Carbon- and Nitrogen-Based Organic Frameworks

This Account provides an overview of organic, covalent, porous frameworks and solid-state materials mainly composed of the elements carbon and nitrogen. The structures under consideration are rather diverse and cover a wide spectrum. This Account will summarize current works on the synthetic concepts leading toward those systems and cover the application side where emphasis is set on the exploration of those systems as candidates for unusual high-performance catalysis, electrocatalysis, electrochemical energy storage, and artificial photosynthesis. These issues are motivated by the new global energy cycles and the fact that sustainable technologies should not be based on rare and expensive resources. We therefore present the strategic design of functionality in cost-effective, affordable artificial materials starting from a spectrum of simple synthetic options to end up with carbon- and nitrogen-based porous frameworks. Following the synthetic strategies, we demonstrate how the electronic structure of polymeric frameworks can be tuned and how this can modify property profiles in a very unexpected fashion. Covalent triazine-based frameworks (CTFs), for instance, showed both enormously high energy and high power density in lithium and sodium battery systems. Other C,N-based organic frameworks, such as triazine-based graphitic carbon nitride, are suggested to show promising band gaps for many (photo)electrochemical reactions. Nitrogen-rich carbonaceous frameworks, which are developed from C,N-based organic framework strategies, are highlighted in order to address their promising electrocatalytic properties, such as in the hydrogen evolution reaction, oxygen reduction reaction (ORR), and oxygen evolution reaction (OER). With careful design, those materials can be multifunctional catalysts, such as a bifunctional ORR/OER electrocatalyst. Although the majority of new C,N-based materials are still not competitive with the best (usually nonsustainable candidates) for each application, the framework/N approach as such is still in its infancy and has already moved organic materials to regions where otherwise only traditional noble metals or special inorganic semiconductors are found. As one potential way to enhance the properties of polymeric frameworks, the idea of catalysts having unique active surfaces based on Mott-Schottky heterojunctions and related concepts are addressed. In order to integrate all of the above versatile subjects from synthesis to applications on C,N-based organic frameworks, we begin the discussion with synthetic concepts and strategies for these frameworks to distinguish these systems from typical covalent organic frameworks based on boron oxide rings. Next we focus on the semiconducting properties of C,N-based organic frameworks in order to show a continuous transition between CTFs and other systems, such as graphitic carbon nitrides. At the end, applications of these materials are shown by highlighting their properties in electrochemical energy storage and photo- and electrocatalysis.