New Class Of Hybrid Materials Research Articles

Delamination of MXene using biomolecule: An effective strategy toward the utilization of delaminated MXene as fillers in polymer composites

AbstractWith the emergence of two‐dimensional (2D) materials analogous to graphene, transition metal carbides and carbonitrides with unique desirable characteristics known as MXenes have turned out to be a hot research topic. Recent studies increasingly focus on the structure–property relationships of MXenes and their hybrid formations with other materials. The exfoliation and delamination of MXenes using various agents is gaining attention, while their application in functional composites presents another exciting research direction. However, the exfoliation of multi‐layered MXene into few‐layered nanosheets using bio‐based agents remains underexplored. In this study, tannic acid (TA) is employed as a bio‐exfoliating agent to delaminate Ti3C2Tx MXene, while optimizing the ratio of TA to achieve efficient exfoliation and dye adsorption. The MXene/TA composites demonstrated a maximum adsorption capacity of 187.264 mg/g and a removal efficiency of 93.69% for methylene blue (MB) in water, in accordance with the Langmuir isotherm model. Furthermore, MB adsorption caused MXene to coagulate into floccules, enabling easy removal via filtration. The study highlights the trifold role of tannic acid in MXene as a delaminating, antimicrobial, and adsorption‐enhancing agent, creating a multifunctional MXene‐tannic acid system. It introduces a new class of hybrid materials with effective applications in water purification. Additionally, incorporating this hybrid material into polymers can fine‐tune their properties, leveraging the synergistic effects of the trio to develop high‐performance smart polymer composites for diverse applications.Highlights Synthesis of MXene from Ti3C2Tx Optimization of the delamination efficiency of the biomolecule tannic acid Characterization of tannic acid‐MXene delaminated composites Analysis of the antibacterial efficiency of tannic acid delaminated MXene Investigation of water purification efficiency of delaminated MXene

Graphene oxide in palladium nanoparticle (GrafeoPlad): A new class of functional materials

Water-soluble graphene oxide was encapsulated within the lattice of Pd nanoparticles using Zn as reducing agent affording a completely new class of functional materials dubbed herein “GrafeoPlad” for designating platinum-group metals doped with 3D entrapped graphene oxide. The first application of this new metal-organic alloy reported herein is in catalysis to convert nitrobenzene to analine with hydrazine as reducing agent at room temperature. GrafeoPlad-Pd is significantly more stable than Pd black showing that the entrapment of GO molecules in the nanoparticle lattice largely improves both its catalytic activity and stability against catalytic deactivation. This new class of hybrid materials may open practically relevant new avenues in many areas of today's material science and technology.

Silk Fibroin-Coated Nano-MOFs Enhance the Thermal Stability and Immunogenicity of HBsAg.

Vaccines are widely regarded as one of the most effective weapons in the fight against infectious diseases. Currently, vaccines must be stored and transported at low temperatures as high temperatures can lead to a loss of vaccine conformation and reduced therapeutic efficacy. Metal-organic frameworks (MOFs), such as zeolitic imidazole framework-8 (ZIF-8), are a new class of hybrid materials with large specific surface areas, high loading rates, and good biocompatibility and are successful systems for vaccine delivery and protection. Silk fibroin (SF) has a good biocompatibility and thermal stability. In this study, the hepatitis B surface antigen (HBsAg) was successfully encapsulated in ZIF-8 to form HBsAg@ZIF-8 (HZ) using a one-step shake and one-pot shake method. Subsequently, the SF coating modifies HZ through hydrophobic interactions to form HBsAg/SF@ZIF-8 (HSZ), which enhanced the thermal stability and immunogenicity of HBsAg. Compared to free HBsAg, HZ and HSZ improved the thermostability of HBsAg, promoted the antigen uptake and lysosomal escape, stimulated dendritic cell maturation and cytokine secretion, formed an antigen reservoir to promote antibody production, and activated CD4+ T and CD8+ T cells to enhance memory T-cell production. Importantly, HSZ induced a strong immune response even after 14 days of storage at 25 °C. Furthermore, the nanoparticles prepared by the one-step shake method exhibited superior properties compared to those prepared by the one-pot shake method. This study highlights the importance of SF-coated ZIF-8, which holds promise for investigating thermostable vaccines and breaking the vaccine cold chain.

Translational applications of magnetic nanocellulose composites.

Nanocellulose has emerged as a potential 'green' material owing to its inimitable properties. Furthermore, the significant development in technology has facilitated the design of multidimensional nanocellulose structures, including one-dimensional (1D: microparticles and nanofibers), two-dimensional (2D: coatings), and three-dimensional (3D: hydrogels/ferrogels) composites. In this case, nanocellulose composites blended with magnetic nanoparticles represent a new class of hybrid materials with improved biocompatibility and biodegradability. The application field of magnetic nanocellulose composites (MNCs) ranges from biomedicine and the environment to catalysis and sensing. In this review, we present the major applications of MNCs, emphasizing their innovative benefits and how they interconnect with translational applications in clinics and the environment. Additionally, we focus on the synthesis techniques and role of different additives in the fabrication of MNCs for achieving extremely precise and intricate tasks related to real-world applications. Subsequently, we reveal the recent interdisciplinary research on MNCs and discuss their mechanical, tribological, electrochemical, magnetic, and biological phenomena. Finally, this review concludes with a portrayal of computational modelling together with a glimpse of the various translational applications of MNCs. Therefore, it is anticipated that the current review will provide the readers with an extensive opportunity and a more comprehensive depiction related to the types, properties, and applications of MNCs.

Geopolymer Based Electrodes as New Class of Material for Electrochemical CO2 Reduction

AbstractTo achieve a successful transition to a sustainable carbon and energy management, it is essential to both reduce CO2 emissions and develop new technologies that utilize CO2 as a starting substrate. In this study, we demonstrate for the first‐time the functionalization of geopolymer binder (GP) with Sn for electrochemical CO2 reduction (eCO2RR) to formate. By substituting cement with Sn‐GP, we have merged CO2 utilisation and emission reduction. Using a simple mixing procedure, we were able to obtain a pourable mortar containing 5 vol. % Sn‐powder. After hardening, the Sn‐GP electrodes were characterized for their mechanical and CO2 electrolysis performance. In 10 h electrolyses, formate concentrations were as high as 22.7±0.9 mmol L−1 with a corresponding current efficiency of 14.0±0.5 % at a current density of 20 mA cm−2. Our study demonstrates the successful design of GP‐electrodes as a new class of hybrid materials that connect eCO2RR and construction materials.

Environmentally-stable eco-friendly pectin-silica bio-hybrid foams for soil remediation

Here we present a new class of hybrid material composed of a polysaccharide macroporous core surrounded by a thin silica layer as new adsorption platforms for the retention of organic pollutants in soil media. The core-shell hybrid foams were fabricated by ice-templating to create highly anisotropic pectin foams, followed by vapor phase silica deposition. The structural stability of the hybrid foams was tested in compression, reaching a Young's Modulus up to 5 MPa, but also, and more importantly, in direct contact with wet soils over more than one month. Hybrid foams showed a sorption capacity for a toxic dye nearly two orders of magnitude higher than the surrounding soils. Altogether, these hybrid foams combine all chemical, structural and functional properties required to be effective materials for soil depollution and, thanks to their easy-recovery, should compete with common particulate sorbents.

Lateral stability analysis of thin-walled fiber-metal laminate beam with varying cross-section by considering nonlinear strains

Fiber metal laminates (FMLs) are a new class of hybrid materials that consist of thin metal sheets and fiber reinforced epoxy composite layers. Due to their significant characteristics, FMLs have been widely employed in a variety of engineering applications specifically aerospace industry. In this paper, the lateral-torsional buckling behavior of thin-walled FML beams with varying I-section is perused using an innovative and accurate methodology. Considering the coupling between the bending displacements and the twist angle, the system of lateral stability equations are derived via energy method in association with Vlasov’s model for thin-walled beam and the classic lamination theory. By uncoupling the equilibrium differential equations, the system of governing equations is transformed to a fourth-order differential equation in terms of the twist angle. The differential quadrature method is then applied to solve the resulting equation and to acquire the lateral buckling loads. The accuracy of the proposed methodology has been investigated by comparing the results with the outcomes obtained using ANSYS finite element software. In the following, the effect of significant parameters such as stacking sequence, fiber angle, fiber type, web tapering ratio, load height parameter and volume fraction of metal on lateral buckling load of fixed-free FML tapered I-beam under uniformly distributed load has been investigated.

DNA Origami Meets Polymers: A Powerful Tool for the Design of Defined Nanostructures.

The combination of DNA origami nanostructures and polymers provides a new possibility to access defined structures in the 100 nm range. In general, DNA origami serves as a versatile template for the highly specific arrangement of polymer chains. Polymer‐DNA hybrid nanostructures can either be created by growing the polymer from the DNA template or by attaching preformed polymers to the DNA scaffold. These conjugations can be of a covalent nature or be based on base‐pair hybridization between respectively modified polymers and DNA origami. Furthermore, the negatively charged DNA backbone permits interaction with positively charged polyelectrolytes to form stable complexes. The combination of polymers with tuneable characteristics and DNA origami allows the creation of a new class of hybrid materials, which could offer exciting applications for controlled energy transfer, nanoscale organic circuits, or the templated synthesis of nanopatterned polymeric structures.

PDMS-urethanesil hybrid multifunctional materials: combining CO2 use and sol–gel processing

CO2 mitigation by cycloaddition to bis-epoxides to obtain bis-cyclocarbonates (CC) paved one way to a new class of polyurethanes (PUs), the non-isocyanate polyurethanes (NIPUs). By using molecules functionalized with alkoxysilyl groups as end chain it is possible to obtain hybrid NIPUs, also called urethanesils, by sol–gel chemistry. Using bis-cyclocarbonate polydimethylsiloxane (CCPDMS) with proper diamines and end-chain amino silanes followed by sol–gel processing leads to versatile hybrid non-isocyanate polydimethylsiloxane urethanes (PDMS-urethanesil). This review reports—besides our recent studies about PDMS-urethanesil materials—the sol–gel chemistry applied to synthesize urethanesil and its applications. While the antimicrobial, photochromic, and anticorrosion properties of urethanesil loaded with phosphotungstic acid as well as the luminescent effect of material loaded with Eu3+ have already been reported, antimicrobial features of urethanesil loaded with phosphoric acid are our newest findings which we herein report for the first time. The impact of the inorganic acid used on the sol–gel process is highlighted together with the importance of antibiofouling properties. Although the antibiofouling mechanism is still under investigation, the broad spectrum of action of phosphoric acid-loaded urethanesil is worth mentioning, since it has been tested to be efficient against some pathogenic bacteria including a drug resistant Staphylococcus aureus strain as well as pathogenic fungi and yeast. Due to the simple, straightforward, and highly reproducible synthesis as well as the opportunity to obtain versatile materials with tuneable mechanical and physical properties, this new class of hybrid materials promises to be applicable in different industrial fields.

Improving the damping behavior of fiber-reinforced polymer composites with embedded superelastic shape memory alloys (SMA)

One-way shape memory alloy wires exhibiting super elastic properties are capable of generating high recovery stresses under constrained conditions upon external mechanical loading. In the present work, the damping response of hybrid composite materials enhanced with super-elastic NiTi alloy wires is examined. The studied system consisted of an aramid reinforced epoxy resin composite in which NiTi wires have been embedded. By conducting damping measurements it was found that the addition of Ni–Ti wires into the aramid/epoxy composite leads to a significant modification of its damping which depends strongly on wire volume fraction. This paves the way for the design of a new class of hybrid materials that combine the stiffness and strength of reinforcing fibers with the increased damping tuning capability offered by the NiTi wires.

Coordination polymer-derived CuO catalysts for oxidative degradation of methylene blue

Coordination polymers (CP) are a new class of hybrid materials consisting of metal clusters connected by organic ligands and forming structures along one, two or three dimensions. Three Cu2+ coordination polymers Cu(1,3-BDC).3H2O, Cu(1,4-BDC), and Cu(5-NH2-1,3-BDC) (BDC = benzenedicarboxylic) were prepared via an electrochemical method and used as precursors for CuO by calcination in air at 650 °C. All the prepared samples were characterized by Powder X-ray Diffraction (PXRD), Attenuated Total Reflectance Fourier Transform Infrared spectroscopy (ATR-FTIR), Thermal Analysis (TGA-DTA), and Scanning Electron Microscopy (SEM). The results confirmed both the crystallization of the CPs and the formation of copper oxide after the thermal treatment. The CP-derived CuO was tested in the catalytic degradation of the methylene blue in the presence of H2O2, and the effect of reaction parameters such as the mass of catalyst and volume of H2O2 were studied. Cu(1,4-BDC)-derived CuO catalyst showed discoloration efficiency about 92% at 308 K, and 100% at 331 K after 120 and 30 min, respectively with good recyclability up to the four cycles (71.77%).

Hierarchical design of Cu-Ni(OH)2/Cu-MnxOy core/shell nanosheet arrays for ultra-high performance of asymmetric supercapacitor

Supercapacitors lack high energy density and long term stability, so a new class of hybrid material with hierarchical structure is desirable. Herein, for the first time we are reporting a rational design of hierarchical Cu-Ni(OH)2/Cu-MnxOy core/shell nanosheet arrays. The Cu-Ni(OH)2/Cu-MnxOy nanosheet arrays were synthesized by a two-step hydrothermal reaction. The as-synthesized Cu-Ni(OH)2/Cu-MnxOy hybrid structure exhibits ultrahigh areal and specific capacitances of 10.14 F cm−2 and 2535 F g−1, respectively at 3 mA cm−2. The electrode exhibits high rate-capability (59.37%) and excellent capacitance retention of 93.09% after 10 000 cycles. In Cu-Ni(OH)2/Cu-MnxOy core/shell hybrid structure, highly conductive and electroactive Cu-Ni(OH)2 core and Cu-MnxOy shell components played a vital role to develop a high-performance and stable electrode material. Furthermore, the unique porous structure of Cu-Ni(OH)2/Cu-MnxOy also provides enough space and short-diffusion lengths for Faradaic reaction. The asymmetric supercapacitors assembled of Cu-Ni(OH)2/Cu-MnxOy as positive electrode and GR/CNTs as negative electrode delivers a high specific capacitance of 267.15 F g−1 at a current density of 1 A g−1 with high-rate capability of 60.30%. Moreover, the as-assembled ASC device also shows an ultra-high energy density of 94.98 W h kg−1 at a power density of 759.89 W kg−1 and a maximum power density of 15 173.5 W kg−1 at an energy density of 57.28 W h kg−1 with capacitance retention of 89.79% after 10 000 cycles. These outstanding results suggest that Cu-Ni(OH)2/Cu-MnxOy hybrid structure can be considered as a cathode material for asymmetric supercapacitor in future.

New Class of Hybrid Materials for Detection, Capture, and "On-Demand" Release of Carbon Monoxide.

Carbon monoxide (CO) is both a substance hazardous to health and a side product of a number of industrial processes, such as methanol steam reforming and large-scale oxidation reactions. The separation of CO from nitrogen (N2) in industrial processes is considered to be difficult because of the similarities of their electronic structures, sizes, and physicochemical properties (e.g., boiling points). Carbon monoxide is also a major poison in fuel cells because of its adsorption onto the active sites of the catalysts. It is therefore of the utmost economic importance to discover new materials that enable effective CO capture and release under mild conditions. However, methods to specifically absorb and easily release CO in the presence of contaminants, such as water, nitrogen, carbon dioxide, and oxygen, at ambient temperature are not available. Here, we report the simple and versatile fabrication of a new class of hybrid materials that allows capture and release of carbon monoxide under mild conditions. We found that carborane-containing metal complexes encapsulated in networks made of poly(dimethylsiloxane) react with CO, even when immersed in water, leading to dramatic color and infrared signature changes. Furthermore, we found that the CO can be easily released from the materials by simply dipping the networks into an organic solvent for less than 1 min, at ambient temperature and pressure, which not only offers a straightforward recycling method, but also a new method for the "on-demand" release of carbon monoxide. We illustrated the utilization of the on-demand release of CO from the networks by carrying out a carbonylation reaction on an electron-deficient metal complex that led to the formation of the CO-adduct, with concomitant recycling of the gel. We anticipate that our sponge-like materials and scalable methodology will open up new avenues for the storage, transport, and controlled release of CO, the silent killer and a major industrial poison.

Fabrication and Characterization of Hybrid Organic-Inorganic Electron Extraction Layers for Polymer Solar Cells toward Improved Processing Robustness and Air Stability.

Organic-inorganic hybrid materials composed of bismuth and diaminopyridine are studied as novel materials for electron extraction layers in polymer solar cells using regular device structures. The hybrid materials are solution processed on top of two different low band gap polymers (PTB7 or PTB7-Th) as donor materials mixed with fullerene PC70BM as the acceptor. The intercalation of the hybrid layer between the photoactive layer and the aluminum cathode leads to solar cells with a power conversion efficiency of 7.8% because of significant improvements in all photovoltaic parameters, that is, short-circuit current density, fill factor, and open-circuit voltage, similar to the reference devices using ZnO as the interfacial layer. However when using thick layers of such hybrid materials for electron extraction, only small losses in photocurrent density are observed in contrast to the reference material ZnO of pronounced losses because of optical spacer effects. Importantly, these hybrid electron extraction layers also strongly improve the device stability in air compared with solar cells processed with ZnO interlayers. Both results underline the high potential of this new class of hybrid materials as electron extraction materials toward robust processing of air stable organic solar cells.

Magnetorheological technology for fabricating tunable solid electrolyte with enhanced conductivity and mechanical property

Ionogels are a new class of hybrid materials where ionic liquids are immobilized by macromolecular support. The excessive amount of crosslinking polymer enhances the mechanical strength but compromises the conductivity. Here, we report an elastomeric magnetorheological (MR) ionogel with an enhanced conductivity and mechanical strength as well. Following the application of magnetic nanoparticles into an ionic liquid containing minimum cross-linking agent, the formation, thus physical properties, of MR ionogels are co-controlled by simultaneously applied UV light and external magnetic field. The application of MR ionogels as solid electrolytes in supercapacitors is also demonstrated to study electrochemical performance. This work opens a new avenue to synthesize robust ionogels with the desired conductivity and controllable mechanical properties for soft flexible electronic devices. Besides, as a new class of conductive MR elastomers, the proposed MR ionogel also possesses the potential for engineering applications, such as sensors and actuators.

Photophysics behind highly luminescent two-dimensional hybrid perovskite (CH3(CH2)2NH3)2(CH3NH3)2Pb3Br10 thin films

Two-dimensional (2D) Ruddlesden–Popper perovskites have emerged as a new class of hybrid materials with high photoluminescence and improved stability compared to their three-dimensional (3D) counterparts.

π‐Conjugated Organosilica Semiconductors: Toward Robust Organic Electronics

The use of novel organosilica materials embedding π‐conjugated moieties as semiconductor into field‐effect transistors is demonstrated. The chosen π‐conjugated core is a [1]benzothieno[3,2‐b][1]benzothiophene that is modified with hydrolyzable and crosslinkable triethoxysilyl moieties. After polycondensation, this compound forms a hybrid material composed of charge transport pathways as well as insulating sublayers made of silicon oxide (SiOx). The hybrid material behaves as a semiconductor and is subsequently integrated as active layer into field‐effect transistors. These precursors show J‐type aggregation that evolves toward H‐type aggregates during the sol–gel process, which improve charge transport. Taking advantage of the sol–gel chemistry involved here, hybrid field‐effect transistors that are fully crosslinked with covalent bonds are built. Molecules are crosslinked to each other, covalently bonded to the silicon oxide dielectric, and also covalently bonded to the gold electrodes, thanks to the use of an appropriate additional interfacial monolayer. This is the first report of fully covalent transistors. Those devices with modest mobilities show impressive resilience against polar, aliphatic, and aromatics solvents even under sonication. This study opens the route toward a new class of hybrid materials to create highly robust electronic applications.

Analysis of tricyclic antidepressants in human plasma using online-restricted access molecularly imprinted solid phase extraction followed by direct mass spectrometry identification/quantification

The use of a new class of hybrid materials, called restricted access molecularly imprinted polymers (RAMIPs) seems to present a good strategy for the sample preparation of complex matrices, since these materials combine good protein elimination capacity with high degree selectivity. Mass spectrometers (MS) have been successfully used for polar drug identification and quantification. In order to combine the advantages of both RAMIPs and mass spectrometry, we proposed a study that joins these properties in a single system, where we could analyse tricyclic antidepressants from human plasma, without offline extraction or chromatographic separation. A RAMIP for amitriptyline was synthesised by the bulk method, using methacrylic acid as a functional monomer and glycidilmethacrylate as a hydrophilic co-monomer. Then, epoxide ring openings were made and the polymer was covered with bovine serum albumin (BSA). A column filled with RAMIP-BSA was coupled to a MS/MS instrument in an online configuration, using water as loading and reconditioning mobile phase and a 0.01% acetic acid aqueous solution: acetonitrile at 30:70 as elution mobile phase. The system was used for on-line extraction and simultaneous quantification of nortriptyline, desipramine, amitriptyline, imipramine, clomipramine and clomipramine-d3 (IS) (from 15.0 to 500.0μgL−1) from plasma samples. The correlation coefficient was higher than 0.99 for all analytes. The CV (coefficient of variation) values ranged from 1.34% to 19.13% for intra assay precision and 1.32–19.77% for inter assay precision. The E% (relative error) values ranged from −19.15% to 19.51% for intra assay accuracy and from −9.04% to 16.22% for inter assay accuracy.

Decoupling the contributions of constituent layers to the strength and ductility of a multi-layered steel

Multi-layered steel (MLS) consisting of alternating soft/ductile austenitic and hard/brittle martensitic stainless steel layers is a new class of hybrid material for structural application as it offers excellent combinations of strength and ductility. In this study, the contributions of each of the constituent layers to the overall strength and ductility of an MLS (having tensile strength > 1.4 GPa and ductility > 20%) were examined by recourse to nanoindentation experiments on each of them. By adapting two different indenter tip radii for the spherical nanoindentation experiments, constituent layers' stress-strain responses within the plastic regime were obtained and then compared with the macroscopic flow curve of the MLS that was obtained through tensile tests, to show that the strength contributions of the constituent steels to the global strength of MLS is as per the rule of mixtures. In order to examine the sources of tensile ductility of the MLS, sharp tip nanoindentation experiments were conducted on specimens extracted from tensile coupons that were subjected to predetermined plastic strains a priori. Results of these experiments show that the tensile failure occurs at a strain at which hardness of the austenitic layer, which is found to be dependent on the prior-plastic strain, is almost equal to the strain-independent hardness of the martensitic layer. The results are discussed in terms of martensitic transformation within austenitic layer and the role of the mechanical environment change imposed by the neighboring martensite layers on it.

Ag-catalyzed InAs nanowires grown on transferable graphite flakes

Semiconducting nanowires grown by quasi-van-der-Waals epitaxy on graphite flakes are a new class of hybrid materials that hold promise for scalable nanostructured devices within opto-electronics. Here we report on high aspect ratio and stacking fault free Ag-seeded InAs nanowires grown on exfoliated graphite flakes by molecular beam epitaxy. Ag catalyzes the InAs nanowire growth selectively on the graphite flakes and not on the underlying InAs substrates. This allows for easy transfer of the flexible graphite flakes with as-grown nanowire ensembles to arbitrary substrates by a micro-needle manipulator. Besides the possibilities for fabricating novel nanostructure device designs, we show how this method is used to study the parasitic growth and bicrystal match between the graphite flake and the nanowires by transmission electron microscopy.