甲烷氧化偶联反应中负载型Na2WO4催化作用再审视

doi:10.1016/S1872-2067(26)65212-6

催化学报 ›› 2027, Vol. 92: 376-386.DOI: 10.1016/S1872-2067(26)65212-6

甲烷氧化偶联反应中负载型Na₂WO₄催化作用再审视

魏赜璟^a,1, 卫锟锟^a,1, 陈旭涛^a,*, 潘洋^b, 刘成园^b, 肖丽萍^a, 施益峰^a,*, 邹世辉^c,*, 范杰^a,*

^a浙江大学化学系, 全省高值化学品低碳合成重点实验室, 浙江杭州 310027;
^b中国科学技术大学, 国家同步辐射重点实验室, 安徽合肥 230029;
^c浙江工业大学材料科学与工程学院, 浙江杭州 310014

收稿日期:2026-01-08 接受日期:2026-04-11 出版日期:2027-01-18 发布日期:2026-10-30
通讯作者: *电子信箱: jfan@zju.edu.cn (范杰), zou@zjut.edu.cn (邹世辉), 12037066@zju.edu.cn (陈旭涛), yifengshi@zju.edu.cn (施益峰).
作者简介:¹共同第一作者.
基金资助:
国家重点研发计划(2022YFA1505500), 国家自然科学基金(22572172, 92045301), 山西浙大新材料与化工研究院.

Revisiting the catalytic role of supported Na₂WO₄ for oxidative coupling of methane reaction

Zejing Wei^a,1, Kunkun Wei^a,1, Xutao Chen^a,*, Yang Pan^b, Chengyuan Liu^b, Liping Xiao^a, Yifeng Shi^a,*, Shihui Zou^c,*, Jie Fan^a,*

^aZhejiang Key Laboratory of Low-Carbon Synthesis of Value-Added Chemicals, Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang, China;
^bNational Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, Anhui, China;
^cCollege of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received:2026-01-08 Accepted:2026-04-11 Online:2027-01-18 Published:2026-10-30
Contact: *E-mail: jfan@zju.edu.cn (J. Fan), zou@zjut.edu.cn (S. Zou), 12037066@zju.edu.cn (X. Chen), yifengshi@zju.edu.cn (Y. Shi).
About author:¹ Contributed equally to this work.
Supported by:
National Key Research and Development Program of China (2022YFA1505500), the National Natural Science Foundation of China (22572172, 92045301), and the Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering.

摘要/Abstract

摘要： 甲烷作为储量丰富、成本低廉的碳基能源与化工原料, 其高值化转化对能源结构优化与化工产业升级具有重要战略意义. 甲烷氧化偶联(OCM)反应可直接将甲烷转化为乙烯、乙烷等高附加值C₂产品, 是极具潜力的甲烷转化路径. Na₂WO₄基催化剂因活性与稳定性突出, 是OCM领域最具工业化前景的催化体系之一. 然而, 传统研究多局限于低负载量(<10 wt%)体系, 仅揭示了Na–WO_x物种活化甲烷生成甲基自由基的单一功能, 对宽负载范围内Na₂WO₄的结构演化规律及构效关系认知不足, 受传统“多相-均相”反应机理约束, 现有催化剂难以突破C₂收率的固有动力学瓶颈, 严重制约了高效OCM催化剂的理性设计.
本文突破传统研究的负载量局限, 以SiO₂与ZrO₂为载体, 制备了0–50 wt%负载量的系列Na₂WO₄催化剂, 系统探究其负载量依赖的结构演化规律. 结合X-射线衍射、拉曼光谱(Raman)、高分辨透射电镜、H₂-程序升温还原、原位同步辐射真空紫外光电离质谱(SVUV-PIMS)等多维表征与OCM性能评价, 揭示了Na₂WO₄的双重催化作用. 研究结果表明, 低负载量(≤ 10 wt%)时, Na₂WO₄在载体表面形成高分散Na-WO_x物种, 具备优异的甲烷活化能力, 但随负载量升高该物种逐渐消失, 导致贫氧OCM反应条件下甲烷转化率持续降低; 高负载量(≥ 20 wt%)时, Na₂WO₄主要以高浓度亚纳米团簇形式存在, 该物种对甲烷活化呈惰性, 故贫氧条件下催化剂活性较低, 但其可高效催化甲基自由基的表面偶联, 显著提升C₂选择性. 在富氧的OCM反应条件下, 气相氧可部分活化甲烷, 此时高负载量Na₂WO₄催化剂表现出更高的C₂产率. 与高分散Na-WO_x物种和Na₂WO₄亚纳米团簇不同, 大尺寸Na₂WO₄晶体在甲烷活化和甲基自由基偶联中均无催化活性. 采用氨水洗脱实验选择性去除高负载量Na₂WO₄催化剂中的大尺寸Na₂WO₄晶体可得到纯的负载型团簇催化剂, 发现其性能与洗脱之前接近, 进一步验证了亚纳米团簇是甲基自由基表面偶联的催化活性位点. 原位SVUV-PIMS结果表明, 富含Na₂WO₄亚纳米团簇的催化剂上甲基自由基的转化效率显著提升, 产物中C₂物种信号大幅增强, 深度氧化产物CO_x的生成被有效抑制.
综上, 本文修正了传统OCM“多相-均相”反应机理, 验证了高负载量下存在的Na₂WO₄亚纳米团簇对甲基自由基的表面选择性偶联机制, 为高效OCM催化剂的设计提供了新思路. 本研究系统阐明了宽负载范围内Na₂WO₄在载体表面的存在形式演化规律, 明确了各表面物种的OCM催化功能, 为突破传统机制中C₂产率的固有动力学瓶颈提供了理论依据, 对推动甲烷氧化偶联技术的工业化进程具有重要的理论指导意义与实践价值.

关键词: 甲烷, 甲烷氧化偶联, Na₂WO₄, 团簇, 甲基自由基

Abstract: Na₂WO₄-based catalysts have shown great promise in the oxidative coupling of methane (OCM). Nevertheless, conventional studies have generally limited Na₂WO₄ loading to relatively low levels (<10 wt%), thereby revealing only the role of the Na-WOₓ species in activating methane to generate methyl radicals. Herein, we systematically investigate the loading-dependent structural evolution of Na₂WO₄ over an exceptionally wide range (0–50 wt%) and reveal a dual role for Na₂WO₄, i.e., surface Na-WO_x sites for CH₄ activation and small Na₂WO₄ clusters for heterogeneous ^•CH₃ coupling. This finding revises the traditional heterogeneous-homogeneous mechanism for OCM and fills the knowledge gap regarding the structure-dependent catalytic function of Na₂WO₄ across a broad loading range. The in-depth understanding of these structure-dependent catalytic functions of various Na₂WO₄ species will substantially contribute to the design of more efficient catalysts to break through the inherent C₂ yield limitation of conventional OCM processes.

Key words: Methane, Oxidative coupling of methane, Na₂WO_4, Cluster, ^•CH₃ radical

魏赜璟, 卫锟锟, 陈旭涛, 潘洋, 刘成园, 肖丽萍, 施益峰, 邹世辉, 范杰. 甲烷氧化偶联反应中负载型Na₂WO₄催化作用再审视[J]. 催化学报, 2027, 92: 376-386.

Zejing Wei, Kunkun Wei, Xutao Chen, Yang Pan, Chengyuan Liu, Liping Xiao, Yifeng Shi, Shihui Zou, Jie Fan. Revisiting the catalytic role of supported Na₂WO₄ for oxidative coupling of methane reaction[J]. Chinese Journal of Catalysis, 2027, 92: 376-386.

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甲烷氧化偶联反应中负载型Na₂WO₄催化作用再审视

Revisiting the catalytic role of supported Na₂WO₄ for oxidative coupling of methane reaction

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