NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsi...NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsic activity limitations and poor stability,primarily due to the asymmetric adsorption of oxygen intermediates.To overcome this,the binding strength must be synergistically tuned to a moderate level to optimize catalytic performance.Here,we engineered NiFeCoCr LDH through Co doping to enhance electrical conductivity and controlled Cr leaching to introduce cationic vacancies for modulating intermediate binding strength in NiFe LDH.X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses reveal that NiFe-LDH with Co doping and Cr vacancies modulates the Ni oxidation state and local coordination environment,leading to a balanced electronic structure and enhanced structural complexity around the Ni sites.Additionally,these vacancies can trap OH^(-)/H_(2)O species,which can serve as a reservoir for OH^(-) transfer,facilitating the rapid formation of OER intermediates and enhancing catalytic performance at high current densities.As a result,V_(Cr)-NiFeCo LDH achieves 1.6 A cm^(-2)current density at 1.7 V vs.RHE while maintaining stable operation for over 1000 h at 500 mA cm^(-2).Density functional theory(DFT)calculations validate the synergistic effects of Co doping and Cr-induced vacancies on intermediate binding energies and improved OER kinetics.Overall,this work presents a rational design strategy to simultaneously enhance the activity and durability of NiFe-based OER catalysts for their application in high-performance alkaline water electrolysis.展开更多
Density functional theory(DFT)calculations were employed to investigate the adsorption behavior of NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)molecules on both pristine and mono-vacancy phosphorene sheets.The pristine pho...Density functional theory(DFT)calculations were employed to investigate the adsorption behavior of NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)molecules on both pristine and mono-vacancy phosphorene sheets.The pristine phosphorene surface showsweak physisorption with all the gasmolecules,inducing onlyminor changes in its structural and electronic properties.However,the introduction ofmono-vacancies significantly enhances the interaction strength with NH_(3),PH_(3),CO_(2),and CH_(4).These variations are attributed to substantial charge redistribution and orbital hybridization in the presence of defects.The defective phosphorene sheet also exhibits enhanced adsorption energies,along with favorable sensitivity and recovery characteristics,highlighting its potential as a promising gas sensor for NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)at ambient conditions.展开更多
Long-afterglow photocatalytic technology offers promising potential fo r all-weather pollutant treatment,yet its efficiency is often constrained by competition between afterglow emission and photocatalytic reactions.T...Long-afterglow photocatalytic technology offers promising potential fo r all-weather pollutant treatment,yet its efficiency is often constrained by competition between afterglow emission and photocatalytic reactions.To address this,we developed a Pr^(3+)-doped Ca_(2)Al_(2)SiO_(7)(CASO)photocatalyst enriched with oxygen vacancies(V_(O)).The introduction of oxygen vacancies significantly increases trap concentration,enhancing both the intensity and du ration of the afterglow emission.A persulfate-assisted photo-Fenton system was designed based on V_(O)-CASO:Pr^(3+)enabling the self-activated degradation of tetracycline hydrochloride(TC)under ultraviolet afterglow.The photo-Fenton reaction consumes excess holes accumulated during the afterglow process,improving carrier utilization efficiency and mitigating rapid recombination.Additionally,persulfate addition can enrich reactive species and facilitate the Fe^(2+)/Fe^(3+)cycle.Benefiting from these synergistic effects,V_(O)-CASO:Pr^(3+)has achieved 75%TC degradation within1 h,significantly outperforming traditional systems.This study provides a new strategy for enhancing long-afterglow photocatalytic performance,paving the way for sustainable pollutant degradation technologies.展开更多
Innovative S-scheme heterostructures face intrinsic limitations in charge separation due to insufficient interfacial driving forces.This work pioneers a dual-vacancy engineering strategy to break this bottleneck,const...Innovative S-scheme heterostructures face intrinsic limitations in charge separation due to insufficient interfacial driving forces.This work pioneers a dual-vacancy engineering strategy to break this bottleneck,constructing a plasmonic ZnIn_(2)S_(4-x)MoO_(3-x)(ZIS/MO)S-scheme heterojunction where oxygen and sulfur vacancies synergistically reconfigure charge transfer dynamics via dual-path modulation.Uniquely,sulfur vacancies amplify the built-in electric field(IEF)intensity by enlarging the Fermi level gap,while oxygen and sulfur dual-vacancies induce localized surface plasmon resonance(LSPR)via free-carrier concentration enhancement.Simultaneously,sulfur vacancies lower the H^(*)adsorption barrier,and dual vacancies amplify photothermal conversion by promoting nonradiative decay,accelerating temperature elevation and kinetics.Electron dynamics confirm that this dual-vacancy synergy prolongs charge carrier lifetime by a factor of 5.23.Consequently,the optimized sulfur vacancy-rich ZnIn_(2)S_(4-x)/MoO_(3-x)(R-ZIS/MO)exhibits remarkable photocatalytic hydrogen production rates of 3.60 mmol g^(-1) h^(-1)under visible light and 22.74 mmol g^(-1) h^(-1) under full-spectrum irradiation,representing 7.8-fold and17.2-fold enhancements,respectively.This study establishes a new paradigm.Targeted dual-vacancy coordination in plasmonic heterostructures enables unprecedented IEF-LSPR co-modulation,opening avenues for high-efficiency solar energy conversion.展开更多
Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a fo...Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a formidable challenge.Herein,we propose a dual-engineering strategy to stabilize Ru-based catalysts by synergizing the oxygen vacancy site-synergized mechanism-lattice oxygen mechanism(OVSM-LOM)with Ru-N bond stabilization.The engineered RuO_(2)@NCC catalyst exhibits exceptional OER performance in 0.5 M H2SO4,achieving an ultralow overpotential of 215 mV at 10 mA cm^(-2) and prolonged stability for over 327 h.The catalyst delivers 300 h of continuous operation at 1 A cm^(-2),with a negligible degradation rate of only 0.067 mV h-1,further demonstrating its potential for practical application.Oxygen vacancies unlock the OVSM-LOM pathway,bypassing the sluggish adsorbate evolution mechanism(AEM)and accelerating reaction kinetics,while the Ru-N bonds suppress Ru dissolution by anchoring low-valent Ru centers.Quasi-in situ X-ray photoelectron spectroscopy(XPS),X-ray absorption spectroscopy(XAS),and isotopic labeling experiments confirm the lattice oxygen participation with *O formation as the rate-determining step.The Ru-N bonds reinforce the structural integrity by stabilizing low-valent Ru centers and inhibiting overoxidation.Theoretical calculations further verify that the synergistic interaction between OVs and Ru-O(N)active sites optimizes the Ru d-band center and stabilizes intermediates,while Ru-N coordination enhances structural integrity.This study establishes a novel paradigm for designing robust acidic OER catalysts through defect and coordination engineering,bridging the gap between activity and stability for sustainable energy technologies.展开更多
Vacancy defects,as fundamental disruptions in metallic lattices,play an important role in shaping the mechanical and electronic properties of aluminum crystals.However,the influence of vacancy position under coupled t...Vacancy defects,as fundamental disruptions in metallic lattices,play an important role in shaping the mechanical and electronic properties of aluminum crystals.However,the influence of vacancy position under coupled thermomechanical fields remains insufficiently understood.In this study,transmission and scanning electron microscopy were employed to observe dislocation structures and grain boundary heterogeneities in processed aluminum alloys,suggesting stress concentrations and microstructural inhomogeneities associated with vacancy accumulation.To complement these observations,first-principles calculations and molecular dynamics simulations were conducted for seven single-vacancy configurations in face-centered cubic aluminum.The stress response,total energy,density of states(DOS),and differential charge density were examined under varying compressive strain(ε=0–0.1)and temperature(0–600 K).The results indicate that face-centered vacancies tend to reduce mechanical strength and perturb electronic states near the Fermi level,whereas corner and edge vacancies appear to have weaker effects.Elevated temperatures may partially restore electronic uniformity through thermal excitation.Overall,these findings suggest that vacancy position exerts a critical but position-dependent influence on coupled structure-property relationships,offering theoretical insights and preliminary experimental support for defect-engineered aluminum alloy design.展开更多
The electrocatalytic oxidation of 5-hydroxymethylfurfural(HMF)offers a promising approach for producing high-value chemicals and hydrogen.While cobalt-based oxides are promising catalysts for the HMF oxidation reactio...The electrocatalytic oxidation of 5-hydroxymethylfurfural(HMF)offers a promising approach for producing high-value chemicals and hydrogen.While cobalt-based oxides are promising catalysts for the HMF oxidation reaction(HMFOR),their performance is limited by inefficient oxidation of CoO_(x)to the active CoO_(2)phase.Here,we demonstrate that introducing oxygen vacancies into CoO_(x)significantly enhances its oxidation kinetics.The oxygen vacancy-rich CoO_(x)supported on copper foam(CoO_(x)/CF)achieves an impressive 98%HMF conversion with a Faradaic efficiency of 98.6%at 1.5 V vs.RHE.Operando Raman spectroscopy reveals that oxygen vacancies facilitate the preferential formation ofγ-CoOOH overβ-CoOOH during electrocatalysis,thereby promoting the generation of the active CoO_(2)phase.Combining in situ infrared spectroscopy with density functional theory(DFT)calculations,we unambiguously establish the reaction pathway,which proceeds via the sequence of HMF→5-hydroxymethyl-2-fur ancarboxylic acid(HMFCA)→2-formyl-5-furancarboxylic acid(FFCA)→2,5-furandicarboxylic acid(FDCA),and reveal the pivotal role of the active CoO_(2)species in accelerating hydroxyl radical oxidation.This work not only provides fundamental mechanistic insights into oxygen vacancy-mediated catalyst design but also offers a novel strategy for developing high-performance transition metal oxide electrocatalysts for biomass valorization.展开更多
Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction(OER).However,the correlation among catalyst structure,magnetic property,and ma...Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction(OER).However,the correlation among catalyst structure,magnetic property,and magnetic field enhanced-electrochemical activity remains to be fully elucidated.Herein,single-domain CoFe_(2)O_(4) catalysts with tunable oxygen vacancies(CFO-V_(O)) were synthesized to probe how V_(O) mediates magnetism and OER activity under magnetic field.The introduction of V_(O) can simultaneously modulate saturation magnetization(M_(s)) and coercivity(H_(c)),where the increased M_(s) dominates the magnetic field-enhanced OER activity.Under a 14,000 G magnetic field,the optimized CFO-V_(O) exhibits up to 16.1 % reduction in overpotential and 365 % enhancement in magnetocurrent(MC).Electrochemical analyses and post-OER characterization reveal that the magnetic field synergistically improves OER kinetics through lattice distortion induction,magnetohydrodynamic effect,and spin charge transfer effect.Importantly,the magnetic field promotes additional Co^(3+) generation to compensate for charge imbalance caused by V_(O) filling,maintaining dynamic equilibrium of V_(O) and effective reactant adsorption-conversion processes.This work unveils the synergistic mechanism of V_(O) and magnetic parameters for enhancing OER performance under the magnetic field,providing new insights into the design of high-efficiency spinregulated OER catalysts.展开更多
Atomic vacancies in oxides induce deviations from ideal stoichiometry,critically influencing their functional properties in applications such as energy storage-conversion,catalysis,and electronic devices.The dynamic b...Atomic vacancies in oxides induce deviations from ideal stoichiometry,critically influencing their functional properties in applications such as energy storage-conversion,catalysis,and electronic devices.The dynamic behavior of these vacancies as main mass transport mediums to exchange chemical species with surroundings under operating conditions is central to oxide redox reactions running with the Mars-van Krevelen(MvK)mechanism;yet in-situ atomic-scale monitoring of the vacancy dynamics and vacancy-induced secondary defects within oxides remains challenging due to both their rapid transport kinetics at buried subsurface/interface and characterization difficulties,arising from the insulating nature of bulk oxides and the spatial-resolution requirement in reaction conditions.These challenges hinder precise defect engineering for the performance optimization of functional oxides.In this review,recent advancements in tracking oxygen vacancy and vacancyinduced secondary defects dynamics in oxides,including surface steps,cation vacancies,interfacial dislocations,ledges,and interfaces,have been summarized.The dynamic interconversion of defects and their synergistic effects on surface/subsurface/interface evolution are mainly discussed.The aim of this review is to enhance understanding of defect dynamics and their pivotal role in modulating structural dynamics and surface reaction reactivity,which is highly relevant to the catalyst activity/selectivity/stability evaluation of functional oxide catalysts for electroreduction and catalytic oxidation reactions.Finally,strategies to control buried subsurface and interfacial defects(interface engineering)through tailored surface reactions are proposed,offering new pathways to customize the performance of advanced oxide-based materials.展开更多
Sodium-based halide solid electrolytes offer excellent electrochemical stability and favorable interfacial compatibility,yet their low ionic conductivity at room temperature limits their application in all-solidstate ...Sodium-based halide solid electrolytes offer excellent electrochemical stability and favorable interfacial compatibility,yet their low ionic conductivity at room temperature limits their application in all-solidstate Na-ion batteries(ASSNIBs),Here,we develop a series of LaCl_(3)-based sodium superionic conductors engineered through cation vacancy-concentration modulation,which facilitates the formation of a threedimensional Na+transport network and increases the density of ion-hopping sites.The optimized Na_(0.4)Ta_(0.236)La_(0.472)Cl_(3)(NTLC)electrolyte achieves a Na+conductivity of 1.38×10^(-3) S/cm at 30℃,with a reduced activation energy of 0.26 eV.It also exhibits excellent mechanical deformation and moderate high-voltage stability,resulting in enhanced interfacial compatibility.When paired directly with an uncoated NaCrO_(2) cathode,the NTLC catholyte enables ASSNIBs to cycle stably over 300 cycles with89.7%capacity retention at 0.3 C and room temperature.This work underscores the potential of vacancy-rich LaCl_(3)-based sodium superionic conductors for advancing high-performance ASSNIBs.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
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
Highly active and stable FeOOH cocatalysts are essential for achieving optimal performance of BiVO_(4)(BVO)photoanodes.Despite offering remarkable structural stability,widely used thick FeOOH cocatalysts often suffer ...Highly active and stable FeOOH cocatalysts are essential for achieving optimal performance of BiVO_(4)(BVO)photoanodes.Despite offering remarkable structural stability,widely used thick FeOOH cocatalysts often suffer from insufficient hole transport capability,which hinders the overall activity.The present study demonstrates that a simple photoetching strategy is able to introduce gradient distributed oxygen vacancies(GO_(V))in the thick FeOOH layer and significantly enhances the photogenerated holes transport dynamics.The incorporation of GO_(V)within FeOOH not only realizes the“relay transport”of photogenerated hole through the progressive upward shift of the valence band in the spatial distribution,but also provides abundant oxidation active sites by efficient hole trapping.These improvements effectively improve the oxygen evolution reaction(OER)activities and mitigate photocorrosion by the instantaneous hole extraction.Consequently,the FeOOH-GO_(V)layer enables the BVO/FeOOH-GO_(V)photoanode to achieve an impressive photocurrent density of 5.37 mA cm^(-2)and a robust operational stability up to 160 h at 1.23 VRHE,setting new benchmarks for current density and stability in FeOOH-based BVO photoanodes.This work provides an effective avenue to optimize OER cocatalysts for constructing highly efficient and stable photoelectrochemical water splitting devices.展开更多
Rectifying circuit,as a crucial component for converting alternating current into direct current,plays a pivotal role in energy harvesting microsystems.Traditional silicon-based or germanium-based rectifier diodes hin...Rectifying circuit,as a crucial component for converting alternating current into direct current,plays a pivotal role in energy harvesting microsystems.Traditional silicon-based or germanium-based rectifier diodes hinder system integration due to their specific manufacturing processes.Conversely,metal oxide diodes,with their simple fabrication techniques,offer advantages for system integration.The oxygen vacancy defect of oxide semiconductor will greatly affect the electrical performance of the device,so the performance of the diode can be effectively controlled by adjusting the oxygen vacancy concentration.This study centers on optimizing the performance of diodes by modulating the oxygen vacancy concentration within InGaZnO films through control of oxygen flows during the sputtering process.Experimental results demonstrate that the diode exhibits a forward current density of 43.82 A·cm^(−2),with a rectification ratio of 6.94×10^(4),efficiently rectifying input sine signals with 1 kHz frequency and 5 V magnitude.These results demonstrate its potential in energy conversion and management.By adjusting the oxygen vacancy,a methodology is provided for optimizing the performance of rectifying diodes.展开更多
Selective catalytic reduction of NO_(x) with CO(CO-SCR)is a process that purifies both NO and CO pollutants through a catalytic reaction.Specifically,the cleavage of NO on the catalyst surface is crucial for promoting...Selective catalytic reduction of NO_(x) with CO(CO-SCR)is a process that purifies both NO and CO pollutants through a catalytic reaction.Specifically,the cleavage of NO on the catalyst surface is crucial for promoting the reaction.During the reaction,the presence of oxygen vacancies can extract oxygen from NO,thereby facilitating the cleavage of NO on the catalyst surface.Thus,the formation of oxygen vacancies is key to accelerating the CO-SCR reaction,with different types of oxygen vacancies being more conducive to their generation.In this study,Rh/CeCuO_(x) catalysts were synthesized using the co-crystallization and impregnation methods,and asymmetric oxygen vacancies were induced through hydrogen thermal treatment.This structuralmodification was aimed at regulating the behavior of NO on the catalyst surface.The Rh/Ce0.95Cu0.05O_(x)-H_(2) catalyst exhibited the best performance in CO-SCR,achieving above 90%NO conversion at 162℃.Various characterization techniques showed that the H_(2) treatment effectively reduced some of the CuO and Rh_(2)O_(3),creating asymmetric oxygen vacancies that accelerated the cleavage of NO on the catalyst surface,rather than forming difficult-to-decompose nitrates.This study offers a novel approach to constructing oxygen vacancies in new CO-SCR catalysts.展开更多
Developing cost-effective and high-activity catalysts for the methanolysis of ammonia borane(AB)has attracted great attention in the field of hydrogen energy recently.Besides the modification of the electronic structu...Developing cost-effective and high-activity catalysts for the methanolysis of ammonia borane(AB)has attracted great attention in the field of hydrogen energy recently.Besides the modification of the electronic structure of the catalysts,external factors such as visible light irradiation can improve the efficiency of hydrogen production as well.In the present study,a Z-scheme heterostructured VO-Cu_(0.5)Ni_(0.5)O catalysts were constructed by introducing a plenteous phase interface and oxygen vacancy(Vo).The catalytic activity of as-prepared VO-Cu_(0.5)Ni_(0.5)O toward AB methanolysis has been improved dramatically with the assistance of visible light irradiation.The turnover frequency(TOF)under visible light irradiation was measured to be 29_(mol)H_(2)·mol_(cat.)^(-1)·min^(-1),which is 1.4 times larger than the TOF in the absence of visible light.Systematic characterization experiments and density functional theory(DFT)calculations were conducted to unveil the causation of enhanced catalytic activity.The results demonstrated that the enhancement of the catalytic activity of VO-Cu_(0.5)Ni_(0.5)O originated from the electronic structure modification induced by the formation of heterojunctions,the introduction of oxygen vacancies,and the assistance of visible light cooperatively.The formation of heterojunction and the introduction of oxygen vacancies provoked the upshift of the d-band center;while the visible light irradiation induced the photogenerated electrons to transfer from Cu to Ni sites at the interface.Such electron structure modulation is beneficial for the construction of abundant active sites,thereby enhancing the adsorption of methanol on the Ni sites,which is considered as the rate-determine step for the methanolysis of AB.The strong interaction between Ni and O weakened the O-H bond of methanol,accelerating the methanolysis of AB.These results demonstrate the utilization of combined heterojunction,oxygen vacancy,and visible light to explore highly active AB methanolysis catalysts,which should shed light on the exploration of more effective catalysts for AB methanolysis.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
Antibiotics and heavy metals usually co-exist in wastewater and pose serious environmental hazards.Herein,a series of VMo-BMO/O_(v)-BOB S-scheme heterojunctions with double vacancy(Mo vacancy and photoexcited O vacanc...Antibiotics and heavy metals usually co-exist in wastewater and pose serious environmental hazards.Herein,a series of VMo-BMO/O_(v)-BOB S-scheme heterojunctions with double vacancy(Mo vacancy and photoexcited O vacancy)were constructed via an electrostatic assembly method.The removal efficiency of Cr(VI)and tetracycline(TC)over VMo-BMO/O_(v)-BOB-0.3 was 2.47 and 1.13 times than that of a single system,respectively.In-situ EPR demonstrated that the surface O vacancies could be generated under LED light irradiation.These photoexcited O vacancies(P-O_(v))enabled VMo-BMO/O_(v)-BOB composites still exhibit satisfactory activity after five successive cycles and an amplified Fermi level gap.The enhancement could be attributed to the enhanced internal electric field and double-vacancy-induced polarization.Additionally,the density functional theory calculation results suggested that double vacancy induced polarization electric field increases the dipole moment,which was conducive to rapid electron transport.Photoluminescence and time-resolved photoluminescence analysis demonstrated that the introduction of S-scheme heterojunction and double vacancy promoted charge transfer and prolonged the lifetime of carriers.Degradation intermediates and toxicity of products were evaluated.In conclusion,a possible mechanism based on VMo-BMO/O_(v)-BOB S-scheme heterojunction in the simultaneous removal of Cr(VI)and TC was proposed.展开更多
The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants,with little attention to the involved selectivity which may correlate with toxicant residues.Herein...The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants,with little attention to the involved selectivity which may correlate with toxicant residues.Herein,an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy(Co-O_(V))on the Co/BiOCl-O_(V)photocatalyst was developed for photocatalytic degradation of glyphosate(GLP)wastewater of high performance/selectivity.Under full-spectrum-light irradiation,a high GLP degradation rate of 99.8%with over 90%C-P bond-breaking selectivity was achieved within 2 h,while effectively circumventing toxicant residues such as aminomethylphosphonic acid(AMPA).X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-O_(V)carrier and photothermal/pyroelectric effect.The oriented formation of more•O_(2)^(−)on Co/BiOCl-O_(V)could be achieved with the Co-O_(V)coupled center that had excellent O2 adsorption/activation capacity,as demonstrated by quantum calculations.The formed unique Co-O_(V)active sites could largely decrease the C-P bond-breaking energy barrier,thus greatly improving the selectivity toward the initial C-P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP.The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C-X bonds.展开更多
Solid-state precipitation is an effective strategy for tuning the mechanical and functional properties of ad-vanced alloys.Structure design and modification necessitate good knowledge of the kinetic evolution of preci...Solid-state precipitation is an effective strategy for tuning the mechanical and functional properties of ad-vanced alloys.Structure design and modification necessitate good knowledge of the kinetic evolution of precipitates during fabrication,which is strongly correlated with defect concentration.For Fe-Ga alloys,giant magnetostriction can be induced by the precipitation of the nanoscale tetragonal L60 phase.By introducing quenched-in vacancies,we significantly enhance the magnetostriction of the aged Fe81Ga19 polycrystalline alloys to~305 ppm,which is close to the level of single crystals.Although vacancies were found to facilitate the generation of the L60 phase,their impact on the precipitation mechanism and kinetics has yet to be revealed.This study combined transmission electron microscopy(TEM)and time-resolved small-angle neutron scattering(SANS)to investigate the precipitation of the L60 phase during the isothermal aging at 350 and 400℃,respectively.The evolution of L60 nanophase in morphology and number density in as-cast(AC)and liquid nitrogen quenched(LN)Fe81Ga19 alloys with aging time were quantitatively compared.Interestingly,the nucleation of the L60 phase proceeds progressively in AC while suddenly in LN specimens,indicating the homogenous to heterogeneous mechanism switching in-duced by concentrated vacancies.Moreover,excess vacancies can change the shape of nanoprecipitates and significantly accelerate the growth and coarsening kinetics.The magnetostrictive coefficient is opti-mized when the size(long-axis)of L60 precipitates lies between 100 and 110Åwith a number density between 3.2-4.3×10-7Å-3.Insight from this study validates the feasibility of achieving high magnetoe-lastic properties through precise manipulation of the nanostructure.展开更多
基金supported by the Natural Science Foundation of China Grant No.52272289 and 5240223,and JSPS(Japan Society for the Promotion of Science)of Grant No.22K19088,23H00313,24H02202,and 24H02205。
文摘NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsic activity limitations and poor stability,primarily due to the asymmetric adsorption of oxygen intermediates.To overcome this,the binding strength must be synergistically tuned to a moderate level to optimize catalytic performance.Here,we engineered NiFeCoCr LDH through Co doping to enhance electrical conductivity and controlled Cr leaching to introduce cationic vacancies for modulating intermediate binding strength in NiFe LDH.X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses reveal that NiFe-LDH with Co doping and Cr vacancies modulates the Ni oxidation state and local coordination environment,leading to a balanced electronic structure and enhanced structural complexity around the Ni sites.Additionally,these vacancies can trap OH^(-)/H_(2)O species,which can serve as a reservoir for OH^(-) transfer,facilitating the rapid formation of OER intermediates and enhancing catalytic performance at high current densities.As a result,V_(Cr)-NiFeCo LDH achieves 1.6 A cm^(-2)current density at 1.7 V vs.RHE while maintaining stable operation for over 1000 h at 500 mA cm^(-2).Density functional theory(DFT)calculations validate the synergistic effects of Co doping and Cr-induced vacancies on intermediate binding energies and improved OER kinetics.Overall,this work presents a rational design strategy to simultaneously enhance the activity and durability of NiFe-based OER catalysts for their application in high-performance alkaline water electrolysis.
基金financial support to conduct this research from the Science and Engineering Research Board(SERB)through a state university research excellence(SURE)grant(SUR/2022/004935).
文摘Density functional theory(DFT)calculations were employed to investigate the adsorption behavior of NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)molecules on both pristine and mono-vacancy phosphorene sheets.The pristine phosphorene surface showsweak physisorption with all the gasmolecules,inducing onlyminor changes in its structural and electronic properties.However,the introduction ofmono-vacancies significantly enhances the interaction strength with NH_(3),PH_(3),CO_(2),and CH_(4).These variations are attributed to substantial charge redistribution and orbital hybridization in the presence of defects.The defective phosphorene sheet also exhibits enhanced adsorption energies,along with favorable sensitivity and recovery characteristics,highlighting its potential as a promising gas sensor for NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)at ambient conditions.
基金Project supported by the National Natural Science Foundation of China(12374181)Fundamental Research Funds for Public Universities in Liaoning(LJ212410140035,LJ212410140037,LJ212410140048)+2 种基金Shenyang Science and Technology Bureau(22-315-6-06)General Project of the Department of Education of Liaoning Province(LJKZ0084)Liaoning Province Science and Technology Plan Joint Program(Natural Science Foundation General Project,2024-MSLH-188)。
文摘Long-afterglow photocatalytic technology offers promising potential fo r all-weather pollutant treatment,yet its efficiency is often constrained by competition between afterglow emission and photocatalytic reactions.To address this,we developed a Pr^(3+)-doped Ca_(2)Al_(2)SiO_(7)(CASO)photocatalyst enriched with oxygen vacancies(V_(O)).The introduction of oxygen vacancies significantly increases trap concentration,enhancing both the intensity and du ration of the afterglow emission.A persulfate-assisted photo-Fenton system was designed based on V_(O)-CASO:Pr^(3+)enabling the self-activated degradation of tetracycline hydrochloride(TC)under ultraviolet afterglow.The photo-Fenton reaction consumes excess holes accumulated during the afterglow process,improving carrier utilization efficiency and mitigating rapid recombination.Additionally,persulfate addition can enrich reactive species and facilitate the Fe^(2+)/Fe^(3+)cycle.Benefiting from these synergistic effects,V_(O)-CASO:Pr^(3+)has achieved 75%TC degradation within1 h,significantly outperforming traditional systems.This study provides a new strategy for enhancing long-afterglow photocatalytic performance,paving the way for sustainable pollutant degradation technologies.
基金supported by the NSF of China(Nos.22579102 and 22405160)the Natural Science Foundation of Hubei Province(2024AFB288)+2 种基金the Natural Science Research Project of Yichang City(Grant A25-3-007)the 111 Project(D20015)the Key Project Foundation of Hubei Three Gorges Laboratory(SC250009)。
文摘Innovative S-scheme heterostructures face intrinsic limitations in charge separation due to insufficient interfacial driving forces.This work pioneers a dual-vacancy engineering strategy to break this bottleneck,constructing a plasmonic ZnIn_(2)S_(4-x)MoO_(3-x)(ZIS/MO)S-scheme heterojunction where oxygen and sulfur vacancies synergistically reconfigure charge transfer dynamics via dual-path modulation.Uniquely,sulfur vacancies amplify the built-in electric field(IEF)intensity by enlarging the Fermi level gap,while oxygen and sulfur dual-vacancies induce localized surface plasmon resonance(LSPR)via free-carrier concentration enhancement.Simultaneously,sulfur vacancies lower the H^(*)adsorption barrier,and dual vacancies amplify photothermal conversion by promoting nonradiative decay,accelerating temperature elevation and kinetics.Electron dynamics confirm that this dual-vacancy synergy prolongs charge carrier lifetime by a factor of 5.23.Consequently,the optimized sulfur vacancy-rich ZnIn_(2)S_(4-x)/MoO_(3-x)(R-ZIS/MO)exhibits remarkable photocatalytic hydrogen production rates of 3.60 mmol g^(-1) h^(-1)under visible light and 22.74 mmol g^(-1) h^(-1) under full-spectrum irradiation,representing 7.8-fold and17.2-fold enhancements,respectively.This study establishes a new paradigm.Targeted dual-vacancy coordination in plasmonic heterostructures enables unprecedented IEF-LSPR co-modulation,opening avenues for high-efficiency solar energy conversion.
基金support from the National Natural Science Foundation of China(Nos.12305373 and 52276220)the Guangzhou Basic Research Program(No.SL2024A04J00234).
文摘Developing efficient and durable electrocatalysts for acidic oxygen evolution reaction(OER)is pivotal for advancing proton exchange membrane water electrolysis(PEMWEs),yet balancing activity and stability remains a formidable challenge.Herein,we propose a dual-engineering strategy to stabilize Ru-based catalysts by synergizing the oxygen vacancy site-synergized mechanism-lattice oxygen mechanism(OVSM-LOM)with Ru-N bond stabilization.The engineered RuO_(2)@NCC catalyst exhibits exceptional OER performance in 0.5 M H2SO4,achieving an ultralow overpotential of 215 mV at 10 mA cm^(-2) and prolonged stability for over 327 h.The catalyst delivers 300 h of continuous operation at 1 A cm^(-2),with a negligible degradation rate of only 0.067 mV h-1,further demonstrating its potential for practical application.Oxygen vacancies unlock the OVSM-LOM pathway,bypassing the sluggish adsorbate evolution mechanism(AEM)and accelerating reaction kinetics,while the Ru-N bonds suppress Ru dissolution by anchoring low-valent Ru centers.Quasi-in situ X-ray photoelectron spectroscopy(XPS),X-ray absorption spectroscopy(XAS),and isotopic labeling experiments confirm the lattice oxygen participation with *O formation as the rate-determining step.The Ru-N bonds reinforce the structural integrity by stabilizing low-valent Ru centers and inhibiting overoxidation.Theoretical calculations further verify that the synergistic interaction between OVs and Ru-O(N)active sites optimizes the Ru d-band center and stabilizes intermediates,while Ru-N coordination enhances structural integrity.This study establishes a novel paradigm for designing robust acidic OER catalysts through defect and coordination engineering,bridging the gap between activity and stability for sustainable energy technologies.
基金supported by the Research Project on Strengthening the Construction of an Important Ecological Security Barrier in Northern China by Higher Education Institutions in the Inner Mongolia Autonomous Region(STAQZX202313)the Inner Mongolia Autonomous Region Education Science‘14th Five-Year Plan’2024 Annual Research Project(NGJGH2024635).
文摘Vacancy defects,as fundamental disruptions in metallic lattices,play an important role in shaping the mechanical and electronic properties of aluminum crystals.However,the influence of vacancy position under coupled thermomechanical fields remains insufficiently understood.In this study,transmission and scanning electron microscopy were employed to observe dislocation structures and grain boundary heterogeneities in processed aluminum alloys,suggesting stress concentrations and microstructural inhomogeneities associated with vacancy accumulation.To complement these observations,first-principles calculations and molecular dynamics simulations were conducted for seven single-vacancy configurations in face-centered cubic aluminum.The stress response,total energy,density of states(DOS),and differential charge density were examined under varying compressive strain(ε=0–0.1)and temperature(0–600 K).The results indicate that face-centered vacancies tend to reduce mechanical strength and perturb electronic states near the Fermi level,whereas corner and edge vacancies appear to have weaker effects.Elevated temperatures may partially restore electronic uniformity through thermal excitation.Overall,these findings suggest that vacancy position exerts a critical but position-dependent influence on coupled structure-property relationships,offering theoretical insights and preliminary experimental support for defect-engineered aluminum alloy design.
基金financial support from the National Natural Science Foundation of China(Nos.22308246,22478278)the Central Government Guides the Local Science and Technology Development Special Fund(No.YDZJSX20231A015)the Fundamental Research Program of Shanxi Province(No.202203021212266)。
文摘The electrocatalytic oxidation of 5-hydroxymethylfurfural(HMF)offers a promising approach for producing high-value chemicals and hydrogen.While cobalt-based oxides are promising catalysts for the HMF oxidation reaction(HMFOR),their performance is limited by inefficient oxidation of CoO_(x)to the active CoO_(2)phase.Here,we demonstrate that introducing oxygen vacancies into CoO_(x)significantly enhances its oxidation kinetics.The oxygen vacancy-rich CoO_(x)supported on copper foam(CoO_(x)/CF)achieves an impressive 98%HMF conversion with a Faradaic efficiency of 98.6%at 1.5 V vs.RHE.Operando Raman spectroscopy reveals that oxygen vacancies facilitate the preferential formation ofγ-CoOOH overβ-CoOOH during electrocatalysis,thereby promoting the generation of the active CoO_(2)phase.Combining in situ infrared spectroscopy with density functional theory(DFT)calculations,we unambiguously establish the reaction pathway,which proceeds via the sequence of HMF→5-hydroxymethyl-2-fur ancarboxylic acid(HMFCA)→2-formyl-5-furancarboxylic acid(FFCA)→2,5-furandicarboxylic acid(FDCA),and reveal the pivotal role of the active CoO_(2)species in accelerating hydroxyl radical oxidation.This work not only provides fundamental mechanistic insights into oxygen vacancy-mediated catalyst design but also offers a novel strategy for developing high-performance transition metal oxide electrocatalysts for biomass valorization.
基金supported by the “Climbing Plan” of Harbin Normal University (No.XKB202301)National Natural Science Foundation of China (Nos.21871065 and 22071038)。
文摘Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction(OER).However,the correlation among catalyst structure,magnetic property,and magnetic field enhanced-electrochemical activity remains to be fully elucidated.Herein,single-domain CoFe_(2)O_(4) catalysts with tunable oxygen vacancies(CFO-V_(O)) were synthesized to probe how V_(O) mediates magnetism and OER activity under magnetic field.The introduction of V_(O) can simultaneously modulate saturation magnetization(M_(s)) and coercivity(H_(c)),where the increased M_(s) dominates the magnetic field-enhanced OER activity.Under a 14,000 G magnetic field,the optimized CFO-V_(O) exhibits up to 16.1 % reduction in overpotential and 365 % enhancement in magnetocurrent(MC).Electrochemical analyses and post-OER characterization reveal that the magnetic field synergistically improves OER kinetics through lattice distortion induction,magnetohydrodynamic effect,and spin charge transfer effect.Importantly,the magnetic field promotes additional Co^(3+) generation to compensate for charge imbalance caused by V_(O) filling,maintaining dynamic equilibrium of V_(O) and effective reactant adsorption-conversion processes.This work unveils the synergistic mechanism of V_(O) and magnetic parameters for enhancing OER performance under the magnetic field,providing new insights into the design of high-efficiency spinregulated OER catalysts.
基金supported by the funding support from the National Key R&D Program of China(2024YFA1509400)the Beijing Natural Science Foundation(F251001)+2 种基金the National Natural Science Foundation of China(No.22479148)the Institute of Weiqiao UCAS Science and Technology(GYY-GDHX-2024-ZY-007)supported by the U.S.National Science Foundation Under Grant No.DMR 2303712。
文摘Atomic vacancies in oxides induce deviations from ideal stoichiometry,critically influencing their functional properties in applications such as energy storage-conversion,catalysis,and electronic devices.The dynamic behavior of these vacancies as main mass transport mediums to exchange chemical species with surroundings under operating conditions is central to oxide redox reactions running with the Mars-van Krevelen(MvK)mechanism;yet in-situ atomic-scale monitoring of the vacancy dynamics and vacancy-induced secondary defects within oxides remains challenging due to both their rapid transport kinetics at buried subsurface/interface and characterization difficulties,arising from the insulating nature of bulk oxides and the spatial-resolution requirement in reaction conditions.These challenges hinder precise defect engineering for the performance optimization of functional oxides.In this review,recent advancements in tracking oxygen vacancy and vacancyinduced secondary defects dynamics in oxides,including surface steps,cation vacancies,interfacial dislocations,ledges,and interfaces,have been summarized.The dynamic interconversion of defects and their synergistic effects on surface/subsurface/interface evolution are mainly discussed.The aim of this review is to enhance understanding of defect dynamics and their pivotal role in modulating structural dynamics and surface reaction reactivity,which is highly relevant to the catalyst activity/selectivity/stability evaluation of functional oxide catalysts for electroreduction and catalytic oxidation reactions.Finally,strategies to control buried subsurface and interfacial defects(interface engineering)through tailored surface reactions are proposed,offering new pathways to customize the performance of advanced oxide-based materials.
基金Financial supports from the National Natural Science Foundation of China(22479009)the National related project。
文摘Sodium-based halide solid electrolytes offer excellent electrochemical stability and favorable interfacial compatibility,yet their low ionic conductivity at room temperature limits their application in all-solidstate Na-ion batteries(ASSNIBs),Here,we develop a series of LaCl_(3)-based sodium superionic conductors engineered through cation vacancy-concentration modulation,which facilitates the formation of a threedimensional Na+transport network and increases the density of ion-hopping sites.The optimized Na_(0.4)Ta_(0.236)La_(0.472)Cl_(3)(NTLC)electrolyte achieves a Na+conductivity of 1.38×10^(-3) S/cm at 30℃,with a reduced activation energy of 0.26 eV.It also exhibits excellent mechanical deformation and moderate high-voltage stability,resulting in enhanced interfacial compatibility.When paired directly with an uncoated NaCrO_(2) cathode,the NTLC catholyte enables ASSNIBs to cycle stably over 300 cycles with89.7%capacity retention at 0.3 C and room temperature.This work underscores the potential of vacancy-rich LaCl_(3)-based sodium superionic conductors for advancing high-performance ASSNIBs.
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.
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supported by the State Key Laboratory of Solidification Processing in NWPU(SKLSP202407)the National Natural Science Foundation of China(52402130)+2 种基金the Natural Science Basis Research Plan in Shaanxi Province of China(2024JC-YBQN-0384)the Shaanxi Science and Technology Innovation Team(2023-CX-TD-44)the National Natural Science Foundation of China(52301015).
文摘Highly active and stable FeOOH cocatalysts are essential for achieving optimal performance of BiVO_(4)(BVO)photoanodes.Despite offering remarkable structural stability,widely used thick FeOOH cocatalysts often suffer from insufficient hole transport capability,which hinders the overall activity.The present study demonstrates that a simple photoetching strategy is able to introduce gradient distributed oxygen vacancies(GO_(V))in the thick FeOOH layer and significantly enhances the photogenerated holes transport dynamics.The incorporation of GO_(V)within FeOOH not only realizes the“relay transport”of photogenerated hole through the progressive upward shift of the valence band in the spatial distribution,but also provides abundant oxidation active sites by efficient hole trapping.These improvements effectively improve the oxygen evolution reaction(OER)activities and mitigate photocorrosion by the instantaneous hole extraction.Consequently,the FeOOH-GO_(V)layer enables the BVO/FeOOH-GO_(V)photoanode to achieve an impressive photocurrent density of 5.37 mA cm^(-2)and a robust operational stability up to 160 h at 1.23 VRHE,setting new benchmarks for current density and stability in FeOOH-based BVO photoanodes.This work provides an effective avenue to optimize OER cocatalysts for constructing highly efficient and stable photoelectrochemical water splitting devices.
文摘Rectifying circuit,as a crucial component for converting alternating current into direct current,plays a pivotal role in energy harvesting microsystems.Traditional silicon-based or germanium-based rectifier diodes hinder system integration due to their specific manufacturing processes.Conversely,metal oxide diodes,with their simple fabrication techniques,offer advantages for system integration.The oxygen vacancy defect of oxide semiconductor will greatly affect the electrical performance of the device,so the performance of the diode can be effectively controlled by adjusting the oxygen vacancy concentration.This study centers on optimizing the performance of diodes by modulating the oxygen vacancy concentration within InGaZnO films through control of oxygen flows during the sputtering process.Experimental results demonstrate that the diode exhibits a forward current density of 43.82 A·cm^(−2),with a rectification ratio of 6.94×10^(4),efficiently rectifying input sine signals with 1 kHz frequency and 5 V magnitude.These results demonstrate its potential in energy conversion and management.By adjusting the oxygen vacancy,a methodology is provided for optimizing the performance of rectifying diodes.
基金supported by the support of the National Natural Science Foundation of China(Nos.22072141,22176185 and 52304429)the National Key Research and Development Program of China(Nos.2022YFB3504200,2021YFB3501900)+4 种基金the Natural Science Foundation of Jiangxi Province for Distinguished Young Scholars(No.20232ACB213004)Jiangxi Provincial Key Research and Development Program(No.20232BBG70012)Jiangxi Provincial Natural Science Foundation(No.20212BAB213032)the Youth Innovation Promotion Association of Chinese Academy of Sciences(No.2018263)the Research Projects of Ganjiang Innovation Academy,Chinese Academy of Sciences(No.E355C001).
文摘Selective catalytic reduction of NO_(x) with CO(CO-SCR)is a process that purifies both NO and CO pollutants through a catalytic reaction.Specifically,the cleavage of NO on the catalyst surface is crucial for promoting the reaction.During the reaction,the presence of oxygen vacancies can extract oxygen from NO,thereby facilitating the cleavage of NO on the catalyst surface.Thus,the formation of oxygen vacancies is key to accelerating the CO-SCR reaction,with different types of oxygen vacancies being more conducive to their generation.In this study,Rh/CeCuO_(x) catalysts were synthesized using the co-crystallization and impregnation methods,and asymmetric oxygen vacancies were induced through hydrogen thermal treatment.This structuralmodification was aimed at regulating the behavior of NO on the catalyst surface.The Rh/Ce0.95Cu0.05O_(x)-H_(2) catalyst exhibited the best performance in CO-SCR,achieving above 90%NO conversion at 162℃.Various characterization techniques showed that the H_(2) treatment effectively reduced some of the CuO and Rh_(2)O_(3),creating asymmetric oxygen vacancies that accelerated the cleavage of NO on the catalyst surface,rather than forming difficult-to-decompose nitrates.This study offers a novel approach to constructing oxygen vacancies in new CO-SCR catalysts.
基金supported the Natural Science Foundation of Guangdong Province(Nos.2022A1515140085,2022A1515111022 and 2022A1515110275)the Major and Special Project in the Field of Intelligent Manufacturing of the Universities in Guangdong Province(No.2020ZDZX2067)+2 种基金the Natural Science Foundation of Huizhou University(No.HZU202004)the Professorial and Doctoral Scientific Research Foundation of Huizhou University(No.2020JB046)the Open Project Program of Guangdong Provincial Key Laboratory of Electronic Functional Materials and Devices,Huizhou University(No.EFMDN2021004M).
文摘Developing cost-effective and high-activity catalysts for the methanolysis of ammonia borane(AB)has attracted great attention in the field of hydrogen energy recently.Besides the modification of the electronic structure of the catalysts,external factors such as visible light irradiation can improve the efficiency of hydrogen production as well.In the present study,a Z-scheme heterostructured VO-Cu_(0.5)Ni_(0.5)O catalysts were constructed by introducing a plenteous phase interface and oxygen vacancy(Vo).The catalytic activity of as-prepared VO-Cu_(0.5)Ni_(0.5)O toward AB methanolysis has been improved dramatically with the assistance of visible light irradiation.The turnover frequency(TOF)under visible light irradiation was measured to be 29_(mol)H_(2)·mol_(cat.)^(-1)·min^(-1),which is 1.4 times larger than the TOF in the absence of visible light.Systematic characterization experiments and density functional theory(DFT)calculations were conducted to unveil the causation of enhanced catalytic activity.The results demonstrated that the enhancement of the catalytic activity of VO-Cu_(0.5)Ni_(0.5)O originated from the electronic structure modification induced by the formation of heterojunctions,the introduction of oxygen vacancies,and the assistance of visible light cooperatively.The formation of heterojunction and the introduction of oxygen vacancies provoked the upshift of the d-band center;while the visible light irradiation induced the photogenerated electrons to transfer from Cu to Ni sites at the interface.Such electron structure modulation is beneficial for the construction of abundant active sites,thereby enhancing the adsorption of methanol on the Ni sites,which is considered as the rate-determine step for the methanolysis of AB.The strong interaction between Ni and O weakened the O-H bond of methanol,accelerating the methanolysis of AB.These results demonstrate the utilization of combined heterojunction,oxygen vacancy,and visible light to explore highly active AB methanolysis catalysts,which should shed light on the exploration of more effective catalysts for AB methanolysis.
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.
文摘Antibiotics and heavy metals usually co-exist in wastewater and pose serious environmental hazards.Herein,a series of VMo-BMO/O_(v)-BOB S-scheme heterojunctions with double vacancy(Mo vacancy and photoexcited O vacancy)were constructed via an electrostatic assembly method.The removal efficiency of Cr(VI)and tetracycline(TC)over VMo-BMO/O_(v)-BOB-0.3 was 2.47 and 1.13 times than that of a single system,respectively.In-situ EPR demonstrated that the surface O vacancies could be generated under LED light irradiation.These photoexcited O vacancies(P-O_(v))enabled VMo-BMO/O_(v)-BOB composites still exhibit satisfactory activity after five successive cycles and an amplified Fermi level gap.The enhancement could be attributed to the enhanced internal electric field and double-vacancy-induced polarization.Additionally,the density functional theory calculation results suggested that double vacancy induced polarization electric field increases the dipole moment,which was conducive to rapid electron transport.Photoluminescence and time-resolved photoluminescence analysis demonstrated that the introduction of S-scheme heterojunction and double vacancy promoted charge transfer and prolonged the lifetime of carriers.Degradation intermediates and toxicity of products were evaluated.In conclusion,a possible mechanism based on VMo-BMO/O_(v)-BOB S-scheme heterojunction in the simultaneous removal of Cr(VI)and TC was proposed.
基金supported by the National Natural Science Foundation of China(No.22368014)Guizhou Provincial S&T Project(Nos.GCC[2023]011,ZK[2022]011)Guizhou Provincial Higher Education Institution Program(No.Qianjiaoji[2023]082).
文摘The typical wastewater treatment is focused on the photocatalytic efficiency in the degradation of organic pollutants,with little attention to the involved selectivity which may correlate with toxicant residues.Herein,an electron localization strategy for specific O2 adsorption/activation enabled by photothermal/pyroelectric effect and in situ constructed active centers of single-atom Co and oxygen vacancy(Co-O_(V))on the Co/BiOCl-O_(V)photocatalyst was developed for photocatalytic degradation of glyphosate(GLP)wastewater of high performance/selectivity.Under full-spectrum-light irradiation,a high GLP degradation rate of 99.8%with over 90%C-P bond-breaking selectivity was achieved within 2 h,while effectively circumventing toxicant residues such as aminomethylphosphonic acid(AMPA).X-ray absorption spectroscopy and relevant characterizations expounded the tailored anchoring of Co single atoms onto the BiOCl-O_(V)carrier and photothermal/pyroelectric effect.The oriented formation of more•O_(2)^(−)on Co/BiOCl-O_(V)could be achieved with the Co-O_(V)coupled center that had excellent O2 adsorption/activation capacity,as demonstrated by quantum calculations.The formed unique Co-O_(V)active sites could largely decrease the C-P bond-breaking energy barrier,thus greatly improving the selectivity toward the initial C-P bond scission and the activity in subsequent conversion steps in the directional photocatalytic degradation of GLP.The electron localization strategy by in situ constructing the coupled active centers provides an efficient scheme and new insights for the low-toxic photodegradation of organic pollutants containing C-X bonds.
基金supported by the National Natural Science Foundation of China(Grant No.12275154)the Guangdong Basic and Applied Basic Research Foundation,China(Project No.2021B1515140028)+1 种基金the Youth Innovation Promotion Association,CAS(No.2020010)the National Key Research and Development Program of China,grant number(Nos.2021YFA1600701 and 2021YFB3501201).
文摘Solid-state precipitation is an effective strategy for tuning the mechanical and functional properties of ad-vanced alloys.Structure design and modification necessitate good knowledge of the kinetic evolution of precipitates during fabrication,which is strongly correlated with defect concentration.For Fe-Ga alloys,giant magnetostriction can be induced by the precipitation of the nanoscale tetragonal L60 phase.By introducing quenched-in vacancies,we significantly enhance the magnetostriction of the aged Fe81Ga19 polycrystalline alloys to~305 ppm,which is close to the level of single crystals.Although vacancies were found to facilitate the generation of the L60 phase,their impact on the precipitation mechanism and kinetics has yet to be revealed.This study combined transmission electron microscopy(TEM)and time-resolved small-angle neutron scattering(SANS)to investigate the precipitation of the L60 phase during the isothermal aging at 350 and 400℃,respectively.The evolution of L60 nanophase in morphology and number density in as-cast(AC)and liquid nitrogen quenched(LN)Fe81Ga19 alloys with aging time were quantitatively compared.Interestingly,the nucleation of the L60 phase proceeds progressively in AC while suddenly in LN specimens,indicating the homogenous to heterogeneous mechanism switching in-duced by concentrated vacancies.Moreover,excess vacancies can change the shape of nanoprecipitates and significantly accelerate the growth and coarsening kinetics.The magnetostrictive coefficient is opti-mized when the size(long-axis)of L60 precipitates lies between 100 and 110Åwith a number density between 3.2-4.3×10-7Å-3.Insight from this study validates the feasibility of achieving high magnetoe-lastic properties through precise manipulation of the nanostructure.
