Organic-inorganic Hybrid Materials Research Articles

Order-disorder structural engineering of vanadium oxide anode: Balancing ionic and electronic dynamic for fast-charging aqueous Li-ion battery

Fast-charging aqueous lithium-ion batteries (ALIBs) are considered as promising energy storage devices because of their non-flammability and environmentally friendly characteristics. However, how to balance the ionic and electronic dynamics for fast charging reactions remains a significant challenge under the current research status. Here, the order-disorder structural engineering strategy is adopted to resolve this issue, considering the difference between ion and electron transportation in the crystalline and amorphous phases, respectively. Vanadium oxide anodes were developed with optimized ionic and electronic dynamics by using an organic-inorganic hybrid material as a precursor along with refined regulation on the calcination temperature and time. This facile and large-scale extendable approach harnesses the benefits of the order-disorder structure to optimize Li+ storage efficiency and facilitate the high reversibility of Li-ion during fast charging. Consequently, the order-disorder V2O5-based full cell with LiMn2O4 as a cathode exhibits high specific capacity (262.71 mAh g−1, 89.35 % of the theoretical capacity of V2O5), high energy density (166.04 Wh kg−1), fast Li-ion diffusion coefficient (7.34×10−5 cm2 s−1) and fast-charging performance (only 6 min achieves 82.84 % of initial state-of-charge capacity). This work explores the ionic and electronic dynamic of ordered-disorder structure and offers new insights into the development of fast-charging metal ion batteries.

Polyaniline/Tungsten Trioxide Organic-Inorganic Hybrid Anode for Aqueous Proton Batteries.

Aqueous proton batteries have received increasing attention due to their outstanding rate performance, stability and high capacity. However, the selection of anode materials in strongly acidic electrolytes poses a challenge in achieving high-performance aqueous proton batteries. This study optimized the proton reaction kinetics of layered metal oxide WO3 by introducing interlayer structured water and coating polyaniline on its surface to prepare organic-inorganic hybrid material (WO3·2H2O@PANI). We constructed an aqueous proton battery with WO3·2H2O@PANI anode and MnO2@GF cathode. After 1500 cycles at a current density of 10 A g-1, the capacity retention rate can still reach 80.2%. These results can inspire the development of new aqueous proton batteries.

Inserting intermolecular hydrogen bonds to achieve dimensional regulation and phase transition temperature enhancement

Organic-inorganic hybrid materials have become potential candidates in fields of light emitting diodes (LEDs), mechanical switches, energy conversion due to their excellent magneto-opto-electronic properties. Further improving the performance of materials is a prerequisite for achieving their commercial application. Currently, many effective strategies have been proposed and validated to enhance the properties of materials, but both simultaneously realizing the improvement phase transition temperature and dimensional regulation of materials remains a huge challenge. Here, we successfully synthesized two hybrid materials, (pyrrolidinium)PbI3 (Com-1) and (3-hydroxypyrrolium)6Pb5I16 (Com-2). In this work, the strategy of inserting intermolecular hydrogen bonds cleverly achieves a significant increase in phase transition temperature (ΔT = 81 K) and dimensional regulation (1D to 2D). Moreover, semiconductor properties of two compounds are investigated to be direct bandgap semiconductor. In short, inserting intermolecular hydrogen bonds between molecules is an effective strategy to improve physical performance.

Ligand Meta-Anchoring Strategy in Metal-Organic Frameworks for Remarkable Promotion of Quantum Yields.

Aggregation is a conventional method to enhance the quantum yields (QYs) of pure organic luminophores due to the restriction of intramolecular motions (RIM). However, how to realize RIM in metal-organic frameworks (MOFs) is still unclear and challenging. In this work, the ligand meta-anchoring strategy is first proposed and proved to be an effective and systematic approach to restrict the intramolecular motions of MOFs for the QY improvement. By simply shifting the substituent position in the ligand from para to meta, the QY of the resulting MOF is significantly enhanced by eleven-fold. The value is even higher than that of ligand aggregates, demonstrating the strong RIM effect of this ligand meta-anchoring strategy. The introduction of co-ligand induces the appearance of visible yellow room temperature phosphorescence with a lifetime of 222 ms due to the QY enhancement and the charge transfer between the donor and accepter units. The present work thus broadens the understanding of the RIM mechanism from a new perspective, develops a novel method to realize RIM and expands the applicable objects from pure organic materials to organic-inorganic hybrid materials.

Novel Tannic Acid-Modified Cobalt-Based Metal-Organic Framework: Synthesis, Characterization, and Antimicrobial Activity.

Metal-organic frameworks (MOFs) are a class of hybrid inorganic-organic materials with typical porous structures and a unique morphology. Due to their diversity, they are extensively used in a wide range of applications such as environmental, catalysis, biomedicine, etc. In this study, a novel cobalt-based MOF modified with tannic acid (Co-TPA/TA) (TPA: terephthalic acid; TA: tannic acid) as a promising material for antimicrobial agents was synthesized and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma-optical emission spectrometry, and thermogravimetric analysis and compared with an as-synthesized cobalt-based framework. Co-TPA/TA demonstrated good antimicrobial efficiency under optimum conditions against yeast Candida albicans ATCC 10231, Gram-negative Escherichia coli ATCC 8739, and Gram-positive Staphylococcus aureus ATCC 6538 with an inhibition zone ranging from 14 to 20 mm. Reduced ATP levels, generation of reactive oxygen species, membrane damage from cobalt ion release, and development of an alkaline microenvironment could all be contributing factors to the possible antimicrobial pathways. The novel framework can be obtained using simple, affordable, and easily accessible commercial ligands and is considered to have the potential to be used as an antimicrobial material in the future.

Intermolecular Forces Regulating the Phase-Transition Temperatures in Organic-Inorganic Hybrid Materials.

Organic-inorganic hybrid phase-transition materials have attracted widespread attention in energy storage and sensor applications due to their structural adaptability and facile synthesis. However, increasing the phase-transition temperature (Tc) effectively remains a formidable challenge. In this study, we employed a strategy to regulate intermolecular interactions (different types of hydrogen bonds and other weak interactions), utilizing bismuth chloride as an inorganic framework and azetidine, 3,3-difluoro azetidine, and 3-carboxyl azetidine as organic components to synthesize three compounds with different Tc values: [C3H8N]2BiCl5 (1, 234 K), [C3H6NF2]3BiCl6 (2, 256 K), and [C4H8O2N]3BiCl6 (3, 350 K). 1 is a one-dimensional chain structure and 2 and 3 are zero-dimensional structures. Analysis of the crystal structure and the Hirshfeld surface and 2D fingerprints further suggests that the intermolecular forces are efficiently modulated. These findings emphasize the efficacy of our strategy in enhancing Tc and may facilitate further research in this area.

Organic-Inorganic Hybrid Materials: Tailoring Carbon Dioxide-Based Polycarbonate with POSS-SH Crosslinking.

A novel functional polycarbonate (PAGC), characterized by the presence of double bonds within its side chain, was successfully synthesized through a ternary copolymerization of propylene oxide (PO), allyl glycidyl ether (AGE), and carbon dioxide (CO2). Polyhedral oligomeric silsesquioxanes octamercaptopropyl (POSS-SH) was employed as a crosslinking agent, contributing to the formation of organic-inorganic hybrid materials. This incorporation was facilitated through thiol-ene click reactions, enabling effective interactions between the POSS molecules and the double bonds in the side chains of the polycarbonate. Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) confirmed a homogeneous distribution of silicon (Si) and sulfur (S) in the polycarbonate matrix. The thiol-ene click reaction between POSS-SH and the polycarbonate led to a micro-crosslinked structure. This enhancement significantly increased the tensile strength of the polycarbonate to 42 MPa, a notable improvement over traditional poly (propylene carbonate) (PPC). Moreover, the cross-linked structure exhibited enhanced solvent resistance, expanding the potential applications of these polycarbonates in various plastic materials.

Hybrid Organic–Inorganic Materials Prepared by Sol–Gel and Sol–Gel-Coating Method for Biomedical Use: Study and Synthetic Review of Synthesis and Properties

The need to improve the expectancy and quality of life of subjects affected by disabling pathologies that require the replacement or regeneration of tissues or parts of the body has fueled the development of innovative, better-performing materials that are capable of integrating into and being tolerated by body tissues. Materials with these characteristics, i.e., bio-functionality, bio-safety, and biocompatibility, are defined as biomaterials. One of the many methods for producing such materials is the sol–gel technique. This process is mainly used for the preparation of ceramic oxides at low temperatures, through hydrolysis and polycondensation reactions of organometallic compounds within a hydroalcoholic solution. This study is based on a specific type of biomaterial: organic–inorganic hybrids. The aim of this study is to provide an overview of the advantages and disadvantages of the sol–gel technique, as well as describe the preparation and chemical and biological characterization, uses, and future prospects of these biomaterials. In particular, the use of plant drugs as organic components of the hybrid material is the innovation of this manuscript. The biological properties of plant extracts are numerous, and for this reason, they deserve great attention from the scientific community.

Modeling of time-dependent mechanical behavior of oleic acid nanocomposites using nanoindentation

Supercrystalline nanocomposites are a burgeoning class of hybrid inorganic-organic materials. Studies showed that self-assembly of iron oxide particles surface-functionalized with organic (e.g. oleic acid) ligands produces a supercrystalline nanocomposite with exceptional mechanical properties. Consequently, significant research has been conducted on these materials to experimentally characterize the mechanical properties of such materials. However, so far all modeling studies used time and rate independent elastoplastic material models. In the light of new experimental results, we propose to extent this view and use time-dependent models to capture viscoelastic behavior. To this end, we quantified this behavior using nanoindentation creep experiments and modelled it using a rheological network model with several parallel Maxwell branches and an additional elasto-plastic branch. We demonstrate how the parameters of such a model can be found using inverse analysis. With the calibrated material model, a good agreement of the time dependent behavior between simulation and experimental results is achieved. Thus, a method is provided to model time dependent behavior using complex non-classical experiments like nanoindentation.

Glassy inorganic-organic hybrid materials for photonic applications

Glassy inorganic-organic hybrid materials for photonic applications

Reaction mechanisms of α,ω-bifunctional molecules toward atomic layer deposition versus molecular layer deposition

Atomic layer deposition (ALD) and molecular layer deposition (MLD) are key techniques used to fabricate high-quality thin films. Organic α,ω-bifunctional precursors often exhibit different growth behaviors depending on the functional groups as well as the chain length of the molecular backbone, so that some organic precursors produce thin films of organic-inorganic hybrid materials, while others may deposit purely inorganic thin films without incorporation of the hydrocarbon moiety. In this study, we investigated the surface reaction mechanisms of α,ω-bifunctional molecules (X(CH2)nX, n = 2, 3, 4, 5, 6, and X = OH, SH, NH2) with diethylzinc toward MLD and ALD using density functional theory (DFT) calculations. It was found that the length of the aliphatic alkyl chain and the terminal functional groups of bifunctional organic precursors significantly influences their reactivity, resulting in the possibility toward removal or incorporation of the organic moiety in the product. Bifunctional reactants with longer alkyl backbones (n > 4) showed higher reactivity for removal of the hydrocarbon chain, facilitated by a ω-2 hydrogen transfer reaction. Furthermore, a reactivity trend of SH > OH > NH2 for removal of the hydrocarbon chains was observed. Our study provides in-depth theoretical insights into the adsorption reaction mechanisms occurring when bifunctional molecules are employed as organic reactants in ALD and MLD processes.

Solvent-Induced Bright Emission in Lead-Free Organic-Inorganic Antimony Bromides with Reversible Transformation.

Lead-free low-dimensional organic-inorganic metal halides have gained increasing attention in a wide range of applications due to their low toxicity, outstanding optical performance, and structural tunability. In this work, a general method of incorporating organic molecule into sodium antimony bromides is introduced. The 1D Na3SbBr6(C2H6OS)6 and Na3SbBr6(C4H8OS)6 single crystals exhibit bright yellow and orange emission with PL peaks at 610 and 664nm, and high photoluminescence quantum yields (PLQYs) of 85% and 60%, respectively. These two compounds can be reversibly converted into each other by the removal and addition of the organic components. Their exceptional luminescent performance enables them to be used as solid-state phosphors for the fabrication of yellow and orange down-conversion LEDs. A white LED with a high color rendering index (CRI) of 95 is also fabricated by using Na3SbBr6(C2H6OS)6 as the yellow phosphor. The universality of this method is demonstrated by synthesizing other members of this family with diverse A-groups, including methylammonium (MA) and formamidinium (FA). This work provides an effective strategy for the development of diverse lead-free and high-performance organic-inorganic hybrid materials and indicates these organic-inorganic hybrid compounds are promising luminescent materials for lighting or displays.

Magnetic suppression for a possible Fe-poor organic–inorganic hybrid superconductor Fe14Se16(tepa)0.8 (tepa = tetraethylenepentamine) with a superconducting transition at ∼42 K

Composition/structure-dependent superconductivity for FeSe-based superconductors attracted great attention not only due to their high superconducting transition temperatures (TC), but also for understanding the origin of iron-based superconductivity. Here, we report a new Fe-poor organic-inorganic hybrid material Fe14Se16(tepa)0.8 with a paramagnetic-diamagnetic transition at ∼42 K grown by a high-temperature organic-solution-phase method with soluble iron/selenium sources in a tepa solution, alternative to previous intercalation strategies. The Fe14Se16(tepa)0.8 phase is in a tetragonal layered hybrid structure with a nanoplate shape. Composition analyses reveal a Fe-poor characteristic of the hybrid in contrast to previous FeSe-intercalated superconductor, and selected area electron diffraction pattern is featured by Fe3Se4 superstructures with a √2 × √2 of Fe vacancy order. Ab initio density functional calculations show that minus Fe3Se4 ions are stable in the hybrid and ∼0.25e−/Fe0.75Se is obviously larger than the reported values of approximately 0.2e−/FeSe in other FeSe-intercalated superconductors. Typical hysteresis loops and temperature dependence of dc/ac susceptibilities of the Fe14Se16(tepa)0.8 measured below ∼42 K suggest a presence of the Meissner effect in this material. Effects of synthesis conditions on structures and magnetic properties of the hybrids show a magnetic evolution from a long-range ferrimagnetic (FIM) order of Fe14Se16(tepa) to a coexistence of FIM and superconducting (SC) orders of Fe14Se16(tepa)0.9 and an SC order of Fe14Se16(tepa)0.8. X-ray absorption spectrum (XAS) confirms the presence of ferric/ferrous irons. Mössbauer studies reveal that the high-TC superconductivity originates from a suppression of the FIM order through tuning the spin states of irons from high-spin Fe3+ (S = 5/2) and Fe2+ (S = 2) in the Fe14Se16(tepa) to low-spin Fe3+ (S = 1/2) and Fe2+ (S = 0) in the Fe14Se16(tepa)0.8. Although no zero resistance is detected even at a temperature of 2 K, the resistivity at 2 K decreases by more than 1600 times compared to that in a normal state calculated by a variable range hopping (VRH) model, suggesting that the high-TC superconductivity of Fe14Se16(tepa)0.8 is possible.

Chitosan-assisted self-assembly of flower-shaped ε-Fe2O3 nanoparticles on screen-printed carbon electrode for Impedimetric detection of Cd2+, Pb2+, and Hg2+ heavy metal ions in various water samples

This study focuses on the fabrication of a novel sensing platform on a screen-printed carbon electrode, modified by a combination of hydrothermally synthesized iron dioxide (ε-Fe2O3) nanoparticles and Chitosan (CS) biopolymer. This unique organic-inorganic hybrid material was developed for Electrochemical Impedance Spectroscopy (EIS) sensing, specifically targeting heavy metal ions that include Hg2+, Cd2+, as well as Pb2+. The investigation encompassed a comprehensive analysis of various aspects of the prepared Fe2O3 and CS/ε-Fe2O3 nanocomposites, including phase identification, determination of crystallite size, assessment of surface morphology, etc. CS/ε-Fe2O3 was drop-casted and deposited on the Screen-Printed Electrode (SPE). The resulting sensor exhibited excellent performance in the precise and selective quantification of Hg2+, Cd2+, and Pb2+ ions, with minimal interference from other substances. The fabricated sensor exhibits excellent performance as the detection range for Hg2+, Cd2+, and Pb2+ ions linearity is 2–20 μM, sensitivity, and LOD are 243 Ω/ μM cm2 and 0.191 μM, 191 Ω/μM cm2, and 0.167 μM, 879 Ω/ μM cm2, and 0.177 μM respectively. The stability of the CS/ε-Fe2O3/SPE electrode is demonstrated by checking its conductivity for up to 60 days for Hg2+, Cd2+, and Pb2+ ions. The reusability of the fabricated electrode is 14 scans, 13 scans, and 12 scans for Hg2+, Cd2+, and Pb2+ ions respectively. The findings indicate the successful development of an innovative CS/ε-Fe2O3 electrode for the EIS sensing platform. This platform demonstrates notable potential for addressing the critical need for efficient and sensitive EIS sensors capable of detecting a range of hazardous heavy metal ions, including Hg2+, Cd2+, and Pb2+.

Evolution of Getter Technology in Electronic Hermetic Packaging

Hermetic packaging is a well-established technology used for sealing electronic and optoelectronic devices. A reliable and enabling way to preserve the proper stable atmosphere conditions in hermetic packages is the integration of engineered getter solutions, specifically designed for the characteristics of different packaged systems. Getter solutions may vary from sintered, compressed or sputtered metallic alloys for vacuum sealed packages to dispensable hybrid organic-inorganic materials for gas back filled devices. The paper will present the main features of getter materials suitable for different type of packages and will show their efficiency in absorbing detrimental gases in the devices.

Metal Organic Frameworks Synthesis: The Versatility of Triethylamine.

Metal Organic Frameworks (MOFs) are organic-inorganic hybrid materials with exceptionally customizable composition and properties. MOFs intrinsically possess open metal sites, tunable pore size/shape and an ultra-large specific surface area, and have obtained significant attention over the past 30 years. Furthermore, through the integration of functional moieties such as, molecules, functional groups, noble metal clusters and nanocrystals or nanoparticles into MOFs, the resulting composites have greatly enriched the physical and chemical properties of pure MOFs, enabling their application in a wider range of fields. Triethylamine (TEA) as an organic base has consistently played a fundamental role in the development of MOFs. In this Concept, the versatility of triethylamine when involved in the synthesis of MOFs is discussed. Four sections are used to elaborate on the role of TEA including: (1) Single crystal synthesis; (2) Size and morphology control; (3) Counterion of MOFs; (4) MOFs composites synthesis. In the last part, we highlight the potential of TEA for further developments.

Hybrid Organic Polymer/Inorganic Nano-materials for Biomedical Applications: Where we are and Where to go?

Abstract: Hybrid functional materials, composed of inorganic and organic components, are considered versatile platforms whose applications in electronics, optics, mechanics, energy storage, informatics, catalysis, sensors, and medicine field have represented a breakthrough for human well-being. Among hybrid materials, micro/nanostructured hybrid colloidal systems have been widely investigated due to the dramatic enhancement of activity provided by the large surface area exposed at the interfaces with respect to the bulk counterpart. Recently, a growing interest has been in the exploration of novel environmental-friendly and versatile procedures that allow the formulation of hybrid nanostructures through safety procedures and mild experimental conditions. This review aims to provide an introduction to hybrid organic-inorganic materials for biomedical applications in particular nanostructured ones, describing the commonly exploited materials for their fabrication and techniques, advantages, and drawbacks.

Nonenzymatic Potentiometric Detection of Ascorbic Acid with Porphyrin/ZnO-Functionalized Laser-Induced Graphene as an Electrode of EGFET Sensors.

Laser-induced graphene (LIG) has emerged as a highly versatile material with significant potential in the development of electrochemical sensors. In this paper, we investigate the use of LIG and LIG functionalized with ZnO and porphyrins-ZnO as the gate electrodes of the extended gate field effect transistors (EGFETs). The resultant sensors exhibit remarkable sensitivity and selectivity, particularly toward ascorbic acid. The intrinsic sensitivity of LIG undergoes a notable enhancement through the incorporation of hybrid organic-inorganic materials. Among the variations tested, the LIG electrode coated with zinc tetraphenylporphyrin-capped ZnO nanoparticles demonstrates superior performance, reaching a limit of detection of approximately 3 nM. Furthermore, the signal ratio for 5 μM ascorbic acid relative to the same concentration of dopamine exceeds 250. The practical applicability of these sensors is demonstrated through the detection of ascorbic acid in real-world samples, specifically in a commercially available food supplement containing l-arginine. Notably, formulations with added vitamin C exhibit signals at least 25 times larger than those without, underscoring the sensors' capability to discern and quantify the presence of ascorbic acid in complex matrices. This research not only highlights the enhanced performance of LIG-based sensors through functionalization but also underscores their potential for practical applications in the analysis of vitamin-rich supplements.

Solution-processed organic-inorganic hybrid material based on P3HT and SnS2 nanoparticles layers: Synthesis and properties

Sn-based nanocomposites attract extensive attention as a new generation of photoelectric hybrid materials due to their high photoelectric conversion efficiency. In this work we synthesized SnS2 nanoparticles by a hydrothermal method employing citric acid (capping agent) and performed a capping agent exchange by pyridine to improve their solution processing and final properties. We fabricated layers with pyridine-capped nanoparticles and poly(3-hexylthiophene-2,5-diyl) (P3HT), employing the classical partial film sequence of a solar cell (ITO/PEDOT:PSS/P3HT:Nps). We found a “coupling" between the nanoparticles and the polymer and highly ordered structures within the layers. The addition of nanoparticles improved the UV–vis absorption of P3HT and allowed the exploitation of the photoluminescence emission to promote extra charge carrier generation. Moreover, we found that SnS2_py nanoparticles form a nanoscopic mixture with the P3HT. Our pyridine-capped SnS2 nanoparticles are good candidates for fabricating hybrid materials, employing P3HT as the organic compound for application in polymeric-inorganic solar cells.

Organic-Inorganic Hybrid Ferroelectric and Antiferroelectric with Afterglow Emission.

Luminescent ferroelectrics are holding exciting prospect for integrated photoelectronic devices due to potential light-polarization interactions at electron scale. Integrating ferroelectricity and long-lived afterglow emission in a single material would offer new possibilities for fundamental research and applications, however, related reports have been a blank to date. For the first time, we here achieved the combination of notable ferroelectricity and afterglow emission in an organic-inorganic hybrid material. Remarkably, the presented (4-methylpiperidium)CdCl3 also shows noticeable antiferroelectric behavior. The implementation of cationic customization and halogen engineering not only enables a dramatic enhancement of Curie temperature of 114.4 K but also brings a record longest emission lifetime up to 117.11 ms under ambient conditions, realizing a leapfrog improvement of at least two orders of magnitude compared to reported hybrid ferroelectrics so far. This finding would herald the emergence of novel application potential, such as multi-level density data storage or multifunctional sensors, towards the future integrated optoelectronic devices with multitasking capabilities.