Rh基/UiO-66复合材料的界面调控及其CO加氢制乙醇性能研究

Based on the characteristics of energy structure in China and the strategic demand of developing clean coal technologies, the development of ethanol synthesis technology from coal (syngas) is of great significance in the fields of energy, chemical engineering, etc. Because of the superior capabilities of CO dissociation and insertion, Rh-based catalysts have been found to display unique efficiency in catalyzing ethanol synthesis from syngas. Therefore, it has attracted much attention in recent years. However, how to regulate the activity center for CO dissociation, CO insertion, and hydrogen activation, and then achieve the catalytic efficiency for industrial applications is still the key to the development of the catalyst. In this project, a novel high-temperature resistant three-dimensional zirconium metal-organic framework (UiO-66) is chosen as the support. By adjusting the pore structure and surface properties of the support, the highly dispersed Rh active center with controllable surface and interface properties is constructed, then the ideal Rh center will be optimized to improve the reactivity and ethanol selectivity. The relationship among the surface property of UiO-66, the activity center, the ability for the activation of CO and H2, and catalytic performance should be suggested after the study, and the research results would lay the foundation for the design of Rh-based catalysts with prospects for industrial applications.

基于我国的能源结构特点和开发清洁化煤资源利用技术的战略需求，煤（合成气）制乙醇技术的开发在能源、化工等领域具有重要意义。Rh基催化剂因其优越的CO解离和插入能力，在CO加氢反应过程中拥有良好的乙醇生成活性，因此成为了研究热点与核心。但如何科学设计催化剂，合理调控Rh基催化剂活性中心对CO解离、插入、及氢的活化能力，进而达到满足工业应用的催化活性及乙醇选择性仍是该催化剂开发的关键。本项目拟选用新型三维网状耐高温的锆金属有机骨架材料(UiO-66)为载体，通过调节载体孔道结构和表面性质，有目的地构建表/界面性质可控的高分散性Rh活性中心，提高催化剂对乙醇的生成效率。通过本项目的研究，建立UiO-66表面性质-Rh活性中心-CO与H2的活化-反应性能之间的构效关系，为开发具有工业应用前景的铑基催化剂提供新的借鉴和思路。

基于我国的能源结构特点和开发清洁化煤资源利用技术的战略需求，煤（合成气）制乙醇技术的开发在能源、化工等领域具有重要意义。由于Rh基催化剂在CO加氢反应过程中拥有卓越的乙醇生成活性，进一步合理调控Rh基催化剂活性中心对CO解离、插入、及氢的活化能力，进而达到满足工业应用的催化活性及乙醇选择性是该技术的核心。项目从Rh基催化剂催化机理发出，设计合成了系列Rh基/Zr-MOF、Rh基/氧化物、Ni-Al2O3催化剂，并应用于合成气转化制乙醇和甲烷干重整制合成气反应。重点研究了载体性质、助剂掺杂等因素对Rh活性中心分散状态、形貌、及电子价态的调控机制，确定了催化材料物理化学性质和催化性能间的关联规律。通过多种原位表征和动力学手段对气相反应物分子在催化剂表面的吸附、解离和加氢转化路径进行研究，揭示了不同催化体系下CO加氢反应机理。本项目的开展为开发新型的合成气转化制乙醇材料、提升其反应性能并促进其产业化应用提供重要的研究基础。