The mechanism of lithospheric removal and destruction of the North China Craton(NCC)has been hotly debated for decades.It is now generally accepted that the subduction of the(Paleo)-Pacific plate played an important r...The mechanism of lithospheric removal and destruction of the North China Craton(NCC)has been hotly debated for decades.It is now generally accepted that the subduction of the(Paleo)-Pacific plate played an important role in this process.However,how the plate subduction contributed to the craton destruction remains unclear.Here we report high oxygen fugacity(fO2)characteristics of the Yunmengshan granite,e.g.,hematitemagnetite intergrowth supported by zircon Ce^4+/Ce^3+ratios and apatite Mn oxygen fugacity indicator.High fO2 magmas are widely discovered in Late Mesozoic(160-130 Ma)adakitic rocks in central NCC.The origin of high fO2 magma is likely related to the input of the"oxidized mantle components",which shows a dose connection between plate subduction and destruction of the craton.The research area is^1500 km away from the current Pacific subduction zone.Considering the back-arc extension of Japan Sea since the Cretaceous,this distance may be shortened to^800 km,which is still too far for normal plate subduction.Ridge subduction is the best candidate that was responsible for the large scale magmatism and the destruction of the NCC.Massive slab-derived fluids and/or melts were liberated into an overlying mantle wedge and modified the lithospheric mantle.Rollback of the subducting plate induced the large-scale upwelling of asthenospheric mantle and triggered the formation of extensive high fO2 intraplate magmas.展开更多
The goal of this work is to produce nanocomposite film with low oxygen permeability by casting an aqueous solution containing xylan,sorbitol and nanocrystalline cellulose.The morphology of the resulting nanocomposite ...The goal of this work is to produce nanocomposite film with low oxygen permeability by casting an aqueous solution containing xylan,sorbitol and nanocrystalline cellulose.The morphology of the resulting nanocomposite films was examined by scanning electron microscopy and atomic force microscopy which showed that control films containing xylan and sorbitol had a more open structure as compared to xylan-sorbitol films containing sulfonated nanocrystalline cellulose.The average pore diameter,bulk density,porosity and tortuosity factor measurements of control xylan films and nanocomposite xylan films were examined by mercury intrusion porosimetry techniques.Xylan films reinforced with nanocrystalline cellulose were denser and exhibited higher tortuosity factor than the control xylan films.Control xylan films had average pore diameter,bulk density,porosity and tortuosity factor of 0.1730 μm,0.6165 g/ml,53.0161% and 1.258,respectively as compared to xylan films reinforced with 50% nanocrystalline cellulose with average pore diameter of 0.0581 μm,bulk density of 1.1513 g/ml,porosity of 22.8906% and tortuosity factor of 2.005.Oxygen transmission rate tests demonstrated that films prepared with xylan,sorbitol and 5%,10%,25% and 50% sulfonated nanocrystalline cellulose exhibited a significantly reduced oxygen permeability of 1.1387,1.0933,0.8986 and 0.1799 cm^3×μm/m^2×d×k Pa respectively with respect to films prepared solely from xylan and sorbitol with a oxygen permeability of 189.1665 cm^3×μm/m^2×d×k Pa.These properties suggested these nanocomposite films have promising barrier properties.展开更多
Oxygen vacancies (V_(o)) engineering has been deemed to an effective tactic for enhancing Li-ion storage kinetics and reversibility of SnO_(2)-based anode materials.Herein,we demonstrated the confinement of ultrahigh ...Oxygen vacancies (V_(o)) engineering has been deemed to an effective tactic for enhancing Li-ion storage kinetics and reversibility of SnO_(2)-based anode materials.Herein,we demonstrated the confinement of ultrahigh V_(o)SnO_(2) nanocrystals into N-doped carbon frameworks to boost their high-rate and cycle life.Density functional theory (DFT) calculations reveal that abundant V_(o) in SnO_(2) facilitates the adsorption to Li-ion with remarkably increased carrier concentration.The 6.0 nm-sized SnO_(2) particles and the embedded design effectively stabilize the structural integrity during de-/lithiation.Meantime,the as-formed large hetero-interface also expedites the electron transfer.These merits guarantee its high-rate performance and superior cycling stability.Consequently,this sample exhibits a high capacity of 1368.9m Ah g^(-1)at 0.1 A g^(-1),and can still maintain 488.5 mAh g^(-1)at 10 A g^(-1)and a long life over 400 cycles at 5 A g^(-1)with 96.6%capacity retention,which is among the best report for Sn-contained anode materials.This work sheds light on ultrahigh Vo and structural design in conversion-type oxides for highperformance lithium-ion batteries (LIBs).展开更多
Several kinds of slide nozzle plate such as Al2O3-C-ZrO2,MgO,Al2O3,Spinel-C and Al2O3-C SN plate for high oxygen steel used in BaoSteel have been analysed,the appearance and size of the SN plate after using have been ...Several kinds of slide nozzle plate such as Al2O3-C-ZrO2,MgO,Al2O3,Spinel-C and Al2O3-C SN plate for high oxygen steel used in BaoSteel have been analysed,the appearance and size of the SN plate after using have been measured.The Al2O3-C SN plate has longer service life in casting high oxygen steel,and the wear mechanism of different SN plates is discussed.展开更多
Cobalt-free perovskite-type oxides Ba Fe_(1-y)Ta_yO_(3-δ)(0 ≤ y ≤ 0.2)were synthesized via a simple solid state reaction.The cubic perovskite structure can be obtained when y is over 0.1.Ba Fe_(0.9)Ta_(0.1)O_(3-δ)...Cobalt-free perovskite-type oxides Ba Fe_(1-y)Ta_yO_(3-δ)(0 ≤ y ≤ 0.2)were synthesized via a simple solid state reaction.The cubic perovskite structure can be obtained when y is over 0.1.Ba Fe_(0.9)Ta_(0.1)O_(3-δ)(BFT0.1)membrane shows the highest oxygen permeation flux,which can reach 1.6 ml·min^(-1)·cm^(-2)at 950 °C under the gradient of air/He.The O_2-TPD results reveal that Ba Fe_(0.9)Ta_(0.1)O_(3-δ)material shows an excellent reversibility and phase structure stability in air.The oxygen permeation flux is limited by the bulk diffusion when the membrane thickness is over 0.8 mm,and it is limited by both the bulk diffusion and the surface exchange when the membrane thickness is below 0.5 mm.Stable oxygen permeation fluxes are obtained during 180 h operation.展开更多
The thermogravimetric analysis of a ternary Cu-25Ni-30Cr alloy prepared by conventional casting was performed in 0.1MPa pure O2 at 700-800℃. The results show that the alloy is composed of three phases, where the ...The thermogravimetric analysis of a ternary Cu-25Ni-30Cr alloy prepared by conventional casting was performed in 0.1MPa pure O2 at 700-800℃. The results show that the alloy is composed of three phases, where the phase with the largest copper and lowest chromium content forms the matrix, while the other two, much richer in chromium, form a dispersion of isolated particles. At variance with another three-phase Cu-20Ni-20Cr alloy, which forms complex scales containing the oxides of the various components and double oxides plus an irregular region composed of alloy and oxides, the present alloy can form a very irregular but continuous chromia layer at the base of the mixed internal region, producing a gradual decrease of the oxidation rate down to very low values. A larger chromium content needed to form chromia layer for a ternary three-phase alloy is attributed to the limitations to the diffusion of the alloy components in the metal substrate imposed by their multiphase nature.展开更多
Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy ...Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.展开更多
The incorporation of partial A-site substitution in perovskite oxides represents a promising strategy for precisely controlling the electronic configuration and enhancing its intrinsic catalytic activity.Conventional ...The incorporation of partial A-site substitution in perovskite oxides represents a promising strategy for precisely controlling the electronic configuration and enhancing its intrinsic catalytic activity.Conventional methods for A-site substitution typically involve prolonged high-temperature processes.While these processes promote the development of unique nanostructures with highly exposed active sites,they often result in the uncontrolled configuration of introduced elements.Herein,we present a novel approach for synthesizing two-dimensional(2D)porous GdFeO_(3) perovskite with A-site strontium(Sr)substitution utilizing microwave shock method.This technique enables precise control of the Sr content and simultaneous construction of 2D porous structures in one step,capitalizing on the advantages of rapid heating and cooling(temperature~1100 K,rate~70 K s^(-1)).The active sites of this oxygen-rich defect structure can be clearly revealed through the simulation of the electronic configuration and the comprehensive analysis of the crystal structure.For electrocatalytic oxygen evolution reaction application,the synthesized 2D porous Gd_(0.8)Sr_(0.2)FeO_(3) electrocatalyst exhibits an exceptional overpotential of 294 mV at a current density of 10 mA cm^(-2)and a small Tafel slope of 55.85 mV dec^(-1)in alkaline electrolytes.This study offers a fresh perspective on designing crystal configurations and the construction of nanostructures in perovskite.展开更多
The sluggish kinetics of the electrochemical oxygen reduction reaction(ORR)in intermediatetemperature solid oxide fuel cells(IT-SOFCs)greatly limits the overall cell performance.In this study,an efficient and durable ...The sluggish kinetics of the electrochemical oxygen reduction reaction(ORR)in intermediatetemperature solid oxide fuel cells(IT-SOFCs)greatly limits the overall cell performance.In this study,an efficient and durable cathode material for IT-SOFCs is designed based on density functional theory(DFT)calculations by co-doping with Nb and Ta the B-site of the SrFeO_(3-δ)perovskite oxide.The DFT calculations suggest that Nb/Ta co-doping can regulate the energy band of the parent SrFeO_(3-δ)and help electron transfer.In symmetrical cells,such cathode with a SrFe_(0.8)Nb_(0.1)Ta_(0.1)O_(3-δ)(SFNT)detailed formula achieves a low cathode polarization resistance of 0.147Ωcm^(2) at 650℃.Electron spin resonance(ESR)and X-ray photoelectron spectroscopy(XPS)analysis confirm that the co-doping of Nb/Ta in SrFeO_(3-δ)B-site increases the balanced concentration of oxygen vacancies,enhancing the electrochemical performance when compared to 20 mol%Nb single-doped perovskite oxide.The cathode button cell with NiSDC|SDC|SFNT configuration achieves an outstanding peak power density of 1.3 W cm^(-2)at 650℃.Moreover,the button cell shows durability for 110 h under 0.65 V at 600℃ using wet H_(2) as fuel.展开更多
The low net efficiency of oxy-fuel circulating fluidized bed(CFB)combustion is mainly due to the addition of air separation unit(ASU)and carbon dioxide compression and purification unit(CPU).High oxygen concentration ...The low net efficiency of oxy-fuel circulating fluidized bed(CFB)combustion is mainly due to the addition of air separation unit(ASU)and carbon dioxide compression and purification unit(CPU).High oxygen concentration is one of the effective methods to improve the net efficiency of oxy-fuel combustion technology in CFB.In this research,a series of calculation and simulation were carried out based on Aspen Plus platform to provide valuable information for further investigation on the CFB oxy-fuel combustion system with high oxygen concentration(40%,50%).A CFB oxy-fuel combustion system model with high oxygen concentration was established including ASU,CPU and CFB oxy-fuel combustion and heat exchange unit.Based on the simulation data,energy and exergy efficiency were analyzed to obtain the following results.The cross-sectional area of furnace and tail flue of 50%CFB oxy-fuel combustion boiler are 43%and 56%of the original size respectively,reducing the construction and investment cost effectively.With the increase of oxygen concentration,the net efficiency of power generation increased significantly,reaching 24.85%and increasing by 6.09%under the condition of 50%oxy-fuel combustion.The total exergy loss increases with the increase of oxygen concentration.In addition,the exergy loss of radiation heat transfer is far higher than convection heat transfer.展开更多
Theanine content is highly correlated with sensory quality and health benefits of tea infusion.The tender shoots of etiolated and albino tea plants contain higher theanine than the normal green tea plants and are valu...Theanine content is highly correlated with sensory quality and health benefits of tea infusion.The tender shoots of etiolated and albino tea plants contain higher theanine than the normal green tea plants and are valuable materials for high quality green tea processing.However,why these etiolated or albino tea plants can highly accumulate theanine is largely unknown.In this study,we observed an Arabidopsis etiolated mutant hy1–100(mutation in Haem Oxygenase 1,HO1)that accumulated higher levels of glutamine(an analog of theanine).We therefore identified CsHO1 in tea plants and found CsHO1 is conserved in amino acid sequences and subcellular localization with its homologs in other plants.Importantly,CsHO1 expression in the new shoots was much lower in an etiolated tea plants‘Huangkui’and an albino tea plant‘Huangshan Baicha’than that in normal green tea plants.The expression levels of CsHO1 were negatively correlated with theanine contents in these green,etiolated and albino shoots.Moreover,CsHO1 expression levels in various organs and different time points were also negatively correlated with theanine accumulation.The hy1–100 was hypersensitive to high levels of theanine and accumulated more theanine under theanine feeding,and these phenotypes were rescued by the expression of CsHO1 in this mutant.Transient knockdown CsHO1 expression in the new shoots of tea plant using antisense oligonucleotides(asODN)increased theanine accumulation.Collectively,these results demonstrated CsHO1 negatively regulates theanine accumulation in tea plants,and that low expression CsHO1 likely contributes to the theanine accumulation in etiolated/albino tea plants.展开更多
The“shuttle effect”of lithium polysulfides(LiPSs)is a huge challenge for practical use of high-energydensity lithium-sulfur(Li-S)batteries,and one of the main reasons is the sluggish kinetics of sulfur conversion.Me...The“shuttle effect”of lithium polysulfides(LiPSs)is a huge challenge for practical use of high-energydensity lithium-sulfur(Li-S)batteries,and one of the main reasons is the sluggish kinetics of sulfur conversion.Metal oxides are able to expedite the sulfur electrochemistry,and the structural defects enhance the adsorption-conversion ability of metal oxides for polysulfides.However,a significant research gap still remains regarding the relationship between the oxygen vacancy concentration and the adsorptivecatalytic performance of metal oxides.Herein,we establish a correlation between oxygen vacancy concentration and adsorptive-catalytic properties by using tungsten oxide(WO_(x))as model catalysts.It is revealed that high-concentration oxygen vacancy is beneficial for enhancing the binding between tungsten oxide and LiPSs,reducing the energy barrier of Li_(2)S decomposition,and promoting polysulfide conversion kinetics.Consequently,the Li-S batteries using the tungsten oxide with high-concentration oxygen vacancies deliver high initial discharge capacity of 1169 mA h g^(-1)at 0.2 C and 865 mA h g^(-1)at 2 C,low attenuation rate of 0.064%per cycle over 1100 cycles at 2 C.With a high sulfur area loading of 5.34 mg cm^(-2),the Li-S batteries still exhibit high initial gravimetric capacity of 982 mA h g^(-1)at 0.1 C and areal capacity of 5.92 mA h cm^(-2).This work promotes the feasibility of defect engineering on metal oxides as an effective mean to enhance the practicality of Li-S batteries.展开更多
Electrocatalytic oxygen reduction via a two-electron pathway(2e^(-)-ORR)is a promising and eco-friendly route for producing hydrogen peroxide(H_(2)O_(2)).Single-atom catalysts(SACs)typically show excellent selectivity...Electrocatalytic oxygen reduction via a two-electron pathway(2e^(-)-ORR)is a promising and eco-friendly route for producing hydrogen peroxide(H_(2)O_(2)).Single-atom catalysts(SACs)typically show excellent selectivity towards 2e^(-)-ORR due to their unique electronic structures and geometrical configurations.The very low density of single-atom active centers,however,often leads to unsatisfactory H_(2)O_(2)yield rate,significantly inhibiting their practical feasibility.Addressing this,we herein introduce fluorine as a secondary doping element into conventional SACs,which does not directly coordinate with the singleatom metal centers but synergize with them in a remote manner.This strategy effectively activates the surrounding carbon atoms and converts them into highly active sites for 2e^(-)-ORR.Consequently,a record-high H_(2)O_(2)yield rate up to 27 mol g^(-1)h^(-1)has been achieved on the Mo–F–C catalyst,with high Faradaic efficiency of 90%.Density functional theory calculations further confirm the very kinetically facile 2e^(-)-ORR over these additional active sites and the superiority of Mo as the single-atom center to others.This strategy thus not only provides a high-performance electrocatalyst for 2e^(-)-ORR but also should shed light on new strategies to significantly increase the active centers number of SACs.展开更多
Electrochemical water splitting is a straightforward process that involves two distinct reactions:the oxygen evolution reaction(OER)which produces oxygen(O_(2))and the hydrogen evolution reaction(HER)which generates h...Electrochemical water splitting is a straightforward process that involves two distinct reactions:the oxygen evolution reaction(OER)which produces oxygen(O_(2))and the hydrogen evolution reaction(HER)which generates hydrogen(H_(2)).However,in the whole process,the OER is a bottleneck as it requires more energy than a four-electron reaction involving critical raw materials(such as RuO_(2)or IrO_(2))as electrocatalysts.Therefore,here,we address the challenge of erratic kinetics/limited durability of OER in water electrolysis,In this paper,we demonstrate that the deposition of ultrasmall amounts of nickel(Ⅱ)nitrate in zeolitic imidazolate framework-67(ZIF-67)can be used as a general approach to enhance the electrocatalytic performance of the framework.We investigated the influence of Ni(NO_(3))·x6H_(2)O loading on ZIF-67(from 0.1 to 0.0001 M)and found that ZIF-67 enriched with only 0.001 M of Ni(NO_(3))2·x6H_(2)O(ZIF-670.001 Ni)exhibited massive promotion in OER.The ZIF-670.001 Ni showed a large specific surface area of 2577 m^(2)g^(-1),a low overpotential of 299 mV,a lower Tafel slope of 94.1 mA dec^(-1),and an outstanding overpotential retention of 99.8%(at 50 mA cm^(-2)).By conducting electron paramagnetic resonance(EPR)measurements,we also discovered that the 0.001 M of Ni(NO_(3))_(2)·x6H_(2)O loading in ZIF-67 introduces Ni^(^(2+))dimers,which contribute to the enhanced electroactivity of the modified ZIF-67.This phenomenon was further revealed during density-functional theory(DFT)calculations,which allowed us to identify different possible forms of Ni^(^(2+))dimers and modeling of active centers.Along with in situ experiments,we provide mechanistic insight into the OER mechanism under alkaline conditions and found that it follows the lattice oxygen mechanism(LOM).Our study proposes a facile and efficient room-temperature route to boost the electrochemical performance of ZIF-67 in OER.For the first time,we demonstrate that modifying ZIF-67 with an ultrasmall amount of different nickel(Ⅱ)salts opens a general route to enhance its electroactivity during water-splitting reactions.展开更多
The development of simple and effective strategies to prepare electrocatalysts,which possess unique and stable structures comprised of metal/nonmetallic atoms for oxygen reduction reaction(ORR)and oxygen evolution rea...The development of simple and effective strategies to prepare electrocatalysts,which possess unique and stable structures comprised of metal/nonmetallic atoms for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),is currently an urgent issue.Herein,an efficient bifunctional electrocatalyst featured by ultralong N,S-doped carbon nano-hollow-sphere chains about 1300 nm with encapsulated Co nanoparticles(Co-CNHSCs)is developed.The multifunctional catalytic properties of Co together with the heteroatom-induced charge redistribution(i.e.,modulating the electronic structure of the active site)result in superior catalytic activities toward OER and ORR in alkaline media.The optimized catalyst Co-CNHSC-3 displays an outstanding electrocatalytic ability for ORR and OER,a high specific capacity of 1023.6 mAh gZn^(-1),and excellent reversibility after 80 h at 10mA cm^(-2)in a Zn-air battery system.This work presents a new strategy for the design and synthesis of efficient multifunctional carbon-based catalysts for energy storage and conversion devices.展开更多
Enhancing the stability of Pt-based electrocatalysts for the sluggish cathodic oxygen reduction reaction(ORR)is critical for proton exchange membrane fuel cells(PEMFCs).Herein,high-entropy intermetallic(HEI)L1_(2)-Pt(...Enhancing the stability of Pt-based electrocatalysts for the sluggish cathodic oxygen reduction reaction(ORR)is critical for proton exchange membrane fuel cells(PEMFCs).Herein,high-entropy intermetallic(HEI)L1_(2)-Pt(FeCoNiCuZn)3is designed for durable ORR catalysis.Benefiting from the unique HEI structure and the enhanced intermetallic phase stability,Pt(FeCoNiCuZn)3/C nanoparticles demonstrate significantly improved stability over Pt/C and PtCu_(3)/C catalysts.The Pt(FeCoNiCuZn)3/C exhibits a negligible decay of the half-wave potential during 30,000 potential cycles from 0.6 to 1.0 V,whereas Pt/C and PtCu_(3)/C are negatively shifted by 46 and 36 m V,respectively.Even after 10,000 cycles at potential up to 1.5 V,the mass activity of Pt(FeCoNiCuZn)3/C still shows~70%retention.As evidenced by the structural characterizations,the HEI structure of Pt(FeCoNiCuZn)3/C is well maintained,while PtCu_(3)/C nanoparticles undergo severe Cu leaching and particle growth.In addition,when assembled Pt(FeCoNiCuZn)3/C as the cathode in high-temperature PEMFC of 160℃,the H_(2)-O_(2)fuel cell delivers almost no degradation even after operating for 150 h,demonstrating the potential for fuel cell applications.This work provides a facile design strategy for the development of high-performance ultrastable electrocatalysts.展开更多
Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utiliza...Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utilization efficiency.However,there is still a lack of systematic screening and optimization of local structures surrounding active centers of SACs for ORR as the local coordination has an essential impact on their electronic structures and catalytic performance.Herein,we systematic study the ORR catalytic performance of M-NC SACs with different central metals and environmental atoms in the first and second coordination sphere by using density functional theory(DFT)calculation and machine learning(ML).The geometric and electronic informed overpotential model(GEIOM)based on random forest algorithm showed the highest accuracy,and its R^(2) and root mean square errors(RMSE)were 0.96 and 0.21,respectively.30 potential high-performance catalysts were screened out by GEIOM,and the RMSE of the predicted result was only 0.12 V.This work not only helps us fast screen high-performance catalysts,but also provides a low-cost way to improve the accuracy of ML models.展开更多
Non-renewable fossil fuels have led to serious problems such as global warming,environmental pollution,etc.Oxygen electrocatalysis including oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)plays a cent...Non-renewable fossil fuels have led to serious problems such as global warming,environmental pollution,etc.Oxygen electrocatalysis including oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)plays a central role in clean energy conversion,enabling a number of sustainable processes for future air battery technologies.Fluorine,as the most electronegative element(4.0)not only can induce more efficient regulation for the electronic structure,but also can bring more abundant defects and other novel effects in materials selection and preparation for favorable catalysis with respect to the other nonmetal elements.However,an individual and comprehensive overview of fluorine-containing functional materials for oxygen electrocatalysis field is still blank.Therefore,it is very meaningful to review the recent progresses of fluorine-containing oxygen electrocatalysts.In this review,we first systematically summarize the controllable preparation methods and their possible development directions based on fluorine-containing materials from four preparation methods.Due to the strong electron-withdrawing properties of fluorine,its control of the electronic structure can effectively enhance the oxygen electrocatalytic activity of the materials.In addition,the catalytic enhancement effect of fluorine on carbonbased materials also includes the prevent oxidation and the layer peeling,and realizes the precise atomic control.And the catalytic improvement mechanism of fluorine containing metal-based compounds also includes the hydration of metal site,the crystal transformation,and the oxygen vacancy induction.Then,based on their various dimensions(0D–3D),we also have summarized the advantages of different morphologies on oxygen electrocatalytic performances.Finally,the prospects and possible future researching direction of F-containing oxygen electrocatalysts are presented(e.g.,novel pathways,advanced methods for measurement and simulation,field assistance and multi-functions).The review is considered valuable and helpful in exploring the novel designs and mechanism analyses of advanced fluorine-containing electrocatalysts.展开更多
Molecular crystals are complex systems exhibiting various crystal structures,and accurately modeling the crystal structures is essential for understanding their physical behaviors under high pressure.Here,we perform a...Molecular crystals are complex systems exhibiting various crystal structures,and accurately modeling the crystal structures is essential for understanding their physical behaviors under high pressure.Here,we perform an extensive structure search of ternary carbon-nitrogen-oxygen(CNO)compound under high pressure with the CALYPSO method and first principles calculations,and successfully identify three polymeric CNO compounds with Pbam,C2/m and I4m2symmetries under 100 GPa.More interestingly,these structures are also dynamically stable at ambient pressure,and are potential high energy density materials(HEDMs).The energy densities of Pbam,C2/m and I4m2 phases of CNO are about2.30 kJ/g,1.37 kJ/g and 2.70 kJ/g,respectively,with the decompositions of graphitic carbon and molecular carbon dioxide andα-N(molecular N_(2))at ambient pressure.The present results provide in-depth insights into the structural evolution and physical properties of CNO compounds under high pressures,which offer crucial insights for designs and syntheses of novel HEDMs.展开更多
基金National Key R&D Program of China(2016YFC0600408)Strategic Priority Research Program(B)of the Chinese Academy of Sciences(XDB18020102)+1 种基金Guangdong Natural Science Funds(2014A030306032 and 2015TQ01Z611)Youth Innovation Promotion Association CAS(2016315)。
文摘The mechanism of lithospheric removal and destruction of the North China Craton(NCC)has been hotly debated for decades.It is now generally accepted that the subduction of the(Paleo)-Pacific plate played an important role in this process.However,how the plate subduction contributed to the craton destruction remains unclear.Here we report high oxygen fugacity(fO2)characteristics of the Yunmengshan granite,e.g.,hematitemagnetite intergrowth supported by zircon Ce^4+/Ce^3+ratios and apatite Mn oxygen fugacity indicator.High fO2 magmas are widely discovered in Late Mesozoic(160-130 Ma)adakitic rocks in central NCC.The origin of high fO2 magma is likely related to the input of the"oxidized mantle components",which shows a dose connection between plate subduction and destruction of the craton.The research area is^1500 km away from the current Pacific subduction zone.Considering the back-arc extension of Japan Sea since the Cretaceous,this distance may be shortened to^800 km,which is still too far for normal plate subduction.Ridge subduction is the best candidate that was responsible for the large scale magmatism and the destruction of the NCC.Massive slab-derived fluids and/or melts were liberated into an overlying mantle wedge and modified the lithospheric mantle.Rollback of the subducting plate induced the large-scale upwelling of asthenospheric mantle and triggered the formation of extensive high fO2 intraplate magmas.
基金the member companies of IPST at the Georgia Institute of Technology and the IPST Fellowship
文摘The goal of this work is to produce nanocomposite film with low oxygen permeability by casting an aqueous solution containing xylan,sorbitol and nanocrystalline cellulose.The morphology of the resulting nanocomposite films was examined by scanning electron microscopy and atomic force microscopy which showed that control films containing xylan and sorbitol had a more open structure as compared to xylan-sorbitol films containing sulfonated nanocrystalline cellulose.The average pore diameter,bulk density,porosity and tortuosity factor measurements of control xylan films and nanocomposite xylan films were examined by mercury intrusion porosimetry techniques.Xylan films reinforced with nanocrystalline cellulose were denser and exhibited higher tortuosity factor than the control xylan films.Control xylan films had average pore diameter,bulk density,porosity and tortuosity factor of 0.1730 μm,0.6165 g/ml,53.0161% and 1.258,respectively as compared to xylan films reinforced with 50% nanocrystalline cellulose with average pore diameter of 0.0581 μm,bulk density of 1.1513 g/ml,porosity of 22.8906% and tortuosity factor of 2.005.Oxygen transmission rate tests demonstrated that films prepared with xylan,sorbitol and 5%,10%,25% and 50% sulfonated nanocrystalline cellulose exhibited a significantly reduced oxygen permeability of 1.1387,1.0933,0.8986 and 0.1799 cm^3×μm/m^2×d×k Pa respectively with respect to films prepared solely from xylan and sorbitol with a oxygen permeability of 189.1665 cm^3×μm/m^2×d×k Pa.These properties suggested these nanocomposite films have promising barrier properties.
基金supported by the National Natural Science Foundation of China (21975074, 91834301 and 51621002)the Innovation Program of Shanghai Municipal Education Commissionthe Fundamental Research Funds for the Central Universities (222201718002)。
文摘Oxygen vacancies (V_(o)) engineering has been deemed to an effective tactic for enhancing Li-ion storage kinetics and reversibility of SnO_(2)-based anode materials.Herein,we demonstrated the confinement of ultrahigh V_(o)SnO_(2) nanocrystals into N-doped carbon frameworks to boost their high-rate and cycle life.Density functional theory (DFT) calculations reveal that abundant V_(o) in SnO_(2) facilitates the adsorption to Li-ion with remarkably increased carrier concentration.The 6.0 nm-sized SnO_(2) particles and the embedded design effectively stabilize the structural integrity during de-/lithiation.Meantime,the as-formed large hetero-interface also expedites the electron transfer.These merits guarantee its high-rate performance and superior cycling stability.Consequently,this sample exhibits a high capacity of 1368.9m Ah g^(-1)at 0.1 A g^(-1),and can still maintain 488.5 mAh g^(-1)at 10 A g^(-1)and a long life over 400 cycles at 5 A g^(-1)with 96.6%capacity retention,which is among the best report for Sn-contained anode materials.This work sheds light on ultrahigh Vo and structural design in conversion-type oxides for highperformance lithium-ion batteries (LIBs).
文摘Several kinds of slide nozzle plate such as Al2O3-C-ZrO2,MgO,Al2O3,Spinel-C and Al2O3-C SN plate for high oxygen steel used in BaoSteel have been analysed,the appearance and size of the SN plate after using have been measured.The Al2O3-C SN plate has longer service life in casting high oxygen steel,and the wear mechanism of different SN plates is discussed.
基金the National Science Fund for Distinguished Young Scholars of China(No.21225625)the National Natural Science Foundation of China(No.21176087)the Specialized Research Fund for the Doctoral Program of Higher Education(No.20110172110013)
文摘Cobalt-free perovskite-type oxides Ba Fe_(1-y)Ta_yO_(3-δ)(0 ≤ y ≤ 0.2)were synthesized via a simple solid state reaction.The cubic perovskite structure can be obtained when y is over 0.1.Ba Fe_(0.9)Ta_(0.1)O_(3-δ)(BFT0.1)membrane shows the highest oxygen permeation flux,which can reach 1.6 ml·min^(-1)·cm^(-2)at 950 °C under the gradient of air/He.The O_2-TPD results reveal that Ba Fe_(0.9)Ta_(0.1)O_(3-δ)material shows an excellent reversibility and phase structure stability in air.The oxygen permeation flux is limited by the bulk diffusion when the membrane thickness is over 0.8 mm,and it is limited by both the bulk diffusion and the surface exchange when the membrane thickness is below 0.5 mm.Stable oxygen permeation fluxes are obtained during 180 h operation.
文摘The thermogravimetric analysis of a ternary Cu-25Ni-30Cr alloy prepared by conventional casting was performed in 0.1MPa pure O2 at 700-800℃. The results show that the alloy is composed of three phases, where the phase with the largest copper and lowest chromium content forms the matrix, while the other two, much richer in chromium, form a dispersion of isolated particles. At variance with another three-phase Cu-20Ni-20Cr alloy, which forms complex scales containing the oxides of the various components and double oxides plus an irregular region composed of alloy and oxides, the present alloy can form a very irregular but continuous chromia layer at the base of the mixed internal region, producing a gradual decrease of the oxidation rate down to very low values. A larger chromium content needed to form chromia layer for a ternary three-phase alloy is attributed to the limitations to the diffusion of the alloy components in the metal substrate imposed by their multiphase nature.
基金supported by the National Natural Science Foundation of China(52363028,21965005)the Natural Science Foundation of Guangxi Province(2021GXNSFAA076001)the Guangxi Technology Base and Talent Subject(GUIKE AD18126001,GUIKE AD20297039)。
文摘Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.
基金financial support from the National Natural Science Foundation of China (52203070)the Open Fund of State Key Laboratory of New Textile Materials and Advanced Processing Technologies (FZ2022005)+2 种基金the Open Fund of Hubei Key Laboratory of Biomass Fiber and Ecological Dyeing and Finishing (STRZ202203)the financial support provided by the China Scholarship Council (CSC)Visiting Scholar Programfinancial support from Institute for Sustainability,Energy and Resources,The University of Adelaide,Future Making Fellowship,Australia。
文摘The incorporation of partial A-site substitution in perovskite oxides represents a promising strategy for precisely controlling the electronic configuration and enhancing its intrinsic catalytic activity.Conventional methods for A-site substitution typically involve prolonged high-temperature processes.While these processes promote the development of unique nanostructures with highly exposed active sites,they often result in the uncontrolled configuration of introduced elements.Herein,we present a novel approach for synthesizing two-dimensional(2D)porous GdFeO_(3) perovskite with A-site strontium(Sr)substitution utilizing microwave shock method.This technique enables precise control of the Sr content and simultaneous construction of 2D porous structures in one step,capitalizing on the advantages of rapid heating and cooling(temperature~1100 K,rate~70 K s^(-1)).The active sites of this oxygen-rich defect structure can be clearly revealed through the simulation of the electronic configuration and the comprehensive analysis of the crystal structure.For electrocatalytic oxygen evolution reaction application,the synthesized 2D porous Gd_(0.8)Sr_(0.2)FeO_(3) electrocatalyst exhibits an exceptional overpotential of 294 mV at a current density of 10 mA cm^(-2)and a small Tafel slope of 55.85 mV dec^(-1)in alkaline electrolytes.This study offers a fresh perspective on designing crystal configurations and the construction of nanostructures in perovskite.
基金supported by the National Natural Science Foundation of China (51702039)。
文摘The sluggish kinetics of the electrochemical oxygen reduction reaction(ORR)in intermediatetemperature solid oxide fuel cells(IT-SOFCs)greatly limits the overall cell performance.In this study,an efficient and durable cathode material for IT-SOFCs is designed based on density functional theory(DFT)calculations by co-doping with Nb and Ta the B-site of the SrFeO_(3-δ)perovskite oxide.The DFT calculations suggest that Nb/Ta co-doping can regulate the energy band of the parent SrFeO_(3-δ)and help electron transfer.In symmetrical cells,such cathode with a SrFe_(0.8)Nb_(0.1)Ta_(0.1)O_(3-δ)(SFNT)detailed formula achieves a low cathode polarization resistance of 0.147Ωcm^(2) at 650℃.Electron spin resonance(ESR)and X-ray photoelectron spectroscopy(XPS)analysis confirm that the co-doping of Nb/Ta in SrFeO_(3-δ)B-site increases the balanced concentration of oxygen vacancies,enhancing the electrochemical performance when compared to 20 mol%Nb single-doped perovskite oxide.The cathode button cell with NiSDC|SDC|SFNT configuration achieves an outstanding peak power density of 1.3 W cm^(-2)at 650℃.Moreover,the button cell shows durability for 110 h under 0.65 V at 600℃ using wet H_(2) as fuel.
基金supported by the National Key Research and Development Program of China(Grant No.2018YFB0605303)Youth Innovation Promotion Association CAS(Grant No.2020150)。
文摘The low net efficiency of oxy-fuel circulating fluidized bed(CFB)combustion is mainly due to the addition of air separation unit(ASU)and carbon dioxide compression and purification unit(CPU).High oxygen concentration is one of the effective methods to improve the net efficiency of oxy-fuel combustion technology in CFB.In this research,a series of calculation and simulation were carried out based on Aspen Plus platform to provide valuable information for further investigation on the CFB oxy-fuel combustion system with high oxygen concentration(40%,50%).A CFB oxy-fuel combustion system model with high oxygen concentration was established including ASU,CPU and CFB oxy-fuel combustion and heat exchange unit.Based on the simulation data,energy and exergy efficiency were analyzed to obtain the following results.The cross-sectional area of furnace and tail flue of 50%CFB oxy-fuel combustion boiler are 43%and 56%of the original size respectively,reducing the construction and investment cost effectively.With the increase of oxygen concentration,the net efficiency of power generation increased significantly,reaching 24.85%and increasing by 6.09%under the condition of 50%oxy-fuel combustion.The total exergy loss increases with the increase of oxygen concentration.In addition,the exergy loss of radiation heat transfer is far higher than convection heat transfer.
基金supported by the National Key R&D Program of China(2021YFD1601101)grants from the National Natural Science Foundation of China(32072624)Anhui Provincial Department of Human Resources and Social Security(2021LXC017)。
文摘Theanine content is highly correlated with sensory quality and health benefits of tea infusion.The tender shoots of etiolated and albino tea plants contain higher theanine than the normal green tea plants and are valuable materials for high quality green tea processing.However,why these etiolated or albino tea plants can highly accumulate theanine is largely unknown.In this study,we observed an Arabidopsis etiolated mutant hy1–100(mutation in Haem Oxygenase 1,HO1)that accumulated higher levels of glutamine(an analog of theanine).We therefore identified CsHO1 in tea plants and found CsHO1 is conserved in amino acid sequences and subcellular localization with its homologs in other plants.Importantly,CsHO1 expression in the new shoots was much lower in an etiolated tea plants‘Huangkui’and an albino tea plant‘Huangshan Baicha’than that in normal green tea plants.The expression levels of CsHO1 were negatively correlated with theanine contents in these green,etiolated and albino shoots.Moreover,CsHO1 expression levels in various organs and different time points were also negatively correlated with theanine accumulation.The hy1–100 was hypersensitive to high levels of theanine and accumulated more theanine under theanine feeding,and these phenotypes were rescued by the expression of CsHO1 in this mutant.Transient knockdown CsHO1 expression in the new shoots of tea plant using antisense oligonucleotides(asODN)increased theanine accumulation.Collectively,these results demonstrated CsHO1 negatively regulates theanine accumulation in tea plants,and that low expression CsHO1 likely contributes to the theanine accumulation in etiolated/albino tea plants.
基金financially supported by National Natural Science Foundation of China(Grant Nos.51972070 and 52062004)Guizhou Provincial High Level Innovative Talents Project(Grant No.QKHPTRC-GCC[2022]013-1)+2 种基金Innovation Team for Advanced Electrochemical Energy Storage Devices and Key Materials of Guizhou Provincial Higher Education Institutions(Grant No.QianJiaoJi[2023]054)Guizhou Provincial Science and Technology Projects(Grant No.QKHJC[2020]1Z042)Cultivation Project of Guizhou University(Grant No.GDPY[2019]01)。
文摘The“shuttle effect”of lithium polysulfides(LiPSs)is a huge challenge for practical use of high-energydensity lithium-sulfur(Li-S)batteries,and one of the main reasons is the sluggish kinetics of sulfur conversion.Metal oxides are able to expedite the sulfur electrochemistry,and the structural defects enhance the adsorption-conversion ability of metal oxides for polysulfides.However,a significant research gap still remains regarding the relationship between the oxygen vacancy concentration and the adsorptivecatalytic performance of metal oxides.Herein,we establish a correlation between oxygen vacancy concentration and adsorptive-catalytic properties by using tungsten oxide(WO_(x))as model catalysts.It is revealed that high-concentration oxygen vacancy is beneficial for enhancing the binding between tungsten oxide and LiPSs,reducing the energy barrier of Li_(2)S decomposition,and promoting polysulfide conversion kinetics.Consequently,the Li-S batteries using the tungsten oxide with high-concentration oxygen vacancies deliver high initial discharge capacity of 1169 mA h g^(-1)at 0.2 C and 865 mA h g^(-1)at 2 C,low attenuation rate of 0.064%per cycle over 1100 cycles at 2 C.With a high sulfur area loading of 5.34 mg cm^(-2),the Li-S batteries still exhibit high initial gravimetric capacity of 982 mA h g^(-1)at 0.1 C and areal capacity of 5.92 mA h cm^(-2).This work promotes the feasibility of defect engineering on metal oxides as an effective mean to enhance the practicality of Li-S batteries.
基金supported by the National Natural Science Foundation of China(Nos.22179093 and 21905202)。
文摘Electrocatalytic oxygen reduction via a two-electron pathway(2e^(-)-ORR)is a promising and eco-friendly route for producing hydrogen peroxide(H_(2)O_(2)).Single-atom catalysts(SACs)typically show excellent selectivity towards 2e^(-)-ORR due to their unique electronic structures and geometrical configurations.The very low density of single-atom active centers,however,often leads to unsatisfactory H_(2)O_(2)yield rate,significantly inhibiting their practical feasibility.Addressing this,we herein introduce fluorine as a secondary doping element into conventional SACs,which does not directly coordinate with the singleatom metal centers but synergize with them in a remote manner.This strategy effectively activates the surrounding carbon atoms and converts them into highly active sites for 2e^(-)-ORR.Consequently,a record-high H_(2)O_(2)yield rate up to 27 mol g^(-1)h^(-1)has been achieved on the Mo–F–C catalyst,with high Faradaic efficiency of 90%.Density functional theory calculations further confirm the very kinetically facile 2e^(-)-ORR over these additional active sites and the superiority of Mo as the single-atom center to others.This strategy thus not only provides a high-performance electrocatalyst for 2e^(-)-ORR but also should shed light on new strategies to significantly increase the active centers number of SACs.
文摘Electrochemical water splitting is a straightforward process that involves two distinct reactions:the oxygen evolution reaction(OER)which produces oxygen(O_(2))and the hydrogen evolution reaction(HER)which generates hydrogen(H_(2)).However,in the whole process,the OER is a bottleneck as it requires more energy than a four-electron reaction involving critical raw materials(such as RuO_(2)or IrO_(2))as electrocatalysts.Therefore,here,we address the challenge of erratic kinetics/limited durability of OER in water electrolysis,In this paper,we demonstrate that the deposition of ultrasmall amounts of nickel(Ⅱ)nitrate in zeolitic imidazolate framework-67(ZIF-67)can be used as a general approach to enhance the electrocatalytic performance of the framework.We investigated the influence of Ni(NO_(3))·x6H_(2)O loading on ZIF-67(from 0.1 to 0.0001 M)and found that ZIF-67 enriched with only 0.001 M of Ni(NO_(3))2·x6H_(2)O(ZIF-670.001 Ni)exhibited massive promotion in OER.The ZIF-670.001 Ni showed a large specific surface area of 2577 m^(2)g^(-1),a low overpotential of 299 mV,a lower Tafel slope of 94.1 mA dec^(-1),and an outstanding overpotential retention of 99.8%(at 50 mA cm^(-2)).By conducting electron paramagnetic resonance(EPR)measurements,we also discovered that the 0.001 M of Ni(NO_(3))_(2)·x6H_(2)O loading in ZIF-67 introduces Ni^(^(2+))dimers,which contribute to the enhanced electroactivity of the modified ZIF-67.This phenomenon was further revealed during density-functional theory(DFT)calculations,which allowed us to identify different possible forms of Ni^(^(2+))dimers and modeling of active centers.Along with in situ experiments,we provide mechanistic insight into the OER mechanism under alkaline conditions and found that it follows the lattice oxygen mechanism(LOM).Our study proposes a facile and efficient room-temperature route to boost the electrochemical performance of ZIF-67 in OER.For the first time,we demonstrate that modifying ZIF-67 with an ultrasmall amount of different nickel(Ⅱ)salts opens a general route to enhance its electroactivity during water-splitting reactions.
基金Collaborative Innovation Center of Suzhou Nano Science and TechnologyNational Natural Science Foundation of China,Grant/Award Numbers:21773163,22271203+3 种基金EPSRC for an Overseas Travel Grant,Grant/Award Number:EP/R023816/1State Key Laboratory of Organometallic Chemistry of Shanghai Institute of Organic Chemistry,Grant/Award Number:KF2021005Priority Academic Program Development of Jiangsu Higher Education InstitutionsProject of Scientific and Technologic Infrastructure of Suzhou,Grant/Award Number:SZS201905。
文摘The development of simple and effective strategies to prepare electrocatalysts,which possess unique and stable structures comprised of metal/nonmetallic atoms for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),is currently an urgent issue.Herein,an efficient bifunctional electrocatalyst featured by ultralong N,S-doped carbon nano-hollow-sphere chains about 1300 nm with encapsulated Co nanoparticles(Co-CNHSCs)is developed.The multifunctional catalytic properties of Co together with the heteroatom-induced charge redistribution(i.e.,modulating the electronic structure of the active site)result in superior catalytic activities toward OER and ORR in alkaline media.The optimized catalyst Co-CNHSC-3 displays an outstanding electrocatalytic ability for ORR and OER,a high specific capacity of 1023.6 mAh gZn^(-1),and excellent reversibility after 80 h at 10mA cm^(-2)in a Zn-air battery system.This work presents a new strategy for the design and synthesis of efficient multifunctional carbon-based catalysts for energy storage and conversion devices.
基金supported by the National Natural Science Foundation(22279036)the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(B21003)。
文摘Enhancing the stability of Pt-based electrocatalysts for the sluggish cathodic oxygen reduction reaction(ORR)is critical for proton exchange membrane fuel cells(PEMFCs).Herein,high-entropy intermetallic(HEI)L1_(2)-Pt(FeCoNiCuZn)3is designed for durable ORR catalysis.Benefiting from the unique HEI structure and the enhanced intermetallic phase stability,Pt(FeCoNiCuZn)3/C nanoparticles demonstrate significantly improved stability over Pt/C and PtCu_(3)/C catalysts.The Pt(FeCoNiCuZn)3/C exhibits a negligible decay of the half-wave potential during 30,000 potential cycles from 0.6 to 1.0 V,whereas Pt/C and PtCu_(3)/C are negatively shifted by 46 and 36 m V,respectively.Even after 10,000 cycles at potential up to 1.5 V,the mass activity of Pt(FeCoNiCuZn)3/C still shows~70%retention.As evidenced by the structural characterizations,the HEI structure of Pt(FeCoNiCuZn)3/C is well maintained,while PtCu_(3)/C nanoparticles undergo severe Cu leaching and particle growth.In addition,when assembled Pt(FeCoNiCuZn)3/C as the cathode in high-temperature PEMFC of 160℃,the H_(2)-O_(2)fuel cell delivers almost no degradation even after operating for 150 h,demonstrating the potential for fuel cell applications.This work provides a facile design strategy for the development of high-performance ultrastable electrocatalysts.
基金financially supported by the National Key Research and Development Program of China (2018YFA0702002)the Beijing Natural Science Foundation (Z210016)the National Natural Science Foundation of China (21935001)。
文摘Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utilization efficiency.However,there is still a lack of systematic screening and optimization of local structures surrounding active centers of SACs for ORR as the local coordination has an essential impact on their electronic structures and catalytic performance.Herein,we systematic study the ORR catalytic performance of M-NC SACs with different central metals and environmental atoms in the first and second coordination sphere by using density functional theory(DFT)calculation and machine learning(ML).The geometric and electronic informed overpotential model(GEIOM)based on random forest algorithm showed the highest accuracy,and its R^(2) and root mean square errors(RMSE)were 0.96 and 0.21,respectively.30 potential high-performance catalysts were screened out by GEIOM,and the RMSE of the predicted result was only 0.12 V.This work not only helps us fast screen high-performance catalysts,but also provides a low-cost way to improve the accuracy of ML models.
基金supported by the National Natural Science Foundation of China,China(52203066,51973157,51673148 and 51678411)the Science and Technology Plans of Tianjin,China(19PTSYJC00010)+3 种基金China Postdoctoral Science Foundation Grant,China(2019M651047)the Tianjin Research Innovation Project for Postgraduate Students,China(2020YJSB062)the Tianjin Municipal College Student’Innovation And Entrepreneurship Training Program,China(202110058052)the National Innovation and Entrepreneurship Training Program for College Students,China(202110058017)。
文摘Non-renewable fossil fuels have led to serious problems such as global warming,environmental pollution,etc.Oxygen electrocatalysis including oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)plays a central role in clean energy conversion,enabling a number of sustainable processes for future air battery technologies.Fluorine,as the most electronegative element(4.0)not only can induce more efficient regulation for the electronic structure,but also can bring more abundant defects and other novel effects in materials selection and preparation for favorable catalysis with respect to the other nonmetal elements.However,an individual and comprehensive overview of fluorine-containing functional materials for oxygen electrocatalysis field is still blank.Therefore,it is very meaningful to review the recent progresses of fluorine-containing oxygen electrocatalysts.In this review,we first systematically summarize the controllable preparation methods and their possible development directions based on fluorine-containing materials from four preparation methods.Due to the strong electron-withdrawing properties of fluorine,its control of the electronic structure can effectively enhance the oxygen electrocatalytic activity of the materials.In addition,the catalytic enhancement effect of fluorine on carbonbased materials also includes the prevent oxidation and the layer peeling,and realizes the precise atomic control.And the catalytic improvement mechanism of fluorine containing metal-based compounds also includes the hydration of metal site,the crystal transformation,and the oxygen vacancy induction.Then,based on their various dimensions(0D–3D),we also have summarized the advantages of different morphologies on oxygen electrocatalytic performances.Finally,the prospects and possible future researching direction of F-containing oxygen electrocatalysts are presented(e.g.,novel pathways,advanced methods for measurement and simulation,field assistance and multi-functions).The review is considered valuable and helpful in exploring the novel designs and mechanism analyses of advanced fluorine-containing electrocatalysts.
基金the National Natural Science Foundation of China(Grant Nos.12174352 and 12111530103)the Fundamental Research Funds for the Central UniversitiesChina University of Geosciences(Wuhan)(Grant No.G1323523065)。
文摘Molecular crystals are complex systems exhibiting various crystal structures,and accurately modeling the crystal structures is essential for understanding their physical behaviors under high pressure.Here,we perform an extensive structure search of ternary carbon-nitrogen-oxygen(CNO)compound under high pressure with the CALYPSO method and first principles calculations,and successfully identify three polymeric CNO compounds with Pbam,C2/m and I4m2symmetries under 100 GPa.More interestingly,these structures are also dynamically stable at ambient pressure,and are potential high energy density materials(HEDMs).The energy densities of Pbam,C2/m and I4m2 phases of CNO are about2.30 kJ/g,1.37 kJ/g and 2.70 kJ/g,respectively,with the decompositions of graphitic carbon and molecular carbon dioxide andα-N(molecular N_(2))at ambient pressure.The present results provide in-depth insights into the structural evolution and physical properties of CNO compounds under high pressures,which offer crucial insights for designs and syntheses of novel HEDMs.
