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
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 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
Electrochemical nitrate reduction(NO_(3)RR)offers a promising avenue for treating nitrate-contaminated water and recovering ammonia(NH_(3)),yet the complexities of direct electron transfer(DET)and hydrogen atom transf...Electrochemical nitrate reduction(NO_(3)RR)offers a promising avenue for treating nitrate-contaminated water and recovering ammonia(NH_(3)),yet the complexities of direct electron transfer(DET)and hydrogen atom transfer(HAT)mechanisms crucial for efficiency remain elusive.This study bridges the gap with a combined experimental and theoretical approach,elucidating the impact of catalyst structure on NO3RR pathways.We discover that catalysts favoring strong NO_(3^(-))adsorption and efficient water dissociation were more inclined towards DET,enhancing denitrification.The Fe@Fe_(3)O_(4)/FF cathode,leveraging the synergistic interplay between metallic Fe and Fe_(3)O_(4),excelled in NO3RR via DET,achieving an NH3yield of 0.28 mmol h-1cm-2and a Faradaic efficiency of 95.7%for NH3at-1.6 V(vs.SCE),with minimal nitrite accumulation at 100 mmol/L nitrate.Conversely,the Fe/FF and Fe_(3)O_(4)/CC cathodes showed reduced NH3production and increased nitrite levels,attributed to the lack of Fe_(3)O_(4)and metallic Fe,respectively,resulting in a dominant HAT mechanism.Moreover,Fe@Fe_(3)O_(4)/FF facilitated complete denitrification in real wastewater treatment by harnessing Cl^(-)for electrochemically mediated breakpoint chlorination.This research not only deepens our understanding of NO3RR mechanisms but also paves the way for designing superior nitrate reduction catalysts.展开更多
Pyridyl-based ketones and 1,6-diketones are both attractive and invaluable scaffolds which play pivotal roles in the construction and structural modification of a plethora of synthetically paramount natural products,p...Pyridyl-based ketones and 1,6-diketones are both attractive and invaluable scaffolds which play pivotal roles in the construction and structural modification of a plethora of synthetically paramount natural products,pharmaceuticals,organic materials and fine chemicals.In this context,we herein demonstrate an unprecedented,robust and generally applicable synthetically strategy to deliver these two crucial ketone frameworks via visible-light-induced ring-opening coupling reactions of cycloalcohols with vinylazaarenes and enones,respectively.A plausible mechanism involves the selectiveβ-C-C bond cleavage of cycloalcohols enabled by proton-coupled electron transfer and ensuing Giese-type addition followed by single electron reduction and protonation.The synthetic methodology exhibits broad substrate scope,excellent functional group compatibility as well as operational simplicity and environmental friendliness.展开更多
The advanced oxidation system based on peracetic acid(PAA)has been proved to be a green and safe oxidation decontamination technology.Among them,the key challenge and complexity in current research lies in the directi...The advanced oxidation system based on peracetic acid(PAA)has been proved to be a green and safe oxidation decontamination technology.Among them,the key challenge and complexity in current research lies in the directional induction of PAA and its utilization for selective removal of refractory pollutants.This study prepared nitrogen-doped biochar(NBC)using compound pharmaceutical residues commonly found in traditional Chinese medicine as a precursor.A system based on NBC-activated PAA was constructed for sulfamethoxazole(SMX)degradation.The introduction of nitrogen significantly enhanced the degree of graphitization in NBC.The degradation system achieved 87.89%SMX degradation efficiency within 60 min.Furthermore,the formation of the intricate NBC-PAA*complex detected by in-situ Raman was of paramount importance as it facilitates enhanced electron transfer processes within the complex,thereby promoting PAA decomposition through electron loss.The formation of a new complex between SMX and NBC-PAA*facilitated the completion of electron transfer process within the complex.In summary,this study explored a novel approach for treating and disposing of solid waste from Chinese medicine residue by successfully inducing non-free radical degradation pathway using PAA system.It offers fresh insights and ideas in the fields of water treatment and solid waste management.展开更多
Nickel-based cathodes in aqueous nickel-zinc batteries typically suffer from sluggish reaction kinetics and limited energy density.In situ introduction of metal phosphides and rational construction of heterostructures...Nickel-based cathodes in aqueous nickel-zinc batteries typically suffer from sluggish reaction kinetics and limited energy density.In situ introduction of metal phosphides and rational construction of heterostructures can effectively promote electron/ion transport.However,the complex evolution of phosphidation and intractable phosphidizing degree greatly affect the composition of active phase,active sites,charge transfer rate,and ion adsorption strength of cathodes.Herein,the critical bimetallic phosphide layer(CBPL)is constructed on the NiCo-layered double hydroxide(NiCo-LDH)skeleton by a controllable anion-exchange strategy,yielding a novel nanohybrid cathode(NiCo-P1.0,1.0 representing the mass ratio of Na_(2)H_(2)PO_(2)to NiCo-LDH).The high-conductivity CBPL with the inner NiCo-LDH forms extensive heterostructures,effectively regulating the electronic structure via charge transfer,thereby improving electrical conductivity.Remarkably,the CBPL exhibits unexpected electrochemical activity and synergizes with NiCo-LDH for electrode reactions,ultimately delivering extra energy.Benefiting from the bifunctional CBPL,NiCo-P1.0 delivers an optimal capacity of 286.64 mAh g^(−1)at 1C(1C=289 mAh g^(−1))and superb rate performance(a capacity retention of 72.22%at 40C).The assembled NiCo-P1.0//Zn battery achieves ultrahigh energy/power density(503.62 Wh kg^(−1)/18.62 kW kg^(−1),based on the mass loading of active material on the cathode),and the flexible quasi-solid-state pouch cell validates its practicality.This work demonstrates the superiority of bifunctional CBPL for surface modification,providing an effective and scalable compositing strategy in achieving high-performance cathodes for aqueous batteries.展开更多
Aqueous Ni-Zn microbatteries are safe,reliable and inexpensive but notoriously suffer from inadequate energy and power densities.Herein,we present a novel mechanism of superoxide-activated Ni substrate that realizes t...Aqueous Ni-Zn microbatteries are safe,reliable and inexpensive but notoriously suffer from inadequate energy and power densities.Herein,we present a novel mechanism of superoxide-activated Ni substrate that realizes the redox reaction featuring three-electron transfers(Ni↔Ni3+).The superoxide activates the direct redox reaction between Ni substrate and KNiO_(2)by lowering the reaction Gibbs free energy,supported by in-situ Raman and density functional theory simulations.The prepared chronopotentiostatic superoxidation-activated Ni(CPS-Ni)electrodes exhibit an ultrahigh capacity of 3.21 mAh cm^(-2)at the current density of 5 mA cm^(-2),nearly 8 times that of traditional one-electron processes electrodes.Even under the ultrahigh 200 mA cm^(-2)current density,the CPS-Ni electrodes show 86.4%capacity retention with a Columbic efficiency of 99.2%after 10,000 cycles.The CPS-Ni||Zn microbattery achieves an exceptional energy density of 6.88 mWh cm^(-2)and power density of 339.56 mW cm^(-2).Device demonstration shows that the power source can continuously operate for more than 7 days in powering the sensing and computation intensive practical application of photoplethysmographic waveform monitoring.This work paves the way to the development of multi-electron transfer mechanisms for advanced aqueous Ni-Zn batteries with high capacity and long lifetime.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.
基金support from the National Natural Science Foundation of China(Nos.U21A2034 and 21876052)the Guangdong Special Support Plan for Innovation Teams(No.2019BT02L218)+1 种基金the Guangdong Special Support Plan for Young Top-notch Talents(No.2019TQ05L179)the Natural Science Foundation of Guangdong Province,China(No.2021B1515120077)。
文摘Electrochemical nitrate reduction(NO_(3)RR)offers a promising avenue for treating nitrate-contaminated water and recovering ammonia(NH_(3)),yet the complexities of direct electron transfer(DET)and hydrogen atom transfer(HAT)mechanisms crucial for efficiency remain elusive.This study bridges the gap with a combined experimental and theoretical approach,elucidating the impact of catalyst structure on NO3RR pathways.We discover that catalysts favoring strong NO_(3^(-))adsorption and efficient water dissociation were more inclined towards DET,enhancing denitrification.The Fe@Fe_(3)O_(4)/FF cathode,leveraging the synergistic interplay between metallic Fe and Fe_(3)O_(4),excelled in NO3RR via DET,achieving an NH3yield of 0.28 mmol h-1cm-2and a Faradaic efficiency of 95.7%for NH3at-1.6 V(vs.SCE),with minimal nitrite accumulation at 100 mmol/L nitrate.Conversely,the Fe/FF and Fe_(3)O_(4)/CC cathodes showed reduced NH3production and increased nitrite levels,attributed to the lack of Fe_(3)O_(4)and metallic Fe,respectively,resulting in a dominant HAT mechanism.Moreover,Fe@Fe_(3)O_(4)/FF facilitated complete denitrification in real wastewater treatment by harnessing Cl^(-)for electrochemically mediated breakpoint chlorination.This research not only deepens our understanding of NO3RR mechanisms but also paves the way for designing superior nitrate reduction catalysts.
基金financial support from National Natural Science Foundation of China(Nos.21801129,22078153 and22378201)National Key Research and Development Program of China(No.2022YFB3805603)+3 种基金Natural science research projects in Jiangsu Higher Education Institutions(No.18KJB150018)Open Research Fund of School of Chemistry and Chemical EngineeringHenan Normal University(No.2024Y16)Nanjing Tech University(Start-up Grant Nos.39837137,39837101 and 3827401739)for financial support。
文摘Pyridyl-based ketones and 1,6-diketones are both attractive and invaluable scaffolds which play pivotal roles in the construction and structural modification of a plethora of synthetically paramount natural products,pharmaceuticals,organic materials and fine chemicals.In this context,we herein demonstrate an unprecedented,robust and generally applicable synthetically strategy to deliver these two crucial ketone frameworks via visible-light-induced ring-opening coupling reactions of cycloalcohols with vinylazaarenes and enones,respectively.A plausible mechanism involves the selectiveβ-C-C bond cleavage of cycloalcohols enabled by proton-coupled electron transfer and ensuing Giese-type addition followed by single electron reduction and protonation.The synthetic methodology exhibits broad substrate scope,excellent functional group compatibility as well as operational simplicity and environmental friendliness.
基金supported by the National Natural Science Foundation of China(No.52200049)the China Postdoctoral Science Foundation(No.2022TQ0089)+2 种基金the Heilongjiang Province Postdoctoral Science Foundation(No.LBH-Z22181)the State Key Laboratory of Urban Water Resource and Environment(Harbin Institute of Technology)(No.2024TS28)the Fundamental Research Funds for the Central Universities。
文摘The advanced oxidation system based on peracetic acid(PAA)has been proved to be a green and safe oxidation decontamination technology.Among them,the key challenge and complexity in current research lies in the directional induction of PAA and its utilization for selective removal of refractory pollutants.This study prepared nitrogen-doped biochar(NBC)using compound pharmaceutical residues commonly found in traditional Chinese medicine as a precursor.A system based on NBC-activated PAA was constructed for sulfamethoxazole(SMX)degradation.The introduction of nitrogen significantly enhanced the degree of graphitization in NBC.The degradation system achieved 87.89%SMX degradation efficiency within 60 min.Furthermore,the formation of the intricate NBC-PAA*complex detected by in-situ Raman was of paramount importance as it facilitates enhanced electron transfer processes within the complex,thereby promoting PAA decomposition through electron loss.The formation of a new complex between SMX and NBC-PAA*facilitated the completion of electron transfer process within the complex.In summary,this study explored a novel approach for treating and disposing of solid waste from Chinese medicine residue by successfully inducing non-free radical degradation pathway using PAA system.It offers fresh insights and ideas in the fields of water treatment and solid waste management.
基金supported by the National Natural Science Foundation of China(No.52373249,W2433146)the Science and Technology Project of Yibin Sanjiang New Area(No.2023SJXQSXZJ003)the Fundamental Research Funds for the Central Universities(No.20822041F4045).
文摘Nickel-based cathodes in aqueous nickel-zinc batteries typically suffer from sluggish reaction kinetics and limited energy density.In situ introduction of metal phosphides and rational construction of heterostructures can effectively promote electron/ion transport.However,the complex evolution of phosphidation and intractable phosphidizing degree greatly affect the composition of active phase,active sites,charge transfer rate,and ion adsorption strength of cathodes.Herein,the critical bimetallic phosphide layer(CBPL)is constructed on the NiCo-layered double hydroxide(NiCo-LDH)skeleton by a controllable anion-exchange strategy,yielding a novel nanohybrid cathode(NiCo-P1.0,1.0 representing the mass ratio of Na_(2)H_(2)PO_(2)to NiCo-LDH).The high-conductivity CBPL with the inner NiCo-LDH forms extensive heterostructures,effectively regulating the electronic structure via charge transfer,thereby improving electrical conductivity.Remarkably,the CBPL exhibits unexpected electrochemical activity and synergizes with NiCo-LDH for electrode reactions,ultimately delivering extra energy.Benefiting from the bifunctional CBPL,NiCo-P1.0 delivers an optimal capacity of 286.64 mAh g^(−1)at 1C(1C=289 mAh g^(−1))and superb rate performance(a capacity retention of 72.22%at 40C).The assembled NiCo-P1.0//Zn battery achieves ultrahigh energy/power density(503.62 Wh kg^(−1)/18.62 kW kg^(−1),based on the mass loading of active material on the cathode),and the flexible quasi-solid-state pouch cell validates its practicality.This work demonstrates the superiority of bifunctional CBPL for surface modification,providing an effective and scalable compositing strategy in achieving high-performance cathodes for aqueous batteries.
基金supported by InnoHK Project at Hong Kong Centre for Cerebro-cardiovascular Health Engineering (COCHE)City University of Hong Kong (7006108)。
文摘Aqueous Ni-Zn microbatteries are safe,reliable and inexpensive but notoriously suffer from inadequate energy and power densities.Herein,we present a novel mechanism of superoxide-activated Ni substrate that realizes the redox reaction featuring three-electron transfers(Ni↔Ni3+).The superoxide activates the direct redox reaction between Ni substrate and KNiO_(2)by lowering the reaction Gibbs free energy,supported by in-situ Raman and density functional theory simulations.The prepared chronopotentiostatic superoxidation-activated Ni(CPS-Ni)electrodes exhibit an ultrahigh capacity of 3.21 mAh cm^(-2)at the current density of 5 mA cm^(-2),nearly 8 times that of traditional one-electron processes electrodes.Even under the ultrahigh 200 mA cm^(-2)current density,the CPS-Ni electrodes show 86.4%capacity retention with a Columbic efficiency of 99.2%after 10,000 cycles.The CPS-Ni||Zn microbattery achieves an exceptional energy density of 6.88 mWh cm^(-2)and power density of 339.56 mW cm^(-2).Device demonstration shows that the power source can continuously operate for more than 7 days in powering the sensing and computation intensive practical application of photoplethysmographic waveform monitoring.This work paves the way to the development of multi-electron transfer mechanisms for advanced aqueous Ni-Zn batteries with high capacity and long lifetime.
