Metal-Free Carbocatalysis in Advanced Oxidation Reactions.

Catalytic processes have remarkably boosted the rapid industrializations in chemical production, energy conversion, and environmental remediation. As one of the emerging applications of carbocatalysis, metal-free nanocarbons have demonstrated promise as catalysts for green remediation technologies to overcome the poor stability and undesirable metal leaching in metal-based advanced oxidation processes (AOPs). Since our reports of heterogeneous activation of persulfates with low-dimensional nanocarbons, the novel oxidative system has raised tremendous interest for degradation of organic contaminants in wastewater without secondary contamination. In this Account, we showcase our recent contributions to metal-free catalysis in advanced oxidation, including design of nanocarbon catalysts, exploration of intrinsic active sites, and identification of reactive species and reaction pathways, and we offer perspectives on carbocatalysis for future environmental applications. The journey starts with the discovery of peroxymonosulfate (PMS) and peroxydisulfate (PDS) activation by graphene-based materials. With the systematic investigations on most carbon allotropes, for the first time the carbocatalysis for PMS or PDS activation was correlated with the pristine carbon configuration, oxygen functionality (ketonic groups), defect degree (exposed edge sites and vacancies), and dimensional structure. Moreover, an intrinsic difference in catalytic oxidation does exist between PMS and PDS activation. For example, the PMS/carbon reaction is dominated by free radicals, while PDS/carbon catalysis was unveiled as a singlet oxygen- or nonradical-based process in which the surface-activated PDS complex directly degrades the organic pollutants without relying on the generation of free radicals. Nitrogen doping significantly enhances the carbocatalysis because of the positively charged carbon domains, which strongly bind with persulfates to form reactive intermediates toward organic reactions. More importantly, N doping substantially alters the catalytic oxidation from a radical process to a nonradical pathway in PMS activation. Codoping of sulfur or boron with nitrogen at a rational level will synergistically promote the catalysis as a result of the formation of more catalytic centers by improved charge/spin redistribution of the carbon framework. Furthermore, a structure-performance relationship was established for annealed nanodiamonds with a characteristic sp/sp (core/shell) hybridization, where the catalytic pathways were intimately dependent on the thickness of the graphitic shells. Interestingly, the introduction of structural defects and N dopants into the well-defined graphitic carbon framework and alteration of graphene/diamond hybrids can transform the persulfate/carbon system from a radical oxidation pathway to a nonradical pathway. Encapsulation of metal nanoparticles within carbon layers further modulates the electronic states of the interacting carbon via charge transport to increase the electron density. Overall, this Account contributes to unveiling the mist of carbocatalysis in AOPs and to summarizing the achievements of metal-free remediation. We also present future research directions on underpinning the knowledge base to facilitate the applications of nanocarbons in sustainable catalysis and environmental chemistry.