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 heteropolyoxotungstate [(C2H4N2)4(P4Co3W4O28H6)(H2C2O4)]n with a three-dimensional framework was hydrothermally synthesized.The compound crystallizes in a tetragonal system,space group I41/a with a = 17.1...A new heteropolyoxotungstate [(C2H4N2)4(P4Co3W4O28H6)(H2C2O4)]n with a three-dimensional framework was hydrothermally synthesized.The compound crystallizes in a tetragonal system,space group I41/a with a = 17.1006(17),b = 17.1006(7),c = 10.7525(5),V = 3144.2(2)3,Z = 4,Dc = 3.795 g·cm-3,F(000) = 3300,MoKα(λ = 0.71073 ),μ = 16.460 mm-1,the final R = 0.0335 and wR = 0.0776.In the heteropolyoxotungstate,tungsten-oxygen octahedra are linked by sharing two cis-vertexes into an infinite helical chain extending along the c axis.Cobalt atoms in the octahedral geometry act as the linkers of these chains,forming a three-dimensional framework.The cobalt and phosphorus atoms in the tetrahedral geometry play a role in stabilizing the three-dimensional framework.Ethylenediamine molecules are polymerized into organic chains which locate in the interspaces of the framework in the way of interwinding with the W-O chains.展开更多
The evolution of the society and economy has stimulated the development of Knowledge Service(KS), making it an indispensable solution to address future challenges facing libraries and information institutions. However...The evolution of the society and economy has stimulated the development of Knowledge Service(KS), making it an indispensable solution to address future challenges facing libraries and information institutions. However at present, academic research on knowledge service is falling short and its definition is far from clear and complete. As such,this article proposes the Three-dimensional Framework Knowledge Service(TdFKS) for libraries and information institutions based on the knowledge value chain model. By making reliability analysis and mean value analysis of a questionnaire survey result, the article clarifies the structure of the three-dimensional framework and verifies the rationality of the TdFKS.展开更多
The Critical Discourse Analysis(CDA)is an interdisciplinary tool in various conditions,which aims to provide a better understanding of sociocultural aspects of texts and accounts of the production of internal structur...The Critical Discourse Analysis(CDA)is an interdisciplinary tool in various conditions,which aims to provide a better understanding of sociocultural aspects of texts and accounts of the production of internal structure,and overall organization of texts as well as to provide a critical dimension in its theoretical and descriptive accounts of texts.Since June last year,HK protests or HK violence have been frequently reported by worldwide media.In this paper,the author aims to find out how the HK protesters and the Mainland media describe the same event based on the three-dimensional framework of CDA.At last,the author concludes that the mainland media generally describe the event as violence and riot while the HK protesters define themselves as warriors striving for more freedom,justice and democracy.Besides,on this event,the Mainland media mainly accuses some western countries of interference into HK affairs,which is undoubtedly of China’s internal affairs,and the media give full support to the HK police in safeguarding the peace and stability of Hong Kong.But from the perspective of HK protesters,they firmly believe that they are using their actions to protect all the people of HK,and they are defending their values such as freedom,democracy and justice.These are two totally different systems of language,and the author also gives its potential reasons in the paper so as to offer some viewpoints in this aspect in combination with the CDA theory.展开更多
A novel Ni(II) coordination polymer [Ni(dtba)(4,4′-bpy)] (1, H2dtba = 2,2′-dithio- bisbenzoic acid, 4,4′-bpy = 4,4′-bipyridine) has been synthesized by H2dtba and Ni(CH3COO)2·4H2O with exo-bidentate...A novel Ni(II) coordination polymer [Ni(dtba)(4,4′-bpy)] (1, H2dtba = 2,2′-dithio- bisbenzoic acid, 4,4′-bpy = 4,4′-bipyridine) has been synthesized by H2dtba and Ni(CH3COO)2·4H2O with exo-bidentate rigid ligand 4,4′-bpy by using hydrothermal method, and its structure was determined by single-crystal X-ray diffraction. X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic, space group Cc with a = 11.7624(9), b = 18.7933(19), c = 10.3071(11), β = 97.6510(10)°, V = 2258.2(4)3, Z = 4, C24H16N2NiO4S2, Mr = 519.22, Dc = 1.527 g/cm3, μ = 1.079 mm-1 and F(000) = 1064. The structure was solved by direct methods and refined to R = 0.0434 and wR = 0.1000 for 3281 observed reflections (I 〉 2σ(I)). The coordination environment of Ni(II) is a distorted octahedron, and a three-dimensional structure was formed with the coordination effect of dtba2- and 4,4′-bpy ligands. The topological analysis reveals that the whole framework of 1 is a 2-nodal net of (52.6)(53.64.72.8) topology. The thermal stability and XRD pattern of 1 were also investigated展开更多
At present,commercial Li-ion batteries are hardly to satisfy the growing demand for high energy density,for this purpose,lithium metal batteries have attracted worldwide attention in recent years.However,its practical...At present,commercial Li-ion batteries are hardly to satisfy the growing demand for high energy density,for this purpose,lithium metal batteries have attracted worldwide attention in recent years.However,its practical applications are hindered by the formation of Li dendrites and volume effect during Li plating/stripping process,which leads to a lot of safety hazards.Herein,we first employed MOF-derived V_(2)O_(5) nanoparticles to decorate the carbon fiber cloth(CFC)backbone to acquire a lithiophilic 3D porous conductive framework(CFC@V_(2)O_(5)).Subsequently,the CFC@V_(2)O_(5) skeleton was permeated with molten Li to prepare CFC@V_(2)O_(5)@Li composite anode.The CFC@V_(2)O_(5)@Li composite anode can be stably cycled for more than 1650 h at high current density(5 mA·cm^(-2))and areal capacity(5 mA·h·cm^(–2)).The prepared full cell can initially maintain a high capacity of about 143 mA·h·g^(-1) even at a high current density of 5 C,and can still maintain 114 mA·h·g^(-1) after 1000 cycles.展开更多
Covalent organic frameworks(COFs) are a class of crystalline porous organic materials with variable structures and fascinating properties. The intrinsic low conductivity impedes their widely application in optoelectro...Covalent organic frameworks(COFs) are a class of crystalline porous organic materials with variable structures and fascinating properties. The intrinsic low conductivity impedes their widely application in optoelectronic. Iodine doping is an effective way to enhance the electrical conductivity of COFs. Here, a novel 3D imine COF with lvt topology is synthesized from two different pentacene derivatives with the same core in the form of structural complementarity. DDHP-COF is a highly crystalline material featuring high surface area of 1679 m^(2)/g and excellent thermal stability up to 490 ℃. Upon doping with iodine, the electrical conductivity can reach as high as 1.5×10^(-2)S/m which is significantly enhanced over 6 orders of magnitude compared with the pristine COF.展开更多
The analysis of the current big data policy for scientific research can promote the ecological optimization of big data policy,and is a positive response to the national big data strategy.This paper constructs a“dual...The analysis of the current big data policy for scientific research can promote the ecological optimization of big data policy,and is a positive response to the national big data strategy.This paper constructs a“dual three-dimensional framework”to analyze the central and local science data policies from 2013 to 2022.With the dissemination and popularization of the concept of scientific data sharing,policies and regulations related to scientific data management have been issued,which promotes the emergence of scientific data policy ecology.The scientific data policy ecology is a complex and multicollaborative dynamic system composed of policy text,policy environment and related personnel,the core of which lies in the policy itself,aiming to ensure the security of scientific data and promote the development of science.There are the following problems in the scientific data policy ecology:In terms of policy text,the policy effectiveness is low and the use of policy tools is uneven.In terms of relevant personnel,the cooperation network density among various subjects is low and there is a lack of highquality talents.In terms of policy environment,there is an imbalance of regional funding support.It also puts forward some optimization strategies,such as strengthening the systematization of policy texts,improving the degree of coordination of policy subjects to form a long-term cooperation network,and improving the degree of compatibility between environment,personnel and policies.展开更多
Although metal–organic frameworks have been heavily tested as the anode materials for lithium-ion batteries(LIBs),the poorer conductivity,easy collapse of frameworks,and serious volume expansion limit their further a...Although metal–organic frameworks have been heavily tested as the anode materials for lithium-ion batteries(LIBs),the poorer conductivity,easy collapse of frameworks,and serious volume expansion limit their further application in LIBs.Herein,we report a facile approach to obtain MXene-encapsulated porous Ni-naphthalene dicarboxylic acid(Ni-NDC)nanosheets by hybridizing ultrathin Ti_(3)C_(2)MXene and three-dimensional(3D)Ni-NDC nanosheet aggregates.In the structure of Ni-NDC/MXene hybrids,the interlayer hydrogen-bond interaction between Ni-NDC and MXene can effectively increase the interlayer spacing and further inhibit the oxidation of pure MXene.Hence,the introduction of MXene(a conductive matrix)could further improve the conductivity of Ni-NDC,avoid self-agglomeration,and buffer the volume expansion of Ni-NDC nanosheets.Benefiting from the synergistic effects between Ni-NDC and MXene,Ni-NDC/MXene hybrid electrode exhibits a reversible discharge capacity(579.8 mA∙h∙g^(−1)at 100 mA∙g^(−1)after 100 cycles)and good long-term cycling performance(310 mA∙h∙g^(−1)at 1 A∙g^(−1)after 500 cycles).展开更多
Si materials are widely considered to be the next-generation anode to replace the current commercial graphite-based anode due to its high energy density.However,the large volume variation of silicon during(de)lithiati...Si materials are widely considered to be the next-generation anode to replace the current commercial graphite-based anode due to its high energy density.However,the large volume variation of silicon during(de)lithiation process leads to rapid capacity decay,hindering its commercial application.Although the various hollow structure designs of Si nanomaterials have improved their cycling stability in the laboratory,the high-pressure calendering process in the current industrial electrode preparation process might collapse the hollow structure and weaken the structural advantages of hollow silicon anode materials.In this work,a silicon carbon composite material(Si@3DC)in which Si nanoparticles were anchored on a three-dimensional carbon framework through carbon films was prepared by a simple proton exchange method.The three-dimensional carbon framework with multiple hierarchical pores of Si@3DC was compatible with the high-pressure calendering process,but also could provide expansion space for Si nanoparticles during the lithiation process,and ensure good electronic and ionic conductivity.The carbon film on the surface of Si nanoparticles promoted the formation of stable solid electrolyte interphase(SEI)films,ensuring the good cycle stability of Si@3DC.展开更多
Two reported three-dimensional covalent organic frameworks(3D-COFs),COF-300 and COF-301,which have hierarchical porous structures and large pore volumes,were synthesized and employed as host materials for lithium-sulf...Two reported three-dimensional covalent organic frameworks(3D-COFs),COF-300 and COF-301,which have hierarchical porous structures and large pore volumes,were synthesized and employed as host materials for lithium-sulfur batteries.Owing to possessing excellent porosities as well as abundant hydroxyl groups in the pore walls,COF-301 can not only trap lithium polysulfides(PSs)via physical adsorption inside the pores,but also capture PSs by chemical interactions to relieve the shuttle effect.Interestingly,it is the first time that 3D-COFs were utilized as host materials for lithium-sulfur batteries as well as hydroxyl groups were introduced into COFs for improving the battery performance.As a result,COF-301@S as cathode material could reserve the capacity of 411.6 mA·h·g^-1 after 500 cycles with only 0.081%fading per cycle at 0.5 C,exhibiting better battery performance compared with COF-300@S.This study not only expands the applications of 3D-COFs but also provides a new route for designing lithium-sulfur batteries.展开更多
The open-framework iron phosphate IIIII21.543FeFe(PO) was hydrothermally synthesized and characterized by elemental analysis, IR, EPR, XPS and single crystal X-ray diffraction analysis. The title compound crystallized...The open-framework iron phosphate IIIII21.543FeFe(PO) was hydrothermally synthesized and characterized by elemental analysis, IR, EPR, XPS and single crystal X-ray diffraction analysis. The title compound crystallized in the triclinic, space group P1with a=0.64724(4) nm, b=0.79651(6) nm, c=0.94229(5) nm, =104.447(2)? =108.919(4)? =101.741(4)? V=0.42302(5) nm3, Z=1 and R1 (wR2)=0.0307 (0.0793). Crystal data were collected on a Rigaku R-AXIS RAPID IP diffractometer with Mo K?(=0.071073 nm) at 293(2) K in the range of 2.43埃迹?7.46? The structure of 1 consists of 19 non-hydrogen atoms including three and a half crystallographically in-dependent Fe and three P atoms. Fe(1) connects its symmetrical Fe(1A) through bridging oxygen forming a dimer and the dimers are connected by Fe(4) forming an infinite staircase-like chain. Fe(2) and Fe(3) connect the infinite chains into a layer with bridging oxygen. Layers are interconnected via Fe(4) forming the six-membered and eight-membered channel systems.展开更多
Lithium-air batteries have attracted significant interest for applications in high energy density mobile power supplies, yet there are considerable challenges to the development of rechargeable Li-air batteries with s...Lithium-air batteries have attracted significant interest for applications in high energy density mobile power supplies, yet there are considerable challenges to the development of rechargeable Li-air batteries with stable cycling performance under ambient conditions. Here we report a three-dimensional (3D) hydrophobic graphene membrane as a moisture-resistive cathode for high performance Li-air batteries. The 3D graphene membrane features a highly interconnected graphene network for efficient charge transport, a highly porous structure for efficient diffusion of oxygen and electrolyte ions, a large specific surface area for high capacity storage of the insulating discharge product, and a network of highly tortuous hydrophobic channels for O2/H20 selectivity. These channels facilitate 02 ingression while retarding moisture diffusion and ensure excellent charge/ discharge cycling stability under ambient conditions. The membrane can thus enable robust Li-air batteries with exceptional performance, including a maximum cathode capacity that exceeds 5,700 mAh/g and excellent recharge cycling behavior (〉2,000 cycles at 140 mAh/g, and 〉100 cycles at 1,400 mAh/g). The graphene membrane air cathode can deliver a lifetime capacity of 100,000-300,000 mAh/g, comparable to that of a typical lithium ion battery cathode. The stable operation of Li-air batteries with significantly improved single charge capacities and lifetime capacities comparable to those of Li-ion batteries may offer an attractive high energy density storage alternative for future mobile power supplies. These batteries may provide much longer battery lives and greatly reduced recharge frequency.展开更多
For several decades,the promise of implementing of lithium(Li)metal anodes for Li batteries has been a"holy grail"for researchers.Herein,we have proposed a facile design of a MOF-derived Co_(3)O_(4)nanoparti...For several decades,the promise of implementing of lithium(Li)metal anodes for Li batteries has been a"holy grail"for researchers.Herein,we have proposed a facile design of a MOF-derived Co_(3)O_(4)nanoparticles modified nickel foam,i.e.,Co_(3)O_(4)-NF,as a 3D host to achieve a uniform infusion of the molten Li.The molten Li was uniformly absorbed on the Co_(3)O_(4)-NF host only in 10 s due to its high Li lithiophilicity.The obtained Li-Co_(3)O_(4)-NF composite electrode shows high cycling stability in symmetric cells with low voltage hysteresis even at a high current density of 5 mA/cm2.The full cells of Li-Co_(3)O_(4)-NF/LiFePO_(4)can cycle for more than 500 cycles at 2C without obvious capacity decay.SEM after cycling and in situ optical microscope results suggest that the unique 3D host structure of the Li-Co_(3)O_(4)-NF anode plays key roles on suppressing the dendrite growth and decreasing the local current inhomogeneity.We believe this work might provide a new strategy for fabricating dendrite-free Li metal anodes and facilitate practical applications in Li batteries.展开更多
Extracting uranium from seawater offers opportunities for sustainable nuclear fuel supply,but the task is quite challenging due to the low uranium concentration(~3 ppb)in seawater.Here,based on the Knoevenagel condens...Extracting uranium from seawater offers opportunities for sustainable nuclear fuel supply,but the task is quite challenging due to the low uranium concentration(~3 ppb)in seawater.Here,based on the Knoevenagel condensation reaction of aldehyde and acetonitrile groups,a novel stable sp^(2)carbon-linked three-dimensional covalent organic framework(3D COF),TFPM-PDANAO was prepared as a porous platform for uranium extraction from seawater.The TFPM-PDAN-AO designed with regular 3D pore channel of 7.12 A provides a specific channel for uranyl diffusion,which exhibits high selectivity and fast kinetics for uranium adsorption.Meanwhile,the superior stability and optoelectronic properties enable it an excellent porous platform for uranium electroextraction.By applying alternating voltages between-5 and 0 V,uranyl ions can rapidly migrate and enrich into the porous structure of TFPM-PDAN-AO,then inducing the electrodeposition of uranium compounds to form the charge neutral species(Na_(2)O(UO_(3)H_(2)O)x)with an unprecedentedly high adsorption capacity of 4,685 mg g^(-1).This work not only expands the application prospects of functionalized 3D COFs,but also provides a technical support for the electrodeposition adsorption of uranium from seawater.展开更多
NiFe composites have been regarded as promising candidates to replace commercial noble-based electrocatalysts for the oxygen evolution reaction(OER).However,their practical applications still suffer from poor conducti...NiFe composites have been regarded as promising candidates to replace commercial noble-based electrocatalysts for the oxygen evolution reaction(OER).However,their practical applications still suffer from poor conductivity,limited activity,durability.To address these issues,herein,by utilizing three-dimensional covalent organic framework(3D-COF)with porous confined structures and abundant coordinate N sites as the precursor,the partially oxidized Ni_(3)Fe nanoalloys wrapped by Ndoped carbon(N-C)layers are constructed via simple pyrolysis and subsequent oxidization.Benefiting from the 3D curved hierarchical structure,high-conductivity of Ni_(3)Fe and N-C layers,well-distributed active sites,the as-synthesized O-Ni_(3)Fe-NC catalyst demonstrates excellent activity and durability for catalyzing OER.Experimental and theoretical analyses disclose that both high-temperature oxidization and the OER process greatly promote the formation and exposure of the Ni(Fe)OOH active species as well as lower charge transfer resistance,inducing its optimized OER activity.The robust graphitized N-C layers with superior conductivity and their couplings with oxidized Ni_(3)Fe nanoalloys are beneficial for stabilizing catalytic centers,thereby imparting O-Ni_(3)Fe-N-C with such outstanding stability.This work not only provides a rational guidance for enriching and stabilizing high-activity catalytic sites towards OER but also offers more insights into the structural evolution of NiFe-based OER catalysts.展开更多
Recently,three-dimensional(3D)conductive frameworks have been chosen as the host for composite lithium(Li)metal anode because of their exceptional electrical conductivity and remarkable thermal and electrochemical sta...Recently,three-dimensional(3D)conductive frameworks have been chosen as the host for composite lithium(Li)metal anode because of their exceptional electrical conductivity and remarkable thermal and electrochemical stability.However,Li tends to accumulate on the top of the 3D frameworks with homogenous lithiophilicity and Li dendrite still growth.This work firstly designed a bimetallic metal-organic framework(MOF)(CuMn-MOF)derived Cu_(2)O and Mn_(3)O_(4) nanoparticles decorated carbon cloth(CC)substrates(CC@Cu_(2)O/Mn_(3)O_(4))to fabricate a composite Li anode.Thanks to the synergistic effects of lithiophilic Cu_(2)O and Mn_(3)O_(4),the CC@Cu_(2)O/Mn_(3)O_(4)@Li symmetrical cell can afford a prolonged cycling lifespan(1400 h)under an ultrahigh current density and areal capacity(6 mA·cm^(-2)/6 mAh·cm^(-2)).When coupled with the LiFePO_(4)(LFP)cathode,the LFP||CC@Cu_(2)O/Mn_(3)O_(4)@Li full cell demonstrated a superior performance of 89.7 mAh·g^(-1) even at an extremely high current density(10 C).Furthermore,it can also be matched well with LiNi_(0.5)Co^(0).2Mn_(0.3)O_(2)(NCM523)cathode.Importantly,to explain the excellent performances of the CC@Cu_(2)O/Mn_(3)O_(4)@Li composite anode,an intermittent model was also proposed.This study offers a novel model that can enhance our comprehension of the Li deposition behavior and pave the way to attain stable and safe Li metal anodes by employing bimetallic MOF-derived materials to construct 3D frameworks.展开更多
In the development of 3D conductive frameworks for lithium metal anode(LMA),two models have been proposed:top growth model and bottom-up growth model.However,Li tends to accumulate on the top of these 3D frameworks wi...In the development of 3D conductive frameworks for lithium metal anode(LMA),two models have been proposed:top growth model and bottom-up growth model.However,Li tends to accumulate on the top of these 3D frameworks with homogenous lithiophilicity(top growth)and Li dendrite still forms.To address this issue,some researchers have focused on developing 3D frameworks with gradient lithio-philicity,which realized bottom-up growth of Li.Nevertheless,partial Li nucleation sites on the top of these frameworks were missed.Inspired by the two models talked above,this work firstly proposed a novel intermittent lithiophilic model for lithium deposition.To demonstrate the feasibility of this model,a bimetallic metal-organic frameworks derived ZnMn_(2)O_(4)-MnO nanoparticles were grown on carbon cloth for LMA.It can cycle stably under ultra-high current and areal capacity(10 mA/cm^(2),10 mAh/cm^(2)).The in-situ optical microscopy(OM)was conducted to observe the Li deposition behavior,no dendrite was found during 80 h in ester-based electrolyte while the pure Li only cycled for 2h.What is more,it can also be well-coupled with LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathode and solid-state electrolyte,which further prove the advantages of the intermittent model for the development of LMAs with high safety and high energy density.展开更多
The scalable preparation of multi-functional three-dimensional (3D) carbon nanotubes and graphene (CNTs-G) hybrids via a well-controlled route is urgently required and challenging. Herein, an easily operated, oxal...The scalable preparation of multi-functional three-dimensional (3D) carbon nanotubes and graphene (CNTs-G) hybrids via a well-controlled route is urgently required and challenging. Herein, an easily operated, oxalic acid-assisted method was developed for the in situ fabrication of a 3D lasagna-like Fe-N-doped CNTs-G framework (LMFC) from a precursor designed at the molecular level. The well-organized architecture of LMFC was constructed by multi-dimensionally interconnected graphene and CNTs which derived from porous graphene sheets, to form a fundamentally robust and hierarchical porous structure, as well as favorable conductive networks. The impressive oxygen reduction reaction (ORR) performances in both alkaline and acidic conditions helped confirm the significance of this technically favorable morphological structure. This product was also the subject of research for the exploration of decisive effects on the performance of ORR catalysts with reasonable control variables. The present work further advances the construction of novel 3D carbon architectures via practical and economic routes.展开更多
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 Analysis and Testing Foundation of Northeast Normal University
文摘A new heteropolyoxotungstate [(C2H4N2)4(P4Co3W4O28H6)(H2C2O4)]n with a three-dimensional framework was hydrothermally synthesized.The compound crystallizes in a tetragonal system,space group I41/a with a = 17.1006(17),b = 17.1006(7),c = 10.7525(5),V = 3144.2(2)3,Z = 4,Dc = 3.795 g·cm-3,F(000) = 3300,MoKα(λ = 0.71073 ),μ = 16.460 mm-1,the final R = 0.0335 and wR = 0.0776.In the heteropolyoxotungstate,tungsten-oxygen octahedra are linked by sharing two cis-vertexes into an infinite helical chain extending along the c axis.Cobalt atoms in the octahedral geometry act as the linkers of these chains,forming a three-dimensional framework.The cobalt and phosphorus atoms in the tetrahedral geometry play a role in stabilizing the three-dimensional framework.Ethylenediamine molecules are polymerized into organic chains which locate in the interspaces of the framework in the way of interwinding with the W-O chains.
基金supported by the National Planning Office of Philosophy and Social Science(Grant No.06BTQ027)
文摘The evolution of the society and economy has stimulated the development of Knowledge Service(KS), making it an indispensable solution to address future challenges facing libraries and information institutions. However at present, academic research on knowledge service is falling short and its definition is far from clear and complete. As such,this article proposes the Three-dimensional Framework Knowledge Service(TdFKS) for libraries and information institutions based on the knowledge value chain model. By making reliability analysis and mean value analysis of a questionnaire survey result, the article clarifies the structure of the three-dimensional framework and verifies the rationality of the TdFKS.
文摘The Critical Discourse Analysis(CDA)is an interdisciplinary tool in various conditions,which aims to provide a better understanding of sociocultural aspects of texts and accounts of the production of internal structure,and overall organization of texts as well as to provide a critical dimension in its theoretical and descriptive accounts of texts.Since June last year,HK protests or HK violence have been frequently reported by worldwide media.In this paper,the author aims to find out how the HK protesters and the Mainland media describe the same event based on the three-dimensional framework of CDA.At last,the author concludes that the mainland media generally describe the event as violence and riot while the HK protesters define themselves as warriors striving for more freedom,justice and democracy.Besides,on this event,the Mainland media mainly accuses some western countries of interference into HK affairs,which is undoubtedly of China’s internal affairs,and the media give full support to the HK police in safeguarding the peace and stability of Hong Kong.But from the perspective of HK protesters,they firmly believe that they are using their actions to protect all the people of HK,and they are defending their values such as freedom,democracy and justice.These are two totally different systems of language,and the author also gives its potential reasons in the paper so as to offer some viewpoints in this aspect in combination with the CDA theory.
基金the National Natural Science Foundation of China (No. 20771006, 20901004 and 20801025)
文摘A novel Ni(II) coordination polymer [Ni(dtba)(4,4′-bpy)] (1, H2dtba = 2,2′-dithio- bisbenzoic acid, 4,4′-bpy = 4,4′-bipyridine) has been synthesized by H2dtba and Ni(CH3COO)2·4H2O with exo-bidentate rigid ligand 4,4′-bpy by using hydrothermal method, and its structure was determined by single-crystal X-ray diffraction. X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic, space group Cc with a = 11.7624(9), b = 18.7933(19), c = 10.3071(11), β = 97.6510(10)°, V = 2258.2(4)3, Z = 4, C24H16N2NiO4S2, Mr = 519.22, Dc = 1.527 g/cm3, μ = 1.079 mm-1 and F(000) = 1064. The structure was solved by direct methods and refined to R = 0.0434 and wR = 0.1000 for 3281 observed reflections (I 〉 2σ(I)). The coordination environment of Ni(II) is a distorted octahedron, and a three-dimensional structure was formed with the coordination effect of dtba2- and 4,4′-bpy ligands. The topological analysis reveals that the whole framework of 1 is a 2-nodal net of (52.6)(53.64.72.8) topology. The thermal stability and XRD pattern of 1 were also investigated
基金supported by National Natural Science Foundation of China(21701083).
文摘At present,commercial Li-ion batteries are hardly to satisfy the growing demand for high energy density,for this purpose,lithium metal batteries have attracted worldwide attention in recent years.However,its practical applications are hindered by the formation of Li dendrites and volume effect during Li plating/stripping process,which leads to a lot of safety hazards.Herein,we first employed MOF-derived V_(2)O_(5) nanoparticles to decorate the carbon fiber cloth(CFC)backbone to acquire a lithiophilic 3D porous conductive framework(CFC@V_(2)O_(5)).Subsequently,the CFC@V_(2)O_(5) skeleton was permeated with molten Li to prepare CFC@V_(2)O_(5)@Li composite anode.The CFC@V_(2)O_(5)@Li composite anode can be stably cycled for more than 1650 h at high current density(5 mA·cm^(-2))and areal capacity(5 mA·h·cm^(–2)).The prepared full cell can initially maintain a high capacity of about 143 mA·h·g^(-1) even at a high current density of 5 C,and can still maintain 114 mA·h·g^(-1) after 1000 cycles.
基金financially supported by the National Natural Science Foundation of China (Nos. 51973153, 22001191)。
文摘Covalent organic frameworks(COFs) are a class of crystalline porous organic materials with variable structures and fascinating properties. The intrinsic low conductivity impedes their widely application in optoelectronic. Iodine doping is an effective way to enhance the electrical conductivity of COFs. Here, a novel 3D imine COF with lvt topology is synthesized from two different pentacene derivatives with the same core in the form of structural complementarity. DDHP-COF is a highly crystalline material featuring high surface area of 1679 m^(2)/g and excellent thermal stability up to 490 ℃. Upon doping with iodine, the electrical conductivity can reach as high as 1.5×10^(-2)S/m which is significantly enhanced over 6 orders of magnitude compared with the pristine COF.
基金supported by the Grant from the Project“Trends,Priorities,and Logic of Science and Technology Policy in the New U.S.Administration(Biden Administration)”commissioned by the International Department of the Ministry of Science and Technology of China(2021ICR12)
文摘The analysis of the current big data policy for scientific research can promote the ecological optimization of big data policy,and is a positive response to the national big data strategy.This paper constructs a“dual three-dimensional framework”to analyze the central and local science data policies from 2013 to 2022.With the dissemination and popularization of the concept of scientific data sharing,policies and regulations related to scientific data management have been issued,which promotes the emergence of scientific data policy ecology.The scientific data policy ecology is a complex and multicollaborative dynamic system composed of policy text,policy environment and related personnel,the core of which lies in the policy itself,aiming to ensure the security of scientific data and promote the development of science.There are the following problems in the scientific data policy ecology:In terms of policy text,the policy effectiveness is low and the use of policy tools is uneven.In terms of relevant personnel,the cooperation network density among various subjects is low and there is a lack of highquality talents.In terms of policy environment,there is an imbalance of regional funding support.It also puts forward some optimization strategies,such as strengthening the systematization of policy texts,improving the degree of coordination of policy subjects to form a long-term cooperation network,and improving the degree of compatibility between environment,personnel and policies.
基金supported by the National Natural Science Foundation of China(Nos.62174085 and 21805136)the Program for Young Changjiang Scholars of the Ministry of Education,the Jiangsu Specially-Appointed Professors Program,the Top-notch Academic Programs Project of Jiangsu Higher Education Institutions(TAPP),the Natural Science Foundation of Jiangsu Province(No.BK20200044)the Startup Foundation for Introducing Talent of NUIST(No.2021r091).
文摘Although metal–organic frameworks have been heavily tested as the anode materials for lithium-ion batteries(LIBs),the poorer conductivity,easy collapse of frameworks,and serious volume expansion limit their further application in LIBs.Herein,we report a facile approach to obtain MXene-encapsulated porous Ni-naphthalene dicarboxylic acid(Ni-NDC)nanosheets by hybridizing ultrathin Ti_(3)C_(2)MXene and three-dimensional(3D)Ni-NDC nanosheet aggregates.In the structure of Ni-NDC/MXene hybrids,the interlayer hydrogen-bond interaction between Ni-NDC and MXene can effectively increase the interlayer spacing and further inhibit the oxidation of pure MXene.Hence,the introduction of MXene(a conductive matrix)could further improve the conductivity of Ni-NDC,avoid self-agglomeration,and buffer the volume expansion of Ni-NDC nanosheets.Benefiting from the synergistic effects between Ni-NDC and MXene,Ni-NDC/MXene hybrid electrode exhibits a reversible discharge capacity(579.8 mA∙h∙g^(−1)at 100 mA∙g^(−1)after 100 cycles)and good long-term cycling performance(310 mA∙h∙g^(−1)at 1 A∙g^(−1)after 500 cycles).
基金supported financially by the National Key Research and Development Program of China(No.2017YFB0307701).
文摘Si materials are widely considered to be the next-generation anode to replace the current commercial graphite-based anode due to its high energy density.However,the large volume variation of silicon during(de)lithiation process leads to rapid capacity decay,hindering its commercial application.Although the various hollow structure designs of Si nanomaterials have improved their cycling stability in the laboratory,the high-pressure calendering process in the current industrial electrode preparation process might collapse the hollow structure and weaken the structural advantages of hollow silicon anode materials.In this work,a silicon carbon composite material(Si@3DC)in which Si nanoparticles were anchored on a three-dimensional carbon framework through carbon films was prepared by a simple proton exchange method.The three-dimensional carbon framework with multiple hierarchical pores of Si@3DC was compatible with the high-pressure calendering process,but also could provide expansion space for Si nanoparticles during the lithiation process,and ensure good electronic and ionic conductivity.The carbon film on the surface of Si nanoparticles promoted the formation of stable solid electrolyte interphase(SEI)films,ensuring the good cycle stability of Si@3DC.
基金supported by the National Natural Science Foundation of China(Nos.21674026,21574032,51573125,51573147,51803149,51973155,and 51633007(the State Key Program))the Sino-German Center for Research Promotion(No.GZ1286)the Chinese Academy of Sciences(No.121D11KYSB20170031).
文摘Two reported three-dimensional covalent organic frameworks(3D-COFs),COF-300 and COF-301,which have hierarchical porous structures and large pore volumes,were synthesized and employed as host materials for lithium-sulfur batteries.Owing to possessing excellent porosities as well as abundant hydroxyl groups in the pore walls,COF-301 can not only trap lithium polysulfides(PSs)via physical adsorption inside the pores,but also capture PSs by chemical interactions to relieve the shuttle effect.Interestingly,it is the first time that 3D-COFs were utilized as host materials for lithium-sulfur batteries as well as hydroxyl groups were introduced into COFs for improving the battery performance.As a result,COF-301@S as cathode material could reserve the capacity of 411.6 mA·h·g^-1 after 500 cycles with only 0.081%fading per cycle at 0.5 C,exhibiting better battery performance compared with COF-300@S.This study not only expands the applications of 3D-COFs but also provides a new route for designing lithium-sulfur batteries.
基金the National Natural Science Foundation of China (No. 20171010).
文摘The open-framework iron phosphate IIIII21.543FeFe(PO) was hydrothermally synthesized and characterized by elemental analysis, IR, EPR, XPS and single crystal X-ray diffraction analysis. The title compound crystallized in the triclinic, space group P1with a=0.64724(4) nm, b=0.79651(6) nm, c=0.94229(5) nm, =104.447(2)? =108.919(4)? =101.741(4)? V=0.42302(5) nm3, Z=1 and R1 (wR2)=0.0307 (0.0793). Crystal data were collected on a Rigaku R-AXIS RAPID IP diffractometer with Mo K?(=0.071073 nm) at 293(2) K in the range of 2.43埃迹?7.46? The structure of 1 consists of 19 non-hydrogen atoms including three and a half crystallographically in-dependent Fe and three P atoms. Fe(1) connects its symmetrical Fe(1A) through bridging oxygen forming a dimer and the dimers are connected by Fe(4) forming an infinite staircase-like chain. Fe(2) and Fe(3) connect the infinite chains into a layer with bridging oxygen. Layers are interconnected via Fe(4) forming the six-membered and eight-membered channel systems.
文摘Lithium-air batteries have attracted significant interest for applications in high energy density mobile power supplies, yet there are considerable challenges to the development of rechargeable Li-air batteries with stable cycling performance under ambient conditions. Here we report a three-dimensional (3D) hydrophobic graphene membrane as a moisture-resistive cathode for high performance Li-air batteries. The 3D graphene membrane features a highly interconnected graphene network for efficient charge transport, a highly porous structure for efficient diffusion of oxygen and electrolyte ions, a large specific surface area for high capacity storage of the insulating discharge product, and a network of highly tortuous hydrophobic channels for O2/H20 selectivity. These channels facilitate 02 ingression while retarding moisture diffusion and ensure excellent charge/ discharge cycling stability under ambient conditions. The membrane can thus enable robust Li-air batteries with exceptional performance, including a maximum cathode capacity that exceeds 5,700 mAh/g and excellent recharge cycling behavior (〉2,000 cycles at 140 mAh/g, and 〉100 cycles at 1,400 mAh/g). The graphene membrane air cathode can deliver a lifetime capacity of 100,000-300,000 mAh/g, comparable to that of a typical lithium ion battery cathode. The stable operation of Li-air batteries with significantly improved single charge capacities and lifetime capacities comparable to those of Li-ion batteries may offer an attractive high energy density storage alternative for future mobile power supplies. These batteries may provide much longer battery lives and greatly reduced recharge frequency.
基金This work was financially supported by National Natural Science Foundation of China(No.21701083)Fok Ying-Tong Education Foundation of China(No.171064)Natural Science Foundation of Hebei Province(Nos.B2022203018,B2018203297).
文摘For several decades,the promise of implementing of lithium(Li)metal anodes for Li batteries has been a"holy grail"for researchers.Herein,we have proposed a facile design of a MOF-derived Co_(3)O_(4)nanoparticles modified nickel foam,i.e.,Co_(3)O_(4)-NF,as a 3D host to achieve a uniform infusion of the molten Li.The molten Li was uniformly absorbed on the Co_(3)O_(4)-NF host only in 10 s due to its high Li lithiophilicity.The obtained Li-Co_(3)O_(4)-NF composite electrode shows high cycling stability in symmetric cells with low voltage hysteresis even at a high current density of 5 mA/cm2.The full cells of Li-Co_(3)O_(4)-NF/LiFePO_(4)can cycle for more than 500 cycles at 2C without obvious capacity decay.SEM after cycling and in situ optical microscope results suggest that the unique 3D host structure of the Li-Co_(3)O_(4)-NF anode plays key roles on suppressing the dendrite growth and decreasing the local current inhomogeneity.We believe this work might provide a new strategy for fabricating dendrite-free Li metal anodes and facilitate practical applications in Li batteries.
基金supported by the National Natural Science Foundation of China(22036003,21976077)the Natural Science Foundation of Jiangxi Province(20212ACB203009,20212ACB-203011)。
文摘Extracting uranium from seawater offers opportunities for sustainable nuclear fuel supply,but the task is quite challenging due to the low uranium concentration(~3 ppb)in seawater.Here,based on the Knoevenagel condensation reaction of aldehyde and acetonitrile groups,a novel stable sp^(2)carbon-linked three-dimensional covalent organic framework(3D COF),TFPM-PDANAO was prepared as a porous platform for uranium extraction from seawater.The TFPM-PDAN-AO designed with regular 3D pore channel of 7.12 A provides a specific channel for uranyl diffusion,which exhibits high selectivity and fast kinetics for uranium adsorption.Meanwhile,the superior stability and optoelectronic properties enable it an excellent porous platform for uranium electroextraction.By applying alternating voltages between-5 and 0 V,uranyl ions can rapidly migrate and enrich into the porous structure of TFPM-PDAN-AO,then inducing the electrodeposition of uranium compounds to form the charge neutral species(Na_(2)O(UO_(3)H_(2)O)x)with an unprecedentedly high adsorption capacity of 4,685 mg g^(-1).This work not only expands the application prospects of functionalized 3D COFs,but also provides a technical support for the electrodeposition adsorption of uranium from seawater.
基金the National Natural Science Foundation of China(Nos.22075062 and 21871167)and the Volkswagen Foundation(Freigeist Fellowship)。
文摘NiFe composites have been regarded as promising candidates to replace commercial noble-based electrocatalysts for the oxygen evolution reaction(OER).However,their practical applications still suffer from poor conductivity,limited activity,durability.To address these issues,herein,by utilizing three-dimensional covalent organic framework(3D-COF)with porous confined structures and abundant coordinate N sites as the precursor,the partially oxidized Ni_(3)Fe nanoalloys wrapped by Ndoped carbon(N-C)layers are constructed via simple pyrolysis and subsequent oxidization.Benefiting from the 3D curved hierarchical structure,high-conductivity of Ni_(3)Fe and N-C layers,well-distributed active sites,the as-synthesized O-Ni_(3)Fe-NC catalyst demonstrates excellent activity and durability for catalyzing OER.Experimental and theoretical analyses disclose that both high-temperature oxidization and the OER process greatly promote the formation and exposure of the Ni(Fe)OOH active species as well as lower charge transfer resistance,inducing its optimized OER activity.The robust graphitized N-C layers with superior conductivity and their couplings with oxidized Ni_(3)Fe nanoalloys are beneficial for stabilizing catalytic centers,thereby imparting O-Ni_(3)Fe-N-C with such outstanding stability.This work not only provides a rational guidance for enriching and stabilizing high-activity catalytic sites towards OER but also offers more insights into the structural evolution of NiFe-based OER catalysts.
基金supported by the National Natural Science Foundation of China(Nos.21701083 and 22279112)Fok Ying-Tong Education Foundation of China(No.171064)the Natural Science Foundation of Hebei Province(Nos.B2022203018 and B2018203297).
文摘Recently,three-dimensional(3D)conductive frameworks have been chosen as the host for composite lithium(Li)metal anode because of their exceptional electrical conductivity and remarkable thermal and electrochemical stability.However,Li tends to accumulate on the top of the 3D frameworks with homogenous lithiophilicity and Li dendrite still growth.This work firstly designed a bimetallic metal-organic framework(MOF)(CuMn-MOF)derived Cu_(2)O and Mn_(3)O_(4) nanoparticles decorated carbon cloth(CC)substrates(CC@Cu_(2)O/Mn_(3)O_(4))to fabricate a composite Li anode.Thanks to the synergistic effects of lithiophilic Cu_(2)O and Mn_(3)O_(4),the CC@Cu_(2)O/Mn_(3)O_(4)@Li symmetrical cell can afford a prolonged cycling lifespan(1400 h)under an ultrahigh current density and areal capacity(6 mA·cm^(-2)/6 mAh·cm^(-2)).When coupled with the LiFePO_(4)(LFP)cathode,the LFP||CC@Cu_(2)O/Mn_(3)O_(4)@Li full cell demonstrated a superior performance of 89.7 mAh·g^(-1) even at an extremely high current density(10 C).Furthermore,it can also be matched well with LiNi_(0.5)Co^(0).2Mn_(0.3)O_(2)(NCM523)cathode.Importantly,to explain the excellent performances of the CC@Cu_(2)O/Mn_(3)O_(4)@Li composite anode,an intermittent model was also proposed.This study offers a novel model that can enhance our comprehension of the Li deposition behavior and pave the way to attain stable and safe Li metal anodes by employing bimetallic MOF-derived materials to construct 3D frameworks.
基金supported by National Natural Science Foundation of China(Nos.21701083,22279112)Fok Ying-Tong Education Foundation of China(No.171064)Natural Science Foundation of Hebei Province(Nos.B2022203018,B2018203297).
文摘In the development of 3D conductive frameworks for lithium metal anode(LMA),two models have been proposed:top growth model and bottom-up growth model.However,Li tends to accumulate on the top of these 3D frameworks with homogenous lithiophilicity(top growth)and Li dendrite still forms.To address this issue,some researchers have focused on developing 3D frameworks with gradient lithio-philicity,which realized bottom-up growth of Li.Nevertheless,partial Li nucleation sites on the top of these frameworks were missed.Inspired by the two models talked above,this work firstly proposed a novel intermittent lithiophilic model for lithium deposition.To demonstrate the feasibility of this model,a bimetallic metal-organic frameworks derived ZnMn_(2)O_(4)-MnO nanoparticles were grown on carbon cloth for LMA.It can cycle stably under ultra-high current and areal capacity(10 mA/cm^(2),10 mAh/cm^(2)).The in-situ optical microscopy(OM)was conducted to observe the Li deposition behavior,no dendrite was found during 80 h in ester-based electrolyte while the pure Li only cycled for 2h.What is more,it can also be well-coupled with LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathode and solid-state electrolyte,which further prove the advantages of the intermittent model for the development of LMAs with high safety and high energy density.
基金Acknowledgements Financial supports from the National Natural Science Foundation of China (Nos. 21622308, 91534114, and 21376208), the the China Ministry of Science and Technology (No. 2016YFA0202900), the Fundamental Research Funds for the Central Universities (No. 2016FZA3006), and the Partner Group Program of the Zhejiang University and the Max-Planck Society are appreciated greatly.
文摘The scalable preparation of multi-functional three-dimensional (3D) carbon nanotubes and graphene (CNTs-G) hybrids via a well-controlled route is urgently required and challenging. Herein, an easily operated, oxalic acid-assisted method was developed for the in situ fabrication of a 3D lasagna-like Fe-N-doped CNTs-G framework (LMFC) from a precursor designed at the molecular level. The well-organized architecture of LMFC was constructed by multi-dimensionally interconnected graphene and CNTs which derived from porous graphene sheets, to form a fundamentally robust and hierarchical porous structure, as well as favorable conductive networks. The impressive oxygen reduction reaction (ORR) performances in both alkaline and acidic conditions helped confirm the significance of this technically favorable morphological structure. This product was also the subject of research for the exploration of decisive effects on the performance of ORR catalysts with reasonable control variables. The present work further advances the construction of novel 3D carbon architectures via practical and economic routes.