Cu/MOF双功能催化剂催化乙酰丙酸制取γ-戊内酯的研究  

Selective hydrogenation of levulinic acid toward GVL over Cu/MOF bifunctional catalyst

作　　者：邬玉珊 王继大 许狄 徐艳飞 定明月 WU Yushan;WANG Jida;XU Di;XU Yanfei;DING Mingyue(School of Power and Mechanical Engineering,Wuhan University,Wuhan 430072,China)

机构地区：[1]武汉大学动力与机械学院,湖北武汉430072

出　　处：《能源环境保护》2024年第2期105-113,共9页Energy Environmental Protection

基　　金：国家重点研发计划资助项目(2022YFA1504700);国家自然科学基金资助项目(52306269,U21A20317,U22A20394)。

摘　　要：传统化石能源的日益消耗引发了严重的能源危机和环境污染等问题,亟需开发和利用可再生能源。生物质因其资源丰富、成本低廉和清洁的特点,引起了人们的广泛关注。采用简单、高效的溶剂热方法构筑了一种金属有机框架封装金属Cu的新型复合材料,Cu/MOF-808,该催化剂中Cu原子锚定在Zr基金属有机框架MOF-808次级结构单元的缺陷位。Cu/MOF-808催化剂在较温和的反应条件下(140℃),以异丙醇为氢源,通过催化转移加氢路径,将生物质平台分子乙酰丙酸选择性加氢转化为γ-戊内酯,产率达到91.5%。溶剂影响因素结果表明,Cu/MOF-808催化剂在异丙醇中表现出最好的活性和选择性,远高于甲醇、乙醇和仲丁醇体系,主要得益于异丙醇优异的供氢能力。此外,Cu/MOF-808催化剂具有良好的稳定性和可重复利用性,在5次循环后仍能保持较高的催化活性和目标产物选择性。机理研究揭示了MOF锚定的高分散Cu金属位点和MOF中Zr簇的Lewis酸性位点的高效协同作用,促进了乙酰丙酸高效催化转化。The rising consumption of fossil fuels has led to a severe energy crisis and environmental pollution,driving researchers to seek renewable alternatives.Biomass is a promising option due to its abundance,low cost,and clean characteristics.Here,a novel Cu catalyst encapsulated in a metal-organic framework,Cu/MOF-808,was prepared by a simple,convenient,and efficient solvothermal method.Cu atoms were anchored to the defective sites within the secondary building units of the Zr-based MOF-808.Cu/MOF-808 catalyst selectively converted the biomass-derived platform chemical levulinic acid(LA)toγ-valerolactone(GVL)with a high yield of 91.5%via catalytic transfer hydrogenation(CTH)using isopropyl alcohol(IPA)as a hydrogen donor under mild reaction conditions(140℃).Solvent effects indicated that Cu/MOF-808 catalyst exhibited the best activity and selectivity in isopropyl alcohol,significantly outperforming methanol,ethanol and 2-butanol due to IPA′s superior hydrogen supply capacity.Additionally,Cu/MOF-808 demonstrated good stability and reusability,maintaining high selectivity for the target product after five consecutive cycles.Mechanistic studies revealed that the efficient conversion of levulinic acid was attributed to the synergistic effect of uniformly distributed Cu metal sites anchored by the MOF and the Zr Lewis acid sites within the MOF structure.

关 键 词：选择性加氢 氢转移 Cu/MOF 乙酰丙酸 γ-戊内酯 

分 类 号：X505[环境科学与工程—环境工程] X705