DESIGNING GOLD CATALYSTS FOR THE UTILISATION OF BIO-RENEWABLE FEEDSTOCKS

这项提议旨在寻找一种用于绿色氧化过程的新的重要催化剂。特别是，我们将研究多相催化剂，其中反应物和产物与催化剂处于不同的相。多相催化在英国经济的福祉中发挥着重要作用，因为它本质上涉及从制药到电子设备的大多数成品的制造。催化是绿色技术的基石；然而，我们的大多数燃料和油漆和聚合物等制成品的原料来自碳氢化合物的化石储量。最近，相当大的兴趣集中在英国国内的生活方式对这些碳氢化合物原料的可获得性和价格可能变化的潜在敏感性上。对于英国来说，这一问题正变得越来越严重，因为经济上可行的北海石油库存现在正在下降，英国将严重依赖进口能源和化工原料。在这种背景下，目前正在采取行动，增加对生物柴油的利用，生物柴油是由甲醇与植物油反应产生的。目前，允许在商品柴油中添加5%的生物柴油，但预计这一比例将会增加。不幸的是，生物柴油生产提供了大量甘油作为副产品，目前还没有大规模使用。这潜在地限制了生物柴油的普及。因此，甘油被广泛用作生物可再生原料，其潜在的绿色用途尚未开发。此外，还有一系列碳水化合物形式的生物可再生原料。这项研究项目的目的是设计可用于各种底物氧化的选择性氧化催化剂，并为在新的绿色技术中有效利用这些生物可再生原料提供基础。目前迫切需要这样一种方法，因为即使在今天，许多非绿色方法目前仍被倡导用于选择性氧化。这项提议的核心在于加的夫申请者的研究小组最近的发现，即负载金-钯纳米颗粒对于氢氧化制过氧化氢和醇氧化制醛都是非常有效的催化剂，其转换频率是之前报道的这一重要反应最佳催化剂的25倍。我们现在寻求扩大这些催化剂可以有效的反应范围，并通过这种方式为特定官能团的选择性氧化反应提供工具箱。这种方法有两个预期的结果。首先，我们的目标是设计能够在实验室中作为标准合成方法使用的金催化剂。第二，我们的目标是证明这些催化剂也可以用于糖和萜类等更为复杂的生物可再生原料的氧化。目前，我们已经在高压反应釜中进行了实验，这符合我们最初的目标，即建立负载型金催化剂作为标准的实验室试剂；我们将使用发现催化和化学工程相结合的方法来评估连续过程的选择。

This proposal seeks to find a new class of important catalysts for use in green oxidation processes. In particular, we will study heterogeneous catalysts, where the reactants and products are in a different phase from the catalyst. Heterogeneous catalysis plays an important role in the well being of the UK economy since it is inherently involved in the manufacture of most finished products from pharmaceuticals to electrical devices. Catalysis is a cornerstone of green technology; however, most of our fuels and feedstocks for manufactured goods such as paints and polymers come from fossil reserves of hydrocarbons. Considerable interest has recently been focussed on the potential sensitivity of the lifestyle within the UK to the possible variation in the availability and price of these hydrocarbon feedstocks. This is becoming increasingly acute for the UK as stocks of economically viable North Sea oil are now declining and the UK will be heavily dependent on imported energy and chemical feedstocks. Against this background there is a current move to increase the utilisation of bio-diesel which is derived from the reaction of methanol with vegetable oils. At present it is permissible to add 5% of bio-diesel to commercial diesel, but this is expected to increase. Unfortunately, bio-diesel production provides large quantities of glycerol as a by-product, for which there is no current large scale use. This is potentially limiting for the take up of biodiesel. Hence glycerol is widely available as a bio-renewable feedstock for which potential green uses have yet to be developed. In addition, there is a range of bio-renewable feedstocks available in the form of carbohydrates. The aim of this research project is to design selective oxidation catalysts that can be used for the oxidation of a wide range of substrates and in addition provide the basis for the efficient utilisation of these bio-renewable feedstocks in new green technologies. Such an approach is desperately needed at present as, even today, many non-green approaches are currently being advocated for selective oxidation. At the heart of this proposal lies the recent discoveries, in the research group of the applicants at Cardiff, that supported gold-palladium nanoparticles are exceptionally effective catalysts for the oxidation of hydrogen to hydrogen peroxide, and the oxidation of alcohols to aldehydes with turnover frequencies >25 times higher than the previously reported best catalysts for this important reaction. We now seek to extend the range of reactions for which these catalysts can be effective and in this way provide a toolbox for selective oxidation reaction of specific functionalities. This approach has two intended outcomes. The first is that we aim to design gold catalysts that can be used in the laboratory as a standard synthetic methodology. In the second, we aim to show that these catalysts can be used also for the oxidation of the significantly more complex bio-renewable feedstocks such as sugars and terpenes. At present we have conducted experiments in autoclave reactors, which are suitable for our initial aim to establish supported gold catalysts as a standard laboratory reagent; we will use a combined discovery catalysis and chemical engineering approach to evaluate options for continuous processes.