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The presence and induced secondary reactions of natural organic matter (NOM) significantly affect the remediation efficacy of in situ chemical oxidation (ISCO) systems. However, it remains unclear how this process relates to organic radicals generated from reactions between the NOM and oxidants. The study, for the first time, reported the vital roles and transformation pathways of carbon-centered radicals (CCR • ) derived from NOM in activated persulfate (PS) systems. Results showed that both typical terrestrial/aquatic NOM isolates and collected NOM samples produced CCR • by scavenging activated PS and greatly enhanced the dehalogenation performance under anoxic conditions. Under oxic conditions, newly formed CCR • could be oxidized by O 2 and generate organic peroxide intermediates (ROO • ) to catalytically yield additional • OH without the involvement of PS. Nuclear magnetic resonance (NMR) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) results indicated that CCR • predominantly formed from carboxyl and aliphatic structures instead of aromatics within NOM through hydrogen abstraction and decarboxylation reactions by SO 4 •- or • OH. Specific anoxic reactions (i.e., dehalogenation and intramolecular cross-coupling reactions) further promoted the transformation of CCR • to more unsaturated and polymerized/condensed compounds. In contrast, oxic propagation of ROO • enhanced bond breakage/ring cleavage and degradation of CCR • due to the presence of additional • OH and self-decomposition. This study provides novel insights into the role of NOM and O 2 in ISCO and the development of engineered strategies for creating organic radicals capable of enhancing the remediation of specific contaminants and recovering organic carbon.

Alcohols are promising fuels for direct alcohol fuel cells and are common scavengers to identify reactive oxygen species (ROS) in electro-Fenton (EF) systems. However, the side impacts of alcohols on oxygen reduction reactions and ROS generation are controversial due to the complex interactions between electrodes and alcohol-containing electrolytes. Herein, we employed synchrotron-Fourier-transform infrared spectroscopy and electron paramagnetic resonance technologies to directly observe the changes of chemical species and electrochemical properties on the electrode surface. Our studies suggested that alcohols exhibited different limiting degrees on proton (H + ) mass transfer toward the catalytic surface, following an order of methanol < ethanol < isopropanol < tert -butyl alcohol (TBA). In addition, the formation of hydrophobic TBA clusters at high concentrations (>400 mM) resulted in a significant reduction in ionic conductivity and an elevation in charge transfer resistance, which impedes H + mass transfer and raises the energy barrier for 2e - oxygen reduction reaction processes. Moreover, the organic radical • CH 2 (CH 3 ) 2 CH 2 OH produced by the interaction of Fe 3+ and • OH with the alcohol in the EF system serves as a crucial intermediate in facilitating H 2 O 2 regeneration, which complicates the quenching effect of alcohols on • OH identification. Therefore, it is recommended that methanol should be used as the scavenger instead of TBA and the concentration should be less than 400 mM in EF systems.

Peracetic acid (PAA) oxidation catalyzed by metal-free carbons is promising for advanced water decontamination. Nevertheless, developing reaction-oriented and high-performance carbocatalysts has been limited by the ambiguous understanding of the intrinsic relationship between carbon chemical/molecular structure and PAA transformation behavior. Herein, we comprehensively investigated the PAA activation using a family of well-defined sp 2 /sp 3 carbon hybrids from annealed nanodiamonds (ANDs). The activity of ANDs displays a volcano-type trend, with respect to the sp 2 /sp 3 ratio. Intriguingly, sp 3 -C-enriched AND exhibits the best catalytic activity for PAA activation and phenolic oxidation, which is different from persulfate chemistry in which the sp 2 network normally outperforms sp 3 hybridization. At the electron-rich sp 2 -C site, PAA undergoes a reduction reaction to generate a reactive complex (AND-PAA*) and induces an electron-transfer oxidation pathway. At the sp 3 -C site adjacent to C═O, PAA is oxidized to surface-confined OH* and O* successively, which ultimately evolves into singlet oxygen ( 1 O 2 ) as the primary reactive species. Benefiting from the dual nonradical regimes on sp 2 /sp 3 hybrids, AND mediates a sustainable redox recycle with PAA to continuously generate reactive species to attack water contaminants, meanwhile maintaining structural/chemical integrity and exceptional reusability in cyclic runs.

This perspective presents the latest advancements in selective polymerization pathways in advanced oxidation processes (AOPs) for removal of featured organic pollutants in wastewater. In radical-based homogeneous reactions, SO 4 •   - -based systems exhibit superior oxidative activity toward aromatics with electron-donating substituents via single electron transfer and radical adduct formation (RAF). The produced organic radical cations subsequently undergo coupling and polymerization reactions to produce polymers. For • OH-based oxidation, metal ions facilitate the production of monomer radicals via RAF. Additionally, heterogeneous catalysts can mediate both coupling and polymerization reactions via persulfate activation without generating inorganic radicals. Metal-based catalysts will mediate a direct oxidation pathway toward polymerization. In contrast, carbon-based catalysts will induce coupling reactions to produce low-molecular-weight oligomers (≤4 units) via an electron transfer process. In comparison to mineralization, polymerization pathways remarkably reduce peroxide usage, quickly separate pollutants from the aqueous phase, and generate polymeric byproducts. Thus, AOP-driven polymerization systems hold significant promise in reducing carbon emission and realizing carbon recycling in water treatment processes.

Naturally occurring iron (Fe) minerals have been proved to activate persulfate (PS) to generate reactive species, but the role of soil-inherent Fe minerals in activating PS as well as the underlying mechanisms remains poorly understood. Here, we investigated sulfamethoxazole (SMX) degradation by PS in two Fe-rich soils and one Fe-poor soil. Unlike with the radical-dominant oxidation processes in Fe-poor soil, PS was effectively activated through nonradical pathways (i.e., surface electron-transfer) in Fe-rich soils, accounting for 68.4%-85.5% of SMX degradation. The nonradical mechanism was evidenced by multiple methods, including electrochemical, in situ Raman, and competition kinetics tests. Inherent Fe-based minerals, especially those containing Fe(II) were the crucial activators of PS in Fe-rich soils. Compared to Fe(III) minerals, Fe(II) minerals (e.g., ilmenite) were more liable to form Fe(II) mineral-PS* complexes to initiate the nonradical pathways, oxidizing adjacent SMX via electron transfer. Furthermore, mineral structural Fe(II) was the dominant component to coordinate such a direct oxidation process. After PS oxidation, low-crystalline Fe minerals in soils were transformed into high-crystalline Fe phases. Collectively, our study shows that soil-inherent Fe minerals can effectively activate PS in Fe-rich soils, so the addition of exogenous iron might not be required for PS-based in situ chemical oxidation. Outcomes also provide new insights into the activation mechanisms when persulfate is used for the remediation of contaminated soils.

A carbon-based advanced oxidation process is featured for the nonradical electron-transfer pathway (ETP) from electron-donating organic compounds to activated persulfate complexes, enabling it as a green technology for the selective oxidation of organic pollutants in complex water environments. However, the thermodynamic and kinetic behaviors of the nonradical electron-transfer regime had been ambiguous due to a neglect of the influence of pH on the mechanisms. In this study, three kinds of organic pollutants were divided in the carbon-based ETP regime: (i) physio-adsorption, (ii) adsorption-dominated ETP (oxidation rate slightly surpasses adsorption rate), and (iii) oxidation-dominated ETP (oxidation rate outpaces the adsorption rate). The differential kinetic behaviors were attributed to the physicochemical properties of the organic pollutants. For example, the hydrophobicity, molecular radius, and positive electrostatic potential controlled the mass-transfer process of the adsorption stage of the reactants (peroxydisulfate (PDS) and organics). Meanwhile, other descriptors, including the Fukui index, oxidation potential, and electron cloud density regulated the electron-transfer processes and thus the kinetics of oxidation. Most importantly, the oxidation pathways of these organic pollutants could be altered by adjusting the water chemistry. This study reveals the principles for developing efficient nonradical systems to selectively remove and recycle organic pollutants in wastewater.

The efficiency of persulfate-assisted advanced oxidation processes (PS-AOPs) in degrading organic pollutants is affected by the electron-donating capability of organic substances present in the water source. In this study, we systematically investigate the electron-donating capacity (EDC) difference between groundwater and surface water and demonstrate the dependence of removal efficiency on the EDC of target water by PS-AOPs with carbon nanotubes (CNTs) as a catalyst. Laboratory analyses and field experiments reveal that the CNT/PS system exhibits higher performance in organic pollutant removal in groundwater with a high concentration of phenols, compared to surface water, which is rich in quinones. We attribute this disparity to the selective electron transfer pathway induced by potential difference between PS-CNT and organic substance-CNT intermediates, which preferentially degrade organic substances with stronger electron-donating capability. This study provides valuable insights into the inherent selective removal mechanism and application scenarios of electron transfer process-dominated PS-AOPs for water treatment based on the electron-donating capacity of organic pollutants.

Urbanization and industrialization have exerted significant adverse effects on water quality, resulting in a growing need for reliable and eco-friendly treatment technologies. Persulfate (PS)-based advanced oxidation processes (AOPs) are emerging as viable technologies to treat challenging industrial wastewaters or remediate groundwater impacted by hazardous wastes. While the generated reactive species can degrade a variety of priority organic contaminants through radical and nonradical pathways, there is a lack of systematic and in-depth comparison of these pathways for practical implementation in different treatment scenarios. Our comparative analysis of reaction rate constants for radical vs. nonradical species indicates that radical-based AOPs may achieve high removal efficiency of organic contaminants with relatively short contact time. Nonradical AOPs feature advantages with minimal water matrix interference for complex wastewater treatments. Nonradical species ( e.g. , singlet oxygen, high-valent metals, and surface activated PS) preferentially react with contaminants bearing electron-donating groups, allowing enhancement of degradation efficiency of known target contaminants. For byproduct formation, analytical limitations and computational chemistry applications are also considered. Finally, we propose a holistically estimated electrical energy per order of reaction (EE/O) parameter and show significantly higher energy requirements for the nonradical pathways. Overall, these critical comparisons help prioritize basic research on PS-based AOPs and inform the merits and limitations of system-specific applications.

Accelerating the rate-limiting Fe 3+ /Fe 2+ circulation in Fenton reactions through the addition of reducing agents (or co-catalysts) stands out as one of the most promising technologies for rapid water decontamination. However, conventional reducing agents such as hydroxylamine and metal sulfides are greatly restricted by three intractable challenges: (1) self-quenching effects, (2) heavy metal dissolution, and (3) irreversible capacity decline. To this end, we, for the first time, introduced redox-active polymers as electron shuttles to expedite the Fe 3+ /Fe 2+ cycle and promote H 2 O 2 activation. The reduction of Fe 3+ mainly took place at active N-H or O-H bonds through a proton-coupled electron transfer process. As electron carriers, H atoms at the solid phase could effectively inhibit radical quenching, avoid metal dissolution, and maintain long-term reducing capacity via facile regeneration. Experimental and density functional theory (DFT) calculation results indicated that the activity of different polymers shows a volcano curve trend as a function of the energy barrier, highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap, and vertical ionization potential. Thanks to the appropriate redox ability, polyaniline outperforms other redox-active polymers (e.g., poypyrrole, hydroquinone resin, poly(2,6-diaminopyridine), and hexaazatrinaphthalene framework) with a highest iron reduction capacity up to 5.5 mmol/g, which corresponds to the state transformation from leucoemeraldine to emeraldine. Moreover, the proposed system exhibited high pollutant removal efficiency in a flow-through reactor for 8000 bed volumes without an obvious decline in performance. Overall, this work established a green and sustainable oxidation system, which offers great potential for practical organic wastewater remediation.

In electrochemical advanced oxidation processes (EAOPs), the rate-limiting step is the mass transfer of pollutants to the electrodes due to the limited active surface areas. To this end, we established a three-dimensional (3D) EAOP system by coupling conventional graphite electrodes with dispersed carbon nanotubes (CNTs). The electrodes (particularly the anode) induced electric field spontaneously polarized CNTs into dispersed reactive particle electrodes (CNT-PEs) in the solution, which remarkably promoted electrochemical activation of peroxydisulfate (PDS) to generate surface CNT-PDS* complexes and surface-bound radicals (SBRs). Based on the excited potential ( E CNT-PEs ) at different positions in the 3D electric field, CNT-PEs were activated into three states. (i) E CNT-PEs < E organic , CNT-PEs are chemically inert toward DCP oxidation; (ii) E organic < E CNT-PEs < E water , CNT-PEs will oxidize DCP via an electron-transfer process (ETP); (iii) E CNT-PEs > E water , both CNT-PDS* complexes and the anode will oxidize water to produce SBRs. Thus, DCP could be oxidized by CNT-PDS* complexes via ETP to form polychlorophenols on the CNT surface, causing rapid deactivation of the micro-electrodes. In contrast, SBRs attack DCP directly into chloride ions and hydroxylated products, maintaining the surface cleanliness and activity of CNT-PEs for long-term operations.

Single-atom catalysts (SACs)-based peroxymonosulfate (PMS) systems are highly selective to the type of organic pollutants while the mechanisms remain ambiguous. In this work, we carried out experimental and theoretical investigations to reveal the origins of selectivity of radical and nonradical pathways in a designated Co-N 4 -C/PMS system. Two typical pollutants [bisphenol A (BPA) and metronidazole (MNZ)] with different molecular structures were employed for comparison. We found that radical oxidation (SO 4 •- and HO • ) and nonradical electron-transfer pathway (ETP) co-existed in the Co-N 4 -C/PMS system. Pollutants (e.g., MNZ) with a high redox potential were degraded primarily by free radicals rather than ETP, while the oxidization of low-redox pollutants (e.g., BPA) was dominated by ETP at the surface region of Co-N 4 -C which overwhelmed the contributions of radicals in the homogeneous phase. Intriguingly, the contributions of radical and nonradical pathways could be manipulated by the PMS loading, which simultaneously increased the radical population and elevated the oxidation potential of Co-N 4 -C-PMS* complexes in ETP. Findings from this work will unravel the mysterious selective behavior of the SACs/PMS systems in the oxidation of different micropollutants.

Single oxygen-based advanced oxidation processes ( 1 O 2 -AOPs) exhibit great prospects in selective degradation of organic pollutants. However, efficient production of 1 O 2 via tailored design of catalysts to achieve selective oxidation of contaminants remains challenging. Herein, we develop a simple strategy to regulate the components and coordination of Co-N-C catalysts at the atomic level by adjusting the Zn/Co ratio of bimetallic zeolitic imidazolate frameworks (Zn x Co 1 -ZIFs). Zn 4 Co 1 -C demonstrates 98% selective removal of phenol in the mixed phenol/benzoic acid (phenol/BA) solutions. Density functional theory calculations and experiments reveal that more active CoN 4 sites are generated in Zn 4 Co 1 -C, which are beneficial to peroxymonosulfate activation to generate 1 O 2 . Furthermore, the correlation between the origin of selectivity and well-defined catalysts is systematically investigated by the electron paramagnetic resonance test and quenching experiments. This work may provide novel insights into selective removal of target pollutants in a complicated water matrix.

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.

Peroxymonosulfate (PMS)-based advanced oxidation processes (PMS-AOPs) as an efficient strategy for organic degradation are highly dependent on catalyst design and structured active sites. However, the identification of the active sites and their relationship with reaction mechanisms for organic degradation are not fully understood for a composite catalyst due to the complex structure. Herein, we developed a family of Co encapsulated in N-doped carbons (Co-PCN) with tailored types and contents of active sites via manipulated pyrolysis for PMS activation and ciprofloxacin (CIP) degradation, focusing on the correlation of active sites to generated reactive species and degradation routes of organics. The structure-function relationships between the different active sites in Co-PCN catalysts and reactive oxygen species (ROS), as well as bond breaking position of CIP, were revealed through regression analysis and density functional theory calculation. Co-N x , O-C═O, C═O, graphitic N, and defects in Co-PCN stimulate the generation of 1 O 2 for oxidizing the C-C bond in the piperazine ring of CIP into C═O. The substitution of F by OH and hydroxylation of the piperazine ring might be induced by SO 4 •- and • OH, whose formation was affected by C-O, Co(0), Co-N x , graphitic N, and defects. The findings provided new insights into reaction mechanisms in PMS-AOP systems and rational design of catalysts for ROS-oriented degradation of pollutants.

Graphitized nanodiamonds (ND) exhibit outstanding capability in activating peroxymonosulfate (PMS) for the removal of aqueous organic micropollutants (OMPs). However, controversial observation and interpretation regarding the effect of graphitization degree on ND's activity and the role of singlet oxygen ( 1 O 2 ) in OMP degradation need to be clarified. Herein, we investigated graphitized ND-mediated PMS activation. Experiments show that the activity of ND increases first and then decreases with the monotonically increased graphitization degree. Further experimental and theoretical studies unveil that the intensified surface graphitization alters the degradation mechanism from singlet oxygenation to an electron-transfer pathway. Moreover, for the first time, we applied a self-constructed, time-resolved phosphorescence detection system to provide direct evidence for 1 O 2 production in the PMS-based system. This work not only elucidates the graphitization degree-dependent activation mechanism of PMS but also provides a reliable detection system for in situ analysis of 1 O 2 in future studies.

Despite the vital roles of reactive radical species in the coupled iron-carbon composite/persulfate (PS) system for eliminating pollutants, nonradical contributions are typically overlooked. Herein, we developed two efficient magnetic iron-char composites via low-temperature (BCFe-400) and high-temperature (BCFe-700) pyrolysis. The two composites activated PS through nonradical pathways for sulfamethoxazole (SMX) degradation. In the BCFe-400/PS system, high-valent iron Fe(IV) was the dominant active species for the oxidation, evidenced by methyl phenyl sulfoxide-based probe tests, Mössbauer spectroscopy, and in situ Raman analyses with kinetic evaluation. In the BCFe-700/PS system, surface-mediated electron transfer dominated the oxidation, and the nonradical regime was probed by the electrochemical test and in situ Raman analysis. Furthermore, the BCFe-400/PS system maintained high efficiency in continuous degradation of SMX due to the feasible Fe 2+ generation toward Fe(IV) formation. In the BCFe-700/PS system, the stability of the system was limited due to the hindered electron transfer between the surface reactive complex (i.e., BCFe-700-PS*) and SMX, and thermal treatment would help recover the reactivity. Both BCFe-400/PS and BCFe-700/PS systems exhibited high performances for SMX removal in the presence of chloride and humic acid and in real water matrixes (e.g., seawater, piggery wastewater, and landfill leachate), exhibiting the great merits of the nonradical system. Overall, the study would provide new insights into PS activation by iron-loaded catalysts to efficiently degrade pollutants via nonradical pathways.

Nanocarbon-based persulfate oxidation emerges as a promising technology for the elimination of organic micropollutants (OMPs). However, the nature of the active site and its working mechanism remain elusive, impeding developments of high-performance oxidative technology for water treatment practice. Here, we report that defect-rich carbon nanotubes (CNTs) exhibit a superior activity in the activation of peroxymonosulfate (PMS) for OMP oxidation. Quantitative structure-activity relationship studies combined with theoretical calculations unveil that the double-vacancy defect on CNTs may be the intrinsic active site, which works as a conductive bridge to facilitate the potential difference-dominated electron transfer from the highest occupied molecular orbital of OMPs to the lowest unoccupied molecular orbital of PMS. Based on this unique mechanism, the established CNTs@PMS oxidative system achieves outstanding selectivity and realizes the target-oriented elimination of specific OMPs in a complicated aquatic environment. This work sheds new light on the mechanism of carbocatalysis for selective oxidation and develops an innovative technology toward remediation of practical wastewater.

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.

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.

This study proposed an electrochemical technique for investigating the mechanism of nonradical oxidation of organics with peroxydisulfate (PDS) activated by carbon nanotubes (CNT). The electrochemical property of twelve phenolic compounds (PCs) was evaluated by their half-wave potentials, which were then correlated to their kinetic rate constants in the PDS/CNT system. Integrated with quantitative structure-activity relationships (QSARs), electron paramagnetic resonance (EPR), and radical scavenging tests, the nature of nonradical pathways of phenolic compound oxidation was unveiled to be an electron-transfer regime other than a singlet oxygenation process. The QSARs were established according to their standard electrode potentials, activation energy, and pre-exponential factor. A facile electrochemical analysis method (chronopotentiometry combined with chronoamperometry) was also employed to probe the mechanism, suggesting that PDS was catalyzed initially by CNT to form a CNT surface-confined and -activated PDS (CNT-PDS*) complex with a high redox potential. Then, the CNT-PDS* complex selectively abstracted electrons from the co-adsorbed PCs to initiate the oxidation. Finally, a comparison of PDS/CNT and graphite anodic oxidation under constant potentials was comprehensively analyzed to unveil the relative activity of the nonradical CNT-PDS* complex toward the oxidation of different PCs, which was found to be dependent on the oxidative potentials of the CNT-PDS* complex and the adsorbed organics.

Minerals and transitional metal oxides of earth-abundant elements are desirable catalysts for in situ chemical oxidation in environmental remediation. However, catalytic activation of peroxydisulfate (PDS) by manganese oxides was barely investigated. In this study, one-dimension manganese dioxides (α- and β-MnO 2 ) were discovered as effective PDS activators among the diverse manganese oxides for selective degradation of organic contaminants. Compared with other chemical states and crystallographic structures of manganese oxide, β-MnO 2 nanorods exhibited the highest phenol degradation rate (0.044 min -1 , 180 min) by activating PDS. A comprehensive study was conducted utilizing electron paramagnetic resonance, chemical probes, radical scavengers, and different solvents to identity the reactive oxygen species (ROS). Singlet oxygen ( 1 O 2 ) was unveiled to be the primary ROS, which was generated by direct oxidation or recombination of superoxide ions and radicals from a metastable manganese intermediate at neutral pH. The study dedicates to the first mechanistic study into PDS activation over manganese oxides and provides a novel catalytic system for selective removal of organic contaminants in wastewater.

Environmentally friendly and low-cost catalysts are important for the rapid mineralization of organic contaminants in powerful advanced oxidation processes (AOPs). In this study, we reported N-doped graphitic biochars (N-BCs) as low-cost and efficient catalysts for peroxydisulfate (PDS) activation and the degradation of diverse organic pollutants in water treatment, including Orange G, phenol, sulfamethoxazole, and bisphenol A. The biochars at high annealing temperatures (>700 °C) presented highly graphitic nanosheets, large specific surface areas (SSAs), and rich doped nitrogen. In particular, N-BC derived at 900 °C (N-BC900) exhibited the highest degradation rate, which was 39-fold and 6.5-fold of that on N-BC400 and pristine biochar, respectively, and the N-BC900 surpassed most popular metal or nanocarbon catalysts. Different from the radical-based oxidation in N-BC400/PDS via the persistent free radicals (PFRs), singlet oxygen and nonradical pathways (surface-confined activated persulfate-carbon complexes) were discovered to dominate the oxidation processes in N-BC900/PDS. Moreover, the adsorption of organics was determined to be the key step determining reaction rate, revealing that the pre-adsorption of reactants significantly accelerated the nonradical oxidation pathway. This study not only provides robust and cheap carbonaceous materials for environmental remediation but also enables the first insight into the graphitic biochar-based nonradical catalysis.