Organic Hybrid Materials Research Articles

Three novel polyoxometalate-based inorganic-organic hybrid materials based on 2,6-bis(1,2,4-triazol-1-yl)pyridine.

Three novel inorganic–organic hybrid materials [Co(btp)2(W5O16)(H2O)]n (1), [Cd3(btp)6(PW12O40)2(H2O)6·6H2O]n (2), and [Ag3(btp)2(PMo12O40)·1.5H2O]n (3) (btp = 2,6-bis(1,2,4-triazol-1-yl)pyridine) have been hydrothermally synthesized and characterized by IR spectroscopy, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), elemental analysis and thermal gravimetric analysis (TGA). The most striking structure feature of compound 1 is a 3D polycatenation framework, interpenetrated by a 2D 4-connected sql topology layer and a 3D 6-connected rob topology framework. Compound 2 exhibits a rare meso-helices 3D network with different chiralities crossing coexistence. Compound 3 also holds a 3D framework formed by linking terminal oxygen atoms of [α-PMo12O40]3− anions and silver ions in a 2D metal–organic layer. Compound 1 displays antiferromagnetic behavior. The luminescence, electrochemical and photocatalytic properties of compounds 1–3 have also been investigated. Compound 3 exhibits significant electrochemical activity for the reduction of H2O2 while compounds 1 and 2 show efficient photocatalytic activities for the degradation of Rhodamine B (RhB). Furthermore, the three compounds display luminescence behaviors in the solid state.

Preparation of novel UV-cured methacrylate hybrid materials with high thermal stability via thiol–ene photopolymerization

Methacryloxypropyl-polyhedral oligomeric silsesquioxane (MAP-POSS) was photopolymerized with the tri- or tetra-functional thiol monomer in different stoichiometry. A novel inorganic–organic methacrylate hybrid material with highly cross-linked network and high performance was synthesized by UV-initiated thiol–ene click chemistry. SEM–EDAX images and XRD diffractograms showed that no agglomeration of MAP-POSS was observed, indicating MAP-POSS dispersed uniformly in the hybrid materials. Real-time FTIR was employed to monitor the conversion of thiol and methacrylate as a function of irradiation time, and the results revealed that highly thiolated monomer could promote the conversion of methacrylate effectively because of stronger chain propagation capability. The TGA indicated that the hybrid materials had high thermal stability of which the onset decomposition temperature rose to 350 °C, approximately 50 °C higher than that of the traditional UV-cured epoxy acrylate/triethylene glycol dimethacrylate (EA/TEGDMA, 70:30 w/w) resin. The highest glass transition temperature (Tg) of the hybrid materials was 76.2 °C. Compared with traditional EA/TEGDMA resins, the novel hybrid materials consisted of MAP-POSS had fast curing rate, high mechanical properties and thermal stability which made the wider practical applications of UV-cured hybrid materials feasible.

A facile strategy for preparation and application of squaraine nanometer hybrids with broad band absorption

Organic materials are receiving more attention in the solar cell due to their better solution process, controllable synthesis, tunable chemical and physical properties. However, the focus problem of compatibility and aggregation is to be solved urgently in organic materials, which inevitably limits them widely application. To this end, an inorganic–organic hybrid materials with wide-band absorption is designed and prepared, that incorporates octavinyl-polyhedral oligomeric silsesquioxane with 6-bromoquanaldine to produce H1, then reacts with squaric acid to design H2, which efficiently avoids the fluorescence quenching due to the steric hindrance. The electrochemical results shows that the energy level of H2 is match well with the commercial dye N719. Hence it shows a better photovoltaic performance based on dye-sensitized solar cell, along with power conversion efficiency up to 7.73% when it is co-sensitized with N719. The hybrid system exhibits good performances in solar cell and long-term stability.

Spectroscopic Investigation of Thermochemical Depolymerization of Lignin Model Compounds in the Presence of Novel Liquidlike Nanoparticle Organic Hybrid Solvents for Efficient Biomass Valorization

This study reports the thermochemical transformation of lignin model compounds using nanoparticle organic hybrid materials (NOHMs). NOHMs have recently been developed as an emerging class of self-suspended nanoparticle solvent systems created by ionically or covalently grafting organic oligomers or polymers (canopy) onto surface-modified inorganic nanoparticles (core). Because NOHMs exhibit negligible vapor pressure with the ability to tailor physicochemical properties, they could be a promising catalytic solvent for the lignin thermochemical conversion process. The thermochemical conversion of lignin model compounds was achieved with the synthesized NOHM at an elevated temperature of 473 K, and the results were compared with the case of the ionic liquid [EMIM][ESO4]. The fractured moieties of the lignin model compounds were qualitatively identified by ATR FT-IR and 2D COSY NMR spectroscopies. The results indicated that the NOHM decomposed the C–O and/or C–C bonds of lignin model chemicals more efficientl...

Study of the samples of polymer composite materials with an uneven surface using hydrostatic weighing

An increase in the size and the number of the elements of the aircraft structures made of polymer composite materials (PCM) required the search for new energy-saving and less expensive non-autoclave technologies. The use of one of them, vacuum infusion, inevitably leads to formation of an uneven surface, thus inhibiting determination of the true thickness by standard methods, and, in turn, affects determination of the physical and mechanical properties of the material. The results of measuring density of carbon plastics by hydrostatic weighing are presented to calculate the true thickness of materials, volume content of binder and porosity. The developed method is also suitable for PCMs based on combustible reinforcing materials like organic plastics, hybrid and other materials that cannot be subjected to burning-off to determine the binder content.

English

English

Metal–Organic Framework Hybrid Materials and Their Applications

The inherent porous nature and facile tunability of metal–organic frameworks (MOFs) make them ideal candidates for use in multiple fields. MOF hybrid materials are derived from existing MOFs hybridized with other materials or small molecules using a variety of techniques. This led to superior performance of the new materials by combining the advantages of MOF components and others. In this review, we discuss several hybridization methods for the preparation of various MOF hybrids with representative examples from the literature. These methods include covalent modifications, noncovalent modifications, and using MOFs as templates or precursors. We also review the applications of the MOF hybrids in the fields of catalysis, drug delivery, gas storage and separation, energy storage, sensing, and others.

(Invited) Fabrication of MOFs Membranes for Molecular Separation

Metal–organic framework (MOF) materials, which are constructed from metal ions or metal ion clusters and bridging organic linkers, exhibit regular crystalline lattices with relatively well-defined pore structures and interesting properties. As emerging inorganic and organic hybrid materials, MOF materials are very appealing to be assembled into MOF membranes for separation and catalysis applications because their pores can be rationally controlled by the interplay of both inorganic metal ions and organic linkers, and their pore surfaces can be readily functionalised through a variety of approaches.[1,2] The ability to rationally tune the structure of the materials may create unique interactions with guest molecules and thus achieve unusual chemicophysical properties in adsorption and separation. Reference: L. Qiu, M. Xue and G. S. Zhu, Chem. Soc. Rev., 2014, 43, 6116.X. Kang, M. Xue, L. L. Fan, L. Huang, L. J. Guo, B. L. Chen, S. L. Qiu, Energy Environ. Sci, 2014, 7, 4053.

Structural-Stability Relationship in a Series of [ZnX]\(^−\) Inorganic Organic Hybrid Materials

To scrutinize the role the weak interactions in structure-stability of [ZnX] - (X = Cl, Br, I) based derivatives, three series of inorganic-organic hybrid materials were studied through single crystal X-ray crystallographic data obtained from IUCr in CIF format. The organic constituent of the hybrid compounds is holding the inorganic moiety through D-H…X interactions, where D is N, C or O of organic moiety acts as H-donor atom and X of inorganic component is Cl, Br I or F behaves as H-acceptor atom. The structural parameters such as the Zn-X bond distance lies in the range of 2.019(5) A [ZnF-3] to 2.730(4) A [ZnCl-1] and X-Zn-X bond angle has minimum value of 82.35 o and maximum value of 180 o for [ZnF-3], were calculated. The maximum twist of X-Zn…Zn-X = 179.8(3) o at symmetry position of 0.5+x, 0.5-y, 0.5+z is observed in [ZnBr-7] derivative.

Recent progress in metal–organic frameworks for precaution and diagnosis of Alzheimer’s disease

Alzheimer’s disease (AD) has become an issue of common concern. With the increasing numbers of people with dementia, the precaution and diagnosis of AD is more and more important. Many reports have pointed out that the AD is closely related to four metal ions within human body, including Zn2+, Fe3+, Al3+ and Cu2+. On the other hand, magnetic resonance imaging (MRI) plays a key role in the diagnosis of AD. Metal–organic frameworks (MOFs), as one of the well-known inorganic–organic hybrid material, have a promising potential in sensing of AD related ions, as well as MRI contrast agent. In this review, we summarized the recent progress in revealing pathogeny and diagnose of AD and discussed the potential of MOFs in this area. Specifically, MOFs as luminescent sensors for Zn2+, Fe3+, Al3+ and Cu2+ ions and MRI contrast agents are highlighted.

Synthesis, Structure, and Band Gap of a Novel Inorganic–Organic Hybrid Material Based on Antimony Halide and Organoamine

Using an organoamine, 2,5-bis (1-imidazoly) pyridine (L), a novel inorganic-organic hybrid material based on antimony halide formulated as {(CH3)2L}2+{(Sb4Cl8I8)0.5}2–(1) was synthesized in situ via solvothermal technique and characterized by the single-crystal X-ray diffraction. During the synthesis, the organoamine L was transformed in situ into the imidazolium ion, {(CH3)2L}2+. In the compound 1, four Sb(III) ions are linked by two $${u_{{3^ - }}}$$ I– and four u $${u_{{2^ - }}}$$ I– ligands into a (Sb4I8Cl8)4–unit, in which eight Cl–ions and two I–ions act as the terminal ligands. The uncoordinated {(CH3)2L}2+ organoamine moieties are linked with the (Sb4I8Cl8)4– clusters via H bonds into three-dimensional (3D) supramolecular architecture. The band structure calculation shows that the compound has an indirect band gap of 2.253 eV.

Hierarchical FAU/ZIF-8 Hybrid Materials as Highly Efficient Acid-Base Catalysts for Aldol Condensation.

The composite of hierarchical faujasite nanosheets and zeolitic imidazolate framework-8 (Hie-FAU-ZIF-8) has been successfully prepared via a stepwise deposition of ZIF-8 on modified zeolite surfaces. Compared to the direct deposition of metal organic frameworks (MOFs) on zeolite surfaces, ZIF-8 nanospheres were selectively attached to the external surfaces of the MOF ligand-grafted FAU crystals because of the enhancing interaction between the zeolite and MOF in the composite. In addition, the degree of surface functionalization can be greatly enhanced because of the presence of hierarchical structures. This behavior leads to an increase in the deposited MOF content, improving the hydrophobic properties of the zeolite surfaces. Interestingly, the designed hierarchical composite exhibits outstanding catalytic properties as an acid-base catalyst for the aldol condensation of 5-hydroxymethylfurfural with acetone. Compared to the isolated FAU and ZIF-8, a high yield of the product, 4-[5-(hydroxymethyl)furan-2-yl]but-3-en-2-one (67%), can be observed in the composite because of the synergistic effect between the Na+-stabilized zeolite framework and the imidazolate linkers bearing basic nitrogen functions. This opens up interesting perspectives for the development of new organic and inorganic hybrid materials as heterogeneous acid-base catalysts.

Advanced Materials by Atom Transfer Radical Polymerization.

Atom transfer radical polymerization (ATRP) has been successfully employed for the preparation of various advanced materials with controlled architecture. New catalysts with strongly enhanced activity permit more environmentally benign ATRP procedures using ppm levels of catalyst. Precise control over polymer composition, topology, and incorporation of site specific functionality enables synthesis of well-defined gradient, block, comb copolymers, polymers with (hyper)branched structures including stars, densely grafted molecular brushes or networks, as well as inorganic-organic hybrid materials and bioconjugates. Examples of specific applications of functional materials include thermoplastic elastomers, nanostructured carbons, surfactants, dispersants, functionalized surfaces, and biorelated materials.

Molecular Layer Deposition for Energy Conversion and Storage

The development of nanoscale coatings with well-controlled properties is critical to the future of nanotechnology for energy applications. As an extension of atomic layer deposition (ALD), molecular layer deposition (MLD), has recently emerged as a thin-film coating technique that can enable the development of high-performance materials in energy-related applications. MLD fabrication can be classified into two categories: polymer-based organics and inorganic–organic hybrid materials. The unique properties of low growth temperature, precise control of film thickness, uniformity, flexibility, and low density make MLD films very promising for energy-related applications. In this Review, we focus on the recent developments and understanding of MLD in the application of batteries, supercapacitors, water splitting, photodegradation, solar cells, and membranes. The different types of MLD films and nanomaterials derived from MLD are discussed based on the specific application and properties. Finally, the future d...

Iron and lithium-iron alkyl phosphates as nanostructured material for rechargeable batteries

Inorganic/organic hybrid materials composed by iron atoms bonded to an alkyl phosphate can be easily synthesized by mixing at 110 °C iron chlorides with tri-alkyl phosphates.Since structural information on these products are lacking and taking into account that lithium/iron organic hybrid materials are important in lithium ion battery technology we report here the physico-chemical characterization of different hybrid lithium/iron butylphosphates. These materials are characterized by the presence of elongated hexagonal crystals stable up to 315 °C. The insertion of lithium does not affect the local structure. Thanks to such structures the material can be electrochemically-cycled and Li ions can find facilitated pathways for travel and redox reactions.

Metal Oxide-Assisted PEDOT Nanostructures via Hydrolysis-Assisted Vapor-Phase Polymerization for Energy Storage

The diversity of nanostructures obtained from organic polymerization is limited when compared to the huge amount of documented inorganic nanostructures. In this paper, we elucidate a synergistic mechanism between in situ inorganic salt hydrolysis and vapor-phase polymerization for the metal oxide-poly(3,4-ethylenedioxythiophene) (PEDOT) hybrid nanostructure growth. The steady state polymer growth and kinetically controlled hydrolysis enables homogeneous deposition of high-aspect-ratio crystal phases such as β-FeOOH, TeO2, and SnO2 coated by a conducting polymer. By controlling the hydrolysis kinetics, the hybrid material is synthesized in one step with morphologies controlled from 1D nanofibers to 2D nanoflowers and nanostructures from monolithic to core–shell. This fundamental understanding of the connection between hydrolysis and polymerization allows the future development of nanostructured inorganic, polymeric, and inorganic–organic hybrid materials. Enabled by this study, electrodes for energy storag...

Copper Iodide Based Hybrid Phosphors for Energy‐Efficient General Lighting Technologies

AbstractSolid‐state‐lighting (SSL) is a new lighting technology that is rapidly replacing conventional lighting sources because it is much more energy efficient, longer lasting, and contributes significantly to environmental protection. A main branch of SSL technology is light‐emitting diodes (LEDs), and white‐light LEDs (WLEDs) are in the greatest demand for general lighting and illumination applications. Current WLED devices rely heavily on rare‐earth elements (REEs), which will likely suffer from cost and supply risks and environmental consequences in the near future. Crystalline inorganic–organic hybrid materials based on I–VII binary semiconductors represent a promising material class as REE‐free phosphor alternatives. This article provides a brief overview of recent advancement on this material family, with a focus on the rational design, energy‐efficient and low‐cost synthesis, systematic modification, and optimization of their electronic, optical, and thermal properties. A particular emphasis will be made on our own progress over the past several years in developing four classes of CuI(L) structures with substantially improved performance as energy‐saving lighting phosphors. General strategies for structural design, synthesis, and property optimization of these materials will also be discussed.

Three in situ-synthesized novel inorganic–organic hybrid materials based on metal (M = Bi, Pb) iodide and organoamine using one-pot reactions: structures, band gaps and optoelectronic properties

The title compounds with different band structures and photocurrent responses possess good water-proof properties due to the hydrophobic aromatic groups.

Selective Separation of Co<Sub>2</Sub> Using Novel Mixed Matrix Membranes Based on Pebax and Liquid-Like Nanoparticle Organic Hybrid Materials

Pebax1657 is known as a promising polymeric membrane material for CO2 separation. In order to further improve its gas separation performance, different polymers containing ethylene oxide (EO) groups were incorporated into the Pebax1657 matrix to form mixed matrix membranes. Liquid-like nanoparticle organic hybrid materials (NOHM-I-HPE, “I” stands for “ionic bond” and “HPE” refers to polyetheramine (“PE”) with a high (“H”) ether group content), which were made of polyetheramine chains tethered onto functionalized silica nanoparticles, have shown high solubility of CO2. In this study, the homogenous NOHM-I-HPE/Pebax1657 mixed matrix membranes with different NOHM-IHPE loadings were prepared and investigated. The results of differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS) indicated that the addition of NOHM-I-HPE resulted in a decrease in glass transition temperature of Pebax1657 and an increase in EO content of the mixed matrix membrane. Single gas permeabilities of CO2, N2 and CH4 at 23 °C and 1 bar were measured using the time-lag method. For the NOHM-I-HPE loading ranging from 0 to 60 wt.%, solubility coefficients of the mixed matrix membranes for CO2 greatly increased from 1.16 to 3.84 cm3 (STP)/(cm3·bar), while those for CH4 and N2 only slightly increased from 0.078 to 0.094 cm3 (STP)/(cm3·bar) and from 0.013 to 0.026 cm3 (STP)/(cm3·bar), respectively. CO2 permeability increased four times compared to the pure Pebax1657 membrane after the incorporation of 60 wt.% NOHM-I-HPE in Pebax1657. Although the CO2/N2 selectivity slightly decreased with an increase in the NOHM-I-HPE loading, the CO2/CH4 selectivity was improved in the newly developed NOHM-IHPE/Pebax1657 mixed matrix membranes. These results indicate that the NOHM-I-HPE/Pebax1657 mixed matrix membranes are very promising candidates for selective CO2 separation for various energy related applications.

Effects of the core of liquid-like SiO2 nanoparticle organic hybrid materials on CO2 capture

A series of specific liquid-like silicon dioxide (SiO2) nanoparticle organic hybrid materials (NOHMs) were successfully prepared by employing different contents of SiO2 as the core, 3-glycidoxypropyl trime thoxysilane (KH-560) or 3-(trihydroxysilyl)-1-propane sulfonic acid (SIT) as the corona and polyetheramine M-1000 (M-1000) as the canopy. These materials showed a solvent-free and liquid-like state at room temperature. The effect of the SiO2 content in the NOHMs with different bonding types on the CO2 capture capacity was investigated at 298 K and CO2 pressures ranging from 1.0 to 2.5 MPa. It was demonstrated that the capacity of the sorbents improved with the decreasing of SiO2 content. This result was due to the larger number of reactive groups and lower viscosity of the NOHMs. The reactive groups, such as secondary amine and ether groups, react with CO2 molecules, while the lower viscosity creates larger molecular gap and weaker intermolecular forces, which facilitates the penetration of CO2 molecules into the potential space between organic chains. In addition, the NOHMs synthesized via covalent bonds had a much better CO2 capture capacity than the NOHMs with ionic bonds and the same content of SiO2, owing to the protonation of the amine groups in the ionic bond-typed NOHMs, which renders them inactive for CO2 uptake.