Quasi-solid electrolytes(QSEs)based on nanoporous materials are promising candidates to construct high-performance Limetal batteries(LMBs).However,simultaneously boosting the ionic conductivity(σ)and lithium-ion tran...Quasi-solid electrolytes(QSEs)based on nanoporous materials are promising candidates to construct high-performance Limetal batteries(LMBs).However,simultaneously boosting the ionic conductivity(σ)and lithium-ion transference number(t^(+)) of liquid electrolyte confined in porous matrix remains challenging.Herein,we report a novel Janus MOFLi/MSLi QSEs with asymmetric porous structure to inherit the benefits of both mesoporous and microporous hosts.This Janus QSE composed of mesoporous silica and microporous MOF exhibits a neat Li^(+) conductivity of 1.5.10^(–4)S cm^(−1) with t^(+) of 0.71.A partially de-solvated structure and preference distribution of Li^(+)near the Lewis base O atoms were depicted by MD simulations.Meanwhile,the nanoporous structure enabled efficient ion flux regulation,promoting the homogenous deposition of Li^(+).When incorporated in Li||Cu cells,the MOFLi/MSLi QSEs demonstrated a high Coulombic efficiency of 98.1%,surpassing that of liquid electrolytes(96.3%).Additionally,NCM 622||Li batteries equipped with MOFLi/MSLi QSEs exhibited promising rate performance and could operate stably for over 200 cycles at 1 C.These results highlight the potential of Janus MOFLi/MSLi QSEs as promising candidates for next-generation LMBs.展开更多
Polyimide(PI)is a promising electronic packaging material,but it remains challenging to obtain an all-organic PI hybrid film with decreased dielectric constant and loss without modifying the monomer.Herein,a series of...Polyimide(PI)is a promising electronic packaging material,but it remains challenging to obtain an all-organic PI hybrid film with decreased dielectric constant and loss without modifying the monomer.Herein,a series of allorganic PI hybrid films were successfully prepared by introducing the covalent organic framework(COF),which could induce the formation of the cross-linking structure in the PI matrix.Due to the synergistic effects of the COF fillers and the cross-linking structure,the PI/COF hybrid film containing 2 wt%COF exhibited the lowest dielectric constant of 2.72 and the lowest dielectric loss(tanδ)of 0.0077 at 1 MHz.It is attributed to the intrinsic low dielectric constant of COF and a large number of mesopores within the PI.Besides,the cross-linking network of PI prevents the molecular chains from stacking and improves the fraction of free volume(FFV).The molecular dynamics simulation results are well consistent with the dielectric properties data.Furthermore,the PI/COF hybrid film with 5 wt%COF showed a significant enhancement in breakdown strength,which increased to 412.8 kV/mm as compared with pure PI.In addition,the PI/COF hybrid film achieve to reduce the dielectric constant and thermal expansion coefficient(CTE).It also exhibited excellent thermal,hydrophobicity,and mechanical performance.The all-organic PI/COF hybrid films have great commercial potential as next-generation electronic packaging materials.展开更多
The establishment of efficient oxygen evolution electrocatalysts is of great value but also challenging.Herein,a durable metal–organic framework(MOF)with minor atomically dispersed ruthenium and an optimized electron...The establishment of efficient oxygen evolution electrocatalysts is of great value but also challenging.Herein,a durable metal–organic framework(MOF)with minor atomically dispersed ruthenium and an optimized electronic structure is constructed as an efficient electrocatalyst.Significantly,the obtained NiRu_(0.08)-MOF with doping Ru only needs an overpotential of 187 mV at 10 mA cm^(-2) with a Tafel slop of 40 mV dec^(-1) in 0.1M KOH for the oxygen evolution reaction,and can work continuously for more than 300 h.Ultrahigh Ru mass activity is achieved,reaching 56.7 Ag^(-1)_(Ru) at an overpotential of 200 mV,which is 36 times higher than that of commercial RuO_(2).X-ray adsorption spectroscopy and density function theory calculations reveal that atomically dispersed ruthenium on metal sites in MOFs is expected to optimize the electronic structure of nickel sites,thus improving the conductivity of the catalyst and optimizing the adsorption energy of intermediates,resulting in significant optimization of electrocatalytic performance.This study could provide a new avenue for the design of efficient and stable MOF electrocatalysts.展开更多
Rational design of hierarchically structured electrocatalysts is particularly important for electrocatalytic oxygen reduction reaction(ORR).Here,ZIF-67 crystals are stringed on core-shell Ag@C nanocables using a coord...Rational design of hierarchically structured electrocatalysts is particularly important for electrocatalytic oxygen reduction reaction(ORR).Here,ZIF-67 crystals are stringed on core-shell Ag@C nanocables using a coordinationmodulated process.Upon pyrolysis,Ag@C strings of Co nanoparticles embedded with three-dimensional porous carbon with beads-on-string hierarchical structures are developed.Due to the advantages of the rich electrochemical active sites of Co-based“beads”and the efficient electron transfer pathways via Ag@C“strings,”the resultant NH_(3)-Ag@C@Co-N-C-700 catalyst shows an improved electrocatalytic activity toward ORR.NH_(3)-Ag@C@Co-N-C-700 shows a high onset potential of 0.99 V versus RHE,a high half-wave potential of 0.88 V versus RHE,and a large limiting current of 5.8 mA cm^(-2),which are better than those of commercial Pt/C electrocatalysts.Additionally,the NH_(3)-Ag@C@Co-N-C-700 catalyst shows high stability and preeminent methanol tolerance,which makes NH_(3)-Ag@C@Co-N-C-700 a promising catalyst for oxygen electrocatalysis in fuel cell applications.展开更多
A new coordination framework, {[Zn(L1)(5-nipc)]·H2O}n(1, L1 = 4ˊ-(4-pyridyl)-4,2ˊ:6ˊ,4ˊˊ-terpyridine, 5-nipc = 5-nitroisophthalic acid), has been prepared under hydrothermal conditions, and determin...A new coordination framework, {[Zn(L1)(5-nipc)]·H2O}n(1, L1 = 4ˊ-(4-pyridyl)-4,2ˊ:6ˊ,4ˊˊ-terpyridine, 5-nipc = 5-nitroisophthalic acid), has been prepared under hydrothermal conditions, and determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR and powder X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a = 29.983(9), b = 13.709(3), c = 14.391(3)A, β = 114.93(4)°, V = 5364(2) A3, Dc = 1.493 g/cm^3, C28H19N5O7 Zn, Mr = 602.85, F(000) = 2464, μ(Mo Kα) = 0.972 mm^-1, Z = 8, R = 0.0935 and w R = 0.1509 for 4724 observed reflections(I 〉 2σ(I)). The structure of 1 exhibits a three-dimensional(3D) network with a layer-pillar structure. The fluorescence property of 1 is also investigated.展开更多
One novel metal-organic framework(MOF), [Ba(L)(HO)](1, HL =aniline-2,5-disulfonic acid), has been synthesized by hydrothermal method. Each barium atom is eleven-coordinated into a distorted monocapped pentagonal antip...One novel metal-organic framework(MOF), [Ba(L)(HO)](1, HL =aniline-2,5-disulfonic acid), has been synthesized by hydrothermal method. Each barium atom is eleven-coordinated into a distorted monocapped pentagonal antiprismatic arrangement. Compound 1 shows an interesting 3 D pillar-layered structure constructed from 2 D inorganic layers[Ba(SO)(HO)]and organic pillars of phenyl moieties of L2-linkages. The inorganic layers are supported by the organic pillars, generating a novel 3 D open framework structure with {3, 4~6, 5~5, 6~5,7~4}2{3}{5} topology. The result of fluorescence measurement can reveal that the decayed emission band centered at 492 nm may be caused by the interactions of the ligands and the metal ions.Compound 1 exhibits selective toward the adsorption of COover Nat 273 K.展开更多
Evolutionary algorithm is time-consuming because of the large number of evolutions and much times of finite element analysis, when it is used to optimize the wing structure of a certain high altitude long endurance un...Evolutionary algorithm is time-consuming because of the large number of evolutions and much times of finite element analysis, when it is used to optimize the wing structure of a certain high altitude long endurance unmanned aviation vehicle(UAV). In order to improve efficiency it is proposed to construct a model management framework to perform the multi-objective optimization design of wing structure. The sufficient accurate approximation models of objective and constraint functions in the wing structure optimization model are built when using the model management framework, therefore in the evolutionary algorithm a number of finite element analyses can he avoided and the satisfactory multi-objective optimization results of the wing structure of the high altitude long endurance UAV are obtained.展开更多
A novel zeolite-like metal-organic framework, [Cd12(trz)12'F10'(SiF6)3]·(H3O)4 (Htrz = 1,2,4-triazole), has been synthesized under solvothermal conditions using 1H-l,2,4-triazole-3- carboxylic acid and ...A novel zeolite-like metal-organic framework, [Cd12(trz)12'F10'(SiF6)3]·(H3O)4 (Htrz = 1,2,4-triazole), has been synthesized under solvothermal conditions using 1H-l,2,4-triazole-3- carboxylic acid and CdF2 as the starting materials. The complex has been characterized by elemental analysis, IR, SEM-EDS, gas adsorption, powder and single-crystal X-ray diffraction analyses. The title complex crystallizes in the cubic 1-43m space group, with a = 14.6436(8), V= 3140.1(3)A3, Z = 2, Mr = 2857.96, D,.= 3.023 g/cm3 and F(000) = 2668. The final R = 0.0653 and wR = 0.1880 for 586 observed reflections with 1 〉 2σ(I). In the title complex, three adjacent Cd(ll) centers are connected by three p3-bridging triazole ligands to form triagonal secondary building units (SBUs), which are further interconnected to form a three-dimensional skeleton with tetrahedral cages.展开更多
This paper puts forward the concept of land use structure optimization under space_time coupling through analyzing the systematic characteristic of land use structure optimization.It mainly expounds the construction o...This paper puts forward the concept of land use structure optimization under space_time coupling through analyzing the systematic characteristic of land use structure optimization.It mainly expounds the construction of land use structure optimization model at different levels.Lastly,this paper explains the practicableness of land use structure optimization under systematic framework through the example of Qionghai city.展开更多
The Zhongtiao Mountains, a typical exposure area of Precambrian rocks, are a concentration area of vari-ous types of copper deposit. The rocks were dated using several dating methods. Based on the age data ob-tained b...The Zhongtiao Mountains, a typical exposure area of Precambrian rocks, are a concentration area of vari-ous types of copper deposit. The rocks were dated using several dating methods. Based on the age data ob-tained by means of three methods, several aspects are dealt with: (1) the dating results obtained by differentmethods and their geological implications have been compared; (2) a chronotectonic framework has been con-structed by means of these reliable ages, which indicates that the ages of the rocks of the Proterozoic mobilebelt fall in a time span of 2400 to 2000 Ma during which global magmatic records are lacking and reflects theages of important events in the mobile belt; (3) according to the ages of inherited zircons, neodymium modelage of the depleted mantle sources (T_(DM)) and geochemical and geological data, a model of Precambrianchronocrustal structure has been constructed, representing a typical for the North China craton.展开更多
The bis(tributyltin) ester of succinic acid was synthesized by the reaction of disodium salt of succinic acid with tributyltin chloride in a molar ratio of 1:2. The crystal structure was determined by X-ray single-cry...The bis(tributyltin) ester of succinic acid was synthesized by the reaction of disodium salt of succinic acid with tributyltin chloride in a molar ratio of 1:2. The crystal structure was determined by X-ray single-crystal diffraction. It belongs to orthorhombic with space group Pccn, a = 20.949(3), b = 17.470(3), c = 20.345(3) Angstrom, V = 7446(2) Angstrom(3), Z = 8, D-c = 1.242 g/cm(3), mu = 1.365 mm(-1), F(000) = 2864, R = 0.0544 and wR = 0.1417. The tin atom is of five-coordination in a trigonal bipyramidal structure by bridging two carboxylate groups in different directions and the resulting structure which contains straight twist large ring channels along the axes of a, b and c is a three-dimensional framework polymer containing two different tin atoms.展开更多
A new Zn(Ⅱ) coordination polymer,namely {[Zn_(1.5)(1,3,5-btc^(3-))(dtb)(H_2O)](H_2O)_2}_n(1)(1,3,5-H_3btc = 1,3,5-benzenetricarboxylic acid,dtb = 1,3-di-(1,2,4-triazole-4-yl)benzene),has been hydr...A new Zn(Ⅱ) coordination polymer,namely {[Zn_(1.5)(1,3,5-btc^(3-))(dtb)(H_2O)](H_2O)_2}_n(1)(1,3,5-H_3btc = 1,3,5-benzenetricarboxylic acid,dtb = 1,3-di-(1,2,4-triazole-4-yl)benzene),has been hydrothermally synthesized and structurally characterized. X-ray single-crystal diffraction determination reveals that 1 crystallizes in the monoclinic C2/c space group with a = 33.811(12),b = 8.406(2),c = 17.296(4) ?,β = 120.593(2)°,V = 4232(2) ?~3,Z = 4,Mr = 1142.88,Dc = 1.794 Mg/m^3,μ = 1.783 mm^(-1),F(000) = 2320,the final R = 0.0338 and wR = 0.0827 for 3043 observed reflections with I 〉 2σ(I). Compound 1 exhibits 1D Zn(Ⅱ)-carboxylate chains,which are connected into a 3D porous framework with large channels by dtb,and then three identical 3D networks are interpenetrated with each other. In addition,the luminescence property of the complex has also been investigated.展开更多
Two different CdⅡ coordination frameworks [Cd(L1)(L2)]∞(1) and [Cd(L1)-(L3)(H2O)]∞(2) based on a flexible dicarboxylic acid ligand were obtained by introducing two different nitrogen heterocyclic auxiliary ligands(...Two different CdⅡ coordination frameworks [Cd(L1)(L2)]∞(1) and [Cd(L1)-(L3)(H2O)]∞(2) based on a flexible dicarboxylic acid ligand were obtained by introducing two different nitrogen heterocyclic auxiliary ligands(L1 = 3,3’-[1,3-benzenebis(carbonylimino)]bi(benzoate), L2 = 1,3-bi(4-pyridyl)propane, L3 = 4,4’-bipyridine). Complex 1 crystallizes in triclinic, space group P■ with a = 8.7415(5), b = 12.2247(7), c =16.2415(10) ?, β = 95.6790(10)°, V = 1525.11(16) ?3, Dc = 1.553 mg·m-3, C35H28CdN4O6, Mr = 713.02, F(000) = 724, μ(MoKα) = 0.770 mm–1, Z = 2, R/wR(I > 2σ(I))a = 0.0302/0.0773. However, complex 2 crystallizes in monoclinic, space group P21/n with a = 11.4986(7), b = 23.0911(14), c = 11.9943(8) ?, β = 115.9500(10)°, V = 2863.6(3) ?3, Dc = 1.598 mg·m-3, C32H24CdN4O7, Mr = 688.96, F(000) = 1392, μ(MoKα) = 0.820 mm–1, Z = 4, R/wR(I > 2σ(I))a = 0.0283/0.0631. The structures of two complexes were characterized. Complexes 1 and 2 have different one-dimensional(1D) chain structures. In addition, we have also made a preliminary study on the properties of the two complexes.展开更多
Multiple failure modes tend to be identified in the reliability analysis of a redundant truss structure.This identification process involves updating the model for identifying the next potential failure members.Herein...Multiple failure modes tend to be identified in the reliability analysis of a redundant truss structure.This identification process involves updating the model for identifying the next potential failure members.Herein we intend to update the finite element model automatically in the identification process of failure modes and further perform the system reliability analysis efficiently.This study presents a framework that is implemented through the joint simulation of MATLAB and APDL and consists of three parts:reliability index of a single member,identification of dominant failure modes,and system-level reliability analysis for system reliability analysis of truss structures.Firstly,RSM(response surface method)combines with a constrained optimization model to calculate the reliability indices ofmembers.Then theβ-unzipping method is adopted to identify the dominant failuremodes,and the system function in MATLAB,as well as the EKILL command in APDL,is used to facilitate the automatic update of the finite element model and realize load-redistribution.Besides,the differential equivalence recursion algorithmis performed to approximate the reliability indices of failuremodes efficiently and accurately.Eventually,the PNET(probabilistic network evaluation technique)is used to calculate the joint failure probability as well as the system reliability index.Two illustrative examples demonstrate the accuracy and efficiency of the proposed system reliability analysis framework through comparison with corresponding references.展开更多
A magnesium metal organic framework, [N-H2(CH3)2][-N(CH3)4][Mgs(bpdc)3(O2CH)6]· 3H2O (1, bpdcH2 = 4,4'-biphenyldicarboxylic acid), has been solvothermally synthesized and structurally characterized. 1 ...A magnesium metal organic framework, [N-H2(CH3)2][-N(CH3)4][Mgs(bpdc)3(O2CH)6]· 3H2O (1, bpdcH2 = 4,4'-biphenyldicarboxylic acid), has been solvothermally synthesized and structurally characterized. 1 crystallizes in the trigonal system, space group R-3, with a = 11.3427(3), c = 41.5662(18) A, V = 4631.3(3) A^3, Z = 3 and the final R = 0.0457. Its structure features a pillared-layered three-dimensional network with 8.21 A cavities, in which cationic [NH2(CH3)2]^+ or [N(CH3)4]^+ and lattice water molecules are located. Thermal stability of the title compound has also been investigated.展开更多
Two metal-organic frameworks [(Zn0.5L)·(H2O)]n (1) and [(Ni0.5L)?(H2O)]n (2) constructed by the 3-formyl-4-(pyridin-4-yl) benzoic acid ligand (HL) were synthesized and characterized by single-cry...Two metal-organic frameworks [(Zn0.5L)·(H2O)]n (1) and [(Ni0.5L)?(H2O)]n (2) constructed by the 3-formyl-4-(pyridin-4-yl) benzoic acid ligand (HL) were synthesized and characterized by single-crystal X-ray diffraction. 1 crystallizes in orthorhombic space group Pnna with a = 16.6152(8), b = 12.6825(6), c = 15.3908(8) A, V = 3243.2(3) ?3, Z = 4, Mr = 511.12, Dc = 1.047 g/cm3, F(000) = 1048, μ = 1.144 mm-1, GOOF = 1.061, the final R = 0.0471 and wR = 0.1262 for 12168 observed reflections with I 〉 2σ(I). 2 is isostructural to 1, which also crystallizes in orthorhombic space group Pnna with a = 16.6152(8), b = 12.6825(6), c = 15.3908(8) ?, V = 3243.2(3) ?3, Z = 4, Mr = 511.12, Dc = 1.047 g/cm3, F(000) = 1048, μ = 1.144 mm-1, GOOF = 1.061, the final R = 0.0471 and wR = 0.1262 for 12168 observed reflections with I 〉 2σ(I). Additionally, thermogravimetric analysis, FT-IR spectroscopy and powder X-ray diffraction were discussed.展开更多
The reaction of Cd(NO_3)_2·4H_2O with 4,4?-dipyridylacetylene(4,4?-DPA) and 2-nitroterephthalic acid(2-NO_2-H_2BDC) in DMF/H_2O mixed solvent has afforded a compound {[Cd(2-NO_2-BDC)(4,4?-DPA)]·...The reaction of Cd(NO_3)_2·4H_2O with 4,4?-dipyridylacetylene(4,4?-DPA) and 2-nitroterephthalic acid(2-NO_2-H_2BDC) in DMF/H_2O mixed solvent has afforded a compound {[Cd(2-NO_2-BDC)(4,4?-DPA)]·(DMF)}_n(1). Compound 1 has been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry analysis, and IR spectrum. Compound 1 crystallizes in the monoclinic system, space group P21/n, with a = 12.1488(3), b = 14.6689(3), c = 13.1615(3) ?, β = 111.809(3)o, V = 2177.63(9) ?~3, Z = 4, C_(23)H_(18)N_4O_7 Cd, M_r = 574.81, D_c = 1.753 g/cm^3, μ = 8.523 mm^(-1), F(000) = 1152, the final R = 0.0411 and wR = 0.1064 for 3589 observed reflections with I 〉 2s(I). In compound 1, the Cd(Ⅱ) ions are linked by the carboxylate groups of 2-NO_2-BDC ligands to give a two-dimensional layered structure based on the centrosymmetric dinuclear Cd_2(COO)_2 units, which are further connected by the 4,4?-DPA ligands to produce a three-dimensional framework with pcu topology. Careful examination revealed that compound 1 is a 2-fold interpenetrating framework. Furthermore, the gas adsorption properties of 1 for N_2 and CO_2 have also been investigated.展开更多
Direct conversion of solar energy into chemical energy in an environmentally friendly manner is one of the most promising strategies to deal with the environmental pollution and energy crisis.Among a variety of materi...Direct conversion of solar energy into chemical energy in an environmentally friendly manner is one of the most promising strategies to deal with the environmental pollution and energy crisis.Among a variety of materials developed as photocatalysts,the core-shell metal/covalent-organic framework(MOF or COF)photocatalysts have garnered significant attention due to their highly porous structure and the adjustability in both structure and functionality.The existing reviews on core-shell organic framework photocatalytic materials have mainly focused on core-shell MOF materials.However,there is still a lack of indepth reviews specifically addressing the photocatalytic performance of core-shell COFs and MOFs@COFs.Simultaneously,there is an urgent need for a comprehensive review encompassing these three types of core-shell structures.Based on this,this review aims to provide a comprehensive understanding and useful guidelines for the exploration of suitable core-shell organic framework photocatalysts towards appropriate photocatalytic energy conversion and environmental governance.Firstly,the classification,synthesis,formation mechanisms,and reasonable regulation of core-shell organic framework were summarized.Then,the photocatalytic applications of these three kinds of core-shell structures in different areas,such as H_(2)evolution,CO_(2)reduction,and pollutants degradation are emphasized.Finally,the main challenges and development prospects of core-shell organic framework photocatalysts were introduced.This review aims to provide insights into the development of a novel generation of efficient and stable core-shell organic framework materials for energy conversion and environmental remediation.展开更多
The Sun et al's training program for clinical research nurses(CRNs)in the World Journal of Clinical Cases is a comprehensive and scientific approach.It includes structured frameworks for CRN training,aiming to imp...The Sun et al's training program for clinical research nurses(CRNs)in the World Journal of Clinical Cases is a comprehensive and scientific approach.It includes structured frameworks for CRN training,aiming to improve CRN competency.This program emphasizes practical abilities,updates training content,and improves evaluation methods.The cultivation of CRN talents focuses on enhancing the training system,establishing a multifaceted evaluation framework,and continuously refining the training programs.Regular feedback and evalua-tion are essential to improve CRNs'competency in practical settings.展开更多
Composite Li metal anodes based on three-dimensional(3D) porous frameworks have been considered as an effective material for achieving stable Li metal batteries with high energy density.However,uneven Li deposition be...Composite Li metal anodes based on three-dimensional(3D) porous frameworks have been considered as an effective material for achieving stable Li metal batteries with high energy density.However,uneven Li deposition behavior still occurs at the top of 3D frameworks owing to the local accumulation of Li ions.To promote uniform Li deposition without top dendrite growth,herein,a layered multifunctional framework based on oxidation-treated polyacrylonitrile(OPAN) and metal-organic framework(MOF) derivatives was proposed for rationally regulating the distribution of Li ions flux,nucleation sites,and electrical conductivity.Profiting from these merits,the OPAN/carbon nano fiber-MOF(CMOF) composite framework demonstrated a reversible Li plating/stripping behavior for 500 cycles with a stable Coulombic efficiency of around 99.0% at the current density of 2 mA/cm~2.Besides,such a Li composite anode exhibited a superior cycle lifespan of over 1300 h under a low polarized voltage of 18 mV in symmetrical cells.When the Li composite anode was paired with LiFePO_(4)(LFP) cathode,the obtained full cell exhibited a stable cycling over 500 cycles.Moreover,the COMSOL Multiphysics simulation was conducted to reveal the effects on homogeneous Li ions distribution derived from the above-mentioned OPAN/CMOF framework and electrical insulation/conduction design.These electrochemical and simulated results shed light on the difficulties of designing stable and safe Li metal anode via optimizing the 3D frameworks.展开更多
基金supported by National Natural Science Foundation of China(Grant No.22005266)Zhejiang Provincial Natural Science Foundation(Grant No.LR21E020003)“the Fundamental Research Funds for the Central Universities”(2021FZZX001-09).
文摘Quasi-solid electrolytes(QSEs)based on nanoporous materials are promising candidates to construct high-performance Limetal batteries(LMBs).However,simultaneously boosting the ionic conductivity(σ)and lithium-ion transference number(t^(+)) of liquid electrolyte confined in porous matrix remains challenging.Herein,we report a novel Janus MOFLi/MSLi QSEs with asymmetric porous structure to inherit the benefits of both mesoporous and microporous hosts.This Janus QSE composed of mesoporous silica and microporous MOF exhibits a neat Li^(+) conductivity of 1.5.10^(–4)S cm^(−1) with t^(+) of 0.71.A partially de-solvated structure and preference distribution of Li^(+)near the Lewis base O atoms were depicted by MD simulations.Meanwhile,the nanoporous structure enabled efficient ion flux regulation,promoting the homogenous deposition of Li^(+).When incorporated in Li||Cu cells,the MOFLi/MSLi QSEs demonstrated a high Coulombic efficiency of 98.1%,surpassing that of liquid electrolytes(96.3%).Additionally,NCM 622||Li batteries equipped with MOFLi/MSLi QSEs exhibited promising rate performance and could operate stably for over 200 cycles at 1 C.These results highlight the potential of Janus MOFLi/MSLi QSEs as promising candidates for next-generation LMBs.
基金supported by National Natural Science Foundation of China(52103029 and 51903075).
文摘Polyimide(PI)is a promising electronic packaging material,but it remains challenging to obtain an all-organic PI hybrid film with decreased dielectric constant and loss without modifying the monomer.Herein,a series of allorganic PI hybrid films were successfully prepared by introducing the covalent organic framework(COF),which could induce the formation of the cross-linking structure in the PI matrix.Due to the synergistic effects of the COF fillers and the cross-linking structure,the PI/COF hybrid film containing 2 wt%COF exhibited the lowest dielectric constant of 2.72 and the lowest dielectric loss(tanδ)of 0.0077 at 1 MHz.It is attributed to the intrinsic low dielectric constant of COF and a large number of mesopores within the PI.Besides,the cross-linking network of PI prevents the molecular chains from stacking and improves the fraction of free volume(FFV).The molecular dynamics simulation results are well consistent with the dielectric properties data.Furthermore,the PI/COF hybrid film with 5 wt%COF showed a significant enhancement in breakdown strength,which increased to 412.8 kV/mm as compared with pure PI.In addition,the PI/COF hybrid film achieve to reduce the dielectric constant and thermal expansion coefficient(CTE).It also exhibited excellent thermal,hydrophobicity,and mechanical performance.The all-organic PI/COF hybrid films have great commercial potential as next-generation electronic packaging materials.
基金National Natural Science Foundation of China,Grant/Award Number:51632008。
文摘The establishment of efficient oxygen evolution electrocatalysts is of great value but also challenging.Herein,a durable metal–organic framework(MOF)with minor atomically dispersed ruthenium and an optimized electronic structure is constructed as an efficient electrocatalyst.Significantly,the obtained NiRu_(0.08)-MOF with doping Ru only needs an overpotential of 187 mV at 10 mA cm^(-2) with a Tafel slop of 40 mV dec^(-1) in 0.1M KOH for the oxygen evolution reaction,and can work continuously for more than 300 h.Ultrahigh Ru mass activity is achieved,reaching 56.7 Ag^(-1)_(Ru) at an overpotential of 200 mV,which is 36 times higher than that of commercial RuO_(2).X-ray adsorption spectroscopy and density function theory calculations reveal that atomically dispersed ruthenium on metal sites in MOFs is expected to optimize the electronic structure of nickel sites,thus improving the conductivity of the catalyst and optimizing the adsorption energy of intermediates,resulting in significant optimization of electrocatalytic performance.This study could provide a new avenue for the design of efficient and stable MOF electrocatalysts.
基金Higher Education Discipline Innovation Project,Grant/Award Number:D17007Xinxiang Major Science and Technology Projects,Grant/Award Number:21ZD001+1 种基金Henan Center for Outstanding Overseas Scientists,Grant/Award Number:GZS2022017National Natural Science Foundation of China,Grant/Award Numbers:51872075,51922008,52072114。
文摘Rational design of hierarchically structured electrocatalysts is particularly important for electrocatalytic oxygen reduction reaction(ORR).Here,ZIF-67 crystals are stringed on core-shell Ag@C nanocables using a coordinationmodulated process.Upon pyrolysis,Ag@C strings of Co nanoparticles embedded with three-dimensional porous carbon with beads-on-string hierarchical structures are developed.Due to the advantages of the rich electrochemical active sites of Co-based“beads”and the efficient electron transfer pathways via Ag@C“strings,”the resultant NH_(3)-Ag@C@Co-N-C-700 catalyst shows an improved electrocatalytic activity toward ORR.NH_(3)-Ag@C@Co-N-C-700 shows a high onset potential of 0.99 V versus RHE,a high half-wave potential of 0.88 V versus RHE,and a large limiting current of 5.8 mA cm^(-2),which are better than those of commercial Pt/C electrocatalysts.Additionally,the NH_(3)-Ag@C@Co-N-C-700 catalyst shows high stability and preeminent methanol tolerance,which makes NH_(3)-Ag@C@Co-N-C-700 a promising catalyst for oxygen electrocatalysis in fuel cell applications.
基金supported by the Startup Foundation for Doctors of Jinzhong University
文摘A new coordination framework, {[Zn(L1)(5-nipc)]·H2O}n(1, L1 = 4ˊ-(4-pyridyl)-4,2ˊ:6ˊ,4ˊˊ-terpyridine, 5-nipc = 5-nitroisophthalic acid), has been prepared under hydrothermal conditions, and determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR and powder X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a = 29.983(9), b = 13.709(3), c = 14.391(3)A, β = 114.93(4)°, V = 5364(2) A3, Dc = 1.493 g/cm^3, C28H19N5O7 Zn, Mr = 602.85, F(000) = 2464, μ(Mo Kα) = 0.972 mm^-1, Z = 8, R = 0.0935 and w R = 0.1509 for 4724 observed reflections(I 〉 2σ(I)). The structure of 1 exhibits a three-dimensional(3D) network with a layer-pillar structure. The fluorescence property of 1 is also investigated.
基金supported by the Liaoning Provincial Education Department(No.L2015299)Innovative training program for College Students(Nos.201710148000118,201710148000147)
文摘One novel metal-organic framework(MOF), [Ba(L)(HO)](1, HL =aniline-2,5-disulfonic acid), has been synthesized by hydrothermal method. Each barium atom is eleven-coordinated into a distorted monocapped pentagonal antiprismatic arrangement. Compound 1 shows an interesting 3 D pillar-layered structure constructed from 2 D inorganic layers[Ba(SO)(HO)]and organic pillars of phenyl moieties of L2-linkages. The inorganic layers are supported by the organic pillars, generating a novel 3 D open framework structure with {3, 4~6, 5~5, 6~5,7~4}2{3}{5} topology. The result of fluorescence measurement can reveal that the decayed emission band centered at 492 nm may be caused by the interactions of the ligands and the metal ions.Compound 1 exhibits selective toward the adsorption of COover Nat 273 K.
文摘Evolutionary algorithm is time-consuming because of the large number of evolutions and much times of finite element analysis, when it is used to optimize the wing structure of a certain high altitude long endurance unmanned aviation vehicle(UAV). In order to improve efficiency it is proposed to construct a model management framework to perform the multi-objective optimization design of wing structure. The sufficient accurate approximation models of objective and constraint functions in the wing structure optimization model are built when using the model management framework, therefore in the evolutionary algorithm a number of finite element analyses can he avoided and the satisfactory multi-objective optimization results of the wing structure of the high altitude long endurance UAV are obtained.
基金National Natural Science Foundation of China(21101090)Natural Science Foundation of Jiangxi Province(20114BAB213001)Education Department of Jiangxi Province(GJJ12041)
文摘A novel zeolite-like metal-organic framework, [Cd12(trz)12'F10'(SiF6)3]·(H3O)4 (Htrz = 1,2,4-triazole), has been synthesized under solvothermal conditions using 1H-l,2,4-triazole-3- carboxylic acid and CdF2 as the starting materials. The complex has been characterized by elemental analysis, IR, SEM-EDS, gas adsorption, powder and single-crystal X-ray diffraction analyses. The title complex crystallizes in the cubic 1-43m space group, with a = 14.6436(8), V= 3140.1(3)A3, Z = 2, Mr = 2857.96, D,.= 3.023 g/cm3 and F(000) = 2668. The final R = 0.0653 and wR = 0.1880 for 586 observed reflections with 1 〉 2σ(I). In the title complex, three adjacent Cd(ll) centers are connected by three p3-bridging triazole ligands to form triagonal secondary building units (SBUs), which are further interconnected to form a three-dimensional skeleton with tetrahedral cages.
文摘This paper puts forward the concept of land use structure optimization under space_time coupling through analyzing the systematic characteristic of land use structure optimization.It mainly expounds the construction of land use structure optimization model at different levels.Lastly,this paper explains the practicableness of land use structure optimization under systematic framework through the example of Qionghai city.
文摘The Zhongtiao Mountains, a typical exposure area of Precambrian rocks, are a concentration area of vari-ous types of copper deposit. The rocks were dated using several dating methods. Based on the age data ob-tained by means of three methods, several aspects are dealt with: (1) the dating results obtained by differentmethods and their geological implications have been compared; (2) a chronotectonic framework has been con-structed by means of these reliable ages, which indicates that the ages of the rocks of the Proterozoic mobilebelt fall in a time span of 2400 to 2000 Ma during which global magmatic records are lacking and reflects theages of important events in the mobile belt; (3) according to the ages of inherited zircons, neodymium modelage of the depleted mantle sources (T_(DM)) and geochemical and geological data, a model of Precambrianchronocrustal structure has been constructed, representing a typical for the North China craton.
基金the National Natural Science Foundation of China (No. 20271025)the Natural Science Foundation of Shandong province (No. Z2001B02)the State Key Laboratory of Crystal Materials,Shandong University
文摘The bis(tributyltin) ester of succinic acid was synthesized by the reaction of disodium salt of succinic acid with tributyltin chloride in a molar ratio of 1:2. The crystal structure was determined by X-ray single-crystal diffraction. It belongs to orthorhombic with space group Pccn, a = 20.949(3), b = 17.470(3), c = 20.345(3) Angstrom, V = 7446(2) Angstrom(3), Z = 8, D-c = 1.242 g/cm(3), mu = 1.365 mm(-1), F(000) = 2864, R = 0.0544 and wR = 0.1417. The tin atom is of five-coordination in a trigonal bipyramidal structure by bridging two carboxylate groups in different directions and the resulting structure which contains straight twist large ring channels along the axes of a, b and c is a three-dimensional framework polymer containing two different tin atoms.
基金supported by the National Natural Science Foundation of China(21372112)the Science and Technology Research Projects of Education Department of Henan Province(15A150064)
文摘A new Zn(Ⅱ) coordination polymer,namely {[Zn_(1.5)(1,3,5-btc^(3-))(dtb)(H_2O)](H_2O)_2}_n(1)(1,3,5-H_3btc = 1,3,5-benzenetricarboxylic acid,dtb = 1,3-di-(1,2,4-triazole-4-yl)benzene),has been hydrothermally synthesized and structurally characterized. X-ray single-crystal diffraction determination reveals that 1 crystallizes in the monoclinic C2/c space group with a = 33.811(12),b = 8.406(2),c = 17.296(4) ?,β = 120.593(2)°,V = 4232(2) ?~3,Z = 4,Mr = 1142.88,Dc = 1.794 Mg/m^3,μ = 1.783 mm^(-1),F(000) = 2320,the final R = 0.0338 and wR = 0.0827 for 3043 observed reflections with I 〉 2σ(I). Compound 1 exhibits 1D Zn(Ⅱ)-carboxylate chains,which are connected into a 3D porous framework with large channels by dtb,and then three identical 3D networks are interpenetrated with each other. In addition,the luminescence property of the complex has also been investigated.
基金supported by the National Natural Science Foundation of China(21501078)the fund for Shanxi “1331 Project” Key Innovative Research Team+1 种基金the Natural Science Foundation of Shanxi Province(2015011026)the 1331 Project for Innovation Team Construction Plan of Jinzhong University
文摘Two different CdⅡ coordination frameworks [Cd(L1)(L2)]∞(1) and [Cd(L1)-(L3)(H2O)]∞(2) based on a flexible dicarboxylic acid ligand were obtained by introducing two different nitrogen heterocyclic auxiliary ligands(L1 = 3,3’-[1,3-benzenebis(carbonylimino)]bi(benzoate), L2 = 1,3-bi(4-pyridyl)propane, L3 = 4,4’-bipyridine). Complex 1 crystallizes in triclinic, space group P■ with a = 8.7415(5), b = 12.2247(7), c =16.2415(10) ?, β = 95.6790(10)°, V = 1525.11(16) ?3, Dc = 1.553 mg·m-3, C35H28CdN4O6, Mr = 713.02, F(000) = 724, μ(MoKα) = 0.770 mm–1, Z = 2, R/wR(I > 2σ(I))a = 0.0302/0.0773. However, complex 2 crystallizes in monoclinic, space group P21/n with a = 11.4986(7), b = 23.0911(14), c = 11.9943(8) ?, β = 115.9500(10)°, V = 2863.6(3) ?3, Dc = 1.598 mg·m-3, C32H24CdN4O7, Mr = 688.96, F(000) = 1392, μ(MoKα) = 0.820 mm–1, Z = 4, R/wR(I > 2σ(I))a = 0.0283/0.0631. The structures of two complexes were characterized. Complexes 1 and 2 have different one-dimensional(1D) chain structures. In addition, we have also made a preliminary study on the properties of the two complexes.
基金support from the National Key R&D Program of China(Grant Nos.2021YFB2600605,2021YFB2600600)the Overseas Scholar Program in the Hebei Province(C20190514)+1 种基金from the State Key Laboratory of Mechanical Behavior and System Safety of Traffic Engineering Structures Project(ZZ2020-20)from the Youth Foundation of Hebei Science and Technology Research Project(QN2018108).
文摘Multiple failure modes tend to be identified in the reliability analysis of a redundant truss structure.This identification process involves updating the model for identifying the next potential failure members.Herein we intend to update the finite element model automatically in the identification process of failure modes and further perform the system reliability analysis efficiently.This study presents a framework that is implemented through the joint simulation of MATLAB and APDL and consists of three parts:reliability index of a single member,identification of dominant failure modes,and system-level reliability analysis for system reliability analysis of truss structures.Firstly,RSM(response surface method)combines with a constrained optimization model to calculate the reliability indices ofmembers.Then theβ-unzipping method is adopted to identify the dominant failuremodes,and the system function in MATLAB,as well as the EKILL command in APDL,is used to facilitate the automatic update of the finite element model and realize load-redistribution.Besides,the differential equivalence recursion algorithmis performed to approximate the reliability indices of failuremodes efficiently and accurately.Eventually,the PNET(probabilistic network evaluation technique)is used to calculate the joint failure probability as well as the system reliability index.Two illustrative examples demonstrate the accuracy and efficiency of the proposed system reliability analysis framework through comparison with corresponding references.
基金supported by the NNSFC (No. 20873149)the Knowledge Innovation Program of the Chinese Academy of Sciences (KJCX2-XW-H21)
文摘A magnesium metal organic framework, [N-H2(CH3)2][-N(CH3)4][Mgs(bpdc)3(O2CH)6]· 3H2O (1, bpdcH2 = 4,4'-biphenyldicarboxylic acid), has been solvothermally synthesized and structurally characterized. 1 crystallizes in the trigonal system, space group R-3, with a = 11.3427(3), c = 41.5662(18) A, V = 4631.3(3) A^3, Z = 3 and the final R = 0.0457. Its structure features a pillared-layered three-dimensional network with 8.21 A cavities, in which cationic [NH2(CH3)2]^+ or [N(CH3)4]^+ and lattice water molecules are located. Thermal stability of the title compound has also been investigated.
基金supported by the National Natural Science Foundation of China(No.21371119,21431004,21401128,21522104,and 21620102001)the National Key Basic Research Program of China(No.2014CB932102 and 2016YFA0203400)the Shanghai“Eastern Scholar”Program
文摘Two metal-organic frameworks [(Zn0.5L)·(H2O)]n (1) and [(Ni0.5L)?(H2O)]n (2) constructed by the 3-formyl-4-(pyridin-4-yl) benzoic acid ligand (HL) were synthesized and characterized by single-crystal X-ray diffraction. 1 crystallizes in orthorhombic space group Pnna with a = 16.6152(8), b = 12.6825(6), c = 15.3908(8) A, V = 3243.2(3) ?3, Z = 4, Mr = 511.12, Dc = 1.047 g/cm3, F(000) = 1048, μ = 1.144 mm-1, GOOF = 1.061, the final R = 0.0471 and wR = 0.1262 for 12168 observed reflections with I 〉 2σ(I). 2 is isostructural to 1, which also crystallizes in orthorhombic space group Pnna with a = 16.6152(8), b = 12.6825(6), c = 15.3908(8) ?, V = 3243.2(3) ?3, Z = 4, Mr = 511.12, Dc = 1.047 g/cm3, F(000) = 1048, μ = 1.144 mm-1, GOOF = 1.061, the final R = 0.0471 and wR = 0.1262 for 12168 observed reflections with I 〉 2σ(I). Additionally, thermogravimetric analysis, FT-IR spectroscopy and powder X-ray diffraction were discussed.
基金Supported by the National Natural Science Foundation of China(No.21361011 and 21101081)the Natural Science Foundation of Jiangxi Province(No.20151BAB203002)
文摘The reaction of Cd(NO_3)_2·4H_2O with 4,4?-dipyridylacetylene(4,4?-DPA) and 2-nitroterephthalic acid(2-NO_2-H_2BDC) in DMF/H_2O mixed solvent has afforded a compound {[Cd(2-NO_2-BDC)(4,4?-DPA)]·(DMF)}_n(1). Compound 1 has been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry analysis, and IR spectrum. Compound 1 crystallizes in the monoclinic system, space group P21/n, with a = 12.1488(3), b = 14.6689(3), c = 13.1615(3) ?, β = 111.809(3)o, V = 2177.63(9) ?~3, Z = 4, C_(23)H_(18)N_4O_7 Cd, M_r = 574.81, D_c = 1.753 g/cm^3, μ = 8.523 mm^(-1), F(000) = 1152, the final R = 0.0411 and wR = 0.1064 for 3589 observed reflections with I 〉 2s(I). In compound 1, the Cd(Ⅱ) ions are linked by the carboxylate groups of 2-NO_2-BDC ligands to give a two-dimensional layered structure based on the centrosymmetric dinuclear Cd_2(COO)_2 units, which are further connected by the 4,4?-DPA ligands to produce a three-dimensional framework with pcu topology. Careful examination revealed that compound 1 is a 2-fold interpenetrating framework. Furthermore, the gas adsorption properties of 1 for N_2 and CO_2 have also been investigated.
基金supported by the National Natural Science Foundation of China(52161145409,21976116)SAFEA of China("Belt and Road”Innovative Talent Exchange Foreign Expert Project#2023041004L)(High-end Foreign Expert Project#G2023041021L)the Alexander-von-Humboldt Foundation of Germany(GroupLinkage Program)。
文摘Direct conversion of solar energy into chemical energy in an environmentally friendly manner is one of the most promising strategies to deal with the environmental pollution and energy crisis.Among a variety of materials developed as photocatalysts,the core-shell metal/covalent-organic framework(MOF or COF)photocatalysts have garnered significant attention due to their highly porous structure and the adjustability in both structure and functionality.The existing reviews on core-shell organic framework photocatalytic materials have mainly focused on core-shell MOF materials.However,there is still a lack of indepth reviews specifically addressing the photocatalytic performance of core-shell COFs and MOFs@COFs.Simultaneously,there is an urgent need for a comprehensive review encompassing these three types of core-shell structures.Based on this,this review aims to provide a comprehensive understanding and useful guidelines for the exploration of suitable core-shell organic framework photocatalysts towards appropriate photocatalytic energy conversion and environmental governance.Firstly,the classification,synthesis,formation mechanisms,and reasonable regulation of core-shell organic framework were summarized.Then,the photocatalytic applications of these three kinds of core-shell structures in different areas,such as H_(2)evolution,CO_(2)reduction,and pollutants degradation are emphasized.Finally,the main challenges and development prospects of core-shell organic framework photocatalysts were introduced.This review aims to provide insights into the development of a novel generation of efficient and stable core-shell organic framework materials for energy conversion and environmental remediation.
文摘The Sun et al's training program for clinical research nurses(CRNs)in the World Journal of Clinical Cases is a comprehensive and scientific approach.It includes structured frameworks for CRN training,aiming to improve CRN competency.This program emphasizes practical abilities,updates training content,and improves evaluation methods.The cultivation of CRN talents focuses on enhancing the training system,establishing a multifaceted evaluation framework,and continuously refining the training programs.Regular feedback and evalua-tion are essential to improve CRNs'competency in practical settings.
基金supported by the National Natural Science Foundation of China (52302292, 52302058, 52302085)the China Postdoctoral Science Foundation (2021M702225)+1 种基金the Anhui Province University Natural Science Research Project (2023AH030093, 2023AH040301)the Startup Research Fund of Chaohu University (KYQD-2023005, KYQD-2023051)。
文摘Composite Li metal anodes based on three-dimensional(3D) porous frameworks have been considered as an effective material for achieving stable Li metal batteries with high energy density.However,uneven Li deposition behavior still occurs at the top of 3D frameworks owing to the local accumulation of Li ions.To promote uniform Li deposition without top dendrite growth,herein,a layered multifunctional framework based on oxidation-treated polyacrylonitrile(OPAN) and metal-organic framework(MOF) derivatives was proposed for rationally regulating the distribution of Li ions flux,nucleation sites,and electrical conductivity.Profiting from these merits,the OPAN/carbon nano fiber-MOF(CMOF) composite framework demonstrated a reversible Li plating/stripping behavior for 500 cycles with a stable Coulombic efficiency of around 99.0% at the current density of 2 mA/cm~2.Besides,such a Li composite anode exhibited a superior cycle lifespan of over 1300 h under a low polarized voltage of 18 mV in symmetrical cells.When the Li composite anode was paired with LiFePO_(4)(LFP) cathode,the obtained full cell exhibited a stable cycling over 500 cycles.Moreover,the COMSOL Multiphysics simulation was conducted to reveal the effects on homogeneous Li ions distribution derived from the above-mentioned OPAN/CMOF framework and electrical insulation/conduction design.These electrochemical and simulated results shed light on the difficulties of designing stable and safe Li metal anode via optimizing the 3D frameworks.