催化学报

催化学报 ›› 2027, Vol. 92: 115-122.DOI: 10.1016/S1872-2067(26)65228-X

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常温常压下丙烯厌氧光催化双羟基化制备丙二醇与氢气

宋欣妤a, 王伟a, 劳晓敏a, 刘奕彤a, 刘焕敏a, 周鹏a,b,c,*   

  1. a北京大学深圳研究生院, 环境与能源学院, 广东深圳 518055;
    b北京大学深圳研究生院, 生态环境与资源研究实验室, 广东深圳 518055;
    c北京大学深圳研究生院, 广东省纳米微米材料重点实验室, 广东深圳 518055
  • 收稿日期:2026-01-31 接受日期:2026-04-16 出版日期:2027-01-18 发布日期:2026-10-30
  • 通讯作者: *电子信箱: pengzhou1209@pku.edu.cn (周鹏).
  • 基金资助:
    广东省基础与应用基础研究基金(2026A1515012231); 深圳市自然科学基金(JCYJ20240813160123030); 北京大学深圳研究生院科研启动经费; 国家自然科学基金优秀青年科学基金项目.

Anaerobic photocatalytic dihydroxylation of propylene to propylene glycol and hydrogen at ambient temperature and pressure

Xinyu Songa, Wei Wanga, Xiaomin Laoa, Yitong Liua, Huanmin Liua, Peng Zhoua,b,c,*   

  1. aSchool of Environment and Energy, Peking University Shenzhen Graduate School, Shenzhen 518055, Guangdong, China;
    bEco-environment and Resource Efficiency Research Laboratory, School of Environment and Energy, Peking University Shenzhen Graduate School, Shenzhen 518055, Guangdong, China;
    cGuangdong Provincial Key Laboratory of Nano-Micro Material Research, Peking University Shenzhen Graduate School, Shenzhen 518055, Guangdong, China
  • Received:2026-01-31 Accepted:2026-04-16 Online:2027-01-18 Published:2026-10-30
  • Contact: *E-mail: pengzhou1209@pku.edu.cn (P. Zhou).
  • Supported by:
    Guangdong Basic and Applied Basic Research Foundation (2026A1515012231), the Shenzhen Natural Science Foundation (JCYJ20240813160123030), the start-up support from Peking University Shenzhen Graduate School, and the National Natural Science Foundation Excellent Young Scientist Project.

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摘要： 以水为羟基源的烯烃(CnH2n)双羟基化过程, 是在无氧常温常压条件下合成二醇(CnH2n+2O2)的一种可持续且温和的合成路线, 至今仍是光催化领域的一大挑战. 目前电催化研究可在常温常压下, 利用外源氧气或原位生成的过氧化氢将C3H6转化为1,2-丙二醇(1,2-PG). 但是由于氧气在水电解质中的反应活性低和溶解度小, 严重限制了催化反应速率. 并且, 电解液中引入的含卤素化合物会增加下游产品提纯的经济与环境成本. 而光催化C3H6转化途径可以仅利用水作为氧化剂, 是一种无需外加O2或其他强氧化剂的光催化过程. 更重要的是, 光生电子可还原水生成H2, 实现近100%的原子利用率. 然而, 现有光催化体系的性能高度依赖丙烯压力(6–10 atm)及CO等有毒气体的辅助作用, 这限制了光催化方法的实际应用.
本文通过光沉积法合成了一系列不同纳米金属颗粒负载的TiO2, 通过对比不同贵金属颗粒负载的TiO2催化剂, 发现仅有负载于TiO2上的银纳米粒子(Ag-TiO2)能够利用阳光、丙烯和水, 通过光催化双羟基化途径在常温常压下直接生成1,2-PG和氢气. 首先通过密度泛函理论(DFT)计算出了一系列贵金属负载TiO2光催化剂在水和C3H6存在下生成1,2-PG的反应路径与吉布斯自由能变化. 可以将整体反应机制划分为四个基本步骤: (1) H2O在金属纳米粒子表面解离形成吸附态*OH物种; (2) C3H6通过C=C双键的两个碳原子与金属颗粒结合形成*Pr; (3)吸附的*OH物种与*Pr反应生成*PrOH; (4)最后另一吸附在纳米颗粒表面的*OH与*PrOH进一步反应生成1,2-PG. 其中Ag-TiO2在*OH与*Pr形成首个C–O键时具有最低能垒(0.33 eV), 表明Ag-TiO2催化C3H6进行双羟基化反应最易发生. 进一步的实验研究表明, 仅有Ag-TiO2可以生成1,2-PG, 生成速率达177.7 μmol g–1 h–1, 选择性为37.1%, 优于其他贵金属, 与DFT计算结果吻合. 采用自然光作为光源的户外中试实验中, 连续反应5 d后, 1,2-PG的总产率可达5.3 mmol, 表明该工艺具备太阳能驱动工业化应用潜力. 结合DFT模拟和原位光谱分析进一步表明, Ag-TiO2的特异性是由于只有Ag纳米颗粒能够捕获TiO2产生的光生空穴而非电子, 从而降低了羟基化这一关键决速步骤在Ag-TiO2界面的能垒. 此外, Ag纳米颗粒在捕获光生空穴后, 可生成高氧化态Agδ+物种以促进*OH与C3H6间C–O键的形成. Agδ+物种的存在既平衡了*OH中间体的生成, 同时促进C3H6的二羟基化反应并抑制了中间产物的过度氧化.
综上, 本研究开创了烯烃在常温常压下无氧双羟基化并联产氢气的光催化路径, 无需外源氧气或其他强氧化剂, 光生电子可以还原水氧化产生的质子, 从而产生副产物H2, 获得近100%的原子利用率, 实现了光生电子和空穴的有效利用, 为太阳能驱动的烯烃高值化转化提供了可行方案.

关键词: 厌氧双羟基化, 产氢, 常温常压, 光催化, 丙烯

Abstract: The oxidant-free dihydroxylation process of olefin using water as hydroxyl source represents a highly desirable strategy for synthesizing diols as it reduces the risk of over-oxidation of the olefin and enhances the safety of the production process, however, remaining to be a challenge under mild reaction conditions. Herein, we demonstrate a photocatalytic non-oxidative dihydroxylation pathway that only can utilize sunlight, propylene, and water to directly produce 1,2-propylene glycol (1,2-PG) and hydrogen over a silver nanoparticle-loaded TiO2 (Ag-TiO2) under ambient pressure and temperature. In-situ spectroscopic analyses combining with density functional theory simulations revealed that only Ag nanoparticles can capture photogenerated holes from TiO2 instead of electrons, enabling the rate-determining hydroxylation step with a lower energy barrier (0.33 eV) at the Ag-TiO2 interface compared to other noble metal-TiO2 interfaces. A 1,2-PG yield of 177.7 μmol g–1 h–1 was achieved on Ag-TiO2 via photocatalytic non-oxidative dihydroxylation pathway under ambient conditions. In contrast, only a trace amount of 1,2-PG was detected on other noble metal-loaded catalysts. More importantly, Ag-TiO2 could consistently produce 1,2-PG (168.4 μmol g–1) and hydrogen without any decline in activity under natural sunlight irradiation. This work establishes an integrated photocatalytic route for non-oxidative dihydroxylation process of olefin coupled with hydrogen production, offering a green and scalable pathway for solar-driven olefin functionalization.

Key words: Anaerobic dihydroxylation, Hydrogen generation, Ambient condition, Photocatalysis, Propylene