The Damiao Fe-Ti-P deposit,located within the Damiao anorthosite complex in northeastern China,features Fe-Ti oxide ores and nelsonites that occur as irregularly inclined stratiform-like bodies,lenses,or veins with sh...The Damiao Fe-Ti-P deposit,located within the Damiao anorthosite complex in northeastern China,features Fe-Ti oxide ores and nelsonites that occur as irregularly inclined stratiform-like bodies,lenses,or veins with sharp contacts against anorthosite and gabbronorite.This deposit is characterized by abundant titanomagnetite that hosts diverse ilmenite exsolution textures,including blocky,lamellar,and cloth-like forms.In this study,we investigate the geochemistry and mineralogy of ilmenite exsolutions in titanomagnetite to understand their formation mechanisms and implications for the ore-forming process.Detailed petrographic observations and electron microprobe analyses reveal that the exsolution textures result from multiple mechanisms:oxy-exsolution due to titanomagnetite oxidation;subsolidus re-equilibration between magnetite and ilmenite involving elemental diffusion of Fe,Ti,Cr,Co,and Ni;and exsolution related to lattice defects caused by rapid cooling.Thermodynamic modeling using Gibbs free energy calculations,and the QUILF program indicates that blocky,lamellar,and cloth-textured ilmenite exsolutions formed at temperatures above and below the solid-solution solvus under decreasing oxygen fugacity.Additionally,our results indicate that the exsolution of zircon and pleonaste at ilmenite grain boundaries is attributed to the saturation and precipitation of elements like Zr and Al,due to the oxidation of titanomagnetite,rather than interactions between ilmenite and adjacent clinopyroxene.Reconstruction of the cooling history suggests that the oxygen fugacity of oxide-apatite gabbronorites was significantly higher than that of Fe-Ti-P ores.This confirms that increasing oxygen fugacity during magma evolution promoted immiscibility,leading to the formation of nelsonitic melts and ultimately the development of Fe-Ti-P ores.展开更多
The exsolutious of diopside and magnetite occur as intergrowth and orient within olivine from the mantle dunite, Luobusa ophiolite, Tibet. The dunite is very fresh with a mineral assemblage of olivine （〉95%） ＋ chr...The exsolutious of diopside and magnetite occur as intergrowth and orient within olivine from the mantle dunite, Luobusa ophiolite, Tibet. The dunite is very fresh with a mineral assemblage of olivine （〉95%） ＋ chromite （1%-4%） ＋ diopside （〈1%）. Two types of olivine are found in thin sections： one （Fo = 94） is coarse-grained, elongated with development of kink bands, wavy extinction and irregular margins; and the other （Fo = 96） is fine-grained and poly-angied. Some of the olivine grains contain minor Ca, Cr and Ni. Besides the exsolutions in olivine, three micron-size inclusions are also discovered. Analyzed through energy dispersive system （EDS） with unitary analytical method, the average compositions of the inclusions are： Na20, 3.12%-3.84%; MgO, 19.51%-23.79%; Al2O3, 9.33%-11.31%; SiO2, 44.89%-46.29%; CaO, 11.46%-12.90%; Cr2O3, 0.74%-2.29%; FeO, 4.26%- 5.27%, which is quite similar to those of amphibole. Diopside is anhedral f＇dling between olivines, or as micro-inclusions oriented in olivines. Chromite appears euhedral distributed between olivines, sometimes with apparent compositional zone. From core to rim of the chromite, Fe content increases and Cr decreases; and A! and Mg drop greatly on the rim. There is always incomplete magnetite zone around the chromite. Compared with the nodular chromite in the same section, the euhedral chromite has higher Fe3O4 and lower MgCr2O4 and MgAI2O4 end member contents, which means it formed under higher oxygen fugacity environment. With a geothermometer estimation, the equilibrium crystalline temperature is 820℃-960℃ for olivine and nodular chromite, 630℃-770℃ for olivine and euhedral chromite, and 350℃-550℃ for olivine and exsoluted magnetite, showing that the exsolutions occurred late at low temperature. Thus we propose that previously depleted mantle harzburgite reacted with the melt containing Na, Al and Ca, and produced an olivine solid solution added with Na^＋, Al^3＋, Ca^2＋, Fe^3＋, Cr^3＋. With temperature decreasing, the olivine solid solution decomposed; and Fe^3＋, Cr^3＋ diffused into magnetite and Ca^2＋ and Na^＋ into clinopyroxene, both of which formed intergrowth textures. A few Fe^3＋ and Cr^3＋ entered interstitial chromite. Through later tectonism, the peridotite recrystallized and formed deformational coarse grained olivine, fine grained and poly-angled olivine, and euhedral grained chromite. Due to the fast cooling rate of the rock or rapid tectonic emplacement, the exsolution textures in olivine and compositional zones of chromite are preserved.展开更多
Zinc-air batteries(ZABs)are promising candidates for flexible electronics due to their high energy density and low cost.However,their development is hindered by the sluggish kinetics of the oxygen evolution reaction(O...Zinc-air batteries(ZABs)are promising candidates for flexible electronics due to their high energy density and low cost.However,their development is hindered by the sluggish kinetics of the oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).Herein,we present a novel heterostructured electrocatalyst composed of vertically aligned N-doped graphene(NVG)arrays anchored on Ru-doped ceria(RCO)nanofibers,synthesized via a one-step plasma-enhanced chemical vapor deposition process.Notably,during the plasma-enhanced driven NVG growth,Ru nanoparticles are spontaneously in-situ exsolved from the RCO lattice,forming a unique Ru@RCO-NVG heterostructure.Density functional theory calculations reveal that the Ru@RCO-NVG heterojunction induces interfacial electronic redistribution,thereby significantly lowering the energy barriers for both OER and ORR.Benefiting from the synergistic effects,the Ru@RCO-NVG catalyst exhibits exceptional intrinsic activity towards OER/ORR(an overpotential of 370 mV for OER at 10 mA cm^(−2)and a half-wave potential of 0.86 V for ORR),and higher all-solid-state flexible ZAB performance(peak power density of 286.1 mW cm^(−2)),surpassing commercial Pt/C-IrO_(2)catalysts.This work not only advances the integration of synergistic graphene/ceria composites but also offers a promising strategy for designing efficient electrocatalysts for next-generation energy conversion technologies.展开更多
Sintering and coking are critical barriers to achieving high performance in dry reforming of methane(DRM)catalysts.A finely dispersed and thermostable Ni-based catalyst is the key to address these issues.By leveraging...Sintering and coking are critical barriers to achieving high performance in dry reforming of methane(DRM)catalysts.A finely dispersed and thermostable Ni-based catalyst is the key to address these issues.By leveraging the intrinsic superiorities of high-entropy oxides in high-temperature stability and low atomic diffusivity,in this study,a highly dispersed Ni-based catalyst is synthesized via an entropycontrolled exsolution of active components.By increasing the number of transition-metal elements in spinel oxides,the active metalsupport interaction(MSI)can be continuously strengthened,which controls the exsolution and thermal stability of Ni-based active metal in harsh reaction conditions of DRM.An optimized medium-entropy spinel(Mg_(0.4)Ni_(0.2)Co_(0.2)Zn_(0.2))Al_(2)O_(4)with the exsolution of finely dispersed Ni–Co nanoparticles displayed superior activity and stability in thermal DRM at 800°C and photothermal DRM.This entropy-controlled MSI and exsolution principle provides a significant strategy for designing robust catalysts resistant to sintering and coking for high-temperature reactions like DRM in thermal and photothermal systems.展开更多
The exsolution lamellae of quartz and clinoen-statite are idenfied in diopside of garnet-pyroxenolite from the North Dabie Mountain by transmission electron microscopy, which is interpreted that the lamellae are origi...The exsolution lamellae of quartz and clinoen-statite are idenfied in diopside of garnet-pyroxenolite from the North Dabie Mountain by transmission electron microscopy, which is interpreted that the lamellae are originally exsolved from a former ultra-high-pressure clinopyroxene due to decreasing of pressure. Study of petrography shows that there is compositional zoning hi the diopside itself. It is implied that the garnet-pyroxenolite had undergone intensive high-temperature granulite fades and high-amphibolitic fades retrogressive metamorphism, while the peridotite (the garnet-pyroxenolite’s host rock) emplaced the展开更多
Reversible solid oxide cells(RSOCs)are capable of converting various energy resources,between electricity and chemical fuels,with high efficiency and flexibility,making them suitable for grid balancing and renewable e...Reversible solid oxide cells(RSOCs)are capable of converting various energy resources,between electricity and chemical fuels,with high efficiency and flexibility,making them suitable for grid balancing and renewable energy consumption.However,the practical application of RSOCs is still limited by the insufficient activity and stability of the electrodes in different operating modes.Herein,a highly efficient symmetrical electrode composed of La_(0.3)Sr_(0.6)Ti_(0.1)Co_(0.2)Fe_(0.7)O_(3-δ)(LSTCF)nanofibers and in situ exsolved Co_(3)Fe_(7) nanoparticles is developed for boosting the performance of RSOCs.The reversible phase transition,high activity and stability of the electrode have been confirmed by a combination of experimental(e.g.,transmission electron microscopy and X-ray absorption fine structure)and computational studies.Electrolyte-supported RSOCs with the symmetrical electrode demonstrate excellent catalytic activity and stability,achieving a high peak power density of 0.98 W cm^(-2)in the fuel cell mode using H_(2)as the fuel(or 0.53 W cm^(-2)using CH_(4)as the fuel)and a high current density of 1.09 A cm^(-2) at 1.4 V in the CO_(2)electrolysis mode(or 1.03 A cm^(-2)at 1.3 V for H_(2)O electrolysis)at 800℃while maintaining excellent durability for over 100 h.展开更多
The exsolution method has garnered significant attention owing to its high efficacy in developing highly efficient and stable metal nanocatalysts.Herein,a versatile exsolution approach is developed to embed size-tunab...The exsolution method has garnered significant attention owing to its high efficacy in developing highly efficient and stable metal nanocatalysts.Herein,a versatile exsolution approach is developed to embed size-tunable metal nanocatalysts within a conductive metal pnictogenide matrix.The gas-phase reaction of Ru-substituted Ni-Fe-layered-double-hydroxide(Ni_(2)Fe_(1-x)Ru_(x)-LDH)with pnictogenation reagents leads to the exsolution of Ru metal nanocatalysts and a phase transformation into metal pnictogenide.The variation in reactivity of pnictogenation reagents allows for control over the size of the exsolved metal nanocatalysts(i.e.,nanoclusters for nitridation and single atoms for phosphidation),underscoring the effectiveness of the pnictogenation-driven exsolution strategy in stabilizing size-tunable metal nanocatalysts.The Ru-exsolved nickel-iron nitride/phosphide demonstrates outstanding electrocatalyst activity for the hydrogen evolution reaction,exhibiting a smaller overpotential and higher stability than Ru-deposited homologs.The high efficacy of pnictogenation-assisted exsolution in optimizing the performance and stability of Ru metal nanocatalysts is ascribed to the efficient interfacial electronic interaction between Ru metals and nitride/phosphide ions assisted by the inner sphere mechanism.In situ spectroscopic analyses highlight that exsolved Ru single atoms facilitate more efficient electron transfer to the reactants than the exsolved Ru nanoclusters,which is primarily responsible for the superior impact of the phosphidation-driven exsolution approach.展开更多
CO_(2)electrolysis using solid oxide electrolysis cells is a promising technology for CO_(2)utilization and conversion,which has attracted more and more attention in recent years because of its extremely high efficien...CO_(2)electrolysis using solid oxide electrolysis cells is a promising technology for CO_(2)utilization and conversion,which has attracted more and more attention in recent years because of its extremely high efficiency.However,traditional Ni-yttria-stabilized zirconia(Ni-YSZ)or Ni-Gd_(0.1)Ce_(0.9)O_(2-δ)(Ni-GDC)metal-ceramic cathode faces many problems such as Ni agglomeration and carbon deposition during long-time operation.Herein,a perovskite oxide La_(0.43-x)Ca_(0.37)Ti_(0.9)Ni_(0.1)O_(3-δ)(LCTN,x=0,0.05,0.1)with nanophase-LaVO_(4)exsolution was investigated as the novel cathode of solid oxide electrolysis cell(SOEC)for efficient CO_(2)electrolysis.The results confirm that the exsolution nanophase on LCTN surface can significantly improve the CO_(2)adsorption and conversion performance.For CO_(2)electrolysis at 1.8 V,an electrolysis current density of 1.24 A/cm2at 800℃can be obtained on SOEC with La_(0.43-x)Ca_(0.37)Ti_(0.9)Ni_(0.1)O_(3-δ)decorated with LaVO_(4)(LCTN-V0.05)cathode.Furthermore,the corresponding cell can maintain stable operation up to 100 h without apparent performance degradation.These results demonstrate that doping-induced second nanophase exsolution is a promising way to design high-performance SOEC cathodes for CO_(2)electrolysis.展开更多
The challenge of wide brine source and its additional problems come from the economy(energy consumption and other costs),security(re-dissolution of surrounding salt rocks),and environment(groundwater pollution by brin...The challenge of wide brine source and its additional problems come from the economy(energy consumption and other costs),security(re-dissolution of surrounding salt rocks),and environment(groundwater pollution by brine)of salt cavern oil storage are worth examining to improve the efficiency of oil storage.Against this background,this work presented an operating mode of salt cavern oil and gas co-storage and using natural gas displacement for petroleum recovery.A gas-oil two-phase flow model with gas dissolution and exsolution was proposed to evaluate the application prospects of the new method precisely.Numerical studies indicated that the gas void fraction at the wellhead under quasi-steady state conditions is approximately 0.153,which belongs to bubbly flow,and the pressure at the wellhead of the central tube increased from 5.54 to 6.12 MPa during the entire transient flow stage,with an increase of 10.47%.Compared to the traditional method of using brine as the working fluid,the pump pressure rises from 2.92 to 14.01 MPa.However,if the new mode can be linked with the salt cavern gas storage and when the initial wellhead gas pressure exceeds 13 MPa,the energy consumption of the new method will be lower than that of the traditional brine-based operational mode.A new empirical formula is proposed to determine the two-phase flow pattern under different operating parameters.A special focus was given to energy consumption for oil recovery,which grows roughly in accordance with the operating pressure and oil recovery rate.However,the energy cost per volume of crude oil remains almost unchanged.This work provided a new solution for the serious brine problem and is expected to achieve petroleum recovery through natural gas displacement.展开更多
Advancing clean energy technologies demands efficient and durable electrode catalysts for solid oxide cells(SOCs).Despite their exceptional catalytic properties,Pt-based materials face critical challenges in high-temp...Advancing clean energy technologies demands efficient and durable electrode catalysts for solid oxide cells(SOCs).Despite their exceptional catalytic properties,Pt-based materials face critical challenges in high-temperature applications owing to particle agglomeration and cost constraints.Here,we demonstrate a rational design strategy utilizing controlled in situ exsolution to create strongly anchored PtSn nanoalloys on oxygen-deficient PrBaMn_(1.8)Pt_(0.1)Sn_(0.1)O_(5+δ)(L-PBMPtSn)perovskite oxide.Through precise compositional engineering and structural control,we achieved a uniform dispersion of PtSn nanoparticles with unique socket-like interfaces that prevent agglomeration while maintaining high catalytic accessibility.The optimized electrode demonstrates remarkable bifunctional performance,achieving a current density of 1.6 A cm^(-2)at 1.8 V for CO_(2)electrolysis and a maximum power density of 316 mW cm^(-2)for fuel cell operation at 800℃.More significantly,the electrode exhibits exceptional stability with only 9.6%performance degradation over 100 h of operation,which is a substantial improvement over conventional electrodes.Our findings establish a new paradigm for designing high-performance SOC electrodes through the controlled exsolution of precious metal alloys,offering broader implications for catalyst design in high-temperature electrochemical systems.展开更多
Fuel flexibility is one of the most distinguished advantages of solid oxide fuel cells(SOFCs)over other low-temperature fuel cells.Furthermore,the combination of ammonia fuel and SOFCs technology should be a promising...Fuel flexibility is one of the most distinguished advantages of solid oxide fuel cells(SOFCs)over other low-temperature fuel cells.Furthermore,the combination of ammonia fuel and SOFCs technology should be a promising clean energy system after considering the high energy density,easy transportation/storage,matured synthesis technology and carbon-free nature of NH_(3) as well as high efficiency of SOFCs.However,the large-scale applications of direct-ammonia SOFCs(DASOFCs)are strongly limited by the inferior anti-sintering capability and catalytic activity for ammonia decomposition reaction of conventional nickel-based cermet anode.Herein,a slightly ruthenium(Ru)doping in perovskite oxides is proposed to promote the alloy nanoparticle exsolution,enabling better DA-SOFCs with enhanced power outputs and operational stability.After treating Ru-doped Pr_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.75)Ru_(0.05)O_(3-δ) single-phase perovskite in a reducing atmosphere,in addition to the formation of two layered Ruddlesden-Popper perovskites and Pr_(2)O_(3) nanoparticles(the same as the Ru-free counterpart,Pr_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)),the exsolution of CoFeRu-based alloy nanoparticles is remarkably promoted.Such reduced Pr_(0.6)Sr0.4Co_(0.2)Fe_(0.75)Ru_(0.05)O_(3-δ) composite anode shows superior catalytic activity and stability for NH_(3) decomposition reaction as well as anti-sintering capability in DA-SOFCs to those of reduced Pr0.6Sr0.4Co0.2Fe0.8O_(3-δ)due to the facilitated nanoparticle exsolution and stronger nanoparticle/substrate interaction.This work provides a facile and effective strategy to design highly active and durable anodes for DA-SOFCs,promoting large-scale applications of this technology.展开更多
Symmetrical solid oxide fuel cells(SSOFCs)could be alternative energy conversion devices due to their simple fabrication process and low cost.Herein,perovskite La_(0.6)Ce_(0.1)Sr_(0.3)Fe_(0.95)Ru_(0.05O3-δ)(LCSFR)was...Symmetrical solid oxide fuel cells(SSOFCs)could be alternative energy conversion devices due to their simple fabrication process and low cost.Herein,perovskite La_(0.6)Ce_(0.1)Sr_(0.3)Fe_(0.95)Ru_(0.05O3-δ)(LCSFR)was synthesized and evaluated as a high-performance electrode for SSOFCs based on the electrolyte of La_(0.9)Sr_(0.1)Ga_(0.8)Mg_(0.2)O_(3-δ)(LSGM).LCSFR retains their stable perovskite crystal structure in both reducing and oxidizing atmospheres,though a minor amount of LaSrFeO4 phase is present under reducing conditions.Morphology investigation shows that homogeneously dispersed Ru metallic nanoparticles are exsolved on the surface of LCSFR after being reduced.The polarization resistance(Rp)of LCSFR-CGO(Ce_(0.9)Gd_(0.1O2-δ))is about 0.11Ω·cm^(2)at 800℃in air,while the value of Rp for LCSFR-CGO in wet H_(2)(3%H_(2)O)increases up to 0.32Ω·cm^(2).The symmetrical LCSFR-CGOILSGMILCSFR-CGO cell demonstrates a performance with an open circuit potential(OCV)of 1.07 V and a maximum peak power density of 904 mW/cm^(2)at 800℃using wet H2 as the fuel.This high performance indicates that LCSFR is a candidate electrode for SSOFCs.展开更多
The processes of solution in, and exsolution from, formation water influence the component content of natural gas by contrasting the relative contents of components before the natural gas dissolves in water and those ...The processes of solution in, and exsolution from, formation water influence the component content of natural gas by contrasting the relative contents of components before the natural gas dissolves in water and those after exsolving from water under different conditions of high temperatures and pressures. Compared with the composition of original natural gas, the relative content of methane and nitrogen increased after the natural gas dissolved in water. The increase of nitrogen content exceeds that of methane, but the content of ethane, propane, pentane etc reduced. At the same temperature and with pressure increasing the content of methane increased and that of heavier hydrocarbons reduced. At the same pressure the content of methane increased quickly from 90~C to 120~C, and the content of heavier hydrocarbons reduced. But at even higher temperatures, the increase of methane slowed down and the content of heavier hydrocarbons increased slightly. At the same temperature and different pressures, heavier hydrocarbons reduced much more with increasing carbon atom number, while with temperature increasing the content difference of heavier hydrocarbons reduced. Therefore, the influence of the solution and exsolution should be considered in the study of the migration and accumulation mechanism of natural gas.展开更多
Nanoparticles anchored on the perovskite surface have gained considerable attention for their wide-ranging applications in heterogeneous catalysis and energy conversion due to their robust and integrated structural co...Nanoparticles anchored on the perovskite surface have gained considerable attention for their wide-ranging applications in heterogeneous catalysis and energy conversion due to their robust and integrated structural configuration.Herein,we employ controlled Co doping to effectively enhance the nanoparticle exsolution process in layered perovskite ferrites materials.CoFe alloy nanoparticles with ultra-high-density are exsolved on the(PrBa)_(0.95)(Fe_(0.8)Co_(0.1)Nb_(0.1))2O_(5+δ)(PBFCN_(0.1))surface under reducing atmosphere,providing significant amounts of reaction sites and good durability for hydrocarbon catalysis.Under a reducing atmosphere,cobalt facilitates the reduction of iron cations within PBFCN_(0.1),leading to the formation of CoFe alloy nanoparticles.This formation is accompanied by a cation exchange process,wherein,with the increase in temperature,partial cobalt ions are substituted by iron.Meanwhile,Co doping significantly enhance the electrical conductivity due to the stronger covalency of the Cosingle bondO bond compared with Fesingle bondO bond.A single cell with the configuration of PBFCN_(0.1)-Sm_(0.2)Ce_(0.8)O_(1.9)(SDC)|SDC|Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3−δ)(BSCF)-SDC achieves an extremely low polarization resistance of 0.0163Ωcm^(2)and a high peak power density of 740 mW cm^(−2)at 800℃.The cell also shows stable operation for 120 h in H_(2)with a constant current density of 285 mA cm^(−2).Furthermore,employing wet C_(2)H_(6)as fuel,the cell demonstrates remarkable performance,achieving peak power densities of 455 mW cm^(−2)at 800℃and 320 mW cm^(−2)at 750℃,marking improvements of 36%and 70%over the cell with(PrBa)_(0.95)(Fe_(0.9)Nb_(0.1))_(2)O_(5+δ)(PBFN)-SDC at these respective temperatures.This discovery emphasizes how temperature influences alloy nanoparticles exsolution within doped layered perovskite ferrites materials,paving the way for the development of high-performance ceramic fuel cell anodes.展开更多
Spinel exsolution is widespread in titanomagnetite from the Fe-Ti oxide gabbro of the Panzhihua intrusion, Emeishan Large Igneous Province, SW China. However, little research has been conducted into the implications o...Spinel exsolution is widespread in titanomagnetite from the Fe-Ti oxide gabbro of the Panzhihua intrusion, Emeishan Large Igneous Province, SW China. However, little research has been conducted into the implications of patterns in the mineralogical characteristics of the spinel for spatial variation in the controls on the exsolution mechanism and, hence, the formation process of the ore deposit. This study selected the Lanjiahuoshan Ore Block in the Panzhihua V-Ti magnetite deposit to explore this issue, systematically studying exsolution textures in the titanomagnetite through petrographic observation and the integrated use of in-situ microanalysis. The results show that the exsolved spinel gradually becomes finer-grained and less abundant from the center to edge and the bottom to top of the ore bodies. Compositionally, there is an inverse correlation between the size of exsolved spinel grains and their Mg# value. In addition, there is compositional zonation in the spinel interiors, with a gradual increase in the Mg content and decrease in Fe content from the core to the rim. The analysis suggests that fractional crystallization of ferrotitanium magma with a high oxygen fugacity in a shallow magma chamber caused compositional differences in the primary magnetite solid solution in different parts of the Panzhihua intrusion. Additionally, the thermal evolution of the magnetite solid solution differed in different parts of orebody, bringing about variations in spinel development. Together, these effects resulted in spatial variation in the abundance, grain size, and morphology of spinel in different parts of the orebody and intrusion that follows an identifiable distribution law. Furthermore, the compositional zonation of exsolved spinels reflects the rapid growth of exsolution features in a high-temperature environment. Thus, the size, morphology, abundance, and composition of spinel exsolution features in titanomagnetite provide a valuable petrogenetic tool for estimating the maturity and formational environment of the deposit.展开更多
In No. 50 kimberlite pipe of Fuxian County, Liaoning Province, an eclogite inclusion(nodule), which is extremely rare in kimberlites, was discovered and phlogopite exsolutionlamellae were found in garnets of the inclu...In No. 50 kimberlite pipe of Fuxian County, Liaoning Province, an eclogite inclusion(nodule), which is extremely rare in kimberlites, was discovered and phlogopite exsolutionlamellae were found in garnets of the inclusion. Microscopic, TEM and energy spectral observa-tions and studies confirmed that these lamellae are phlogopite. They are colourless and acicularin section, generally 0.5-5μm in width and 10-100μm in length. Nevertheless, fine lamellae,0.05-0.1μm wide and 1-2μm long, are also well developed. Along [111] of the garnet, three setsof phlogopite lamellae show oriented arrangement approximately at angles of 60°-70°, indi-cating that these lamellae might be the product of exsolution from garnet as a result ofpressure-release when eclogite ascended from the relatively deep level to the relatively shallowlevel of the mantle. Tiny acicular exsolution minerals (or inclusions) are commonly found ingarnet and pyroxene in eclogite inclusions of kimberlites all over the world and it has been re-ported that the identified exsolution minerals include pyroxene and rutile. This is the first timethat phlogopite exsolution lamillae were found in eclogite inclusions in the world.展开更多
As a powerful tracer in high-temperature geochemistry,Fe isotopes have been studied for their behaviour during fl uid exsolution and evolution related to felsic magma system,but that for carbonatite magma system remai...As a powerful tracer in high-temperature geochemistry,Fe isotopes have been studied for their behaviour during fl uid exsolution and evolution related to felsic magma system,but that for carbonatite magma system remains unknown.Here we study the Fe isotope fractionation behaviour during fenitization–processes that widely occur associated with carbonatite or alkaline intrusions.Nine fenite/carbonatite samples from carbonatite dykes at Bayan Obo area are analyzed for their Fe isotope compositions as well as elemental compositions.Combined with previous reported carbonatite δ^(56)Fe data,the results show that carbonatites range from-0.35‰to 0.28‰,with an average of-0.10‰in δ^(56)Fe values,while fenites range from-0.17‰to 0.30‰,with an average of 0.11‰in δ^(56)Fe values.This indicates that fenitizing fl uids exsolved from carbonatite melts are enriched in heavier Fe isotopes.Such a Fe isotope fractionation trend is diff erent from that for fl uid exsolution from felsic magmatism.δ^(56)Fe values in fenites are negatively correlated with indicators of fenitization intensity such as(Na+K),Ti,Ba,Th,Nb,U or Pb abundances,likely refl ecting that Fe isotopes fractionate during the evolution of the fenitizing fl uids.Thus,Fe isotopes are a valuable tool for tracing fl uid exsolution and evolution relevant to carbonatite magmatism and related metal mineralization.展开更多
The studies on ultra microstructure characteristics of quartz exsolution in eclogite and coesite in UHP eclogite of several localities are done with the appliance of laser Raman spectroscopy and U stage. Research re...The studies on ultra microstructure characteristics of quartz exsolution in eclogite and coesite in UHP eclogite of several localities are done with the appliance of laser Raman spectroscopy and U stage. Research results show that the phase transformation of coesite quartz in garnet and/or omphacite is a continuous process. Topological relationship is present between quartz exsolution in omphacite and its host mineral which shows orientations of two long axes of quartz exsolution parallel to (100) and (-101) of omphacite. At present, some scholars suggest that the quartz exsolution in omphacite of eclogite is the evidence of UHP metamorphism. However, temperature and pressure condition and the exsolution mechanism of oriented needlelike quartz in omphacite still remain unclear. Therefore, further study should be enhanced on experimental research on exsolution mechanism of super silicate clinopyroxene, which could provide experimental quantitative constraint on quartz exsolution as UHP indicator.展开更多
Electrochemical reduction of CO_(2)into valuable fuels and chemicals has become a contemporary research area,where the heterogeneous catalyst plays a critical role.Metal nanoparticles supported on oxides performing as...Electrochemical reduction of CO_(2)into valuable fuels and chemicals has become a contemporary research area,where the heterogeneous catalyst plays a critical role.Metal nanoparticles supported on oxides performing as active sites of electrochemical reactions have been the focus of intensive investigation.Here,we review the CO_(2)reduction with active materials prepared by exsolution.The fundamental of exsolution was summarized in terms of mechanism and models,materials,and driven forces.The advances in the exsolved materials used in hightemperature CO_(2)electrolysis were catalogued into tailored interfaces,synergistic effects on alloy particles,phase transition,reversibility and electrochemical switching.展开更多
Excessive emission of carbon dioxide(CO_(2))has posed an imminent threat to human's environment and global prosperity.To achieve a sustainable future,solid oxide electrolysis cell(SOEC),which can efficiently combin...Excessive emission of carbon dioxide(CO_(2))has posed an imminent threat to human's environment and global prosperity.To achieve a sustainable future,solid oxide electrolysis cell(SOEC),which can efficiently combine CO_(2)reduction reaction(CO_(2)RR)and renewable energy storage,has become increasingly attractive owing to its unique functionalities.Additionally,symmetrical SOEC(SSOEC)has been considered as one of the most versatile cell configurations due to its simplified process,high compatibility,and low cost.However,the electrode material requirements become very demanding since efficient catalytic-activities are required for both CO_(2)RR and oxygen evolution reaction(OER).Herein,we demonstrate a novel high-entropy perovskite type symmetrical electrode Pr_(0.5)Ba_(0.5)Mn_(0.2)Fe_(0.2)Co_(0.2)Ni_(0.2)Cu_(0.2)O_(3-δ)(HE-PBM)for SSOEC.B-site doping of transition metals such as Mn,Fe,Co,Ni,and Cu in HE-PBM anode has been found to strongly accelerate the OER in the anode.Moreover,the presence of in-situ formed Fe–Co–Ni–Cu quaternary alloy nanocatalysts from HE-PBM cathode under reducing atmosphere has resulted in superior catalytic-activity towards CO_(2)RR.The faster kinetics are also reflected by the significantly low polarization resistance of 0.289Ω⋅cm^(-2)and high electrolysis current density of 1.21 A⋅cm^(-2)for CO_(2)RR at 2.0 V and 800℃.The excellent electrochemical performance and stability demonstrate that the highentropy perovskite material is a promising electrode material in SSOEC for efficient and durable CO_(2)RR.展开更多
基金funded by the National Natural Science Foundation of China(grant 42102094)Natural Science Foundation of Hebei(Grant D2022402028).
文摘The Damiao Fe-Ti-P deposit,located within the Damiao anorthosite complex in northeastern China,features Fe-Ti oxide ores and nelsonites that occur as irregularly inclined stratiform-like bodies,lenses,or veins with sharp contacts against anorthosite and gabbronorite.This deposit is characterized by abundant titanomagnetite that hosts diverse ilmenite exsolution textures,including blocky,lamellar,and cloth-like forms.In this study,we investigate the geochemistry and mineralogy of ilmenite exsolutions in titanomagnetite to understand their formation mechanisms and implications for the ore-forming process.Detailed petrographic observations and electron microprobe analyses reveal that the exsolution textures result from multiple mechanisms:oxy-exsolution due to titanomagnetite oxidation;subsolidus re-equilibration between magnetite and ilmenite involving elemental diffusion of Fe,Ti,Cr,Co,and Ni;and exsolution related to lattice defects caused by rapid cooling.Thermodynamic modeling using Gibbs free energy calculations,and the QUILF program indicates that blocky,lamellar,and cloth-textured ilmenite exsolutions formed at temperatures above and below the solid-solution solvus under decreasing oxygen fugacity.Additionally,our results indicate that the exsolution of zircon and pleonaste at ilmenite grain boundaries is attributed to the saturation and precipitation of elements like Zr and Al,due to the oxidation of titanomagnetite,rather than interactions between ilmenite and adjacent clinopyroxene.Reconstruction of the cooling history suggests that the oxygen fugacity of oxide-apatite gabbronorites was significantly higher than that of Fe-Ti-P ores.This confirms that increasing oxygen fugacity during magma evolution promoted immiscibility,leading to the formation of nelsonitic melts and ultimately the development of Fe-Ti-P ores.
文摘The exsolutious of diopside and magnetite occur as intergrowth and orient within olivine from the mantle dunite, Luobusa ophiolite, Tibet. The dunite is very fresh with a mineral assemblage of olivine （〉95%） ＋ chromite （1%-4%） ＋ diopside （〈1%）. Two types of olivine are found in thin sections： one （Fo = 94） is coarse-grained, elongated with development of kink bands, wavy extinction and irregular margins; and the other （Fo = 96） is fine-grained and poly-angied. Some of the olivine grains contain minor Ca, Cr and Ni. Besides the exsolutions in olivine, three micron-size inclusions are also discovered. Analyzed through energy dispersive system （EDS） with unitary analytical method, the average compositions of the inclusions are： Na20, 3.12%-3.84%; MgO, 19.51%-23.79%; Al2O3, 9.33%-11.31%; SiO2, 44.89%-46.29%; CaO, 11.46%-12.90%; Cr2O3, 0.74%-2.29%; FeO, 4.26%- 5.27%, which is quite similar to those of amphibole. Diopside is anhedral f＇dling between olivines, or as micro-inclusions oriented in olivines. Chromite appears euhedral distributed between olivines, sometimes with apparent compositional zone. From core to rim of the chromite, Fe content increases and Cr decreases; and A! and Mg drop greatly on the rim. There is always incomplete magnetite zone around the chromite. Compared with the nodular chromite in the same section, the euhedral chromite has higher Fe3O4 and lower MgCr2O4 and MgAI2O4 end member contents, which means it formed under higher oxygen fugacity environment. With a geothermometer estimation, the equilibrium crystalline temperature is 820℃-960℃ for olivine and nodular chromite, 630℃-770℃ for olivine and euhedral chromite, and 350℃-550℃ for olivine and exsoluted magnetite, showing that the exsolutions occurred late at low temperature. Thus we propose that previously depleted mantle harzburgite reacted with the melt containing Na, Al and Ca, and produced an olivine solid solution added with Na^＋, Al^3＋, Ca^2＋, Fe^3＋, Cr^3＋. With temperature decreasing, the olivine solid solution decomposed; and Fe^3＋, Cr^3＋ diffused into magnetite and Ca^2＋ and Na^＋ into clinopyroxene, both of which formed intergrowth textures. A few Fe^3＋ and Cr^3＋ entered interstitial chromite. Through later tectonism, the peridotite recrystallized and formed deformational coarse grained olivine, fine grained and poly-angled olivine, and euhedral grained chromite. Due to the fast cooling rate of the rock or rapid tectonic emplacement, the exsolution textures in olivine and compositional zones of chromite are preserved.
基金supported by the National Natural Science Foundation of China(Grant No.22479133,and No.22469008)the Natural Science Foundation of Guangdong Province(Grant No.2024A1515012235).
文摘Zinc-air batteries(ZABs)are promising candidates for flexible electronics due to their high energy density and low cost.However,their development is hindered by the sluggish kinetics of the oxygen evolution reaction(OER)and oxygen reduction reaction(ORR).Herein,we present a novel heterostructured electrocatalyst composed of vertically aligned N-doped graphene(NVG)arrays anchored on Ru-doped ceria(RCO)nanofibers,synthesized via a one-step plasma-enhanced chemical vapor deposition process.Notably,during the plasma-enhanced driven NVG growth,Ru nanoparticles are spontaneously in-situ exsolved from the RCO lattice,forming a unique Ru@RCO-NVG heterostructure.Density functional theory calculations reveal that the Ru@RCO-NVG heterojunction induces interfacial electronic redistribution,thereby significantly lowering the energy barriers for both OER and ORR.Benefiting from the synergistic effects,the Ru@RCO-NVG catalyst exhibits exceptional intrinsic activity towards OER/ORR(an overpotential of 370 mV for OER at 10 mA cm^(−2)and a half-wave potential of 0.86 V for ORR),and higher all-solid-state flexible ZAB performance(peak power density of 286.1 mW cm^(−2)),surpassing commercial Pt/C-IrO_(2)catalysts.This work not only advances the integration of synergistic graphene/ceria composites but also offers a promising strategy for designing efficient electrocatalysts for next-generation energy conversion technologies.
基金supported by the National Key R&D Program of China(2023YFB4104600)National Natural Science Foundation of China(52572313)+1 种基金Tangshan Talent Funding Project(A202202007)Shenzhen Science and Technology Innovation Commission under Grant No.20231120185819001。
文摘Sintering and coking are critical barriers to achieving high performance in dry reforming of methane(DRM)catalysts.A finely dispersed and thermostable Ni-based catalyst is the key to address these issues.By leveraging the intrinsic superiorities of high-entropy oxides in high-temperature stability and low atomic diffusivity,in this study,a highly dispersed Ni-based catalyst is synthesized via an entropycontrolled exsolution of active components.By increasing the number of transition-metal elements in spinel oxides,the active metalsupport interaction(MSI)can be continuously strengthened,which controls the exsolution and thermal stability of Ni-based active metal in harsh reaction conditions of DRM.An optimized medium-entropy spinel(Mg_(0.4)Ni_(0.2)Co_(0.2)Zn_(0.2))Al_(2)O_(4)with the exsolution of finely dispersed Ni–Co nanoparticles displayed superior activity and stability in thermal DRM at 800°C and photothermal DRM.This entropy-controlled MSI and exsolution principle provides a significant strategy for designing robust catalysts resistant to sintering and coking for high-temperature reactions like DRM in thermal and photothermal systems.
基金the Ministry of Science and Technology of China (Grant No. G1999075501) the National Natural Science Foundation of China (Grant No. 49794041) the Postdoctor Science Foundation of China, the State Key Laboratory of Mineral Deposit, University of Nanji
文摘The exsolution lamellae of quartz and clinoen-statite are idenfied in diopside of garnet-pyroxenolite from the North Dabie Mountain by transmission electron microscopy, which is interpreted that the lamellae are originally exsolved from a former ultra-high-pressure clinopyroxene due to decreasing of pressure. Study of petrography shows that there is compositional zoning hi the diopside itself. It is implied that the garnet-pyroxenolite had undergone intensive high-temperature granulite fades and high-amphibolitic fades retrogressive metamorphism, while the peridotite (the garnet-pyroxenolite’s host rock) emplaced the
基金supported by the National Natural Science Foundation of China(No.52377212 and 51877173)program of Beijing Huairou Laboratory(ZD2022006A)+2 种基金the Key R&D Project of Shaanxi Province(2023-YBGY-057)the State Key Laboratory of Electrical Insulation and Power Equipment(EIPE22314,EIPE22306)the Natural Science Basic Research Program of Shaanxi(No.2023-JC-QN-0483).
文摘Reversible solid oxide cells(RSOCs)are capable of converting various energy resources,between electricity and chemical fuels,with high efficiency and flexibility,making them suitable for grid balancing and renewable energy consumption.However,the practical application of RSOCs is still limited by the insufficient activity and stability of the electrodes in different operating modes.Herein,a highly efficient symmetrical electrode composed of La_(0.3)Sr_(0.6)Ti_(0.1)Co_(0.2)Fe_(0.7)O_(3-δ)(LSTCF)nanofibers and in situ exsolved Co_(3)Fe_(7) nanoparticles is developed for boosting the performance of RSOCs.The reversible phase transition,high activity and stability of the electrode have been confirmed by a combination of experimental(e.g.,transmission electron microscopy and X-ray absorption fine structure)and computational studies.Electrolyte-supported RSOCs with the symmetrical electrode demonstrate excellent catalytic activity and stability,achieving a high peak power density of 0.98 W cm^(-2)in the fuel cell mode using H_(2)as the fuel(or 0.53 W cm^(-2)using CH_(4)as the fuel)and a high current density of 1.09 A cm^(-2) at 1.4 V in the CO_(2)electrolysis mode(or 1.03 A cm^(-2)at 1.3 V for H_(2)O electrolysis)at 800℃while maintaining excellent durability for over 100 h.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(RS-2023-00208355,RS-2024-00439825,and 2022M3H4A408610313)supported by the Global Science Research Center Program(RS-2024-00411134)+1 种基金funded by the National Research Foundation of KoreaThe experiments at PAL were supported in part by MOST and POSTECH。
文摘The exsolution method has garnered significant attention owing to its high efficacy in developing highly efficient and stable metal nanocatalysts.Herein,a versatile exsolution approach is developed to embed size-tunable metal nanocatalysts within a conductive metal pnictogenide matrix.The gas-phase reaction of Ru-substituted Ni-Fe-layered-double-hydroxide(Ni_(2)Fe_(1-x)Ru_(x)-LDH)with pnictogenation reagents leads to the exsolution of Ru metal nanocatalysts and a phase transformation into metal pnictogenide.The variation in reactivity of pnictogenation reagents allows for control over the size of the exsolved metal nanocatalysts(i.e.,nanoclusters for nitridation and single atoms for phosphidation),underscoring the effectiveness of the pnictogenation-driven exsolution strategy in stabilizing size-tunable metal nanocatalysts.The Ru-exsolved nickel-iron nitride/phosphide demonstrates outstanding electrocatalyst activity for the hydrogen evolution reaction,exhibiting a smaller overpotential and higher stability than Ru-deposited homologs.The high efficacy of pnictogenation-assisted exsolution in optimizing the performance and stability of Ru metal nanocatalysts is ascribed to the efficient interfacial electronic interaction between Ru metals and nitride/phosphide ions assisted by the inner sphere mechanism.In situ spectroscopic analyses highlight that exsolved Ru single atoms facilitate more efficient electron transfer to the reactants than the exsolved Ru nanoclusters,which is primarily responsible for the superior impact of the phosphidation-driven exsolution approach.
基金Project supported by the National Key Research&Development Project(2023YFB4006001)National Natural Science Foundation of China(52172199)。
文摘CO_(2)electrolysis using solid oxide electrolysis cells is a promising technology for CO_(2)utilization and conversion,which has attracted more and more attention in recent years because of its extremely high efficiency.However,traditional Ni-yttria-stabilized zirconia(Ni-YSZ)or Ni-Gd_(0.1)Ce_(0.9)O_(2-δ)(Ni-GDC)metal-ceramic cathode faces many problems such as Ni agglomeration and carbon deposition during long-time operation.Herein,a perovskite oxide La_(0.43-x)Ca_(0.37)Ti_(0.9)Ni_(0.1)O_(3-δ)(LCTN,x=0,0.05,0.1)with nanophase-LaVO_(4)exsolution was investigated as the novel cathode of solid oxide electrolysis cell(SOEC)for efficient CO_(2)electrolysis.The results confirm that the exsolution nanophase on LCTN surface can significantly improve the CO_(2)adsorption and conversion performance.For CO_(2)electrolysis at 1.8 V,an electrolysis current density of 1.24 A/cm2at 800℃can be obtained on SOEC with La_(0.43-x)Ca_(0.37)Ti_(0.9)Ni_(0.1)O_(3-δ)decorated with LaVO_(4)(LCTN-V0.05)cathode.Furthermore,the corresponding cell can maintain stable operation up to 100 h without apparent performance degradation.These results demonstrate that doping-induced second nanophase exsolution is a promising way to design high-performance SOEC cathodes for CO_(2)electrolysis.
基金The financial support from the National Science and Technology Major Project,China(No.2024ZD1004107)the Natural Science Foundation of Wuhan(No.2024040701010062)is greatly appreciated。
文摘The challenge of wide brine source and its additional problems come from the economy(energy consumption and other costs),security(re-dissolution of surrounding salt rocks),and environment(groundwater pollution by brine)of salt cavern oil storage are worth examining to improve the efficiency of oil storage.Against this background,this work presented an operating mode of salt cavern oil and gas co-storage and using natural gas displacement for petroleum recovery.A gas-oil two-phase flow model with gas dissolution and exsolution was proposed to evaluate the application prospects of the new method precisely.Numerical studies indicated that the gas void fraction at the wellhead under quasi-steady state conditions is approximately 0.153,which belongs to bubbly flow,and the pressure at the wellhead of the central tube increased from 5.54 to 6.12 MPa during the entire transient flow stage,with an increase of 10.47%.Compared to the traditional method of using brine as the working fluid,the pump pressure rises from 2.92 to 14.01 MPa.However,if the new mode can be linked with the salt cavern gas storage and when the initial wellhead gas pressure exceeds 13 MPa,the energy consumption of the new method will be lower than that of the traditional brine-based operational mode.A new empirical formula is proposed to determine the two-phase flow pattern under different operating parameters.A special focus was given to energy consumption for oil recovery,which grows roughly in accordance with the operating pressure and oil recovery rate.However,the energy cost per volume of crude oil remains almost unchanged.This work provided a new solution for the serious brine problem and is expected to achieve petroleum recovery through natural gas displacement.
基金supported by the National Natural Science Foundation of China(Nos.22272081 and 52473235)Postgraduate Research and Practice Innovation Program of Jiangsu Province(No.KYCX24_1527)National Research Foundation of Korea(NRF)grant funded by the Korea governement(MSIT)(No.RS-2024-00347253)
文摘Advancing clean energy technologies demands efficient and durable electrode catalysts for solid oxide cells(SOCs).Despite their exceptional catalytic properties,Pt-based materials face critical challenges in high-temperature applications owing to particle agglomeration and cost constraints.Here,we demonstrate a rational design strategy utilizing controlled in situ exsolution to create strongly anchored PtSn nanoalloys on oxygen-deficient PrBaMn_(1.8)Pt_(0.1)Sn_(0.1)O_(5+δ)(L-PBMPtSn)perovskite oxide.Through precise compositional engineering and structural control,we achieved a uniform dispersion of PtSn nanoparticles with unique socket-like interfaces that prevent agglomeration while maintaining high catalytic accessibility.The optimized electrode demonstrates remarkable bifunctional performance,achieving a current density of 1.6 A cm^(-2)at 1.8 V for CO_(2)electrolysis and a maximum power density of 316 mW cm^(-2)for fuel cell operation at 800℃.More significantly,the electrode exhibits exceptional stability with only 9.6%performance degradation over 100 h of operation,which is a substantial improvement over conventional electrodes.Our findings establish a new paradigm for designing high-performance SOC electrodes through the controlled exsolution of precious metal alloys,offering broader implications for catalyst design in high-temperature electrochemical systems.
基金financially supported by the National Natural Science Foundation of China(Nos.22108121,21908106 and21878158)Jiangsu Natural Science Foundation(No.BK20190682)a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)。
文摘Fuel flexibility is one of the most distinguished advantages of solid oxide fuel cells(SOFCs)over other low-temperature fuel cells.Furthermore,the combination of ammonia fuel and SOFCs technology should be a promising clean energy system after considering the high energy density,easy transportation/storage,matured synthesis technology and carbon-free nature of NH_(3) as well as high efficiency of SOFCs.However,the large-scale applications of direct-ammonia SOFCs(DASOFCs)are strongly limited by the inferior anti-sintering capability and catalytic activity for ammonia decomposition reaction of conventional nickel-based cermet anode.Herein,a slightly ruthenium(Ru)doping in perovskite oxides is proposed to promote the alloy nanoparticle exsolution,enabling better DA-SOFCs with enhanced power outputs and operational stability.After treating Ru-doped Pr_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.75)Ru_(0.05)O_(3-δ) single-phase perovskite in a reducing atmosphere,in addition to the formation of two layered Ruddlesden-Popper perovskites and Pr_(2)O_(3) nanoparticles(the same as the Ru-free counterpart,Pr_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)),the exsolution of CoFeRu-based alloy nanoparticles is remarkably promoted.Such reduced Pr_(0.6)Sr0.4Co_(0.2)Fe_(0.75)Ru_(0.05)O_(3-δ) composite anode shows superior catalytic activity and stability for NH_(3) decomposition reaction as well as anti-sintering capability in DA-SOFCs to those of reduced Pr0.6Sr0.4Co0.2Fe0.8O_(3-δ)due to the facilitated nanoparticle exsolution and stronger nanoparticle/substrate interaction.This work provides a facile and effective strategy to design highly active and durable anodes for DA-SOFCs,promoting large-scale applications of this technology.
基金Project supported by the State of Grid(SGSDJN00FZQT1700446)。
文摘Symmetrical solid oxide fuel cells(SSOFCs)could be alternative energy conversion devices due to their simple fabrication process and low cost.Herein,perovskite La_(0.6)Ce_(0.1)Sr_(0.3)Fe_(0.95)Ru_(0.05O3-δ)(LCSFR)was synthesized and evaluated as a high-performance electrode for SSOFCs based on the electrolyte of La_(0.9)Sr_(0.1)Ga_(0.8)Mg_(0.2)O_(3-δ)(LSGM).LCSFR retains their stable perovskite crystal structure in both reducing and oxidizing atmospheres,though a minor amount of LaSrFeO4 phase is present under reducing conditions.Morphology investigation shows that homogeneously dispersed Ru metallic nanoparticles are exsolved on the surface of LCSFR after being reduced.The polarization resistance(Rp)of LCSFR-CGO(Ce_(0.9)Gd_(0.1O2-δ))is about 0.11Ω·cm^(2)at 800℃in air,while the value of Rp for LCSFR-CGO in wet H_(2)(3%H_(2)O)increases up to 0.32Ω·cm^(2).The symmetrical LCSFR-CGOILSGMILCSFR-CGO cell demonstrates a performance with an open circuit potential(OCV)of 1.07 V and a maximum peak power density of 904 mW/cm^(2)at 800℃using wet H2 as the fuel.This high performance indicates that LCSFR is a candidate electrode for SSOFCs.
文摘The processes of solution in, and exsolution from, formation water influence the component content of natural gas by contrasting the relative contents of components before the natural gas dissolves in water and those after exsolving from water under different conditions of high temperatures and pressures. Compared with the composition of original natural gas, the relative content of methane and nitrogen increased after the natural gas dissolved in water. The increase of nitrogen content exceeds that of methane, but the content of ethane, propane, pentane etc reduced. At the same temperature and with pressure increasing the content of methane increased and that of heavier hydrocarbons reduced. At the same pressure the content of methane increased quickly from 90~C to 120~C, and the content of heavier hydrocarbons reduced. But at even higher temperatures, the increase of methane slowed down and the content of heavier hydrocarbons increased slightly. At the same temperature and different pressures, heavier hydrocarbons reduced much more with increasing carbon atom number, while with temperature increasing the content difference of heavier hydrocarbons reduced. Therefore, the influence of the solution and exsolution should be considered in the study of the migration and accumulation mechanism of natural gas.
基金supported by National Natural Science Foundation of China Project (Grant No. 52374133, 52262034)the Guangdong Basic and Applied Basic Research Committee Foundation (Grant No. KCXST20221021111601003)Shenzhen Science and Technology Innovation Commission Foundation (Grant No. KCXST20221021111601003)
文摘Nanoparticles anchored on the perovskite surface have gained considerable attention for their wide-ranging applications in heterogeneous catalysis and energy conversion due to their robust and integrated structural configuration.Herein,we employ controlled Co doping to effectively enhance the nanoparticle exsolution process in layered perovskite ferrites materials.CoFe alloy nanoparticles with ultra-high-density are exsolved on the(PrBa)_(0.95)(Fe_(0.8)Co_(0.1)Nb_(0.1))2O_(5+δ)(PBFCN_(0.1))surface under reducing atmosphere,providing significant amounts of reaction sites and good durability for hydrocarbon catalysis.Under a reducing atmosphere,cobalt facilitates the reduction of iron cations within PBFCN_(0.1),leading to the formation of CoFe alloy nanoparticles.This formation is accompanied by a cation exchange process,wherein,with the increase in temperature,partial cobalt ions are substituted by iron.Meanwhile,Co doping significantly enhance the electrical conductivity due to the stronger covalency of the Cosingle bondO bond compared with Fesingle bondO bond.A single cell with the configuration of PBFCN_(0.1)-Sm_(0.2)Ce_(0.8)O_(1.9)(SDC)|SDC|Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3−δ)(BSCF)-SDC achieves an extremely low polarization resistance of 0.0163Ωcm^(2)and a high peak power density of 740 mW cm^(−2)at 800℃.The cell also shows stable operation for 120 h in H_(2)with a constant current density of 285 mA cm^(−2).Furthermore,employing wet C_(2)H_(6)as fuel,the cell demonstrates remarkable performance,achieving peak power densities of 455 mW cm^(−2)at 800℃and 320 mW cm^(−2)at 750℃,marking improvements of 36%and 70%over the cell with(PrBa)_(0.95)(Fe_(0.9)Nb_(0.1))_(2)O_(5+δ)(PBFN)-SDC at these respective temperatures.This discovery emphasizes how temperature influences alloy nanoparticles exsolution within doped layered perovskite ferrites materials,paving the way for the development of high-performance ceramic fuel cell anodes.
基金funded by the National Natural Science Foundation of China(Grant No.41172047)the Open Fund of the Key Laboratory of Ore Deposit Geochemistry(Institute of Geochemistry,Chinese Academy of Sciences,Guiyang),(Grant No.201308)the Open Fund of the Key Laboratory Metallogeny and Mineral Resource Assessment,Ministry of Land and Resources(Institute of Mineral Resources,Chinese Academy of Geological Sciences,Beijing)(Grant No.ZS1407)
文摘Spinel exsolution is widespread in titanomagnetite from the Fe-Ti oxide gabbro of the Panzhihua intrusion, Emeishan Large Igneous Province, SW China. However, little research has been conducted into the implications of patterns in the mineralogical characteristics of the spinel for spatial variation in the controls on the exsolution mechanism and, hence, the formation process of the ore deposit. This study selected the Lanjiahuoshan Ore Block in the Panzhihua V-Ti magnetite deposit to explore this issue, systematically studying exsolution textures in the titanomagnetite through petrographic observation and the integrated use of in-situ microanalysis. The results show that the exsolved spinel gradually becomes finer-grained and less abundant from the center to edge and the bottom to top of the ore bodies. Compositionally, there is an inverse correlation between the size of exsolved spinel grains and their Mg# value. In addition, there is compositional zonation in the spinel interiors, with a gradual increase in the Mg content and decrease in Fe content from the core to the rim. The analysis suggests that fractional crystallization of ferrotitanium magma with a high oxygen fugacity in a shallow magma chamber caused compositional differences in the primary magnetite solid solution in different parts of the Panzhihua intrusion. Additionally, the thermal evolution of the magnetite solid solution differed in different parts of orebody, bringing about variations in spinel development. Together, these effects resulted in spatial variation in the abundance, grain size, and morphology of spinel in different parts of the orebody and intrusion that follows an identifiable distribution law. Furthermore, the compositional zonation of exsolved spinels reflects the rapid growth of exsolution features in a high-temperature environment. Thus, the size, morphology, abundance, and composition of spinel exsolution features in titanomagnetite provide a valuable petrogenetic tool for estimating the maturity and formational environment of the deposit.
文摘In No. 50 kimberlite pipe of Fuxian County, Liaoning Province, an eclogite inclusion(nodule), which is extremely rare in kimberlites, was discovered and phlogopite exsolutionlamellae were found in garnets of the inclusion. Microscopic, TEM and energy spectral observa-tions and studies confirmed that these lamellae are phlogopite. They are colourless and acicularin section, generally 0.5-5μm in width and 10-100μm in length. Nevertheless, fine lamellae,0.05-0.1μm wide and 1-2μm long, are also well developed. Along [111] of the garnet, three setsof phlogopite lamellae show oriented arrangement approximately at angles of 60°-70°, indi-cating that these lamellae might be the product of exsolution from garnet as a result ofpressure-release when eclogite ascended from the relatively deep level to the relatively shallowlevel of the mantle. Tiny acicular exsolution minerals (or inclusions) are commonly found ingarnet and pyroxene in eclogite inclusions of kimberlites all over the world and it has been re-ported that the identified exsolution minerals include pyroxene and rutile. This is the first timethat phlogopite exsolution lamillae were found in eclogite inclusions in the world.
基金the National Key R&D Programmes of China(Nos.2019YFA0708604 and 2019YFA0708404)the National Natural Science Foundation of China(No.41773018)the Key Laboratory of Deep-Earth Dynamics of Ministry of Natural Resources(No.J1901-29)。
文摘As a powerful tracer in high-temperature geochemistry,Fe isotopes have been studied for their behaviour during fl uid exsolution and evolution related to felsic magma system,but that for carbonatite magma system remains unknown.Here we study the Fe isotope fractionation behaviour during fenitization–processes that widely occur associated with carbonatite or alkaline intrusions.Nine fenite/carbonatite samples from carbonatite dykes at Bayan Obo area are analyzed for their Fe isotope compositions as well as elemental compositions.Combined with previous reported carbonatite δ^(56)Fe data,the results show that carbonatites range from-0.35‰to 0.28‰,with an average of-0.10‰in δ^(56)Fe values,while fenites range from-0.17‰to 0.30‰,with an average of 0.11‰in δ^(56)Fe values.This indicates that fenitizing fl uids exsolved from carbonatite melts are enriched in heavier Fe isotopes.Such a Fe isotope fractionation trend is diff erent from that for fl uid exsolution from felsic magmatism.δ^(56)Fe values in fenites are negatively correlated with indicators of fenitization intensity such as(Na+K),Ti,Ba,Th,Nb,U or Pb abundances,likely refl ecting that Fe isotopes fractionate during the evolution of the fenitizing fl uids.Thus,Fe isotopes are a valuable tool for tracing fl uid exsolution and evolution relevant to carbonatite magmatism and related metal mineralization.
文摘The studies on ultra microstructure characteristics of quartz exsolution in eclogite and coesite in UHP eclogite of several localities are done with the appliance of laser Raman spectroscopy and U stage. Research results show that the phase transformation of coesite quartz in garnet and/or omphacite is a continuous process. Topological relationship is present between quartz exsolution in omphacite and its host mineral which shows orientations of two long axes of quartz exsolution parallel to (100) and (-101) of omphacite. At present, some scholars suggest that the quartz exsolution in omphacite of eclogite is the evidence of UHP metamorphism. However, temperature and pressure condition and the exsolution mechanism of oriented needlelike quartz in omphacite still remain unclear. Therefore, further study should be enhanced on experimental research on exsolution mechanism of super silicate clinopyroxene, which could provide experimental quantitative constraint on quartz exsolution as UHP indicator.
基金This work is supported by the National Key Research and Development Program of China(No.2021YFA0718900)the National Natural Science Foundation of China(No.NSCF52102137)+1 种基金We also appreciate the support from Tsinghua University Initiative Scientific Research Program and Open Funds of the State Key Laboratory of Rare Earth Resource Utilization(RERU2022006EPSRC)the Institute for Guo Qiang,Tsinghua University(2020GQG1003).
文摘Electrochemical reduction of CO_(2)into valuable fuels and chemicals has become a contemporary research area,where the heterogeneous catalyst plays a critical role.Metal nanoparticles supported on oxides performing as active sites of electrochemical reactions have been the focus of intensive investigation.Here,we review the CO_(2)reduction with active materials prepared by exsolution.The fundamental of exsolution was summarized in terms of mechanism and models,materials,and driven forces.The advances in the exsolved materials used in hightemperature CO_(2)electrolysis were catalogued into tailored interfaces,synergistic effects on alloy particles,phase transition,reversibility and electrochemical switching.
基金supported by National Natural Science Foundation of China(U21A20317),the National Key Research and Development Program of China(2022YFA1504701)the Fundamental Research Funds for the Central University(2042022gf0002)the U.S.National Science Foundation(1832809)and the start-up research funds from Wuhan Institute of Technology(K202201).
文摘Excessive emission of carbon dioxide(CO_(2))has posed an imminent threat to human's environment and global prosperity.To achieve a sustainable future,solid oxide electrolysis cell(SOEC),which can efficiently combine CO_(2)reduction reaction(CO_(2)RR)and renewable energy storage,has become increasingly attractive owing to its unique functionalities.Additionally,symmetrical SOEC(SSOEC)has been considered as one of the most versatile cell configurations due to its simplified process,high compatibility,and low cost.However,the electrode material requirements become very demanding since efficient catalytic-activities are required for both CO_(2)RR and oxygen evolution reaction(OER).Herein,we demonstrate a novel high-entropy perovskite type symmetrical electrode Pr_(0.5)Ba_(0.5)Mn_(0.2)Fe_(0.2)Co_(0.2)Ni_(0.2)Cu_(0.2)O_(3-δ)(HE-PBM)for SSOEC.B-site doping of transition metals such as Mn,Fe,Co,Ni,and Cu in HE-PBM anode has been found to strongly accelerate the OER in the anode.Moreover,the presence of in-situ formed Fe–Co–Ni–Cu quaternary alloy nanocatalysts from HE-PBM cathode under reducing atmosphere has resulted in superior catalytic-activity towards CO_(2)RR.The faster kinetics are also reflected by the significantly low polarization resistance of 0.289Ω⋅cm^(-2)and high electrolysis current density of 1.21 A⋅cm^(-2)for CO_(2)RR at 2.0 V and 800℃.The excellent electrochemical performance and stability demonstrate that the highentropy perovskite material is a promising electrode material in SSOEC for efficient and durable CO_(2)RR.
