In this paper, photoinduced electron transfer(PET) phosphoroionophore, N-(1-bromo- 2-naphthylmethyl)-diethanolamine (BND) was synthesized and its phosphorescent characteristics were studied. The experimental results ...In this paper, photoinduced electron transfer(PET) phosphoroionophore, N-(1-bromo- 2-naphthylmethyl)-diethanolamine (BND) was synthesized and its phosphorescent characteristics were studied. The experimental results showed that strong phosphorescence could be observed in b-cyclodextrin aqueous solution only at low pH value. This system combined AND and NOT function to produce a three-input inhibit (INH) logic gate.展开更多
In this study,we meticulously designed a layered carbon-based catalytic material to induce the degradation of a series of organic pollutants by activating peroxymonosulfate(PMS) in the PMS-based advanced oxidation pro...In this study,we meticulously designed a layered carbon-based catalytic material to induce the degradation of a series of organic pollutants by activating peroxymonosulfate(PMS) in the PMS-based advanced oxidation processes(AOPs).Results indicated that the silicon and oxygen elements from the montmorillonite were incorporated into the catalyst matrix to form the Si-O-C structure.It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array,achieving over 90 % removal rate of most pollutants within 60 min.It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array.The salt bridge system confirmed that pollutants can provide electrons to the Si-O-C/PMS system,and we verified that the electron transfer process(ETP) mechanism was the main pathway for the degradation of pollutants in the Si-O-C/PMS system via the open-circuit potential analysis.In combination with the structural properties of different pollutants,we discovered that electron-donating pollutants can supply more electrons to the Si-O-C/PMS system,thereby enhancing the ETP process.The findings of this study are anticipated to advance the development and practical application of layered carbonaceous materials-based catalysts and support the design and implementation of nanoconfined catalysts in the field of AOPs.展开更多
Recent advancements in Zn-halogen batteries have focused on enhancing the adsorptive or catalytic capability of host materials and stabilizing complex intermediates with electrolyte additives,while the halogen-ion ele...Recent advancements in Zn-halogen batteries have focused on enhancing the adsorptive or catalytic capability of host materials and stabilizing complex intermediates with electrolyte additives,while the halogen-ion electrolyte modifications exhibit strong potential for integrated interfacial regulation.Herein,we design an electrically insulating rigid electrolyte container to immobilize a liquid halogen-ion electrolyte for separator-free Zn-halogen batteries with customizable electron transfer.Robust hydrogen bonding of hydroxyl groups in SiO_(2)with fluorinated moieties in PVDF-hfp regulates Zn^(2+)solvation and suppresses H_(2)O activity,while multi-channels formed by microcracks and interparticle gaps not only enhance mass transfer but also buffer interfacial electric field,jointly enabling a durable Zn plating/stripping.Effective confinement of intermediates also ensures the high reversibility across single-(I^(-)/I0),double-(I^(-)/I0/I^(-)),and triple-(I^(-)/I0/I^(-),Cl-/Cl0)electron transfer mechanisms at cathode,as evidenced by the double-electron transfer systems exhibiting a low capacity decay rate of 0.02‰over 4500 cycles at 10 mA cm^(-2)and a high areal capacity of 11.9 mAh cm^(-2)at 2 mA cm^(-2).This work presents a novel“container engineering”approach to halogen-ion electrolyte design and provides fundamental insights into the relationships between redox reversibility and reaction kinetics.展开更多
Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt ...Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt oxyhydroxide @covalent organic frameworks(CoOOH@COFs) S-scheme heterojunction was synthesized,which combined the visible-light-driven photocatalysis and peroxymonosulfate(PMS) activation to synergistically generate abundant reactive oxygen species(ROSs) for TCS degradation.The degradation efficiency of TCS reached 100 % within 8 min in the Vis-CoOOH@COFs/PMS system,and the reaction rate constant was 0.456 min^(-1),which was nearly 1.90 and 2.85 times that of single Co OOH and COFs,and2.36 times that under dark condition,respectively.The density functional theory(DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to Co OOH.Both experimental and theoretical analyses indicated that Co OOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation,enhanced interfacial electron transfer,accelerated PMS activation,and generated multiple ROSs.In particular,photogenerated electrons(e^(-))accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle,while the PMS captured the e-,which significantly decreased the charge combination of Co OOH@COFs.Radicals(O_(2)^(·-),^(·)OH,and SO_(4)^(·-)) and non-radicals(such as ^(1)O_(2),h^(+),and e^(-)) were both presented in the Vis-CoOOH@COFs/PMS system,with O_(2)^(-) playing a dominant role in TCS degradation.Furthermore,the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification.Importantly,the environmentally friendly CoOOH@COFs S-scheme heterojunction exhibited excellent stability and reusability.In conclusion,this study innovatively designed an S-scheme heterojunction in the photocatalytic-PMS activation system,providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.展开更多
Cryptochromes are blue light photorecep-tors that mediate key biological processes through photoinduced electron transfer(ET).We present a theoretical study of the second ET step along the conserved trypto-phan triad ...Cryptochromes are blue light photorecep-tors that mediate key biological processes through photoinduced electron transfer(ET).We present a theoretical study of the second ET step along the conserved trypto-phan triad in Arabidopsis thaliana cryp-tochrome,focusing on how vibrational envi-ronments affect the ultrafast electron trans-fer.Using the numerically exact low temper-ature quantum Fokker-Planck equation(LT-QFPE)within the hierarchical equations of motion(HEOM)framework,we resolve the contributions of individual Brownian oscillator modes:low frequency modes with large reorganization energies markedly reduce the ET rate,whereas weakly damped high frequency modes generate oscillations linked to electronic-vibra-tional coherence.The LT-QFPE results are also used to benchmark three second order pertur-bative methods:the non-equilibrium Fermi’s golden rule(NE-FGR),non-interacting blip ap-proximation(NIBA),and the time local generalized quantum master equation.Although all approximate methods reproduce correct long-time ET rates,they fail to capture short time non-equilibrium dynamics.These findings clarify how spectral width and bath correlation time,in addition to total reorganization energy,govern the validity of perturbative treat-ments and highlight the need for numerically exact methods such as HEOM in modeling non-equilibrium cryptochrome ET dynamics.s.展开更多
Photo-induced intramolecular electron transfer （PIET） and intramolecular vibrational relaxation （IVR） dynamics of the excited state of rhodamine 6G （Rh6G＋） in DMSO are investigated by multiplex transient gratin...Photo-induced intramolecular electron transfer （PIET） and intramolecular vibrational relaxation （IVR） dynamics of the excited state of rhodamine 6G （Rh6G＋） in DMSO are investigated by multiplex transient grating. Two major compo- nents are resolved in the dynamics of Rh6G＋. The first component, with a lifetime τTPIET = 140 fs-260 fs, is attributed to PIET from the phenyl ring to the xanthene plane. The IVR process occurring in the range ZIVR = 3.3 ps-5.2 ps is much slower than the first component. The PIET and IVR processes occurring in the excited state of Rh6G＋ are quantitatively determined, and a better understanding of the relationship between these processes is obtained.展开更多
1 Introduction Fulgide derivatives are well known as one kind of important organic photochromic compounds and a candidate for application to erasable optical storage materials. But there are many unsolved problems, e....1 Introduction Fulgide derivatives are well known as one kind of important organic photochromic compounds and a candidate for application to erasable optical storage materials. But there are many unsolved problems, e.g. the maximum absorption wavelength of the closed form of fulgides is not long enough to match the commercial diode laser(780-830nm). Up to now, it is very difficult for organic chemists to synthesize the qualified organic compounds.展开更多
1 Introduction Much research work has been done on the mechanism of photo-induced reduction of quinone dyes by electron donors with visible light. Two ways to obtain the net two-electron reduction product QH^- bave be...1 Introduction Much research work has been done on the mechanism of photo-induced reduction of quinone dyes by electron donors with visible light. Two ways to obtain the net two-electron reduction product QH^- bave been proposed. One is the direct two-electron transfer (electron-proton-electron transfer) within the complex and the other is the disproportionatioh of the semiquinone radical QH·formed by one-electron transfer.展开更多
Photo-induced electron transfer versus molecular structure of acceptors is investigated using ultrafast time-resolved transient grating spectroscopy. Typical laser dyes Rhodamine 101 (Rh101) and Rhodamine 6G (Rh6G) in...Photo-induced electron transfer versus molecular structure of acceptors is investigated using ultrafast time-resolved transient grating spectroscopy. Typical laser dyes Rhodamine 101 (Rh101) and Rhodamine 6G (Rh6G) in electron donor solvent-aniline are adopted as the objects. The forward electron transfer time constant from aniline to the excited singlet state of two Rhodamine dyes and subsequent back electron transfer from two dyes to aniline are measured. The experimental results denote that Rh6G presents faster electron transfer rates with aniline in both forward electron transfer and back electron transfer processes. With chemical calculation and qualitative analysis, it is found that the flexible molecular geometry of Rh6G leads to stronger electron coupling with donor solvent and further gives rise to larger electron transfer rates.展开更多
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 lowefficiency and difficul...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 lowefficiency and difficult recovery of the catalysts in a powdery form.Herein,a three-dimensional(3D)framework of Fe-incorporated Ni_(3)S_(2)nanosheets in-situ grown on Ni foam(Fe-Ni_(3)S_(2)@NF)was fabricated by a facile two-step hydrothermal process and applied to trigger peroxymonosulfate(PMS)oxidation of organic compounds inwater.A homogeneous growth environment enabled the uniform and scalable growth of Fe-Ni_(3)S_(2)nanosheets on the Ni foam.Fe-Ni_(3)S_(2)@NF possessed outstanding activity and durability in activating PMS,as it effectively facilitated electron transfer from organic pollutants to PMS.Fe-Ni_(3)S_(2)@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 Ni_(3)S_(2)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-Ni_(3)S_(2),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-Ni_(3)S_(2)@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.展开更多
Layered double hydroxide(LDH)based heterogonous peroxymonosulfate(PMS)activation degradation of pollutants has attracted extensive attention.The challenge is to selectively regulate the traditional free radical domina...Layered double hydroxide(LDH)based heterogonous peroxymonosulfate(PMS)activation degradation of pollutants has attracted extensive attention.The challenge is to selectively regulate the traditional free radical dominant degradation pathway into a nonradical degradation pathway.Herein,an interface ar-chitecture of Ti_(3) C_(2) T_(x)-MXene(MXene)loading on the Fe-Al LDH scaffold was developed,which showed excellent stability and robust resistance against harsh conditions.Significantly,the rate constant for tetra-cycline hydrochloride(TC)degradation in the MXene-LDH/PMS process was 0.421 min^(-1),which was ten times faster than the rate constant for pure Fe-Al LDH(0.042 min^(-1)).Specifically,more reactive Fe with the closer d-band center to the Fermi level results in higher electron transfer efficiency.The occupa-tions of Fe-3d orbitals in Mxene/Fe-Al LDH are pushed above the Fermi level to generate,which results in higher PMS adsorption and inhibition of the release of oxygen-containing active species intermedi-ates,leading to the enhanced^(1)O_(2) generation.Additionally,the built-in electric field in the heterojunc-tion was driven by the charge redistribution between MXene and Fe-Al LDH,resulting in a mediated-electron transfer mechanism,differentiating it from the Fe-Al LDH/PMS system.It was fascinating that MXene/Fe-Al LDH achieved satisfactory treatment efficiency in continuous column reactor and real landfill leachate.展开更多
In situ electron paramagnetic resonance(EPR)monitoring of the photocatalytic halogen atom transfer(XAT)reaction with organic amines has provided insights into the dynamic transformations of intermediates,including cat...In situ electron paramagnetic resonance(EPR)monitoring of the photocatalytic halogen atom transfer(XAT)reaction with organic amines has provided insights into the dynamic transformations of intermediates,including catalyst intermediate states,amine alkyl radicals,and the dehalogenation of halogenated hydrocarbons to form carbon-centered radicals.This approach facilitated the photocatalytic single-linear state oxygen-promoted halogen atom transfer quinoxalinone alkylation reaction.展开更多
In this study,a Fe,N-decorated carbocatalyst(FeCN@X)based on Fe-MOFs was synthesized to activate peroxydisulfate(PDS)for removing sulfadiazine(SDZ)from water.The surface morphology and structure of FeCN@X was characte...In this study,a Fe,N-decorated carbocatalyst(FeCN@X)based on Fe-MOFs was synthesized to activate peroxydisulfate(PDS)for removing sulfadiazine(SDZ)from water.The surface morphology and structure of FeCN@X was characterized by scanning electron microscopy,X-ray diffraction,and X-ray photoelectron spec troscopy.FeCN@1000,formed at the pyrolysis temperature of 1000℃,exhibited the best catalytic performance for degrade SDZ in the presence of 0.15 g·L^(-1)catalyst and 0.5 mmol·L^(-1)PDS,and the reaction conversion rate was 0.199 L·mmol^(-1).Moreover,the effects of experimental conditions,coexisting anions and fulvic acid on catalytic performance of FeCN@1000 were investigated.The excellent potential of FeCN@1000 as a PDS activator in environmental applications was also suggested by the results of its reusability and adaptability experiments.The result of XPS,ROS quenching,EPR and electrochemical experiments showed the degradation of SDZ was primarily driven by an electron transfer process(ETP).Furthermore,Fe(Ⅲ)instead of Fe(Ⅱ)plays a major role in ETP,as Fe(Ⅲ)sites can interact with PDS and form the low-spin surface complexes(Fe(Ⅲ)/CN-PDS).Meanwhile,the small number of~1O_(2) and O_(2)~-·generated by the activation of PDS will promote the system degradation of SDZ activity by accelerating the conversion of Fe(Ⅱ)to Fe(Ⅲ).This study provides new insights for the design of novel PDS activator for efficient degradation of emerging pollutants by ETP.展开更多
Heterostructures of organic semi-conductors and transition metal dichalcogenides(TMDs)are viable candidates for superior optoelec-tronic devices.Photoinduced inter-facial charge transfer is crucial for the performance...Heterostructures of organic semi-conductors and transition metal dichalcogenides(TMDs)are viable candidates for superior optoelec-tronic devices.Photoinduced inter-facial charge transfer is crucial for the performance efficiency of such devices,yet the underlying mecha-nism,especially the roles of optical-ly dark triplets and spatially sepa-rated charge transfer states,is poorly understood.In the present work,we obtain the struc-tures of distinct excited states and investigate how they are involved in the charge transfer process at the Pd-octaethylporphyrin(PdOEP)and WS_(2) interface in terms of their energies and couplings.The results show that electron transfer from the triplet PdOEP formed via intersystem crossing prevails over direct electron transfer from the singlet(two orders of magnitude faster).Further analysis reveals that the relatively higher rate of triplet electron transfer compared to singlet electron transfer is mainly attributed to a smaller reorganization energy,which is dominated by the out-of-plane vibrations of the organic component.The work emphasizes the important roles of the optically dark triplets in the electron transfer of the PdOEP@WS_(2) heterostructure,and provides valuable theoretical insights for further improv-ing the optoelectronic performance of TMD-based devices.展开更多
Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not y...Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not yet fully understood.In this study,the V(V)reduction mechanisms with concomitant V isotope fractionation by the Gram-positive bacterium Bacillus subtilis(B.subtilis)and the Gramnegative bacterium Thauera humireducens(T.humireducens)were investigated.Both strains could effectively reduce V(V),removing(90.5%±1.6%)and(93.0%±1.8%)of V(V)respectively from an initial concentration of 50 mg L^(-1) during a 10-day incubation period.V(V)was bioreduced to insoluble vanadium(IV),which was distributed both inside and outside the cells.Electron transfer via cytochrome C,nicotinamide adenine dinucleotide,and glutathione played critical roles in V(V)reduction.Metabolomic analysis showed that differentially enriched metabolites(quinone,biotin,and riboflavin)mediated electron transfer in both strains.The aqueous V in the remaining solution became isotopically heavier as V(V)bioreduction proceeded.The obtained V isotope composition dynamics followed a Rayleigh fractionation model,and the isotope enrichment factor(e)was(–0.54‰±0.04‰)for B.subtilis and(–0.32‰±0.03‰)for T.humireducens,with an insignificant difference.This study provides molecular insights into electron transfer for V(V)bioreduction and reveals V isotope fractionation during this bioprocess,which is helpful for understanding V biogeochemistry and developing novel strategies for V remediation.展开更多
Photochromic materials attract significant attention for their applications in anticounterfeiting devices,optical switches and molecular sensors.However,the influence of solvent molecules,particularly coordinated solv...Photochromic materials attract significant attention for their applications in anticounterfeiting devices,optical switches and molecular sensors.However,the influence of solvent molecules,particularly coordinated solvents,on electron transfer(ET)photochromic systems remains poorly understood.In this study,we synthesized a series of isostructural metal-organic complexes(MOCs),[Mn(ADC)(L)]n(ADC=9,10-anthracenedicarboxylic acid,L=DMF for 1,DMA for 2,MEA for 3,and DMSO for 4)to investigate the solvent-chromic behavior.All these MOCs exhibit typical radical-induced chromism upon illumination with a xenon lamp at room temperature.It is worth noting that coordination solvent molecules significantly modulate the photochromic response rate.Among the compounds studied,compound 1 exhibits the fastest response,while compound 3 shows the slowest.This variation in rate correlates with differences in the optimal ET path length within their structures.Specifically,solvent molecules regulate the C-H…π interaction distance through their steric hindrance and electronic prop-erties.Shorter C-H…π paths facilitate more efficient ET upon photoexcitation,thus leading to faster photo-chromic response rates.Furthermore,illumination actuates magnetic couplings between photogenerated radicals and Mn^(2+)centers,resulting in a significant increase in room-temperature magnetization,demonstrating a photomagnetic response.This study demonstrates that coordinating solvent selection effectively controls photoinduced ET behavior,providing new insights for designing advanced photoactive materials.展开更多
For the effective treatment of the wastewater with low-medium concentration ammonia nitrogen and low strength COD,a high-performance Co_(3)O_(4) catalyst supported on carbon nanocages(CNCs)was prepared.By isovolumetri...For the effective treatment of the wastewater with low-medium concentration ammonia nitrogen and low strength COD,a high-performance Co_(3)O_(4) catalyst supported on carbon nanocages(CNCs)was prepared.By isovolumetric im pregnation,Co_(3)O_(4) could be uniformly dispersed on surface of CNCs,which possess tiny particle size and strong electron transfer capability.The catalytic performance of the prepared Co_(3)O_(4)/CNCs catalysts with different Co_(3)O_(4) loadings was systematically evaluated and compared with Co_(3)O_(4)/CNTs.It is found that 20 wt.%Co_(3)O_(4)/CNCs shows the best catalytic performance,achieving an ammonia nitrogen conversion rate of 71.0%and a nitrogen selectivity of 81.8%.Compared to commonly used Co_(3)O_(4),ammonia conversion and nitrogen selectivity of Co_(3)O_(4)/CNCs increased by 28.9%and 15.8%respectively.In the five consecutive cycles,the catalytic activity remained stable.The mechanism that CNCs support effectively increases the surface oxygen vacancies of Co_(3)O_(4) through XPS analysis was also elucidated,and DFT calculations confirm strong electron transfer between CNCs and Co_(3)O_(4),rendering Co_(3)O_(4) nanoparticles as the primary catalytic active sites.The results may contribute to the development of highperformance catalytic ozone oxidation catalysts for ammonia nitrogen.展开更多
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 ...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 Kedge 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.展开更多
Lithium-sulfur batteries(LSBs)are a promising candidate for next-generation energy storage solutions.However,challenges such as the shuttling effect and sluggish Li-S reaction kinetics of lithium polysulfides hinder t...Lithium-sulfur batteries(LSBs)are a promising candidate for next-generation energy storage solutions.However,challenges such as the shuttling effect and sluggish Li-S reaction kinetics of lithium polysulfides hinder their practical application.In this work,we present a mixed-phase heterostructure comprising Co_(0.85)Se and MoSe_(2),supported on nitrogen-doped carbon polyhedrons(NCP),as an effective sulfur host in the LSB cathode.Through a combination of theoretical calculations and experimental validation,we demonstrate that the Co_(0.85)Se-MoSe_(2)heterointerface significantly enhances electron transfer efficiency,thereby boosting the overall reaction kinetics of the sulfur cathode.As a result,the Co_(0.85)Se-MoSe_(2)/NCP/S electrodes exhibit initial specific capacities exceeding 1500 mAh g^(-1)at 0.1 C and retain 666 m Ah g^(-1)at 3 C,with a capacity fade rate of 0.044%per cycle over 500 cycles at 1.0 C.Notably,even at a high sulfur loading of 3 mg cm^(-2)and a reduced electrolyte volume of 6.7μL mgS^(-1),the Co_(0.85)SeMoSe_(2)/NCP/S electrodes maintain a capacity of 432 mAh g^(-1)after 100 cycles at 0.2 C.展开更多
Electron transfer processes at polymer electrolyte/electrode interfaces play a central role in modern electrochemical devices of energy conversion,however,current understanding of electron transfers through electroche...Electron transfer processes at polymer electrolyte/electrode interfaces play a central role in modern electrochemical devices of energy conversion,however,current understanding of electron transfers through electrochemical interfaces was established exclusively based on the studies of liquid/solid electrochemical interfaces.Thus,similarities and differences of liquid and polymer electrolyte/electrode interfaces need to be mapped out to guide the design of device level electrochemical interfaces.In this work,we employ the sulfonate adsorption/desorption as a probe reaction to understand the electron-transfer steps in polymer and liquid electrolytes.Through cyclic voltametric investigations on the well-define single-crystal Pd_(ML)Pt(111)electrode,we demonstrate that the oxidative adsorption and reductive desorption of sulfonates at the polymer electrolyte/electrode interface are chemically distinct from those in liquid electrolytes,with the former occurring mostly via the proton-coupled pathway while the latter proceeding mainly through the solvation-mediated pathway.Importantly,the sulfonate adsorption/desorption behaviors of alkylsulfonates become increasingly similar to those in Nafion with longer alkyl chains,suggesting that the interfacial hydrophobicity and solvation environment conferred by the perfluorinated polymer play a decisive role in the electron-transfer mechanism.Results reported in this study highlight the mechanistic distinctions between electron-transfer processes at electrochemical interfaces involving polymer and liquid electrolytes,and provide a framework for understanding electron-transfer processes at polymer electrolyte/electrode interfaces.展开更多
文摘In this paper, photoinduced electron transfer(PET) phosphoroionophore, N-(1-bromo- 2-naphthylmethyl)-diethanolamine (BND) was synthesized and its phosphorescent characteristics were studied. The experimental results showed that strong phosphorescence could be observed in b-cyclodextrin aqueous solution only at low pH value. This system combined AND and NOT function to produce a three-input inhibit (INH) logic gate.
基金supported by National Natural Science Foundation of China (Nos.52170086,22476116,52074176)Natural Science Foundation of Shandong Province (Nos.ZR2021ME013,ZR2024ME156,ZR2022QB250)。
文摘In this study,we meticulously designed a layered carbon-based catalytic material to induce the degradation of a series of organic pollutants by activating peroxymonosulfate(PMS) in the PMS-based advanced oxidation processes(AOPs).Results indicated that the silicon and oxygen elements from the montmorillonite were incorporated into the catalyst matrix to form the Si-O-C structure.It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array,achieving over 90 % removal rate of most pollutants within 60 min.It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array.The salt bridge system confirmed that pollutants can provide electrons to the Si-O-C/PMS system,and we verified that the electron transfer process(ETP) mechanism was the main pathway for the degradation of pollutants in the Si-O-C/PMS system via the open-circuit potential analysis.In combination with the structural properties of different pollutants,we discovered that electron-donating pollutants can supply more electrons to the Si-O-C/PMS system,thereby enhancing the ETP process.The findings of this study are anticipated to advance the development and practical application of layered carbonaceous materials-based catalysts and support the design and implementation of nanoconfined catalysts in the field of AOPs.
基金supported by the Science Fund for Distinguished Young Scholars of Hunan Province(2023JJ10060)the National Natural Science Foundation of China(22575269)Young Elite Scientists Sponsorship Program by CAST(2023QNRC001)。
文摘Recent advancements in Zn-halogen batteries have focused on enhancing the adsorptive or catalytic capability of host materials and stabilizing complex intermediates with electrolyte additives,while the halogen-ion electrolyte modifications exhibit strong potential for integrated interfacial regulation.Herein,we design an electrically insulating rigid electrolyte container to immobilize a liquid halogen-ion electrolyte for separator-free Zn-halogen batteries with customizable electron transfer.Robust hydrogen bonding of hydroxyl groups in SiO_(2)with fluorinated moieties in PVDF-hfp regulates Zn^(2+)solvation and suppresses H_(2)O activity,while multi-channels formed by microcracks and interparticle gaps not only enhance mass transfer but also buffer interfacial electric field,jointly enabling a durable Zn plating/stripping.Effective confinement of intermediates also ensures the high reversibility across single-(I^(-)/I0),double-(I^(-)/I0/I^(-)),and triple-(I^(-)/I0/I^(-),Cl-/Cl0)electron transfer mechanisms at cathode,as evidenced by the double-electron transfer systems exhibiting a low capacity decay rate of 0.02‰over 4500 cycles at 10 mA cm^(-2)and a high areal capacity of 11.9 mAh cm^(-2)at 2 mA cm^(-2).This work presents a novel“container engineering”approach to halogen-ion electrolyte design and provides fundamental insights into the relationships between redox reversibility and reaction kinetics.
文摘Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt oxyhydroxide @covalent organic frameworks(CoOOH@COFs) S-scheme heterojunction was synthesized,which combined the visible-light-driven photocatalysis and peroxymonosulfate(PMS) activation to synergistically generate abundant reactive oxygen species(ROSs) for TCS degradation.The degradation efficiency of TCS reached 100 % within 8 min in the Vis-CoOOH@COFs/PMS system,and the reaction rate constant was 0.456 min^(-1),which was nearly 1.90 and 2.85 times that of single Co OOH and COFs,and2.36 times that under dark condition,respectively.The density functional theory(DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to Co OOH.Both experimental and theoretical analyses indicated that Co OOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation,enhanced interfacial electron transfer,accelerated PMS activation,and generated multiple ROSs.In particular,photogenerated electrons(e^(-))accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle,while the PMS captured the e-,which significantly decreased the charge combination of Co OOH@COFs.Radicals(O_(2)^(·-),^(·)OH,and SO_(4)^(·-)) and non-radicals(such as ^(1)O_(2),h^(+),and e^(-)) were both presented in the Vis-CoOOH@COFs/PMS system,with O_(2)^(-) playing a dominant role in TCS degradation.Furthermore,the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification.Importantly,the environmentally friendly CoOOH@COFs S-scheme heterojunction exhibited excellent stability and reusability.In conclusion,this study innovatively designed an S-scheme heterojunction in the photocatalytic-PMS activation system,providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.
基金supported by the National Natural Science Foundation of China(No.22433006).
文摘Cryptochromes are blue light photorecep-tors that mediate key biological processes through photoinduced electron transfer(ET).We present a theoretical study of the second ET step along the conserved trypto-phan triad in Arabidopsis thaliana cryp-tochrome,focusing on how vibrational envi-ronments affect the ultrafast electron trans-fer.Using the numerically exact low temper-ature quantum Fokker-Planck equation(LT-QFPE)within the hierarchical equations of motion(HEOM)framework,we resolve the contributions of individual Brownian oscillator modes:low frequency modes with large reorganization energies markedly reduce the ET rate,whereas weakly damped high frequency modes generate oscillations linked to electronic-vibra-tional coherence.The LT-QFPE results are also used to benchmark three second order pertur-bative methods:the non-equilibrium Fermi’s golden rule(NE-FGR),non-interacting blip ap-proximation(NIBA),and the time local generalized quantum master equation.Although all approximate methods reproduce correct long-time ET rates,they fail to capture short time non-equilibrium dynamics.These findings clarify how spectral width and bath correlation time,in addition to total reorganization energy,govern the validity of perturbative treat-ments and highlight the need for numerically exact methods such as HEOM in modeling non-equilibrium cryptochrome ET dynamics.s.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.21003033 and 21203047)the Guangxi Provincial Natural Science Foundation,China(Grant Nos.2012GXNSFBA053012 and 2014GXNSFAA118019)the Research Foundation of Education Bureau of Guangxi Zhuang Autonomous Region,China(Grant No.ZD2014127)
文摘Photo-induced intramolecular electron transfer （PIET） and intramolecular vibrational relaxation （IVR） dynamics of the excited state of rhodamine 6G （Rh6G＋） in DMSO are investigated by multiplex transient grating. Two major compo- nents are resolved in the dynamics of Rh6G＋. The first component, with a lifetime τTPIET = 140 fs-260 fs, is attributed to PIET from the phenyl ring to the xanthene plane. The IVR process occurring in the range ZIVR = 3.3 ps-5.2 ps is much slower than the first component. The PIET and IVR processes occurring in the excited state of Rh6G＋ are quantitatively determined, and a better understanding of the relationship between these processes is obtained.
基金Project supported by the National Natural Science Foundation of China.
文摘1 Introduction Fulgide derivatives are well known as one kind of important organic photochromic compounds and a candidate for application to erasable optical storage materials. But there are many unsolved problems, e.g. the maximum absorption wavelength of the closed form of fulgides is not long enough to match the commercial diode laser(780-830nm). Up to now, it is very difficult for organic chemists to synthesize the qualified organic compounds.
基金Project supported by the National Natural Science Foundation of China
文摘1 Introduction Much research work has been done on the mechanism of photo-induced reduction of quinone dyes by electron donors with visible light. Two ways to obtain the net two-electron reduction product QH^- bave been proposed. One is the direct two-electron transfer (electron-proton-electron transfer) within the complex and the other is the disproportionatioh of the semiquinone radical QH·formed by one-electron transfer.
基金supported by the Science Challenge Project(No.TZ2016001)the National Natural Science Foundation of China(No.21673211)
文摘Photo-induced electron transfer versus molecular structure of acceptors is investigated using ultrafast time-resolved transient grating spectroscopy. Typical laser dyes Rhodamine 101 (Rh101) and Rhodamine 6G (Rh6G) in electron donor solvent-aniline are adopted as the objects. The forward electron transfer time constant from aniline to the excited singlet state of two Rhodamine dyes and subsequent back electron transfer from two dyes to aniline are measured. The experimental results denote that Rh6G presents faster electron transfer rates with aniline in both forward electron transfer and back electron transfer processes. With chemical calculation and qualitative analysis, it is found that the flexible molecular geometry of Rh6G leads to stronger electron coupling with donor solvent and further gives rise to larger electron transfer rates.
基金supported by the National Natural Science Foundation of China(No.21876039)Y.Yao acknowledges the scholarship support from the China Scholarship Council(No.202106695010)Partial support from the Australian Research Council for DP230102406 is also acknowledged.
文摘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 lowefficiency and difficult recovery of the catalysts in a powdery form.Herein,a three-dimensional(3D)framework of Fe-incorporated Ni_(3)S_(2)nanosheets in-situ grown on Ni foam(Fe-Ni_(3)S_(2)@NF)was fabricated by a facile two-step hydrothermal process and applied to trigger peroxymonosulfate(PMS)oxidation of organic compounds inwater.A homogeneous growth environment enabled the uniform and scalable growth of Fe-Ni_(3)S_(2)nanosheets on the Ni foam.Fe-Ni_(3)S_(2)@NF possessed outstanding activity and durability in activating PMS,as it effectively facilitated electron transfer from organic pollutants to PMS.Fe-Ni_(3)S_(2)@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 Ni_(3)S_(2)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-Ni_(3)S_(2),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-Ni_(3)S_(2)@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.
基金financially supported by the Second Tibetan Plateau Scientific Expedition and Research Program(STEP)(No.2019QZKK1003)the Science and Technology Innovation Pro-gram of Hunan Province(No.2022RC1122)。
文摘Layered double hydroxide(LDH)based heterogonous peroxymonosulfate(PMS)activation degradation of pollutants has attracted extensive attention.The challenge is to selectively regulate the traditional free radical dominant degradation pathway into a nonradical degradation pathway.Herein,an interface ar-chitecture of Ti_(3) C_(2) T_(x)-MXene(MXene)loading on the Fe-Al LDH scaffold was developed,which showed excellent stability and robust resistance against harsh conditions.Significantly,the rate constant for tetra-cycline hydrochloride(TC)degradation in the MXene-LDH/PMS process was 0.421 min^(-1),which was ten times faster than the rate constant for pure Fe-Al LDH(0.042 min^(-1)).Specifically,more reactive Fe with the closer d-band center to the Fermi level results in higher electron transfer efficiency.The occupa-tions of Fe-3d orbitals in Mxene/Fe-Al LDH are pushed above the Fermi level to generate,which results in higher PMS adsorption and inhibition of the release of oxygen-containing active species intermedi-ates,leading to the enhanced^(1)O_(2) generation.Additionally,the built-in electric field in the heterojunc-tion was driven by the charge redistribution between MXene and Fe-Al LDH,resulting in a mediated-electron transfer mechanism,differentiating it from the Fe-Al LDH/PMS system.It was fascinating that MXene/Fe-Al LDH achieved satisfactory treatment efficiency in continuous column reactor and real landfill leachate.
基金Project supported by the Domestic Visiting Fellows Program of Hangzhou Normal University(No.4095C5022521106)。
文摘In situ electron paramagnetic resonance(EPR)monitoring of the photocatalytic halogen atom transfer(XAT)reaction with organic amines has provided insights into the dynamic transformations of intermediates,including catalyst intermediate states,amine alkyl radicals,and the dehalogenation of halogenated hydrocarbons to form carbon-centered radicals.This approach facilitated the photocatalytic single-linear state oxygen-promoted halogen atom transfer quinoxalinone alkylation reaction.
基金supported by Key Research and Development Projects of Shanghai Municipal Commission of Science and Technology(20dz1204000)。
文摘In this study,a Fe,N-decorated carbocatalyst(FeCN@X)based on Fe-MOFs was synthesized to activate peroxydisulfate(PDS)for removing sulfadiazine(SDZ)from water.The surface morphology and structure of FeCN@X was characterized by scanning electron microscopy,X-ray diffraction,and X-ray photoelectron spec troscopy.FeCN@1000,formed at the pyrolysis temperature of 1000℃,exhibited the best catalytic performance for degrade SDZ in the presence of 0.15 g·L^(-1)catalyst and 0.5 mmol·L^(-1)PDS,and the reaction conversion rate was 0.199 L·mmol^(-1).Moreover,the effects of experimental conditions,coexisting anions and fulvic acid on catalytic performance of FeCN@1000 were investigated.The excellent potential of FeCN@1000 as a PDS activator in environmental applications was also suggested by the results of its reusability and adaptability experiments.The result of XPS,ROS quenching,EPR and electrochemical experiments showed the degradation of SDZ was primarily driven by an electron transfer process(ETP).Furthermore,Fe(Ⅲ)instead of Fe(Ⅱ)plays a major role in ETP,as Fe(Ⅲ)sites can interact with PDS and form the low-spin surface complexes(Fe(Ⅲ)/CN-PDS).Meanwhile,the small number of~1O_(2) and O_(2)~-·generated by the activation of PDS will promote the system degradation of SDZ activity by accelerating the conversion of Fe(Ⅱ)to Fe(Ⅲ).This study provides new insights for the design of novel PDS activator for efficient degradation of emerging pollutants by ETP.
基金supported by the Fundamental Re-search Funds for the Central Universities(Ganglong Cui)and National Key Research and Development Pro-gram of China(No.2021YFA1500703 to Ganglong Cui)National Natural Science Foundation of China(No.22103067 to Xiao-Ying Xie)and Natural Science Foundation of Shandong Province(No.ZR2021QB105 to Xiao-Ying Xie).
文摘Heterostructures of organic semi-conductors and transition metal dichalcogenides(TMDs)are viable candidates for superior optoelec-tronic devices.Photoinduced inter-facial charge transfer is crucial for the performance efficiency of such devices,yet the underlying mecha-nism,especially the roles of optical-ly dark triplets and spatially sepa-rated charge transfer states,is poorly understood.In the present work,we obtain the struc-tures of distinct excited states and investigate how they are involved in the charge transfer process at the Pd-octaethylporphyrin(PdOEP)and WS_(2) interface in terms of their energies and couplings.The results show that electron transfer from the triplet PdOEP formed via intersystem crossing prevails over direct electron transfer from the singlet(two orders of magnitude faster).Further analysis reveals that the relatively higher rate of triplet electron transfer compared to singlet electron transfer is mainly attributed to a smaller reorganization energy,which is dominated by the out-of-plane vibrations of the organic component.The work emphasizes the important roles of the optically dark triplets in the electron transfer of the PdOEP@WS_(2) heterostructure,and provides valuable theoretical insights for further improv-ing the optoelectronic performance of TMD-based devices.
基金supported by the National Natural Science Foundation of China(U21A2033)the Fundamental Research Funds for the Central Universities(2652022103).
文摘Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not yet fully understood.In this study,the V(V)reduction mechanisms with concomitant V isotope fractionation by the Gram-positive bacterium Bacillus subtilis(B.subtilis)and the Gramnegative bacterium Thauera humireducens(T.humireducens)were investigated.Both strains could effectively reduce V(V),removing(90.5%±1.6%)and(93.0%±1.8%)of V(V)respectively from an initial concentration of 50 mg L^(-1) during a 10-day incubation period.V(V)was bioreduced to insoluble vanadium(IV),which was distributed both inside and outside the cells.Electron transfer via cytochrome C,nicotinamide adenine dinucleotide,and glutathione played critical roles in V(V)reduction.Metabolomic analysis showed that differentially enriched metabolites(quinone,biotin,and riboflavin)mediated electron transfer in both strains.The aqueous V in the remaining solution became isotopically heavier as V(V)bioreduction proceeded.The obtained V isotope composition dynamics followed a Rayleigh fractionation model,and the isotope enrichment factor(e)was(–0.54‰±0.04‰)for B.subtilis and(–0.32‰±0.03‰)for T.humireducens,with an insignificant difference.This study provides molecular insights into electron transfer for V(V)bioreduction and reveals V isotope fractionation during this bioprocess,which is helpful for understanding V biogeochemistry and developing novel strategies for V remediation.
基金supported by the National Natural Science Foundation of China(22171155,22571174)Natural Science Foundation of Shandong Province(ZR2022YQ07)+1 种基金Taishan Scholar Program(tsqn202306166)the State Key Laboratory of Fine Chemicals,Dalian University of Technology(KF 2409).
文摘Photochromic materials attract significant attention for their applications in anticounterfeiting devices,optical switches and molecular sensors.However,the influence of solvent molecules,particularly coordinated solvents,on electron transfer(ET)photochromic systems remains poorly understood.In this study,we synthesized a series of isostructural metal-organic complexes(MOCs),[Mn(ADC)(L)]n(ADC=9,10-anthracenedicarboxylic acid,L=DMF for 1,DMA for 2,MEA for 3,and DMSO for 4)to investigate the solvent-chromic behavior.All these MOCs exhibit typical radical-induced chromism upon illumination with a xenon lamp at room temperature.It is worth noting that coordination solvent molecules significantly modulate the photochromic response rate.Among the compounds studied,compound 1 exhibits the fastest response,while compound 3 shows the slowest.This variation in rate correlates with differences in the optimal ET path length within their structures.Specifically,solvent molecules regulate the C-H…π interaction distance through their steric hindrance and electronic prop-erties.Shorter C-H…π paths facilitate more efficient ET upon photoexcitation,thus leading to faster photo-chromic response rates.Furthermore,illumination actuates magnetic couplings between photogenerated radicals and Mn^(2+)centers,resulting in a significant increase in room-temperature magnetization,demonstrating a photomagnetic response.This study demonstrates that coordinating solvent selection effectively controls photoinduced ET behavior,providing new insights for designing advanced photoactive materials.
基金supported by the National Natural Science Foundation of China(No.22278202).
文摘For the effective treatment of the wastewater with low-medium concentration ammonia nitrogen and low strength COD,a high-performance Co_(3)O_(4) catalyst supported on carbon nanocages(CNCs)was prepared.By isovolumetric im pregnation,Co_(3)O_(4) could be uniformly dispersed on surface of CNCs,which possess tiny particle size and strong electron transfer capability.The catalytic performance of the prepared Co_(3)O_(4)/CNCs catalysts with different Co_(3)O_(4) loadings was systematically evaluated and compared with Co_(3)O_(4)/CNTs.It is found that 20 wt.%Co_(3)O_(4)/CNCs shows the best catalytic performance,achieving an ammonia nitrogen conversion rate of 71.0%and a nitrogen selectivity of 81.8%.Compared to commonly used Co_(3)O_(4),ammonia conversion and nitrogen selectivity of Co_(3)O_(4)/CNCs increased by 28.9%and 15.8%respectively.In the five consecutive cycles,the catalytic activity remained stable.The mechanism that CNCs support effectively increases the surface oxygen vacancies of Co_(3)O_(4) through XPS analysis was also elucidated,and DFT calculations confirm strong electron transfer between CNCs and Co_(3)O_(4),rendering Co_(3)O_(4) nanoparticles as the primary catalytic active sites.The results may contribute to the development of highperformance catalytic ozone oxidation catalysts for ammonia nitrogen.
基金supported by the National Natural Science Foundation of China(Nos.42030709 and 42377303)the National Key Research and Development Program of China(No.2020YFC1806803).
文摘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 Kedge 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.
基金support from the 2BoSS project of the ERA-MIN3 program with the Spanish grant number PCI2022-132985/AEI/10.13039/501100011033funding from the Generalitat de Catalunya 2021SGR01581 and 2021SGR00457+9 种基金the European Union NextGenerationEU/PRTR,the Natural Science Foundation of Chongqing(No.2023NSCQ-MSX1669)the Science and Technology Research Program of Chongqing Municipal Education Commission(No.KJZDK202401110)support of the Supercomputing Center of Lanzhou University,Chinasupported by MCIN with funding from European Union NextGenerationEU(PRTR-C17.I1)by Generalitat de Catalunya(In-CAEM Project)support from the project AMaDE(PID2023-149158OB-C43)funded by MCIN/AEI/10.13039/501100011033/funding from the CSC-UAB PhD scholarship programfunding from Grant IU16-014206(METCAM-FIB)funded by the European Union through the European Regional Development Fund(ERDF)support of the Ministry of Research and Universities,Generalitat de Catalunya。
文摘Lithium-sulfur batteries(LSBs)are a promising candidate for next-generation energy storage solutions.However,challenges such as the shuttling effect and sluggish Li-S reaction kinetics of lithium polysulfides hinder their practical application.In this work,we present a mixed-phase heterostructure comprising Co_(0.85)Se and MoSe_(2),supported on nitrogen-doped carbon polyhedrons(NCP),as an effective sulfur host in the LSB cathode.Through a combination of theoretical calculations and experimental validation,we demonstrate that the Co_(0.85)Se-MoSe_(2)heterointerface significantly enhances electron transfer efficiency,thereby boosting the overall reaction kinetics of the sulfur cathode.As a result,the Co_(0.85)Se-MoSe_(2)/NCP/S electrodes exhibit initial specific capacities exceeding 1500 mAh g^(-1)at 0.1 C and retain 666 m Ah g^(-1)at 3 C,with a capacity fade rate of 0.044%per cycle over 500 cycles at 1.0 C.Notably,even at a high sulfur loading of 3 mg cm^(-2)and a reduced electrolyte volume of 6.7μL mgS^(-1),the Co_(0.85)SeMoSe_(2)/NCP/S electrodes maintain a capacity of 432 mAh g^(-1)after 100 cycles at 0.2 C.
基金supported by the National Key R&D Program of China(No.2021YFA1501003)。
文摘Electron transfer processes at polymer electrolyte/electrode interfaces play a central role in modern electrochemical devices of energy conversion,however,current understanding of electron transfers through electrochemical interfaces was established exclusively based on the studies of liquid/solid electrochemical interfaces.Thus,similarities and differences of liquid and polymer electrolyte/electrode interfaces need to be mapped out to guide the design of device level electrochemical interfaces.In this work,we employ the sulfonate adsorption/desorption as a probe reaction to understand the electron-transfer steps in polymer and liquid electrolytes.Through cyclic voltametric investigations on the well-define single-crystal Pd_(ML)Pt(111)electrode,we demonstrate that the oxidative adsorption and reductive desorption of sulfonates at the polymer electrolyte/electrode interface are chemically distinct from those in liquid electrolytes,with the former occurring mostly via the proton-coupled pathway while the latter proceeding mainly through the solvation-mediated pathway.Importantly,the sulfonate adsorption/desorption behaviors of alkylsulfonates become increasingly similar to those in Nafion with longer alkyl chains,suggesting that the interfacial hydrophobicity and solvation environment conferred by the perfluorinated polymer play a decisive role in the electron-transfer mechanism.Results reported in this study highlight the mechanistic distinctions between electron-transfer processes at electrochemical interfaces involving polymer and liquid electrolytes,and provide a framework for understanding electron-transfer processes at polymer electrolyte/electrode interfaces.
