Operando Studies of Electrocatalysis for Hydrogen Production Using Pioneering Vibrational Spectroscopic Techniques

1. 248nm样品界面无荧光紫外拉曼仪的研制探索bp.3内部拉曼应用的其他过程分析机会。水水解过程中不同电极或电极涂层材料拉曼显微镜原位细胞的设计与构建探索催化剂降解，电极腐蚀和污垢选定的电催化系统结合替代电子显微镜和质谱为基础的表征技术。该博士项目旨在利用248纳米的新激光技术开发拉曼光谱的机会。最近，美国国家航空航天局（NASA）在火星探测器上发射了一个最先进的例子（使用相同的激光），以表征火星岩石样本。优化这种新型光谱仪的灵敏度与最近可用的紫外光学器件，如光纤，滤波器（带通和陷波）以及多元分析光谱的应用将提供一个强大的表征工具。bp感兴趣的几个应用已经被确定，如分析机油和芳香有机物，荧光可能是一个问题。对于这些应用，有必要开发用于UV拉曼系统的静态和流动电池。该项目的第二个主要目标是开发拉曼显微镜，用于生产氢的电催化电池的操作研究，以便对所涉及的过程有更详细的科学理解。许多先进的表征技术不能在歌剧中使用。定制化表征系统的开发可以在操作过程中进行测量，这对于理解催化剂降解、电极腐蚀和结垢等挑战是一个重要的进步。由于要求在不干扰所观察过程的情况下进行光学访问，因此在操作或原位研究是一项真正的技术挑战。我们的团队与Holmes教授最近展示了直接甲醇燃料电池膜的操作研究的概念证明。拉曼显微镜（雷尼绍InVia系统，785 nm激发，另外，EPSRC已经为532 nm激光器提供了资金）将用于实现电催化反应中电极表面的二维化学表征。深度剖面也可以通过改变激发激光的焦点到表面以下来实现，因此原则上可以对化学成分进行3D扫描。其他最先进的拉曼技术，如表面增强拉曼光谱（SERS）也将作为这项工作的一部分进行探索。由于激发光束与金属纳米粒子的耦合，这可以使信号增加几个数量级。对于项目的这一部分，与同事一起探索类似的系统与其他先进的表征技术，如XPS， SEM， TEM， SIMS和NMR，在UoM和bpICAM可用。

1. Development of UV Raman (248 nm) instrument for fluorescence free measurements with sample interface.2. Explore additional process analytical opportunities for Raman applications within bp.3. Design and construction of in situ cell for Raman microscopy of various electrodes or electrode coating materials during operation for water hydrolysis processes4. Exploration of catalyst degradation, electrode corrosion and fouling of selected electrocatalytic systems in combination with alternative electron microscopy and mass spectrometry- based characterisation techniques.This PhD project aims to develop the Raman spectroscopy opportunities with new laser technology at 248 nm. A recent state-of-art example of this (with the same laser) was launched by NASA on the Mars rover for characterisation of Martian rock samples. Optimising the sensitivity of this novel spectrometer with recently available uv optics such as fibre optics, filters (band-pass and notch) as well as the application of multivariate analysis to the spectra will provide a powerful characterisation tool. Several applications of bp interest have already been identified such as the analysis of motor oils and aromatic organics where fluorescence can be a problem. For these applications it will be necessary to develop both static and flow cells for use with the UV Raman system. The second main aim of the project is the development of Raman microscopy for in operando studies of electrocatalytic cells for hydrogen production in order to develop a more detailed scientific understanding of the processes involved. Many advanced characterisation techniques cannot operate in operando. The development of bespoke characterisation systems to measure during operation is an important advance to understanding the challenges such as catalyst degradation, electrode corrosion and fouling. In operando or in situ studies are a real technical challenge due to the requirements for optical access without disturbing the processes being observed. Our group, with Prof Holmes, have recently demonstrated a proof of concept for the in operando study of direct methanol fuel cell membranes. Raman microscopy (Renishaw InVia system with 785 nm excitation - additionally, funding has been applied from EPSRC for a 532 nm laser) will be used to enable 2D chemical characterisation of the electrode surface in the electrocatalytic reactions. Depth profiling can be also achieved by varying the focus of the excitation laser to below the surface so in principle 3D scans of chemical composition can be made. Other state of the art Raman techniques such as surface enhanced Raman spectroscopy (SERS) will also be explored as part of this work. This can give several orders of magnitude signal increase due to coupling of the excitation beam with metal nano-particles. For this part of the project it will be beneficial to explore similar systems with other advanced characterisation techniques such as XPS, SEM, TEM, SIMS and NMR available at UoM and bpICAM with colleagues.