The severe degradation of electrochemical performance for lithium-ion batteries(LIBs)at low temperatures poses a significant challenge to their practical applications.Consequently,extensive efforts have been contribut...The severe degradation of electrochemical performance for lithium-ion batteries(LIBs)at low temperatures poses a significant challenge to their practical applications.Consequently,extensive efforts have been contributed to explore novel anode materials with high electronic conductivity and rapid Li^(+)diffusion kinetics for achieving favorable low-temperature performance of LIBs.Herein,we try to review the recent reports on the synthesis and characterizations of low-temperature anode materials.First,we summarize the underlying mechanisms responsible for the performance degradation of anode materials at subzero temperatures.Second,detailed discussions concerning the key pathways(boosting electronic conductivity,enhancing Li^(+)diffusion kinetics,and inhibiting lithium dendrite)for improving the low-temperature performance of anode materials are presented.Third,several commonly used low-temperature anode materials are briefly introduced.Fourth,recent progress in the engineering of these low-temperature anode materials is summarized in terms of structural design,morphology control,surface&interface modifications,and multiphase materials.Finally,the challenges that remain to be solved in the field of low-temperature anode materials are discussed.This review was organized to offer valuable insights and guidance for next-generation LIBs with excellent low-temperature electrochemical performance.展开更多
The widespread interest in layered P2-type Mn-based cathode materials for sodium-ion batteries(SIBs)stems from their cost-effectiveness and abundant resources.However,the inferior cycle stability and mediocre rate per...The widespread interest in layered P2-type Mn-based cathode materials for sodium-ion batteries(SIBs)stems from their cost-effectiveness and abundant resources.However,the inferior cycle stability and mediocre rate performance impede their further development in practical applications.Herein,we devised a wet chemical precipitation method to deposit an amorphous aluminum phosphate(AlPO_(4),denoted as AP)protective layer onto the surface of P2-type Na_(0.55)Ni_(0.1)Co_(0.7)Mn_(0.8)O_(2)(NCM@AP).The resulting NCM@5AP electrode,with a 5 wt%coating,exhibits extended cycle life(capacity retention of78.4%after 200 cycles at 100 mA g^(-1))and superior rate performance(98 mA h g^(-1)at 500 mA g^(-1))compared to pristine NCM.Moreover,our investigation provides comprehensive insights into the phase stability and active Na^(+)ion kinetics in the NCM@5AP composite electrode,shedding light on the underlying mechanisms responsible for the enhanced performance observed in the coated electrode.展开更多
TiNb_(2)O_(7)has been emerged as one of the most promising electrode materials for high-energy lithium-ion batteries.However,limited by the slow electron/ion transport kinetics,and insufficient active sites in the bul...TiNb_(2)O_(7)has been emerged as one of the most promising electrode materials for high-energy lithium-ion batteries.However,limited by the slow electron/ion transport kinetics,and insufficient active sites in the bulk structure,the TiNb_(2)O_(7)electrode still suffers from unsatisfactory lithium storage performance.Herein,we demonstrate a spatially confined strategy toward a novel TiNb_(2)O_(7)-NMC/MXene composite through a triblock copolymer-directed one-pot solvothermal route,where TiNb_(2)O_(7)quantum dots with a particle size of 2-3 nm are evenly embedded into N-doped mesoporous carbon(NMC)and Ti_(3)C_(2)T_(X)MXene.Impressively,the as-prepared TiNb_(2)O_(7)-NMC/MXene anode exhibits a high reversible capacity(486.2 mAh g^(-1)at 0.1 A g^(-1)after 100 cycles)and long cycle lifespan(363.4 mAh g^(-1)at ss1 A g^(-1)after 500 cycles).Both experimental and theorical results further demonstrate that such a superior lithium storage performance is mainly ascribed to the synergistic effect among 0D TiNb_(2)O_(7)quantum dots,2D Ti_(3)C_(2)T_(X)MXene nanosheets,and N-doped mesoporous carbon.The strategy presented also opens up new horizon for space-confined preparation of high-performance electrode materials.展开更多
Metal–organic gel(MOG)derived composites are promising multi-functional materials due to their alterable composition,identifiable chemical homogeneity,tunable shape,and porous structure.Herein,stable metal–organic h...Metal–organic gel(MOG)derived composites are promising multi-functional materials due to their alterable composition,identifiable chemical homogeneity,tunable shape,and porous structure.Herein,stable metal–organic hydrogels are prepared by regulating the complexation effect,solution polarity and curing speed.Meanwhile,collagen peptide is used to facilitate the fabrication of a porous aerogel with excellent physical properties as well as the homogeneous dispersion of magnetic particles during calcination.Subsequently,two kinds of heterometallic magnetic coupling systems are obtained through the application of Kirkendall effect.FeCo/nitrogen-doped carbon(NC)aerogel demonstrates an ultra-strong microwave absorption of−85 dB at an ultra-low loading of 5%.After reducing the time taken by atom shifting,a FeCo/Fe3O4/NC aerogel containing virus-shaped particles is obtained,which achieves an ultra-broad absorption of 7.44 GHz at an ultra-thin thickness of 1.59 mm due to the coupling effect offered by dual-soft-magnetic particles.Furthermore,both aerogels show excellent thermal insulation property,and their outstanding radar stealth performances in J-20 aircraft are confirmed by computer simulation technology.The formation mechanism of MOG is also discussed along with the thermal insulation and electromagnetic wave absorption mechanism of the aerogels,which will enable the development and application of novel and lightweight stealth coatings.展开更多
Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides a promising way to convert CO_(2)to chemicals.The multicarbon(C_(2+))products,especially ethylene,are of great interest due to their versatile indust...Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides a promising way to convert CO_(2)to chemicals.The multicarbon(C_(2+))products,especially ethylene,are of great interest due to their versatile industrial applications.However,selectively reducing CO_(2)to ethylene is still challenging as the additional energy required for the C–C coupling step results in large overpotential and many competing products.Nonetheless,mechanistic understanding of the key steps and preferred reaction pathways/conditions,as well as rational design of novel catalysts for ethylene production have been regarded as promising approaches to achieving the highly efficient and selective CO_(2)RR.In this review,we first illustrate the key steps for CO_(2)RR to ethylene(e.g.,CO_(2)adsorption/activation,formation of~*CO intermediate,C–C coupling step),offering mechanistic understanding of CO_(2)RR conversion to ethylene.Then the alternative reaction pathways and conditions for the formation of ethylene and competitive products(C_1 and other C_(2+)products)are investigated,guiding the further design and development of preferred conditions for ethylene generation.Engineering strategies of Cu-based catalysts for CO_(2)RR-ethylene are further summarized,and the correlations of reaction mechanism/pathways,engineering strategies and selectivity are elaborated.Finally,major challenges and perspectives in the research area of CO_(2)RR are proposed for future development and practical applications.展开更多
Advanced analytical methodology based on comprehensive two-dimensional gas chromatography-time of flight mass spectrometry(GC×GC-TOFMS) is proposed for investigation of organic chlorides in different oilfield che...Advanced analytical methodology based on comprehensive two-dimensional gas chromatography-time of flight mass spectrometry(GC×GC-TOFMS) is proposed for investigation of organic chlorides in different oilfield chemicals.The target screening was initially carried out on 8 suspected organic chlorides by evaluating the capability of the enhanced separation and reliable identification at a trace concentration. GC×GC-TOFMS allowed for the fast and automated analysis of organic chlorides at a level of 200 μg/L. This method was subsequently applied for non-target screening of organic chlorides in different oilfield chemicals at various locations across China. 22 organic chlorides were identified and verified by comparison with pure standards in the mixed sample. Finally, this method was used to determine the content of the organic chlorides in individual samples. The result showed that the organic chloride levels in 19 of the 39 tested oilfield chemicals were above the threshold limit of 1.0 mg/L.展开更多
Atomic-scale doping strategies and structure design play pivotal roles in tailoring the electronic structure and physicochemical property of electromagnetic wave absorption(EMWA)materials.However,the relationship betw...Atomic-scale doping strategies and structure design play pivotal roles in tailoring the electronic structure and physicochemical property of electromagnetic wave absorption(EMWA)materials.However,the relationship between configuration and electromagnetic(EM)loss mechanism has remained elusive.Herein,drawing inspiration from the DNA transcription process,we report the successful synthesis of novel in situ Mn/N co-doped helical carbon nanotubes with ultrabroad EMWA capability.Theoretical calculation and EM simulation confirm that the orbital coupling and spin polarization of the Mn–N4–C configuration,along with cross polarization generated by the helical structure,endow the helical converters with enhanced EM loss.As a result,HMC-8 demonstrates outstanding EMWA performance,achieving a minimum reflection loss of−63.13 dB at an ultralow thickness of 1.29 mm.Through precise tuning of the graphite domain size,HMC-7 achieves an effective absorption bandwidth(EAB)of 6.08 GHz at 2.02 mm thickness.Furthermore,constructing macroscale gradient metamaterials enables an ultrabroadband EAB of 12.16 GHz at a thickness of only 5.00 mm,with the maximum radar cross section reduction value reaching 36.4 dB m2.This innovative approach not only advances the understanding of metal–nonmetal co-doping but also realizes broadband EMWA,thus contributing to the development of EMWA mechanisms and applications.展开更多
Electrocatalysis for the oxygen evolution reactions(OER)has attracted much attention due to its important role in water splitting and rechargeable metal-air batteries.Therefore,designing highly efficient and low-cost ...Electrocatalysis for the oxygen evolution reactions(OER)has attracted much attention due to its important role in water splitting and rechargeable metal-air batteries.Therefore,designing highly efficient and low-cost catalysts for OER process is essential as the conventional catalysts still rely on precious metals.Transition metal-based compounds have been widely investigated as active OER catalysts,and renewed interest in the high valence metals engineered compounds has been achieved for superior catalytic activity and stability.However,an in-depth understanding of the construction strategies and induced effects for the high valence metals engineered catalysts is still lacking and desired.In this review,we have summarized the construction strategies of high valence metals as dopants or formed heterostructures with the iron/cobalt/nickel(Fe/Co/Ni)-based catalysts.Then the induced effects on Fe/Co/Ni-based catalysts by incorporating high valence metals,e.g.,accelerating the surface reconstruction,forming amorphous structure,generating vacancies/defects,and acting as stabilizers,are highlighted.The impacts of high valence metals on OER performance are elucidated based on different elements,including molybdenum(Mo),tungsten(W),cerium(Ce),vanadium(V),chromium(Cr),manganese(Mn),niobium(Nb),zirconium(Zr).The correlations of construction strategies,induced effects,catalytic activity and OER reaction pathways are elaborated.Finally,the remaining challenges for further enhancements of OER performance induced by high valence metals are presented.展开更多
The uncontrolled formation of lithium(Li)dendrites and the unnecessary consumption of electrolyte during the Li plating/stripping process have been major obstacles in developing safe and stable Li metal batteries.Here...The uncontrolled formation of lithium(Li)dendrites and the unnecessary consumption of electrolyte during the Li plating/stripping process have been major obstacles in developing safe and stable Li metal batteries.Herein,we report a cucumber-like lithiophilic composite skeleton(CLCS)fabricated through a facile oxidationimmersion-reduction method.The stepwise Li deposition and stripping,determined using in situ Raman spectra during the galvanostatic Li charging/discharging process,promote the formation of a dendrite-free Li metal anode.Furthermore,numerous pyridinic N,pyrrolic N,and CuxN sites with excellent lithiophilicity work synergistically to distribute Li ions and suppress the formation of Li dendrites.Owing to these advantages,cells based on CLCS exhibit a high Coulombic efficiency of 97.3%for 700 cycles and an improved lifespan of 2000 h for symmetric cells.The full cells assembled with LiFePO_(4)(LFP),SeS_(2) cathodes and CLCS@Li anodes demonstrate high capacities of 110.1 mAh g^(−1) after 600 cycles at 0.2 A g^(−1) in CLCS@Li|LFP and 491.8 mAh g^(−1) after 500 cycles at 1 A g^(−1) in CLCS@Li|SeS2.The unique design of CLCS may accelerate the application of Li metal anodes in commercial Li metal batteries.展开更多
Polylactic acid(PLA)has been extensively applied in the fields of biology and renewable biodegradable materials because of its superior biodegradability.PLA has excellent potential as a renewable biodegradable adsorbe...Polylactic acid(PLA)has been extensively applied in the fields of biology and renewable biodegradable materials because of its superior biodegradability.PLA has excellent potential as a renewable biodegradable adsorbent in wastewater treatment.However,its poor photocatalytic properties have hindered its practical application.In this study,polyvinylpyrrolidone(PVPP)or glutaraldehyde(GA)was utilized as an adhesive agent to prepare Ag/AgCl/PLA photocatalysts with highly efficient visible light photocatalysis on a PLA fabric by utilizing the electron beam irradiation method.The photocatalytic activities of the Ag/AgCl/PLA samples were examined under visible light irradiation to analyze the degradation of methylene blue(MB)and chloramphenicol(CPL).Our experimental results demonstrate that the nanomaterial Ag/AgCl was uniformly distributed on the PLA fiber surface;this can be attributed to the effects of the crosslinking PVPP or GA.Under electron beam irradiation,adding crosslinking PVPP(or GA)is beneficial to the loading of Ag/AgCl onto the PLA.For the composite Ag/AgCl/PLA,the degradation rate for MB was as high as 97% after 150 min of visible light irradiation.The addition of 4 mg/ml of Ag/AgCl solution resulted in the greatest photocatalytic activity for CPL,and we advanced the possible degradation pathways of CPL with the best sample.Additionally,the as-prepared composite Ag/Ag Cl/PLA exhibited favorable antibacterial activity against E.coli and S.aureus,with a bacterial removal rate of >77%.展开更多
Thin and flexible composite solid-state electrolyte(SSE) is considered to be a prospective candidate for lithium-oxygen(Li-O_(2)) batteries with the aim to address the problems of unsatisfied safety, terrible durabili...Thin and flexible composite solid-state electrolyte(SSE) is considered to be a prospective candidate for lithium-oxygen(Li-O_(2)) batteries with the aim to address the problems of unsatisfied safety, terrible durability as well as inferior electrochemical performance. Herein, in order to improve the safety and durability, a succinonitrile(SN) modified composite SSE is proposed. In this SSE, SN is introduced for eliminating the boundary between ceramic particles, increasing the amorphous region of polymer and ensuring fast ionic transport. Subsequently, the symmetric battery based on the proposed SSE achieves a long cycle life of 3000 h. Moreover, the elaborate cathode interface through the SN participation effectively reduces the barriers to the combination between lithium ions and electrons, facilitating the corresponding electrochemical reactions.As a result, the solid-state Li-O_(2)battery based on this SSE and tuned cathode interface achieves improved electrochemical performance including large specific capacity over 12,000 m Ah g^(-1), enhanced rate capacity as well as stable cycle life of 54 cycles at room temperature. This ingenious design provides a new orientation for the evolution of solid-state Li-O_(2)batteries.展开更多
Hydrogen evolution reaction(HER),oxygen evolution reaction(OER),and oxygen reduction reaction(ORR)serve as the most promising electrochemical processes for renewable energy.Developing multifunctional electrocatalysts ...Hydrogen evolution reaction(HER),oxygen evolution reaction(OER),and oxygen reduction reaction(ORR)serve as the most promising electrochemical processes for renewable energy.Developing multifunctional electrocatalysts with high performance for HER,OER and ORR still remains a challenge.Herein,we report a facile method to prepare P,N-co-doped porous carbon encapsulated Fe-CoP(A-FeCoP/CPN)electrocatalyst through freeze drying,carbonization,and KOH activation.The acquired A-FeCoP/CPN possesses abundant pores with large surface area,which provides sufficient defect-rich sites for HER,OER,and ORR,in alkaline or acidic electrolytes.The A-Fe-CoP/CPN shows low overpotential and good stability for HER and OER in alkaline electrolyte.Density functional theory(DFT)computations reveal that the addition of Fe greatly facilitates the rate-determining step and overall catalytic pathway for both HER and OER.A-Fe-CoP/CPN also exhibits low half-wave potential(E1/2)for ORR,which indicates an enhanced performance than that of the noble Pt/C catalyst.Zn-air battery equipped with the A-Fe-CoP/CPN catalyst exhibits a high energy density(849 m Ah g^(-1))and a long-time stability at 5 m A cm^(-2).This finding not only offers a facile strategy to prepare porous carbon materials with defect-rich sites,but also provides guidance for developing multifunctional electrocatalysts for wide electrochemical reactions.展开更多
With the advantages of the multiple oxidation states and highly open crystal structures,vanadium-based composites have been considered as the promising cathode materials for aqueous zinc-ion batteries(ZIBs).However,th...With the advantages of the multiple oxidation states and highly open crystal structures,vanadium-based composites have been considered as the promising cathode materials for aqueous zinc-ion batteries(ZIBs).However,the inherent inferior electrical conductivity,low specific surface area,and sluggish Zn^(2+)diffusion kinetics of the traditional vanadium-based oxides have greatly impeded their development.Herein,a novel hierarchical porous spindle-shaped Ag-V_(2)O_(5) with unique heterostructures was rationally designed via a simple MOF-assisted synthetic method and applied as stable cathode for aqueous ZIBs.The high specific surface area and hierarchically porous superstructures endowed Ag-V_(2)O_(5) with sufficient electrochemical active sites and shortened the diffusion pathways of Zn^(2+),which was beneficial to accelerate the reversible transport of Zn^(2+)and deliver a high specific capacity(426 mA h g^(-1) at 0.1 A g^(-1) and 96.5%capacity retention after 100 cycles).Meanwhile,the self-built-in electric fields at the heterointerface of Ag-V_(2)O_(5) electrode could strengthen the synergistic coupling interaction between Ag and V_(2)O_(5),which can effectively enhance the electric conductivity and maintain the structural integrity,resulting in superb rate capability(326.1 mA h g^(-1) at 5.0 A g^(-1))and remarkable cycling stability(89.7%capacity retention after 2000 cycles at 5.0 A g^(-1)).Moreover,the reversible Zn^(2+)storage mechanism was further investigated and elucidated by kinetics analysis and DFT calculations.展开更多
Although lithium-sulfur batteries(Li SBs)are regarded as one of the most promising candidates for the next-generation energy storage system,the actual industrial application is hindered by the sluggish solid–liquid p...Although lithium-sulfur batteries(Li SBs)are regarded as one of the most promising candidates for the next-generation energy storage system,the actual industrial application is hindered by the sluggish solid–liquid phase conversion kinetics,severe shuttle effect,and low sulfur loadings.Herein,a zeolitic imidazolate framework(ZIF)derived heterogeneous ZnSe-CoSe nanoparticles encapsulated in hollow N-doped carbon nanocage(ZnSe-CoSe-HNC)was designed by etching with tannic acid as a multifunctional electrocatalyst to boost the polysulfide conversion kinetics in LiSBs.The hollow structure in ZIF ensures large inner voids for sulfur and buffering volume expansions.Abundant exposed ZnSe-CoSe heterogeneous interfaces serve as bifunctional adsorption-catalytic centers to accelerate the conversion kinetics and alleviate the shuttle effect.Together with the highly conductive framework,the ZnSe-CoSeHNC/S cathode exhibits a high initial reversible capacity of 1305.3 m A h g-1at 0.2 C,high-rate capability,and reliable cycling stability under high sulfur loading and lean electrolyte(maintaining at 745 m A h g-1after 200 cycles with a high sulfur loading of 6.4 mg cm-2and a low electrolyte/sulfur ratio of 6μL mg^(-1)).Theoretical calculations have demonstrated the heterostructures of ZnSe-CoSe offer higher binding energy to lithium polysulfides than that of ZnSe or CoSe,facilitating the electron transfer to lithium polysulfides.This work provides a novel heterostructure with superior catalytic ability and hollow conductive architecture,paving the way for the practical application of functional sulfur electrodes.展开更多
Estrogens as a kind of steroidal sex hormone are widely used in humans, especially quinestrol(QS),dienestrol(DS) and norethindrone(NET, 19-nor-17-alphaethinltestoster-one), which cannot be completely degraded after ap...Estrogens as a kind of steroidal sex hormone are widely used in humans, especially quinestrol(QS),dienestrol(DS) and norethindrone(NET, 19-nor-17-alphaethinltestoster-one), which cannot be completely degraded after application. Steroidal estrogens at low concentration pulling into environment can disturb the normal biological function of wide life and thus lead to great threat to humans. So it is important to explore its degradation mechanism and its behavior in the environment. In this study, we investigated the oxidation or reduction system under gamma irradiation for reducing estrogenic activity in the aqueous solutions as well as degradation kinetics, its by-products and yield of transformation by different analytical methods such as GC–MS and HPLC. Gamma irradiation could effectively degrade estrogens in aqueous solution. The degradation reaction of estrogens could be depicted by first-order reaction kinetics. The total organic carbon of solution decreased with an increasing absorbed dose with the order: quinestrol [ norethindrone [ dienestrol. The toxicity of the three estrogens was declined after irradiation. Mono- and quadric-hydroxylated intermediates as well as organic acids were formed after gamma irradiation.展开更多
Using time-dependent terahertz spectroscopy, we investigate the role of mixed-cation and mixed-halide on the ultrafast photoconductivity dynamics of two different methylammonium(MA) lead-iodide perovskite thin films. ...Using time-dependent terahertz spectroscopy, we investigate the role of mixed-cation and mixed-halide on the ultrafast photoconductivity dynamics of two different methylammonium(MA) lead-iodide perovskite thin films. It is found that the dynamics of conductivity after photoexcitation reveals significant correlation on the microscopy crystalline features of the samples. Our results show that mixed-cation and lead mixed-halide affect the charge carrier dynamics of the lead-iodide perovskites. In the(5-AVA)_(0.05)(MA)_(0.95) PbI_(2.95) Cl_(0.05)/spiro thin film, we observe a much weaker saturation trend of the initial photoconductivity with high excitation fluence, which is attributed to the combined effect of sequential charge carrier generation, transfer, cooling and polaron formation.展开更多
Cyclocarbon fully consists of sp-hybridized carbon atoms,which shows quite unusual electronic and geometric structures compared to common molecules.In this work,we systematically studied strain energy(SE)of cyclocarbo...Cyclocarbon fully consists of sp-hybridized carbon atoms,which shows quite unusual electronic and geometric structures compared to common molecules.In this work,we systematically studied strain energy(SE)of cyclocarbons of different sizes using regression analysis method based on electronic energies evaluated at the very accurate DLPNO-CCSD(T)/ccp VTZ theoretical level.In addition,ring strain of two systems closely related to cyclocarbon,boron nitride(BN)ring,and cyclic polyacetylene(c-PA),is also explored.Very ideal relationships between SE and number of repeat units(n)are built for cyclo[2n]carbon,B_(n)N_(n),and[2n]c-PA as SE=555.0·n^(-1),145.1·n^(-1),and 629.8·n^(-1)kcal·mol^(-1),respectively,and the underlying reasons of the difference and similarity in their SEs are discussed from electronic structure perspective.In addition,force constant of harmonic potential of C-C-C angles in cyclocarbon is derived based on SE values,the result is found to be 56.23 kcal·mol^(-1)·rad^(-2).The possibility of constructing homodesmotic reactions to calculate SEs of cyclocarbons is also explored in this work,although this method is far less rigorous than the regression analysis method,its result is qualitatively correct and has the advantage of much lower computational cost.In addition,comparisons show thatωB97XD/def2-TZVP is a good inexpensive alternative to the DLPNO-CCSD(T)/cc-p VTZ for evaluating energies used in deriving SE,while the popular and very cheap B3LYP/6-31G(d)level should be used with caution for systems with global electron conjugation such as c-PA.展开更多
MoS_(2) is a promising anode material in sodium-ion battery technologies for possessing high theoretical capacity.However,the sluggish Na^(+) diffusion kinetics and low electronic conductivity hinder the promises.Here...MoS_(2) is a promising anode material in sodium-ion battery technologies for possessing high theoretical capacity.However,the sluggish Na^(+) diffusion kinetics and low electronic conductivity hinder the promises.Herein,a unique MoS_(2)/FeS_(2)/C heterojunction with abundant defects and hollow structure(MFCHHS)was constructed.The synergy of defect engineering in MoS_(2),FeS_(2),and the carbon layer of MFCHHS with a larger specific surface area provides multiple storage sites of Na^(+)corresponding to the surface-controlled process.The MoS_(2)/FeS_(2)/C heterostructure and rich defects in MoS_(2) and carbon layer lower the Na^(+) diffusion energy barrier.Additionally,the construction of MoS_(2)/FeS_(2) heterojunction promotes electron transfer at the interface,accompanying with excellent conductivity of the carbon layer to facilitate reversible electrochemical reactions.The abundant defects and mismatches at the interface of MoS_(2)/FeS_(2) and MoS_(2)/C heterojunctions could relieve lattice stress and volume change sequentially.As a result,the MFCHHS anode exhibits the high capacity of 613.1 mA h g^(-1)at 0.5 A g^(-1) and 306.1 mA h g^(-1) at 20 A g^(-1).The capacity retention of 85.0%after 1400 cycles at 5.0 A g^(-1) is achieved.The density functional theory(DFT)calculation and in situ transmission electron microscope(TEM),Raman,ex-situ X-ray photon spectroscopy(XPS)studies confirm the low volume change during intercalation/deintercalation process and the efficient Na^(+)storage in the layered structure of MoS_(2) and carbon layer,as well as the defects and heterostructures in MFCHHS.We believe this work could provide an inspiration for constructing heterojunction with abundant defects to foster fast electron and Na^(+) diffusion kinetics,resulting in excellent rate capability and cycling stability.展开更多
The doping of ZnO has attracted lots of attention because it is an important way to tune the properties of ZnO.Postdoping after growth is one of the efficient strategies.Here,we report a unique approach to successfull...The doping of ZnO has attracted lots of attention because it is an important way to tune the properties of ZnO.Postdoping after growth is one of the efficient strategies.Here,we report a unique approach to successfully dope the single crystalline ZnO with Ag by the laser-induced method,which can effectively further post-treat grown samples.Magnetron sputtering was used to coat the Ag film with a thickness of about 50 nm on the single crystalline ZnO.Neodymium-doped yttrium aluminum garnet(Nd:YAG)laser was chosen to irradiate the Ag-capped ZnO samples,followed by annealing at700℃for two hours to form ZnO:Ag.The three-dimensional(3D)information of the elemental distribution of Ag in ZnO was obtained through time-of-flight secondary ion mass spectrometry(TOF-SIMS).TOF-SIMS and core-level x-ray photoelectron spectroscopy(XPS)demonstrated that the Ag impurities could be effectively doped into single crystalline ZnO samples as deep as several hundred nanometers.Obvious broadening of core level XPS profiles of Ag from the surface to depths of hundred nms was observed,indicating the variance of chemical state changes in laser-induced Ag-doped ZnO.Interesting features of electronic mixing states were detected in the valence band XPS of ZnO:Ag,suggesting the strong coupling or interaction of Ag and ZnO in the sample rather than their simple mixture.The Ag-doped ZnO also showed a narrower bandgap and a decrease in thermal diffusion coefficient compared to the pure ZnO,which would be beneficial to thermoelectric performance.展开更多
Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-elect...Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-electron reaction between sulfur and lithium in liquid electrolyte makes the capacity much smaller than the theoretical value.Many methods were proposed for inhibiting the shuttle effect of polysulfide,improving corresponding redox kinetics and enhancing the integral performance of Li–S batteries.Here,we will comprehensively and systematically summarize the strategies for inhibiting the shuttle effect from all components of Li–S batteries.First,the electrochemical principles/mechanism and origin of the shuttle effect are described in detail.Moreover,the efficient strategies,including boosting the sulfur conversion rate of sulfur,confining sulfur or lithium polysulfides(LPS)within cathode host,confining LPS in the shield layer,and preventing LPS from contacting the anode,will be discussed to suppress the shuttle effect.Then,recent advances in inhibition of shuttle effect in cathode,electrolyte,separator,and anode with the aforementioned strategies have been summarized to direct the further design of efficient materials for Li–S batteries.Finally,we present prospects for inhibition of the LPS shuttle and potential development directions in Li–S batteries.展开更多
基金supported by the National Key Research and Development Program of China(No.2019YFA0705601)the National Natural Science Foundation of China(No.U23A20122,52101267)the Key Science and Technology Special Project of Henan Province(No.201111311400).
文摘The severe degradation of electrochemical performance for lithium-ion batteries(LIBs)at low temperatures poses a significant challenge to their practical applications.Consequently,extensive efforts have been contributed to explore novel anode materials with high electronic conductivity and rapid Li^(+)diffusion kinetics for achieving favorable low-temperature performance of LIBs.Herein,we try to review the recent reports on the synthesis and characterizations of low-temperature anode materials.First,we summarize the underlying mechanisms responsible for the performance degradation of anode materials at subzero temperatures.Second,detailed discussions concerning the key pathways(boosting electronic conductivity,enhancing Li^(+)diffusion kinetics,and inhibiting lithium dendrite)for improving the low-temperature performance of anode materials are presented.Third,several commonly used low-temperature anode materials are briefly introduced.Fourth,recent progress in the engineering of these low-temperature anode materials is summarized in terms of structural design,morphology control,surface&interface modifications,and multiphase materials.Finally,the challenges that remain to be solved in the field of low-temperature anode materials are discussed.This review was organized to offer valuable insights and guidance for next-generation LIBs with excellent low-temperature electrochemical performance.
基金financially supported by the Australian Research Council(ARC) through the Future Fellowship(FT180100705)the financial support from China Scholarship Council+3 种基金the support from UTS-HUST Key Technology Partner Seed Fundthe support from Open Project of State Key Laboratory of Advanced Special Steel,the Shanghai Key Laboratory of Advanced Ferrometallurgy,Shanghai University(SKLASS 2021-04)the Science and Technology Commission of Shanghai Municipality(22010500400)“Joint International Laboratory on Environmental and Energy Frontier Materials”and“Innovation Research Team of High–Level Local Universities in Shanghai”in Shanghai University。
文摘The widespread interest in layered P2-type Mn-based cathode materials for sodium-ion batteries(SIBs)stems from their cost-effectiveness and abundant resources.However,the inferior cycle stability and mediocre rate performance impede their further development in practical applications.Herein,we devised a wet chemical precipitation method to deposit an amorphous aluminum phosphate(AlPO_(4),denoted as AP)protective layer onto the surface of P2-type Na_(0.55)Ni_(0.1)Co_(0.7)Mn_(0.8)O_(2)(NCM@AP).The resulting NCM@5AP electrode,with a 5 wt%coating,exhibits extended cycle life(capacity retention of78.4%after 200 cycles at 100 mA g^(-1))and superior rate performance(98 mA h g^(-1)at 500 mA g^(-1))compared to pristine NCM.Moreover,our investigation provides comprehensive insights into the phase stability and active Na^(+)ion kinetics in the NCM@5AP composite electrode,shedding light on the underlying mechanisms responsible for the enhanced performance observed in the coated electrode.
基金support from the Natural Science Foundation of Shanghai(23ZR1423800),Shuguang Program supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission(18SG35)Open Research Fund of Shanghai Key Laboratory of Green Chemistry and Chemical Processes(East China Normal University)Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),Nankai University.
文摘TiNb_(2)O_(7)has been emerged as one of the most promising electrode materials for high-energy lithium-ion batteries.However,limited by the slow electron/ion transport kinetics,and insufficient active sites in the bulk structure,the TiNb_(2)O_(7)electrode still suffers from unsatisfactory lithium storage performance.Herein,we demonstrate a spatially confined strategy toward a novel TiNb_(2)O_(7)-NMC/MXene composite through a triblock copolymer-directed one-pot solvothermal route,where TiNb_(2)O_(7)quantum dots with a particle size of 2-3 nm are evenly embedded into N-doped mesoporous carbon(NMC)and Ti_(3)C_(2)T_(X)MXene.Impressively,the as-prepared TiNb_(2)O_(7)-NMC/MXene anode exhibits a high reversible capacity(486.2 mAh g^(-1)at 0.1 A g^(-1)after 100 cycles)and long cycle lifespan(363.4 mAh g^(-1)at ss1 A g^(-1)after 500 cycles).Both experimental and theorical results further demonstrate that such a superior lithium storage performance is mainly ascribed to the synergistic effect among 0D TiNb_(2)O_(7)quantum dots,2D Ti_(3)C_(2)T_(X)MXene nanosheets,and N-doped mesoporous carbon.The strategy presented also opens up new horizon for space-confined preparation of high-performance electrode materials.
基金the National Natural Science Foundation of China(22265021)the Aeronautical Science Foundation of China(2020Z056056003).
文摘Metal–organic gel(MOG)derived composites are promising multi-functional materials due to their alterable composition,identifiable chemical homogeneity,tunable shape,and porous structure.Herein,stable metal–organic hydrogels are prepared by regulating the complexation effect,solution polarity and curing speed.Meanwhile,collagen peptide is used to facilitate the fabrication of a porous aerogel with excellent physical properties as well as the homogeneous dispersion of magnetic particles during calcination.Subsequently,two kinds of heterometallic magnetic coupling systems are obtained through the application of Kirkendall effect.FeCo/nitrogen-doped carbon(NC)aerogel demonstrates an ultra-strong microwave absorption of−85 dB at an ultra-low loading of 5%.After reducing the time taken by atom shifting,a FeCo/Fe3O4/NC aerogel containing virus-shaped particles is obtained,which achieves an ultra-broad absorption of 7.44 GHz at an ultra-thin thickness of 1.59 mm due to the coupling effect offered by dual-soft-magnetic particles.Furthermore,both aerogels show excellent thermal insulation property,and their outstanding radar stealth performances in J-20 aircraft are confirmed by computer simulation technology.The formation mechanism of MOG is also discussed along with the thermal insulation and electromagnetic wave absorption mechanism of the aerogels,which will enable the development and application of novel and lightweight stealth coatings.
基金financially supported via Australian Research Council(FT180100705)the support by the National Natural Science Foundation of China(22209103)+3 种基金the support from UTS Chancellor's Research Fellowshipsthe support from Open Project of State Key Laboratory of Advanced Special Steel,the Shanghai Key Laboratory of Advanced Ferrometallurgy,Shanghai University(SKLASS 2021-**)Joint International Laboratory on Environmental and Energy Frontier MaterialsInnovation Research Team of High-Level Local Universities in Shanghai。
文摘Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides a promising way to convert CO_(2)to chemicals.The multicarbon(C_(2+))products,especially ethylene,are of great interest due to their versatile industrial applications.However,selectively reducing CO_(2)to ethylene is still challenging as the additional energy required for the C–C coupling step results in large overpotential and many competing products.Nonetheless,mechanistic understanding of the key steps and preferred reaction pathways/conditions,as well as rational design of novel catalysts for ethylene production have been regarded as promising approaches to achieving the highly efficient and selective CO_(2)RR.In this review,we first illustrate the key steps for CO_(2)RR to ethylene(e.g.,CO_(2)adsorption/activation,formation of~*CO intermediate,C–C coupling step),offering mechanistic understanding of CO_(2)RR conversion to ethylene.Then the alternative reaction pathways and conditions for the formation of ethylene and competitive products(C_1 and other C_(2+)products)are investigated,guiding the further design and development of preferred conditions for ethylene generation.Engineering strategies of Cu-based catalysts for CO_(2)RR-ethylene are further summarized,and the correlations of reaction mechanism/pathways,engineering strategies and selectivity are elaborated.Finally,major challenges and perspectives in the research area of CO_(2)RR are proposed for future development and practical applications.
基金supported by grants from the contract of China Petrochemical Corporation (3020001914-ZC0607-0013)the National Natural Science Foundation of China (20107073)+1 种基金the Guangdong Science and Technology Project (2014B030301030)the Innovative Research Team in University (No.IRT13078)
文摘Advanced analytical methodology based on comprehensive two-dimensional gas chromatography-time of flight mass spectrometry(GC×GC-TOFMS) is proposed for investigation of organic chlorides in different oilfield chemicals.The target screening was initially carried out on 8 suspected organic chlorides by evaluating the capability of the enhanced separation and reliable identification at a trace concentration. GC×GC-TOFMS allowed for the fast and automated analysis of organic chlorides at a level of 200 μg/L. This method was subsequently applied for non-target screening of organic chlorides in different oilfield chemicals at various locations across China. 22 organic chlorides were identified and verified by comparison with pure standards in the mixed sample. Finally, this method was used to determine the content of the organic chlorides in individual samples. The result showed that the organic chloride levels in 19 of the 39 tested oilfield chemicals were above the threshold limit of 1.0 mg/L.
基金supported by the National Natural Science Foundation of China(22265021)the Aeronautical Science Foundation of China(2020Z056056003)Jiangxi Provincial Natural Science Foundation(20232BAB212004).
文摘Atomic-scale doping strategies and structure design play pivotal roles in tailoring the electronic structure and physicochemical property of electromagnetic wave absorption(EMWA)materials.However,the relationship between configuration and electromagnetic(EM)loss mechanism has remained elusive.Herein,drawing inspiration from the DNA transcription process,we report the successful synthesis of novel in situ Mn/N co-doped helical carbon nanotubes with ultrabroad EMWA capability.Theoretical calculation and EM simulation confirm that the orbital coupling and spin polarization of the Mn–N4–C configuration,along with cross polarization generated by the helical structure,endow the helical converters with enhanced EM loss.As a result,HMC-8 demonstrates outstanding EMWA performance,achieving a minimum reflection loss of−63.13 dB at an ultralow thickness of 1.29 mm.Through precise tuning of the graphite domain size,HMC-7 achieves an effective absorption bandwidth(EAB)of 6.08 GHz at 2.02 mm thickness.Furthermore,constructing macroscale gradient metamaterials enables an ultrabroadband EAB of 12.16 GHz at a thickness of only 5.00 mm,with the maximum radar cross section reduction value reaching 36.4 dB m2.This innovative approach not only advances the understanding of metal–nonmetal co-doping but also realizes broadband EMWA,thus contributing to the development of EMWA mechanisms and applications.
基金supported by the Australian Research Council(ARC)through the Discovery Project(DP180102297)the Future Fellow Project(FT180100705)+2 种基金the support from the Open Project of State Key Laboratory of Advanced Special Steelthe Shanghai Key Laboratory of Advanced Ferrometallurgy,Shanghai University(SKLASS 2021-**)the Science and Technology Commission of Shanghai Municipality(No.19DZ2270200,20511107700)。
文摘Electrocatalysis for the oxygen evolution reactions(OER)has attracted much attention due to its important role in water splitting and rechargeable metal-air batteries.Therefore,designing highly efficient and low-cost catalysts for OER process is essential as the conventional catalysts still rely on precious metals.Transition metal-based compounds have been widely investigated as active OER catalysts,and renewed interest in the high valence metals engineered compounds has been achieved for superior catalytic activity and stability.However,an in-depth understanding of the construction strategies and induced effects for the high valence metals engineered catalysts is still lacking and desired.In this review,we have summarized the construction strategies of high valence metals as dopants or formed heterostructures with the iron/cobalt/nickel(Fe/Co/Ni)-based catalysts.Then the induced effects on Fe/Co/Ni-based catalysts by incorporating high valence metals,e.g.,accelerating the surface reconstruction,forming amorphous structure,generating vacancies/defects,and acting as stabilizers,are highlighted.The impacts of high valence metals on OER performance are elucidated based on different elements,including molybdenum(Mo),tungsten(W),cerium(Ce),vanadium(V),chromium(Cr),manganese(Mn),niobium(Nb),zirconium(Zr).The correlations of construction strategies,induced effects,catalytic activity and OER reaction pathways are elaborated.Finally,the remaining challenges for further enhancements of OER performance induced by high valence metals are presented.
基金This work is well supported by National Natural Science Foundation of China(52073170,21975154)Shanghai Municipal Education Commission(Innovation Program(2019-01-07-00-09-E00021)Innovative Research Team of High-level Local Universities in Shanghai.The authors also acknowledge Lab for Microstructure,Instrumental Analysis&Research Center,Shanghai University,for their help on materials characterization.Moreover,the authors thank High Performance Computing Center of Shanghai University,and Shanghai Engineering Research Center of Intelligent Computing System(No.19DZ2252600)for the assistance of computing resources and technical support.
文摘The uncontrolled formation of lithium(Li)dendrites and the unnecessary consumption of electrolyte during the Li plating/stripping process have been major obstacles in developing safe and stable Li metal batteries.Herein,we report a cucumber-like lithiophilic composite skeleton(CLCS)fabricated through a facile oxidationimmersion-reduction method.The stepwise Li deposition and stripping,determined using in situ Raman spectra during the galvanostatic Li charging/discharging process,promote the formation of a dendrite-free Li metal anode.Furthermore,numerous pyridinic N,pyrrolic N,and CuxN sites with excellent lithiophilicity work synergistically to distribute Li ions and suppress the formation of Li dendrites.Owing to these advantages,cells based on CLCS exhibit a high Coulombic efficiency of 97.3%for 700 cycles and an improved lifespan of 2000 h for symmetric cells.The full cells assembled with LiFePO_(4)(LFP),SeS_(2) cathodes and CLCS@Li anodes demonstrate high capacities of 110.1 mAh g^(−1) after 600 cycles at 0.2 A g^(−1) in CLCS@Li|LFP and 491.8 mAh g^(−1) after 500 cycles at 1 A g^(−1) in CLCS@Li|SeS2.The unique design of CLCS may accelerate the application of Li metal anodes in commercial Li metal batteries.
基金supported by the National Natural Science Foundation of China(Nos.11775138,11675098,and 41473089)Innovation Program of the Shanghai Municipal Education Commission(No.13YZ017)Program for Changjiang Scholars and Innovative Research Teams in Universities(No.IRT13078)
文摘Polylactic acid(PLA)has been extensively applied in the fields of biology and renewable biodegradable materials because of its superior biodegradability.PLA has excellent potential as a renewable biodegradable adsorbent in wastewater treatment.However,its poor photocatalytic properties have hindered its practical application.In this study,polyvinylpyrrolidone(PVPP)or glutaraldehyde(GA)was utilized as an adhesive agent to prepare Ag/AgCl/PLA photocatalysts with highly efficient visible light photocatalysis on a PLA fabric by utilizing the electron beam irradiation method.The photocatalytic activities of the Ag/AgCl/PLA samples were examined under visible light irradiation to analyze the degradation of methylene blue(MB)and chloramphenicol(CPL).Our experimental results demonstrate that the nanomaterial Ag/AgCl was uniformly distributed on the PLA fiber surface;this can be attributed to the effects of the crosslinking PVPP or GA.Under electron beam irradiation,adding crosslinking PVPP(or GA)is beneficial to the loading of Ag/AgCl onto the PLA.For the composite Ag/AgCl/PLA,the degradation rate for MB was as high as 97% after 150 min of visible light irradiation.The addition of 4 mg/ml of Ag/AgCl solution resulted in the greatest photocatalytic activity for CPL,and we advanced the possible degradation pathways of CPL with the best sample.Additionally,the as-prepared composite Ag/Ag Cl/PLA exhibited favorable antibacterial activity against E.coli and S.aureus,with a bacterial removal rate of >77%.
基金the partial financial support from the National Natural Science Foundation of China (22075171,21805182 and 22179080)。
文摘Thin and flexible composite solid-state electrolyte(SSE) is considered to be a prospective candidate for lithium-oxygen(Li-O_(2)) batteries with the aim to address the problems of unsatisfied safety, terrible durability as well as inferior electrochemical performance. Herein, in order to improve the safety and durability, a succinonitrile(SN) modified composite SSE is proposed. In this SSE, SN is introduced for eliminating the boundary between ceramic particles, increasing the amorphous region of polymer and ensuring fast ionic transport. Subsequently, the symmetric battery based on the proposed SSE achieves a long cycle life of 3000 h. Moreover, the elaborate cathode interface through the SN participation effectively reduces the barriers to the combination between lithium ions and electrons, facilitating the corresponding electrochemical reactions.As a result, the solid-state Li-O_(2)battery based on this SSE and tuned cathode interface achieves improved electrochemical performance including large specific capacity over 12,000 m Ah g^(-1), enhanced rate capacity as well as stable cycle life of 54 cycles at room temperature. This ingenious design provides a new orientation for the evolution of solid-state Li-O_(2)batteries.
基金financially supported by the National Natural Science Foundation of China(21872119,22072127)the Natural Science Foundation of Hebei Province(B2021203016)the Special Project for Local Science and Technology Development Guided by the Central Government of China(216Z1301G)。
文摘Hydrogen evolution reaction(HER),oxygen evolution reaction(OER),and oxygen reduction reaction(ORR)serve as the most promising electrochemical processes for renewable energy.Developing multifunctional electrocatalysts with high performance for HER,OER and ORR still remains a challenge.Herein,we report a facile method to prepare P,N-co-doped porous carbon encapsulated Fe-CoP(A-FeCoP/CPN)electrocatalyst through freeze drying,carbonization,and KOH activation.The acquired A-FeCoP/CPN possesses abundant pores with large surface area,which provides sufficient defect-rich sites for HER,OER,and ORR,in alkaline or acidic electrolytes.The A-Fe-CoP/CPN shows low overpotential and good stability for HER and OER in alkaline electrolyte.Density functional theory(DFT)computations reveal that the addition of Fe greatly facilitates the rate-determining step and overall catalytic pathway for both HER and OER.A-Fe-CoP/CPN also exhibits low half-wave potential(E1/2)for ORR,which indicates an enhanced performance than that of the noble Pt/C catalyst.Zn-air battery equipped with the A-Fe-CoP/CPN catalyst exhibits a high energy density(849 m Ah g^(-1))and a long-time stability at 5 m A cm^(-2).This finding not only offers a facile strategy to prepare porous carbon materials with defect-rich sites,but also provides guidance for developing multifunctional electrocatalysts for wide electrochemical reactions.
基金supported by the China Academy of Space Technology Innovation fund(2017ZY601026)。
文摘With the advantages of the multiple oxidation states and highly open crystal structures,vanadium-based composites have been considered as the promising cathode materials for aqueous zinc-ion batteries(ZIBs).However,the inherent inferior electrical conductivity,low specific surface area,and sluggish Zn^(2+)diffusion kinetics of the traditional vanadium-based oxides have greatly impeded their development.Herein,a novel hierarchical porous spindle-shaped Ag-V_(2)O_(5) with unique heterostructures was rationally designed via a simple MOF-assisted synthetic method and applied as stable cathode for aqueous ZIBs.The high specific surface area and hierarchically porous superstructures endowed Ag-V_(2)O_(5) with sufficient electrochemical active sites and shortened the diffusion pathways of Zn^(2+),which was beneficial to accelerate the reversible transport of Zn^(2+)and deliver a high specific capacity(426 mA h g^(-1) at 0.1 A g^(-1) and 96.5%capacity retention after 100 cycles).Meanwhile,the self-built-in electric fields at the heterointerface of Ag-V_(2)O_(5) electrode could strengthen the synergistic coupling interaction between Ag and V_(2)O_(5),which can effectively enhance the electric conductivity and maintain the structural integrity,resulting in superb rate capability(326.1 mA h g^(-1) at 5.0 A g^(-1))and remarkable cycling stability(89.7%capacity retention after 2000 cycles at 5.0 A g^(-1)).Moreover,the reversible Zn^(2+)storage mechanism was further investigated and elucidated by kinetics analysis and DFT calculations.
基金financially supported by the Natural Science Foundation of Shandong Province,China(ZR2021QE192)the National Natural Science Foundation of China(21975154,22179078)+1 种基金the Postdoctoral Science Foundation of China(2018M63074)Qingdao Post-doctoral Applied Research Project(QDBSH20220202040)。
文摘Although lithium-sulfur batteries(Li SBs)are regarded as one of the most promising candidates for the next-generation energy storage system,the actual industrial application is hindered by the sluggish solid–liquid phase conversion kinetics,severe shuttle effect,and low sulfur loadings.Herein,a zeolitic imidazolate framework(ZIF)derived heterogeneous ZnSe-CoSe nanoparticles encapsulated in hollow N-doped carbon nanocage(ZnSe-CoSe-HNC)was designed by etching with tannic acid as a multifunctional electrocatalyst to boost the polysulfide conversion kinetics in LiSBs.The hollow structure in ZIF ensures large inner voids for sulfur and buffering volume expansions.Abundant exposed ZnSe-CoSe heterogeneous interfaces serve as bifunctional adsorption-catalytic centers to accelerate the conversion kinetics and alleviate the shuttle effect.Together with the highly conductive framework,the ZnSe-CoSeHNC/S cathode exhibits a high initial reversible capacity of 1305.3 m A h g-1at 0.2 C,high-rate capability,and reliable cycling stability under high sulfur loading and lean electrolyte(maintaining at 745 m A h g-1after 200 cycles with a high sulfur loading of 6.4 mg cm-2and a low electrolyte/sulfur ratio of 6μL mg^(-1)).Theoretical calculations have demonstrated the heterostructures of ZnSe-CoSe offer higher binding energy to lithium polysulfides than that of ZnSe or CoSe,facilitating the electron transfer to lithium polysulfides.This work provides a novel heterostructure with superior catalytic ability and hollow conductive architecture,paving the way for the practical application of functional sulfur electrodes.
基金supported by the National Natural Science Foundation of China (Nos. 41473089, 4143064, 41340035, 11025526 and 41373098)Program for Innovative Research Team in University (No. IRT13078)
文摘Estrogens as a kind of steroidal sex hormone are widely used in humans, especially quinestrol(QS),dienestrol(DS) and norethindrone(NET, 19-nor-17-alphaethinltestoster-one), which cannot be completely degraded after application. Steroidal estrogens at low concentration pulling into environment can disturb the normal biological function of wide life and thus lead to great threat to humans. So it is important to explore its degradation mechanism and its behavior in the environment. In this study, we investigated the oxidation or reduction system under gamma irradiation for reducing estrogenic activity in the aqueous solutions as well as degradation kinetics, its by-products and yield of transformation by different analytical methods such as GC–MS and HPLC. Gamma irradiation could effectively degrade estrogens in aqueous solution. The degradation reaction of estrogens could be depicted by first-order reaction kinetics. The total organic carbon of solution decreased with an increasing absorbed dose with the order: quinestrol [ norethindrone [ dienestrol. The toxicity of the three estrogens was declined after irradiation. Mono- and quadric-hydroxylated intermediates as well as organic acids were formed after gamma irradiation.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11604202,11674213,61735010 and 51603119the Young Eastern Scholar under Grant Nos QD2015020 and QD2016027+3 种基金the Shanghai Rising-Star Program under Grant No18QA1401700the ‘Chen Guang’ Project under Grant Nos 16CG45 and 16CG46the Shanghai Municipal Education Commissionthe Shanghai Education Development Foundation
文摘Using time-dependent terahertz spectroscopy, we investigate the role of mixed-cation and mixed-halide on the ultrafast photoconductivity dynamics of two different methylammonium(MA) lead-iodide perovskite thin films. It is found that the dynamics of conductivity after photoexcitation reveals significant correlation on the microscopy crystalline features of the samples. Our results show that mixed-cation and lead mixed-halide affect the charge carrier dynamics of the lead-iodide perovskites. In the(5-AVA)_(0.05)(MA)_(0.95) PbI_(2.95) Cl_(0.05)/spiro thin film, we observe a much weaker saturation trend of the initial photoconductivity with high excitation fluence, which is attributed to the combined effect of sequential charge carrier generation, transfer, cooling and polaron formation.
文摘Cyclocarbon fully consists of sp-hybridized carbon atoms,which shows quite unusual electronic and geometric structures compared to common molecules.In this work,we systematically studied strain energy(SE)of cyclocarbons of different sizes using regression analysis method based on electronic energies evaluated at the very accurate DLPNO-CCSD(T)/ccp VTZ theoretical level.In addition,ring strain of two systems closely related to cyclocarbon,boron nitride(BN)ring,and cyclic polyacetylene(c-PA),is also explored.Very ideal relationships between SE and number of repeat units(n)are built for cyclo[2n]carbon,B_(n)N_(n),and[2n]c-PA as SE=555.0·n^(-1),145.1·n^(-1),and 629.8·n^(-1)kcal·mol^(-1),respectively,and the underlying reasons of the difference and similarity in their SEs are discussed from electronic structure perspective.In addition,force constant of harmonic potential of C-C-C angles in cyclocarbon is derived based on SE values,the result is found to be 56.23 kcal·mol^(-1)·rad^(-2).The possibility of constructing homodesmotic reactions to calculate SEs of cyclocarbons is also explored in this work,although this method is far less rigorous than the regression analysis method,its result is qualitatively correct and has the advantage of much lower computational cost.In addition,comparisons show thatωB97XD/def2-TZVP is a good inexpensive alternative to the DLPNO-CCSD(T)/cc-p VTZ for evaluating energies used in deriving SE,while the popular and very cheap B3LYP/6-31G(d)level should be used with caution for systems with global electron conjugation such as c-PA.
基金the National Natural Science Foundation of China(NSFC)(22105059,22279112)the Talent Introduction Program of Hebei Agricultural University(YJ201810)+5 种基金the Youth Topnotch Talent Foundation of Hebei Provincial Universities(BJK2022023)the Natural Science Foundation of Hebei Province(B2022203018)the Fok Ying-Tong Education Foundation of China(171064)the Natural Science Foundation of Shandong Province,China(ZR2021QE192)the China Postdoctoral Science Foundation(2018M630747)the 333 Talent Program of Hebei Province(C20221018)for their support。
文摘MoS_(2) is a promising anode material in sodium-ion battery technologies for possessing high theoretical capacity.However,the sluggish Na^(+) diffusion kinetics and low electronic conductivity hinder the promises.Herein,a unique MoS_(2)/FeS_(2)/C heterojunction with abundant defects and hollow structure(MFCHHS)was constructed.The synergy of defect engineering in MoS_(2),FeS_(2),and the carbon layer of MFCHHS with a larger specific surface area provides multiple storage sites of Na^(+)corresponding to the surface-controlled process.The MoS_(2)/FeS_(2)/C heterostructure and rich defects in MoS_(2) and carbon layer lower the Na^(+) diffusion energy barrier.Additionally,the construction of MoS_(2)/FeS_(2) heterojunction promotes electron transfer at the interface,accompanying with excellent conductivity of the carbon layer to facilitate reversible electrochemical reactions.The abundant defects and mismatches at the interface of MoS_(2)/FeS_(2) and MoS_(2)/C heterojunctions could relieve lattice stress and volume change sequentially.As a result,the MFCHHS anode exhibits the high capacity of 613.1 mA h g^(-1)at 0.5 A g^(-1) and 306.1 mA h g^(-1) at 20 A g^(-1).The capacity retention of 85.0%after 1400 cycles at 5.0 A g^(-1) is achieved.The density functional theory(DFT)calculation and in situ transmission electron microscope(TEM),Raman,ex-situ X-ray photon spectroscopy(XPS)studies confirm the low volume change during intercalation/deintercalation process and the efficient Na^(+)storage in the layered structure of MoS_(2) and carbon layer,as well as the defects and heterostructures in MFCHHS.We believe this work could provide an inspiration for constructing heterojunction with abundant defects to foster fast electron and Na^(+) diffusion kinetics,resulting in excellent rate capability and cycling stability.
基金Project supported by the National Key Research and Development Program of China(Grant No.2022YFB3605403)。
文摘The doping of ZnO has attracted lots of attention because it is an important way to tune the properties of ZnO.Postdoping after growth is one of the efficient strategies.Here,we report a unique approach to successfully dope the single crystalline ZnO with Ag by the laser-induced method,which can effectively further post-treat grown samples.Magnetron sputtering was used to coat the Ag film with a thickness of about 50 nm on the single crystalline ZnO.Neodymium-doped yttrium aluminum garnet(Nd:YAG)laser was chosen to irradiate the Ag-capped ZnO samples,followed by annealing at700℃for two hours to form ZnO:Ag.The three-dimensional(3D)information of the elemental distribution of Ag in ZnO was obtained through time-of-flight secondary ion mass spectrometry(TOF-SIMS).TOF-SIMS and core-level x-ray photoelectron spectroscopy(XPS)demonstrated that the Ag impurities could be effectively doped into single crystalline ZnO samples as deep as several hundred nanometers.Obvious broadening of core level XPS profiles of Ag from the surface to depths of hundred nms was observed,indicating the variance of chemical state changes in laser-induced Ag-doped ZnO.Interesting features of electronic mixing states were detected in the valence band XPS of ZnO:Ag,suggesting the strong coupling or interaction of Ag and ZnO in the sample rather than their simple mixture.The Ag-doped ZnO also showed a narrower bandgap and a decrease in thermal diffusion coefficient compared to the pure ZnO,which would be beneficial to thermoelectric performance.
基金support from the “Joint International Laboratory on Environmental and Energy Frontier Materials”“Innovation Research Team of High-Level Local Universities in Shanghai”support from the National Natural Science Foundation of China (22209103)
文摘Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-electron reaction between sulfur and lithium in liquid electrolyte makes the capacity much smaller than the theoretical value.Many methods were proposed for inhibiting the shuttle effect of polysulfide,improving corresponding redox kinetics and enhancing the integral performance of Li–S batteries.Here,we will comprehensively and systematically summarize the strategies for inhibiting the shuttle effect from all components of Li–S batteries.First,the electrochemical principles/mechanism and origin of the shuttle effect are described in detail.Moreover,the efficient strategies,including boosting the sulfur conversion rate of sulfur,confining sulfur or lithium polysulfides(LPS)within cathode host,confining LPS in the shield layer,and preventing LPS from contacting the anode,will be discussed to suppress the shuttle effect.Then,recent advances in inhibition of shuttle effect in cathode,electrolyte,separator,and anode with the aforementioned strategies have been summarized to direct the further design of efficient materials for Li–S batteries.Finally,we present prospects for inhibition of the LPS shuttle and potential development directions in Li–S batteries.
