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Tailoring the dynamic reconstruction of transition metal compounds into highly active oxyhydroxides through surface electron state modification is crucial for advancing water oxidation, yet remains a formidable challenge. In this study, a unique polyaniline (PANI) electron bridge was integrated into the metal-organic frameworks (MOFs)/layer double hydroxides (LDHs) heterojunction to expedite electron transfer from MOFs to LDHs, facilitating electron accumulation at the metal sites within MOF and electron-deficient LDHs. This configuration promotes the surface dynamic reconstruction of LDHs into highly active oxyhydroxides while safeguarding the MOF from corrosion in harsh environments over extended periods. The optimized electronic structure modification of both MOFs and LDHs enhances reaction kinetics. The superior MIL-88B(Fe)@PANI@NiCo LDH catalyst achieved 10 mAâcm-2 at an overpotential of 202 mV and demonstrated stable operation for 120 h at this current density. This research introduces an innovative approach for guiding electron transfer and dynamic catalyst reconstruction by constructing a PANI electron bridge, potentially paving the way for more efficient catalytic systems.
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Electrochemical synthesis of ammonia is a green and sustainable way for nitrogen fixation, but the development of efficient electrocatalysts still faces challenges. The modulation of electronic structure through interface engineering and vacancy engineering is a new approach to enhance the performance of electrocatalysts. In this work, a phosphorus-doped core-shell heterojunction P-Sb2S3/MoS2 was designed and synthesized by combining antimony, which is inert to H+ adsorption, with molybdenum, which has good affinity and reducibility with nitrogen. The synthesis involved both interfacial engineering and vacancy engineering strategies.DFT calculations demonstrate that the formationofSb2S3/MoS2 heterojunction enhances the creation of a built-in electric field, thereby expediting electron flow.Additionally, phosphorus doping induced the formation of abundant sulfur vacancies, significantly enhancing nitrogen adsorption performance in this material.As a result, our designed structure exhibited excellent NRR performance with an ammonia production rate of 41.22 µg·h-1·mg-1cat and a Faraday efficiency of 15.70 %.The unique structural of this catalyst contribute to a more optimal balance between the rate of ammonia production and the Faraday efficiency. The successful preparation of the highly efficient P-Sb2S3/MoS2 heterojunctionsprovidesanew strategyfor catalyst design in electrocatalytic nitrogen reduction.
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Microbial oxidation and the mechanism of Sb(III) are key governing elements in biogeochemical cycling. A novel Sb oxidizing bacterium, Klebsiella aerogenes HC10, was attracted early and revealed that extracellular metabolites were the main fractions driving Sb oxidation. However, linkages between the extracellular metabolite driven Sb oxidation process and mechanism remain elusive. Here, model phenolic and quinone compounds, i.e., anthraquinone-2,6-disulfonate (AQDS) and hydroquinone (HYD), representing extracellular oxidants secreted by K. aerogenes HC10, were chosen to further study the Sb(III) oxidation mechanism. N2 purging and free radical quenching showed that oxygen-induced oxidation accounted for 36.78% of Sb(III) in the metabolite reaction system, while hydroxyl free radicals (·OH) accounted for 15.52%. ·OH and H2O2 are the main driving factors for Sb oxidation. Radical quenching, methanol purification and electron paramagnetic resonance (EPR) analysis revealed that ·OH, superoxide radical (O2â¢-) and semiquinone (SQ-â¢) were reactive intermediates of the phenolic induced oxidation process. Phenolic-induced ROS are one of the main oxidants in metabolites. Cyclic voltammetry (CV) showed that electron transfer of quinone also mediated Sb(III) oxidation. Part of Sb(V) was scavenged by the formation of the secondary Sb(V)-bearing mineral mopungite [NaSb(OH)6] in the incubation system. Our study demonstrates the microbial role of oxidation detoxification and mineralization of Sb and provides scientific references for the biochemical remediation of Sb-contaminated soil.
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Antimônio , Oxirredução , Espécies Reativas de Oxigênio , Transporte de Elétrons , Antimônio/metabolismo , Espécies Reativas de Oxigênio/metabolismoRESUMO
In present work, blue carbon dots (b-CDs) were derived from ammonium citrate and guanidine hydrochloride, and red carbon dots (r-CDs) were stemmed from malonate, ethylenediamine and mesotetra (4-carboxyphenyl) porphin based on facile hydrothermal method. Eco-friendly ratiometric fluorescence probe was innovatively constructed to effectively measure Hg2+ utilizing b-CDs and r-CDs. The developed probe displayed two typical emission peaks at 450 nm from b-CDs and 650 nm from r-CDs under the excitation at 360 nm. Mercury ion has strong quenching effect on the fluorescence intensity at 450 nm due to the electron transfer process and the fluorescence change at 450 nm was used as the response signal, whereas the fluorescence intensity at 650 nm kept unchangeable which resulted from the chemical inertness between Hg2+ and r-CDs, serving as the reference signal in the sensing system. Under optimal circumstances, this probe exhibited an excellent linearity between the fluorescence response values of ΔF450/F650 and Hg2+ concentrations over range of 0.01-10 µmol/L, and the limit of detection was down to 5.3 nmol/L. Furthermore, this probe was successfully employed for sensing Hg2+ in practical environmental water samples with satisfied recoveries of 98.5%-105.0%. The constructed ratiometric fluorescent probe provided a rapid, environmental-friendly, reliable, and efficient platform for measuring trace Hg2+ in environmental field.
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Carbono , Corantes Fluorescentes , Mercúrio , Pontos Quânticos , Poluentes Químicos da Água , Mercúrio/análise , Carbono/química , Corantes Fluorescentes/química , Poluentes Químicos da Água/análise , Pontos Quânticos/química , Monitoramento Ambiental/métodos , Espectrometria de Fluorescência/métodos , Limite de Detecção , FluorescênciaRESUMO
The capability of traditional ligand in countering rapid passivation on nanoscale zero-valent iron (nZVI) surface is inadequate, and the precise electron transfer mechanism remains elusive. In this study, we reported that myo-inositol hexakisphosphate (IHP), a redox-inactive organophosphorus in soil, could highly enhance Cr(VI) reduction and immobilization in comparison with typical ligands (TPP, EDTA, oxalate and phosphate). And the effects of IHP concentration, Cr(VI) concentration and initial pH were systematically investigated. Cr K-edge XANES and XPS analysis revealed that Cr(III) was the exclusive form in solid products regardless of IHP existence. Results of ATR-FTIR and FESEM inferred that IHP was adsorbed on nZVI surface via inner-sphere complexation, thus averting encapsulation of [Fe, Cr](OH)3 coprecipitate and impeding solid particles agglomeration. Additionally, IHP expedited the production of surface-bound Fe(II), primarily attributable to the interaction between nZVI and oxygen. These surface-bound Fe(II) species played a pivotal role in Cr(VI) reduction. Electrochemical analysis unveiled that IHP lowered redox potential of Fe(III)/Fe(II), thereby facilitating reaction between Fe(II) and Cr(VI), whereas inhibited direct electron transfer from nZVI core to Cr(VI). Our findings proposed a novel potential ligand for alleviating nZVI passivation in Cr(VI) removal and deepened our understanding in the process of electron transfer.
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Cromo , Ferro , Cromo/química , Ferro/química , Ácido Fítico/química , Oxirredução , Modelos Químicos , Transporte de Elétrons , Poluentes do Solo/química , AdsorçãoRESUMO
Catalytic oxidation of organic pollutants is a well-known and effective technique for pollutant abatement. Unfortunately, this method is significantly hindered in practical applications by the low efficiency and difficult recovery of the catalysts in a powdery form. Herein, a three-dimensional (3D) framework of Fe-incorporated Ni3S2 nanosheets in-situ grown on Ni foam (Fe-Ni3S2@NF) was fabricated by a facile two-step hydrothermal process and applied to trigger peroxymonosulfate (PMS) oxidation of organic compounds in water. A homogeneous growth environment enabled the uniform and scalable growth of Fe-Ni3S2 nanosheets on the Ni foam. Fe-Ni3S2@NF possessed outstanding activity and durability in activating PMS, as it effectively facilitated electron transfer from organic pollutants to PMS. Fe-Ni3S2@NF initially supplied electrons to PMS, causing the catalyst to undergo oxidation, and subsequently accepted electrons from organic compounds, returning to its initial state. The introduction of Fe into the Ni3S2 lattice enhanced electrical conductivity, promoting mediated electron transfer between PMS and organic compounds. The 3D conductive Ni foam provided an ideal platform for the nucleation and growth of Fe-Ni3S2, accelerating pollutant abatement due to its porous structure and high conductivity. Furthermore, its monolithic nature simplified the catalyst recycling process. A continuous flow packed-bed reactor by encapsulating Fe-Ni3S2@NF catalyst achieved complete pollutant abatement with continuous operation for 240 h, highlighting its immense potential for practical environmental remediation. This study presents a facile synthesis method for creating a novel type of monolithic catalyst with high activity and durability for decontamination through Fenton-like processes.
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Ferro , Níquel , Oxirredução , Peróxidos , Poluentes Químicos da Água , Níquel/química , Ferro/química , Poluentes Químicos da Água/química , Peróxidos/química , Catálise , Nanoestruturas/química , Transporte de ElétronsRESUMO
Laser-induced graphene (LIG) has emerged as a promising solvent-free strategy for producing highly porous, 3D graphene structures, particularly for electrochemical applications. However, the unique character of LIG and hydrogel membrane (HM) coated LIG requires accounting for the specific conditions of its charge transfer process. This study investigates electron transfer kinetics and the electroactive surface area of LIG electrodes, finding efficient kinetics for the [Fe(CN)6]3-/4- redox process, with a high rate constant of 4.89 x 10-3 cm/s. The impact of polysaccharide HM coatings (cationic chitosan, neutral agarose and anionic sodium alginate) on LIG's charge transfer behavior is elucidated, considering factors like ohmic drop across porous LIG and Coulombic interactions/permeability affecting diffusion coefficient (D), estimated from amperometry.It was found that D of redox species is lower for HM-coated LIGs, and is the lowest for chitosan HM. Chitosan coating results in increased capacitive share in the total current while does not apparently reduce Faradaic current. Experimental findings are supported by ab-initio calculations showing an electrostatic potential map's negative charge distribution upon chitosan chain protonation, having an effect in over a two-fold redox current increase upon switching the pH from 7.48 to 1.73. This feature is absent for other studied HMs. It was also revealed that the chitosan's band gap was reduced to 3.07 eV upon acetylation, due to the introduction of a new LUMO state. This study summarizes the operating conditions enhanced by HM presence, impacting redox process kinetics and presenting unique challenges for prospective LIG/HM systems' electrochemical applications.
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Radionuclide contamination has become a global environmental concern due to the high mobility and toxicity of certain isotopes. Bioreduction mediated by electrochemically active bacteria (EAB) with unique extracellular electron transfer (EET) capability is recognized as a promising approach for nuclear waste treatment. However, it is difficult to achieve bidirectional regulation of EET pathway through traditional genetic manipulation, limiting the bioremediation application of EAB. Here, we designed and optimized a novel Esa quorum sensing (EQS) system for highly efficient gene expression and interleaved cellular functional output. By promoting dimethyl sulfoxide reductase at low cell density and increasing the synthesis of electron conductive complex and flavins at high cell density, the EQS system dynamically switched the extracellular respiratory pathway of Shewanella oneidensis MR-1 according to cell density. The engineered strain exhibited precise switching and substantial improvement in the extracellular remediation of multiple nuclides, sequentially increasing the reduction of iodine IO3- and uranium U(VI) by 2.51- and 2.05-fold compared with the control, respectively. Furthermore, a mobile bacterial biofilm material was fabricated for collecting uranium precipitates coupled with U(VI) reduction. This work clearly demonstrates that EQS system contributes to the bidirectional regulation of EET pathway in EAB, providing an effective and refined strategy for bioremediation of multi-nuclide contamination.
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The efficiency of energy transfer among microorganisms presents a substantial hurdle for the widespread implementation of anaerobic digestion techniques. Nonetheless, recent studies have demonstrated that enhancing the extracellular electron transfer (EET) can markedly enhance this efficiency. This review highlights recent advancements in EET for anaerobic digestion and examines the contribution of external additives to fostering enhanced efficiency within this context. Diverse mechanisms through which additives are employed to improve EET in anaerobic environments are delineated. Furthermore, specific strategies for effectively regulating EET are proposed, aiming to augment methane production from anaerobic digestion. This review thus offers a perspective on future research directions aimed at optimizing waste resources, enhancing methane production efficiency, and improving process predictability in anaerobic digestion.
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Exploiting electrogenic microorganisms as unconventional chassis hosts offers potential solutions to global energy and environmental challenges. However, their limited electrogenic efficiency and metabolic versatility, due to genetic and metabolic constraints, hinder broader applications. Herein, we developed a multifaceted approach to fabricate an enhanced electrogenic chassis, starting with streamlining the genome by removing extrachromosomal genetic material. This reduction led to faster lactate consumption, higher intracellular NADH/NAD+ and ATP/ADP levels, and increased growth and biomass accumulation, as well as promoted electrogenic activity. Transcriptome profiling showed an overall activation of cellular metabolism. We further established a molecular toolkit with a vector vehicle incorporating native replication block and refined promoter components for precise gene expression control. This enabled engineered primary metabolism for greater environmental robustness and fine-tuned extracellular electron transfer (EET) for improved efficiency. The enhanced chassis demonstrated substantially improved pollutant biodegradation and radionuclide removal, establishing a new paradigm for utilizing electrogenic organisms as novel biotechnology chassis.
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Exploring nonequilibrium hot carriers from plasmonic metal nanostructures is a dynamic field in optoelectronics, with applications including photochemical reactions for solar fuel generation. The hot carrier injection mechanism and the reaction rate are highly impacted by the metal/molecule interaction. However, determining the primary type of reaction and thus the injection mechanism of hot carriers has remained elusive. In this work, we reveal an electron injection mechanism deviating from a purely outer-sphere process for the reduction of ferricyanide redox molecule in a gold/p-type gallium nitride (Au/p-GaN) photocathode system. Combining our experimental approach with ab initio simulations, we discovered that an efficient inner-sphere transfer of low-energy electrons leads to an enhancement in the photocathode device performance in the interband regime. These findings provide important mechanistic insights, showing our methodology as a powerful tool for analyzing and engineering hot-carrier-driven processes in plasmonic photocatalytic systems and optoelectronic devices.
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Methylsuccinate is a branched-chain, 5-carbon (C5) dicarboxylate that can be generated from the O2-independent activation of methane via fumarate addition. However, no established metabolic pathway enables growth and product synthesis from methylsuccinate. Here, we report a synthetic pathway that converts methylsuccinate into two precursor metabolites: pyruvate and acetyl-CoA. The pathway was constructed through rational design and validated both in vitro and in vivo using E. coli as the host. Subsequently, growth on methylsuccinate as the sole carbon source was achieved using two parallel strategies: adaptive laboratory evolution and enzyme mining. Through the latter approach, we identified a heterologous electron transfer pathway mediated by previously uncharacterized enzymes and integrated into E. coli enabling the conversion of methylsuccinyl-CoA to mesaconyl-C4-CoA. The engineered strain demonstrated efficient growth on various C5 dicarboxylates including methylsuccinate, mesaconate, and itaconate, with a specific growth rate of 0.11â¯h-1 on methylsuccinate. This study represents an important step toward achieving synthetic methanotrophy, as the engineered strain can serve as a platform for screening potential methane activation enzymes and ultimately as a production chassis for the bioconversion of methane into various value-added products.
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Enhancing extracellular electron transfer (EET) efficiency is crucial for improving the anaerobic digestion (AD) system's capability to treat recalcitrant wastewater. In this study, a novel S, N co-doped biochar (S-N-BC) was prepared through surface engineering to optimize EET within AD systems. The addition of S-N-BC significantly enhanced the performance of a mesophilic AD system treating Congo red wastewater, increasing the decolorization rate by 78 %, COD degradation rate by 82 %, and methane yield by 87 % compared to the control. Additionally, the shock resistance of anaerobic granular sludge was improved, as evidenced by the formation of the protective extracellular polymeric substances (EPS) barrier and the enhanced activities of the electron transport system. Mechanistic analysis revealed that adding S-N-BC did not alter the Congo red decolorization pathway but significantly enriched various electrochemically active bacteria and established EET pathways between microbial-pollutant and inter-microbial. This significantly accelerated EET efficiency within the AD system, ensuring stable and efficient operation under challenging conditions. This study proposed a novel approach using S-N-BC to simultaneously enhance "dual-pathway EET" between microbial-pollutant and inter-microbial while constructing an EPS protective barrier, addressing the issues of low efficiency and fragile stability of AD systems for treating recalcitrant wastewater.
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We previously reported that choline chloride and N-allylglycine stimulate photosynthesis in wheat protoplasts. Treatment of Arabidopsis thaliana and Brassica rapa plants with both compounds promoted growth and photosynthesis. To clarify the relationship between the enhancement of photosynthesis and increased growth, A. thaliana T87 cells, which show photosynthesis-dependent growth, and YG1 cells, which use sugar in the medium for growth, were treated with choline chloride or N-allylglycine. Only the T87 cells showed increased growth, suggesting that choline chloride and N-allylglycine promote growth by increasing photosynthetic activity. Transcriptome analysis using choline chloride and N-allylglycine-treated plants showed that the most abundant transcripts corresponded to photosynthetic electron transfer-related genes among the genes upregulated by both compounds. Furthermore, the compounds also upregulated genes encoding transcription factors that may control the expression of these photosynthetic genes. These results suggest that choline chloride and N-allylglycine promote photosynthesis through increased expression of photosynthetic electron transfer-related genes.
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Developing efficient and earth-abundant alkaline HER electrocatalysts is pivotal for sustainable energy, but co-regulating its intricate multi-step process, encompassing water dissociation, OH- desorption, and hydrogen generation, is still a great challenge. Herein, we tackle these obstacles by fabricating a vertically integrated electrode featuring a nanosheet array with prominent dual-nitride metallic heterostructures characterized by impeccable lattice matching and excellent conductivity, functioning as a multi-purpose catalyst to fine-tune the bonding affinity with alkaline HER intermediates. Detailed structural characterization and theoretical calculation elucidate that charge redistribution at the heterointerface creates electron-accumulating W-W sites, which reduces the O p-W d and H s-W d interactions vs. single nitride, thereby enhancing OH- transfer and H2 release. As anticipated, the resulting WN-NiN/CFP catalyst demonstrates a gratifying low overpotential of 36.8 mV at 10 mA/cm² for alkaline HER, while concurrently maintaining operational stability for 1300 h at 100 mA/cm² for overall water splitting. This work presents an effective approach to meticulously optimize multiple site-intermediate interactions in alkaline HER, laying the foundation for efficient energy conversion.
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One or multiple chlorophyll molecules are employed in the reaction center of photosystem II's main electron donor (defined as P680). We have a poor understanding of how the reaction center facilitates water oxidation and the roles that mono- and/or multimeric chlorophyll groups play when P680 oxidizes a neighboring tyrosine in order to drive water oxidation at the oxygen evolving complex. We have prepared a dimeric MgII-porphyrin complex [Mg2(BTPP)] (1, H4-BTPP = 1,2-bis-(10,15,20-triphenylporphyrin-5-yl)-benzene) as a structural and functional mimic of the dimeric core of P680. 1 was oxidized by one-electron to the corresponding π-cation radical complex 2. The radical cation was characterized by UV-Vis-NIR, FT-IR, and EPR spectroscopic techniques. 2 was shown to be reactive towards phenols to give the corresponding phenoxyl radicals, mimicking the reactivity of the P680 cation radical which oxidizes tyrosine to tyrosyl radical. Critically, the dimeric π-cation radical showed markedly higher rates of proton coupled electron transfer oxidation (PCET) of phenols when compared to its monomeric counterpart [Mg(TPP)] (TPP = 5,10,15,20-tetraphenylporphyrin). Our findings demonstrate that MgII-porphyrin complexes are reliable mimics of photosynthetic PCET processes and suggest that photosynthetic reaction centers with multiple π-conjugated complexes likely lower the barrier to PCET oxidation by π-cation radical species.
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Although Type-I photodynamic therapy has attracted increasingly growing interest due to its reduced dependence on oxygen, the design of effective Type-I photosensitizers remains a challenge. In this work, we report a design strategy for Type-I photosensitizers by the involvement of hydrogen atom transfer (HAT). As a proof of concept, a HAT-involved Type-I PS, which simultaneously generates superoxide and carbon-centered radicals under light-irradiation, was synthesized. This photosensitizer is comprised of a fluorene-substituted BODIPY unit as an electron acceptor covalently linked with a triphenylamine moiety as an electron donor. Under light-irradiation, photo-induced intramolecular electron transfer occurs to generate the BODIPY anion radical and triphenylamine cation radical. The former transfers electrons to oxygen to generate O2-â¢, while the latter loses a proton to produce a benzyl carbon-centered radical which is well characterized. The resulting carbon-centered radicals efficiently oxidize NADH by HAT reaction. This photosensitizer demonstrates remarkable photocytotoxicity even under hypoxic conditions, along with outstanding in vivo antitumor efficacy in mouse models bearing HeLa tumors. This work offers a novel strategy for the design of Type-I photosensitizers by involvement of HAT.
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Ethanol-mediated Anaerobic digestion (Ethanol-AD) is a biological process that converts organic waste into biogas, predominantly composed of methane (CH4), hydrogen (H2), and carbon dioxide (CO2), through the breakdown of complex organic materials while ethanol is an intermediate metabolite. Ethanol improves the digestion of complex organic waste by serving as an electron precursor for interspecies electron transfer, leading to enhanced biogas production. It further serves as a substrate for acetogens or syntrophic bacteria, while mean its oxidation leads to acetate formation, which methanogens can then consume to generate methane. Methanogenesis, the final and crucial step in the anaerobic digestion in which methanogens produce methane through various metabolic routes, most notably via the hydrogenotrophic and syntrophic pathways. In hydrogenotrophic methanogenesis, methanogens consume hydrogen as an electron precursor and carbon dioxide as an electron acceptor, leading to methane generation. Alternatively, syntrophic methanogenesis, which is increasingly recognized for its efficiency, is dominated by DIET between syntrophic partners, bypassing the need for hydrogen as a mediator. This mode of electron transfer enhances the metabolic cooperation between microbes, facilitating a more efficient methanogenesis process. As research continues to explore the mechanisms underlying DIET and the role of (semi) conductive materials, there is potential for optimizing AD systems for renewable energy production by advancing the methanogenesis process, and enhancing biogas quality. The novelty of this review lies in its dual exploration of direct and indirect interspecies electron transfer (DIET and IIET) within ethanol-mediated anaerobic digestion. While DIET in ethanol-driven systems has been previously discussed, this review is the first to comprehensively examine the interplay between both direct and indirect electron transfer mechanisms, offering new insights into optimizing microbial interactions and improving methane production efficiency.
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The non-radical pathway dominated by the electron transfer process (ETP) has gained considerable attention for the removal of organic contaminants in persulfate-based advanced oxidation processes. Rationally designing new catalysts with optimized composition and structural merits and further elucidating the enhanced removal mechanism are of great importance. In this work, we successfully synthesized a nitrogen-sulfur co-doped carbon encapsulated cobalt phosphide (Co2P) on both sides of MXene nanosheets (MZPC) to degrade bisphenol A (BPA) from organic wastewater. The results indicated that BPA was degraded by 98.2 % in a mere 5 min using 0.1 g L-1 of peroxymonosulfate (PMS) and 0.05 g L-1 of the optimized catalyst (MZPC-9), exhibiting an excellent pseudo-first-order kinetics rate constant (k = 1.485 min-1). Uniformly dispersed Co2P nanoparticles (approximately 9.4 nm, calculated using the Scherrer equation) on both sides of MXene exhibited enhanced binding affinity with PMS, forming the MZPC-9-PMS* metastable complexes with potent oxidative capability. The resultant MZPC-9-PMS* complexes induced the polymerization reaction of BPA and achieved 81 % total organic carbon (TOC) removal. This study offers a novel perspective on the design of metal active centers to enhance the ETP-dominated non-radical pathway for pollutant degradation.
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Examples of how metalloproteins feature in electron transfer processes in biological systems are reviewed. Attention is focused on the electron transport chains of cellular respiration and photosynthesis, and on metalloproteins that directly couple electron transfer to a chemical reaction. Brief mention is also made of extracellular electron transport. While covering highlights of the recent and the current literature, this review is aimed primarily at introducing the senior undergraduate and the novice postgraduate student to this important aspect of bioinorganic chemistry.