The preparation of bifunctional catalysts for oxygen reduction(ORR)and oxygen evolution(OER)is crucial for Zn-air batteries.Here,we report a La doped CoFe_(2)O_(4) spinel catalyst supported on threedimensional graphen...The preparation of bifunctional catalysts for oxygen reduction(ORR)and oxygen evolution(OER)is crucial for Zn-air batteries.Here,we report a La doped CoFe_(2)O_(4) spinel catalyst supported on threedimensional graphene(3D-G),where La can facilitate electron transfer from Co to Fe,leading to increased electron cloud density in Fe and improved catalytic performance.The redshift of the G peak in the Raman spectra indicates the interaction between theπbond of 3D-G and d orbitals in La_(0.2)CoFe_(1.8)O_(4).La_(0.2)CoFe_(1.8)/3D-G exhibits superior ORR performance(E_(1/2)=0.86 V vs.RHE)and OER performance(E_(j=10)=1.55 V vs.RHE)to CoFe_(2)O_(4)/3D-G(E_(1/2)=0.831 V vs.RHE,E_(j=10)=1.603 V vs.RHE).Furthermore,it demonstrates excellent bifunctional oxygen catalytic performance while maintaining high power density and stability in liquid zinc-air batteries(ZABs)and flexible ZABs(F-ZABs).This work presents a viable strategy for utilizing rare earth element doped spinels to enhance oxygen catalyst and ZABs performance.展开更多
Geometrical configurations play a crucial role in dual-atom catalysts(DACs)for electrocatalytic applications.Significant progress has been made to design DACs electrocatalysts with various geometri-cal configurations,...Geometrical configurations play a crucial role in dual-atom catalysts(DACs)for electrocatalytic applications.Significant progress has been made to design DACs electrocatalysts with various geometri-cal configurations,but in-depth understanding the relationship between geometrical configurations and metal-metal interaction mechanisms for designing targeted DACs is still required.In this review,the recent progress in engineering of geometrical configurations of DACs is systematically summarized.Based on the polarity of geometrical configuration,DACs can be classified into two different types that are homonuclear and heteronuclear DACs.Furthermore,with regard to the geometrical configurations of the active sites,homonuclear DACs are identified into adjacent and bridged configurations,and heteronuclear DACs can be classified into adjacent,bridged,and separated configurations.Subsequently,metal-metal interactions in DACs with different geometrical configurations are introduced.Additionally,the applications of DACs in different electrocatalytic reactions are discussed,including the oxygen reduction reaction(ORR),oxygen evolution reaction(OER),hydrogen evolution reaction(HER),and other catalysis.Finally,the future challenges and perspectives for advancements in DACs are high-lighted.This review aims to provide inspiration for the design of highly effcient DACs towards energy relatedapplications.展开更多
Silicon monoxide(SiO)is regarded as a potential candidate for anode materials of lithium-ion batteries(LIBs).Unfortunately,the application of SiO is limited by poor initial Coulombic efficiency(ICE)and unsteady solid ...Silicon monoxide(SiO)is regarded as a potential candidate for anode materials of lithium-ion batteries(LIBs).Unfortunately,the application of SiO is limited by poor initial Coulombic efficiency(ICE)and unsteady solid electrolyte interface(SEI),which induce low energy,short cycling life,and poor rate properties.To address these drawbacks of SiO,we achieve in-situ construction of robust and fast-ion conducting F,N-rich SEI layer on prelithiated micro-sized SiO(P-μSiO)via the simple and continuous treatment ofμSiO in mild lithium 4,4′-dimethylbiphenyl solution and nonflammable hexafluorocyclotriphosphazene solution.Chemical prelithiation eliminates irreversible capacity through pre-forming inactive lithium silicates.Meanwhile,the symbiotic F,N-rich SEI with good mechanical stability and fast Li^(+)permeability is conductive to relieve volume expansion ofμSiO and boost the Li+diffusion kinetics.Consequently,the P-μSiO realizes an impressive electrochemical performance with an elevated ICE of 99.57%and a capacity retention of 90.67%after 350 cycles.Additionally,the full cell with P-μSiO anode and commercial LiFePO_(4) cathode displays an ICE of 92.03%and a high reversible capacity of 144.97 mA h g^(-1).This work offers a general construction strategy of robust and ionically conductive SEI for advanced LIBs.展开更多
Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the...Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions.展开更多
Microwave absorbing materials(MAMs)characterized by high absorption efficiency and good environmental tolerance are highly desirable in practical applications.Both silicon carbide and carbon are considered as stable M...Microwave absorbing materials(MAMs)characterized by high absorption efficiency and good environmental tolerance are highly desirable in practical applications.Both silicon carbide and carbon are considered as stable MAMs under some rigorous conditions,while their composites still fail to produce satisfactory microwave absorption performance regardless of the improvements as compared with the individuals.Herein,we have successfully implemented compositional and structural engineering to fabricate hollow SiC/C microspheres with controllable composition.The simultaneous modulation on dielectric properties and impedance matching can be easily achieved as the change in the composition of these composites.The formation of hollow structure not only favors lightweight feature,but also generates considerable contribution to microwave attenuation capacity.With the synergistic effect of composition and structure,the optimized SiC/C composite exhibits excellent performance,whose the strongest reflection loss intensity and broadest effective absorption reach−60.8 dB and 5.1 GHz,respectively,and its microwave absorption properties are actually superior to those of most SiC/C composites in previous studies.In addition,the stability tests of microwave absorption capacity after exposure to harsh conditions and Radar Cross Section simulation data demonstrate that hollow SiC/C microspheres from compositional and structural optimization have a bright prospect in practical applications.展开更多
In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl gro...In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.展开更多
Covalent organic frameworks(COFs),a rapidly developing category of crystalline conjugated organic polymers,possess highly ordered structures,large specific surface areas,stable chemical properties,and tunable pore mic...Covalent organic frameworks(COFs),a rapidly developing category of crystalline conjugated organic polymers,possess highly ordered structures,large specific surface areas,stable chemical properties,and tunable pore microenvironments.Since the first report of boroxine/boronate ester-linked COFs in 2005,COFs have rapidly gained popularity,showing important application prospects in various fields,such as sensing,catalysis,separation,and energy storage.Among them,COFs-based electrochemical(EC)sensors with upgraded analytical performance are arousing extensive interest.In this review,therefore,we summarize the basic properties and the general synthesis methods of COFs used in the field of electroanalytical chemistry,with special emphasis on their usages in the fabrication of chemical sensors,ions sensors,immunosensors,and aptasensors.Notably,the emerged COFs in the electrochemiluminescence(ECL)realm are thoroughly covered along with their preliminary applications.Additionally,final conclusions on state-of-the-art COFs are provided in terms of EC and ECL sensors,as well as challenges and prospects for extending and improving the research and applications of COFs in electroanalytical chemistry.展开更多
Polymer solid electrolytes(SPEs)based on the[solvate-Li+]complex structure have promising prospects in lithium metal batteries(LMBs)due to their unique ion transport mechanism.However,the solvation structure may compr...Polymer solid electrolytes(SPEs)based on the[solvate-Li+]complex structure have promising prospects in lithium metal batteries(LMBs)due to their unique ion transport mechanism.However,the solvation structure may compromise the mechanical performance and safety,hindering practical application of SPEs.In this work,a composite solid electrolyte(CSE)is designed through the organic-inorganic syner-gistic interaction among N,N-dimethylformamide(DMF),polycarbonate(PC),and Mg_(2)B_(2)O_(5) in poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP).Flame-retardant Mg_(2)B_(2)O_(5) nanowires provide non-flammability to the prepared CSEs,and the addition of PC improves the dispersion of Mg_(2)B_(2)O_(5) nanowires.Simultaneously,the organic-inorganic synergistic action of PC plasticizer and Mg_(2)B_(2)O_(5) nanowires pro-motes the dissociation degree of LiTFSI and reduces the crystallinity of PVDF-HFP,enabling rapid Li ion transport.Additionally,Raman spectroscopy and DFT calculations confirm the coordination between Mg atoms in Mg_(2)B_(2)O_(5) and N atoms in DMF,which exhibits Lewis base-like behavior attacking adjacent C-F and C-H bonds in PVDF-HFP while inducing dehydrofluorination of PVDF-HFP.Based on the syner-gistic coupling of Mg_(2)B_(2)O_(5),PC,and DMF in the PVDF-HFP matrix,the prepared CSE exhibits superior ion conductivity(9.78×10^(-4) s cm^(-1)).The assembled Li symmetric cells cycle stably for 3900 h at a current density of 0.1 mA cm^(-2) without short circuit.The LFP||Li cells assembled with PDL-Mg_(2)B_(2)O_(5)/PC CSEs show excellent rate capability and cycling performance,with a capacity retention of 83.3%after 1000 cycles at 0.5 C.This work provides a novel approach for the practical application of organic-inorganic Synergistic CSEs in LMBs.展开更多
Spinel oxide(NiCo_(2)O_(4))has demonstrated great potential to replace noble metal catalysts for the oxidation reaction of air pollutants.To further boost the oxidation ability of such catalysts,in this study,a facile...Spinel oxide(NiCo_(2)O_(4))has demonstrated great potential to replace noble metal catalysts for the oxidation reaction of air pollutants.To further boost the oxidation ability of such catalysts,in this study,a facile surface-engineering strategy wherein NiCo_(2)O_(4) was treated with different alkali solvents was developed.The obtained catalyst(NiCo_(2)O_(4)-OH)showed a higher surface alkalinity and more surface defects compared to the pristine spinel oxide,including enhanced structural distortion as well as promoted oxygen vacancies.The propane oxidation ability of NiCo_(2)O_(4)-OH was greatly enhanced,with a propane conversion rate that was approximately 6.4 times higher than that of pristine NiCo_(2)O_(4) at a reaction temperature 193℃.This work sets a valuable paradigm for the surface modulation of spinel oxide via alkali treatment to ensure a high-performance oxidation catalyst.展开更多
As an alternative to conventional energy conversion and storage reactions,gas-involved electrochemical reactions,including the carbon dioxide reduction reaction(CO_(2)RR),nitrogen reduction reaction(NRR)and hydrogen e...As an alternative to conventional energy conversion and storage reactions,gas-involved electrochemical reactions,including the carbon dioxide reduction reaction(CO_(2)RR),nitrogen reduction reaction(NRR)and hydrogen evolution reaction(HER),have become an emerging research direction and have gained increasing attention due to their advantages of environmental friendliness and sustainability.Various studies have been designed to accelerate sluggish kinetics but with limited results.Most of them promote the reaction by modulating the intrinsic properties of the catalyst,ignoring the synergistic effect of the reaction as a whole.Due to the introduction of gas,traditional liquid-solid two-phase reactions are no longer applicable to future research.Since gas-involved electrochemical reactions mostly occur at the junctions of gaseous reactants,liquid electrolytes and solid catalysts,the focus of future research on reaction kinetics should gradually shift to three-phase reaction interfaces.In this review,we briefly introduce the formation and constraints of the three-phase interface and propose three criteria to judge its merit,namely,the active site,mass diffusion and electron mass transfer.Subsequently,a series of modulation methods and relevant works are discussed in detail from the three improvement directions of‘exposing more active sites,promoting mass diffusion and accelerating electron transfer’.Definitively,we provide farsighted insights into the understanding and research of three-phase interfaces in the future and point out the possible development direction of future regulatory methods,hoping that this review can broaden the future applications of the three-phase interface,including but not limited to gas-involved electrochemical reactions.展开更多
Bio-photoelectrochemical cells(BPECs)can further expand the use of conventional biofuel cells for renewable energy,but the poor stability of the photoelectrode still hinders their practical application.Herein,a BPEC c...Bio-photoelectrochemical cells(BPECs)can further expand the use of conventional biofuel cells for renewable energy,but the poor stability of the photoelectrode still hinders their practical application.Herein,a BPEC capable of long-term operating in a fuel-free model is fabricated by WO3-xphotoanode with oxygen vacancy(Ov)and bilirubin oxidase catalyzed biocathode.The construction of Ov on the WO3surface significantly suppresses the dissolution of W species into the electrolyte,and improves the charge separation efficiency and the reaction kinetics during the photoelectrochemical oxygen evolution process,thus enhancing the stability and power output performance of the BPEC.As a result,the assembled BPEC can output an open circuit voltage of 0.81 V and deliver a maximum output power of up to 283μW cm^(-2).Impressively,the BPECs maintain 97%of their original power after 36000 s of consecutive discharge under an enclosed environment.This fuel-free BPEC based on a robust WO3-xphotoanode shows excellent promise for accurate application.展开更多
Herein,we designed and constructed a mesoporous LaAlOx via a solvent evaporation induced self-assembly protocol.The structure and physicochemical property of the corresponding NiMo supported catalyst was analyzed by a...Herein,we designed and constructed a mesoporous LaAlOx via a solvent evaporation induced self-assembly protocol.The structure and physicochemical property of the corresponding NiMo supported catalyst was analyzed by a set of characterizations,and its catalytic activity was investigated for hydrodesulfurization(HDS)of 4,6-dimethyldibenzothiophene.It has confirmed that the incorporation of La profoundly facilitate the generation of“Type II”NiMoS phase by weakening the interaction of Mo–O–Al leakage and promoting the sulfidation of both Ni and Mo oxides as well as changing the morphology of Ni promoted MoS2 slabs,thereafter boosting the HDS performance substantially.The finding here may contribute to the fundamental understanding of structure-activity in ultra-deep desulfurization and inspire the advancement of highly-efficient HDS catalyst in future.展开更多
The extraction of lithium from salt lakes or seawater has attracted worldwide attention because of the explosive growth of global demand for lithium products. The LiMn_(2)O_(4)-based electrochemical lithium recovery s...The extraction of lithium from salt lakes or seawater has attracted worldwide attention because of the explosive growth of global demand for lithium products. The LiMn_(2)O_(4)-based electrochemical lithium recovery system is one of the strongest candidates for commercial application due to its high inserted capacity and low energy consumption. However, the surface orientation of LiMn_(2)O_(4)that facilitates Li diffusion happens to be prone to manganese dissolution making it a great challenge to obtain high lithium inserted capacity and long life simultaneously. Herein, we address this problem by designing a truncated octahedral LiMn_(2)O_(4)(Tr-oh LMO) in which the dominant(111) facets minimize Mn dissolution while a small portion of(100) facets facilitate the Li diffusion. Thus, this Tr-oh LMO-based electrochemical lithium recovery system shows excellent Li recovery performance with high inserted capacity(20.25 mg g^(-1)per cycle) in simulated brine. In addition, the dissolution rate of manganese per 30 cycles is only 0.44% and the capacity maintained 85% of the initial after 30 cycles. These promising findings accelerate the practical application of LiMn_(2)O_(4)in electrochemical lithium recovery.展开更多
Traditional urea synthesis under harsh conditions is usually associated with high energy input and has aroused severe environmental concerns.Electrocatalytic C-N coupling by converting nitrate and CO_(2) into urea und...Traditional urea synthesis under harsh conditions is usually associated with high energy input and has aroused severe environmental concerns.Electrocatalytic C-N coupling by converting nitrate and CO_(2) into urea under ambient conditions represents a promising alternative process.But it was still limited by the strong competition between nitrate electrochemical reduction(NO_(3)ER) and CO_(2) electrochemical reduction(CO_(2)ER).Here,Fe^(Ⅱ)-Fe~ⅢOOH@BiVO_(4)-n heterostructures are constructed through hydrothermal synthesis and exhibited superior performance toward urea electrosynthesis with NO_(3)~-and CO_(2) as feedstocks.The optimized urea yield and Faradaic efficiency over Fe^(Ⅱ)-Fe~ⅢOOH@BiVO_(4)-2 can reach13.8 mmol h^(-1) g^(-1) and 11.5% at-0.8 V vs.reversible hydrogen electrode,which is much higher than that of bare FeOOH(3.2 mmol h^(-1) g^(-1) and 1.3%),pristine BiVO_(4)(2.0 mmol h^(-1) g^(-1) and 5.4%),and the other Fe^(Ⅱ)-Fe~ⅢOOH@BiVO_(4)-n(n=1,3,5) heterostructures.Systematic experiments have verified that BiVO_(4)and FeOOH are subreaction active sites towards simultaneous CO_(2)ER and NO_(3)ER,respectively,achieving co-activation of CO_(2) and NO_(3)~-on Fe^(Ⅱ)-Fe~ⅢOOH@BiVO_(4)-2.Moreover,the urea synthesis via the ^(*)CO and NO*intermediates and C-N coupling was confirmed by the in situ Fourier transform infrared spectroscopy.This work not only alleviates the CO_(2) emission and nitrate pollution but also presents an efficient catalyst for synergistic catalysis towards sustainable urea synthesis.展开更多
Interface engineering can improve the charge separation efficiency and inhibit photocorrosion is an emerging direction of developing more efficient and cost-effective photocatalytic systems.Herein,we report the sulfur...Interface engineering can improve the charge separation efficiency and inhibit photocorrosion is an emerging direction of developing more efficient and cost-effective photocatalytic systems.Herein,we report the sulfur-confined intimate Cd S intergrown Cd(Cd S/Cd)Ohmic junction(peanut-chocolate-ball like)for high-efficient H2production with superior anti-photocorrosion ability,which was fabricated from in-situ photoreduction of CdS intergrown Cd2SO4(OH)2(CdS/Cd2SO4(OH)2)prepared through a facile space-controlled-solvothermal method.The ratios of CdS/Cd can be effectively controlled by tunning that of CdS/Cd2SO4(OH)2which were prepared by adjusting the volume of reaction liquid and the remaining space of the reactor.Experiments investigations and density functional theory(DFT)calculations reveal that the Cd S intergrown Cd Ohmic junction interfaces(with appropriate content Cd intergrown on Cd S(19.54 wt%))are beneficial in facilitating the transfer of photogenerated electrons by constructing an interfacial electric field and forming sulfur-confined structures for preventing the positive holes(h+)oxidize the Cd S.This contributes to a high photocatalytic H2production activity of 95.40μmol h-1(about 32.3 times higher than bare Cd S)and possesses outstanding photocatalytic stability over 205 h,much longer than most Cd S-based photocatalysts previously reported.The interface engineering design inspired by the structure of peanut-chocolate-ball can greatly promote the future development of catalytic systems for wider application.展开更多
Substantial progress has been made in the understanding of gas-involving electrochemical reactions recently for the sake of clean,renewable,and efficient energy technologies.However,the specific influence mechanism of...Substantial progress has been made in the understanding of gas-involving electrochemical reactions recently for the sake of clean,renewable,and efficient energy technologies.However,the specific influence mechanism of the microenvironment at the reaction interface on the electrocatalytic performance(activity,selectivity,and durability)remains unclear.Here,we provide a comprehensive understanding of the interfacial microenvironment of gas-involving electrocatalysis,including carbon dioxide reduction reaction and nitrogen reduction reaction,and classify the factors affecting the reaction thermodynamics and kinetics into gas diffusion,proton supply,and electron transfer.This categorization allows a systematic survey of the literature focusing on electrolyzer-level(optimization of the device,control of the experimental condition,and design of the working electrode),electrolytelevel(increase of gas solubility,regulation of proton supply,and substitution of anodic reaction),and electrocatalyst-level strategies(promotion of gas affinity,adjustment of hydrophobicity,and enhancement of conductivity),aiming to retrieve the correlations between the microenvironment and electrochemical performance.Finally,priorities for future studies are suggested to support the comprehensive improvement of next-generation gas-involving electrochemical reactions.展开更多
The development of economical,efficient,and robust electrocatalysts toward the hydrogen evolution reaction(HER)is highly imperative for the rapid advancement of renewable H2 energy-associated technologies.Extensive ut...The development of economical,efficient,and robust electrocatalysts toward the hydrogen evolution reaction(HER)is highly imperative for the rapid advancement of renewable H2 energy-associated technologies.Extensive utilization of the heterointerface effect can endow the catalysts with remarkably boosted electrocatalytic performance due to the modified electronic state of active sites.Herein,we demonstrate deliberate crafting of CoP/CoO heterojunction porous nanotubes(abbreviated as CoP/CoO PNTs hereafter)using a self-sacrificial template-engaged strategy.Precise control over the Kirkendall diffusion process of the presynthesized cobalt–aspartic acid complex nanowires is indispensable for the formation of CoP/CoO heterostructures.The topochemical transformation strategy of the reactive templates enables uniform and maximized construction of CoP/CoO heterojunctions throughout all the porous nanotubes.The establishment of CoP/CoO heterojunctions could considerably modify the electronic configuration of the active sites and also improve the electric conductivity,which endows the resultant CoP/CoO PNTs with enhanced intrinsic activity.Simultaneously,the hollow and porous nanotube architectures allow sufficient accessibility of exterior/interior surfaces and molecular permeability,drastically promoting the reaction kinetics.Consequently,when used as HER electrocatalysts,the well-designed CoP/CoO PNTs show Pt-like activity,with an overpotential of only 61 mV at 10mA cm^(−2) and excellent stability in 1.0M KOH medium,exceeding those of the vast majority of the previously reported nonprecious candidates.Density functional theory calculations further substantiate that the construction of CoP/CoO heterojunctions enables optimization of the Gibbs free energies for water adsorption and H adsorption,resulting in boosted HER intrinsic activity.The present study may provide in-depth insights into the fundamental mechanisms of heterojunction-induced electronic regulation,which may pave the way for the rational design of advanced Earth-abundant electrocatalysts in the future.展开更多
The electrocatalytic water splitting technology can generate highpurity hydrogen without emitting carbon dioxide,which is in favor of relieving environmental pollution and energy crisis and achieving carbon neutrality...The electrocatalytic water splitting technology can generate highpurity hydrogen without emitting carbon dioxide,which is in favor of relieving environmental pollution and energy crisis and achieving carbon neutrality.Electrocatalysts can effectively reduce the reaction energy barrier and increase the reaction efficiency.Facet engineering is considered as a promising strategy in controlling the ratio of desired crystal planes on the surface.Owing to the anisotropy,crystal planes with different orientations usually feature facet-dependent physical and chemical properties,leading to differences in the adsorption energies of oxygen or hydrogen intermediates,and thus exhibit varied electrocatalytic activity toward hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).In this review,a brief introduction of the basic concepts,fundamental understanding of the reaction mechanisms as well as key evaluating parameters for both HER and OER are provided.The formation mechanisms of the crystal facets are comprehensively overviewed aiming to give scientific theory guides to realize dominant crystal planes.Subsequently,three strategies of selective capping agent,selective etching agent,and coordination modulation to tune crystal planes are comprehensively summarized.Then,we present an overview of significant contributions of facet-engineered catalysts toward HER,OER,and overall water splitting.In particular,we highlight that density functional theory calculations play an indispensable role in unveiling the structure–activity correlation between the crystal plane and catalytic activity.Finally,the remaining challenges in facet-engineered catalysts for HER and OER are provided and future prospects for designing advanced facet-engineered electrocatalysts are discussed.展开更多
In order to satisfy the growing global demand for lithium, selective extraction of lithium from brine has attracted extensive attention. LiMn_(2)O_(4)-based electrochemical lithium recovery system is one of the best c...In order to satisfy the growing global demand for lithium, selective extraction of lithium from brine has attracted extensive attention. LiMn_(2)O_(4)-based electrochemical lithium recovery system is one of the best choices for commercial applications because of its high selectivity and low energy consumption.However, the low ion diffusion coefficient of lithium manganate limits the further development of electrochemical lithium recovery system. In this work, a novel porous disc-like LiMn_(2)O_(4) was successfully synthesized for the first time via two-step annealing manganese(Ⅱ) precursors. The as-prepared LiMn_(2)O_(4) exhibits porous disc-like morphology, excellent crystallinity, high Li^(+)diffusion coefficient(average 7.6×10^(-9)cm^(2)·s^(-1)), high cycle stability(after 30 uninterrupted extraction and release cycles, the crystal structure hardly changed) and superior rate capacity(93.5% retention from 10-120 mA·g^(-1)). The porous structure and disc-like morphology further promote the contact between lithium ions and electrode materials. Therefore, the assembled electrochemical lithium extraction device with LiMn_(2)O_(4) as positive electrode and silver as negative electrode can realize the rapid and selective extraction of lithium in simulated brine(adsorption capacity of lithium can reach 4.85 mg·g^(-1) in 1 h). The mechanism of disc-like LiMn_(2)O_(4) in electrochemical lithium extraction was proposed based on the analysis of electrochemical characterization and quasi in situ XRD. This novel structure may further promote the practical application of electrochemical lithium extraction from brine.展开更多
The high-nickel layered cathodes Li[Ni_(x)Co_(y)Mn_(1-x-y)]O_(2)(x≥0.8)with high specific capacity and long cycle life are considered as prospective cathodes for lithium-ion batteries.However,the microcrack formation...The high-nickel layered cathodes Li[Ni_(x)Co_(y)Mn_(1-x-y)]O_(2)(x≥0.8)with high specific capacity and long cycle life are considered as prospective cathodes for lithium-ion batteries.However,the microcrack formation and poor structural stability give rise to inferior rate performance and undesirable cycling life.Herein,we propose a dual modification strategy combining primary particle structure design and element doping to modify Li[Ni_(0.95)Co_(0.025)Mn_(0.025)]O_(2) cathode by tungsten and fluorine co-doped(W-F-NCM95).The doping of W can convert the microstructure of primary particles to the unique rod-like shape,which is beneficial to enhance the reversibility of phase transition and alleviate the generation of microcracks.F doping is conducive to alleviating the surface side reactions.Thus,due to the synergistic effect of W,F codoping,the obtained W-F-NCM95 cathodes deliver a high initial capacity of 236.1 mA h g^(-1) at 0.1 C and superior capacity retention of 88.7%over 100 cycles at 0.5 C.Moreover,the capacity still maintains73.8%after 500 cycles at 0.5 C and the texture of primary particle is intact.This work provides an available strategy by W and F co-doping to enhance the electrochemistry performance of high-nickel cathodes for practical application.展开更多
基金financially supported by the National Natural Science Foundation of China(22172093 and 21776167)the Natural Science Foundation of Shandong Province,China(ZR2023MB061).
文摘The preparation of bifunctional catalysts for oxygen reduction(ORR)and oxygen evolution(OER)is crucial for Zn-air batteries.Here,we report a La doped CoFe_(2)O_(4) spinel catalyst supported on threedimensional graphene(3D-G),where La can facilitate electron transfer from Co to Fe,leading to increased electron cloud density in Fe and improved catalytic performance.The redshift of the G peak in the Raman spectra indicates the interaction between theπbond of 3D-G and d orbitals in La_(0.2)CoFe_(1.8)O_(4).La_(0.2)CoFe_(1.8)/3D-G exhibits superior ORR performance(E_(1/2)=0.86 V vs.RHE)and OER performance(E_(j=10)=1.55 V vs.RHE)to CoFe_(2)O_(4)/3D-G(E_(1/2)=0.831 V vs.RHE,E_(j=10)=1.603 V vs.RHE).Furthermore,it demonstrates excellent bifunctional oxygen catalytic performance while maintaining high power density and stability in liquid zinc-air batteries(ZABs)and flexible ZABs(F-ZABs).This work presents a viable strategy for utilizing rare earth element doped spinels to enhance oxygen catalyst and ZABs performance.
基金supported by the Natural Science Foundation of China (22179062,52125202,and U2004209)the Natural Science Foundation of Jiangsu Province (BK20230035)+1 种基金the Fundamental Research Funds for the Central Universities (30922010303)the Intergovernmental Cooperation Projects in the National Key Research and Development Plan of the Ministry of Science and Technology of PRC (2022YFE0196800)
文摘Geometrical configurations play a crucial role in dual-atom catalysts(DACs)for electrocatalytic applications.Significant progress has been made to design DACs electrocatalysts with various geometri-cal configurations,but in-depth understanding the relationship between geometrical configurations and metal-metal interaction mechanisms for designing targeted DACs is still required.In this review,the recent progress in engineering of geometrical configurations of DACs is systematically summarized.Based on the polarity of geometrical configuration,DACs can be classified into two different types that are homonuclear and heteronuclear DACs.Furthermore,with regard to the geometrical configurations of the active sites,homonuclear DACs are identified into adjacent and bridged configurations,and heteronuclear DACs can be classified into adjacent,bridged,and separated configurations.Subsequently,metal-metal interactions in DACs with different geometrical configurations are introduced.Additionally,the applications of DACs in different electrocatalytic reactions are discussed,including the oxygen reduction reaction(ORR),oxygen evolution reaction(OER),hydrogen evolution reaction(HER),and other catalysis.Finally,the future challenges and perspectives for advancements in DACs are high-lighted.This review aims to provide inspiration for the design of highly effcient DACs towards energy relatedapplications.
基金financially supported by the National Natural Science Foundation of China(Nos.51972198 and 62133007)the Natural Science Foundation of Shandong Province(ZR2020JQ19)the Taishan Scholars Program of Shandong Province(Nos.tsqn201812002 and ts20190908)。
文摘Silicon monoxide(SiO)is regarded as a potential candidate for anode materials of lithium-ion batteries(LIBs).Unfortunately,the application of SiO is limited by poor initial Coulombic efficiency(ICE)and unsteady solid electrolyte interface(SEI),which induce low energy,short cycling life,and poor rate properties.To address these drawbacks of SiO,we achieve in-situ construction of robust and fast-ion conducting F,N-rich SEI layer on prelithiated micro-sized SiO(P-μSiO)via the simple and continuous treatment ofμSiO in mild lithium 4,4′-dimethylbiphenyl solution and nonflammable hexafluorocyclotriphosphazene solution.Chemical prelithiation eliminates irreversible capacity through pre-forming inactive lithium silicates.Meanwhile,the symbiotic F,N-rich SEI with good mechanical stability and fast Li^(+)permeability is conductive to relieve volume expansion ofμSiO and boost the Li+diffusion kinetics.Consequently,the P-μSiO realizes an impressive electrochemical performance with an elevated ICE of 99.57%and a capacity retention of 90.67%after 350 cycles.Additionally,the full cell with P-μSiO anode and commercial LiFePO_(4) cathode displays an ICE of 92.03%and a high reversible capacity of 144.97 mA h g^(-1).This work offers a general construction strategy of robust and ionically conductive SEI for advanced LIBs.
基金support of National Natural Science Foundation of China(22179027)gratefully acknowledged.This work was also supported by the Natural Science Foundation of Guangxi Province(2021GXNSFAA075063,2018GXNSFDA281005)+1 种基金the National Key Research and Development Program of China(2017YFE0105500)Science&Technology Research Project of Guangdong Province(2017A020216009).
文摘Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions.
基金supported by the National Natural Science Foundation of China(No.21676065 and No.52373262)China Postdoctoral Science Foundation(2021MD703944,2022T150782).
文摘Microwave absorbing materials(MAMs)characterized by high absorption efficiency and good environmental tolerance are highly desirable in practical applications.Both silicon carbide and carbon are considered as stable MAMs under some rigorous conditions,while their composites still fail to produce satisfactory microwave absorption performance regardless of the improvements as compared with the individuals.Herein,we have successfully implemented compositional and structural engineering to fabricate hollow SiC/C microspheres with controllable composition.The simultaneous modulation on dielectric properties and impedance matching can be easily achieved as the change in the composition of these composites.The formation of hollow structure not only favors lightweight feature,but also generates considerable contribution to microwave attenuation capacity.With the synergistic effect of composition and structure,the optimized SiC/C composite exhibits excellent performance,whose the strongest reflection loss intensity and broadest effective absorption reach−60.8 dB and 5.1 GHz,respectively,and its microwave absorption properties are actually superior to those of most SiC/C composites in previous studies.In addition,the stability tests of microwave absorption capacity after exposure to harsh conditions and Radar Cross Section simulation data demonstrate that hollow SiC/C microspheres from compositional and structural optimization have a bright prospect in practical applications.
基金The authors gratefully acknowledge the financial support of the Natural Science Foundation of China,China(Grant No.21975082 and 21736003)the Guangdong Basic and Applied Basic Research Foundation(Grant Number:2019A1515011472 and 2022A1515011341)the Science and Technology Program of Guangzhou(Grant Number:202102080479).
文摘In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.
基金This research was supported by Natural Science Foundation of Jiangsu Province(BK20220405)National Natural Science Foundation of China(21834004,22276100,22304086)+5 种基金Key Laboratory for Organic Electronics&Information Displays,NJUPT(GZR2022010010,GZR2023010045)Nanjing Science and Technology Innovation Project for Chinese Scholars Studying Abroad(NJKCZYZZ2022-01)Research Fund for Jiangsu Distinguished Professor(RK030STP22001)Natural Science Research Start-up Foundation of Recruiting Talents of NJUPT(NY221006,NY223051)Natural Science Foundation of the Jiangsu Higher Education Institutions of China(23KJB150025)State Key Laboratory of Analytical Chemistry for Life Science,Nanjing University(SKLACLS2311).
文摘Covalent organic frameworks(COFs),a rapidly developing category of crystalline conjugated organic polymers,possess highly ordered structures,large specific surface areas,stable chemical properties,and tunable pore microenvironments.Since the first report of boroxine/boronate ester-linked COFs in 2005,COFs have rapidly gained popularity,showing important application prospects in various fields,such as sensing,catalysis,separation,and energy storage.Among them,COFs-based electrochemical(EC)sensors with upgraded analytical performance are arousing extensive interest.In this review,therefore,we summarize the basic properties and the general synthesis methods of COFs used in the field of electroanalytical chemistry,with special emphasis on their usages in the fabrication of chemical sensors,ions sensors,immunosensors,and aptasensors.Notably,the emerged COFs in the electrochemiluminescence(ECL)realm are thoroughly covered along with their preliminary applications.Additionally,final conclusions on state-of-the-art COFs are provided in terms of EC and ECL sensors,as well as challenges and prospects for extending and improving the research and applications of COFs in electroanalytical chemistry.
基金supported by the National Natural Science Foundation of China(Grant Nos.51604089,51874110,22173066,and 21903058)Natural Science Foundation of Heilongjiang Province(Grant No.YQ2021B004).
文摘Polymer solid electrolytes(SPEs)based on the[solvate-Li+]complex structure have promising prospects in lithium metal batteries(LMBs)due to their unique ion transport mechanism.However,the solvation structure may compromise the mechanical performance and safety,hindering practical application of SPEs.In this work,a composite solid electrolyte(CSE)is designed through the organic-inorganic syner-gistic interaction among N,N-dimethylformamide(DMF),polycarbonate(PC),and Mg_(2)B_(2)O_(5) in poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP).Flame-retardant Mg_(2)B_(2)O_(5) nanowires provide non-flammability to the prepared CSEs,and the addition of PC improves the dispersion of Mg_(2)B_(2)O_(5) nanowires.Simultaneously,the organic-inorganic synergistic action of PC plasticizer and Mg_(2)B_(2)O_(5) nanowires pro-motes the dissociation degree of LiTFSI and reduces the crystallinity of PVDF-HFP,enabling rapid Li ion transport.Additionally,Raman spectroscopy and DFT calculations confirm the coordination between Mg atoms in Mg_(2)B_(2)O_(5) and N atoms in DMF,which exhibits Lewis base-like behavior attacking adjacent C-F and C-H bonds in PVDF-HFP while inducing dehydrofluorination of PVDF-HFP.Based on the syner-gistic coupling of Mg_(2)B_(2)O_(5),PC,and DMF in the PVDF-HFP matrix,the prepared CSE exhibits superior ion conductivity(9.78×10^(-4) s cm^(-1)).The assembled Li symmetric cells cycle stably for 3900 h at a current density of 0.1 mA cm^(-2) without short circuit.The LFP||Li cells assembled with PDL-Mg_(2)B_(2)O_(5)/PC CSEs show excellent rate capability and cycling performance,with a capacity retention of 83.3%after 1000 cycles at 0.5 C.This work provides a novel approach for the practical application of organic-inorganic Synergistic CSEs in LMBs.
基金financially supported by the National Natural Science Foundation of China(No.22072069)the Key Laboratory of Hubei Province for Coal Conversion and New Carbon Materials(Wuhan University of Science and Technology No.WKDM202303).
文摘Spinel oxide(NiCo_(2)O_(4))has demonstrated great potential to replace noble metal catalysts for the oxidation reaction of air pollutants.To further boost the oxidation ability of such catalysts,in this study,a facile surface-engineering strategy wherein NiCo_(2)O_(4) was treated with different alkali solvents was developed.The obtained catalyst(NiCo_(2)O_(4)-OH)showed a higher surface alkalinity and more surface defects compared to the pristine spinel oxide,including enhanced structural distortion as well as promoted oxygen vacancies.The propane oxidation ability of NiCo_(2)O_(4)-OH was greatly enhanced,with a propane conversion rate that was approximately 6.4 times higher than that of pristine NiCo_(2)O_(4) at a reaction temperature 193℃.This work sets a valuable paradigm for the surface modulation of spinel oxide via alkali treatment to ensure a high-performance oxidation catalyst.
基金supported by the National Natural Science Foundation of China(U21A20332,52103226,52202275,52203314,and 12204253)the Distinguished Young Scholars Fund of Jiangsu Province(BK20220061)the Fellowship of China Postdoctoral Science Foundation(2021 M702382)。
文摘As an alternative to conventional energy conversion and storage reactions,gas-involved electrochemical reactions,including the carbon dioxide reduction reaction(CO_(2)RR),nitrogen reduction reaction(NRR)and hydrogen evolution reaction(HER),have become an emerging research direction and have gained increasing attention due to their advantages of environmental friendliness and sustainability.Various studies have been designed to accelerate sluggish kinetics but with limited results.Most of them promote the reaction by modulating the intrinsic properties of the catalyst,ignoring the synergistic effect of the reaction as a whole.Due to the introduction of gas,traditional liquid-solid two-phase reactions are no longer applicable to future research.Since gas-involved electrochemical reactions mostly occur at the junctions of gaseous reactants,liquid electrolytes and solid catalysts,the focus of future research on reaction kinetics should gradually shift to three-phase reaction interfaces.In this review,we briefly introduce the formation and constraints of the three-phase interface and propose three criteria to judge its merit,namely,the active site,mass diffusion and electron mass transfer.Subsequently,a series of modulation methods and relevant works are discussed in detail from the three improvement directions of‘exposing more active sites,promoting mass diffusion and accelerating electron transfer’.Definitively,we provide farsighted insights into the understanding and research of three-phase interfaces in the future and point out the possible development direction of future regulatory methods,hoping that this review can broaden the future applications of the three-phase interface,including but not limited to gas-involved electrochemical reactions.
基金supported by the National Natural Science Foundation of China(81871506 and 81301345)。
文摘Bio-photoelectrochemical cells(BPECs)can further expand the use of conventional biofuel cells for renewable energy,but the poor stability of the photoelectrode still hinders their practical application.Herein,a BPEC capable of long-term operating in a fuel-free model is fabricated by WO3-xphotoanode with oxygen vacancy(Ov)and bilirubin oxidase catalyzed biocathode.The construction of Ov on the WO3surface significantly suppresses the dissolution of W species into the electrolyte,and improves the charge separation efficiency and the reaction kinetics during the photoelectrochemical oxygen evolution process,thus enhancing the stability and power output performance of the BPEC.As a result,the assembled BPEC can output an open circuit voltage of 0.81 V and deliver a maximum output power of up to 283μW cm^(-2).Impressively,the BPECs maintain 97%of their original power after 36000 s of consecutive discharge under an enclosed environment.This fuel-free BPEC based on a robust WO3-xphotoanode shows excellent promise for accurate application.
基金financial support of the National Natural Science Foundation of China(22002050,22178154)the Project of Jiangsu University Senior Talents Foundation(20JDG35)+1 种基金Postdoctoral Science Foundation of China(2022T150765,2020M683154)National Engineering Laboratory for Mobile Source Emission Control Technology(NELMS2020B01).
文摘Herein,we designed and constructed a mesoporous LaAlOx via a solvent evaporation induced self-assembly protocol.The structure and physicochemical property of the corresponding NiMo supported catalyst was analyzed by a set of characterizations,and its catalytic activity was investigated for hydrodesulfurization(HDS)of 4,6-dimethyldibenzothiophene.It has confirmed that the incorporation of La profoundly facilitate the generation of“Type II”NiMoS phase by weakening the interaction of Mo–O–Al leakage and promoting the sulfidation of both Ni and Mo oxides as well as changing the morphology of Ni promoted MoS2 slabs,thereafter boosting the HDS performance substantially.The finding here may contribute to the fundamental understanding of structure-activity in ultra-deep desulfurization and inspire the advancement of highly-efficient HDS catalyst in future.
基金supported by the National Natural Science Foundation of China (21878133,21908082,22178154)the Natural Science Foundation of Jiangsu Province(BK20190854)+1 种基金the China Postdoctoral Science Foundation(2020M671364,2021M701472)the Science&Technology Foundation of Zhenjiang (GY2020027)。
文摘The extraction of lithium from salt lakes or seawater has attracted worldwide attention because of the explosive growth of global demand for lithium products. The LiMn_(2)O_(4)-based electrochemical lithium recovery system is one of the strongest candidates for commercial application due to its high inserted capacity and low energy consumption. However, the surface orientation of LiMn_(2)O_(4)that facilitates Li diffusion happens to be prone to manganese dissolution making it a great challenge to obtain high lithium inserted capacity and long life simultaneously. Herein, we address this problem by designing a truncated octahedral LiMn_(2)O_(4)(Tr-oh LMO) in which the dominant(111) facets minimize Mn dissolution while a small portion of(100) facets facilitate the Li diffusion. Thus, this Tr-oh LMO-based electrochemical lithium recovery system shows excellent Li recovery performance with high inserted capacity(20.25 mg g^(-1)per cycle) in simulated brine. In addition, the dissolution rate of manganese per 30 cycles is only 0.44% and the capacity maintained 85% of the initial after 30 cycles. These promising findings accelerate the practical application of LiMn_(2)O_(4)in electrochemical lithium recovery.
基金financially supported by the Science Foundation of China (92161103, 22071180, and 22104110)。
文摘Traditional urea synthesis under harsh conditions is usually associated with high energy input and has aroused severe environmental concerns.Electrocatalytic C-N coupling by converting nitrate and CO_(2) into urea under ambient conditions represents a promising alternative process.But it was still limited by the strong competition between nitrate electrochemical reduction(NO_(3)ER) and CO_(2) electrochemical reduction(CO_(2)ER).Here,Fe^(Ⅱ)-Fe~ⅢOOH@BiVO_(4)-n heterostructures are constructed through hydrothermal synthesis and exhibited superior performance toward urea electrosynthesis with NO_(3)~-and CO_(2) as feedstocks.The optimized urea yield and Faradaic efficiency over Fe^(Ⅱ)-Fe~ⅢOOH@BiVO_(4)-2 can reach13.8 mmol h^(-1) g^(-1) and 11.5% at-0.8 V vs.reversible hydrogen electrode,which is much higher than that of bare FeOOH(3.2 mmol h^(-1) g^(-1) and 1.3%),pristine BiVO_(4)(2.0 mmol h^(-1) g^(-1) and 5.4%),and the other Fe^(Ⅱ)-Fe~ⅢOOH@BiVO_(4)-n(n=1,3,5) heterostructures.Systematic experiments have verified that BiVO_(4)and FeOOH are subreaction active sites towards simultaneous CO_(2)ER and NO_(3)ER,respectively,achieving co-activation of CO_(2) and NO_(3)~-on Fe^(Ⅱ)-Fe~ⅢOOH@BiVO_(4)-2.Moreover,the urea synthesis via the ^(*)CO and NO*intermediates and C-N coupling was confirmed by the in situ Fourier transform infrared spectroscopy.This work not only alleviates the CO_(2) emission and nitrate pollution but also presents an efficient catalyst for synergistic catalysis towards sustainable urea synthesis.
基金supported by the National Natural Science Foundation of China(22162008,22162007)the Science and Technology Supporting Project of Guizhou Province([2022]208,[2021]480)the Basic Research Program of Science&Technology Department of Guizhou Province([2020]1Y055)。
文摘Interface engineering can improve the charge separation efficiency and inhibit photocorrosion is an emerging direction of developing more efficient and cost-effective photocatalytic systems.Herein,we report the sulfur-confined intimate Cd S intergrown Cd(Cd S/Cd)Ohmic junction(peanut-chocolate-ball like)for high-efficient H2production with superior anti-photocorrosion ability,which was fabricated from in-situ photoreduction of CdS intergrown Cd2SO4(OH)2(CdS/Cd2SO4(OH)2)prepared through a facile space-controlled-solvothermal method.The ratios of CdS/Cd can be effectively controlled by tunning that of CdS/Cd2SO4(OH)2which were prepared by adjusting the volume of reaction liquid and the remaining space of the reactor.Experiments investigations and density functional theory(DFT)calculations reveal that the Cd S intergrown Cd Ohmic junction interfaces(with appropriate content Cd intergrown on Cd S(19.54 wt%))are beneficial in facilitating the transfer of photogenerated electrons by constructing an interfacial electric field and forming sulfur-confined structures for preventing the positive holes(h+)oxidize the Cd S.This contributes to a high photocatalytic H2production activity of 95.40μmol h-1(about 32.3 times higher than bare Cd S)and possesses outstanding photocatalytic stability over 205 h,much longer than most Cd S-based photocatalysts previously reported.The interface engineering design inspired by the structure of peanut-chocolate-ball can greatly promote the future development of catalytic systems for wider application.
基金National Natural Science Foundationof China,Grant/Award Numbers:U21A20332,52103226,52071226Outstanding Youth Foundation of Jiangsu Province,Grant/Award Number:BK20220061+2 种基金Natural Science Foundation of Jiangsu Province,Grant/Award Number:BK20201171Key Research and Development Plan of Jiangsu Province,Grant/Award Number:BE2020003-3Fellowship of China Postdoctoral Science Foundation,Grant/Award Number:2021M702382。
文摘Substantial progress has been made in the understanding of gas-involving electrochemical reactions recently for the sake of clean,renewable,and efficient energy technologies.However,the specific influence mechanism of the microenvironment at the reaction interface on the electrocatalytic performance(activity,selectivity,and durability)remains unclear.Here,we provide a comprehensive understanding of the interfacial microenvironment of gas-involving electrocatalysis,including carbon dioxide reduction reaction and nitrogen reduction reaction,and classify the factors affecting the reaction thermodynamics and kinetics into gas diffusion,proton supply,and electron transfer.This categorization allows a systematic survey of the literature focusing on electrolyzer-level(optimization of the device,control of the experimental condition,and design of the working electrode),electrolytelevel(increase of gas solubility,regulation of proton supply,and substitution of anodic reaction),and electrocatalyst-level strategies(promotion of gas affinity,adjustment of hydrophobicity,and enhancement of conductivity),aiming to retrieve the correlations between the microenvironment and electrochemical performance.Finally,priorities for future studies are suggested to support the comprehensive improvement of next-generation gas-involving electrochemical reactions.
基金supported by the National Natural Science Foundation of China(Grant Nos.21972068,21875112,and 22075290)the Nanjing IPE Institute of Green Manufacturing Industrythe Beijing Natural Science Foundation(Grant No.Z200012).
文摘The development of economical,efficient,and robust electrocatalysts toward the hydrogen evolution reaction(HER)is highly imperative for the rapid advancement of renewable H2 energy-associated technologies.Extensive utilization of the heterointerface effect can endow the catalysts with remarkably boosted electrocatalytic performance due to the modified electronic state of active sites.Herein,we demonstrate deliberate crafting of CoP/CoO heterojunction porous nanotubes(abbreviated as CoP/CoO PNTs hereafter)using a self-sacrificial template-engaged strategy.Precise control over the Kirkendall diffusion process of the presynthesized cobalt–aspartic acid complex nanowires is indispensable for the formation of CoP/CoO heterostructures.The topochemical transformation strategy of the reactive templates enables uniform and maximized construction of CoP/CoO heterojunctions throughout all the porous nanotubes.The establishment of CoP/CoO heterojunctions could considerably modify the electronic configuration of the active sites and also improve the electric conductivity,which endows the resultant CoP/CoO PNTs with enhanced intrinsic activity.Simultaneously,the hollow and porous nanotube architectures allow sufficient accessibility of exterior/interior surfaces and molecular permeability,drastically promoting the reaction kinetics.Consequently,when used as HER electrocatalysts,the well-designed CoP/CoO PNTs show Pt-like activity,with an overpotential of only 61 mV at 10mA cm^(−2) and excellent stability in 1.0M KOH medium,exceeding those of the vast majority of the previously reported nonprecious candidates.Density functional theory calculations further substantiate that the construction of CoP/CoO heterojunctions enables optimization of the Gibbs free energies for water adsorption and H adsorption,resulting in boosted HER intrinsic activity.The present study may provide in-depth insights into the fundamental mechanisms of heterojunction-induced electronic regulation,which may pave the way for the rational design of advanced Earth-abundant electrocatalysts in the future.
基金support from the National Natural Science Foundation of China(No.22005147)Dr.You acknowledges the financial support from the National Key Research and Development Program of China(2021YFA1600800)+1 种基金the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(B21003)the Open Research Fund of Key Laboratory of Material Chemistry for Energy Conversion and Storage(HUST),Ministry of Education(2021JYBKF03).
文摘The electrocatalytic water splitting technology can generate highpurity hydrogen without emitting carbon dioxide,which is in favor of relieving environmental pollution and energy crisis and achieving carbon neutrality.Electrocatalysts can effectively reduce the reaction energy barrier and increase the reaction efficiency.Facet engineering is considered as a promising strategy in controlling the ratio of desired crystal planes on the surface.Owing to the anisotropy,crystal planes with different orientations usually feature facet-dependent physical and chemical properties,leading to differences in the adsorption energies of oxygen or hydrogen intermediates,and thus exhibit varied electrocatalytic activity toward hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).In this review,a brief introduction of the basic concepts,fundamental understanding of the reaction mechanisms as well as key evaluating parameters for both HER and OER are provided.The formation mechanisms of the crystal facets are comprehensively overviewed aiming to give scientific theory guides to realize dominant crystal planes.Subsequently,three strategies of selective capping agent,selective etching agent,and coordination modulation to tune crystal planes are comprehensively summarized.Then,we present an overview of significant contributions of facet-engineered catalysts toward HER,OER,and overall water splitting.In particular,we highlight that density functional theory calculations play an indispensable role in unveiling the structure–activity correlation between the crystal plane and catalytic activity.Finally,the remaining challenges in facet-engineered catalysts for HER and OER are provided and future prospects for designing advanced facet-engineered electrocatalysts are discussed.
基金supported by the National Natural Science Foundation of China (21878133, 21908082, 22178154)the Natural Science Foundation of Jiangsu Province (BK20190854)+1 种基金the China Postdoctoral Science Foundation (2020 M671364, 2021 M701472)the Science & Technology Foundation of Zhenjiang (GY2020027)。
文摘In order to satisfy the growing global demand for lithium, selective extraction of lithium from brine has attracted extensive attention. LiMn_(2)O_(4)-based electrochemical lithium recovery system is one of the best choices for commercial applications because of its high selectivity and low energy consumption.However, the low ion diffusion coefficient of lithium manganate limits the further development of electrochemical lithium recovery system. In this work, a novel porous disc-like LiMn_(2)O_(4) was successfully synthesized for the first time via two-step annealing manganese(Ⅱ) precursors. The as-prepared LiMn_(2)O_(4) exhibits porous disc-like morphology, excellent crystallinity, high Li^(+)diffusion coefficient(average 7.6×10^(-9)cm^(2)·s^(-1)), high cycle stability(after 30 uninterrupted extraction and release cycles, the crystal structure hardly changed) and superior rate capacity(93.5% retention from 10-120 mA·g^(-1)). The porous structure and disc-like morphology further promote the contact between lithium ions and electrode materials. Therefore, the assembled electrochemical lithium extraction device with LiMn_(2)O_(4) as positive electrode and silver as negative electrode can realize the rapid and selective extraction of lithium in simulated brine(adsorption capacity of lithium can reach 4.85 mg·g^(-1) in 1 h). The mechanism of disc-like LiMn_(2)O_(4) in electrochemical lithium extraction was proposed based on the analysis of electrochemical characterization and quasi in situ XRD. This novel structure may further promote the practical application of electrochemical lithium extraction from brine.
基金supported by the National Key R&D Program of China(2018YFB0905600)。
文摘The high-nickel layered cathodes Li[Ni_(x)Co_(y)Mn_(1-x-y)]O_(2)(x≥0.8)with high specific capacity and long cycle life are considered as prospective cathodes for lithium-ion batteries.However,the microcrack formation and poor structural stability give rise to inferior rate performance and undesirable cycling life.Herein,we propose a dual modification strategy combining primary particle structure design and element doping to modify Li[Ni_(0.95)Co_(0.025)Mn_(0.025)]O_(2) cathode by tungsten and fluorine co-doped(W-F-NCM95).The doping of W can convert the microstructure of primary particles to the unique rod-like shape,which is beneficial to enhance the reversibility of phase transition and alleviate the generation of microcracks.F doping is conducive to alleviating the surface side reactions.Thus,due to the synergistic effect of W,F codoping,the obtained W-F-NCM95 cathodes deliver a high initial capacity of 236.1 mA h g^(-1) at 0.1 C and superior capacity retention of 88.7%over 100 cycles at 0.5 C.Moreover,the capacity still maintains73.8%after 500 cycles at 0.5 C and the texture of primary particle is intact.This work provides an available strategy by W and F co-doping to enhance the electrochemistry performance of high-nickel cathodes for practical application.