催化学报

催化学报 ›› 2026, Vol. 83: 132-142.DOI: 10.1016/S1872-2067(26)64999-6

• 论文 • 上一篇    下一篇

缺陷工程Pt/Nb2O5光催化剂实现高效羟乙基自由基介导的苯并咪唑合成与析氢协同反应

谢瑶瑶a, 谭昌龙b, 毛梁c,*(), 唐紫蓉a,d,*(), 徐艺军a,b,*()   

  1. a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
    b电子科技大学基础与前沿研究院, 四川成都 611731
    c中国矿业大学材料科学与物理学院, 江苏徐州 221116
    d电子科技大学材料与能源学院, 四川成都 611731
  • 收稿日期:2025-10-20 接受日期:2025-11-18 出版日期:2026-04-18 发布日期:2026-03-04
  • 通讯作者: * 电子信箱: maoliang@cumt.edu.cn (毛梁), zrtang@uestc.edu.cn (唐紫蓉), yjxu@uestc.edu.cn (徐艺军).
  • 基金资助:
    国家自然科学基金(22472032);国家自然科学基金(22572017);国家自然科学基金(22172030);国家自然科学基金(22072023);国家自然科学基金(U1463204);国家自然科学基金(22209203);国家科技创新领军人才计划(00387072);电子科技大学杰出人才研究基金(A1098531023601522);中国博士后创新人才支持计划(BX20240055);中国博士后科学基金(2023M740513);江西省"双千计划"(jxsq2023102143)

Highly efficient hydroxyethyl radicals-mediated photocatalytic benzimidazole synthesis and hydrogen evolution over defect-engineered Pt/Nb2O5

Yao-Yao Xiea, Chang-Long Tanb, Liang Maoc,*(), Zi-Rong Tanga,d,*(), Yi-Jun Xua,b,*()   

  1. aCollege of Chemistry, State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, Fuzhou 350116, Fujian, China
    bInstitute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 611731, Sichuan, China
    cSchool of Materials Science and Physics, China University of Mining and Technology, Xuzhou 221116, Jiangsu, China
    dSchool of Materials and Energy, University of Electronic Science and Technology of China, Chengdu 611731, Sichuan, China
  • Received:2025-10-20 Accepted:2025-11-18 Online:2026-04-18 Published:2026-03-04
  • Contact: * E-mail: maoliang@cumt.edu.cn (L. Mao), zrtang@uestc.edu.cn (Z.-R. Tang), yjxu@uestc.edu.cn (Y.-J. Xu).
  • Supported by:
    National Natural Science Foundation of China(22472032);National Natural Science Foundation of China(22572017);National Natural Science Foundation of China(22172030);National Natural Science Foundation of China(22072023);National Natural Science Foundation of China(U1463204);National Natural Science Foundation of China(22209203);Program for National Science and Technology Innovation Leading Talents(00387072);Research Fund for Outstanding Talents at University of Electronic Science and Technology of China(A1098531023601522);China National Postdoctoral Program for Innovative Talents(BX20240055);China Postdoctoral Science Foundation(2023M740513);Jiangxi Province “Double Thousand Plan”(jxsq2023102143)

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摘要：

苯并咪唑类化合物在结构上与天然核苷酸类似, 凭借其抗菌、抗寄生虫及抗癌等多种生物活性, 在医药研发与农业生产中占据着重要地位. 这类化合物的传统合成方式通常依赖于邻苯二胺与羧酸及其衍生物的交叉偶联, 或是与醛的缩合反应. 然而, 这些方法都需要在强酸、高温或强氧化剂等苛刻条件下进行, 不仅能耗高, 还易产生有毒副产物, 对环境和经济造成重大负担. 相比之下, 在温和条件下利用可再生的清洁太阳能作为驱动力的光催化多相体系, 为苯并咪唑绿色可持续合成提供了一种新思路.
在光催化体系中, 通过乙醇活化产生的羟乙基自由基(•CH(CH3)OH)介导的反应体系可以规避醛类中间体的生成, 有效抑制副产物的累积, 是一种更加高效的合成策略. 但由于乙醇中存在O-H键、C-O键及其他C-H键(特别是α-C-H和β-C-H键)的竞争性断裂, 在此反应路径中实现乙醇α-C-H键的选择性活化和断裂是一个关键挑战. 此外, 由于传统光催化剂中光生载流子的快速复合无法为反应提供足够的驱动力, 会进一步限制反应效率. 因此, 研发精准调控乙醇α-C-H键活化的同时定向诱导光生载流子高效分离的新型光催化剂是实现此路径合成苯并咪唑的核心突破口. 本研究通过控制煅烧温度在Nb2O5表面构建丰富的氧空位(VO), 并负载铂纳米颗粒(Pt NPs), 制备了具有优异光催化性能的Pt/Nb2O5-VO光催化剂. 当Pt NPs负载量达到0.4%时, 复合材料展现出了最佳的光催化性能, 2-甲基苯并咪唑的光催化产率可达4.0 mmol g-1 h-1, 氢气的生成速率近10.2 mmol g-1 h-1. 实验和密度泛函理论计算结果证实, VO作为主要活性位点增强了对乙醇的吸附, 并选择性促进其脱氢生成•CH(CH3)OH; 而Pt NPs不仅能与VO协同促进光生载流子的分离和迁移, 还能富集光生电子驱动氢质子还原产氢, 进一步提升光催化性能.
综上, 本研究通过缺陷工程与金属修饰策略, 成功设计了一种高效双功能光催化剂, 实现了乙醇与邻苯二胺在温和条件下的高选择性转化为苯并咪唑和氢气, 为绿色合成高附加值化学品及清洁能源联产提供了新思路.

关键词: 羟基乙基自由基, 铂纳米颗粒, 氧空位, 五氧化二铌, 苯并咪唑

Abstract:

The hydroxyethyl radical (•CH(CH3)OH)-mediated pathway, by avoiding the formation of aldehyde intermediates, constitutes a promising approach for the highly selective photocatalytic synthesis of benzimidazoles from ethanol and o-phenylenediamine. However, inefficient reactant adsorption and activation, as well as severe recombination of photogenerated charge carriers of traditional photocatalysts, impose a fundamental challenge for this reaction pathway. Herein, we construct an oxygen vacancy (VO)-rich Nb2O5 decorated with Pt nanoparticles (NPs), which exhibits the highest photocatalytic activity to date, with production rates of 4.0 mmol g-1 h-1 for 2-methylbenzimidazole and 10.2 mmol g-1 h-1 for H2, respectively. The synergistic interaction between VO and Pt NPs markedly promotes the migration and separation of photogenerated charge carriers. The electron-accumulating Pt NPs drive efficient H2 evolution through proton reduction, while the engineered VO sites enhance ethanol adsorption and selectively activate α-C-H bond cleavage to generate •CH(CH3)OH radicals, suppressing the accumulation of N-ethyl-2-methylbenzimidazole by-products inherent to conventional aldehyde-mediated reaction pathways, significantly facilitating the co-production of benzimidazoles and H2. This work achieves directional pathway regulation via rational design of semiconductor defects and metal co-catalysts, establishing a radical-mediated strategy for efficient and selective green synthesis of N-heterocyclic compounds.

Key words: Hydroxyethyl radical, Pt nanoparticles, Oxygen vacancy, Nb2O5, Benzimidazoles synthesis