SHINERS for the Study of Electrochemical and Catalytic Processes

壳隔离纳米粒子增强拉曼光谱（SHINERS）是一种非常有用和敏感的光谱表征工具，它不仅可以研究分子的结构，还可以跟踪原位/operando反应。原位/operando分析允许对反应和过程进行实时研究，因此可以看到任何中间物质和反应。拉曼光谱本身不够灵敏，无法完成对反应中痕量物质和中间体的详细分析，这通常是由于拉曼截面小，寿命有限，导致产生的信号较弱。这导致很难确定所观察到的是什么。利用金、银、铜等金属纳米粒子，我们可以利用表面等离子体共振现象来增强被探测到的信号。通过将这些纳米颗粒覆盖在一层非常薄（2-4纳米）的惰性层（如SiO2或Al-2O3）上，它们就变成了壳隔离纳米颗粒（SHINs）。这允许金属纳米颗粒的增强作用被利用，而不会对正在研究的反应、过程或分子产生影响。SHINERS在使用过渡金属的催化过程的原位研究中显示出巨大的潜力，因为SHINs不会干扰该过程，因此可以深入了解正在发生的通常复杂的反应。由于这些原因，SHINERS也允许在原位研究电化学过程。在这项研究中，金纳米颗粒将被包裹在SiO2或Al2O3的惰性层中，通过拉曼光谱研究铂和铜催化醛加氢的过程。这些壳隔离金纳米颗粒也将用于研究发生在电池电极上的过程和降解机制。本研究将与Johnson-Matthey PLC共同完成。

Shell isolated nanoparticle enhanced Raman spectroscopy (SHINERS) is a highly useful and sensitive spectroscopic characterisation tool that allows us not only to study the structure of a molecule but to follow reactions in situ/operando. In situ/operando analysis allows for reactions and processes to be studied in real time and therefore, for any intermediate species and reactions to be seen. Raman spectroscopy by itself is not sensitive enough to complete detailed analysis of trace amounts of species and intermediates in reactions, often due to small Raman cross sections and limited lifetimes, which lead to weak signals being produced. This leads to difficulty determining what has been observed. Using metal nanoparticles, such as gold, silver, and copper, we can use the surface plasmon resonance phenomenon to enhance the signals being detected. By covering these nanoparticles in a very thin (2-4 nm) inert layer, such as SiO2 or Al-2O3, they become shell isolated nanoparticles (SHINs). This allows for the enhancing effect of the metal nanoparticles to be utilised without having an effect on the reaction, process, or molecule being studied. SHINERS show great potential for use in the in situ study of catalytic processes that use transition metals, as the SHINs will not interfere with the process and can therefore provide insight into the often complex reactions taking place. SHINERS also allow for electrochemical processes to be studied in situ for these reasons. In this research endeavour, gold nanoparticles will be encased in an inert layer of SiO2 or Al2O3 to study the catalytic process of aldehyde hydrogenation using platinum and copper via Raman spectroscopy. These shell isolated gold nanoparticles will also be used to study processes occurring on and the degradation mechanism of battery electrodes. This research will be done in conjunction with Johnson-Matthey PLC.