催化学报

催化学报 ›› 2026, Vol. 86: 99-111.DOI: 10.1016/S1872-2067(26)65047-4

• 论文 • 上一篇    下一篇

Sn-MFI沸石负载PtIn合金催化剂高效催化甘油氧化制乳酸

谢浩东a,1, 佛雨萌a,1, 张宏伟b, 徐华a,c, 张逍a, 郭盈铄a, 李润泽a, 张若霖c, 刘贵林a, 贾希成d, 李家州a, 张玉明a, 荆湄赞a,*(), 宋卫余a,*(), 罗文豪e,*(), 吴志杰a,*()   

  1. a 中国石油大学(北京), 重质油全国重点实验室和CNPC催化重点实验室, 北京 102249
    b 农业农村部成都沼气科学研究所, 四川成都 610041
    c 中国石油天然气股份有限公司石油化工研究院, 北京 102206
    d 中国石油大学(北京)克拉玛依校区工学院, 新疆克拉玛依 834000
    e 内蒙古大学化学化工学院, 内蒙古自治区稀土催化重点实验室, 内蒙古呼和浩特 010021
  • 收稿日期:2025-10-31 接受日期:2026-01-04 出版日期:2026-07-05 发布日期:2026-06-12
  • 通讯作者: *电子信箱: jingmeizan@163.com (荆湄赞),
    songwy@cup.edu.cn (宋卫余),
    w.luo@imu.edu.cn (罗文豪),
    zhijiewu@cup.edu.cn (吴志杰).
  • 作者简介:第一联系人：1共同第一作者.
  • 基金资助:
    国家重点研发计划(2022YFB3805602)

PtIn nanoalloy supported on Sn-MFI for efficient selective oxidation of glycerol to lactic acid

Haodong Xiea,1, Yumeng Foa,1, Hongwei Zhangb, Hua Xua,c, Xiao Zhanga, Yingshuo Guoa, Runze Lia, Ruolin Zhangc, Guilin Liua, Xicheng Jiad, Jiazhou Lia, Yuming Zhanga, Meizan Jinga,*(), Weiyu Songa,*(), Wenhao Luoe,*(), Zhijie Wua,*()   

  1. a State Key Laboratory of Heavy Oil Processing and Key Laboratory of Catalysis of CNPC, China University of Petroleum-Beijing, Beijing 102249, China
    b Biogas Institute of Ministry of Agriculture and Rural Affairs， Chinese Academy of Agricultural Sciences, Chengdu 610041, Sichuan, China
    c Petrochemical Research Institute, PetroChina, Beijing 102206, China
    d Department of Chemical Engineering, China University of Petroleum-Beijing at Karamay, Karamay 834000, Xinjiang, China
    e College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, Inner Mongolia, China
  • Received:2025-10-31 Accepted:2026-01-04 Online:2026-07-05 Published:2026-06-12
  • About author:First author contact:1Contributed equally to this work.
  • Supported by:
    National Key Research and Development Program of China(2022YFB3805602)

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摘要：

甘油作为生物柴油生产的主要副产物, 其高效转化制备乳酸等高附加值化学品具有重要的经济价值和环保意义. 乳酸是一种重要的化学中间体, 广泛应用于食品、医药、化妆品和生物降解塑料等领域. 甘油选择性氧化制乳酸具有原子经济性高、反应条件温和等优点, 既解决了副产物甘油的过剩问题, 又为乳酸生产提供了绿色可持续的新路径. 目前该反应体系多依赖于碱性添加剂, 存在设备腐蚀、废液处理困难及过程成本增加等问题, 限制了其工业化应用. 此外, 现有的Pt基催化剂普遍面临Pt负载量高、稳定性差等问题. 因此, 开发高效稳定、低Pt负载量的催化剂对于推动甘油高值化利用具有重要意义.

本文以水热法合成的Sn-MFI沸石为载体, 通过简单的共浸渍法制备了一系列低铂负载量(0.5 wt%)的PtIn/Sn-MFI催化剂, 并将其应用于无碱条件下的甘油氧化反应体系. 采用球差校正透射电镜、X-射线吸收光谱、X-射线光电子能谱及CO吸附红外光谱等表征技术, 系统分析了催化剂的微观结构与表面电子状态. 结果表明, Pt与In在Sn-MFI沸石表面形成了均匀分散的PtIn2纳米合金, 且存在从In到Pt的电子转移, 使Pt物种呈现富电子状态(Ptδ-), 该独特结构显著增强了催化剂对甘油分子中O−H键的活化能力. 催化性能评价结果表明, 对于不同In含量的PtIn/Sn-MFI催化剂, 反应转化频率(TOF)随In/Pt摩尔比呈典型的火山型变化趋势. 其中, Pt0.5In1.0/Sn-MFI催化剂表现出最优性能: TOF值高达1283 h-1, 甘油转化率达96.8%, 乳酸选择性为73.5%, 显著优于单金属Pt0.5/Sn-MFI催化剂. 此外, 催化剂循环使用测试表明, 该催化剂经5次重复使用后性能无明显衰减; 表征证实其结构保持完整, 未发生明显金属流失, 展现出优异的化学与结构稳定性. 结合动力学研究与密度泛函理论(DFT)计算深入阐明了合金化提升氧化性能的作用机制: In诱导的电子转移使Pt的d带中心下移, 调控甘油的吸附强度, 有效抑制了过度吸附; 同时, PtIn2纳米合金有效降低了反应路径中甘油仲羟基脱氢步骤的活化能垒, 从而显著提升反应效率; 此外, 载体Sn-MFI中的Lewis酸位点协同促进中间体脱水与重排生成乳酸.

综上, 本文通过低Pt负载合金化策略, 实现了无碱条件下甘油高效氧化制乳酸, 为设计经济稳定的双金属催化剂提供了重要参考, 对推动生物质资源的高效利用及绿色合成工艺的可持续发展具有积极作用.

关键词: 铂铟纳米合金, 甘油氧化, 乳酸, Sn-MFI沸石, 协同催化

Abstract:

Developing efficient Pt-based catalysts is crucial for sustainable lactic acid (LA) production via glycerol oxidation. Herein, we synthesized a series of robust PtIn/Sn-MFI catalysts with low Pt loading of 0.5 wt% for glycerol oxidation under base-free conditions. The PtIn/Sn-MFI catalysts with varying In contents exhibited a volcano-shaped trend between turnover frequency (TOF) and In/Pt molar ratio. Among all tested catalysts, the Pt0.5In1.0/Sn-MFI sample exhibited the highest catalytic activity (1283 h-1), achieving 96.8% glycerol conversion with 73.5% LA selectivity, surpassing the monometallic Pt0.5/Sn-MFI catalyst. Furthermore, the Pt0.5In1.0/Sn-MFI catalyst maintained excellent stability, with no significant degradation in catalytic performance even after five consecutive recycling runs. Experimental analysis and characterizations verified the formation of PtIn2 nanoalloys, accompanied by electron transfer from In to Pt, which significantly enhanced the catalysts’ O−H bond activation ability, resulting in high activity and selectivity. Combined with kinetic studies and density functional theory calculations, we further revealed that PtIn2 nanoalloy active sites significantly reduce the activation energy barrier for the dehydrogenation of the secondary hydroxy group in the reaction pathway. This work offers new perspectives on the rational design of cost-effective, high-efficiency catalysts for the sustainable oxidation of glycerol to LA.

Key words: PtIn nanoalloy, Glycerol oxidation, Lactic acid, Sn-MFI zeolite, Synergistic catalysis