The paper presents experimental investigation results of crack pattern change in cement pastes caused by external sulfate attack(ESA).To visualize the formation and development of cracks in cement pastes under ESA,an ...The paper presents experimental investigation results of crack pattern change in cement pastes caused by external sulfate attack(ESA).To visualize the formation and development of cracks in cement pastes under ESA,an X-ray computed tomography(X-ray CT)was used,i e,the tomography system of Zeiss Xradia 510 versa.The results indicate that X-CT can monitor the development process and distribution characteristics of the internal cracks of cement pastes under ESA with attack time.In addition,the C3A content in the cement significantly affects the damage mode of cement paste specimens during sulfate erosion.The damage of ordinary Portland cement(OPC)pastes subjected to sulfate attack with high C3A content are severe,while the damage of sulfate resistant Portland cement(SRPC)pastes is much smaller than that of OPC pastes.Furthermore,a quadratic function describes the correlation between the crack volume fraction and development depth for two cement pastes immermed in sulfate solution.展开更多
Background The Bundelkhand Craton is significant for preserving the multiphase granitoids magmatism from Paleoarchean to Neoarchean periods.It consists of a variety of granite rocks,including TTGs,sanukitoids,and high...Background The Bundelkhand Craton is significant for preserving the multiphase granitoids magmatism from Paleoarchean to Neoarchean periods.It consists of a variety of granite rocks,including TTGs,sanukitoids,and high-K granitoids.This study presents geochemical characteristics of high-silica(68.97 wt.%–73.99 wt.%),low-silica(58.73wt.%–69.94 wt.%),and high K_(2)O(2.77 wt.%–6.16 wt.%)contents of granitoids.Objective The data on Bundelkhand Craton’s granitic magmatism and geodynamics is not sufficiently robust.Geochemical data from this study will be used to further understand the origin,source,and petrogenesis of granitoid rocks and their implications for the evolution of geodynamics.Methodology Twenty-one samples were collected and analyzed for major,trace,and REE elements.Major elements were measured using X-ray fluorescence spectrometry(XRF),and trace and REE elements were analyzed by ICP-MS.Standard procedures from the Geological Survey of India were followed.Results The geochemical analysis presents high-silica(68.97-73.99 wt.%),low-silica(58.73-69.94 wt.%),and high K2O(2.77-6.16 wt.%)contents in granitoids,classified as granite-granodiorite.The rocks are calcic to calcalkalic,magnesian,and range from peraluminous to metaluminous composition.REE patterns showed strong LREE enrichment relative to HREEs,with prominent negative Eu anomalies corresponding to earlier plagioclase fractionation.Multi-element patterns revealed negative anomalies in Nb,Sr,P,and Ti and positive anomalies in Pb.Conclusion The geochemical signatures attributed to the post-collisional magma generation and continental crustal contamination.The studied rocks show A-type and A2-type lineage,suggesting they originated from the melting of continental crust during transitional/post-collisional tectonic activity.The formation of hybrid granitoids in the Bundelkhand Craton is connected to the fractionation of hybrid magmas in shallow-seated magma chambers during these tectonic processes.展开更多
Five tectonic modes of mantle convection are obtained and analyzed with three-dimensional numerical models in a spherical shell domain.The five tectonic convective modes are non-plate mobile-lid,plate-like mobile-lid,...Five tectonic modes of mantle convection are obtained and analyzed with three-dimensional numerical models in a spherical shell domain.The five tectonic convective modes are non-plate mobile-lid,plate-like mobile-lid,episodic plate-like mobile-lid,episodic stagnant-lid,and stagnant-lid convective modes,respectively.The typical characteristics of these five tectonic modes and their numerical classification criteria based on plateness,mobility,and their standard deviations are presented and discussed.The results show that the yield stress of the lithosphere has profound effects on the tectonic convective modes.With the gradual increase of yield stress,the tectonic mode of mantle convection changes from one to another sequentially through the aforementioned five modes.Additionally,as the Rayleigh number increases,the range of yield stress for the platelike mobile-lid convective mode decreases,and the dimensionless transition stress between different tectonic modes increases.Specifically,the dimensional transition stress between the non-plate mobile-lid convective mode and plate-like mobile-lid convective mode increases with the increase of Rayleigh number,but decreases between other tectonic modes.Furthermore,we find that the transition stress between different tectonic modes is inversely proportional to the internal heating rate,with the transition stress decreasing as the internal heating rate increases.The fitting analysis of the transition stress between tectonic modes shows that Earth's current plate tectonics correspond to a lithospheric yield stress of 150–250 MPa,which aligns with the strength of serpentinized mantle rock determined by experimental petrography.If the Archean mantle was 300℃warmer than it is today,then the Earth was in an episodic stagnant-lid convective mode.The tectonic evolution of the Earth's surface is closely related to the lithospheric strength and the process of thermal evolution.If the lithospheric strength was only 150 MPa,plate tectonics in the early mantle rapid cooling model would have begun before 3.8 Ga,and plate tectonics in the late mantle rapid cooling model would have begun at approximately 1.5 Ga.However,at a lithospheric strength of 200 MPa,plate tectonics in the late mantle rapid cooling model would have begun later than 0.95 Ga,and plate tectonics in the early mantle rapid cooling model would have begun at approximately 2 Ga.The early Earth was in the episodic stagnant-lid convective mode,which means that subduction might still have occurred at that time.The presence of the episodic plate-like mobile-lid convective mode in Earth's later history indicates that there might also have been intermittent surface stagnation during plate tectonics,which may provide an explanation for the quiet period of tectonic activity at approximately 1.0 Ga on Earth.This indicates that tectonic inactivity during a geological period is not an indicator that plate tectonics did not begin.展开更多
The Ordos Basin(OB)in the western part of the North China Craton(NCC),was located at the jointed area of multi-plates and has recorded the Mesozoic tectonic characteristics.Its tectonic evolution in the Mesozoic is si...The Ordos Basin(OB)in the western part of the North China Craton(NCC),was located at the jointed area of multi-plates and has recorded the Mesozoic tectonic characteristics.Its tectonic evolution in the Mesozoic is significant to understand the tectonic transformation of the northern margin of the NCC.In this work,the detrital zircon and apatite(U-Th)/He chronological system were analyzed in the northern part of the OB,and have provided new evidence for the regional tectonic evolution.The(U-Th)/He chronological data states the weighted ages of 240‒235 Ma,141 Ma with the peak distribution of 244 Ma,219 Ma,173 Ma,147‒132 Ma.The thermal evolution,geochronological data,and regional unconformities have proved four stages of regional tectonic evolution for the OB and its surroundings in the Mesozoic:(1)The Late Permian-Early Triassic;(2)the Late Triassic-Early Jurassic;(3)the Late Jurassic-Early Cretaceous;(4)the Late Cretaceous-Early Paleogene.It is indicated that the multi-directional convergence from the surrounding tectonic units has controlled the Mesozoic tectonic evolution of the OB.Four-stage tectonic evolution reflected the activation or end of different plate movements and provided new time constraints for the regional tectonic evolution of the NCC in the Mesozoic.展开更多
Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this s...Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.展开更多
The utilization of iron coke provides a green pathway for low-carbon ironmaking.To uncover the influence mechanism of iron ore on the behavior and kinetics of iron coke gasification,the effect of iron ore on the micro...The utilization of iron coke provides a green pathway for low-carbon ironmaking.To uncover the influence mechanism of iron ore on the behavior and kinetics of iron coke gasification,the effect of iron ore on the microstructure of iron coke was investigated.Furthermore,a comparative study of the gasification reactions between iron coke and coke was conducted through non-isothermal thermogravimetric method.The findings indicate that compared to coke,iron coke exhibits an augmentation in micropores and specific surface area,and the micropores further extend and interconnect.This provides more adsorption sites for CO_(2) molecules during the gasification process,resulting in a reduction in the initial gasification temperature of iron coke.Accelerating the heating rate in non-isothermal gasification can enhance the reactivity of iron coke.The metallic iron reduced from iron ore is embedded in the carbon matrix,reducing the orderliness of the carbon structure,which is primarily responsible for the heightened reactivity of the carbon atoms.The kinetic study indicates that the random pore model can effectively represent the gasification process of iron coke due to its rich pore structure.Moreover,as the proportion of iron ore increases,the activation energy for the carbon gasification gradually decreases,from 246.2 kJ/mol for coke to 192.5 kJ/mol for iron coke 15wt%.展开更多
Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3...Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.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
Gradient magnetic heterointerfaces have injected infinite vitality in optimizing impedance matching,adjusting dielectric/magnetic resonance and promoting electromagnetic(EM)wave absorption,but still exist a significan...Gradient magnetic heterointerfaces have injected infinite vitality in optimizing impedance matching,adjusting dielectric/magnetic resonance and promoting electromagnetic(EM)wave absorption,but still exist a significant challenging in regulating local phase evolution.Herein,accordion-shaped Co/Co_(3)O_(4)@N-doped carbon nanosheets(Co/Co_(3)O_(4)@NC)with gradient magnetic heterointerfaces have been fabricated via the cooperative high-temperature carbonization and lowtemperature oxidation process.The results indicate that the surface epitaxial growth of crystal Co_(3)O_(4) domains on local Co nanoparticles realizes the adjustment of magnetic-heteroatomic components,which are beneficial for optimizing impedance matching and interfacial polarization.Moreover,gradient magnetic heterointerfaces simultaneously realize magnetic coupling,and long-range magnetic diffraction.Specifically,the synthesized Co/Co_(3)O_(4)@NC absorbents display the strong electromagnetic wave attenuation capability of−53.5 dB at a thickness of 3.0 mm with an effective absorption bandwidth of 5.36 GHz,both are superior to those of single magnetic domains embedded in carbon matrix.This design concept provides us an inspiration in optimizing interfacial polarization,regulating magnetic coupling and promoting electromagnetic wave absorption.展开更多
Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal int...Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.展开更多
Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then...Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then Ru3+was introduced for ion exchange,and the porous Ru-doped Co_(3)O_(4)/rGO(Ru-Co_(3)O_(4)/rGO)composite electrocatalyst was prepared by annealing.The phase structure,morphology,and valence state of the catalyst were analyzed by X-ray powder diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).In 1 mol·L^(-1)KOH,the oxygen evolution reaction(OER)performance of the catalyst was measured by linear sweep voltammetry,cyclic voltammetry,and chronoamperometry.The results show that the combination of Ru doping and rGO provides a fast channel for collaborative electron transfer.At the same time,rGO as a carbon carrier can improve the electrical conductivity of Ru-Co_(3)O_(4)particles,and the uniformly dispersed nanoparticles enable the reactants to diffuse freely on the catalyst.The results showed that the electrochemical performance of Ru-Co_(3)O_(4)/rGO was much better than that of Co_(3)O_(4)/rGO,and the overpotential of Ru-Co_(3)O_(4)/rGO was 363.5 mV at the current density of 50 mA·cm^(-2).展开更多
With the rapid urbanization process,the space of traditional villages in China is undergoing significant changes.Studying the spatial evolution of traditional villages is significant in promoting rural spatial transfo...With the rapid urbanization process,the space of traditional villages in China is undergoing significant changes.Studying the spatial evolution of traditional villages is significant in promoting rural spatial transformation and realizing rural revitalization and sustainable rural development.Based on the traceability analysis of spatial production theory,this paper constructed an analytical framework for the spatial production evolution of traditional villages,analyzed the spatial evolution process and characteristics of traditional villages by using buffer analysis,spatial syntax,and other research methods,and revealed the characteristics of the spatial production evolution of traditional villages and the driving mechanism.The results show that:(1)The village spatial formation and development follow the village life cycle theory and usually develop from embryonic villages to diversified and integrated villages;(2)The evolution of village spatial production is characterized by the diversity of material space,the sublimation of daily life space,and the integration of social system space and generalization of emotional space;(3)The evolution of village spatial production from backward and poor village to ecologically well-off village is influenced by a combination of factors;(4)The village has formed a spatial structure of"people-land-scape-culture-industry",realized comprehensive reconstruction and spatial reproduction.The study results reflect the spatial evolution characteristics of traditional villages in mountainous areas in a more comprehensive way,which helps to promote the protection and development of traditional villages in mountainous areas and,to a certain extent,provides a reference for the development of rural revitalization.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
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
Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key hal...Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key half-reaction of performance-limiting in water splitting.Given the complicated reaction process and surface reconstruction of the involved catalysts under actual working conditions,unraveling the real active sites,probing multiple reaction intermediates and clarifying catalytic pathways through in-situ characterization techniques and theoretical calculations are essential.In this review,we summarize the recent advancements in understanding the catalytic process,unlocking the water oxidation active phase and elucidating catalytic mechanism of water oxidation by various in-situ characterization techniques.Firstly,we introduce conventionally proposed traditional catalytic mechanisms and novel evolutionary mechanisms of OER,and highlight the significance of optimal catalytic pathways and intrinsic stability.Next,we provide a comprehensive overview of the fundamental working principles,different detection modes,applicable scenarios,and limitations associated with the in-situ characterization techniques.Further,we exemplified the in-situ studies and discussed phase transition detection,visualization of speciation evolution,electronic structure tracking,observation of reaction active intermediates,and monitoring of catalytic products,as well as establishing catalytic structure-activity relationships and catalytic mechanism.Finally,the key challenges and future perspectives for demystifying the water oxidation process are briefly proposed.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 frost deterioration and deformation of porous rock are commonly investigated under uniform freeze-thaw(FT)conditions.However,the unidirectional FT condition,which is also prevalent in engineering practice,has rece...The frost deterioration and deformation of porous rock are commonly investigated under uniform freeze-thaw(FT)conditions.However,the unidirectional FT condition,which is also prevalent in engineering practice,has received limited attention.Therefore,a comparative study on frost deformation and microstructure evolution of porous rock under both uniform and unidirectional FT conditions was performed.Firstly,frost deformation experiments of rock were conducted under cyclic uniform and unidirectional FT action,respectively.Results illustrate that frost deformation of saturated rock exhibits isotropic characteristics under uniform FT cycles,while it shows anisotropic characteristics under unidirectional FT condition with both the frost heaving strain and residual strain along FT direction much higher than those perpendicular to FT direction.Moreover,the peak value and residual value of cumulative frost strain vary as logarithmic functions with cycle number under both uniform and unidirectional FT conditions.Subsequently,the microstructure evolution of rock suffered cyclic uniform and unidirectional FT action were measured.Under uniform FT cycles,newly generated pores uniformly distribute in rock and pore structure of rock remains isotropic in micro scale,and thus the frost deformation shows isotropic characteristics in macro scale.Under unidirectional FT cycles,micro-cracks or pore belts generate with their orientation nearly perpendicular to the FT direction,and rock structure gradually becomes anisotropic in micro scale,resulting in the anisotropic characteristics of frost deformation in macro scale.展开更多
Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au...Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au nanoparticles(NPs)(denoted as HP-Au@CoxSy@ZIF-67)hybrid is synthesized by low-temperature sulfuration treatment.The well-defined macroporous-mesoporous-microporous structure is obtained based on the combination of polystyrene spheres,as-formed CoxSy nanosheets,and ZIF-67 frameworks.This novel three-dimensional hierarchical structure significantly enlarges the three-phase interfaces,accelerating the mass transfer and exposing the active centers for oxygen evolution reaction.The electronic structure of Co is modulated by Au through charge transfer,and a series of experiments,together with theoretical analysis,is performed to ascertain the electronic modulation of Co by Au.Meanwhile,HP-Au@CoxSy@ZIF-67 catalysts with different amounts of Au were synthesized,wherein Au and NaBH4 reductant result in an interesting“competition effect”to regulate the relative ratio of Co^(2+)/Co^(3+),and moderate Au assists the electrochemical performance to reach the highest value.Consequently,the optimized HP-Au@CoxSy@ZIF-67 exhibits a low overpotential of 340 mV at 10 mA cm^(-2)and a Tafel slope of 42 mV dec-1 for OER in 0.1 M aqueous KOH,enabling efficient water splitting and Zn-air battery performance.The work here highlights the pivotal roles of both microstructural and electronic modulation in enhancing electrocatalytic activity and presents a feasible strategy for designing and optimizing advanced electrocatalysts.展开更多
The influence of thermal damage on macroscopic and microscopic characteristics of different rocks has received much attention in the field of rock engineering.When the rocks are subjected to thermal treatment,the chan...The influence of thermal damage on macroscopic and microscopic characteristics of different rocks has received much attention in the field of rock engineering.When the rocks are subjected to thermal treatment,the change of macroscopic characteristics and evolution of micro-structure would be induced,ultimately resulting in different degrees of thermal damage in rocks.To better understand the thermal damage mechanism of different rocks and its effect on the rock performance,this study reviews a large number of test results of rock specimens experiencing heating and cooling treatment in the laboratory.Firstly,the variations of macroscopic behaviors,including physical parameters,mechanical parameters,thermal conductivity and permeability,are examined.The variations of mechanical parameters with thermal treatment variables(i.e.temperature or the number of thermal cycles)are divided into four types.Secondly,several measuring methods for microstructure,such as polarizing microscopy,fluorescent method,scanning electron microscopy(SEM),X-ray computerized tomography(CT),acoustic emission(AE)and ultrasonic technique,are introduced.Furthermore,the effect of thermal damage on the mechanical parameters of rocks in response to different thermal treatments,involving temperature magnitude,cooling method and thermal cycle,are discussed.Finally,the limitations and prospects for the research of rock thermal damage are proposed.展开更多
High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion te...High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion technologies.Herein,we report a robust method for the synthesis of a bimetallic alkoxide for efficient oxygen evolution reaction(OER)for alkaline electrolysis,which yields current density of 10 mA cm^(-2)at an overpotential of 215 mV in 0.1 M KOH electrolyte.The catalyst demonstrates an excellent durability for more than 540 h operation with negligible degradation in activity.Raman spectra revealed that the catalyst underwent structure reconstruction during OER,evolving into oxyhydroxide,which was the active site proceeding OER in alkaline electrolyte.In-situ synchrotron X-ray absorption experiment combined with density functional theory calculation suggests a lattice oxygen involved electrocatalytic reaction mechanism for the in-situ generated nickel–iron bimetal-oxyhydroxide catalyst.This mechanism together with the synergy between nickel and iron are responsible for the enhanced catalytic activity and durability.These findings provide promising strategies for the rational design of nonnoble metal OER catalysts.展开更多
基金Funded by Chinese National Natural Science Foundation of China(No.U2006224)。
文摘The paper presents experimental investigation results of crack pattern change in cement pastes caused by external sulfate attack(ESA).To visualize the formation and development of cracks in cement pastes under ESA,an X-ray computed tomography(X-ray CT)was used,i e,the tomography system of Zeiss Xradia 510 versa.The results indicate that X-CT can monitor the development process and distribution characteristics of the internal cracks of cement pastes under ESA with attack time.In addition,the C3A content in the cement significantly affects the damage mode of cement paste specimens during sulfate erosion.The damage of ordinary Portland cement(OPC)pastes subjected to sulfate attack with high C3A content are severe,while the damage of sulfate resistant Portland cement(SRPC)pastes is much smaller than that of OPC pastes.Furthermore,a quadratic function describes the correlation between the crack volume fraction and development depth for two cement pastes immermed in sulfate solution.
基金Geological Survey of India,Northern Region have provided the fi nancial funding for the study.
文摘Background The Bundelkhand Craton is significant for preserving the multiphase granitoids magmatism from Paleoarchean to Neoarchean periods.It consists of a variety of granite rocks,including TTGs,sanukitoids,and high-K granitoids.This study presents geochemical characteristics of high-silica(68.97 wt.%–73.99 wt.%),low-silica(58.73wt.%–69.94 wt.%),and high K_(2)O(2.77 wt.%–6.16 wt.%)contents of granitoids.Objective The data on Bundelkhand Craton’s granitic magmatism and geodynamics is not sufficiently robust.Geochemical data from this study will be used to further understand the origin,source,and petrogenesis of granitoid rocks and their implications for the evolution of geodynamics.Methodology Twenty-one samples were collected and analyzed for major,trace,and REE elements.Major elements were measured using X-ray fluorescence spectrometry(XRF),and trace and REE elements were analyzed by ICP-MS.Standard procedures from the Geological Survey of India were followed.Results The geochemical analysis presents high-silica(68.97-73.99 wt.%),low-silica(58.73-69.94 wt.%),and high K2O(2.77-6.16 wt.%)contents in granitoids,classified as granite-granodiorite.The rocks are calcic to calcalkalic,magnesian,and range from peraluminous to metaluminous composition.REE patterns showed strong LREE enrichment relative to HREEs,with prominent negative Eu anomalies corresponding to earlier plagioclase fractionation.Multi-element patterns revealed negative anomalies in Nb,Sr,P,and Ti and positive anomalies in Pb.Conclusion The geochemical signatures attributed to the post-collisional magma generation and continental crustal contamination.The studied rocks show A-type and A2-type lineage,suggesting they originated from the melting of continental crust during transitional/post-collisional tectonic activity.The formation of hybrid granitoids in the Bundelkhand Craton is connected to the fractionation of hybrid magmas in shallow-seated magma chambers during these tectonic processes.
基金supported by the National Natural Science Foundation of China(Grant Nos.42074105 and 92155204)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB 41000000)。
文摘Five tectonic modes of mantle convection are obtained and analyzed with three-dimensional numerical models in a spherical shell domain.The five tectonic convective modes are non-plate mobile-lid,plate-like mobile-lid,episodic plate-like mobile-lid,episodic stagnant-lid,and stagnant-lid convective modes,respectively.The typical characteristics of these five tectonic modes and their numerical classification criteria based on plateness,mobility,and their standard deviations are presented and discussed.The results show that the yield stress of the lithosphere has profound effects on the tectonic convective modes.With the gradual increase of yield stress,the tectonic mode of mantle convection changes from one to another sequentially through the aforementioned five modes.Additionally,as the Rayleigh number increases,the range of yield stress for the platelike mobile-lid convective mode decreases,and the dimensionless transition stress between different tectonic modes increases.Specifically,the dimensional transition stress between the non-plate mobile-lid convective mode and plate-like mobile-lid convective mode increases with the increase of Rayleigh number,but decreases between other tectonic modes.Furthermore,we find that the transition stress between different tectonic modes is inversely proportional to the internal heating rate,with the transition stress decreasing as the internal heating rate increases.The fitting analysis of the transition stress between tectonic modes shows that Earth's current plate tectonics correspond to a lithospheric yield stress of 150–250 MPa,which aligns with the strength of serpentinized mantle rock determined by experimental petrography.If the Archean mantle was 300℃warmer than it is today,then the Earth was in an episodic stagnant-lid convective mode.The tectonic evolution of the Earth's surface is closely related to the lithospheric strength and the process of thermal evolution.If the lithospheric strength was only 150 MPa,plate tectonics in the early mantle rapid cooling model would have begun before 3.8 Ga,and plate tectonics in the late mantle rapid cooling model would have begun at approximately 1.5 Ga.However,at a lithospheric strength of 200 MPa,plate tectonics in the late mantle rapid cooling model would have begun later than 0.95 Ga,and plate tectonics in the early mantle rapid cooling model would have begun at approximately 2 Ga.The early Earth was in the episodic stagnant-lid convective mode,which means that subduction might still have occurred at that time.The presence of the episodic plate-like mobile-lid convective mode in Earth's later history indicates that there might also have been intermittent surface stagnation during plate tectonics,which may provide an explanation for the quiet period of tectonic activity at approximately 1.0 Ga on Earth.This indicates that tectonic inactivity during a geological period is not an indicator that plate tectonics did not begin.
基金This study was jointly supported by the Science&Technology Fundamental Resources Investigation Program(2022FY101800)National Science Foundation(92162212)+1 种基金the project from the Key Laboratory of Tectonics and Petroleum Resources(China University of Geosciences,Wuhan)(TPR-2022-22)the International Geoscience Programme(IGCP-675)。
文摘The Ordos Basin(OB)in the western part of the North China Craton(NCC),was located at the jointed area of multi-plates and has recorded the Mesozoic tectonic characteristics.Its tectonic evolution in the Mesozoic is significant to understand the tectonic transformation of the northern margin of the NCC.In this work,the detrital zircon and apatite(U-Th)/He chronological system were analyzed in the northern part of the OB,and have provided new evidence for the regional tectonic evolution.The(U-Th)/He chronological data states the weighted ages of 240‒235 Ma,141 Ma with the peak distribution of 244 Ma,219 Ma,173 Ma,147‒132 Ma.The thermal evolution,geochronological data,and regional unconformities have proved four stages of regional tectonic evolution for the OB and its surroundings in the Mesozoic:(1)The Late Permian-Early Triassic;(2)the Late Triassic-Early Jurassic;(3)the Late Jurassic-Early Cretaceous;(4)the Late Cretaceous-Early Paleogene.It is indicated that the multi-directional convergence from the surrounding tectonic units has controlled the Mesozoic tectonic evolution of the OB.Four-stage tectonic evolution reflected the activation or end of different plate movements and provided new time constraints for the regional tectonic evolution of the NCC in the Mesozoic.
基金financially supported by the National Natural Science Foundation of China(No.5217042069)the Young Elite Scientist Sponsorship Program by China Association for Science and Technology(CAST)(No.YESS20200103)the Fundamental Research Funds for the Central Universities(No.265QZ2022004)。
文摘Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.
基金financially supported by the National Science Foundation of China(Nos.51974212 and 52274316)the China Baowu Low Carbon Metallurgy Innovation Foundation(No.BWLCF202116)+1 种基金the Science and Technology Major Project of Wuhan(No.2023020302020572)the Foundation of Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education(No.FMRUlab23-04)。
文摘The utilization of iron coke provides a green pathway for low-carbon ironmaking.To uncover the influence mechanism of iron ore on the behavior and kinetics of iron coke gasification,the effect of iron ore on the microstructure of iron coke was investigated.Furthermore,a comparative study of the gasification reactions between iron coke and coke was conducted through non-isothermal thermogravimetric method.The findings indicate that compared to coke,iron coke exhibits an augmentation in micropores and specific surface area,and the micropores further extend and interconnect.This provides more adsorption sites for CO_(2) molecules during the gasification process,resulting in a reduction in the initial gasification temperature of iron coke.Accelerating the heating rate in non-isothermal gasification can enhance the reactivity of iron coke.The metallic iron reduced from iron ore is embedded in the carbon matrix,reducing the orderliness of the carbon structure,which is primarily responsible for the heightened reactivity of the carbon atoms.The kinetic study indicates that the random pore model can effectively represent the gasification process of iron coke due to its rich pore structure.Moreover,as the proportion of iron ore increases,the activation energy for the carbon gasification gradually decreases,from 246.2 kJ/mol for coke to 192.5 kJ/mol for iron coke 15wt%.
基金Research Institute for Smart Energy(CDB2)the grant from the Research Institute for Advanced Manufacturing(CD8Z)+4 种基金the grant from the Carbon Neutrality Funding Scheme(WZ2R)at The Hong Kong Polytechnic Universitysupport from the Hong Kong Polytechnic University(CD9B,CDBZ and WZ4Q)the National Natural Science Foundation of China(22205187)Shenzhen Municipal Science and Technology Innovation Commission(JCYJ20230807140402006)Start-up Foundation for Introducing Talent of NUIST and Natural Science Foundation of Jiangsu Province of China(BK20230426).
文摘Catalyst–support interaction plays a crucial role in improving the catalytic activity of oxygen evolution reaction(OER).Here we modulate the catalyst–support interaction in polyaniline-supported Ni_(3)Fe oxide(Ni_(3)Fe oxide/PANI)with a robust hetero-interface,which significantly improves oxygen evolution activities with an overpotential of 270 mV at 10 mA cm^(-2)and specific activity of 2.08 mA cm_(ECSA)^(-2)at overpotential of 300 mV,3.84-fold that of Ni_(3)Fe oxide.It is revealed that the catalyst–support interaction between Ni_(3)Fe oxide and PANI support enhances the Ni–O covalency via the interfacial Ni–N bond,thus promoting the charge and mass transfer on Ni_(3)Fe oxide.Considering the excellent activity and stability,rechargeable Zn-air batteries with optimum Ni_(3)Fe oxide/PANI are assembled,delivering a low charge voltage of 1.95 V to cycle for 400 h at 10 mA cm^(-2).The regulation of the effect of catalyst–support interaction on catalytic activity provides new possibilities for the future design of highly efficient OER catalysts.
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financially supported by the National Natural Science Foundation of China(52373271)Science,Technology and Innovation Commission of Shenzhen Municipality under Grant(KCXFZ20201221173004012)+1 种基金National Key Research and Development Program of Shaanxi Province(No.2023-YBNY-271)Open Testing Foundation of the Analytical&Testing Center of Northwestern Polytechnical University(2023T019).
文摘Gradient magnetic heterointerfaces have injected infinite vitality in optimizing impedance matching,adjusting dielectric/magnetic resonance and promoting electromagnetic(EM)wave absorption,but still exist a significant challenging in regulating local phase evolution.Herein,accordion-shaped Co/Co_(3)O_(4)@N-doped carbon nanosheets(Co/Co_(3)O_(4)@NC)with gradient magnetic heterointerfaces have been fabricated via the cooperative high-temperature carbonization and lowtemperature oxidation process.The results indicate that the surface epitaxial growth of crystal Co_(3)O_(4) domains on local Co nanoparticles realizes the adjustment of magnetic-heteroatomic components,which are beneficial for optimizing impedance matching and interfacial polarization.Moreover,gradient magnetic heterointerfaces simultaneously realize magnetic coupling,and long-range magnetic diffraction.Specifically,the synthesized Co/Co_(3)O_(4)@NC absorbents display the strong electromagnetic wave attenuation capability of−53.5 dB at a thickness of 3.0 mm with an effective absorption bandwidth of 5.36 GHz,both are superior to those of single magnetic domains embedded in carbon matrix.This design concept provides us an inspiration in optimizing interfacial polarization,regulating magnetic coupling and promoting electromagnetic wave absorption.
基金financially supported by the National Natural Science Foundation of China(22309137,22279095)Open subject project State Key Laboratory of New Textile Materials and Advanced Processing Technologies(FZ2023001).
文摘Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.
文摘Binary composites(ZIF-67/rGO)were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source,2-methylimidazole as organic ligand,and reduced graphene oxide(rGO)as carbon carrier.Then Ru3+was introduced for ion exchange,and the porous Ru-doped Co_(3)O_(4)/rGO(Ru-Co_(3)O_(4)/rGO)composite electrocatalyst was prepared by annealing.The phase structure,morphology,and valence state of the catalyst were analyzed by X-ray powder diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM),and X-ray photoelectron spectroscopy(XPS).In 1 mol·L^(-1)KOH,the oxygen evolution reaction(OER)performance of the catalyst was measured by linear sweep voltammetry,cyclic voltammetry,and chronoamperometry.The results show that the combination of Ru doping and rGO provides a fast channel for collaborative electron transfer.At the same time,rGO as a carbon carrier can improve the electrical conductivity of Ru-Co_(3)O_(4)particles,and the uniformly dispersed nanoparticles enable the reactants to diffuse freely on the catalyst.The results showed that the electrochemical performance of Ru-Co_(3)O_(4)/rGO was much better than that of Co_(3)O_(4)/rGO,and the overpotential of Ru-Co_(3)O_(4)/rGO was 363.5 mV at the current density of 50 mA·cm^(-2).
基金supported by the National Natural Science Foundation of China(Grant No.42061035)the Guizhou Provincial Program on Commercialization of Scientific and Technological Achievements([2022]010).
文摘With the rapid urbanization process,the space of traditional villages in China is undergoing significant changes.Studying the spatial evolution of traditional villages is significant in promoting rural spatial transformation and realizing rural revitalization and sustainable rural development.Based on the traceability analysis of spatial production theory,this paper constructed an analytical framework for the spatial production evolution of traditional villages,analyzed the spatial evolution process and characteristics of traditional villages by using buffer analysis,spatial syntax,and other research methods,and revealed the characteristics of the spatial production evolution of traditional villages and the driving mechanism.The results show that:(1)The village spatial formation and development follow the village life cycle theory and usually develop from embryonic villages to diversified and integrated villages;(2)The evolution of village spatial production is characterized by the diversity of material space,the sublimation of daily life space,and the integration of social system space and generalization of emotional space;(3)The evolution of village spatial production from backward and poor village to ecologically well-off village is influenced by a combination of factors;(4)The village has formed a spatial structure of"people-land-scape-culture-industry",realized comprehensive reconstruction and spatial reproduction.The study results reflect the spatial evolution characteristics of traditional villages in mountainous areas in a more comprehensive way,which helps to promote the protection and development of traditional villages in mountainous areas and,to a certain extent,provides a reference for the development of rural revitalization.
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.
基金support from National Natural Science Foundation of China(Grant Nos.22125903,22209174)the National Key R&D Program of China(Grants 2022YFA1504100)+2 种基金Dalian Innovation Support Plan for High Level Talents(2019RT09)Dalian National Laboratory For Clean Energy(DNL),CAS,DNL Cooperation Fund,CAS(DNL202016,DNL202019)DICP(DICP I2020032).
文摘Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key half-reaction of performance-limiting in water splitting.Given the complicated reaction process and surface reconstruction of the involved catalysts under actual working conditions,unraveling the real active sites,probing multiple reaction intermediates and clarifying catalytic pathways through in-situ characterization techniques and theoretical calculations are essential.In this review,we summarize the recent advancements in understanding the catalytic process,unlocking the water oxidation active phase and elucidating catalytic mechanism of water oxidation by various in-situ characterization techniques.Firstly,we introduce conventionally proposed traditional catalytic mechanisms and novel evolutionary mechanisms of OER,and highlight the significance of optimal catalytic pathways and intrinsic stability.Next,we provide a comprehensive overview of the fundamental working principles,different detection modes,applicable scenarios,and limitations associated with the in-situ characterization techniques.Further,we exemplified the in-situ studies and discussed phase transition detection,visualization of speciation evolution,electronic structure tracking,observation of reaction active intermediates,and monitoring of catalytic products,as well as establishing catalytic structure-activity relationships and catalytic mechanism.Finally,the key challenges and future perspectives for demystifying the water oxidation process are briefly proposed.
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This research was supported by the National Natural Science Foundation of China(52108370)Jiangxi Provincial Natural Science Foundation(No.20212BAB214062,20224BAB204061).
文摘The frost deterioration and deformation of porous rock are commonly investigated under uniform freeze-thaw(FT)conditions.However,the unidirectional FT condition,which is also prevalent in engineering practice,has received limited attention.Therefore,a comparative study on frost deformation and microstructure evolution of porous rock under both uniform and unidirectional FT conditions was performed.Firstly,frost deformation experiments of rock were conducted under cyclic uniform and unidirectional FT action,respectively.Results illustrate that frost deformation of saturated rock exhibits isotropic characteristics under uniform FT cycles,while it shows anisotropic characteristics under unidirectional FT condition with both the frost heaving strain and residual strain along FT direction much higher than those perpendicular to FT direction.Moreover,the peak value and residual value of cumulative frost strain vary as logarithmic functions with cycle number under both uniform and unidirectional FT conditions.Subsequently,the microstructure evolution of rock suffered cyclic uniform and unidirectional FT action were measured.Under uniform FT cycles,newly generated pores uniformly distribute in rock and pore structure of rock remains isotropic in micro scale,and thus the frost deformation shows isotropic characteristics in macro scale.Under unidirectional FT cycles,micro-cracks or pore belts generate with their orientation nearly perpendicular to the FT direction,and rock structure gradually becomes anisotropic in micro scale,resulting in the anisotropic characteristics of frost deformation in macro scale.
基金National Natural Science Foundation of China,Grant/Award Numbers:52102260,52171211,51972220,61903235,U22A20145Shandong Provincial Natural Science Foundation,Grant/Award Numbers:ZR2020QB069,ZR2022ME051+4 种基金National Key Research and Development Program of China,Grant/Award Number:2022YFB4002004Scientific and Technological Innovation Ability Improvement Project of Minor Enterprises in Shandong Province,Grant/Award Number:2022TSGC1021Announce the List and Take Charge Project in Jinan,Grant/Award Number:202214012Major innovation project for integrating science,education and industry of Qilu University of Technology (Shandong Academy of Sciences),Grant/Award Numbers:2022JBZ01-07,2022PY044China Postdoctoral Science Foundation,Grant/Award Number:2022M711545。
文摘Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au nanoparticles(NPs)(denoted as HP-Au@CoxSy@ZIF-67)hybrid is synthesized by low-temperature sulfuration treatment.The well-defined macroporous-mesoporous-microporous structure is obtained based on the combination of polystyrene spheres,as-formed CoxSy nanosheets,and ZIF-67 frameworks.This novel three-dimensional hierarchical structure significantly enlarges the three-phase interfaces,accelerating the mass transfer and exposing the active centers for oxygen evolution reaction.The electronic structure of Co is modulated by Au through charge transfer,and a series of experiments,together with theoretical analysis,is performed to ascertain the electronic modulation of Co by Au.Meanwhile,HP-Au@CoxSy@ZIF-67 catalysts with different amounts of Au were synthesized,wherein Au and NaBH4 reductant result in an interesting“competition effect”to regulate the relative ratio of Co^(2+)/Co^(3+),and moderate Au assists the electrochemical performance to reach the highest value.Consequently,the optimized HP-Au@CoxSy@ZIF-67 exhibits a low overpotential of 340 mV at 10 mA cm^(-2)and a Tafel slope of 42 mV dec-1 for OER in 0.1 M aqueous KOH,enabling efficient water splitting and Zn-air battery performance.The work here highlights the pivotal roles of both microstructural and electronic modulation in enhancing electrocatalytic activity and presents a feasible strategy for designing and optimizing advanced electrocatalysts.
基金supported by the National Key Research and Development Plan(Grant No.2022YFC2905700)Natural Science Foundation of Anhui Province(Grant No.2208085ME120)Key Research and Development Plan of Anhui Province(Grant No.2022m07020001).
文摘The influence of thermal damage on macroscopic and microscopic characteristics of different rocks has received much attention in the field of rock engineering.When the rocks are subjected to thermal treatment,the change of macroscopic characteristics and evolution of micro-structure would be induced,ultimately resulting in different degrees of thermal damage in rocks.To better understand the thermal damage mechanism of different rocks and its effect on the rock performance,this study reviews a large number of test results of rock specimens experiencing heating and cooling treatment in the laboratory.Firstly,the variations of macroscopic behaviors,including physical parameters,mechanical parameters,thermal conductivity and permeability,are examined.The variations of mechanical parameters with thermal treatment variables(i.e.temperature or the number of thermal cycles)are divided into four types.Secondly,several measuring methods for microstructure,such as polarizing microscopy,fluorescent method,scanning electron microscopy(SEM),X-ray computerized tomography(CT),acoustic emission(AE)and ultrasonic technique,are introduced.Furthermore,the effect of thermal damage on the mechanical parameters of rocks in response to different thermal treatments,involving temperature magnitude,cooling method and thermal cycle,are discussed.Finally,the limitations and prospects for the research of rock thermal damage are proposed.
基金the staff at Beamline (BL08U1-A and BL11B)of the Shanghai Synchrotron Radiation Facility (SSRF)the support from the National Key Research&Development Program of China (2022YFB3803700)+2 种基金the National Natural Science Foundation of China (52171186)the support through the Overseas Outstanding Youth Fund and Shanghai Pujiang Talent Project (21PJ1408500)the financial support from the Center of Hydrogen Science,Shanghai Jiao Tong University。
文摘High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion technologies.Herein,we report a robust method for the synthesis of a bimetallic alkoxide for efficient oxygen evolution reaction(OER)for alkaline electrolysis,which yields current density of 10 mA cm^(-2)at an overpotential of 215 mV in 0.1 M KOH electrolyte.The catalyst demonstrates an excellent durability for more than 540 h operation with negligible degradation in activity.Raman spectra revealed that the catalyst underwent structure reconstruction during OER,evolving into oxyhydroxide,which was the active site proceeding OER in alkaline electrolyte.In-situ synchrotron X-ray absorption experiment combined with density functional theory calculation suggests a lattice oxygen involved electrocatalytic reaction mechanism for the in-situ generated nickel–iron bimetal-oxyhydroxide catalyst.This mechanism together with the synergy between nickel and iron are responsible for the enhanced catalytic activity and durability.These findings provide promising strategies for the rational design of nonnoble metal OER catalysts.