Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3...Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.展开更多
Although poly(lactic acid)(PLA)is a good environmentally-friendly bio-degradable polymer which is used to substitute traditional petrochemical-based polymer packaging films,the barrier properties of PLA films are stil...Although poly(lactic acid)(PLA)is a good environmentally-friendly bio-degradable polymer which is used to substitute traditional petrochemical-based polymer packaging films,the barrier properties of PLA films are still insufficient for high-barrier packaging applications.In this study,oxygen scavenger hydroxyl-terminated polybutadiene(HTPB)and cobalt salt catalyst were incorporated into the PLA/poly(butylene adipate-co-terephthalate)(PLA/PBAT),followed by melting extrusion and three-layer co-extrusion blown film process to prepare the composite films.The oxygen permeability coefficient of the composite film combined with 6 wt%oxygen scavenger and 0.4 wt%catalyst was decreased significantly from 377.00 cc·mil·m^(-2)·day^(-1)·0.1 MPa^(-1) to 0.98 cc·mil·m^(-2)·day^(-1)·0.1 MPa^(-1),showing a remarkable enhancement of 384.69 times compared with the PLA/PBAT composite film.Meanwhile,the degradation behavior of the composite film was also accelerated,exhibiting a mass loss of nearly 60%of the original mass after seven days of degradation in an alkaline environment,whereas PLA/PBAT composite film only showed a mass loss of 32%.This work has successfully prepared PLA/PBAT composite films with simultaneously improved oxygen barrier property and degradation behavior,which has great potential for high-demanding green chemistry packaging industries,including food,agricultural,and military packaging.展开更多
Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal int...Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.展开更多
Sulfide-based all-solid-state lithium batteries(ASSLBs) with nickel-rich oxide cathodes are emerging as primary contenders for the next generation rechargeable batteries,owing to their superior safety and energy densi...Sulfide-based all-solid-state lithium batteries(ASSLBs) with nickel-rich oxide cathodes are emerging as primary contenders for the next generation rechargeable batteries,owing to their superior safety and energy density.However,the all-solid-state batteries with nickel-rich oxide cathodes suffer from performance degradation due to the reactions between the highly reactive surface oxygen of the cathode and the electrolyte,as well as the instability of the bulk oxygen structure in the cathode.Herein,we propose a synergistic modification design scheme to adjust the oxygen activity from surface to bulk.The LiBO_(2)coating inhibits the reactivity of surface lattice oxygen ions.Meanwhile,Zr doping in the bulk phase forms strong Zr-O covalent bonds that stabilize the bulk lattice oxygen structure.The synergistic effect of these modifications prevents the release of oxygen,thus avoiding the degradation of the cathode/SE interface.Additionally,the regulation of surface-to-bulk oxygen activity establishes a highly stable interface,thereby enhancing the lithium ion diffusion kinetics and mechanical stability of the cathode.Consequently,cathodes modified with this synergistic strategy exhibit outstanding performance in sulfide-based ASSLBs,including an ultra-long cycle life of 100,000 cycles,ultra-high rate capability at 45C,and 85% high active material content in the composite cathode.Additionally,ASSLB exhibits stable cycling under high loading conditions of 82.82 mg cm^(-2),achieving an areal capacity of 17.90 mA h cm^(-2).These encouraging results pave the way for practical applications of ASSLBs in fast charging,long cycle life,and high energy density in the future.展开更多
In recent years,aqueous aluminum ion batteries have been widely studied owing to their abundant energy storage and high theo retical capacity.An in-depth study of vanadium oxide materials is necessary to address the p...In recent years,aqueous aluminum ion batteries have been widely studied owing to their abundant energy storage and high theo retical capacity.An in-depth study of vanadium oxide materials is necessary to address the precipitation of insoluble products covered cathode surface and the slow reaction kinetics.Therefore,a method using a simple one-step hydrothermal preparation and oxalic acid to regulate oxygen vacancies has been reported.A high starting capacity(400 mAh g^(-1))can be achieved by Ov-V2O5,and it is capable of undergoing 200 cycles at 0.4 A g^(-1),with a termination discharge capacity of103 mAh g^(-1).Mechanism analysis demonstrated that metastable structures(AlxV2O5and HxV2O5)were constructed through the insertion of Al^(3+)/H^(+)during discharging,which existed in the lattice intercalation with V2O5.The incorporation of oxygen vacancies lowers the reaction energy barrier while improving the ion transport efficiency.In addition,the metastable structure allows the electrostatic interaction between Al3+and the main backbone to establish protection and optimize the transport channel.In parallel,this work exploits ex-situ characterization and DFT to obtain a profound insight into the instrumental effect of oxygen vacancies in the construction of metastable structures during in-situ electrochemical activation,with a view to better understanding the mechanism of the synergistic participation of Al3+and H+in the reaction.This work not only reports a method for cathode materials to modulate oxygen vacancies,but also lays the foundation for a deeper understanding of the metastable structure of vanadium oxides.展开更多
The ability to unlock the interplay between the activity and stability of oxygen reduction reaction(ORR)represents an important endeavor toward creating robust ORR catalysts for efficient fuel cells.Herein,we report a...The ability to unlock the interplay between the activity and stability of oxygen reduction reaction(ORR)represents an important endeavor toward creating robust ORR catalysts for efficient fuel cells.Herein,we report an effective strategy to concurrent enhance the activity and stability of ORR catalysts via constructing atomically dispersed Fe-Mn dualmetal sites on N-doped carbon(denoted(FeMn-DA)-N-C)for both anion-exchange membrane fuel cells(AEMFC)and proton exchange membrane fuel cells(PEMFC).The(FeMn-DA)-N-C catalysts possess ample dual-metal atoms consisting of adjacent Fe-N_(4)and Mn-N_(4)sites on the carbon surface,yielded via a facile doping-adsorption-pyrolysis route.The introduction of Mn carries several advantageous attributes:increasing the number of active sites,effectively anchoring Fe due to effective electron transfer to Mn(revealed by X-ray absorption spectroscopy and density-functional theory(DFT),thus preventing the aggregation of Fe),and effectively circumventing the occurrence of Fenton reaction,thus reducing the consumption of Fe.The(FeMn-DA)-N-C catalysts showcase half-wave potentials of 0.92 and 0.82 V in 0.1 M KOH and 0.1 M HClO_(4),respectively,as well as outstanding stability.As manifested by DFT calculations,the introduction of Mn affects the electronic structure of Fe,down-shifts the d-band Fe active center,accelerates the desorption of OH groups,and creates higher limiting potentials.The AEMFC and PEMFC with(FeMn-DA)-N-C as the cathode catalyst display high power densities of 1060 and 746 mW cm^(-2),respectively,underscoring their promising potential for practical applications.Our study highlights the robustness of designing Fe-containing dual-atom ORR catalysts to promote both activity and stability for energy conversion and storage materials and devices.展开更多
Transition metal-based nanomaterials have emerged as promising electrocatalysts for oxygen evolution reaction(OER).Considerable research efforts have shown that self-reconstruction occurs on these nanomaterials under ...Transition metal-based nanomaterials have emerged as promising electrocatalysts for oxygen evolution reaction(OER).Considerable research efforts have shown that self-reconstruction occurs on these nanomaterials under operating conditions of OER process.However,most of them undergo incomplete reconstruction with limited thickness of reconstruction layer,leading to low component utilization and arduous exploration of real catalytic mechanism.Herein,we identify the dynamic behaviors in complete reconstruction of Co-based complexes during OER.The hollow phytic acid(PA)cross-linked CoFe-based complex nanoboxes with porous nanowalls are designed because of their good electrolyte penetration and mass transport ability,in favor of the fast and complete reconstruction.A series of experiment characterizations demonstrate that the reconstruction process includes the fast substitution of PA by OH-to form Co(Fe)(OH)xand subsequent potential-driven oxidation to Co(Fe)OOH.The obtained CoFeOOH delivers a low overpotential of 290 mV at a current density of 10 mA cm^(-2)and a long-term stability.The experiment results together with theory calculations reveal that the Fe incorporation can result in the electron rearrangement of reconstructed CoFeOOH and optimization of their electronic structure,accounting for the enhanced OER activity.The work provides new insights into complete reconstruction of metal-based complexes during OER and offers guidelines for rational design of high-performance electrocatalysts.展开更多
BACKGROUND:Intracranial hemorrhage (ICH),a severe complication among adults receiving extracorporeal membrane oxygenation (ECMO),is often related to poor outcomes.This study aimed to establish a predictive model for I...BACKGROUND:Intracranial hemorrhage (ICH),a severe complication among adults receiving extracorporeal membrane oxygenation (ECMO),is often related to poor outcomes.This study aimed to establish a predictive model for ICH in adults receiving ECMO treatment.METHODS:Adults who received ECMO between January 2017 and June 2022 were the subjects of a single-center retrospective study.Patients under the age of 18 years old,with acute ICH before ECMO,with less than 24 h of ECMO support,and with incomplete data were excluded.ICH was diagnosed by a head computed tomography scan.The outcomes included the incidence of ICH,in-hosptial mortality and 28-day mortality.Multivariate logistic regression analysis was used to identify relevant risk factors of ICH,and a predictive model of ICH with a nomogram was constructed.RESULTS:Among the 227 patients included,22 developed ICH during ECMO.Patients with ICH had higher in-hospital mortality (90.9%vs.47.8%,P=0.001) and higher 28-day mortality (81.8%vs.47.3%,P=0.001) than patients with non-ICH.ICH was associated with decreased grey-white-matter ratio (GWR)(OR=0.894,95%CI:0.841–0.951,P<0.001),stroke history (OR=4.265,95%CI:1.052–17.291,P=0.042),fresh frozen plasma (FFP) transfusion (OR=1.208,95%CI:1.037–1.408,P=0.015)and minimum platelet (PLT) count during ECMO support (OR=0.977,95%CI:0.958–0.996,P=0.019).The area under the receiver operating characteristic curve of the ICH predictive model was 0.843 (95%CI:0.762–0.924,P<0.001).CONCLUSION:ECMO-treated patients with ICH had a higher risk of death.GWR,stroke history,FFP transfusion,and the minimum PLT count were independently associated with ICH,and the ICH predictive model showed that these parameters performed well as diagnostic tools.展开更多
Designing highly active and stable electrocatalysts of oxygen evolution reaction(OER)is one of the crucial challenges.In this study,a novel OER electrocatalyst,NiFe-MIL-53 modified with ultra-low rhodium(Rh@NiFe-MIL-5...Designing highly active and stable electrocatalysts of oxygen evolution reaction(OER)is one of the crucial challenges.In this study,a novel OER electrocatalyst,NiFe-MIL-53 modified with ultra-low rhodium(Rh@NiFe-MIL-53),is successfully prepared via the hydrothermal method.In-situ Raman spectroscopy and electrochemical impedance spectroscopy reveal that the doped Rh accelerates the phase transformation of NiFe-MIL-53 and the in-situ formed Rh@NiFeOOH is the actual active species.More importantly,the enhanced reversibility of electrochemical reconstruction between NiFeOOH and NiFe(OH)_(2)after doping Rh is beneficial for improving the electrochemical stability of the catalyst.X-ray photoelectron spectroscopy spectra show the strong electronic interaction between single-atom Rh and Ni/Fe in Rh@NiFeOOH.Furthermore,theoretical calculations confirm that the integration of single-atom Rh into the NiFeOOH successfully reduces the band gap,regulates the d-band center(εd),accelerates the charge transfer,and optimizes the adsorption behavior of oxygen-containing intermediates,thereby lowering the energy barrier of rate-determining steps.Consequently,the optimized Rh@NiFe-MIL-53 exhibits excellent OER activity(240 mV)with a small Tafel slope of 48.2 mV dec^(-1)and long-term durability(over1270 h at 10 m A cm^(-2)and 110 h at 200 mA cm^(-2)).This work presents a new perspective on designing highly efficient OER electrocatalysts.展开更多
Energetic compounds bearing the trinitromethyl group are garnering broad attraction as potential candidates for a new generation of high energy dense oxidizers.In this work,an effective dual modulation strategy involv...Energetic compounds bearing the trinitromethyl group are garnering broad attraction as potential candidates for a new generation of high energy dense oxidizers.In this work,an effective dual modulation strategy involving both molecular isomerization and crystal morphology control was employed to design and optimize trinitromethyl-oxadiazole with improved comprehensive performance.Utilizing this dual strategy,3,5-bis(trinitromethyl)-1,2,4-oxadiazole(3)was synthesized,resulting in the formation of two distinct crystal morphologies(needle and sheet)corresponding to two crystal forms(3-a and3-b).Encouragingly,while maintaining ultra-high oxygen balance(21.73%),3 achieves impressive densities(1.97-1.98 g/cm^(3)).To our knowledge,the density of 1.98 g/cm^(3)for 3-a sets a new record among that of nitrogen-rich monocyclic compounds.Notably,practical crystal morphology prediction was creatively introduced to guide the experimental crystallization conditions of 3,increasing the impact sensitivity and friction sensitivity from 1 J to 80 N(3-a)to 10 J and 240 N(3-b),respectively.Additionally,the crystal structural analyses and theoretical calculations were conducted to elucidate the reasons of differences between 3-a and 3-b in density and stability.This work provides an efficient strategy to enhance performance of trinitromethyl derivatives,broadening the path and expanding the toolbox for energetic materials.展开更多
In recent years,studies focusing on the conversion of renewable lignin-derived oxygenates(LDOs)have emphasized their potential as alternatives to fossil-based products.However,LDOs,existing as complex aromatic mixture...In recent years,studies focusing on the conversion of renewable lignin-derived oxygenates(LDOs)have emphasized their potential as alternatives to fossil-based products.However,LDOs,existing as complex aromatic mixtures with diverse oxygen-containing functional groups,pose a challenge as they cannot be easily separated via distillation for direct utilization.A promising solution to this challenge lies in the efficient removal of oxygen-containing functional groups from LDOs through hydrodeoxygenation(HDO),aiming to yield biomass products with singular components.However,the high dissociation energy of the carbon-oxygen bond,coupled with its similarity to the hydrogenation energy of the benzene ring,creates a competition between deoxygenation and benzene ring hydrogenation.Considering hydrogen consumption and lignin properties,the preference is directed towards generating aromatic hydrocarbons rather than saturated components.Thus,the goal is to selectively remove oxygen-containing functional groups while preserving the benzene ring structure.Studies on LDOs conversion have indicated that the design of active components and optimization of reaction conditions play pivotal roles in achieving selective deoxygenation,but a summary of the correlation between these factors and the reaction mechanism is lacking.This review addresses this gap in knowledge by firstly summarizing the various reaction pathways for HDO of LDOs.It explores the impact of catalyst design strategies,including morphology modulation,elemental doping,and surface modification,on the adsorption-desorption dynamics between reactants and catalysts.Secondly,we delve into the application of advanced techniques such as spectroscopic techniques and computational modeling,aiding in uncovering the true active sites in HDO reactions and understanding the interaction of reactive reactants with catalyst surface-interfaces.Additionally,fundamental insights into selective deoxygenation obtained through these techniques are highlighted.Finally,we outline the challenges that lie ahead in the design of highly active and selective HDO catalysts.These challenges include the development of detection tools for reactive species with high activity at low concentrations,the study of reaction medium-catalyst interactions,and the development of theoretical models that more closely approximate real reaction situations.Addressing these challenges will pave the way for the development of efficient and selective HDO catalysts,thus advancing the field of renewable LDOs conversion.展开更多
Oxygen vacancies(Ov)within metal oxide electrodes can enhance mass/charge transfer dynamics in energy storage systems.However,construction of surface Ovoften leads to instability in electrode structure and irreversibl...Oxygen vacancies(Ov)within metal oxide electrodes can enhance mass/charge transfer dynamics in energy storage systems.However,construction of surface Ovoften leads to instability in electrode structure and irreversible electrochemical reactions,posing a significant challenge.To overcome these challenges,atomic heterostructures are employed to address the structural instability and enhance the mass/charge transfer dynamics associated with phase conversion mechanism in aqueous electrodes,Herein,we introduce an atomic S-Bi_(2)O_(3)heterostructure(sulfur(S)anchoring on the surface Ovof Bi_(2)O_(3)).The integration of S within Bi_(2)O_(3)lattice matrix triggers a charge imbala nce at the heterointerfaces,ultimately resulting in the creation of a built-in electric field(BEF).Thus,the BEF attracts OH-ions to be adsorbed onto Bi within the regions of high electron cloud overlap in S-Bi_(2)O_(3),facilitating highly efficient charge transfer.Furthermore,the anchored S plays a pivotal role in preserving structural integrity,thus effectively stabilizing the phase conversion reaction of Bi_(2)O_(3).As a result,the S-Bi_(2)O_(3)electrode achieves72.3 mA h g^(-1)at 10 A g^(-1)as well as high-capacity retention of 81.9%after 1600 cycles.Our innovative SBi_(2)O_(3)design presents a groundbreaking approach for fabricating electrodes that exhibit efficient and stable mass and charge transfer capabilities.Furthermore,it enhances our understanding of the underlying reaction mechanism within energy storage electrodes.展开更多
Artificial carbon fixation is a promising pathway for achieving the carbon cycle and environment remediation.However,the sluggish kinetics of oxygen evolution reaction(OER)and poor selectivity of CO_(2) reduction seri...Artificial carbon fixation is a promising pathway for achieving the carbon cycle and environment remediation.However,the sluggish kinetics of oxygen evolution reaction(OER)and poor selectivity of CO_(2) reduction seriously limited the overall conversion efficiencies of solar energy to chemical fuels.Herein,we demonstrated a facile and feasible strategy to rationally regulate the coordination environment and electronic structure of surface-active sites on both photoanode and cathode.More specifically,the defect engineering has been employed to reduce the coordination number of ultrathin FeNi catalysts decorated on BiVO4 photoanodes,resulting in one of the highest OER activities of 6.51 mA cm^(−2)(1.23 VRHE,AM 1.5G).Additionally,single-atom cobalt(II)phthalocyanine anchoring on the N-rich carbon substrates to increase Co–N coordination number remarkably promotes CO_(2) adsorption and activation for high selective CO production.Their integration achieved a record activity of 109.4μmol cm^(−2) h−1 for CO production with a faradaic efficiency of>90%,and an outstanding solar conversion efficiency of 5.41%has been achieved by further integrating a photovoltaic utilizing the sunlight(>500 nm).展开更多
Lithium plating/stripping occurs at the a node/electrolyte interface which involves the flow of electrons from the current collector and the migration of lithium ions from the solid-electrolyte interphase(SEI).The dua...Lithium plating/stripping occurs at the a node/electrolyte interface which involves the flow of electrons from the current collector and the migration of lithium ions from the solid-electrolyte interphase(SEI).The dual continuous rapid transport of interfacial electron/ion is required for homogeneous Li deposition.Herein,we propose a strategy to improve the Li metal anode performance by rationally regulating the interfacial electron density and Li ion transport through the SEI film.This key technique involves decreasing the interfacial oxygen density of biomass-derived carbon host by regulating the arrangement of the celluloses precursor fibrils.The higher specific surface area and lower interfacial oxygen density decrease the local current density and ensure the formation of thin and even SEI film,which stabilized Li^(+)transfer through the Li/electrolyte interface.Moreover,the improved graphitization and the interconnected conducting network enhance the surface electronegativity of carbon and enable uninterruptible electron conduction.The result is continuous and rapid coupled interfacial electron/ion transport at the anode/electrolyte reaction interface,which facilitates uniform Li deposition and improves Li anode performance.The Li/C anode shows a high initial Coulombic efficiency of 98%and a long-term lifespan of over 150cycles at a practical low N/P(negative-to-positive)ratio of 1.44 in full cells.展开更多
Conversion of CO_(2)back to hydrocarbons is the most direct way of closing the“carbon cycle”,and its significance is further enlarged if this process is driven by renewable energies such as electricity.However,preci...Conversion of CO_(2)back to hydrocarbons is the most direct way of closing the“carbon cycle”,and its significance is further enlarged if this process is driven by renewable energies such as electricity.However,precisely controlling the product selectivity towards hydrocarbons against the competitive hydrogen evolution remains challenging,especially for Cu-based catalysts.Herein,we report a novel defect engineering strategy,by which Cu-doping-induced oxygen vacancies on CeO_(2)nanorods were effectively created,with adjustable vacancy/Cu ratio.The resulting optimum catalyst shows up to 79%catalytic current density to hydrocarbons(excluding CO),with 49%faradaic efficiency to CH4.Experiments and density functional theory unveil that the ratio between oxygen vacancy and Cu affects significantly the formation of*CHO and activation of H2O,which leads to the following deep hydrogenation to hydrocarbons.These findings may spur new insights for designing and developing more controllable chemical process relevant to CO_(2)utilization.展开更多
Oxygen release and electrolyte decomposition under high voltage endlessly exacerbate interfacial ramifications and structu ral degradation of high energy-density Li-rich layered oxide(LLO),leading to voltage and capac...Oxygen release and electrolyte decomposition under high voltage endlessly exacerbate interfacial ramifications and structu ral degradation of high energy-density Li-rich layered oxide(LLO),leading to voltage and capacity fading.Herein,the dual-strategy of Cr,B complex coating and local gradient doping is simultaneously achieved on LLO surface by a one-step wet chemical reaction at room temperature.Density functional theory(DFT)calculations prove that stable B-O and Cr-O bonds through the local gradient doping can significantly reduce the high-energy O 2p states of interfacial lattice O,which is also effective for the near-surface lattice O,thus greatly stabilizing the LLO surface,Besides,differential electrochemical mass spectrometry(DEMS)indicates that the Cr_(x)B complex coating can adequately inhibit oxygen release and prevents the migration or dissolution of transition metal ions,including allowing speedy Li^(+)migration,The voltage and capacity fading of the modified cathode(LLO-C_(r)B)are adequately suppressed,which are benefited from the uniformly dense cathode electrolyte interface(CEI)composed of balanced organic/inorganic composition.Therefore,the specific capacity of LLO-CrB after 200 cycles at 1C is 209.3 mA h g^(-1)(with a retention rate of 95.1%).This dual-strategy through a one-step wet chemical reaction is expected to be applied in the design and development of other anionic redox cathode materials.展开更多
By manipulating the distribution of surface electrons,defect engineering enables effective control over the adsorption energy between adsorbates and active sites in the CO_(2)reduction reaction(CO_(2)RR).Herein,we rep...By manipulating the distribution of surface electrons,defect engineering enables effective control over the adsorption energy between adsorbates and active sites in the CO_(2)reduction reaction(CO_(2)RR).Herein,we report a hollow indium oxide nanotube containing both oxygen vacancy and sulfur doping(V_o-Sx-In_(2)O_(3))for improved CO_(2)-to-HCOOH electroreduction and Zn-CO_(2)battery.The componential synergy significantly reduces the*OCHO formation barrier to expedite protonation process and creates a favorable electronic micro-environment for*HCOOH desorption.As a result,the CO_(2)RR performance of Vo-Sx-In_(2)O_(3)outperforms Pure-In_(2)O_(3)and V_o-In_(2)O_(3),where V_o-S53-In_(2)O_(3)exhibits a maximal HCOOH Faradaic efficiency of 92.4%at-1,2 V vs.reversible hydrogen electrode(RHE)in H-cell and above 92%over a wide window potential with high current density(119.1 mA cm^(-2)at-1.1 V vs.RHE)in flow cell.Furthermore,the rechargeable Zn-CO_(2)battery utilizing V_o-S53-In_(2)O_(3)as cathode shows a high power density of 2.29 mW cm^(-2)and a long-term stability during charge-discharge cycles.This work provides a valuable perspective to elucidate co-defective catalysts in regulating the intermediates for efficient CO_(2)RR.展开更多
Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utiliz...Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.展开更多
Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy ...Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.展开更多
The sluggish kinetics of the electrochemical oxygen reduction reaction(ORR)in intermediatetemperature solid oxide fuel cells(IT-SOFCs)greatly limits the overall cell performance.In this study,an efficient and durable ...The sluggish kinetics of the electrochemical oxygen reduction reaction(ORR)in intermediatetemperature solid oxide fuel cells(IT-SOFCs)greatly limits the overall cell performance.In this study,an efficient and durable cathode material for IT-SOFCs is designed based on density functional theory(DFT)calculations by co-doping with Nb and Ta the B-site of the SrFeO_(3-δ)perovskite oxide.The DFT calculations suggest that Nb/Ta co-doping can regulate the energy band of the parent SrFeO_(3-δ)and help electron transfer.In symmetrical cells,such cathode with a SrFe_(0.8)Nb_(0.1)Ta_(0.1)O_(3-δ)(SFNT)detailed formula achieves a low cathode polarization resistance of 0.147Ωcm^(2) at 650℃.Electron spin resonance(ESR)and X-ray photoelectron spectroscopy(XPS)analysis confirm that the co-doping of Nb/Ta in SrFeO_(3-δ)B-site increases the balanced concentration of oxygen vacancies,enhancing the electrochemical performance when compared to 20 mol%Nb single-doped perovskite oxide.The cathode button cell with NiSDC|SDC|SFNT configuration achieves an outstanding peak power density of 1.3 W cm^(-2)at 650℃.Moreover,the button cell shows durability for 110 h under 0.65 V at 600℃ using wet H_(2) as fuel.展开更多
基金Research Institute for Smart Energy(CDB2)the grant from the Research Institute for Advanced Manufacturing(CD8Z)+4 种基金the grant from the Carbon Neutrality Funding Scheme(WZ2R)at The Hong Kong Polytechnic Universitysupport from the Hong Kong Polytechnic University(CD9B,CDBZ and WZ4Q)the National Natural Science Foundation of China(22205187)Shenzhen Municipal Science and Technology Innovation Commission(JCYJ20230807140402006)Start-up Foundation for Introducing Talent of NUIST and Natural Science Foundation of Jiangsu Province of China(BK20230426).
文摘Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.
基金financial support of this work by the National Natural Science Foundation of China(Nos.22378332,52003219)the Open Fund of Zhejiang Key Laboratory of Flexible Electronics(No.2022FE008)+1 种基金the Natural Science Foundation of Ningbo(NO.2022J058)Ministry of Industry and Information Technology high quality development project(TC220A04A-206).
文摘Although poly(lactic acid)(PLA)is a good environmentally-friendly bio-degradable polymer which is used to substitute traditional petrochemical-based polymer packaging films,the barrier properties of PLA films are still insufficient for high-barrier packaging applications.In this study,oxygen scavenger hydroxyl-terminated polybutadiene(HTPB)and cobalt salt catalyst were incorporated into the PLA/poly(butylene adipate-co-terephthalate)(PLA/PBAT),followed by melting extrusion and three-layer co-extrusion blown film process to prepare the composite films.The oxygen permeability coefficient of the composite film combined with 6 wt%oxygen scavenger and 0.4 wt%catalyst was decreased significantly from 377.00 cc·mil·m^(-2)·day^(-1)·0.1 MPa^(-1) to 0.98 cc·mil·m^(-2)·day^(-1)·0.1 MPa^(-1),showing a remarkable enhancement of 384.69 times compared with the PLA/PBAT composite film.Meanwhile,the degradation behavior of the composite film was also accelerated,exhibiting a mass loss of nearly 60%of the original mass after seven days of degradation in an alkaline environment,whereas PLA/PBAT composite film only showed a mass loss of 32%.This work has successfully prepared PLA/PBAT composite films with simultaneously improved oxygen barrier property and degradation behavior,which has great potential for high-demanding green chemistry packaging industries,including food,agricultural,and military packaging.
基金financially supported by the National Natural Science Foundation of China(22309137,22279095)Open subject project State Key Laboratory of New Textile Materials and Advanced Processing Technologies(FZ2023001).
文摘Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.
基金financially supported by the National Natural Science Foundation of China (52474338,22109084 and 52304338)the Hunan Provincial Key Research and Development Program (2024JK2093,2023GK2016)supported in part by the High Performance Computing Center of Central South University.
文摘Sulfide-based all-solid-state lithium batteries(ASSLBs) with nickel-rich oxide cathodes are emerging as primary contenders for the next generation rechargeable batteries,owing to their superior safety and energy density.However,the all-solid-state batteries with nickel-rich oxide cathodes suffer from performance degradation due to the reactions between the highly reactive surface oxygen of the cathode and the electrolyte,as well as the instability of the bulk oxygen structure in the cathode.Herein,we propose a synergistic modification design scheme to adjust the oxygen activity from surface to bulk.The LiBO_(2)coating inhibits the reactivity of surface lattice oxygen ions.Meanwhile,Zr doping in the bulk phase forms strong Zr-O covalent bonds that stabilize the bulk lattice oxygen structure.The synergistic effect of these modifications prevents the release of oxygen,thus avoiding the degradation of the cathode/SE interface.Additionally,the regulation of surface-to-bulk oxygen activity establishes a highly stable interface,thereby enhancing the lithium ion diffusion kinetics and mechanical stability of the cathode.Consequently,cathodes modified with this synergistic strategy exhibit outstanding performance in sulfide-based ASSLBs,including an ultra-long cycle life of 100,000 cycles,ultra-high rate capability at 45C,and 85% high active material content in the composite cathode.Additionally,ASSLB exhibits stable cycling under high loading conditions of 82.82 mg cm^(-2),achieving an areal capacity of 17.90 mA h cm^(-2).These encouraging results pave the way for practical applications of ASSLBs in fast charging,long cycle life,and high energy density in the future.
基金financially supported by the National Natural Science Foundation of China(52102233)Science and Technology Project of Hebei Education Department(QN2023019).
文摘In recent years,aqueous aluminum ion batteries have been widely studied owing to their abundant energy storage and high theo retical capacity.An in-depth study of vanadium oxide materials is necessary to address the precipitation of insoluble products covered cathode surface and the slow reaction kinetics.Therefore,a method using a simple one-step hydrothermal preparation and oxalic acid to regulate oxygen vacancies has been reported.A high starting capacity(400 mAh g^(-1))can be achieved by Ov-V2O5,and it is capable of undergoing 200 cycles at 0.4 A g^(-1),with a termination discharge capacity of103 mAh g^(-1).Mechanism analysis demonstrated that metastable structures(AlxV2O5and HxV2O5)were constructed through the insertion of Al^(3+)/H^(+)during discharging,which existed in the lattice intercalation with V2O5.The incorporation of oxygen vacancies lowers the reaction energy barrier while improving the ion transport efficiency.In addition,the metastable structure allows the electrostatic interaction between Al3+and the main backbone to establish protection and optimize the transport channel.In parallel,this work exploits ex-situ characterization and DFT to obtain a profound insight into the instrumental effect of oxygen vacancies in the construction of metastable structures during in-situ electrochemical activation,with a view to better understanding the mechanism of the synergistic participation of Al3+and H+in the reaction.This work not only reports a method for cathode materials to modulate oxygen vacancies,but also lays the foundation for a deeper understanding of the metastable structure of vanadium oxides.
基金supported by the National Key R&D Program of China (2021YFF0500504)National Natural Science Foundation of China (No. 51976169)the financial supports from the Fundamental Research Funds for the Central Universities。
文摘The ability to unlock the interplay between the activity and stability of oxygen reduction reaction(ORR)represents an important endeavor toward creating robust ORR catalysts for efficient fuel cells.Herein,we report an effective strategy to concurrent enhance the activity and stability of ORR catalysts via constructing atomically dispersed Fe-Mn dualmetal sites on N-doped carbon(denoted(FeMn-DA)-N-C)for both anion-exchange membrane fuel cells(AEMFC)and proton exchange membrane fuel cells(PEMFC).The(FeMn-DA)-N-C catalysts possess ample dual-metal atoms consisting of adjacent Fe-N_(4)and Mn-N_(4)sites on the carbon surface,yielded via a facile doping-adsorption-pyrolysis route.The introduction of Mn carries several advantageous attributes:increasing the number of active sites,effectively anchoring Fe due to effective electron transfer to Mn(revealed by X-ray absorption spectroscopy and density-functional theory(DFT),thus preventing the aggregation of Fe),and effectively circumventing the occurrence of Fenton reaction,thus reducing the consumption of Fe.The(FeMn-DA)-N-C catalysts showcase half-wave potentials of 0.92 and 0.82 V in 0.1 M KOH and 0.1 M HClO_(4),respectively,as well as outstanding stability.As manifested by DFT calculations,the introduction of Mn affects the electronic structure of Fe,down-shifts the d-band Fe active center,accelerates the desorption of OH groups,and creates higher limiting potentials.The AEMFC and PEMFC with(FeMn-DA)-N-C as the cathode catalyst display high power densities of 1060 and 746 mW cm^(-2),respectively,underscoring their promising potential for practical applications.Our study highlights the robustness of designing Fe-containing dual-atom ORR catalysts to promote both activity and stability for energy conversion and storage materials and devices.
基金National Natural Science Foundation of China(22478310,U21A20286 and 22206054)。
文摘Transition metal-based nanomaterials have emerged as promising electrocatalysts for oxygen evolution reaction(OER).Considerable research efforts have shown that self-reconstruction occurs on these nanomaterials under operating conditions of OER process.However,most of them undergo incomplete reconstruction with limited thickness of reconstruction layer,leading to low component utilization and arduous exploration of real catalytic mechanism.Herein,we identify the dynamic behaviors in complete reconstruction of Co-based complexes during OER.The hollow phytic acid(PA)cross-linked CoFe-based complex nanoboxes with porous nanowalls are designed because of their good electrolyte penetration and mass transport ability,in favor of the fast and complete reconstruction.A series of experiment characterizations demonstrate that the reconstruction process includes the fast substitution of PA by OH-to form Co(Fe)(OH)xand subsequent potential-driven oxidation to Co(Fe)OOH.The obtained CoFeOOH delivers a low overpotential of 290 mV at a current density of 10 mA cm^(-2)and a long-term stability.The experiment results together with theory calculations reveal that the Fe incorporation can result in the electron rearrangement of reconstructed CoFeOOH and optimization of their electronic structure,accounting for the enhanced OER activity.The work provides new insights into complete reconstruction of metal-based complexes during OER and offers guidelines for rational design of high-performance electrocatalysts.
基金supported by the National Natural Science Foundation of China (82072159)。
文摘BACKGROUND:Intracranial hemorrhage (ICH),a severe complication among adults receiving extracorporeal membrane oxygenation (ECMO),is often related to poor outcomes.This study aimed to establish a predictive model for ICH in adults receiving ECMO treatment.METHODS:Adults who received ECMO between January 2017 and June 2022 were the subjects of a single-center retrospective study.Patients under the age of 18 years old,with acute ICH before ECMO,with less than 24 h of ECMO support,and with incomplete data were excluded.ICH was diagnosed by a head computed tomography scan.The outcomes included the incidence of ICH,in-hosptial mortality and 28-day mortality.Multivariate logistic regression analysis was used to identify relevant risk factors of ICH,and a predictive model of ICH with a nomogram was constructed.RESULTS:Among the 227 patients included,22 developed ICH during ECMO.Patients with ICH had higher in-hospital mortality (90.9%vs.47.8%,P=0.001) and higher 28-day mortality (81.8%vs.47.3%,P=0.001) than patients with non-ICH.ICH was associated with decreased grey-white-matter ratio (GWR)(OR=0.894,95%CI:0.841–0.951,P<0.001),stroke history (OR=4.265,95%CI:1.052–17.291,P=0.042),fresh frozen plasma (FFP) transfusion (OR=1.208,95%CI:1.037–1.408,P=0.015)and minimum platelet (PLT) count during ECMO support (OR=0.977,95%CI:0.958–0.996,P=0.019).The area under the receiver operating characteristic curve of the ICH predictive model was 0.843 (95%CI:0.762–0.924,P<0.001).CONCLUSION:ECMO-treated patients with ICH had a higher risk of death.GWR,stroke history,FFP transfusion,and the minimum PLT count were independently associated with ICH,and the ICH predictive model showed that these parameters performed well as diagnostic tools.
基金Natural Science Foundation of China(Grant No.NSFC-22072062,22202098)。
文摘Designing highly active and stable electrocatalysts of oxygen evolution reaction(OER)is one of the crucial challenges.In this study,a novel OER electrocatalyst,NiFe-MIL-53 modified with ultra-low rhodium(Rh@NiFe-MIL-53),is successfully prepared via the hydrothermal method.In-situ Raman spectroscopy and electrochemical impedance spectroscopy reveal that the doped Rh accelerates the phase transformation of NiFe-MIL-53 and the in-situ formed Rh@NiFeOOH is the actual active species.More importantly,the enhanced reversibility of electrochemical reconstruction between NiFeOOH and NiFe(OH)_(2)after doping Rh is beneficial for improving the electrochemical stability of the catalyst.X-ray photoelectron spectroscopy spectra show the strong electronic interaction between single-atom Rh and Ni/Fe in Rh@NiFeOOH.Furthermore,theoretical calculations confirm that the integration of single-atom Rh into the NiFeOOH successfully reduces the band gap,regulates the d-band center(εd),accelerates the charge transfer,and optimizes the adsorption behavior of oxygen-containing intermediates,thereby lowering the energy barrier of rate-determining steps.Consequently,the optimized Rh@NiFe-MIL-53 exhibits excellent OER activity(240 mV)with a small Tafel slope of 48.2 mV dec^(-1)and long-term durability(over1270 h at 10 m A cm^(-2)and 110 h at 200 mA cm^(-2)).This work presents a new perspective on designing highly efficient OER electrocatalysts.
基金supported by the National Natural Science Foundation of China(No.22375021,22235003,22261132516&22205021)the BIT Research and Innovation 265 Promoting Project(Grant No.2023YCXZ017)。
文摘Energetic compounds bearing the trinitromethyl group are garnering broad attraction as potential candidates for a new generation of high energy dense oxidizers.In this work,an effective dual modulation strategy involving both molecular isomerization and crystal morphology control was employed to design and optimize trinitromethyl-oxadiazole with improved comprehensive performance.Utilizing this dual strategy,3,5-bis(trinitromethyl)-1,2,4-oxadiazole(3)was synthesized,resulting in the formation of two distinct crystal morphologies(needle and sheet)corresponding to two crystal forms(3-a and3-b).Encouragingly,while maintaining ultra-high oxygen balance(21.73%),3 achieves impressive densities(1.97-1.98 g/cm^(3)).To our knowledge,the density of 1.98 g/cm^(3)for 3-a sets a new record among that of nitrogen-rich monocyclic compounds.Notably,practical crystal morphology prediction was creatively introduced to guide the experimental crystallization conditions of 3,increasing the impact sensitivity and friction sensitivity from 1 J to 80 N(3-a)to 10 J and 240 N(3-b),respectively.Additionally,the crystal structural analyses and theoretical calculations were conducted to elucidate the reasons of differences between 3-a and 3-b in density and stability.This work provides an efficient strategy to enhance performance of trinitromethyl derivatives,broadening the path and expanding the toolbox for energetic materials.
基金supported by the National Natural Science Foundation of China,Pilot Group Program of the Research Fund for International Senior Scientists(22250710676)National Natural Science Foundation of China(22078064,22378062,22304028)+1 种基金Natural Science Foundation of Fujian Province(2021J02009)Tianjin University-Fuzhou University Independent Innovation Fund Cooperation Project(TF2023-1,TF2023-8).
文摘In recent years,studies focusing on the conversion of renewable lignin-derived oxygenates(LDOs)have emphasized their potential as alternatives to fossil-based products.However,LDOs,existing as complex aromatic mixtures with diverse oxygen-containing functional groups,pose a challenge as they cannot be easily separated via distillation for direct utilization.A promising solution to this challenge lies in the efficient removal of oxygen-containing functional groups from LDOs through hydrodeoxygenation(HDO),aiming to yield biomass products with singular components.However,the high dissociation energy of the carbon-oxygen bond,coupled with its similarity to the hydrogenation energy of the benzene ring,creates a competition between deoxygenation and benzene ring hydrogenation.Considering hydrogen consumption and lignin properties,the preference is directed towards generating aromatic hydrocarbons rather than saturated components.Thus,the goal is to selectively remove oxygen-containing functional groups while preserving the benzene ring structure.Studies on LDOs conversion have indicated that the design of active components and optimization of reaction conditions play pivotal roles in achieving selective deoxygenation,but a summary of the correlation between these factors and the reaction mechanism is lacking.This review addresses this gap in knowledge by firstly summarizing the various reaction pathways for HDO of LDOs.It explores the impact of catalyst design strategies,including morphology modulation,elemental doping,and surface modification,on the adsorption-desorption dynamics between reactants and catalysts.Secondly,we delve into the application of advanced techniques such as spectroscopic techniques and computational modeling,aiding in uncovering the true active sites in HDO reactions and understanding the interaction of reactive reactants with catalyst surface-interfaces.Additionally,fundamental insights into selective deoxygenation obtained through these techniques are highlighted.Finally,we outline the challenges that lie ahead in the design of highly active and selective HDO catalysts.These challenges include the development of detection tools for reactive species with high activity at low concentrations,the study of reaction medium-catalyst interactions,and the development of theoretical models that more closely approximate real reaction situations.Addressing these challenges will pave the way for the development of efficient and selective HDO catalysts,thus advancing the field of renewable LDOs conversion.
基金supported by the Research Program of Jilin Province Development and Reform Commission(2024C018-6).
文摘Oxygen vacancies(Ov)within metal oxide electrodes can enhance mass/charge transfer dynamics in energy storage systems.However,construction of surface Ovoften leads to instability in electrode structure and irreversible electrochemical reactions,posing a significant challenge.To overcome these challenges,atomic heterostructures are employed to address the structural instability and enhance the mass/charge transfer dynamics associated with phase conversion mechanism in aqueous electrodes,Herein,we introduce an atomic S-Bi_(2)O_(3)heterostructure(sulfur(S)anchoring on the surface Ovof Bi_(2)O_(3)).The integration of S within Bi_(2)O_(3)lattice matrix triggers a charge imbala nce at the heterointerfaces,ultimately resulting in the creation of a built-in electric field(BEF).Thus,the BEF attracts OH-ions to be adsorbed onto Bi within the regions of high electron cloud overlap in S-Bi_(2)O_(3),facilitating highly efficient charge transfer.Furthermore,the anchored S plays a pivotal role in preserving structural integrity,thus effectively stabilizing the phase conversion reaction of Bi_(2)O_(3).As a result,the S-Bi_(2)O_(3)electrode achieves72.3 mA h g^(-1)at 10 A g^(-1)as well as high-capacity retention of 81.9%after 1600 cycles.Our innovative SBi_(2)O_(3)design presents a groundbreaking approach for fabricating electrodes that exhibit efficient and stable mass and charge transfer capabilities.Furthermore,it enhances our understanding of the underlying reaction mechanism within energy storage electrodes.
基金supported by the National Natural Science Foundation of China(21832005,22072168,22002175)Major Program of the Lanzhou Institute of Chemical Physics,CAS(No.ZYFZFX-3)+1 种基金Major Science and Technology Projects in Gansu Province(22ZD6GA003)West Light Foundation of The Chinese Academy of Sciences(xbzg-zdsys-202209).
文摘Artificial carbon fixation is a promising pathway for achieving the carbon cycle and environment remediation.However,the sluggish kinetics of oxygen evolution reaction(OER)and poor selectivity of CO_(2) reduction seriously limited the overall conversion efficiencies of solar energy to chemical fuels.Herein,we demonstrated a facile and feasible strategy to rationally regulate the coordination environment and electronic structure of surface-active sites on both photoanode and cathode.More specifically,the defect engineering has been employed to reduce the coordination number of ultrathin FeNi catalysts decorated on BiVO4 photoanodes,resulting in one of the highest OER activities of 6.51 mA cm^(−2)(1.23 VRHE,AM 1.5G).Additionally,single-atom cobalt(II)phthalocyanine anchoring on the N-rich carbon substrates to increase Co–N coordination number remarkably promotes CO_(2) adsorption and activation for high selective CO production.Their integration achieved a record activity of 109.4μmol cm^(−2) h−1 for CO production with a faradaic efficiency of>90%,and an outstanding solar conversion efficiency of 5.41%has been achieved by further integrating a photovoltaic utilizing the sunlight(>500 nm).
基金supported by the National Natural Science Foundation of China(21975091,22122902,and 52272208)the Fundamental Research Fund for the Central Universities of China(2662023LXPY001 and 2662021JC004).
文摘Lithium plating/stripping occurs at the a node/electrolyte interface which involves the flow of electrons from the current collector and the migration of lithium ions from the solid-electrolyte interphase(SEI).The dual continuous rapid transport of interfacial electron/ion is required for homogeneous Li deposition.Herein,we propose a strategy to improve the Li metal anode performance by rationally regulating the interfacial electron density and Li ion transport through the SEI film.This key technique involves decreasing the interfacial oxygen density of biomass-derived carbon host by regulating the arrangement of the celluloses precursor fibrils.The higher specific surface area and lower interfacial oxygen density decrease the local current density and ensure the formation of thin and even SEI film,which stabilized Li^(+)transfer through the Li/electrolyte interface.Moreover,the improved graphitization and the interconnected conducting network enhance the surface electronegativity of carbon and enable uninterruptible electron conduction.The result is continuous and rapid coupled interfacial electron/ion transport at the anode/electrolyte reaction interface,which facilitates uniform Li deposition and improves Li anode performance.The Li/C anode shows a high initial Coulombic efficiency of 98%and a long-term lifespan of over 150cycles at a practical low N/P(negative-to-positive)ratio of 1.44 in full cells.
基金National Natural Science Foundation of China(21968020,22302222)Natural Science Foundation of Inner Mongolia(2022MS02011)+3 种基金China Postdoctoral Science Foundation under Grant Number(2024T170965,2023M743641)Science and Technology Projects of China Northern Rare Earth(BFXT-2022-D-0023)Science and Technology Department of Shanxi Province(202303021222409)Education Department of Inner Mongolia Autonomous Region(NJZZ23094,NJYT23039)。
文摘Conversion of CO_(2)back to hydrocarbons is the most direct way of closing the“carbon cycle”,and its significance is further enlarged if this process is driven by renewable energies such as electricity.However,precisely controlling the product selectivity towards hydrocarbons against the competitive hydrogen evolution remains challenging,especially for Cu-based catalysts.Herein,we report a novel defect engineering strategy,by which Cu-doping-induced oxygen vacancies on CeO_(2)nanorods were effectively created,with adjustable vacancy/Cu ratio.The resulting optimum catalyst shows up to 79%catalytic current density to hydrocarbons(excluding CO),with 49%faradaic efficiency to CH4.Experiments and density functional theory unveil that the ratio between oxygen vacancy and Cu affects significantly the formation of*CHO and activation of H2O,which leads to the following deep hydrogenation to hydrocarbons.These findings may spur new insights for designing and developing more controllable chemical process relevant to CO_(2)utilization.
基金financially supported by the National Natural Science Foundation of China(No.12304077)the Natural Science Foundation of Science and Technology Department of Sichuan Province(No.23NSFSC6224)+3 种基金Sichuan Science and Technology Program(No.2024NSFSC0989)the Key Laboratory of Computational Physics of Sichuan Province(No.YBUJSWL-YB-2022-03)the Material Corrosion and Protection Key Laboratory of Sichuan Province(No.2023CL14 and No.2023CL01)the National Innovation Practice Project(No.202411079005S).
文摘Oxygen release and electrolyte decomposition under high voltage endlessly exacerbate interfacial ramifications and structu ral degradation of high energy-density Li-rich layered oxide(LLO),leading to voltage and capacity fading.Herein,the dual-strategy of Cr,B complex coating and local gradient doping is simultaneously achieved on LLO surface by a one-step wet chemical reaction at room temperature.Density functional theory(DFT)calculations prove that stable B-O and Cr-O bonds through the local gradient doping can significantly reduce the high-energy O 2p states of interfacial lattice O,which is also effective for the near-surface lattice O,thus greatly stabilizing the LLO surface,Besides,differential electrochemical mass spectrometry(DEMS)indicates that the Cr_(x)B complex coating can adequately inhibit oxygen release and prevents the migration or dissolution of transition metal ions,including allowing speedy Li^(+)migration,The voltage and capacity fading of the modified cathode(LLO-C_(r)B)are adequately suppressed,which are benefited from the uniformly dense cathode electrolyte interface(CEI)composed of balanced organic/inorganic composition.Therefore,the specific capacity of LLO-CrB after 200 cycles at 1C is 209.3 mA h g^(-1)(with a retention rate of 95.1%).This dual-strategy through a one-step wet chemical reaction is expected to be applied in the design and development of other anionic redox cathode materials.
基金supported by the Fundamental Research Funds for the Central Universities(22120230104).
文摘By manipulating the distribution of surface electrons,defect engineering enables effective control over the adsorption energy between adsorbates and active sites in the CO_(2)reduction reaction(CO_(2)RR).Herein,we report a hollow indium oxide nanotube containing both oxygen vacancy and sulfur doping(V_o-Sx-In_(2)O_(3))for improved CO_(2)-to-HCOOH electroreduction and Zn-CO_(2)battery.The componential synergy significantly reduces the*OCHO formation barrier to expedite protonation process and creates a favorable electronic micro-environment for*HCOOH desorption.As a result,the CO_(2)RR performance of Vo-Sx-In_(2)O_(3)outperforms Pure-In_(2)O_(3)and V_o-In_(2)O_(3),where V_o-S53-In_(2)O_(3)exhibits a maximal HCOOH Faradaic efficiency of 92.4%at-1,2 V vs.reversible hydrogen electrode(RHE)in H-cell and above 92%over a wide window potential with high current density(119.1 mA cm^(-2)at-1.1 V vs.RHE)in flow cell.Furthermore,the rechargeable Zn-CO_(2)battery utilizing V_o-S53-In_(2)O_(3)as cathode shows a high power density of 2.29 mW cm^(-2)and a long-term stability during charge-discharge cycles.This work provides a valuable perspective to elucidate co-defective catalysts in regulating the intermediates for efficient CO_(2)RR.
基金supported by the National Natural Science Foundation of China(22234005,21974070)the Natural Science Foundation of Jiangsu Province(BK20222015)。
文摘Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.
基金supported by the National Natural Science Foundation of China(52363028,21965005)the Natural Science Foundation of Guangxi Province(2021GXNSFAA076001)the Guangxi Technology Base and Talent Subject(GUIKE AD18126001,GUIKE AD20297039)。
文摘Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.
基金supported by the National Natural Science Foundation of China (51702039)。
文摘The sluggish kinetics of the electrochemical oxygen reduction reaction(ORR)in intermediatetemperature solid oxide fuel cells(IT-SOFCs)greatly limits the overall cell performance.In this study,an efficient and durable cathode material for IT-SOFCs is designed based on density functional theory(DFT)calculations by co-doping with Nb and Ta the B-site of the SrFeO_(3-δ)perovskite oxide.The DFT calculations suggest that Nb/Ta co-doping can regulate the energy band of the parent SrFeO_(3-δ)and help electron transfer.In symmetrical cells,such cathode with a SrFe_(0.8)Nb_(0.1)Ta_(0.1)O_(3-δ)(SFNT)detailed formula achieves a low cathode polarization resistance of 0.147Ωcm^(2) at 650℃.Electron spin resonance(ESR)and X-ray photoelectron spectroscopy(XPS)analysis confirm that the co-doping of Nb/Ta in SrFeO_(3-δ)B-site increases the balanced concentration of oxygen vacancies,enhancing the electrochemical performance when compared to 20 mol%Nb single-doped perovskite oxide.The cathode button cell with NiSDC|SDC|SFNT configuration achieves an outstanding peak power density of 1.3 W cm^(-2)at 650℃.Moreover,the button cell shows durability for 110 h under 0.65 V at 600℃ using wet H_(2) as fuel.
