原位合成双氧水用于甲烷高选择性氧化制甲醇

doi:10.1016/S1872-2067(26)65141-8

催化学报 ›› 2026, Vol. 88: 347-355.DOI: 10.1016/S1872-2067(26)65141-8

原位合成双氧水用于甲烷高选择性氧化制甲醇

王松玲^a^,^b^,^c^,^*(), 黄安华^b, 尹风星^a, 卢瑞祥^a, 刘文刚^d^,^*(), 张云^a^,^*(), 乔波涛^e^,^*()

^a 中国科学院福建物质结构研究所, 结构化学国家重点实验室, 福建福州 350002
^b 上海交通大学深圳研究所, 广东深圳 518057
^c 新加坡国立大学苏州研究院, 江苏苏州 215123
^d 青岛科技大学材料科学与工程学院, 山东青岛 266042
^e 中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连 116023

收稿日期:2025-09-09 接受日期:2026-05-11 出版日期:2026-09-18 发布日期:2026-09-05
通讯作者: *电子信箱: xmwangsl@fjirsm.ac.cn (王松玲),
liuwengang@qust.edu.cn (刘文刚),
zhangy@fjirsm.ac.cn (张云),
bqiao@dicp.ac.cn (乔波涛).
基金资助:
深圳科技项目(JCYJ20230807152559002);上海自然科学基金(23ZR1469300);福建省自然科学基金(2026J011454)

In-situ synthesis of hydrogen peroxide for highly selective oxidation of methane to methanol over noble-metal-free catalyst

Songling Wang^a^,^b^,^c^,^*(), Anhua Huang^b, Fengxing Yin^a, Ruixiang Lu^a, Wengang Liu^d^,^*(), Yun Zhang^a^,^*(), Botao Qiao^e^,^*()

^a State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, China
^b Shenzhen Research Institute of Shanghai Jiao Tong University, Shenzhen 518057, Guangdong, China
^c Suzhou Research Institute, National University of Singapore, Suzhou 215123, Jiangsu, China
^d College of Material Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, Shandong, China
^e State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2025-09-09 Accepted:2026-05-11 Online:2026-09-18 Published:2026-09-05
Supported by:
The Shenzhen Science and Technology Program(JCYJ20230807152559002);The Natural Science Foundation of Shanghai(23ZR1469300);The Natural Science Foundation of Fujian Province(2026J011454)

摘要/Abstract

摘要：

甲烷在高效、温和条件下选择性氧化为甲醇是催化领域的“圣杯”反应之一. 传统方法依赖高成本、高风险的H₂O₂作为氧化剂提供羟基自由基(•OH), 但其储存、运输及使用过程中的安全问题限制了实际应用. 光催化原位合成H₂O₂耦合甲烷氧化为甲醇, 是实现可持续、低能耗C1化学的理想路径, 但当前面临H₂O₂光合成效率低、可见光响应差、需添加牺牲剂等挑战. 因此, 开发可见光驱动、无牺牲剂的低成本非贵金属催化体系实现原位H₂O₂合成, 对实现甲烷高选择性氧化为甲醇具有重要科学意义和应用价值.
本文设计了一种氨基修饰的锆基金属有机框架(UiO-66(Zr)-NH₂, 简称U-NH₂)作为非贵金属光催化剂. 利用氨基调控电子结构, 增强可见光吸收和载流子分离, 在纯水、无牺牲剂的可见光条件下实现高效原位光合成H₂O₂, 产率达189 μmol g^-1. 原位生成的H₂O₂无需额外添加, 即可直接用于甲烷氧化. 在Fe²⁺存在下, U-NH₂催化甲烷氧化为甲醇的选择性接近100%, 甲醇产率高达412 mL·g_cat^-1, 优于已报道的贵金属基催化剂及外加H₂O₂体系. 经过5次循环, 催化剂活性无明显下降, 结构保持稳定. 机理研究表明, 在可见光激发下的U-NH₂可以产生光生电子和空穴, 电子还原O₂经两电子过程生成H₂O₂; 同时, Fe^II与H₂O₂发生芬顿反应产生大量•OH, 与光生空穴共同活化CH₄生成•CH₃, 最终•CH₃与•OH结合生成甲醇. 分子动力学模拟进一步揭示, 氨基官能团使O₂优先富集于U-NH₂的Zr活性位点周围, 形成局部高浓度O₂区, 显著促进了H₂O₂的原位合成. 相比直接外加H₂O₂, 原位合成的H₂O₂氧化甲烷生成甲醇的产率高出近3倍, 证明原位策略具有独特优势.
综上, 本工作为可见光驱动、非贵金属催化甲烷直接转化为甲醇提供了一条绿色、高效的路径, 展示了MOF材料在精确调控活性微环境及原位生成氧化剂方面的巨大潜力. 未来可进一步拓展其它功能化MOF或共价有机框架材料, 优化光生电荷动力学和O₂富集能力, 推动室温甲烷低成本、高效率转化技术的进步.

关键词: 甲烷, 甲醇, 选择性, 氧化, 过氧化氢

Abstract:

Hydroxyl radicals (•OH) are crucial in the photocatalytic oxidation of methane (CH₄) to methanol (CH₃OH) at room temperature. Hydrogen peroxide (H₂O₂) is generally employed to drive CH₄ oxidation by providing •OH radicals; however, its practice use is often limited by high cost and handling challenges. Here we report a Zr-based metal-organic framework material modified by amino groups (U-NH₂), which severs as a noble-metal-free catalyst enabling visible light absorption and electron density redistribution. The U-NH₂ catalyst performs outstanding in-situ photosynthesis of H₂O₂ with O₂ under visible light in a sacrificial-agent-free system, achieving an H₂O₂ yield up to 189 µmol g^-1. Molecular dynamics simulations reveal that O₂ preferentially accumulates near the amino-functionalized pores of U-NH₂, creating localized O₂-enriched microenvironments that are critical for efficient H₂O₂ synthesis. The in situ synthesized H₂O₂ promotes the generation of •OH radicals, driving CH₄ oxidation to CH₃OH. Remarkably, highly selective generation of CH₃OH is achieved with a selectivity of near 100% and a yield of up to 412 mL g_cat^-1 per concentration of H₂O₂. Our finding opens up an appealing avenue for efficient solar energy activation of CH₄ to generate CH₃OH at ambient temperatures.

Key words: Methane, Methanol, Selectivity, Oxidation, Hydrogen peroxide

王松玲, 黄安华, 尹风星, 卢瑞祥, 刘文刚, 张云, 乔波涛. 原位合成双氧水用于甲烷高选择性氧化制甲醇[J]. 催化学报, 2026, 88: 347-355.

Songling Wang, Anhua Huang, Fengxing Yin, Ruixiang Lu, Wengang Liu, Yun Zhang, Botao Qiao. In-situ synthesis of hydrogen peroxide for highly selective oxidation of methane to methanol over noble-metal-free catalyst[J]. Chinese Journal of Catalysis, 2026, 88: 347-355.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65141-8

https://www.cjcatal.com/CN/Y2026/V88/I9/347

图/表 7

Fig. 1. Schematic reaction processes of in-situ synthesis of H2O2 and conversion of methane to methanol with solar light.

Fig. 2. Structural characterizations of U, U-NO2, and U-NH2 materials. (a) Schematic synthesis. (b) XRD patterns. (c) FTIR spectra. High-resolution XPS spectra of N 1s (d) and C 1s (e).

Fig. 3. Optical properties and electronic band structure of U, U-NO2, and U-NH2 materials. (a) UV-Vis DRS absorbance spectra. (b) Plots obtained using the Kubelka-Munk function transformation for the calculated absorbance versus the photon energy. (c) Mott-Schottky plots examined by a three-electrodes system without light irradiation. (d) Band energy diagram and redox potentials of O2/H2O2 and H2O2/H2O.

Fig. 4. Characterizations and photocatalytic activity under visible light irradiation of U, U-NO2, and U-NH2 materials. (a) Photocurrent detection. (b) EIS. (c) Generation yield of H2O2 with reaction time. (d) Photo-oxidative performance of CH4. (e) Stability test of photo-oxidative activity of methane to methanol product over U-NH2 catalyst. (f) EPR spectra of active species formed during the methane oxidation in 1 h.

Table 1 Comparison of catalytic activity of methane to methanol under visible light irradiation (λ ≥ 420 nm) with different oxidants external added. Note that PMS is an oxidant potassium persulfate.

Catalyst	Oxidants	Products (μmol g_cat.^-1)			Yield of CH₃OH per C_H2O2 (mL g_cat^-1)	Selectivity of CH₃OH (%)	Ref.
Catalyst	Oxidants	CH₃OH	HCHO	CO₂	Yield of CH₃OH per C_H2O2 (mL g_cat^-1)	Selectivity of CH₃OH (%)	Ref.
Pd₁/TiO₂	H₂O₂ (adding 100 mmol L^-1)	175	10	0	1.8	94	[14]
Au/WO₃	H₂O₂ (adding 500 mmol L^-1)	77	10	0	0.2	89	[44]
Au/WO₃	PMS	0	5	0	—	0	[44]
Cu/PCN	N/A	24.5	0	0	—	18.8	[45]
Cu_0.029/WO₃	O₂	0	4979	166	—	0	[46]
In₂O₃	O₂	0	15.8	0	—	0	[47]
U-NH₂	H₂O₂ (in-situ formed 189 μmol L^-1)	78	0	0	412	-100	this work

Fig. 5. Molecular dynamics snapshots of O2 molecules in U (a) and U-NH2 (b) unit cells over time. Red regions indicate the O2 molecule density field, and blue regions indicate the Zr atom density field in 3D isosurfaces.

Scheme 2. Schematic illustration of in-situ synthesis of H2O2 and partial oxidation of methane to methanol over U-NH2.

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原位合成双氧水用于甲烷高选择性氧化制甲醇

In-situ synthesis of hydrogen peroxide for highly selective oxidation of methane to methanol over noble-metal-free catalyst

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