Electrocatalysis for alcohol oxidation, ammonia oxidation and organic transformations. From catalyst development to unified organic electrocatalysis

早在研究单位“UNODE”的第一个资助期内，我们就提议用氧化反应取代电解槽中常用的析氧反应，在氧化反应中，将可用物质转化为增值产品。总的目标将仍然是不寻常的阳极反应的电催化剂改性电极的调查。然而，研究的反应将从甘油和HMF氧化扩展到将有机反应物转化为具有工业相关性的增值化学品的策略和机制，重点是选择性作为最关键的性能参数。最终目标是从在惰性电极界面处与有机反应交换电子的范式转变，所述有机反应在溶液中引发化学后续反应，到有机分子在催化剂表面上的特异性吸附和吸附状态下的电子转移。在成功的情况下，这种方法将允许不仅通过施加的电势/电流、电解质和浓度而且通过与催化剂材料的相互作用来调节选择性。这一概念对于有机合成过程的电气化至关重要。此外，NH3在水溶液中的电氧化为NO，氮化物和硝酸盐，这是一个新的领域，将被探索。新催化剂材料的合成策略，特别是多元元素复合固溶体（高熵材料），将开发保持可扩展性。所获得的电催化剂将固定在稳定的电极基底上，如镍泡沫或碳布，并将在先前开发的小型流通式电解槽中对甘油氧化、有机电合成和NH3氧化的活性、稳定性和选择性进行评价。催化剂修饰的电极将由联盟中的合作伙伴使用，所获得的结果将得到ATR-FTIR光谱电化学的机理见解的支持。

Already during the 1st funding period of the research unit "UNODE", we proposed to replace the commonly used oxygen evolution reaction in electrolyzers with oxidation reactions in which an available substance is converted to a value-added product. The overall objective will remain the investigation of electrocatalyst-modified electrodes for unusual anode reactions. However, the investigated reactions will be extended from glycerol and HMF oxidation to strategies and mechanisms to convert organic reactants to value-added chemicals of industrial relevance with emphasis on selectivity as the most critical parameter of performance. The ultimate goal is a paradigm shift from exchanging electrons at an inert electrode interface with organic reactions invoking chemical follow-up reactions in the solution to specific adsorption of organic molecules on catalyst surfaces and electron transfer in the adsorbed state. In case of success, this approach will allow tuning selectivity not only with the applied potential/current, the electrolyte, and concentrations but also by the interaction with catalyst materials. This concept will be of utmost importance for the electrification of organic synthesis processes. Additionally, the electrooxidation of NH3 to NO, nitride, and nitrate in aqueous solution, a new field of supposedly significant impact, will be explored. Synthesis strategies for new catalyst materials, specifically multinary elements complex solid solutions (high-entropy materials), will be developed keeping scalability in mind. The obtained electrocatalysts will be immobilized on stable electrode substrates like Ni foam or carbon cloth and will be evaluated regarding activity, stability and selectivity in the previously developed small flow-through electrolyzer cell for glycerol oxidation, organo-electrosynthesis and NH3 oxidation. The catalyst-modified electrodes will be used by the partners in the consortium and the obtained results will be supported by mechanistic insights from ATR-FTIR spectroelectrochemistry.