调控电荷动力学与表面反应性用于Au/Ti-CeO<sub>2</sub>光催化甲烷选择性氧化制乙烷

引用本文: 徐新宇, 陆迦勒, 苏波, 陈佳义, 陈雄, 汪思波. 调控电荷动力学与表面反应性用于Au/Ti-CeO₂光催化甲烷选择性氧化制乙烷[J]. 物理化学学报, 2025, 41(11): 100153. doi: 10.1016/j.actphy.2025.100153 shu

Citation: Xinyu Xu, Jiale Lu, Bo Su, Jiayi Chen, Xiong Chen, Sibo Wang. Steering charge dynamics and surface reactivity for photocatalytic selective methane oxidation to ethane over Au/Ti-CeO₂[J]. Acta Physico-Chimica Sinica, 2025, 41(11): 100153. doi: 10.1016/j.actphy.2025.100153 shu

调控电荷动力学与表面反应性用于Au/Ti-CeO₂光催化甲烷选择性氧化制乙烷

徐新宇 ^{1, 2,} ,
陆迦勒 ^{1, 2,} ,
苏波 ^{1, 2,} ,
陈佳义 ^{1, 2,
,} ,
陈雄 ^{1, 2,
,} ,
汪思波 ^{1, 2,
,}

1.
福州大学化学学院, 核生化防护化学全国重点实验室, 福建福州 350116
2.
福州大学化学学院, 能源与环境光催化国家重点实验室, 福建福州 350116

通讯作者: 陈佳义, jiayi9236@fzu.edu.cn; 陈雄, chenxiong987@fzu.edu.cn; 汪思波, sibowang@fzu.edu.cn

基金项目:
国家自然科学基金 2237203

国家自然科学基金 22302039

111计划 D16008

摘要: 温和条件下甲烷选择性氧化制备高附加值化学品是一条可持续但极具挑战的路径，其瓶颈在于CH₄活化能垒高且易发生过度氧化。本研究通过Ti掺杂与Au负载的协同策略，构建了高效Au/Ti-CeO₂光催化剂用于甲烷氧化偶联制乙烷。优化后的催化剂在20次循环反应中保持稳定，C₂H₆产率达2971.4 μmol·g⁻¹·h⁻¹，C₂₊选择性达85.1%。原位X射线光电子能谱、电子顺磁共振和漫反射红外傅里叶变换光谱分析表明：Ti掺杂向CeO₂中引入杂质能级，通过内建电场促进电子定向迁移至表面金纳米颗粒(Au NPs)；Au NPs作为电子富集位点可活化O₂、促进*CH₃自由基偶联为C₂H₆并稳定活性中间体，从而增强电荷分离并抑制中间体过度氧化。该研究揭示了元素掺杂与助催化剂协同调控电荷动力学和表面反应活性对实现高效光催化甲烷转化的重要作用。

关键词:

English

Steering charge dynamics and surface reactivity for photocatalytic selective methane oxidation to ethane over Au/Ti-CeO₂

Xinyu Xu ^{1, 2,} ,
Jiale Lu ^{1, 2,} ,
Bo Su ^{1, 2,} ,
Jiayi Chen ^{1, 2,
,} ,
Xiong Chen ^{1, 2,
,} ,
Sibo Wang ^{1, 2,
,}

1.
State Key Laboratory of Chemistry for NBC Hazards Protection, College of Chemistry, Fuzhou University, Fuzhou 350116, Fujian Province, China
2.
State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350116, Fujian Province, China

Corresponding author: Email: jiayi9236@fzu.edu.cn (J.C.); Email: chenxiong987@fzu.edu.cn (X.C.); Email: sibowang@fzu.edu.cn (S.W.)

Received Date: 19 July 2025
Accepted Date: 06 August 2025
Revised Date: 04 August 2025
Available Online: 15 November 2025
Fund Project:
the financial support from the National Natural Science Foundation of China

the financial support from the National Natural Science Foundation of China

the 111 Proiect

Abstract: The selective oxidation of methane to value-added chemicals under mild conditions presents a sustainable yet challenging route, hindered by sluggish CH₄ activation and overoxidation. Herein, we report a delicate strategy combining Ti doping and Au loading to construct a high-performance Au/Ti−CeO₂ photocatalyst for ethane production from oxidative methane coupling. The optimized catalyst achieves a C₂H₆ production rate of 2971.4 μmol·g⁻¹·h⁻¹ with 85.1% C₂₊ selectivity, stably operating over 20 reaction cycles. In situ X-ray photoelectron spectroscopy, electron paramagnetic resonance, and diffuse reflectance infrared Fourier transform spectroscopy analyses reveal that Ti doping introduces impurity energy levels into CeO₂, promoting directional electron migration to surface Au nanoparticles (NPs) via a built-in electric field. The Au NPs act as electron accumulation sites to activate O₂, facilitate *CH₃ radical coupling into C₂H₆, and stabilize reactive intermediates, thus enhancing charge separation and suppressing intermediate overoxidation. This study highlights the significance of synergistic modulation via elemental doping and cocatalyst engineering in tuning charge dynamics and surface reactivity for efficient photocatalytic methane conversion.

Key words:

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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

调控电荷动力学与表面反应性用于Au/Ti-CeO₂光催化甲烷选择性氧化制乙烷

通讯作者: 陈佳义, jiayi9236@fzu.edu.cn; 陈雄, chenxiong987@fzu.edu.cn; 汪思波, sibowang@fzu.edu.cn

English

Steering charge dynamics and surface reactivity for photocatalytic selective methane oxidation to ethane over Au/Ti-CeO₂

Corresponding author: Email: jiayi9236@fzu.edu.cn (J.C.); Email: chenxiong987@fzu.edu.cn (X.C.); Email: sibowang@fzu.edu.cn (S.W.)

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调控电荷动力学与表面反应性用于Au/Ti-CeO2光催化甲烷选择性氧化制乙烷

通讯作者: 陈佳义, jiayi9236@fzu.edu.cn; 陈雄, chenxiong987@fzu.edu.cn; 汪思波, sibowang@fzu.edu.cn

English

Steering charge dynamics and surface reactivity for photocatalytic selective methane oxidation to ethane over Au/Ti-CeO2

Corresponding author: Email: jiayi9236@fzu.edu.cn (J.C.); Email: chenxiong987@fzu.edu.cn (X.C.); Email: sibowang@fzu.edu.cn (S.W.)

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

调控电荷动力学与表面反应性用于Au/Ti-CeO₂光催化甲烷选择性氧化制乙烷

Steering charge dynamics and surface reactivity for photocatalytic selective methane oxidation to ethane over Au/Ti-CeO₂

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs