Copper(Cu)-based catalysts show significant potential for producing high value-added C_(2+)products in electrocatalytic CO_(2)/CO reduction reactions(CO(2)RR).However,the structural reconfiguration during operation po...Copper(Cu)-based catalysts show significant potential for producing high value-added C_(2+)products in electrocatalytic CO_(2)/CO reduction reactions(CO(2)RR).However,the structural reconfiguration during operation poses substantial challenges in identifying the intrinsic catalytic active site,especially under similar mass transport conditions.Herein,three typical and commercial Cu-based catalysts(Cu,CuO,and Cu_(2)O)are chosen as representatives to elucidate the structure-activity relationship of CORR in the membrane electrode assembly electrolyzer.Notably,only the Cu catalyst demonstrates the most suppression of hydrogen evolution reaction,thus achieving the highest FE of 86.7% for C_(2+)products at a current density of 500 mA cm^(-2) and maintaining a stable electrolysis over 110 h at a current of 200 mA cm^(-2).The influence of chemical valence state of Cu,electrochemical surface area,and local pH were firstly investigated and ruled out for the significant FE differences.Finally,based on the structure analysis from high resolution transmission electron microscope,OH-adsorption,in situ infrared spectroscopy and density functional theory calculations,it is suggested that the asymmetric C-C coupling(via ^(*)CHO and ^(*)CO)is the most probable reaction pathway for forming C_(2+)products,with Cu(100)-dominant grain boundaries(GBs)being the most favorable active sites.These findings provide deeper insights into the synergistic relationship between crystal facets and GBs in electrocatalytic systems.展开更多
A thoroughly mechanistic understanding of the electrochemical CO reduction reaction(eCORR)at the interface is significant for guiding the design of high-performance electrocatalysts.However,unintentionally ignored fac...A thoroughly mechanistic understanding of the electrochemical CO reduction reaction(eCORR)at the interface is significant for guiding the design of high-performance electrocatalysts.However,unintentionally ignored factors or unreasonable settings during mechanism simulations will result in false positive results between theory and experiment.Herein,we computationally identified the dynamic site preference change of CO adsorption with potentials on Cu(100),which was a previously unnoticed factor but significant to potential-dependent mechanistic studies.Combined with the different lateral interactions among adsorbates,we proposed a new C–C coupling mechanism on Cu(100),better explaining the product distribution at different potentials in experimental eCORR.At low potentials(from–0.4 to–0.6 V_(RHE)),the CO forms dominant adsorption on the bridge site,which couples with another attractively aggregated CO to form a C–C bond.At medium potentials(from–0.6 to–0.8 VRHE),the hollow-bound CO becomes dominant but tends to isolate with another adsorbate due to the repulsion,thereby blocking the coupling process.At high potentials(above–0.8 VRHE),the CHO intermediate is produced from the electroreduction of hollow-CO and favors the attraction with another bridge-CO to trigger C–C coupling,making CHO the major common intermediate for C–C bond formation and methane production.We anticipate that our computationally identified dynamic change in site preference of adsorbates with potentials will bring new opportunities for a better understanding of the potential-dependent electrochemical processes.展开更多
Research interest in the electrochemical reduction reaction of carbon dioxide(CO_(2)RR)into multicarbon(C_(2+))compounds has been growing significantly with numerous theoretical and experimental studies employing a va...Research interest in the electrochemical reduction reaction of carbon dioxide(CO_(2)RR)into multicarbon(C_(2+))compounds has been growing significantly with numerous theoretical and experimental studies employing a variety of surface modification techniques,such as strong support interactions,heteroatom doping,surface functionalization,and morphology and defect engineering.The collective goal of these strategies is to fine-tune the electrochemical properties of catalysts,thereby breaking the C-C coupling barrier to achieve efficient and selective formation of C_(2+)products.In this review,we critically examine these research efforts,with a particular focus on achieving a comprehensive understanding of the innovative catalyst surface that dictates pathways for electrochemical CO_(2)RR to C_(2+)compounds.We begin by discussing the essential characteristics of catalyst surfaces that demonstrate superior catalytic activity and selectivity.Next,we explore the range of strategies used to create conducive catalyst surfaces.Finally,we provide an overview of catalytic performance and selectivity of materials in synthesizing C_(2+)products based on some high-throughput density functional theory and machine learning screening techniques.展开更多
Light-driven CO_(2) reduction reaction(CO_(2)RR)to value-added ethylene(C2H4)holds significant promise for addressing energy and environmental challenges.While the high energy barriers for*CO intermediates hydrogenati...Light-driven CO_(2) reduction reaction(CO_(2)RR)to value-added ethylene(C2H4)holds significant promise for addressing energy and environmental challenges.While the high energy barriers for*CO intermediates hydrogenation and C–C coupling limit the C_(2)H_(4)generation.Herein,CuxP/g-C_(3)N_(4) heterojunction prepared by an in-situ phosphating technique,achieved collaborative photocatalytic CO_(2) and H2O,producing CO and C_(2)H_(4)as the main products.Notably,the selectivity of C_(2)H_(4)produced by CuxP/g-C_(3)N_(4) attained to 64.25%,which was 9.85 times that of CuxP(6.52%).Detailed time-resolution photoluminescence spectra,femtosecond transient absorption spectroscopy tests and density functional theory(DFT)calculation validate the ultra-fast interfacial electron transfer mechanism in CuxP/g-C_(3)N_(4) heterojunction.Successive*H on P sites caused by adsorbed H2O splitting with moderate hydrogenation ability enables the multi-step hydrogenation during CO_(2)RR process over CuxP/g-C_(3)N_(4).With the aid of mediated asymmetric Cu and P dual sites by g-C_(3)N_(4) nanosheet,the produced*CHO shows an energetically favorable for C–C coupling.The coupling formed*CHOCHO further accepts photoexcited efficient e–and*H to deeply produce C_(2)H_(4)according to the C^(2+)intermediates,which has been detected by in-situ diffuse reflectance infrared Fourier transform spectroscopy and interpreted by DFT calculation.The novel insight mechanism offers an essential understanding for the development of CuxP-based heterojunctions for photocatalytic CO_(2) to C^(2+)value-added fuels.展开更多
The copper-based electrocatalysts feature attractive potentials of converting CO_(2)into multi-carbon(C_(2+))products,while the instability of Cu-O often induces the reduction of Cu^(+)/Cu^(0) catalytic sites at the c...The copper-based electrocatalysts feature attractive potentials of converting CO_(2)into multi-carbon(C_(2+))products,while the instability of Cu-O often induces the reduction of Cu^(+)/Cu^(0) catalytic sites at the cathode and refrains the capability of stable electrolysis especially at high powers.In this work,we developed an Erbium(Er)oxide-modified Cu(Er-O-Cu)catalyst with enhanced covalency of Cu-O and more stable active sites.The f-p-d coupling strengthens the covalency of Cu-O,and the stability of Cu^(+)sites under electroreduction condition is critical for promoting the C-C coupling and improving the C_(2+)product selectivity.As a result,the Er-O-Cu sites exhibited a high Faradaic efficiency of C_(2+)products(FEC_(2+))of 86%at 2200 mA cm^(-2),and a peak partial current density of|j_(C2+)|of 1900 mA cm^(-2),comparable to the best reported values for the CO_(2)-to-C_(2+)electroreduction.The CO_(2)electrolysis by the Er-O-Cu sites was further scaled up to 100 cm^(2)to achieve high-power(~200 W)electrolysis with ethylene production rate of 16 mL min^(-1).展开更多
Electrochemical carbon dioxide reduction reaction(CO_(2)RR)produces valuable chemicals by consuming gaseous CO_(2)as well as protons from the electrolyte.Protons,produced by water dissociation in alkaline electrolyte,...Electrochemical carbon dioxide reduction reaction(CO_(2)RR)produces valuable chemicals by consuming gaseous CO_(2)as well as protons from the electrolyte.Protons,produced by water dissociation in alkaline electrolyte,are critical for the reaction kinetics which involves multiple proton coupled electron transfer steps.Herein,we demonstrate that the two key steps(CO_(2)-^(*)COOH and^(*)CO-^(*)COH)efficiency can be precisely tuned by introducing proper amount of water dissociation center,i.e.,Fe single atoms,locally surrounding the Cu catalysts.In alkaline electrolyte,the Faradaic efficiency(FE)of multi-carbon(C^(2+))products exhibited a volcano type plot depending on the density of water dissociation center.A maximum FE for C^(2+)products of 73.2%could be reached on Cu nanoparticles supported on N-doped Carbon nanofibers with moderate Fe single atom sites,at a current density of 300 mA cm^(–2).Experimental and theoretical calculation results reveal that the Fe sites facilitate water dissociation kinetics,and the locally generated protons contribute significantly to the CO_(2)activation and^(*)CO protonation process.On the one hand,in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy(in-situ ATR-SEIRAS)clearly shows that the^(*)COOH intermediate can be observed at a lower potential.This phenomenon fully demonstrates that the optimized local water dissociation kinetics has a unique advantage in guiding the hydrogenation reaction pathway of CO₂molecules and can effectively reduce the reaction energy barrier.On the other hand,abundant^(*)CO and^(*)COH intermediates create favorable conditions for the asymmetric^(*)CO-^(*)COH coupling,significantly increasing the selectivity of the reaction for C^(2+)products and providing strong support for the efficient conversion of related reactions to the target products.This work provides a promising strategy for the design of a dual sites catalyst to achieve high FE of C^(2+)products through the optimized local water dissociation kinetics.展开更多
Engineering the desired dual metal sites to realize C-C coupling of CO_(2)is of great importance for the practical applications of CO_(2)electroreduction reaction(CER).Herein,an efficient strategy for constructing het...Engineering the desired dual metal sites to realize C-C coupling of CO_(2)is of great importance for the practical applications of CO_(2)electroreduction reaction(CER).Herein,an efficient strategy for constructing heterogeneous Pt^(δ+)-Cu^(δ+)dual sites to strengthen the generation and coupling of*CO and*CHO(or*COH)during CER process is presented in this work.The radiilarger Pt not only stabilizes the Cu^(δ+)ut also induces a tensile strain in Pt^(δ+)-Cu^(δ+)dual sites.The obtained Pt^(δ+)-Cu^(δ+)dual sites achieve a total Faradaic efficiency and current density of C2products with 70.9%and586.9 mA·cm-2at-1.20 V(vs.RHE),which is higher than that of Cu^(δ+)single site(55.4%,286.9 mA·cm^(-2)).The in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy(ATR-SEIRAS)reveals that the Pt^(δ+)-Cu^(δ+)dual sites can promote the generation of C1intermediates(such as*CO,*COOH,*COH,and*CHO)and C-C coupling.Additional in situ surface-enhanced Raman spectra demonstrate that Pt^(δ+)Cu^(δ+)dual sites can induce the generation of the high-frequency peak for*CO_(atop),thus accelerating the C-C coupling.This work provides a promising avenue for stabilizing and enhancing the performance of Cu^(δ+)sites toward CER.展开更多
Photothermal catalytic CO_(2) conversion provides an effective solution targeting carbon neutrality by synergistic utilization of photon and heat.However,the C-C coupling initiated by photothermal catalysis is still a...Photothermal catalytic CO_(2) conversion provides an effective solution targeting carbon neutrality by synergistic utilization of photon and heat.However,the C-C coupling initiated by photothermal catalysis is still a big challenge.Herein,a three-dimensional(3D)hierarchical W_(18)O_(49)/WTe_(2) hollow nanosphere is constructed through in-situ embodying of oxygen vacancy and tellurium on the scaffold of WO_(3).The light absorption towards near-infrared spectral region and CO_(2) adsorption are enhanced by the formation of half-metal WTe_(2) and the unique hierarchical hollow architecture.Combining with the generation of oxygen vacancy with strengthened CO_(2) capture,the photothermal effect on the samples can be sufficiently exploited for activating the CO_(2) molecules.In particular,the close contact between W_(18)O_(49)and WTe_(2) largely promotes the photoinduced charge separation and mass transfer,and thus the~*CHO intermediate formation and fixedness are facilitated.As a result,the C-C coupling can be evoked between tungsten and tellurium atoms on WTe_(2).The ethylene production by optimized W_(18)O_(49)/WTe_(2) reaches 147.6μmol g^(-1)with the selectivity of 80%.The in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and density functional theory(DFT)calculations are performed to unveil the presence and significance of aldehyde intermediate groups in C-C coupling.The half-metallic WTe_(2) cocatalyst proposes a new approach for efficient CO_(2) conversion with solar energy,and may especially create a new platform for the generation of multi-carbon products.展开更多
A fundamental study on C-C coupling,that is the crucial step in the Fischer-Tropsch synthesis(FTS)process to obtain multi-carbon products,is of great importance to tailor catalysts and then guide a more promising path...A fundamental study on C-C coupling,that is the crucial step in the Fischer-Tropsch synthesis(FTS)process to obtain multi-carbon products,is of great importance to tailor catalysts and then guide a more promising pathway.It has been demonstrated that the coupling of CO with the metal carbide can represent the early stage in the FTS process,while the related mechanism is elusive.Herein,the reactions of the CuC3H-and CuC3-cluster anions with CO have been studied by using mass spectrometry and theoretical calculations.The experimental results showed that the coupling of CO with the C3H-moiety of CuC3H can generate the exclusive ion product COC3H-.The reactivity and selectivity of this reaction of CuC3H-with CO are greatly higher than that of the reaction of CuC3-with CO,and this H-assisted C-C coupling process was rationalized by theoretical calculations.展开更多
Photo-reforming methanol into valuable chemicals represents an energetically sustainable alternative to conventional thermal catalysis,yet controlling-specific C-C coupling way still remains elusive.In this work,we re...Photo-reforming methanol into valuable chemicals represents an energetically sustainable alternative to conventional thermal catalysis,yet controlling-specific C-C coupling way still remains elusive.In this work,we report a sulfide-based photocatalytic paradigm,where atomic-level control of nickel species directly dictates reaction selectivity.The electrostatic constructing ZnIn_(2)S_(4)/Zn_(0.5)Cd_(0.5)S(ZIS/ZCS)heterostructures enable single atom Ni to facilitate ethylene glycol(EG)production with a rate of 11.2 mmol·gcat^(−1)·h^(−1),surpassing reported non-precious metal systems,whereas the Ni aggregates drive exclusive formaldehyde formation.The operando spectroscopy and density functional theory reveal dual roles of Ni as electron reservoir and chemical bond breakage inducers,lowering C-H activation barriers while stabilizing·CH2OH intermediates for cross-coupling.This interfacial configuration engineering creates an electron highway that couples carrier dissociation with radical recombination kinetics,achieving atom-economic steering of methanol oxidative valorization.The metal dispersion assisting catalysis correlation here provides a design blueprint for selective bond scission and reconstruction in sustainable organic synthesis.展开更多
Pyridyl-based ketones and 1,6-diketones are both attractive and invaluable scaffolds which play pivotal roles in the construction and structural modification of a plethora of synthetically paramount natural products,p...Pyridyl-based ketones and 1,6-diketones are both attractive and invaluable scaffolds which play pivotal roles in the construction and structural modification of a plethora of synthetically paramount natural products,pharmaceuticals,organic materials and fine chemicals.In this context,we herein demonstrate an unprecedented,robust and generally applicable synthetically strategy to deliver these two crucial ketone frameworks via visible-light-induced ring-opening coupling reactions of cycloalcohols with vinylazaarenes and enones,respectively.A plausible mechanism involves the selectiveβ-C-C bond cleavage of cycloalcohols enabled by proton-coupled electron transfer and ensuing Giese-type addition followed by single electron reduction and protonation.The synthetic methodology exhibits broad substrate scope,excellent functional group compatibility as well as operational simplicity and environmental friendliness.展开更多
Magnetization convenience is crucial consideration for design of valve magnetic actuators.The existing repulsive-magnetic-coupling of 2D maglev valve is not oriented to the integral-magnetization-processes,resulting i...Magnetization convenience is crucial consideration for design of valve magnetic actuators.The existing repulsive-magnetic-coupling of 2D maglev valve is not oriented to the integral-magnetization-processes,resulting in the high assembly cost.This paper presents a novel tractive-magnetic-coupling(TMC)and its application on a 2D electro-hydraulic proportional flow valve(2D-EHPFV),whose configuration not only fulfill the requirements of 2D valve,but also oriented to integral-magnetization-process.To investigate the output torque of TMC,a detailed analytical model considering leakage flux,edge effect and tooth magnetic saturation is formulated based on the equivalent magnetic circuit method.To facilitate the magnetic saturation calculation,a special magnetic permeability database is established for tooth region of TMC using Ansoft/Maxwell software.Prototype of TMC is machined and an exclusive experimental platform is built.Torque-displacement characteristics under different working airgap and tooth number are measured.The experimental results are in good agreement with the analytical results,which verifies the correctness of the analytical model.Then the TMC is integrated into the 2D-EHPFV by replacing the repulsive-magnetic-coupling.Prototype of 2D-EHPFV is designed and manufactured to test the no-load flow characteristics,load flow characteristics,leakage characteristics,frequency characteristics and step response.Under working pressure of 15 MPa,the maximum no-load flow rate is 82.2 L/min with the hysteresis of 2.6%,and the amplitude and phase frequency width is 21.6 Hz,and 28.9 Hz.The detailed experimental results show that TMC can be applied to 2D valves to form 2D-EHPFV,which can reduce hysteresis and cost,and improve response speed.展开更多
Photoelectrocatalytic coupling CO_(2)and volatile organic compounds (VOCs) is a promising green strategy for the synergistic conversion of the two carbon-containing resources to C2products.The catalytic efficiency is ...Photoelectrocatalytic coupling CO_(2)and volatile organic compounds (VOCs) is a promising green strategy for the synergistic conversion of the two carbon-containing resources to C2products.The catalytic efficiency is always at the mercy of chemical inertness of CO_(2)and the competitive hydrogen evolution of H2O.Herein,a modified g-C_(3)N_(4)/ZnAl-LDH Z-scheme heterojunction catalyst with dual reaction site was rationally designed and precisely constructed.The Faraday efficiency of ethanol reached 68.67%with a corresponding formation rate of 227.3μmol g^(-1)h^(-1).As revealed by in-situ characterizations and density functional theory calculations,CO_(2)and HCHO were absorbed at Zn site and N site,respectively.Then,*CO generated from CO_(2)and HCHO was converted to*CH_(3)O and*CHO on the dual-active-site heterojunction.The detailed reaction mechanism experiments indicated that C–C coupling only occurred between*CO and*CH_(3)O in electrocatalysis process.Apart from the“*CO+*CH_(3)O”path,another“*CO+*CHO”coupling path was also detected in photoelectrocatalytic process.The selectivity of ethanol was significantly enhanced due to the synthesis of dual-site catalyst and the dual-path coupling path between CO_(2)and HCHO simultaneously driven by light and electricity.展开更多
Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of...Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of CO_(2) reduction products.The development of high-performance catalysts is the key to the both electrocatalytic reactions.In this review,we present a systematic summary of the reaction systems for electrocatalytic CO_(2) reduction,along with the coupling mechanisms of C-C and C-N bonds over outstanding electrocatalytic materials recently developed.The key intermediate species and reaction pathways related to the coupling as well as the catalyst-structure relationship will be also discussed,aiming to provide insights and guidance for designing efficient CO_(2) reduction systems.展开更多
Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,how...Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,however,constrain their delicate constructions.Herein,an innovative alternative is proposed:carrageenan-assistant cations-regulated(CACR)strategy,which induces a series of sulfides nanoparticles rooted in situ on the surface of carbon matrix.This unique configuration originates from strategic vacancy formation energy of sulfides and strong sulfides-carbon support interaction,benefiting the delicate construction of defects-rich heterostructures in M_(x)S_(y)/carbon composites(M-CAs).Impressively,these generated sulfur vacancies are firstly found to strengthen electron accumulation/consumption ability at heterointerfaces and,simultaneously,induct local asymmetry of electronic structure to evoke large dipole moment,ultimately leading to polarization coupling,i.e.,defect-type interfacial polarization.Such“Janus effect”(Janus effect means versatility,as in the Greek two-headed Janus)of interfacial sulfur vacancies is intuitively confirmed by both theoretical and experimental investigations for the first time.Consequently,the sulfur vacancies-rich heterostructured Co/Ni-CAs displays broad absorption bandwidth of 6.76 GHz at only 1.8 mm,compared to sulfur vacancies-free CAs without any dielectric response.Harnessing defects-rich heterostructures,this one-pot CACR strategy may steer the design and development of advanced nanomaterials,boosting functionality across diverse application domains beyond electromagnetic response.展开更多
The occurrence of top-down(TD)cracking has gradually become a prevalent issue in semi-rigid base asphalt pavements after prolonged service.A coupled simulation model integrating the finite difference method(FDM)and di...The occurrence of top-down(TD)cracking has gradually become a prevalent issue in semi-rigid base asphalt pavements after prolonged service.A coupled simulation model integrating the finite difference method(FDM)and discrete element method(DEM)was employed to investigate the mechanical behavior of asphalt pavement containing a pre-existing TD crack.The mesoscopic parameters of the model were calibrated based on the mixture modulus and the static mechanical response on the MLS66 test road.Finally,an analysis was performed to assess how variations in TD crack depth and longitudinal length affect the distribution patterns of transverse tensile stress,vertical shear stress,and vertical compressive stress.The results indicate that the vertical propagation of TD crack significantly increases both the tensile stress value and range on the middle surface,while the longitudinal development of TD crack has minimal impact.This phenomenon may result in more severe fatigue failure on the middle surface.With the vertical and longitudinal development of TD crack,the vertical shear stress and compressive stress show obvious"two-stage"characteristics.When the crack's vertical length reaches 40 mm,there is a sharp increase in stress on the upper surface.As the crack continues to propagate vertically,the growth of stress on the upper surface becomes negligible,while the stress in the middle and lower layers increased significantly.Conversely,for longitudinal development of TD crack,any changes in stress are insignificant when their length is less than 180 mm;however,as they continue to develop longitudinally beyond this threshold,there is a sharp increase in stress levels.These findings hold great significance for understanding pavement structure deterioration and maintenance behavior associated with TD crack.展开更多
Electrochemical conversion of lignin for the production of high-value heterocyclic aromatic compounds has great potential.We demonstrate the targeted synthesis and cation modulation of NiCo_(2)O_(4)spinel nanoboxes,sy...Electrochemical conversion of lignin for the production of high-value heterocyclic aromatic compounds has great potential.We demonstrate the targeted synthesis and cation modulation of NiCo_(2)O_(4)spinel nanoboxes,synthesized via cation exchange and calcination oxidation.These catalysts exhibit excellent efficacy in the electrocatalytic conversion of lignin model compounds,specifically 2-phenoxy-1-phenylethanol,into nitrogen-containing aromatics,achieving high conversion rates and selectivities.These catalysts were synthesized via a cation exchange and calcination oxidation process,using Prussian blue nanocubes as precursors.The porous architecture and polymetallic composition of the NiCo_(2)O_(4)spinel demonstrated superior performance in electrocatalytic oxidative coupling,achieving a 99.2 wt%conversion rate of the 2-phenoxy-1-phenylethanol with selectivities of 37.5 wt%for quinoline derivatives and 31.5 wt%for phenol.Key innovations include the development of a sustainable one-pot synthesis method for quinoline derivatives,the elucidation of a multistage reaction pathway involving CAO bond cleavage,hydroxyaldol condensation,and CAN bond formation,and a deeper mechanistic understanding derived from DFT simulations.This work establishes a new strategy for lignin valorization,offering a sustainable route to produce high-value nitrogen-containing aromatics from renewable biomass under mild conditions,without the need for additional reagents.展开更多
Deep tight reservoirs exhibit complex stress and seepage fields due to varying pore structures,thus the seepage characteristics are significant for enhancing oil production.This study conducted triaxial compression an...Deep tight reservoirs exhibit complex stress and seepage fields due to varying pore structures,thus the seepage characteristics are significant for enhancing oil production.This study conducted triaxial compression and permeability tests to investigate the mechanical and seepage properties of tight sandstone.A digital core of tight sandstone was built using Computed Tomography(CT)scanning,which was divided into matrix and pore phases by a pore equivalent diameter threshold.A fluid-solid coupling model was established to investigate the seepage characteristics at micro-scale.The results showed that increasing the confining pressure decreased porosity,permeability,and flow velocity,with the pore phase becoming the dominant seepage channel.Cracks and large pores closed first under increasing pressure,resulted in a steep drop in permeability.However,permeability slightly decreased under high confining pressure,which followed a first-order exponential function.Flow velocity increased with seepage pressure.And the damage mainly occurred in stress-concentration regions under low seepage pressure.Seepage behavior followed linear Darcy flow,the damage emerged at seepage entrances under high pressure,which decreased rock elastic modulus and significantly increased permeability.展开更多
This study investigates the coordination between regional economic growth and ecological sustainability within the context of high-quality town economy development.To address the challenges of balancing economic expan...This study investigates the coordination between regional economic growth and ecological sustainability within the context of high-quality town economy development.To address the challenges of balancing economic expansion with environmental protection,a comprehensive evaluation index system is constructed,encompassing two key dimensions:regional economy and ecological environment.Using panel data from 2013 to 2022,the coupling coordination degree model is employed to quantify the interactions and synergy between these dimensions.Additionally,spatial econometric methods are applied to calculate both global and local Moran’s Index,revealing spatial clustering patterns,regional disparities,and heterogeneity.The relative development model further identifies critical factors influencing regional coordination,with a focus on the lagging development of basic infrastructure and public services.The findings demonstrate a positive temporal trend toward improved regional coordination and reduced development gaps,with a spatial pattern characterized by higher coupling degrees in eastern and central regions compared to western areas.Based on these results,this study proposes actionable strategies to enhance coordinated development,emphasizing ecological conservation,the establishment of green production and consumption systems,ecological restoration,and strengthened municipal collaboration.This revised abstract emphasizes the study’s purpose,methods,and key findings more clearly while maintaining a professional and concise tone.Finally,based on the above analysis results,the corresponding coordinated development suggestions of regional economy and ecological environment are given from the aspects of ecological environment protection measures,green production and consumption system construction,ecological environment restoration and municipal coordination.展开更多
Dislocations and disclinations are fundamental topological defects within crystals,which determine the mechanical properties of metals and alloys.Despite their important roles in multiple physical mechanisms,e.g.,dyna...Dislocations and disclinations are fundamental topological defects within crystals,which determine the mechanical properties of metals and alloys.Despite their important roles in multiple physical mechanisms,e.g.,dynamic recovery and grain boundary mediated plasticity,the intrinsic coupling and correlation between disclinations and dislocations,and their impacts on the deformation behavior of metallic materials still remain obscure,partially due to the lack of a theoretical tool to capture the rotational nature of disclinations.By using a Lie-algebra-based theoretical framework,we obtain a general equation to quantify the intrinsic coupling of disclinations and dislocations.Through quasi in-situ electron backscatter diffraction characterizations and disclination/dislocation density analyses in Mg alloys,the generation,coevolution and reactions of disclinations and dislocations during dynamic recovery and superplastic deformation have been quantitatively analyzed.It has been demonstrated that the obtained governing equation can capture multiple physical processes associated with mechanical deformation of metals,e.g.,grain rotation and grain boundary migration,at both room temperature and high temperature.By establishing the disclination-dislocation coupling equation within a Lie algebra description,our work provides new insights for exploring the coevolution and reaction of disclinations/dislocations,with profound implications for elucidating the microstructure-property relationship and underlying deformation mechanisms in metallic materials.展开更多
文摘Copper(Cu)-based catalysts show significant potential for producing high value-added C_(2+)products in electrocatalytic CO_(2)/CO reduction reactions(CO(2)RR).However,the structural reconfiguration during operation poses substantial challenges in identifying the intrinsic catalytic active site,especially under similar mass transport conditions.Herein,three typical and commercial Cu-based catalysts(Cu,CuO,and Cu_(2)O)are chosen as representatives to elucidate the structure-activity relationship of CORR in the membrane electrode assembly electrolyzer.Notably,only the Cu catalyst demonstrates the most suppression of hydrogen evolution reaction,thus achieving the highest FE of 86.7% for C_(2+)products at a current density of 500 mA cm^(-2) and maintaining a stable electrolysis over 110 h at a current of 200 mA cm^(-2).The influence of chemical valence state of Cu,electrochemical surface area,and local pH were firstly investigated and ruled out for the significant FE differences.Finally,based on the structure analysis from high resolution transmission electron microscope,OH-adsorption,in situ infrared spectroscopy and density functional theory calculations,it is suggested that the asymmetric C-C coupling(via ^(*)CHO and ^(*)CO)is the most probable reaction pathway for forming C_(2+)products,with Cu(100)-dominant grain boundaries(GBs)being the most favorable active sites.These findings provide deeper insights into the synergistic relationship between crystal facets and GBs in electrocatalytic systems.
文摘A thoroughly mechanistic understanding of the electrochemical CO reduction reaction(eCORR)at the interface is significant for guiding the design of high-performance electrocatalysts.However,unintentionally ignored factors or unreasonable settings during mechanism simulations will result in false positive results between theory and experiment.Herein,we computationally identified the dynamic site preference change of CO adsorption with potentials on Cu(100),which was a previously unnoticed factor but significant to potential-dependent mechanistic studies.Combined with the different lateral interactions among adsorbates,we proposed a new C–C coupling mechanism on Cu(100),better explaining the product distribution at different potentials in experimental eCORR.At low potentials(from–0.4 to–0.6 V_(RHE)),the CO forms dominant adsorption on the bridge site,which couples with another attractively aggregated CO to form a C–C bond.At medium potentials(from–0.6 to–0.8 VRHE),the hollow-bound CO becomes dominant but tends to isolate with another adsorbate due to the repulsion,thereby blocking the coupling process.At high potentials(above–0.8 VRHE),the CHO intermediate is produced from the electroreduction of hollow-CO and favors the attraction with another bridge-CO to trigger C–C coupling,making CHO the major common intermediate for C–C bond formation and methane production.We anticipate that our computationally identified dynamic change in site preference of adsorbates with potentials will bring new opportunities for a better understanding of the potential-dependent electrochemical processes.
基金financial support from the National Natural Science Foundation of China(grant no.22373027)。
文摘Research interest in the electrochemical reduction reaction of carbon dioxide(CO_(2)RR)into multicarbon(C_(2+))compounds has been growing significantly with numerous theoretical and experimental studies employing a variety of surface modification techniques,such as strong support interactions,heteroatom doping,surface functionalization,and morphology and defect engineering.The collective goal of these strategies is to fine-tune the electrochemical properties of catalysts,thereby breaking the C-C coupling barrier to achieve efficient and selective formation of C_(2+)products.In this review,we critically examine these research efforts,with a particular focus on achieving a comprehensive understanding of the innovative catalyst surface that dictates pathways for electrochemical CO_(2)RR to C_(2+)compounds.We begin by discussing the essential characteristics of catalyst surfaces that demonstrate superior catalytic activity and selectivity.Next,we explore the range of strategies used to create conducive catalyst surfaces.Finally,we provide an overview of catalytic performance and selectivity of materials in synthesizing C_(2+)products based on some high-throughput density functional theory and machine learning screening techniques.
文摘Light-driven CO_(2) reduction reaction(CO_(2)RR)to value-added ethylene(C2H4)holds significant promise for addressing energy and environmental challenges.While the high energy barriers for*CO intermediates hydrogenation and C–C coupling limit the C_(2)H_(4)generation.Herein,CuxP/g-C_(3)N_(4) heterojunction prepared by an in-situ phosphating technique,achieved collaborative photocatalytic CO_(2) and H2O,producing CO and C_(2)H_(4)as the main products.Notably,the selectivity of C_(2)H_(4)produced by CuxP/g-C_(3)N_(4) attained to 64.25%,which was 9.85 times that of CuxP(6.52%).Detailed time-resolution photoluminescence spectra,femtosecond transient absorption spectroscopy tests and density functional theory(DFT)calculation validate the ultra-fast interfacial electron transfer mechanism in CuxP/g-C_(3)N_(4) heterojunction.Successive*H on P sites caused by adsorbed H2O splitting with moderate hydrogenation ability enables the multi-step hydrogenation during CO_(2)RR process over CuxP/g-C_(3)N_(4).With the aid of mediated asymmetric Cu and P dual sites by g-C_(3)N_(4) nanosheet,the produced*CHO shows an energetically favorable for C–C coupling.The coupling formed*CHOCHO further accepts photoexcited efficient e–and*H to deeply produce C_(2)H_(4)according to the C^(2+)intermediates,which has been detected by in-situ diffuse reflectance infrared Fourier transform spectroscopy and interpreted by DFT calculation.The novel insight mechanism offers an essential understanding for the development of CuxP-based heterojunctions for photocatalytic CO_(2) to C^(2+)value-added fuels.
基金the National Key Research and Development Program of China(2024YFB4106400,2024YFB4106401)the National Natural Science Foundation of China(22025502,U23A20552)。
文摘The copper-based electrocatalysts feature attractive potentials of converting CO_(2)into multi-carbon(C_(2+))products,while the instability of Cu-O often induces the reduction of Cu^(+)/Cu^(0) catalytic sites at the cathode and refrains the capability of stable electrolysis especially at high powers.In this work,we developed an Erbium(Er)oxide-modified Cu(Er-O-Cu)catalyst with enhanced covalency of Cu-O and more stable active sites.The f-p-d coupling strengthens the covalency of Cu-O,and the stability of Cu^(+)sites under electroreduction condition is critical for promoting the C-C coupling and improving the C_(2+)product selectivity.As a result,the Er-O-Cu sites exhibited a high Faradaic efficiency of C_(2+)products(FEC_(2+))of 86%at 2200 mA cm^(-2),and a peak partial current density of|j_(C2+)|of 1900 mA cm^(-2),comparable to the best reported values for the CO_(2)-to-C_(2+)electroreduction.The CO_(2)electrolysis by the Er-O-Cu sites was further scaled up to 100 cm^(2)to achieve high-power(~200 W)electrolysis with ethylene production rate of 16 mL min^(-1).
文摘Electrochemical carbon dioxide reduction reaction(CO_(2)RR)produces valuable chemicals by consuming gaseous CO_(2)as well as protons from the electrolyte.Protons,produced by water dissociation in alkaline electrolyte,are critical for the reaction kinetics which involves multiple proton coupled electron transfer steps.Herein,we demonstrate that the two key steps(CO_(2)-^(*)COOH and^(*)CO-^(*)COH)efficiency can be precisely tuned by introducing proper amount of water dissociation center,i.e.,Fe single atoms,locally surrounding the Cu catalysts.In alkaline electrolyte,the Faradaic efficiency(FE)of multi-carbon(C^(2+))products exhibited a volcano type plot depending on the density of water dissociation center.A maximum FE for C^(2+)products of 73.2%could be reached on Cu nanoparticles supported on N-doped Carbon nanofibers with moderate Fe single atom sites,at a current density of 300 mA cm^(–2).Experimental and theoretical calculation results reveal that the Fe sites facilitate water dissociation kinetics,and the locally generated protons contribute significantly to the CO_(2)activation and^(*)CO protonation process.On the one hand,in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy(in-situ ATR-SEIRAS)clearly shows that the^(*)COOH intermediate can be observed at a lower potential.This phenomenon fully demonstrates that the optimized local water dissociation kinetics has a unique advantage in guiding the hydrogenation reaction pathway of CO₂molecules and can effectively reduce the reaction energy barrier.On the other hand,abundant^(*)CO and^(*)COH intermediates create favorable conditions for the asymmetric^(*)CO-^(*)COH coupling,significantly increasing the selectivity of the reaction for C^(2+)products and providing strong support for the efficient conversion of related reactions to the target products.This work provides a promising strategy for the design of a dual sites catalyst to achieve high FE of C^(2+)products through the optimized local water dissociation kinetics.
基金financially supported by the National Natural Science Foundation of China(No.22305101)the Natural Science Foundation of Jiangsu Province(No.BK20231032)+2 种基金the Special Fund Project of Jiangsu Province for Scientific and Technological Innovation in Carbon Peaking and Carbon Neutrality(No.BK20220023)the Fundamental Research Funds for the Central Universities(No.JUSRP123020)the Startup Funding at Jiangnan University(No.1045219032220100)。
文摘Engineering the desired dual metal sites to realize C-C coupling of CO_(2)is of great importance for the practical applications of CO_(2)electroreduction reaction(CER).Herein,an efficient strategy for constructing heterogeneous Pt^(δ+)-Cu^(δ+)dual sites to strengthen the generation and coupling of*CO and*CHO(or*COH)during CER process is presented in this work.The radiilarger Pt not only stabilizes the Cu^(δ+)ut also induces a tensile strain in Pt^(δ+)-Cu^(δ+)dual sites.The obtained Pt^(δ+)-Cu^(δ+)dual sites achieve a total Faradaic efficiency and current density of C2products with 70.9%and586.9 mA·cm-2at-1.20 V(vs.RHE),which is higher than that of Cu^(δ+)single site(55.4%,286.9 mA·cm^(-2)).The in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy(ATR-SEIRAS)reveals that the Pt^(δ+)-Cu^(δ+)dual sites can promote the generation of C1intermediates(such as*CO,*COOH,*COH,and*CHO)and C-C coupling.Additional in situ surface-enhanced Raman spectra demonstrate that Pt^(δ+)Cu^(δ+)dual sites can induce the generation of the high-frequency peak for*CO_(atop),thus accelerating the C-C coupling.This work provides a promising avenue for stabilizing and enhancing the performance of Cu^(δ+)sites toward CER.
基金the National Natural Science Foundation of China(51303083)the National Natural Science Foundation of China for Excellent Young Scholars(51922050)+1 种基金the Natural Science Foundation of Jiangsu Province(BK20191293)the Fundamental Research Funds for the Central Universities(30920021123)。
文摘Photothermal catalytic CO_(2) conversion provides an effective solution targeting carbon neutrality by synergistic utilization of photon and heat.However,the C-C coupling initiated by photothermal catalysis is still a big challenge.Herein,a three-dimensional(3D)hierarchical W_(18)O_(49)/WTe_(2) hollow nanosphere is constructed through in-situ embodying of oxygen vacancy and tellurium on the scaffold of WO_(3).The light absorption towards near-infrared spectral region and CO_(2) adsorption are enhanced by the formation of half-metal WTe_(2) and the unique hierarchical hollow architecture.Combining with the generation of oxygen vacancy with strengthened CO_(2) capture,the photothermal effect on the samples can be sufficiently exploited for activating the CO_(2) molecules.In particular,the close contact between W_(18)O_(49)and WTe_(2) largely promotes the photoinduced charge separation and mass transfer,and thus the~*CHO intermediate formation and fixedness are facilitated.As a result,the C-C coupling can be evoked between tungsten and tellurium atoms on WTe_(2).The ethylene production by optimized W_(18)O_(49)/WTe_(2) reaches 147.6μmol g^(-1)with the selectivity of 80%.The in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and density functional theory(DFT)calculations are performed to unveil the presence and significance of aldehyde intermediate groups in C-C coupling.The half-metallic WTe_(2) cocatalyst proposes a new approach for efficient CO_(2) conversion with solar energy,and may especially create a new platform for the generation of multi-carbon products.
基金supported by the National Natural Science Foundation of China(No.21773254)the Youth Innovation Promotion Association Chinese Academy of Sciences(No.2016030)。
文摘A fundamental study on C-C coupling,that is the crucial step in the Fischer-Tropsch synthesis(FTS)process to obtain multi-carbon products,is of great importance to tailor catalysts and then guide a more promising pathway.It has been demonstrated that the coupling of CO with the metal carbide can represent the early stage in the FTS process,while the related mechanism is elusive.Herein,the reactions of the CuC3H-and CuC3-cluster anions with CO have been studied by using mass spectrometry and theoretical calculations.The experimental results showed that the coupling of CO with the C3H-moiety of CuC3H can generate the exclusive ion product COC3H-.The reactivity and selectivity of this reaction of CuC3H-with CO are greatly higher than that of the reaction of CuC3-with CO,and this H-assisted C-C coupling process was rationalized by theoretical calculations.
基金supported by the National Natural Science Foundation of China(No.22275139)the Key Project of Natural Science Foundation of Tianjin City(No.22JCZDJC00510)The authors thank the Shanghai Synchrotron Radiation Facility of Experiment Assist System(https://cstr.cn/31124.02.SSRF.LAB)for the assistance on BL11B.
文摘Photo-reforming methanol into valuable chemicals represents an energetically sustainable alternative to conventional thermal catalysis,yet controlling-specific C-C coupling way still remains elusive.In this work,we report a sulfide-based photocatalytic paradigm,where atomic-level control of nickel species directly dictates reaction selectivity.The electrostatic constructing ZnIn_(2)S_(4)/Zn_(0.5)Cd_(0.5)S(ZIS/ZCS)heterostructures enable single atom Ni to facilitate ethylene glycol(EG)production with a rate of 11.2 mmol·gcat^(−1)·h^(−1),surpassing reported non-precious metal systems,whereas the Ni aggregates drive exclusive formaldehyde formation.The operando spectroscopy and density functional theory reveal dual roles of Ni as electron reservoir and chemical bond breakage inducers,lowering C-H activation barriers while stabilizing·CH2OH intermediates for cross-coupling.This interfacial configuration engineering creates an electron highway that couples carrier dissociation with radical recombination kinetics,achieving atom-economic steering of methanol oxidative valorization.The metal dispersion assisting catalysis correlation here provides a design blueprint for selective bond scission and reconstruction in sustainable organic synthesis.
基金financial support from National Natural Science Foundation of China(Nos.21801129,22078153 and22378201)National Key Research and Development Program of China(No.2022YFB3805603)+3 种基金Natural science research projects in Jiangsu Higher Education Institutions(No.18KJB150018)Open Research Fund of School of Chemistry and Chemical EngineeringHenan Normal University(No.2024Y16)Nanjing Tech University(Start-up Grant Nos.39837137,39837101 and 3827401739)for financial support。
文摘Pyridyl-based ketones and 1,6-diketones are both attractive and invaluable scaffolds which play pivotal roles in the construction and structural modification of a plethora of synthetically paramount natural products,pharmaceuticals,organic materials and fine chemicals.In this context,we herein demonstrate an unprecedented,robust and generally applicable synthetically strategy to deliver these two crucial ketone frameworks via visible-light-induced ring-opening coupling reactions of cycloalcohols with vinylazaarenes and enones,respectively.A plausible mechanism involves the selectiveβ-C-C bond cleavage of cycloalcohols enabled by proton-coupled electron transfer and ensuing Giese-type addition followed by single electron reduction and protonation.The synthetic methodology exhibits broad substrate scope,excellent functional group compatibility as well as operational simplicity and environmental friendliness.
基金Supported by National Natural Science Foundation of China(Grant Nos.51975524,52375067)Zhejiang Provincial Natural Science Foundation of China(Grant No.Y23E050014).
文摘Magnetization convenience is crucial consideration for design of valve magnetic actuators.The existing repulsive-magnetic-coupling of 2D maglev valve is not oriented to the integral-magnetization-processes,resulting in the high assembly cost.This paper presents a novel tractive-magnetic-coupling(TMC)and its application on a 2D electro-hydraulic proportional flow valve(2D-EHPFV),whose configuration not only fulfill the requirements of 2D valve,but also oriented to integral-magnetization-process.To investigate the output torque of TMC,a detailed analytical model considering leakage flux,edge effect and tooth magnetic saturation is formulated based on the equivalent magnetic circuit method.To facilitate the magnetic saturation calculation,a special magnetic permeability database is established for tooth region of TMC using Ansoft/Maxwell software.Prototype of TMC is machined and an exclusive experimental platform is built.Torque-displacement characteristics under different working airgap and tooth number are measured.The experimental results are in good agreement with the analytical results,which verifies the correctness of the analytical model.Then the TMC is integrated into the 2D-EHPFV by replacing the repulsive-magnetic-coupling.Prototype of 2D-EHPFV is designed and manufactured to test the no-load flow characteristics,load flow characteristics,leakage characteristics,frequency characteristics and step response.Under working pressure of 15 MPa,the maximum no-load flow rate is 82.2 L/min with the hysteresis of 2.6%,and the amplitude and phase frequency width is 21.6 Hz,and 28.9 Hz.The detailed experimental results show that TMC can be applied to 2D valves to form 2D-EHPFV,which can reduce hysteresis and cost,and improve response speed.
基金Natural Science Foundation of Shanxi Province,China (Grant No. 20210302123001)DNL Cooperation Fund,CAS (DNL202004),ICC CAS (Grant No. SCJCWRW-2023-21)Key Research and Development Program of Shanxi Province (202202090301020)。
文摘Photoelectrocatalytic coupling CO_(2)and volatile organic compounds (VOCs) is a promising green strategy for the synergistic conversion of the two carbon-containing resources to C2products.The catalytic efficiency is always at the mercy of chemical inertness of CO_(2)and the competitive hydrogen evolution of H2O.Herein,a modified g-C_(3)N_(4)/ZnAl-LDH Z-scheme heterojunction catalyst with dual reaction site was rationally designed and precisely constructed.The Faraday efficiency of ethanol reached 68.67%with a corresponding formation rate of 227.3μmol g^(-1)h^(-1).As revealed by in-situ characterizations and density functional theory calculations,CO_(2)and HCHO were absorbed at Zn site and N site,respectively.Then,*CO generated from CO_(2)and HCHO was converted to*CH_(3)O and*CHO on the dual-active-site heterojunction.The detailed reaction mechanism experiments indicated that C–C coupling only occurred between*CO and*CH_(3)O in electrocatalysis process.Apart from the“*CO+*CH_(3)O”path,another“*CO+*CHO”coupling path was also detected in photoelectrocatalytic process.The selectivity of ethanol was significantly enhanced due to the synthesis of dual-site catalyst and the dual-path coupling path between CO_(2)and HCHO simultaneously driven by light and electricity.
基金support from the Tangshan Talent Funding Project(Grant No.A202202007)National Natural Science Foundation of China(Grant Nos.22102136 and 21703065)+2 种基金Natural Science Foundation of Hebei Province(Grant Nos.B2018209267 and E2022209039)Natural Science Foundation of Hubei Province(Grant No.2022CFB1001)Department of Education of Hubei Province(Grant No.Q20221701).
文摘Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of CO_(2) reduction products.The development of high-performance catalysts is the key to the both electrocatalytic reactions.In this review,we present a systematic summary of the reaction systems for electrocatalytic CO_(2) reduction,along with the coupling mechanisms of C-C and C-N bonds over outstanding electrocatalytic materials recently developed.The key intermediate species and reaction pathways related to the coupling as well as the catalyst-structure relationship will be also discussed,aiming to provide insights and guidance for designing efficient CO_(2) reduction systems.
基金financially supported by the National Natural Science Foundation of China(Grants nos.62201411,62371378,22205168,52302150 and 62304171)the China Postdoctoral Science Foundation(2022M722500)+1 种基金the Fundamental Research Funds for the Central Universities(Grants nos.ZYTS2308 and 20103237929)Startup Foundation of Xidian University(10251220001).
文摘Defects-rich heterointerfaces integrated with adjustable crystalline phases and atom vacancies,as well as veiled dielectric-responsive character,are instrumental in electromagnetic dissipation.Conventional methods,however,constrain their delicate constructions.Herein,an innovative alternative is proposed:carrageenan-assistant cations-regulated(CACR)strategy,which induces a series of sulfides nanoparticles rooted in situ on the surface of carbon matrix.This unique configuration originates from strategic vacancy formation energy of sulfides and strong sulfides-carbon support interaction,benefiting the delicate construction of defects-rich heterostructures in M_(x)S_(y)/carbon composites(M-CAs).Impressively,these generated sulfur vacancies are firstly found to strengthen electron accumulation/consumption ability at heterointerfaces and,simultaneously,induct local asymmetry of electronic structure to evoke large dipole moment,ultimately leading to polarization coupling,i.e.,defect-type interfacial polarization.Such“Janus effect”(Janus effect means versatility,as in the Greek two-headed Janus)of interfacial sulfur vacancies is intuitively confirmed by both theoretical and experimental investigations for the first time.Consequently,the sulfur vacancies-rich heterostructured Co/Ni-CAs displays broad absorption bandwidth of 6.76 GHz at only 1.8 mm,compared to sulfur vacancies-free CAs without any dielectric response.Harnessing defects-rich heterostructures,this one-pot CACR strategy may steer the design and development of advanced nanomaterials,boosting functionality across diverse application domains beyond electromagnetic response.
基金supported by National Key R&D Program of China(Grant No.2021YFB2601200)Open Fund of National Engineering Research Center of Highway Maintenance Technology(Changsha University of Science&Technology)(No.kfj230207).
文摘The occurrence of top-down(TD)cracking has gradually become a prevalent issue in semi-rigid base asphalt pavements after prolonged service.A coupled simulation model integrating the finite difference method(FDM)and discrete element method(DEM)was employed to investigate the mechanical behavior of asphalt pavement containing a pre-existing TD crack.The mesoscopic parameters of the model were calibrated based on the mixture modulus and the static mechanical response on the MLS66 test road.Finally,an analysis was performed to assess how variations in TD crack depth and longitudinal length affect the distribution patterns of transverse tensile stress,vertical shear stress,and vertical compressive stress.The results indicate that the vertical propagation of TD crack significantly increases both the tensile stress value and range on the middle surface,while the longitudinal development of TD crack has minimal impact.This phenomenon may result in more severe fatigue failure on the middle surface.With the vertical and longitudinal development of TD crack,the vertical shear stress and compressive stress show obvious"two-stage"characteristics.When the crack's vertical length reaches 40 mm,there is a sharp increase in stress on the upper surface.As the crack continues to propagate vertically,the growth of stress on the upper surface becomes negligible,while the stress in the middle and lower layers increased significantly.Conversely,for longitudinal development of TD crack,any changes in stress are insignificant when their length is less than 180 mm;however,as they continue to develop longitudinally beyond this threshold,there is a sharp increase in stress levels.These findings hold great significance for understanding pavement structure deterioration and maintenance behavior associated with TD crack.
基金National Natural Science Foundation of China (U23A6005 and 22078069)Project funded by China Postdoctoral Science Foundation (GZB20230172 and 2023M740748)。
文摘Electrochemical conversion of lignin for the production of high-value heterocyclic aromatic compounds has great potential.We demonstrate the targeted synthesis and cation modulation of NiCo_(2)O_(4)spinel nanoboxes,synthesized via cation exchange and calcination oxidation.These catalysts exhibit excellent efficacy in the electrocatalytic conversion of lignin model compounds,specifically 2-phenoxy-1-phenylethanol,into nitrogen-containing aromatics,achieving high conversion rates and selectivities.These catalysts were synthesized via a cation exchange and calcination oxidation process,using Prussian blue nanocubes as precursors.The porous architecture and polymetallic composition of the NiCo_(2)O_(4)spinel demonstrated superior performance in electrocatalytic oxidative coupling,achieving a 99.2 wt%conversion rate of the 2-phenoxy-1-phenylethanol with selectivities of 37.5 wt%for quinoline derivatives and 31.5 wt%for phenol.Key innovations include the development of a sustainable one-pot synthesis method for quinoline derivatives,the elucidation of a multistage reaction pathway involving CAO bond cleavage,hydroxyaldol condensation,and CAN bond formation,and a deeper mechanistic understanding derived from DFT simulations.This work establishes a new strategy for lignin valorization,offering a sustainable route to produce high-value nitrogen-containing aromatics from renewable biomass under mild conditions,without the need for additional reagents.
基金financially supported by the National Natural Science Foundation of China(Nos.42272153 and 42472195)the Research Fund of PetroChina Tarim Oilfield Company(No.671023060003)the Research Fund of China National Petroleum Corporation Limited(No.2023ZZ16YJ04).
文摘Deep tight reservoirs exhibit complex stress and seepage fields due to varying pore structures,thus the seepage characteristics are significant for enhancing oil production.This study conducted triaxial compression and permeability tests to investigate the mechanical and seepage properties of tight sandstone.A digital core of tight sandstone was built using Computed Tomography(CT)scanning,which was divided into matrix and pore phases by a pore equivalent diameter threshold.A fluid-solid coupling model was established to investigate the seepage characteristics at micro-scale.The results showed that increasing the confining pressure decreased porosity,permeability,and flow velocity,with the pore phase becoming the dominant seepage channel.Cracks and large pores closed first under increasing pressure,resulted in a steep drop in permeability.However,permeability slightly decreased under high confining pressure,which followed a first-order exponential function.Flow velocity increased with seepage pressure.And the damage mainly occurred in stress-concentration regions under low seepage pressure.Seepage behavior followed linear Darcy flow,the damage emerged at seepage entrances under high pressure,which decreased rock elastic modulus and significantly increased permeability.
基金support from Guangdong Science and Technology(20230505)Guangdong Provincial Philosophy and Social Science Planning Project(GD20SQ25)Guangdong Provincial Special Fund for Science and Technology Innovation Strategy in 2024(Cultivation of College Students’Science and Technology Innovation)(pdjh2024a391)during preparation of this manuscript.
文摘This study investigates the coordination between regional economic growth and ecological sustainability within the context of high-quality town economy development.To address the challenges of balancing economic expansion with environmental protection,a comprehensive evaluation index system is constructed,encompassing two key dimensions:regional economy and ecological environment.Using panel data from 2013 to 2022,the coupling coordination degree model is employed to quantify the interactions and synergy between these dimensions.Additionally,spatial econometric methods are applied to calculate both global and local Moran’s Index,revealing spatial clustering patterns,regional disparities,and heterogeneity.The relative development model further identifies critical factors influencing regional coordination,with a focus on the lagging development of basic infrastructure and public services.The findings demonstrate a positive temporal trend toward improved regional coordination and reduced development gaps,with a spatial pattern characterized by higher coupling degrees in eastern and central regions compared to western areas.Based on these results,this study proposes actionable strategies to enhance coordinated development,emphasizing ecological conservation,the establishment of green production and consumption systems,ecological restoration,and strengthened municipal collaboration.This revised abstract emphasizes the study’s purpose,methods,and key findings more clearly while maintaining a professional and concise tone.Finally,based on the above analysis results,the corresponding coordinated development suggestions of regional economy and ecological environment are given from the aspects of ecological environment protection measures,green production and consumption system construction,ecological environment restoration and municipal coordination.
基金Financial supports from the National Natural Science Foundation of China(Nos.52171116,U22A20109,52334010 and T2325013)are greatly acknowledgedPartial financial support came from The Program for the Central University Youth Innovation Team,and the Fundamental Research Funds for the Central Universities,JLU.
文摘Dislocations and disclinations are fundamental topological defects within crystals,which determine the mechanical properties of metals and alloys.Despite their important roles in multiple physical mechanisms,e.g.,dynamic recovery and grain boundary mediated plasticity,the intrinsic coupling and correlation between disclinations and dislocations,and their impacts on the deformation behavior of metallic materials still remain obscure,partially due to the lack of a theoretical tool to capture the rotational nature of disclinations.By using a Lie-algebra-based theoretical framework,we obtain a general equation to quantify the intrinsic coupling of disclinations and dislocations.Through quasi in-situ electron backscatter diffraction characterizations and disclination/dislocation density analyses in Mg alloys,the generation,coevolution and reactions of disclinations and dislocations during dynamic recovery and superplastic deformation have been quantitatively analyzed.It has been demonstrated that the obtained governing equation can capture multiple physical processes associated with mechanical deformation of metals,e.g.,grain rotation and grain boundary migration,at both room temperature and high temperature.By establishing the disclination-dislocation coupling equation within a Lie algebra description,our work provides new insights for exploring the coevolution and reaction of disclinations/dislocations,with profound implications for elucidating the microstructure-property relationship and underlying deformation mechanisms in metallic materials.
