Tailored nanocomposites through the controlled reduction of metal nanoparticle-MOF templates.

高效催化剂的开发依赖于制备尺寸、形状和成分可控的金属和金属氧化物材料。金属纳米颗粒（NPs）和半导体金属氧化物支架的结合提供了高活性的异质结，这是已知的促进化学反应。最近，我们已经证明了沉积在金属有机框架（MOF）结构上的金属纳米颗粒可以用作模板来制备定制的金属/金属氧化物复合材料；在这种情况下，PdCu NPs沉积在半导体Cu2O上。这些样品对4-硝基苯酚的加氢具有很高的活性，比我们的标准Pd/TiO2催化剂的活性高得多。这项概念验证研究提供了令人兴奋的初步结果，支持了进一步研究的需要。PdCu/Cu2O体系在光催化、甲醇合成和甲酸分解等方面具有重要的潜在应用前景。PdCu NPs和Cu2O具有固有的特性，这使它们成为有价值的催化材料，然而，两种系统之间的协同作用有可能提供更多的好处。该项目旨在了解如何使用这些金属纳米颗粒/MOF材料来控制生成的金属/金属氧化物界面并最终控制其催化性能。为了回答这些问题，该项目将严重依赖于钻石光源的设施。纳米颗粒的结构将使用x射线吸收精细结构（XAFS-B18,I20）进行表征，而MOF结构的变化将使用PDF （I15）和传统衍射技术（I11）进行评估。SAXS在了解这些复合材料性质方面的潜力也将被探索。(I22 B21)。此外，我们将使用operando方法来了解i)这些材料的形成以及ii)这些定制复合材料的结构如何影响催化过程。

The development of efficient catalysts is dependent on preparing materials, both metals and metal oxides, of controlled size, shape, and composition. The combination of metal nanoparticles (NPs) and semiconductor metal oxide supports provide highly active heterojunctions, which are known to promote chemical reactions. Recently, we have demonstrated how metal nanoparticles deposited on metal organic framework (MOF) architectures can be used as templates to prepare tailored metal/metal oxide composites; in this instance PdCu NPs deposited on the semiconductor Cu2O. These samples proved highly active for the hydrogenation of 4-nitrophenol, demonstrating significantly higher activity than our standard Pd/TiO2 catalysts. This proof-of-concept study has provided exciting preliminary results, which support the need for further investigation. The PdCu/Cu2O system alone has significant potential applications in photocatalysis, methanol synthesis, and formic acid decomposition. PdCu NPs and Cu2O have innate characteristics, which make them valuable catalytic materials, however, the synergy between the two systems, has the potential to provide further benefits. This project seeks to understand how these metal nanoparticle/MOF materials can be used to control the resultant metal/metal oxide interface and ultimately their catalytic properties. To answer these questions the project will rely heavily on the facilities at Diamond Light Source. The structures of the nanoparticles will be characterised using X-ray absorption fine structure (XAFS-B18,I20), whilst changes to the MOF architecture will be assessed using PDF (I15) and conventional diffraction techniques (I11). The potential of SAXS to understand the nature of these composites will also be explored. (I22, B21). Moreover, we will use operando methods to understand i) the formation of these materials and ii) how the structures of these tailored composites affect catalytic processes.