Organic-inorganic Hybrid Networks Research Articles

Inorganic–organic polymer networks derived from a cyclic siloxane tetrafunctional glycidyl ether resin

AbstractA tetrafunctional glycidyl ether cyclic siloxane epoxy resin (TGTS) has been synthesized, characterized and cured with four aromatic amine hardeners: 1,3‐phenylenediamine (PDA), diethyltoluenediamine (DETDA), 4,4‐diaminodiphenylmethane (DDM) and 1,3‐bis(4‐aminophenoxy)benzene (APB). Each of the cured networks produces transparent and homogeneous networks, although when TGTS is cured with DETDA, reduced compatibility led to lower epoxide consumption, a more heterogenous microstructure and deleterious effects upon properties. Reduced miscibility of DETDA significantly impacts the chemical structure and microstructure of the network, resulting in significant reductions in thermal and mechanical properties but higher UV‐A transmission. The PDA‐, APB‐ and DDM‐cured networks conversely were more miscible and display properties typical of organic–inorganic hybrid networks, such as good mechanical properties at ambient and sub‐ambient temperatures, comparatively high glass transition temperatures, improved resistance to oxidation and lower UV‐A transmission. © 2024 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Biomimetic metal-phenolic network with cyclolactam hydrogel coating on PPENK implant facilitate bone repair

Bone defects are often accompanied by infection, which causes great physical pain to patients. Metal-phenolic networks (MPNs) are a newly organic–inorganic hybrid networks system, which has become a multifunctional surface modifier based on the universal adhesion properties of phenolic molecules. Hence, we fabricate a MPN hydrogel coating based on cyclolactam network by spin-coating a mixture of gelatin, iron ions, and polyphenol monomer containing phthalazinone structure (THPZB) on the surface of poly(aryl ether nitrile ketone) (PPENK) (G/THPZB/Fe/PPENK). The method can easily obtain a high strength and versatile surface hydrogel coating based on the combination of the entangled structure on phthalazinone and the characteristic functions of MPNs. The residual polyphenol on the surface not only confer good adhesion ability, but also can cooperate with lactam ring to confer outstanding antibacterial ability to the PPENK implant. Importantly, the antibacterial mechanism of this modified PPENK implant might be consistent with that of penicillin. Besides, it has excellent ability to promote angiogenesis and healing in vitro. Notably, significant effects on biomineralization and osteogenesis in vitro and in vivo are observed. We hypothesis that cyclolactam-based MPN multifunctional hydrogel coating can provide great application prospects for PPENK bone implant materials in the field of bone defect repair.

Dynamic organic–inorganic hybrid network for self-healing and self-powered fire hazard sensor

With the rapid development of the 5G era and smart homes, self-healing and self-powered smart fire sensors are considered a promising solution for emerging applications, but fabricating such sensors remains a great challenge. In this study, a highly efficient dynamic crosslinking strategy was developed to construct a self-healing organic–inorganic hybrid material (OIH). More precisely, self-healing OIHs were fabricated through a simple Schiff reaction between chitosan and a Ti3O5 metal–insulator transitional material. The incorporation of multi-crosslinked networks (CN, hydrogen bonds, electrostatic interactions) provided stable charge migration paths for the free movement of protons and hot electrons. Accordingly, the OIH exhibited a substantially enhanced fire-response sensitivity (1.09 s). Moreover, this OIH was capable of self-healing while recovering its fire-warning properties. The OIH intelligent system exhibited good universality on various substrates, such as wood, paper, fiberglass fabrics, and polyurethane (PU) foam. By introducing a self-healing OIH into a fire alarm platform, a highly sensitive warning signal can be sent via Wi-fi or Internet applications. Moreover, a self-powered fire-warning system with triboelectric nanogenerator (TENG) is also demonstrated using OIH. The concept of combining a self-healing and self-powered fire-sensing system may provide potential solutions for applying OIH in emerging applications.

The wondrous world of ABX3 molecular perovskites.

The substitution of atoms with molecular building blocks to form hybrid organic-inorganic networks has been an important research theme for several decades. ABX3 molecular perovskites (MolPs) are a subclass of hybrid networks, adopting the perovskite structure with cationic and anionic molecules on the A-site and X-site. MolPs such as ((CH3)2NH2)Zn(HCOO)3 or ((n-C3H7)4N)Mn(C2N3)3 show a range of fascinating structure-chemical properties, including temperature-driven phase transitions that include a change of polarity as interesting for ferroelectrics, pressure-driven order-disorder phase transitions as interesting for barocaloric solid-state refrigeration, and most recently, melting-behaviour before decomposition with subsequent glass formation after cooling. In this feature article, we take a more personal perspective, overviewing the field's current state and outlining future directions. We start by comparing the MolPs' structural chemistry with their inorganic parents, a comparison that helps us identify opportunities for material design. After discussing the MolPs' potential as barocalorics, ferroelectrics, and in the area of glasses, we outline some challenges that lie ahead. Beyond their relevance as a hybrid analogue of inorganic perovskites, we find that MolPs' chemical parameter space provides exciting opportunities for systematically developing design guidelines for functional materials.

Poly(ionic liquid) Grafted MXene via Si-ATRP and its Polyurethane Composite Foam: Mechanical, Flame Retardant and Sensing Properties

Compared with other types of sensors, capacitive flexible pressure sensors (CFPS), with low sensitivity, are more susceptible to environmental changes. It is still a considerable challenge to achieve high sensitivity, excellent mechanical properties and long-time structural stability simultaneously. Targeting the aforementioned issues, herein, Ti3C2 (MXene) with high dielectric constant was firstly chemically modified with a poly(ionic liquid) (PIL) via surface-initiated ATRP, and then combined with a porous polyurethane foam (PUF) 3D network structure via a one-step blending foaming method. Thanks to the organic-inorganic hybrid network based on the PU/MXene porous structures and the uniformly distributed micro-capacitor structure provided by MXene@PIL, the mechanical properties, structural stability, flame retardancy and dielectric properties of the composite foam were all significantly enhanced. When the content of MXene@PIL was 10%, the sensitivity of CFPS based on this dielectric were 17.1, 5.2, and 2.5/KPa in the pressure ranges of 0-1 KPa, 1-12 KPa and 12-100 KPa, respectively. In addition, the sensor showed the response and recovery times of 88 and 82 ms under a low pressure of 355 Pa. The light, flexible sensor prepared in this work is expected to be used in wearable devices to monitor physiological signals, and it should also be a good candidate for the next generation of man-machine interface characterization devices.

Three in One: Superoleophilic, Chemically and Mechanically Resistant ZIF-7 and ZIF-11 Percolation Networks for Selective Permeation of Oils and Chlorinated Solvents.

Imbuing superwetting functions to organic-inorganic hybrid networks displaying chemical resistance, self-cleaning ability, and selective permeation of liquids has received increasing attention in recent years. Here we report superhydrophobic ZIF-7 and ZIF-11 on multilayer fluorinated graphene (FG) nanosheets with long-lasting water-repellent features. By exploring the solution processing of these chemically resistant dispersions, superoleophilic FG-ZIF-7 stainless steel mesh (FG-ZIF-7-SSM) and FG-ZIF-11 over cotton cloth (FG-ZIF-11-CC) possessing superior adhesion were fabricated. These permselective oil-liking prototypes were explored toward mesitylene and crude oil pickup from chemically harsh marine conditions such as seawater, acidic water, and alkaline water, with a separation efficiency of 96-94% up to 10 cycles. Furthermore, using an FG-ZIF-11-CC-wrapped glass pipet, upward diffusion of chloroform from sea, acidic, and alkaline water in 45 s was demonstrated with a separation efficacy of 94% up to 20 cycles. In addition to the chemical resistance and reusability, the mechanical stability of FG-ZIF-7-SSM and FG-ZIF-11-CC was investigated through folding, tape peeling, and dragging through sandpaper up to 250 cycles, showing no signs of changes in the hydrophobic responses. This research sheds light on the application of physiochemically resistant percolation coatings based on fluorinated graphene multilayers supporting ZIF-7 and ZIF-11 toward oil/water separation.

Network of Inorganic Nanocrystals Can Swell: Study of Swelling-Induced Surface Instability.

A unique organic-inorganic hybrid network composed of inorganic nanocores (ranging from semiconductors to metallic ones) interconnected through organic molecules can be produced by crosslinking the organic ligands of colloidal inorganic nanocrystals in assemblies. This work reports that this network, which is conventionally considered an inorganic film, can swell when exposed to a solvent because of the interaction between the solvent and the organic linkage within the network. Intriguingly, this work discovers that drying the solvent of the swollen organic-inorganic hybrid network can significantly affect the morphology owing to the swelling-induced compress stress, which is widely observed in various organic network systems. This work studies the surface instability of crosslinked organic-inorganic hybrid networks swollen by various organic solvents, which led to buckling delamination. Specifically, this work investigates the effects of the i) solvent-network interaction, ii) crosslinking density of the network, and iii) thickness of the film on the delamination behavior of the crosslinked network.

UV-cured organic-inorganic hybrid networks for durable antifogging coating

Preventing surface fogging is critical for maintaining transparency in various transparent applications such as windows, mirrors and goggles. However, the fabrication of durable antifogging surfaces has been significantly challenging. The challenges include the lack of a simple preparation method, low coating hardness, poor water resistance and inability to self-healing. In this work, we developed an organic-inorganic interpenetrating hydrophilic antifogging coating using vinyl hybridized silica nanoparticles (VSNPs), polyvinyl alcohol (PVA), and methacrylic acid (MAA). A durable antifogging coating with self-healing capabilities has been prepared using a facile UV curing process. Such a hybrid coating can maintain its outstanding antifogging performance even after 4000 cycles of sand abrasion and 36 h of water immersion. Due to these outstanding properties and facile preparation, VSNPs-PVA/PMAA coating shows great potential in practical applications.

Rapid room-temperature polymerization strategy to prepare organic/inorganic hybrid conductive organohydrogel for terahertz wave responsiveness

Conductive organohydrogel with better environmental stability than conductive hydrogel, has more promising applications in the fields of soft robots, wearable electronics and electromagnetic interference shielding. However, the current organohydrogels still face the trade-off dilemma between environmental stability and conductivity, and their preparation is usually time-consuming and complicated. Here, we report a room-temperature rapid polymerization strategy to prepare conductive organohydrogel using PEDOT:PSS and MXene nanosheets as conductive fillers as well as cross-linking sites, which is applicable to a variety of binary solvent systems. The synergistic effect between PEDOT:PSS and MXene nanosheets activates the formation of abundant hydrogen bonds, chelation interaction and electrostatic interaction between different components, thus significantly shortening the polymerization time from several hours to less than five minutes. Meanwhile, the organic–inorganic hybrid network constructs efficient conductive paths and strengthens the mechanical properties. Over a wide temperature range (−18 to 70 °C), this composite organohydrogel shows excellent stretchability, self-healing, adhesion, environmental stability. More interestingly, the organohydrogel with reasonably designed binary solvent system and conductive network achieves absorption-dominated shielding performance and wireless displacement sensing in the frequency of 2–10 terahertz. The revealed contributions of binary solvent system and conductive network to the absorption and reflection of terahertz waves are conducive to promote the development of organohydrogel-based terahertz responsive materials.

Organic-inorganic hybrid network to enhance the electrostatic shielding of multifunctional soybean meal-based adhesive

Static electricity and formaldehyde pollution are not only severely harmful to ecological environment but also seriously affecting human health. It is of great importance but still challenging to develop an eco-friendly and multifunctional adhesive for electrostatic shielding. Protein adhesives were considered to be an effective substitute for formaldehyde resin adhesives, but show poor water resistance and conductive, limiting their practical applications in many fields, such as antistatic materials and antistatic floors. Therefore, this study aimed to develop a multifunctional adhesive by a facile organic-inorganic hybrid network to enhance the electrostatic shielding for antistatic materials. As we expected, the volume resistivity of the resultant adhesive for antistatic floors is only 2.73 × 10 8 Ω·cm, which is five orders of magnitude less than that of soybean meal (SM) adhesive and shows excellent electrostatic shielding performance. After experiencing a rapid thermal shock cycle between two extreme temperature conditions for 30 times, the mechanical performance of adhesive still remained stable. Furthermore, the adhesives are not only eco-friendly and non-formaldehyde, but excellent mildew resistance and flame retardancy. This multifunctional SM-based adhesive opens a new way to replace harmful formaldehyde-based adhesives, which have potential applications in the field of antistatic floors. • A high-performance adhesive was prepared by a facile and green organic-inorganic hybrid strategy for electrostatic shielding. • The multiple bonding structures were formed between protein chains and hydroxylated BT nanoparticles. • The adhesive exhibited mechanical stability under two extreme temperature cycling. • This adhesive could be used for antistatic materials with flame retardance and antimicrobial properties.

Optically Induced Long-Lived Chirality Memory in the Color-Tunable Chiral Lead-Free Semiconductor (R)/(S)-CHEA4Bi2BrxI10-x (x = 0-10).

Hybrid organic-inorganic networks that incorporate chiral molecules have attracted great attention due to their potential in semiconductor lighting applications and optical communication. Here, we introduce a chiral organic molecule (R)/(S)-1-cyclohexylethylamine (CHEA) into bismuth-based lead-free structures with an edge-sharing octahedral motif, to synthesize chiral lead-free (R)/(S)-CHEA4Bi2BrxI10-x crystals and thin films. Using single-crystal X-ray diffraction measurements and density functional theory calculations, we identify crystal and electronic band structures. We investigate the materials' optical properties and find circular dichroism, which we tune by the bromide-iodide ratio over a wide wavelength range, from 300 to 500 nm. We further employ transient absorption spectroscopy and time-correlated single photon counting to investigate charge carrier dynamics, which show long-lived excitations with optically induced chirality memory up to tens of nanosecond timescales. Our demonstration of chirality memory in a color-tunable chiral lead-free semiconductor opens a new avenue for the discovery of high-performance, lead-free spintronic materials with chiroptical functionalities.

Recent Advances in the Development and Antimicrobial Applications of Metal-Phenolic Networks.

Due to the abuse of antibiotics and the emergence of multidrug resistant microorganisms, medical devices, and related biomaterials are at high risk of microbial infection during use, placing a heavy burden on patients and healthcare systems. Metal–phenolic networks (MPNs), an emerging organic–inorganic hybrid network system developed gradually in recent years, have exhibited excellent multifunctional properties such as anti‐inflammatory, antioxidant, and antibacterial properties by making use of the coordination between phenolic ligands and metal ions. Further, MPNs have received widespread attention in antimicrobial infections due to their facile synthesis process, excellent biocompatibility, and excellent antimicrobial properties brought about by polyphenols and metal ions. In this review, different categories of biomaterials based on MPNs (nanoparticles, coatings, capsules, hydrogels) and their fabrication strategies are summarized, and recent research advances in their antimicrobial applications in biomedical fields (e.g., skin repair, bone regeneration, medical devices, etc.) are highlighted.

Performance improvement of magnesium oxychloride cement via nanoparticles-enhanced organic–inorganic hybrid network

It is a big challenge to improve both water resistance and mechanical properties for magnesium oxychloride cement (MOC). In this paper, hydroxyapatite (HA)/polyester (PEs) was introduced to improve both properties of MOC. The HA was evenly dispersed and had a good interfacial compatibility with the polyester, forming a stable nanoparticle reinforced organic–inorganic hybrid network (HAPEs). By introducing the organic–inorganic hybrid structure into MOC, the adverse effects caused by the uneven dispersion of nanoparticles can be avoided. The softening coefficient of the obtained MOC-HAPEs1.2% was 0.98, increasing by 206% compared to unmodified MOC. The enhanced water resistance was associated with the molecular network structure and abundant cross-linking points of the HAPEs. In the meantime, the mechanical properties of MOC were slightly improved. Moreover, the setting time of MOC was prolonged, which was conducive to the operability of its construction.

Sugar-derived bio-based resins as platforms for the development of multifunctional hybrids with potential application for stone conservation

This research is focused on the design of a bio-based epoxy-silica hybrid, enriched with SiO2 nanoparticles, to be used in stone conservation. For this purpose, isosorbide, a sugar derivative coming from renewable sources, was selected for the development of epoxy thermosets that were functionalized adding fixed amounts of silica-forming mixtures, to gain hybrid organic-inorganic networks. Fourier Transform Infrared (FTIR), Attenuated Total Reflection Infrared (ATR-FTIR) and Raman spectroscopies were exploited to follow the synthetic procedures, whereas the homogeneity of the networks was ascertained by scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDS). The materials were investigated by thermogravimetric (TG-DTA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and contact angle measurements. Once the proper epoxy-silica product was identified, specifically synthesized nanoparticles were incorporated. The obtained nanocomposite showed excellent thermo-mechanical (Tonset, Tg and Tα of 327, 55.9 and 70.1 °C, respectively) and hydrophobic (105°) properties making it a potential candidate for stone conservation.

Phase and Morphology Control of Organic-Inorganic Hybrid Network Polymer by Means of Hydrosilylation Reaction of Cubic Silsesquioxane or Cyclic Polysiloxane and Divinyl or Diallyl Compounds

Organic-inorganic hybrid network polymers have been synthesized from cubic silsesquioxane, 1,3,5,7,9,11,13,15-octakis(dimethylsilyloxy)pentacyclo[9,5,1,1,1,1] octasilsesquioxane (POSS) and divinyl ...

Nanocomposite solid polymer electrolytes based on semi-interpenetrating hybrid polymer networks for high performance lithium metal batteries

This research reports the synthesis of nanocomposite solid polymer electrolytes (ncSPEs) for solid state lithium metal batteries. These materials are composed of a controlled hybrid organic-inorganic network of glycidyl POSS® and Jeffamine® ED2003, in which linear high molecular weight poly (ethylene oxide) (PEO) chains are entangled to improve both mechanical and electrochemical properties of the ncSPE. Synthesis and preparation of self-standing membranes are achieved with a facile one-pot catalyst-free method with considerably reduced amount of organic solvent, which is a plus toward a future scale-up. We found that the component ratio plays a crucial role in ncSPEs’ performance as a simple variation (i.e. cross-linking degree) is sufficient to completely change the electrochemical behavior of the solid state cell. For instance, increasing POSS® amount guarantees better resistance to lithium dendrites penetration, better electro-oxidation stability, and significantly extends cycle life in Li/ncSPE/LiFePO4 solid state cells. Furthermore, besides improving cell performance at higher C-rate of Li/LiFePO4 cells, this PEO-based ncSPE gives better response than reference PEO-LiTFSI electrolyte in high voltage Li/LiNi0.6Mn0.2Co0.2O2 cells with up to 10 cycles at 60 °C with discharge capacity retention above 80%. Despite the poor performance, to the best of our knowledge, this electrolyte is one of the few examples of PEO-based solid polymer electrolytes being capable of cycling with high voltage cathodes.

Synthesis and Properties of Organic-Inorganic Hybrid Porous Polymers Obtained with Click Addition Reactions of Thiol-Functionalized Random Type Silsesquioxane by and Diacrylate or Diisocyanate Compounds

Organic-inorganic hybrid network polymers have been synthesized by addition reaction of a thiol-functionalized random type silsesquioxane (SQ109) and alkyl diacrylate or diisocyanate compounds. Thiol-ene reaction of SQ109 and 1,4-butanediol diacrylate (BDA) successfully yield porous polymer in toluene initiated by azobis(isobutyronitrile) (AIBN) at 60°C. Morphology of the porous polymers was composed by connected globules, and the diameter of the globules decreased with increasing in the monomer concentration of the reaction system. By contrast, the reaction with 1,6-hexanediol diacrylate or 1,5-hexadiene yielded homogeneous clear gels. Thermal analyses of SQ109-BDA porous polymers indicated that thermal degradation of ester groups of BDA in the polymer network occurred at around 300°C. The porous polymer was also obtained by the reaction using a photo-initiator (Irugacure184) at room temperature, and showed higher Young’s modulus than the corresponding porous polymer obtained with the reaction with AIBN due to the small size of the globules. Young’s modulus of SQ109-BDA porous polymer increased with increasing in the monomer concentration of the reaction systems. Thiolisocyanate addition reactions between SQ109 and hexamethylene diisocyanate (HDI) or methylenediphenyl 4,4’-diisocyanate (MDI) were investigated to obtain network polymers. The reactions in toluene yielded the corresponding homogeneous clear gels. By contrast the reactions in a mixed solvent of toluene (50 vol.%) and N,N-dimethylformamide (50 vol.%) produced porous polymers. The morphology of the porous polymers was composed by connected globules or aggregated particles. The size of globules and particles in the SQ109-HDI porous polymers was larger than those in the SQ109-MDI porous polymers. Thermal degradation of SQ109-HDI and SQ109-MDI porous polymers started at round 260°C and showed endothermic peak at around 350°C derived from degradation of thio-urethane bond.

Magnetic Nanoparticles@Metal-Organic Framework Composites as Sustainable Environment Adsorbents

Metal-organic frameworks (MOFs) are an intriguing class of porous inorganic-organic hybrid networks synthesized from metal ions with multidentate organic ligands. MOFs have uniform and tunable cavities and tailorable chemistry, making them promising materials for hazardous component removal from the environment. Controllable integration of magnetic nanoparticles (NPs) and MOFs is leading to the creation of many novel multifunctional MOF-based composites, which exhibit advanced performance that is superior to both of the individual units. This review summarizes the recent significant advances in the development of MOF-based magnetic heterostructure materials for the removal of hazardous contaminants from the environment. The successful methods reported till date for the magnetic MOF synthesis are also provided. In the final section, we provide our views on the future development of the magnetic MOF heterostructure materials for the pollution management.

Formation of an Organic–Inorganic Hybrid Network Structure by In Situ Polymerization of Silicone to Protect Cultural Heritage Stonework

AbstractYujia Memorial Archway in Jixian County, Hunan Province, can be considered a typical weathered stone artifact. Different ratios of 3-glycidyl ether propyl trimethoxy silane (GPTMS), 3-amino...

RESEARCH PROGRESS ON TITANIUM-CONTAINING ORGANIC–INORGANIC HYBRID PROTECTIVE COATINGS

In this paper, we summarize research progress on the design and preparation of organic–inorganic hybrid coating molecular networks, which are based on the basic theory of organic–inorganic hybrid network construction. Among them, we focus on expounding the essential problems of hydrolysis during sol preparation particularly. In addition, the status of research related to titanium-containing organic–inorganic hybrid protective coatings for the surfaces of lightweight alloys such as steel, aluminum and magnesium is introduced here.