New trimetallic nanoparticles as catalysts for the conversion of carbon dioxide to renewable fuels

加的夫催化研究所、英国催化中心、荷兰多尺度催化能量转换中心(MCEC，乌得勒支)和马克斯·普朗克学会弗里茨-哈伯研究所(FHI，柏林)将使用一种新的理论指导方法来设计新的三金属纳米粒子催化剂。负载型金属纳米粒子具有独特而迷人的物理化学性质，具有广泛的应用前景。根据定义，纳米颗粒的直径在一到一百纳米之间。对于如此小的结构，特别是接近尺寸范围的低端，每个原子都可以计算，因为纳米粒子的性质可以通过添加或移除几个原子来改变。因此，金属纳米颗粒的性质可以通过改变其尺寸(原子数)、形态(形状)和组成(原子类型和化学计量比，即包括元素金属、纯化合物、固溶体和金属合金)以及作为纳米颗粒载体的载体的选择来调节。纳米粒子的组成原子要么是表面的一部分，要么是靠近表面的，可以暴露在光、电子和X射线下进行表征，这是发生反应的区域。我们的领先应用将是催化，这是一个对英国和全球经济具有巨大重要性的战略性全球行业。许多催化剂都含有负载型金属纳米颗粒，这是一个正在迅速发展的催化领域。金属纳米颗粒已被广泛用于改善氢燃料电池和生物质反应堆发电，以及减少汽车发动机的有害废气污染物。许多传统催化剂含有大量昂贵的贵金属，可以通过设计新的多元纳米催化剂来大幅减少贵金属的使用量，这些催化剂可以进行调整，以提高催化活性、选择性和寿命，并降低工艺和材料成本。纳米催化领域的一个主要全球挑战是找到一种合理、可重复和可靠的方法来设计和制造纳米催化剂，从而使它们更适合于商业应用。目前，大多数负载型金属纳米催化剂包含一种或最多两种金属作为合金，但这个项目试图利用三金属来探索更复杂的结构，因为我们现在有概念验证研究表明，只引入少量的第三金属可以显著提高催化性能。我们的目标是用理论来预测多金属纳米粒子的结构和反应活性，并通过它们的合成和实验表征(例如，使用电子显微镜和X射线光谱)来验证这些数值模拟，特别是使用现场方法和对当前非常重要的反应的催化测试，即二氧化碳加氢生成液体运输燃料。制定该方案是为了使实验验证为理论研究提供反馈，从而设计出大大改进的催化剂。用理论来驱动催化剂设计是这项建议的一个新特点，我们认为理论方法现在已经得到了充分的发展和测试，能够确保以理论为指导的催化剂设计能够实现。为了实现这些雄心勃勃的目标，我们召集了一个国际专家团队来解决这一关键领域，他们有成功合作的记录。该提案中的研究中心拥有互补的专门知识，这将使研究一类新的复杂多相催化剂，即三金属合金成为可能。这项“中心对中心”拨款的授予将使英国走在国际催化研究的前沿。

The Cardiff Catalysis Institute, UK Catalysis Hub, Netherlands Centre for Multiscale Catalytic Energy Conversion (MCEC, Utrecht), and the Fritz-Haber-Institute of the Max Planck Society (FHI, Berlin) will use a novel theory-led approach to the design of new trimetallic nanoparticle catalysts. Supported metal nanoparticles have unique and fascinating physical and chemical properties that lead to wide ranging applications. A nanoparticle, by definition, has a diameter in the range one to one hundred nanometres. For such small structures, particularly towards the lower end of the size range, every atom can count as the properties of the nanoparticle can be changed upon the addition or removal of just a few atoms. Thus, properties of metal nanoparticles can be tuned by changing their size (number of atoms), morphology (shape) and composition (atom types and stoichiometry, i.e., including elemental metals, pure compounds, solid solutions, and metal alloys) as well as the choice of the support used as a carrier for the nanoparticle. The constituent atoms of a nanoparticle that are either part of, or are near the surface, can be exposed to light, electrons and X-rays for characterisation, and this is the region where reactions occur. Our lead application will be catalysis, which is a strategic worldwide industry of huge importance to the UK and global economy. Many catalysts comprise supported metal nanoparticles and this is now a rapidly growing field of catalysis. Metallic NPs already have widespread uses e.g., in improving hydrogen fuel cells and biomass reactors for energy generation, and in reducing harmful exhaust pollutants from automobile engines. Many traditional catalysts contain significant amounts of expensive precious metals, the use of which can be dramatically reduced by designing new multi-element nanocatalysts that can be tuned to improve catalytic activity, selectivity, and lifetime, and to reduce process and materials costs. A major global challenge in the field of nanocatalysis is to find a route to design and fabricate nanocatalysts in a rational, reproducible and robust way, thus making them more amenable for commercial applications. Currently, most supported metal nanocatalysts comprise one or at most two metals as alloys, but this project seeks to explore more complex structures using trimetallics as we now have proof-of-concept studies which show that the introduction of just a small amount of a third metal can markedly enhance catalytic performance.We aim to use theory to predict the structures and reactivities of multi-metallic NPs and to validate these numerical simulations by their synthesis and experimental characterisation (e.g., using electron microscopy and X-ray spectroscopy), particularly using in-situ methodologies and catalytic testing on a reaction of immense current importance; namely the hydrogenation of carbon dioxide to produce liquid transportation fuels. The programme is set out so that the experimental validation will provide feedback into the theoretical studies leading to the design of greatly improved catalysts. The use of theory to drive catalyst design is a novel feature of this proposal and we consider that theoretical methods are now sufficiently well developed and tested to be able to ensure theory-led catalyst design can be achieved.To achieve these ambitious aims, we have assembled a team of international experts to tackle this key area who have a track record of successful collaboration. The research centres in this proposal have complementary expertise that will allow for the study of a new class of complex heterogeneous catalysts, namely trimetallic alloys. The award of this Centre-to-Centre grant will place the UK at the forefront of international catalytic research.