Electrocatalytic nanocarbon (EN) is a class of material receiving intense interest as a potential replacement for expensive, metal-based electrocatalysts for energy conversion and chemical production applications. The further development of EN will require an intricate knowledge of its catalytic behaviors, however, the true nature of their electrocatalytic activity remains elusive. This review highlights work that contributed valuable knowledge in the elucidation of EN catalytic mechanisms. Experimental evidence from spectroscopic studies and well-defined molecular models, along with the survey of computational studies, is summarized to document our current mechanistic understanding of EN-catalyzed oxygen, carbon dioxide and nitrogen electrochemistry. We hope this review will inspire future development of synthetic methods and in situ spectroscopic tools to make and study well-defined EN structures.

Metal-free motifs, such as graphitic carbon nitride, conjugated polymers, and doped nanostructures, are emerging as a new class of Earth-abundant materials for solar fuel devices. Although these metal-free structures show great potential, detailed mechanistic understanding of their performance remains limited. Here, we review important experimental and theoretical findings relevant to the role of metal-free motifs as either photoelectrodes or electrocatalysts. First, the light-harvesting characteristics of metal-free photoelectrodes (band energetics, exciton binding energies, charge carrier mobilities and lifetimes) are discussed and contrasted with those in traditional inorganic semiconductors (such as Si). Second, the mechanistic insights into the electrocatalytic oxygen reduction and evolution reactions, hydrogen evolution reaction, and carbon dioxide reduction reaction by metal-free motifs are summarized, including experimental surface-sensitive spectroscopy findings, studies on small molecular models, and computational modeling of these chemical transformations.

Exciton size and dynamics were studied in assemblies of two well-defined graphene quantum dots of varying size: hexabenzocoronene (HBC), where the aromatic core consists of 42 C atoms, and carbon quantum dot (CQD) with 78 C atoms. The synthesis of HBC and CQD were achieved using bottom-up chemical methods, while their assembly was studied using steady-state UV/vis spectroscopy, X-ray scattering, and electron microscopy. While HBC forms long ordered fibers, CQD was found not to assemble well. The exciton size and dynamics were studied using time-resolved laser spectroscopy. At early times (∼100 fs), the exciton was found to delocalize over ∼1−2 molecular units in both assemblies, which reflects the confined nature of excitons in carbon-based materials and is consistent with the calculated value of ∼2 molecular units. Exciton−exciton annihilation measurements provided the exciton diffusion lengths of 16 and 3 nm for HBC and CQD, respectively.