Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)...Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)FeO_(3-δ) perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocata lytic activity and chemical stability of cathode.At 600℃,Bi_(0.675)Sm_(0.025)Sr_(0.3)FeO_(3-δ)(BSSF25) cathode has been found to be the optimum composition with a polarization resistance of 0.098 Ω cm^2,which is only around 22.8% of Bi_(0.7)Sr_(0.3)FeO_(3-δ)(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm^(-2),which can operate continuously over100 h without obvious degradation.The remarkable electrochemical performance observed can be attributed to the improved O_(2) transport kinetics,superior surface oxygen adsorption capacity,as well as O_(2)p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE) and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO_(2) on the cathode surface,resulting in excellent CO_(2) resistivity.This work provides valuable guidance for systematic design of efficient and durable catalysts for LT-SOFCs.展开更多
Cu catalysts,known for their unparalleled catalytic capabilities due to their unique electronic structure,have faced inherent challenges in maintaining long-term effectiveness under harsh hydrogenation conditions.Here...Cu catalysts,known for their unparalleled catalytic capabilities due to their unique electronic structure,have faced inherent challenges in maintaining long-term effectiveness under harsh hydrogenation conditions.Here,we demonstrate a molybdenum-mediated redispersion behavior of Cu under hightemperature oxidation conditions.The oxidized Cu nanoparticles with rich metal-support interfaces tend to dissolve into the MoO_(3)support upon heating to 600℃,which facilitates the subsequent regeneration in a reducing atmosphere.A similar redispersion phenomenon is observed for Cu nanoparticles supported on Zn O-modified MoO_(3).The modification of ZnO significantly improves the performance of the Cu catalyst for CO_(2)hydrogenation to methanol,with the high activity being well maintained after four repeated oxidation-reduction cycles.In situ spectroscopic and theoretical analyses suggest that the interaction involved in the formation of the copper molybdate-like compound is the driving force for the redispersion of Cu.This method is applicable to various Mo-based oxide supports,offering a practical strategy for the regeneration of sintered Cu particles in hydrogenation applications.展开更多
For the application of carbon capture by membrane process,it is crucial to develop a highly permeable CO_(2)-selective membrane.In this work,we reported an ultra-thin polyether-block-amide(Pebax)mixedmatrix membranes(...For the application of carbon capture by membrane process,it is crucial to develop a highly permeable CO_(2)-selective membrane.In this work,we reported an ultra-thin polyether-block-amide(Pebax)mixedmatrix membranes(MMMs)incorporated by graphene oxide(GO),in which the interlayer channels were regulated to optimize the CO_(2)/N_(2) separation performance.Various membrane preparation conditions were systematically investigated on the influence of the membrane structure and separation performance,including the lateral size of GO nanosheets,GO loading,thermal reduction temperature,and time.The results demonstrated that the precisely regulated interlayer channel of GO nanosheets can rapidly provide CO_(2)-selective transport channels due to the synergetic effects of size sieving and preferential adsorption.The GO/Pebax ultra-thin MMMs exhibited CO_(2)/N_(2) selectivity of 72 and CO_(2) permeance of 400 GPU(1 GPU=106 cm^(3)(STP)·cm^(2)·s^(-1)·cmHg^(-1)),providing a promising candidate for CO_(2) capture.展开更多
In this study,the perovskite nanocomposite PrFe_(x)Co_(1-x)O_(3)(Pr(S))was successfully synthesized by the sol-gel method;PrFe_(x)Co_(1-x)O_(3)/Al-pillared montmorillonite(Pr(S)/Mt)catalysts were prepared by impregnat...In this study,the perovskite nanocomposite PrFe_(x)Co_(1-x)O_(3)(Pr(S))was successfully synthesized by the sol-gel method;PrFe_(x)Co_(1-x)O_(3)/Al-pillared montmorillonite(Pr(S)/Mt)catalysts were prepared by impregnation(D)method and solid-melting(G)method,respectively,with Pr(S)as the active component and Al-pillared montmorillonite as the carrier.The catalysts were applied to treat the 2-hydroxybenzoic acid(2-HA)-simulated wastewater by catalytic wet peroxide oxidation(CWPO)technique,and the chemical oxygen demand(COD)removal rate and the 2-HA degradation rate were used as indicators to evaluate the catalytic performance.The results of the experiment indicated that the solid-melting method was more conducive to preparing the catalyst when the Co/Fe molar ratio of 7:3 and the optimal structural properties of the catalysts were achieved.The influence of operating parameters,including reaction temperature,catalyst dosage,H_(2)O_(2)dosage,pH,and initial 2-HA concentration,were optimized for the degradation of 2-HA by CWPO.The results showed that 97.64%of 2-HA degradation and 75.23%of COD removal rate were achieved under more suitable experimental conditions.In addition,after the catalyst was used five times,the degradation rate of 2-HA could still reach 76.93%,which implied the high stability and reusability of the catalyst.The high catalytic activity of the catalyst was due to the doping of Co into PrFeO_(3),which could promote the generation of HO·,and the high stability could be attributed to the loading of Pr(S)onto Al-Mt,which reduced the leaching of reactive metals.The study of reaction mechanism and kinetics showed that the whole degradation process conformed to the pseudo-firstorder kinetic equation,and the Langmuir-Hinshelwood method was applied to demonstrate that catalysis was dominant in the degradation process.展开更多
The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous me...The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.展开更多
Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(...Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.展开更多
The unique characteristics of nanofibers in rational electrode design enable effec-tive utilization and maximizing material properties for achieving highly efficient and sustainable CO_(2) reduction reactions( CO_(2)R...The unique characteristics of nanofibers in rational electrode design enable effec-tive utilization and maximizing material properties for achieving highly efficient and sustainable CO_(2) reduction reactions( CO_(2)RRs)in solid oxide elec-trolysis cells(SOECs).However,practical appli-cation of nanofiber-based electrodes faces chal-lenges in establishing sufficient interfacial contact and adhesion with the dense electrolyte.To tackle this challenge,a novel hybrid nanofiber electrode,La_(0.6)Sr_(0.4)Co_(0.15)Fe_(0.8)Pd_(0.05)O_(3-δ)(H-LSCFP),is developed by strategically incorporating low aspect ratio crushed LSCFP nanofibers into the excess porous interspace of a high aspect ratio LSCFP nanofiber framework synthesized via electrospinning technique.After consecutive treatment in 100% H_(2) and CO_(2) at 700°C,LSCFP nanofibers form a perovskite phase with in situ exsolved Co metal nanocatalysts and a high concentration of oxygen species on the surface,enhancing CO_(2) adsorption.The SOEC with the H-LSCFP electrode yielded an outstanding current density of 2.2 A cm^(-2) in CO_(2) at 800°C and 1.5 V,setting a new benchmark among reported nanofiber-based electrodes.Digital twinning of the H-LSCFP reveals improved contact adhesion and increased reaction sites for CO_(2)RR.The present work demonstrates a highly catalytically active and robust nanofiber-based fuel electrode with a hybrid structure,paving the way for further advancements and nanofiber applications in CO_(2)-SOECs.展开更多
Vanadium oxides,par-ticularly hydrated forms like V_(2)O_(5)·nH_(2)O(VOH),stand out as promising cathode candidates for aqueous zinc ion batteries due to their adjustable layered structure,unique electronic chara...Vanadium oxides,par-ticularly hydrated forms like V_(2)O_(5)·nH_(2)O(VOH),stand out as promising cathode candidates for aqueous zinc ion batteries due to their adjustable layered structure,unique electronic characteristics,and high theoretical capacities.However,challenges such as vanadium dissolution,sluggish Zn^(2+)diffusion kinetics,and low operating voltage still hinder their direct application.In this study,we present a novel vanadium oxide([C_(6)H_(6)N(CH_(3))_(3)]_(1.08)V_(8)O_(20)·0.06H_(2)O,TMPA-VOH),developed by pre-inserting trimethylphenylammonium(TMPA+)cations into VOH.The incorporation of weakly polarized organic cations capitalizes on both ionic pre-intercalation and molecular pre-intercalation effects,resulting in a phase and morphology transition,an expansion of the interlayer distance,extrusion of weakly bonded interlayer water,and a substantial increase in V^(4+)content.These modifications synergistically reduce the electrostatic interactions between Zn^(2+)and the V-O lattice,enhancing structural stability and reaction kinetics during cycling.As a result,TMPA-VOH achieves an elevated open circuit voltage and operation voltage,exhibits a large specific capacity(451 mAh g^(-1)at 0.1 A g^(-1))coupled with high energy efficiency(89%),the significantly-reduced battery polarization,and outstanding rate capability and cycling stability.The concept introduced in this study holds great promise for the development of high-performance oxide-based energy storage materials.展开更多
P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phas...P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.展开更多
The development of active yet stable catalysts for oxygen reduction reaction(ORR)is still a major issue for the extensive permeation of fuel cells into everyday technology.While nanostructured Pt catalysts are to date...The development of active yet stable catalysts for oxygen reduction reaction(ORR)is still a major issue for the extensive permeation of fuel cells into everyday technology.While nanostructured Pt catalysts are to date the best available systems in terms of activity,the same is not true for stability,particularly under operating conditions.In this work,Pt_(Х)Y alloy nanoparticles are proposed as active and durable electrocatalysts for ORR.Pt_(Х)Y nanoalloys are synthesized and further optimized by laser ablation in liquid followed by laser fragmentation in liquid.The novel integrated laser-assisted methodology succeeded in producing Pt_(Х)Y nanoparticles with the ideal size(<10 nm)of commercial Pt catalysts,yet resulting remarkably more active with E_(1/2)=0.943 V vs.RHE,specific activity=1095μA cm^(-2) and mass activity>1000 A g^(-1).At the same time,the nanoalloys are embedded in a fine Pt oxide matrix,which allows a greater stability of the catalyst than the commercial Pt reference,as directly verified on a gas diffusion electrode.展开更多
Recently,poly(ethylene oxide)(PEO)-based solid polymer electrolytes have been attracting great attention,and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performa...Recently,poly(ethylene oxide)(PEO)-based solid polymer electrolytes have been attracting great attention,and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performance all-solid-state lithium metal batteries.In this article,a novel sandwich structured solid-state PEO composite electrolyte is developed for high performance all-solid-state lithium metal batteries.The PEO-based composite electrolyte is fabricated by hot-pressing PEO,LiTFSI and Ti_(3)C_(2)T_(x) MXene nanosheets into glass fiber cloth(GFC).The as-prepared GFC@PEO-MXene electrolyte shows high mechanical properties,good electrochemical stability,and high lithium-ion migration number,which indicates an obvious synergistic effect from the microscale GFC and the nanoscale MXene.Such as,the GFC@PEO-1 wt%MXene electrolyte shows a high tensile strength of 43.43 MPa and an impressive Young's modulus of 496 MPa,which are increased by 1205%and 6048%over those of PEO.Meanwhile,the ionic conductivity of GFC@PEO-1 wt%MXene at 60℃ reaches 5.01×10^(-2) S m^(-1),which is increased by around 200%compared with that of GFC@PEO electrolyte.In addition,the Li/Li symmetric battery based on GFC@PEO-1 wt%MXene electrolyte shows an excellent cycling stability over 800 h(0.3 mA cm^(-2),0.3 mAh cm^(-2)),which is obviously longer than that based on PEO and GFC@PEO electrolytes due to the better compatibility of GFC@PEO-1 wt%MXene electrolyte with Li anode.Furthermore,the solid-state Li/LiFePO_(4) battery with GFC@PEO-1 wt%MXene as electrolyte demonstrates a high capacity of 110.2–166.1 mAh g^(-1) in a wide temperature range of 25–60C,and an excellent capacity retention rate.The developed sandwich structured GFC@PEO-1 wt%MXene electrolyte with the excellent overall performance is promising for next generation high performance all-solid-state lithium metal batteries.展开更多
The electrochemical CO_(2)reduction reaction to produce multi-carbon(C_(2+)) hydrocarbons or oxygenate compounds is a promising route to obtain a renewable fuel of high energy density.However,producing C_(2+)at high c...The electrochemical CO_(2)reduction reaction to produce multi-carbon(C_(2+)) hydrocarbons or oxygenate compounds is a promising route to obtain a renewable fuel of high energy density.However,producing C_(2+)at high current densities is still a challenge.Herein,we develop a Cu-Zn alloy/Cu-Zn aluminate oxide composite electrocatalytic system for enhanced conversion of CO_(2)to C_(2+)products.The Cu-Zn-Al-Layered Double Hydroxide(LDH) is used as a precursor to decompose into uniform Cu-Zn oxide/Cu-Zn aluminate pre-catalyst.Under electrochemical reduction,Cu-Zn oxide generates Cu-Zn alloy while Cu-Zn aluminate oxide remains unchanged.The alloy and oxide are closely stacked and arranged alternately,and the aluminate oxide induces the strong electron interaction of Cu,Zn and Al,creating a large number of highly active reaction interfaces composed of 0 to+3 valence metal sites.With the help of the interface effect,the optimized Cu_(9)Zn_(1)/Cu_(0.8)Zn_(0.2)Al_(2)O_(4)catalyst achieves a Faradaic efficiency of 88.5% for C_(2+)products at a current density of 400 mA cm^(-2)at-1.15 V versus reversible hydrogen electrode.The in-situ Raman and attenuate total reflectance-infrared absorption spectroscopy(ATR-IRAS) spectra show that the aluminate oxide at the interface significantly enhances the adsorption and activation of CO_(2)and the dissociation of H2O and strengthens the adsorption of CO intermediates,and the alloy promotes the C-C coupling to produce C_(2+)products.This work provides an efficient strategy to construct highly active reaction interfaces for industrial-scale electrochemical CO_(2)RR.展开更多
Reduced graphene oxide(rGO)aerogels are emerging as very attractive scaffolds for high-performance electromagnetic wave absorption materials(EWAMs)due to their intrinsic conductive networks and intricate interior micr...Reduced graphene oxide(rGO)aerogels are emerging as very attractive scaffolds for high-performance electromagnetic wave absorption materials(EWAMs)due to their intrinsic conductive networks and intricate interior microstructure,as well as good compatibility with other electromagnetic(EM)components.Herein,we realized the decoration of rGO aerogel with Mo_(2)C nanoparticles by sequential hydrothermal assembly,freeze-drying,and high-temperature pyrolysis.Results show that Mo_(2)C nanoparticle loading can be easily controlled by the ammonium molybdate to glucose molar ratio.The hydrophobicity and thermal insulation of the rGO aerogel are effectively improved upon the introduction of Mo_(2)C nanoparticles,and more importantly,these nanoparticles regulate the EM properties of the rGO aerogel to a large extent.Although more Mo_(2)C nanoparticles may decrease the overall attenuation ability of the rGO aerogel,they bring much better impedance matching.At a molar ratio of 1:1,a desirable balance between attenuation ability and impedance matching is observed.In this context,the Mo_(2)C/r GO aerogel displays strong reflection loss and broad response bandwidth,even with a small applied thickness(1.7 mm)and low filler loading(9.0wt%).The positive effects of Mo_(2)C nanoparticles on multifunctional properties may render Mo_(2)C/r GO aerogels promising candidates for high-performance EWAMs under harsh conditions.展开更多
Physical vapor deposition(PVD)can be used to produce high-quality Gd_(2)O_(3)-doped CeO2(GDC)films.Among various PVD methods,reactive sputtering provides unique benefits,such as high deposition rates and easy upscalin...Physical vapor deposition(PVD)can be used to produce high-quality Gd_(2)O_(3)-doped CeO2(GDC)films.Among various PVD methods,reactive sputtering provides unique benefits,such as high deposition rates and easy upscaling for industrial applications.GDC thin films were successfully fabricated through reactive sputtering using a Gd_(0.2)Ce_(0.8)(at%)metallic target,and their application in solid oxide fuel cells,such as buffer layers between yttria-stabilized zirconia(YSZ)/La0.6Sr0.4Co0.2Fe0.8O_(3−δ)and as sublayers in the steel/coating system,was evaluated.First,the direct current(DC)reactive-sputtering behavior of the GdCe metallic target was determined.Then,the GDC films were deposited on NiO-YSZ/YSZ half-cells to investigate the influence of oxygen flow rate on the quality of annealed GDC films.The results demonstrated that reactive sputtering can be used to prepare thin and dense GDC buffer layers without high-temperature sintering.Furthermore,the cells with a sputtered GDC buffer layer showed better electrochemical performance than those with a screen-printed GDC buffer layer.In addition,the insertion of a GDC sublayer between the SUS441 interconnects and the Mn-Co spinel coatings contributed to the reduction of the oxidation rate for SUS441 at operating temperatures,according to the area-specific resistance tests.展开更多
Globally,the efficient utilization of polymer wastes is one of the most important issues for current sustainable development topics.Herein,a green and efficient low-temperature combustion approach is proposed to deal ...Globally,the efficient utilization of polymer wastes is one of the most important issues for current sustainable development topics.Herein,a green and efficient low-temperature combustion approach is proposed to deal with polymer wastes and recover heat energy,simultaneously alleviating the environment and energy crisis.Non-noble metal oxides(Al_(2)O_(3),Fe_(2)O_(3),NiO_(2),ZrO_(2),La_(2)O_(3)and CeO_(2)) were prepared,characterized and screened to boost the low-temperature combustion of polyethylene waste at 300℃ in air.The mass change,heat release and CO_(x) formation were studied in details and employed to evaluate the combustion rate and efficiency.It was found that CeO_(2)significantly enhanced the combustion rate and efficiency,which was respectively 2 and 7 times that of non-catalytic case.An interesting phenomenon was observed that the catalytic performance of CeO_(2) in polyethylene low-temperature combustion was significantly improved by the 7-day storage in the room environment or water treatment.XPS analysis confirmed the co-existence of Ce^(3+) and Ce^(4+) in CeO_(2),and the 7-day storage and water treatment promoted the amount of Ce^(3+),which facilitated the formation of the oxygen vacancies.That may be the reason why CeO_(2) exhibited excellent catalytic performance in polyethylene low-temperature combustion.展开更多
Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the i...Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the involvement of oxygen redox.Herein,a Co-free Li-rich layered oxide Li_(1.286)Ni_(0.071)Mn_(0.643)O_(2)has been prepared by a co-precipitation method to systematically investigate the undefined effects of the oxygen defects.A significant O_(2)release and the propagation of oxygen vacancies were detected by operando differential electrochemical mass spectroscopy(DEMS)and electron energy loss spectroscopy(EELS),respectively.Scanning transmission electron microscopy-high angle annular dark field(STEMHAADF)reveals the oxygen vacancies fusing to nanovoids and monitors a stepwise electrochemical activation process of the large Li_(2)MnO_(3)domain upon cycling.Combined with the quantitative analysis conducted by the energy dispersive spectrometer(EDS),existed nano-scale oxygen defects actually expose more surface to the electrolyte for facilitating the electrochemical activation and subsequently increasing available capacity.Overall,this work persuasively elucidates the function of oxygen defects on oxygen redox in Co-free Li-rich layered oxides.展开更多
Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,...Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,we fabricated self-supported ultrathin NiCo layered double hydroxides(LDHs)electrodes as anode for methanol electrooxidation to achieve a high formate production rate(5.89 mmol h^(-1)cm^(-2))coupled with CO_(2)electro-reduction at the cathode.A total formate faradic efficiency of both anode for methanol oxidation and cathode for CO_(2)reduction can reach up to 188%driven by a low cell potential of only 2.06 V at 100 mA cm^(-2)in membrane-electrode assembly(MEA).Physical characterizations demonstrated that Ni^(3+)species,formed on the electrochemical oxidation of Ni-containing hydroxide,acted as catalytically active species for the oxidation of methanol to formate.Furthermore,DFT calculations revealed that ultrathin LDHs were beneficial for the formation of Ni^(3+)in hydroxides and introducing oxygen vacancy in NiCo-LDH could decrease the energy barrier of the rate-determining step for methanol oxidation.This work presents a promising approach for fabricating advanced electrodes towards electrocatalytic reactions.展开更多
Undoped nickel-based catalysts supported on depleted uranium oxide allow one to carry out CO_(2)methanation process under extremely low reaction temperature under atmospheric pressure and powered by a contactless indu...Undoped nickel-based catalysts supported on depleted uranium oxide allow one to carry out CO_(2)methanation process under extremely low reaction temperature under atmospheric pressure and powered by a contactless induction heating.By adjusting the reaction conditions,the catalyst is able to perform CO_(2)methanation reaction under autothermal process operated inside a non-adiabatic reactor,without any external energy supply.Such autothermal process is possible thanks to the high apparent density of the UO_x which allows one to confine the reaction heat in a small catalyst volume in order to confine the exothermicity of the reaction inside the catalyst and to operate the reaction at equilibrium heat in-heat out.Such autothermal operation mode allows one to significantly reduce the complexity of the process compared to that operated using adiabatic reactor,where complete insulation is required to prevent heat disequilibrium,in order to reduce as much as possible,the heat exchange with the external medium.The catalyst displays an extremely high stability as a function of time on stream as no apparent deactivation.It is expected that such new catalyst with unprecedented catalytic performance could open new era in the field of heterogeneous catalysis where traditional supports show their limitations to operate catalytic processes under severe reaction conditions.展开更多
Electrochemical reduction of Bi-based metal oxides is regarded as an effective strategy to rationally design advanced electrocatalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR).Realizing high selectivity ...Electrochemical reduction of Bi-based metal oxides is regarded as an effective strategy to rationally design advanced electrocatalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR).Realizing high selectivity at high current density is important for formate production,but remains challenging.Herein,the BiIn hybrid electrocatalyst,deriving from the Bi2O3/In2O3heterojunction(MOD-Biln),shows excellent catalytic performance for CO_(2)RR.The Faradaic efficiency of formate(FEHCOO-) can be realized over 90% at a wide potential window from-0.4 to-1.4 V vs.RHE,while the partial current density of formate(jHCOO-) reaches about 136.7 mA cm^(-2)at-1.4 V in flow cell without IR-compensation.In additio n,the MOD-Biln exhibits superior stability with high selectivity of formate at 100 mA cm^(-2).Systematic characterizations prove the optimized catalytic sites and interface charge transfer of MOD-Biln,while theoretical calculation confirms that the hybrid structure with dual Bi/In metal sites contribute to the optimal free energy of*H and*OCHO intermediates on MOD-Biln surface,thus accelerating the formation and desorption step of*HCOOH to final formate production.Our work provides a facile and useful strategy to develop highly-active and stable electrocatalysts for CO_(2)RR.展开更多
Cotton(Gossypium spp.) yield is reduced by stress. In this study, high temperature(HT) suppressed the expression of the jasmonic acid(JA) biosynthesis gene allene oxide cyclase 2(GhAOC2), reducing JA content and causi...Cotton(Gossypium spp.) yield is reduced by stress. In this study, high temperature(HT) suppressed the expression of the jasmonic acid(JA) biosynthesis gene allene oxide cyclase 2(GhAOC2), reducing JA content and causing male sterility in the cotton HT-sensitive line H05. Anther sterility was reversed by exogenous application of methyl jasmonate(MeJA) to early buds. To elucidate the role of GhAOC2 in JA biosynthesis and identify its putative contribution to the anther response to HT, we created gene knockout cotton plants using the CRISPR/Cas9 system. Ghaoc2 mutant lines showed male-sterile flowers with reduced JA content in the anthers at the tetrad stage(TS), tapetum degradation stage(TDS), and anther dehiscence stage(ADS). Exogenous application of MeJA to early mutant buds(containing TS or TDS anthers) rescued the sterile pollen and indehiscent anther phenotypes, while ROS signals were reduced in ADS anthers. We propose that HT downregulates the expression of GhAOC2 in anthers, reducing JA biosynthesis and causing excessive ROS accumulation in anthers, leading to male sterility. These findings suggest exogenous JA application as a strategy for increasing male fertility in cotton under HT.展开更多
基金supported by the National Natural Science Foundation of China(22279025,21773048)the Natural Science Foundation of Heilongjiang Province(LH2021A013)+1 种基金the Sichuan Science and Technology Program(2021YFSY0022)the Fundamental Research Funds for the Central Universities(2023FRFK06005,HIT.NSRIF202204)。
文摘Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)FeO_(3-δ) perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocata lytic activity and chemical stability of cathode.At 600℃,Bi_(0.675)Sm_(0.025)Sr_(0.3)FeO_(3-δ)(BSSF25) cathode has been found to be the optimum composition with a polarization resistance of 0.098 Ω cm^2,which is only around 22.8% of Bi_(0.7)Sr_(0.3)FeO_(3-δ)(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm^(-2),which can operate continuously over100 h without obvious degradation.The remarkable electrochemical performance observed can be attributed to the improved O_(2) transport kinetics,superior surface oxygen adsorption capacity,as well as O_(2)p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE) and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO_(2) on the cathode surface,resulting in excellent CO_(2) resistivity.This work provides valuable guidance for systematic design of efficient and durable catalysts for LT-SOFCs.
基金the National Key Research and Development Program of China[No.2021YFB4000700]the CAS Project for Young Scientists in Basic Research[YSBR-022]+1 种基金the National Natural Science Foundation of China[22008136,21925803]the Welsh Government funded Taith Research Mobility Programme[No.524339]。
文摘Cu catalysts,known for their unparalleled catalytic capabilities due to their unique electronic structure,have faced inherent challenges in maintaining long-term effectiveness under harsh hydrogenation conditions.Here,we demonstrate a molybdenum-mediated redispersion behavior of Cu under hightemperature oxidation conditions.The oxidized Cu nanoparticles with rich metal-support interfaces tend to dissolve into the MoO_(3)support upon heating to 600℃,which facilitates the subsequent regeneration in a reducing atmosphere.A similar redispersion phenomenon is observed for Cu nanoparticles supported on Zn O-modified MoO_(3).The modification of ZnO significantly improves the performance of the Cu catalyst for CO_(2)hydrogenation to methanol,with the high activity being well maintained after four repeated oxidation-reduction cycles.In situ spectroscopic and theoretical analyses suggest that the interaction involved in the formation of the copper molybdate-like compound is the driving force for the redispersion of Cu.This method is applicable to various Mo-based oxide supports,offering a practical strategy for the regeneration of sintered Cu particles in hydrogenation applications.
基金financially supported by The Natural Science Foundation of the Jiangsu Higher Education Institutions of China(22KJB530007,22KJA530001)National Natural Science Foundation of China(22208151)+1 种基金the Natural Science Foundation of Jiangsu Province(BK20220002)the State Key Laboratory of MaterialsOriented Chemical Engineering(SKL-MCE-22B07).
文摘For the application of carbon capture by membrane process,it is crucial to develop a highly permeable CO_(2)-selective membrane.In this work,we reported an ultra-thin polyether-block-amide(Pebax)mixedmatrix membranes(MMMs)incorporated by graphene oxide(GO),in which the interlayer channels were regulated to optimize the CO_(2)/N_(2) separation performance.Various membrane preparation conditions were systematically investigated on the influence of the membrane structure and separation performance,including the lateral size of GO nanosheets,GO loading,thermal reduction temperature,and time.The results demonstrated that the precisely regulated interlayer channel of GO nanosheets can rapidly provide CO_(2)-selective transport channels due to the synergetic effects of size sieving and preferential adsorption.The GO/Pebax ultra-thin MMMs exhibited CO_(2)/N_(2) selectivity of 72 and CO_(2) permeance of 400 GPU(1 GPU=106 cm^(3)(STP)·cm^(2)·s^(-1)·cmHg^(-1)),providing a promising candidate for CO_(2) capture.
基金supported by the Key Research and Development Program of Shaanxi,China(2018GY-067).
文摘In this study,the perovskite nanocomposite PrFe_(x)Co_(1-x)O_(3)(Pr(S))was successfully synthesized by the sol-gel method;PrFe_(x)Co_(1-x)O_(3)/Al-pillared montmorillonite(Pr(S)/Mt)catalysts were prepared by impregnation(D)method and solid-melting(G)method,respectively,with Pr(S)as the active component and Al-pillared montmorillonite as the carrier.The catalysts were applied to treat the 2-hydroxybenzoic acid(2-HA)-simulated wastewater by catalytic wet peroxide oxidation(CWPO)technique,and the chemical oxygen demand(COD)removal rate and the 2-HA degradation rate were used as indicators to evaluate the catalytic performance.The results of the experiment indicated that the solid-melting method was more conducive to preparing the catalyst when the Co/Fe molar ratio of 7:3 and the optimal structural properties of the catalysts were achieved.The influence of operating parameters,including reaction temperature,catalyst dosage,H_(2)O_(2)dosage,pH,and initial 2-HA concentration,were optimized for the degradation of 2-HA by CWPO.The results showed that 97.64%of 2-HA degradation and 75.23%of COD removal rate were achieved under more suitable experimental conditions.In addition,after the catalyst was used five times,the degradation rate of 2-HA could still reach 76.93%,which implied the high stability and reusability of the catalyst.The high catalytic activity of the catalyst was due to the doping of Co into PrFeO_(3),which could promote the generation of HO·,and the high stability could be attributed to the loading of Pr(S)onto Al-Mt,which reduced the leaching of reactive metals.The study of reaction mechanism and kinetics showed that the whole degradation process conformed to the pseudo-firstorder kinetic equation,and the Langmuir-Hinshelwood method was applied to demonstrate that catalysis was dominant in the degradation process.
基金funded by the National Natural Science Foundation of China,China (Nos.52272303 and 52073212)the General Program of Municipal Natural Science Foundation of Tianjin,China (Nos.17JCYBJC22700 and 17JCYBJC17000)the State Scholarship Fund of China Scholarship Council,China (Nos.201709345012 and 201706255009)。
文摘The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.
基金supported by the National Key R&D Program of China(2022YFA2105900)the National Natural Science Foundation of China(No.22178197)。
文摘Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.
基金This work was supported by the National Research Foundation of Korea(NRF)grant funded by the Korean Government(MSIT)(2019M3E6A1103944,2020R1A2C2010690).
文摘The unique characteristics of nanofibers in rational electrode design enable effec-tive utilization and maximizing material properties for achieving highly efficient and sustainable CO_(2) reduction reactions( CO_(2)RRs)in solid oxide elec-trolysis cells(SOECs).However,practical appli-cation of nanofiber-based electrodes faces chal-lenges in establishing sufficient interfacial contact and adhesion with the dense electrolyte.To tackle this challenge,a novel hybrid nanofiber electrode,La_(0.6)Sr_(0.4)Co_(0.15)Fe_(0.8)Pd_(0.05)O_(3-δ)(H-LSCFP),is developed by strategically incorporating low aspect ratio crushed LSCFP nanofibers into the excess porous interspace of a high aspect ratio LSCFP nanofiber framework synthesized via electrospinning technique.After consecutive treatment in 100% H_(2) and CO_(2) at 700°C,LSCFP nanofibers form a perovskite phase with in situ exsolved Co metal nanocatalysts and a high concentration of oxygen species on the surface,enhancing CO_(2) adsorption.The SOEC with the H-LSCFP electrode yielded an outstanding current density of 2.2 A cm^(-2) in CO_(2) at 800°C and 1.5 V,setting a new benchmark among reported nanofiber-based electrodes.Digital twinning of the H-LSCFP reveals improved contact adhesion and increased reaction sites for CO_(2)RR.The present work demonstrates a highly catalytically active and robust nanofiber-based fuel electrode with a hybrid structure,paving the way for further advancements and nanofiber applications in CO_(2)-SOECs.
基金This work was supported by the National Science Foundation(CBET-1803256)Dr.C.Liu acknowledges the support from National Natural Science Foundation of China(52102277)the Fundamental Research Funds for the Central Universities,conducted by Tongji University.
文摘Vanadium oxides,par-ticularly hydrated forms like V_(2)O_(5)·nH_(2)O(VOH),stand out as promising cathode candidates for aqueous zinc ion batteries due to their adjustable layered structure,unique electronic characteristics,and high theoretical capacities.However,challenges such as vanadium dissolution,sluggish Zn^(2+)diffusion kinetics,and low operating voltage still hinder their direct application.In this study,we present a novel vanadium oxide([C_(6)H_(6)N(CH_(3))_(3)]_(1.08)V_(8)O_(20)·0.06H_(2)O,TMPA-VOH),developed by pre-inserting trimethylphenylammonium(TMPA+)cations into VOH.The incorporation of weakly polarized organic cations capitalizes on both ionic pre-intercalation and molecular pre-intercalation effects,resulting in a phase and morphology transition,an expansion of the interlayer distance,extrusion of weakly bonded interlayer water,and a substantial increase in V^(4+)content.These modifications synergistically reduce the electrostatic interactions between Zn^(2+)and the V-O lattice,enhancing structural stability and reaction kinetics during cycling.As a result,TMPA-VOH achieves an elevated open circuit voltage and operation voltage,exhibits a large specific capacity(451 mAh g^(-1)at 0.1 A g^(-1))coupled with high energy efficiency(89%),the significantly-reduced battery polarization,and outstanding rate capability and cycling stability.The concept introduced in this study holds great promise for the development of high-performance oxide-based energy storage materials.
基金supported by the National Natural Science Foundation of China (22169002)the Chongzuo Key Research and Development Program of China (20220603)the Counterpart Aid Project for Discipline Construction from Guangxi University(2023M02)
文摘P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.
基金the P-DISC Grant PROMETEO(project number:P-DiSC#03NExuS_BIRD2021-UNIPD)DYNAMO(project number:P-P-DiSC#01BIRD2020-UNIPD)the financial support of the Fellowship in Applied Electrochemistry 2020。
文摘The development of active yet stable catalysts for oxygen reduction reaction(ORR)is still a major issue for the extensive permeation of fuel cells into everyday technology.While nanostructured Pt catalysts are to date the best available systems in terms of activity,the same is not true for stability,particularly under operating conditions.In this work,Pt_(Х)Y alloy nanoparticles are proposed as active and durable electrocatalysts for ORR.Pt_(Х)Y nanoalloys are synthesized and further optimized by laser ablation in liquid followed by laser fragmentation in liquid.The novel integrated laser-assisted methodology succeeded in producing Pt_(Х)Y nanoparticles with the ideal size(<10 nm)of commercial Pt catalysts,yet resulting remarkably more active with E_(1/2)=0.943 V vs.RHE,specific activity=1095μA cm^(-2) and mass activity>1000 A g^(-1).At the same time,the nanoalloys are embedded in a fine Pt oxide matrix,which allows a greater stability of the catalyst than the commercial Pt reference,as directly verified on a gas diffusion electrode.
基金support of the Fundamental Research Funds for the Central Universities(No.2022CDJQY-004)the Fund for Innovative Research Groups of Natural Science Foundation of Hebei Province(No.A2020202002).
文摘Recently,poly(ethylene oxide)(PEO)-based solid polymer electrolytes have been attracting great attention,and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performance all-solid-state lithium metal batteries.In this article,a novel sandwich structured solid-state PEO composite electrolyte is developed for high performance all-solid-state lithium metal batteries.The PEO-based composite electrolyte is fabricated by hot-pressing PEO,LiTFSI and Ti_(3)C_(2)T_(x) MXene nanosheets into glass fiber cloth(GFC).The as-prepared GFC@PEO-MXene electrolyte shows high mechanical properties,good electrochemical stability,and high lithium-ion migration number,which indicates an obvious synergistic effect from the microscale GFC and the nanoscale MXene.Such as,the GFC@PEO-1 wt%MXene electrolyte shows a high tensile strength of 43.43 MPa and an impressive Young's modulus of 496 MPa,which are increased by 1205%and 6048%over those of PEO.Meanwhile,the ionic conductivity of GFC@PEO-1 wt%MXene at 60℃ reaches 5.01×10^(-2) S m^(-1),which is increased by around 200%compared with that of GFC@PEO electrolyte.In addition,the Li/Li symmetric battery based on GFC@PEO-1 wt%MXene electrolyte shows an excellent cycling stability over 800 h(0.3 mA cm^(-2),0.3 mAh cm^(-2)),which is obviously longer than that based on PEO and GFC@PEO electrolytes due to the better compatibility of GFC@PEO-1 wt%MXene electrolyte with Li anode.Furthermore,the solid-state Li/LiFePO_(4) battery with GFC@PEO-1 wt%MXene as electrolyte demonstrates a high capacity of 110.2–166.1 mAh g^(-1) in a wide temperature range of 25–60C,and an excellent capacity retention rate.The developed sandwich structured GFC@PEO-1 wt%MXene electrolyte with the excellent overall performance is promising for next generation high performance all-solid-state lithium metal batteries.
基金supported by the National Natural Science Foundation of China (NSFC)(22075201)the National Key Research and Development Program of China (2022YFB4101800)。
文摘The electrochemical CO_(2)reduction reaction to produce multi-carbon(C_(2+)) hydrocarbons or oxygenate compounds is a promising route to obtain a renewable fuel of high energy density.However,producing C_(2+)at high current densities is still a challenge.Herein,we develop a Cu-Zn alloy/Cu-Zn aluminate oxide composite electrocatalytic system for enhanced conversion of CO_(2)to C_(2+)products.The Cu-Zn-Al-Layered Double Hydroxide(LDH) is used as a precursor to decompose into uniform Cu-Zn oxide/Cu-Zn aluminate pre-catalyst.Under electrochemical reduction,Cu-Zn oxide generates Cu-Zn alloy while Cu-Zn aluminate oxide remains unchanged.The alloy and oxide are closely stacked and arranged alternately,and the aluminate oxide induces the strong electron interaction of Cu,Zn and Al,creating a large number of highly active reaction interfaces composed of 0 to+3 valence metal sites.With the help of the interface effect,the optimized Cu_(9)Zn_(1)/Cu_(0.8)Zn_(0.2)Al_(2)O_(4)catalyst achieves a Faradaic efficiency of 88.5% for C_(2+)products at a current density of 400 mA cm^(-2)at-1.15 V versus reversible hydrogen electrode.The in-situ Raman and attenuate total reflectance-infrared absorption spectroscopy(ATR-IRAS) spectra show that the aluminate oxide at the interface significantly enhances the adsorption and activation of CO_(2)and the dissociation of H2O and strengthens the adsorption of CO intermediates,and the alloy promotes the C-C coupling to produce C_(2+)products.This work provides an efficient strategy to construct highly active reaction interfaces for industrial-scale electrochemical CO_(2)RR.
基金supported by the China Postdoctoral Science Foundation(No.2021MD703944)the Fund of Science and Technology on Near-Surface Detection Laboratory(No.6142414211808)+1 种基金the Director Fund of State Key Laboratory of Pulsed Power Laser Technology(No.SKL2021ZR06)the National Natural Science Foundation of China(No.21776053)。
文摘Reduced graphene oxide(rGO)aerogels are emerging as very attractive scaffolds for high-performance electromagnetic wave absorption materials(EWAMs)due to their intrinsic conductive networks and intricate interior microstructure,as well as good compatibility with other electromagnetic(EM)components.Herein,we realized the decoration of rGO aerogel with Mo_(2)C nanoparticles by sequential hydrothermal assembly,freeze-drying,and high-temperature pyrolysis.Results show that Mo_(2)C nanoparticle loading can be easily controlled by the ammonium molybdate to glucose molar ratio.The hydrophobicity and thermal insulation of the rGO aerogel are effectively improved upon the introduction of Mo_(2)C nanoparticles,and more importantly,these nanoparticles regulate the EM properties of the rGO aerogel to a large extent.Although more Mo_(2)C nanoparticles may decrease the overall attenuation ability of the rGO aerogel,they bring much better impedance matching.At a molar ratio of 1:1,a desirable balance between attenuation ability and impedance matching is observed.In this context,the Mo_(2)C/r GO aerogel displays strong reflection loss and broad response bandwidth,even with a small applied thickness(1.7 mm)and low filler loading(9.0wt%).The positive effects of Mo_(2)C nanoparticles on multifunctional properties may render Mo_(2)C/r GO aerogels promising candidates for high-performance EWAMs under harsh conditions.
基金financially supported by the National Key R&D Program of China (No. 2018YFB1502203-1)the Guangdong Basic and Applied Basic Research Foundation (No. 2021B1515120087)the Stable Supporting Fund of Shenzhen, China (No. GXWD20201230155427003-202007 28114835006)
文摘Physical vapor deposition(PVD)can be used to produce high-quality Gd_(2)O_(3)-doped CeO2(GDC)films.Among various PVD methods,reactive sputtering provides unique benefits,such as high deposition rates and easy upscaling for industrial applications.GDC thin films were successfully fabricated through reactive sputtering using a Gd_(0.2)Ce_(0.8)(at%)metallic target,and their application in solid oxide fuel cells,such as buffer layers between yttria-stabilized zirconia(YSZ)/La0.6Sr0.4Co0.2Fe0.8O_(3−δ)and as sublayers in the steel/coating system,was evaluated.First,the direct current(DC)reactive-sputtering behavior of the GdCe metallic target was determined.Then,the GDC films were deposited on NiO-YSZ/YSZ half-cells to investigate the influence of oxygen flow rate on the quality of annealed GDC films.The results demonstrated that reactive sputtering can be used to prepare thin and dense GDC buffer layers without high-temperature sintering.Furthermore,the cells with a sputtered GDC buffer layer showed better electrochemical performance than those with a screen-printed GDC buffer layer.In addition,the insertion of a GDC sublayer between the SUS441 interconnects and the Mn-Co spinel coatings contributed to the reduction of the oxidation rate for SUS441 at operating temperatures,according to the area-specific resistance tests.
基金the financial support from the National Natural Science Foundation of China(21908010)Jilin Provincial Department of Science and Technology(20220101089JC)the Education Department of Jilin Province(JJKH20220694KJ)。
文摘Globally,the efficient utilization of polymer wastes is one of the most important issues for current sustainable development topics.Herein,a green and efficient low-temperature combustion approach is proposed to deal with polymer wastes and recover heat energy,simultaneously alleviating the environment and energy crisis.Non-noble metal oxides(Al_(2)O_(3),Fe_(2)O_(3),NiO_(2),ZrO_(2),La_(2)O_(3)and CeO_(2)) were prepared,characterized and screened to boost the low-temperature combustion of polyethylene waste at 300℃ in air.The mass change,heat release and CO_(x) formation were studied in details and employed to evaluate the combustion rate and efficiency.It was found that CeO_(2)significantly enhanced the combustion rate and efficiency,which was respectively 2 and 7 times that of non-catalytic case.An interesting phenomenon was observed that the catalytic performance of CeO_(2) in polyethylene low-temperature combustion was significantly improved by the 7-day storage in the room environment or water treatment.XPS analysis confirmed the co-existence of Ce^(3+) and Ce^(4+) in CeO_(2),and the 7-day storage and water treatment promoted the amount of Ce^(3+),which facilitated the formation of the oxygen vacancies.That may be the reason why CeO_(2) exhibited excellent catalytic performance in polyethylene low-temperature combustion.
基金supported by the National Natural Science Foundation of China(52272253)the"Lingyan"Research and Development Plan of Zhejiang Province(2022C01071)+2 种基金the S&T Innovation 2025 Major Special Programme of Ningbo(2018B10081)the Natural Science Foundation of Ningbo(202003N4030)the Youth Innovation Promotion Association of Chinese Academy of Sciences(2022299)。
文摘Though oxygen defects are associated with deteriorated structures and aggravated cycling performance in traditional layered cathodes,the role of oxygen defects is still ambiguous in Li-rich layered oxides due to the involvement of oxygen redox.Herein,a Co-free Li-rich layered oxide Li_(1.286)Ni_(0.071)Mn_(0.643)O_(2)has been prepared by a co-precipitation method to systematically investigate the undefined effects of the oxygen defects.A significant O_(2)release and the propagation of oxygen vacancies were detected by operando differential electrochemical mass spectroscopy(DEMS)and electron energy loss spectroscopy(EELS),respectively.Scanning transmission electron microscopy-high angle annular dark field(STEMHAADF)reveals the oxygen vacancies fusing to nanovoids and monitors a stepwise electrochemical activation process of the large Li_(2)MnO_(3)domain upon cycling.Combined with the quantitative analysis conducted by the energy dispersive spectrometer(EDS),existed nano-scale oxygen defects actually expose more surface to the electrolyte for facilitating the electrochemical activation and subsequently increasing available capacity.Overall,this work persuasively elucidates the function of oxygen defects on oxygen redox in Co-free Li-rich layered oxides.
基金the financial support from the National Nature Science Foundation of China(22078232 and 21938008)the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Electrochemical CO_(2)reduction into energy-carrying compounds,such as formate,is of great importance for carbon neutrality,which however suffers from high electrical energy input and liquid products crossover.Herein,we fabricated self-supported ultrathin NiCo layered double hydroxides(LDHs)electrodes as anode for methanol electrooxidation to achieve a high formate production rate(5.89 mmol h^(-1)cm^(-2))coupled with CO_(2)electro-reduction at the cathode.A total formate faradic efficiency of both anode for methanol oxidation and cathode for CO_(2)reduction can reach up to 188%driven by a low cell potential of only 2.06 V at 100 mA cm^(-2)in membrane-electrode assembly(MEA).Physical characterizations demonstrated that Ni^(3+)species,formed on the electrochemical oxidation of Ni-containing hydroxide,acted as catalytically active species for the oxidation of methanol to formate.Furthermore,DFT calculations revealed that ultrathin LDHs were beneficial for the formation of Ni^(3+)in hydroxides and introducing oxygen vacancy in NiCo-LDH could decrease the energy barrier of the rate-determining step for methanol oxidation.This work presents a promising approach for fabricating advanced electrodes towards electrocatalytic reactions.
基金ORANO Chimie-Enrichissement Co.for the financial support of this project。
文摘Undoped nickel-based catalysts supported on depleted uranium oxide allow one to carry out CO_(2)methanation process under extremely low reaction temperature under atmospheric pressure and powered by a contactless induction heating.By adjusting the reaction conditions,the catalyst is able to perform CO_(2)methanation reaction under autothermal process operated inside a non-adiabatic reactor,without any external energy supply.Such autothermal process is possible thanks to the high apparent density of the UO_x which allows one to confine the reaction heat in a small catalyst volume in order to confine the exothermicity of the reaction inside the catalyst and to operate the reaction at equilibrium heat in-heat out.Such autothermal operation mode allows one to significantly reduce the complexity of the process compared to that operated using adiabatic reactor,where complete insulation is required to prevent heat disequilibrium,in order to reduce as much as possible,the heat exchange with the external medium.The catalyst displays an extremely high stability as a function of time on stream as no apparent deactivation.It is expected that such new catalyst with unprecedented catalytic performance could open new era in the field of heterogeneous catalysis where traditional supports show their limitations to operate catalytic processes under severe reaction conditions.
基金financially supported by the National Natural Science Foundation of China (Grant Nos. 22205205)the Zhejiang Provincial Natural Science Foundation of China (Grant Nos.LQ22B030008)the Science Foundation of Zhejiang Sci-Tech University (ZSTU)(Grant Nos. 21062337-Y and 22062312-Y)。
文摘Electrochemical reduction of Bi-based metal oxides is regarded as an effective strategy to rationally design advanced electrocatalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR).Realizing high selectivity at high current density is important for formate production,but remains challenging.Herein,the BiIn hybrid electrocatalyst,deriving from the Bi2O3/In2O3heterojunction(MOD-Biln),shows excellent catalytic performance for CO_(2)RR.The Faradaic efficiency of formate(FEHCOO-) can be realized over 90% at a wide potential window from-0.4 to-1.4 V vs.RHE,while the partial current density of formate(jHCOO-) reaches about 136.7 mA cm^(-2)at-1.4 V in flow cell without IR-compensation.In additio n,the MOD-Biln exhibits superior stability with high selectivity of formate at 100 mA cm^(-2).Systematic characterizations prove the optimized catalytic sites and interface charge transfer of MOD-Biln,while theoretical calculation confirms that the hybrid structure with dual Bi/In metal sites contribute to the optimal free energy of*H and*OCHO intermediates on MOD-Biln surface,thus accelerating the formation and desorption step of*HCOOH to final formate production.Our work provides a facile and useful strategy to develop highly-active and stable electrocatalysts for CO_(2)RR.
基金funding support from the National Natural Science Foundation of China (32072024)the Fundamental Research Funds for the Central Universities (2021ZKPY019)the National Key Research and Development Program of China (2018YFD0100403, 2016YFD0101402)。
文摘Cotton(Gossypium spp.) yield is reduced by stress. In this study, high temperature(HT) suppressed the expression of the jasmonic acid(JA) biosynthesis gene allene oxide cyclase 2(GhAOC2), reducing JA content and causing male sterility in the cotton HT-sensitive line H05. Anther sterility was reversed by exogenous application of methyl jasmonate(MeJA) to early buds. To elucidate the role of GhAOC2 in JA biosynthesis and identify its putative contribution to the anther response to HT, we created gene knockout cotton plants using the CRISPR/Cas9 system. Ghaoc2 mutant lines showed male-sterile flowers with reduced JA content in the anthers at the tetrad stage(TS), tapetum degradation stage(TDS), and anther dehiscence stage(ADS). Exogenous application of MeJA to early mutant buds(containing TS or TDS anthers) rescued the sterile pollen and indehiscent anther phenotypes, while ROS signals were reduced in ADS anthers. We propose that HT downregulates the expression of GhAOC2 in anthers, reducing JA biosynthesis and causing excessive ROS accumulation in anthers, leading to male sterility. These findings suggest exogenous JA application as a strategy for increasing male fertility in cotton under HT.