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

1.研制了紫外拉曼光谱仪（248 nm），用于样品界面的无荧光测量.探索bp.3中拉曼应用的其他过程分析机会。设计和构建用于在水水解过程操作期间对各种电极或电极涂层材料进行拉曼显微镜检查的原位池4.探索催化剂降解，电极腐蚀和污垢的选择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。这个博士项目的目的是发展的拉曼光谱的机会与新的激光技术在248纳米。最近的一个最先进的例子（使用相同的激光）是由美国宇航局在火星漫游者上发射的，用于表征火星岩石样本。优化这种新型光谱仪的灵敏度与最近可用的紫外光学，如光纤，过滤器（带通和陷波），以及应用多元分析的光谱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，如分析发动机油和芳香族有机物，其中荧光可能是一个问题。对于这些应用，将有必要开发与UV拉曼系统一起使用的静态池和流动池。该项目的第二个主要目标是开发拉曼显微镜，用于制氢电催化电池的操作研究，以便对所涉过程有更详细的科学了解。许多先进的特征化技术不能在歌剧中发挥作用。开发定制的表征系统以在运行期间进行测量是了解催化剂降解、电极腐蚀和结垢等挑战的重要进展。由于需要在不干扰所观察过程的情况下进行光学访问，因此在操作中或原位研究是一项真实的技术挑战。我们的团队与Holmes教授最近证明了直接甲醇燃料电池膜的操作研究的概念证明。将使用拉曼显微镜（Renishaw InVia系统，785 nm激发-此外，EPSRC已为532 nm激光器提供资金）来实现电催化反应中电极表面的2D化学表征。深度剖析也可以通过将激发激光的焦点改变到表面以下来实现，因此原则上可以进行化学成分的3D扫描。其他最先进的拉曼技术，如表面增强拉曼光谱（Sers）也将探讨作为这项工作的一部分。由于激发光束与金属纳米颗粒的耦合，这可以给出几个数量级的信号增加。对于该项目的这一部分，它将是有益的，探索类似的系统与其他先进的表征技术，如XPS，SEM，TEM，西姆斯和NMR可在UoM和bpICAM与同事。

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.