分子筛限域铜基催化剂上糠醛的精确受限过渡态构型选择性加氢

doi:10.1016/S1872-2067(25)64741-3

催化学报 ›› 2025, Vol. 74: 71-81.DOI: 10.1016/S1872-2067(25)64741-3

分子筛限域铜基催化剂上糠醛的精确受限过渡态构型选择性加氢

梁婉滢^a, 许光月^b^,^c, 傅尧^a^,^*()

^a中国科学技术大学精密与智能化学重点实验室, 中国科学院城市污染物转化重点实验室, 安徽省生物质化学重点实验室, 安徽合肥 230026
^b北京国电集团股份有限公司, 北京 102299
^c浙江科卓环保科技有限公司, 浙江上虞 212300

收稿日期:2025-03-10 接受日期:2025-04-28 出版日期:2025-07-18 发布日期:2025-07-20
通讯作者: *电子信箱: fuyao@ustc.edu.cn (傅尧).
基金资助:
国家自然科学基金(22293011);国家自然科学基金(T2341001);安徽省重大科技专项(2022e03020005);新基石科学基金会XPLORER奖

Accurate restricted transition-state shape selective hydrogenation of furfural over zeolite confined Cu catalyst

Wanying Liang^a, Guangyue Xu^b^,^c, Yao Fu^a^,^*()

^aKey Laboratory of Precision and Intelligent Chemistry, CAS Key Laboratory of Urban Pollutant Conversion, Anhui Province Key Laboratory of Biomass Chemistry, University of Science and Technology of China, Hefei 230026, Anhui, China
^bBeijing Nation Power Group Co., Ltd., Beijing 102299, China
^cZhejiang Kezhuo Environmental Protection Technology Co., Ltd., Shangyu 212300, Zhejiang, China

Received:2025-03-10 Accepted:2025-04-28 Online:2025-07-18 Published:2025-07-20
Contact: *E-mail: fuyao@ustc.edu.cn (Y. Fu).
Supported by:
National Natural Science Foundation of China(22293011);National Natural Science Foundation of China(T2341001);Anhui Provincial Major Science and Technology Project(2022e03020005);New Cornerstone Science Foundation through the XPLORER PRIZE

摘要/Abstract

摘要：

过渡态构型选择性在多相催化体系中具有关键作用, 尤其在反应物与产物分子尺寸相近的体系中, 通过限制反应中间体的构型空间可精准调控反应路径. 生物质平台分子糠醛的高效转化对缓解化石资源消耗及环境问题具有重要意义, 但其加氢生成糠醇的过程中易因副反应(如Piancatelli重排)导致环状副产物环戊酮与环戊醇生成. 传统抑制副反应的策略(如毒化催化剂或调控反应条件)往往以牺牲活性为代价, 而基于分子筛的限域效应通过空间约束限制过渡态构型, 为选择性调控提供了新思路. 现有分子筛负载金属催化剂常因骨架缺陷或传质受阻难以兼顾活性与选择性. 本研究通过孔道限域策略设计Cu@MFI催化剂, 旨在解决上述矛盾, 为生物质定向转化及限域催化体系的理性设计提供理论依据与实践范例.

本研究基于分子筛拓扑限域效应与金属位点协同作用, 提出“孔道精准限域双活性位点”设计策略: 通过高温快速混合水热法将铜物种封装于MFI分子筛的交叉直连10元环孔道中, 构建兼具骨架完整性、畅通传质通道及双功能活性位点的Cu@MFI催化剂. 结构表征结果表明, Cu@MFI中铜以单原子(笼内Cu)与双核氧桥联结构(10元环孔道内[Cu₂(μ-O)_x]²⁺)共存, 且未阻塞孔道或破坏骨架. 对比传统浸渍法负载的Cu/S-1, Cu/SiO₂及大孔沸石Cu@MOR, Cu@MFI在糠醛水相加氢中展现出独特的催化性能: 70 °C下即可实现100%糠醛转化率与100%糠醇选择性, 且活性在50-150 °C宽温域内保持稳定, 而其他催化剂因孔道限制不足或酸性位点诱导副反应生成环戊酮与环戊醇. 结合密度泛函理论计算与实验验证, 揭示了Cu@MFI的构效关系与反应机制: (1)双活性位点协同: 笼内单原子Cu优先解离H₂, 孔道内双核Cu通过d-π共轭与σ键协同极化C=O键, 降低加氢能垒(糠醛到糠醇反应能垒0.31 eV, 低于Cu(111)的0.45 eV); (2)过渡态限域效应: MFI的10元环孔道通过空间位阻限制双分子过渡态(如糠醇与H₂O的Piancatelli重排中间体), 其反应能垒(2.13 eV)显著高于开放Cu表面(0.17 eV), 从而阻断副反应路径. 此外, 引入微量Pt (0.2 wt%)可加速氢溢流, 进一步缩短反应时间至2 h (100%转化率与选择性), 且未破坏限域功能.

综上, 本文通过精准限域双活性位点设计与过渡态构型调控, 为生物质定向转化提供了高效催化体系. 未来可拓展至其他涉及多分子过渡态的选择性反应(如C-C偶联或级联反应), 并通过多元金属协同与分子筛拓扑适配进一步优化限域效应. 本工作为多相催化中“活性-选择性-稳定性”矛盾的解决及工业催化过程绿色化提供了新范式.

关键词: 生物质, Cu@MFI催化剂, 过渡态构型选择性, 糠醛加氢, 金属-分子筛协同效应

Abstract:

Transition-state shape selectivity plays a crucial role in catalytic systems where reactants and products exhibit comparable molecular dimensions, as it restricts the accessible configuration space of reaction intermediates. Herein, we designed a Cu@MFI catalyst by encapsulating Cu active sites within the well-defined micropores of MFI zeolite through a pore confinement strategy. This architecture preserves the zeolite framework integrity while maintaining unhindered internal mass transport, thereby enabling precise spatial control over transition-state configurations. Employing furfural hydrogenation as a probe reaction, the metal-zeolite synergy in Cu@MFI endowed the catalyst with exceptional activity (100% furfural conversion) and quantitative selectivity (100% furfuryl alcohol) at 70 °C, sustained across a broad temperature window. Mechanistic studies reveal that the transition-state shape selectivity effectively prevented H₂O interaction with the furan ring, offering valuable insights for other reaction systems seeking to exploit shape selectivity for specific transformations.

Key words: Biomass, Cu@MFI catalyst, Transition-state shape selectivity, Furfural hydrogenation, Metal-zeolite synergy

梁婉滢, 许光月, 傅尧. 分子筛限域铜基催化剂上糠醛的精确受限过渡态构型选择性加氢[J]. 催化学报, 2025, 74: 71-81.

Wanying Liang, Guangyue Xu, Yao Fu. Accurate restricted transition-state shape selective hydrogenation of furfural over zeolite confined Cu catalyst[J]. Chinese Journal of Catalysis, 2025, 74: 71-81.

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图/表 6

Scheme 1. The accurate hydrogenation of furfural to furfuryl alcohol on Cu@MFI.

Fig. 1. Catalyst characterization and catalytic performance of various catalysts for FA to FOL. (a) The design and synthesis of Cu@MFI. (b-f) TEM and mapping image of Cu@MFI. (g) XRD patterns. (h) FT-IR spectra. (i) 29Si MAS NMR spectra. (j) Various Cu catalysts at low temperature (50 °C). (k) Various Cu catalysts at high temperature (130 °C). Reaction conditions: 1 mmol FA, 100 mg catalyst, 10 mL H2O, 4 MPa H2, 5 h.

Fig. 2. Analysis of Cu components. (a) XPS spectra of Cu 2p. (b) LMM Auger spectra of Cu. (c) H2-TPD profiles. (d) UV-vis spectra.

Fig. 3. Structure and location of Cu species in MFI zeolite predicted by DFT. (a) The zeolite model contained intra-cage Cu and secondary framework Cu. (b-e) Experimental (brown) and fitted (green) curves of the magnitude and imaginary part of the Fourier transform of the Cu K-edge k3-weighted EXAFS spectra of oxygen-activated Cu@MFI samples.

Fig. 4. Reaction mechanism and structure-performance: (a) Reaction mechanism. (b) Optimized structures for the aqueous-phase hydrogenation-rearrangement of FA to CPO and calculated energy profiles for the potential comparative free energy of FA to CPO on Cu@MFI. Energy barriers are reported to two decimal places in the in the activation energy discussion section to emphasize quantitative differences in transition-state configurations.

Fig. 5. Texture properties and catalytic performance. (a) Pore size distribution of Cu@MFI and Cu/S-1. (b) Cu@MFI at various temperature. (c) Catalytic local state density. (d) Cu@MFI at maximum condition. (e) Catalytic performance comparison of Cu@MFI and Pt/Cu@MFI. Reaction conditions: 1 mmol FA, 100 mg catalyst, 10 mL H2O, 4 MPa H2, 130 °C, 5 h.

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分子筛限域铜基催化剂上糠醛的精确受限过渡态构型选择性加氢

Accurate restricted transition-state shape selective hydrogenation of furfural over zeolite confined Cu catalyst

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