C1 chemistry is the essence of coal chemistry and natural gas chemistry. Catalytic methods to efficiently convert C1 molecules into fuels and chemicals have been extensively studied. Syngas（CO ＋H_2） conversion is t...C1 chemistry is the essence of coal chemistry and natural gas chemistry. Catalytic methods to efficiently convert C1 molecules into fuels and chemicals have been extensively studied. Syngas（CO ＋H_2） conversion is the most important industrial reaction system in C1 chemistry, and Fe and Co catalysts, two major industrial catalysts, have been the focus of fundamental research and industrial application. In the last decade, considerable research efforts have been devoted to discoveries concerning catalyst structure and increasing market demands for olefins and oxygenates. Since the development of efficient catalysts would strongly benefit from catalyst design and the establishment of a new reaction system, this review comprehensively overviews syngas conversion in three main reactions, highlights the advances recently made and the challenges that remain open, and will stimulate future research activities. The first part of the review summarizes the breakthroughs in Fischer-Tropsch synthesis regarding the optimization of activity and stability, determination of the active phase, and mechanistic studies. The second part overviews the modulation of catalytic structure and product selectivity for Fischer-Tropsch to olefins（FTO）. Catalysts designed to produce higher alcohols, as well as to tune product selectivity in C1 chemistry, are described in the third section. Finally, present challenges in syngas conversion are proposed, and the solutions and prospects are discussed from the viewpoint of fundamental research and practical application. This review summarizes the latest advances in the design, preparation, and application of Fe/Co-based catalysts toward syngas conversion and presents the challenges and future directions in producing value-added fuels.展开更多
Two-dimensional(2D)metal organic frameworks(MOFs)are emerging as low-cost oxygen evolution reaction(OER)electrocatalysts,however,suffering aggregation and poor operation stability.Herein,ultrafine Fe_(3)O_(4) nanopart...Two-dimensional(2D)metal organic frameworks(MOFs)are emerging as low-cost oxygen evolution reaction(OER)electrocatalysts,however,suffering aggregation and poor operation stability.Herein,ultrafine Fe_(3)O_(4) nanoparticles(diameter:6±2 nm)are homogeneously immobilized on 2D Ni based MOFs(Ni-BDC,thickness:5±1 nm)to improve the OER stability.Electronic structure modulation for enhanced catalytic activity is studied via adjusting the amount of Fe_(3)O_(4) nanoparticles on Ni-BDC.The optimal Fe_(3)O_(4)/Ni-BDC achieves the best OER performance with an overpotential of 295 mV at 10 mA cm^(-2),a Tafel slope of 47.8 mV dec^(-1) and a considerable catalytic durability of more than 40 h(less than 5 h for Ni-BDC alone).DFT calculations confirm that the active sites for Fe_(3)O_(4)/Ni-BDC are mainly contributed by Fe species with a higher oxidation state,and the potential-determining step(PDS)is the formation of the adsorbed O*species,which are facilitated in the composite.展开更多
Organic semiconductors are inherently soft,making it possible to increase their mobilities by strains.Such a unique feature can be exploited directly in flexible electronics for improved device performance.The 2,7-dio...Organic semiconductors are inherently soft,making it possible to increase their mobilities by strains.Such a unique feature can be exploited directly in flexible electronics for improved device performance.The 2,7-dioctyl[1]benzothieno[3,2-b][1]-benzothiophene derivative,C8-BTBT is one of the best small-molecule hole transport materials.Here,we demonstrated its band structure modulation under strains by combining the non-equilibrium molecular dynamics simulations and first-principles calculations.We found that the C8-BTBT lattice undergoes a transition from monoclinic to triclinic crystal system at the temperature below 160 K.Both shear and uniaxial strains were applied to the low-temperature triclinic phase of C8-BTBT,and polymorphism was identified in the shear process.The band width enhancement is up to 8%under 2%of compressive strain along the x direction,and 14%under 4%of tensile strain along the y direction.The band structure modulation of C8-BTBT can be well related to its herringbone packing motifs,where the edge to face and edge to edge pairs constitute two-dimensional charge transport pathways and their electronic overlaps determine the band widths along the two directions respectively.These findings pave the way for utilizing strains towards improved performance of organic semiconductors on flexible substrates,for example,by bending the substrates.展开更多
The laminated transition metal disulfides(TMDs),which are well known as typical two-dimensional(2D)semiconductive materials,possess a unique layered structure,leading to their wide-spread applications in various field...The laminated transition metal disulfides(TMDs),which are well known as typical two-dimensional(2D)semiconductive materials,possess a unique layered structure,leading to their wide-spread applications in various fields,such as catalysis,energy storage,sensing,etc.In recent years,a lot of research work on TMDs based functional materials in the fields of electromagnetic wave absorption(EMA)has been carried out.Therefore,it is of great significance to elaborate the influence of TMDs on EMA in time to speed up the application.In this review,recent advances in the development of electromagnetic wave(EMW)absorbers based on TMDs,ranging from the VIB group to the VB group are summarized.Their compositions,microstructures,electronic properties,and synthesis methods are presented in detail.Particularly,the modulation of structure engineering from the aspects of heterostructures,defects,morphologies and phases are systematically summarized,focusing on optimizing impedance matching and increasing dielectric and magnetic losses in the EMA materials with tunable EMW absorption performance.Milestones as well as the challenges are also identified to guide the design of new TMDs based dielectric EMA materials with high performance.展开更多
The sluggish electrochemical catalytic activity of the graphite felt electrodes for anode reaction is still a barrier for achieving high-performance vanadium redox flow battery(VRFB).It is significant to leverage the ...The sluggish electrochemical catalytic activity of the graphite felt electrodes for anode reaction is still a barrier for achieving high-performance vanadium redox flow battery(VRFB).It is significant to leverage the exceptional conductivity,excellent electrocatalytic activity,and structural tunability of MXene to address this issue.Herein,this work introduces nitrogen atoms to modulate the carbon layer structure of Ti_(3)C_(2)T_(x)MXene,inducing a reconfiguration of the local electronic structure,which enhances the anode interface activity and thereby improves the performance of VRFB.Ti_(3)C_(2)T_(x)exhibits high conductivity,excellent hydrophilicity,and a large specific surface area,providing excellent interface characteristics for V^(3+)/V^(2+)redox reaction.Moreover,interlayer treatment to modulate the mesoporous structure of MXene further increases the reactive surface area.Importantly,doping nitrogen atoms at carbon layer induces lattice distortions in Ti_(3)C_(2)T_(x),which enhances the charge transfer processes of the V^(3+)/V^(2+)redox reaction.The catalysis mechanism is also validated through density functional theory.Furthermore,the modified graphite felt electrode,as the anode of VRFB,relieves a higher energy efficiency of 68%at 250 mA cm^(-2),while the pristine electrode cannot operate at this current density.In addition,at 150 mA cm^(-2),the modified battery maintains energy efficiency at 75%without degradation after 500 cycles.This study utilizes rational atomic-level engineering for effective structural modulation to significantly enhance the catalytic activity of electrode reaction,offering a unique perspective for developing high-performance MXene electrocatalysts of VRFB.展开更多
Significant two-way shape memory effect(TWSME)was achieved in single crystals of single-phase multielement Ni42-x Cu8 Cox Mn37 Ga13(8≤x≤12)alloys by performing thermomechanical training.However,anomalous dependence ...Significant two-way shape memory effect(TWSME)was achieved in single crystals of single-phase multielement Ni42-x Cu8 Cox Mn37 Ga13(8≤x≤12)alloys by performing thermomechanical training.However,anomalous dependence of the martensitic transformation temperature span on Co content was observed.Before training,quite a narrow temperature span of the martensitic transformation,nearly independent of the Co content,was observed in all single crystals.After training the temperature span was still narrow for 8≤x≤10.9 but was obviously expanded for 10.9<x≤12.High-resolution transmission electron microscopy revealed that at the atomic scale,there exists incommensurate modulated structure in the single phase single crystals,as evidenced by nonperiodic satellite spots in the selected area electronic diffraction patterns.Moreover,the modulated wave vector of the satellite spots was increased by higher Co contents.Combining first principal calculations it was considered that the incommensurate modulated structure originates from the formation of Co-Co pairs.After training arrays of ordered dislocations with the same Burgers vector were introduced for 8≤x≤10.9 but the network of dislocations was formed for 10.9<x≤12.Based on analysis of transmission electron microscopy,geometric phase,thermodynamics,and Landau theory,it was considered that the austenite/martensite phase interface was pinned by the network of dislocations,expanding the temperature span of the martensitic transformation.This work supplies new insights for understanding the microstructure and martensitic transformation of Ni-Mn-Ga-based alloys.展开更多
Regulating the electronic structure and oxygencontaining intermediates adsorption behavior on Fe-based catalysts is of great significance to cope with the sluggish oxygen reduction reaction(ORR)kinetics,but it still r...Regulating the electronic structure and oxygencontaining intermediates adsorption behavior on Fe-based catalysts is of great significance to cope with the sluggish oxygen reduction reaction(ORR)kinetics,but it still remains a great challenge.In this work,Fe atom clusters(Fe_(AC))modified by high-density Cu single atoms(Cu_(SA))in a N,S-doped porous carbon substrate(Fe_(AC)/Cu_(SA)@NCS)is reported for enhanced ORR electrocatalysis.Fe_(AC)/Cu_(SA)@NCS exhibits excellent ORR performance with a half-wave potential(E_(1/2))of 0.911 V,a high four-electron process selectivity and excellent stability.The ORR performance is also verified in the Fe_(AC)/Cu_(SA)@NCS-based Zn-air battery,which shows a high peak power density of 192.67 mW cm^(-2),a higher specific capacity of 808.3 mAh g^(-1)and impressive charge-discharge cycle stability.Moreover,density functional theory calculations show that Cu single atoms synergistically modulate the electronic structure Fe active atoms in Fe atomic clusters,reducing the energy barrier of the rate-determining step(i.e.,*OH desorption)on Fe_(AC)/Cu_(SA)@NCS.This work provides an effective way to regulate the electronic structure of Fe-based catalysts and optimize their electrocatalytic activity based on the introduction of a second metal source.展开更多
Single-atom catalysts are promising for H_(2)O_(2) photosynthesis from O_(2) and H_(2)O,but their efficiency is still limited by the ill-defined electronic structure.In this study,Co single-atoms with unique four plan...Single-atom catalysts are promising for H_(2)O_(2) photosynthesis from O_(2) and H_(2)O,but their efficiency is still limited by the ill-defined electronic structure.In this study,Co single-atoms with unique four planar N-coordination and one axial P-coordination(Co-N_(4)P_(1))are decorated on the lateral edges of nanorod-like crystalline g-C_(3)N_(4)(CCN)photocatalysts.Significantly,the electronic structures of central Co as active sites for O_(2) reduction reaction(ORR)and planar N-coordinator as active sites for H_(2)O oxidation reaction(WOR)in Co-N_(4)P_(1) can be well regulated by the synergetic effects of introducing axial P-coordinator,in contrast to the decorated Co single-atoms with only four planar N-coordination(Co-N_(4)).Specifically,directional photoelectron accumulation at central Co active sites,induced by an introduced midgap level in Co-N_(4)P_(1),mediates the ORR active sites from 4e–-ORR-selective terminal–NH_(2) sites to 2e–-ORR-selective Co sites,moreover,an elevated d-band center of Co 3d orbital strengthens ORR intermediate*OOH adsorption,thus jointly facilitating a highly selective and active 2e^(–)-ORR pathway to H_(2)O_(2) photosynthesis.Simultaneously,a downshifted p-band center of N_(2)p orbital in Co-N_(4)P_(1) weakens WOR intermediate*OH adsorption,thus enabling a preferable 2e^(–)-WOR pathway toward H_(2)O_(2) photosynthesis.Subsequently,Co-N_(4)P_(1) exhibits exceptional H_(2)O_(2) photosynthesis efficiency,reaching 295.6μmol g^(-1) h^(-1) with a remarkable solar-to-chemical conversion efficiency of 0.32%,which is 15 times that of Co-N_(4)(19.2μmol g^(-1) h^(-1))and 10 times higher than CCN(27.6μmol g^(-1) h^(-1)).This electronic structure modulation on single-atom catalysts offers a promising strategy for boosting the activity and selectivity of H_(2)O_(2) photosynthesis.展开更多
Efficient energy storage devices with suitable electrode materials,that integrate high power and high energy,are the crucial requisites of the renewable power source,which have unwrapped new possibilities in the susta...Efficient energy storage devices with suitable electrode materials,that integrate high power and high energy,are the crucial requisites of the renewable power source,which have unwrapped new possibilities in the sustainable development of energy and the environment.Herein,a facile collagen microstructure modulation strategy is proposed to construct a nitrogen/oxygen dual-doped hierarchically porous carbon fiber with ultrahigh specific surface area(2788 m^(2)g^(-1))and large pore volume(4.56 cm^(3)g^(-1))via local microfibrous breakage/disassembly of natural structured proteins.Combining operando spectroscopy and density functional theory unveil that the dual-heteroatom doping could effectively regulate the electronic structure of carbon atom framework with enhanced electric conductivity and electronegativity as well as decreased diffusion resistance in favor of rapid pseudocapacitive-dominated Li^(+)-storage(353 mAh g^(-1)at 10 A g^(-1)).Theoretical calculations reveal that the tailored micro-/mesoporous structures favor the rapid charge transfer and ion storage,synergistically realizing high capacity and superior rate performance for NPCF-H cathode(75.0 mAh g^(-1)at 30 A g^(-1)).The assembled device with NPCF-H as both anode and cathode achieves extremely high energy density(200 Wh kg^(-1))with maximum power density(42600 W kg^(-1))and ultralong lifespan(80%capacity retention over 10000 cycles).展开更多
The electrochemical CO_(2) reduction(ECR)into value-added products presents an appealing approach to mitigate CO_(2) emission caused by excess consumption of fossil fuels.To obtain high catalytic activity and selectiv...The electrochemical CO_(2) reduction(ECR)into value-added products presents an appealing approach to mitigate CO_(2) emission caused by excess consumption of fossil fuels.To obtain high catalytic activity and selectivity toward target product in ECR,designing and developing a stable and efficient electrocatalyst is of significant importance.To date,metal nanomaterials have been widely applied as electrocatalysts for ECR due to their unique physicochemical properties.The structural modulation of metal nanomaterials is an attractive strategy to improve the catalytic performance.In this review,the recent progress of structural modulation,including size,facet,grain boundary,composition,interface,ligand modification,and crystal phase,is systematically summarized from both theoretical and experimental aspects.Finally,the opportunities and perspectives of structural modulation of metal nanomaterials for ECR are proposed.展开更多
As a promising cathode material for sodium ion batteries,honeycomb-ordered layered Na_(3)Ni_(2)Sb O_(6)still suffers from rapid capacity fading because of partially irreversible phase transition.Herein,a substitution ...As a promising cathode material for sodium ion batteries,honeycomb-ordered layered Na_(3)Ni_(2)Sb O_(6)still suffers from rapid capacity fading because of partially irreversible phase transition.Herein,a substitution of Na+by Rb+with a larger ionic radius in honeycomb layered Na_(3)-xRbxNi_(2)Sb O_(6)is proposed to modulate the interlayer structure.The results unveil that biphasic transition reversibility of the intermediate P′3phase is substantially enhanced,and the structure evolution behavior during the charge/discharge process changes due to the structural modulation,which contributes to a suppression of the unfavorable O_(1)phase and an alleviation of the lattice distortion.Moreover,Rb substituted samples exhibited an improved Na+(de)intercalation thermodynamics and kinetics.Attributed to the modifications,the sample with optimized Rb content delivers superior cycle stability and rate capacity,demonstrating a feasible strategy for suppressing irreversible phase transition and developing high-performance honeycomb layered materials for sodium ion batteries.展开更多
Transmission electron microscopy （TEM） study of SrPt2As2 reveals two incommensurate modulations appearing in the charge-density-wave （CDW） state below TCDW ≈ 470 K. These two structural modulations can be well ex...Transmission electron microscopy （TEM） study of SrPt2As2 reveals two incommensurate modulations appearing in the charge-density-wave （CDW） state below TCDW ≈ 470 K. These two structural modulations can be well explained in terms of condensations of two-coupled phonon modes with wave vectors of q1=0.62a＊ on the a＊-b＊ plane and q2 = 0.23a＊ on the a＊-c＊ plane. The atomic displacements occur along the b-axis direction for q1 and along the c-axis direction for q2, respectively. Moreover, the correlation between ql and q2 can be generally written as q1 = （q2 ＋ a＊）/2 in the CDW state, suggesting the presence of essential coupling between q1 and q2. A small fraction of Ir doping on the Pt site in Sr（Pt1-xIrx）2As2 （x ≤ 0.06） could moderately change these CDW modulations and also affect their superconductivities.展开更多
1.IntroductionSince the theory of spinodal decompo-sition in a supersaturated solid solution wasformulated by Hillert[1]and Cahn[2],thephenomena of spinodal decomposition havebeen found in many alloys.Tamura[3]haspoin...1.IntroductionSince the theory of spinodal decompo-sition in a supersaturated solid solution wasformulated by Hillert[1]and Cahn[2],thephenomena of spinodal decomposition havebeen found in many alloys.Tamura[3]haspointed out that spinodal decompositioncould also occur in maraging steels.A mod-ulated structure in 8Ni maraging steel was展开更多
The Nd Fe B/Co multilayer films were prepared by magnetron sputtering. After that, the samples were annealed at 600 ℃ for 20 min. The surface morphology, phase structures and magnetic properties of Mo（50 nm）/[Nd F...The Nd Fe B/Co multilayer films were prepared by magnetron sputtering. After that, the samples were annealed at 600 ℃ for 20 min. The surface morphology, phase structures and magnetic properties of Mo（50 nm）/[Nd Fe B（100 nm）/Co（y）]×10/Mo（50 nm） thin films were researched by AFM, XRD and VSM, respectively. The results show that the films show stronger perpendicular magnetic anisotropy. When the thickness of Co layers is 10 nm, the coercivity Hc⊥ is the maximum, 295 k A/m. However, for y=10-20, the reduced remanence M/Ms of films has increased. When the thickness of Co layers is 20-30 nm, the Nd Fe B/Co multilayer films obtained more superior magnetic properties with M/Ms =0.95.展开更多
A series of perovskite compounds of La1-x-yCaxKyMnO3 was prepared by hydrothermal disproportionation reaction of MnO2. The three oxidation states of manganese（Mn3＋, Mn4＋ and Mn5＋） can stably exist in the compound...A series of perovskite compounds of La1-x-yCaxKyMnO3 was prepared by hydrothermal disproportionation reaction of MnO2. The three oxidation states of manganese（Mn3＋, Mn4＋ and Mn5＋） can stably exist in the compounds. Under room temperature conditions, twice and three times modulated structure produced by the charge ordering can be observed by X-ray diffraction（XRD）, select area electron diffraction（SAED） and high resolution transmission electron microscopy（HR-TEM）. The splits of the diffraction peaks of the single crystals confirmed by synchrotron X-ray diffraction experiment are in accordance with those of the powder sample. The existence of the different oxidation states of Mn3＋, Mn4＋ and Mn5＋ can be considered to be the dominating reason of the complicated room temperature modulated structure.展开更多
Metal Fe/Pd compositionally modulated films(CMFs) were prepared by vapour depo- sition from two sources onto glass substrate under vacuum.The modulation and crystal structures of the films were examined by X-ray diffr...Metal Fe/Pd compositionally modulated films(CMFs) were prepared by vapour depo- sition from two sources onto glass substrate under vacuum.The modulation and crystal structures of the films were examined by X-ray diffraction.The magnetic properties were determined by vibrating sample magnetometer.The Pd layers in the Fe/Pd CMFs are of fcc structure,and the Fe layer structure transits from bcc into amorphous,state with decreasing thickness of Fe layer.The dependence of specific saturation magnetization on thickness of Fe layers has also been discussed.展开更多
Oxygen evolution reaction(OER)as the foremost stumbling block to generate cost-effective clean fuels has received extensive attention in recent years.But,it still maintains the challenge to manipulate the geometric an...Oxygen evolution reaction(OER)as the foremost stumbling block to generate cost-effective clean fuels has received extensive attention in recent years.But,it still maintains the challenge to manipulate the geometric and electronic structure during single reaction process under the same conditions.Herein,we report a simple self-template strategy to generate honeycomb-like Ni_(2)P/N,P-C hybrids with preferred electronic architecture.Experiments coupled with theoretical results revealed that the synthesized catalyst has two characteristics:firstly,the unique honeycomb-like morphology not only enables the fully utilization of catalytic active sites but also optimizes the mass/electron transportation pathway,which favor the diffusion of electrolyte to accessible active sites.Secondly,N,P-C substrate,on the one hand,largely contributes the electronic distribution near Fermi level(E_(F))thus boosting its electrical conductivity.On the other hand,the support effect result in the upshift of d-band center and electropositivity of Ni sites,which attenuates the energy barrier for the adsorption of OH~àand the formation of*OOH.In consequence,the optimized Ni_(2)P/N,P-C catalysts feature high electrocatalytic activity towards OER(a low overpotential of 252 m V to achieve10 m A cm^(-2))and 10 h long-term stability,the outstanding performance is comparable to most of transition metal catalysts.This work gives a innovative tactics for contriving original OER electrocatalysts,inspirng deeper understanding of fabricating catalysts by combining theoretical simulation and experiment design.展开更多
With the continuous improvement of China's science and technology, the design method of steel structure is also more and more, how to better apply the module building design method to the related buildings, is the...With the continuous improvement of China's science and technology, the design method of steel structure is also more and more, how to better apply the module building design method to the related buildings, is the current issue to focus on consideration. Therefore, this paper will focus on the design method of multi-layer steel structure module and steel frame composite building structure, and analyze and study its structure, so as to improve the utilization rate of steel structure and promote the development of the construction industry.展开更多
The importance of the zeros of multwariable linear systems is well-knoiun in terms of measure obstructions to the controllability and the. observability. In this paper, a recursive decarnposi Am oj interconnected syst...The importance of the zeros of multwariable linear systems is well-knoiun in terms of measure obstructions to the controllability and the. observability. In this paper, a recursive decarnposi Am oj interconnected systems is outlined by taking into account the sequential structure of the connnections. The paper extends the, coordinate, module-theoretic studies from the elementary algebraic systems theory to include the case oj such linear interconnected systems which need not to be controllable or observable. Also, the properties of controllability and observability, the decoupling zeros and the signal Making issues are characterized.展开更多
Polyvinyl chloride is the most widely used general-purpose plastic and plays a vital role in various industries.Mercury-based catalysts severely limit the green sustainability of industry.Non-metallic carbon materials...Polyvinyl chloride is the most widely used general-purpose plastic and plays a vital role in various industries.Mercury-based catalysts severely limit the green sustainability of industry.Non-metallic carbon materials are very promising alternatives in acetylene hydrochlorination,but their stability remains a challenge of major concern at present.Based on the principle of green chemistry,structurally tunable and defect-rich carbon materials were synthesized by hydrothermal carbonization and pyrolysis using glucose as carbon source and m-phenylenediamine as nitrogen source and cross-linking agent.Experimental characterization and density functional theory confirmed that pyridinic N was the main active site.The introduction of N not only regulated the formation of the hierarchically porous structure of the carbon material,but also increased the adsorption of HCl and decreased the adsorption strength of C_(2)H_(2).The synergistic effect of high N content and porous structure significantly enhanced the catalytic performance of the catalysts in acetylene hydrochlorination.The C_(2)H_(2)conversion was maintained at around98%after 100 h under the reaction conditions(T=220°C,GHSV(C_(2)H_(2))=30 h^(-1),V_(HCl)/VC_(2)H_(2)=1.15).Thus,the one-pot synthesis process used here is a good benchmark for future catalyst research.展开更多
文摘C1 chemistry is the essence of coal chemistry and natural gas chemistry. Catalytic methods to efficiently convert C1 molecules into fuels and chemicals have been extensively studied. Syngas（CO ＋H_2） conversion is the most important industrial reaction system in C1 chemistry, and Fe and Co catalysts, two major industrial catalysts, have been the focus of fundamental research and industrial application. In the last decade, considerable research efforts have been devoted to discoveries concerning catalyst structure and increasing market demands for olefins and oxygenates. Since the development of efficient catalysts would strongly benefit from catalyst design and the establishment of a new reaction system, this review comprehensively overviews syngas conversion in three main reactions, highlights the advances recently made and the challenges that remain open, and will stimulate future research activities. The first part of the review summarizes the breakthroughs in Fischer-Tropsch synthesis regarding the optimization of activity and stability, determination of the active phase, and mechanistic studies. The second part overviews the modulation of catalytic structure and product selectivity for Fischer-Tropsch to olefins（FTO）. Catalysts designed to produce higher alcohols, as well as to tune product selectivity in C1 chemistry, are described in the third section. Finally, present challenges in syngas conversion are proposed, and the solutions and prospects are discussed from the viewpoint of fundamental research and practical application. This review summarizes the latest advances in the design, preparation, and application of Fe/Co-based catalysts toward syngas conversion and presents the challenges and future directions in producing value-added fuels.
基金support from the Chinese Scholarship Council(201706220080)for W.H.the Natural Science Foundation of Hunan Province(2019JJ50526)for C.P.+1 种基金The Danish Council for Independent Research for the YDUN project(DFF 4093-00297)to J.Z.Villum Experiment(grant No.35844)for X.X.
文摘Two-dimensional(2D)metal organic frameworks(MOFs)are emerging as low-cost oxygen evolution reaction(OER)electrocatalysts,however,suffering aggregation and poor operation stability.Herein,ultrafine Fe_(3)O_(4) nanoparticles(diameter:6±2 nm)are homogeneously immobilized on 2D Ni based MOFs(Ni-BDC,thickness:5±1 nm)to improve the OER stability.Electronic structure modulation for enhanced catalytic activity is studied via adjusting the amount of Fe_(3)O_(4) nanoparticles on Ni-BDC.The optimal Fe_(3)O_(4)/Ni-BDC achieves the best OER performance with an overpotential of 295 mV at 10 mA cm^(-2),a Tafel slope of 47.8 mV dec^(-1) and a considerable catalytic durability of more than 40 h(less than 5 h for Ni-BDC alone).DFT calculations confirm that the active sites for Fe_(3)O_(4)/Ni-BDC are mainly contributed by Fe species with a higher oxidation state,and the potential-determining step(PDS)is the formation of the adsorbed O*species,which are facilitated in the composite.
基金supported by the National Natural Science Foundation of China(21273124,21290190,21290191 and 91333202)the Innovative Research Groups of the National Science Foundation of China(21421064)the National Basic Research Program of China(2013CB933503 and 2015CB655002)
文摘Organic semiconductors are inherently soft,making it possible to increase their mobilities by strains.Such a unique feature can be exploited directly in flexible electronics for improved device performance.The 2,7-dioctyl[1]benzothieno[3,2-b][1]-benzothiophene derivative,C8-BTBT is one of the best small-molecule hole transport materials.Here,we demonstrated its band structure modulation under strains by combining the non-equilibrium molecular dynamics simulations and first-principles calculations.We found that the C8-BTBT lattice undergoes a transition from monoclinic to triclinic crystal system at the temperature below 160 K.Both shear and uniaxial strains were applied to the low-temperature triclinic phase of C8-BTBT,and polymorphism was identified in the shear process.The band width enhancement is up to 8%under 2%of compressive strain along the x direction,and 14%under 4%of tensile strain along the y direction.The band structure modulation of C8-BTBT can be well related to its herringbone packing motifs,where the edge to face and edge to edge pairs constitute two-dimensional charge transport pathways and their electronic overlaps determine the band widths along the two directions respectively.These findings pave the way for utilizing strains towards improved performance of organic semiconductors on flexible substrates,for example,by bending the substrates.
基金This work was supported by the National Natural Science Foundation of China(52372289,52102368,52072192 and 51977009)Regional Joint Fund for Basic Research and Applied Basic Research of Guangdong Province(No.2020SA001515110905).
文摘The laminated transition metal disulfides(TMDs),which are well known as typical two-dimensional(2D)semiconductive materials,possess a unique layered structure,leading to their wide-spread applications in various fields,such as catalysis,energy storage,sensing,etc.In recent years,a lot of research work on TMDs based functional materials in the fields of electromagnetic wave absorption(EMA)has been carried out.Therefore,it is of great significance to elaborate the influence of TMDs on EMA in time to speed up the application.In this review,recent advances in the development of electromagnetic wave(EMW)absorbers based on TMDs,ranging from the VIB group to the VB group are summarized.Their compositions,microstructures,electronic properties,and synthesis methods are presented in detail.Particularly,the modulation of structure engineering from the aspects of heterostructures,defects,morphologies and phases are systematically summarized,focusing on optimizing impedance matching and increasing dielectric and magnetic losses in the EMA materials with tunable EMW absorption performance.Milestones as well as the challenges are also identified to guide the design of new TMDs based dielectric EMA materials with high performance.
基金financially supported by the National Natural Science Foundation of China(51872090,51772097)Hebei Natural Science Fund for Distinguished Young Scholar(E2019209433)+3 种基金Youth Talent Program of Hebei Provincial Education Department(BJ2018020)Natural Science Foundation of Hebei Province(E2020209151,E2024209029)National Key R&D Plan Project(2022YFB4200305)Research Projects of China National Petroleum Corporation(2024ZG50,2023DQ03-04)。
文摘The sluggish electrochemical catalytic activity of the graphite felt electrodes for anode reaction is still a barrier for achieving high-performance vanadium redox flow battery(VRFB).It is significant to leverage the exceptional conductivity,excellent electrocatalytic activity,and structural tunability of MXene to address this issue.Herein,this work introduces nitrogen atoms to modulate the carbon layer structure of Ti_(3)C_(2)T_(x)MXene,inducing a reconfiguration of the local electronic structure,which enhances the anode interface activity and thereby improves the performance of VRFB.Ti_(3)C_(2)T_(x)exhibits high conductivity,excellent hydrophilicity,and a large specific surface area,providing excellent interface characteristics for V^(3+)/V^(2+)redox reaction.Moreover,interlayer treatment to modulate the mesoporous structure of MXene further increases the reactive surface area.Importantly,doping nitrogen atoms at carbon layer induces lattice distortions in Ti_(3)C_(2)T_(x),which enhances the charge transfer processes of the V^(3+)/V^(2+)redox reaction.The catalysis mechanism is also validated through density functional theory.Furthermore,the modified graphite felt electrode,as the anode of VRFB,relieves a higher energy efficiency of 68%at 250 mA cm^(-2),while the pristine electrode cannot operate at this current density.In addition,at 150 mA cm^(-2),the modified battery maintains energy efficiency at 75%without degradation after 500 cycles.This study utilizes rational atomic-level engineering for effective structural modulation to significantly enhance the catalytic activity of electrode reaction,offering a unique perspective for developing high-performance MXene electrocatalysts of VRFB.
基金support from the National Key Research and Development Program of China(Grant No.2021YFB3501402)the National Natural Science Foundation of China(Grant Nos.52250313 and 52121001)Yang Liu and Chen Si acknowledge financial support from the National Natural Science Foundation of China(Grant No.12274013).
文摘Significant two-way shape memory effect(TWSME)was achieved in single crystals of single-phase multielement Ni42-x Cu8 Cox Mn37 Ga13(8≤x≤12)alloys by performing thermomechanical training.However,anomalous dependence of the martensitic transformation temperature span on Co content was observed.Before training,quite a narrow temperature span of the martensitic transformation,nearly independent of the Co content,was observed in all single crystals.After training the temperature span was still narrow for 8≤x≤10.9 but was obviously expanded for 10.9<x≤12.High-resolution transmission electron microscopy revealed that at the atomic scale,there exists incommensurate modulated structure in the single phase single crystals,as evidenced by nonperiodic satellite spots in the selected area electronic diffraction patterns.Moreover,the modulated wave vector of the satellite spots was increased by higher Co contents.Combining first principal calculations it was considered that the incommensurate modulated structure originates from the formation of Co-Co pairs.After training arrays of ordered dislocations with the same Burgers vector were introduced for 8≤x≤10.9 but the network of dislocations was formed for 10.9<x≤12.Based on analysis of transmission electron microscopy,geometric phase,thermodynamics,and Landau theory,it was considered that the austenite/martensite phase interface was pinned by the network of dislocations,expanding the temperature span of the martensitic transformation.This work supplies new insights for understanding the microstructure and martensitic transformation of Ni-Mn-Ga-based alloys.
基金financially supported by the National Natural Science Foundation of China(No.22278042)the National Natural Science Foundation of Jiangsu Province(No.BK20240567)+2 种基金the Introduction and Cultivation of Leading Innovative Talents Foundation of Changzhou,Jiangsu Province(No.CQ20220093)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.24KJD530001)the Open Project Program of Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science(No.M2024-7),MOE
文摘Regulating the electronic structure and oxygencontaining intermediates adsorption behavior on Fe-based catalysts is of great significance to cope with the sluggish oxygen reduction reaction(ORR)kinetics,but it still remains a great challenge.In this work,Fe atom clusters(Fe_(AC))modified by high-density Cu single atoms(Cu_(SA))in a N,S-doped porous carbon substrate(Fe_(AC)/Cu_(SA)@NCS)is reported for enhanced ORR electrocatalysis.Fe_(AC)/Cu_(SA)@NCS exhibits excellent ORR performance with a half-wave potential(E_(1/2))of 0.911 V,a high four-electron process selectivity and excellent stability.The ORR performance is also verified in the Fe_(AC)/Cu_(SA)@NCS-based Zn-air battery,which shows a high peak power density of 192.67 mW cm^(-2),a higher specific capacity of 808.3 mAh g^(-1)and impressive charge-discharge cycle stability.Moreover,density functional theory calculations show that Cu single atoms synergistically modulate the electronic structure Fe active atoms in Fe atomic clusters,reducing the energy barrier of the rate-determining step(i.e.,*OH desorption)on Fe_(AC)/Cu_(SA)@NCS.This work provides an effective way to regulate the electronic structure of Fe-based catalysts and optimize their electrocatalytic activity based on the introduction of a second metal source.
文摘Single-atom catalysts are promising for H_(2)O_(2) photosynthesis from O_(2) and H_(2)O,but their efficiency is still limited by the ill-defined electronic structure.In this study,Co single-atoms with unique four planar N-coordination and one axial P-coordination(Co-N_(4)P_(1))are decorated on the lateral edges of nanorod-like crystalline g-C_(3)N_(4)(CCN)photocatalysts.Significantly,the electronic structures of central Co as active sites for O_(2) reduction reaction(ORR)and planar N-coordinator as active sites for H_(2)O oxidation reaction(WOR)in Co-N_(4)P_(1) can be well regulated by the synergetic effects of introducing axial P-coordinator,in contrast to the decorated Co single-atoms with only four planar N-coordination(Co-N_(4)).Specifically,directional photoelectron accumulation at central Co active sites,induced by an introduced midgap level in Co-N_(4)P_(1),mediates the ORR active sites from 4e–-ORR-selective terminal–NH_(2) sites to 2e–-ORR-selective Co sites,moreover,an elevated d-band center of Co 3d orbital strengthens ORR intermediate*OOH adsorption,thus jointly facilitating a highly selective and active 2e^(–)-ORR pathway to H_(2)O_(2) photosynthesis.Simultaneously,a downshifted p-band center of N_(2)p orbital in Co-N_(4)P_(1) weakens WOR intermediate*OH adsorption,thus enabling a preferable 2e^(–)-WOR pathway toward H_(2)O_(2) photosynthesis.Subsequently,Co-N_(4)P_(1) exhibits exceptional H_(2)O_(2) photosynthesis efficiency,reaching 295.6μmol g^(-1) h^(-1) with a remarkable solar-to-chemical conversion efficiency of 0.32%,which is 15 times that of Co-N_(4)(19.2μmol g^(-1) h^(-1))and 10 times higher than CCN(27.6μmol g^(-1) h^(-1)).This electronic structure modulation on single-atom catalysts offers a promising strategy for boosting the activity and selectivity of H_(2)O_(2) photosynthesis.
基金financial support from the National Natural Science Foundation of China(21878192 and 51904193)the Fundamental Research Funds for the Central Universities(YJ2021141)the Science and Technology Cooperation Special Fund of Sichuan University and Zigong City(2021CDZG-14)
文摘Efficient energy storage devices with suitable electrode materials,that integrate high power and high energy,are the crucial requisites of the renewable power source,which have unwrapped new possibilities in the sustainable development of energy and the environment.Herein,a facile collagen microstructure modulation strategy is proposed to construct a nitrogen/oxygen dual-doped hierarchically porous carbon fiber with ultrahigh specific surface area(2788 m^(2)g^(-1))and large pore volume(4.56 cm^(3)g^(-1))via local microfibrous breakage/disassembly of natural structured proteins.Combining operando spectroscopy and density functional theory unveil that the dual-heteroatom doping could effectively regulate the electronic structure of carbon atom framework with enhanced electric conductivity and electronegativity as well as decreased diffusion resistance in favor of rapid pseudocapacitive-dominated Li^(+)-storage(353 mAh g^(-1)at 10 A g^(-1)).Theoretical calculations reveal that the tailored micro-/mesoporous structures favor the rapid charge transfer and ion storage,synergistically realizing high capacity and superior rate performance for NPCF-H cathode(75.0 mAh g^(-1)at 30 A g^(-1)).The assembled device with NPCF-H as both anode and cathode achieves extremely high energy density(200 Wh kg^(-1))with maximum power density(42600 W kg^(-1))and ultralong lifespan(80%capacity retention over 10000 cycles).
基金financially supported by the National Key R&D Program(N os.2017 YF A0204503 and 2016YFB0401100)the National Natural Science Foundation of China(Nos.91833306,21875158,51633006 and 51703159)。
文摘The electrochemical CO_(2) reduction(ECR)into value-added products presents an appealing approach to mitigate CO_(2) emission caused by excess consumption of fossil fuels.To obtain high catalytic activity and selectivity toward target product in ECR,designing and developing a stable and efficient electrocatalyst is of significant importance.To date,metal nanomaterials have been widely applied as electrocatalysts for ECR due to their unique physicochemical properties.The structural modulation of metal nanomaterials is an attractive strategy to improve the catalytic performance.In this review,the recent progress of structural modulation,including size,facet,grain boundary,composition,interface,ligand modification,and crystal phase,is systematically summarized from both theoretical and experimental aspects.Finally,the opportunities and perspectives of structural modulation of metal nanomaterials for ECR are proposed.
基金funded by the NSFC Grant(52177213)supported through NSFC Committee of Chinathe foundation(2020A1414010346 and 2019622163008)supported through the Science and Technology Bureau of Guangdong Governmentsponsored by the Student Research Program(X202110561688)supported through South China University of Technology。
文摘As a promising cathode material for sodium ion batteries,honeycomb-ordered layered Na_(3)Ni_(2)Sb O_(6)still suffers from rapid capacity fading because of partially irreversible phase transition.Herein,a substitution of Na+by Rb+with a larger ionic radius in honeycomb layered Na_(3)-xRbxNi_(2)Sb O_(6)is proposed to modulate the interlayer structure.The results unveil that biphasic transition reversibility of the intermediate P′3phase is substantially enhanced,and the structure evolution behavior during the charge/discharge process changes due to the structural modulation,which contributes to a suppression of the unfavorable O_(1)phase and an alleviation of the lattice distortion.Moreover,Rb substituted samples exhibited an improved Na+(de)intercalation thermodynamics and kinetics.Attributed to the modifications,the sample with optimized Rb content delivers superior cycle stability and rate capacity,demonstrating a feasible strategy for suppressing irreversible phase transition and developing high-performance honeycomb layered materials for sodium ion batteries.
基金Project supported by the National Basic Research Program of China(Grant Nos.2011CBA00101,2010CB923002,2012CB821404,and 2011CB921703)the National Natural Science Foundation of China(Grant Nos.11190022,11274368,and 51272277)the Funds from the Chinese Academy of Sciences
文摘Transmission electron microscopy （TEM） study of SrPt2As2 reveals two incommensurate modulations appearing in the charge-density-wave （CDW） state below TCDW ≈ 470 K. These two structural modulations can be well explained in terms of condensations of two-coupled phonon modes with wave vectors of q1=0.62a＊ on the a＊-b＊ plane and q2 = 0.23a＊ on the a＊-c＊ plane. The atomic displacements occur along the b-axis direction for q1 and along the c-axis direction for q2, respectively. Moreover, the correlation between ql and q2 can be generally written as q1 = （q2 ＋ a＊）/2 in the CDW state, suggesting the presence of essential coupling between q1 and q2. A small fraction of Ir doping on the Pt site in Sr（Pt1-xIrx）2As2 （x ≤ 0.06） could moderately change these CDW modulations and also affect their superconductivities.
文摘1.IntroductionSince the theory of spinodal decompo-sition in a supersaturated solid solution wasformulated by Hillert[1]and Cahn[2],thephenomena of spinodal decomposition havebeen found in many alloys.Tamura[3]haspointed out that spinodal decompositioncould also occur in maraging steels.A mod-ulated structure in 8Ni maraging steel was
文摘The Nd Fe B/Co multilayer films were prepared by magnetron sputtering. After that, the samples were annealed at 600 ℃ for 20 min. The surface morphology, phase structures and magnetic properties of Mo（50 nm）/[Nd Fe B（100 nm）/Co（y）]×10/Mo（50 nm） thin films were researched by AFM, XRD and VSM, respectively. The results show that the films show stronger perpendicular magnetic anisotropy. When the thickness of Co layers is 10 nm, the coercivity Hc⊥ is the maximum, 295 k A/m. However, for y=10-20, the reduced remanence M/Ms of films has increased. When the thickness of Co layers is 20-30 nm, the Nd Fe B/Co multilayer films obtained more superior magnetic properties with M/Ms =0.95.
基金Supported by the National Natural Science Foundation of China(No.90922034)
文摘A series of perovskite compounds of La1-x-yCaxKyMnO3 was prepared by hydrothermal disproportionation reaction of MnO2. The three oxidation states of manganese（Mn3＋, Mn4＋ and Mn5＋） can stably exist in the compounds. Under room temperature conditions, twice and three times modulated structure produced by the charge ordering can be observed by X-ray diffraction（XRD）, select area electron diffraction（SAED） and high resolution transmission electron microscopy（HR-TEM）. The splits of the diffraction peaks of the single crystals confirmed by synchrotron X-ray diffraction experiment are in accordance with those of the powder sample. The existence of the different oxidation states of Mn3＋, Mn4＋ and Mn5＋ can be considered to be the dominating reason of the complicated room temperature modulated structure.
文摘Metal Fe/Pd compositionally modulated films(CMFs) were prepared by vapour depo- sition from two sources onto glass substrate under vacuum.The modulation and crystal structures of the films were examined by X-ray diffraction.The magnetic properties were determined by vibrating sample magnetometer.The Pd layers in the Fe/Pd CMFs are of fcc structure,and the Fe layer structure transits from bcc into amorphous,state with decreasing thickness of Fe layer.The dependence of specific saturation magnetization on thickness of Fe layers has also been discussed.
基金supported by the Major Science and Technology Program for Water Pollution Control and Treatment(2017ZX07402001)the Ministry of Science and Technology of China for their financial support and the associated project is the Key Program for International S&T Cooperation Projects(No.2018YFE0124600)。
文摘Oxygen evolution reaction(OER)as the foremost stumbling block to generate cost-effective clean fuels has received extensive attention in recent years.But,it still maintains the challenge to manipulate the geometric and electronic structure during single reaction process under the same conditions.Herein,we report a simple self-template strategy to generate honeycomb-like Ni_(2)P/N,P-C hybrids with preferred electronic architecture.Experiments coupled with theoretical results revealed that the synthesized catalyst has two characteristics:firstly,the unique honeycomb-like morphology not only enables the fully utilization of catalytic active sites but also optimizes the mass/electron transportation pathway,which favor the diffusion of electrolyte to accessible active sites.Secondly,N,P-C substrate,on the one hand,largely contributes the electronic distribution near Fermi level(E_(F))thus boosting its electrical conductivity.On the other hand,the support effect result in the upshift of d-band center and electropositivity of Ni sites,which attenuates the energy barrier for the adsorption of OH~àand the formation of*OOH.In consequence,the optimized Ni_(2)P/N,P-C catalysts feature high electrocatalytic activity towards OER(a low overpotential of 252 m V to achieve10 m A cm^(-2))and 10 h long-term stability,the outstanding performance is comparable to most of transition metal catalysts.This work gives a innovative tactics for contriving original OER electrocatalysts,inspirng deeper understanding of fabricating catalysts by combining theoretical simulation and experiment design.
文摘With the continuous improvement of China's science and technology, the design method of steel structure is also more and more, how to better apply the module building design method to the related buildings, is the current issue to focus on consideration. Therefore, this paper will focus on the design method of multi-layer steel structure module and steel frame composite building structure, and analyze and study its structure, so as to improve the utilization rate of steel structure and promote the development of the construction industry.
文摘The importance of the zeros of multwariable linear systems is well-knoiun in terms of measure obstructions to the controllability and the. observability. In this paper, a recursive decarnposi Am oj interconnected systems is outlined by taking into account the sequential structure of the connnections. The paper extends the, coordinate, module-theoretic studies from the elementary algebraic systems theory to include the case oj such linear interconnected systems which need not to be controllable or observable. Also, the properties of controllability and observability, the decoupling zeros and the signal Making issues are characterized.
基金supported by the Tianchi Innovation Leading Talent Development Fund(No.CZ002710)in Xinjiangthe Taishan Scholars Program of Shandong Province(No.tsqn202103051)+4 种基金the Project of Science and Technology Development of Yantai City(No.2023JCYJ073)Natural science foundation of Shandong province(No.ZR2023MB064)special funds for over provincial level leading talent of Yantai citythe Start-Up Foundation for High-level Professionals of Shihezi University(No.RCZK201932)Tianshan Talents Training Program of Xinjiang(Science and Technology Innovation Team,No.2022TSYCTD0021)。
文摘Polyvinyl chloride is the most widely used general-purpose plastic and plays a vital role in various industries.Mercury-based catalysts severely limit the green sustainability of industry.Non-metallic carbon materials are very promising alternatives in acetylene hydrochlorination,but their stability remains a challenge of major concern at present.Based on the principle of green chemistry,structurally tunable and defect-rich carbon materials were synthesized by hydrothermal carbonization and pyrolysis using glucose as carbon source and m-phenylenediamine as nitrogen source and cross-linking agent.Experimental characterization and density functional theory confirmed that pyridinic N was the main active site.The introduction of N not only regulated the formation of the hierarchically porous structure of the carbon material,but also increased the adsorption of HCl and decreased the adsorption strength of C_(2)H_(2).The synergistic effect of high N content and porous structure significantly enhanced the catalytic performance of the catalysts in acetylene hydrochlorination.The C_(2)H_(2)conversion was maintained at around98%after 100 h under the reaction conditions(T=220°C,GHSV(C_(2)H_(2))=30 h^(-1),V_(HCl)/VC_(2)H_(2)=1.15).Thus,the one-pot synthesis process used here is a good benchmark for future catalyst research.
