The investigated area around Sarvapuram represents a part of the Karimnagar granulite terrane of the Eastern Dharwar Craton, India. Garnet–bearing gneiss is hosted as enclaves, pods within granite gneiss and charnock...The investigated area around Sarvapuram represents a part of the Karimnagar granulite terrane of the Eastern Dharwar Craton, India. Garnet–bearing gneiss is hosted as enclaves, pods within granite gneiss and charnockite. It is largely made up of garnet, orthopyroxene, cordierite, biotite, plagioclase, K–feldspar, sillimanite and quartz. The peak metamorphic stage is represented by the equilibrium mineral assemblage i.e. garnet, orthopyroxene, cordierite, biotite, plagioclase, sillimanite and quartz. Breakdown of the garnet as well as preservation of the orthopyroxene–cordierite symplectite, formation of cordierite with the consumption of the garnet + sillimanite + quartz represents the decompressional event. The thermobarometric calculations suggest a retrograde P–T path with a substantial decompression of c. 3.0 kbar. The water activity(XH2 O) conditions obtained with the win TWQ program for core and symplectite compositions from garnet–bearing gneiss are 0.07–0.14 and 0.11–0.16 respectively. The quantitative estimation of oxygen fugacity in garnet–bearing gneiss reveal log f O2 values ranging from-11.38 to-14.05. This high oxidation state could be one of the reasons that account for the absence of graphite in these rocks.展开更多
The oxygen fugacity(f_(O2)) may affect the ionic conductivity of olivine under upper mantle conditions because Mg vacancies can be produced in the crystal structure by the oxidization of iron from Fe^(2+) to Fe3+. Her...The oxygen fugacity(f_(O2)) may affect the ionic conductivity of olivine under upper mantle conditions because Mg vacancies can be produced in the crystal structure by the oxidization of iron from Fe^(2+) to Fe3+. Here we investigated olivine ionic conductivity at 4 GPa, as a function of temperature, crystallographic orientation, and oxygen fugacity, corresponding to the topmost asthenospheric conditions. The results demonstrate that the ionic conductivity is insensitive to f_(O2) under relatively reduced conditions(f_(O2) below Re-ReO_(2) buffer), whereas it has a clear f_(O2)-dependence under relatively oxidized conditions(f_(O2) around the magnetite-hematite buffer). The ionic conduction in olivine may contribute significantly to the conductivity anomaly in the topmost asthenosphere especially at relatively oxidized conditions.展开更多
We present a novel technique for controlling oxygen fugacity,which is broadly used to in-situ measure the electrical conductivities in minerals and rocks during diamond anvil cell experiments.The electrical conductivi...We present a novel technique for controlling oxygen fugacity,which is broadly used to in-situ measure the electrical conductivities in minerals and rocks during diamond anvil cell experiments.The electrical conductivities of olivine are determined under controlled oxygen fugacity conditions(Mo–MoO2)at pressures up to 4.0 GPa and temperatures up to 873 K.The advantages of this new technique enable the measuring of the activation enthalpy,activation energy,and activation bulk volume in the Arrhenius relationship.This provides an improved understanding of the mechanism of conduction in olivine.Electrical conduction in olivine is best explained by small polaron movement,given the oxygen fugacity-dependent variations in conductivity.展开更多
Plate subduction is the largest natural factory that processes elements,which controls recycling and mineralization of a variety of elements.There are three major ore deposit belts in the world:the circumPacific,the c...Plate subduction is the largest natural factory that processes elements,which controls recycling and mineralization of a variety of elements.There are three major ore deposit belts in the world:the circumPacific,the centralAsian,and the Tethys belts.All the three belts are closely associated with plate subductions,the mechanism remains obscure.We approached this problem from systematic studies on the behaviours of elements during geologic processes.This contribution summaries the recent progress of our research group.Our results suggest that porphyry Cu deposits form through partial melting of subducted young oceanic crust under oxygen fugacities higher than AFMQ^+1.5,which is promoted after the elevation of atmospheric oxygen at ca.550 Ma.Tin deposits are associated with reducing magmatic rocks formed as a consequence of slab rollback.The Neo-Tethys tectonic regime hosts more than 60%of the world's total Sn reserves.This is due to the reducing environment formed during the subduction of organic rich sediments.For the same reason,porphyry Cu deposits formed in the late stages during the closure of the Neo-Tethys Ocean.Tungsten deposits are also controlled by slab rollback,but is not so sensitive to oxygen fugacity.Subduction related W/Sn deposits are mostly accompanied by abundant accessory fluorites due to the breakdown of phengite and apatite.Decomposition of phengite is also significant for hard rock lithium deposits,whereas orogenic belt resulted from plate subduction promote the formation of Li brine deposits.Cretaceous red bed basins near the Nanling region are favorable for Li brines.Both Mo and Re are enriched in the oxidationreduction cycle during surface processes,and may get further enriched once Mo-,Re-enriched sediments are subducted and involved in magmatism.During plate subduction,Mo and Re fractionate from each other.Molybdenum is mainly hosted in porphyry Mo deposits and to a less extent,porphyry Cu-Mo deposits,whereas Re is predominantly hosted in porphyry Cu-Mo deposits and sedimentary sulfide deposits.展开更多
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
Economic concentrations of Fe–Ti oxides occurring as massive layers in the middle and upper parts of the Hongge intrusion are different from other layered intrusions(Panzhihua and Baima) in the Emeishan large igneous...Economic concentrations of Fe–Ti oxides occurring as massive layers in the middle and upper parts of the Hongge intrusion are different from other layered intrusions(Panzhihua and Baima) in the Emeishan large igneous province, SW China. This paper reports on the new mineral compositions of magnetite and ilmenite for selected cumulate rocks and clinopyroxene and plagioclase for basalts. We use these data to estimate the oxidation state of parental magmas and during ore formation to constrain the factors leading to the abundant accumulation of Fe–Ti oxides involved with the Hongge layered intrusion. The results show that the oxygen fugacities of parental magma are in the range of FMQ-1.56 to FMQ+0.14, and the oxygen fugacities during the ore formation of the Fe–Ti oxides located in the lower olivine clinopyroxenite zone(LOZ) and the middle clinopyroxenite zone(MCZ) of the Hongge intrusion are in the range of FMQ-1.29 to FMQ-0.2 and FMQ-0.49 to FMQ+0.82, respectively.The MELTS model demonstrates that, as the oxygen fugacity increases from the FMQ-1 to FMQ+1, the proportion of crystallization magnetite increases from 11 % to 16 % and the crystallization temperature of the Fe–Ti oxides advances from 1134 to 1164 °C. The moderate oxygen fugacities for the Hongge MCZ indicate that the oxygen fugacity was not the only factor affecting the crystallization of Fe–Ti oxides. We speculated that theinitial anhydrous magma that arrived at the Hongge shallow magma chamber became hydrous by attracting the H_2O of the strata. In combination with increasing oxygen fugacities from the LOZ(FMQ-1.29 to FMQ-0.2) to the MCZ(FMQ-0.49 to FMQ+0.82), these two factors probably account for the large-scale Fe–Ti oxide ore layers in the MCZ of the Hongge intrusion.展开更多
In this paper,a new of oxygen fugacity controltechnique that can be widely applied to in-situ measurement of the grain interior electrical conductivities of minerals and rocks is presented for high temperature and hig...In this paper,a new of oxygen fugacity controltechnique that can be widely applied to in-situ measurement of the grain interior electrical conductivities of minerals and rocks is presented for high temperature and high pressure. Inside the sample assembly,a metal and corresponding metal oxide form a solid oxygen buffer. The principle of this technique is to randomly monitor and adjust oxygen fugacity in the large-volume multi-anvil press by changing the types of solid oxygen buffer,metal shielding case and electrodes. At a pressure of up to 5.0 GPa and a temperature of up to 1423 K,the electrical conductivities of the dry peridotite are tested under the conditions of different oxygen fugacities. By virtue of this new technique,more and more reasonable and accurate laboratory electrical property data will be successfully obtained under controlled thermodynamic conditions.展开更多
Major and accessory minerals from the Ibity granite, Tsarasaotra monzonitic and granite dykes, and Antsahakely granite of the Itremo domain in the Precambrian basement of Madagascar were characterized by using microsc...Major and accessory minerals from the Ibity granite, Tsarasaotra monzonitic and granite dykes, and Antsahakely granite of the Itremo domain in the Precambrian basement of Madagascar were characterized by using microscopic observations and chemical analyses with the aim of understanding their chemical characteristics and estimating the crystallization pressure and oxygen fugacity of their host rocks. Plagioclases in these rocks are albite and oligoclase, while alkali feldspars are orthoclase. For the phlogopite-micas, Fe-biotite and Li-phengite are common for the Ibity and Antsahakely granites, Mg-biotite is common for the Ibity granite and the Tsarasaotra monzonitic and granite dykes, and siderophyllite and Zinnwaldite are specific to the Ibity granite. Phlogopite-micas in the studied rocks are mainly primary, accessorily re-equilibrated, and rarely secondary. Calcic amphiboles distributed in the Magnesio-and Ferro-hornblende are identified in the Tsarasaotra monzonitic, whereas amphibole is rare and absent in the other rocks. Igneous titanite is observed in the Ibity granite and in the Tsarasaotra monzonitic rocks, which have similar compositions to some REE oxide-rich titanites. Concerning the Fe-Ti oxide phases, the rhombohedral and spinel/trifer tetroxide phases are found in both the Tsarasaotra monzonitic and the Tsarasaotra granite dyke, the trifer tetroxide and spinel + wüstite phases are found only in the Ibity granite, and the pseudobrookite + rhombohedral phase is found only in the Tsarasaotra granite dyke. The epidote mineral, rarely found in the Antsahakely granite, could be an indicator of metamorphism or hydrothermal activity involved during the emplacement of this rock. Aluminum in hornblende geobarometer gave pressure ranges of around 5 kbar for the Tsarasaotra monzonitic rocks. The Titanite geobarometer gave pressures of 2.5 - 3.2 kbar for the Ibity granite, 2.9 kbar for the Tsarasaotra monzonitic, and 7.1 kbar for the Antsahakely granite. Both amphibole and Fe-Ti oxide-base oxygen fugacity reveal high oxygen fugacity conditions for the Tsarasaotra monzonitic and granite dyke emplacements, which might have a relationship with a porphyritic environment.展开更多
Objective Oxygen fugacity is an important physicochemical parameter of magmas in addition to temperature,pressure and elemental concentrations,representing a major research topic in natural and experimental petrology....Objective Oxygen fugacity is an important physicochemical parameter of magmas in addition to temperature,pressure and elemental concentrations,representing a major research topic in natural and experimental petrology.Aside from oxygen probe work,where a direct measurement is made using an oxygen sensor to detect the oxygen content in the fluid and molten metal.展开更多
By using two oxygen specific electrolyte discs and applying a dc voltage between the sample and an oxygen buffer,oxygen can be driven into or pumped from the sample at a fixed temperature and pressure.By measuring the...By using two oxygen specific electrolyte discs and applying a dc voltage between the sample and an oxygen buffer,oxygen can be driven into or pumped from the sample at a fixed temperature and pressure.By measuring the voltage between the sample and a reference buffer,the oxygen fugacity in the sample is simultaneously monitored.Therefore,the oxygen fugacity in the sample at high temperature and high pressure can be in situ controlled independently of temperature and pressure.展开更多
The amount of oxygen blown into the converter is one of the key parameters for the control of the converter blowing process,which directly affects the tap-to-tap time of converter. In this study, a hybrid model based ...The amount of oxygen blown into the converter is one of the key parameters for the control of the converter blowing process,which directly affects the tap-to-tap time of converter. In this study, a hybrid model based on oxygen balance mechanism (OBM) and deep neural network (DNN) was established for predicting oxygen blowing time in converter. A three-step method was utilized in the hybrid model. First, the oxygen consumption volume was predicted by the OBM model and DNN model, respectively. Second, a more accurate oxygen consumption volume was obtained by integrating the OBM model and DNN model. Finally, the converter oxygen blowing time was calculated according to the oxygen consumption volume and the oxygen supply intensity of each heat. The proposed hybrid model was verified using the actual data collected from an integrated steel plant in China, and compared with multiple linear regression model, OBM model, and neural network model including extreme learning machine, back propagation neural network, and DNN. The test results indicate that the hybrid model with a network structure of 3 hidden layer layers, 32-16-8 neurons per hidden layer, and 0.1 learning rate has the best prediction accuracy and stronger generalization ability compared with other models. The predicted hit ratio of oxygen consumption volume within the error±300 m^(3)is 96.67%;determination coefficient (R^(2)) and root mean square error (RMSE) are0.6984 and 150.03 m^(3), respectively. The oxygen blow time prediction hit ratio within the error±0.6 min is 89.50%;R2and RMSE are0.9486 and 0.3592 min, respectively. As a result, the proposed model can effectively predict the oxygen consumption volume and oxygen blowing time in the converter.展开更多
The interaction between metal and support is critical in oxygen catalysis as it governs the charge transfer between these two entities,influences the electronic structures of the supported metal,affects the adsorption...The interaction between metal and support is critical in oxygen catalysis as it governs the charge transfer between these two entities,influences the electronic structures of the supported metal,affects the adsorption energies of reaction intermediates,and ultimately impacts the catalytic performance.In this study,we discovered a unique charge transfer reversal phenomenon in a metal/carbon nanohybrid system.Specifically,electrons were transferred from the metal-based species to N-doped carbon,while the carbon support reciprocally donated electrons to the metal domain upon the introduction of nickel.This led to the exceptional electrocatalytic performances of the resulting Ni-Fe/Mo_(2)C@nitrogen-doped carbon catalyst,with a half-wave potential of 0.91 V towards oxygen reduction reaction(ORR)and a low overpotential of 290 m V at 10 mA cm^(-2)towards oxygen evolution reaction(OER)under alkaline conditions.Additionally,the Fe-Ni/Mo_(2)C@carbon heterojunction catalyst demonstrated high specific capacity(794 mA h g_(Zn)~(-1))and excellent cycling stability(200 h)in a Zn-air battery.Theoretical calculations revealed that Mo_(2)C effectively inhibited charge transfer from Fe to the support,while secondary doping of Ni induced a charge transfer reversal,resulting in electron accumulation in the Fe-Ni alloy region.This local electronic structure modulation significantly reduced energy barriers in the oxygen catalysis process,enhancing the catalytic efficiency of both ORR and OER.Consequently,our findings underscore the potential of manipulating charge transfer reversal between the metal and support as a promising strategy for developing highly-active and durable bi-functional oxygen electrodes.展开更多
Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous ...Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.展开更多
A rice cyclase gene,OsCYL4b,identified as an alternative splice variant of the cyclase gene OsCYL4a,is involved in the regulation of drought stress and oxidative response.Compared with OsCYL4a,OsCYL4b lacks the second...A rice cyclase gene,OsCYL4b,identified as an alternative splice variant of the cyclase gene OsCYL4a,is involved in the regulation of drought stress and oxidative response.Compared with OsCYL4a,OsCYL4b lacks the second exon,which is located in the conserved motif 3,and may be a functionally important site.Our results suggested that OsCYL4b was responsive to multiple abiotic stresses,and was localized to both the cytoplasm and plasma membrane.The overexpression of OsCYL4b resulted in significantly enhanced drought and osmotic stress tolerance,reduced water loss,and increased abscisic acid(ABA)content compared with the wild type(WT).展开更多
Industry decarbonization requires the development of highly efficient and flexible technologies relying on renewable energy resources,especially biomass and solar/wind electricity.In the case of pure oxygen production...Industry decarbonization requires the development of highly efficient and flexible technologies relying on renewable energy resources,especially biomass and solar/wind electricity.In the case of pure oxygen production,oxygen transport membranes(OTMs)appear as an alternative technology for the cryogenic distillation of air,the industrially-established process of producing oxygen.Moreover,OTMs could provide oxygen from different sources(air,water,CO_(2),etc.),and they are more flexible in adapting to current processes,producing oxygen at 700^(-1)000℃.Furthermore,OTMs can be integrated into catalytic membrane reactors,providing new pathways for different processes.The first part of this study was focused on electrification on a traditional OTM material(Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)),imposing different electric currents/voltages along a capillary membrane.Thanks to the emerging Joule effect,the membrane-surface temperature and the associated O_(2) permeation flux could be adjusted.Here,the OTM is electrically and locally heated and reaches 900℃on the surface,whereas the surrounding of the membrane was maintained at 650℃.The O_(2)permeation flux reached for the electrified membranes was~3.7 NmL min^(-1)cm^(-2),corresponding to the flux obtained with an OTM non-electrified at 900℃.The influence of depositing a porous Ce_(0.8)Tb_(0.2)O_(2-δ) catalytic/protective layer on the outer membrane surface revealed that lower surface temperatures(830℃)were detected at the same imposed electric power.Finally,the electrification concept was demonstrated in a catalytic membrane reactor(CMR)where the oxidative dehydrogenation of ethane(ODHE)was carried out.ODHE reaction is very sensitive to temperature,and here,we demonstrate an improvement of the ethylene yield by reaching moderate temperatures in the reaction chamber while the O_(2) injection into the reaction can be easily fine-tuned.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
Industrial water splitting has long been suppressed by the sluggish kinetics of the oxygen evolution reaction(OER),which requires a catalyst to be efficient.Herein,we propose a molecular-level proton acceptor strategy...Industrial water splitting has long been suppressed by the sluggish kinetics of the oxygen evolution reaction(OER),which requires a catalyst to be efficient.Herein,we propose a molecular-level proton acceptor strategy to produce an efficient OER catalyst that can boost industrial-scale water splitting.Molecular-level phosphate(-PO_(4))group is introduced to modify the surface of PrBa_(0.5)Ca_(0.5)Co_(2)O_(5)+δ(PBCC).The achieved catalyst(PO_(4)-PBCC)exhibits significantly enhanced catalytic performance in alkaline media.Based on the X-ray absorption spectroscopy results and density functional theory(DFT)calculations,the PO_(4)on the surface,which is regarded as the Lewis base,is the key factor to overcome the kinetic limitation of the proton transfer process during the OER.The use of the catalyst in a membrane electrode assembly(MEA)is further evaluated for industrial-scale water splitting,and it only needs a low voltage of 1.66 V to achieve a large current density of 1 A cm^(-2).This work provides a new molecular-level strategy to develop highly efficient OER electrocatalysts for industrial applications.展开更多
Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na...Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na-ion cathodes.Here,we reveal the correlation between cationic ordering transition and OR degradation in ribbon-ordered P3-Na_(0.6)Li_(0.2)Mn_(0.8)O_(2) via in situ structural analysis.Comparing two different voltage windows,the OR capacity can be improved approximately twofold when suppressing the in-plane cationic ordering transition.We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn^(4+)to Jahn–Teller Mn^(3+)and the concomitant NaO_(6) stacking transformation from triangular prisms to octahedra,resulting in the loss of ribbon ordering and electrochemical decay.First-principles calculations reveal that Mn^(4+)/Mn^(3+)charge ordering and alignment of the degenerate eg orbital induce lattice-level collective Jahn–Teller distortion,which favors intralayer Mn-ion migration and thereby accelerates OR degradation.These findings unravel the relationship between in-plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR-active layered oxide cathodes.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
Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult...Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.展开更多
文摘The investigated area around Sarvapuram represents a part of the Karimnagar granulite terrane of the Eastern Dharwar Craton, India. Garnet–bearing gneiss is hosted as enclaves, pods within granite gneiss and charnockite. It is largely made up of garnet, orthopyroxene, cordierite, biotite, plagioclase, K–feldspar, sillimanite and quartz. The peak metamorphic stage is represented by the equilibrium mineral assemblage i.e. garnet, orthopyroxene, cordierite, biotite, plagioclase, sillimanite and quartz. Breakdown of the garnet as well as preservation of the orthopyroxene–cordierite symplectite, formation of cordierite with the consumption of the garnet + sillimanite + quartz represents the decompressional event. The thermobarometric calculations suggest a retrograde P–T path with a substantial decompression of c. 3.0 kbar. The water activity(XH2 O) conditions obtained with the win TWQ program for core and symplectite compositions from garnet–bearing gneiss are 0.07–0.14 and 0.11–0.16 respectively. The quantitative estimation of oxygen fugacity in garnet–bearing gneiss reveal log f O2 values ranging from-11.38 to-14.05. This high oxidation state could be one of the reasons that account for the absence of graphite in these rocks.
基金financially supported by the annual budget of Bayerisches Geoinstitut to H.Fei and the German Research Foundation (DFG) to T.Katsura (KA3434/3-1,KA3434/3-2,KA3434/7-1,KA3434/8-1,and KA3434/9-1)。
文摘The oxygen fugacity(f_(O2)) may affect the ionic conductivity of olivine under upper mantle conditions because Mg vacancies can be produced in the crystal structure by the oxidization of iron from Fe^(2+) to Fe3+. Here we investigated olivine ionic conductivity at 4 GPa, as a function of temperature, crystallographic orientation, and oxygen fugacity, corresponding to the topmost asthenospheric conditions. The results demonstrate that the ionic conductivity is insensitive to f_(O2) under relatively reduced conditions(f_(O2) below Re-ReO_(2) buffer), whereas it has a clear f_(O2)-dependence under relatively oxidized conditions(f_(O2) around the magnetite-hematite buffer). The ionic conduction in olivine may contribute significantly to the conductivity anomaly in the topmost asthenosphere especially at relatively oxidized conditions.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11674404,41330206,and 11374121)
文摘We present a novel technique for controlling oxygen fugacity,which is broadly used to in-situ measure the electrical conductivities in minerals and rocks during diamond anvil cell experiments.The electrical conductivities of olivine are determined under controlled oxygen fugacity conditions(Mo–MoO2)at pressures up to 4.0 GPa and temperatures up to 873 K.The advantages of this new technique enable the measuring of the activation enthalpy,activation energy,and activation bulk volume in the Arrhenius relationship.This provides an improved understanding of the mechanism of conduction in olivine.Electrical conduction in olivine is best explained by small polaron movement,given the oxygen fugacity-dependent variations in conductivity.
基金Supported by the National Key R&D Program of China(No.2016YFC0600408)
文摘Plate subduction is the largest natural factory that processes elements,which controls recycling and mineralization of a variety of elements.There are three major ore deposit belts in the world:the circumPacific,the centralAsian,and the Tethys belts.All the three belts are closely associated with plate subductions,the mechanism remains obscure.We approached this problem from systematic studies on the behaviours of elements during geologic processes.This contribution summaries the recent progress of our research group.Our results suggest that porphyry Cu deposits form through partial melting of subducted young oceanic crust under oxygen fugacities higher than AFMQ^+1.5,which is promoted after the elevation of atmospheric oxygen at ca.550 Ma.Tin deposits are associated with reducing magmatic rocks formed as a consequence of slab rollback.The Neo-Tethys tectonic regime hosts more than 60%of the world's total Sn reserves.This is due to the reducing environment formed during the subduction of organic rich sediments.For the same reason,porphyry Cu deposits formed in the late stages during the closure of the Neo-Tethys Ocean.Tungsten deposits are also controlled by slab rollback,but is not so sensitive to oxygen fugacity.Subduction related W/Sn deposits are mostly accompanied by abundant accessory fluorites due to the breakdown of phengite and apatite.Decomposition of phengite is also significant for hard rock lithium deposits,whereas orogenic belt resulted from plate subduction promote the formation of Li brine deposits.Cretaceous red bed basins near the Nanling region are favorable for Li brines.Both Mo and Re are enriched in the oxidationreduction cycle during surface processes,and may get further enriched once Mo-,Re-enriched sediments are subducted and involved in magmatism.During plate subduction,Mo and Re fractionate from each other.Molybdenum is mainly hosted in porphyry Mo deposits and to a less extent,porphyry Cu-Mo deposits,whereas Re is predominantly hosted in porphyry Cu-Mo deposits and sedimentary sulfide deposits.
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supported by the National 973 Program of China (2012CB416804 and 2014CB440906)CAS/SAFEA International Partnership Program for Creative Research Teams (KZZD-EW-TZ-20)National Natural Sciences Foundations of China (41473051) to Tao yan
文摘Economic concentrations of Fe–Ti oxides occurring as massive layers in the middle and upper parts of the Hongge intrusion are different from other layered intrusions(Panzhihua and Baima) in the Emeishan large igneous province, SW China. This paper reports on the new mineral compositions of magnetite and ilmenite for selected cumulate rocks and clinopyroxene and plagioclase for basalts. We use these data to estimate the oxidation state of parental magmas and during ore formation to constrain the factors leading to the abundant accumulation of Fe–Ti oxides involved with the Hongge layered intrusion. The results show that the oxygen fugacities of parental magma are in the range of FMQ-1.56 to FMQ+0.14, and the oxygen fugacities during the ore formation of the Fe–Ti oxides located in the lower olivine clinopyroxenite zone(LOZ) and the middle clinopyroxenite zone(MCZ) of the Hongge intrusion are in the range of FMQ-1.29 to FMQ-0.2 and FMQ-0.49 to FMQ+0.82, respectively.The MELTS model demonstrates that, as the oxygen fugacity increases from the FMQ-1 to FMQ+1, the proportion of crystallization magnetite increases from 11 % to 16 % and the crystallization temperature of the Fe–Ti oxides advances from 1134 to 1164 °C. The moderate oxygen fugacities for the Hongge MCZ indicate that the oxygen fugacity was not the only factor affecting the crystallization of Fe–Ti oxides. We speculated that theinitial anhydrous magma that arrived at the Hongge shallow magma chamber became hydrous by attracting the H_2O of the strata. In combination with increasing oxygen fugacities from the LOZ(FMQ-1.29 to FMQ-0.2) to the MCZ(FMQ-0.49 to FMQ+0.82), these two factors probably account for the large-scale Fe–Ti oxide ore layers in the MCZ of the Hongge intrusion.
基金supported by the Knowledge Innovation Key Orientation Project of the Chinese Academy of Sciences (CAS) (Grant Nos. KZCX2-YW-Q08-3-4,KZCX2-YW-QN110,and KZCX3-SW-124)Large-scale Scientific Apparatus Development Program of CAS (Grant No. YZ200720)+1 种基金the National High Technology Research and Development Program of China (Grant No. 2006AA09Z205)the National Natural Science Foundation of China (Grant Nos. 40974051,40704010 and 40573046)
文摘In this paper,a new of oxygen fugacity controltechnique that can be widely applied to in-situ measurement of the grain interior electrical conductivities of minerals and rocks is presented for high temperature and high pressure. Inside the sample assembly,a metal and corresponding metal oxide form a solid oxygen buffer. The principle of this technique is to randomly monitor and adjust oxygen fugacity in the large-volume multi-anvil press by changing the types of solid oxygen buffer,metal shielding case and electrodes. At a pressure of up to 5.0 GPa and a temperature of up to 1423 K,the electrical conductivities of the dry peridotite are tested under the conditions of different oxygen fugacities. By virtue of this new technique,more and more reasonable and accurate laboratory electrical property data will be successfully obtained under controlled thermodynamic conditions.
文摘Major and accessory minerals from the Ibity granite, Tsarasaotra monzonitic and granite dykes, and Antsahakely granite of the Itremo domain in the Precambrian basement of Madagascar were characterized by using microscopic observations and chemical analyses with the aim of understanding their chemical characteristics and estimating the crystallization pressure and oxygen fugacity of their host rocks. Plagioclases in these rocks are albite and oligoclase, while alkali feldspars are orthoclase. For the phlogopite-micas, Fe-biotite and Li-phengite are common for the Ibity and Antsahakely granites, Mg-biotite is common for the Ibity granite and the Tsarasaotra monzonitic and granite dykes, and siderophyllite and Zinnwaldite are specific to the Ibity granite. Phlogopite-micas in the studied rocks are mainly primary, accessorily re-equilibrated, and rarely secondary. Calcic amphiboles distributed in the Magnesio-and Ferro-hornblende are identified in the Tsarasaotra monzonitic, whereas amphibole is rare and absent in the other rocks. Igneous titanite is observed in the Ibity granite and in the Tsarasaotra monzonitic rocks, which have similar compositions to some REE oxide-rich titanites. Concerning the Fe-Ti oxide phases, the rhombohedral and spinel/trifer tetroxide phases are found in both the Tsarasaotra monzonitic and the Tsarasaotra granite dyke, the trifer tetroxide and spinel + wüstite phases are found only in the Ibity granite, and the pseudobrookite + rhombohedral phase is found only in the Tsarasaotra granite dyke. The epidote mineral, rarely found in the Antsahakely granite, could be an indicator of metamorphism or hydrothermal activity involved during the emplacement of this rock. Aluminum in hornblende geobarometer gave pressure ranges of around 5 kbar for the Tsarasaotra monzonitic rocks. The Titanite geobarometer gave pressures of 2.5 - 3.2 kbar for the Ibity granite, 2.9 kbar for the Tsarasaotra monzonitic, and 7.1 kbar for the Antsahakely granite. Both amphibole and Fe-Ti oxide-base oxygen fugacity reveal high oxygen fugacity conditions for the Tsarasaotra monzonitic and granite dyke emplacements, which might have a relationship with a porphyritic environment.
基金financially supported by the National Key R&D Program of China(Grant No.2017YFC0602600)Nuclear Power Development(No.HXS1403)Uranium Geology Research Program of China Nuclear Geology(No.201588)。
文摘Objective Oxygen fugacity is an important physicochemical parameter of magmas in addition to temperature,pressure and elemental concentrations,representing a major research topic in natural and experimental petrology.Aside from oxygen probe work,where a direct measurement is made using an oxygen sensor to detect the oxygen content in the fluid and molten metal.
基金Supported by the National Natural Science Foundation of China under Grant No.49674221the National Science Council under NSC-86-2111-M-001-021,Taipei.
文摘By using two oxygen specific electrolyte discs and applying a dc voltage between the sample and an oxygen buffer,oxygen can be driven into or pumped from the sample at a fixed temperature and pressure.By measuring the voltage between the sample and a reference buffer,the oxygen fugacity in the sample is simultaneously monitored.Therefore,the oxygen fugacity in the sample at high temperature and high pressure can be in situ controlled independently of temperature and pressure.
基金financially supported by the National Natural Science Foundation of China (Nos.51974023 and52374321)the funding of State Key Laboratory of Advanced Metallurgy,University of Science and Technology Beijing,China (No.41620007)。
文摘The amount of oxygen blown into the converter is one of the key parameters for the control of the converter blowing process,which directly affects the tap-to-tap time of converter. In this study, a hybrid model based on oxygen balance mechanism (OBM) and deep neural network (DNN) was established for predicting oxygen blowing time in converter. A three-step method was utilized in the hybrid model. First, the oxygen consumption volume was predicted by the OBM model and DNN model, respectively. Second, a more accurate oxygen consumption volume was obtained by integrating the OBM model and DNN model. Finally, the converter oxygen blowing time was calculated according to the oxygen consumption volume and the oxygen supply intensity of each heat. The proposed hybrid model was verified using the actual data collected from an integrated steel plant in China, and compared with multiple linear regression model, OBM model, and neural network model including extreme learning machine, back propagation neural network, and DNN. The test results indicate that the hybrid model with a network structure of 3 hidden layer layers, 32-16-8 neurons per hidden layer, and 0.1 learning rate has the best prediction accuracy and stronger generalization ability compared with other models. The predicted hit ratio of oxygen consumption volume within the error±300 m^(3)is 96.67%;determination coefficient (R^(2)) and root mean square error (RMSE) are0.6984 and 150.03 m^(3), respectively. The oxygen blow time prediction hit ratio within the error±0.6 min is 89.50%;R2and RMSE are0.9486 and 0.3592 min, respectively. As a result, the proposed model can effectively predict the oxygen consumption volume and oxygen blowing time in the converter.
基金financially supported by the Outstanding Youth Scientific Research Project for Colleges and Universities of Anhui Province of China (2022AH020054)the Anhui Provincial Natural Science Foundation (2208085Y06)+2 种基金the National Natural Science Foundation of China (Nos.21975001 and U2002213)the Support Program of Excellent Young Talents in Anhui Provincial Colleges and Universities (gxyq ZD2022034)the Double Tops Joint Fund of the Yunnan Science and Technology Bureau and Yunnan University (2019FY003025)。
文摘The interaction between metal and support is critical in oxygen catalysis as it governs the charge transfer between these two entities,influences the electronic structures of the supported metal,affects the adsorption energies of reaction intermediates,and ultimately impacts the catalytic performance.In this study,we discovered a unique charge transfer reversal phenomenon in a metal/carbon nanohybrid system.Specifically,electrons were transferred from the metal-based species to N-doped carbon,while the carbon support reciprocally donated electrons to the metal domain upon the introduction of nickel.This led to the exceptional electrocatalytic performances of the resulting Ni-Fe/Mo_(2)C@nitrogen-doped carbon catalyst,with a half-wave potential of 0.91 V towards oxygen reduction reaction(ORR)and a low overpotential of 290 m V at 10 mA cm^(-2)towards oxygen evolution reaction(OER)under alkaline conditions.Additionally,the Fe-Ni/Mo_(2)C@carbon heterojunction catalyst demonstrated high specific capacity(794 mA h g_(Zn)~(-1))and excellent cycling stability(200 h)in a Zn-air battery.Theoretical calculations revealed that Mo_(2)C effectively inhibited charge transfer from Fe to the support,while secondary doping of Ni induced a charge transfer reversal,resulting in electron accumulation in the Fe-Ni alloy region.This local electronic structure modulation significantly reduced energy barriers in the oxygen catalysis process,enhancing the catalytic efficiency of both ORR and OER.Consequently,our findings underscore the potential of manipulating charge transfer reversal between the metal and support as a promising strategy for developing highly-active and durable bi-functional oxygen electrodes.
基金This work was supported by the Fundamental Research Funds for the Central Universities(DUT20LAB123 and DUT20LAB307)the Natural Science Foundation of Jiangsu Province(BK20191167).
文摘Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.
基金supported by the Fundamental Research Funds for the Central Universities,South-Central Minzu University,China(Grant No.CZY23002)Hubei Province Natural Science Foundation of China(Grant No.2019CFB804).
文摘A rice cyclase gene,OsCYL4b,identified as an alternative splice variant of the cyclase gene OsCYL4a,is involved in the regulation of drought stress and oxidative response.Compared with OsCYL4a,OsCYL4b lacks the second exon,which is located in the conserved motif 3,and may be a functionally important site.Our results suggested that OsCYL4b was responsive to multiple abiotic stresses,and was localized to both the cytoplasm and plasma membrane.The overexpression of OsCYL4b resulted in significantly enhanced drought and osmotic stress tolerance,reduced water loss,and increased abscisic acid(ABA)content compared with the wild type(WT).
基金Financial support by the Spanish Ministry of Science(PID2022139663OB-I00 and CEX2021-001230-S grant funded by MCIN/AE I/10.13039/501100011033)with funding from Next Generation EU(PRTR-C17.I1)within the Planes Complementarios con CCAA(Area of Green Hydrogen and Energy)+2 种基金carried out in the CSIC Interdisciplinary Thematic Platform(PTI+)Transición Energética Sostenible+(PTI-TRANSENER+)the Universitat Politècnica de València(UPV)the support of the Servicio de Microscopía Elcectronica of the UPV。
文摘Industry decarbonization requires the development of highly efficient and flexible technologies relying on renewable energy resources,especially biomass and solar/wind electricity.In the case of pure oxygen production,oxygen transport membranes(OTMs)appear as an alternative technology for the cryogenic distillation of air,the industrially-established process of producing oxygen.Moreover,OTMs could provide oxygen from different sources(air,water,CO_(2),etc.),and they are more flexible in adapting to current processes,producing oxygen at 700^(-1)000℃.Furthermore,OTMs can be integrated into catalytic membrane reactors,providing new pathways for different processes.The first part of this study was focused on electrification on a traditional OTM material(Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)),imposing different electric currents/voltages along a capillary membrane.Thanks to the emerging Joule effect,the membrane-surface temperature and the associated O_(2) permeation flux could be adjusted.Here,the OTM is electrically and locally heated and reaches 900℃on the surface,whereas the surrounding of the membrane was maintained at 650℃.The O_(2)permeation flux reached for the electrified membranes was~3.7 NmL min^(-1)cm^(-2),corresponding to the flux obtained with an OTM non-electrified at 900℃.The influence of depositing a porous Ce_(0.8)Tb_(0.2)O_(2-δ) catalytic/protective layer on the outer membrane surface revealed that lower surface temperatures(830℃)were detected at the same imposed electric power.Finally,the electrification concept was demonstrated in a catalytic membrane reactor(CMR)where the oxidative dehydrogenation of ethane(ODHE)was carried out.ODHE reaction is very sensitive to temperature,and here,we demonstrate an improvement of the ethylene yield by reaching moderate temperatures in the reaction chamber while the O_(2) injection into the reaction can be easily fine-tuned.
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supported by the National Natural Sci-ence Foundation of China(22272081),Jiangsu Provincial Specially Appointed Professors Foundation.
文摘Industrial water splitting has long been suppressed by the sluggish kinetics of the oxygen evolution reaction(OER),which requires a catalyst to be efficient.Herein,we propose a molecular-level proton acceptor strategy to produce an efficient OER catalyst that can boost industrial-scale water splitting.Molecular-level phosphate(-PO_(4))group is introduced to modify the surface of PrBa_(0.5)Ca_(0.5)Co_(2)O_(5)+δ(PBCC).The achieved catalyst(PO_(4)-PBCC)exhibits significantly enhanced catalytic performance in alkaline media.Based on the X-ray absorption spectroscopy results and density functional theory(DFT)calculations,the PO_(4)on the surface,which is regarded as the Lewis base,is the key factor to overcome the kinetic limitation of the proton transfer process during the OER.The use of the catalyst in a membrane electrode assembly(MEA)is further evaluated for industrial-scale water splitting,and it only needs a low voltage of 1.66 V to achieve a large current density of 1 A cm^(-2).This work provides a new molecular-level strategy to develop highly efficient OER electrocatalysts for industrial applications.
基金funding supports from the National Key R&D Program of China(Grant Nos.2022YFB2404400 and 2019YFA0308500)Beijing Natural Science Foundation(Z190010)National Natural Science Foundation of China(Grant Nos.51991344,52025025,52072400,and 52002394)。
文摘Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na-ion cathodes.Here,we reveal the correlation between cationic ordering transition and OR degradation in ribbon-ordered P3-Na_(0.6)Li_(0.2)Mn_(0.8)O_(2) via in situ structural analysis.Comparing two different voltage windows,the OR capacity can be improved approximately twofold when suppressing the in-plane cationic ordering transition.We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn^(4+)to Jahn–Teller Mn^(3+)and the concomitant NaO_(6) stacking transformation from triangular prisms to octahedra,resulting in the loss of ribbon ordering and electrochemical decay.First-principles calculations reveal that Mn^(4+)/Mn^(3+)charge ordering and alignment of the degenerate eg orbital induce lattice-level collective Jahn–Teller distortion,which favors intralayer Mn-ion migration and thereby accelerates OR degradation.These findings unravel the relationship between in-plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR-active layered oxide cathodes.
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This work was supported by National Key R&D Program of China(2021YFF0500503)National Natural Science Foundation of China(21925202,U22B2071)International Joint Mission on Climate Change and Carbon Neutrality.
文摘Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.
