Fenton-like activity and pathway modulation via single-atom sites and pollutants comediates the electron transfer process.

The studies on the origin of versatile oxidation pathways toward targeted pollutants in the single-atom catalysts (SACs)/peroxymonosulfate (PMS) systems were always associated with the coordination structures rather than the perspective of pollutant characteristics, and the analysis of mechanism commonality is lacking. In this work, a variety of single-atom catalysts (M-SACs, M: Fe, Co, and Cu) were fabricated via a pyrolysis process using lignin as the complexation agent and substrate precursor. Sixteen kinds of commonly detected pollutants in various references were selected, and their lnkobs values in M-SACs/PMS systems correlated well (R2 = 0.832 to 0.883) with their electrophilic indexes (reflecting the electron accepting/donating ability of the pollutants) as well as the energy gap (R2 = 0.801 to 0.840) between the pollutants and M-SACs/PMS complexes. Both the electron transfer process (ETP) and radical pathways can be significantly enhanced in the M-SACs/PMS systems, while radical oxidation was overwhelmed by the ETP oxidation toward the pollutants with lower electrophilic indexes. In contrast, pollutants with higher electrophilic indexes represented the weaker electron-donating capacity to the M-SACs/PMS complexes, which resulted in the weaker ETP oxidation accompanied with noticeable radical oxidation. In addition, the ETP oxidation in different M-SACs/PMS systems can be regulated via the energy gaps between the M-SACs/PMS complexes and pollutants. As a result, the Fenton-like activities in the M-SACs/PMS systems could be well modulated by the reaction pathways, which were determined by both electrophilic indexes of pollutants and single-atom sites. This work provided a strategy to establish PMS-based AOP systems with tunable oxidation capacities and pathways for high-efficiency organic decontamination.

Microenvironment Engineering of Heterogeneous Catalysts for Liquid-Phase Environmental Catalysis.

Environmental catalysis has emerged as a scientific frontier in mitigating water pollution and advancing circular chemistry and reaction microenvironment significantly influences the catalytic performance and efficiency. This review delves into microenvironment engineering within liquid-phase environmental catalysis, categorizing microenvironments into four scales: atom/molecule-level modulation, nano/microscale-confined structures, interface and surface regulation, and external field effects. Each category is analyzed for its unique characteristics and merits, emphasizing its potential to significantly enhance catalytic efficiency and selectivity. Following this overview, we introduced recent advancements in advanced material and system design to promote liquid-phase environmental catalysis (e.g., water purification, transformation to value-added products, and green synthesis), leveraging state-of-the-art microenvironment engineering technologies. These discussions showcase microenvironment engineering was applied in different reactions to fine-tune catalytic regimes and improve the efficiency from both thermodynamics and kinetics perspectives. Lastly, we discussed the challenges and future directions in microenvironment engineering. This review underscores the potential of microenvironment engineering in intelligent materials and system design to drive the development of more effective and sustainable catalytic solutions to environmental decontamination.

Shielding Mn3+ Disproportionation with Graphitic Carbon-Interlayered Manganese Oxide Cathodes for Enhanced Aqueous Energy Storage System.

Manganese dioxide (MnO2) materials have recently garnered attention as prospective high-capacity cathodes, owing to their theoretical two-electron redox reaction in charge storage processes. However, their practical application in aqueous energy storage systems faces a formidable challenge: the disproportionation of Mn3+ ions, leading to a significant reduction in their capacity. To address this limitation, the study presents a novel graphitic carbon interlayer-engineered manganese oxide (CI-MnOx) characterized by an open structure and abundant defects. This innovative material serves several essential functions for efficient aqueous energy storage. First, a graphitic carbon layer coats the MnOx molecular interlayer, effectively inhibiting Mn3+ disproportionation and substantially enhancing electrode conductivity. Second, the phase variation within MnOx generates numerous crystal defects, vacancies, and active sites, optimizing electron-transfer capability. Third, the flexible carbon layer acts as a buffer, mitigating the volume expansion of MnOx during extended cycling. The synergistic effects of these features result in the CI-MnOx exhibiting an impressive high capacity of 272 mAh g-1 (1224 F g-1) at 0.25 A g-1. Notably, the CI-MnOx demonstrates zero capacity loss after 90 000 cycles (≈3011 h), an uncommon longevity for manganese oxide materials. Spectral characterizations reveal reversible cation intercalation and conversion reactions with multielectron transfer in a LiCl electrolyte.

Dual Nonradical Catalytic Pathways Mediated by Nanodiamond-Derived sp2/sp3 Hybrids for Sustainable Peracetic Acid Activation and Water Decontamination.

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 sp2/sp3 carbon hybrids from annealed nanodiamonds (ANDs). The activity of ANDs displays a volcano-type trend, with respect to the sp2/sp3 ratio. Intriguingly, sp3-C-enriched AND exhibits the best catalytic activity for PAA activation and phenolic oxidation, which is different from persulfate chemistry in which the sp2 network normally outperforms sp3 hybridization. At the electron-rich sp2-C site, PAA undergoes a reduction reaction to generate a reactive complex (AND-PAA*) and induces an electron-transfer oxidation pathway. At the sp3-C site adjacent to C═O, PAA is oxidized to surface-confined OH* and O* successively, which ultimately evolves into singlet oxygen (1O2) as the primary reactive species. Benefiting from the dual nonradical regimes on sp2/sp3 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.

Transformative Removal of Aqueous Micropollutants into Polymeric Products by Advanced Oxidation Processes.

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, SO4• --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.

Critical Functions of Soil Components for In Situ Persulfate Oxidation of Sulfamethoxazole: Inherent Fe(II) Minerals-Coordinated Nonradical Pathway.

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.

Overlooked Impacts of Alcohols in Electro-H2O2 and Fenton Chemistry.

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 •CH2(CH3)2CH2OH produced by the interaction of Fe3+ and •OH with the alcohol in the EF system serves as a crucial intermediate in facilitating H2O2 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.

Overlooked Roles and Transformation of Carbon-Centered Radicals Produced from Natural Organic Matter in a Thermally Activated Persulfate System.

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 O2 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 SO4•- 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 O2 in ISCO and the development of engineered strategies for creating organic radicals capable of enhancing the remediation of specific contaminants and recovering organic carbon.

Overlooked Complexation and Competition Effects of Phenolic Contaminants in a Mn(II)/Nitrilotriacetic Acid/Peroxymonosulfate System: Inhibited Generation of Primary and Secondary High-Valent Manganese Species.

Organic contaminants with lower Hammett constants are typically more prone to being attacked by reactive oxygen species (ROS) in advanced oxidation processes (AOPs). However, the interactions of an organic contaminant with catalytic centers and participating ROS are complex and lack an in-depth understanding. In this work, we observed an abnormal phenomenon in AOPs that the degradation of electron-rich phenolics, such as 4-methoxyphenol, acetaminophen, and 4-presol, was unexpectedly slower than electron-deficient phenolics in a Mn(II)/nitrilotriacetic acid/peroxymonosulfate (Mn(II)/NTA/PMS) system. The established quantitative structure-activity relationship revealed a volcano-type dependence of the degradation rates on the Hammett constants of pollutants. Leveraging substantial analytical techniques and modeling analysis, we concluded that the electron-rich phenolics would inhibit the generation of both primary (Mn(III)NTA) and secondary (Mn(V)NTA) high-valent manganese species through complexation and competition effects. Specifically, the electron-rich phenolics would form a hydrogen bond with Mn(II)/NTA/PMS through outer-sphere interactions, thereby reducing the electrophilic reactivity of PMS to accept the electron transfer from Mn(II)NTA, and slowing down the generation of reactive Mn(III)NTA. Furthermore, the generated Mn(III)NTA is more inclined to react with electron-rich phenolics than PMS due to their higher reaction rate constants (8314 ± 440, 6372 ± 146, and 6919 ± 31 M-1 s-1 for 4-methoxyphenol, acetaminophen, and 4-presol, respectively, as compared with 671 M-1 s-1 for PMS). Consequently, the two-stage inhibition impeded the generation of Mn(V)NTA. In contrast, the complexation and competition effects are insignificant for electron-deficient phenolics, leading to declined reaction rates when the Hammett constants of pollutants increase. For practical applications, such complexation and competition effects would cause the degradation of electron-rich phenolics to be more susceptible to water matrixes, whereas the degradation of electron-deficient phenolics remains largely unaffected. Overall, this study elucidated the intricate interaction mechanisms between contaminants and reactive metal species at both the electronic and kinetic levels, further illuminating their implications for practical treatment.

Hydrogen Bonding Chemistry in Aqueous Ammonium Ion Batteries.

Aqueous ammonium ion batteries (AIBs) pose the advantages of high safety, low cost, and high efficiency, capturing substantial research interest. The intrinsic chemical properties of NH4 + promote the formation of hydrogen bonds with other constituents in AIBs, critically influencing the processes of NH4 + transfer, storage, and diffusion. This review delves into the pivotal role of hydrogen bonding chemistry in AIBs. Firstly, the principles of hydrogen bond are elucidated as the dominant chemical interaction governing NH4 + dynamics in AIBs. Subsequently, a detailed analysis is conducted on the impacts of hydrogen bonds in both electrolytes and electrode materials. Furthermore, the practical applications of hydrogen bonding chemistry within the context of AIBs are assessed. Finally, strategic insights and future research directions are proposed to harness hydrogen bonding effects for optimizing AIB performance. This review aims to define the mechanisms and impacts of hydrogen bonds in AIBs, providing robust strategies to enhance electrochemical performance, deepen the understanding of energy storage mechanisms, and guide the future advancement of AIBs technology.

Piezo-catalysis Mechanism Elucidation by Tracking Oxygen Reduction to Hydrogen Peroxide with In situ EPR Spectroscopy.

For piezoelectric catalysis, the catalytic mechanism is a topic of great controversy, with debates centered around whether it belongs to the energy band theory or the screening charge effect which are similar to mechanisms of photocatalysis and electrochemical catalysis, respectively. Due to the formation of different intermediate active-species during two-electron oxygen reduction reaction (ORR) via electro- and photo-catalysis, the key to solving this problem is precisely monitoring the active species involved in ORR during electro-, photo-, and piezo-catalysis under identical condition. Here, a semiconductor material, BiOBr with abundant oxygen vacancies (BOB-OV) was found remarkable catalytic activity in H2O2 production by all three catalytic methods. By employing in situ electron paramagnetic resonance (EPR) spectroscopy, the H2O2 evolution pathway through piezo-catalysis over BOB-OV was monitored, which showed a similar reaction pathway to that observed in photo-catalytic process. This finding represents solid evidence supporting the notion that piezo-catalytic mechanism of ORR is more inclined towards photo-catalysis rather than electro-catalysis. Significantly, this exploratory conclusion provides insight to deepen our understanding of piezo-catalysis.

Confined Tri-Functional FeOx @MnO2 @SiO2 Flask Micromotors for Long-Lasting Motion and Catalytic Reactions.

H2 O2 -fueled micromotors are state-of-the-art mobile microreactors in environmental remediation. In this work, a magnetic FeOx @MnO2 @SiO2 micromotor with multi-functions is designed and demonstrated its catalytic performance in H2 O2 /peroxymonosulfate (PMS) activation for simultaneously sustained motion and organic degradation. Moreover, this work reveals the correlations between catalytic efficiency and motion behavior/mechanism. The inner magnetic FeOx nanoellipsoids primarily trigger radical species (• OH and O2 •- ) to attack organics via Fenton-like reactions. The coated MnO2 layers on FeOx surface are responsible for decomposing H2 O2 into O2 bubbles to provide a propelling torque in the solution and generating SO4 •- and • OH for organic degradation. The outer SiO2 microcapsules with a hollow head and tail result in an asymmetrical Janus structure for the motion, driven by O2 bubbles ejecting from the inner cavity via the opening tail. Intriguingly, PMS adjusts the local environment to control over-violent O2 formation from H2 O2 decomposition by occupying the Mn sites via inter-sphere interactions and enhances organic removal due to the strengthened contacts and Fenton-like reactions between inner FeOx and peroxides within the microreactor. The findings will advance the design of functional micromotors and the knowledge of micromotor-based remediation with controlled motion and high-efficiency oxidation using multiple peroxides.

Synthesis of the 5-6-7 Tricyclic Core of Daphnicyclidin-Type Alkaloids via a Tiffeneau-Demjanov Ring Enlargement Strategy.

An expedient construction of the 5-6-7 tricyclic core of daphnicyclidin-type alkaloids is described. The synthetically challenging cycloheptanone C ring was constructed via a Tiffeneau-Demjanov ring enlargement reaction from a 5-6-6 tricyclic precursor commonly found in calyciphylline A-type alkaloids. Other key transformations included Davis oxidation, 1,2-addition, oxidation, and dehydration to elaborate the essential cyclcohept-2-enone motif.

Selective Removal of Organic Pollutants in Groundwater and Surface Water by Persulfate-Assisted Advanced Oxidation: The Role of Electron-Donating Capacity.

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.

Merits and Limitations of Radical vs. Nonradical Pathways in Persulfate-Based Advanced Oxidation Processes.

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.

Thermodynamic and Kinetic Behaviors of Persulfate-Based Electron-Transfer Regime in Carbocatalysis.

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.

Redox-Active Polymers as Robust Electron-Shuttle Co-Catalysts for Fast Fe3+/Fe2+ Circulation and Green Fenton Oxidation.

Accelerating the rate-limiting Fe3+/Fe2+ 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 Fe3+/Fe2+ cycle and promote H2O2 activation. The reduction of Fe3+ 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.

Directional and Ultrafast Charge Transfer in Oxygen-Vacancy-Rich ZnO@Single-Atom Cobalt Core-Shell Junction for Photo-Fenton-Like Reaction.

In photosynthesis, solar energy is harvested by photosensitizers, and then, the excited electrons transfer via a Z-Scheme mode to enzymatic catalytic centers to trigger redox reactions. Herein, we constructed a core-shell Z-scheme heterojunction of semiconductor@single-atom catalysts (SACs). The oxygen-vacancy-rich ZnO core and single-atom Co-N4 sites supported on nitrogen-rich carbon shell (SA-Co-CN) act as the photosensitizer and the enzyme-mimicking active centers, respectively. Driven by built-in electric field across the heterojunction, photoexcited electrons could rapidly (2 ps) transfer from the n-type ZnO core to the p-type SA-Co-CN shell, finally boosting the catalytic performance of the surface-exposed single-atom Co-N4 sites for peroxymonosulfate (PMS) activation under light irradiation. The synergies between photocatalysis and heterogeneous Fenton-like reaction lead to phenomenally enhanced production of various reactive oxygen species for rapid degradation of various microcontaminants in water. Experimental and theoretical results validate that the interfacial coupling of SA-Co-CN with ZnO greatly facilitates PMS adsorption and activation by reducing the adsorption energy and enhancing the cascade electron transfer processes for the photo-Fenton-like reaction.

Unveiling the Relationship of Surface Roughness on Superliquid-Repelling Properties with Randomly Distributed Rough Surface Structures.

Though superliquid-repelling surfaces are universally important in the fields of fundamental research and industrial production, the understanding and development of these surfaces to impacting liquid droplets remain elusive, especially the changes of wettability states. Surface roughness is required to obtain superliquid-repelling surfaces. However, the effect of surface roughness on the transition of these surfaces' wettability states is uncertain. Herein, we unveiled the relationship of surface roughness on regulating the wettability states of superliquid-repelling surfaces with randomly distributed rough structures through experiment and calculations. The roughness was controlled via regulating the size of surface rough structures, which were formed by a facile coating method. The results indicated that the surface rough structures could impact the value of the polar component (γsp) and then impact the wettability states of superliquid-repelling surfaces. Quantitatively, when the increment of surface roughness was low, the decrement of γsp was low and the wettability state of the superliquid-repelling surface was superhydrophobicity. When the increment of surface roughness was high, the decrement of γsp was high and the wettability state of the superliquid-repelling surface converted to superamphiphobicity. The findings will shed light onto the development of superliquid-repelling surfaces in future studies.

Origins of Electron-Transfer Regime in Persulfate-Based Nonradical Oxidation Processes.

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.