The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clu...The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.展开更多
Recently,the newly synthesized septuple-atomic layer two-dimensional(2D)material MoSi_(2)N_(4)(MSN)has attracted attention worldwide.Our work delves into the effect of vacancies and external electric fields on the ele...Recently,the newly synthesized septuple-atomic layer two-dimensional(2D)material MoSi_(2)N_(4)(MSN)has attracted attention worldwide.Our work delves into the effect of vacancies and external electric fields on the electronic properties of the MSN/graphene(Gr)heterostructure using first-principles calculation.We find that four types of defective structures,N-in,N-out,Si and Mo vacancy defects of monolayer MSN and MSN/Gr heterostructure are stable in air.Moreover,vacancy defects can effectively modulate the charge transfer at the interface of the MSN/Gr heterostructure as well as the work function of the pristine monolayer MSN and MSN/Gr heterostructure.Finally,the application of an external electric field enables the dynamic switching between n-type and p-type Schottky contacts.Our work may offer the possibility of exceeding the capabilities of conventional Schottky diodes based on MSN/Gr heterostructures.展开更多
The photocatalytic conversion of CO_(2)into solar‐powered fuels is viewed as a forward‐looking strategy to address energy scarcity and global warming.This work demonstrated the selective photoreduction of CO_(2)to C...The photocatalytic conversion of CO_(2)into solar‐powered fuels is viewed as a forward‐looking strategy to address energy scarcity and global warming.This work demonstrated the selective photoreduction of CO_(2)to CO using ultrathin Bi_(12)O_(17)Cl_(2)nanosheets decorated with hydrothermally synthesized bismuth clusters and oxygen vacancies(OVs).The characterizations revealed that the coexistences of OVs and Bi clusters generated in situ contributed to the high efficiency of CO_(2)–CO conversion(64.3μmol g^(−1)h^(−1))and perfect selectivity.The OVs on the facet(001)of the ultrathin Bi_(12)O_(17)Cl_(2)nanosheets serve as sites for CO_(2)adsorption and activation sites,capturing photoexcited electrons and prolonging light absorption due to defect states.In addition,the Bi‐cluster generated in situ offers the ability to trap holes and the surface plasmonic resonance effect.This study offers great potential for the construction of semiconductor hybrids as multiphotocatalysts,capable of being used for the elimination and conversion of CO_(2)in terms of energy and environment.展开更多
This study explores the impact of introducing vacancy in the transition metal layer of rationally designed Na_(0.6)[Ni_(0.3)Ru_(0.3)Mn_(0.4)]O_(2)(NRM)cathode material.The incorporation of Ru,Ni,and vacancy enhances t...This study explores the impact of introducing vacancy in the transition metal layer of rationally designed Na_(0.6)[Ni_(0.3)Ru_(0.3)Mn_(0.4)]O_(2)(NRM)cathode material.The incorporation of Ru,Ni,and vacancy enhances the structural stability during extensive cycling,increases the operation voltage,and induces a capacity increase while also activating oxygen redox,respectively,in Na_(0.7)[Ni_(0.2)V_(Ni0.1)Ru_(0.3)Mn_(0.4)]O_(2)(V-NRM)compound.Various analytical techniques including transmission electron microscopy,X-ray absorption near edge spectroscopy,operando X-ray diffraction,and operando differential electrochemical mass spectrometry are employed to assess changes in the average oxidation states and structural distortions.The results demonstrate that V-NRM exhibits higher capacity than NRM and maintains a moderate capacity retention of 81%after 100 cycles.Furthermore,the formation of additional lone-pair electrons in the O 2p orbital enables V-NRM to utilize more capacity from the oxygen redox validated by density functional calculation,leading to a widened dominance of the OP4 phase without releasing O_(2) gas.These findings offer valuable insights for the design of advanced high-capacity cathode materials with improved performance and sustainability in sodium-ion batteries.展开更多
The photoreduction of greenhouse gas CO_(2) using photocatalytic technologies not only benefits en-vironmental remediation but also facilitates the production of raw materials for chemicals.Howev-er,the efficiency of ...The photoreduction of greenhouse gas CO_(2) using photocatalytic technologies not only benefits en-vironmental remediation but also facilitates the production of raw materials for chemicals.Howev-er,the efficiency of CO_(2) photoreduction remains generally low due to the challenging activation of CO_(2) and the limited light absorption and separation of charge.Defect engineering of catalysts rep-resents a pivotal strategy to enhance the photocatalytic activity for CO_(2),with most research on met-al oxide catalysts focusing on the creation of anionic vacancies.The exploration of metal vacancies and their effects,however,is still underexplored.In this study,we prepared an In2O3 catalyst with indium vacancies(VIn)through defect engineering for CO_(2) photoreduction.Experimental and theo-retical calculations results demonstrate that VIn not only facilitate light absorption and charge sepa-ration in the catalyst but also enhance CO_(2) adsorption and reduce the energy barrier for the for-mation of the key intermediate*COOH during CO_(2) reduction.Through metal vacancy engineering,the activity of the catalyst was 7.4 times,reaching an outstanding rate of 841.32μmol g(-1)h^(-1).This work unveils the mechanism of metal vacancies in CO_(2) photoreduction and provides theoretical guidance for the development of novel CO_(2) photoreduction catalysts.展开更多
To attain a circular carbon economy and resolve CO_(2) electroreduction technology obstacles,single‐atom catalysts(SACs)have emerged as a logical option for electrocatalysis because of their extraordinary catalytic a...To attain a circular carbon economy and resolve CO_(2) electroreduction technology obstacles,single‐atom catalysts(SACs)have emerged as a logical option for electrocatalysis because of their extraordinary catalytic activity.Among SACs,metal–organic frameworks(MOFs)have been recognized as promising support materials because of their exceptional ability to prevent metal aggregation.This study shows that atomically dispersed Ni single atoms on a precisely engineered MOF nanosheet display a high Faradaic efficiency of approximately 100% for CO formation in H‐cell and three‐compartment microfluidic flow‐cell reactors and an excellent turnover frequency of 23,699 h^(−1),validating their intrinsic catalytic potential.These results suggest that crystallographic variations affect the abundant vacancy sites on the MOF nanosheets,which are linked to the evaporation of Zn‐containing organic linkers during pyrolysis.Furthermore,using X‐ray absorption spectroscopy and density functional theory calculations,a comprehensive investigation of the unsaturated atomic coordination environments and the underlying mechanism involving CO^(*) preadsorbed sites as initial states was possible and provided valuable insights.展开更多
In order to explore the effect of vacancy defects on the structural,electronic,magnetic and optical properties of CoS_(2) and FeS_(2),first-principles calculation method was used to investigate the alloys.The calculat...In order to explore the effect of vacancy defects on the structural,electronic,magnetic and optical properties of CoS_(2) and FeS_(2),first-principles calculation method was used to investigate the alloys.The calculated results of materials without vacancy are consistent with those reported in the literatures,while the results of materials with vacancy defect were different from those of literatures due to the difference vacancy concentration.The Co vacancy defect hardly changes the half-metallic characteristic of CoS_(2).The Fe vacancy defect changes FeS_(2) from semiconductor to half-metal,and the bottom of the spin-down conduction band changes from the p orbital state of S to the d(t_(2g))orbital state of Fe,while the top of the valence band remains the d orbital d(eg)state of Fe.The half-metallic Co vacancy defects of CoS_(2) and Fe vacancy defects of FeS_(2) are expected to be used in spintronic devices.S vacancy defects make both CoS_(2) and FeS_(2) metallic.Both the Co and S vacancy defects lead to the decrease of the magnetic moment of CoS_(2),while both the Fe and S vacancy defects lead to the obvious magnetic property of FeS_(2).Vacancy defects enhance the absorption coefficient of infrared band and long band of visible light obviously,and produce obvious red shift phenomenon,which is expected to be used in photoelectric devices.展开更多
Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme hetero...Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme heterojunction with O and Zn vacancies(VO,Zn-ZnO/ZnS)is rationally constructed via ion-exchange and calcination treatments.In such a photocatalytic system,the hollow structure combined with the introduction of dual vacancies endows the adequate light absorption.Moreover,the O and Zn vacancies serve as the trapping sites for photo-induced electrons and holes,respectively,which are beneficial for promoting the photo-induced carrier separation.Meanwhile,the S-scheme charge transfer mechanism can not only improve the separation and transfer efficiencies of photo-induced carrier but also retain the strong redox capacity.As expected,the optimized VO,Zn-ZnO/ZnS heterojunction exhibits a superior photocatalytic H_(2) production rate of 160.91 mmol g^(-1)h^(-1),approximately 643.6 times and 214.5 times with respect to that obtained on pure ZnO and ZnS,respectively.Simultaneously,the experimental results and density functional theory calculations disclose that the photo-induced carrier transfer pathway follows the S-scheme heterojunction mechanism and the introduction of O and Zn vacancies reduces the surface reaction barrier.This work provides an innovative strategy of vacancy engineering in S-scheme heterojunction for solar-to-fuel energy conversion.展开更多
Entanglement in macroscopic systems,as a fundamental quantum resource,has been utilized to propel the advancement of quantum technology and probe the boundary between the quantum and classical realms.This study focuse...Entanglement in macroscopic systems,as a fundamental quantum resource,has been utilized to propel the advancement of quantum technology and probe the boundary between the quantum and classical realms.This study focuses on a unique hybrid quantum system comprising of an ensemble of silicon vacancy(SiV)centers coupled to phononic waveguides in diamond via strain interactions.By employing two sets of time-dependent,non-overlapping driving fields,we investigate the generation process and dynamic properties of macroscopic quantum entanglement,providing fresh insights into the behavior of such hybrid quantum systems.Furthermore,it paves the way for new possibilities in utilizing quantum entanglement as an information carrier in quantum information processing and quantum communication.展开更多
Theoretical studies of the diffusionalisotope effect in solids are still stuck in the 1960s and 1970s.With the development of high spatial resolution mass spectrometers,isotopic data of mineral grains are rapidly accu...Theoretical studies of the diffusionalisotope effect in solids are still stuck in the 1960s and 1970s.With the development of high spatial resolution mass spectrometers,isotopic data of mineral grains are rapidly accumulated.To dig up information from these data,molecularlevel theoretical models are urgently needed.Based on the microscopic definition of the diffusion coe fficient(D),a new theoretical framework for calculating the diffusional isotope effect(DIE(v))(intermsofD*/D)forvacancy-mediated impurity diffusion in solids is provided based on statistical mechanics formalism.The newly derived equation shows that theDIE(v)can be easily calculated as long as the vibration frequencies of isotope-substituted solids are obtained.The calculatedDIE(v)values of^(199)Au/^(195)Au and^(60)Co/^(57)Co during diffusion in Cu and Au metals are all within 1%of errors compared to the experimental data,which shows that this theoretical model is reasonable and precise.展开更多
MgH_(2) is a promising high-capacity solid-state hydrogen storage material,while its application is greatly hindered by the high desorption temperature and sluggish kinetics.Herein,intertwined 2D oxygen vacancy-rich V...MgH_(2) is a promising high-capacity solid-state hydrogen storage material,while its application is greatly hindered by the high desorption temperature and sluggish kinetics.Herein,intertwined 2D oxygen vacancy-rich V_(2)O_(5) nanosheets(H-V_(2)O_(5))are specifically designed and used as catalysts to improve the hydrogen storage properties of MgH_(2).The as-prepared MgH_(2)-H-V_(2)O_(5) composites exhibit low desorption temperatures(Tonset=185℃)with a hydrogen capacity of 6.54 wt%,fast kinetics(Ea=84.55±1.37 kJ mol^(-1) H_(2) for desorption),and long cycling stability.Impressively,hydrogen absorption can be achieved at a temperature as low as 30℃ with a capacity of 2.38 wt%within 60 min.Moreover,the composites maintain a capacity retention rate of~99%after 100 cycles at 275℃.Experimental studies and theoretical calculations demonstrate that the in-situ formed VH_(2)/V catalysts,unique 2D structure of H-V_(2)O_(5) nanosheets,and abundant oxygen vacancies positively contribute to the improved hydrogen sorption properties.Notably,the existence of oxygen vacancies plays a double role,which could not only directly accelerate the hydrogen ab/de-sorption rate of MgH_(2),but also indirectly affect the activity of the catalytic phase VH_(2)/V,thereby further boosting the hydrogen storage performance of MgH_(2).This work highlights an oxygen vacancy excited“hydrogen pump”effect of VH_(2)/V on the hydrogen sorption of Mg/MgH_(2).The strategy developed here may pave a new way toward the development of oxygen vacancy-rich transition metal oxides catalyzed hydride systems.展开更多
With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption...With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption ability and provide extra active sites for Na+adsorption.However,their synchronous engineering is rarely reported.Herein,a hybrid of Co_(0.85)Se/WSe_(2) heterostructure with Se vacancies and N-doped carbon polyhedron(CoWSe/NCP)has been fabricated for the first time via a hydrothermal and subsequent selenization strategy.Spherical aberration-corrected transmission electron microscopy confirms the phase interface of the Co_(0.85)Se/WSe_(2) heterostructure and the existence of Se vacancies.Density functional theory simulations reveal the accelerated charge transfer and enhanced Na+adsorption ability,which are contributed by the Co_(0.85)Se/WSe_(2) heterostructure and Se vacancies,respectively.As expected,the CoWSe/NCP anode in sodium-ion battery achieves outstanding rate capability(339.6 mAh g^(−1) at 20 A g^(−1)),outperforming almost all Co/W-based selenides.展开更多
Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performan...Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performance for hydrogen evolution reaction(HER). With the VS concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS_(2)-VS 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential(68 m V) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy(ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S-H* peak of the Ni S_(2)-VS 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the Ni S_(2)-VS 5.9% has the optimal |ΔG^(H*)| of 0.17 e V. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.展开更多
Although the internal electric field(IEF)of photocatalysts is acknowledged as a potent driving force for photocharge separation,modulating the IEF intensity to achieve enhanced photocatalytic performances remains a ch...Although the internal electric field(IEF)of photocatalysts is acknowledged as a potent driving force for photocharge separation,modulating the IEF intensity to achieve enhanced photocatalytic performances remains a challenge.Herein,cuprous sulfide nanosheets with different Cu vacancy concentration were employed to study IEF modulation and corresponding direct charge transfer.Among the samples,Cu_(1.8)S nanosheets possessed intensified IEF intensity compared with those of Cu_(2)S and Cu_(1.95)S nanosheets,suggesting that an enhanced IEF intensity could be achieved by introducing more Cu vacancies.This intensified IEF of Cu_(1.8)S nanosheets induced numerous photogenerated electrons to migrate to its surface,and the dissociative electrons were then captured by Cu vacancies,resulting in efficient charge separation spatially.In addition,the Cu vacancies on Cu_(1.8)S nanosheets accumulated electrons as active sites to lower the energy barrier of rate-determining step of CO_(2)photoreduction,leading to the selective conversion of CO_(2)to CO.Herein,the manipulation of IEF intensity through Cu vacancy concentration regulation of cuprous sulfide photocatalysts for efficient charge separation has been discussed,providing a scientific strategy to rationally improve photocata lytic performances for solar energy conversion.展开更多
The artificial nitrogen(N_(2)) reduction reaction(NRR) via electrocatalysis is a newly developed methodology to produce ammonia(NH3) at ambient conditions,but faces the challenges in N_(2)activation and poor reaction ...The artificial nitrogen(N_(2)) reduction reaction(NRR) via electrocatalysis is a newly developed methodology to produce ammonia(NH3) at ambient conditions,but faces the challenges in N_(2)activation and poor reaction selectivity.Herein,Nb-based MXenes are developed to remarkably enhance the NRR activity through the engineering of the stretched 3D structure and oxygen vacancies(VO).The theoretical studies indicate that N_(2)could be initially adsorbed on VOwith an end-on configuration,and the potential determining step might be the first hydrogenation step.The catalysts achieve an NH3production rate of 29.1 μg h^(-1)mg_(cat)^(-1)and excellent Faradic efficiency of 11.5%,surpassing other Nbbased catalysts.The selectivity of NRR is assigned to the unique structure of the catalysts,including(1) the layered graphitic structure for fast electron transfer and active site distribution,(2) the reactive VOfor N_(2)adsorption and activation,and(3) the expanded interlayer space for mass transfer.展开更多
The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of...The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.展开更多
The“shuttle effect”of lithium polysulfides(LiPSs)is a huge challenge for practical use of high-energydensity lithium-sulfur(Li-S)batteries,and one of the main reasons is the sluggish kinetics of sulfur conversion.Me...The“shuttle effect”of lithium polysulfides(LiPSs)is a huge challenge for practical use of high-energydensity lithium-sulfur(Li-S)batteries,and one of the main reasons is the sluggish kinetics of sulfur conversion.Metal oxides are able to expedite the sulfur electrochemistry,and the structural defects enhance the adsorption-conversion ability of metal oxides for polysulfides.However,a significant research gap still remains regarding the relationship between the oxygen vacancy concentration and the adsorptivecatalytic performance of metal oxides.Herein,we establish a correlation between oxygen vacancy concentration and adsorptive-catalytic properties by using tungsten oxide(WO_(x))as model catalysts.It is revealed that high-concentration oxygen vacancy is beneficial for enhancing the binding between tungsten oxide and LiPSs,reducing the energy barrier of Li_(2)S decomposition,and promoting polysulfide conversion kinetics.Consequently,the Li-S batteries using the tungsten oxide with high-concentration oxygen vacancies deliver high initial discharge capacity of 1169 mA h g^(-1)at 0.2 C and 865 mA h g^(-1)at 2 C,low attenuation rate of 0.064%per cycle over 1100 cycles at 2 C.With a high sulfur area loading of 5.34 mg cm^(-2),the Li-S batteries still exhibit high initial gravimetric capacity of 982 mA h g^(-1)at 0.1 C and areal capacity of 5.92 mA h cm^(-2).This work promotes the feasibility of defect engineering on metal oxides as an effective mean to enhance the practicality of Li-S batteries.展开更多
The defect chemistry is successfully modulated on free-standing and binder-free carbon cathodes for highly efficient Li-S redox reactions.Such rationally regulated defect engineering realizes the synchronization of io...The defect chemistry is successfully modulated on free-standing and binder-free carbon cathodes for highly efficient Li-S redox reactions.Such rationally regulated defect engineering realizes the synchronization of ion/electron-conductive and defect-rich networks on the threedimension carbon cathode,leading to its tunable activity for both relieving the shuttle phenomenon and accelerating the sulfur redox reaction kinetics.As expected,the defective carbon cathode harvests a high rate capacity of 1217.8 mAh g^(-1)at 0.2 C and a superior capacity retention of61.7%at 2 C after 500 cycles.Even under the sulfur mass loading of 11.1 mg cm^(-2),the defective cathode still holds a remarkable areal capacity of 8.5 mAh cm^(-2).展开更多
The development of highly efficient OER catalysts with superior durability for seawater electrolysis and Zn-air battery is important but challenging.Herein,the vacancy-modified heterostructured bimetallic Fe Mo S_(x)/...The development of highly efficient OER catalysts with superior durability for seawater electrolysis and Zn-air battery is important but challenging.Herein,the vacancy-modified heterostructured bimetallic Fe Mo S_(x)/Co Ni P_(x)OER electrocatalyst is exploited.Benefiting from the electron redistribution and reaction kinetics modulation resulting from vacancy introduction and heterojunction formation,it yields ultralow OER overpotentials of 196,276,303 m V in 1 M KOH and 197,318,348 m V in 1 M KOH+seawater at 10,500,1000 m A cm^(-2),respectively,surviving 600 h at 800 m A cm^(-2)without obvious decay.Further,FeMoS_(x)/CoNiP_(x)-based Zn-air battery not only affords the high peak power density of 214.5 m W cm^(-2)but also exhibits the small voltage gap of 0.698 V and long lifetime of 500 h at 10 m A cm^(-2),overmatching overwhelming majority of reported advanced catalysts.It is revealed experimentally that the OER process on rationally designed Fe Mo S_(x)/Co Ni P_(x)follows the adsorbate evolution mechanism and the ratedetermining step shifts from^(*)OOH formation in individual building blocks to^(*)OOH deprotonation process in FeMoS_(x)/CoNiP_(x),providing the directly proof of how the vacancy introduction and heterojunction formation affect the reaction kinetics.展开更多
Instead of the energy-intensive Haber-Bosch process,the researchers proposed a way to produce ammonia using water and nitrogen as feedstock,powered by electricity,without polluting the environment.Nevertheless,how to ...Instead of the energy-intensive Haber-Bosch process,the researchers proposed a way to produce ammonia using water and nitrogen as feedstock,powered by electricity,without polluting the environment.Nevertheless,how to design efficient electrocatalyst for electrocatalytic nitrogen reduction reaction(NRR)is still urgent and challenging.Herein,a strategy is proposed to adjust the morphology and surface electronic structure of electrocatalyst by optimizing material synthesis method.LiNbO3(lithium niobate,LN)cubes with oxygen-rich vacancy and regular morphology were synthesized by hydrothermal synthesis and followed molten salt calcination process,which were used for electrocatalytic NRR under mild conditions.Compared with LN nanoparticles synthesized by solid phase reaction,LN cubes exhibit better NRR performance,with the highest ammonia yield rate(13.74μg.h^(-1).mg^(-1))at the best potential of-0.45V(vs.reversible hydrogen electrode,RHE)and the best Faradaic efficiency(85.43%)at-0.4 V.Moreover,LN cubes electrocatalyst also demonstrates high stability in 7 cycles and 18 h current-time tests.Further investigation of the reaction mechanism confirmed that the structure of oxygen vacancy could adjust the electronic structure of the electrocatalyst,which was conducive to the adsorption and activation of N_(2) molecule and also increased the ECSA of electrocatalyst,thus providing more active sites for the NRR process.展开更多
基金supported by the National Natural Science Foundation of China(22205209,52202373 and U21A200972)China Postdoctoral Science Foundation(2022M722867)Key Research Project of Higher Education Institutions in Henan Province(23A530001)。
文摘The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.
基金Project supported by the Industry and Education Combination Innovation Platform of Intelligent Manufacturing and Graduate Joint Training Base at Guizhou University(Grant No.2020-520000-83-01-324061)the National Natural Science Foundation of China(Grant No.61264004)the High-level Creative Talent Training Program in Guizhou Province of China(Grant No.[2015]4015).
文摘Recently,the newly synthesized septuple-atomic layer two-dimensional(2D)material MoSi_(2)N_(4)(MSN)has attracted attention worldwide.Our work delves into the effect of vacancies and external electric fields on the electronic properties of the MSN/graphene(Gr)heterostructure using first-principles calculation.We find that four types of defective structures,N-in,N-out,Si and Mo vacancy defects of monolayer MSN and MSN/Gr heterostructure are stable in air.Moreover,vacancy defects can effectively modulate the charge transfer at the interface of the MSN/Gr heterostructure as well as the work function of the pristine monolayer MSN and MSN/Gr heterostructure.Finally,the application of an external electric field enables the dynamic switching between n-type and p-type Schottky contacts.Our work may offer the possibility of exceeding the capabilities of conventional Schottky diodes based on MSN/Gr heterostructures.
基金Natural Science Foundation of Shandong Province,Grant/Award Number:ZR2022MB106national training program of innovation and entrepreneurship for undergraduates,Grant/Award Number:202210424099National Natural Science Foundation of China,Grant/Award Numbers:21601067,21701057,21905147。
文摘The photocatalytic conversion of CO_(2)into solar‐powered fuels is viewed as a forward‐looking strategy to address energy scarcity and global warming.This work demonstrated the selective photoreduction of CO_(2)to CO using ultrathin Bi_(12)O_(17)Cl_(2)nanosheets decorated with hydrothermally synthesized bismuth clusters and oxygen vacancies(OVs).The characterizations revealed that the coexistences of OVs and Bi clusters generated in situ contributed to the high efficiency of CO_(2)–CO conversion(64.3μmol g^(−1)h^(−1))and perfect selectivity.The OVs on the facet(001)of the ultrathin Bi_(12)O_(17)Cl_(2)nanosheets serve as sites for CO_(2)adsorption and activation sites,capturing photoexcited electrons and prolonging light absorption due to defect states.In addition,the Bi‐cluster generated in situ offers the ability to trap holes and the surface plasmonic resonance effect.This study offers great potential for the construction of semiconductor hybrids as multiphotocatalysts,capable of being used for the elimination and conversion of CO_(2)in terms of energy and environment.
基金supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education,Science and Technology(NRF-2020R1A6A1A03043435,NRF-2023R1A2C2003210,and NRF-2022M3H4A1A04096478)by Technology Innovation Program(Alchemist Project,20012196,Al based supercritical materials discovery)funded by the Ministry of Trade,Industry&Energy,Korea.support from the“Bundesministerium fur Bildung und Forschung”(BMBF)and the computing time granted through JARA-HPC on the supercomputer JURECA at Forschungszentrum Julich.
文摘This study explores the impact of introducing vacancy in the transition metal layer of rationally designed Na_(0.6)[Ni_(0.3)Ru_(0.3)Mn_(0.4)]O_(2)(NRM)cathode material.The incorporation of Ru,Ni,and vacancy enhances the structural stability during extensive cycling,increases the operation voltage,and induces a capacity increase while also activating oxygen redox,respectively,in Na_(0.7)[Ni_(0.2)V_(Ni0.1)Ru_(0.3)Mn_(0.4)]O_(2)(V-NRM)compound.Various analytical techniques including transmission electron microscopy,X-ray absorption near edge spectroscopy,operando X-ray diffraction,and operando differential electrochemical mass spectrometry are employed to assess changes in the average oxidation states and structural distortions.The results demonstrate that V-NRM exhibits higher capacity than NRM and maintains a moderate capacity retention of 81%after 100 cycles.Furthermore,the formation of additional lone-pair electrons in the O 2p orbital enables V-NRM to utilize more capacity from the oxygen redox validated by density functional calculation,leading to a widened dominance of the OP4 phase without releasing O_(2) gas.These findings offer valuable insights for the design of advanced high-capacity cathode materials with improved performance and sustainability in sodium-ion batteries.
文摘The photoreduction of greenhouse gas CO_(2) using photocatalytic technologies not only benefits en-vironmental remediation but also facilitates the production of raw materials for chemicals.Howev-er,the efficiency of CO_(2) photoreduction remains generally low due to the challenging activation of CO_(2) and the limited light absorption and separation of charge.Defect engineering of catalysts rep-resents a pivotal strategy to enhance the photocatalytic activity for CO_(2),with most research on met-al oxide catalysts focusing on the creation of anionic vacancies.The exploration of metal vacancies and their effects,however,is still underexplored.In this study,we prepared an In2O3 catalyst with indium vacancies(VIn)through defect engineering for CO_(2) photoreduction.Experimental and theo-retical calculations results demonstrate that VIn not only facilitate light absorption and charge sepa-ration in the catalyst but also enhance CO_(2) adsorption and reduce the energy barrier for the for-mation of the key intermediate*COOH during CO_(2) reduction.Through metal vacancy engineering,the activity of the catalyst was 7.4 times,reaching an outstanding rate of 841.32μmol g(-1)h^(-1).This work unveils the mechanism of metal vacancies in CO_(2) photoreduction and provides theoretical guidance for the development of novel CO_(2) photoreduction catalysts.
基金National Research Foundation of Korea(NRF),Grant/Award Numbers:2021R1A4A3027878,RS‐2023‐00209139,2015M3D3A1A01064929Korea Institute of Energy Technology&Energy(MOTIE)of the Republic of Korea,Grant/Award Number:20212010100040。
文摘To attain a circular carbon economy and resolve CO_(2) electroreduction technology obstacles,single‐atom catalysts(SACs)have emerged as a logical option for electrocatalysis because of their extraordinary catalytic activity.Among SACs,metal–organic frameworks(MOFs)have been recognized as promising support materials because of their exceptional ability to prevent metal aggregation.This study shows that atomically dispersed Ni single atoms on a precisely engineered MOF nanosheet display a high Faradaic efficiency of approximately 100% for CO formation in H‐cell and three‐compartment microfluidic flow‐cell reactors and an excellent turnover frequency of 23,699 h^(−1),validating their intrinsic catalytic potential.These results suggest that crystallographic variations affect the abundant vacancy sites on the MOF nanosheets,which are linked to the evaporation of Zn‐containing organic linkers during pyrolysis.Furthermore,using X‐ray absorption spectroscopy and density functional theory calculations,a comprehensive investigation of the unsaturated atomic coordination environments and the underlying mechanism involving CO^(*) preadsorbed sites as initial states was possible and provided valuable insights.
基金Funded by the Scientific and Technologial Innovation Programs of Higher Education Institutions in Shanxi (No. 2020L0628)the Taiyuan Institute of Technology Scientific Research Initial Funding (No. 2022KJ072)+2 种基金the Program for the (Reserved) Discipline Leaders of Taiyuan Institute of Technologythe Fundamental Research Funds for the Central Universities (Nos. 2017TS004, 2017TS006, and GK201704005)Supported by HZWTECH for providing computational facilities
文摘In order to explore the effect of vacancy defects on the structural,electronic,magnetic and optical properties of CoS_(2) and FeS_(2),first-principles calculation method was used to investigate the alloys.The calculated results of materials without vacancy are consistent with those reported in the literatures,while the results of materials with vacancy defect were different from those of literatures due to the difference vacancy concentration.The Co vacancy defect hardly changes the half-metallic characteristic of CoS_(2).The Fe vacancy defect changes FeS_(2) from semiconductor to half-metal,and the bottom of the spin-down conduction band changes from the p orbital state of S to the d(t_(2g))orbital state of Fe,while the top of the valence band remains the d orbital d(eg)state of Fe.The half-metallic Co vacancy defects of CoS_(2) and Fe vacancy defects of FeS_(2) are expected to be used in spintronic devices.S vacancy defects make both CoS_(2) and FeS_(2) metallic.Both the Co and S vacancy defects lead to the decrease of the magnetic moment of CoS_(2),while both the Fe and S vacancy defects lead to the obvious magnetic property of FeS_(2).Vacancy defects enhance the absorption coefficient of infrared band and long band of visible light obviously,and produce obvious red shift phenomenon,which is expected to be used in photoelectric devices.
文摘Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme heterojunction with O and Zn vacancies(VO,Zn-ZnO/ZnS)is rationally constructed via ion-exchange and calcination treatments.In such a photocatalytic system,the hollow structure combined with the introduction of dual vacancies endows the adequate light absorption.Moreover,the O and Zn vacancies serve as the trapping sites for photo-induced electrons and holes,respectively,which are beneficial for promoting the photo-induced carrier separation.Meanwhile,the S-scheme charge transfer mechanism can not only improve the separation and transfer efficiencies of photo-induced carrier but also retain the strong redox capacity.As expected,the optimized VO,Zn-ZnO/ZnS heterojunction exhibits a superior photocatalytic H_(2) production rate of 160.91 mmol g^(-1)h^(-1),approximately 643.6 times and 214.5 times with respect to that obtained on pure ZnO and ZnS,respectively.Simultaneously,the experimental results and density functional theory calculations disclose that the photo-induced carrier transfer pathway follows the S-scheme heterojunction mechanism and the introduction of O and Zn vacancies reduces the surface reaction barrier.This work provides an innovative strategy of vacancy engineering in S-scheme heterojunction for solar-to-fuel energy conversion.
基金the National Natural Science Foundationof China (Grant No. 12265022)the Natural ScienceFoundation of Inner Mongolia Autonomous Region, China(Grant No. 2021MS01012)the Inner Mongolia FundamentalResearch Funds for the Directly Affiliated Universities(Grant No. 2023RCTD014).
文摘Entanglement in macroscopic systems,as a fundamental quantum resource,has been utilized to propel the advancement of quantum technology and probe the boundary between the quantum and classical realms.This study focuses on a unique hybrid quantum system comprising of an ensemble of silicon vacancy(SiV)centers coupled to phononic waveguides in diamond via strain interactions.By employing two sets of time-dependent,non-overlapping driving fields,we investigate the generation process and dynamic properties of macroscopic quantum entanglement,providing fresh insights into the behavior of such hybrid quantum systems.Furthermore,it paves the way for new possibilities in utilizing quantum entanglement as an information carrier in quantum information processing and quantum communication.
基金suppor ted by Chinese NSF projects(42173021,41873024,42130114)the strategic priority research program(B)of CAS(XDB41000000)+1 种基金the preresearch Project on Civil Aerospace Technologies No.D020202 funded by the Chinese National Space Administration(CNSA)Guizhou Provincial 2021 Science and Technology Subsidies(No.GZ2021SIG)。
文摘Theoretical studies of the diffusionalisotope effect in solids are still stuck in the 1960s and 1970s.With the development of high spatial resolution mass spectrometers,isotopic data of mineral grains are rapidly accumulated.To dig up information from these data,molecularlevel theoretical models are urgently needed.Based on the microscopic definition of the diffusion coe fficient(D),a new theoretical framework for calculating the diffusional isotope effect(DIE(v))(intermsofD*/D)forvacancy-mediated impurity diffusion in solids is provided based on statistical mechanics formalism.The newly derived equation shows that theDIE(v)can be easily calculated as long as the vibration frequencies of isotope-substituted solids are obtained.The calculatedDIE(v)values of^(199)Au/^(195)Au and^(60)Co/^(57)Co during diffusion in Cu and Au metals are all within 1%of errors compared to the experimental data,which shows that this theoretical model is reasonable and precise.
基金the support from the National Key Research&Development Program(2022YFB3803700)of ChinaNational Natural Science Foundation(No.52171186)the financial support from the Center of Hydrogen Science,Shanghai Jiao Tong University。
文摘MgH_(2) is a promising high-capacity solid-state hydrogen storage material,while its application is greatly hindered by the high desorption temperature and sluggish kinetics.Herein,intertwined 2D oxygen vacancy-rich V_(2)O_(5) nanosheets(H-V_(2)O_(5))are specifically designed and used as catalysts to improve the hydrogen storage properties of MgH_(2).The as-prepared MgH_(2)-H-V_(2)O_(5) composites exhibit low desorption temperatures(Tonset=185℃)with a hydrogen capacity of 6.54 wt%,fast kinetics(Ea=84.55±1.37 kJ mol^(-1) H_(2) for desorption),and long cycling stability.Impressively,hydrogen absorption can be achieved at a temperature as low as 30℃ with a capacity of 2.38 wt%within 60 min.Moreover,the composites maintain a capacity retention rate of~99%after 100 cycles at 275℃.Experimental studies and theoretical calculations demonstrate that the in-situ formed VH_(2)/V catalysts,unique 2D structure of H-V_(2)O_(5) nanosheets,and abundant oxygen vacancies positively contribute to the improved hydrogen sorption properties.Notably,the existence of oxygen vacancies plays a double role,which could not only directly accelerate the hydrogen ab/de-sorption rate of MgH_(2),but also indirectly affect the activity of the catalytic phase VH_(2)/V,thereby further boosting the hydrogen storage performance of MgH_(2).This work highlights an oxygen vacancy excited“hydrogen pump”effect of VH_(2)/V on the hydrogen sorption of Mg/MgH_(2).The strategy developed here may pave a new way toward the development of oxygen vacancy-rich transition metal oxides catalyzed hydride systems.
基金support from the Natural Science Foundation of Jilin Province(Grant No.20200201073JC)the National Natural Science Foundation of China(Grant No.52130101)+1 种基金Interdisciplinary Integration and Innovation Project of JLU(Grant No.JLUXKJC2021ZY01)the Fundamental Research Funds for the Central Universities.
文摘With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption ability and provide extra active sites for Na+adsorption.However,their synchronous engineering is rarely reported.Herein,a hybrid of Co_(0.85)Se/WSe_(2) heterostructure with Se vacancies and N-doped carbon polyhedron(CoWSe/NCP)has been fabricated for the first time via a hydrothermal and subsequent selenization strategy.Spherical aberration-corrected transmission electron microscopy confirms the phase interface of the Co_(0.85)Se/WSe_(2) heterostructure and the existence of Se vacancies.Density functional theory simulations reveal the accelerated charge transfer and enhanced Na+adsorption ability,which are contributed by the Co_(0.85)Se/WSe_(2) heterostructure and Se vacancies,respectively.As expected,the CoWSe/NCP anode in sodium-ion battery achieves outstanding rate capability(339.6 mAh g^(−1) at 20 A g^(−1)),outperforming almost all Co/W-based selenides.
基金funded by the National Natural Science Foundation of China (NSFC) (Nos. 22221001, 22201115, 21931001, and 21922105)the Special Fund Project of Guiding Scientific and Technological Innovation Development of Gansu Province (2019ZX–04)+3 种基金the 111 Project (B20027)by the Fundamental Research Funds for the Central Universities (lzujbky-2023-eyt03)support Natural Science Foundation of Gansu Providence (22JR5RA540)Gansu Province Youth Science and Technology Talent Promotion Project (GXH202220530-02)。
文摘Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performance for hydrogen evolution reaction(HER). With the VS concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS_(2)-VS 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential(68 m V) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy(ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S-H* peak of the Ni S_(2)-VS 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the Ni S_(2)-VS 5.9% has the optimal |ΔG^(H*)| of 0.17 e V. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.
基金supported by the National Natural Science Foundation of China(52200123)the Open Project of Key Laboratory of Green Chemical Engineering Process of Ministry of Education(GCP2022007)the Scientific Research and Innovation Team Program of Sichuan University of Science and Engineering(SUSE652A014)。
文摘Although the internal electric field(IEF)of photocatalysts is acknowledged as a potent driving force for photocharge separation,modulating the IEF intensity to achieve enhanced photocatalytic performances remains a challenge.Herein,cuprous sulfide nanosheets with different Cu vacancy concentration were employed to study IEF modulation and corresponding direct charge transfer.Among the samples,Cu_(1.8)S nanosheets possessed intensified IEF intensity compared with those of Cu_(2)S and Cu_(1.95)S nanosheets,suggesting that an enhanced IEF intensity could be achieved by introducing more Cu vacancies.This intensified IEF of Cu_(1.8)S nanosheets induced numerous photogenerated electrons to migrate to its surface,and the dissociative electrons were then captured by Cu vacancies,resulting in efficient charge separation spatially.In addition,the Cu vacancies on Cu_(1.8)S nanosheets accumulated electrons as active sites to lower the energy barrier of rate-determining step of CO_(2)photoreduction,leading to the selective conversion of CO_(2)to CO.Herein,the manipulation of IEF intensity through Cu vacancy concentration regulation of cuprous sulfide photocatalysts for efficient charge separation has been discussed,providing a scientific strategy to rationally improve photocata lytic performances for solar energy conversion.
基金financially supported by China Postdoctoral Science Foundation (2019M652305)Qingdao Postdoctoral Application Research Project。
文摘The artificial nitrogen(N_(2)) reduction reaction(NRR) via electrocatalysis is a newly developed methodology to produce ammonia(NH3) at ambient conditions,but faces the challenges in N_(2)activation and poor reaction selectivity.Herein,Nb-based MXenes are developed to remarkably enhance the NRR activity through the engineering of the stretched 3D structure and oxygen vacancies(VO).The theoretical studies indicate that N_(2)could be initially adsorbed on VOwith an end-on configuration,and the potential determining step might be the first hydrogenation step.The catalysts achieve an NH3production rate of 29.1 μg h^(-1)mg_(cat)^(-1)and excellent Faradic efficiency of 11.5%,surpassing other Nbbased catalysts.The selectivity of NRR is assigned to the unique structure of the catalysts,including(1) the layered graphitic structure for fast electron transfer and active site distribution,(2) the reactive VOfor N_(2)adsorption and activation,and(3) the expanded interlayer space for mass transfer.
基金the National Natural Science Foundation of China (92034301,22078063 and 22022804)Major Program of Qingyuan Innovation Laboratory (00121003)the Natural Science Foundation of Fujian Province (2020H6007)。
文摘The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.
基金financially supported by National Natural Science Foundation of China(Grant Nos.51972070 and 52062004)Guizhou Provincial High Level Innovative Talents Project(Grant No.QKHPTRC-GCC[2022]013-1)+2 种基金Innovation Team for Advanced Electrochemical Energy Storage Devices and Key Materials of Guizhou Provincial Higher Education Institutions(Grant No.QianJiaoJi[2023]054)Guizhou Provincial Science and Technology Projects(Grant No.QKHJC[2020]1Z042)Cultivation Project of Guizhou University(Grant No.GDPY[2019]01)。
文摘The“shuttle effect”of lithium polysulfides(LiPSs)is a huge challenge for practical use of high-energydensity lithium-sulfur(Li-S)batteries,and one of the main reasons is the sluggish kinetics of sulfur conversion.Metal oxides are able to expedite the sulfur electrochemistry,and the structural defects enhance the adsorption-conversion ability of metal oxides for polysulfides.However,a significant research gap still remains regarding the relationship between the oxygen vacancy concentration and the adsorptivecatalytic performance of metal oxides.Herein,we establish a correlation between oxygen vacancy concentration and adsorptive-catalytic properties by using tungsten oxide(WO_(x))as model catalysts.It is revealed that high-concentration oxygen vacancy is beneficial for enhancing the binding between tungsten oxide and LiPSs,reducing the energy barrier of Li_(2)S decomposition,and promoting polysulfide conversion kinetics.Consequently,the Li-S batteries using the tungsten oxide with high-concentration oxygen vacancies deliver high initial discharge capacity of 1169 mA h g^(-1)at 0.2 C and 865 mA h g^(-1)at 2 C,low attenuation rate of 0.064%per cycle over 1100 cycles at 2 C.With a high sulfur area loading of 5.34 mg cm^(-2),the Li-S batteries still exhibit high initial gravimetric capacity of 982 mA h g^(-1)at 0.1 C and areal capacity of 5.92 mA h cm^(-2).This work promotes the feasibility of defect engineering on metal oxides as an effective mean to enhance the practicality of Li-S batteries.
基金supported by the National Natural Science Foundation of China(52172239)Project of State Key Laboratory of Environment-Friendly Energy Materials+2 种基金Southwest University of Science and Technology(Grant Nos.21fksy24 and 18ZD320304)Chongqing Talents:Exceptional Young Talents Project(Grant No.CQYC201905041)Natural Science Foundation of Chongqing China(Grant No.cstc2021jcyj-jqX0031)。
文摘The defect chemistry is successfully modulated on free-standing and binder-free carbon cathodes for highly efficient Li-S redox reactions.Such rationally regulated defect engineering realizes the synchronization of ion/electron-conductive and defect-rich networks on the threedimension carbon cathode,leading to its tunable activity for both relieving the shuttle phenomenon and accelerating the sulfur redox reaction kinetics.As expected,the defective carbon cathode harvests a high rate capacity of 1217.8 mAh g^(-1)at 0.2 C and a superior capacity retention of61.7%at 2 C after 500 cycles.Even under the sulfur mass loading of 11.1 mg cm^(-2),the defective cathode still holds a remarkable areal capacity of 8.5 mAh cm^(-2).
基金supported by the National Natural Science Foundation of China (21975136,22102076)the Fundamental Research Funds for the Central Universities (63185015)+2 种基金the Shenzhen Science,Technology and Innovation Committee (JCYJ20190808151603654,JCYJ20210324121002007)the Open Funds from National Engineering Lab for Mobile Source Emission Control Technology (NELMS2020A12)the Open Fund for Key Laboratory of Civil Aviation Thermal Hazards Prevention and Emergency Response (RZH2021-KF-03)。
文摘The development of highly efficient OER catalysts with superior durability for seawater electrolysis and Zn-air battery is important but challenging.Herein,the vacancy-modified heterostructured bimetallic Fe Mo S_(x)/Co Ni P_(x)OER electrocatalyst is exploited.Benefiting from the electron redistribution and reaction kinetics modulation resulting from vacancy introduction and heterojunction formation,it yields ultralow OER overpotentials of 196,276,303 m V in 1 M KOH and 197,318,348 m V in 1 M KOH+seawater at 10,500,1000 m A cm^(-2),respectively,surviving 600 h at 800 m A cm^(-2)without obvious decay.Further,FeMoS_(x)/CoNiP_(x)-based Zn-air battery not only affords the high peak power density of 214.5 m W cm^(-2)but also exhibits the small voltage gap of 0.698 V and long lifetime of 500 h at 10 m A cm^(-2),overmatching overwhelming majority of reported advanced catalysts.It is revealed experimentally that the OER process on rationally designed Fe Mo S_(x)/Co Ni P_(x)follows the adsorbate evolution mechanism and the ratedetermining step shifts from^(*)OOH formation in individual building blocks to^(*)OOH deprotonation process in FeMoS_(x)/CoNiP_(x),providing the directly proof of how the vacancy introduction and heterojunction formation affect the reaction kinetics.
基金the financial support from the National Natural Science Foundation of China(22075196,21878204)Key Research and Development Program of Shanxi Province(International Cooperation,201903D421073)Research Project Supported by Shanxi Scholarship Council of China(2022-050).
文摘Instead of the energy-intensive Haber-Bosch process,the researchers proposed a way to produce ammonia using water and nitrogen as feedstock,powered by electricity,without polluting the environment.Nevertheless,how to design efficient electrocatalyst for electrocatalytic nitrogen reduction reaction(NRR)is still urgent and challenging.Herein,a strategy is proposed to adjust the morphology and surface electronic structure of electrocatalyst by optimizing material synthesis method.LiNbO3(lithium niobate,LN)cubes with oxygen-rich vacancy and regular morphology were synthesized by hydrothermal synthesis and followed molten salt calcination process,which were used for electrocatalytic NRR under mild conditions.Compared with LN nanoparticles synthesized by solid phase reaction,LN cubes exhibit better NRR performance,with the highest ammonia yield rate(13.74μg.h^(-1).mg^(-1))at the best potential of-0.45V(vs.reversible hydrogen electrode,RHE)and the best Faradaic efficiency(85.43%)at-0.4 V.Moreover,LN cubes electrocatalyst also demonstrates high stability in 7 cycles and 18 h current-time tests.Further investigation of the reaction mechanism confirmed that the structure of oxygen vacancy could adjust the electronic structure of the electrocatalyst,which was conducive to the adsorption and activation of N_(2) molecule and also increased the ECSA of electrocatalyst,thus providing more active sites for the NRR process.
