Organic-inorganic Hybrid Composites Research Articles

Layered assembly of PEGylated graphene oxide and Mg–Al layered double hydroxide nanosheets with superior adsorption capacity and selective isolation of hemoglobin

This study developed a novel organic-inorganic hybrid composite, shortly as GO-PEG-LDHs, by self-assembly of exfoliated Mg–Al layer double hydroxide (LDHs) on the polyethylene glycol (PEG) grafted graphene oxide (GO) to achieve the selective adsorption of hemoglobin (Hb). The prepared GO-PEG-LDHs has a hierarchical structure with a homogeneous loading of exfoliated LDHs nano-sheets on its surface. The adsorption test reveals that GO-PEG-LDHs exhibits an adsorption efficiency of 95.03% for Hb and 3.45% for bovine serum albumin (BSA). The adsorption of Hb follows the Langmuir model, with an ultrahigh adsorption capacity of 55248.6 mg/g, which is higher than any previously reported materials. Meanwhile, the adsorbed Hb can be efficiently recovered through elution with a 50 mM Tris-HCl buffer, with an elution efficiency of 80.77%. Circular dichroism (CD) spectra indicate no conformational change for Hb during the process of adsorption/desorption. Furthermore, the composite demonstrates the ability to selectively isolate Hb in the presence of interfering protein BSA, indicating its potential for practical applications.

Construction of heteropolyacid-anchored magnetic g-C3N4/Fe3O4@polyindole hybrids for efficient photocatalytic destruction of methyl orange and bacteria

Given the treatment of wastewater contaminated with organic dyes and bacteria, it is essential to fabricate high-performance, eco-friendly, and cost-effective photocatalytic materials. Herein, a new separatable and efficient organic–inorganic hybrid composite of tungstophosphoric acid(TPA) anchored by conducting polyindole (PID) onto magnetic graphitic carbon nitride (g-C3N4) was synthesized and used for photocatalytic degradation of methyl orange (MO) and gram-negative bacteria (P. aeruginosa) in the presence of visible LED illumination. The obtained g-C3N4/Fe3O4@PID-TPA photocatalyst was characterized by XRD, VSM, FESEM, EDX, TEM, BET surface area, DRS, PL, and FTIR methods. The g-C3N4/Fe3O4@PID-TPA catalyst (0.1 g/l catalyst dose) revealed high destruction activity (97.5%) for MO within 70 min. Due to the presence of controllable electronic structured g-C3N4, conductive PID polymer, and highly redox property of TPA heteropolyacid, boosted degradation activity was achieved by the g-C3N4/Fe3O4@PID-TPA heterostructure. Besides, the magnetic g-C3N4/Fe3O4@PID-TPA catalysts could be recycled five times without reduction in their photocatalytic performances. The g-C3N4/Fe3O4@PID-TPA catalyst demonstrates extraordinary antibacterial activity against P. aeruginosa (94.49%) at low g-C3N4/Fe3O4@PID-TPA dose. Besides, the antibacterial mechanism showed that the synergistic performance between g-C3N4/Fe3O4@PID and TPA harms the cell membranes, improves the levels of oxidative stress, and ultimately kills of P. aeruginosa. Also, the cytotoxic effect of g-C3N4/Fe3O4@PID-TPA catalyst was assessed in vitro by a MTT assay (achieving 25% to 29 % reduction in the colorectal carcinoma HCT116 cell viability). This work introduces a new outlook on developing organic–inorganic composite as photocatalysts based on heteropolyacids that serve multiple functions, particularly for environmental applications.

Precisely modulate interfacial Bi-O bridge bond in Co-TCPP/Bi3O4Br to trigger long-lasting charge separation for boosting CO2 photoreduction

Insufficient charge separation and feeble CO2 activation limit the CO2 photoreduction efficiency. It is highly desirable to consciously construct organic–inorganic hybrid composites to simultaneously accelerate charge separation and provide favorable active sites. Herein, a defect-induced interfacial Bi-O bridge bond is constructed by grafting terminal O of cobalt porphyrin (Co-TCPP) with Bi3O4Br. Systematic investigations reveal that the Bi-O bridge bond as the charge migration bridge accelerates the extraction and transfer of electron from the external [Bi3O4] layers to Co-TCPP, and the millisecond separation lifetime of electrons on Co-TCPP can be achieved. Co atoms as the active sites optimized the CO2 adsorption and activation, thus promoting the formation of COOH*. As a result, the CO2 photoreduction rate of 0.5% Co-TCPP/Bi3O4Br reaches 71.3 μmol g-1h-1 in pure water, 2.53-fold of that on the pristine Bi3O4Br. This work provides atomistic insights and strategies for the construction of new organic–inorganic hybrid materials for artificial photosynthesis and CO2 photoreduction.

Metal-organic frameworks/cellulose hybrids with their modern technological implementation towards water treatment

Metal-organic frameworks (MOFs) are amongst the most attractive porous polymeric networks with appealing properties. However, their inherent fragility, powder nature, low processibility, and handling present some exceptional challenges for high-tech commercial applications. Currently, economic and environmental concerns drive the development of some bioinspired polymeric matrices containing MOFs. As an artifact, the availability of previously unattainable properties is negotiated by conjugating cellulosic materials with crystalline MOFs. Thus, multi-dimensional organic-inorganic hybrid composites are formed with high electrical, optical, mechanical, and thermal features. These MOF/cellulose hybrids, known as CelloMOFs (cellulose MOFs), have remarkable mechanical properties with tunable porosities, specific surface area and accessible active sites, making them ideal for real-world troubleshooting applications such as wastewater treatment, chemical sensing, energy storage, and so on. In this review, current state-of-the-art strategic synthesis routes for fabrication of MOF/cellulose composites with a specific focus on CelloMOFs as a potential tool for mitigation of the targeted emerging water contaminants have been done under the same umbrella, which has previously been less explored. Streamlining discussions on general properties such as raw material selection, structural analysis of cellulose, availability of surface functional groups, cellulose-metal node interactions, cellulose charging, and so on have been emphasized, as has integration with robust MOFs. A better understanding of these fundamental properties is critical because they will have a significant impact on the performance of MOF/cellulose composites in a variety of applications. Furthermore, at the end of this review, the challenges and perspectives of using CelloMOFs have been discussed in a concise manner in order to improve their practical utility rather than just concept mapping.

In Vitro Study for Yttrium addition on titanium - 15 Molybdenum after Immersion in Simulated Body Fluid

Multiple attempts are made to develop bioactive alloy for the construction of the implant to enhance osseointegration and support implant functions. The titanium – 15 Molybdenum alloy with and without the addition of Yttrium makes an organic-inorganic hybrid composite that has the ability to make a network with or without covalent bonds between components. In this study the immersion of Titanium – 15 Molybdenum disc and titanium – 15 Molybdenum- 1.5 Yttrium in simulated body fluid.The unique biomaterial multi-component Ti-Mo-1.5Y alloys were created as a way to improve the bioactivity characteristics and lessen the toxicity of biomaterials for implants in order to create new biomaterials for implant applications. The purpose of this study is to look at how adding yttrium (Y) changes the alloy's bioactivity. Through the use of powder metallurgy, Ti-Mo-1.5Y alloys are created. Atmospheric pressure high-purity argon gas is used to sinter the metals. samples were immersed in SBF in closed containers and placed in incubators at a temperature of 370 C for 30 days. Analysis of the surface includes thickness measurement, X-ray diffraction (XRD), and an optical microscope. The results of showed an increase in the thickness of (HA) with the addition of yttrium after immersion in SBF compared with thickness before the addition of yttrium. The results of XRD showed the appearance of new peaks of HA, and showed there are additional accumulates of HA granules when adding yttrium content after immersion in SBF.

Bioactivity of a gelatin/organic-inorganic hybrid biomaterial fibre enhanced by metronidazole release

• Loading an acidic drug metronidazole triggered the bioactivity of the gelatin/OI-BM fibers. • The acidic drug promoted the exchange of Ca 2+ in the fibers with H + in the SBF. • Addition of OI-BM improved the mechanical property of the gelatin fiber mats. An organic-inorganic hybrid composite (OI-BM) was combined with gelatin fibres to improve the bioactivity and mechanical properties. An acidic drug metronidazole was loaded in the gelatin/OI-BM fibres to increase the bioactivity. The gelatin/OI-BM/metronidazole fibres induced the formation of hydroxyapatite in 1 h. The tensile strength and Young’s modulus of the gelatin/OI-BM/metronidazole fibres were 2.0 MPa and 25 MPa, while those of the gelatin fibres were 1.0 MPa and 17 MPa. This work revealed that acidic drugs could improve the bioactivity of hybrid biomaterials significantly. This finding has great significance for drug-loaded organic-inorganic hybrid biomaterials with poor bioactivity.

Two‐dimensional Zn(II) coordination polymer and hydrogen bond‐mediated two‐dimensional Cu(II) network based on trans‐2‐aminocyclopentanecarboxylate

AbstractCoordination polymers from α‐amino acids are promising organic–inorganic hybrid composites with chirality and biocompatibility. However, coordination polymers from unnatural amino acids are rarely studied. Here, we report the transition metal complexes from an unnatural β‐amino acid, (1S,2S)‐2‐aminocyclopentanecarboxylic acid, affording two possible coordination modes from the conformationally rigid cyclopentane ring. X‐ray crystallographic analysis revealed that Zn(II) formed a two‐dimensional (2D) coordination polymer via N,O‐bridging mode. In contrast, Cu(II) formed a discrete complex via N,O‐chelating mode and then constructed a 2D supramolecular network stabilized by hydrogen bonding between water and the ligands.

The Labile Nature of Air Stable Ni(II)/Ni(0)-phosphine/Olefin Catalysts/Intermediates: EDA-NOCV Analysis.

Metal ions-based inorganic-organic hybrid composites are often reported acting as good to excellent catalysts with various substrate scopes under milder reaction conditions. The active catalyst of a catalytic cycle is sometimes proposed to be a short-lived reactive intermediate species. A three coordinate (L-Me)Ni(II) intermediate species [L-Me=O2 N donor dianionic ligand] can bind with short-lived carbene-ester ligands to produce four coordinate Ni(II) species which can act as carbene transfer intermediate under suitable reaction conditions for C-H functionalization and/or cyclopropanation reactions. The dissociation of phosphine (PPh3 ) from the Ni(II) centre of (L-Me)Ni(II)(PPh3 ) (1 a) and binding of short lived carbene esters (:CR1 -CO2 R2 ; R1 =H, Ph; R2 =aliphatic group; 2-4 and other carbenes; 5-10) to Ni(II) rationalize the phenomenon in solution. Air stable Ni(0)-olefin complexes/intermediates (12-18) have recently been shown to mediate a variety of organic transformations. This analysis will further help organic/organometallic chemists to rationalize the design and synthesis of future catalysts for organic transformation. EDA-NOCV calculations have been performed to shed light on the stability and bonding of those species. Additionally, our analysis provides a proper reason why the analogous (L-Me)Pd-PPh3 complex (1 b) does not dissociate in solution and hence, a similar catalytic product has not been isolated from identical reaction conditions. The stability and the labile nature of Ni(II/0) complexes have been investigated by state-of-the-art EDA-NOCV analyses.

Combining Polymer Zwitterions and Zinc Oxide for High-Performance Inverted Organic Solar Cells.

Zinc oxide (ZnO) is a widely used cathode interlayer material in inverted organic solar cells (OSCs). However, there are lots of surfaces or bulk film defects in ZnO layers, which degrade solar cell performance. Here, the typical phosphorylcholine- and sulfobetaine-based polymer zwitterions (PMPC and PDMAPS) are synthesized via reversible addition-fragmentation chain-transfer (RAFT) polymerization to modify ZnO interlayers for inverted OSCs. The polymer zwitterions can efficiently passivate the defects in ZnO films and thus increase the conductivity of the ZnO interlayers. Both PMPC and PDMAPS modified ZnO interlayers show some general advantages in improving the performance of fullerene-based and non-fullerene-based OSCs. The highest efficiency of 16.69% is achieved by using PMPC modified ZnO interlayers in PM6:Y6 based solar cell devices, which is among the best performance in inverted OSCs. Such an improvement in device performance is attributed to the work function reduction of the polymer zwitterions modified ZnO films, which provides an efficient cathode platform to extract and transport electrons from the active layers, to the benefit of suppressing interfacial charge recombination. As a result, the organic-inorganic hybrid composites (ZnO: polymer zwitterions) show efficient interfacial modification to align energy levels at the device interface, which have promising application prospects in organic electronics.

Functionalized organic–inorganic hybrid composites used as colorimetric chemosensors for hydrogen sulfide detection

AbstractDetection of trace‐level hydrogen sulfide (H2S) gas is of great importance both in industrial production and disease diagnosis. In this article, two simple but smart colorimetric chemosensors for H2S detection were designed based upon the principle of colorimetric reaction. Ag NPs, as the main detection agent was loaded onto the primary carrier, silica sulfonic acid. Thus, a silver‐modified silica sulfonic acid (Ag‐SSA) was prepared successfully. Then the Ag‐SSA was integrated with two kinds of secondary substrate materials. One is the cotton‐woven textile and the other one is polyvinyl alcohol (PVA) nanofibrous membrane. Finally, two functionalized organic–inorganic hybrid composite systems for H2S detection were formed. Both of them were able to exhibit a rapid visual color change in response to H2S. Ag‐SSA/cotton textile was tested in the aqueous state and the limit of detection (LOD) of H2S solution was around 10−6 mol/L. For the Ag‐SSA/PVA nanofibers membrane detected in the atmospheric condition, the LOD of H2S gas reached 6.5 ppm. This research has been successfully demonstrated for the application in sensitive and selective detection of hydrogen sulfide in aqueous solution and gaseous state.

Preparation and characterization of a high heat resistant phthalonitrile resin modified by polyborosilazane ceramic precursor

AbstractPhthalonitrile resins were an important kind of matrix with high thermal stability. Novel organic–inorganic hybrid composites were prepared by employing 4,4′‐(1,3‐phenylenebis[oxy]) diphthalonitrile (DPN) modified with polyborosilazane ceramic precursor (PBSN) in this work to explore the methods for synthesis of phthalonitrile resin with good processability as well as high heat‐resistance. The maximal glass transition temperature (Tg) and 10% weight loss temperatures were about 615.0 and 608.1°C (N2), respectively. The detailed thermal oxygen decomposition processes and mechanisms were studied and Avrami‐Erofeev models were used for decomposition kinetic analysis of the hybrid matrix. According to the result of the scanning electron microscope, the PBSN was completely integrated into the phthalonitrile resin, and the heat‐resistant structure (SiO, BN and BO) could improve the heat resistance of DPN. The hybrid matrix could be used for heat‐resistant materials.

A novel composite of monosodiumtitanate-amidoximatedpolyacrylonitrilefor the sequestration of uranium from contaminated water: An experimental and simulation study

A new inorganic–organic hybrid composite, comprising Monosodiumtitanate(MST) and AmidoximatedPolyacrylonitrile (MPA), has been developed in bead form for the separation of uranium from contaminated water.Inline with the design objectives, asynergistic effect on uranium uptake by MST and Amidoximewas obtained.The measured U uptake capacity is 280 mg/g, the highest ever reported U uptake by any composite in column useable form. U uptake by the composite follows the Langmuir isotherm mechanism. The uptake performance remains unaltered even in the presence of sulphate, nitrate, chloride ion, and carbonate ions. The column performance of the composite was demonstrated by removing U over 12,000-bed volumes of waste effluent from 1000 ppb to down below < 60 ppb level. A mathematicalmodel is developed and used to predict process performance under various operating conditions mimicking scale-up operations with an eye in generating potable water from groundwater.

Fabricating biopolymer-inorganic hybrid microspheres for enzyme immobilization: Connect membrane emulsification with biomimetic mineralization

The organic-inorganic hybrid composites displayed great potential for biotechnological and biomedical application. In this research, a gelatin/alginate/silica hybrid microsphere was developed by a synergy of membrane emulsification process and biomimetic mineralization method. The gelatin was mixed and complexed with alginate solutions (water phase). The water phase was extruded through a Shirasu Porous Glass (SPG) membrane, and then was crosslinked, which formed gelatin/alginate microspheres. The biomimetic mineralization was occurred in situ by immersing gelatin/alginate complex in a Na2SiO3 solution, while silica was formed around the organic microspheres, resulting in the final gelatin/alginate/silica hybrid microspheres. These microspheres were characterized by SEM, TEM, EDS, TGA/DTA, and DSC. The hybrid microcapsules present a more than 40% mass fraction of the inorganic component, and displayed superior swelling resistance to biopolymer complex microspheres. Glycerol dehydrogenase (GlyDH) was immobilized in the obtained novel gelatin/alginate-silica hybrid microspheres as the model enzyme. Due to the protective effect of carriers, the pH tolerance stability, storage and recycling stability of the immobilized GlyDH were all improved in comparison with free GlyDH.

Self-energized organic-inorganic hybrid composite for surface enhanced Raman spectroscopy

In this study, we integrate plasmonic metal nanomaterials with a piezoelectric polyvinylidene fluoride (PVDF) polymer and lithium niobate (LiNbO3) based composite to form an all-solid-state flexible self-energized sensor. We demonstrate that following the application of a load, the film enhances the surface-enhanced Raman spectroscopy (SERS) signal of an analyte molecule up to 14 times. The piezoelectric β-phase of PVDF in the film is optimized through the introduction of multi-walled carbon nanotubes and post-fabrication UV irradiation annealing. Additionally, the SERS signal enhancement can be further increased by the application of in situ UV light irradiation of the sample, resulting in the generation of photoexcited electrons from LiNbO3 microparticles introduced into the composite. Both the application of a mechanical displacement and the UV light-induced charge generation result in an improved charge transfer between the film and an analyte molecule. The piezoelectric PVDF/LiNbO3 film has been shown to be a suitable SERS platform for the detection of important biological molecules, demonstrating the potential of the substrate for fast on-site detection applications.

In Vitro Study for Nano Hydroxyl Apatite and Chitosan Coated Surface after Immersion in Simulated Body Fluid

Multiple attempts are made to develop coating layers on the implant surface to enhance ossiointegration andsupport implant functions. The mixture of chitosan with HA prepared by sol–gel process to make organic–inorganic hybrid composite that has the ability to make network with or without covalent bonds betweencomponents.In this study the immersion of titanium disc coated via sol – gel technique by nano-HA and chitosan insimulated body fluid.Materials and Method: Composite of nano hydroxy apatite/chitosan was prepared by sol – gel techniqueafter preparation of two solutions of calcium nitride and phosphorous pentaoxide, then the magnetic stirrerwas used for mixing of these solutions, then 3 mg of chitosan were added to the mixture and the mixturewas stirrer for 15 hours to complete the mixing. Dip coated of titanium samples, then the samples wereremoved and dried by hot air oven, finally samples were sintered at 4000C for one hour. Coated sampleswere immersed in SBF in closed containers and placed in incubators at temperature 370C for 30 days.Analysis of the surface include thickness measurement, X-ray diffraction (XRD), scanning electronmicroscopy (SEM) and energy-dispersive x-ray spectroscopy (EDX).The results of thickness measurement showed increase in thickness of the coated layer after immersion inSBF compared with thickness before immersion. The results of XRD showed the appearance of new peaksof HA, SEM showed there are additional accumulation of HA granules on the original coating layer. EDXtest showed decreased in the concentration of the main ions component (Ca, Na, P, O and K) when comparedwith coated samples before immersion in SBF.

Correction to: Transparent conductive organic-inorganic hybrid composites based on Ag nanowires

Correction to: Transparent conductive organic-inorganic hybrid composites based on Ag nanowires

Preparation of novel cobalt ferrite coated-porous carbon composite by simple chemical co-precipitation method and their mechanistic performance

The consumption of agricultural wastes as environmentally friendly and endorses green chemistry. The potential use of agricultural waste sources with additional treatment for the removal of anionic pollutants from water was examined. Herein, the removal performance of a stable inorganic-organic hybrid composite of porous carbon (Porous carbon derived from papaya seeds) was fabricated through one-pot synthesis and employed for the removal of phosphate and nitrate from water. The as-prepared hybrid composite properties were examined using FTIR, XRD, SEM, VSM, TGA-DSC, BET and EDAX with mapping analysis. The various parameters for the removal of phosphate and nitrate from water using cobalt ferrite coated-porous carbon composite (CoFe2O4@PC) were optimized. The maximum adsorption capacity is 92.34 for phosphate and 78.98 mg/g for nitrate at 303 K. Freundlich adsorption isotherm model is found to be superior fir and heterogeneous surface interaction of phosphate and nitrate ions onto the CoFe2O4@PC composite. The pseudo-second-order and intra-particle diffusion kinetic model describes the removal mechanism and rate-determining steps. Thermodynamic studies recommend that the adsorption process to be endothermic and spontaneous nature. The prepared CoFe2O4@PC composite displayed good removal capacity and was effectively utilized for the removal of phosphate and nitrate ions in real water sample. In addition, this study provides useful insights into the removal of phosphate and nitrate by magnetic separable CoFe2O4@PC composite in water/wastewater.

Microbial Fuel Cell for Electrical Power Generation from Waste Water

In the last decades, the microbial fuel cell (MFC) has increased great opportunity as an alternative energy source through electrochemical process for producing bio-energy. MFC has been involved in anode and cathode for electric energy generation from organic ingredients such as bacteria in waste water treatment. In this review, we discussed the different types of MFC (anode and cathode) materials with various integrations. In addition, it includes the gainful, biocompatible and exceedingly constant electrode materials with enhanced microbial fuel cell performance. Following this review, expansion in membrane materials such as hydrocarbon polymer, perfluorinated polymer, organic-organic hybrid polymer, ceramics, organic-inorganic hybrid composite, and biopolymer membranes are clarified in detail. In this paper, also highlighted the application of MFC technology and the methods used in the MFC in electricity production.

Preparation and characterization of CdSe/POMA photoactive composites electrochemically grown on HOPG surfaces

Visible light driven photoactive inorganic-organic hybrid composites were prepared containing cadmium selenide (CdSe) and poly(o-methoxyaniline) nanofilms. The films were fabricated in three different configurations: i. Composite of CdSe deposited onto HOPG with o-methoxyaniline (POMA) deposited on top (HOPG/CdSe/POMA), ii. Composite of POMA deposited onto the HOPG substrate with CdSe deposited on top (HOPG/POMA/CdSe), iii. Composite made through the simultaneous deposition of CdSe and POMA (HOPG/(CdSe/POMA)) on HOPG substrate. The photoactivity and physico-chemical properties of the fabricated composites were examined through electrochemical, XPS, Raman, in situ AFM and STS techniques. The changes in morphology, optical, spectroscopic, photoactive properties and elemental composition of the hybrids were monitored depending on the composite design, namely: number of the deposition cycles or order of component deposition. The HOPG/CdSe/POMA was identified as the most photoactive and stable composite and hence this material was further examined for its properties. In all cases of the fabricated hybrids, n-type and p-type photocurrents were observed. As the thickness of POMA increases, the p-type photocurrent decreases, while the n-type photocurrent increases. It is proposed that the p-type photocurrent observed is due to the presence of elemental selenium. The n-type photocurrent is attributed to CdSe layer. The amount of the polymer was optimized in order to maximize the photoactivity of the fabricated composite. The optimal POMA thickness, prepared in 5 deposition cycles, was determined by the AFM scratching technique to be 150 nm prepared. The highest photocurrent (224 μAcm−2) and highest photopotential (230 mV) were observed for the composite deposited on HOPG substrate with 20 deposition cycles of CdSe and 5 deposition cycles of POMA. The bandgap of the HOPG/CdSe/POMA composite was determined by the STS technique to be 2.2 eV.

Synthesis of mesoporous nickel–titanium-trimesic acid inorganic–organic hybrid composite in ionic liquid microemulsions for adsorption of rhodamine B from aqueous solution

For the first time, mesoporous nickel–titanium-trimesic acid (NTT) inorganic–organic hybrid composite was synthesized in water-in-[Bmim]PF6 ionic liquid microemulsions using the trimesic acid (BTC) as the linker. The synthesized NTT was characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) analysis, powder X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR) methods, etc. Then, the isotherm and kinetic of adsorption were studied. The experimental data were well fitted with isotherm models of Langmuir and Freundlich (IMLF) at 298 K and 308 K and better fitted with the isotherm model of Langmuir (IML) at 318 K with the adsorption capacity of 662.212 μmol/g (maximum). The adsorption of rhodamine B (RhB) on NTT can be described by pseudo-second-order (PSO) kinetic model. This proposed method for synthesis of mesoporous NTT inorganic–organic hybrid composite is facile, environment-friendly and operated at room temperature, which could be applied to synthesis of other mesoporous inorganic–organic hybrid composites.