Inorganic Hybrid Polymer Research Articles

Morphology Control of Polymer–Inorganic Hybrid Nanomaterials Prepared in Miniemulsion: From Solid Particles to Capsules

The preparation of so-called hybrid nanomaterials has been widely developed in terms of functional and morphological complexity. However, the specific control of the arrangement of organic and inorganic species, which determines the properties of the final material, still remains a challenge. This article offers a review of the strategies that have been used for the preparation of polymer–inorganic hybrid nanoparticles and nanocapsules via processes involving miniemulsions. Different polymer–inorganic nanostructures are classified into four main groups according to the sequential order followed between the synthesis of the polymer and the inorganic species, and the presence or not of their counterpart precursors. The minimization of the energy of the system governs the self-assembly of the different material components and can be addressed by the miniemulsion formulation to reduce the interfacial tensions between the phases involved. The state of the art in the preparation of hybrid nanoparticles is reviewed, offering insight into the structural possibilities allowed by miniemulsion as a versatile synthetic technique.

Solid-state polymer-particle hybrid electrolytes: Structure and electrochemical properties.

Solid-state electrolytes (SSEs) are challenged by complex interfacial chemistry and poor ion transport through the interfaces they form with battery electrodes. Here, we investigate a class of SSE composed of micrometer-sized lithium oxide (Li2O) particles dispersed in a polymerizable 1,3-dioxolane (DOL) liquid. Ring-opening polymerization (ROP) of the DOL by Lewis acid salts inside a battery cell produces polymer-inorganic hybrid electrolytes with gradient properties on both the particle and battery cell length scales. These electrolytes sustain stable charge-discharge behavior in Li||NCM811 and anode-free Cu||NCM811 electrochemical cells. On the particle length scale, Li2O retards ROP, facilitating efficient ion transport in a fluid-like region near the particle surface. On battery cell length scales, gravity-assisted settling creates physical and electrochemical gradients in the hybrid electrolytes. By means of electrochemical and spectroscopic analyses, we find that Li2O particles participate in a reversible redox reaction that increases the effective CE in anode-free cells to values approaching 100%, enhancing battery cycle life.

Silica based on inorganic–polymer hybrid materials for removing toxic ions from wastewater

As a result of the adsorption of copolymer 5-(4-nitro)phenylazo-8-methacryloxyquinoline with methyl methacrylate on the surface of mesoporous silica gel, a new polymer-inorganic composite material was obtained. Based on the comparison of the sorption capacity of the synthesized composite and the composite based on silica gel with in situ immobilized poly-5-(4-nitro)phenylazo-8-methacryloxyquinoline, it was concluded that the method of in situ immobilization of complex-forming polymers on the surface of silica gel is more effective compared to their physical adsorption.

Rational Design of an In-Situ Polymer-Inorganic Hybrid Solid Electrolyte Interphase for Realising Stable Zn Metal Anode under Harsh Conditions.

The in-depth understanding of the composition-property-performance relationship of solid electrolyte interphase (SEI) is the basis of developing a reliable SEI to stablize the Zn anode-electrolyte interface, but it remains unclear in rechargeable aqueous zinc ion batteries. Herein, a well-designed electrolyte based on 2 M Zn(CF3SO3)2-0.2 M acrylamide-0.2 M ZnSO4 is proposed. A robust polymer (polyacrylamide)-inorganic (Zn4SO4(OH)6.xH2O) hybrid SEI is in situ constructed on Zn anodes through controllable polymerization of acrylamide and coprecipitation of SO4 2- with Zn2+ and OH-. For the first time, the underlying SEI composition-property-performance relationship is systematically investigated and correlated. The results showed that the polymer-inorganic hybrid SEI, which integrates the high modulus of the inorganic component with the high toughness of the polymer ingredient, can realize high reversibility and long-term interfacial stability, even under ultrahigh areal current density and capacity (30 mA cm-2~30 mAh cm-2). The resultant Zn||NH4V4O10 cell also exhibits excellent cycling stability. This work will provide a guidance for the rational design of SEI layers in rechargeable aqueous zinc ion batteries.

Synthesis of cobalt nanoparticles in aqueous solutions assisted by polymer/inorganic hybrid

Hydrophilic polymer/inorganic hybrids (PIH) containing silica nanoparticles and polyacrylamide chains proved to be effective matrices for the in situ synthesis of cobalt nanoparticles. PIH sample was synthesized by free-radical polymerization of acrylamide from the unmodified surface of SiO2 nanoparticles and characterized by elemental analysis, dynamic thermogravimetric analysis, static light scattering, potentiometric titration, viscometry and transmission electron microscopy (TEM). The processes of borohydride reduction of cobalt ions from the Co(NO3)2·6H2O solution to nanoparticles in water medium and aqueous solutions of PIH were studied as a function of the concentrations of metal salt and hybrid concentrations using UV-Vis spectroscopy and TEM. A special approach to characterize the kinetics and efficiency of CoNPs formation in water medium and hybrid solutions using UV-Vis spectroscopy was implemented. The kinetic parameters of the CoNPs formation process as well as the yield, size, and morphology of nanoparticles in hybrid solutions and water medium at various concentrations of metal salt and hybrid were determined. The growth of both concentrations of reagents had a positive effect on the rate of formation of metal nanoparticles and their yield, but in all cases, the reduction process developed much slower in hybrid solutions compared to pure water. The morphology of the CoNPs/PIH nanocomposites was mainly represented by separate swollen hybrid particles containing metal nanoparticles with dav~3 nm.

Direct Evidence of π–π Interactions in Transparent Organic–Inorganic Polymer Hybrids of Polystyrene and Silica Gel

Polystyrene and silica gel polymer hybrids derived from polystyrene and phenyltrimethoxysilane via π–π interactions were synthesized by a slight modification of the previous method. Spectroscopic evidence of the π–π interaction is provided. The obtained polymer hybrids were optically transparent, and no phase separation was observed by scanning electron microscopy measurements. In the FT-IR spectrum of the resulting polymer hybrids, the absorption peaks corresponding to C–H wagging vibration shifted to a lower wavenumber range as the content of silica in the hybrids increased. A UV–vis spectrum of the polystyrene and silica gel polymer hybrids showed a shoulder peak at around 260 nm that shifted toward longer wavenumbers side as the content of silica increased. These results clearly indicate that π–π interactions contribute to the formation of these transparent hybrids.

Facile fabrication of polymeric-inorganic hybrid coated membrane with super-hydrophilic and underwater super-oleophobic properties for highly efficient crude oil-in-water emulsion separation

The oily wastewater is a huge wastewater stream that can potentially serve as an enormous source of clean water for water reuse applications such as groundwater recharge or irrigation. Given the huge potential of cleaning oily wastewater, we have developed an amino-functionalized nickel oxide nanoparticles coated inorganic-polymeric hybrid membrane with superhydrophilic and underwater superoleophobic properties for excellent crude oil-in-water (O/W) emulsion separation potential using a cross-flow filtration system. The use of ceramic alumina (Al2O3) support offers increased chemical, thermal, and mechanical stability while nickel oxide (NiO) decoration equips the membrane with special surface wettability to avoid membrane fouling. Moreover, the amino-functionalized NiO-coated polyamide network (F-NiO/PA) offers an active layer dense enough to separate the oil from water when the surfactant-stabilized crude oil-in-water emulsion was used as feed during separation experiments. Hence fabricated F-NiO/PA@Alumina membrane was studied by using different membrane characterization techniques to explore the features and understand the structure of F-NiO/PA@Alumina membrane. The F-NiO/PA@Alumina membrane possessed a superhydrophilic (water contact angle; θW, A = 0°) and underwater superoleophobic (oil contact angle; θO, W = 161°) surface wettability which is an ideal feature required for O/W emulsion separation. The F-NiO/PA@Alumina membrane demonstrated a high O/W emulsion separation efficiency of >99 % even with crude oil concentrations as high as 200 ppm using a cross-flow filtration system. The stability test of the separation performance of the F-NiO/PA@Alumina membrane also revealed a separation performance of >99 % for the duration of the test using a cross-flow filtration system.

Chemically and Physically Cross-Linked Inorganic–Polymer Hybrid Solvent-Free Electrolytes

Safe, self-standing, all-solid-state batteries with improved solid electrolytes that have adequate mechanical strength, ionic conductivity, and electrochemical stability are strongly desired. Hybrid electrolytes comprising flexible polymers and highly conductive inorganic electrolytes must be compatible with soft thin films with high ionic conductivity. Herein, we propose a new type of solid electrolyte hybrid comprising a glass–ceramic inorganic electrolyte powder (Li1+x+yAlxTi2−xSiyP3−yO12; LICGC) in a poly(ethylene)oxide (PEO)-based polymer electrolyte that prevents decreases in ionic conductivity caused by grain boundary resistance. We investigated the cross-linking processes taking place in hybrid electrolytes. We also prepared chemically cross-linked PEO/LICGC and physically cross-linked poly(norbornene)/LICGC electrolytes, and evaluated them using thermal and electrochemical analyses, respectively. All of the obtained electrolyte systems were provided with homogenous, white, flexible, and self-standing thin films. The main ionic conductive phase changed from the polymer to the inorganic electrolyte at low temperatures (close to the glass transition temperature) as the LICGC concentration increased, and the Li+ ion transport number also improved. Cyclic voltammetry using [Li metal|Ni] cells revealed that Li was reversibly deposited/dissolved in the prepared hybrid electrolytes, which are expected to be used as new Li+-conductive solid electrolyte systems.

High specific surface area MXene/SWCNT/cellulose nanofiber aerogel film as an electrode for flexible supercapacitors

Transition metal carbonitrides (MXene) with two-dimensional layered structures are a recent research topic in the field of supercapacitors. However, because MXene can easily self-stack, its capacitance performance is affected. To this end, one-dimensional cellulose nanofibers (CNF) and carboxylic single-walled carbon nanotubes (SWCNT) were used to intercalate MXene to obtain well-dispersed MXene/SWCNT/CNF aqueous suspensions and their hybrid hydrogels, and to obtain hybrid aerogels through supercritical drying. CNF gives aerogel excellent porosity, a high specific surface area (301.03 m2 g−1), good electrolyte infiltration, and gentle mechanical flexibility, while SWCNT imparts high conductivity to aerogel film. We assembled a symmetrical all-solid-state flexible supercapacitor and interdigitated micro-supercapacitors using an aerogel film as a flexible electrode. The area specific capacity of the above electrode reaches 746.68 mF cm−2 and 244.50 mF cm−2, respectively. This study provides a fabrication method of polymer–inorganic hybrid nanocomposite aerogel film electrodes for flexible supercapacitors.

Low Concentration Sulfolane-Based Electrolyte for High Voltage Lithium Metal Batteries.

Electrolyte engineering is crucial for the commercialization of lithium metal batteries. Here, lithium metal is stabilized in the highly reactive sulfolane-based electrolyte under low concentration (0.25 M) for the first time. Inorganic-polymer hybrid solid electrolyte interphase (SEI) with high ionic conductivity, low bonding with lithium and high flexibility enables dense chunky lithium deposition and high plating/stripping efficiency. Low concentration electrolyte (LCE) also enables excellent cycling stability of LiNi0.5 Co0.2 Mn0.3 O2 (NCM523)/Li cells at 1 C (90.7 % retention after 500 cycles) and 0.3 C (83.3 % retention after 1000 cycles). With a low N/P ratio (≈2), the capacity retention for NCM523/Li cells can achieve 94.3 % after 100 cycles at 0.3 C. Exploring the LCE is of paramount significance because it provides more possibilities of the lithium salt selections, especially reviving some lithium salts that are excluded before due to their low solubility. More importantly, LCE has the significant advantage of commercialization due to its cost-effectiveness.

A Janus Au-Polymersome Heterostructure with Near-Field Enhancement Effect for Implant-Associated Infection Phototherapy.

Polymer-inorganic hybrid Janus nanoparticles (PI-JNPs) have attracted extensive attention due to their special structures and functions. However, achieving the synergistic enhancement of photochemical activity between polymer and inorganic moieties in PI-JNPs remains challenging. Herein, the construction of a novel Janus Au-porphyrin polymersome (J-AuPPS) heterostructure by a facile one-step photocatalytic synthesis is reported. The near-field enhancement (NFE) effect between porphyrin polymersome (PPS) and Au nanoparticles in J-AuPPS is achieved to enhance its near-infrared (NIR) light absorption and electric/thermal field intensity at their interface, which improves the energy transfer and energetic charge-carrier generation. Therefore, J-AuPPS shows a higher NIR-activated photothermal conversion efficiency (48.4%) and generates more singlet oxygen compared with non-Janus core-particle Au-PPS nanostructure (28.4%). As a result, J-AuPPS exhibits excellent dual-mode (photothermal/photodynamic) antibacterial and anti-biofilm performance, thereby significantly enhancingthe in vivo therapeutic effect in an implant-associated-infection rat model. This work is believed to motivate the rational design of advanced hybrid JNPs with desirable NFE effect and further extend their biological applications.

Preparation and Characterization of a Polyetherketoneketone/Hydroxyapatite Hybrid for Dental Applications.

Here, we developed a new synthetic method for the production of a new class of polymeric inorganic hybrid biomaterial that has potential for dental implant applications and, in general, other orthopedic applications owing to its excellent mechanical properties and biomechanical compatibility. The new hybrid biomaterial is a composite consisting of polyetherketoneketone (PEKK) and hydroxyapatite (HA). This hybrid material boasts several unique features, including its high HA loading (up to 50 wt%), which is close to that of natural human bone; the homogeneous HA distribution in the PEKK matrix without phase separation; and the fact that the addition of HA has no effect on the molecular weight of PEKK. Nanoindentation analysis was used to investigate the mechanical properties of the composite, and its nano/microstructure variations were investigated through a structural model developed here. Through nanoindentation technology, the newly developed PEKK/HA hybrid biomaterial has an indentation modulus of 12.1 ± 2.5 GPa and a hardness of 0.42 ± 0.09 GPa, which are comparable with those of human bone. Overall, the new PEKK/HA biomaterial exhibits excellent biomechanical compatibility and shows great promise for application to dental and orthopedic devices.

Mesoporous Silica and Oligo (Ethylene Glycol) Methacrylates-Based Dual-Responsive Hybrid Nanogels.

Polymeric-inorganic hybrid nanomaterials have emerged as novel multifunctional platforms because they combine the intrinsic characteristics of both materials with unexpected properties that arise from synergistic effects. In this work, hybrid nanogels based on mesoporous silica nanoparticles, oligo (ethylene glycol) methacrylates, and acidic moieties were developed employing ultrasound-assisted free radical precipitation/dispersion polymerization. Chemical structure was characterized by infrared spectroscopy and nuclear magnetic resonance. Hydrodynamic diameters at different temperatures were determined by dynamic light scattering, and cloud point temperatures were determined by turbidimetry. Cell viability in fibroblast (NIH 3T3) and human prostate cancer (LNCaP) cell lines were studied by a standard colorimetric assay. The synthetic approach allows covalent bonding between the organic and inorganic components. The composition of the polymeric structure of hybrid nanogels was optimized to incorporate high percentages of acidic co-monomer, maintaining homogeneous nanosized distribution, achieving appropriate volume phase transition temperature values for biomedical applications, and remarkable pH response. The cytotoxicity assays show that cell viability was above 80% even at the highest nanogel concentration. Finally, we demonstrated the successful cell inhibition when they were treated with camptothecin-loaded hybrid nanogels.

Positron annihilation study of chitosan and its derived carbon/pillared montmorillonite clay stabilized Pd species nanocomposites

To establish the structure-properties relations of an organic polymer-inorganic hybrid nanocomposite, insightful investigation of the molecules packing and interfacial interactions is essential. Positron annihilation lifetime spectroscopy (PALS) has been proven as one of the most suitable technique to characterize the free volume structure (molecular packing) of polymer matrices. However, most of the attentions were paid limitedly in organic polymer-based hybrid systems rather than inorganic-based hybrid systems. Classic spherical model was the most frequently used model in free volume holes size calculation of polymer matrix. In the present study, molecular level micro-defects within inorganic-based hybrid systems encaging polymers and carbon species, i.e. novel biological macromolecules of chitosan and its derived carbon/Al pillared montmorillonite clay (CS/PILC and CS-derived C/PILC) stabilized palladium species hybrid nanocomposites, have been investigated by PALS. Besides the classic spherical model, cuboidal and cylindrical models were used to evaluate the molecules packing behavior within the interlayer space of PILC matrices encaging of polymers of CS or CS-derived carbons. The layered porous structure of the nanocomposites was also characterized with other methods, such as X-ray diffraction, N2 adsorption/desorption, and high-resolution transmission electron microscopy, etc. The correlations of the microstructure and catalytic properties applied in Sonogashira coupling reactions of the nanocomposites were discussed.

Entropy-Driven Self-Healing of Metal Oxides Assisted by Polymer-Inorganic Hybrid Materials.

Enabling self-healing of materials is crucially important for saving resources and energy in numerous emerging applications. While strategies for the self-healing of polymers are advanced, mechanisms for semiconducting inorganic materials are scarce due to the lack of suitable healing agents. Here a concept for the self-healing of metal oxides is developed. This concept consists of metal oxide nanoparticle growth inside the bulk of halogenated polymers and their subsequent entropy-driven migration to externally induced defect sites, leading to recovery of the defect. Herein, it is demonstrated that the pool of self-healing materials is expanded to include semiconductors, thereby increasing the reliability and sustainability of functional materials through the use of metal oxides. It is revealed that electrical properties of tin-doped indium oxide can be partially restored upon healing. Such properties are of immediate interest for the further development of transparent flexible electrodes.

Resolving the Conflict between Strength and Toughness in Bioactive Silica-Polymer Hybrid Materials.

Simultaneously improving the strength and toughness of materials is a major challenge. Inorganic-polymer hybrids offer the potential to combine mechanical properties of a stiff inorganic glass with a flexible organic polymer. However, the toughening mechanism at the atomic scale remains largely unknown. Based on combined experimental and molecular dynamics simulation results, we find that the deformation and fracture behavior of hybrids are governed by noncovalent intermolecular interactions between polymer and silica networks rather than the breakage of covalent bonds. We then attempt three methods to improve the balance between strength and toughness of hybrids, namely the total inorganic/organic (I/O) weight ratio, the size of silica nanoparticles, and the ratio of -C-O vs -C-C bonds in the polymer chains. Specifically, for a hybrid with matched silica size and I/O ratio, we demonstrate optimized mechanical properties in terms of strength (1.75 MPa at breakage), degree of elongation at the fracture point (31%), toughness (219 kPa), hardness (1.08 MPa), as well as Young's modulus (3.0 MPa). We also demonstrate that this hybrid material shows excellent biocompatibility and ability to support cell attachment as well as proliferation. This supports the possible application of this material as a strong yet tough bone scaffold material.

Structural regulation of vanadium oxide by poly(3,4-ethylenedioxithiophene) intercalation for ammonium-ion supercapacitors

Recently, ammonium-ion (NH4+) storage is in a booming stage in aqueous energy storage systems due to its multitudinous merits. To seek suitable electrode materials with excellent NH4+-storage is still in the exploratory stage and full of challenge. Herein, an inorganic-polymer hybrid, poly(3,4-ethylenedioxithiophene) (PEDOT) intercalated hydrated vanadium oxide (VOH), named as VOH/PEDOT, is developed to tune the structure of VOH for boosting NH4+ storage. By the intercalation of PEDOT, the interlayer space of VOH is increased from 11.5 Å to 14.2 Å, which notably facilitates the rapid transport of electrons and charges between layers and improves the electrochemical properties for NH4+ storage. The achieved performances are much better than progressive NH4+ hosting materials. In addition, the concentration of polyvinyl alcohol/ammonium chloride (PVA/NH4Cl) electrolyte exerts a great impact on the NH4+ storage in VOH/PEDOT. The VOH/PEDOT electrode delivers specific capacitance of 327 F g−1 in 1 M PVA/NH4Cl electrolyte at −0.2–1 V. Furthermore, the quasi-solid-state VOH/PEDOT//active carbon hybrid supercapacitor (QSS VOH/PEDOT//AC HSC) device is assembled for NH4+ storage, and it exhibits the capacitance of 328 mF cm−2 at 1 mA cm−2. The energy density of QSS VOH/PEDOT//AC NH4+-HSC can reach 2.9 Wh m−2 (2.6 mWh cm−3, 10.4 Wh kg−1) at 1 W m−2 (0.9 mWh cm−3, 35.7 W kg−1). This work not only proves that the PEDOT intercalation can boost the NH4+ storage capacity of vanadium oxides, but also provides a novel direction for the development of NH4+ storage materials.

Mild Sol–Gel Conditions and High Dielectric Contrast: A Facile Processing toward Large-Scale Hybrid Photonic Crystals for Sensing and Photocatalysis

Solution processing of highly performing photonic crystals has been a towering ambition for making them technologically relevant in applications requiring mass and large-area production. It would indeed represent a paradigm changer for the fabrication of sensors and for light management nanostructures meant for photonics and advanced photocatalytic systems. On the other hand, solution-processed structures often suffer from low dielectric contrast and poor optical quality or require complex deposition procedures due to the intrinsic properties of components treatable from solution. This work reports on a low-temperature sol–gel route between the alkoxides of Si and Ti and poly(acrylic acid), leading to stable polymer–inorganic hybrid materials with tunable refractive index and, in the case of titania hybrid, photoactive properties. Alternating thin films of the two hybrids allows planar photonic crystals with high optical quality and dielectric contrast as large as 0.64. Moreover, low-temperature treatments also allow coupling the titania hybrids with several temperature-sensitive materials including dielectric and semiconducting polymers to fabricate photonic structures. These findings open new perspectives in several fields; preliminary results demonstrate that the hybrid structures are suitable for sensing and the enhancement of the catalytic activity of photoactive media and light emission control.

A compact polymer\u2013inorganic hybrid gas barrier nanolayer for flexible organic light-emitting diode displays

Atomic layer infiltration technology allows the formation of a nanometer-thick polymer-inorganic hybrid barrier layer in polymer material for flexible organic light-emitting diode (OLED) displays. In this study, according to transmission electron microscopy and secondary-ion mass spectrometry analysis results under various process conditions, a compact polymer-inorganic hybrid nanolayer was successfully formed in a polymer and good barrier performance was revealed with a low water vapor transmission rate under optimal process conditions. Additionally, through gas chromatography-mass spectrometry measurements after ultra-violet radiation testing, polymer out-gassing decreased compared to bare polymers. Based on barrier properties, the polymer with a polymer-inorganic hybrid barrier nanolayer was applied to a flexible OLED display as a substrate. During storage tests and folding tests, the flexible OLED display exhibits good reliability and better flexibility compared to those with an inorganic barrier layer. These results confirm that the polymer-inorganic hybrid nanolayer is suitable for barrier layer formation in flexible OLED displays.

FLOCCULATION OF DISPERSE SYSTEMS BY POLYFUNCTIONAL POLYMER-INORGANIC HYBRIDS

Development of novel high-capacity multifunctional flocculants is a promising solution to selective separation of clay suspensions. Among such flocculants, polymer-inorganic hybrids are the most attractive for their excellent performance as compared with inorganic coagulants or syn-thetic polymers. Synthesis of polymer-inorganic hybrids was carried out in two stages. At the first stage, Al(OH)3sol was obtained by condensation of aluminum chloride and ammonium carbonate in the following conditions: t = 70°C, pH = 3-4, intensive stirring. In the second stage, Al(OH)3was mixed with aqueous solutions of polymers at room temperature. By changing the melting tem-perature of hybrid samples, the presence of interactionsbetween the Al3+cation and the carboxylate groups of the analyzed acrylamide copolymers were established. This paper reports synthesis and comparative efficiency analysis of systems that contain water-soluble anionic copolymers of acryla-mide and respective polyfunctional polymer-inorganic hybrids. We performed a quantitative char-acterization of concentration and structural effects of polymer flocculants on the flocculation mechanism and sludge thickening. Sludge thickening constants were determined. Higher values of thickening constants were noted in systems with additives of hybrid samples, due to the participa-tion of their macromolecules in the formation of floccules at the first stage of the sediment process, and at the stage of thickening of sediments,their deformation and compaction were revealed while maintaining a loose structure with the formation of bulk floccules. We considered the factors al-lowing to optimize flocculation of clay dispersions by polymer-inorganic hybrids in aqueous media. These novel flocculants were shown to have a good potential for applications in filtration or flota-tion processes as well as for wastewater treatment for removal of disperse impurities.