Metal-Free and Noble Metal-Free Heteroatom-Doped Nanostructured Carbons as Prospective Sustainable Electrocatalysts.

The large-scale deployment of many types of fuel cells and electrolyzers is currently constrained by the lack of sustainable and efficient catalysts that can replace the less earth-abundant, noble metal-based catalysts, which are commonly used in these renewable energy systems. This burgeoning issue has led to explosive research efforts worldwide to find alternative, metal-free and noble metal-free catalysts that are composed of inexpensive and earth-abundant elements. Hence, the recent discoveries that doping carbon nanomaterials with heteroatoms (such as N, S, B, etc.) can give sustainable materials with good electrocatalytic activity for reactions carried out in fuel cells and electrolyzers have been not only quite exciting but also very promising to address these challenging issues. Interestingly, even though they contain no metals or involve only the inexpensive, more earth-abundant ones, the catalytic activity of some of these materials fares well with those of the commercially used noble metal-based electrocatalysts, such as Pt/C. However, research efforts to improve the catalytic activity, selectivity, and stability of some of these materials for various reactions are still necessary and thus continuing. While some of these efforts have focused on finding synthetic methods that can tune the structures and compositions of already known materials and thereby improve their catalytic properties (activity, selectivity, stability, etc.), others have focused on developing entirely new materials that can exhibit better or superior catalytic properties. In these efforts, additional considerations are also being paid to find facile synthetic routes or renewable and inexpensive precursors that can lead to such types of catalysts in order to make the entire process highly sustainable and widely applicable. In this Account, notable heteroatom-doped carbon catalysts that have been developed for reactions in fuel cells and water electrolyzers, the various synthetic procedures employed to make them, and the challenges involved in their synthesis as well as their characterizations are discussed. The methods used to systematically vary the structures and compositions of the precursors of these materials, as well as the materials themselves, and the different experimental, imaging, and spectroscopic methods used to investigate the properties and structure-property relationships of the materials for various energy related reactions are also included. The discussions focus mainly around the recent notable results reported on these materials by the author's and other research groups worldwide, albeit not exhaustively. Finally, the author's perspective about the challenges remaining in the field that need to be addressed, the many existing unanswered questions that beg for more research, and the future prospects for research related to the above topics are also mentioned.