Persulfate-based nonradical oxidation processes (PS-NOPs) are appealing in wastewater purification due to their high efficiency and selectivity for removing trace organic contaminants in complicated water matrices. In this review, we showcased the recent progresses of state-of-the-art strategies in the nonradical electron-transfer regimes in PS-NOPs, including design of metal and metal-free heterogeneous catalysts, in situ/operando characterization/analytical techniques, and insights into the origins of electron-transfer mechanisms. In a typical electron-transfer process (ETP), persulfate is activated by a catalyst to form surface activated complexes, which directly or indirectly interact with target pollutants to finalize the oxidation. We discussed different analytical techniques on the fundamentals and tactics for accurate analysis of ETP. Moreover, we demonstrated the challenges and proposed future research strategies for ETP-based systems, such as computation-enabled molecular-level investigations, rational design of catalysts, and real-scenario applications in the complicated water environment. Overall, this review dedicates to sharpening the understanding of ETP in PS-NOPs and presenting promising applications in remediation technology and green chemistry.

Persulfates activation by carbon nanotubes (CNT) has been evidenced as nonradical systems for oxidation of organic pollutants. Peroxymonosulfate (PMS) and peroxydisulfate (PDS) possess discrepant atomic structures and redox potentials, while the nature of their distinct behaviors in carbocatalytic activation has not been investigated. Herein, we illustrated that the roles of nitrogen species in CNT-based persulfate systems are intrinsically different. In PMS activation mediated by nitrogen-doped CNT (N-CNT), surface chemical modification (N-doping) can profoundly promote the adsorption quantity of PMS, consequently elevate potential of derived nonradical N-CNT–PMS* complexes, and boost organic oxidation efficiency via an electron-transfer regime. In contrast, PDS adsorption was not enhanced upon incorporating N into CNT due to the limited equilibrium adsorption quantity of PDS, leading to a relatively lower oxidative potential of PDS/N-CNT system and a mediocre degradation rate. However, with equivalent persulfate adsorption on N-CNT at a low quantity, PDS/N-CNT exhibited a stronger oxidizing capacity than PMS/N-CNT because of the intrinsic higher redox potential of PDS than PMS. The oxidation rates of the two systems were in great linearity with the potentials of carbon–persulfate* complexes, suggesting N-CNT activation of PMS and PDS shared the similar electron-transfer oxidation mechanism. Therefore, this study provides new insights into the intrinsic roles of heteroatom doping in nanocarbons for persulfates activation and unveils the principles for a rational design of reaction-oriented carbocatalysts for persulfate-based advanced oxidation processes.

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Carbon-driven advanced oxidation processes are appealing in wastewater purification because of the metal-free feature of the carbocatalysts. However, the regime of the emerging nonradical pathway is ambiguous because of the intricate carbon structure. To this end, this study was dedicated to unveil the intrinsic structure-performance relationship of peroxydisulfate (PDS) activation by carbon nanotubes (CNTs) toward nonradical oxidation of organics such as phenol (PE) via electron transfer. Eighteen analogical CNTs were synthesized and functionalized with different categories and contents of oxygen species. The quenching tests and chronopotentiometry suggest that an improved reactivity of surface-regulated CNTs was attributed to the reinforced electron-transfer regime without generation of free radicals and singlet oxygen. The quantitative structure–activity relationships were established and correlated to the Tafel equation, which unveils the nature of the nonradical oxidation by CNT-activated PDS complexes (CNT-PDS*). First, a decline in the concentration of oxygen groups in CNTs will make the zeta potential of the CNT become less negative in neutral solutions, which facilitated the adsorption of PDS because of weaker electrostatic repulsion. Then, the metastable CNT-PDS* was formed, which elevated the oxidation capacity of the CNT. Finally, PE would be oxidized over CNT-PDS* via electron transfer to fulfill the redox cycle. Moreover, the nonradical oxidation rate was uncovered to be exponentially related with the potential of the complexes, suggesting that the nonradical oxidation by the CNT-PDS* undergoes a mechanism analogous to anodic oxidation.