负载型双金属Re-M催化剂的理性设计、化学制备及其生物基丁二酸水相催化加氢性能

Aqueous hydrogenation of bio-based succinic acid to value-added chemicals, e.g. 1,4-butanediol, tetrahydrofuran, and γ-butyrolactone, is one of the perspective topics in catalysis science and technology. This proposal plans to design rationally the bimetallic Re-based catalysts by density functional calculations according to the electronic structure theory, and to prepare controllably ZrO2, TiO2, Nb2O5 or carbon supported bimetallic Re-based catalysts with different structures and compositions by Metal-organic Chemical Vapor Deposition (MOCVD) by mono/binuclear complexes according to the characteristics of aqueous hydrogenation of bio-based succinic acid. To understand formation mechanism and structural changes of the bimetallic catalysts, a number of in situ charaterization techniques will be performed.Thereby, the structures and the compositions of the bimetallic catalysts can be tuned by the precursors and process parameters. Aqueous hydrogenation of bio-based succinic acid over the bimetallic Re-based catalysts will be investigated in detail to well understand the relationship among their structure, composition, and properties. Meanwhile, effect of the byproducts like acetic acid, formic acid, lactic acid, and pyruvic acid from the fermentation will also be studied on activity and selectivity of the bimetallic Re-based catalysts The density functional theory will be used to correlate the structure and the catalytic properties of the bimetallic catalysts. Combining theoritical and experimental results,the formation mechanism and the relationship between structure and hydrogenation property of the bimetallic catalysts will be concluded.The implementation of the project will lay the scientific basis on the controllable synthesis of new bimetallic Re-based catalysts and their applications in aqueous hydrogenation of bio-based succinic acid to value-added chemicals at "molecular engineering" level. The related conclusions will be explanded into design and controlled preparation of the other catalytic materials for aqueous hydrogenation reactions.

丁二酸水相催化加氢制备高附加值丁二醇、γ-丁内酯和四氢呋喃等化学品是催化领域具有挑战性的课题之一。本申请项目拟针对丁二酸水相催化加氢反应特点，通过设计并合成金属有机前体，采用化学气相沉积技术可控制备耐水性载体如炭材料和氧化锆/钛/铌等负载的Re基双金属催化剂；利用多种原位表征技术弄清双金属催化剂的形成机理和结构变化规律，从而实现双金属催化剂结构和组成的调变；研究Re基双金属催化剂上丁二酸水相催化加氢催化性能，以及生物基丁二酸中杂质如乙酸、甲酸、乳酸和丙酮酸等对其性能的影响规律，揭示Re基双金属催化剂结构和组成与丁二酸水相催化加氢性能的内在关系；采用理论计算对丁二酸水相催化加氢反应中结构和性能以及动力学等进行模拟，结合实验结果确定负载型Re基双金属催化剂结构和催化加氢选择性的调控规律。课题的实施将在分子层面理解Re基双金属催化剂结构与性能的内在关系，为生物基丁二酸水相选择转化提供理论基础。

生物基羧酸水相催化加氢制备高附加值二醇、γ-丁内酯和四氢呋喃等化学品是催化领域具有挑战性的课题之一。在本项目的资助下，项目组针对丁二酸水相催化加氢反应特点，通过设计并合成金属有机前体，采用微波辅助热解法和强静电化学吸附法可控制备耐水性炭材料负载的Re基双金属催化剂，通过H2-TPR、HRTEM、XPS等手段揭示了双金属催化剂的形成机理和结构变化规律，从而实现双金属催化剂结构和组成的调变。通过研究Re基双金属催化剂在丁二酸水相加氢反应中的动力学，并探究了不同组成、类型的Re-M金属间协同作用在丁二酸加氢反应中的作用机理。通过对丁二酸加氢机理的认识实现其定向转化。此外，我们还扩展性研究了C4-C6不同碳链长度的双羧酸加氢反应过程，进一步明确了中间产物对反应产物的重要作用，并将Re基双金属催化剂应用于其他选择加氢反应制备高值精细化学品。本项目的实施在分子层面理解了Re基双金属催化剂结构与性能的内在关系，为生物基有机酸水相选择转化提供理论基础。在本学科领域ACS Catalysis、ChemSusChem、Catalysis Science & Technology、Industrial & Engineering Chemistry Research等高水平期刊上发表研究论文26篇（项目标注），发表会议论文3篇，申请发明专利5项；培养硕士研究生5名，博士生6名。