DEVELOPMENT OF HIGH PERFORMANCE INTEGRATED CATALYSTS FOR SUSTAINABLE CHEMICAL TRANSFORMATION SYSTEMS

在这项研究项目中，我们致力于开发高性能的集成催化剂，用于环境友好和可持续的材料转化系统。目标反应是(1)使用分子氧和/或水的氧化反应，(2)选择性的碳-碳键形成反应，这对合成精细化学品非常重要。我们以无机微晶如羟基磷灰石(HAPS)、水滑石(HTS)和蒙脱石(Monts)为唯一载体，开发了能够被多种活性物种协同活化的新型纳米结构多相催化剂。对于乙醇的氧化，制备了RuHAP功能化的纳米Fe_2O_3，它对乙醇的好氧氧化表现出极高的活性，并具有磁回收催化剂的作用。此外，还可以开发用于环己醇转化为环己酮的高活性高温催化剂，这是一种难于氧化的反应。最近对…的兴趣更多的醇氧化在不使用任何氧化剂的情况下被脱氢。Ag/HT催化剂对各种醇类的脱氢反应具有极高的活性。HT的表面碱性和在其上形成的银纳米颗粒表明醇的协同活化作用，并定量地生成氢气。将该催化剂的应用范围扩展到以钒负载的高温为催化剂的丁腈水合反应中。有趣的是，蒙脱石的酸性粘土材料可以用作含有质子或各种金属阳离子的固体酸催化剂。这些固体酸可以催化各种亲核试剂与烯烃的加成反应，形成各种C-C、C-O和C-N键，这些催化剂制备简单，性能优异，为可持续绿色有机合成开辟了新的途径。上述转化的突出催化剂行为与无机微晶的表面性质和金属活性物种之间的协同作用有关。较少

In this research project, we aimed development of high performance integrated catalysts for environmentally-friendly and sustainable materials conversion systems. The target reactions are (1) oxidation reactions using molecular oxygen and/or water, and (2) selective carbon-carbon bond formation reactions, which are highly important for synthesis of finechemicals. We have developed novel nanostructured heterogeneous catalysts capable of cooperative activation by several active species, using inorganic crystallites, e. g., hydroxyapatites (HAPs), hydrotalcites (HTs), and montmorillonites (monts), as unique supports. As for the alcohol oxidation, RuHAP functionalized Fe_2O_3 nanoparticles was prepared, which showed extremely high activity fort aerobic alcohol oxidation and also acted as magnetically recoverable catalyst. Furthermore, highly active HT catalyst for conversion of cyclohexanol to cyclohexanone, which is known as difficult oxidation, could be developed. Recent interest in the … More alcohol oxidation has been dehydrogenation without using any oxidants. The Ag/HT catalyst could be extremely high activity for the dehydrogenation of various alcohols. The surface basicity of the HT and the Ag nanoparticles formed on the HT showed the concerted activation of alcohols and generated hydrogen quatitatively. Utilities of the HT catalysts were expanded to hydration of nitrile to amide using vanadium supported HT. Interestingly, acidic clay materials of montmorillonites could be used as solid acid catalysts having protons or various metal cations. These solid acids could catalyze addition reaction of various nucleophiles to olefins forming various C-C, C-O, and C-N bonds.These integrated catalysts can be easily prepared and exhibit outstanding performances, which open a new avenue for sustainable green organic syntheses. The prominent catalyst behavior for the above transformations is focused in relation to the concerted functions between the surface properties of the inorganic crystallites and the metal active species. Less