Synthesis Of Hybrid Materials Research Articles

Synthesis of novel Al2O3 nanoparticle organic hybrid materials for enhancing the CO2-separation performance of prepared Al2O3-NOHMs/Pebax mixed matrix membrane

In this study, a novel liquid-like nanoparticle organic hybrid materials (NOHMs) is synthesized, in which Al2O3 was used as core, called as Al2O3-NOHMs, and it has been used for the first time to improve the performance of mixed matrix membranes (MMMs) for CO2 capture. In addition, the Al2O3-NOHMs with core/corona/canopy structure observed by TEM possess unique enthalpy effect and entropy effect, which can break through the trade-off effect of membrane separation process. According to gas separation permeation tests, the Al2O3-NOHMs/Pebax mixed matrix membranes with 2 wt% Al2O3-NOHMs showed higher CO2 permeability of 137.15 Barrer and CO2/N2 selectivity of 77.8 compared with neat Pebax membranes, and surpassed 2008 Robeson upper bound. Hence, this novel NOHMs is a very promising alternative to prepare MMMs for CO2 capture.

SI-ATRP on the lab bench: A facile recipe for oxygen-tolerant PDMAEMA brushes synthesis using microliter volumes of reagents

Facile, low-cost, and environmentally friendly procedures for the synthesis of hybrid materials are highly desirable for industrial applications and large-scale synthesis. To meet these needs, this paper presents an ultra-simple, organic solvent-free and yet effective method for the synthesis of hybrid materials consisting of an inorganic core and an organic layer of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes. Bearing in mind the numerous works published in recent years on the synthesis of PDMAEMA via “normal” and low ppm ATRP using additional reductants or complicated and expensive apparatus, e.g. a photoreactor or potentiostat, this article is a step forward, reducing the costs of the process and increasing the safety of the experimenter. In order to develop the title “facile recipe” a series of reactions aimed at optimizing the synthesis conditions in which the monomer plays a dual role and participates simultaneously as a reducing agent according to the activators regenerated by electron transfer (ARGET) atom transfer radical polymerizations (ATRP) were carried out. As a result, an in-depth analysis of the synthesis conditions and the influence of the presence of oxygen allowed the development of a monomer-mediated ATRP procedure inspired by the principles of green chemistry. Finally, 30 ppm of Cu II Br 2 /TPMA (where TPMA: tris(2-pyridylmethyl)amine) and 20 μl/cm 2 of the reaction mixture were used to obtain a homogeneous polymeric brush layer with the thickness of 331 nm, which was revealed by atomic force microscopy (AFM) measurements. Additionally, the presence and composition of the obtained polymer brushes were confirmed by X-ray photoelectron spectroscopy (XPS) analyses and scanning electron microscope (SEM) with imaging of elemental composition on the decorated silicon surface. • Ultra-simple technique of ATRP was developed due to reducing properties of DMAEMA. • Oxygen-toletant SI-ATRP can be carried out directly on the lab bench. • 20 μL of reaction mixure as suffice to graft PDMAEMA brushes up to 330 nm. • Green procedure for PDMAEMA synthesis with application only 30 ppm Cu II Br 2 /TPMA.

Thermal stabilization of the smectic-Cα* phase by doping with photo-active reactive mesogen

• The incorporation of monomers into liquid crystals changes their physical properties. • Dielectric properties and switching behaviour of liquid crystal molecules depend on the monomer concentration. • A new method for thermal stabilization of the smectic-Ca* phase is presented. • The admixture of monomer causes a relatively small decrease in spontaneous polarization of the liquid crystal system. The effect of a photo-active reactive mesogen 4-(3-acryloyloxypropyloxy)-benzoesure2-methyl-1,4-phenylester on an antiferroelectric liquid crystal was investigated in the context of possible broadening of the temperature range in which the smectic-C α * phase exists in newly synthesized hybrid materials promising for optical applications. In the mixtures of various reactive mesogen concentrations from 1 to 9 wt. %, dielectric spectroscopy and reversal current method were used to determine the temperature range and switching time of the smectic-C α * phase. As a result of reactive mesogen doping, the thermal stabilization of the smectic-C α * phase over 21.5 °C, around a room temperature, i.e. between 26.5 and 48 °C, was confirmed in the modified liquid crystal system.

Luminescent Hybrid Material Based on Boron Organic Phosphor and Silica Aerogel Matrix.

A new luminescent hybrid material based on silica aerogel and a boron-containing coordination compound with 8-hydroxyquinoline was created, and its physicochemical and spectral-luminescent characteristics were studied. A simple scheme for the synthesis of a hybrid luminescent material was developed. Simultaneously with the synthesis of the aerogel, the formation of a boron-containing phosphor was carried out using an isopropanol solution of boric acid and 8-hydroxyquinoline. Using in situ luminescent measurements, the mechanisms of the formation of boron-based luminescent complexes in isopropanol and tetrahydrofuran media were established. Both hydrophilic and hydrophobic silica aerogels were tested as matrices for the hybrid material. The formation of a thin layer of a boron-containing coordination luminescent compound on the highly developed surface of the SiO2 aerogel made it possible to strongly stabilize the aerogel structure and noticeably increase the thermal stability of the synthesized hybrid material.

Cross-linked polymer modified layered double hydroxide nanosheet stabilized CsPbBr3 perovskite quantum dots for white light-emitting diode

Metal halide perovskite quantum dot (PQD) has received high attention from researchers owing to their excellent optical properties and broad application prospects in the past few years. However, the disadvantages of poor stability and low synthesis yield severely limit the further applications. Therefore, we developed an effective strategy to ameliorate the optical performance and environmental stability of PQD. Herein, a reversible addition-fragmentation chain transfer (RAFT) polymerization was applied to graft hydrophobic polymer chains on the surface of LDH nanosheets, and a cross-linked polymer network functionalized LDH (LDH-CP) was obtained through a quaternized reaction. Subsequently, LDH-CP-CsPbBr3 hybrid material was prepared by growing PQD on the surface of LDH-CPs by a simple ligand-assisted co-precipitation (LARP) technique. The synthesized hybrid material exhibited bright green luminescence with a narrow FWHM (~25 nm) and a high solid photoluminescence quantum yield (PLQY) (~51.9%). With the help of dual protection of the unique two-dimensional (2D) LDH nanosheets and the hydrophobic polymer cross-linked network, the nanohybrid displayed excellent water stability, thermal stability, and photostability. In addition, the white lighting-emitting diode (WLED) based on the LDH-CP-CsPbBr3 hybrid material also emerges with great white light emission and excellent device performance, proving that the hybrid material has great development potential in lighting and display applications.

Cover Picture: One‐For‐All Polyolefin Functionalization: Active Ester as Gateway to Combine Insertion Polymerization with ROP, NMP, and RAFT (Angew. Chem. Int. Ed. 33/2022)

A polyolefin active ester exchange (PACE) process was developed for polyolefin-containing block copolymer synthesis and serves as a bridge connecting coordination–insertion polymerization to multiple controlled polymerization methods. As reported by Krzysztof Matyjaszewski, Eva Harth et al. in their Research Article (e202205931), PACE allows for the synthesis of hybrid materials that comprise olefins and ester, styrene, vinylic, acrylate, and acrylamide segments with a broad window for tunability. Nano-objects with higher-order morphologies can be obtained directly via RAFT-mediated PISA.

Halloysite nanotubes loaded with HKUST-1 for CO2 adsorption

Halloysite nanotubes (HNTs) loaded with HKUST-1 (HKUST-1@HNT) were synthesized and characterized. HKUST-1, a metal-organic framework, was encapsulated in HNTs that served as nanocarriers of precursor solutions allowing for the formation of nanosized HKUST-1 crystals. In this study, HKUST-1@HNT composites were prepared using vacuum loading and solvothermal reactions. HNTs were modified by etching the inner layers and amine functionalizing the outer surface. Electron microscopy, X-ray diffraction, and thermogravimetric analysis were used to characterize the concentration of HKUST-1 in HNTs, and Brunauer-Emmett-Teller (BET) methods were employed to investigate N2 and CO2 gas adsorption performances. Results showed that the loading capacity of HKUST-1 crystals increased with the magnitude of etching treatment. The crystalline structure was established in conjunction with the tubular structure of the HNTs. The gas adsorption capacity was enhanced in HKUST-1@HNT and increased with the loading capacity of HKUST-1. Furthermore, when amine-functionalized HNTs were used, the composites exhibited effective CO2 adsorption performance. Results showed that the synthesis of HKUST-1 and HNTs hybrid materials is a promising strategy for the development of novel adsorbing materials.

Facile synthesis of surfactant-modified layered double hydroxide magnetic hybrid composite and its application for bisphenol A adsorption: Statistical optimization of operational variables

A novel hexadecyltributylphosphonium bromide modified magnetic composite based on calcined Ni-Mn layered double hydroxide (HDTBP@Fe3O4@NiMn-CLDH) was synthesized and evaluated for the removal of bisphenol A (BPA) from aquatic media. The structural features of the synthesized hybrid material were determined by Fourier transform infrared (FTIR) spectroscopy, vibrating-sample magnetometer (VSM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray analysis (EDX). Response surface methodology (RSM) was used to investigate the influences of operational variables and optimize the adsorption process. The BPA adsorption process was developed by considering a central composite design (CCD) under RSM with four independent variables (initial BPA concentration (Co), agitation time, initial pH, and adsorbent dosage). From the statistical results, the optimal adsorption conditions for Co, agitation time, initial pH, and adsorbent dosage were determined as 22.53 mg/L, 80.05 min, 7.07, and 1.14 g/L, respectively, and under these conditions, the maximum yield was obtained as 86.85%. The kinetic study results showed the kinetic data was perfectly represented by the pseudo-second-order model. Furthermore, the isotherm data fitted very well to the Langmuir and Dubinin-Radushkevich (D-R) models. Additionally, the results based on the adsorption thermodynamics indicated that the process was spontaneous and endothermic. The findings of the present work indicate that RSM is suitable for optimization of the BPA adsorption process onto HDTBP@Fe3O4@NiMn-CLDH and the synthesized composite has great application potential for the remediation of water polluted with organic contaminants like BPA.

Synthesis of reduced graphene oxide-based hybrid compounds and investigation of their sensing behavior against some nitroaromatic explosives

In the scope of this study, the usability of rGO-based hybrid materials obtained by using different Schiff bases in the detection of some nitroaromatic explosives was investigated. In the first step, synthesis of graphene oxide (GO) containing functional groups (-COOH, –OH etc.) was carried out by the oxidation of graphite via the modified Hummers' method. These functional groups were reduced by the hydrothermal method to obtain the reduced graphene oxide (rGO). In another step, rGO-Cl was obtained from rGO using SOCl2. The purpose of obtaining the rGO-Cl compound is to make the synthesis of hybrid compounds easier from the reaction of rGO-Cl and imine compounds (ER1-ER5). The hybrid materials (FB1-FB5) were successfully synthesized from the reaction of rGO-Cl and imine compounds. FT-IR, UV, FL, SEM, TEM and XRD methods were used to determine the structure of the synthesized materials. The sensing behavior of the synthesized hybrid materials towards some nitroaromatic explosives was investigated. The quenching effect of nitroaromatic explosives on the fluorescence of rGO-based hybrid materials was measured using the fluorimetric titrations. Although GO derivatives are generally sensitive to 2,4-dinitrophenol, it has been determined that the synthesized hybrid compounds are sensitive to different nitroaromatic explosives. The lowest LOD values of the materials were found as (FB1: 8.76 μM; nitrobenzene), (FB2: 16.35 μM; 4-nitrophenol), (FB3: 20.50 μM; picric acid), (FB4: 12.54 μM; 2,4- dinitrophenol) and (FB5: 8.64 μM; 4-nitrophenol), respectively.

Effects of Incorporating Titanium Dioxide with Titanium Carbide on Hybrid Materials Reinforced with Polyaniline: Synthesis, Characterization, Electrochemical and Supercapacitive Properties

We report on the synthesis of titanium dioxide by titanium carbide for the preparation of hybrid material reinforced with polyaniline (PANI@TiO2–TiC) using the in situ polymerization technique. The effectiveness of the samples on the thermal, optical and electrochemical properties was investigated. The XRD, XPS, FTIR, SEM and TEM results confirm the successful synthesis of the PANI, PANI@TiC and PANI@TiO2–TiC samples. Through this, a good connection, an excellent relationship between the structures and the properties of the synthesized hybrid materials were obtained. Moreover, the electrical conductivity and optical bandgap were also tested. Remarkably good electrochemical characteristics were identified by cyclic voltammetry. Moreover, the galvanostatic charge–discharge (GCD) of the supercapacitor was remarkably high. Cyclic stability showed good retention after 1500 cycles at 1.5 A·g−1.

Synthesis of 3D Hollow Layered Double Hydroxide-Molybdenum Disulfide Hybrid Materials and Their Application in Flame Retardant Thermoplastic Polyurethane.

The development of high-performance thermoplastic polyurethane (TPU) with high flame retardancy and low toxicity has always been the focus of its research. In this paper, the novel 3D hollow layered double hydroxide/molybdenum disulfide (LDH/MoS2) hybrid materials were synthesized by hydrothermal method using the MIL-88A as in situ sacrificial template and MoS2 as synergistic flame retardant. Among all TPU composites, the peak heat release rate, total heat release rate, and total smoke release rate of TPU/NiFeTb-LDH/MoS2 were reduced by 50.9%, 18.2%, and 35.8% compared with pure TPU, respectively. The results of the thermogravimetric infrared analysis demonstrated that the contents of combustible volatiles (hydrocarbons) and toxic volatiles (CO and HCN) emitted from TPU/LDH/MoS2 were significantly reduced, indicating that LDH/MoS2 hybrid materials can dramatically enhance the fire safety of TPU composites. Combined with the analysis of carbon residues and thermal stability of TPU composites, the enhanced flame retardancy and smoke suppression performances are primarily attributed to the catalytic carbonization of LDH and the physical barrier effect of MoS2.

Controlled synthesis of NixP-Co2P hybrid materials as robust overall water splitting electrocatalyst

Environmentally friendly overall water splitting electrocatalysts can be exploited through construction of efficient heterogeneous interfaces. Flexible preparation of lattice-matching Ni 2 P–Co 2 P heterointerfaces is exploited to promote electrochemical activity for overall water splitting because of the outstanding electrical conductivity of Co 2 P and admirable durability of Ni 2 P. Density functional theory calculations demonstrate that construction of lattice-matching Ni 2 P–Co 2 P heterogeneous interfaces and the regulation of density of states between the heterogeneous interfaces can effectively optimize the water adsorption energy. Hence, a series of Ni x P-Co 2 P hybrid materials were in site grown on nickel foam through hydrothermal synthesis and phosphorization approach. What is noteworthy is that the Ni 2 P–Co 2 P-0.5//Ni 2 P–Co 2 P-1 electrode couple presents superior electrochemical performance with only 1.60 V cell voltage to obtain a current density of 10 mA cm −2 under alkaline condition. In addition, the Ni 2 P–Co 2 P-0.5//Ni 2 P–Co 2 P-1 electrode couple display superior durability over 15 h at large current densities of 30 mA cm −2 during water electrolysis process. The construction of heterostructures is conducive to the regulation of state density and the maximization of synergistic catalytic effect. The work provides a novel idea for the exploitation of highly efficient and robust water electrolysis catalysts and this work might be a new breakthrough for the construction of lattice-matching hybrid structures. • A series of Ni x P-Co 2 P materials were prepared through hydrothermal and phosphorization approach. • The electrode presents superior electrochemical performance with 1.60 V to drive 10 mA cm −2 . • These experimental results are consistent with the DFT calculations predictions.

Out with Acetonitrile: Water-Assisted Accelerated-Aging Synthesis of CuI-Pyrazine Hybrid Materials

Out with Acetonitrile: Water-Assisted Accelerated-Aging Synthesis of CuI-Pyrazine Hybrid Materials

Organic-Inorganic Hybrid Material Synthesis by on Line Coupling Twin Screw Extruder with a Microwave Oven

Abstract A new process for elaborating continuously organic-inorganic hybrid materials by reactive extrusion is presented. This synthesis consists in formulating a copolymer of ethylene and vinyl acetate (EVA)/tetrapropoxysilane (TPOS or Si(OC3H7)4)/catalyst blend by a corotating twin screw extruder followed by two successive reaction steps: on line microwave crosslinking reaction and hydrolysis-condensation reactions leading to a silica network cografted onto the organic matrix. Extrusion feed rate (Q), temperature, microwave oven power (P), and microwave curing time (tmw) were studied. Crosslinking density was evaluated before and after hydrolysis-condensation reactions and compared with the previous results obtained in static conditions. These materials tailored by an on line process present a permanent elasticity at high temperature (up to 200 °C) and a certain optical transparency. This new approach offers the possibility to synthesize massive samples based on organic-inorganic hybrid material.

Hydrothermal method of synthesis, characterization and TFN FO membrane performances of silverton-type anion with 1, 3, 5-triazine hybrid material

Silverton-type anion (denoted as PMA) is broadly used in the synthesis of hybrid material because of it stability and ability of sharing oxygen atoms in the wide range of reactions. The hybrid material has been synthesized hydrothermally using silverton-type anion 1, 3, 5-triazine molecules. The synthesized hybrid material has been successfully isolated and characterized using FT-IR/ATR, XRD, SEM, EDS, NMR, TGA, UV, and contact angle measurements. Scanning electron microscopy technique reveals that PMA/1, 3, 5-triazine powder are uniformly arranged and hybrid material structure is not heterogeneous. The contact angle measurement results show that membrane absorption is hydrophilic nature. The hybrid material sustainably enhanced the performances of the membranes. The postulates helps to understand the water molecules could puncture through the pores present in the selective polyamide (PA) active layer, hydrophilic nanoparticles and those in the structure of hybrid material. It results in an increase in permeate flux and surface hydrophilicity to enhance the FO membrane performances. In this paper, the synthesis and characterization and the performances of the membrane has been discussed in detail.

Fluorescent and Easy-Make Hybrid Sensor Based-on Silica Gel & BODIPY for the Detection of Cu (II) in Aqueous Medium: Fully Characterized, Effective and Visual Data

Cu (II) ion has potential roles in a lot of living metabolisms that its detection and removal are extremely important for flagship branches of science. In this paper, fluorescent and easy-make silica gel immobilized BODIPY were successfully prepared via a simple synthesis procedure for the rapid recognition of Cu (II) ions. The optimal emission and excitation wavelength of the synthesized hybrid material, Si-APTMS-BODIPY, was 543 nm and 460 nm, respectively. The new solid support surface fully characterized by several techniques has notable results and visual data for the detection of Cu (II) ion. The maximum fluorescent intensity of Si-APTMS-BODIPY was clearly quenched following the adding of Cu (II) ion owing to static and dynamic quenching mechanisms. Maybe, more importantly, there was a notable linear correlation between several concentrations of Cu (II) solution and the fluorescence quenching processes with a limit of detection (LOD) of <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$1.7 ~\mu \text{M}$ </tex-math></inline-formula> . Based on these, a fluorescent hybrid material having high selectivity and sensitivity was made up, and it provides a precious proposal for the recognition of Cu (II) ions.

Light-Induced Color Switching of Single Metal–Organic Framework Nanocrystals

Photoinduced modulation of the optical parameters of nanomaterials underlies the operating principles of all-optical nanodevices. Here, we demonstrate the laser-induced 10% modulation of the refractive index and 16-fold modulation of the extinction coefficient of the dynamic metal-organic framework (HKUST-1) nanocrystals within the whole visible range. Using the laser-induced water sorption/desorption process inside HKUST-1, we have achieved size-dependent reversible tuning of brightness and color of its nanocrystals over the different spatial directions and color palette. The numerical analysis also confirmed the detected optical tuning through the evolution of optical spectra and directivity of the scattered light. The results of the work demonstrate the promising nature of the dynamic metal-organic frameworks for nonlinear optics and expand the library of chemically synthesized hybrid materials with light-controlled optical properties.

Synthesis of graphene oxide-cobalt oxide hybrid materials for gas sensors application

The development of acetone gas sensors has been tremendous within these past few years due to their ability to prevent casualty events such as damage to vision and central nervous system after exposure to high concentration of acetone gas. Highly sensitive acetone gas sensors are used for air quality control, projection of environmental patterns, health monitoring programs, and many more. In this study, hybrid materials containing graphene oxide and cobalt oxide were synthesized via hydrothermal method for gas sensors. Graphene holds the potential of replacing silicon due to its unique distinguishable features especially in lowering bandgaps for metal oxides. Graphene oxide (GO) was synthesized using improved Hummers' method. Then, graphene oxide-cobalt oxide (GO-Co3O4) was prepared using the hydrothermal method which results in the formation of porous structure materials that might hold the key to lowering the operating temperature of pristine GO and Co3O4 for low concentration gas sensing purposes. This leads to a highly responsive gas sensing system which is said to be beneficial, especially in developing affordable and sophisticated non-invasive early detection of diabetes systems in the medical field. This nanostructure is expected to detect acetone concentrations up to 20 ppm at a temperature close to the room environment.

A dual initiator approach for oxygen tolerant RAFT polymerization.

Reversible-deactivation radical polymerizations are privileged approaches for the synthesis of functional and hybrid materials. A bottleneck for conducting these processes is the need to maintain oxygen free conditions. Herein we report a broadly applicable approach to "polymerize through" oxygen using the synergistic combination of two radical initiators having different rates of homolysis. The in situ monitoring of the concentrations of oxygen and monomer simultaneously provided insight into the function of the two initiators and enabled the identification of conditions to effectively remove dissolved oxygen and control polymerization under open-to-air conditions. By understanding how the surface area to volume ratio of reaction vessels influence open-to-air polymerizations, well-defined polymers were produced using acrylate, styrenic, and methacrylate monomers, which each represent an expansion of scope for the "polymerizing through" oxygen approach. Demonstration of this method in tubular reactors using continuous flow chemistry provided a more complete structure-reactivity understanding of how reaction headspace influences PTO RAFT polymerizations.

Development of Efficient One-Pot Methods for the Synthesis of Luminescent Dyes and Sol-Gel Hybrid Materials.

This paper presents a comparison of the simultaneous preparation of di-O-alkylated and ether–ester derivatives of fluorescein using different methods (conventional or microwave heating). Shortening of the reaction time and increased efficiency were observed when using a microwave reactor. Moreover, described here for the first time is the application of a fast, simple, and eco-friendly ball-assisted method to exclusively obtain ether–ester derivatives. We also demonstrate that fluorescein can be effectively functionalized by O-alkylation carried out under microwave or ball-milling conditions, saving time and energy and affording the desired products with good yields and minimal byproduct formation. All the synthesized products as well as pH-dependent (prototropic) forms trapped in the SiO2 matrix were examined using UV–Vis and fluorescence spectroscopy.