The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly unders...The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly understood due to challenges in atomic-level structural characterizations and analysis of reaction intermediates.In this study,we prepared two Zn-Al spinel oxide catalysts via coprecipitation(ZnAl-C)and hydrothermal(ZnAl-H)methods,and conducted a comparative investigation in the CO_(2)hydrogenation reaction.Surprisingly,under similar conditions,ZnAl-C exhibited significantly higher selectivity towards methanol and DME compared to ZnAl-H.Comprehensive characterizations using X-ray diffraction(XRD),Raman spectroscopy and electron paramagnetic resonance(EPR)unveiled that ZnAl-C catalyst had abundant ZnO species on its surface,and the interaction between the ZnO species and its ZnAl spinel oxide matrix led to the formation of oxygen vacancies,which are crucial for CO_(2)adsorption and activation.Additionally,state-of-the-art solid-state nuclear magnetic resonance(NMR)techniques,including ex-situ and in-situ NMR analyses,confirmed that the surface ZnO facilitates the formation of unique highly reactive interfacial formate species,which was readily hydrogenated to methanol and DME.These insights elucidate the promotion effects of ZnO on the ZnAl spinel oxide in regulating active sites and reactive intermediates for CO_(2)-to-methanol hydrogenation reaction,which is further evidenced by the significant enhancement in methanol and DME selectivity observed upon loading ZnO onto the ZnAl-H catalyst.These molecular-level mechanism understandings reinforce the idea of optimizing the ZnO-ZnAl interface through tailored synthesis methods to achieve activity-selectivity balance.展开更多
The rapid industrial growth and increasing population have led to significant pollution and deterioration of the natural atmospheric environment.Major atmospheric pollutants include NO_(2)and CO_(2).Hence,it is impera...The rapid industrial growth and increasing population have led to significant pollution and deterioration of the natural atmospheric environment.Major atmospheric pollutants include NO_(2)and CO_(2).Hence,it is imperative to develop NO_(2)and CO_(2)sensors for ambient conditions,that can be used in indoor air quality monitoring,breath analysis,food spoilage detection,etc.In the present study,two thin film nanocomposite(nickel oxide-graphene and nickel oxide-silver nanowires)gas sensors are fabricated using direct ink writing.The nano-composites are investigated for their structural,optical,and electrical properties.Later the nano-composite is deposited on the interdigitated electrode(IDE)pattern to form NO_(2)and CO_(2)sensors.The deposited films are then exposed to NO_(2)and CO_(2)gases separately and their response and recovery times are determined using a custom-built gas sensing setup.Nickel oxide-graphene provides a good response time and recovery time of 10 and 9 s,respectively for NO_(2),due to the higher electron affinity of graphene towards NO_(2).Nickel oxide-silver nanowire nano-composite is suited for CO_(2)gas because silver is an excellent electrocatalyst for CO_(2)by giving response and recovery times of 11 s each.This is the first report showcasing NiO nano-composites for NO_(2)and CO_(2)sensing at room temperature.展开更多
The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the ...The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the long-cycling stability of batteries needs to be improved.Herein,the Mn-based Li-rich cathode materials with small amounts of Li2 MnO3 crystal domains and gradient doping of Al and Ti elements from the surface to the bulk have been developed to improve the structure and interface stability.Then the batteries with a high energy density of 600 Wh kg^(-1),excellent capacity retention of 99.7%with low voltage decay of 0.03 mV cycle^(-1) after 800 cycles,and good rates performances can be achieved.Therefore,the structure and cycling stability of low voltage Mn-based Li-rich cathode materials can be significantly improved by the bulk structure design and interface regulation,and this work has paved the way for developing low-cost and high-energy Mn-based energy storage batteries with long lifetime.展开更多
Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+d...Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.展开更多
Broadband transparent films play a pivotal role in various applications such as lenses and solar cells,particularly porous structured transparent films exhibit significant potential.This study investigates a porous Si...Broadband transparent films play a pivotal role in various applications such as lenses and solar cells,particularly porous structured transparent films exhibit significant potential.This study investigates a porous SiO_(2) refractive index gradient anti-reflective film prepared by atomic layer deposition(ALD).A porous SiO_(2) film with gradual porosity was obtained by phosphoric acid etching of Al_(2)O_(3)/SiO_(2) multilayers with gradient Al2O3 ratios,achieving a gradual decrease in refractive index from the substrate to the surface.The film exhibited an average transmittance as high as 97.8%within the wavelength range from 320 nm to 1200 nm.The environmental adaptability was further enhanced by surface modification using rare earth oxide(REO)La_(2)O_(3),resulting in formation of a lotus leaf-like structure and achieving a water contact angle of 100.0°.These data proved that the modification significantly improved hydrophobic self-cleaning capability while maintaining exceptional transparency of the film.The surface structure of the modified film remained undamaged even after undergoing wipe testing,demonstrating its excellent surface durability.展开更多
Optical polarizers,which allow the transmission of specific polarization states,are essential components in modern optical systems.Here,we experimentally demonstrate integrated photonic polarizers incorporating reduce...Optical polarizers,which allow the transmission of specific polarization states,are essential components in modern optical systems.Here,we experimentally demonstrate integrated photonic polarizers incorporating reduced graphene oxide(rGO)films.2D graphene oxide(GO)films are integrated onto silicon waveguides and microring resonators(MRRs)with precise control over their thicknesses and sizes,followed by GO reduction via two different methods including uniform thermal reduction and localized photothermal reduction.We measure devices with various lengths,thicknesses,and reduction degrees of GO films.The results show that the devices with rGO exhibit better performance than those with GO,achieving a polarization-dependent loss of~47 dB and a polarization extinction ratio of~16 dB for the hybrid waveguides and MRRs with rGO,respectively.By fitting the experimental results with theory,it is found that rGO exhibits more significant anisotropy in loss,with an anisotropy ratio over 4 times that of GO.In addition,rGO shows higher thermal stability and greater robustness to photothermal reduction than GO.These results highlight the strong potential of rGO films for implementing high-performance polarization selective devices in integrated photonic platforms.展开更多
Ta-doped SnO_(2)(TTO)is a suitable candidate to replace transparent conductive oxide(TCO)composed of expensive indium used for optoelectronics and silicon heterojunction solar cells fabricated below 200℃.However,TTO ...Ta-doped SnO_(2)(TTO)is a suitable candidate to replace transparent conductive oxide(TCO)composed of expensive indium used for optoelectronics and silicon heterojunction solar cells fabricated below 200℃.However,TTO films fabricated by sputtering at low temperature still demonstrate too high resistance and optical absorptance for application in industry.In this study,we investigate the influence of sputtering ambient on the optoelectrical properties of TTO films.The addition of hydrogen and oxygen to argon during sputtering leads to a large improvement in the optoelectrical properties of TTO films.The best TTO film has a low average absorptance of 1.9%and a low resistance of 3.8×10^(-3)Ω·cm with a high carrier density of 9.3×10^(19)cm^(-3)and mobility of 17.8 cm^(2)·V^(-1)·s^(-1).The micros tructural and compositional properties of TTO films were characterized using x-ray diffraction,x-ray photoelectron spectroscopy and UV-Vis spectrophotometry.A proper ratio of hydrogen to oxygen in the sputtering gas improves the crystallinity and the doping efficiency of Ta.Optical absorptance is also reduced with suppressed formation of Sn(Ⅱ)in the TTO films.Therefore,our findings exhibit remarkable potential for the industrial application of TTO as a low-cost TCO.展开更多
Two-dimensional(2D)metal oxides(2DMOs),such as MoO_(2),have made impressive strides in recent years,and their applicability in a number of fields such as electronic devices,optoelectronic devices and lasers has been d...Two-dimensional(2D)metal oxides(2DMOs),such as MoO_(2),have made impressive strides in recent years,and their applicability in a number of fields such as electronic devices,optoelectronic devices and lasers has been demonstrated.However,2DMOs present challenges in their synthesis using conventional methods due to their non-van der Waals nature.We report that KCl acts as a flux to prepare large-area 2DMOs with sub-millimeter scale.We systematically investigate the effects of temperature,homogeneous time and cooling rate on the products in the flux method,demonstrating that in this reaction a saturated homogenous solution is obtained upon the melting of the salt and precursor.Afterward,the cooling rate was adjusted to regulate the thickness of the target crystals,leading to the precipitation of 2D non-layered material from the supersaturated solution;by applying this method,the highly crystalline non-layered 2D MoO_(2)flakes with so far the largest lateral size of up to sub-millimeter scale(~464μm)were yielded.Electrical studies have revealed that the 2D MoO_(2)features metallic properties,with an excellent sheet resistance as low as 99Ω·square^(-1 )at room temperature,and exhibits a property of charge density wave in the measurement of resistivity as a function of temperature.展开更多
Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocat...Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocatalysts,while concurrently preventing side reactions and photocorrosion on the semiconductor surface.Herein,Ni-Co bimetallic hydroxides with varying Ni/Co molar ratios(Ni_(x)Co_(1-x)(OH)_(2),x=1,0.75,0.5,0.25,and 0)were grown in situ on a model 2D/2D S-scheme heterojunction composed of Cu_(2)O nanosheets and Fe_(2)O_(3)nanoplates to form a series of Cu_(2)O/Fe_(2)O_(3)@Ni_(x)Co_(1-x)(OH)_(2)(CF@NiCo)photocatalysts.The combined experimental and theoretical investigation demonstrates that incorporating an appropriate amount of Co into Ni(OH)_(2)not only modulates the energy band structure of Ni_(x)Co_(1-x)(OH)_(2),balances the electron-and hole-trapping abilities of the bifunctional cocatalyst and maximizes the charge separation efficiency of the heterojunction,but also regulates the d-band center of Ni_(x)Co_(1-x)(OH)_(2),reinforcing the adsorption and activation of CO_(2)and H_(2)O on the cocatalyst surface and lowering the rate-limiting barriers in the CO_(2)-to-CO and H_(2)O-to-O_(2)conversion.Benefiting from the Ni-Co synergy,the redox reactions proceed stoichiometrically.The optimized CF@Ni_(0.75)Co_(0.25)achieves CO and O_(2)yields of 552.7 and 313.0μmol gcat^(-1)h^(-1),respectively,11.3/9.9,1.6/1.7,and 4.5/5.9-fold higher than those of CF,CF@Ni,and CF@Co.This study offers valuable insights into the design of bifunctional noble-metal-free cocatalysts for high-performance artificial photosynthesis.展开更多
Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient cat...Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient catalysts and lack of understanding the mechanism of catalysis.Herein,we demonstrate a novel strategy by generation of oxyhydroxide layers on two-dimensional iron-doped layered nickel phosphorus trisulfides(Ni1-xFexPS_(3))during the oxidation of benzylamine(BA).In-depth structural and surface chemical characterizations during the electrocatalytic process combined with theoretical calculations reveal that Ni(1-x)FexPS_(3) undergoes surface reconstruction under alkaline conditions to form the metal oxyhydroxide/phosphorus trichalcogenide(NiFeOOH/Ni1-xFexPS_(3))heterostructure.Interestingly,the generated heterointerface facilitates BA oxidation with a low onset potential of 1.39 V and Faradaic efficiency of 53%for benzonitrile(BN)synthesis.Theoretical calculations further indicate that the as-formed NiFeOOH/Ni1-xFexPS_(3) heterostructure could offer optimum free energy for BA adsorption and BN desorption,resulting in promising BN synthesis.展开更多
Paired electrolysis of waste feedstocks holds an energy-efficient alternative for chemical production;however,the sluggish anodic oxidation limited the total efficiency under larger current density.Herein,we construct...Paired electrolysis of waste feedstocks holds an energy-efficient alternative for chemical production;however,the sluggish anodic oxidation limited the total efficiency under larger current density.Herein,we constructed ultralow-coordinated Ni species with Ni–O coordination number of∼3 via a hydrothermal synthesis-sulfidation-annealing process and electrochemical activation and demonstrated the vital role in accelerating the proton deintercalation and reactive oxygen intermediate·OH formation during electro-reforming polyethylene terephthalate hydrolysate(POR).The target catalyst NiCoSx/NF afforded a high formate productivity of 7.4 mmol cm^(−2)h^(−1)at∼600 mA cm^(−2)with a formate Faradic efficiency(FE_(formate))of 92.4%in POR and maintained a FE_(formate)of∼90%for 100 h at 2 A in a membrane electrode assembly electrolyzer.Coupling POR on NiCoSx/NF with carbon dioxide reduction reaction on oxygen vacancies enriched Vo-BiSnO reached effective concurrent formate production with 172.7%of FE_(formate)at 500 mA cm^(−2)and long-term stability.Such excellent performance shows the great prospect of electrocatalyst design by regulating the local metal environment.展开更多
Against the backdrop of global energy and environmental crises,the technology of CO_(2)hydrogenation to produce methanol is garnering widespread attention as an innovative carbon capture and utilization solution.Bimet...Against the backdrop of global energy and environmental crises,the technology of CO_(2)hydrogenation to produce methanol is garnering widespread attention as an innovative carbon capture and utilization solution.Bimetallic oxide catalysts have emerged as the most promising research subject in the field due to their exceptional catalytic performance and stability.The performance of bimetallic oxide catalysts is influenced by multiple factors,including the selection of carrier materials,the addition of promoters,and the synthesis process.Different types of bimetallic oxide catalysts exhibit significant differences in microstructure,surface active sites,and electronic structure,which directly determine the yield and selectivity of methanol.Although bimetallic oxide catalysts offer significant advantages over traditional copper-based catalysts,they still encounter challenges related to activity and cost.In order to enhance catalyst performance,future investigations must delve into microstructure control,surface modification,and reaction kinetics.展开更多
The production of hydrogen peroxide(H_(2)O_(2))via artificial photosynthesis using single-atom semiconductor photocatalysts represents a promising green and sustainable technology.However,its efficiency is still limit...The production of hydrogen peroxide(H_(2)O_(2))via artificial photosynthesis using single-atom semiconductor photocatalysts represents a promising green and sustainable technology.However,its efficiency is still limited by sluggish water oxidation kinetics,poor photogenerated charge separation,and insufficient O_(2)adsorption and activation capabilities.Herein,uniformly dispersed single-atom catalysts(SACs)with a Co-N_(4)coordination structure have been synthesized by thermally transforming cobalt phthalocyanine(CoPc)assemblies pre-anchored on phosphate functionalized reduced graphene oxide(Co@rGO-P),and then used to construct heterojunctions with perylenetetracarboxylic acid(PTA)nanosheets for photocatalytic H_(2)O_(2)production by an in-situ growth method.The optimized Co@rGO-P/PTA achieved an H_(2)O_(2)production rate of 1.4 mmol g^(-1)h^(-1)in pure water,with a 12.9-fold enhancement compared to pristine PTA nanosheets exhibiting competitive photoactivity among reported perylene-based materials.Femtosecond transient absorption spectra,in-situ diffuse reflectance infrared Fourier transform spectra and theoretical calculations reveal that the exceptional performance is attributed to the enhanced electron transfer from PTA to rGO via the phosphate bridge and then to the Co-N_(4),and to the promoted O_(2)adsorption and activation at Co-N_(4)active sites.This work provides a feasible and effective strategy for designing highly efficient single-atom semiconductor heterojunction photocatalysts for H_(2)O_(2)production.展开更多
Herein,vacancy engineering is utilized reasonably to explore molybdenum tungsten oxide nanowires(W_(4)MoO_(3)NWs)rich in O-vacancies as an advanced electrochemical nitrogen reduction reaction(eNRR)electrocatalyst,real...Herein,vacancy engineering is utilized reasonably to explore molybdenum tungsten oxide nanowires(W_(4)MoO_(3)NWs)rich in O-vacancies as an advanced electrochemical nitrogen reduction reaction(eNRR)electrocatalyst,realizing further enhancement of NRR performance.In 0.1 mol/L Na_(2)SO_(4),W_(4)MoO_(3)NWs rich in O vacancies(CTAB-D-W_(4)MoO_(3))achieve a large NH3yield of 60.77μg h^(-1)mg^(-1)cat.at-0.70 V vs.RHE and a high faradaic efficiency of 56.42%at-0.60 V,much superior to the W_(4)MoO_(3)NWs deficient in oxygen vacancies(20.26μg h^(-1)mg^(-1)cat.and 17.1%at-0.70 V vs.RHE).Meanwhile,W_(4)MoO_(3)NWs rich in O-vacancies also show high electrochemical stability.Density functional theory(DFT)calculations present that O vacancies in CTAB-D-W_(4)MoO_(3)reduce the energy barrier formed by the intermediate of^(*)N-NH,facilitate the activation and further hydrogenation of^(*)N-N,promote the NRR process,and improve NRR activity.展开更多
The insufficient electrocatalytic activity and CO_(2)resistance hinder the application of cathode mate-rial for solid oxide fuel cells(SOFCs).In this study,we introduce a series of Pr-doped perovskite Bi_(0.8-x)Pr_(x)...The insufficient electrocatalytic activity and CO_(2)resistance hinder the application of cathode mate-rial for solid oxide fuel cells(SOFCs).In this study,we introduce a series of Pr-doped perovskite Bi_(0.8-x)Pr_(x)Ca_(0.2)FeO_(3-δ)(BPCF_(x),x=0,0.10,0.15,0.20)as candidate cathode materials,with a focus on its phase structure,oxygen desorption ability,catalytic activity,and electrochemical reduction kinetics.Among all the components,the Bi_(0.6)Pr_(0.2)Ca_(0.2)FeO_(3-δ)(BPCF0.20)catalyst shows impressive oxygen reduc-tion reaction(ORR)activity,with a low polarization resistance of 0.06Ωcm^(2)at 700℃and peak power density of 810 mW cm^(−2)at 800℃.Moreover,the BPCF0.20 cathode shows outstanding CO_(2)resistance in different CO_(2)concentrations(1%-10%)due to the larger average bond energy and higher relative acidity of Bi,Pr,and Fe ions.These findings demonstrate that BPCF_(x)are advanced cathode electrocatalysts for SOFCs.展开更多
The reduction of global carbon emissions and the achievement of carbon neutrality have become the focus of addressing climate change and global warming.Electrochemical CO_(2) reduction(CO_(2)RR),as a technology that c...The reduction of global carbon emissions and the achievement of carbon neutrality have become the focus of addressing climate change and global warming.Electrochemical CO_(2) reduction(CO_(2)RR),as a technology that can efficiently convert CO_(2) into value-added products,is receiving widespread attention.This article reviews the current research status of Cu/metal oxide heterostructures in the field of electrochemical reduction of CO_(2).The review first introduces the importance of electrochemical reduction of CO_(2) and the application potential of Cu/metal oxide heterostructures in this field.Subsequently,a comprehensive discussion is presented on the exploration of various Cu/metal oxide heterostructures and their corresponding structure-performance relationship,with particular emphasis on the catalysts'activity,selectivity,stability and the nature of active sites.Lastly,the review provides an overview of the current research challenges and future development trends in this field.展开更多
Enhancing the specific capacity of P2-type layered oxide cathodes via elevating the upper operation voltage would inevitably deteriorate electrochemical properties owing to the irreversible anionic redox reaction at h...Enhancing the specific capacity of P2-type layered oxide cathodes via elevating the upper operation voltage would inevitably deteriorate electrochemical properties owing to the irreversible anionic redox reaction at high voltage.In this work,the strategy of the electron donor was utilized to address this issue.Remarkably,the earth-abundant P2-layered cathode Na_(2/3)Al_(1/6)Fe_(1/6)Mn_(2/3)O_(2)with the presence of K_(2)S renders superior rate capability(187.4 and 79.5 mA h g^(-1)at 20 and 1000 mA g^(-1))and cycling stability(a capacity retention of 85.6% over 300 cycles at 1000 mA g^(-1))within the voltage region of 2-4.4 V Na^(+)/Na.Furthermore,excellent electrochemical performance is also demonstrated in the full cell.Detailed structural analysis of as-proposed composite cathode illustrates that even at 4.4 V irreversible phase transition can be avoided as well as a cell volume variation of only 0.88%,which are attributed to the enhanced performance compared with the control group.Meanwhile,further investigation of charge compensation reveals the crucial role of sulfur ions in actively control of reversible redox reaction of oxygen species in the lattice structure.This work inspires a new strategy to enhance the structural stability of layered sodium ion cathode materials at high voltages.展开更多
The global ocean is a major source of the climate-relevant atmospheric trace gas nitrous oxide(N_(2)O).However,an accurate assessment of the global oceanic emissions of N_(2)O is hampered by missing data on dissolved ...The global ocean is a major source of the climate-relevant atmospheric trace gas nitrous oxide(N_(2)O).However,an accurate assessment of the global oceanic emissions of N_(2)O is hampered by missing data on dissolved N_(2)O from large regions such as the Southern Ocean.To address this deficit,N_(2)O was measured in the Prydz Bay in February 2015 during the 31st Chinese National Antarctic Research Expedition.N_(2)O concentrations(saturation)in the surface layer were generally low(undersaturation with respect to atmospheric equilibrium)and ranged from 13.3 nmol/L to 16.1 nmol/L(83%–102%)at the time of sampling.A comparison of our observations with archived data revealed that no discernible trend in N_(2)O concentrations in the surface waters of Prydz Bay could be detected for the period between 2006 and 2015.Temperature and salinity changes driven by meltwater input were the predominant controls on N_(2)O concentrations in surface waters.At depth,the distribution of N_(2)O concentrations was dominated by production via nitrification in offshore deep waters and vertical convection in the shelf waters,where concentrations were lower and gradients were less steep.Our results suggest a rather unusual pattern of N_(2)O distribution in the Prydz Bay(low N_(2)O in shelf waters compared with the open ocean),providing important insights into the coastal dynamics of N_(2)O in high-latitude polar regions.展开更多
Reversible solid oxide cells(RSOCs)are capable of converting various energy resources,between electricity and chemical fuels,with high efficiency and flexibility,making them suitable for grid balancing and renewable e...Reversible solid oxide cells(RSOCs)are capable of converting various energy resources,between electricity and chemical fuels,with high efficiency and flexibility,making them suitable for grid balancing and renewable energy consumption.However,the practical application of RSOCs is still limited by the insufficient activity and stability of the electrodes in different operating modes.Herein,a highly efficient symmetrical electrode composed of La_(0.3)Sr_(0.6)Ti_(0.1)Co_(0.2)Fe_(0.7)O_(3-δ)(LSTCF)nanofibers and in situ exsolved Co_(3)Fe_(7) nanoparticles is developed for boosting the performance of RSOCs.The reversible phase transition,high activity and stability of the electrode have been confirmed by a combination of experimental(e.g.,transmission electron microscopy and X-ray absorption fine structure)and computational studies.Electrolyte-supported RSOCs with the symmetrical electrode demonstrate excellent catalytic activity and stability,achieving a high peak power density of 0.98 W cm^(-2)in the fuel cell mode using H_(2)as the fuel(or 0.53 W cm^(-2)using CH_(4)as the fuel)and a high current density of 1.09 A cm^(-2) at 1.4 V in the CO_(2)electrolysis mode(or 1.03 A cm^(-2)at 1.3 V for H_(2)O electrolysis)at 800℃while maintaining excellent durability for over 100 h.展开更多
Advancing clean energy technologies demands efficient and durable electrode catalysts for solid oxide cells(SOCs).Despite their exceptional catalytic properties,Pt-based materials face critical challenges in high-temp...Advancing clean energy technologies demands efficient and durable electrode catalysts for solid oxide cells(SOCs).Despite their exceptional catalytic properties,Pt-based materials face critical challenges in high-temperature applications owing to particle agglomeration and cost constraints.Here,we demonstrate a rational design strategy utilizing controlled in situ exsolution to create strongly anchored PtSn nanoalloys on oxygen-deficient PrBaMn_(1.8)Pt_(0.1)Sn_(0.1)O_(5+δ)(L-PBMPtSn)perovskite oxide.Through precise compositional engineering and structural control,we achieved a uniform dispersion of PtSn nanoparticles with unique socket-like interfaces that prevent agglomeration while maintaining high catalytic accessibility.The optimized electrode demonstrates remarkable bifunctional performance,achieving a current density of 1.6 A cm^(-2)at 1.8 V for CO_(2)electrolysis and a maximum power density of 316 mW cm^(-2)for fuel cell operation at 800℃.More significantly,the electrode exhibits exceptional stability with only 9.6%performance degradation over 100 h of operation,which is a substantial improvement over conventional electrodes.Our findings establish a new paradigm for designing high-performance SOC electrodes through the controlled exsolution of precious metal alloys,offering broader implications for catalyst design in high-temperature electrochemical systems.展开更多
基金financially National Key R&D Program of China(No.2022YFA1504800)National Natural Science Foundation of China(Grant No.22325405,22372160,22321002)+1 种基金Liaoning Revitalization Talents Program(XLYC1807207)DICP I202104。
文摘The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly understood due to challenges in atomic-level structural characterizations and analysis of reaction intermediates.In this study,we prepared two Zn-Al spinel oxide catalysts via coprecipitation(ZnAl-C)and hydrothermal(ZnAl-H)methods,and conducted a comparative investigation in the CO_(2)hydrogenation reaction.Surprisingly,under similar conditions,ZnAl-C exhibited significantly higher selectivity towards methanol and DME compared to ZnAl-H.Comprehensive characterizations using X-ray diffraction(XRD),Raman spectroscopy and electron paramagnetic resonance(EPR)unveiled that ZnAl-C catalyst had abundant ZnO species on its surface,and the interaction between the ZnO species and its ZnAl spinel oxide matrix led to the formation of oxygen vacancies,which are crucial for CO_(2)adsorption and activation.Additionally,state-of-the-art solid-state nuclear magnetic resonance(NMR)techniques,including ex-situ and in-situ NMR analyses,confirmed that the surface ZnO facilitates the formation of unique highly reactive interfacial formate species,which was readily hydrogenated to methanol and DME.These insights elucidate the promotion effects of ZnO on the ZnAl spinel oxide in regulating active sites and reactive intermediates for CO_(2)-to-methanol hydrogenation reaction,which is further evidenced by the significant enhancement in methanol and DME selectivity observed upon loading ZnO onto the ZnAl-H catalyst.These molecular-level mechanism understandings reinforce the idea of optimizing the ZnO-ZnAl interface through tailored synthesis methods to achieve activity-selectivity balance.
文摘The rapid industrial growth and increasing population have led to significant pollution and deterioration of the natural atmospheric environment.Major atmospheric pollutants include NO_(2)and CO_(2).Hence,it is imperative to develop NO_(2)and CO_(2)sensors for ambient conditions,that can be used in indoor air quality monitoring,breath analysis,food spoilage detection,etc.In the present study,two thin film nanocomposite(nickel oxide-graphene and nickel oxide-silver nanowires)gas sensors are fabricated using direct ink writing.The nano-composites are investigated for their structural,optical,and electrical properties.Later the nano-composite is deposited on the interdigitated electrode(IDE)pattern to form NO_(2)and CO_(2)sensors.The deposited films are then exposed to NO_(2)and CO_(2)gases separately and their response and recovery times are determined using a custom-built gas sensing setup.Nickel oxide-graphene provides a good response time and recovery time of 10 and 9 s,respectively for NO_(2),due to the higher electron affinity of graphene towards NO_(2).Nickel oxide-silver nanowire nano-composite is suited for CO_(2)gas because silver is an excellent electrocatalyst for CO_(2)by giving response and recovery times of 11 s each.This is the first report showcasing NiO nano-composites for NO_(2)and CO_(2)sensing at room temperature.
基金supported by the National Key R&D Program of China(No.2022YFB2404400)the National Natural Science Foundation of China(Nos.U23A20577,52372168,92263206 and 21975006)+1 种基金the“The Youth Beijing Scholars program”(No.PXM2021_014204_000023)the Beijing Natural Science Foundation(Nos.2222001 and KM202110005009).
文摘The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost,high energy density,and good performance at low temperatures,and is the promising choice for energy storage batteries.However,the long-cycling stability of batteries needs to be improved.Herein,the Mn-based Li-rich cathode materials with small amounts of Li2 MnO3 crystal domains and gradient doping of Al and Ti elements from the surface to the bulk have been developed to improve the structure and interface stability.Then the batteries with a high energy density of 600 Wh kg^(-1),excellent capacity retention of 99.7%with low voltage decay of 0.03 mV cycle^(-1) after 800 cycles,and good rates performances can be achieved.Therefore,the structure and cycling stability of low voltage Mn-based Li-rich cathode materials can be significantly improved by the bulk structure design and interface regulation,and this work has paved the way for developing low-cost and high-energy Mn-based energy storage batteries with long lifetime.
基金supported by the National Natural Science Foundation of China(No.21805018)by Sichuan Science and Technology Program(Nos.2022ZHCG0018,2023NSFSC0117 and 2023ZHCG0060)Yibin Science and Technology Program(No.2022JB005)and China Postdoctoral Science Foundation(No.2022M722704).
文摘Layered transition metal oxides have emerged as promising cathode materials for sodium ion batteries.However,irreversible phase transitions cause structural distortion and cation rearrangement,leading to sluggish Na+dynamics and rapid capacity decay.In this study,we propose a medium-entropy cathode by simultaneously introducing Fe,Mg,and Li dopants into a typical P2-type Na_(0.75)Ni_(0.25)Mn_(0.75)O_(2)cathode.The modified Na_(0.75)Ni_(0.2125)Mn_(0.6375)Fe_(0.05)Mg_(0.05)Li_(0.05)O_(2)cathode predominantly exhibits a main P2 phase(93.5%)with a minor O3 phase(6.5%).Through spectroscopy techniques and electrochemical investigations,we elucidate the redox mechanisms of Ni^(2+/3+/4+),Mn^(3+/4+),Fe^(3+/4+),and O_(2)-/O_(2)^(n-)during charging/discharging.The medium-entropy doping mitigates the detrimental P2-O_(2)phase transition at high-voltage,replacing it with a moderate and reversible structural evolution(P2-OP4),thereby enhancing structural stability.Consequently,the modified cathode exhibits a remarkable rate capacity of 108.4 mAh·g^(-1)at 10C,with a capacity retention of 99.0%after 200 cycles at 1C,82.5%after 500 cycles at 5C,and 76.7%after 600 cycles at 10C.Furthermore,it also demonstrates superior electrochemical performance at high cutoff voltage of 4.5 V and extreme temperature(55 and 0℃).This work offers solutions to critical challenges in sodium ion batteries cathode materials.
文摘Broadband transparent films play a pivotal role in various applications such as lenses and solar cells,particularly porous structured transparent films exhibit significant potential.This study investigates a porous SiO_(2) refractive index gradient anti-reflective film prepared by atomic layer deposition(ALD).A porous SiO_(2) film with gradual porosity was obtained by phosphoric acid etching of Al_(2)O_(3)/SiO_(2) multilayers with gradient Al2O3 ratios,achieving a gradual decrease in refractive index from the substrate to the surface.The film exhibited an average transmittance as high as 97.8%within the wavelength range from 320 nm to 1200 nm.The environmental adaptability was further enhanced by surface modification using rare earth oxide(REO)La_(2)O_(3),resulting in formation of a lotus leaf-like structure and achieving a water contact angle of 100.0°.These data proved that the modification significantly improved hydrophobic self-cleaning capability while maintaining exceptional transparency of the film.The surface structure of the modified film remained undamaged even after undergoing wipe testing,demonstrating its excellent surface durability.
基金supported by the Australian Research Council Centre of Excellence Project in Optical Microcombs for Breakthrough Science(No.CE230100006)the Australian Research Council Discovery Projects Programs(Nos.P190103186 and FT210100806)+4 种基金Linkage Program(Nos.LP210200345 and LP210100467)the Swinburne ECR-SUPRA program,the Industrial Transformation Training Centres scheme(No.IC180100005)the National Natural Science Foundation of China(No.12404375)the Beijing Natural Science Foundation(No.Z180007)the Innovation Program for Quantum Science and Technology(No.2021ZD0300703).
文摘Optical polarizers,which allow the transmission of specific polarization states,are essential components in modern optical systems.Here,we experimentally demonstrate integrated photonic polarizers incorporating reduced graphene oxide(rGO)films.2D graphene oxide(GO)films are integrated onto silicon waveguides and microring resonators(MRRs)with precise control over their thicknesses and sizes,followed by GO reduction via two different methods including uniform thermal reduction and localized photothermal reduction.We measure devices with various lengths,thicknesses,and reduction degrees of GO films.The results show that the devices with rGO exhibit better performance than those with GO,achieving a polarization-dependent loss of~47 dB and a polarization extinction ratio of~16 dB for the hybrid waveguides and MRRs with rGO,respectively.By fitting the experimental results with theory,it is found that rGO exhibits more significant anisotropy in loss,with an anisotropy ratio over 4 times that of GO.In addition,rGO shows higher thermal stability and greater robustness to photothermal reduction than GO.These results highlight the strong potential of rGO films for implementing high-performance polarization selective devices in integrated photonic platforms.
基金Project supported by the Key-Area Research and Development Program of Guangdong Province,China(Grant No.2021B0101260001)the Guangdong Basic and Applied Basic Research Foundation(Grant No.2019A1515110411)。
文摘Ta-doped SnO_(2)(TTO)is a suitable candidate to replace transparent conductive oxide(TCO)composed of expensive indium used for optoelectronics and silicon heterojunction solar cells fabricated below 200℃.However,TTO films fabricated by sputtering at low temperature still demonstrate too high resistance and optical absorptance for application in industry.In this study,we investigate the influence of sputtering ambient on the optoelectrical properties of TTO films.The addition of hydrogen and oxygen to argon during sputtering leads to a large improvement in the optoelectrical properties of TTO films.The best TTO film has a low average absorptance of 1.9%and a low resistance of 3.8×10^(-3)Ω·cm with a high carrier density of 9.3×10^(19)cm^(-3)and mobility of 17.8 cm^(2)·V^(-1)·s^(-1).The micros tructural and compositional properties of TTO films were characterized using x-ray diffraction,x-ray photoelectron spectroscopy and UV-Vis spectrophotometry.A proper ratio of hydrogen to oxygen in the sputtering gas improves the crystallinity and the doping efficiency of Ta.Optical absorptance is also reduced with suppressed formation of Sn(Ⅱ)in the TTO films.Therefore,our findings exhibit remarkable potential for the industrial application of TTO as a low-cost TCO.
基金supported by the National Key Research and Development Program of China(Nos.2023YFB3608703 and 2023YFB3608700)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(Nos.2021ZZ122 and 2020ZZ110)Fujian provincial projects(Nos.2021HZ0114 and 2021J01583).
文摘Two-dimensional(2D)metal oxides(2DMOs),such as MoO_(2),have made impressive strides in recent years,and their applicability in a number of fields such as electronic devices,optoelectronic devices and lasers has been demonstrated.However,2DMOs present challenges in their synthesis using conventional methods due to their non-van der Waals nature.We report that KCl acts as a flux to prepare large-area 2DMOs with sub-millimeter scale.We systematically investigate the effects of temperature,homogeneous time and cooling rate on the products in the flux method,demonstrating that in this reaction a saturated homogenous solution is obtained upon the melting of the salt and precursor.Afterward,the cooling rate was adjusted to regulate the thickness of the target crystals,leading to the precipitation of 2D non-layered material from the supersaturated solution;by applying this method,the highly crystalline non-layered 2D MoO_(2)flakes with so far the largest lateral size of up to sub-millimeter scale(~464μm)were yielded.Electrical studies have revealed that the 2D MoO_(2)features metallic properties,with an excellent sheet resistance as low as 99Ω·square^(-1 )at room temperature,and exhibits a property of charge density wave in the measurement of resistivity as a function of temperature.
文摘Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocatalysts,while concurrently preventing side reactions and photocorrosion on the semiconductor surface.Herein,Ni-Co bimetallic hydroxides with varying Ni/Co molar ratios(Ni_(x)Co_(1-x)(OH)_(2),x=1,0.75,0.5,0.25,and 0)were grown in situ on a model 2D/2D S-scheme heterojunction composed of Cu_(2)O nanosheets and Fe_(2)O_(3)nanoplates to form a series of Cu_(2)O/Fe_(2)O_(3)@Ni_(x)Co_(1-x)(OH)_(2)(CF@NiCo)photocatalysts.The combined experimental and theoretical investigation demonstrates that incorporating an appropriate amount of Co into Ni(OH)_(2)not only modulates the energy band structure of Ni_(x)Co_(1-x)(OH)_(2),balances the electron-and hole-trapping abilities of the bifunctional cocatalyst and maximizes the charge separation efficiency of the heterojunction,but also regulates the d-band center of Ni_(x)Co_(1-x)(OH)_(2),reinforcing the adsorption and activation of CO_(2)and H_(2)O on the cocatalyst surface and lowering the rate-limiting barriers in the CO_(2)-to-CO and H_(2)O-to-O_(2)conversion.Benefiting from the Ni-Co synergy,the redox reactions proceed stoichiometrically.The optimized CF@Ni_(0.75)Co_(0.25)achieves CO and O_(2)yields of 552.7 and 313.0μmol gcat^(-1)h^(-1),respectively,11.3/9.9,1.6/1.7,and 4.5/5.9-fold higher than those of CF,CF@Ni,and CF@Co.This study offers valuable insights into the design of bifunctional noble-metal-free cocatalysts for high-performance artificial photosynthesis.
基金National Natural Science Foundation of China,Grant/Award Number:22179029Fundamental Research Funds for the Central Universities,Grant/Award Number:buctrc202324+2 种基金Young Elite Scientists Sponsorship Program by BAST,Grant/Award Number:BYESS2023093Ministero dell'Istruzione,dell'Universitàe della Ricerca,Grant/Award Number:2022FNL89YKempestiftelserna。
文摘Selective oxidation of amines to imines through electrocatalysis is an attractive and efficient way for the chemical industry to produce nitrile compounds,but it is limited by the difficulty of designing efficient catalysts and lack of understanding the mechanism of catalysis.Herein,we demonstrate a novel strategy by generation of oxyhydroxide layers on two-dimensional iron-doped layered nickel phosphorus trisulfides(Ni1-xFexPS_(3))during the oxidation of benzylamine(BA).In-depth structural and surface chemical characterizations during the electrocatalytic process combined with theoretical calculations reveal that Ni(1-x)FexPS_(3) undergoes surface reconstruction under alkaline conditions to form the metal oxyhydroxide/phosphorus trichalcogenide(NiFeOOH/Ni1-xFexPS_(3))heterostructure.Interestingly,the generated heterointerface facilitates BA oxidation with a low onset potential of 1.39 V and Faradaic efficiency of 53%for benzonitrile(BN)synthesis.Theoretical calculations further indicate that the as-formed NiFeOOH/Ni1-xFexPS_(3) heterostructure could offer optimum free energy for BA adsorption and BN desorption,resulting in promising BN synthesis.
基金We highly thank the funding from the National Natural Science Foundation of China(grants 22222806,22178162,22072065,and 22408170)the Distinguished Youth Foundation of Jiangsu Province(BK20220053)+2 种基金the National Key Research and Development Program of China(2024YFE0206900)the Six Talent Peaks Project in Jiangsu Province(grant JNHB-035)Agency for Science,Technology and Research(A*STAR)through Low Carbon Energy Research Finding Initiative(LCERFI01-0033|U2102d2006).
文摘Paired electrolysis of waste feedstocks holds an energy-efficient alternative for chemical production;however,the sluggish anodic oxidation limited the total efficiency under larger current density.Herein,we constructed ultralow-coordinated Ni species with Ni–O coordination number of∼3 via a hydrothermal synthesis-sulfidation-annealing process and electrochemical activation and demonstrated the vital role in accelerating the proton deintercalation and reactive oxygen intermediate·OH formation during electro-reforming polyethylene terephthalate hydrolysate(POR).The target catalyst NiCoSx/NF afforded a high formate productivity of 7.4 mmol cm^(−2)h^(−1)at∼600 mA cm^(−2)with a formate Faradic efficiency(FE_(formate))of 92.4%in POR and maintained a FE_(formate)of∼90%for 100 h at 2 A in a membrane electrode assembly electrolyzer.Coupling POR on NiCoSx/NF with carbon dioxide reduction reaction on oxygen vacancies enriched Vo-BiSnO reached effective concurrent formate production with 172.7%of FE_(formate)at 500 mA cm^(−2)and long-term stability.Such excellent performance shows the great prospect of electrocatalyst design by regulating the local metal environment.
文摘Against the backdrop of global energy and environmental crises,the technology of CO_(2)hydrogenation to produce methanol is garnering widespread attention as an innovative carbon capture and utilization solution.Bimetallic oxide catalysts have emerged as the most promising research subject in the field due to their exceptional catalytic performance and stability.The performance of bimetallic oxide catalysts is influenced by multiple factors,including the selection of carrier materials,the addition of promoters,and the synthesis process.Different types of bimetallic oxide catalysts exhibit significant differences in microstructure,surface active sites,and electronic structure,which directly determine the yield and selectivity of methanol.Although bimetallic oxide catalysts offer significant advantages over traditional copper-based catalysts,they still encounter challenges related to activity and cost.In order to enhance catalyst performance,future investigations must delve into microstructure control,surface modification,and reaction kinetics.
文摘The production of hydrogen peroxide(H_(2)O_(2))via artificial photosynthesis using single-atom semiconductor photocatalysts represents a promising green and sustainable technology.However,its efficiency is still limited by sluggish water oxidation kinetics,poor photogenerated charge separation,and insufficient O_(2)adsorption and activation capabilities.Herein,uniformly dispersed single-atom catalysts(SACs)with a Co-N_(4)coordination structure have been synthesized by thermally transforming cobalt phthalocyanine(CoPc)assemblies pre-anchored on phosphate functionalized reduced graphene oxide(Co@rGO-P),and then used to construct heterojunctions with perylenetetracarboxylic acid(PTA)nanosheets for photocatalytic H_(2)O_(2)production by an in-situ growth method.The optimized Co@rGO-P/PTA achieved an H_(2)O_(2)production rate of 1.4 mmol g^(-1)h^(-1)in pure water,with a 12.9-fold enhancement compared to pristine PTA nanosheets exhibiting competitive photoactivity among reported perylene-based materials.Femtosecond transient absorption spectra,in-situ diffuse reflectance infrared Fourier transform spectra and theoretical calculations reveal that the exceptional performance is attributed to the enhanced electron transfer from PTA to rGO via the phosphate bridge and then to the Co-N_(4),and to the promoted O_(2)adsorption and activation at Co-N_(4)active sites.This work provides a feasible and effective strategy for designing highly efficient single-atom semiconductor heterojunction photocatalysts for H_(2)O_(2)production.
基金supported by the National Natural Science Foundation of China(No.51872173)Natural Science Foundation of Shandong Province(No.ZR2022JQ21)。
文摘Herein,vacancy engineering is utilized reasonably to explore molybdenum tungsten oxide nanowires(W_(4)MoO_(3)NWs)rich in O-vacancies as an advanced electrochemical nitrogen reduction reaction(eNRR)electrocatalyst,realizing further enhancement of NRR performance.In 0.1 mol/L Na_(2)SO_(4),W_(4)MoO_(3)NWs rich in O vacancies(CTAB-D-W_(4)MoO_(3))achieve a large NH3yield of 60.77μg h^(-1)mg^(-1)cat.at-0.70 V vs.RHE and a high faradaic efficiency of 56.42%at-0.60 V,much superior to the W_(4)MoO_(3)NWs deficient in oxygen vacancies(20.26μg h^(-1)mg^(-1)cat.and 17.1%at-0.70 V vs.RHE).Meanwhile,W_(4)MoO_(3)NWs rich in O-vacancies also show high electrochemical stability.Density functional theory(DFT)calculations present that O vacancies in CTAB-D-W_(4)MoO_(3)reduce the energy barrier formed by the intermediate of^(*)N-NH,facilitate the activation and further hydrogenation of^(*)N-N,promote the NRR process,and improve NRR activity.
基金supported by the Natural Science Foundation of Heilongjiang Province(No.ZD2022E007).
文摘The insufficient electrocatalytic activity and CO_(2)resistance hinder the application of cathode mate-rial for solid oxide fuel cells(SOFCs).In this study,we introduce a series of Pr-doped perovskite Bi_(0.8-x)Pr_(x)Ca_(0.2)FeO_(3-δ)(BPCF_(x),x=0,0.10,0.15,0.20)as candidate cathode materials,with a focus on its phase structure,oxygen desorption ability,catalytic activity,and electrochemical reduction kinetics.Among all the components,the Bi_(0.6)Pr_(0.2)Ca_(0.2)FeO_(3-δ)(BPCF0.20)catalyst shows impressive oxygen reduc-tion reaction(ORR)activity,with a low polarization resistance of 0.06Ωcm^(2)at 700℃and peak power density of 810 mW cm^(−2)at 800℃.Moreover,the BPCF0.20 cathode shows outstanding CO_(2)resistance in different CO_(2)concentrations(1%-10%)due to the larger average bond energy and higher relative acidity of Bi,Pr,and Fe ions.These findings demonstrate that BPCF_(x)are advanced cathode electrocatalysts for SOFCs.
基金supported by the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.SJCX23_0120)the National Natural Science Foundation of China(Nos.22275088 and 52101260)+3 种基金the Project of Shuangchuang Scholar of Jiangsu Province(No.JSSCBS20210212)the Fundamental Research Funds for the Central Universities(No.30921011203)the Start-Up Grant(No.AE89991/340)from Nanjing University of Science and Technology,the Foundation of Jiangsu Educational Committee(No.22KJB310008)the Senior Talent Program of Jiangsu University(No.20JDG073).
文摘The reduction of global carbon emissions and the achievement of carbon neutrality have become the focus of addressing climate change and global warming.Electrochemical CO_(2) reduction(CO_(2)RR),as a technology that can efficiently convert CO_(2) into value-added products,is receiving widespread attention.This article reviews the current research status of Cu/metal oxide heterostructures in the field of electrochemical reduction of CO_(2).The review first introduces the importance of electrochemical reduction of CO_(2) and the application potential of Cu/metal oxide heterostructures in this field.Subsequently,a comprehensive discussion is presented on the exploration of various Cu/metal oxide heterostructures and their corresponding structure-performance relationship,with particular emphasis on the catalysts'activity,selectivity,stability and the nature of active sites.Lastly,the review provides an overview of the current research challenges and future development trends in this field.
基金funding support from the Beijing Natural Science Foundation(2252055)National Natural Science Foundation of China(52072033)BIT Research and Innovation Promoting Project(2024YCXY040,GIIP2023-34)。
文摘Enhancing the specific capacity of P2-type layered oxide cathodes via elevating the upper operation voltage would inevitably deteriorate electrochemical properties owing to the irreversible anionic redox reaction at high voltage.In this work,the strategy of the electron donor was utilized to address this issue.Remarkably,the earth-abundant P2-layered cathode Na_(2/3)Al_(1/6)Fe_(1/6)Mn_(2/3)O_(2)with the presence of K_(2)S renders superior rate capability(187.4 and 79.5 mA h g^(-1)at 20 and 1000 mA g^(-1))and cycling stability(a capacity retention of 85.6% over 300 cycles at 1000 mA g^(-1))within the voltage region of 2-4.4 V Na^(+)/Na.Furthermore,excellent electrochemical performance is also demonstrated in the full cell.Detailed structural analysis of as-proposed composite cathode illustrates that even at 4.4 V irreversible phase transition can be avoided as well as a cell volume variation of only 0.88%,which are attributed to the enhanced performance compared with the control group.Meanwhile,further investigation of charge compensation reveals the crucial role of sulfur ions in actively control of reversible redox reaction of oxygen species in the lattice structure.This work inspires a new strategy to enhance the structural stability of layered sodium ion cathode materials at high voltages.
基金The National Natural Science Foundation of China under contract No.41906193the Scientific Research Foundation of Third Institute of Oceanography,Ministry of Natural Resources,under contract No.2019033+2 种基金the Natural Science Foundation of Fujian Province under contract No.2019J05147the Federal Ministry of Education and Research of Germany under contract No.FKZ 03F03F0783Athe National Polar Special Program under contract Nos IRASCC 01-01-02 and IRASCC 02-02.
文摘The global ocean is a major source of the climate-relevant atmospheric trace gas nitrous oxide(N_(2)O).However,an accurate assessment of the global oceanic emissions of N_(2)O is hampered by missing data on dissolved N_(2)O from large regions such as the Southern Ocean.To address this deficit,N_(2)O was measured in the Prydz Bay in February 2015 during the 31st Chinese National Antarctic Research Expedition.N_(2)O concentrations(saturation)in the surface layer were generally low(undersaturation with respect to atmospheric equilibrium)and ranged from 13.3 nmol/L to 16.1 nmol/L(83%–102%)at the time of sampling.A comparison of our observations with archived data revealed that no discernible trend in N_(2)O concentrations in the surface waters of Prydz Bay could be detected for the period between 2006 and 2015.Temperature and salinity changes driven by meltwater input were the predominant controls on N_(2)O concentrations in surface waters.At depth,the distribution of N_(2)O concentrations was dominated by production via nitrification in offshore deep waters and vertical convection in the shelf waters,where concentrations were lower and gradients were less steep.Our results suggest a rather unusual pattern of N_(2)O distribution in the Prydz Bay(low N_(2)O in shelf waters compared with the open ocean),providing important insights into the coastal dynamics of N_(2)O in high-latitude polar regions.
基金supported by the National Natural Science Foundation of China(No.52377212 and 51877173)program of Beijing Huairou Laboratory(ZD2022006A)+2 种基金the Key R&D Project of Shaanxi Province(2023-YBGY-057)the State Key Laboratory of Electrical Insulation and Power Equipment(EIPE22314,EIPE22306)the Natural Science Basic Research Program of Shaanxi(No.2023-JC-QN-0483).
文摘Reversible solid oxide cells(RSOCs)are capable of converting various energy resources,between electricity and chemical fuels,with high efficiency and flexibility,making them suitable for grid balancing and renewable energy consumption.However,the practical application of RSOCs is still limited by the insufficient activity and stability of the electrodes in different operating modes.Herein,a highly efficient symmetrical electrode composed of La_(0.3)Sr_(0.6)Ti_(0.1)Co_(0.2)Fe_(0.7)O_(3-δ)(LSTCF)nanofibers and in situ exsolved Co_(3)Fe_(7) nanoparticles is developed for boosting the performance of RSOCs.The reversible phase transition,high activity and stability of the electrode have been confirmed by a combination of experimental(e.g.,transmission electron microscopy and X-ray absorption fine structure)and computational studies.Electrolyte-supported RSOCs with the symmetrical electrode demonstrate excellent catalytic activity and stability,achieving a high peak power density of 0.98 W cm^(-2)in the fuel cell mode using H_(2)as the fuel(or 0.53 W cm^(-2)using CH_(4)as the fuel)and a high current density of 1.09 A cm^(-2) at 1.4 V in the CO_(2)electrolysis mode(or 1.03 A cm^(-2)at 1.3 V for H_(2)O electrolysis)at 800℃while maintaining excellent durability for over 100 h.
基金supported by the National Natural Science Foundation of China(Nos.22272081 and 52473235)Postgraduate Research and Practice Innovation Program of Jiangsu Province(No.KYCX24_1527)National Research Foundation of Korea(NRF)grant funded by the Korea governement(MSIT)(No.RS-2024-00347253)
文摘Advancing clean energy technologies demands efficient and durable electrode catalysts for solid oxide cells(SOCs).Despite their exceptional catalytic properties,Pt-based materials face critical challenges in high-temperature applications owing to particle agglomeration and cost constraints.Here,we demonstrate a rational design strategy utilizing controlled in situ exsolution to create strongly anchored PtSn nanoalloys on oxygen-deficient PrBaMn_(1.8)Pt_(0.1)Sn_(0.1)O_(5+δ)(L-PBMPtSn)perovskite oxide.Through precise compositional engineering and structural control,we achieved a uniform dispersion of PtSn nanoparticles with unique socket-like interfaces that prevent agglomeration while maintaining high catalytic accessibility.The optimized electrode demonstrates remarkable bifunctional performance,achieving a current density of 1.6 A cm^(-2)at 1.8 V for CO_(2)electrolysis and a maximum power density of 316 mW cm^(-2)for fuel cell operation at 800℃.More significantly,the electrode exhibits exceptional stability with only 9.6%performance degradation over 100 h of operation,which is a substantial improvement over conventional electrodes.Our findings establish a new paradigm for designing high-performance SOC electrodes through the controlled exsolution of precious metal alloys,offering broader implications for catalyst design in high-temperature electrochemical systems.
