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

在研究单位“unnode”的第一个资助期内，我们已经提出用氧化反应取代电解槽中常用的析氧反应，在氧化反应中，可用物质转化为增值产品。总的目标仍然是研究电催化剂修饰的电极用于不寻常的阳极反应。然而，所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工业相关的增值化学品的策略和机制，重点是选择性作为性能的最关键参数。最终目标是将惰性电极界面上的电子交换与溶液中引发化学后续反应的有机反应转变为有机分子在催化剂表面的特定吸附和吸附状态下的电子转移。在成功的情况下，这种方法不仅可以根据所施加的电位/电流、电解质和浓度，还可以通过与催化剂材料的相互作用来调整选择性。这一概念对于有机合成过程的电气化至关重要。此外，NH3在水溶液中电氧化为NO，氮化物和硝酸盐，这是一个据称具有重大影响的新领域，将被探索。新催化剂材料的合成策略，特别是多元素复杂固溶体（高熵材料），将在考虑可扩展性的情况下开发。获得的电催化剂将固定在稳定的电极衬底上，如Ni泡沫或碳布，并将在先前开发的小流量电解槽中对甘油氧化，有机电合成和NH3氧化进行活性，稳定性和选择性评估。催化剂修饰的电极将由联盟中的合作伙伴使用，所获得的结果将由ATR-FTIR光谱电化学的机理见解支持。

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.