Influenced by globalization,rural transition in developed Western countries has experienced processes of productivism,post-productivism,and multifunctional development.By contrast,rural transition in most developing c...Influenced by globalization,rural transition in developed Western countries has experienced processes of productivism,post-productivism,and multifunctional development.By contrast,rural transition in most developing countries has been accompanied by rapid urbanization,which has become a core topic in geography research.As the world’s largest developing country,China has undergone profound development since the reform and opening-up.Moreover,rural spaces in some eastern coastal areas have entered the stage of reconstruction after decades of industrialization and urbanization.This paper takes Suzhou as the case area and measures the process of rural transition from 1990 to 2015 by constructing an index system.It then analyzes the characteristics of space-time evolution using exploratory spatial data analysis(ESDA)methods to reveal the influence of economic and social development on rural transition.The results show that rural transition,which generally entails the weakening of rurality and enhancing of urbanity on a macro scale,tends to be heterogeneous across different regions on a micro scale.This paper argues that multifunctionality will be the main future trend of rural transition in rapidly urbanizing areas.The experience in Suzhou could provide an example for establishing policies on sustainable development in rural spaces and achieving urban-rural co-governance.展开更多
Fine-grained rocks(FGR) are the important source rocks and reservoirs of shale hydrocarbon which is the prospect hotspot at present. Widely distributed fine-grained sediments(FGS) of the upper fourth member of Sha...Fine-grained rocks(FGR) are the important source rocks and reservoirs of shale hydrocarbon which is the prospect hotspot at present. Widely distributed fine-grained sediments(FGS) of the upper fourth member of Shahejie Formation in Dongying depression are taken as an example to study the space-time evolution and controlling factor of FGS in this paper. Based on the analysis of well cores, thin sections, inorganic and organic geochemistry indicators, FGR are divided into 7 types of lithofacies. Through the study of ‘point-line-plane', this study shows that FGS has the characteristics of rhythum, diversity and succession. The first stage is characterized by clayey FGS(massive claystone). The second stage is characterized by carbonate FGS(low-TOC laminated limestone) and dolomitic FGS(dolomitic-silty shale) formed by transgression. The third stage is characterized by organic-rich carbonate FGS(middle/high-TOC laminated limestone) distributed in cycle. The fourth stage is characterized by FGS mixed carbonate and siliciclastic sediments(calcareous-silty shale). A variety of space-time evolution of FGS are controlled by multiple factors including tectonism, climate and lake conditions.展开更多
By using MTS815 rock mechanics test system,a series of acoustic emission(AE) location experiments were performed under unloading confining pressure,increasing the axial stress.The AE space-time evolution regularities ...By using MTS815 rock mechanics test system,a series of acoustic emission(AE) location experiments were performed under unloading confining pressure,increasing the axial stress.The AE space-time evolution regularities and energy releasing characteristics during deformation and failure process of coal of different loading rates are compared,the influence mechanism of loading rates on the microscopic crack evolution were studied,combining the AE characteristics and the macroscopic failure modes of the specimens,and the precursory characteristics of coal failure were also analyzed quantitatively.The results indicate that as the loading rate is higher,the AE activity and the main fracture will begin earlier.The destruction of coal body is mainly the function of shear strain at lower loading rate and tension strain at higher rate,and will transform from brittleness to ductility at critical velocities.When the deformation of the coal is mainly plasticity,the amplitude of the AE ringing counting rate increases largely and the AE energy curves appear an obvious ''step'',which can be defined as the first failure precursor point.Statics of AE information shows that the strongest AE activity begins when the axial stress level was 92-98%,which can be defined as the other failure precursor point.As the loading rate is smaller,the coal more easily reaches the latter precursor point after the first one,so attention should be aroused to prevent dynamic disaster in coal mining when the AE activity reaches the first precursor point.展开更多
Designing effective electrocatalysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is essential for the advancement of water electrolysis.Herein,iridium-doped CoSe2(Ir–CoSe2)nanobelts wi...Designing effective electrocatalysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is essential for the advancement of water electrolysis.Herein,iridium-doped CoSe2(Ir–CoSe2)nanobelts with tailored d-band center are designed to boost both HER and OER in alkaline electrolytes.On the one hand,the adsorption ability of H2O and hydrogen on Ir–CoSe2 is increased due to the upshifted d-band center induced by the electron transfer from CoSe2 to Ir,inducing good HER activity with an overpotential of 126 mV at 10 mA cm-2.On the other hand,the upshifted d-band center of Ir–CoSe2 facilitates the H2O adsorption and ensures the effective exposure of real active sites,resulting in good OER activity with an overpotential of 239 mV at 10 mA cm-2.Meanwhile,when using Ir–CoSe2 as catalysts for alkaline overall water splitting on both HER and OER,a lower voltage of 1.57 V at 10 mA cm-2 is achieved,indicating a good activity and great potential for practical water electrolysis.This work gives an effective method for the rational design of electrocatalysts with customized d-band structures for bifunctional catalysis.展开更多
Acetolactate synthase(ALS)-targeting herbicides are among the most widely used weed-control chemicals globally.Mutations in the ALS gene can confer herbicide resistance in crops,thereby allowing selective elimination ...Acetolactate synthase(ALS)-targeting herbicides are among the most widely used weed-control chemicals globally.Mutations in the ALS gene can confer herbicide resistance in crops,thereby allowing selective elimination of weeds without harming crops.Herbicide-resistant ALS alleles were initially discovered in weeds and subsequently developed through artificial mutagenesis techniques.With the advancement of CRISPR/Cas technologies,various genome-editing tools are now available to introduce these resistant alleles,as well as novel variants,into diverse crop species.Moreover,emerging methodologies,such as directed evolution,enable the generation and screening of large populations of random ALS mutants.Consequently,ALS has become one of the most extensively targeted genes in plant gene evolution.This paper provides a comprehensive overview of both conventional and recently developed strategies for ALS evolution,with particular emphasis on CRISPR/Cas-based genome editing and directed evolution.Future perspectives on technological application are also discussed.By advancing our understanding of herbicide-resistant ALS allele development for crop improvement,these methodologies may also pave the way for their application to the evolution of other agronomically important genes.展开更多
The study of the effects of thermal damage on the mineral components,microstructure,and macroscopic physico-mechanical properties of rocks can provide valuable references for rock engineering design and long-term safe...The study of the effects of thermal damage on the mineral components,microstructure,and macroscopic physico-mechanical properties of rocks can provide valuable references for rock engineering design and long-term safety evaluations.In this work,we systematically study the evolution of microstructure and variations in the mechanical properties of granite under high-temperature conditions.The microstructural changes and macro-mechanical properties of rocks are investigated across a temperature range of 25℃–1000℃ through the application of characterization techniques,macro-mechanical experiments,and numerical simulations.High temperatures induce the gradual evolution of micropores and mesopores into macropores,culminating in a significant increase in porosity,with the most rapid rate of increase occurring at 400℃.The X-ray diffraction(XRD)results indicate that the high-temperature environment(below 1000℃)specifically affects the intensity of the maximum diffraction peaks and the half-height width(FWHM)of each mineral component in the granite.The scanning electron microscope(SEM)observation confirms the development of fracture and the reduction in cementation between mineral particles under different temperatures.Additionally,uniaxial and triaxial compression tests were conducted using the GCTS mechanical loading system.Experimental results reveal that the threshold temperature for granite damage is 400℃,and the temperature range for the brittle-ductile transition of granite lies roughly between 600℃ and 800℃.Numerical simulations were performed by employing non-homogeneous rock damage theory and a thermal-mechanical-damage coupling model.Simulated results align well with experimental data.Specifically,the simulations demonstrate that high-temperature treatment causes the redistribution of microstructure in granite,resulting in increased heterogeneity and a change in the failure morphology.展开更多
The reaction pathway plays a pivotal role in determining the catalytic activity of the oxygen evolution reaction(OER).However,regulating the microscopic reaction pathway through interface construction remains a signif...The reaction pathway plays a pivotal role in determining the catalytic activity of the oxygen evolution reaction(OER).However,regulating the microscopic reaction pathway through interface construction remains a significant challenge.In this study,an interface between amorphous rare earth hydroxides and crystalline spinel NiCo2O4was constructed via selective oxidation.The interface structural units accelerate reconstruction,leading to enhanced catalytic activity,which was observed by in situ Raman spectroscopy.The amorphous RE(OH)3(RE=Y and Eu)optimize asymmetric Ni-Co dual-sites,thereby altering the OER reaction pathway.Specifically,Y(OH)3/NiCo2O4operates through the lattice oxygen mechanism(LOM)at the expense of structural stability,whereas Eu(OH)3/NiCo2O4follows the oxygen pathway mechanism(OPM),preserving both catalytic activity and stability.This study offers a novel approach to controlling reaction pathways and proposes a new strategy for interface construction using rare earth hydroxides.展开更多
Alleviating the imbalance between urban and rural areas for regional coordinated development is an imperative response to the Sustainable Development Goal 10 of the United Nations.To track China’s urban-rural integra...Alleviating the imbalance between urban and rural areas for regional coordinated development is an imperative response to the Sustainable Development Goal 10 of the United Nations.To track China’s urban-rural integration progress and address the uneven issues in specific fields,this study constructed a novel seven-dimension index system of urban-rural integration,comprising free population mobility,efficient land transfer,interactive economic growth,highly-linked transportation,equal public services,joint environmental governance and unimpeded informatization between urban and rural areas.Based on a comprehensive measurement framework and multi-source panel data,we uncovered the spatial-temporal evolution of urban-rural integration in China’s 367 prefecture-level administrative units from 1980 to 2022.The results demonstrated that China’s urban-rural integration steadily increased from 27.51 to 57.35 with an average annual growth rate of 3.40%.Whereas,the overall urban-rural integration was relatively inferior in 2022,at the level of moderate integration whose proportion of China’s land area was 88.08%.The urban-rural integration level in eastern region and urban agglomerations was higher than that in mid-west and non-urban agglomerations.From the perspective of seven dimensions,interactive economic growth,joint environmental governance and unimpeded informatization made an obvious improvement and reached higher integration,while free population mobility,efficient land transfer,highly-linked transportation and equal public services maintained the stage of moderate integration in 2022.In the future,China should make targeted efforts for urban-rural integration in terms of population,land use,transportation and public services,and accelerate urban-rural common prosperity in the mid-west and economically underdeveloped areas.展开更多
Multi-component transition metal carbides(MTMCs)have garnered significant attention for their out-standing high-temperature stability and versatile properties,which make them ideal candidates for a wide range of indus...Multi-component transition metal carbides(MTMCs)have garnered significant attention for their out-standing high-temperature stability and versatile properties,which make them ideal candidates for a wide range of industrial applications.However,the underlying mechanisms governing the crystal growth and morphological evolution of MTMCs remain poorly understood,hindering the design of materials with tailored characteristics.In this paper,we employ an in-situ liquid-solid reaction method to synthesize(HfTaZrNbTi)C MTMC powders and explore their crystal growth and morphology evolution.The synthesized(TiZrHfNbTa)C powders exhibit two distinct morphologies:cubic,primarily composed of Ti,Hf,Ta,and Zr with a small amount of Nb,and octahedral,rich in Ti and Ta with minor amounts of Hf,Nb,and Zr.First-principles calculations show that the surface energy of the(100)plane is lower than the(111)plane,leading to the formation of the cubic morphology.The octahedral morphology forms due to decreased mixing entropy and higher theoretical density compared to cubic particles.Our findings provide valuable insights into the crystal growth and morphology evolution mechanisms of high-entropy ceramics,contributing to the rational design of MTMCs with engineered crystal structures for diverse structural and functional applications.展开更多
The CO2 electroreduction reaction(CO2RR)is a promising approach of using renewable electricity to synthesize fuels and value-added chemicals.At present,Cu is generally considered to be the major monometallic cat...The CO2 electroreduction reaction(CO2RR)is a promising approach of using renewable electricity to synthesize fuels and value-added chemicals.At present,Cu is generally considered to be the major monometallic catalyst capable of producing multicarbon products(C2+)with high current densities from the CO2RR,but it still suffers from the low activity and high overpotential.The challenge of sluggish CO2RR kinetics can be overcome by developing efficient Cu-based catalysts,which undergo the dynamic evolution during the reaction process.The dynamic evolution of the Cu-based catalysts taking place under working conditions makes it difficult to study the structure-activity correlation and reaction mechanism present during CO2RR.Recently,a number of important works have observed and revealed the dynamic evolution process of Cu-based catalysts by operando characterization techniques.This aspect,however,remains less summarized and prospected in the CO2RR literature.In this Review,we summarize the dynamic evolution of Cu-based catalysts during the CO2RR from aspects of structure,composition and oxidation state.We highlight the correlations between evolution behaviors and catalytic properties.Then,we discuss the dynamic deactivation process of Cu-based catalysts during CO2RR,including metal impurities contamination and carbon accumulation.In particular,we introduce recent advancements in in situ characterization techniques those are employed to probe the dynamic evolution under operating conditions.We end the Review by outlining the challenges and offering personal perspectives on the future development opportunities in this field.展开更多
The unique geomorphology of rivers in the eastern Himalaya has long intrigued geologists,yet their drainage history remains debated.Drainage reorganization can have a significant impact on genetic differentiation in f...The unique geomorphology of rivers in the eastern Himalaya has long intrigued geologists,yet their drainage history remains debated.Drainage reorganization can have a significant impact on genetic differentiation in freshwater taxa.This study employs the cold-adapted fish genus Schizothorax as a biogeographic proxy to reconstruct the evolutionary history of the Yarlung Tsangpo-Brahmaputra River(YTB),with a focus on a prominent hanging valley tributary-trunk stream system.Phylogeographic analyses of mitochondrial cyt b gene sequences identified a monophyletic QTP-YGP clade comprising species from the Qinghai-Tibet Plateau(QTP)and the Yunnan-Guizhou Plateau(YGP).Within the QTP-YGP lineage,YTB species represent the earliest diverging clade.In contrast,species from the Indus and Ganges basins are more closely related to congeners from the southeastern QTP and YGP.The YTB assemblage is further subdivided into two distinct clades.Molecular dating suggests that the YTB lineage diverged from the broader QTP-YGP group during the early Late Miocene,with the two YTB clades separating in the Late Miocene.We propose that a paleo-Yarlung Tsangpo-Dingba(Dibang)-Brahmaputra river and a Yigong-Parlung-Zayul(Lohit)river were established prior to the Late Miocene and were subsequently captured by the lower Yarlung Tsangpo River—via the Siang and Zhaqu,respectively—during the late Miocene and Quaternary.The modern YTB drainage configuration was established by the late Early Pleistocene.This study underscores the importance of integrating genetic,fauna and geomorphological data to understand the complex evolution of drainages in the eastern Himalayas.展开更多
The development of economical,highly efficient,and stable bifunctional electrocatalysts for both the oxygen evolution reaction(OER)and the oxygen reduction reaction(ORR)remains a critical focus in advancing rechargeab...The development of economical,highly efficient,and stable bifunctional electrocatalysts for both the oxygen evolution reaction(OER)and the oxygen reduction reaction(ORR)remains a critical focus in advancing rechargeable metal-air battery systems.Significant progress has been made in the design of high-performance bifunctional electrocatalysts,the development of novel oxygen electrode architectures,and the in-depth understanding of electrocatalytic mechanisms through combined experimental and computational studies.This work provides a comprehensive review of recent advancements in design strategies for oxygen catalysts,including homogeneous electrodes,asymmetric electrodes,and biomimetic electrodes,are thoroughly discussed and summarized.Then,the advanced catalyst modification strategies for ORR/OER are summarized,focusing on critical factors such as enhancement effect of metalonmental and synergistic enhancement effect in multiple catalyst.Subsequently,a representative performance evaluation is presented,based on the reported oxygen electrodes used in rechargeable metal-air battery applications.By focusing on these key areas,the review outlines the current challenges and future prospects for the development of bifunctional oxygen electrocatalysts,aiming to guide the design of high-performance bifunctional electrocatalysts and to elucidate the underlying mechanisms involved.展开更多
Phosphorous compounds have garnered significant interest as catalysts for the oxygen evolution reaction(OER).However,their catalytic performance often falls short,limiting their widespread application in electrocataly...Phosphorous compounds have garnered significant interest as catalysts for the oxygen evolution reaction(OER).However,their catalytic performance often falls short,limiting their widespread application in electrocatalysis.The objective of this work is to improve the OER performance of nickel metaphosphate(Ni(PO3)2)by incorporating rare-earth europium(Eu).The prepared Eu-Ni(PO3)2exhibits significant electron redistribution and features porous nanosheet arrays.The optimized Eu-Ni(PO3)2exhibits outstanding OER activity,with an overpotential of 273 mV at 10 mA/cm,rapid OER kinetics with a Tafel slope of 39.4 m V/dec,and excellent electrochemical stability.These results surpass the performance of Ni(PO3)2,many reported Ni-based catalysts,and even commercial RuO2.Operando Raman spectroscopy reveals that the improvement of OER performance on Eu-Ni(PO3)2is due to the accelerated formation of surface Ni OOH active species and the enhanced interfacial water enrichment during OER.Density functional theory(DFT)calculations further demonstrate that Eu doping induces electronic modulation between the Eu sites and adjacent O-Ni sites,resulting in an optimized thermodynamic pathway with balanced adsorption energies for key oxygen intermediates,thus alleviating thermodynamic limitations during OER.展开更多
Root-inspired anchorage systems in the field of bio-inspired geotechnics are renowned for enhancing the pullout capacity of traditional geotechnical anchorage systems by simulating the morphology and architecture of p...Root-inspired anchorage systems in the field of bio-inspired geotechnics are renowned for enhancing the pullout capacity of traditional geotechnical anchorage systems by simulating the morphology and architecture of plant root systems.However,limited studies have explored their practical applications,particularly in improving slope stability.To fill this gap,this study investigates the reinforcement effect of root-inspired anchors on slope stabilization using transparent soil modeling and 3D-printed anchors,and examines the impact of anchor branching patterns(i.e.branching numbers,branching angle,and branching nodes)on slope bearing capacity,shear band evolution,and temporal and spatial variation of slope deformation.The results show that peak slope bearing capacity increases with branching numbers and branching angles,correlating with the envelope area of the curved shear band.Upper anchors result in step-like deflections in the shear band near the trailing edge,while lower anchors convert the upward concave shear band into an upward convex one,thus increasing the slope bearing capacity.Slope deformation is minimized with intermediate branching parameters,such as a branching number of 4 and a branching angle of 45°.The anchor reinforcement mechanisms,i.e.anchor rod shear resistance,interface friction,anchor pullout capacity,and plate tightening effects,are comprehensively discussed,and the installation effects resulting from compromise slope modeling are identified as the contributors.These findings shed light on the failure process of root-inspired anchors reinforced slopes and provide a preliminary reference for potential applications,especially for the tradeoff between anchor branching,slope deformation,and slope stability.展开更多
Cemented rockfill(CRF)combines structural support with sustainable reuse of coal-derived solid waste.This study integrates digital image correlation,acoustic emission monitoring,and finite-discrete element simulations...Cemented rockfill(CRF)combines structural support with sustainable reuse of coal-derived solid waste.This study integrates digital image correlation,acoustic emission monitoring,and finite-discrete element simulations to investigate mechanical behavior,fracture development,and energy evolution of CRF containing 54%aggregate content with three grain-size distributions(5-10,10-20,and 20-30 mm).Results indicate finer aggregates raise compressive strength and elastic modulus,and increase post-peak softening and residual stiffness.Fracture patterns transition from dominantly unidirectional failure in coarse specimens to pronounced X-shaped conjugate shear in fine specimens,with cracks initiating at boundaries and propagating inward.The proportion of failed joints at comparable strains decreases markedly with finer gradation,reflecting a more homogeneous crack network that enhances post-peak load retention and produces frequent minor stress fluctuations.Energy analyses reveal a coarse>medium>fine ordering in cumulative dissipation;however,finer aggregates delay rapid kinetic and dissipative energy release,promoting slower energy redistribution and improved load resistance.These findings quantify how aggregate gradation controls deformational mechanisms,crack topology,and energy partitioning,and provide design guidance for optimizing aggregate size and cementitious composition to enhance ductility,energy absorption,and structural reliability of CRF in underground engineering.展开更多
Underground carbon sequestration(CS)by solid waste backfill(SWB)offers an effective pathway for collaborative disposal of coal-based solid waste and CO2,where the amount of carbon sequestration is an important eval...Underground carbon sequestration(CS)by solid waste backfill(SWB)offers an effective pathway for collaborative disposal of coal-based solid waste and CO2,where the amount of carbon sequestration is an important evaluation parameter.In this study,the concept of whole-process carbon sequestration using coal-based solid waste and CO2,including sequential stirring and curing stages,was proposed to evaluate the performance evolution of CS.The results showed that CO2 pressure and ambient temperature positively correlated with the CS amount from coal-based SWB.In particular,CO2 pressure prevailed in the stirring stage,while the ambient temperature effect was more significant in the curing stage.The CS amounts obtained during the stirring stage alone,the curing stage alone,and two sequential stages ranged from 0.66%–3.10%,3.53%–5.09%,and 5.12%–6.02%,respectively.The functional group and micromorphology analyses revealed that the prevailing mechanism at the CS stirring stage was the stirringdriven gas dissolution-leaching-mineralization reaction,while that at the curing stage was the hydration-driven gas permeation-dissociation-CS reaction.Both were essentially solid-liquid-gas multiphase chemical reactions.The results are instrumental in substantiating the coal-based SWB carbon sequestration evolution patterns and mechanisms and providing data support for waste disposal and carbon emission reduction in the coal industry.展开更多
The oxygen evolution reaction(OER)suffers from sluggish kinetics,necessitating efficient electrocatalysts to reduce overpotentials in water splitting.Currently recognized OER mechanisms primarily include the adsorbate...The oxygen evolution reaction(OER)suffers from sluggish kinetics,necessitating efficient electrocatalysts to reduce overpotentials in water splitting.Currently recognized OER mechanisms primarily include the adsorbate evolution mechanism(AEM),lattice oxygen mechanism(LOM),and oxide path mechanism(OPM).Compared to AEM,limited by scaling relationships,and LOM,constrained by stability issues,the OPM offers a promising alternative by enabling direct O-O bond formation via dual active sites,thus bypassing*OOH intermediates and lattice O involvement and achieving a balance between activity and durability.However,activating the OPM process requires precise control over the spatial and electronic structure of active sites,making the design of OPM-based catalysts challenging.While previous reviews have focused on homo/heteronuclear diatomic perspectives of OPM-based catalysts,it is urgent to systematically summarize design strategies to provide a rational reference for their development.Herein,a review of design strategies for OPM-based OER catalysts across three scales is comprehensively presented,including in-situ engineering,doping-enabled sites reconstruction,and introducing new sites for nanoparticles,direct synthesis or post-treatments for molecular catalysts,and doping or template strategies for atom pairs or arrays.The unique advantage of atom arrays is also highlighted,and their future research directions and possible strategies are discussed.This review provides a systematic summary and forward-looking perspectives for rationally designing high-performance OPM-based OER catalysts.展开更多
The dynamic evolution of fracture permeability presents a critical scientific challenge in rock masses.Understanding the mechanisms of rock mass permeability evolution is vital for engineering project design and opera...The dynamic evolution of fracture permeability presents a critical scientific challenge in rock masses.Understanding the mechanisms of rock mass permeability evolution is vital for engineering project design and operations.By integrating the discrete element method(DEM)with the finite element method(FEM),a numerical simulation framework for shear seepage in rough fractured shale has been developed to investigate the dynamic mechanisms of permeability evolution under varying confining pressures and during the shearing process.Numerical simulations were conducted on rough fractured samples under effective confining pressures ranging from 5 MPa to 20 MPa to monitor the aperture and permeability evolution of the fracture.The results of the numerical simulation are consistent with the experimental observations,indicating that both the shearing process and confining pressure significantly influence permeability.Moreover,the magnitude of the confining pressure is a crucial factor influencing the trend in permeability changes.Under a confining pressure of 5 MPa,fracture permeability initially increases significantly but decreases post-shearing.In contrast,a continuous decrease in fracture permeability is observed when the confining pressure exceeds 10 MPa.The results of the shear numerical simulation indicate that the confining pressure restricts fracture dilation during shearing,promotes the generation of rock debris,and decreases both the permeability and transmissivity of the fracture.The wear results obtained from numerical simulations are consistent with the experimental patterns and correlate with the joint roughness coefficient(JRC).This study proposed an effective numerical simulation method to reveal the evolution mechanism of fracture flow capacity,taking into account the wear of the fracture surface in shear simulations and the initial stress state of the rock in seepage simulations.This research explains the permeability evolution mechanism of fractured shale from a microscopic perspective,and the proposed numerical simulation method for shear seepage provides a powerful means to uncover the dynamic evolution mechanisms governing fracture permeability.展开更多
The augmented evolution equation is established under the framework of the Variation Evolving Method(VEM)that seeks optimal solutions by solving the transformed Initial-Value Problems(IVPs).To improve the numerical pe...The augmented evolution equation is established under the framework of the Variation Evolving Method(VEM)that seeks optimal solutions by solving the transformed Initial-Value Problems(IVPs).To improve the numerical performance,its compact form is developed herein.Through replacing the states and costates variation evolution with that of the controls,the dimension-reduced Evolution Partial Differential Equation(EPDE)only solves the control variables along the variation time to get the optimal solution,and the initial conditions for the definite solution may be arbitrary.With this equation,the scale of the resulting IVPs,obtained via the semi-discrete method,is significantly reduced and they may be solved with common Ordinary Differential Equation(ODE)integration methods conveniently.Meanwhile,the state and the costate dynamics share consistent stability in the numerical computation and this avoids the intrinsic numerical difficulty as in the indirect methods.Numerical examples are solved and it is shown that the compact form evolution equation outperforms the primary form in the precision,and the efficiency may be higher for the dense discretization.Actually,it is uncovered that the compact form of the augmented evolution equation is a continuous realization of the Newton type iteration mechanism.展开更多
As a core component in the electrochemical water splitting system,the cathode catalyst is capable of boosting the kinetics of the hydrogen evolution reaction(HER),while the scarcity and expenditure of current noble me...As a core component in the electrochemical water splitting system,the cathode catalyst is capable of boosting the kinetics of the hydrogen evolution reaction(HER),while the scarcity and expenditure of current noble metal-based electrocatalysts seriously restrict the large-scale commercial development of hydrogen manufacturing devices.Here,we present a robust and controllable self-assembly method for the spatial construction of three-dimensional(3D)porous ternary nanoarchitectures comprising Ti3C2Tx MXene,MoS2nanosheets,and graphene(MX/MoS2/G).This bottom-up strategy contributes to the intriguing structural features of the resulting nanoarchitectures,including 3D crosslinked porous networks,ultrathin walls,plentiful exposed reactive sites,and numerous efficient electron channels.As a consequence,the optimized MX/MoS2/G electrocatalyst depicts superior electrocatalytic HER performance in terms of a competitive onset potential,a small Tafel slope,a large electrochemically active surface area,and exceptional durability,which significantly outperforms the bare MXene,MoS2,graphene,as well as binary MXene/graphene and MoS2/graphene electrocatalysts.展开更多
基金National Social Science Foundation of China,No.21FSHB014National Natural Science Foundation of China,No.42001196。
摘要Influenced by globalization,rural transition in developed Western countries has experienced processes of productivism,post-productivism,and multifunctional development.By contrast,rural transition in most developing countries has been accompanied by rapid urbanization,which has become a core topic in geography research.As the world’s largest developing country,China has undergone profound development since the reform and opening-up.Moreover,rural spaces in some eastern coastal areas have entered the stage of reconstruction after decades of industrialization and urbanization.This paper takes Suzhou as the case area and measures the process of rural transition from 1990 to 2015 by constructing an index system.It then analyzes the characteristics of space-time evolution using exploratory spatial data analysis(ESDA)methods to reveal the influence of economic and social development on rural transition.The results show that rural transition,which generally entails the weakening of rurality and enhancing of urbanity on a macro scale,tends to be heterogeneous across different regions on a micro scale.This paper argues that multifunctionality will be the main future trend of rural transition in rapidly urbanizing areas.The experience in Suzhou could provide an example for establishing policies on sustainable development in rural spaces and achieving urban-rural co-governance.
基金supported by the National Science and Technology Special Grant of China (No. 2017zx05036-004)
摘要Fine-grained rocks(FGR) are the important source rocks and reservoirs of shale hydrocarbon which is the prospect hotspot at present. Widely distributed fine-grained sediments(FGS) of the upper fourth member of Shahejie Formation in Dongying depression are taken as an example to study the space-time evolution and controlling factor of FGS in this paper. Based on the analysis of well cores, thin sections, inorganic and organic geochemistry indicators, FGR are divided into 7 types of lithofacies. Through the study of ‘point-line-plane', this study shows that FGS has the characteristics of rhythum, diversity and succession. The first stage is characterized by clayey FGS(massive claystone). The second stage is characterized by carbonate FGS(low-TOC laminated limestone) and dolomitic FGS(dolomitic-silty shale) formed by transgression. The third stage is characterized by organic-rich carbonate FGS(middle/high-TOC laminated limestone) distributed in cycle. The fourth stage is characterized by FGS mixed carbonate and siliciclastic sediments(calcareous-silty shale). A variety of space-time evolution of FGS are controlled by multiple factors including tectonism, climate and lake conditions.
摘要By using MTS815 rock mechanics test system,a series of acoustic emission(AE) location experiments were performed under unloading confining pressure,increasing the axial stress.The AE space-time evolution regularities and energy releasing characteristics during deformation and failure process of coal of different loading rates are compared,the influence mechanism of loading rates on the microscopic crack evolution were studied,combining the AE characteristics and the macroscopic failure modes of the specimens,and the precursory characteristics of coal failure were also analyzed quantitatively.The results indicate that as the loading rate is higher,the AE activity and the main fracture will begin earlier.The destruction of coal body is mainly the function of shear strain at lower loading rate and tension strain at higher rate,and will transform from brittleness to ductility at critical velocities.When the deformation of the coal is mainly plasticity,the amplitude of the AE ringing counting rate increases largely and the AE energy curves appear an obvious ''step'',which can be defined as the first failure precursor point.Statics of AE information shows that the strongest AE activity begins when the axial stress level was 92-98%,which can be defined as the other failure precursor point.As the loading rate is smaller,the coal more easily reaches the latter precursor point after the first one,so attention should be aroused to prevent dynamic disaster in coal mining when the AE activity reaches the first precursor point.
基金supported by the National Natural Science Foundation of China(No.22279036)the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(No.B21003).
摘要Designing effective electrocatalysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)is essential for the advancement of water electrolysis.Herein,iridium-doped CoSe2(Ir–CoSe2)nanobelts with tailored d-band center are designed to boost both HER and OER in alkaline electrolytes.On the one hand,the adsorption ability of H2O and hydrogen on Ir–CoSe2 is increased due to the upshifted d-band center induced by the electron transfer from CoSe2 to Ir,inducing good HER activity with an overpotential of 126 mV at 10 mA cm-2.On the other hand,the upshifted d-band center of Ir–CoSe2 facilitates the H2O adsorption and ensures the effective exposure of real active sites,resulting in good OER activity with an overpotential of 239 mV at 10 mA cm-2.Meanwhile,when using Ir–CoSe2 as catalysts for alkaline overall water splitting on both HER and OER,a lower voltage of 1.57 V at 10 mA cm-2 is achieved,indicating a good activity and great potential for practical water electrolysis.This work gives an effective method for the rational design of electrocatalysts with customized d-band structures for bifunctional catalysis.
基金Guangdong Basic and Applied Basic Research Foundation(2023B1515120050,2023A1515110529 and 2024A1515012454)Shenzhen Science and Technology Program(JCYJ20230807145759008 and KJZD20240903100206009).
摘要Acetolactate synthase(ALS)-targeting herbicides are among the most widely used weed-control chemicals globally.Mutations in the ALS gene can confer herbicide resistance in crops,thereby allowing selective elimination of weeds without harming crops.Herbicide-resistant ALS alleles were initially discovered in weeds and subsequently developed through artificial mutagenesis techniques.With the advancement of CRISPR/Cas technologies,various genome-editing tools are now available to introduce these resistant alleles,as well as novel variants,into diverse crop species.Moreover,emerging methodologies,such as directed evolution,enable the generation and screening of large populations of random ALS mutants.Consequently,ALS has become one of the most extensively targeted genes in plant gene evolution.This paper provides a comprehensive overview of both conventional and recently developed strategies for ALS evolution,with particular emphasis on CRISPR/Cas-based genome editing and directed evolution.Future perspectives on technological application are also discussed.By advancing our understanding of herbicide-resistant ALS allele development for crop improvement,these methodologies may also pave the way for their application to the evolution of other agronomically important genes.
基金funded by the Beijing Natural Science Foundation(Grant No.JQ21028)the National Natural Science Foundation of China(Grant Nos.52311530070 and 52004015).
摘要The study of the effects of thermal damage on the mineral components,microstructure,and macroscopic physico-mechanical properties of rocks can provide valuable references for rock engineering design and long-term safety evaluations.In this work,we systematically study the evolution of microstructure and variations in the mechanical properties of granite under high-temperature conditions.The microstructural changes and macro-mechanical properties of rocks are investigated across a temperature range of 25℃–1000℃ through the application of characterization techniques,macro-mechanical experiments,and numerical simulations.High temperatures induce the gradual evolution of micropores and mesopores into macropores,culminating in a significant increase in porosity,with the most rapid rate of increase occurring at 400℃.The X-ray diffraction(XRD)results indicate that the high-temperature environment(below 1000℃)specifically affects the intensity of the maximum diffraction peaks and the half-height width(FWHM)of each mineral component in the granite.The scanning electron microscope(SEM)observation confirms the development of fracture and the reduction in cementation between mineral particles under different temperatures.Additionally,uniaxial and triaxial compression tests were conducted using the GCTS mechanical loading system.Experimental results reveal that the threshold temperature for granite damage is 400℃,and the temperature range for the brittle-ductile transition of granite lies roughly between 600℃ and 800℃.Numerical simulations were performed by employing non-homogeneous rock damage theory and a thermal-mechanical-damage coupling model.Simulated results align well with experimental data.Specifically,the simulations demonstrate that high-temperature treatment causes the redistribution of microstructure in granite,resulting in increased heterogeneity and a change in the failure morphology.
基金Project supported by the National Key R&D Program of China(2021YFA1501101)the National Natural Science Foundation of China(22425105,22221001,22271124,22471103,22201111)+3 种基金the 111 Project(B2007)the Young Elite Scientists Sponsorship Program by CAST(2023QNRC001)Science and Technology Major Plan of Gansu Province(24ZD13GA015,23ZDGA012,23ZDKA014)the Natural Science Foundation Key Project of Gansu Province(24JRRA394)
摘要The reaction pathway plays a pivotal role in determining the catalytic activity of the oxygen evolution reaction(OER).However,regulating the microscopic reaction pathway through interface construction remains a significant challenge.In this study,an interface between amorphous rare earth hydroxides and crystalline spinel NiCo2O4was constructed via selective oxidation.The interface structural units accelerate reconstruction,leading to enhanced catalytic activity,which was observed by in situ Raman spectroscopy.The amorphous RE(OH)3(RE=Y and Eu)optimize asymmetric Ni-Co dual-sites,thereby altering the OER reaction pathway.Specifically,Y(OH)3/NiCo2O4operates through the lattice oxygen mechanism(LOM)at the expense of structural stability,whereas Eu(OH)3/NiCo2O4follows the oxygen pathway mechanism(OPM),preserving both catalytic activity and stability.This study offers a novel approach to controlling reaction pathways and proposes a new strategy for interface construction using rare earth hydroxides.
基金supported by the Innovative Research Group Project of the National Natural Science Foundation of China(Grant No.42121001).
摘要Alleviating the imbalance between urban and rural areas for regional coordinated development is an imperative response to the Sustainable Development Goal 10 of the United Nations.To track China’s urban-rural integration progress and address the uneven issues in specific fields,this study constructed a novel seven-dimension index system of urban-rural integration,comprising free population mobility,efficient land transfer,interactive economic growth,highly-linked transportation,equal public services,joint environmental governance and unimpeded informatization between urban and rural areas.Based on a comprehensive measurement framework and multi-source panel data,we uncovered the spatial-temporal evolution of urban-rural integration in China’s 367 prefecture-level administrative units from 1980 to 2022.The results demonstrated that China’s urban-rural integration steadily increased from 27.51 to 57.35 with an average annual growth rate of 3.40%.Whereas,the overall urban-rural integration was relatively inferior in 2022,at the level of moderate integration whose proportion of China’s land area was 88.08%.The urban-rural integration level in eastern region and urban agglomerations was higher than that in mid-west and non-urban agglomerations.From the perspective of seven dimensions,interactive economic growth,joint environmental governance and unimpeded informatization made an obvious improvement and reached higher integration,while free population mobility,efficient land transfer,highly-linked transportation and equal public services maintained the stage of moderate integration in 2022.In the future,China should make targeted efforts for urban-rural integration in terms of population,land use,transportation and public services,and accelerate urban-rural common prosperity in the mid-west and economically underdeveloped areas.
基金supported by the National Natural Science Foun-dation of China(Nos.U24A2026 and52271033)the Natural Science Foundation of Jiangsu Province,China(No.BK20221493).
摘要Multi-component transition metal carbides(MTMCs)have garnered significant attention for their out-standing high-temperature stability and versatile properties,which make them ideal candidates for a wide range of industrial applications.However,the underlying mechanisms governing the crystal growth and morphological evolution of MTMCs remain poorly understood,hindering the design of materials with tailored characteristics.In this paper,we employ an in-situ liquid-solid reaction method to synthesize(HfTaZrNbTi)C MTMC powders and explore their crystal growth and morphology evolution.The synthesized(TiZrHfNbTa)C powders exhibit two distinct morphologies:cubic,primarily composed of Ti,Hf,Ta,and Zr with a small amount of Nb,and octahedral,rich in Ti and Ta with minor amounts of Hf,Nb,and Zr.First-principles calculations show that the surface energy of the(100)plane is lower than the(111)plane,leading to the formation of the cubic morphology.The octahedral morphology forms due to decreased mixing entropy and higher theoretical density compared to cubic particles.Our findings provide valuable insights into the crystal growth and morphology evolution mechanisms of high-entropy ceramics,contributing to the rational design of MTMCs with engineered crystal structures for diverse structural and functional applications.
基金supported by the National Basic Research Program of China(No.2018YFA0702001)the National Natural Science Foundation of China(Nos.22225901,22175162 and 21975237)+7 种基金the Fundamental Research Funds for the Central Universities(No.WK2340000101)the USTC Research Funds of the Double First-Class Initiative(Nos.YD2340002007 and YD9990002017)the Open Funds of the State Key Laboratory of Rare Earth Resource Utilization(No.RERU2022007)the China Postdoctoral Science Foundation(Nos.2023M733371,2022M723032 and 2023T160617)the Natural Science Foundation Youth Project of Anhui Province(No.2308085QB37)the China National Postdoctoral Program for Innovative Talents(No.BX20230340)Statesponsored Postdoctoral Researcher Program(No.GZC20230008)Postdoctoral Research Funding Project of Anhui Province(No.2023B727).
摘要The CO2 electroreduction reaction(CO2RR)is a promising approach of using renewable electricity to synthesize fuels and value-added chemicals.At present,Cu is generally considered to be the major monometallic catalyst capable of producing multicarbon products(C2+)with high current densities from the CO2RR,but it still suffers from the low activity and high overpotential.The challenge of sluggish CO2RR kinetics can be overcome by developing efficient Cu-based catalysts,which undergo the dynamic evolution during the reaction process.The dynamic evolution of the Cu-based catalysts taking place under working conditions makes it difficult to study the structure-activity correlation and reaction mechanism present during CO2RR.Recently,a number of important works have observed and revealed the dynamic evolution process of Cu-based catalysts by operando characterization techniques.This aspect,however,remains less summarized and prospected in the CO2RR literature.In this Review,we summarize the dynamic evolution of Cu-based catalysts during the CO2RR from aspects of structure,composition and oxidation state.We highlight the correlations between evolution behaviors and catalytic properties.Then,we discuss the dynamic deactivation process of Cu-based catalysts during CO2RR,including metal impurities contamination and carbon accumulation.In particular,we introduce recent advancements in in situ characterization techniques those are employed to probe the dynamic evolution under operating conditions.We end the Review by outlining the challenges and offering personal perspectives on the future development opportunities in this field.
基金supported by the Second Qinghai-Tibet Plateau Scientific Expedition and Research Program(Grant no.2024QZKK0200)the National Natural Science Foundation of China(Grant no.32070436)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB31040101).
摘要The unique geomorphology of rivers in the eastern Himalaya has long intrigued geologists,yet their drainage history remains debated.Drainage reorganization can have a significant impact on genetic differentiation in freshwater taxa.This study employs the cold-adapted fish genus Schizothorax as a biogeographic proxy to reconstruct the evolutionary history of the Yarlung Tsangpo-Brahmaputra River(YTB),with a focus on a prominent hanging valley tributary-trunk stream system.Phylogeographic analyses of mitochondrial cyt b gene sequences identified a monophyletic QTP-YGP clade comprising species from the Qinghai-Tibet Plateau(QTP)and the Yunnan-Guizhou Plateau(YGP).Within the QTP-YGP lineage,YTB species represent the earliest diverging clade.In contrast,species from the Indus and Ganges basins are more closely related to congeners from the southeastern QTP and YGP.The YTB assemblage is further subdivided into two distinct clades.Molecular dating suggests that the YTB lineage diverged from the broader QTP-YGP group during the early Late Miocene,with the two YTB clades separating in the Late Miocene.We propose that a paleo-Yarlung Tsangpo-Dingba(Dibang)-Brahmaputra river and a Yigong-Parlung-Zayul(Lohit)river were established prior to the Late Miocene and were subsequently captured by the lower Yarlung Tsangpo River—via the Siang and Zhaqu,respectively—during the late Miocene and Quaternary.The modern YTB drainage configuration was established by the late Early Pleistocene.This study underscores the importance of integrating genetic,fauna and geomorphological data to understand the complex evolution of drainages in the eastern Himalayas.
基金financially supported by the National Natural Science Foundation of China(52302084)the National Key Research and Development Program of China(2022YFE0138900)+1 种基金Fundamental Research Funds for the Central Universities(2232025D-24)the Qin Shen Scholar Program of Jiaxing University。
摘要The development of economical,highly efficient,and stable bifunctional electrocatalysts for both the oxygen evolution reaction(OER)and the oxygen reduction reaction(ORR)remains a critical focus in advancing rechargeable metal-air battery systems.Significant progress has been made in the design of high-performance bifunctional electrocatalysts,the development of novel oxygen electrode architectures,and the in-depth understanding of electrocatalytic mechanisms through combined experimental and computational studies.This work provides a comprehensive review of recent advancements in design strategies for oxygen catalysts,including homogeneous electrodes,asymmetric electrodes,and biomimetic electrodes,are thoroughly discussed and summarized.Then,the advanced catalyst modification strategies for ORR/OER are summarized,focusing on critical factors such as enhancement effect of metalonmental and synergistic enhancement effect in multiple catalyst.Subsequently,a representative performance evaluation is presented,based on the reported oxygen electrodes used in rechargeable metal-air battery applications.By focusing on these key areas,the review outlines the current challenges and future prospects for the development of bifunctional oxygen electrocatalysts,aiming to guide the design of high-performance bifunctional electrocatalysts and to elucidate the underlying mechanisms involved.
基金Project supported by Natural Science Foundation of Jiangsu Province(BK20221321)JSPS KAKENHI(JP23K13703)
摘要Phosphorous compounds have garnered significant interest as catalysts for the oxygen evolution reaction(OER).However,their catalytic performance often falls short,limiting their widespread application in electrocatalysis.The objective of this work is to improve the OER performance of nickel metaphosphate(Ni(PO3)2)by incorporating rare-earth europium(Eu).The prepared Eu-Ni(PO3)2exhibits significant electron redistribution and features porous nanosheet arrays.The optimized Eu-Ni(PO3)2exhibits outstanding OER activity,with an overpotential of 273 mV at 10 mA/cm,rapid OER kinetics with a Tafel slope of 39.4 m V/dec,and excellent electrochemical stability.These results surpass the performance of Ni(PO3)2,many reported Ni-based catalysts,and even commercial RuO2.Operando Raman spectroscopy reveals that the improvement of OER performance on Eu-Ni(PO3)2is due to the accelerated formation of surface Ni OOH active species and the enhanced interfacial water enrichment during OER.Density functional theory(DFT)calculations further demonstrate that Eu doping induces electronic modulation between the Eu sites and adjacent O-Ni sites,resulting in an optimized thermodynamic pathway with balanced adsorption energies for key oxygen intermediates,thus alleviating thermodynamic limitations during OER.
基金supported by the High-end Foreign Expert Introduction Program(Grant No.G2022165004L)the Sichuan Transportation Science and Technology Project(Grant No.2018-ZL-01)China Railway 20th Bureau Science and Technology Project(Grant No.YF1900SD07B).
摘要Root-inspired anchorage systems in the field of bio-inspired geotechnics are renowned for enhancing the pullout capacity of traditional geotechnical anchorage systems by simulating the morphology and architecture of plant root systems.However,limited studies have explored their practical applications,particularly in improving slope stability.To fill this gap,this study investigates the reinforcement effect of root-inspired anchors on slope stabilization using transparent soil modeling and 3D-printed anchors,and examines the impact of anchor branching patterns(i.e.branching numbers,branching angle,and branching nodes)on slope bearing capacity,shear band evolution,and temporal and spatial variation of slope deformation.The results show that peak slope bearing capacity increases with branching numbers and branching angles,correlating with the envelope area of the curved shear band.Upper anchors result in step-like deflections in the shear band near the trailing edge,while lower anchors convert the upward concave shear band into an upward convex one,thus increasing the slope bearing capacity.Slope deformation is minimized with intermediate branching parameters,such as a branching number of 4 and a branching angle of 45°.The anchor reinforcement mechanisms,i.e.anchor rod shear resistance,interface friction,anchor pullout capacity,and plate tightening effects,are comprehensively discussed,and the installation effects resulting from compromise slope modeling are identified as the contributors.These findings shed light on the failure process of root-inspired anchors reinforced slopes and provide a preliminary reference for potential applications,especially for the tradeoff between anchor branching,slope deformation,and slope stability.
基金funding from the National Natural Science Foundation of China(Nos.52478389 and 52525401).
摘要Cemented rockfill(CRF)combines structural support with sustainable reuse of coal-derived solid waste.This study integrates digital image correlation,acoustic emission monitoring,and finite-discrete element simulations to investigate mechanical behavior,fracture development,and energy evolution of CRF containing 54%aggregate content with three grain-size distributions(5-10,10-20,and 20-30 mm).Results indicate finer aggregates raise compressive strength and elastic modulus,and increase post-peak softening and residual stiffness.Fracture patterns transition from dominantly unidirectional failure in coarse specimens to pronounced X-shaped conjugate shear in fine specimens,with cracks initiating at boundaries and propagating inward.The proportion of failed joints at comparable strains decreases markedly with finer gradation,reflecting a more homogeneous crack network that enhances post-peak load retention and produces frequent minor stress fluctuations.Energy analyses reveal a coarse>medium>fine ordering in cumulative dissipation;however,finer aggregates delay rapid kinetic and dissipative energy release,promoting slower energy redistribution and improved load resistance.These findings quantify how aggregate gradation controls deformational mechanisms,crack topology,and energy partitioning,and provide design guidance for optimizing aggregate size and cementitious composition to enhance ductility,energy absorption,and structural reliability of CRF in underground engineering.
基金supported by the National Key R&D Program of China(No.2023YFC3904304)the National Natural Science Foundation of China(No.52304158)Jiangsu Key Laboratory for Clean Utilization of Carbon Resources Research Project(No.BM2024007)。
摘要Underground carbon sequestration(CS)by solid waste backfill(SWB)offers an effective pathway for collaborative disposal of coal-based solid waste and CO2,where the amount of carbon sequestration is an important evaluation parameter.In this study,the concept of whole-process carbon sequestration using coal-based solid waste and CO2,including sequential stirring and curing stages,was proposed to evaluate the performance evolution of CS.The results showed that CO2 pressure and ambient temperature positively correlated with the CS amount from coal-based SWB.In particular,CO2 pressure prevailed in the stirring stage,while the ambient temperature effect was more significant in the curing stage.The CS amounts obtained during the stirring stage alone,the curing stage alone,and two sequential stages ranged from 0.66%–3.10%,3.53%–5.09%,and 5.12%–6.02%,respectively.The functional group and micromorphology analyses revealed that the prevailing mechanism at the CS stirring stage was the stirringdriven gas dissolution-leaching-mineralization reaction,while that at the curing stage was the hydration-driven gas permeation-dissociation-CS reaction.Both were essentially solid-liquid-gas multiphase chemical reactions.The results are instrumental in substantiating the coal-based SWB carbon sequestration evolution patterns and mechanisms and providing data support for waste disposal and carbon emission reduction in the coal industry.
基金funding from the National Natural Science Foundation of China(22378289)the Key Central Government Guides Local Funds for Science and Technology Development(YDZJSX2022A021)the special fund for Science and Technology Innovation Teams of Shanxi Province(202304051001026)。
摘要The oxygen evolution reaction(OER)suffers from sluggish kinetics,necessitating efficient electrocatalysts to reduce overpotentials in water splitting.Currently recognized OER mechanisms primarily include the adsorbate evolution mechanism(AEM),lattice oxygen mechanism(LOM),and oxide path mechanism(OPM).Compared to AEM,limited by scaling relationships,and LOM,constrained by stability issues,the OPM offers a promising alternative by enabling direct O-O bond formation via dual active sites,thus bypassing*OOH intermediates and lattice O involvement and achieving a balance between activity and durability.However,activating the OPM process requires precise control over the spatial and electronic structure of active sites,making the design of OPM-based catalysts challenging.While previous reviews have focused on homo/heteronuclear diatomic perspectives of OPM-based catalysts,it is urgent to systematically summarize design strategies to provide a rational reference for their development.Herein,a review of design strategies for OPM-based OER catalysts across three scales is comprehensively presented,including in-situ engineering,doping-enabled sites reconstruction,and introducing new sites for nanoparticles,direct synthesis or post-treatments for molecular catalysts,and doping or template strategies for atom pairs or arrays.The unique advantage of atom arrays is also highlighted,and their future research directions and possible strategies are discussed.This review provides a systematic summary and forward-looking perspectives for rationally designing high-performance OPM-based OER catalysts.
基金funded by the Joint Funds of the National Natural Science Foundation of China(Grant No.U23A20671)the Major Project of Inner Mongolia Science and Technology(Grant No.2021ZD0034)the Open Research Fund of State Key Laboratory of Geomechanics and Geotechnical Engi-neering(Grant No.Z021003).
摘要The dynamic evolution of fracture permeability presents a critical scientific challenge in rock masses.Understanding the mechanisms of rock mass permeability evolution is vital for engineering project design and operations.By integrating the discrete element method(DEM)with the finite element method(FEM),a numerical simulation framework for shear seepage in rough fractured shale has been developed to investigate the dynamic mechanisms of permeability evolution under varying confining pressures and during the shearing process.Numerical simulations were conducted on rough fractured samples under effective confining pressures ranging from 5 MPa to 20 MPa to monitor the aperture and permeability evolution of the fracture.The results of the numerical simulation are consistent with the experimental observations,indicating that both the shearing process and confining pressure significantly influence permeability.Moreover,the magnitude of the confining pressure is a crucial factor influencing the trend in permeability changes.Under a confining pressure of 5 MPa,fracture permeability initially increases significantly but decreases post-shearing.In contrast,a continuous decrease in fracture permeability is observed when the confining pressure exceeds 10 MPa.The results of the shear numerical simulation indicate that the confining pressure restricts fracture dilation during shearing,promotes the generation of rock debris,and decreases both the permeability and transmissivity of the fracture.The wear results obtained from numerical simulations are consistent with the experimental patterns and correlate with the joint roughness coefficient(JRC).This study proposed an effective numerical simulation method to reveal the evolution mechanism of fracture flow capacity,taking into account the wear of the fracture surface in shear simulations and the initial stress state of the rock in seepage simulations.This research explains the permeability evolution mechanism of fractured shale from a microscopic perspective,and the proposed numerical simulation method for shear seepage provides a powerful means to uncover the dynamic evolution mechanisms governing fracture permeability.
基金supported by the National Nature Science Foundation of China under Grant No.11902332。
摘要The augmented evolution equation is established under the framework of the Variation Evolving Method(VEM)that seeks optimal solutions by solving the transformed Initial-Value Problems(IVPs).To improve the numerical performance,its compact form is developed herein.Through replacing the states and costates variation evolution with that of the controls,the dimension-reduced Evolution Partial Differential Equation(EPDE)only solves the control variables along the variation time to get the optimal solution,and the initial conditions for the definite solution may be arbitrary.With this equation,the scale of the resulting IVPs,obtained via the semi-discrete method,is significantly reduced and they may be solved with common Ordinary Differential Equation(ODE)integration methods conveniently.Meanwhile,the state and the costate dynamics share consistent stability in the numerical computation and this avoids the intrinsic numerical difficulty as in the indirect methods.Numerical examples are solved and it is shown that the compact form evolution equation outperforms the primary form in the precision,and the efficiency may be higher for the dense discretization.Actually,it is uncovered that the compact form of the augmented evolution equation is a continuous realization of the Newton type iteration mechanism.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.22209037 and 52472092)。
摘要As a core component in the electrochemical water splitting system,the cathode catalyst is capable of boosting the kinetics of the hydrogen evolution reaction(HER),while the scarcity and expenditure of current noble metal-based electrocatalysts seriously restrict the large-scale commercial development of hydrogen manufacturing devices.Here,we present a robust and controllable self-assembly method for the spatial construction of three-dimensional(3D)porous ternary nanoarchitectures comprising Ti3C2Tx MXene,MoS2nanosheets,and graphene(MX/MoS2/G).This bottom-up strategy contributes to the intriguing structural features of the resulting nanoarchitectures,including 3D crosslinked porous networks,ultrathin walls,plentiful exposed reactive sites,and numerous efficient electron channels.As a consequence,the optimized MX/MoS2/G electrocatalyst depicts superior electrocatalytic HER performance in terms of a competitive onset potential,a small Tafel slope,a large electrochemically active surface area,and exceptional durability,which significantly outperforms the bare MXene,MoS2,graphene,as well as binary MXene/graphene and MoS2/graphene electrocatalysts.