和条件下甲烷选择性氧化制甲醇催化性能研究
Preparation of ε-Keggin type zeolitic octahedral metal oxides and their catalytic performances for selective methane oxidation to methanol under mild conditions
摘要
Abstract
The activation and selective oxidation of C—H bonds under mild conditions are challenges in both academic and industrial chemistry.Single-atom catalysts have become a research hotspot in the field of catalysis due to their high atomic utilization efficiency and low-coordination environments of surface metals.ε-Keggin type zeolitic octahedral metal oxides(ZOMOs)are novel inorganic porous materials formed by the ordered assembly of polyoxometalate frameworks and transition metals.This structure can provide a large number of single-atom transition metal sites,making ε-Keggin-ZOMOs ideal catalytic materials for methane(CH4)oxidation to methanol(CH3OH).By varying molybdenum sources and transition metal sources,ten different ε-Keggin-ZOMOs materials were synthesized by hydrothermal method.The geometric and electronic structures of the materials were comprehensively analyzed by characterization techniques such as SEM,TEM and XRD.The catalytic performances of different ε-Keggin-ZOMOs materials for selective CH4 oxidation to CH3OH in H2 and O2 atmospheres under mild conditions were tested,and corresponding structure-activity relationships were studied.The results show that the morphologies and crystal structures of synthesized ε-Keggin-ZOMOs materials are highly similar,but completely different from the original oxides,and ε-Keggin-ZOMOs materials have a completely new structure.The Mo—O framework constitutes a stable skeleton of the material,but the framework structure begins to undergo progressive destruction when the calcination temperature exceeds 200℃and completely collapses at 400℃.NH4-MM material demonstrates the best catalytic performance,with the CH3OH space-time yield of 2.65 mmol/(g·h)and the CH3OH selectivity of 93.9%(70℃,3 MPa and 0.5 h).The symmetry of the electron clouds density distribution in the transition metal 3d orbitals and the atomic radius are key factors influencing the catalytic performances of ε-Keggin-ZOMOs materials.关键词
甲烷/甲醇/ε-Keggin-ZOMOs材料/选择性氧化Key words
methane/methanol/ε-Keggin-ZOMOs materials/selective oxidation分类
化学化工引用本文复制引用
贺嘉熙,高嘉诚,苏敏,袁立,杨磊,胡志彪,郑珩,欧阳李科..ε-Keggin型类沸石八面体金属氧化物制备及其温和条件下甲烷选择性氧化制甲醇催化性能研究[J].低碳化学与化工,2026,51(3):1-11,77,12.基金项目
国家自然科学基金青年基金(22008158) （22008158）
四川省区域创新合作项目(2023YFQ0086). （2023YFQ0086）
