Organic-inorganic Hybrid Structures Research Articles

A single layered organic-inorganic hybrid compound [(FBMA)2PbBr4] with reversible phase transition and intense fluorescent property

Reactions of 3-fluoro-N-methylbenzylamine (FBMA) with PbBr2 in concentrated HBr aqueous solution afforded a two-dimensional (2D) single layered organic-inorganic hybrid material [(FBMA)2PbBr4], which was confirmed by X-ray single crystal diffraction, infrared (IR) spectroscopy and powder X-ray diffraction (PXRD). The thermodynamic DSC analysis revealed it has a pair of reversible phase transition peaks with large thermal hysteresis exhibiting a first-order type phase transition. The variable-temperature single crystal diffraction proved the phase transition is originated from the order and disorder of organic-inorganic hybrid structures at room and high temperatures. Simultaneously compound [(FBMA)2PbBr4] exhibited a strong emission peak at 443 nm when under an excitation wavelength of 380 nm.

Fabrication of highly durable polysiloxane-zinc oxide (ZnO) coated polyethylene terephthalate (PET) fabric with improved ultraviolet resistance, hydrophobicity, and thermal resistance

Developing a universal strategy to improve the properties of polyethylene terephthalate (PET) fibers, such as UV resistance, hydrophobicity, and thermal resistance, is highly desirable in expanding the application of PET fibers. Herein, a highly durable and robust ZnO layer was deposited onto PET fabric via radiation-induced graft polymerization (RIGP) of γ-methacryloxypropyl trimethoxysilane (MAPS) and the subsequent sol-gel in situ mineralization with zinc acetate to produce wurtzite nanocrystalline ZnO. The as-obtained material, denoted as PET-g-PMAPS/ZnO. The interfacial layer consisted of Zn-O-Si and Si-O-Si covalent bonds not only leads to an improvement in adhesion between ZnO nanoparticles and its support, but it also overcomes the poor film-forming ability of inorganic particles. Most importantly, photocatalytic self-degradation of its organic support caused by the high photocatalytic activity of ZnO can be eliminated because of high bond energy of the organic-inorganic hybrid structure. PET-g-PMAPS/ZnO exhibited excellent thermal resistance, UV resistance and durability. Superhydrophobicity was achieved by simply annealing the PET-g-PMAPS/ZnO fabric at 200 °C in ambient air, and the coated fabric still retains its superhydrophobicity after 40 laundering cycles test and even stored for a few weeks. This study presents an effective method to overcome the bottle-necks in growing inorganic nanocrystals on polymeric supports surface.

Photosensitive organic-inorganic hybrid structures based on porous silicon

In this study, the photovoltaic organic-inorganic structures were created by deposition of poly(3,4-ethylenedioxythiophene) film doped by poly(styrenesulfonate) and reduced graphene oxide on the porous silicon/silicon substrate. Formation of the hybrid structure was confirmed by means of atomic-force microscopy and Fourier transform infrared spectroscopy. The current-voltage characteristics of the obtained structures were studied. It was found the increase of electrical conductivity and photo-induced signal in organic-inorganic structures. Temporal parameters and spectral characteristics of photoresponse in the 400–1100 nm wavelength range were investigated. The widening of spectral photosensitivity in a short-wavelength range due to light absorption in various layers of the multijunction structure in comparison with single crystal silicon was revealed.

A simple fabrication route of porous palladium/palladium oxide/carbon nanostructures using one-step combustion waves for high-performance pH sensors

Reduction-oxidation controls and synthesis of organic-inorganic hybrid structures are key features associated with their electrochemical properties. However, they involve bulky setup and long-time processes that incur high-cost. Herein, we report one-step combustion waves (CWs) for the fabrication of hybrid-porous palladium/palladium oxides/carbon (Pd/PdxOy@C) nanostructures with controllable atomic composition and their application as a high-performance pH sensor. Hybrid composites of Pd/formaldehyde (FA)/nitrocellulose (NC) were prepared as precursors. Self-propagating CWs through the NC networks carried out the transformation from Pd to PdO2 in the higher oxidation state and the formation of a carbon layer, while the fast release of chemicals in CWs developed the porous nanostructures with large surface areas. The flexible pH sensor using the synthesized Pd/PdxOy@C powders exhibited the outstanding specific voltage potential (2.08 V/mg at pH 2.83) and sensitivity (167 mV/mg pH). It showed no hysteresis during cycling of pH values and high stability over 4 h (voltage change <0.89%). The high oxidation states and conductive carbon layers of Pd/PdxOy@C with large surface areas improved the specific potential and the stability in minute changes of pH values and forward-reverse proton exchanges. The physicochemical synthesis using CWs would contribute to developing scalable processing for electrochemical applications, including chemical sensors.

A Facile Approach to Generate Cross-Linked Poly(cyclotriphosphazene-co-oxyresveratrol) Nanoparticle with Intrinsically Fluorescence

Highly cross-linked and monodisperse polyphosphazene nanoparticles exhibiting strong fluorescence with oxyresvertrol structure was facilely generated via a one-pot prediction polycondensation of hexachlorocyclotriphosphazene and oxyresveratrol. The results reveal that the diameter of the microspheres can be well adjusted (typically in a range from 200 to 400 nm). Attractively, the as-prepared nanoparticle with oxyresveratrol structure possess outstanding disperse ability in both aqueous and organic media. Moreover, it exhibits significantly enhanced fluorescent intensity and outstanding photobleaching stability under ultraviolet–visible irradiation, owing to the highly cross-linked and organic–inorganic hybrid structure. Due to these superior properties and novelty of our synthesized material, it has shown great potential in application as fluorescent labels, carriers and potent biomaterials in drug delivery.

Synthesis of titania nanoparticle-dispersed hybrid membranes from allyloxytitanium and phosphonic acid derivatives for fuel cell

Inorganic-organic hybrid membranes consisting of an aliphatic backbone and amorphous TiO2 nanoparticles (NPs) were synthesized from tetraallyloxytitanium and phosphonic acid methacrylate via a simple copolymerization-hydrolysis method. Tetraallyoxytitanium (TAT) was copolymerized with 2-hydroxyethyl methacrylate acid phosphate (HEMAP), and then hydrolyzed, yielding inorganic-organic hybrid composites. IR and 13C NMR spectroscopy confirmed the formation of the inorganic-organic hybrid structure. TEM and SAXS showed that amorphous TiO2 NPs were dispersed in the polymer matrix. The membranes exhibited good thermal stability up to 180 °C. The aliphatic chains of the methacrylate derivative dispersed with TiO2 NPs improved the mechanical properties of the membranes. The tensile modulus of the HEMAP/TAT membrane with a composition of 95:5 was 505 MPa. The conductivity of the 95:5 membranes was 4.1 × 10-2 S cm-1 at 130 °C and 100% relative humidity (RH), while it was 4.7 × 10-4 S cm-1 at 130 °C and 19.3% RH. The peak power of the 95:5 membrane was 4.8 mW/cm2 at 140 °C and 30% RH. The cell utilizing the hybrid membrane was operated at 140 °C and 30% RH for 72 h without any drop in cell voltage.

Direct Evidence of Exciton-Exciton Annihilation in Single-Crystalline Organic Metal Halide Nanotube Assemblies.

Excitons in low-dimensional organic-inorganic metal halide hybrid structures are commonly thought to undergo rapid self-trapping following creation due to strong quantum confinement and exciton-phonon interaction. Here we report an experimental study probing the dynamics of these self-trapped excitons in the single-crystalline bulk assemblies of 1D organic metal halide nanotubes, (C6H13N4)3Pb2Br7. Through time-resolved photoluminescence (PL) measurements at different excitation intensities, we observed a marked variation in the PL decay behavior that is manifested by an accelerated decay rate with increasing excitation fluence. Our results offer direct evidence of the occurrence of an exciton-exciton annihilation process, a nonlinear relaxation phenomenon that takes place only when some of the self-trapped excitons become mobile and can approach either each other or those trapped excitons. We further identify a fast and dominant PL decay component with a lifetime of ∼2 ns with a nearly invariant relative area for all acquired PL kinetics, suggesting that this rapid relaxation process is intrinsic.

Design Strategy for Improving Optical and Electrical Properties and Stability of Lead-Halide Semiconductors.

Broad absorption, long-lived photogenerated carriers, high conductance, and high stability are all required for a light absorber toward its real application on solar cells. Inorganic-organic hybrid lead-halide materials have shown tremendous potential for applications in solar cells. This work offers a new design strategy to improve the absorption range, conductance, photoconductance, and stability of these materials. We synthesized a new photochromic lead-chloride semiconductor by incorporating a photoactive viologen zwitterion into a lead-chloride system in the coordinating mode. This semiconductor has a novel inorganic-organic hybrid structure, where 1-D semiconducting inorganic lead-chloride nanoribbons covalently bond to 1-D semiconducting organic π-aggregates. It shows high stability against light, heat, and moisture. After photoinduced electron transfer (PIET), it yields a long-lived charge-separated state with a broad absorption band covering the 200-900 nm region while increasing its conductance and photoconductance. This work is the first to modify the photoconductance of semiconductors by PIET. The observed increasing times of conductivity reached 3 orders of magnitude, which represents a record for photoswitchable semiconductors. The increasing photocurrent comes mainly from the semiconducting organic π-aggregates, which indicates a chance to improve the photocurrent by modifying the organic component. These findings contribute to the exploration of light absorbers for solar cells.

Room-Temperature Direct Heterogeneous Bonding of Glass and Polystyrene Substrates

Organic-inorganic hybrid structures enable new opportunities for ubiquitous sensors. Bonding of organic and inorganic materials is highly desirable but challenging. Polystyrene and glass are two of typical substrate materials for micro/nanofluidic devices. However, they are very difficult to be combined due to their extremely large thermal expansion mismatches. To avoid thermal stress generated at elevated temperatures, we developed a room-temperature direct bonding process between polystyrene and glass substrates using vacuum ultraviolet-ozone (VUV/O3) surface irradiation without employing heat. After storage at room temperature (∼25°C) for 24 h, the bonding strengths were measured to be >2 MPa, representing a robust interfacial bonding. The bonded polystyrene-glass pair exhibited excellent optical transparency due to nearly no deterioration at the bonding interface. The details of VUV/O3 treated surfaces and bonding interfaces were characterized and a bonding model was demonstrated to elucidate the glass-polystyrene bonding mechanism.

Preparation of Se-based solar cell using spin-coating method in ambient condition**Project supported by the National Natural Science Foundation of China (Grant Nos. 51579057, 5177090655, and 51379052) and the State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, China (Grant No. 2016DX07).

A new hybrid organic-inorganic structure of FTO/TiO2/Se/HTL/Au based selenium solar cell has been fabricated through a low-cost spin-coating process in air. In this process, selenium is completely dissolved in hydrazine, to form a homogeneous precursor solution. After spin-coating the precursor solution on the TiO2 substrates, following by sintering at 200 °C for 5min, a uniform selenium film with crystalline grains is formed. The selenium based solar cell exhibits an efficiency of 1.23% under AM1.5 illumination (100 mW⋅cm−2), short-circuit current density of 8 mA⋅cm−2, open-circuit voltage of 0.55 V, and fill factor of 0.37. Moreover, the device shows a stable ability with almost the same performance after 60 days.

Structural insights into two inorganic-organic hybrids based on chiral amino acids and polyoxomolybdates

A new chiral inorganic-organic hybrid with the formula (L-His)2(H7CoMo6O24)·6H2O (1), based on natural amino acid and Anderson type polyoxomolybdate was synthesized through mild condition. The chiral l-histidine molecules induced chirality to the whole structure through various types of strong and unconventional hydrogen bond (HB) interactions (CH⋯O, NH⋯O and CH···π interactions), as well as bifurcated hydrogen bonds (BHBs) between l-histidine amino acid, hexamer water cluster molecules, and H7CoMo6O24·xH2O. Following, important non-covalent CH⋯O interactions is investigated in another chiral inorganic-organic hybrid structure, (L-Pro)3(PMo12O40).4.5H2O (2), in detail. The CH⋯O hydrogen bonds lead to a chiral network similar to the DNA strands affording a promising candidate to bio-inorganic studies.

SYNTHESIS AND CHARACTERIZATION OF BISMERCAPTO (2, 2&amp;#8242;:6&amp;#8242;, 2&amp;#8243;-terpyridine) Ru(II)-COMPLEXES STABILIZED GOLD NANOPARTICLES AND THEIR ELECTRO CATALYTIC REDUCTION OF NITRITE

Inorganic-organic hybrid structures based on metal-complexes particularly, octahedral bis-2,2′:6′,2″- terpyridine metal complexes provide an advantages of increased symmetry and in the case of ruthenium(III)/ruthenium(II) complexation an entrance to a directed complexation Method. The Ru (II) terpyridine methane thiolate protected gold nanoparticle was synthesized through covalent bonding of Ru terpyridine methane thiolates over gold nanoparticles surfaces. The ligand terpyridine methanethiolate was synthesized successfully in good percentage of yield. The structures were confirmed and characterized by different physical, analytical, spectral data like FTIR, UV, SEM and Cyclic voltammetry. All the data are shown the expected results.

Biogenic Calcium Carbonate with Hierarchical Organic–Inorganic Composite Structure Enhancing the Removal of Pb(II) from Wastewater

Calcium carbonate from geological sources (geo-CaCO3, e.g., calcite, aragonite) is used extensively in removing heavy metals from wastewater through replacement reaction. However, geo-CaCO3 has an intrinsically compact crystalline structure that results in low efficiency in pollutant removal and thus its use may produce enormous sludge. In this work, biogenic calcium carbonate (bio-CaCO3) derived from oyster shells was used to remove Pb(II) from wastewater and found to significantly outperform geo-CaCO3 (calcite). The thermodynamics study revealed that the maximum adsorption capacity of bio-CaCO3 for Pb(II) was three times that of geo-CaCO3, reaching up to 1667 mg/g. The kinetics study disclosed that the dissolution kinetics and the rate of intraparticle diffusion of bio-CaCO3 were faster than those of geo-CaCO3. Extensive mechanism research through X-ray powder diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption/desorption test and mercury intrusion porosimetry showed that the hierarchical porous organic-inorganic hybrid structure of bio-CaCO3 expedited the dissolution of CaCO3 to provide abundant CO32- active sites and facilitated the permeation and diffusion of Pb(II) into the bulk solid phases. In addition, Fourier transform infrared spectroscopy (FTIR) study, X-ray photoelectron spectroscopy (XPS) analysis, and the examination of Pb(II) removal ability of bio-CaCO3 after calcination indicated that the organic functional groups of bio-CaCO3 also facilitated the immobilization of Pb(II) into CaCO3 particles, although the major contribution was from the hierarchical porous structure of bio-CaCO3.

Inorganic Anions Regulate the Phase Transition in Two Organic Cation Salts Containing [(4-Nitroanilinium)(18-crown-6)]+ Supramolecules

Inorganic Anions Regulate the Phase Transition in Two Organic Cation Salts Containing [(4-Nitroanilinium)(18-crown-6)]+ Supramolecules

Rationally Controlling the Self-Assembly Behavior of Triarmed POSS–Organic Hybrid Macromolecules: From Giant Surfactants to Macroions

Two triarmed organic–inorganic hybrid materials based on carboxylic acid-functionalized polyhedral oligomeric silsesquioxane (APOSS) with/without PS linkers are designed and synthesized (tri-PS-APOSS and tri-APOSS). They can both self-assemble into hollow spherical nanostructures in water/organic mixed solvents, as confirmed by light scattering and TEM techniques, yet they possess completely different mechanisms and driving forces. With the PS linkers, the hybrid forms bilayer vesicles similar to surfactants; while without the PS linkers, the hybrid behaves like hydrophilic macroions and assembles into single-layered, vesicle-like “blackberry”-type structure. Consequently, the trend of the assembly size in response to the change of the solvent polarity is different for the two scenarios. This work shows a simple, universal approach of controlling the mechanism and product of the self-assembly process via minor adjustment of the organic–inorganic hybrid structures.

Preparation, characterization and evaluation of the catalytic power of an hybrid compound [H3PMo12O40-chitosan] for the azoic-colored solutions

Inorganic–organic hybrid structures have become novel alternatives for many applications as they combine the advantages of both systems. In this current study, a hybrid compound [H3PMo12O40-chitosan] was prepared using a wet impregnation method with different proportions (0-100 wt. %, considering the polymer as the main component). The chemical structure and the morphology of the synthesized compounds were studied using FT-IR and SEM. Their catalytic powers were evaluated for Naphtol Blue Black and Eriochrome Blue Black B. Experimental data revealed that the decolorization phenomenon depends on the structure of the dye it-self, the pH value, the initial dye concentration, the time contact, the oxidant dose and the temperature. Kinetic data, well described using the first order model, allowed us to establish the thermodynamic parameters. The calculated low values of Ea (7.48 and 8.14 KJ. mol-1) proved the efficiency of the prepared catalyst. Eriochrome Blue Black B could be decomposed more rapidly than Naphtol Blue Black. As example, after a period of 30 min of reaction, the target removals were, respectively, 70% and 15% for mono and bi-azoic dyes. The reuse of the catalyst is carried out and it was found to be recyclable more than three consecutives cycles.

Structural, dynamic mechanical and dielectric properties of mesoporous silica/epoxy resin nanocomposites

Research of mesoporous silica/polymer composite indicated that the mechanical property and thermal stability of the composite were remarkably enhanced due to the effective utilization of nanopore specific surface area. Furthermore, the performance of the mesoporous silica/polymer under a high electric field was promising. In this work, an organic-inorganic hybrid structure composed of mesoporous silica (SBA-15) and epoxy resin was prepared. The silane coupling agent, KH550, was used to enhance the interaction between the particles and the epoxy molecules, and the particles were more evenly dispersed in the polymer matrix. Nitrogen adsorption-desorption and Fourier transform infrared spectroscopy experiments showed that the KH550 molecules spread into the nanopores, and reacted with the hydroxyl group of the SBA-15 particles. The transmission electron microscopy analysis for the composites showed that the epoxy was inserted into the nanopores of SBA-15, and an organic-inorganic hybrid structure composite was formed. The dynamic mechanical and dielectric properties of the composite were studied. The storage modulus at 120 °C, glass transition temperature, and AC breakdown strength for 0.3 wt% SBA-15-KH550/epoxy composite were 1784 MPa, 148.2 °C, and 56.2 kV/mm, increased 1241%, 14%, and 73% compared to those of pure epoxy, respectively. Moreover, the permittivity for the 0.3 wt% SBA-15-KH550/epoxy composite decreased from 3.10 (pure epoxy) to 2.73 due to the voids provided by the unfilled nanopores and the improved interfacial interaction between the SBA-15 and the epoxy.

Zinc Oxide–Porphyrin Hybrid Rhombuses: Catalytically Active Microstructures via Self‐Assembly

AbstractA novel self‐assembled organic–inorganic hybrid structure consisting of zinc oxide and two oppositely charged porphyrins, showing significantly enhanced photocatalytic activity, is presented. Electrostatic self‐assembly of the cationic tetra‐(N‐methyl‐4‐pyridyl)porphyrin (TMPyP) with preformed assemblies of ZnO nanorods and the anionic tetra‐(4‐sulfonatophenyl)porphyrin (TPPS) in ethanol results in porphyrin microrhombuses decorated with ZnO nanorods. The structure formation is followed spectroscopically. The shape of the microrhombuses and the number of attached ZnO nanoparticles can be tuned through the porphyrin ratio TMPyP/TPPS. An enhanced and selective catalytic activity is found, giving insight into the degradation mechanism. Due to the tool‐box principle and its versatility, the concept may have great impact in fields such as solar‐energy conversion and optoelectronics.

Synthesis of inorganic-organic hybrid membranes consisting of organotrisiloxane linkages and their fuel cell properties at intermediate temperatures

Inorganic-organic hybrid membranes consisting of an aliphatic main-chain polymer and trisiloxane bond were synthesized using a simple, one-pot process from a trisiloxane derivative, phosphonic acid acrylate, and vinylbenzotriazole. 1,5-Divinyl-3-phenylpentamethyltrisiloxane (DPPMTS) was copolymerized with 2-hydroxyethyl methacrylate acid phosphate (HEMAP), and N-vinylbenzotriazole (VBT), yielding inorganic-organic hybrid composites. The formation of the inorganic-organic hybrid structure was confirmed by IR, 13C, and 29Si NMR spectroscopy. The membranes exhibited good thermal stabilities up to 200 °C. The aliphatic chains of the methacrylate derivative copolymerized with trisiloxane in the hybrid membranes improved the mechanical properties of the membranes. The tensile modulus of the VBT/HEMAP/DPPMTS membrane with a composition of 1:9:5 was 1.19 GPa. The conductivities of the 1:9:5 membranes were 5.3 × 10−2 S cm−1 and 4.1 × 10−4 S cm−1 at 100 and 19.3% relative humidity (RH), respectively, and 130 °C. The membrane electrode assembly (MEA) using the hybrid membrane exhibited a peak power of 7.8 mW cm−2 at 140 °C and 30% RH.

Near band gap luminescence in hybrid organic-inorganic structures based on sputtered GaN nanorods

Novel hybrid organic-inorganic nanostructures fabricated to utilize non-radiative resonant energy transfer mechanism are considered to be extremely attractive for a variety of light emitters for down converting of ultaviolet light and for photovoltaic applications since they can be much more efficient compared to devices grown with common design. Organic-inorganic hybrid structures based on green polyfluorene (F8BT) and GaN (0001) nanorods grown by magnetron sputtering on Si (111) substrates are studied. In such nanorods, stacking faults can form periodic polymorphic quantum wells characterized by bright luminescence. In difference to GaN exciton emission, the recombination rate for the stacking fault related emission increases in the presence of polyfluorene film, which can be understood in terms of Förster interaction mechanism. From comparison of dynamic properties of the stacking fault related luminescence in the hybrid structures and in the bare GaN nanorods, the pumping efficiency of non-radiative resonant energy transfer in hybrids was estimated to be as high as 35% at low temperatures.