Multifunctional Hybrid Materials Research Articles

Alkali Metal–Substitution–Induced Confinement Effect for Designing High Phase–Transition–Temperature Molecular–Based Compounds Exhibiting Strong Photoluminescence

AbstractOrganic–inorganic hybrid phase–transition molecular materials have attracted increasing attention due to their excellent properties of combining inorganic and organic components. However, few research has been conducted on rare‐earth–based bimetallic organic–inorganic hybrids. Here, we successfully constructed a series of rare–earth–based organic–inorganic hybrid multifunctional materials, (C6H14N2)2EuX(NO3)6O2 (X=Na, K, Rb), with reversible phase transition, switchable dielectric, photoluminescence and semiconductor properties. Specifically, the phase‐transition temperature of three compounds are determined to be 364, 405 and 440 K, respectively. By the confinement effect caused by the variation of alkali metal elements in the two–dimensional structure, the phase transition temperature is successfully increased by 76 K. Meanwhile, the solid–state photoluminescence of three compounds displays bright red light at room temperature. Additionally, the bandgaps of three compounds are determined to be 3.21, 3.53 and 3.32 eV, respectively. It is expected that the strategy of alkali metal substitution proposed in this work will provide new thoughts for the design of multifunctional organic‐inorganic hybrid crystals.

Multifunctional Hybrid Material for Endoprosthetic Implants Based on Alumina-Toughened Zirconia Ceramics and Additively Manufactured TiNbTa Alloys.

Aseptic implant loosening after a total joint replacement is partially influenced by material-specific factors when cobalt-chromium alloys are used, including osteolysis induced by wear and corrosion products and stress shielding. Here, we aim to characterize a hybrid material consisting of alumina-toughened zirconia (ATZ) ceramics and additively manufactured Ti-35Nb-6Ta (TiNbTa) alloys, which are joined by a glass solder. The structure of the joint, the static and fatigue shear strength, the influence of accelerated aging, and the cytotoxicity with human osteoblasts are characterized. Furthermore, the biomechanical properties of the functional demonstrators of a femoral component for total knee replacements are evaluated. The TiNbTa-ATZ specimens showed a homogenous joint with statistically distributed micro-pores and a slight accumulation of Al-rich compounds at the glass solder-TiNbTa interface. Shear strengths of 26.4 ± 4.2 MPa and 38.2 ± 14.4 MPa were achieved for the TiNbTa-ATZ and Ti-ATZ specimens, respectively, and they were not significantly affected by the titanium material used, nor by accelerated aging (p = 0.07). All of the specimens survived 107 cycles of shear loading to 10 MPa. Furthermore, the TiNbTa-ATZ did not impair the proliferation and metabolic activity of the human osteoblasts. Functional demonstrators made of TiNbTa-ATZ provided a maximum bearable extension-flexion moment of 40.7 ± 2.2 Nm. The biomechanical and biological properties of TiNbTa-ATZ demonstrate potential applications for endoprosthetic implants.

Functionalized metal oxide particles with antioxidant as new carriers providing higher stability of polyolefin products

The aim of this research was to expand the current state of knowledge regarding the impact of the use of inorganic metal oxides and HALS stabilizers on the aging and stabilization processes of polyolefin products. For this purpose, the influence of functionalized metal oxide particles with an antioxidant on the aging behavior of ethylene-norbornene copolymer (EN) was analyzed. Innovatively, Hostavin N321 stabilizer was deposited on metal oxide surfaces (SiO2, TiO2, ZnO, Fe3O4) by mechano-chemical modification using a planetary ball mill. Unmodified and functionalized metal oxides with antioxidant were introduced into the EN, and the resulting composites were subjected to accelerated thermal and UV aging tests for 400 h. All tested samples showed high resistance to the thermooxidation process, but much greater changes were observed as a result of their exposure to UV radiation. In the case of unmodified oxides, Fe3O4 was characterized by the highest anti-aging behavior, which allowed for almost complete preservation of the EN functional properties and this could be the reason that the effect of the modification performed for this oxide was not visible. However, the proposed stabilizer immobilization on SiO2, ZnO and TiO2 surfaces enabled obtaining more complex stabilizing systems with long-term effective anti-aging activity, in which first the metal oxide provided a preventive effect as a UV absorber, and then when 100% heat conversion was not achieved, Hostavin N321 inhibited degradation through reactions with free radicals. Silica particles provided the strongest interactions with HALS antioxidant and prevented its diffusion towards the EN surface even at elevated temperatures, thus leading to the highest UV stability. This novel approach not only opens new perspectives for the production of multifunctional hybrid materials with their practical applications, but also reduces the cost of the final product, which is particularly important from the point of view of designing polymer materials in industry.

Cell‐Membrane Inspired Multifunctional Nanocoating for Rescuing the Active‐Material Microenvironment in High‐Capacity Sulfur Cathode

AbstractAchieving healthy active‐material microenvironment (ME@AM) for stable and efficient electron/ion transport around each active‐material particle is crucial for high‐performance battery electrodes. However, this goal has been proved extremely challenging for most high‐capacity AMs such as sulfur, owing to its notable volume change and severe shuttle effect. Here, a multifunctional hybrid material with zein protein reinforced catalytic single Cu atom/carbon composite (Cu─C) (zein/Cu─C) is coated onto sulfur/carbon (SC) particle, to prepare the advanced zein/Cu─C@SC core–shell particle. Similar to the multifunctional cell membrane well‐known in biology, this multifunctional zein/Cu─C coating helps build a healthy and stable ME@AM within sulfur cathode. Specifically, it can simultaneously provide robust protective shell for the AM particle, adsorption and catalyst function to the dissolved polysulfides, and AM surface treatment to improve AM/conductive agent interface. All these functions are the keys to build and maintain a healthy ME@AM in sulfur cathode. This study not only brings effective solutions to the challenges in volume‐change high‐capacity sulfur active materials and beyond, but also helps achieve comprehensive understanding of the key factors controlling the structuring and final quality of ME@AM.

Investigating the Structure-property Relationships of Two Cd-based Hybrid Multifunctional Compounds with High Tc, Bright Fluorescence and Wide Band-gap.

Organic-inorganic hybrid multifunctional materials have shown significant application in lighting and sensor fields, owing to their prominent performance and diversity structures. Herein, we synthesized two multifunctional compounds: (propyl-quinuclidone)2 CdBr4 (1) and (F-butyl-quinuclidone)2 CdBr4 (2). By introducing light-emitting organic cation with flexible long chain, 1 and 2 exhibit excellent transition properties and bright blue-white fluorescence. Then, combine fluorescence lifetime and first-principal calculation, providing evidence for the electron transfer emission. Subsequently, investigated the impact of substituent carbon chain length (methyl to butyl), structural rigidity (C-C to C-F) and halide framework (Cl to I) on the fluorescence properties. Results indicate that Cd⋅⋅⋅Cd distance and structural rigidity play an important role in fluorescence. Overall, our research provides valuable insight and example for chemical modifications enhance compound performance.

Incorporation of Photo- and Thermoresponsive N-Salicylidene Aniline Derivatives into Cobalt and Zinc Layered Hydroxides.

In search of new multifunctional hybrid materials and in order to investigate the influence of chemical modification on the possible synergy between properties, the carboxylate and sulfonate derivatives of photo- and thermochromic N-salicylidene aniline were successfully inserted into Co(II)- and Zn(II)-based layered simple hydroxides, resulting in four novel hybrids: Co-N-Sali-COO, Co-N-Sali-SO3, Zn-N-Sali-COO, and Zn-N-Sali-SO3. All synthesized hybrids adopt a double organic layered configuration, which prevents the cis-trans photoisomerization ability of N-Sali-R molecules in the hybrids. However, the Zn hybrids exhibit fluorescence upon exposure to UV light due to the excited-state intramolecular proton transfer (ESIPT) mechanism. The thermally stimulated keto-enol tautomerization of N-salicylidene aniline in the hybrids was related with the changes in interlamellar spacings observed by temperature-dependent PXRD. This tautomerization process was prominently evident in the Co-N-Sali-SO3 hybrid (about 11% increase in d-spacing upon decreasing the temperature to -180 °C). Finally, the Co-N-Sali-R hybrids exhibit the typical magnetic behavior associated with Co(II)-based LSHs (ferrimagnetic ordering at TN = 6.8 and 7.7 K for Co-N-Sali-COO and Co-N-Sali-SO3, respectively). This work offers insights into isomerization in LSHs and the ESIPT mechanism's potential in new luminescent materials and prospects for designing new multifunctional materials.

Utilizing a defective MgO layer for engineering multifunctional Co-MOF hybrid materials with tailored leaf-like and polyhedral structures for optimal electrochemical and photocatalytic activities

The hybridization of metal-organic framework (MOF) with inorganic layers would lead to the discovery of novel hybrid materials that can provide a compelling strategy for enhancing its photocatalytic and electrochemical response. In the present study, a highly efficient multifunctional hybrid material was developed by exploiting the defective layer formed on AZ31 Mg alloy through plasma electrolytic oxidation (PEO) as a nucleation and growth site for Co-MOF. The concentrations of the organic linker 2-Methylimidazole (2,MIm) and cobalt nitrate as a source of Co2+ ions were varied to control the growth of the obtained Co-MOF. Lower concentrations of the 2, MIm ligand favored the formation of leaf-like MOF structures through an anisotropic, two-dimensional growth, while higher concentrations led to rapid, isotropic nucleation and the creation of polyhedral Co-MOF structures. The sample characterized by polyhedral Co-MOF structures exhibited superior electrochemical stability, with the lowest corrosion current density (3.11 ​× ​10−9 A/cm2) and the highest top layer resistance (2.34 ​× ​106 ​Ω ​cm2), and demonstrated outstanding photocatalytic efficiency, achieving a remarkable 99.98 ​% degradation of methylene blue, an organic pollutant, in model wastewater. To assess the active adsorption sites of the Co-MOF, density functional theory (DFT) was utilized. This study explores the changes in morphologies of the coatings of Co-MOF with the change of solution concentration to form coatings with enhanced properties on the metallic substrate, which could establish the groundwork for the development of next-generation multifunctional frameworks with diverse applications.

X‐Ray Excited Luminescence Materials for Cancer Diagnosis and Theranostics

AbstractX‐rays are rays that penetrate the human tissue and are capable of penetrating water, air, and oxygen in various biological tissues or tumors. In recent years, significant progress has been made in the research of X‐ray‐excited luminescent materials for cancer diagnosis and treatment. In this study, the application of X‐ray‐excited luminescent materials is reviewed for tumor imaging and therapy. First, two classes of luminescent materials are briefly introduced for a form of enhanced X‐ray computed tomography, X‐ray‐excited optical luminescence imaging. Subsequently, the design of multifunctional hybrid materials is evaluated for radiotherapy and other treatments and their synergistic effects under X‐ray excitation are studied. Finally, current key issues and solutions in the field are discussed in detail.

Biochar-based materials for electroanalytical applications: An overview

Biochar-based materials, derived from renewable biomass resources, have emerged as promising candidates for electroanalytical applications due to their unique physicochemical properties, such as high surface area, excellent biocompatibility, and good chemical stability. This review provides a comprehensive overview of recent advancements in the development and application of biochar-based materials in electrochemical devices, including sensors, energy storage, and catalysis. We discuss the synthesis and functionalization of biochar materials, focusing on the effects of feedstock and pyrolysis conditions on their properties. The applications of biochar-based materials in electrochemical devices are reviewed, with a particular emphasis on enzyme-based biosensors, DNA-based biosensors, and immunosensors. Despite their promising performance, challenges such as reproducibility, electrical conductivity, and long-term stability need to be addressed to facilitate their widespread adoption in the industry. We also discuss emerging trends, such as the development of multifunctional hybrid materials and integration into flexible devices. Finally, we highlight the importance of policy, regulatory aspects, and environmental assessments to ensure the safe and sustainable use of biochar-based materials in electroanalytical applications.

A theoretical protocol for the rational design of the bioinspired multifunctional hybrid material MIP@cercosporin.

Rational design of polymeric materials prepared with the molecular imprinting technology is gaining even more space, as it can provide the optimal conditions to direct the laboratory molecularly imprinting polymer (MIP) preparation, maximizing their efficiency while reducing costs and preparation time, when compared to try-and-error approaches. We perform a rational design of an MIP with specific cavities for cercosporin accommodation by means of computational tools. The main steps of an MIP preparation were simulated and it was found that the most appropriated functional monomer to be used in the MIP preparation for cercosporin is the acrylamide, while the most suitable crosslinking agent is found to be p-divinylbenzene. Also, the most suitable solvents to remove cercosporin from the cavity are those with low dielectric constant, such as chloroform. This kind of solvent can then be used in washing step, in the case of use the MIP for sensing destinations. On the other hand, solvents like water, which has high dielectric constants, can efficiently improve the interactions between cercosporin and the functional monomer acrylamide, being indicated when the objective is to attract or maintain the cercosporin inside the MIP cavity. Thus, a MIP@cercosporin hybrid material can be used in aqueous solutions more reliably, or even the cercosporin detection in this media can be favoured. In the selectivity analysis of the material prepared in this specific condition, the results point that this MIP can also detect elsinochrome A with high efficiency, and could be more selective for hypericin, altertoxin, hypocrelin A, and phleichrome mycotoxins. The main steps of a MIP synthesis were theoretically simulated trough density functional theory (DFT) calculations aiming to direct and optimize the synthesis and applications of the material before the bench tests. Initially, in order to choose the most suitable functional to be employed for cercosporin calculations, eight of the DFT functionals that had been previously used for cercosporin calculations in literature were tested, which were the LCWPBE, B3LYP, CAM-B3LYP, M062-X, mPW1PW91, PBE0, TPSSh, and ωb97Xd. The theoretical 1H NMR chemical shifts for cercosporin molecule were calculated and compared with experimental results to analyze the performance of the functionals. Of all these, the best results were obtained with the TPSSh functional, employing the 6-31G(d,p) basis set, and this level of theory was then used for all the following steps. All the simulations were performed by means of geometry optimizations and frequency calculations. Additionally, AIM calculations were employed for further analysis of the interactions between the chosen functional monomer and cercosporin template in step 1, which was functional monomer selection. In washing step, the calculations were done using implicit solvation model, and finally, in selectivity tests, the putative "solid" MIP was simulated by freezing the positions of the monomers after the template remotion, and then other structurally similar toxins were placed in its cavity for the geometry optimizations and frequency calculations.

A Novel Hybrid Multifunctional Compound: (CMQ)BiCl5 Showing Enhancement in Physical Properties by Halogen Substitution

AbstractOrganic‐inorganic hybrid multifunctional materials have received significant attention due to their potential applications in smart devices such as phase‐change memory (PCM), resistive random‐access memory (ReRAM). Yet, devices application requires achieving a balance between fast switching speeds, long‐term stability, and high cycling endurance in materials still facing difficulties. Herein, we report two hybrid phase transition compounds: (CMQ)BiCl5(CMQ=Chloromethyl Quinuclidin‐3‐one) (1) and (FMQ)2SbBr5(FMQ=Fluoromethyl Quinuclidin‐3‐one) (2), both two compounds exhibit high phase transition temperature, dual‐stable behavior in dielectric during reversible phase transition process. Notably, 1 exhibit small dielectric change after multiple dielectric state switching. Furthermore, investigate the influence of halogen substitution (F to Cl) for compound properties, which show an Increasing transition temperature (9 K) and raising structural dimension (0D to 1D). Additionally, using first principles, analyze the electronic structure of 1 and find that it has a 3.4 eV wide bandgap, closing to GaN semiconductor (3.4 eV). This work provides a new insight into developing the next‐generation phase transition compounds and chemical modification enhances material performance.

Ab Initio Study of Optical Properties of Hybrid Films Based on Bilayer Graphene and Single-Walled Carbon Nanotubes

In recent years, the possibility of combining graphene and carbon nanotubes has attracted much attention from researchers attempting to obtain new multifunctional hybrid materials with promising properties. Optoelectronics shows potential as a field of application for such hybrid structures. The variety of existing structural configurations of graphene-nanotube hybrids requires preliminary detailed studies of their optical properties by computer simulation methods. In this paper, we consider island-type graphene-nanotube hybrid films formed by AB-stacked bilayer graphene and single-walled carbon nanotubes (SWCNTs). In this case, bilayer graphene is located above the surface of the nanotube, forming areas with an increased density of carbon atoms, creating so-called “islands.” To meet the conditions of a real experiment, we chose chiral SWCNTs (12,6) with a diameter of 1.2 nm, which are most often synthesized in real experiments. All constructed atomistic models of bilayer graphene-chiral SWCNT films were tested for thermodynamic stability at room temperature and proved their suitability for research. Using Kubo-Greenwood formalism, we calculated the complex optical conductivity tensor and absorbance coefficient in the wavelengths of ultraviolet, visible, and near-infrared radiations. The photocurrent spectra are calculated based on the obtained absorption spectra and solar radiation spectra on the earth’s surface (AM1.5) and outside the earth’s atmosphere (AM0). The results of calculations revealed regularities in the influence of structural parameters (nanotube diameter, graphene width) on the optical and optoelectronic properties of graphene-chiral SWCNT (12,6) with an island structure.

In situ modification of LiMn3/4Fe1/4PO4/C cathode realized by hierarchical porous α-LiAlO2 as channel for lithium-ion batteries

In view of the lower electronic and ionic conductivity of LiMnPO4 cathode materials, we use α-LiAlO2 solid electrolyte with pore structure to compound LiMn3/4Fe1/4PO4/C solid solution on the basis of Mn site doped Fe, forming a conductive connection network between them. Using anode aluminum oxide as porous structure template, a series of LiMn3/4Fe1/4PO4/C@α-LiAlO2 nano composites are constructed by hydrothermal in-situ deposition and subsequent heat treatment. Through the first-principles calculation, it is found that the modification of α-LiAlO2 leads to an increase in the number of states near Fermi level, and the adjustment energy band width affects the electronic conductivity of LiMn3/4Fe1/4PO4 electrode. When the content of α-LiAlO2 is 6 wt%, the electronic structure of LiMn3/4Fe1/4PO4@α-LiAlO2 composite is the best and has the best performance. This material material exhibits a better specific discharge capacity, that is, 142.6, 137.7, 130.3, 117.1, 100.6, 79.2 and 68.5 mAh·g−1 at 0.5C, 2C, 4C, 8C, 10C, 15C and 20C, respectively. In addition, its DLi + is 2.02 × 10−12 cm2·s−1, which is an order of magnitude higher than that of other α-LiAlO2-containing electrodes. Hence, it is significant in cathode for lithium-ion batteries to reasonably design multi-functional hybrid materials.

Construction of strong built-in electric field in binary metal sulfide heterojunction to propel high-loading lithium-sulfur batteries

The practical application of lithium-sulfur (Li-S) batteries is greatly hindered by soluble polysulfides shuttling and sluggish sulfur redox kinetics. Rational design of multifunctional hybrid materials with superior electronic conductivity and high electrocatalytic activity, e.g., heterostructures, is a promising strategy to solve the above obstacles. Herein, a binary metal sulfide MnS-MoS2 heterojunction electrocatalyst is first designed for the construction of high-sulfur-loaded and durable Li-S batteries. The MnS-MoS2 p-n heterojunction shows a unique structure of MoS2 nanosheets decorated with ample MnS nanodots, which contributes to the formation of a strong built-in electric field at the two-phase interface. The MnS-MoS2 hybrid host shows strong soluble polysulfide affinity, enhanced electronic conductivity, and exceptional catalytic effect on sulfur reduction. Benefiting from the synergistic effect, the as-derived S/MnS-MoS2 cathode delivers a superb rate capability (643 mA h g−1 at 6 C) and a durable cyclability (0.048% decay per cycle over 1000 cycles). More impressively, an areal capacity of 9.9 mA h cm−2 can be achieved even under an extremely high sulfur loading of 14.7 mg cm−2 and a low electrolyte to sulfur ratio of 2.9 μL mg−1. This work provides an in-depth understanding of the interfacial catalytic effect of binary metal compound heterojunctions on sulfur reaction kinetics.

Multifunctional heterogeneous catalysts: Tetrakis(pentafluorophenyl)porphinato]iron(III) immobilized on amine–functionalized Diatomaceous Earth for catalytic and adsorption applications

The use of Diatomaceous Earth (DE) as a promising support of a synthetic metalloporphyrin is reported, trying to heterogenize metalloporphyrin catalysts to mimicking enzyme site isolation and improving reaction selectivity. New multifunctional hybrid materials consisting of DE amino–functionalized with aminopropyltriethoxysilane (DE–APTES), followed by grafting with [meso–tetrakis(pentafluorophenyl)porphinato]iron(III) (DE–APTES–FeTFPP), were prepared and fully characterized. FeTFPP was grafted into DE–APTES via the amine groups (band at 1570 cm–1). The brown color of the materials indicated that FeTFPP was immobilized in the matrix; a Soret band characteristic of ironporphyrin located in a confined space, was found at 416 nm. Leaching studies confirmed that the ironporphyrin was entrapped and not just adsorbed on the silica surface. DE was composed of typical quartz and cristobalite crystalline phases and amorphous silica. The intensity of its characteristic reflection at 22° (2θ) decreased in the presence of FeTFPP, evidencing that the ironporphyrin influenced the organization of the material. Catalytic tests using DE–APTES–FeTFPP in cyclooctene epoxidation to cyclooctene oxide (56 % yield, with complete selectivity for the epoxide) and cyclohexane oxidation (4 % yield of oxidized products, with ketone/alcohol selectivity ∼ 3:1), evidenced the versatility of the catalyst and the multifunctionality of the resulting hybrid materials and the ability of DE as a promising natural support for ironporphyrin catalysts. Finally, the capacity of the materials as CO2 adsorbents was evaluated in the temperature range 100–200 °C. DE–APTES showed a maximum adsorption capacity of 1.26 mmol/g at 100 °C, 18 times higher than the value found under the same conditions for the non–functionalized support.

Hybrid Fiber Materials according to the Manufacturing Technology Methods and IOT Materials: A Systematic Review

With the development of convergence technology, the Internet of Things (IoT), and artificial intelligence (AI), there has been increasing interest in the materials industry. In recent years, numerous studies have attempted to identify and explore multi-functional cutting-edge hybrid materials. In this paper, the international literature on the materials used in hybrid fibers and manufacturing technologies were investigated and their future utilization in the industry is predicted. Furthermore, a systematic review is also conducted. This includes sputtering, electrospun nanofibers, 3D (three-dimensional) printing, shape memory, and conductive materials. Sputtering technology is an eco-friendly, intelligent material that does not use water and can be applied as an advantageous military stealth material and electromagnetic blocking material, etc. Electrospinning can be applied to breathable fabrics, toxic chemical resistance, fibrous drug delivery systems, and nanoliposomes, etc. 3D printing can be used in various fields, such as core-sheath fibers and artificial organs, etc. Conductive materials include metal nanowires, polypyrrole, polyaniline, and CNT (Carbon Nano Tube), and can be used in actuators and light-emitting devices. When shape-memory materials deform into a temporary shape, they can return to their original shape in response to external stimuli. This study attempted to examine in-depth hybrid fiber materials and manufacturing technologies.

Superhydrophobic and Conductive Foams with Antifouling and Oil–Water Separation Properties

Hybrid organic-inorganic materials are attracting enormous interest in materials science due to the combination of multiple advantageous properties of both organic and inorganic components. Taking advantage of a simple, scalable, solvent-free hard-sacrificial method, we report the successful fabrication of three-dimensional hybrid porous foams by integrating two types of fillers into a poly(dimethylsiloxane) (PDMS) framework. These fillers consist of hydrophobic electrically conductive graphene (GR) nanoplatelets and hydrophobic bactericidal copper (Cu) microparticles. The fillers were utilized to create the hierarchical rough structure with low-surface-energy properties on the PDMS foam surfaces, leading to remarkable superhydrophobicity/superoleophilicity with contact angles of 158 and 0° for water and oil, respectively. The three-dimensional interconnected porous foam structures facilitated high oil adsorption capacity and excellent reusability as well as highly efficient oil/organic solvent-water separation in turbulent, corrosive, and saline environments. Moreover, the introduction of the fillers led to a significant improvement in the electrical conductivity and biofouling resistance (vs whole blood, fibrinogen, platelet cells, and Escherichia coli) of the foams. We envision that the developed composite strategy will pave a facile, scalable, and effective way for fabricating novel multifunctional hybrid materials with ideal properties that may find potential use in a broad range of biomedical, energy, and environmental applications.

Highly efficient iodine capture and ultrafast fluorescent detection of heavy metals using PANI/LDH@CNT nanocomposite

Here, the hybrid material of polyaniline/layered double hydroxide@carbonnanotubes (PANI/LDH@CNT) is considered a multifunctional material. Instrumental methods, including FTIR, XRD, TEM, SEM, and TGA/DTA were utilized to characterize PANI/LDH@CNT. The polymerization method created PANI/LDH@CNT as an adsorbent to remove toxic iodine in hexane solution with a capture capacity of 303.20 mg g−1 during 9 h. It is 900 mg g−1 in the vapor phase within 24 h. After three cycles, the PANI/LDH@CNT could be regenerated while maintaining 91.90 % iodine adsorption efficiency. Due to the presence of free amine (-N) groups, OH−, CO2H, and π-π conjugated structures in the PANI/LDH@CNT, it is also explored for efficient iodine uptake. It was demonstrated that the pseudo-first-order (PFO) and Langmuir model had the optimum correlation with the kinetic and isotherm data, respectively. Moreover, the use of PANI/LDH@CNT is not only limited to iodine capture; it can also be utilized as a sensitive sensor that displays a fluorescence “turn-off” response for Mn7+ and Cr6+ ions and a fluorescence “turn-on” response in the case of Al3+ ions. The fluorescence intensity of the PANI/LDH@CNT was turned off in the presence of Mn7+ and Cr6+ because of the fluorescence inner filter effect (IFE) mechanism. In contrast, the fluorescence intensity was turned on in the case of Al3+, relying on the chelation-enhanced fluorescence (CHEF) effect mechanism. Under optimal conditions, the limit of detection (LOD) of 51, 59, and 81 nM for Mn7+, Cr6+, and Al3+, respectively. According to the literature, this is probably the first example based on PANI/LDH@CNT as a multifunctional hybrid material employed as an adsorbent for capturing radioactive iodine and as a chemosensor for detecting heavy metal ions in aqueous solutions.

θ-[Mo8O26]4--based multifunctional hybrid material for high catalytic performance on the cycloaddition of CO2, esterification and knoevenagel condensation.

Developing materials with excellent properties has become the norm in the field of basic research, prompting us to explore highly robust hybrid materials based on electron-rich POMs and electron-deficient MOFs. Herein, a θ-[Mo8O26]4--based hybrid material of [Cu2(BPPP)2]{θ-[Mo8O26]} (NUC-62) with excellent physicochemical stability was self-assembled under acidic solvothermal conditions from Na2MoO4 and CuCl2 in the presence of a designed chelated ligand of 1,3-bis(3-(2-pyridyl)pyrazol-1-yl)propane (BPPP), which has sufficient coordination sites, spatial self-regulation and great deformation ability. In NUC-62, each of two tetra-coordinated CuII ions and two BPPP are unified into one dinuclear unit serving as the cation, which is interactively linked to θ-[Mo8O26]4- anions via rich hydrogen bonds of C-H⋯O. Because of the unsaturated Lewis acidic CuII sites, NUC-62 exhibits high catalytic performance on the cycloaddition reactions of CO2 with epoxides under mild conditions with a high turnover number and turnover frequency. Furthermore, NUC-62, as a recyclable heterogeneous catalyst, shows high catalytic activity for the esterification of aromatic acid under refluxing, which is much better than the inorganic acid catalyst of H2SO4 in terms of turnover number and turnover frequency. Moreover, because of open metal sites and rich terminal oxygen atoms, NUC-62 shows high catalytic activity for Knoevenagel condensation reactions of aldehydes and malononitrile. Hence, this study lays the groundwork for constructing heterometallic cluster-based microporous MOFs with excellent Lewis acidic catalysis and chemical stability. Therefore, this study lays a foundation for the construction of functional polyoxometalate complexes.

Organic–inorganic hybrid multifunctional materials with high-Tc reversible phase transition and wide bandgap properties

A new reversible phase change multifunctional material [C5H10N (CH3) CH2CH2CH3]2CdBr4 (1), which has high temperature reversible phase change properties at 333 K and the first-principle calculation band gap is 3.99 eV.