催化学报 ›› 2026, Vol. 91: 327-340.DOI: 10.1016/S1872-2067(26)65130-3

• 论文 • 上一篇    下一篇

Zr1/NC@SBA-15单原子催化剂高效稳定催化乙醇/乙醛转化制1,3-丁二烯

赵于嘉a,b, 李显泉a, 井日峥a,b, 庞纪峰a, 于文广c, 王华a, 徐斐斐c, 郑明远a,*()   

  1. a 中国科学院大连化学物理研究所, 催化基础国家重点实验室, 辽宁大连 116023
    b 中国科学院大学, 北京 100049
    c 中国科学院大连化学物理研究所, 洁净能源国家实验室, 辽宁大连 116023
  • 收稿日期:2026-02-19 接受日期:2026-04-13 出版日期:2026-12-18 发布日期:2026-10-13
  • 通讯作者: *电子信箱: myzheng@dicp.ac.cn (郑明远).
  • 基金资助:
    新材料重大专项(2025ZD0614502);国家自然科学基金(22388102);国家自然科学基金(22378383);国家自然科学基金(22502191)

Efficient and stable conversion of ethanol/acetaldehyde to 1,3-butadiene over a Zr1/NC@SBA-15 single-atom catalyst

Yujia Zhaoa,b, Xianquan Lia, Rizheng Jinga,b, Jifeng Panga, Wenguang Yuc, Hua Wanga, Feifei Xuc, Mingyuan Zhenga,*()   

  1. a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, Liaoning, China
    b University of Chinese Academy of Sciences, Beijing 100049, China
    c Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
  • Received:2026-02-19 Accepted:2026-04-13 Online:2026-12-18 Published:2026-10-13
  • Supported by:
    Advanced Materials-National Science and Technology Major Project(2025ZD0614502);National Nat-ural Science Foundation of China(22388102);National Nat-ural Science Foundation of China(22378383);National Nat-ural Science Foundation of China(22502191)

摘要:

1,3-丁二烯(丁二烯)是合成橡胶、树脂及高端精细化学品的关键C4原料, 全球年消耗量超1200万吨. 其生产目前几乎完全依赖石脑油蒸汽裂解, 面临高碳排放、资源不可持续等问题, 且页岩气与甲醇制烯烃技术发展进一步压缩了传统工艺的供给能力. 随着生物质乙醇及CO2加氢制乙醇技术的快速发展, 以可再生乙醇为原料的乙醇制1,3-丁二烯(ETB)工艺成为实现可持续供应链与CO2减排的重要途径, 展现出高效、可持续的替代优势. 尽管单原子催化剂因其独特的催化性能在乙醇增值化过程中被广泛报道, 但目前高效稳定的乙醇转化制丁二烯的单原子催化剂仍鲜有报道, 且对活性位点本质、定量构效关系及反应条件下真实反应机理的认识不足, 严重制约了催化剂的理性设计.
本文通过氮碳(NC)修饰策略构建了Zr1/NC@SBA-15单原子催化剂, 并应用于乙醇/乙醛催化转化制丁二烯反应. 相较于传统负载型纳米Zr/SBA-15, 该催化剂不仅实现了超过80%的转化率和高于70%的丁二烯选择性, 还在300 h连续运行中展现出卓越的稳定性. 结合X-射线吸收谱、X-射线光电子能谱、低温CO-红外光谱(FTIR)及球差电镜等多谱学表征辅以密度泛函理论计算, 阐明了Zr原子以单原子形式均匀分散, 形成丰富的Lewis酸位点[(Si-N)-Zr(O-Si)2(OH)], 该结构赋予催化剂增强的中强酸性, 是乙醇制丁二烯反应的高活性中心, 酸性位点较纳米催化剂提升近一倍, 为高效催化转化提供了充足的活性位点. 基于乙醇/乙醛-程序升温脱附及原位FTIR等谱学表征, 提出了乙醛在单原子Zr位点上的双分子协同吸附模式, 并证实在350 oC, 该模式下乙醛羟醛缩合为整个反应的决速步骤, 该步骤遵循Langmuir-Hinshelwood机制, 即两分子乙醛在同一活性中心上协同吸附、高效耦合. 通过理论计算进一步揭示了羟醛缩合过程的微观机理: 乙醛通过羰基氧与Zr活性位点结合形成活化物种, 第二个乙醛分子经氢键吸附于Zr-OH上, 形成稳定双分子吸附态后, 经质子转移生成CH2CHO和CH3CHOH中间体; CH2CHO迁移至相邻N位点并通过α-碳与N结合, 对CH3CHOH发起亲核攻击实现C-C键合, 并经分子内脱水形成巴豆醛. 动力学结果表明, Zr1/NC@SBA-15上乙醛羟醛缩合的表观活化能(27.2 kJ mol-1)较纳米Zr/SBA-15降低了18.8 kJ mol-1, 这是单原子催化剂具有高活性的关键; 同时, Zr-N配位带来的高热力学稳定性、活性位点抗烧结能力以及对积碳的显著抑制作用, 共同赋予催化剂超长周期稳定运行的特性.
综上, 本工作通过NC修饰策略成功构筑了Zr单原子催化剂, 实现了乙醇/乙醛向丁二烯的高效、高稳定性催化转化. 通过深入探究其在反应物活化及C-C偶联中的催化行为, 深化了对单原子催化剂在乙醇催化转化机制方面的基础认识, 为设计高性能乙醇增值转化反应的单原子催化剂提供了理论指导.

关键词: 乙醇, 乙醛, 1,3-丁二烯, 单原子催化剂, 羟醛缩合, Zr基催化剂

Abstract:

The design of high-performance single-atom catalysts (SACs) with excellent stability for the ethanol-to-1,3-butadiene (1,3-BD) (ETB) process remains a significant challenge and has rarely been reported. Herein, a Zr single-atom catalyst Zr1/NC@SBA-15 was constructed and employed in the ETB process. Compared with the conventional nano-Zr/SBA-15 catalyst, the Zr1/NC@SBA-15 catalyst delivered notably higher performance: the reactant conversion exceeded 80%, the selectivity toward 1,3-BD was above 70%, and unprecedentedly high stability of 300 h on stream was achieved without notable deactivation. Systematic characterizations, operando spectroscopy, and density functional theory calculations revealed that the Zr atoms were uniformly dispersed on the Zr1/NC@SBA-15 catalyst in the single-atom state, forming abundant Lewis acid sites (LAS) of [(Si-N)-Zr(O-Si)2(OH)]. A dual acetaldehyde adsorption mode was proposed for the ETB reaction over the Zr1/NC@SBA-15 catalyst. The rate-determining step of acetaldehyde condensation proceeded via the Langmuir-Hinshelwood mechanism over the [(Si-N)-Zr(O-Si)2(OH)] sites, with apparent activation energy decreased by 18.8 kJ/mol compared with that over the nano-Zr/SBA-15 catalyst. The N-coordinated single Zr atom with lowered energy endows the Zr1/NC@SBA-15 catalyst with outstanding stability during the reaction; meanwhile, the unique coordination of the [(Si-N)-Zr(O-Si)2(OH)] sites and the enhanced LAS acidity result in the high activity of Zr1/NC@SBA-15 in the ETB reaction. This work provides a good example of SAC application in the ETB process and opens a new route for exploring more effective catalysts.

Key words: Ethanol, Acetaldehyde, 1,3-Butadiene, Single-atom catalyst, Aldol condensation, Zirconium-based catalyst