单糖直接转化制DMF的双功能催化剂可控构建及催化机理研究

2,5-二甲基呋喃（DMF）是潜在的液体生物燃料并可用于多种高附加值化学品的合成。DMF由单糖经脱水-氢解串联反应制得，采用一锅法避免了中间产物的分离提纯，具有重要研究价值。本项目针对一锅法中非贵金属催化剂活性和DMF选择性低等问题，提出利用原子层沉积技术（ALD）表面自限制反应特征，构建以硫酸化氧化锆（SZ）改性碳材料为载体的Ni-M双功能催化剂（M为Fe、Co、Cu），分别以SZ和Ni-M作为酸性位点和金属位点催化脱水和氢解反应。通过调节ALD温度和前驱体脉冲时间等参数分别构筑单原子、团簇和纳米颗粒，探究Ni-M颗粒生长特性；亚纳米尺度精准调控颗粒尺寸、优化酸性位点与金属位点比例，提升催化剂活性和DMF选择性；d轨道态密度计算与实验验证结合，探究Ni和M间电子转移机制，阐明催化剂尺寸效应和碳载体作用，揭示酸性位点与金属位点协同催化机制，为设计优化双功能催化剂、高效制备DMF提供新思路。

2,5-Dimethylfuran (DMF) is a potential liquid biofuel and can be used in the synthesis of a variety of high value-added chemicals. DMF is prepared from monosaccharides through dehydration-hydrogenolysis tandem reaction, and the one-pot method avoids the separation and purification of intermediate products, which has important research value. In view of the problems of low activity and poor DMF selectivity of non-noble metal catalysts in the one-pot process, this project proposes to take advantage of the surface self-limiting reaction characteristics of atomic layer deposition (ALD) and construct Ni-M bifunctional catalysts (M=Fe, Co, or Cu) using sulfated zirconia (SZ) modified carbon materials as the supports. SZ and Ni-M will be used as acid sites and metal sites to catalyze the dehydration and hydrogenolysis reactions, respectively. Through adjusting parameters such as ALD temperature and the pulse time of precursors, single atoms, clusters and nanoparticles will be constructed separately, and the growth characteristics of Ni-M particles will be explored; through precisely adjusting the particle size at sub-nanometer scale and optimizing the ratio of acid sites to metal sites, the activity and DMF selectivity of the catalysts will be improved; through d-orbital density of state calculation and experiments verification, the electron transfer mechanism between Ni and M will be explore, the catalyst size effect and roles of carbon supports will be clarified, and the synergistic catalytic mechanism of acid sites and metal sites will be revealed, to provide new ideas for the design and optimization of bifunctional catalysts and the efficient preparation of DMF.