Interplay of nitrogen- and oxygen functionalities of carbon based catalysts in redox reactions

长期以来，人们一直对碳材料的催化性能感兴趣。近年来，由于能量存储和转换的新应用的发展，这种兴趣甚至增加了。此外，还讨论了碳基催化剂作为工业化学中长期使用的催化体系的一种节能替代品。然而，到目前为止，大多数所研究的碳催化剂在大多数所研究的反应中都没有表现出足够的催化活性。碳的氮掺杂可以显著提高不同氧化还原反应的活性。然而，基本问题仍然悬而未决，需要澄清，并由此得出该项目的目标。这一方面涉及特定的氮官能团对催化功能的贡献，另一方面也涉及氮和氧官能团之间的相互作用。在此背景下，还必须考虑氮官能团对特定氧官能团形成的影响。为了研究这个问题，需要一个催化剂合成的模块化概念。这一概念的实施应采用模板辅助路线，该路线能够形成具有受控表面成分、结构和孔隙率的碳复制品。催化剂将含有不同比例的吡咯和吡啶类物种的氮官能团。氮物种对氧官能团形成的影响将通过使用氧化剂进行明确的后处理来研究。这些催化剂将在不同的测试反应中进行研究，如碳氢化合物的氧化脱氢和亚硫酸的氧化。实验结果将通过对模型碳中氮官能团性质的量子化学计算来完成。提交的研究项目的预期结果将使人们更好地了解氮和氧官能团在所考察的反应中相互作用的情况，并提高对氮掺杂碳材料的新合成方法和可能的催化应用的了解。

There is a long-standing interest on the catalytic properties of carbon materials. This interest has even been increased in the recent years due to the developments of novel applications for energy storage and conversion, respectively. Furthermore, carbon based catalysts are also discussed as an energy-saving alternative to long-standing used catalytic systems of the industrial chemistry. Nevertheless, up to date most of the examined carbon catalysts do not exhibit sufficient catalytic activity in a majority of studied reactions. Nitrogen doping of the carbons can enhance the activity for different redox reactions considerably. However, fundamental questions are still open and needed to be clarified, and from that the objectives of the project are derived. This concerns on the one hand the contribution of particular nitrogen functionalities to the catalytic functions and, on the other hand, the interaction of nitrogen and oxygen functionalities with each other as well. In this context, the impact of nitrogen functionalities on the formation of particular oxygen functionalities has to be considered, too. A modular concept of catalyst synthesis is required to investigate the matter. That concept shall be executed applying template assisted routes, which enable the formation of carbon replicas with controlled surface composition, structure and porosity. The catalysts will contain nitrogen functionalities with varied ratios of pyrrole- to pyridine-like species. The impact of the nitrogen species on the formation of oxygen functionalities will be investigated applying defined post treatments with oxidizing agents. The catalysts will be investigated in different test reactions such as the oxidative dehydrogenation of hydrocarbons, and the oxidation of sulphurous acid. The experimental findings shall be completed by quantum chemical calculations on the nature of nitrogen functionalities in model carbons. The prospective results of the submitted research project will provide a better understanding of the interplay of nitrogen and oxygen functionalities with each other in the examined reactions as well as improve a knowledge about new synthesis methods and possible catalytic applications of nitrogen-doped carbon materials.