High-valent metal-oxo species transformation and regulation by co-existing chloride: Reaction pathways and impacts on the generation of chlorinated by-products.

High-valent metal-oxo species (HMOS) have been extensively recognized in advanced oxidation processes (AOPs) owing to their high selectivity and high chemical utilization efficiency. However, the interactions between HMOS and halide ions in sewage wastewater are complicated, leading to ongoing debates on the intrinsic reactive species and impacts on remediation. Herein, we prepared three typical HMOS, including Fe(IV), Mn(V)-nitrilotriacetic acid complex (Mn(V)NTA) and Co(IV) through peroxymonosulfate (PMS) activation and comparatively studied their interactions with Cl- to reveal different reactive chlorine species (RCS) and the effects of HMOS types on RCS generation pathways. Our results show that the presence of Cl- alters the cleavage behavior of the peroxide OO bond in PMS and prohibits the generation of Fe(IV), spontaneously promoting SO4•- production and its subsequent transformation to secondary radicals like Cl• and Cl2•-. The generation and oxidation capacity of Mn(V)NTA was scarcely influenced by Cl-, while Cl- would substantially consume Co(IV) and promote HOCl generation through an oxygen-transfer reaction, evidenced by density functional theory (DFT) and deuterium oxide solvent exchange experiment. The two-electron-transfer standard redox potentials of Fe(IV), Mn(V)NTA and Co(IV) were calculated as 2.43, 2.55 and 2.85 V, respectively. Due to the different reactive species and pathways in the presence of Cl-, the amounts of chlorinated by-products followed the order of Co(II)/PMS > Fe(II)/PMS > Mn(II)NTA/PMS. Thus, this work renovates the knowledge of halide chemistry in HMOS-based systems and sheds light on the impact on the treatment of salinity-containing wastewater.

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.

Atomic-level Engineered Cobalt Catalysts for Fenton-Like Reactions: Synergy of Single Atom Metal Sites and Nonmetal-bonded Functionalities.

Single atom catalysts (SACs) are atomic-level-engineered materials with high intrinsic activity. Catalytic centers of SACs are typically the transition metal (TM)-nonmetal coordination sites, while the functions of co-existing non-TM-bonded functionalities are usually overlooked in catalysis. Herein, we reported the scalable preparation of carbon-supported cobalt-anchored SACs (CoCN) with controlled Co-N sites and free functional N species. We first systematically study the role of metal and nonmetal bonded functionalities in the SACs for peroxymonosulfate (PMS)-driven Fenton-like reactions, revealing their contribution to performance improvement and pathway steering. Experiments and computations demonstrate that the Co-N3C coordination plays a vital role in the formation of a surface-confined PMS* complex to trigger the electron transfer pathway and promote kinetics because of the optimized electronic state of Co centers, while the non-metal-coordinated graphitic N sites act as preferable pollutant adsorption sites and additional PMS activation sites to accelerate electron transfer. Synergistically, CoCN exhibits ultrahigh activity in PMS activation for p-hydroxybenzoic acid oxidation, achieving complete degradation within 10 min with an ultrahigh turnover frequency of 0.38 min-1, surpassing most reported materials. These findings offer new insights into the versatile functions of N species in SACs and inspire rational design of high-performance catalysts in complicated heterogeneous systems. This article is protected by copyright. All rights reserved.

Size-Dependent Catalysis in Fenton-like Chemistry: From Nanoparticles to Single Atoms.

State-of-the-art Fenton-like reactions are crucial in advanced oxidation processes (AOPs) for water purification. This review explores the latest advancements in heterogeneous metal-based catalysts within AOPs, covering nanoparticles (NPs), single-atom catalysts (SACs), and ultra-small atom clusters. A distinct connection between the physical properties of these catalysts, such as size, degree of unsaturation, electronic structure, and oxidation state, and their impacts on catalytic behavior and efficacy in Fenton-like reactions. In-depth comparative analysis of metal NPs and SACs is conducted focusing on how particle size variations and metal-support interactions affect oxidation species and pathways. The review highlights the cutting-edge characterization techniques and theoretical calculations, indispensable for deciphering the complex electronic and structural characteristics of active sites in downsized metal particles. Additionally, the review underscores innovative strategies for immobilizing these catalysts onto membrane surfaces, offering a solution to the inherent challenges of powdered catalysts. Recent advances in pilot-scale or engineering applications of Fenton-like-based devices are also summarized for the first time. The paper concludes by charting new research directions, emphasizing advanced catalyst design, precise identification of reactive oxygen species, and in-depth mechanistic studies. These efforts aim to enhance the application potential of nanotechnology-based AOPs in real-world wastewater treatment.

Oxidative polymerization versus degradation of organic pollutants in heterogeneous catalytic persulfate chemistry.

Catalytic polymerization pathways in advanced oxidation processes (AOPs) have recently drawn much attention for organic pollutant elimination owing to the rapid removal kinetics, high selectivity, and recovery of organic carbon from wastewater. This work presents a review on the polymerization regimes in AOPs and their applications in wastewater decontamination. The review mainly highlights three critical issues in polymerization reactions induced by persulfate activation (Poly-PS-AOPs), including heterogeneous catalysts, persulfate activation pathways, and properties of organic substrates. The dominant influencing factors on the selection of catalysts, activation regimes of reactive oxygen species, and polymerization processes of organic substrates are discussed in detail. Moreover, we systematically demonstrate the merits and challenges of Poly-PS-AOPs upon pollutant degradation and polymer synthesis. We particularly highlight that Poly-PS-AOPs technology could be promising in the treatment of industrial wastewater containing heterocyclic organics and the synthesis of polymers and polymer-functionalized materials for advanced environmental and energy applications.

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.

Synergy of Dendrites-Impeded Atomic Clusters Dissociation and Side Reactions Suppressed Inert Interface Protection for Ultrastable Zn Anode.

The sluggish ions-transfer and inhomogeneous ions-nucleation induce the formation of randomly oriented dendrites on Zn anode, while the chemical instability at anode-electrolyte interface triggers detrimental side reactions. Herein, this report in situ designs a multifunctional hybrid interphase of Bi/Bi2O3, for the first time resulting in a novel synergistic regulation mechanism involving: (i) chemically inert interface protection mechanism suppresses side reactions; and more fantastically, (ii) innovative thermodynamically favorable Zn atomic clusters dissociation mechanism impedes dendrites formation. Assisted by collaborative modulation behavior, the Zn@Bi/Bi2O3 symmetry cell delivers an ultrahigh cumulative plating capacity of 1.88 Ah cm-2 at 5 mA cm-2 and ultralong lifetimes of 300 h even at high current density and depth of discharge (10 mA cm-2, DODZn: 60%). Furthermore, under a low electrolyte-to-capacity ratio (E/C: 45 µL mAh-1) and negative-to-positive capacity ratio (N/P: 6.3), Zn@Bi/Bi2O3||MnO2 full-cell exhibits a superior capacity retention of 86.7% after 500 cycles at 1 A g-1, which outperforms most existing interphases. The scaled-up Zn@Bi/Bi2O3||MnO2 battery module (6 V, 1 Ah), combined with the photovoltaic panel, presents excellent renewable-energy storage ability and long output lifetime (12 h). This work provides a fantastic synergistic mechanism to achieve the ultrastable Zn anode and can be greatly promised to apply it into other metal-based batteries.

Enhancing Green Ammonia Electrosynthesis Through Tuning Sn Vacancies in Sn-Based MXene/MAX Hybrids.

Renewable energy driven N2 electroreduction with air as nitrogen source holds great promise for realizing scalable green ammonia production. However, relevant out-lab research is still in its infancy. Herein, a novel Sn-based MXene/MAX hybrid with abundant Sn vacancies, Sn@Ti2CTX/Ti2SnC-V, was synthesized by controlled etching Sn@Ti2SnC MAX phase and demonstrated as an efficient electrocatalyst for electrocatalytic N2 reduction. Due to the synergistic effect of MXene/MAX heterostructure, the existence of Sn vacancies and the highly dispersed Sn active sites, the obtained Sn@Ti2CTX/Ti2SnC-V exhibits an optimal NH3 yield of 28.4 µg h-1 mgcat-1 with an excellent FE of 15.57% at - 0.4 V versus reversible hydrogen electrode in 0.1 M Na2SO4, as well as an ultra-long durability. Noticeably, this catalyst represents a satisfactory NH3 yield rate of 10.53 µg h-1 mg-1 in the home-made simulation device, where commercial electrochemical photovoltaic cell was employed as power source, air and ultrapure water as feed stock. The as-proposed strategy represents great potential toward ammonia production in terms of financial cost according to the systematic technical economic analysis. This work is of significance for large-scale green ammonia production.

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.

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.

Mineralization versus polymerization pathways in heterogeneous Fenton-like reactions.

Fenton reaction has been widespread application in water purification due to the excellent oxidation performances. However, the poor cycle efficiency of Fe(III)/Fe(II) is one of the biggest bottlenecks. In this study, graphite (GP) was used as a green carbon catalyst to accelerate Fenton-like (H2O2/Fe3+ and persulfate/Fe3+) reactions by promoting ferric ion reduction and intensifying diverse peroxide activation pathways. Significantly, the carboxyl group on GP anchors iron ions to form GP-COOFe(III) which promote persulfate adsorption to form surface complexes and induce an electron transfer pathway (ETP). While the electron-rich hydroxyl and carbonyl groups will combine to from GP-COFe(II), a reductive intermediate to activate peroxide to generate free radicals (from H2O2 and PDS) or high-value iron [Fe(IV)] (from PMS). Consequently, different pathways lead to distinct degree of oxidation: i) radicals in H2O2/Fe3+/GP prefer to mineralize bisphenol A (BPA) with no selectivity; ii) Fe(IV) in PMS/Fe3+/GP partially oxidizes BPA but cannot open the aromatic ring; iii) ETP in PMS/ or PDS/Fe3+/GP drives coupling reactions to form polymeric products covered on catalyst surface. Thus, rational engineering surface functionality of graphite and selecting proper peroxides can realize on-demand selectivity and oxidation capacity in Fenton-like systems.

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.

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.

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.

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.

Kinetics study of chloride-activated peracetic acid for purifying bisphenol A: Role of Cl2/HClO and carbon-centered radicals.

Peracetic acid is an emerging oxidant and disinfectant for wastewater purification. In this study, we first developed a comprehensive and accurate model to elucidate the reaction mechanisms and simulate reaction kinetics of peracetic acid (PAA, CH3C(=O)OOH) activated by chloride (Cl-) based on experimental results and literature. A diversity of experiments methods (e.g., quenching experiments, probe compounds degradation, electron paramagnetic resonance (EPR) measurements) and kinetic modeling were used to determine the reactive species. As a result, carbon-centered radicals and free chlorine reactive species (Cl2 and HClO) were devoted to BPA degradation in the PAA/Cl- system. The carbon-centered radicals CH3C(=O)OO•, CH3C(=O)O•, CH3OO•, and •CH3 greatly accelerated BPA degradation with their corresponding kinetics of kCH3C(=O)OO•, BPA = 2 × 108 M-1 s-1, kCH3C(=O)O•, BPA = 2 × 107 M-1 s-1, k•CH3, BPA = 2 × 106 M-1 s-1 and kCH3OO•, BPA = 2 × 104 M-1 s-1. Dissolved Cl2(l) species was also important for BPA degradation with kCl2, BPA of 2 × 107 M-1 s-1, much higher than HClO/ClO- of kHClO, BPA = 1.2 × 101 M-1 s-1 and kClO-, BPA = 9 × 10-3 M-1 s-1. While free chlorine tends to transform BPA to estrogenic chlorinated organic products, the primary degradation of BPA by carbon-centered radicals results in chlorine-free products, reducing the production of disinfection byproducts during the treatment of saline wastewater. This study improves the knowledge of reaction kinetics and mechanism and reactive species generation in the PAA/Cl- system.

Catalytic Pollutant Upgrading to Dual-Asymmetric MnO2 @polymer Nanotubes as Self-Propelled and Controlled Micromotors for H2 O2 Decomposition.

Industrial and disinfection wastewater typically contains high levels of organic pollutants and residue hydrogen peroxide, which have caused environmental concerns. In this work, dual-asymmetric MnO2 @polymer microreactors are synthesized via pollutant polymerization for self-driven and controlled H2 O2 decomposition. A hollow and asymmetric MnO2 nanotube is derived from MnO2 nanorods by selective acid etching and then coated by a polymeric layer from an aqueous phenolic pollutant via catalytic peroxymonosulfate (PMS)-induced polymerization. The evolution of particle-like polymers is controlled by solution pH, molar ratios of PMS/phenol, and reaction duration. The polymer-covered MnO2 tubing-structured micromotors presented a controlled motion velocity, due to the reverse torque driven by the O2 bubbles from H2 O2 decomposition in the inner tunnels. In addition, the partially coated polymeric layer can regulate the exposure and population of Mn active sites to control the H2 O2 decomposition rate, thus avoiding violent motions and massive heat caused by vigorous H2 O2 decomposition. The microreactors can maintain the function of mobility in an ultra-low H2 O2 environment (<0.31 wt.%). This work provides a new strategy for the transformation of micropollutants to functional polymer-based microreactors for safe and controlled hydrogen peroxide decomposition for environmental remediation.

A purified membrane protein from Akkermansia muciniphila blunted the sepsis-induced acute lung injury by modulation of gut microbiota in rats.

The gut microbiota has been implicated in the pathogenesis and progression of sepsis. Akkermansia muciniphila is considered to be a promising probiotic with reduced abundance in cecal ligation and puncture (CLP)-induced sepsis model, and its specific outer membrane protein (Amuc_1100) can partially recapitulate the probiotic function of Akkermansia muciniphila. However, its role in sepsis is unclear. This study aimed to investigate the effect of Amuc_1100 on the gut microbiota of septic rats, thereby improving the prognosis of septic acute lung injury (ALI). A total of 42 adult Sprague-Dawley (SD) rats were randomly divided into three groups: the sham control (SC group), the septic ALI induced by CLP method (CLP group), and administered Amuc_1100 by oral gavage (3 µg/d) for 7 d before the CLP procedure (AMUC group). The survival of the three groups was recorded and the feces and lung tissues of rats were collected 24 h after treatment for 16S rRNA sequencing and histopathological evaluation. Oral administration of Amuc_1100 improved the survival rate and alleviated lung histopathological damage induced by sepsis. Serum levels of pro-inflammatory cytokines and chemokines were substantially attenuated. Amuc_1100 significantly increased the abundance of some beneficial bacteria in septic rats. Additionally, the Firmicutes/Bacteroidetes ratio was low in septic rats, which was partially corrected by increasing Firmicutes and decreasing Bacteroidetes after oral administration of Amuc_1100 (p < 0.05). In addition, Escherichia-Shigella, Bacteroides, and Parabacteroides were relatively enriched in septic rats, while in the AMUC group, their abundance was restored to levels similar to that of the healthy group. Amuc_1100 protects against sepsis by enhancing beneficial bacteria and reducing potential pathogenic bacteria. These findings indicate that Amuc_1100 can blunt CLP-induced ALI through the modulation of gut microbiota, thereby providing a new promising therapeutic target in sepsis.

A General Strategy to Synthesize Fluidic Single Atom Electrodes for Selective Reactive Oxygen Species Production.

Fine-tuning the geometric and electronic structure of catalytic metal centers via N-coordination engineering offers an effective design for the electrocatalytic transformation of O2 to singlet oxygen (1O2). Herein, we develop a general coordination modulation strategy to synthesize fluidic single-atom electrodes for selective electrocatalytic activation of O2 to 1O2. Using a single Cr atom system as an example, >98% 1O2 selectivity can be achieved from electrocatalytic O2 activation due to the subtle engineering of Cr-N4 sites. Both theoretical simulations and experimental results determined that "end-on" adsorption of O2 onto the Cr-N4 sites lowers the overall activation energy barrier of O2 and promotes the breakage of Cr-OOH bonds to form •OOH intermediates. In addition, the flow-through configuration (k = 0.097 min-1) endowed convection-enhanced mass transport and improved charge transfer imparted by spatial confinement within the lamellar electrode structure compared to that of batch reactor (k = 0.019 min-1). In a practical demonstration, the Cr-N4/MXene electrocatalytic system exhibits a high selectivity toward electron-rich micropollutants (e.g., sulfamethoxazole, bisphenol A, and sulfadimidine). The flow-through design of the fluidic electrode achieves a synergy with the molecular microenvironment that enables selective electrocatalytic 1O2 generation, which could be used in numerous ways, including the treatment of environmental pollution.