Metal-organic framework-derived porous carbon for the advanced aqueous zinc-ion hybrid capacitor

Aqueous zinc ion hybrid capacitors(ZIHCs)are considered one of the most promising electrochemical energy storage systems due to their high safety,environmental friendliness,low cost,and high power density.However,the low energy density and the lack of sustainable design strategies for the cathodes hinder the practical application of ZIHCs.Herein,we design the N and O co-doped porous carbon cathode by annealing metal-organic framework(ZIF-8).ZIF-8 retains the original dodecahedral structure with a high specific surface(2814.67 m^(2)/g)and I_(G)/I_(D) ratio of 1.0 during carbonization and achieves self-doping of N and O heteroatoms.Abundant defect sites are introduced into the porous carbon to provide additional active sites for ion adsorption after the activation of carbonized ZIF-8 by KOH treatment.The ZIHCs assembled with modified ZIF-8 as the cathode and commercial zinc foil as the anode show an energy density of 125 W∙h/kg and a power density of 79 W/kg.In addition,this ZIHCs device achieves capacity retention of 77.8%after 9000 electrochemical cycles,which is attributed to the diverse pore structure and plentiful defect sites of ZIF-8-800(KOH).The proposed strategy may be useful in developing high-performance metal-ion hybrid capacitors for large-scale energy storage.

Construction of all-organic low dielectric polyimide hybrids via synergistic effect between covalent organic framework and cross-linking structure

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.

Inorganic-organic hybrid photocatalysts:Syntheses,mechanisms,and applications

Inorganic-organic hybrid materials are promising for application in the field of photocatalysis because of their excellent properties.Therefore,their syntheses,mechanisms,and applications are reviewed in this paper.First,we introduce the role of inorganic-organic photocatalysts,their advantages and disadvantages,and their design principles.Second,we present the top-down and bottom-up synthesis methods of the hybrid materials.The interaction between inorganic and organic components in hybrid materials is discussed,followed by how to improve inorganic-organic photocatalysts.Third,the applications of hybrid materials in the field of photocatalysis,such as realizing hydrogen evolution,organic pollutant degradation,heavy metals and CO_(2) reduction,sterilization,and nitrogen fixation,are examined.Finally,the application prospects and development directions of inorganic-organic hybrid materials are explored and the unsolved problems are described.

Accelerating Oxygen Electrocatalysis Kinetics on Metal-Organic Frameworks via Bond Length Optimization

Metal-organic frameworks(MOFs)have been developed as an ideal platform for exploration of the relationship between intrinsic structure and catalytic activity,but the limited catalytic activity and stability has hampered their practical use in water splitting.Herein,we develop a bond length adjustment strategy for optimizing naphthalene-based MOFs that synthesized by acid etching Co-naphthalenedicarboxylic acid-based MOFs(donated as AE-CoNDA)to serve as efficient catalyst for water splitting.AE-CoNDA exhibits a low overpotential of 260 mV to reach 10 mA cm^(−2)and a small Tafel slope of 62 mV dec^(−1)with excellent stability over 100 h.After integrated AE-CoNDA onto BiVO_(4),photocurrent density of 4.3 mA cm^(−2)is achieved at 1.23 V.Experimental investigations demonstrate that the stretched Co-O bond length was found to optimize the orbitals hybridization of Co 3d and O 2p,which accounts for the fast kinetics and high activity.Theoretical calculations reveal that the stretched Co-O bond length strengthens the adsorption of oxygen-contained intermediates at the Co active sites for highly efficient water splitting.

Electrostatic Interaction-directed Construction of Hierarchical Nanostructured Carbon Composite with Dual Electrical Conductive Networks for Zinc-ion Hybrid Capacitors with Ultrastability

Metal-organic framework(MOF)-derived carbon composites have been considered as the promising materials for energy storage.However,the construction of MOF-based composites with highly controllable mode via the liquid-liquid synthesis method has a great challenge because of the simultaneous heterogeneous nucleation on substrates and the self-nucleation of individual MOF nanocrystals in the liquid phase.Herein,we report a bidirectional electrostatic generated self-assembly strategy to achieve the precisely controlled coatings of single-layer nanoscale MOFs on a range of substrates,including carbon nanotubes(CNTs),graphene oxide(GO),MXene,layered double hydroxides(LDHs),MOFs,and SiO_(2).The obtained MOF-based nanostructured carbon composite exhibits the hierarchical porosity(V_(meso)/V_(micro)∶2.4),ultrahigh N content of 12.4 at.%and"dual electrical conductive networks."The assembled aqueous zinc-ion hybrid capacitor(ZIC)with the prepared nanocarbon composite as a cathode shows a high specific capacitance of 236 F g^(-1)at 0.5 A g^(-1),great rate performance of 98 F g^(-1)at 100 A g^(-1),and especially,an ultralong cycling stability up to 230000 cycles with the capacitance retention of 90.1%.This work develops a repeatable and general method for the controlled construction of MOF coatings on various functional substrates and further fabricates carbon composites for ZICs with ultrastability.

A Novel Inorganic-organic Hybrid Borate with Unique One-dimensional Infinite Aluminium-oxygen Chains

A novel inorganic-organic hybrid borate,[Al2（fum）（H3BO3）（OH） 4]n·n（H3BO3） （1,H2fum = fumaric acid） ,has been synthesized and characterized by single-crystal X-ray diffraction,FTIR and elemental analysis. Crystal data for compound 1： orthorhombic,space group Pnma,a = 14.108（3） ,b = 6.9412（14） ,c = 14.995（3）A,V = 1468.3（5）A^3,Z = 4,Mr = 359.72,Dc = 1.627 g/cm^3,μ = 0.254 mm^-1,F（000） = 736,the final R = 0.0492 and wR = 0.1650 with I 〉 2σ（I） . In compound 1,each Al^Ⅲ ion is coordinated by six oxygen atoms to adopt a distorted octahedral geometry. Both fumarate anion and the coordinated boric acid act as bidentate bridging ligands to link two neighboring Al^Ⅲ centers simultaneously. Each Al^Ⅲ ion is bridged by two μ2-hydroxyl ligands to construct an infinite wave-like [Al2（fum）（H3BO3）（OH） 4]n chain. These one-dimensional chains form hydrogen bonds with free boric acid molecules giving rise to a three-dimensional supramolecular network.

An ionic 2D inorganic-organic hybrid of tris[((1H-tetrazol-5-yl)methyl)morpholine] dodecatungstophosphate(Ⅴ) pentahydrate:Synthesis X-ray crystal structure and spectroscopic characterizations

A unique ionic hybrid material[C_6H_(12)N_5O]_3[(PO_4)W__(12)O_(36)]·5H_2O has been synthesized from the reaction of((1H-tetrazole-5- yl)methyl)morpholine andα-H_3[(PO_4)W_(12)O_(36)]·21H_2O.It has successfully been characterized by elemental analysis,IR and ~1H NMR spectroscopies,TGA and single-crystal X-ray diffraction method.The title compound is constructed from the three [C_6H_(12)N_5O]^+ cations andα-Keggin[(PO_4)W_(12)O_(36)]^(3-) polyoxoanion.The most remarkable structural feature of this hybrid can...

A New Inorganic-organic Hybrid Based on Biisoquinoline and Hexachloridostannate:Structure, Photoluminescence, Electrochemical Behavior and Theoretical Study

A new inorganic-organic hybrid constructed from biisoquinoline dication and tin halide, [（BIQBT）（Sn Cl6）]n（1, BIQBT = 1,4-bis（isoquinoline） butane）, has been synthesized and structurally determined by X-ray diffraction method. 1 crystallizes in the monoclinic system, space group Cc with Mr = 644.82, a = 16.589（3）, b = 18.388（4）, c = 8.5532（17）A, β = 108.75（3）°, V = 2470.6（9） A3, Z = 4, Dc = 1.736 g/cm^3, F（000） = 1281, μ（Mo Kα） = 1.697 mm^–1, the final R = 0.0197 and wR = 0.0493 for 4614 observed reflections with I 〉 2（I）. 1 consists of BIQBT^2＋dications and mononuclear hexachloridostannate Sn Cl62- anion, and hydrogen bonds among them contribute to the formation of a 1-D chain. Strong fluorescence can be detected in 1, which was explained by theoretical calculation. Its electrochemical behavior was investigated, and the theoretical calculations reveal that the π···π stacking interaction is dominated for their structural stabilization.

Hydrothermal Synthesis and Crystal Structure of Inorganic-organic Hybrid Compound [H_3NC_2H_4NH_2]VOPO_4

An inorganic-organic hybrid compound, [H_3NC_2H_4NH_2]VOPO_4 was synthesized by means of the hydrothermal method. It was crystallized in a monoclinic system, a space group P2_1/c, with the crystal cell parameters: a=0.92285(11) nm, b=0.72994(9) nm, c=0.98495(11) nm, β=101.280(3)°, V=0.65067(13) nm^3, M_r=223.02 g/mol, D_c=2.277 g/cm^3, Z=4, R=0.0315, ωR=0.0865, GOF=1.085. The VO_5N octahedra chains are corner-linked by PO_4 tetrahedra; the VO_5N octahedra are all trans-linked with V—O bonds being alternately short and long. The monoprotonated ethylenediamine was intercalated between the layers with one end coordinating to V and the other end as an H-bond donor interacting with a terminal O atom of PO_4 from a neighboring sheet. The elementary analysis, infrared spectrum characters and thermal stability were also given.

Supramolecular Structural Inorganic-organic Hybrid[(4-Bromoanilimiun)([18]crown-6)]3[PMo(12)O(40)]·CH3CN

A novel supramolecular structural inorganic-organic hybrid [（4-bromoanilimiun）（[18]crown-6）]3[PMo（12）O40]·CH3 CN has been synthesized through standard solvent evaporated method. The structure of the title compound was determined through single-crystal X-ray diffraction analysis. It crystallizes in monoclinic system with P21/n space group. The crystal data are a = 18.9529（4）, b = 26.4444（5）, c = 19.0985（4） A, β = 90.132（6）o, V = 9572.1（3） A^3, Z = 4, Dc= 2.203 g·cm^（–1）, μ = 14.956 mm^（–1）, F（000） = 6192, S = 1.098, the final R = 0.0859 and w R（I 〉 2σ（I）） = 0.2100. Supramolecular cations are constructed through strong N–H…O hydrogen bonding interaction between the six oxygen atoms of [18]crown-6 molecule and nitrogen atom of（4-bromoanilimiun） cation. Three kinds of different arranged supramolecular cations exist in the title compound, which are filled into the large space formed by [PMo（12）O40] polyoxoanions. Thermogravimentic differential thermal analysis revealed that hydrogen bonding interaction and intermolecular interaction play an important role in maintaining the stability of the title compound.

Synthesis, Structure, and Photoluminescence Property of a Novel One-dimensional Inorganic-organic Hybrid Gallophosphate JGP-2

A novel one-dimensional inorganic-organic hybrid gallophosphate compound, Ga（2,2＇-bipy）（HPO4）. （H2PO4）（denoted JGP-2） was synthesized hydrothermally with 2,2＇-bipyridine as a ligand and characterized by X-ray powder diffraction （XRD）, elemental analysis, inductively coupled plasma（ICP）, TGA analysis, solid-state ^31p NMR, and luminescence spectra and structurally determined by single-crystal X-ray diffraction analysis. JGP-2 crystallized in the triclinic system, space group P^-1（No.2）, with a=0.7818（1） nm, b=0.8611 （2） nm, c=1.0908（2） nm, V=0.6727（2） nm^3 and Z=2 with R1=0.0223. The structure of JGP-2 was built up by alternate arrangement of GaO4N2 octahedra, and HPO4（or H2PO4） tetrahedra to form an infinite one-dimensional corner-sharing-corner（CSC） chain. Through P sites, the CSC chains link with an unusual edge-sharing dimmer, Ga2F4（H2O）2, giving rise to a 4,10-membered ring net layered structure of JGP-7. On excitation at 254 nm, JGP-2 can emit strong blue light at ,λmax=388 rim. JGP-7 presents a strong fluorescence emission band centered at 394 nm（λex=340 nm）, the emission energy of JGP-7 is red-shifted comoared with that of JGP-2.

New Inorganic-organic Hybrid Compound Containing One Dimensional Keggin Polyoxometalate [SiW_(11)O_(39)Co]^(6-) Chains: Preparation, Characterization and Application in Chemically Bulk-modified Electrode

A new inorganic-organic hybrid compound based on polyoxometalate and organic ligand formulated as （H2bpp）3[SiWlIO39Co]-2H20（1）[bpp=l,3-bis（4-pyridyl）propane] was hydrothermally synthesized and structurally characterized by elemental analysis, single-crystal X-ray diffraction, IR, TG, and cyclic voltammetry. Single-crystal X-ray diffraction analysis reveals that compound 1 consists of interesting cobalt-monosubstituted POMs one dimensional chain together with protonated bpp ligands. Additionally, the polyoxoanions combined with the discrete organic substrates by hydrogen bond interactions to afford a supramolecular 3D network structure. The hybrid compound 1 was used as a bulk modifier to fabricate a three-dimensional chemically modified carbon paste electrode（1-CPE） by direct mixing. The electrochemical behavior and electrocatalysis of 1-CPE were studied in detail. The results indicate that 1-CPE has good electrocatalytic activities toward the reduction of nitrite or bromate in 1 mol/L 1-12SO4 aqueous solution. 1-CPE shows remarkable stability that can be ascribed to the insolubility of compound 1 and the supramolecular interactions existed between 1D POM anion chains and organic ligand bpp, which is very important for practical applications in electrode modification.

The Inorganic-organic Hybrid Junction with n-ZnO Nanorods/p-polyfluorene Structure Grown with Low-temperature Aqueous Chemical Growth Method

The inorganic-organic hybrid junction was synthesized on ITO glass substrate, which was consisted of an n-type ZnO nanorods （NRs） grown by low-temperature aqueous chemical growth method and a p-type polyfluorene （PF） organic film fabricated by spin-coating. The experimental results indicate that densely and uniformly distributed ZnO nanorods are successfully grown on the PF layer. The thickness of the PF layer plays a dominant role for the current-voltage （I-V） characteristic of the ZnO NRs/PF inorganic-organic hybrid junction device, and a p-n junction with obviously rectifying behavior is achieved with optimal PF layer thickness. The photoluminescence （PL） spectrum covering the broad visible range was obtained from the n-ZnO nanorods/p-polyfluorene （PF） structure, which was originated from the combination of the PF-related blue emission and the ZnO-related deep level emission.

Hydrothermal synthesis and characterization of two novel inorganic-organic hybrid materials

By using different organic ligands, two 3D inorganic-organic hybrid compounds Co（C4H4N2）（VO3）2 1 and Co（C12H12N2）（VO3）2 2 were synthesized by hydrothermal reaction and characterized by X-ray crystallography. Crystal data： 1. crystal system orthorhombic, space group Pnna, a=1 0.188（2） A, b=1 1.497（2） A, c=7.3975（15） A, V=866.5（3） A^3, Z=4, Dcalcd= 2.705 g/cm^3; 2. crystal system triclinic, space group P1^- （No. 2）, a=8.3190（17） A, b=8.4764（17） A, c=1 1.183（2） A, a=95.48（3）°, β=92.03（3）°, γ=107.24（3）°,V=748.0（3） A^3, Z=2, Dcalcd= 1.958 g/cm^3. The framework of compound 1 contains both {Co（C4H4N2）} and infinite metavanadate chains. Crystal structure of compound 2 is constructed with inorganic {CoV2O6} layers across-linked by organic 1,2-bis（4-pyridyl） ethane ligands. The two compounds are thermally stable to approximately 410 ℃ and 350 ℃, respectively. Their optical band gaps are determined to be 2.13 eV and 2.12 eV by UV-VIS-NIR diffuse reflectance spectra, which revealed their nature of semiconductor and optical absorption features.

Nanojunctions Contributing to High Performance Thermoelectric ZnO-Based Inorganic-Organic Hybrids

Organic-inorganic nanojunctions can result in a selective scattering of charge carrier depending on their energy, which leads to a simultaneous increase in the Seebeck coefficient S and the power factor. In this work, the nanojunction is successfully employed at the organic-inorganic semiconductor interface of polyparaphenylene （PPP） and Zn1-xAgxO nanoparticles through the sol-gel method. The presence of nanoinclusions PPP in Zno.gAgoa 0 matrix is found to be effective in improving the figure of merit （ZT） by the dual effects of an increase in the power factor consistent with the heterojunetion effect and a reduction in thermal conductivity. Zno.gAgo.10/0.1 wt% PPP exhibits a maximum figure of merit, i.e., ZT= 0.22.

Synthesis and Structure of a Novel Chain-like Inorganic-organic Hybrid Constructed from Isopolyanion and Oxalato-bridged Dinuclear Copper Complex

A novel inorganic-organic hybrid based on isopolyanion,{[Cu2（phen）2（μ-ox）][H2Mo8O26]}·4EtOH·Et2O（1） （phen=phenanthroline,ox=oxalate）,was synthesized under open-air mild reaction conditions,and characterized by elemental analysis,IR,ICP,TG and single crystal X-ray diffraction analysis.The crystal structure belongs to triclinic system with space group Pī and cell parameters：a=1.1075（5） nm,b=1.1608（5） nm,c=1.3333（5） nm,α=91.683（5）o,β=113.996（5）o,γ=112.170（5）o,V=1.4159（10） nm3,Mr=2017.44,Z=1,Dc=2.366 g/cm3 and F（000）=980.0.The structure of hybrid 1 is a 1D chain constructed of alternating octamolybdate isopolyanions [β-（Mo8O26）4-] and oxalato-bridged dinuclear copper complex cations [Cu2（phen）2（μ-ox）]2＋.Ultimately,a 3D supramolecular network was formed by hydrogen bond interactions among the adjacent chains.The result shows that hybrid 1 is the first example of inorganic-organic hybrid constructed from isopolyanion and oxalato-bridged dinuclear copper complex fragment （CCDC No.665101）.

Rare earth inorganic-organic hybrid compounds based on Keggin-type polyoxometalate {SiW_(12)} with fast-responsive photochromism and switchable luminescence properties

Four rare earth inorganic-organic hybrid compounds based on Keggin-type polyoxometalate {SiW_(12)}with general formula [{RE(DMF)_(4)(H_(2)O)_4RE(DMF)_(6)}_(2){SiW_(12)O_(40)}_(3)](RE = La(1),Pr(2),Sm(3),Eu(4),DMF=N,N-dimethylformamide) were synthesized by the conventional solution method.Structure analyses indicate that four compounds are isostructural and are all built from three [SiW_(12)O_(40)]^(4-) polyoxoanions and DMF ligands linked by RE^(3+).Compounds 1-4 are extremely sensitive to UV light and present excellent photochromic properties,in which the coloring and fading time of samples are both no more than 2 min,and the reversible coloring-fading process can be repeated for at least 10 cycles with little fatigue,suggesting that compounds 1-4 can be a series of fast-responsive and durable photochromic materials.Moreover,the solid-state photoluminescence spectra of compounds 3(Sm) and 4(Eu)display strong characteristic emissions of rare earth ions based on f-f transitions.Meanwhile,compound4(Eu) has a longer fluorescence lifetime up to 566.74 μs.Notably,co mpounds 3(Sm) and 4(Eu) exhibit the switchable luminescence behavior induced by photochromism,which allows them to be used as potential molecular switches.

Hybridization of metal–organic framework and monodisperse spherical silica for chromatographic separation of xylene isomers

Metal–organic frameworks(MOFs) packed in the column have been a promising candidate as the stationary phase for high performance liquid chromatography(HPLC). However, the direct packing of irregular MOF powder could raise some problems like high back pressure and low column efficiency in the HPLC separation. In this work, UiO-66 capable of separating xylenes was supported effectively on the surface of the monodisperse spherical silica microspheres by one-pot method. The hybridization of Ui O-66 and silica microspheres(termed UiO-66@SiO2 shell–core composite) was prepared by stirring the suspension of the precursors of Ui O-66 and\\COOH terminated silica in the N,N-dimethylformamide with heating. The shell–core composite material UiO66@SiO2 was characterized by SEM, TEM, PXRD and FTIR. Then, it was used as a packing material for the chromatographic separation of xylene isomers. Xylene isomers including o-xylene, m-xylene and p-xylene were efficiently separated on the column with high resolution and good reproducibility. Moreover, the Ui O-66@SiO2 shell–core composites packed column still remained reverse shape selectivity as Ui O-66 possessed, and the retention of xylenes was probably ascribed to the hydrophobic effect between analytes and the aromatic rings of the Ui O-66 shell. The Ui O-66@SiO2 shell–core composites obtained in this study have some potential for the separation of structural isomers in HPLC.

Ultrathin 2D Metal–Organic Framework Nanosheets In situ Interpenetrated by Functional CNTs for Hybrid Energy Storage Device

The controllable construction of two-dimensional(2D)metal–organic framework(MOF)nanosheets with favorable electrochemical performances is greatly challenging for energy storage.Here,we design an in situ induced growth strategy to construct the ultrathin carboxylated carbon nanotubes(C-CNTs)interpenetrated nickel MOF(Ni-MOF/C-CNTs)nanosheets.The deliberate thickness and specific surface area of novel 2D hybrid nanosheets can be effectively tuned via finely controlling C-CNTs involvement.Due to the unique microstructure,the integrated 2D hybrid nanosheets are endowed with plentiful electroactive sites to promote the electrochemical performances greatly.The prepared Ni-MOF/C-CNTs nanosheets exhibit superior specific capacity of 680 C g^−1 at 1 A g^−1 and good capacity retention.The assembled hybrid device demonstrated the maximum energy density of 44.4 Wh kg^−1 at a power density of 440 W kg^−1.Our novel strategy to construct ultrathin 2D MOF with unique properties can be extended to synthesize various MOF-based functional materials for diverse applications.

Pyridinic nitrogen enriched porous carbon derived from bimetal organic frameworks for high capacity zinc ion hybrid capacitors with remarkable rate capability

Aqueous zinc ion hybrid capacitors(ZIHCs)hold great potential for large-scale energy storage applications owing to their high safety and low cost,but suffer from low capacity and energy density.Herein,pyridinic nitrogen enriched porous carbon(nPC)was successfully synthesized via the growth,subsequent annealing and acid etching of bimetal organic frameworks for high capacity and safe ZIHCs with exceptional rate capability.Benefiting from the mesopores for easy ion diffusion,high electrical conductivity enabled by in-situ grown carbon nanotubes matrix and residual metal Co nanoparticles for fast electron transfer,sufficient micropores and high N content(8.9 at%)with dominated pyridinic N(54%)for enhanced zinc ion storage,the resulting nPC cathodes for ZIHCs achieved high capacities of 302 and137 m Ah g^(-1) at 1 and 18 A g^(-1),outperforming most reported carbon based cathodes.Theoretical results further disclosed that pyridinic N possessed larger binding energy of-4.99 eV to chemically coordinate with Zn2+than other N species.Moreover,quasi-solid-state ZIHCs with gelatin based gel electrolytes exhibited high energy density of 157.6 Wh kg^(-1) at 0.69 kW kg^(-1),high safety and mechanical flexibility to withstand mechanical deformation and drilling.This strategy of developing pyridinic nitrogen enriched porous carbon will pave a new avenue to construct safe ZIHCs with high energy densities.