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
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
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
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
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
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
Wire arc additive manufacturing(WAAM)has emerged as a promising approach for fabricating large-scale components.However,conventional WAAM still faces challenges in optimizing microstructural evolution,minimizing addit...Wire arc additive manufacturing(WAAM)has emerged as a promising approach for fabricating large-scale components.However,conventional WAAM still faces challenges in optimizing microstructural evolution,minimizing additive-induced defects,and alleviating residual stress and deformation,all of which are critical for enhancing the mechanical performance of the manufactured parts.Integrating interlayer friction stir processing(FSP)into WAAM significantly enhances the quality of deposited materials.However,numerical simulation research focusing on elucidating the associated thermomechanical coupling mechanisms remains insufficient.A comprehensive numerical model was developed to simulate the thermomechanical coupling behavior in friction stir-assisted WAAM.The influence of post-deposition FSP on the coupled thermomechanical response of the WAAM process was analyzed quantitatively.Moreover,the residual stress distribution and deformation behavior under both single-layer and multilayer deposition conditions were investigated.Thermal analysis of different deposition layers in WAAM and friction stir-assisted WAAM was conducted.Results show that subsequent layer deposition induces partial remelting of the previously solidified layer,whereas FSP does not cause such remelting.Furthermore,thermal stress and deformation analysis confirm that interlayer FSP effectively mitigates residual stresses and distortion in WAAM components,thereby improving their structural integrity and mechanical properties.展开更多
Based on the Smit-Suhl formula,we propose a universal approach for solving the magnon-magnon coupling problem in bilayer coupled systems(e.g.,antiferromagnets).This method requires only the energy expression,enabling ...Based on the Smit-Suhl formula,we propose a universal approach for solving the magnon-magnon coupling problem in bilayer coupled systems(e.g.,antiferromagnets).This method requires only the energy expression,enabling the automatic derivation of analytical expressions for the eigenmatrix elements via symbolic computation,eliminating the need for tedious manual calculations.Using this approach,we investigate the impact of magnetic hysteresis on magnon-magnon coupling in a system with interlayer Dzyaloshinskii-Moriya interaction(DMI).The magnetic hysteresis leads to an asymmetric magnetic field dependence of the resonance frequency and alters the number of degeneracy points between the pure optical and acoustic modes.Moreover,it can result in the coupling strength at the gap of the f–H phase diagram being nearly vanishing,contrary to the conventionally expected maximum.These results deepen the understanding of the effect of interlayer DMI on magnon–magnon coupling and the proposed universal method significantly streamlines the solving process of magnon–magnon coupling problems.展开更多
To address the deficiencies in comprehensive surface contamination prevention strategies within China's nitrate-affected regions,this research innovatively proposes the DITAPH model-a systematic framework integrat...To address the deficiencies in comprehensive surface contamination prevention strategies within China's nitrate-affected regions,this research innovatively proposes the DITAPH model-a systematic framework integrating groundwater nitrate vulnerability assessment and Nitrate Vulnerable Zones(NVZs)delineation through optimization of hydrogeological parameters.Based on detailed hydrogeological and hydrochemical investigations,the DITAPH model was applied in the plain areas of Quanzhou to evaluate its applicability.The model selected hydrogeological parameters(depth of groundwater,lithology of the vadose zone,topographic slope,aquifer water yield property),one climatic parameter(precipitation),and two anthropogenic parameters(land use type and population density)as assessment indicators.The results of the groundwater nitrate vulnerability assessment showed that the low,relatively low,relatively high,and high groundwater nitrate vulnerability zones in the study area accounted for 5.96%,35.44%,53.74%and 4.86%of the total area,respectively.Groundwater nitrate vulnerability was most strongly influenced by human activities,followed by groundwater depth and topographic slope.The high vulnerability zone is mainly affected by domestic and industrial wastewater,whereas the relatively high groundwater nitrate vulnerability zone is primarily influenced by agricultural activities.Validation of the DITAPH model revealed a significant positive correlation between the DITAPH index(DI)and nitrate concentration(ρ(NO3−)).The results of the NVZs delineated by the DITAPH model are reliable and can serve as a tool for water resource management planning,guiding the development of targeted measures in the NVZs to prevent groundwater contamination.展开更多
Deep insights into electrocatalytic mechanisms are vital for the rational design of catalysts for oxygen evolution reaction(OER).Mechanistically,the OER driven by adsorbate evolution mechanism(AEM)is limited by the li...Deep insights into electrocatalytic mechanisms are vital for the rational design of catalysts for oxygen evolution reaction(OER).Mechanistically,the OER driven by adsorbate evolution mechanism(AEM)is limited by the linear scaling relationship,thereby exhibiting large overpotentials.In the lattice oxygen mechanism(LOM),the OER can be enhanced by enabling direct O_(2)formation.However,this enhancement is accompanied by the generation of oxygen vacancies,which presents a significant challenge to the long-term stability of LOMOER,particularly when operating at high current densities.Recently,the*O-*O coupling mechanism(OCM)has emerged as a promising alternative;it not only breaks the linear scaling relationship but also ensures catalytic stability.This review encapsulates the cutting-edge advancements in electrocatalysts that are grounded in the OCM,offering a detailed interpretation on the foundational principles guiding the design of OCM-OER catalysts.It also highlights recent theoretical investigations combining machine learning(ML)with density functional theory(DFT)calculations to reveal OER mechanisms.At the end of this review,the challenges and opportunities associated with OCM-OER electrocatalysts are discussed.展开更多
Since the United Nations launched the Sustainable Development Goals(SDGs)in 2015,global implementation has steadily advanced,yet prominent challenges persist.Progress has been uneven across regions and countries,with ...Since the United Nations launched the Sustainable Development Goals(SDGs)in 2015,global implementation has steadily advanced,yet prominent challenges persist.Progress has been uneven across regions and countries,with Tajikistan representing a typical example of such disparities.Based on 81 SDG indicators for Tajikistan from 2001 to 2023,this study applied a three-level coupling network framework:at the microscale,it identified synergies and trade-offs between indicators;at the mesoscale,it examined the strength and direction of linkages within four SDG-related components(society,finance,governance,and environment);and at the global level,it focused on the overall SDG interlinkages.Spearman’s rank correlation,sliding window method,and topological properties were employed to analyze the coupling dynamics of SDGs.Results showed that over 70.00%of associations in the global SDG network were of medium-to-low intensity,alongside extremely strong ones(|r|value approached 1.00,where r is the correlation coefficient).SDG interactions were generally limited,with stable local synergy clusters in core livelihood sectors.Network modularity fluctuated,reflecting a cycle of differentiation,integration,and fragmentation,while coupling efficiency varied with the external environment.Each component exhibited distinct functional characteristics.The social component maintained high connectivity through the“poverty alleviation-education-healthcare”loop.The environmental component shifted toward coordinated eco-economic governance.The governance-related component broke interdepartmental barriers,while the financial component showed weak links between resource-based indicators and consumption/employment indicators.Tajikistan’s SDG coupling evolved through three phases:survival-oriented(2001–2012),policy integration(2013–2018),and shock adaptation(2019–2023).These phases were driven by policy changes,resource industries,governance optimization,and external factors.This study enriches the analytical framework for understanding the dynamic coupling of SDGs in mountainous resource-dependent countries and provides empirical evidence to support similar countries in formulating phase-specific SDG promotion strategies.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
In this study,three specific scenarios of a novel accelerator light source mechanism called steady-state microbunching(SSMB)were studied:longitudinal weak focusing,longitudinal strong focusing,and generalized longitud...In this study,three specific scenarios of a novel accelerator light source mechanism called steady-state microbunching(SSMB)were studied:longitudinal weak focusing,longitudinal strong focusing,and generalized longitudinal strong focusing(GLSF).At present,GLSF is the most promising method for realizing high-power short-wavelength coherent radiation with mild requirements on modulation laser power.Its essence is to exploit the ultrasmall natural vertical emittance of an electron beam in a planar storage ring for efficient microbunching formation,like a partial transverse-longitudinal emittance exchange in the optical laser wavelength range.Based on an in-depth investigation of related beam physics,a solution for a GLSF SSMB storage ring that can deliver 1 kW average-power EUV light is presented.The work in this paper,such as the generalized Courant–Snyder formalism,analysis of theoretical minimum emittances,transverse-longitudinal coupling dynamics,and derivation of the bunching factor and modulation strengths for laser-induced microbunching schemes,is expected to be useful not only for the development of SSMB but also for future accelerator light sources in general that demand increasingly precise electron beam phase space manipulations.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
Electrocatalytic reduction of carbon dioxide(CO_(2))to multicarbon(C2+)products involves intricate multiple protons and electron transfer of C-C coupling,which is dictated by not only the intrinsic reactivity but also...Electrocatalytic reduction of carbon dioxide(CO_(2))to multicarbon(C2+)products involves intricate multiple protons and electron transfer of C-C coupling,which is dictated by not only the intrinsic reactivity but also the spin states of electrons in the catalyst.Here,we observe spin-enhanced CO_(2)reduction(CO_(2)RR)electrocatalytic activity on an oxidederived copper(OD-Cu)catalyst due to the existence of a specific Cu*site that carried the magnetic moments.Due to the correlation of magnetic and catalytic properties in OD-Cu,the current density through the OD-Cu electrode increases by nearly 10%at 350 mT.The field strength and angle dependence of such magnetic field effect(MFE),together with the time-resolved measurements proved that it originated from the alignment of magnetic moments on Cu*sites.The MFE on the electrocatalytic process enabled an enhancement(up to 15%)of the CO_(2)RR Faradaic efficiency using the OD-Cu catalyst.Importantly,the enhancement was attributed to the spinantiparallel alignment of electrons to promote C-C coupling on asymmetric Cu*-Cu sites;consequently,the optimal bias was reduced by∼0.2 V under the magnetic field for C2 products with Faradaic efficiency>30%and selectivity>75%.Our work uncovers a new paradigmfor spin-enhanced catalysis applicable to a broad range of chemical reactions involving spin singlet products.展开更多
Au and Au-containing bimetallic nanoparticles are promising catalysts for the green synthesis of fine chemicals. Here, we used a Au6Pd/resin catalyst for the aerobic C-C cross-coupling of primary and secondary alcohol...Au and Au-containing bimetallic nanoparticles are promising catalysts for the green synthesis of fine chemicals. Here, we used a Au6Pd/resin catalyst for the aerobic C-C cross-coupling of primary and secondary alcohols to produce higher ketones under mild conditions. This is of importance to the construction of a C-C bond. Various substrates were used in the reaction system, and moderate to good yields were obtained. The catalysts can be reused at least five times without decrease of yield. The control experiment and XAFS characterization results showed that hydrogen au- to-transfer occurred on metallic Pd sites even under oxidative conditions. On alloying with Au, the Pd sites became resistant to oxidation and readily abstracted the β-H of the alcohols and transferred the hydride to the C=C bond in the reaction intermediate to give the saturated product.展开更多
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.
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.
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.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National Key Research and Development Program of China(2022YFB4600902)Shandong Provincial Science Foundation for Outstanding Young Scholars(ZR2024YQ020)。
文摘Wire arc additive manufacturing(WAAM)has emerged as a promising approach for fabricating large-scale components.However,conventional WAAM still faces challenges in optimizing microstructural evolution,minimizing additive-induced defects,and alleviating residual stress and deformation,all of which are critical for enhancing the mechanical performance of the manufactured parts.Integrating interlayer friction stir processing(FSP)into WAAM significantly enhances the quality of deposited materials.However,numerical simulation research focusing on elucidating the associated thermomechanical coupling mechanisms remains insufficient.A comprehensive numerical model was developed to simulate the thermomechanical coupling behavior in friction stir-assisted WAAM.The influence of post-deposition FSP on the coupled thermomechanical response of the WAAM process was analyzed quantitatively.Moreover,the residual stress distribution and deformation behavior under both single-layer and multilayer deposition conditions were investigated.Thermal analysis of different deposition layers in WAAM and friction stir-assisted WAAM was conducted.Results show that subsequent layer deposition induces partial remelting of the previously solidified layer,whereas FSP does not cause such remelting.Furthermore,thermal stress and deformation analysis confirm that interlayer FSP effectively mitigates residual stresses and distortion in WAAM components,thereby improving their structural integrity and mechanical properties.
基金supported by the National Key Research and Development Program of China (MOST)(Grant No.2022YFA1402800)the Chinese Academy of Sciences (CAS) Presidents International Fellowship Initiative (PIFI)(Grant No.2025PG0006)+3 种基金the National Natural Science Foundation of China (NSFC)(Grant Nos.51831012,12274437,and 52161160334)the CAS Project for Young Scientists in Basic Research (Grant No.YSBR-084)the CAS Youth Interdisciplinary Teamthe China Postdoctoral Science Foundation (Grant No.2025M773402)。
文摘Based on the Smit-Suhl formula,we propose a universal approach for solving the magnon-magnon coupling problem in bilayer coupled systems(e.g.,antiferromagnets).This method requires only the energy expression,enabling the automatic derivation of analytical expressions for the eigenmatrix elements via symbolic computation,eliminating the need for tedious manual calculations.Using this approach,we investigate the impact of magnetic hysteresis on magnon-magnon coupling in a system with interlayer Dzyaloshinskii-Moriya interaction(DMI).The magnetic hysteresis leads to an asymmetric magnetic field dependence of the resonance frequency and alters the number of degeneracy points between the pure optical and acoustic modes.Moreover,it can result in the coupling strength at the gap of the f–H phase diagram being nearly vanishing,contrary to the conventionally expected maximum.These results deepen the understanding of the effect of interlayer DMI on magnon–magnon coupling and the proposed universal method significantly streamlines the solving process of magnon–magnon coupling problems.
基金supported by the National Key Research and Development Program of China(No.2022YFF1301301)the Natural Science Foundation of Xiamen Municipality(No.3502Z202472047)the Geological Survey Program of China Geological Survey(DD20190303).
文摘To address the deficiencies in comprehensive surface contamination prevention strategies within China's nitrate-affected regions,this research innovatively proposes the DITAPH model-a systematic framework integrating groundwater nitrate vulnerability assessment and Nitrate Vulnerable Zones(NVZs)delineation through optimization of hydrogeological parameters.Based on detailed hydrogeological and hydrochemical investigations,the DITAPH model was applied in the plain areas of Quanzhou to evaluate its applicability.The model selected hydrogeological parameters(depth of groundwater,lithology of the vadose zone,topographic slope,aquifer water yield property),one climatic parameter(precipitation),and two anthropogenic parameters(land use type and population density)as assessment indicators.The results of the groundwater nitrate vulnerability assessment showed that the low,relatively low,relatively high,and high groundwater nitrate vulnerability zones in the study area accounted for 5.96%,35.44%,53.74%and 4.86%of the total area,respectively.Groundwater nitrate vulnerability was most strongly influenced by human activities,followed by groundwater depth and topographic slope.The high vulnerability zone is mainly affected by domestic and industrial wastewater,whereas the relatively high groundwater nitrate vulnerability zone is primarily influenced by agricultural activities.Validation of the DITAPH model revealed a significant positive correlation between the DITAPH index(DI)and nitrate concentration(ρ(NO3−)).The results of the NVZs delineated by the DITAPH model are reliable and can serve as a tool for water resource management planning,guiding the development of targeted measures in the NVZs to prevent groundwater contamination.
基金supported by the National Natural Science Foundation of China(Nos.22373063 and 22302005)Fundamental Research Funds for the Central Universities of China(No.GK202203002)+1 种基金China Postdoctoral Science Foundation(No.2023M730044)Technology Innovation Leading Program of Shaanxi(Program No.2023KXJ-007).
文摘Deep insights into electrocatalytic mechanisms are vital for the rational design of catalysts for oxygen evolution reaction(OER).Mechanistically,the OER driven by adsorbate evolution mechanism(AEM)is limited by the linear scaling relationship,thereby exhibiting large overpotentials.In the lattice oxygen mechanism(LOM),the OER can be enhanced by enabling direct O_(2)formation.However,this enhancement is accompanied by the generation of oxygen vacancies,which presents a significant challenge to the long-term stability of LOMOER,particularly when operating at high current densities.Recently,the*O-*O coupling mechanism(OCM)has emerged as a promising alternative;it not only breaks the linear scaling relationship but also ensures catalytic stability.This review encapsulates the cutting-edge advancements in electrocatalysts that are grounded in the OCM,offering a detailed interpretation on the foundational principles guiding the design of OCM-OER catalysts.It also highlights recent theoretical investigations combining machine learning(ML)with density functional theory(DFT)calculations to reveal OER mechanisms.At the end of this review,the challenges and opportunities associated with OCM-OER electrocatalysts are discussed.
文摘Since the United Nations launched the Sustainable Development Goals(SDGs)in 2015,global implementation has steadily advanced,yet prominent challenges persist.Progress has been uneven across regions and countries,with Tajikistan representing a typical example of such disparities.Based on 81 SDG indicators for Tajikistan from 2001 to 2023,this study applied a three-level coupling network framework:at the microscale,it identified synergies and trade-offs between indicators;at the mesoscale,it examined the strength and direction of linkages within four SDG-related components(society,finance,governance,and environment);and at the global level,it focused on the overall SDG interlinkages.Spearman’s rank correlation,sliding window method,and topological properties were employed to analyze the coupling dynamics of SDGs.Results showed that over 70.00%of associations in the global SDG network were of medium-to-low intensity,alongside extremely strong ones(|r|value approached 1.00,where r is the correlation coefficient).SDG interactions were generally limited,with stable local synergy clusters in core livelihood sectors.Network modularity fluctuated,reflecting a cycle of differentiation,integration,and fragmentation,while coupling efficiency varied with the external environment.Each component exhibited distinct functional characteristics.The social component maintained high connectivity through the“poverty alleviation-education-healthcare”loop.The environmental component shifted toward coordinated eco-economic governance.The governance-related component broke interdepartmental barriers,while the financial component showed weak links between resource-based indicators and consumption/employment indicators.Tajikistan’s SDG coupling evolved through three phases:survival-oriented(2001–2012),policy integration(2013–2018),and shock adaptation(2019–2023).These phases were driven by policy changes,resource industries,governance optimization,and external factors.This study enriches the analytical framework for understanding the dynamic coupling of SDGs in mountainous resource-dependent countries and provides empirical evidence to support similar countries in formulating phase-specific SDG promotion strategies.
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 the National Key Research and Development Program of China(No.2022YFA1603401)National Natural Science Foundation of China(Nos.12035010 and 12342501)+1 种基金Beijing Outstanding Young Scientist Program(No.JWZQ20240101006)the Tsinghua University Dushi Program.
文摘In this study,three specific scenarios of a novel accelerator light source mechanism called steady-state microbunching(SSMB)were studied:longitudinal weak focusing,longitudinal strong focusing,and generalized longitudinal strong focusing(GLSF).At present,GLSF is the most promising method for realizing high-power short-wavelength coherent radiation with mild requirements on modulation laser power.Its essence is to exploit the ultrasmall natural vertical emittance of an electron beam in a planar storage ring for efficient microbunching formation,like a partial transverse-longitudinal emittance exchange in the optical laser wavelength range.Based on an in-depth investigation of related beam physics,a solution for a GLSF SSMB storage ring that can deliver 1 kW average-power EUV light is presented.The work in this paper,such as the generalized Courant–Snyder formalism,analysis of theoretical minimum emittances,transverse-longitudinal coupling dynamics,and derivation of the bunching factor and modulation strengths for laser-induced microbunching schemes,is expected to be useful not only for the development of SSMB but also for future accelerator light sources in general that demand increasingly precise electron beam phase space manipulations.
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supported by the National Natural Science Foundation of China(grant no.21873105)the National Key Research and Development Program of China(grant no.2020YFA0710303)the CAS Project for Young Scientists in Basic Research(grant no.YSBR-004).
文摘Electrocatalytic reduction of carbon dioxide(CO_(2))to multicarbon(C2+)products involves intricate multiple protons and electron transfer of C-C coupling,which is dictated by not only the intrinsic reactivity but also the spin states of electrons in the catalyst.Here,we observe spin-enhanced CO_(2)reduction(CO_(2)RR)electrocatalytic activity on an oxidederived copper(OD-Cu)catalyst due to the existence of a specific Cu*site that carried the magnetic moments.Due to the correlation of magnetic and catalytic properties in OD-Cu,the current density through the OD-Cu electrode increases by nearly 10%at 350 mT.The field strength and angle dependence of such magnetic field effect(MFE),together with the time-resolved measurements proved that it originated from the alignment of magnetic moments on Cu*sites.The MFE on the electrocatalytic process enabled an enhancement(up to 15%)of the CO_(2)RR Faradaic efficiency using the OD-Cu catalyst.Importantly,the enhancement was attributed to the spinantiparallel alignment of electrons to promote C-C coupling on asymmetric Cu*-Cu sites;consequently,the optimal bias was reduced by∼0.2 V under the magnetic field for C2 products with Faradaic efficiency>30%and selectivity>75%.Our work uncovers a new paradigmfor spin-enhanced catalysis applicable to a broad range of chemical reactions involving spin singlet products.
基金supported by the National Natural Science Foundation of China (21373206, 21202163, 21303194, 21476227, 21503219)~~
文摘Au and Au-containing bimetallic nanoparticles are promising catalysts for the green synthesis of fine chemicals. Here, we used a Au6Pd/resin catalyst for the aerobic C-C cross-coupling of primary and secondary alcohols to produce higher ketones under mild conditions. This is of importance to the construction of a C-C bond. Various substrates were used in the reaction system, and moderate to good yields were obtained. The catalysts can be reused at least five times without decrease of yield. The control experiment and XAFS characterization results showed that hydrogen au- to-transfer occurred on metallic Pd sites even under oxidative conditions. On alloying with Au, the Pd sites became resistant to oxidation and readily abstracted the β-H of the alcohols and transferred the hydride to the C=C bond in the reaction intermediate to give the saturated product.
