物理化学学报 >> 2025, Vol. 41 >> Issue (11): 100153.doi: 10.1016/j.actphy.2025.100153

论文 上一篇    

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. 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
  • 收稿日期:2025-07-19 修回日期:2025-08-04 录用日期:2025-08-06 发布日期:2025-09-29
  • 通讯作者: Email: jiayi9236@fzu.edu.cn (陈佳义)chenxiong987@fzu.edu.cn (陈雄)sibowang@fzu.edu.cn (汪思波)
  • 基金资助:
    国家自然科学基金(2237203); 国家自然科学基金(22302039); 111计划(D16008)

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

Xinyu Xu1,2, Jiale Lu1,2, Bo Su1,2, Jiayi Chen1,2,*(), Xiong Chen1,2,*(), Sibo Wang1,2,*()   

  1. 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
  • Received:2025-07-19 Revised:2025-08-04 Accepted:2025-08-06 Published:2025-09-29
  • Contact: Email: jiayi9236@fzu.edu.cn (Jiayi Chen)chenxiong987@fzu.edu.cn (Xiong Chen)sibowang@fzu.edu.cn (Sibo Wang)
  • Supported by:
    the financial support from the National Natural Science Foundation of China(2237203); the financial support from the National Natural Science Foundation of China(22302039); the 111 Proiect(D16008)

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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: 光催化, 甲烷氧化, 乙烷生产, Ti掺杂, 二氧化铈, 电荷分离

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: Photocatalysis, Methane oxidation, Ethane production, Ti doping, CeO2, Charge separation