The escalating pace of industrialization has significantly intensified water pollution challenges,for instance,the persistent organic pollutants like methyl orange(MO).Conventional remediation techniques,such as adsor...The escalating pace of industrialization has significantly intensified water pollution challenges,for instance,the persistent organic pollutants like methyl orange(MO).Conventional remediation techniques,such as adsorption and biological degradation,are often hampered by low efficiency and the risk of secondary pollution.Photocatalysis emerges as a promising sustainable alternative;however,the benchmark material titanium dioxide(TiO_(2))suffers from its intrinsic limitations,notably its wide bandgap energy(≥3.4 eV)restricting its activity to the region of the ultraviolet light and its rapid recombination of photogenerated charge carriers.To overcome these constraints,this research focused on synthesizing novel TiO_(2)/Sn_(3)O_(4) heterojunction composite photocatalysts via a solvothermal approach.Comprehensive characterization techniques confirmed the successful formation of the composite,which revealed that ultrathin Sn3O4 nanosheets uniformly coated TiO_(2) nanospheres.This unique architecture effectively reduced the overall crystallinity and introduced the beneficial oxygen vacancies.Under visible-light irradiation(λ≥420 nm),the optimized TiO_(2)/Sn3O4 composite exhibited the exceptional photocatalytic performance,which achieved 96%degradation of MO within just 60 minutes.The calculated apparent kinetic rate constant(0.103 min^(-1))was remarkably(5.15 times)higher than that of pristine TiO_(2).ESR experiments identified that hydroxyl radicals(·OH)was the predominant active species driving the degradation.Furthermore,cyclic degradation tests demonstrated its excellent material stability,with the composite retaining 85%of its initial efficiency after four consecutive reuse cycles.This work underscored the synergistic effects within the TiO_(2)/Sn_(3)O_(4) heterojunction,which significantly enhanced the visible-light absorption,charge separation,and photocatalytic activity,which provided the valuable insights for designing efficient,stable catalysts for the advanced environmental remediation applications.展开更多
The carboxylation of alkynes with CO_(2) has attracted considerable interest due to the valorization of C1resources and atomic economy.Much effort focused on active metals(e.g.,Au,Ag,Cu),while the mechanistic role of ...The carboxylation of alkynes with CO_(2) has attracted considerable interest due to the valorization of C1resources and atomic economy.Much effort focused on active metals(e.g.,Au,Ag,Cu),while the mechanistic role of active supports,particularly the oxygen vacancy(O_(v)),in modulating C-H bond carboxylation remains unknown.Herein,ultra-small silver clusters and morphologically engineered CeO_(2) support(nanorods,nanocubes,and nano particles)were employed to construct Ag cluster/O_(v) synergistic catalyst,which exhibits variations in Oy concentration by an in situ auto-reduction method.The 0.197%Ag/CeO_(2)-NR catalyst exhibited a high reaction rate for the phenylacetylene carboxylation reaction and the maximal silver utilization efficiency.The characterization and DFT calculations demonstrated that vacancies enhanced CO_(2) adsorption via polarization-induced molecular bending and C-O bond elongation.Positively charged Ag clusters induced by metal-support interactions serve as deprotonation activation centers for alkynes.This synergistic interplay between dual active sites efficiently facilitates the C(sp)-H carboxylation with CO_(2).These findings offer critical insights for the rational selection of active supports in designing efficient C-H carboxylation catalysts.展开更多
Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied ...Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied to photocatalytic nitrogen fixation for the first time,and its photocatalytic performance was effectively enhanced through Cu doping.The catalyst was synthesized via a simple reduction method,and its morphology,structure,and physicochemical properties were systematically investigated using various characterization techniques and density functional theory calculations.The results revealed that the incorporation of Cu2+partially replaced Pb2+,inducing lattice distortion in PbBiO_(2)Br,promoting the formation of oxygen vacancies,and modifying its electronic band structure.Specifically,Cu doping led to a slight bandgap narrowing,a reduction in work function,and a significant upward shift in the conduction band position.These changes enhanced light absorption,facilitated charge carrier migration and separation,and improved the reduction ability of photogenerated electrons.Moreover,Cu doping promoted N_(2)adsorption and activation.Consequently,the photocatalytic nitrogen fixation performance of Cu-doped PbBiO_(2)Br was significantly enhanced,achieving an optimal nitrogen fixation rate of 293μmol L^(−1)g^(−1)h^(−1),which is 3.6 times higher than that of pristine PbBiO_(2)Br.Additionally,Cu–PbBiO_(2)Br also showed good activity in the photocatalytic degradation of RhB,with a degradation rate 4.6 times higher than that of PbBiO_(2)Br.This work offers new insights into the application of PbBiO_(2)Br in photocatalytic nitrogen fixation and offers valuable guidance for the development of highly efficient nitrogen fixation materials in the future.展开更多
4-Nitrophenol(4-NP),a toxic and persistent pollutant in chemical wastewater,presents significant challenges in degradation and mineralization.Conventional ozone oxidation catalysts are hindered by low efficiency,mass ...4-Nitrophenol(4-NP),a toxic and persistent pollutant in chemical wastewater,presents significant challenges in degradation and mineralization.Conventional ozone oxidation catalysts are hindered by low efficiency,mass transfer constraints and metal leaching,necessitating the development of stable and efficient catalysts.Herein,BCn-H/MS,the derivative of Bi(Ce)-MOF,was prepared by in situ incorporation,thermal decomposition and acid etching.The resulting materials were characterized and employed in catalytic ozonation for the reduction of 4-NP.Under the specific experimental conditions of the O_(3)+BC0.3-H/MS system,the total organic carbon(TOC)and chemical oxygen demand(COD)removal rates of 4-NP were observed to reach 94.6%and 91.8%within 30 min,respectively.These two parameters were improved by raising the initial pH,reducing the pollutant concentration and increasing the catalyst dosage.The abundant oxygen vacancies(OVs)were regarded as the pivotal catalytic site of BC0.3-H/MS,which was conducive to the adsorption of O_(3) and the acceleration of the formation of reactive oxygen species(ROS).The regular hollow square structure effectively boosted the specific surface area,increased OVs exposure and accelerated the adsorption and mass transfer process.The electron paramagnetic resonance(EPR)results demonstrated that the primary ROS engaged in the degradation reaction were⋅OH and⋅O_(2)−.BC0.3-H/MS demonstrated excellent stability and reusability in cyclic experiments.Toxicity analysis revealed that the O_(3)+BC0.3-H/MS system exhibited an effective detoxification effect.Ultimately,the primary degradation pathway of 4-NP was proposed through liquid chromatography-mass spectroscopy(LC-MS)and in-situ diffuse reflectance infrared fourier-transform spectroscopy(DRIFTS)analyses at varying reaction times.展开更多
Simultaneous integration of rich oxygen vacancies(OVs)and twin crystals in a photocatalyst can not only significantly enhance the near-infrared(NIR)light response but also greatly improve the photocharge separation an...Simultaneous integration of rich oxygen vacancies(OVs)and twin crystals in a photocatalyst can not only significantly enhance the near-infrared(NIR)light response but also greatly improve the photocharge separation and transfer efficiency owing to the induced high electrical conductivity and strong built-in electric field.However,thus far,there has been a lack of a model catalyst containing both twin crystals and OVs.Herein,we develop a simple wet chemical strategy for synthesizing of unprecedented NIR light-responsive OVs-rich Cu_(2)O black nanoparticles with high-density of twin crystals(denoted as black twinned Cu_(2)O).As expected,the black twinned Cu_(2)O exhibits higher visible-NIR and NIR light-driven photodegradation of tetracycline(TC)solution than the counterparts.Significantly,the mechanism insight into twin-dependent photocatalysis in NIR light-responsive Cu_(2)O black nanocrystals with rich OVs is uncovered in depth by density functional theory(DFT)calculations and a series of experimental evidence.Expectantly,this work would be beneficial for the scientific researchers currently focusing on the NIR light-responsive photocatalysis and twin engineering of photocatalysts.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
Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR pr...Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR products,liquid oxygenates(Oxys)are especially attractive due to their high energy density,high safety and transportability that could be adapted to the existing infrastructure and transportation system.However,efficiently generating these highly reduced oxygen-containing products by ECR remains challenging due to the complexity of coupled proton and electron transfer processes.In recent years,in-depth studies of reaction mechanisms have advanced the design of catalysts and the regulation of reaction systems for ECR to produce Oxys,Here,by focusing on the production of typical Oxys,such as methanol,acetic acid,ethanol,acetone,n-propanol,and isopropanol,we outline various reaction paths and key intermediates for the electrochemical conversion of CO_(2)into these target products.We also summarize the current research status and recent advances in catalysts based on their elemental composition,and consider recent studies on the change of catalyst geometry and electronic structure,as well as the optimization of reaction systems to increase ECR performance.Finally,we analyze the challenges in the field of ECR to Oxys and provide an outlook on future directions for high-efficiency catalyst prediction and design,as well as the development of advanced reaction systems.展开更多
The development of highly active, durable, and low-cost electrocatalysts is crucial for electrocatalytic hydrogen production. Ultrathin two-dimensional (2D) nanomaterials have extremely large specific surface areas, m...The development of highly active, durable, and low-cost electrocatalysts is crucial for electrocatalytic hydrogen production. Ultrathin two-dimensional (2D) nanomaterials have extremely large specific surface areas, making them highly desirable electrocatalyst morphologies. Medium-entropy alloys (MEAs) exhibit compositional tunability and entropy-driven structural stability, making them ideal electrocatalyst candidates. In this study, MoCoNi MEA with ultrathin 2D morphology was successfully developed using a facile ionic lay-er epitaxial method. The ultrathin 2D MoCoNi MEA showed an excellent oxygen evolution reaction (OER) electrocatalytic performance, with a low overpotential of 167 mV at a current density of 10 mA/cm^(2) and small Tafel slope of 33.2 mV/dec. At the overpotential of 167 mV, the ultrathin 2D MoCoNi MEA exhibited ultrahigh mass activity of 3359.6 A/g, which is three orders of magnitude higher than that of the commercial noble metal oxide RuO_(2) (1.15 A/g). This excellent electrocatalytic performance was attributed to the synergy of multiple active metal-induced medium entropies, as well as the ultrathin thickness, which considerably shortened the charge-transfer dis-tance and thus significantly promoted charge transfer. Owing to the natural entropy-stabilizing effect, the ultrathin 2D MoCoNi MEA maintained 90% of the initial current after a continuous OER electrocatalytic test for 134 h, showing impressive electrocatalytic stability. This study opens new avenues for the development of high-performance and low-cost electrocatalyst materials by creating MEAs with ultrathin 2D morphology.展开更多
Lithium-sulfur batteries(LSBs)have attracted widespread attention due to their high theoretical energy density.However,the dissolution of long-chain polysulfides into the electrolyte(the“shuttle effect”)leads to rap...Lithium-sulfur batteries(LSBs)have attracted widespread attention due to their high theoretical energy density.However,the dissolution of long-chain polysulfides into the electrolyte(the“shuttle effect”)leads to rapid capacity decay.Therefore,finding suitable materials to mitigate the shuttle effect of polysulfides is crucial for enhancing the electrochemical performance of lithium-sulfur batteries.In this study,LSBs’separator is modified with Ni_(3)V_(2)O_(8)nanoparticles@carboxylated carbon nanotubes(Ni_(3)V_(2)O_(8)@CNTs)composite.There are abundant oxygen vacancies in Ni_(3)V_(2)O_(8)@CNTs composite which plays a synergistic effect on shuttle effect.The Ni_(3)V_(2)O_(8)can tightly anchor soluble polysulfides through oxygen vacancies,while the CNTs not only facilitate the transport of ions and electrons but also weaken the migration of polysulfides,limiting shuttle effect.As a result,the cycling stability of LSBs using Ni_(3)V_(2)O_(8)@CNTs-modified separator has been significantly improved(with a capacity decay rate of only 0.0334%after 1500 cycles at 4.0C).This study proposes a strategy to design modified separator for high-performance LSBs.展开更多
Dry reforming of methane(DRM)has gained significant attention as a promising route to convert two major greenhouse gases(CO_(2) and CH4)to syngas.The development of efficient catalysts is critical for the engineering ...Dry reforming of methane(DRM)has gained significant attention as a promising route to convert two major greenhouse gases(CO_(2) and CH4)to syngas.The development of efficient catalysts is critical for the engineering applications.In this study,the Ce_(x)Zr_(1-x)O_(2)/ZSM-5 composites with different oxygen vacancy concentrations were synthesized by tuning the Ce/Zr ratio,followed by the deposition of metal Ni to island-like Ce_(x)Zr_(1-x)O_(2)on ZSM-5,forming a variety of Ni-Ce_(x)Zr_(1-x)O_(2)/ZSM-5 catalysts,which were applied for the DRM reaction under 750◦C.Combined with various characterizations,it was found that the oxygen vacancy concentration illustrated the volcanic tendency with the decreased Ce/Zr ratio,and the interaction between metal Ni and Ce_(x)Zr_(1-x)O_(2)exhibited a positive relationship with oxygen vacancy concentration.The enhanced between Ni and Ce_(x)Zr_(1-x)O_(2)interaction could improve the strength and amount of Ni-O-M(M=Ce/Zr)species,making the d-band centers of catalysts closer to the Fermi energy level,which was beneficial to the CH4 and CO_(2) activation,along with the improved capacity to resist sintering and coking.Especially,the C1Z3(Ni-Ce0.25Zr0.75O_(2)/ZSM-5)catalyst with the Ce/Zr ratio of 1/3 demonstrated the optimal catalytic performance with 91.9%CH4 and 93.8%CO_(2) conversions within 50 h,accompanied by the best structural and catalytic stability after 100 h.In-situ DRIFTS was employed to study the reaction path and mechanism,discovering that significant amounts of strengthened Ni-O-M species were conducive to activating adsorbed CH4 and CO_(2),and desorbing the linear CO species.展开更多
The adsorption of CO on different lattice oxygen sites in Cu doped CeO_(2)(111)was studied by DFT method,and the geometrical structure and electronic properties of adsorption systems were analyzed.The results showed t...The adsorption of CO on different lattice oxygen sites in Cu doped CeO_(2)(111)was studied by DFT method,and the geometrical structure and electronic properties of adsorption systems were analyzed.The results showed that CO interacted with lattice oxygen on the first layer formed CO_(2).However,when adsorbed on the second layer lattice oxygen,carbonate species were formed with the participation of first layer lattice oxygens,i.e.,CO co-adsorbed on first and second layer lattice oxygens.For the second layer adsorption,the absolute CO adsorption energy was big on the Oss nearby Cu.This kind of carbonates was thermodynamically stable,and it was attributed to the facilitation of Cu on CO adsorption,manifested by an electron migration behavior from the C 2p orbitals to the Cu 3d orbitals.However,the absolute CO adsorption energy on the Oss away from Cu was small.Compared to the formation of carbonates,the formation CO_(2)had very small absolute adsorption energy,suggesting the formed carbonates on second layer was stable.Further,when CO adsorbed on the systems with a carbonate,the absolute CO adsorption energy was significantly smaller than that of the non-carbonated system,indicating that the formation of carbonates inhibited CO oxidation on Cu/CeO_(2)(111).Therefore,the formation of carbonates was unfavorable for CO oxidation reaction on Cu/CeO_(2)(111).The results of this study provide theoretical support for the negative effect of CO_(2)on ceria-based catalysts.展开更多
On the surfaces of celestial bodies with no or thin atmospheres,such as the Moon and Mars,the solar wind irradiation process leads to the formation of hydrogen and helium enriched regions in the extraterrestrial soil ...On the surfaces of celestial bodies with no or thin atmospheres,such as the Moon and Mars,the solar wind irradiation process leads to the formation of hydrogen and helium enriched regions in the extraterrestrial soil particles.However,soil particles on the Earth with the similar composition lack such structures and properties.This discrepancy raises a key question whether there is a direct relationship between solar wind irradiation and the alterations in the structure and chemical performance of extraterrestrial materials.To address this question,this work investigates the effects of proton irradiation,simulating solar wind radiation,on the structure and photothermal catalytic properties of the classic catalyst In_(2)O_(3).It reveals that proton irradiation induces structural features in In_(2)O_(3) analogous to those characteristics of solar wind weathering observed in extraterrestrial materials.Furthermore,after proton beam irradiation with an energy of 30 keV and a dose of 3×10^(17) protons·cm^(-2),the methanol production yield of the In_(2)O_(3) catalyst increased to 2.6 times of its preirradiation level,and the methanol selectivity improved to 2.1 times of the original value.This work provides both theoretical and experimental support for the development of high-efficiency,radiation-resistant photothermal catalysts.展开更多
Lithium-oxygen batteries attract considerable attention due to exceptionally high theoretical energy density,while the development remains in its early stage.As is widely suggested,the solution mechanism induces great...Lithium-oxygen batteries attract considerable attention due to exceptionally high theoretical energy density,while the development remains in its early stage.As is widely suggested,the solution mechanism induces greater discharge capacity,while the surface mechanism induces greater cycle stability.Therefore,battery performance can be improved by adjusting the reaction mechanism.Previous studies predominantly focus on extremely thin or flat electrodes.In contrast,this work utilizes thick electrodes,emphasizing the importance of mass transport.Given that the electrolyte solvent is the main site of mass transport,the effects of two typical solvents on mass transport and battery performance are investigated:dimethyl sulfoxide with low viscosity and a high O_(2) diffusion rate and tetraethylene glycol dimethyl ether with high O_(2) solubility and high Li+transport capability.The results reveal a novel pathway for reaction mechanism induction where the mechanism varies with the spatial position of the electrode.As the spatial distribution of the electrode progresses,a layered appearance of solution mechanism products,transition state products,and surface mechanism products emerges,which is attributed to the increase in the mass transfer resistance.This work presents a distinct perspective on the way solvents influence reaction pathways and offers a new approach to regulating reaction pathways.展开更多
Amorphous Ga_(2)O_(3)(a-Ga_(2)O_(3))thin films were prepared on flexible polyimide,rigid quartz glass,and Si substrates via radio frequency magnetron sputtering at room temperature.The effect of oxygen/Ar flow rate ra...Amorphous Ga_(2)O_(3)(a-Ga_(2)O_(3))thin films were prepared on flexible polyimide,rigid quartz glass,and Si substrates via radio frequency magnetron sputtering at room temperature.The effect of oxygen/Ar flow rate ratio on the structure,optical property,surface morphology,and chemical bonding properties of the a-Ga_(2)O_(3) films was investigated.Results show that the average optical transmittance of the a-Ga_(2)O_(3) films is over 80%within the wavelength range of 300-2000 nm.The extracted optical band gap of the a-Ga_(2)O_(3) films is increased from 4.97 eV to 5.13 eV with the increase in O_(2)/Ar flow rate ratio from 0 to 0.25,due to the decrease in concentration of oxygen vacancy defects in the film.Furthermore,the optical refractive index and surface roughness of the a-Ga_(2)O_(3) films are optimized when the O_(2)/Ar flow rate ratio reaches 0.25.X-ray photoelectron spectroscopy analysis also shows that the proportion of oxygen vacancies(VO)and Ga-O chemical bonds in the O 1s peak is gradually decreased with the increase in O_(2)/Ar flow rate ratio from 0 to 0.25,proving that increasing the O_(2)/Ar flow rate ratio during film growth can reduce the concentration of oxygen vacancy defects in a-Ga_(2)O_(3) films.In this case,a-Ga_(2)O_(3) with optimal properties can be obtained.This work provides a research basis for high-performance flexible and rigid deep ultraviolet solar-blind detection devices based on a-Ga_(2)O_(3) films.展开更多
The oxygen evolution reaction(OER)serves as a fundamental half–reaction in the electrolysis of water for hydrogen production,which is restricted by the sluggish OER reaction kinetics and unable to be practically appl...The oxygen evolution reaction(OER)serves as a fundamental half–reaction in the electrolysis of water for hydrogen production,which is restricted by the sluggish OER reaction kinetics and unable to be practically applied.The traditional lattice oxygen oxidation mechanism(LOM)offers an advantageous route by circumventing the formation of M-OOH^(*)in the adsorption evolution mechanism(AEM),thus enhancing the reaction kinetics of the OER but resulting in possible structural destabilization due to the decreased M–O bond order.Fortunately,the asymmetry of tetrahedral and octahedral sites in transition metal spinel oxides permits the existence of non-bonding oxygen,which could be activated by rational band structure design for direct O-O coupling,where the M–O bond maintains its initial bond order.Here,non-bonding oxygen was introduced into NiFe_(2)O_(4)via annealing in an oxygen-deficient atmosphere.Then,in-situ grown sulfate species on octahedral nickel sites significantly improved the reactivity of the non-bonding oxygen electrons,thereby facilitating the transformation of the redox center from metal to oxygen.LOM based on non-bonding oxygen(LOMNB)was successfully activated within NiFe_(2)O_(4),exhibiting a low overpotential of 206 mV to achieve a current density of 10 mA cm^(-2)and excellent durability of stable operation for over 150 h.Additionally,catalysts featuring varying band structures were synthesized for comparative analysis,and it was found that the reversible redox processes of non-bonding oxygen and the accumulation of non-bonding oxygen species containing 2p holes are critical prerequisites for triggering and sustaining the LOMNB pathway in transition metal spinel oxides.These findings may provide valuable insights for the future development of spinel-oxide-based LOM catalysts.展开更多
Oxygen vacancy engineering is a valid strategy to boost the oxygen reduction reaction(ORR) performance of nanostructured electrocatalysts.Current methods for generating surface oxygen vacancies(Vos) in nanostructured ...Oxygen vacancy engineering is a valid strategy to boost the oxygen reduction reaction(ORR) performance of nanostructured electrocatalysts.Current methods for generating surface oxygen vacancies(Vos) in nanostructured MnO_(2) is mostly lab-scale,which cannot meet the requirement of large-scale production.Herein,we employed a mechanochemical method of ball milling to introduce surface Vos into the β-MnO_(2) nanoparticles.The ball milling process generated abundant surface Vos,which significantly facilitated the adsorption and activation of O_(2).Consequently,the ORR performance of ball-milled β-MnO_(2) was markedly boosted by varying the ball milling time.As an air cathode catalyst for zinc-air battery(ZAB),the β-MnO_(2) ball-milled for 4 h displayed a high specific capacity of 804 mA·h·g^(-1) and excellent cycling over 500 h at 5 mA·cm^(-2),which were superior than those of pristine β-MnO_(2)-based ZAB.Our work offers a feasible strategy to enhance electrocatalytic ORR performance of MnO_(2),which shows significant potential for large-scale production of efficient ORR electrocatalysts.展开更多
Four-electron oxygen evolving reaction is limited by proton adsorption and desorption,making its reaction kinetics sluggish,which poses a major challenge for catalyst design.Here,we present an unsaturated coordination...Four-electron oxygen evolving reaction is limited by proton adsorption and desorption,making its reaction kinetics sluggish,which poses a major challenge for catalyst design.Here,we present an unsaturated coordination interface by constructing a fast electron transfer channel between Cu_(2)V_(2)O_(7)(CVO)and BiVO4(BVO).X-ray absorption spectroscopy(XAS)and theoretical calculations results confirm that CVO and BVO between interfaces are bonded by the way of unsaturated coordination oxygen(Ouc).The Ouc optimizes the O-O coupled energy barrier at the V active site and promotes the disconnection of O-H bond,which increases the photocurrent intensity of CVO by 6 times.In addition,due to the high electronegativity of the Ouc,the bonding energies of Bi-O and Cu-O at the interface are enhanced,resulting in the long-term stability of the photoanode during the water splitting.Finally,by integrating the working electrode with a polysilicon solar cell,we assembled a device that demonstrated exceptional catalytic performance,achieving a hydrogen production rate of 100.6μmol·cm^(-2),and maintaining a hydrogen-to-oxygen volume ratio of 2:1 after continuous operation for 4 h.This discovery aids in a deeper understanding of photoanode design and offers further insights for industrial applications.展开更多
Single carbon products(C1 compounds) are simple but important chemicals in the road towards energy transition.Catalytic conversion of CO_(2) with H_(2)(desirably renewable) can be performed over reducible oxides suppo...Single carbon products(C1 compounds) are simple but important chemicals in the road towards energy transition.Catalytic conversion of CO_(2) with H_(2)(desirably renewable) can be performed over reducible oxides supporting transition metals to obtain products such as CH_(4),CO and MeOH.Oxygen vacancies(O-vacancies),which are inherent defects of reducible metal oxides,play an enormous role in driving the catalytic performance(activity,selectivity,stability) for the desired reactions.Yet,the assessment of O-defects at realistic conditions is often complex.Only few techniques can provide direct evidence for their existence and influence in CO_(2) activation.Among them,electron paramagnetic spectroscopy(EPR),Raman spectroscopy,scanning probe microscopies(SPM) and environmental transmission electron microscopy(ETEM) are nowadays the most informative.In most cases,however,the measurements require reaction conditions far away from CO_(2) valorization applications.Although great efforts have been fruitful in explaining and demonstrating the huge importance of O-vacancies in CO_(2) catalysis,still ambiguous or erroneous interpretations about structure-function correlations involving O-vacancies are found in literature,especially,when information is not properly gathered,e.g.,by O 1s ex-situ X-ray photon spectroscopy(XPS).Moreover,despite the recognized importance of O-vacancies for CO_(2) valorization,critical literature compilations about their effects in thermal processes are scarce.Herein,we attempt to contribute in closing this gap by integrally encompassing representative investigations on the thermo-catalytic production of CH_(4),CO and MeOH.Particularly,we emphasize on the proper selection of assessment tools(direct/indirect) to unambiguously establish structure-function relationships to design optimized O-defective catalysts for the targeted compounds.展开更多
Zinc-ion capacitors(ZICs)are promising energy storage devices due to their balance between the energy and power densities inherited from Zn-ion batteries and supercapacitors,respectively.However,the low specific capac...Zinc-ion capacitors(ZICs)are promising energy storage devices due to their balance between the energy and power densities inherited from Zn-ion batteries and supercapacitors,respectively.However,the low specific capacitance of carbon cathode materials and the dendrite growth on Zn anode have set fatal drawbacks to their energy density and cycle stability.Herein,we demonstrate that,in 1 M Zn(CF_(3)SO_(3))_(2)/DMF(N,N-dimethylformamide)electrolyte,confining oxygen in carbon cathode materials via high-energy ball milling can synergistically introduce additional pseudocapacitance on the cathode side while suppressing the dendrite growth on Zn anode side,which jointly lead to high energy density(94 Wh kg^(−1)at 448 W kg^(−1))and long cycle stability of ZICs.The hydroxyl group in carbon cathode can be transformed to C–O–Zn together with the release of protons during the initial discharge,which in turn stimulates the defluorination of CF_(3)SO_(3)^(-)anions and formation of ZnF_(2)on both cathode and anode.The ZnF2 formed on the surface of the Zn anode suppresses the dendrite growth by regulating the Zn^(2+)deposition/stripping in a reticular structure,resulting in the excellent cycle stability.This work provides a facile strategy to rationally design and construct high energy and stable ZICs through engineering the oxygen-bearing functional groups in carbon cathode materials.展开更多
文摘The escalating pace of industrialization has significantly intensified water pollution challenges,for instance,the persistent organic pollutants like methyl orange(MO).Conventional remediation techniques,such as adsorption and biological degradation,are often hampered by low efficiency and the risk of secondary pollution.Photocatalysis emerges as a promising sustainable alternative;however,the benchmark material titanium dioxide(TiO_(2))suffers from its intrinsic limitations,notably its wide bandgap energy(≥3.4 eV)restricting its activity to the region of the ultraviolet light and its rapid recombination of photogenerated charge carriers.To overcome these constraints,this research focused on synthesizing novel TiO_(2)/Sn_(3)O_(4) heterojunction composite photocatalysts via a solvothermal approach.Comprehensive characterization techniques confirmed the successful formation of the composite,which revealed that ultrathin Sn3O4 nanosheets uniformly coated TiO_(2) nanospheres.This unique architecture effectively reduced the overall crystallinity and introduced the beneficial oxygen vacancies.Under visible-light irradiation(λ≥420 nm),the optimized TiO_(2)/Sn3O4 composite exhibited the exceptional photocatalytic performance,which achieved 96%degradation of MO within just 60 minutes.The calculated apparent kinetic rate constant(0.103 min^(-1))was remarkably(5.15 times)higher than that of pristine TiO_(2).ESR experiments identified that hydroxyl radicals(·OH)was the predominant active species driving the degradation.Furthermore,cyclic degradation tests demonstrated its excellent material stability,with the composite retaining 85%of its initial efficiency after four consecutive reuse cycles.This work underscored the synergistic effects within the TiO_(2)/Sn_(3)O_(4) heterojunction,which significantly enhanced the visible-light absorption,charge separation,and photocatalytic activity,which provided the valuable insights for designing efficient,stable catalysts for the advanced environmental remediation applications.
基金financially supported by the National Natural Science Foundation of China(22102194)the Science and Technology Plan of Gansu Province(24JRRA067,23ZDFA016)the Youth Innovation Promotion Association of CAS(2022427)。
文摘The carboxylation of alkynes with CO_(2) has attracted considerable interest due to the valorization of C1resources and atomic economy.Much effort focused on active metals(e.g.,Au,Ag,Cu),while the mechanistic role of active supports,particularly the oxygen vacancy(O_(v)),in modulating C-H bond carboxylation remains unknown.Herein,ultra-small silver clusters and morphologically engineered CeO_(2) support(nanorods,nanocubes,and nano particles)were employed to construct Ag cluster/O_(v) synergistic catalyst,which exhibits variations in Oy concentration by an in situ auto-reduction method.The 0.197%Ag/CeO_(2)-NR catalyst exhibited a high reaction rate for the phenylacetylene carboxylation reaction and the maximal silver utilization efficiency.The characterization and DFT calculations demonstrated that vacancies enhanced CO_(2) adsorption via polarization-induced molecular bending and C-O bond elongation.Positively charged Ag clusters induced by metal-support interactions serve as deprotonation activation centers for alkynes.This synergistic interplay between dual active sites efficiently facilitates the C(sp)-H carboxylation with CO_(2).These findings offer critical insights for the rational selection of active supports in designing efficient C-H carboxylation catalysts.
基金financially supported by the National Natural Science Foundation of China(No.22172144 and 22272151)Key Research and Development Program of Zhejiang Province(2023C03148).
文摘Photocatalytic nitrogen fixation has emerged as a sustainable alternative for ammonia synthesis,playing a crucial role in alleviating energy shortages and environmental pollution.In this study,PbBiO_(2)Br was applied to photocatalytic nitrogen fixation for the first time,and its photocatalytic performance was effectively enhanced through Cu doping.The catalyst was synthesized via a simple reduction method,and its morphology,structure,and physicochemical properties were systematically investigated using various characterization techniques and density functional theory calculations.The results revealed that the incorporation of Cu2+partially replaced Pb2+,inducing lattice distortion in PbBiO_(2)Br,promoting the formation of oxygen vacancies,and modifying its electronic band structure.Specifically,Cu doping led to a slight bandgap narrowing,a reduction in work function,and a significant upward shift in the conduction band position.These changes enhanced light absorption,facilitated charge carrier migration and separation,and improved the reduction ability of photogenerated electrons.Moreover,Cu doping promoted N_(2)adsorption and activation.Consequently,the photocatalytic nitrogen fixation performance of Cu-doped PbBiO_(2)Br was significantly enhanced,achieving an optimal nitrogen fixation rate of 293μmol L^(−1)g^(−1)h^(−1),which is 3.6 times higher than that of pristine PbBiO_(2)Br.Additionally,Cu–PbBiO_(2)Br also showed good activity in the photocatalytic degradation of RhB,with a degradation rate 4.6 times higher than that of PbBiO_(2)Br.This work offers new insights into the application of PbBiO_(2)Br in photocatalytic nitrogen fixation and offers valuable guidance for the development of highly efficient nitrogen fixation materials in the future.
基金supported by the National Natural Science Foundation of China(Regional Fund)(No.51868054)the Natural Science Foundation of Inner Mongolia of China(General Program)(No.2022MS05052).
文摘4-Nitrophenol(4-NP),a toxic and persistent pollutant in chemical wastewater,presents significant challenges in degradation and mineralization.Conventional ozone oxidation catalysts are hindered by low efficiency,mass transfer constraints and metal leaching,necessitating the development of stable and efficient catalysts.Herein,BCn-H/MS,the derivative of Bi(Ce)-MOF,was prepared by in situ incorporation,thermal decomposition and acid etching.The resulting materials were characterized and employed in catalytic ozonation for the reduction of 4-NP.Under the specific experimental conditions of the O_(3)+BC0.3-H/MS system,the total organic carbon(TOC)and chemical oxygen demand(COD)removal rates of 4-NP were observed to reach 94.6%and 91.8%within 30 min,respectively.These two parameters were improved by raising the initial pH,reducing the pollutant concentration and increasing the catalyst dosage.The abundant oxygen vacancies(OVs)were regarded as the pivotal catalytic site of BC0.3-H/MS,which was conducive to the adsorption of O_(3) and the acceleration of the formation of reactive oxygen species(ROS).The regular hollow square structure effectively boosted the specific surface area,increased OVs exposure and accelerated the adsorption and mass transfer process.The electron paramagnetic resonance(EPR)results demonstrated that the primary ROS engaged in the degradation reaction were⋅OH and⋅O_(2)−.BC0.3-H/MS demonstrated excellent stability and reusability in cyclic experiments.Toxicity analysis revealed that the O_(3)+BC0.3-H/MS system exhibited an effective detoxification effect.Ultimately,the primary degradation pathway of 4-NP was proposed through liquid chromatography-mass spectroscopy(LC-MS)and in-situ diffuse reflectance infrared fourier-transform spectroscopy(DRIFTS)analyses at varying reaction times.
基金supported by the National Natural Science Foundation of China(NSFC Nos.52271228,52127802,52201279,52301288,52202298,and 22208262)the Natural Science Foundation of Shaanxi Province(No.2023-JC-ZD-21)+1 种基金the Key Research and Development Plan of Shaanxi Province(No.2023GXLH-046)the Science and Technology Project of Xi'an(No.2021SFGX0004)。
文摘Simultaneous integration of rich oxygen vacancies(OVs)and twin crystals in a photocatalyst can not only significantly enhance the near-infrared(NIR)light response but also greatly improve the photocharge separation and transfer efficiency owing to the induced high electrical conductivity and strong built-in electric field.However,thus far,there has been a lack of a model catalyst containing both twin crystals and OVs.Herein,we develop a simple wet chemical strategy for synthesizing of unprecedented NIR light-responsive OVs-rich Cu_(2)O black nanoparticles with high-density of twin crystals(denoted as black twinned Cu_(2)O).As expected,the black twinned Cu_(2)O exhibits higher visible-NIR and NIR light-driven photodegradation of tetracycline(TC)solution than the counterparts.Significantly,the mechanism insight into twin-dependent photocatalysis in NIR light-responsive Cu_(2)O black nanocrystals with rich OVs is uncovered in depth by density functional theory(DFT)calculations and a series of experimental evidence.Expectantly,this work would be beneficial for the scientific researchers currently focusing on the NIR light-responsive photocatalysis and twin engineering of photocatalysts.
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financial supports from the National Natural Science Foundation of China(52201237)the Talent Introduction Project of Chinese Academy of Sciences(E344011)+4 种基金the Shenzhen High Level Talent Team Project(KQTD2022110109364705)the Joint Research Project of China Merchants Group and SIAT(E2Z1521)the Cross Institute Joint Research Youth Team Project of SIAT(E25427)National Natural Science Foundation of China(52402136)the China Postdoctoral Science Foundation(E325281005)。
文摘Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR products,liquid oxygenates(Oxys)are especially attractive due to their high energy density,high safety and transportability that could be adapted to the existing infrastructure and transportation system.However,efficiently generating these highly reduced oxygen-containing products by ECR remains challenging due to the complexity of coupled proton and electron transfer processes.In recent years,in-depth studies of reaction mechanisms have advanced the design of catalysts and the regulation of reaction systems for ECR to produce Oxys,Here,by focusing on the production of typical Oxys,such as methanol,acetic acid,ethanol,acetone,n-propanol,and isopropanol,we outline various reaction paths and key intermediates for the electrochemical conversion of CO_(2)into these target products.We also summarize the current research status and recent advances in catalysts based on their elemental composition,and consider recent studies on the change of catalyst geometry and electronic structure,as well as the optimization of reaction systems to increase ECR performance.Finally,we analyze the challenges in the field of ECR to Oxys and provide an outlook on future directions for high-efficiency catalyst prediction and design,as well as the development of advanced reaction systems.
基金supported by the Fundamental Research Funds for the Central Universities(No.2024JBZY008)National Natural Science Foundation of China(No.52401031)+1 种基金the Talent Fund of Beijing Jiaotong University,China(No.2024XKRC064)the National College Students Innovative Entrepreneurial Training Program(No.202510004157).
文摘The development of highly active, durable, and low-cost electrocatalysts is crucial for electrocatalytic hydrogen production. Ultrathin two-dimensional (2D) nanomaterials have extremely large specific surface areas, making them highly desirable electrocatalyst morphologies. Medium-entropy alloys (MEAs) exhibit compositional tunability and entropy-driven structural stability, making them ideal electrocatalyst candidates. In this study, MoCoNi MEA with ultrathin 2D morphology was successfully developed using a facile ionic lay-er epitaxial method. The ultrathin 2D MoCoNi MEA showed an excellent oxygen evolution reaction (OER) electrocatalytic performance, with a low overpotential of 167 mV at a current density of 10 mA/cm^(2) and small Tafel slope of 33.2 mV/dec. At the overpotential of 167 mV, the ultrathin 2D MoCoNi MEA exhibited ultrahigh mass activity of 3359.6 A/g, which is three orders of magnitude higher than that of the commercial noble metal oxide RuO_(2) (1.15 A/g). This excellent electrocatalytic performance was attributed to the synergy of multiple active metal-induced medium entropies, as well as the ultrathin thickness, which considerably shortened the charge-transfer dis-tance and thus significantly promoted charge transfer. Owing to the natural entropy-stabilizing effect, the ultrathin 2D MoCoNi MEA maintained 90% of the initial current after a continuous OER electrocatalytic test for 134 h, showing impressive electrocatalytic stability. This study opens new avenues for the development of high-performance and low-cost electrocatalyst materials by creating MEAs with ultrathin 2D morphology.
基金supported by the Key Research and Development Projects of Anhui Province(No.202304a05020031).
文摘Lithium-sulfur batteries(LSBs)have attracted widespread attention due to their high theoretical energy density.However,the dissolution of long-chain polysulfides into the electrolyte(the“shuttle effect”)leads to rapid capacity decay.Therefore,finding suitable materials to mitigate the shuttle effect of polysulfides is crucial for enhancing the electrochemical performance of lithium-sulfur batteries.In this study,LSBs’separator is modified with Ni_(3)V_(2)O_(8)nanoparticles@carboxylated carbon nanotubes(Ni_(3)V_(2)O_(8)@CNTs)composite.There are abundant oxygen vacancies in Ni_(3)V_(2)O_(8)@CNTs composite which plays a synergistic effect on shuttle effect.The Ni_(3)V_(2)O_(8)can tightly anchor soluble polysulfides through oxygen vacancies,while the CNTs not only facilitate the transport of ions and electrons but also weaken the migration of polysulfides,limiting shuttle effect.As a result,the cycling stability of LSBs using Ni_(3)V_(2)O_(8)@CNTs-modified separator has been significantly improved(with a capacity decay rate of only 0.0334%after 1500 cycles at 4.0C).This study proposes a strategy to design modified separator for high-performance LSBs.
基金the following financial supports:National Natural Science Foundation of China(22075225 and 22038011)Innovative Scientific Program of CNNC,State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology(MJNYSKL202401,MJNYSKL202404).
文摘Dry reforming of methane(DRM)has gained significant attention as a promising route to convert two major greenhouse gases(CO_(2) and CH4)to syngas.The development of efficient catalysts is critical for the engineering applications.In this study,the Ce_(x)Zr_(1-x)O_(2)/ZSM-5 composites with different oxygen vacancy concentrations were synthesized by tuning the Ce/Zr ratio,followed by the deposition of metal Ni to island-like Ce_(x)Zr_(1-x)O_(2)on ZSM-5,forming a variety of Ni-Ce_(x)Zr_(1-x)O_(2)/ZSM-5 catalysts,which were applied for the DRM reaction under 750◦C.Combined with various characterizations,it was found that the oxygen vacancy concentration illustrated the volcanic tendency with the decreased Ce/Zr ratio,and the interaction between metal Ni and Ce_(x)Zr_(1-x)O_(2)exhibited a positive relationship with oxygen vacancy concentration.The enhanced between Ni and Ce_(x)Zr_(1-x)O_(2)interaction could improve the strength and amount of Ni-O-M(M=Ce/Zr)species,making the d-band centers of catalysts closer to the Fermi energy level,which was beneficial to the CH4 and CO_(2) activation,along with the improved capacity to resist sintering and coking.Especially,the C1Z3(Ni-Ce0.25Zr0.75O_(2)/ZSM-5)catalyst with the Ce/Zr ratio of 1/3 demonstrated the optimal catalytic performance with 91.9%CH4 and 93.8%CO_(2) conversions within 50 h,accompanied by the best structural and catalytic stability after 100 h.In-situ DRIFTS was employed to study the reaction path and mechanism,discovering that significant amounts of strengthened Ni-O-M species were conducive to activating adsorbed CH4 and CO_(2),and desorbing the linear CO species.
基金supported by National Natural Science Foundation of China(22379059)Applied Basic Research Program Project of Liaoning Province(2023JH2/101300224)+4 种基金Service Local Project of the Education Department of Liaoning Province(Enlisting and Leading)(LJKFZ20220201)General Project of the Educational Department of Liaoning Province(LJKMZ20220728)supported by Talent Scientific Research Fund of Liaoning Petrochemical University(2019-XJJL-028)Collaborative Innovation Project of Beijing-Tianjin-Hebei(Tianjin)(22PTXTHZ00020)Basic scientific research project of Liaoning Provincial Department of Education(LJ212410148019)。
文摘The adsorption of CO on different lattice oxygen sites in Cu doped CeO_(2)(111)was studied by DFT method,and the geometrical structure and electronic properties of adsorption systems were analyzed.The results showed that CO interacted with lattice oxygen on the first layer formed CO_(2).However,when adsorbed on the second layer lattice oxygen,carbonate species were formed with the participation of first layer lattice oxygens,i.e.,CO co-adsorbed on first and second layer lattice oxygens.For the second layer adsorption,the absolute CO adsorption energy was big on the Oss nearby Cu.This kind of carbonates was thermodynamically stable,and it was attributed to the facilitation of Cu on CO adsorption,manifested by an electron migration behavior from the C 2p orbitals to the Cu 3d orbitals.However,the absolute CO adsorption energy on the Oss away from Cu was small.Compared to the formation of carbonates,the formation CO_(2)had very small absolute adsorption energy,suggesting the formed carbonates on second layer was stable.Further,when CO adsorbed on the systems with a carbonate,the absolute CO adsorption energy was significantly smaller than that of the non-carbonated system,indicating that the formation of carbonates inhibited CO oxidation on Cu/CeO_(2)(111).Therefore,the formation of carbonates was unfavorable for CO oxidation reaction on Cu/CeO_(2)(111).The results of this study provide theoretical support for the negative effect of CO_(2)on ceria-based catalysts.
基金National Key Research and Development Program of China(2020YFA0710302)The Major Research Plan of the National Natural Science Foundation of China(91963206)+2 种基金The National Natural Science Foundation of China(52072169,51972164,51972167,22279053)The Fundamental Research Funds for the Central Universities(14380193)The Program for Guangdong Introducing Innovative and Entrepreneurial Teams(2019ZT08L101).
文摘On the surfaces of celestial bodies with no or thin atmospheres,such as the Moon and Mars,the solar wind irradiation process leads to the formation of hydrogen and helium enriched regions in the extraterrestrial soil particles.However,soil particles on the Earth with the similar composition lack such structures and properties.This discrepancy raises a key question whether there is a direct relationship between solar wind irradiation and the alterations in the structure and chemical performance of extraterrestrial materials.To address this question,this work investigates the effects of proton irradiation,simulating solar wind radiation,on the structure and photothermal catalytic properties of the classic catalyst In_(2)O_(3).It reveals that proton irradiation induces structural features in In_(2)O_(3) analogous to those characteristics of solar wind weathering observed in extraterrestrial materials.Furthermore,after proton beam irradiation with an energy of 30 keV and a dose of 3×10^(17) protons·cm^(-2),the methanol production yield of the In_(2)O_(3) catalyst increased to 2.6 times of its preirradiation level,and the methanol selectivity improved to 2.1 times of the original value.This work provides both theoretical and experimental support for the development of high-efficiency,radiation-resistant photothermal catalysts.
基金supported by the National Natural Science Foundation of China(52376080 and 52306122)the Anhui Provincial Natural Science Foundation(2308085QE174)+3 种基金the China Postdoctoral Science Foundation(2023TQ0346)the Postdoctoral Fellowship Program of CPSF(GZC20232522)the Fundamental Research Funds for the Central Universities(WK2090000057)the Students’Innovation and Entrepreneurship Foundation of USTC(CY2023C008).
文摘Lithium-oxygen batteries attract considerable attention due to exceptionally high theoretical energy density,while the development remains in its early stage.As is widely suggested,the solution mechanism induces greater discharge capacity,while the surface mechanism induces greater cycle stability.Therefore,battery performance can be improved by adjusting the reaction mechanism.Previous studies predominantly focus on extremely thin or flat electrodes.In contrast,this work utilizes thick electrodes,emphasizing the importance of mass transport.Given that the electrolyte solvent is the main site of mass transport,the effects of two typical solvents on mass transport and battery performance are investigated:dimethyl sulfoxide with low viscosity and a high O_(2) diffusion rate and tetraethylene glycol dimethyl ether with high O_(2) solubility and high Li+transport capability.The results reveal a novel pathway for reaction mechanism induction where the mechanism varies with the spatial position of the electrode.As the spatial distribution of the electrode progresses,a layered appearance of solution mechanism products,transition state products,and surface mechanism products emerges,which is attributed to the increase in the mass transfer resistance.This work presents a distinct perspective on the way solvents influence reaction pathways and offers a new approach to regulating reaction pathways.
基金Research Project of Shenzhen Science and Technology Innovation Committee(JCYJ20180306170801080)。
文摘Amorphous Ga_(2)O_(3)(a-Ga_(2)O_(3))thin films were prepared on flexible polyimide,rigid quartz glass,and Si substrates via radio frequency magnetron sputtering at room temperature.The effect of oxygen/Ar flow rate ratio on the structure,optical property,surface morphology,and chemical bonding properties of the a-Ga_(2)O_(3) films was investigated.Results show that the average optical transmittance of the a-Ga_(2)O_(3) films is over 80%within the wavelength range of 300-2000 nm.The extracted optical band gap of the a-Ga_(2)O_(3) films is increased from 4.97 eV to 5.13 eV with the increase in O_(2)/Ar flow rate ratio from 0 to 0.25,due to the decrease in concentration of oxygen vacancy defects in the film.Furthermore,the optical refractive index and surface roughness of the a-Ga_(2)O_(3) films are optimized when the O_(2)/Ar flow rate ratio reaches 0.25.X-ray photoelectron spectroscopy analysis also shows that the proportion of oxygen vacancies(VO)and Ga-O chemical bonds in the O 1s peak is gradually decreased with the increase in O_(2)/Ar flow rate ratio from 0 to 0.25,proving that increasing the O_(2)/Ar flow rate ratio during film growth can reduce the concentration of oxygen vacancy defects in a-Ga_(2)O_(3) films.In this case,a-Ga_(2)O_(3) with optimal properties can be obtained.This work provides a research basis for high-performance flexible and rigid deep ultraviolet solar-blind detection devices based on a-Ga_(2)O_(3) films.
文摘The oxygen evolution reaction(OER)serves as a fundamental half–reaction in the electrolysis of water for hydrogen production,which is restricted by the sluggish OER reaction kinetics and unable to be practically applied.The traditional lattice oxygen oxidation mechanism(LOM)offers an advantageous route by circumventing the formation of M-OOH^(*)in the adsorption evolution mechanism(AEM),thus enhancing the reaction kinetics of the OER but resulting in possible structural destabilization due to the decreased M–O bond order.Fortunately,the asymmetry of tetrahedral and octahedral sites in transition metal spinel oxides permits the existence of non-bonding oxygen,which could be activated by rational band structure design for direct O-O coupling,where the M–O bond maintains its initial bond order.Here,non-bonding oxygen was introduced into NiFe_(2)O_(4)via annealing in an oxygen-deficient atmosphere.Then,in-situ grown sulfate species on octahedral nickel sites significantly improved the reactivity of the non-bonding oxygen electrons,thereby facilitating the transformation of the redox center from metal to oxygen.LOM based on non-bonding oxygen(LOMNB)was successfully activated within NiFe_(2)O_(4),exhibiting a low overpotential of 206 mV to achieve a current density of 10 mA cm^(-2)and excellent durability of stable operation for over 150 h.Additionally,catalysts featuring varying band structures were synthesized for comparative analysis,and it was found that the reversible redox processes of non-bonding oxygen and the accumulation of non-bonding oxygen species containing 2p holes are critical prerequisites for triggering and sustaining the LOMNB pathway in transition metal spinel oxides.These findings may provide valuable insights for the future development of spinel-oxide-based LOM catalysts.
基金financially supported by the Science and Technology Program of Guangzhou (202201010373)。
文摘Oxygen vacancy engineering is a valid strategy to boost the oxygen reduction reaction(ORR) performance of nanostructured electrocatalysts.Current methods for generating surface oxygen vacancies(Vos) in nanostructured MnO_(2) is mostly lab-scale,which cannot meet the requirement of large-scale production.Herein,we employed a mechanochemical method of ball milling to introduce surface Vos into the β-MnO_(2) nanoparticles.The ball milling process generated abundant surface Vos,which significantly facilitated the adsorption and activation of O_(2).Consequently,the ORR performance of ball-milled β-MnO_(2) was markedly boosted by varying the ball milling time.As an air cathode catalyst for zinc-air battery(ZAB),the β-MnO_(2) ball-milled for 4 h displayed a high specific capacity of 804 mA·h·g^(-1) and excellent cycling over 500 h at 5 mA·cm^(-2),which were superior than those of pristine β-MnO_(2)-based ZAB.Our work offers a feasible strategy to enhance electrocatalytic ORR performance of MnO_(2),which shows significant potential for large-scale production of efficient ORR electrocatalysts.
基金supported by the Natural Science Foundation of China(Nos.22278094 and 22379033)Guangdong Graduate Education Innovation Program(No.2023JGXM_102)+2 种基金the Basic and Applied Basic Research Program of Guangzhou(No.SL2024A03J00499)the University Innovation Team Scientific Research Project of Guangzhou(No.202235246)Hainan Province Graduate Innovation Research Project(No.Qhyb2023-143).
文摘Four-electron oxygen evolving reaction is limited by proton adsorption and desorption,making its reaction kinetics sluggish,which poses a major challenge for catalyst design.Here,we present an unsaturated coordination interface by constructing a fast electron transfer channel between Cu_(2)V_(2)O_(7)(CVO)and BiVO4(BVO).X-ray absorption spectroscopy(XAS)and theoretical calculations results confirm that CVO and BVO between interfaces are bonded by the way of unsaturated coordination oxygen(Ouc).The Ouc optimizes the O-O coupled energy barrier at the V active site and promotes the disconnection of O-H bond,which increases the photocurrent intensity of CVO by 6 times.In addition,due to the high electronegativity of the Ouc,the bonding energies of Bi-O and Cu-O at the interface are enhanced,resulting in the long-term stability of the photoanode during the water splitting.Finally,by integrating the working electrode with a polysilicon solar cell,we assembled a device that demonstrated exceptional catalytic performance,achieving a hydrogen production rate of 100.6μmol·cm^(-2),and maintaining a hydrogen-to-oxygen volume ratio of 2:1 after continuous operation for 4 h.This discovery aids in a deeper understanding of photoanode design and offers further insights for industrial applications.
基金the financial support from the European Commission through the H2020-MSCA-RISE-2020 BIOALL project(Grant Agreement: 101008058)。
文摘Single carbon products(C1 compounds) are simple but important chemicals in the road towards energy transition.Catalytic conversion of CO_(2) with H_(2)(desirably renewable) can be performed over reducible oxides supporting transition metals to obtain products such as CH_(4),CO and MeOH.Oxygen vacancies(O-vacancies),which are inherent defects of reducible metal oxides,play an enormous role in driving the catalytic performance(activity,selectivity,stability) for the desired reactions.Yet,the assessment of O-defects at realistic conditions is often complex.Only few techniques can provide direct evidence for their existence and influence in CO_(2) activation.Among them,electron paramagnetic spectroscopy(EPR),Raman spectroscopy,scanning probe microscopies(SPM) and environmental transmission electron microscopy(ETEM) are nowadays the most informative.In most cases,however,the measurements require reaction conditions far away from CO_(2) valorization applications.Although great efforts have been fruitful in explaining and demonstrating the huge importance of O-vacancies in CO_(2) catalysis,still ambiguous or erroneous interpretations about structure-function correlations involving O-vacancies are found in literature,especially,when information is not properly gathered,e.g.,by O 1s ex-situ X-ray photon spectroscopy(XPS).Moreover,despite the recognized importance of O-vacancies for CO_(2) valorization,critical literature compilations about their effects in thermal processes are scarce.Herein,we attempt to contribute in closing this gap by integrally encompassing representative investigations on the thermo-catalytic production of CH_(4),CO and MeOH.Particularly,we emphasize on the proper selection of assessment tools(direct/indirect) to unambiguously establish structure-function relationships to design optimized O-defective catalysts for the targeted compounds.
基金financially supported by the Natural Science Foundation of Xiamen,China(No.3502Z202373070).
文摘Zinc-ion capacitors(ZICs)are promising energy storage devices due to their balance between the energy and power densities inherited from Zn-ion batteries and supercapacitors,respectively.However,the low specific capacitance of carbon cathode materials and the dendrite growth on Zn anode have set fatal drawbacks to their energy density and cycle stability.Herein,we demonstrate that,in 1 M Zn(CF_(3)SO_(3))_(2)/DMF(N,N-dimethylformamide)electrolyte,confining oxygen in carbon cathode materials via high-energy ball milling can synergistically introduce additional pseudocapacitance on the cathode side while suppressing the dendrite growth on Zn anode side,which jointly lead to high energy density(94 Wh kg^(−1)at 448 W kg^(−1))and long cycle stability of ZICs.The hydroxyl group in carbon cathode can be transformed to C–O–Zn together with the release of protons during the initial discharge,which in turn stimulates the defluorination of CF_(3)SO_(3)^(-)anions and formation of ZnF_(2)on both cathode and anode.The ZnF2 formed on the surface of the Zn anode suppresses the dendrite growth by regulating the Zn^(2+)deposition/stripping in a reticular structure,resulting in the excellent cycle stability.This work provides a facile strategy to rationally design and construct high energy and stable ZICs through engineering the oxygen-bearing functional groups in carbon cathode materials.
