光催化甲烷氧化偶联：反应机理和光催化剂设计及性能

裴欣雅; 宋辉; 杨江峰

doi:10.12434/j.issn.2097-2547.20260128

您当前的位置：

首页 >

文章列表页 >

光催化甲烷氧化偶联：反应机理和光催化剂设计及性能

更新时间：2026-06-11

- 光催化甲烷氧化偶联：反应机理和光催化剂设计及性能
- Photocatalytic oxidative coupling of methane: Reaction mechanisms and design and performances of photocatalysts
- 低碳化学与化工 2026: 1-10.
- 作者机构：
  
  1.天津大学材料科学与工程学院，天津 300072
  2.太原理工大学化学与化工学院，山西太原 030024
- 作者简介：
  
  裴欣雅（1998—），博士研究生，研究方向为光催化小分子转化，E-mail：peixinya@tju.edu.cn。
  宋辉（1988—），博士，副教授，研究方向为光催化甲烷转化，E-mail：hui.song@tju.edu.cn；
  杨江峰（1982—），博士，教授，研究方向为废弃甲烷资源化利用，E-mail：yangjiangfeng@tyut.edu.cn。
- 基金信息：
  
  国家自然科学基金(U25A20624;U23A20139;22372118);中国石油科技创新基金(2024DQ02-0214)
- DOI：10.12434/j.issn.2097-2547.20260128
  中图分类号： TQ032;O643.32
- 收稿：2026-03-18，
  
  修回：2026-04-02，
  
  网络首发：2026-06-08，
- 稿件说明：
移动端阅览
裴欣雅,宋辉,杨江峰.光催化甲烷氧化偶联：反应机理和光催化剂设计及性能[J].低碳化学与化工,

PEI Xinya,SONG Hui,YANG Jiangfeng.Photocatalytic oxidative coupling of methane: Reaction mechanisms and design and performances of photocatalysts[J].Low-Carbon Chemistry and Chemical Engineering,
裴欣雅,宋辉,杨江峰.光催化甲烷氧化偶联：反应机理和光催化剂设计及性能[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20260128.

PEI Xinya,SONG Hui,YANG Jiangfeng.Photocatalytic oxidative coupling of methane: Reaction mechanisms and design and performances of photocatalysts[J].Low-Carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20260128.

摘要

甲烷氧化偶联（OCM）反应实现了由最简单的烷烃直接构建C—C键生成C

烃类化合物，是甲烷高值化利用的理想路径之一。光催化反应以太阳能为驱动力，条件温和且绿色环保，为甲烷选择性活化提供了新思路。光照下，光生载流子在半导体表面生成并分离，通过界面迁移与表面反应构建特定氧化还原环境，驱动目标活性物种生成，实现C—H键定向活化与氧化程度精细调控。光生空穴与活性氧自由基协同作用，使得在传统热催化下难以实现的甲烷高选择性转化成为可能。系统梳理了当前光催化OCM反应的研究进展，重点分析了C—H键活化机理、自由基偶联路径，提出了原位表征、同位素标记和密度泛函理论计算相结合的机理研究方法，分析了本征半导体催化剂、负载型或助催化剂改性催化剂以及基于缺陷工程调控的催化剂催化性能，以期为提升目标产物产率与选择性、实现太阳能驱动甲烷高效转化提供理论依据与设计思路。

Abstract

The oxidative coupling of methane (OCM) reaction enables the direct construction of C—C bonds from the simplest alkane to produce C

hydrocarbons

representing an ideal pathway for the high-value utilization of methane. Photocatalytic reactions

driven by solar energy

provide a new approach for the selective activation of methane with mild and environment

ally friendly conditions. Under light irradiation

photogenerated charge carriers are generated and separated on the semiconductor surface. Through interfacial migration and surface reactions

a specific redox environment is established to drive the generation of target activation species

achieving directional activation of C—H bonds and precise control of oxidation degree. The synergistic effect of photogenerated holes and reactive oxygen species makes it possible to achieve highly selective conversion of methane

which is difficult to achieve under traditional thermal catalysis. Recent research progresses on photocatalytic OCM reaction were systematically summarized

with a focus on analyzing the activation mechanisms of C—H bonds and radical coupling pathways. A mechanism research method combining in-situ characterization

isotope labeling and density functional theory calculation was proposed

and the catalytic performances of intrinsic semiconductor catalysts

supported or co-catalyst modified catalysts

and catalysts based on defect engineering regulation were analyzed

in order to provide a theoretical basis and design strategies for improving yield and selectivity of target products and achieving high-efficiency methane conversion driven by solar energy.

关键词

Keywords

references

赖利娜 , 鲍蕴心 , 王一鸣 , 等 . 碳中和背景下甲烷高值转化路径分析 [J ] . 高等学校化学学报 , 2025 , 46 ( 9 ): 29 - 45 .

LAI L N , BAO Y X , WANG Y M , et al . Analysis of high value methane conversion pathways in the context of carbon neutrality [J ] . Chemical Journal of Chinese Universities , 2025 , 46 ( 9 ): 29 - 45 .

GUNSALUS N J , KOPPAKA A , PARK S H , et al . Homogeneous functionalization of methane [J ] . Chemical Reviews , 2017 , 117 ( 13 ): 8521 - 8573 .

KERR R A . Natural gas from shale bursts onto the scene [J ] . Science , 2010 , 328 ( 5986 ): 1624 - 1626 .

SCHWACH P , PAN X L , BAO X H . Direct conversion of methane to value-added chemicals over heterogeneous catalysts: Challenges and prospects [J ] . Chemical Reviews , 2017 , 117 ( 13 ): 8497 - 8520 .

TANG Y , LI Y T , TAO F . Activation and catalytic transformation of methane under mild conditions [J ] . Chemical Society Reviews , 2022 , 51 ( 1 ): 376 - 423 .

BUELENS L C , GALVITA V V , POELMAN H , et al . Super-dry reforming of methane intensifies CO 2 utilization via Le Chatelier’s principle [J ] . Science , 2016 , 354 ( 6311 ): 449 - 452 .

CHEN Y P , WEI J T , DUYAR M S , et al . Carbon-based catalysts for Fischer-Tropsch synthesis [J ] . Chemical Society Reviews , 2021 , 50 ( 4 ): 2337 - 2366 .

李振华 , 施润 , 赵家琦 , 等 . 光驱动C1转换到高附加值化学品的研究进展 [J ] . 高等学校化学学报 , 2020 , 41 ( 4 ): 604 - 615 .

LI Z H , SHI R , ZHAO J Q , et al . Research progress of photo-driven C1 conversion to value-added chemicals [J ] . Chemical Journal of Chinese Universities , 2020 , 41 ( 4 ): 604 - 615 .

LI Y F , LI Z W , WANG N , et al . Strong activity-based volcano-type relationship for dry reforming of methane through modulating Ni-CeO 2 interaction over Ni/CeO 2 -SiO 2 catalysts [J ] . Chem Catalysis , 2025 , 5 ( 2 ): 101189 .

LI W X , SUN J K , WANG M D , et al . Contact-electro-catalysis for direct oxidation of methane under ambient conditions [J ] . Angewandte Chemie International Edition , 2024 , 63 ( 20 ): e202403114 .

许振民 , 卞振锋 . 光催化甲烷转化研究进展 [J ] . 物理化学学报 , 2020 , 36 ( 3 ): 1907013 .

XU Z M , BIAN Z F . Photocatalytic methane conversion [J ] . Acta Physico Chimica Sinica , 2020 , 36 ( 3 ): 1907013 .

SONG H , YE J H . Direct photocatalytic conversion of methane to value-added chemicals [J ] . Trends in Chemistry , 2022 , 4 ( 12 ): 1094 - 1105 .

CHEN Y P , MU X L , LUO X , et al . Catalytic conversion of methane at low temperatures: A critical review [J ] . Energy Technology , 2019 , 8 ( 8 ): 1900750 .

SONG H , MENG X G , WANG S Y , et al . Direct and selective photocatalytic oxidation of CH 4 to oxygenates with O 2 on cocatalysts/ZnO at room temperature in water [J ] . Journal of the American Chemical Society , 2019 , 141 ( 51 ): 20507 - 20515 .

LI X Y , WANG C , YANG J L , et al . PdCu nanoalloy decorated photocatalysts for efficient and selective oxidative coupling of methane in flow reactors [J ] . Nature Communications , 2023 , 14 ( 1 ): 6343 .

WANG C , LI X Y , REN Y F , et al . Synergy of Ag and AgBr in a pressurized flow reactor for selective photocatalytic oxidative coupling of methane [J ] . ACS Catalysis , 2023 , 13 ( 6 ): 3768 - 3774 .

LI N X , JIANG R M , LI Y , et al . Plasma-assisted photocatalysis of CH 4 and CO 2 into ethylene [J ] . ACS Sustainable Chemistry & Engineering , 2019 , 7 ( 13 ): 11455 - 11463 .

WANG P , SHI R , ZHAO J Q , et al . Photodriven methane conversion on transition metal oxide catalyst: Recent progress and prospects [J ] . Advanced Science , 2023 , 11 ( 8 ): 2305471 .

ZHENG K , WU Y , HU Z X , et al . Selective CH 4 partial photooxidation by positively charged metal clusters anchored on carbon aerogel under mild conditions [J ] . Nano Letters , 2021 , 21 ( 24 ): 10368 - 10376 .

ZHANG J Y , FENG X Y , LI L , et al . Selective photocatalytic oxidative coupling of methane via directional activation of oxygen over Au-loaded ZnSn-LDH with defect structure [J ] . Applied Catalysis B: Environment and Energy , 2025 , 361 : 124670 .

YANG J L , XIONG L Q , WANG C , et al . Selective synthesis of ethane from methane by a photocatalytic chemical cycle process [J ] . Advanced Energy Materials , 2024 , 15 ( 9 ): 2404202 .

ZHENG K , WU M Y , ZHU J C , et al . Breaking the activity-selectivity trade-off for CH 4 -to-C 2 H 6 photoconversion [J ] . Journal of the American Chemical Society , 2024 , 146 ( 17 ): 12233 - 12242 .

ZOU S H , LI Z N , ZHOU Q Y , et al . Surface coupling of methyl radicals for efficient low-temperature oxidative coupling of methane [J ] . Chinese Journal of Catalysis , 2021 , 42 ( 7 ): 1117 - 1125 .

WANG Y F , QI M Y , CONTE M , et al . Bimetallic single atom/nanoparticle ensemble for efficient photochemical cascade synthesis of ethylene from methane [J ] . Angewandte Chemie International Edition , 2024 , 63 ( 34 ): e202407791 .

JIANG W B , LOW J X , MAO K K , et al . Pd-modified ZnO-Au enabling alkoxy intermediates formation and dehydrogenation for photocatalytic conversion of methane to ethylene [J ] . Journal of the American Chemical Society , 2021 , 143 ( 1 ): 269 - 278 .

SONG H , MENG X G , WANG S Y , et al . Selective photo-oxidation of methane to methanol with oxygen over dual-cocatalyst-modified titanium dioxide [J ] . ACS Catalysis , 2020 , 10 ( 23 ): 14318 - 14326 .

HAO Y D , MAO F , ZHAO Y H , et al . Selective oxidation of CH 4 to valuable HCHO over a defective rTiO 2 /GO metal-free photocatalyst [J ] . Catalysis Science & Technology , 2022 , 12 ( 19 ): 5869 - 5878 .

ZHAI G Y , YANG S Y , CHEN Y H , et al . Direct photocatalytic oxidation of methane to formic acid with high selectivity via a concerted proton-electron transfer process [J ] . Journal of the American Chemical Society , 2025 , 147 ( 3 ): 2444 - 2454 .

WANG P , SHI R , ZHAO Y X , et al . Selective photocatalytic oxidative coupling of methane via regulating methyl intermediates over metal/ZnO nanoparticles [J ] . Angewandte Chemie International Edition , 2023 , 62 ( 23 ): e202304301 .

LI X Y , LI C , XU Y X , et al . Efficient hole abstraction for highly selective oxidative coupling of methane by Au-sputtered TiO 2 photocatalysts [J ] . Nature Energy , 2023 , 8 ( 9 ): 1013 - 1022 .

SONG H , SUN K , HUANG H M , et al . Integrating photochemical and photothermal effects for selective oxidative coupling of methane into C 2+ hydrocarbons with multiple active sites [J ] . Nature Communications , 2025 , 16 ( 1 ): 2831 .

PEI X Y , SUN K , HUANG H M , et al . Solar-driven C—N coupling over Pd/TiO 2 enables high-yield synthesis of methylamine hydrochlorides from methanol and ammonium chloride [J ] . Journal of the American Chemical Society , 2025 , 147 ( 49 ): 44962 - 44971 .

SUN X L , LIU G H , SHEN T Y , et al . Directional activation of oxygen by the Au-loaded ZnAl-LDH with defect structure for highly efficient photocatalytic oxidative coupling of methane [J ] . Small , 2024 , 20 ( 28 ): 2310857 .

CHEN Y H , ZHAO Y , LIU D , et al . Continuous flow system for highly efficient and durable photocatalytic oxidative coupling of methane [J ] . Journal of the American Chemical Society , 2024 , 146 ( 4 ): 2465 - 2473 .

WU P P , CHU Y Y , WANG M L , et al . Subnanometric MoO x clusters limit overoxidation during photocatalytic CH 4 conversion to oxygenates over TiO 2 [J ] . Nature Communications , 2025 , 16 ( 1 ): 4207 .

YOU J K , ZHANG Y Z , WANG Z L , et al . Tuning reaction pathway with surface metal cocatalyst for ethylene production via photocatalytic methane conversion [J ] . Journal of the American Chemical Society , 2025 , 147 ( 47 ): 44011 - 44020 .

LI X Y , XIE J J , RAO H , et al . Platinum- and CuO x -decorated TiO 2 photocatalyst for oxidative coupling of methane to C 2 hydrocarbons in a flow reactor [J ] . Angewandte Chemie International Edition , 2020 , 59 ( 44 ): 19702 - 19707 .

SONG S , SONG H , LI L M , et al . A selective Au-ZnO/TiO 2 hybrid photocatalyst for oxidative coupling of methane to ethane with dioxygen [J ] . Nature Catalysis , 2021 , 4 ( 12 ): 1032 - 1042 .

BAI S , ZHANG N , GAO C , et al . Defect engineering in photocatalytic materials [J ] . Nano Energy , 2018 , 53 : 296 - 336 .

FANG Z L , BUEKEN B , DE VOS D E , et al . Defect-engineered metal-organic frameworks [J ] . Angewandte Chemie International Edition , 2015 , 54 ( 25 ): 7234 - 7254 .

PEI X Y , BIAN J W , ZHANG W , et al . Overcoming defect limitations in photocatalysis: Boron-incorporation engineered crystalline red phosphorus for enhanced hydrogen production [J ] . Advanced Functional Materials , 2024 , 34 ( 29 ): 2400542 .

WANG W C , BAI X Q , CI Q , et al . Near-field drives long-lived shallow trapping of polymeric C 3 N 4 for efficient photocatalytic hydrogen evolution [J ] . Advanced Functional Materials , 2021 , 31 ( 35 ): 2103978 .

ZHANG J J , ZHANG J H , SHEN J N , et al . Regulation of oxygen activation pathways to optimize photocatalytic methane oxidative coupling selectivity [J ] . ACS Catalysis , 2024 , 14 ( 6 ): 3855 - 3866 .

XU F Y , ZHENG L X , ZHANG J J , et al . Co 3 O 4 as full-solar-spectrum photocatalyst for selective methane conversion through reactive oxygen species control [J ] . Nature Catalysis , 2026 , 9 ( 1 ): 73 - 86 .

NIE W F , CHEN L W , HAO Y C , et al . Photocatalytic oxidative coupling of methane to C 3+ hydrocarbons via nanopore-confined microenvironments [J ] . Nature Energy , 2025 , 10 ( 9 ): 1095 - 1106 .

SUN M Y , CHEN Y J , FAN X Q , et al . Electronic asymmetry of lattice oxygen sites in ZnO promotes the photocatalytic oxidative coupling of methane [J ] . Nature Communications , 2024 , 15 : 9900 .

FEI M C , WILLIAMS B , WANG L Z , et al . Highly selective photocatalytic methane coupling by Au-modified Bi 2 WO 6 [J ] . ACS Catalysis , 2024 , 14 ( 3 ): 1855 - 1861 .

ZHAI G Y , CAI L J , MA J , et al . Highly efficient, selective, and stable photocatalytic methane coupling to ethane enabled by lattice oxygen looping [J ] . Science Advances , 10 ( 26 ): eado4390 .

浏览量

下载量

CNKI被引量

文章被引用时，请邮件提醒。

提交

工具集

关联资源

光热催化甲烷低碳转化技术进展

DBD等离子体辅助甲烷无氧偶联技术研究进展

无模板剂合成束状多级孔ZSM-5分子筛及其催化剂的甲烷无氧芳构化反应性能研究

天然气脱汞机理与技术发展现状

减压蒸馏法回收变质胺液及CO2捕集性能研究