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
Exploring carbon emission effects based on the evolution of residents’ dietary structure to achieve the carbon neutrality goal and mitigate climate change is an important task.This study took China as the research ob...Exploring carbon emission effects based on the evolution of residents’ dietary structure to achieve the carbon neutrality goal and mitigate climate change is an important task.This study took China as the research object(data excluding Hong Kong,Macao and Taiwan) and used the carbon emission coefficient method to quantitatively measure the food carbon emissions from 1987–2020,then analyzed the carbon emission effects under the evolution of dietary structure.The results showed that during the study period,the Chinese dietary structure gradually changed to a high-carbon consumption pattern.The dietary structure of urban residents developed to a balanced one,while that of rural residents developed to a high-quality one.During the study period,the per capita food carbon emissions and total food consumption of Chinese showed an increasing trend.The per capita food carbon emissions of residents in urban and rural showed an overall upward trend.The total food carbon emissions in urban increased significantly,while that in rural increased first and then decreased.The influence of beef and mutton on carbon emissions is the highest in dietary structure.Compared with the balanced dietary pattern,the food carbon emissions of Chinese residents had not yet reached the peak,but were evolving to a high-carbon consumption pattern.展开更多
The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct ...The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.展开更多
Rock-encased-backfill(RB)structures are common in underground mining,for example in the cut-andfill and stoping methods.To understand the effects of cyclic excavation and blasting activities on the damage of these RB ...Rock-encased-backfill(RB)structures are common in underground mining,for example in the cut-andfill and stoping methods.To understand the effects of cyclic excavation and blasting activities on the damage of these RB structures,a series of triaxial stepwise-increasing-amplitude cyclic loading experiments was conducted with cylindrical RB specimens(rock on outside,backfill on inside)with different volume fractions of rock(VF=0.48,0.61,0.73,and 0.84),confining pressures(0,6,9,and 12 MPa),and cyclic loading rates(200,300,400,and 500 N/s).The damage evolution and meso-crack formation during the cyclic tests were analyzed with results from stress-strain hysteresis loops,acoustic emission events,and post-failure X-ray 3D fracture morphology.The results showed significant differences between cyclic and monotonic loadings of RB specimens,particularly with regard to the generation of shear microcracks,the development of stress memory and strain hardening,and the contact forces and associated friction that develops along the rock-backfill interface.One important finding is that as a function of the number of cycles,the elastic strain increases linearly and the dissipated energy increases exponentially.Also,compared with monotonic loading,the cyclic strain hardening characteristics are more sensitive to rising confining pressures during the initial compaction stage.Another finding is that compared with monotonic loading,more shear microcracks are generated during every reloading stage,but these microcracks tend to be dispersed and lessen the likelihood of large shear fracture formation.The transition from elastic to plastic behavior varies depending on the parameters of each test(confinement,volume fraction,and cyclic rate),and an interesting finding was that the transformation to plastic behavior is significantly lower under the conditions of 0.73 rock volume fraction,400 N/s cyclic loading rate,and 9 MPa confinement.All the findings have important practical implications on the ability of backfill to support underground excavations.展开更多
The majority of the projectiles used in the hypersonic penetration study are solid flat-nosed cylindrical projectiles with a diameter of less than 20 mm.This study aims to fill the gap in the experimental and analytic...The majority of the projectiles used in the hypersonic penetration study are solid flat-nosed cylindrical projectiles with a diameter of less than 20 mm.This study aims to fill the gap in the experimental and analytical study of the evolution of the nose shape of larger hollow projectiles under hypersonic penetration.In the hypersonic penetration test,eight ogive-nose AerMet100 steel projectiles with a diameter of 40 mm were launched to hit concrete targets with impact velocities that ranged from 1351 to 1877 m/s.Severe erosion of the projectiles was observed during high-speed penetration of heterogeneous targets,and apparent localized mushrooming occurred in the front nose of recovered projectiles.By examining the damage to projectiles,a linear relationship was found between the relative length reduction rate and the initial kinetic energy of projectiles in different penetration tests.Furthermore,microscopic analysis revealed the forming mechanism of the localized mushrooming phenomenon for eroding penetration,i.e.,material spall erosion abrasion mechanism,material flow and redistribution abrasion mechanism and localized radial upsetting deformation mechanism.Finally,a model of highspeed penetration that included erosion was established on the basis of a model of the evolution of the projectile nose that considers radial upsetting;the model was validated by test data from the literature and the present study.Depending upon the impact velocity,v0,the projectile nose may behave as undistorted,radially distorted or hemispherical.Due to the effects of abrasion of the projectile and enhancement of radial upsetting on the duration and amplitude of the secondary rising segment in the pulse shape of projectile deceleration,the predicted DOP had an upper limit.展开更多
Lop Nur is located at the eastmost end of the Tarim Basin in Xinjiang,Northwestern China.This study reviews the hydrochemical characteristics and evolution of underground brine in Lop Nur,based on analytical data from...Lop Nur is located at the eastmost end of the Tarim Basin in Xinjiang,Northwestern China.This study reviews the hydrochemical characteristics and evolution of underground brine in Lop Nur,based on analytical data from 429 water samples(mainly brine).It is found that in the NE-SW direction,from the periphery to the Luobei sub-depression,while the hydrochemical type varies from the sodium sulfate subtype(S)to the magnesium sulfate subtype(M),the corresponding brine in the phase diagram transfers from the thenardite phase(Then)area,through the bloedite phase(Blo),epsomite phase(Eps),picromerite phase(Picro),finally reaching the sylvite phase(Syl)area.As for the degree of evolution,the sequence is the periphery<Luobei horizontally and the overlying glauberite brine<the underlying clastic brine vertically.It is concluded that the oxygen and hydrogen isotopic compositions of the brine have evidently been affected through the effects of evaporation and altitude,as well as the changes in local water circulation in recent years.Boron and chloride isotopic compositions show that the glauberite brine is formed under more arid conditions than the clastic one.The strontium isotopic composition indicates that the Lop Nur brine primarily originates from surface water;however,deep recharge may also be involved in the evolution of the brine,according to previous noble gas studies.It is confirmed that the brine in Lop Nur has become enriched with potassium prior to halite precipitation over the full course of the salt lake's evolution.Based on chemical compositions of brine from drillhole LDK01 and previous lithological studies,the evolution of the salt lake can be divided into three stages and it is inferred that the brine in Lop Nur may have undergone at least two significant concentration-dilution periods.展开更多
Polyploidy is a major factor in the evolution of plants,yet we know little about the origin and evolution of polyploidy in intertidal species.This study aimed to identify the evolutionary transitions in three truemang...Polyploidy is a major factor in the evolution of plants,yet we know little about the origin and evolution of polyploidy in intertidal species.This study aimed to identify the evolutionary transitions in three truemangrove species of the genus Acanthus distributed in the Indo-West Pacific region.For this purpose,we took an integrative approach that combined data on morphology,cytology,climatic niche,phylogeny,and biogeography of 493 samples from 42 geographic sites.Our results show that the Acanthus ilicifolius lineage distributed east of the Thai-Malay Peninsula possesses a tetraploid karyotype,which is morphologically distinct from that of the lineage on the west side.The haplotype networks and phylogenetic trees for the chloroplast genome and eight nuclear genes reveal that the tetraploid species has two sub-genomes,one each from A.ilicifolius and A.ebracteatus,the paternal and maternal parents,respectively.Population structure analysis also supports the hybrid speciation history of the new tetraploid species.The two sub-genomes of the tetraploid species diverged from their diploid progenitors during the Pleistocene.Environmental niche models revealed that the tetraploid species not only occupied the near-entire niche space of the diploids,but also expanded into novel environments.Our findings suggest that A.ilicifolius species distributed on the east side of the Thai-Malay Peninsula should be regarded as a new species,A.tetraploideus,which originated from hybridization between A.ilicifolius and A.ebracteatus,followed by chromosome doubling.This is the first report of a true-mangrove allopolyploid species that can reproduce sexually and clonally reproduction,which explains the long-term adaptive potential of the species.展开更多
The far-field microdynamic disturbance caused by the excavation of deep mineral resources and underground engineering can induce surrounding rock damage in high-stress conditions and even lead to disasters.However,the...The far-field microdynamic disturbance caused by the excavation of deep mineral resources and underground engineering can induce surrounding rock damage in high-stress conditions and even lead to disasters.However,the mechanical properties and damage/fracture evolution mechanisms of deep rock induced by microdynamic disturbance under three-dimensional stress states are unclear.Therefore,a true triaxial multilevel disturbance test method is proposed,which can completely simulate natural geostress,excavation stress redistribution(such as stress unloading,concentration and rotation),and subsequently the microdynamic disturbance triggering damaged rock failure.Based on a dynamic true triaxial test platform,true triaxial microdynamic disturbance tests under different frequency and amplitudes were carried out on monzogabbro.The results show that increasing amplitude or decreasing frequency diminishes the failure strength of monzogabbro.Deformation modulus gradually decreases during disturbance failure.As frequency and amplitude increase,the degradation rate of deformation modulus decreases slightly,disturbance dissipated energy increases significantly,and disturbance deformation anisotropy strengthens obviously.A damage model has been proposed to quantitatively characterize the disturbance-induced damage evolution at different frequency and amplitude under true triaxial stress.Before disturbance failure,the micro-tensile crack mechanism is dominant,and the micro-shear crack mechanism increases significantly at failure.With the increase of amplitude and frequency,the micro-shear crack mechanism increases.When approaching disturbance failure,the acoustic emission fractal dimension changes from a stable value to local large oscillation,and finally increases sharply to a high value at failure.Finally,the disturbance-induced failure mechanism of surrounding rock in deep engineering is clearly elucidated.展开更多
Black shales are important products of material cycling and energy exchange among the lithosphere,atmosphere,hydrosphere,and biosphere.They are widely distributed throughout geological history and provide essential en...Black shales are important products of material cycling and energy exchange among the lithosphere,atmosphere,hydrosphere,and biosphere.They are widely distributed throughout geological history and provide essential energy and mineral resources for the development of human society.They also record the evolution process of the earth and improve the understanding of the earth.This review focuses on the diagenesis and formation mechanisms of black shales sedimentation,composition,evolution,and reconstruction,which have had a significant impact on the formation and enrichment of shale oil and gas.In terms of sedimentary environment,black shales can be classified into three types:Marine,terrestrial,and marine-terrestrial transitional facies.The formation processes include mechanisms such as eolian input,hypopycnal flow,gravity-driven and offshore bottom currents.From a geological perspective,the formation of black shales is often closely related to global or regional major geological events.The enrichment of organic matter is generally the result of the interaction and coupling of several factors such as primary productivity,water redox condition,and sedimentation rate.In terms of evolution,black shales have undergone diagenetic evolution of inorganic minerals,thermal evolution of organic matter and hydrocarbon generation,interactions between organic matter and inorganic minerals,and pore evolution.In terms of reconstruction,the effects of fold deformation,uplift and erosion,and fracturing have changed the stress state of black shale reservoirs,thereby having a significant impact on the pore structure.Fluid activity promotes the formation of veins,and have changed the material composition,stress structure,and reservoir properties of black shales.Regarding resource effects,the deposition of black shales is fundamental for shale oil and gas resources,the evolution of black shales promotes the shale oil and gas formation and storage,and the reconstruction of black shales would have caused the heterogeneous distribution of oil and gas in shales.Exploring the formation mechanisms and interactions of black shales at different scales is a key to in-depth research on shale formation and evolution,as well as the key to revealing the mechanism controlling shale oil and gas accumulation.The present records can reveal how these processes worked in geological history,and improve our understanding of the coupling mechanisms among regional geological events,black shales evolution,and shale oil and gas formation and enrichment.展开更多
A series of carbon nitride(CN)materials represented by graphitic carbon nitride(g-C3N4)have been widely used in bioimaging,biosensing,and other fields in recent years due to their nontoxicity,low cost,and high lumines...A series of carbon nitride(CN)materials represented by graphitic carbon nitride(g-C3N4)have been widely used in bioimaging,biosensing,and other fields in recent years due to their nontoxicity,low cost,and high luminescent quantum efficiency.What is more attractive is that the luminescent properties such as wavelength and intensity can be regulated by controlling the structure at the molecular level.Hence,it is time to summarize the related research on CN structural evolution and make a prospect on future developments.In this review,we first summarize the research history and multiple structural evolution of CN.Then,the progress of improving the luminescence performance of CN through structural evolution was discussed.Significantly,the relationship between CN structure evolution and energy conversion in the forms of photoluminescence,chemiluminescence,and electrochemiluminescence was reviewed.Finally,key challenges and opportunities such as nanoscale dispersion strategy,luminous efficiency improving methods,standardization evaluation,and macroscopic preparation of CN are highlighted.展开更多
Accurate measurement of the evolution of rock joint void geometry is essential for comprehending the distribution characteristics of asperities responsible for shear and seepage behaviors.However,existing techniques o...Accurate measurement of the evolution of rock joint void geometry is essential for comprehending the distribution characteristics of asperities responsible for shear and seepage behaviors.However,existing techniques often require specialized equipment and skilled operators,posing practical challenges.In this study,a cost-effective photogrammetric approach is proposed.Particularly,local coordinate systems are established to facilitate the alignment and precise quantification of the relative position between two halves of a rock joint.Push/pull tests are conducted on rock joints with varying roughness levels to induce different contact states.A high-precision laser scanner serves as a benchmark for evaluating the photogrammetry method.Despite certain deviations exist,the measured evolution of void geometry is generally consistent with the qualitative findings of previous studies.The photogrammetric measurements yield comparable accuracy to laser scanning,with maximum errors of 13.2%for aperture and 14.4%for void volume.Most joint matching coefficient(JMC)measurement errors are below 20%.Larger measurement errors occur primarily in highly mismatched rock joints with JMC values below 0.2,but even in cases where measurement errors exceed 80%,the maximum JMC error is only 0.0434.Thus,the proposed photogrammetric approach holds promise for widespread application in void geometry measurements in rock joints.展开更多
During the mining process of impact-prone coal seams,drilling pressure relief can reduce the impact propensity of the coal seam,but it also reduces the integrity and strength of the coal mass at the side of the roadwa...During the mining process of impact-prone coal seams,drilling pressure relief can reduce the impact propensity of the coal seam,but it also reduces the integrity and strength of the coal mass at the side of the roadway.Therefore,studying the mechanical properties and energy evolution rules of coal samples containing holes and filled structures has certain practical significance for achieving coordinated control of coal mine rockburst disasters and the stability of roadway surrounding rocks.To achieve this aim,seven types of burst-prone coal samples were prepared and subject to uniaxial compression experiments with the aid of a TAW-3000 electro-hydraulic servo testing machine.Besides,the stress–strain curves,acoustic emission signals,DIC strain fields and other data were collected during the experiments.Furthermore,the failure modes and energy evolutions of samples with varying drilled hole sizes and filling materials were analyzed.The results show that the indexes related to burst propensity of the drilled coal samples decline to some extent compared with those of the intact one,and the decline is positively corelated to the diameter of the drilled hole.After hole filling,the strain concentration degree around the drilled hole is lowered to a certain degree,and polyurethane filling has a more remarkable effect than cement filling.Meanwhile,hole filling can enhance the strength and deformation resistance of coal.Hole drilling can accelerate the release of accumulated elastic strain energy,turning the acoustic emission events from low-frequency and high-energy ones to high-frequency and low-energy ones,whereas hole filling can reduce the intensity of energy release.The experimental results and theoretical derivation demonstrate that hole filling promotes coal deformability and strength mainly by weakening stress concentration surrounding the drilled holes.Moreover,the fillings can achieve a better filling effect if their elastic modulus and Poisson’s ratio are closer to those of the coal body.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
Surface reconstruction yields real active species in electrochemical oxygen evolution reaction(OER)conditions;however,rationally regulating reconstruction in a targeted manner for constructing highly active OER electr...Surface reconstruction yields real active species in electrochemical oxygen evolution reaction(OER)conditions;however,rationally regulating reconstruction in a targeted manner for constructing highly active OER electrocatalysts remains a formidable challenge.Here,an electrochemical activation strategy with selective etching was utilized to guide the reconstruction process of a hybrid cobalt-molybdenum oxide(CoMoO_(4)/Co_(3)O_(4)@CC)in a favorable direction to improve the OER performance.Both in-situ Raman and multiple ex-situ characterization tools demonstrate that controlled surface reconstruction can be easily achieved through Mo etching,with the formation of a dynamically stable amorphous-crystalline heterostructure.Theoretical calculations together with experimental results reveal that the synergistic effects between amorphous CoOOH and crystalline Co_(3)O_(4) are crucial in enhancing the catalytic performance.Consequently,the reconstructed CoMoO_(4)/Co_(3)O_(4)@CC exhibits a low overpotential of 250 mV to achieve a current density of 10 mA cm^(-2) in 1 M KOH,and more importantly it can be practiced in electrolytic water splitting and rechargeable zinc-air batteries devices,achieving ultra-long stability for over 500 and 1200 h,respectively.This work provides a promising route for the construction of high-performance electrocatalysts.展开更多
The oxygen evolution reaction(OER)is a crucial step in metal-air batteries and water splitting technologies,playing a significant role in the efficiency and achievable heights of these two technologies.However,the OER...The oxygen evolution reaction(OER)is a crucial step in metal-air batteries and water splitting technologies,playing a significant role in the efficiency and achievable heights of these two technologies.However,the OER is a four-step,four-electron reaction,and its slow kinetics result in high overpotentials,posing a challenge.To address this issue,numerous strategies involving modified catalysts have been proposed and proven to be highly efficient.In these strategies,the introduction of strain has been widely reported because it is generally believed to effectively regulate the electronic structure of metal sites and alter the adsorption energy of catalyst surfaces with reaction intermediates.However,strain has many other effects that are not well known,making it an important yet unexplored area.Based on this,this review provides a detailed introduction to the various roles of strain in OER.To better explain these roles,the review also presents the definition of strain and elucidates the potential mechanisms of strain in OER based on the d-band center theory and adsorption volcano plot.Additionally,the review showcases various ways of introducing strain in OER through examples reported in the latest literature,aiming to provide a comprehensive perspective for the development of strain engineering.Finally,the review analyzes the appropriate proportion of strain introduction,compares compressive and tensile strain,and examines the impact of strain on stability.And the review offers prospects for future research directions in this emerging field.展开更多
Gypsum caprocks'sealing ability is affected by temperature-pressure coupling.Due to the limitations of experimental conditions,there is still a lack of triaxial stress-strain experiments that simultaneously consid...Gypsum caprocks'sealing ability is affected by temperature-pressure coupling.Due to the limitations of experimental conditions,there is still a lack of triaxial stress-strain experiments that simultaneously consider changes in temperature and pressure conditions,which limits the accuracy of the comprehensive evaluation of the brittle plastic evolution and sealing ability of gypsum rocks using temperature pressure coupling.Triaxial stress-strain tests were utilized to investigate the differences in the evolution of the confinement capacity of gypsum rocks under coupled temperaturepressure action and isothermal-variable pressure action on the basis of sample feasibility analysis.According to research,the gypsum rock's peak and residual strengths decrease under simultaneous increases in temperature and pressure over isothermal pressurization experimental conditions,and it becomes more ductile.This reduces the amount of time it takes for the rock to transition from brittle to plastic.When temperature is taken into account,both the brittle–plastic transformation's depth limit and the lithological transformation of gypsum rocks become shallower,and the evolution of gypsum rocks under variable temperature and pressure conditions is more complicated than that under isothermal pressurization.The sealing ability under the temperature-pressure coupling is more in line with the actual geological context when the application results of the Well#ZS5 are compared.This provides a theoretical basis for precisely determining the process of hydrocarbon accumulation and explains why the early hydrocarbon were not well preserved.展开更多
The corrosion rates of additive-manufactured Mg alloys are higher than their as-cast counterparts,possibly due to increased kinetics for the hydrogen evolution reaction on secondary phases,which may include oxide incl...The corrosion rates of additive-manufactured Mg alloys are higher than their as-cast counterparts,possibly due to increased kinetics for the hydrogen evolution reaction on secondary phases,which may include oxide inclusions.Scanning Kelvin Probe Force Microscopy demonstrated that MgO inclusions could act as cathodes for Mg corrosion,but their low conductivity likely precludes this.However,the density of state calculations through density functional theory using hybrid HSE06 functional revealed overlapping electronic states at the Mg/MgO interface,which facilitates electron transfers and participates in redox reactions.Subsequent determination of the hydrogen absorption energy at the Mg/MgO interface reveals it to be an excellent catalytic site,with HER being found to be a factor of 23x more efficient at the interface than on metallic Mg.The results not only support the plausibility of the Mg/MgO interface being an effective cathode to the adjacent anodic Mg matrix during corrosion but also contribute to the understanding of the enhanced cathodic activities observed during the anodic dissolution of magnesium.展开更多
Based on the petrology,isotope geochemistry and fluid inclusions analysis,we established the evolutionary mode of the diagenetic fluid of dawsonite-bearing sandstone in the Jiyang Depression.Dawsonite-bearing sandston...Based on the petrology,isotope geochemistry and fluid inclusions analysis,we established the evolutionary mode of the diagenetic fluid of dawsonite-bearing sandstone in the Jiyang Depression.Dawsonite-bearing sandstone is characterized by double injection of CO_(2)and oil-gas in the Jiyang Depression that have experienced a relatively complex diagenetic fluid evolution process.The diagenetic sequence of secondary minerals involves secondary enlargement of quartz,kaolinite,first-stage calcite,dawsonite,second-stage calcite,ferrocalcite,dolomite and ankerite.Hydrocarbon charging in the dawsonite-bearing sandstone occurred at around 2.6–0 Myr.The CO_(2)charging event occurred during Dongying tectonism,forming the Pingfangwang CO_(2)gas reservoir,which provided an abundant carbon source for dawsonite precipitation.Carbon and oxygen isotopic compositions of dawsonite demonstrate that CO_(2)forming the dawsonite was of an inorganic origin derived from the mantle,and that water mediating the proc-ess during dawsonite precipitation was sequestered brine with a fluid temperature of 82℃.The evolutionary sequence of the diagenetic fluid in the dawsonite-bearing sandstone was:alkaline syngenetic fluids,weak alkaline fluids during organic acid forma-tion,acidic fluids in the early stage of CO_(2)injection,alkaline fluids in the late stage of CO_(2)injection,and weak alkaline fluids during oil and gas charging.The mode indicates an increase in-HCO_(3)because of the CO_(2)injection,and the loss of Ca^(2+)and Mg^(2+)due to the precipitation of carbonate minerals.Therefore,the evolutionary mode of diagenetic fluids is in good agreement with high HCO_(3)^(-),low Ca^(2+)and low Mg^(2+)composition of the present formation water in the dawsonite-bearing sandstone.展开更多
We discussed the decrease in residual stress,precipitation evolution,and mechanical properties of GH4151 alloy in different annealing temperatures,which were studied by the scanning electron microscope(SEM),high-resol...We discussed the decrease in residual stress,precipitation evolution,and mechanical properties of GH4151 alloy in different annealing temperatures,which were studied by the scanning electron microscope(SEM),high-resolution transmission electron microscopy(HRTEM),and electron backscatter diffraction(EBSD).The findings reveal that annealing processing has a significant impact on diminishing residual stresses.As the annealing temperature rose from 950 to 1150℃,the majority of the residual stresses were relieved from 60.1 MPa down to 10.9 MPa.Moreover,the stress relaxation mechanism transitioned from being mainly controlled by dislocation slip to a combination of dislocation slip and grain boundary migration.Meanwhile,the annealing treatment promotes the decomposition of the Laves,accompanied by the precipitation ofμ-(Mo_(6)Co_(7))starting at 950℃ and reaching a maximum value at 1050℃.The tensile strength and plasticity of the annealing alloy at 1150℃ reached the maximum(1394 MPa,56.1%)which was 131%,200%fold than those of the as-cast alloy(1060 MPa,26.6%),but the oxidation process in the alloy was accelerated at 1150℃.The enhancement in durability and flexibility is primarily due to the dissolution of the brittle phase,along with the shape and dispersal of theγ′phase.展开更多
The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clu...The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.展开更多
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Under the auspices of National Natural Science Foundation of China(No.42171230)。
文摘Exploring carbon emission effects based on the evolution of residents’ dietary structure to achieve the carbon neutrality goal and mitigate climate change is an important task.This study took China as the research object(data excluding Hong Kong,Macao and Taiwan) and used the carbon emission coefficient method to quantitatively measure the food carbon emissions from 1987–2020,then analyzed the carbon emission effects under the evolution of dietary structure.The results showed that during the study period,the Chinese dietary structure gradually changed to a high-carbon consumption pattern.The dietary structure of urban residents developed to a balanced one,while that of rural residents developed to a high-quality one.During the study period,the per capita food carbon emissions and total food consumption of Chinese showed an increasing trend.The per capita food carbon emissions of residents in urban and rural showed an overall upward trend.The total food carbon emissions in urban increased significantly,while that in rural increased first and then decreased.The influence of beef and mutton on carbon emissions is the highest in dietary structure.Compared with the balanced dietary pattern,the food carbon emissions of Chinese residents had not yet reached the peak,but were evolving to a high-carbon consumption pattern.
基金supported by the Taishan Scholar Program of Shandong Province,China (tsqn202211162)the National Natural Science Foundation of China (22102079)the Natural Science Foundation of Shandong Province of China (ZR2021YQ10,ZR2022QB163)。
文摘The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.
基金We acknowledge the funding support from the National Natural Science Foundation of China Youth Fund(Grant No.52004019)the National Natural Science Foundation of China(Grant No.41825018)China Postdoctoral Science Foundation(Grant No.2023M733481).
文摘Rock-encased-backfill(RB)structures are common in underground mining,for example in the cut-andfill and stoping methods.To understand the effects of cyclic excavation and blasting activities on the damage of these RB structures,a series of triaxial stepwise-increasing-amplitude cyclic loading experiments was conducted with cylindrical RB specimens(rock on outside,backfill on inside)with different volume fractions of rock(VF=0.48,0.61,0.73,and 0.84),confining pressures(0,6,9,and 12 MPa),and cyclic loading rates(200,300,400,and 500 N/s).The damage evolution and meso-crack formation during the cyclic tests were analyzed with results from stress-strain hysteresis loops,acoustic emission events,and post-failure X-ray 3D fracture morphology.The results showed significant differences between cyclic and monotonic loadings of RB specimens,particularly with regard to the generation of shear microcracks,the development of stress memory and strain hardening,and the contact forces and associated friction that develops along the rock-backfill interface.One important finding is that as a function of the number of cycles,the elastic strain increases linearly and the dissipated energy increases exponentially.Also,compared with monotonic loading,the cyclic strain hardening characteristics are more sensitive to rising confining pressures during the initial compaction stage.Another finding is that compared with monotonic loading,more shear microcracks are generated during every reloading stage,but these microcracks tend to be dispersed and lessen the likelihood of large shear fracture formation.The transition from elastic to plastic behavior varies depending on the parameters of each test(confinement,volume fraction,and cyclic rate),and an interesting finding was that the transformation to plastic behavior is significantly lower under the conditions of 0.73 rock volume fraction,400 N/s cyclic loading rate,and 9 MPa confinement.All the findings have important practical implications on the ability of backfill to support underground excavations.
基金the National Natural Science Foundation of China(Grant No.12102050)the Open Fund of State Key Laboratory of Explosion Science and Technology(Grant No.SKLEST-ZZ-21-18).
文摘The majority of the projectiles used in the hypersonic penetration study are solid flat-nosed cylindrical projectiles with a diameter of less than 20 mm.This study aims to fill the gap in the experimental and analytical study of the evolution of the nose shape of larger hollow projectiles under hypersonic penetration.In the hypersonic penetration test,eight ogive-nose AerMet100 steel projectiles with a diameter of 40 mm were launched to hit concrete targets with impact velocities that ranged from 1351 to 1877 m/s.Severe erosion of the projectiles was observed during high-speed penetration of heterogeneous targets,and apparent localized mushrooming occurred in the front nose of recovered projectiles.By examining the damage to projectiles,a linear relationship was found between the relative length reduction rate and the initial kinetic energy of projectiles in different penetration tests.Furthermore,microscopic analysis revealed the forming mechanism of the localized mushrooming phenomenon for eroding penetration,i.e.,material spall erosion abrasion mechanism,material flow and redistribution abrasion mechanism and localized radial upsetting deformation mechanism.Finally,a model of highspeed penetration that included erosion was established on the basis of a model of the evolution of the projectile nose that considers radial upsetting;the model was validated by test data from the literature and the present study.Depending upon the impact velocity,v0,the projectile nose may behave as undistorted,radially distorted or hemispherical.Due to the effects of abrasion of the projectile and enhancement of radial upsetting on the duration and amplitude of the secondary rising segment in the pulse shape of projectile deceleration,the predicted DOP had an upper limit.
基金The Major Projects of Xinjiang Uyghur Autonomous Region of China(Grant Nos.2020A03005-2 and 2022A03009-2)from the Chinese governmentthe National Natural Science Foundation of China(Grant No.40830420)provided the funding for this study。
文摘Lop Nur is located at the eastmost end of the Tarim Basin in Xinjiang,Northwestern China.This study reviews the hydrochemical characteristics and evolution of underground brine in Lop Nur,based on analytical data from 429 water samples(mainly brine).It is found that in the NE-SW direction,from the periphery to the Luobei sub-depression,while the hydrochemical type varies from the sodium sulfate subtype(S)to the magnesium sulfate subtype(M),the corresponding brine in the phase diagram transfers from the thenardite phase(Then)area,through the bloedite phase(Blo),epsomite phase(Eps),picromerite phase(Picro),finally reaching the sylvite phase(Syl)area.As for the degree of evolution,the sequence is the periphery<Luobei horizontally and the overlying glauberite brine<the underlying clastic brine vertically.It is concluded that the oxygen and hydrogen isotopic compositions of the brine have evidently been affected through the effects of evaporation and altitude,as well as the changes in local water circulation in recent years.Boron and chloride isotopic compositions show that the glauberite brine is formed under more arid conditions than the clastic one.The strontium isotopic composition indicates that the Lop Nur brine primarily originates from surface water;however,deep recharge may also be involved in the evolution of the brine,according to previous noble gas studies.It is confirmed that the brine in Lop Nur has become enriched with potassium prior to halite precipitation over the full course of the salt lake's evolution.Based on chemical compositions of brine from drillhole LDK01 and previous lithological studies,the evolution of the salt lake can be divided into three stages and it is inferred that the brine in Lop Nur may have undergone at least two significant concentration-dilution periods.
基金supported by grants from the National Natural Science Foundation of China (Grant Nos.32160051,42076117,and 41776166)Guangdong Basic and Applied Basic Research Foundation (Grant Nos.2022A1515012015,2023A1515012772)the Foreign Cultural and Educational Experts Project of the Ministry of Science and Technology (No.QNJ2021162001L)。
文摘Polyploidy is a major factor in the evolution of plants,yet we know little about the origin and evolution of polyploidy in intertidal species.This study aimed to identify the evolutionary transitions in three truemangrove species of the genus Acanthus distributed in the Indo-West Pacific region.For this purpose,we took an integrative approach that combined data on morphology,cytology,climatic niche,phylogeny,and biogeography of 493 samples from 42 geographic sites.Our results show that the Acanthus ilicifolius lineage distributed east of the Thai-Malay Peninsula possesses a tetraploid karyotype,which is morphologically distinct from that of the lineage on the west side.The haplotype networks and phylogenetic trees for the chloroplast genome and eight nuclear genes reveal that the tetraploid species has two sub-genomes,one each from A.ilicifolius and A.ebracteatus,the paternal and maternal parents,respectively.Population structure analysis also supports the hybrid speciation history of the new tetraploid species.The two sub-genomes of the tetraploid species diverged from their diploid progenitors during the Pleistocene.Environmental niche models revealed that the tetraploid species not only occupied the near-entire niche space of the diploids,but also expanded into novel environments.Our findings suggest that A.ilicifolius species distributed on the east side of the Thai-Malay Peninsula should be regarded as a new species,A.tetraploideus,which originated from hybridization between A.ilicifolius and A.ebracteatus,followed by chromosome doubling.This is the first report of a true-mangrove allopolyploid species that can reproduce sexually and clonally reproduction,which explains the long-term adaptive potential of the species.
基金the financial support from the National Natural Science Foundation of China(No.52109119)the Guangxi Natural Science Foundation(No.2021GXNSFBA075030)+2 种基金the Guangxi Science and Technology Project(No.Guike AD20325002)the Chinese Postdoctoral Science Fund Project(No.2022M723408)the Open Research Fund of State Key Laboratory of Simulation and Regulation of Water Cycle in River Basin(China Institute of Water Resources and Hydropower Research)(No.IWHR-SKL-202202)。
文摘The far-field microdynamic disturbance caused by the excavation of deep mineral resources and underground engineering can induce surrounding rock damage in high-stress conditions and even lead to disasters.However,the mechanical properties and damage/fracture evolution mechanisms of deep rock induced by microdynamic disturbance under three-dimensional stress states are unclear.Therefore,a true triaxial multilevel disturbance test method is proposed,which can completely simulate natural geostress,excavation stress redistribution(such as stress unloading,concentration and rotation),and subsequently the microdynamic disturbance triggering damaged rock failure.Based on a dynamic true triaxial test platform,true triaxial microdynamic disturbance tests under different frequency and amplitudes were carried out on monzogabbro.The results show that increasing amplitude or decreasing frequency diminishes the failure strength of monzogabbro.Deformation modulus gradually decreases during disturbance failure.As frequency and amplitude increase,the degradation rate of deformation modulus decreases slightly,disturbance dissipated energy increases significantly,and disturbance deformation anisotropy strengthens obviously.A damage model has been proposed to quantitatively characterize the disturbance-induced damage evolution at different frequency and amplitude under true triaxial stress.Before disturbance failure,the micro-tensile crack mechanism is dominant,and the micro-shear crack mechanism increases significantly at failure.With the increase of amplitude and frequency,the micro-shear crack mechanism increases.When approaching disturbance failure,the acoustic emission fractal dimension changes from a stable value to local large oscillation,and finally increases sharply to a high value at failure.Finally,the disturbance-induced failure mechanism of surrounding rock in deep engineering is clearly elucidated.
基金supported by the projects of the China Geological Survey(DD20230043,DD20240048)the project of the National Natural Science Foundation of China(42102123)。
文摘Black shales are important products of material cycling and energy exchange among the lithosphere,atmosphere,hydrosphere,and biosphere.They are widely distributed throughout geological history and provide essential energy and mineral resources for the development of human society.They also record the evolution process of the earth and improve the understanding of the earth.This review focuses on the diagenesis and formation mechanisms of black shales sedimentation,composition,evolution,and reconstruction,which have had a significant impact on the formation and enrichment of shale oil and gas.In terms of sedimentary environment,black shales can be classified into three types:Marine,terrestrial,and marine-terrestrial transitional facies.The formation processes include mechanisms such as eolian input,hypopycnal flow,gravity-driven and offshore bottom currents.From a geological perspective,the formation of black shales is often closely related to global or regional major geological events.The enrichment of organic matter is generally the result of the interaction and coupling of several factors such as primary productivity,water redox condition,and sedimentation rate.In terms of evolution,black shales have undergone diagenetic evolution of inorganic minerals,thermal evolution of organic matter and hydrocarbon generation,interactions between organic matter and inorganic minerals,and pore evolution.In terms of reconstruction,the effects of fold deformation,uplift and erosion,and fracturing have changed the stress state of black shale reservoirs,thereby having a significant impact on the pore structure.Fluid activity promotes the formation of veins,and have changed the material composition,stress structure,and reservoir properties of black shales.Regarding resource effects,the deposition of black shales is fundamental for shale oil and gas resources,the evolution of black shales promotes the shale oil and gas formation and storage,and the reconstruction of black shales would have caused the heterogeneous distribution of oil and gas in shales.Exploring the formation mechanisms and interactions of black shales at different scales is a key to in-depth research on shale formation and evolution,as well as the key to revealing the mechanism controlling shale oil and gas accumulation.The present records can reveal how these processes worked in geological history,and improve our understanding of the coupling mechanisms among regional geological events,black shales evolution,and shale oil and gas formation and enrichment.
基金supported by the Natural Science Foundation of Hebei Province(Grant No.E2022209039)Key Research Project of North China University of Science and Technology(Grant No.ZD-YG-202301)Tangshan Talent Funding Project(Grant No.A202202007).
文摘A series of carbon nitride(CN)materials represented by graphitic carbon nitride(g-C3N4)have been widely used in bioimaging,biosensing,and other fields in recent years due to their nontoxicity,low cost,and high luminescent quantum efficiency.What is more attractive is that the luminescent properties such as wavelength and intensity can be regulated by controlling the structure at the molecular level.Hence,it is time to summarize the related research on CN structural evolution and make a prospect on future developments.In this review,we first summarize the research history and multiple structural evolution of CN.Then,the progress of improving the luminescence performance of CN through structural evolution was discussed.Significantly,the relationship between CN structure evolution and energy conversion in the forms of photoluminescence,chemiluminescence,and electrochemiluminescence was reviewed.Finally,key challenges and opportunities such as nanoscale dispersion strategy,luminous efficiency improving methods,standardization evaluation,and macroscopic preparation of CN are highlighted.
基金supported by the National Natural Science Foundation of China (Nos.42207175 and 42177117)the Ningbo Natural Science Foundation (No.2022J115)。
文摘Accurate measurement of the evolution of rock joint void geometry is essential for comprehending the distribution characteristics of asperities responsible for shear and seepage behaviors.However,existing techniques often require specialized equipment and skilled operators,posing practical challenges.In this study,a cost-effective photogrammetric approach is proposed.Particularly,local coordinate systems are established to facilitate the alignment and precise quantification of the relative position between two halves of a rock joint.Push/pull tests are conducted on rock joints with varying roughness levels to induce different contact states.A high-precision laser scanner serves as a benchmark for evaluating the photogrammetry method.Despite certain deviations exist,the measured evolution of void geometry is generally consistent with the qualitative findings of previous studies.The photogrammetric measurements yield comparable accuracy to laser scanning,with maximum errors of 13.2%for aperture and 14.4%for void volume.Most joint matching coefficient(JMC)measurement errors are below 20%.Larger measurement errors occur primarily in highly mismatched rock joints with JMC values below 0.2,but even in cases where measurement errors exceed 80%,the maximum JMC error is only 0.0434.Thus,the proposed photogrammetric approach holds promise for widespread application in void geometry measurements in rock joints.
基金National Natural Science Foundation of China(Grant Nos.52174080 and 51974160)Science Foundation of Tiandi Technology Co.,Ltd.(2022-2-TD-ZD016).
文摘During the mining process of impact-prone coal seams,drilling pressure relief can reduce the impact propensity of the coal seam,but it also reduces the integrity and strength of the coal mass at the side of the roadway.Therefore,studying the mechanical properties and energy evolution rules of coal samples containing holes and filled structures has certain practical significance for achieving coordinated control of coal mine rockburst disasters and the stability of roadway surrounding rocks.To achieve this aim,seven types of burst-prone coal samples were prepared and subject to uniaxial compression experiments with the aid of a TAW-3000 electro-hydraulic servo testing machine.Besides,the stress–strain curves,acoustic emission signals,DIC strain fields and other data were collected during the experiments.Furthermore,the failure modes and energy evolutions of samples with varying drilled hole sizes and filling materials were analyzed.The results show that the indexes related to burst propensity of the drilled coal samples decline to some extent compared with those of the intact one,and the decline is positively corelated to the diameter of the drilled hole.After hole filling,the strain concentration degree around the drilled hole is lowered to a certain degree,and polyurethane filling has a more remarkable effect than cement filling.Meanwhile,hole filling can enhance the strength and deformation resistance of coal.Hole drilling can accelerate the release of accumulated elastic strain energy,turning the acoustic emission events from low-frequency and high-energy ones to high-frequency and low-energy ones,whereas hole filling can reduce the intensity of energy release.The experimental results and theoretical derivation demonstrate that hole filling promotes coal deformability and strength mainly by weakening stress concentration surrounding the drilled holes.Moreover,the fillings can achieve a better filling effect if their elastic modulus and Poisson’s ratio are closer to those of the coal body.
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 financial support of the Guangxi Science and Technology Major Projects(Guike AA23023033)。
文摘Surface reconstruction yields real active species in electrochemical oxygen evolution reaction(OER)conditions;however,rationally regulating reconstruction in a targeted manner for constructing highly active OER electrocatalysts remains a formidable challenge.Here,an electrochemical activation strategy with selective etching was utilized to guide the reconstruction process of a hybrid cobalt-molybdenum oxide(CoMoO_(4)/Co_(3)O_(4)@CC)in a favorable direction to improve the OER performance.Both in-situ Raman and multiple ex-situ characterization tools demonstrate that controlled surface reconstruction can be easily achieved through Mo etching,with the formation of a dynamically stable amorphous-crystalline heterostructure.Theoretical calculations together with experimental results reveal that the synergistic effects between amorphous CoOOH and crystalline Co_(3)O_(4) are crucial in enhancing the catalytic performance.Consequently,the reconstructed CoMoO_(4)/Co_(3)O_(4)@CC exhibits a low overpotential of 250 mV to achieve a current density of 10 mA cm^(-2) in 1 M KOH,and more importantly it can be practiced in electrolytic water splitting and rechargeable zinc-air batteries devices,achieving ultra-long stability for over 500 and 1200 h,respectively.This work provides a promising route for the construction of high-performance electrocatalysts.
基金financially supported by the National Natural Science Foundation of China(52071072)the Fundamental Research Funds for the Central Universities(2023GFZD03)+4 种基金the Natural Science Foundation-Steel,the Iron Foundation of Hebei Province(E2022501030)the Key Research and Development Plan of Qinhuangdao City(202302B013)the Liaoning Applied Basic Research Program(2023JH2/101300011)the Basic scientific research project of Liaoning Province Department of Education(LJKZZ20220024)the Shenyang Science and Technology Project(23-407-3-13)。
文摘The oxygen evolution reaction(OER)is a crucial step in metal-air batteries and water splitting technologies,playing a significant role in the efficiency and achievable heights of these two technologies.However,the OER is a four-step,four-electron reaction,and its slow kinetics result in high overpotentials,posing a challenge.To address this issue,numerous strategies involving modified catalysts have been proposed and proven to be highly efficient.In these strategies,the introduction of strain has been widely reported because it is generally believed to effectively regulate the electronic structure of metal sites and alter the adsorption energy of catalyst surfaces with reaction intermediates.However,strain has many other effects that are not well known,making it an important yet unexplored area.Based on this,this review provides a detailed introduction to the various roles of strain in OER.To better explain these roles,the review also presents the definition of strain and elucidates the potential mechanisms of strain in OER based on the d-band center theory and adsorption volcano plot.Additionally,the review showcases various ways of introducing strain in OER through examples reported in the latest literature,aiming to provide a comprehensive perspective for the development of strain engineering.Finally,the review analyzes the appropriate proportion of strain introduction,compares compressive and tensile strain,and examines the impact of strain on stability.And the review offers prospects for future research directions in this emerging field.
基金funded by the National Natural Science Foundation of China(Grant No.42172147)PetroChina Major Science and Technology Project(Grant No.ZD2019-183-002).
文摘Gypsum caprocks'sealing ability is affected by temperature-pressure coupling.Due to the limitations of experimental conditions,there is still a lack of triaxial stress-strain experiments that simultaneously consider changes in temperature and pressure conditions,which limits the accuracy of the comprehensive evaluation of the brittle plastic evolution and sealing ability of gypsum rocks using temperature pressure coupling.Triaxial stress-strain tests were utilized to investigate the differences in the evolution of the confinement capacity of gypsum rocks under coupled temperaturepressure action and isothermal-variable pressure action on the basis of sample feasibility analysis.According to research,the gypsum rock's peak and residual strengths decrease under simultaneous increases in temperature and pressure over isothermal pressurization experimental conditions,and it becomes more ductile.This reduces the amount of time it takes for the rock to transition from brittle to plastic.When temperature is taken into account,both the brittle–plastic transformation's depth limit and the lithological transformation of gypsum rocks become shallower,and the evolution of gypsum rocks under variable temperature and pressure conditions is more complicated than that under isothermal pressurization.The sealing ability under the temperature-pressure coupling is more in line with the actual geological context when the application results of the Well#ZS5 are compared.This provides a theoretical basis for precisely determining the process of hydrocarbon accumulation and explains why the early hydrocarbon were not well preserved.
基金Agency for Science,Technology and Research(A*STAR),under the RIE2020 Advanced Manufacturing and Engineering(AME)Programmatic Grant(Grant no.A18B1b0061)。
文摘The corrosion rates of additive-manufactured Mg alloys are higher than their as-cast counterparts,possibly due to increased kinetics for the hydrogen evolution reaction on secondary phases,which may include oxide inclusions.Scanning Kelvin Probe Force Microscopy demonstrated that MgO inclusions could act as cathodes for Mg corrosion,but their low conductivity likely precludes this.However,the density of state calculations through density functional theory using hybrid HSE06 functional revealed overlapping electronic states at the Mg/MgO interface,which facilitates electron transfers and participates in redox reactions.Subsequent determination of the hydrogen absorption energy at the Mg/MgO interface reveals it to be an excellent catalytic site,with HER being found to be a factor of 23x more efficient at the interface than on metallic Mg.The results not only support the plausibility of the Mg/MgO interface being an effective cathode to the adjacent anodic Mg matrix during corrosion but also contribute to the understanding of the enhanced cathodic activities observed during the anodic dissolution of magnesium.
基金supported by the National Natural Science Foundation of China(Nos.42072130,41872152).
文摘Based on the petrology,isotope geochemistry and fluid inclusions analysis,we established the evolutionary mode of the diagenetic fluid of dawsonite-bearing sandstone in the Jiyang Depression.Dawsonite-bearing sandstone is characterized by double injection of CO_(2)and oil-gas in the Jiyang Depression that have experienced a relatively complex diagenetic fluid evolution process.The diagenetic sequence of secondary minerals involves secondary enlargement of quartz,kaolinite,first-stage calcite,dawsonite,second-stage calcite,ferrocalcite,dolomite and ankerite.Hydrocarbon charging in the dawsonite-bearing sandstone occurred at around 2.6–0 Myr.The CO_(2)charging event occurred during Dongying tectonism,forming the Pingfangwang CO_(2)gas reservoir,which provided an abundant carbon source for dawsonite precipitation.Carbon and oxygen isotopic compositions of dawsonite demonstrate that CO_(2)forming the dawsonite was of an inorganic origin derived from the mantle,and that water mediating the proc-ess during dawsonite precipitation was sequestered brine with a fluid temperature of 82℃.The evolutionary sequence of the diagenetic fluid in the dawsonite-bearing sandstone was:alkaline syngenetic fluids,weak alkaline fluids during organic acid forma-tion,acidic fluids in the early stage of CO_(2)injection,alkaline fluids in the late stage of CO_(2)injection,and weak alkaline fluids during oil and gas charging.The mode indicates an increase in-HCO_(3)because of the CO_(2)injection,and the loss of Ca^(2+)and Mg^(2+)due to the precipitation of carbonate minerals.Therefore,the evolutionary mode of diagenetic fluids is in good agreement with high HCO_(3)^(-),low Ca^(2+)and low Mg^(2+)composition of the present formation water in the dawsonite-bearing sandstone.
基金This work was financially supported by the National Science and Technology Major Project of China(No.J2019-VI-0006-0120)the National Key R&D Program of China(No.2021YFB3700402)the National Natural Science Foundation of China(Nos.52074092 and 52274330).
文摘We discussed the decrease in residual stress,precipitation evolution,and mechanical properties of GH4151 alloy in different annealing temperatures,which were studied by the scanning electron microscope(SEM),high-resolution transmission electron microscopy(HRTEM),and electron backscatter diffraction(EBSD).The findings reveal that annealing processing has a significant impact on diminishing residual stresses.As the annealing temperature rose from 950 to 1150℃,the majority of the residual stresses were relieved from 60.1 MPa down to 10.9 MPa.Moreover,the stress relaxation mechanism transitioned from being mainly controlled by dislocation slip to a combination of dislocation slip and grain boundary migration.Meanwhile,the annealing treatment promotes the decomposition of the Laves,accompanied by the precipitation ofμ-(Mo_(6)Co_(7))starting at 950℃ and reaching a maximum value at 1050℃.The tensile strength and plasticity of the annealing alloy at 1150℃ reached the maximum(1394 MPa,56.1%)which was 131%,200%fold than those of the as-cast alloy(1060 MPa,26.6%),but the oxidation process in the alloy was accelerated at 1150℃.The enhancement in durability and flexibility is primarily due to the dissolution of the brittle phase,along with the shape and dispersal of theγ′phase.
基金supported by the National Natural Science Foundation of China(22205209,52202373 and U21A200972)China Postdoctoral Science Foundation(2022M722867)Key Research Project of Higher Education Institutions in Henan Province(23A530001)。
文摘The valence states and coordination structures of doped heterometal atoms in two-dimensional(2D)nanomaterials lack predictable regulation strategies.Hence,a robust method is proposed to form unsaturated heteroatom clusters via the metal-vacancy restraint mechanism,which can precisely regulate the bonding and valence state of heterometal atoms doped in 2D molybdenum disulfide.The unsaturated valence state of heterometal Pt and Ru cluster atoms form a spatial coordination structure with Pt–S and Ru–O–S as catalytically active sites.Among them,the strong binding energy of negatively charged suspended S and O sites for H+,as well as the weak adsorption of positively charged unsaturated heterometal atoms for H*,reduces the energy barrier of the hydrogen evolution reaction proved by theoretical calculation.Whereupon,the electrocatalytic hydrogen evolution performance is markedly improved by the ensemble effect of unsaturated heterometal atoms and highlighted with an overpotential of 84 mV and Tafel slope of 68.5 mV dec^(−1).In brief,this metal vacancy-induced valence state regulation of heterometal can manipulate the coordination structure and catalytic activity of heterometal atoms doped in the 2D atomic lattice but not limited to 2D nanomaterials.