Tailoring the Electrocatalytic Properties of sp2‐Hybridized Carbon Nanomaterials with Molecule Doping

Abstract For electrocatalytic processes, the electronic structure especially the density of states (DOS) of electrode materials plays a dominant role in process of electron transfer kinetics for redox reactions. The unusual electronic properties of sp 2 ‐hybridized carbon nanomaterials with adjustable DOS offer great promise in constructing high performance electrodes for electrochemical applications. However, researchers are still confronted with challenges such as how the electronic properties influence the kinetics of electron transfer and how to modulate the electronic structure appropriate strategy for achieving efficient electrochemical reactions of different sp 2 carbon nanomaterials. With the aim of understanding the impacts of electronic structures on electrocatalytic properties, we selected several typical 0D to 3D carbon nanomaterials, and tailored the electrocatalytic performance of carbon nanomaterials by doping electron donor and electron acceptor. The results demonstrate that different molecular doping give rise to entirely different modifications in electronic structure of the sp 2 ‐hybridized carbon nanomaterials, endowing modulation of the electrocatalytic properties for the appropriate redox reaction. When doped with electron acceptor, it is more conducive to the oxidation reaction. Conversely, doping with electron donors is more conducive to the occurrence of reduction reactions. This strategy reveals electronic structure effects on the electron transfer of electrocatalytic redox reaction and provides an efficient approach on tailoring the electrocatalytic performance of sp 2 ‐hybridized carbon nanomaterials. For further electrochemical applications, that can ultimately provide rational guidance toward the development of improved catalysts.