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 chara...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).展开更多
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.Fi...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.展开更多
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...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.展开更多
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 successf...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...展开更多
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 di...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.展开更多
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...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.展开更多
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 c...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.展开更多
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-ra...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.展开更多
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 chara...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.展开更多
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 (P...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.展开更多
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. C...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.展开更多
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,...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.展开更多
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-...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.展开更多
In millimeter wave(mmWave) multiple-input multiple-output(MIMO) systems, hybrid precoding has been widely used to overcome the severe propagation loss. In order to improve the spectrum efficiency with low complexity, ...In millimeter wave(mmWave) multiple-input multiple-output(MIMO) systems, hybrid precoding has been widely used to overcome the severe propagation loss. In order to improve the spectrum efficiency with low complexity, we propose a joint hybrid precoding algorithm for single-user mmWave MIMO systems in this paper. By using the concept of equivalent channel, the proposed algorithm skillfully utilizes the idea of alternating optimization to complete the design of RF precoder and combiner. Then, the baseband precoder and combiner are computed by calculating the singular value decomposition of the equivalent channel. Simulation results demonstrate that the proposed algorithm can achieve satisfactory performance with quite low complexity. Moreover, we investigate the effects of quantization on the analog components and find that the proposed scheme is effective even with coarse quantization.展开更多
Ethyl methacrylate (EMA) doped with luminescent ternary terbium complex (Tb(acac) 3·dam) with acetylacetone (Hacac) and diantipylmethane (dam) was incorporated into the microporous silica gel. With the polymeriz...Ethyl methacrylate (EMA) doped with luminescent ternary terbium complex (Tb(acac) 3·dam) with acetylacetone (Hacac) and diantipylmethane (dam) was incorporated into the microporous silica gel. With the polymerization of EMA, the hybrid material containing Tb(acac) 3·dam was obtained. The hybrid material exhibited good toughness and transparency and higher thermal stability than that of the pure complex and pure polymer matrix. In the range of doping concentration of Tb(acac) 3·dam (0.05%, 0.1%, 0.2%, 0.5%, 1.0%, 2.0% and 5.0%), emission intensity increases with the increasing of corresponding doping concentration and concentration quenching effect has not taken place.展开更多
Polyoxometalates(POMs) with Cd-coordination complexes acting as supporting units are rarely reported. The linkage of the supporting units with inorganic building block(polyanion) is generally established on termin...Polyoxometalates(POMs) with Cd-coordination complexes acting as supporting units are rarely reported. The linkage of the supporting units with inorganic building block(polyanion) is generally established on terminal O-atoms, but scarcely via bridging O-atoms. By introducing liquid small organic molecule(pyridine, C5NH5) as assistant "structure-directing agent", we obtained a novel organic-inorganic hybrid polytungstate,(Hpy)4[Cd(phen)2(P2W18O62)]·nH2O(1, n ≈ 3, py = pyridine, phen = 1,10-phenanthroline), under hydrothermal conditions. The single-crystal X-ray diffraction analysis shows that 1 is the first compound containing an asymmetric heteropolyanion, [Cd(phen)2(P2W18O62)]4–, a Wells-Dawson-type polyanion monosupported by Cd-coordination complex via di-bridging O-atoms.展开更多
Ternary europium complex with dibenzoylmethane(DBM)and 1,10phenanthroline(phen)was insitu synthesized in thin SiO2/polyvinyl butyral(PVB)hybrid films by a twostep solgel process and characterized by means of fluoresce...Ternary europium complex with dibenzoylmethane(DBM)and 1,10phenanthroline(phen)was insitu synthesized in thin SiO2/polyvinyl butyral(PVB)hybrid films by a twostep solgel process and characterized by means of fluorescence spectroscopy.The luminescence spectra,fluorescence lifetimes and photostability were all investigated.The results showed that the hybrid films exhibited the characteristic emission bands of the central rare earth Eu3+.In addition,Eu3+presented longer fluorescence lifetime than in an ethanol solution and the complex had a higher photostability in the hybrid film than in the PVB film containing the corresponding pure complex.展开更多
The organic rare earth complex was embedded in silica spheres to form inorganic-organic hybrid. Photoactive rare earth complexes with various organic ligands exhibit intense narrow emission band, and the silica is an ...The organic rare earth complex was embedded in silica spheres to form inorganic-organic hybrid. Photoactive rare earth complexes with various organic ligands exhibit intense narrow emission band, and the silica is an excellent matrix for inorganic-organic structure. The transmission electron microscope image presents the hybrid nanospheres. The diameter of the hybrid is about 100 nm. The europium complex that incorporated into silica sphere is also proved by the IR spectra, the excitation and emission spectra. The lifetimes of the Eu 3+ ions in the hybrid nanospheres and in the pure europium complex were also detected. This hybrid with inhomogeneous compositions exhibits specifically tailored chemical and optical properties, such as perfect thermal and mechanical stability, colorimetric purity and so on. It can be used as luminescent and optical material in EL and PL fields.展开更多
Minimizing the impact of the mixed uncertainties(i.e.,the aleatory uncertainty and the epistemic uncertainty) for a complex product of compliant mechanism(CPCM) quality improvement signifies a fascinating research top...Minimizing the impact of the mixed uncertainties(i.e.,the aleatory uncertainty and the epistemic uncertainty) for a complex product of compliant mechanism(CPCM) quality improvement signifies a fascinating research topic to enhance the robustness.However, most of the existing works in the CPCM robust design optimization neglect the mixed uncertainties, which might result in an unstable design or even an infeasible design. To solve this issue, a response surface methodology-based hybrid robust design optimization(RSM-based HRDO) approach is proposed to improve the robustness of the quality characteristic for the CPCM via considering the mixed uncertainties in the robust design optimization. A bridge-type amplification mechanism is used to manifest the effectiveness of the proposed approach. The comparison results prove that the proposed approach can not only keep its superiority in the robustness, but also provide a robust scheme for optimizing the design parameters.展开更多
The reactions of the four-coordinated macrocyclic copper complex [CuL](ClO4)2(L = 1,4,8,11-tetraazacyclotetradecane) with NH4VO3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO...The reactions of the four-coordinated macrocyclic copper complex [CuL](ClO4)2(L = 1,4,8,11-tetraazacyclotetradecane) with NH4VO3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO3]2·2.33H2O(1), [CuL]3[V(10)O(28)]·8H2O(2) and [Cu L]3[V6O(18)]·8H2O(3). Single-crystal X-ray diffraction analyses reveal that three diverse vanadium polyoxoanions, [V6O(18)]6- ring, [V(10)O(28)]6- cluster, and [V(12)O(35)]^10- ring, were isolated from the same reactant NH4VO3 under different conditions. The [CuL]^2+ bridges the [V10O28]6- clusters to form a two-dimensional sheet in 2, and link the [V6O(18)]^6- rings in 1 and [V(12)O(35)]^10- rings in 3 into three-dimensional frameworks, respectively.展开更多
基金Supported by the National Natural Science Foundation of China(No.20871022)Natural Science Foundation of Liaoning Province,China(No.20061073)
文摘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).
文摘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.
基金supported by the Ningbo Natural Science Foundation (2009A610052)the "Qianjiang Talent" Programs of Zhejiang Province (2009R10032)the K. C. Wang Magna Fund in Ningbo University
文摘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.
文摘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...
文摘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.
基金Supported by the National Natural Science Foundation of China.
文摘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.
基金thank the foundation of Wuhan Textile University(No.165002)Hubei Key Laboratory of Biomass Fibers and Eco-dyeing&Finishing for supporting this work
文摘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.
基金Supported by the National Natural Science Foundation of China(Nos.20671025 and 20771030)China Postdoctoral Science Foundation Funded Project(No.65204)Heilongjiang Province Natural Science Foundation, China(No.B200603).
文摘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.
基金Supported by the Natural Science Foundation of Liaoning Province, China(No20061073)Education Committee Foun-dation of Liaoning Province, China(No2006031)
文摘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.
基金Funded by the National Natural Science Foundation of China (Nos.10804014,11004092,60807009)the Fundamental Research Funds for the Central Universities (No.DUT10LK01)
文摘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.
文摘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.
基金Supported by the National Natural Science Foundation of China under Grant Nos 51476095 and 51206103the Innovation Program of Shanghai Municipal Education Commission under Grant No 13YZ128the Program for Professor of Special Appointment(Eastern Scholar) at Shanghai Institutions of Higher Learning
文摘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.
基金Project supported by the National Natural Science Foundation of China(22172022,21872021,21671033,21901135)。
文摘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.
基金supported by NSFC (No. 61571055)fund of SKL of MMW (No. K201815) Important National Science & Technology Specific Projects (2017ZX03001028)
文摘In millimeter wave(mmWave) multiple-input multiple-output(MIMO) systems, hybrid precoding has been widely used to overcome the severe propagation loss. In order to improve the spectrum efficiency with low complexity, we propose a joint hybrid precoding algorithm for single-user mmWave MIMO systems in this paper. By using the concept of equivalent channel, the proposed algorithm skillfully utilizes the idea of alternating optimization to complete the design of RF precoder and combiner. Then, the baseband precoder and combiner are computed by calculating the singular value decomposition of the equivalent channel. Simulation results demonstrate that the proposed algorithm can achieve satisfactory performance with quite low complexity. Moreover, we investigate the effects of quantization on the analog components and find that the proposed scheme is effective even with coarse quantization.
文摘Ethyl methacrylate (EMA) doped with luminescent ternary terbium complex (Tb(acac) 3·dam) with acetylacetone (Hacac) and diantipylmethane (dam) was incorporated into the microporous silica gel. With the polymerization of EMA, the hybrid material containing Tb(acac) 3·dam was obtained. The hybrid material exhibited good toughness and transparency and higher thermal stability than that of the pure complex and pure polymer matrix. In the range of doping concentration of Tb(acac) 3·dam (0.05%, 0.1%, 0.2%, 0.5%, 1.0%, 2.0% and 5.0%), emission intensity increases with the increasing of corresponding doping concentration and concentration quenching effect has not taken place.
基金supported by the Foundation of Education Department of Fujian Province(Nos.JB12199 and JA11245)the National Natural Science Foundation of China(Nos.21233004 and 40972035)
文摘Polyoxometalates(POMs) with Cd-coordination complexes acting as supporting units are rarely reported. The linkage of the supporting units with inorganic building block(polyanion) is generally established on terminal O-atoms, but scarcely via bridging O-atoms. By introducing liquid small organic molecule(pyridine, C5NH5) as assistant "structure-directing agent", we obtained a novel organic-inorganic hybrid polytungstate,(Hpy)4[Cd(phen)2(P2W18O62)]·nH2O(1, n ≈ 3, py = pyridine, phen = 1,10-phenanthroline), under hydrothermal conditions. The single-crystal X-ray diffraction analysis shows that 1 is the first compound containing an asymmetric heteropolyanion, [Cd(phen)2(P2W18O62)]4–, a Wells-Dawson-type polyanion monosupported by Cd-coordination complex via di-bridging O-atoms.
文摘Ternary europium complex with dibenzoylmethane(DBM)and 1,10phenanthroline(phen)was insitu synthesized in thin SiO2/polyvinyl butyral(PVB)hybrid films by a twostep solgel process and characterized by means of fluorescence spectroscopy.The luminescence spectra,fluorescence lifetimes and photostability were all investigated.The results showed that the hybrid films exhibited the characteristic emission bands of the central rare earth Eu3+.In addition,Eu3+presented longer fluorescence lifetime than in an ethanol solution and the complex had a higher photostability in the hybrid film than in the PVB film containing the corresponding pure complex.
文摘The organic rare earth complex was embedded in silica spheres to form inorganic-organic hybrid. Photoactive rare earth complexes with various organic ligands exhibit intense narrow emission band, and the silica is an excellent matrix for inorganic-organic structure. The transmission electron microscope image presents the hybrid nanospheres. The diameter of the hybrid is about 100 nm. The europium complex that incorporated into silica sphere is also proved by the IR spectra, the excitation and emission spectra. The lifetimes of the Eu 3+ ions in the hybrid nanospheres and in the pure europium complex were also detected. This hybrid with inhomogeneous compositions exhibits specifically tailored chemical and optical properties, such as perfect thermal and mechanical stability, colorimetric purity and so on. It can be used as luminescent and optical material in EL and PL fields.
基金supported by the National Natural Science Foundation of China(71702072 71811540414+2 种基金 71573115)the Natural Science Foundation for Jiangsu Institutions(BK20170810)the Ministry of Education of Humanities and Social Science Planning Fund(18YJA630008)
文摘Minimizing the impact of the mixed uncertainties(i.e.,the aleatory uncertainty and the epistemic uncertainty) for a complex product of compliant mechanism(CPCM) quality improvement signifies a fascinating research topic to enhance the robustness.However, most of the existing works in the CPCM robust design optimization neglect the mixed uncertainties, which might result in an unstable design or even an infeasible design. To solve this issue, a response surface methodology-based hybrid robust design optimization(RSM-based HRDO) approach is proposed to improve the robustness of the quality characteristic for the CPCM via considering the mixed uncertainties in the robust design optimization. A bridge-type amplification mechanism is used to manifest the effectiveness of the proposed approach. The comparison results prove that the proposed approach can not only keep its superiority in the robustness, but also provide a robust scheme for optimizing the design parameters.
基金Supported by the Opening Project of Key Laboratory of Comprehensive Utilization of Advantage Plants Resources in Hunan South(XNZW14C08)the NSF of Hunan Province(2015JJ2072)+2 种基金the Construct Program of the Key Discipline in Hunan Provincethe Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Provincethe Project for Undergraduate Research Study and Innovative Experiment of Hunan Provincial(2016-283)
文摘The reactions of the four-coordinated macrocyclic copper complex [CuL](ClO4)2(L = 1,4,8,11-tetraazacyclotetradecane) with NH4VO3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO3]2·2.33H2O(1), [CuL]3[V(10)O(28)]·8H2O(2) and [Cu L]3[V6O(18)]·8H2O(3). Single-crystal X-ray diffraction analyses reveal that three diverse vanadium polyoxoanions, [V6O(18)]6- ring, [V(10)O(28)]6- cluster, and [V(12)O(35)]^10- ring, were isolated from the same reactant NH4VO3 under different conditions. The [CuL]^2+ bridges the [V10O28]6- clusters to form a two-dimensional sheet in 2, and link the [V6O(18)]^6- rings in 1 and [V(12)O(35)]^10- rings in 3 into three-dimensional frameworks, respectively.