Nanostructured Hybrid Materials Research Articles

Zeolite-Like Boron Imidazolate Frameworks (BIFs): Synthesis and Application

This review is devoted to discussion of the latest advances in design and applications of boron imidazolate frameworks (BIFs) that are a particular sub-family of zeolite-like metal–organic frameworks family. A special emphasis is made on nanostructured hybrid materials based on BIF matrices and their modern applications, especially in environment remediation and energy conversion.

Crystallization vs Metal Chelation: Solution Self-Assembly of Dual Responsive Block Copolymers

We herein report the synthesis and characterization of dual stimuli-responsive poly(2-iso-propyl-2-oxazoline)-block-poly(2-acrylamido glycolic acid) (PiPrOx-b-PAGA) double hydrophilic block copolymers (BCPs) by an effective combination of ring-opening and reversible addition–fragmentation chain transfer (RAFT) polymerization. The resulting materials are responsive toward several external triggers: (1) the PiPrOx segment undergoes a coil-to-globule transition upon heating above the cloud point temperature (TCP), (2) the PAGA block chelates M2+ metal ions and provides straightforward access to nanostructured hybrid materials, and (3) prolonged heating above the TCP for PiPrOx enables crystallization-driven solution self-assembly (CDSA) toward anisotropic micelles and superstructures. We are further able to show that the cloud point temperature (TCP) of PiPrOx-b-PAGA micelles can be tuned from ∼30 to 68 °C by varying either the BCP composition (PiPrOx to PAGA ratio) or by the amount of metal ions being present. The different aggregates were characterized by transmission electron microscopy (TEM), wide-angle X-ray scattering (WAXS), and dynamic light scattering (DLS). Our results indicate that micellar size, shape, and TCP are closely connected to BCP composition and the nature of chelated metal ions. In our opinion, such inorganic–organic hybrid materials are of interest with regard to (photo)catalysis, as sensors, or as potential drug delivery systems.

Synthesis, charaterization and optical properties of nanostructured silica hybrid materials obtained by soft chemistry from perhydropolysilazane/1,2,4-triazole precursors

Nanostructured silica hybrid materials have been synthesized via soft chemistry way, by the incorporation of functional 1,2,4-triazole components into a silica network, using a perhydropolysilazane (PHPS) as a silica source and 1,2,4-triazole components as templates. The compositions, morphological and textural properties of the as-synthesized samples have been studied by 13C and 29Si CP MAS NMR, FTIR and SEM. The spectroscopy results suggest that the organic moieties have been chemically linked to the silica skeleton leading to hybrid materials in which Si–N, Si–O and Si–S bridges are created. Nitrogen adsorption-desorption analysis (BET) shows that the surface area varied between 385 and 425 m2 g−1. The 29Si CP-MAS NMR displays signals between -70 and -120 ppm corresponding to Q2, Q3 and Q4 units. The optical properties have been studied also by UV–visible diffuse reflection spectroscopy and photoluminescence (PL). This study reveals that the direct gap energies varied between 0.71 and 2.53 eV. Photoluminescence shows that the silica nanohybrids are suitable to the emission of blue light with wavelength (λem) values of about 470-480 nm. The PL emission results also from some silicon/oxygen-related defect species.

Recent Trends in Electrochemical Sensors for Vital Biomedical Markers Using Hybrid Nanostructured Materials.

This work provides a succinct insight into the recent developments in electrochemical quantification of vital biomedical markers using hybrid metallic composite nanostructures. After a brief introduction to the biomarkers, five types of crucial biomarkers, which require timely and periodical monitoring, are shortlisted, namely, cancer, cardiac, inflammatory, diabetic and renal biomarkers. This review emphasizes the usage and advantages of hybrid nanostructured materials as the recognition matrices toward the detection of vital biomarkers. Different transduction methods (fluorescence, electrophoresis, chemiluminescence, electrochemiluminescence, surface plasmon resonance, surface‐enhanced Raman spectroscopy) reported for the biomarkers are discussed comprehensively to present an overview of the current research works. Recent advancements in the electrochemical (amperometric, voltammetric, and impedimetric) sensor systems constructed with metal nanoparticle‐derived hybrid composite nanostructures toward the selective detection of chosen vital biomarkers are specifically analyzed. It describes the challenges involved and the strategies reported for the development of selective, sensitive, and disposable electrochemical biosensors with the details of fabrication, functionalization, and applications of hybrid metallic composite nanostructures.

Evaluation of Nickel Neurotoxicity and High Sorption through a Hybrid Yeast / Silsesquioxane Material

The presence of heavy metals in water is one of the major concerns in the public health area. So, the characterization of inorganic compounds toxicity and their detection, speciation and removal are some of the biggest environmental challenges today. Within this context, the present work evaluated the effect caused by Ni2+ in neuronal autofluorescence recorded in brain slices. Besides, a bioinorganic nanostructured hybrid material with great potential for heavy metals removal: yeast Saccharomyces cerevisiae modified with Silsesquioxane was applied for Ni2 sorption. The neurotoxicity tests revealed that in the presence of Ni2+ concentrations of 10, 20 and 30 μM (0.5, 1.0 and 1.5 ppm), irreversible autofluorescence changes occurred. In the sorption tests, the hybrid material revealed a maximum capacity of sorption of 64.6 mg/g. This material was able to reach 77.7% of removal of the initial Ni2+ solution using a 100 cm3/g liquid/solid ratio, at pH 6 and 15 min of contact time.

Development of inorganic-organic hybrid nanostructured material for H2O2 sensing application

An organic-inorganic hybrid nanoparticle (HNPs) composed of Sm(TTA)3Phen, a coordination compound, and NaY0.78Er0.02Yb0.20F4, an upconversion nanoparticles (UCNPs), has been developed and used for H2O2 sensing application. Herein, Sm(TTA)3Phen absorbs ultraviolet (UV) light and gives fluorescence in yellow-red-near infrared (NIR) region. Whereas, the UCNPs absorb NIR radiations (980 nm) and consequently emit in green-red region through photon upconversion process. Two important optical phenomena are observed when HNPs are simultaneously excited with UV (266 nm) and NIR (980 nm) laser radiation- (i) an energy transfer from Sm3+ to Er3+ ions, and (ii) color tunable emission from red to green, if the power of 980 nm laser is varied. Further, the material is highly competent to sense H2O2 through fluorescence quenching of Sm3+ emission in presence of H2O2. The nature of quenching is conspicuously different for different concentration/volume range of H2O2. For lower volume range, the rate of decrease of emission/excitation intensity is linear, while for higher volume range the decay in intensity is exponential. The attained minimum detection limit for H2O2 is 2 μl, which is significant for sensing applications.

Pioglitazone-Loaded Nanostructured Hybrid Material for Skin Ulcer Treatment.

Pioglitazone, a popular antidiabetic drug, which was recently shown to be effective in the treatment of skin ulcers, was successfully encapsulated in polysaccharide nanoparticles and used as a bioactive component of the wound-dressing material based on modified bacterial nanocellulose. Alginate and hydroxypropyl cellulose were used as a matrix for the nanoparticulate drug-delivery system. The matrix composition and particles’ size, as well as drug encapsulation efficiency and loading, were optimized. Pioglitazone hydrochloride (PIO) loaded particles were coated with chitosan introduced into the crosslinking medium, and covalently attached to the surface of bacterial nanocellulose functionalized with carboxyl groups. PIO was released from the surface of the hybrid material in a controlled manner for 5 days. Preliminary cytotoxicity studies confirmed safety of the system at PIO concentrations as high as 20 mg/mL. The obtained hybrid system may have potential application in the treatment of skin ulcers e.g., in diabetic foot.

Development and characterisation of a nanostructured hybrid material with vitamin B12 and bagasse-derived activated carbon for anaerobic chlordecone (Kepone) removal.

Intensive use of the chlorinated pesticide chlordecone from the 1970s to 1993 to prevent crop damage in banana plantations of Guadeloupe and Martinique led to diffuse pollution of soils and surface waters, affecting both fauna and human beings in the contaminated areas. Since 2001, drinking water production plants have been equipped with filters containing activated carbon that must be treated after saturation. The objective of this work is to produce a hybrid material composed of activated carbon and vitamin B12 (VB12) for the degradation of chlordecone (CLD). The preparation of such a hybrid material is carried out by non-covalent fixation to achieve an eco-friendly solution for the serious environmental problem of contamination by chlorinated pesticides. It is thus proposed to degrade CLD by a physico-chemical treatment allowing salvage of the catalyst, which is adsorbed on the carbon surface to generate less waste that is inexpedient to treat. Activated carbon (AC) is produced locally from available sugarcane bagasse subjected to phosphoric acid activation. The main characteristics of this material are a major mesoporous structure (0.91%) and a specific (BET) surface area ranging from 1000 to 1500m2g-1. The experimental results showed that BagP1.5 has a high adsorption capacity for VB12 due to its large surface area (1403m2g-1). The binding of VB12 to the bagasse-derived AC is favoured at high temperatures. The adsorption is optimal at a pH of approximately 6. The maximum adsorption capacity of VB12 on the AC, deduced from the Langmuir model, was 306mgg-1, confirming the high affinity between the two components. The hybrid material was characterised by FTIR, Raman, X-ray fluorescence spectroscopy and SEM analysis. CLD removal by this hybrid material was faster than that by VB12 or BagP1.5 alone. The CLD degradation products were characterised by mass spectrometry.

Carbon nanotube/ZnO nanowire/polyvinylidene fluoride hybrid nanocomposites for enhanced electromagnetic interference shielding

AbstractLightweight and flexible materials with high conductivity and low thickness are highly desirable for electromagnetic interference (EMI) shielding applications. Developing hybrid nanostructured materials, which combine the properties of their constituents, is an excellent strategy to create highly effective EMI shields. In this study, we report a hybrid polymer nanocomposite composed of carbon nanotube (CNT) and ZnO nanowire (ZnONW) for EMI shielding applications. We found that the combination of a conductive filler (CNT) and a dielectric filler (ZnONW) with a similar geometry is an effective method to fabricate nanocomposites with enhanced EMI shielding. We achieved high average shielding effectiveness of 27.3 dB (with a maximum of 41 dB at 10.2 GHz) for a sample of CNT:ZnONW (5.0:2.5 wt%) with only 1.1 mm thickness, which is among the best‐reported values in the literature for polymer nanocomposites with similar filler loading and thickness. This performance originates from the excellent electrical conductivity and dielectric properties of hybrid nanocomposites, combined with the geometry of ZnO nanowire. A comparison of the shielding properties of the developed hybrid nanocomposites with the literature implies that they are promising functional materials in the world of EMI shielding applications.

Hybrid 2D nanofibers based on poly(ethylene oxide)/polystyrene matrix and poly(ferrocenylphosphinoboranes) as functional agents

AbstractTemplate smart inorganic polymers within an organic polymeric matrix to form hybrid nanostructured materials are a unique approach to induce novel multifunctionality. In particular, the fabrication of one‐dimensional materials via electrospinning is an advanced tool, which has gained success in fulfilling the purpose to fabricate two‐dimensional nanostructured materials. We have explored the formation of novel hybrid nanofibers by co‐spinning of poly(ferrocenylphosphinoboranes) Fe A [{Fe(C5H5)(C5H4CH2PHBH2)} n] and Fe B [{Fe(C5H5)(C5H4PHBH2)} n] with poly(ethylene oxide) (PEO) and polystyrene (PS). Fe A and Fe B contain main‐group elements and a ferrocene moiety as pendent group and have different properties compared to their only carbon‐containing counterparts. The use of PEO and polystyrene provided a matrix to spin those inorganic polymers as hybrid nanofibers which were collected in the form of a nonwoven mat. They were characterized by multinuclear NMR spectroscopy, scanning electron microscopy (SEM), and IR spectroscopy. Thermal properties of the polymers have been checked by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). 1H, 31P, and 11B NMR and IR spectroscopy revealed the nature and types of interactions of the components after co‐spinning. The SEM micrographs identify the underlying unidirectional morphology of the generated hybrid nanofibers. Nonetheless, the DSC and TGA confirmed the significant boost toward the thermal stability of the resultant multifunctional fibers. It is believed that these unique types of multifunctional electrospun nanofibers will open new avenues toward the next generation of miniaturized devices.

Influence of the Synthesis Route on the Properties of Hybrid NiO-MnCo2 O4 -Ni6 MnO8 Anode Materials and their Electrochemical Performances.

New materials with different morphologies, nanostructures, and components can have structural advantages for application in materials science. Multicomponent-active hybrid nanostructured materials are among the best candidates for application in electrode materials. Spray pyrolysis and solvothermal synthesis are two popular methods for the preparation of multicomponent-active hybrid nanostructured materials. In this study, the two types of NiO-MnCo2 O4 -Ni6 MnO8 hybrid anode materials for use in lithium-ion batteries were synthesized by two different methods (spray pyrolysis and solvothermal synthesis), and the differences in their physical and electrochemical properties were compared. The two types of anode material exhibited the same hierarchical hybrid composition, but some different physical characteristics, which affected their electrochemical performance.

Highly Efficient Energy Transfer from Fluorescent Gold Nanoclusters to Organic J-Aggregates

With an aim to understand the interaction between the inorganic and organic components in inorganic–organic hybrid nanostructured materials, we have designed and developed an inorganic–organic nano...

Photosensitive Hybrid Nanostructured Materials: The Big Challenges for Sunlight Capture

Solar radiation is becoming increasingly appreciated because of its influence on living matter and the feasibility of its application for a variety of purposes. It is an available and everlasting natural source of energy, rapidly gaining ground as a supplement and alternative to the nonrenewable energy feedstock. Actually, an increasing interest is involved in the development of efficient materials as the core of photocatalytic and photothermal processes, allowing solar energy harvesting and conversion for many technological applications, including hydrogen production, CO2 reduction, pollutants degradation, as well as organic syntheses. Particularly, photosensitive nanostructured hybrid materials synthesized coupling inorganic semiconductors with organic compounds, and polymers or carbon-based materials are attracting ever-growing research attention since their peculiar properties overcome several limitations of photocatalytic semiconductors through different approaches, including dye or charge transfer complex sensitization and heterostructures formation. The aim of this review was to describe the most promising recent advances in the field of hybrid nanostructured materials for sunlight capture and solar energy exploitation by photocatalytic processes. Beside diverse materials based on metal oxide semiconductors, emerging photoactive systems, such as metal-organic frameworks (MOFs) and hybrid perovskites, were discussed. Finally, future research opportunities and challenges associated with the design and development of highly efficient and cost-effective photosensitive nanomaterials for technological claims were outlined.

Hybrid Nanostructured Magnetite Nanoparticles: From Bio-Detection and Theragnostics to Regenerative Medicine

Nanotechnology offers the possibility of operating on the same scale length at which biological processes occur, allowing to interfere, manipulate or study cellular events in disease or healthy conditions. The development of hybrid nanostructured materials with a high degree of chemical control and complex engineered surface including biological targeting moieties, allows to specifically bind to a single type of molecule for specific detection, signaling or inactivation processes. Magnetite nanostructures with designed composition and properties are the ones that gather most of the designs as theragnostic agents for their versatility, biocompatibility, facile production and good magnetic performance for remote in vitro and in vivo for biomedical applications. Their superparamagnetic behavior below a critical size of 30 nm has allowed the development of magnetic resonance imaging contrast agents or magnetic hyperthermia nanoprobes approved for clinical uses, establishing an inflection point in the field of magnetite based theragnostic agents.

Construction of T-Nb2O5 nanoparticles on/in N-doped carbon hollow tubes for Li-ion hybrid supercapacitors

In recent years, hybrid supercapacitors (HSCs) with good characteristics of both lithium batteries (LIBs) and supercapacitors (SCs) have become a hot research topic to meet the growing market demand for electric and hybrid electric vehicles. The key for high-performance HSCs is the reaction kinetics imbalance between the slow faradaic intercalation anode and fast non-faradaic physical adsorption/desorption cathode. Herein, we simultaneously grow ultrafine Nb2O5 nanoparticles on the inner walls and outer surface of hollow heteroatomic (N) carbon tube, giving a unique hierarchical hybrid nanostructure materials named T-Nb2O5@NC. The LIB test show its excellent high-rate capability and long-term cyclic stability. At current density of 0.25C (1.0–3.0 V, vs Li/Li+), the reversible specific capacity of this material is up to 194 mAh g−1. Importantly, the HSC device, assembled by T-Nb2O5@NC as anode and commercial activated carbon as cathode with an organic electrolyte, exhibits good electrochemical performance, including high energy density (49.7 Wh kg−1) and power density (8750 W kg−1), obviously superior to traditional HSC electrode materials. The results prove that T-Nb2O5@NC can be used as a promising HSC anode material.

A core-shell molybdenum nanoparticles entrapped f-MWCNTs hybrid nanostructured material based non-enzymatic biosensor for electrochemical detection of dopamine neurotransmitter in biological samples

Dopamine (DA) is a critical neurotransmitter and has been known to be liable for several neurological diseases. Hence, its sensitive and selective detection is essential for the early diagnosis of diseases related to abnormal levels of DA. In this study, we reported novel molybdenum nanoparticles self-supported functionalized multiwalled carbon nanotubes (Mo NPs@f-MWCNTs) based core-shell hybrid nanomaterial with an average diameter of 40–45 nm was found to be the best for electrochemical DA detection. The Mo NPs@f-MWCNTs hybrid material possesses tremendous superiority in the DA sensing is mainly due to the large surface area and numerous electroactive sites. The morphological and structural characteristics of the as-synthesized hybrid nanomaterial were examined by XRD, Raman, FE-SEM, HR-TEM, EDX. The electrochemical characteristics and catalytic behavior of the as-prepared Mo NPs@f-MWCNTs modified screen-printed carbon electrode for the determination of DA were systematically investigated via electrochemical impedance spectroscopy, cyclic voltammetry, and amperometry. The results demonstrate that the developed DA biosensor exhibit a low detection limit of 1.26 nM, excellent linear response of 0.01 µM to 1609 µM with good sensitivity of 4.925 µA µM−1 cm−2. We proposed outstanding appreciable stability sensor was expressed to the real-time detection of DA in the real sample analysis of rat brain, human blood serum, and DA hydrochloride injection.

Fabrication and Characterization of High Capacity and Long Cycle Life Lithium-Sulfur Battery Using Porous Material As a Polysulfide Adsorbent

The need for large-scale energy storage, improved safety, and sustainable transport are driving research into alternative battery technologies with higher specific energies. Rechargeable Li-S batteries have high capacities (1675 mAh g-1) and theoretical energy densities as high as 2600 Wh kg-1 making them promising candidates for the next-generation of energy storage systems. However, due to its insulating nature, polysulfide dissolution and poor cycle life, it has been challenging to achieve the existing technology requirement. Herein we choose porous carbon as conducting agent and TiO2 nanotube as polysulfide adsorbent and forming hybrid nanostructured materials to overcome active material utilization and polysulfide dissolution problems. The porous host materials for sulfur was produced by a low cost, hydrothermal and annealing process with one step green synthesis approach. The process is facile, cheap, scalable and environmental friendly. The material was characterized and examined by XRD, BET, XPS, SEM, TEM, Raman, TGA, CV, EIS and galvanostatic charge-discharge tastes. It is found that the materials are highly porous and show both the characteristics of microporous and mesoporous behavior and contain large pore volume to impregnate large amount of sulfur. Moreover, the microporous carbon can effectively adsorb smaller sulfur (S2-4) molecules in their narrow pores with increasing the electrical conductivity of the cathode by decreasing the resistance of sulfur and enhance active material utilization. Meanwhile, mesoporous carbon doped TiO2 nanotube were placed on the surface to prevent the overflow of sulfur as well as the dissolution of polysulfides in the electrolyte effectively and improve the strength of the entire electrode thereby enhancing the electrochemical performance. As a result, using the porous host-sulfur nanocomposite as a cathode material, we demonstrate excellent cycle stability with initial discharge capacity of 916 mAh g-1 with coulombic efficiency of over 98.6% at a current density of 0.2 C after 140 cycles. This improved performance is due to the unique design of the porous host materials and the good dispersion of sulfur in the narrow pores of microporous host with TiO2 support. Thus, our approach is a promising strategy to control the dissolution of polysulfides and cycle life problems of the battery. Key words: porous materials, lithium-sulfur battery, polysulfide adsorbent, cycle stability

Palladium nanoparticles supported on silica, alumina or titania: greener alternatives for Suzuki–Miyaura and other C–C coupling reactions

Most of the catalytic systems for C–C coupling reactions are based on homogeneous catalysts which are normally used only once and do not have a sustainable molecular economy, as they cannot be easily separated from the reaction products to be subsequently recycled and used in other catalytic cycles. The alternative use of heterogeneous catalytic systems, which follow better the principles of green chemistry, is of current environmental and industrial interest for C–C coupling reactions. In this context, although heterogeneous C–C coupling catalysis research has a long history focused on the development of palladium nanoparticles, this field still has several drawbacks to overcome and is an area in continuous evolution, which has developed novel systems based on reusable supported palladium nanoparticles or supported palladium complexes with improved catalytic properties. In this review, the recent research developments of novel hybrid nanostructured materials based on silica, titania and alumina as efficient supports for palladium complexes or palladium nanoparticles are revisited, with special regards to synthetic methodology, characterization methods and catalytic performance. The most relevant results concerning the improvement in the environmental impact of the use of palladium complexes or palladium nanoparticles supported onto silica, titania and alumina reported in the last 10 years on Suzuki–Miyaura and other C–C coupling reactions of interest are also described.

Cationic Polymerization of (3‐Aminopropyl)‐tris‐furfuryloxysilane Derivatives—a New Strategy for Complex Hybrid Material Synthesis

AbstractThe trifunctional (3‐aminopropyl)‐tris‐furfuryloxysilane monomer (1) is able to undergo both twin polymerization and reaction with electrophilic compounds such as isocyanates. 1 can be readily synthesized from 3‐aminopropyptrimethoxysilane (APTMS) and furfuryl alcohol (FA). The reaction of 1 with three different aromatic isocyanates, namely phenyl isocyanate, diphenylmethane‐4,4′‐diisocyanate (MDI), and a prepolymer consisting of MDI end‐capped polytetramethylene ether glycole (PTMEG), to the corresponding substituted urea derivatives is presented. Three urea derivatives 1‐phenyl‐3‐(3‐tris‐furfuryloxysilyl)propylurea (2), diphenylmethan‐4,4′‐bis[3(tris‐furfuryloxysilyl)propyl]urea (3), bis[3(tris‐furfuryloxysilyl)‐propyl]urea‐capped PTMEG‐MDI‐prepolymer (4) as well as 1 were polymerized to multicomponent organic/inorganic hybrid materials in a one step procedure using methane sulfonic acid as catalyst. The simultaneous formations of poly furfuryl alcohol and polysiloxane networks within the hybrid material are proven by means of solid‐state NMR spectroscopic measurements. The homogeneous distribution of silicon within the solidified hybrid materials is analyzed by scanning electron microscopy, energy dispersive X‐ray spectroscopy, and high‐angle annular dark field‐scanning transmission electron microscopy (HAADF)‐STEM. Homogeneous nanostructured hybrid materials with silicon cluster sizes in the range of 2 nm have been obtained by polymerization of the urea derivatives 2, 3, and 4.

Characterizing Polymer-Grafted Nanoparticles: From Basic Defining Parameters to Behavior in Solvents and Self-Assembled Structures.

Polymer-grafted nanoparticles, often called hairy nanoparticles (HNPs), are an intriguing class of nanostructured hybrid materials with great potential in a variety of applications, including advanced polymer nanocomposite fabrication, drug delivery, imaging, and lubrication. This Feature provides an introduction to characterization of various aspects of HNPs, from basic defining parameters to behavior of HNPs in solvents and self-assembled structures of multicomponent brush nanoparticles, by using a broad range of analytical tools.