多元醇选择性氧化反应中二维催化材料的制备及作用机理研究

Catalytic transformation of platform chemicals to valuable products is of great importance for the development of biorefinery. Many biobased chemicals can substitute their fossil derived counterparts and may more easily be produced from biomass. According to the recent progresses in the selective oxidation of ployols, the performance of solid catalysts depend mainly on its the electron properties, and electron transformation between catalysts and reactants played a crucial role in the production distribution. .At the same time, ultrathin two-dimensional (2D) nanomaterials have attracted increasing attentions of many scientists all over the world. Beside graphene, several kinds of ultrathin 2D materials that possess similar layered structure but versatile properties were reported intensively. And these 2D materials have large surface area, ultrahigh carrier mobility, excellent optical transparency and thermal conductivity. Apart from these popularly reported applications in electronics, energy storage-conversion and biomedicine, we think that 2D materials are also promising catalysts and/or supports for their high electron mobility, easy modification of the electron properties, high surface area and good mechanical strength. The reason for this suggestion lies in that all those elementary steps in heterogenous catalysis reaction (such as, the adsorption of reactants, surface diffusion of adsorbed species, the formation of new bonds between adsorbed species and desorption of products) are electron transformation processes between catalysts and reactants. That is, the real reaction process and its activation energy depend strongly on the electron transform and valence electron characteristics of catalyst. In this case, the main object of this project is to disclose the electronic relationship between 2D structured catalysts and its performance in the transformation of bio-based platform chemicals. .The main works of this project include (1) synthesis of 4-6 kinds of new hybrid catalysts with 2D structure (such as N and/or O-doped graphene and these grapheme supported catalysts), (2) new synthesis techniques which can depress the re-graphitization and/or decrease the sintering of 2D catalysts, (3) new characterization methods to disclose the real electron properties of 2D catalysts and the electron transfer between catalyst and reactants, (4) reaction kinetics and mechanism of selective oxidation of ethanol and glycerol over these 2D catalysts. On the base of these experiments, we want to disclose (1) the relationship between the composition, structure and dimension of these 2D materials with their electronic properties, (2) the relationship between the electronic properties of 2D catalysts and their performance in selective oxidation of ployols. .We think that this project has obvious novelty in the catalytic process design, in the synthesis strategy of well-defined catalysts and also in the in-situ characterization method near the real reaction conditions. The research group of this project is well experienced and well-known in the area of catalytic upgrading of glycerol. During the process, we will discuss our results and suggestions with those famous scientists in this area via manuscript submission, international congress and lectures. Several young scientists will grow up. We believe that the foundings and conclusions of this project will contribute to the development of heterogeneous catalysis, especially in the area of selective oxidation of biobased chemicals.

生物质平台化合物的高效转化具有重要的意义和应用前景、可以推动生物质能源的健康发展；本课题是依据氧化还原反应的理论基础、多相催化剂的作用机理和二维材料电子特征而设计和提出的。项目拟以碳基二维材料为前驱体设计和制备系列表界面特性可控的催化剂，探索新催化材料的制备策略和新方法；考察上述催化剂在乙醇/甘油选择性氧化反应中的作用规律，采用原位拉曼技术检测反应的历程，总结催化剂的表面及界面的电子特征、以及这些特征与催化反应的能垒和产物分布之间的关系规律，在分子、原子水平上揭示催化剂的活性中心及其作用机理，寻找并验证决定催化效率的关键因素。本项目瞄准国际科学前沿、面向国家在新材料和可持续发展的重大战略需求，为生物质平台化合物的高效转化提供理论支持、为新催化剂的设计提供指导，希望在催化剂的可控合成和反应机理的原位拉曼表征技术上取得突破。

本项目严格按照项目计划书的内容，详细开展了项目计划书中各项研究，并取得了重要的进展。我们认为在以下几个方面取得了重要的进展：①在二维催化材料的制备、表征及其在生物质多元醇的高效转化方面取得重要发现突破，采用MOFs前驱体、水滑石前驱体等制备出具有超高活性、高温度性、具有特殊结构的催化剂。②在甘油制备大宗化学品（乙醇）、精细化学品（丙烯醇）和燃料添加剂等方面取得了重要的突破，得到国内外研究同行的广泛关注。③在固体酸催化剂的设计、合成、表征及应用等方面进行了大量的探索，并取得了重要的进展。④拓展研究了其它多元醇（乙醇、丙三醇、1,4-丁二醇、1,3-丁二醇等）的转化利用方向取得了重要的研究进展和知识积累，取得了多项具有自主知识产物的前期研究结果。.新发现：①首次提出了甘油制备大宗化学品(乙醇)的反应机理、研制出来可以实现这个过程的高效催化剂，这个结果得到国内外同行的关注和推荐。②在甘油制备精细化学品（丙烯醇）方面提出了全新的机理、研制出高效的催化剂，目的产物丙烯醇的收率是已有文献的2倍多。③在新型固体酸催化剂中酸性中心的生成方法、分散性及防止其流失和中毒等方面提出了全新的观点。.上述研究成果引起国内外研究同行的重点关注和积极评价。先后发表SCI论文19篇、申请国家发明专利10件（其中4件已授权）、培养硕博士研究生11人、参加国际国内学术会议8人次。