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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- 低碳化学与化工 2026, 51(3): 1-11.
- 作者机构：
1.四川大学 化学工程学院，四川 成都 610207
2.西南化工研究设计院有限公司，四川 成都 610225
- 作者简介：
贺嘉熙（2000—），硕士研究生，研究方向为制药工程，E-mail：13975035275@163.com。
欧阳李科（1987—），博士，副教授，研究方向为绿色化工、能源与环境领域催化反应工程，E-mail：like.ouyang@scu.edu.cn。
- 基金信息：国家自然科学基金青年基金(22008158);四川省区域创新合作项目(2023YFQ0086)
DOI：10.12434/j.issn.2097-2547.20250191
中图分类号： TQ426收稿：2025-04-21，
修回：2025-05-13，
纸质出版：2026-03-25
- 稿件说明：
移动端阅览
贺嘉熙,高嘉诚,苏敏等.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.
HE Jiaxi,GAO Jiacheng,SU Min,et al.Preparation of ε-Keggin type zeolitic octahedral metal oxides and their catalytic performances for selective methane oxidation to methanol under mild conditions[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(3):1-11.
贺嘉熙,高嘉诚,苏敏等.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. DOI： 10.12434/j.issn.2097-2547.20250191.
HE Jiaxi,GAO Jiacheng,SU Min,et al.Preparation of ε-Keggin type zeolitic octahedral metal oxides and their catalytic performances for selective methane oxidation to methanol under mild conditions[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(3):1-11. DOI： 10.12434/j.issn.2097-2547.20250191.
摘要
在温和条件下进行C—H键的活化与选择性氧化是化学学术界和工业界的挑战。单原子催化剂凭借其高原子利用率、表面金属的低配位环境等优势成为催化领域的研究热点。
ε
-Keggin型类沸石金属氧化物（ZOMOs）是由多金属氧酸盐骨架和过渡金属有序组装而成的新型无机多孔材料，其结构可以提供大量的单原子过渡金属位点，因此
ε
-Keggin-ZOMOs材料是一种理想的用于甲烷（CH
4
）氧化制甲醇（CH
3
OH）的催化剂。通过改变钼源和过渡金属源，采用水热法合成了10种不同的
ε
-Keggin-ZOMOs材料，通过SEM、TEM和XRD等表征技术对材料的几何和电子结构进行了全面的分析，测试了在温和条件下，不同
ε
-Keggin-ZOMOs材料在H
2
和O
2
氛围中CH
4
选择性氧化制CH
3
OH催化性能并探究了相应的构效关系。结果表明，合成的
ε
-Keggin-ZOMOs材料的形貌和晶体结构具有高度相似性，但完全不同于原始氧化物，是一种全新的结构。Mo—O骨架构成了材料中稳定的框架结构，但煅烧温度在200 ℃以上时，材料的框架结构开始发生渐进式破坏，400 ℃时完全坍塌。NH
4
-MM材料表现出最佳催化性能，CH
3
OH时空产率达到2.65 mmol/(g·h)，且CH
3
OH选择性高达93.9%（70 ℃、3 MPa和0.5 h）。过渡金属3d轨道电子云密度分布的对称性以及原子半径是影响
ε
-Keggin-ZOMOs材料催化性能的关键因素。
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 (CH
4
) oxidation to methanol (CH
3
OH). By var
ying 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 CH
4
oxidation to CH
3
OH in H
2
and O
2
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 ℃. NH
4
-MM material demonstrates the best catalytic performance
with the CH
3
OH space-time yield of 2.65 mmol/(g·h) and the CH
3
OH 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
Keywords
references
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