生物质基多孔催化材料构筑及其对含羰基生物质衍生物选择性加氢催化性能的研究

Selective conversion of biomass-derived carbonyl-containing compounds is a promising route to convert biomass into value-added chemicals, which has received much attention in recent years. Meanwhile, using natural compounds as building unit to design and prepare catalysts opens new way for the conversion of biomass-derived compounds. In this project, porous catalytic materials will be designed and prepared by using naturally-occurred phytic acid and tannic acid as the building blocks to coordinate with various metal ions, which will be used as catalysts or the supports to synthesize nano-metal catalysts. In the presence of H2 or alcohols as the reductant, the catalytic performance of these catalysts for the hydrogenation of 5-hydroxymethylfurfural into 2,5-dihydroxymethylfuran, levulinic acid and esters into γ-valerolacton, and 2,5-hexanedione into 2,5-dimethyltetrahydrofuran will be studied. The influence of metal ions, the structure of phytic acid and tannic acid, and the type and size of supported nano-metals on the properties of the catalysts will be investigated in detail. At the same time, the reaction mechanism will be explored. With various selected efficient phytic acid and tannic acid based catalysts, the influence of catalyst types, reaction temperatures, and pressure, etc., on the activity and selectivity of the reactions will be studied systematically. Finally, some efficient routes and approaches for the transformation of the biomass-derived carbonyl-containing compounds will be obtained. The results of this project will provide scientific basis for the design and preparation of efficient biomass-based catalytic materials and the highly efficient conversion of biomass-derived carbonyl-containing compounds.

含羰基生物质衍生物的选择性转化是生物质高值化转化的重要途径，也是目前国内外普遍关注的重要课题。以天然化合物为结构单元构筑催化剂为生物质衍生物的转化提供了新的发展空间。本项目拟以天然化合物植酸和单宁酸与金属离子结合构筑多孔催化材料，以其为催化剂或以其为载体制备负载纳米金属催化剂。以H2或者醇类化合物为还原剂，研究这些催化剂对5-羟甲基糠醛加氢转化为2,5-二羟甲基呋喃、乙酰丙酸及酯加氢转化为γ-戊内酯、2,5-己二酮加氢转化为2,5-二甲基四氢呋喃反应的催化性能，研究催化剂的性质随金属离子、植酸及单宁酸的结构、负载纳米金属种类与尺寸等因素的变化规律，探索催化反应机理。通过筛选出多种以植酸和单宁酸为结构单元的高效催化剂，系统研究催化剂种类、温度、压力等对反应转化率和选择性的影响规律，获得多种高效反应的方法和途径，为生物质基高效催化材料的设计制备、含羰基生物质衍生物的高效转化利用奠定科学基础。

含羰基生物质衍生物的选择性转化是生物质转化利用的重要途径。本项目以含羰基生物质衍生物的选择性转化为目标，构筑功能催化材料，特别是以天然化合物植酸和单宁酸为结构单元构筑催化材料，研究了多种含羰基生物质衍生物的转化反应，主要结果如下：（1）以单宁酸为结构单元构筑负载钌催化剂，实现糠醛的选择性加氢。通过控制反应温度，糠醛加氢产物可以控制为糠醇或四氢糠醇；（2）以植酸为结构单元构筑多孔性植酸铪催化剂，实现了多种生物质衍生醛的选择性氢转移加氢反应；（3）构筑多孔性TiO2纳米片负载Pt催化材料，通过载体TiO2纳米片的强酸性与Pt纳米粒子表面相对较低的电子密度的协同作用，首次实现常温常压条件下乙酰丙酸选择性还原氨化制备吡咯烷酮类化合物。本工作克服了该反应需要高温高压的缺点；（4）以植酸为磷源，制备了磷酸钛纳米片负载Ru催化材料，室温下实现了生物质羰基衍生化合物的还原氨化反应，选择性得到伯胺；（5）通过不同温度煅烧PbS进行表面氧化处理，可以将PbS不同程度氧化为PbSO4，所得材料可以高效催化以水为氢源的乙酰丙酸的加氢反应制备γ-戊内酯，γ-戊内酯的电流效率可以达到78.6%，远高于文献报道的最好结果；（6）低共熔溶剂中制备的CuS纳米片，可以高效催化糠醛电催化氧化制备5-羟基-2(5H)-呋喃酮，选择性可以达到83.6%；（7）发现氧缺陷能够极大提高CoO对5-羟甲基糠醛电催化氧化制备2,5-呋喃二甲酸的催化性能。综上所述，本项目研究了含羰基生物质衍生物的选择性转化，发展新催化方法和催化剂，详细研究了催化剂多活性位点的协同作用规律及机理，获得多种高效反应的方法和途径。本项目为生物质资源的高效转化及利用奠定了科学基础，促进了学科发展。