Selective Oxidations Using Colloidal Metal Particles with Non-Innocent Ligands

使用具有非无害配体的胶体金属颗粒的选择性氧化

• 批准号: 1947391
• 金额: --
• 依托单位: CARDIFF UNIVERSITY
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2017
• 资助国家: 英国
• 起止时间: 2017 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-1947391
• 关键词: Selective; Oxidations; Using; Colloidal; Metal

The project will fall at the boundary of heterogeneous catalysis, materials synthesis and colloidal science. Traditionally heterogeneous catalysis has been based on supporting precious metal nanoparticles on high surface area oxides or carbons to improve stability. However; supporting these particles forces them from there solution phase equilibrium structure. The particles become faceted in order to increase their interaction with the support material and in some cases this is detrimental to catalytic activity. Recently we have shown that by forming bimetallic nanoparticles which are stabilised with polymers in the liquid phase, rather than solid oxide materials certain challenging reactions can be carried out with high rates that are supressed with the faceted particles. One such challenging reaction is the selective oxidation of terminal hydrocarbon C-H such as methane, ethane, propane and liquid phase substrates such as cyclohexane. The project will investigate the effect of using colloidal particles rather than solid catalysts for the selective oxidation of these molecules to primary alcohols, which are important industrially. Understanding of the material synthesis is crucial in order to control particle size and composition and is not trivial at the nanoscale. One area of the colloidal synthesis that is not commonly investigated it the effect of the ligand used to stabilise the particles. Recent results have suggested that the polymer can affect the composition of the metal particles, the nature of the surface and the structure of the particle. By carful control of the ligand design, through the use of systematic molecule (N-heterocyclic carbenes) or polymer libraries, the effect of the electron donation or withdrawal from the metal particles on reactivity can be studied. Hence the aim of this PhD project will be to study the effect of decorating colloidal nanoparticles with these ligands and studying the effect on catalysed reactions involved in alkane activation.

该项目将落在多相催化、材料合成和胶体科学的边缘。传统上，多相催化的基础是将贵金属纳米颗粒负载在高比表面积的氧化物或碳上以提高稳定性。然而，支撑这些颗粒会迫使它们脱离溶液相平衡结构。为了增加它们与载体材料的相互作用，颗粒变得多面化，在某些情况下，这不利于催化活性。最近，我们已经证明，通过形成双金属纳米颗粒，这些纳米颗粒在液态中与聚合物稳定，而不是与固体氧化物材料一起形成，某些具有挑战性的反应可以以高速率进行，而这些反应被小平面颗粒抑制。其中一个具有挑战性的反应是末端碳氢化合物(如甲烷、乙烷、丙烷)和液体底物(如环己烷)的选择性氧化。该项目将研究使用胶体颗粒而不是固体催化剂将这些分子选择性氧化为伯醇的效果，这在工业上具有重要意义。了解材料的合成对于控制颗粒的大小和组成是至关重要的，在纳米尺度上也不是微不足道的。胶体合成的一个领域通常不被研究，那就是用来稳定颗粒的配体的作用。最近的结果表明，聚合物可以影响金属颗粒的组成、表面的性质和颗粒的结构。通过精心控制配体的设计，通过使用系统分子(N-杂环卡宾)或高分子库，可以研究金属粒子上电子的给予或退出对反应活性的影响。因此，本PHD项目的目的将是研究用这些配体修饰胶体纳米颗粒的效果，并研究其对烷烃活化所涉及的催化反应的影响。