MXene-based hybrid materials for electrochemical and photoelectrochemical H_(2) generation

The conversion of solar energy to produce clean hydrogen fuel through water splitting is an emerging strategy for efficiently storing solar energy in the form of solar fuel.This aligns with the increasing global demand for the development of an ideal energy alternative to fossil fuels that does not emit greenhouse gases.Electrochemical(EC) and photoelectrochemical(PEC) water splitting technologies have garnered significant attention worldwide for advanced hydrogen solar fuel production in recent decades.To achieve sustainable green H_(2) production,it is essential to create efficient catalyst materials that are low-cost and can replace expensive noble metal-based catalysts.These characteristics make them an ideal catalyst material for the process.Two-dimensional MXenes with M_(n+1)X_(n) structure have been identified as a promising option for EC and PEC water splitting due to their superior hydrophilicity,metal-like conductivity,large surface area,and adjustable surface chemistry.Here,we present a summary of recent advancements in the synthesis and performance enhancement methods for MXene hybrid materials in hydrogen production through EC and PEC water splitting.Furthermore,we examine the challenges and insights associated with the rational design of MXene-based hybrid materials to facilitate efficient water splitting for sustainable solar fuel production.

SYNTHESIS OF MESOPOROUS POLY(STYRENE-co-MALEIC ANHYDRIDE)/SILICA HYBRID MATERIALS VIA A NONSURFACTANT-TEMPLATED SOL-GEL PROCESS

Mesoporous poly(styrene-co-maleic anhydride)/silica hybrid materials have been prepared. The synthesis was achieved by the HCl-catalyzed sol-gel reactions of tetraethyl orthosilicate (TEOS) and styrene-maleic anhydride copolymer in the presence of 3-aminopropyl triethoxysilane (APTES) as a coupling agent and citric acid as a nonsurfactant template or pore-forming agent, followed by ethanol extraction. Characterization results from nitrogen sorption isotherms and powder X-ray diffraction indicate that polymer-modified mesoporous materials with large specific surface areas (e.g. 900 m(2)/g) and pore volumes (e.g. 0.6 cm(3)/g) could be prepared. As the citric acid concentration is increased, the specific surface areas, pore volumes and pore diameters of the hybrid materials increase.

Characteristic evaluation of Al_2O_3/CNTs hybrid materials for micro-electrical discharge machining

The characteristic evaluation of aluminum oxide （A1203）/carbon nanotubes （CNTs） hybrid composites for micro-electrical discharge machining （EDM） was described. Alumina matrix composites reinforced with CNTs were fabricated by a catalytic chemical vapor deposition method. A1203 composites with different CNT concentrations were synthesized. The electrical characteristic of A1203/CNTs composites was examined. These composites were machined by the EDM process according to the various EDM parameters, and the characteristics of machining were analyzed using field emission scanning electron microscope （FESEM）. The electrical conductivity has a increasing tendency as the CNTs content is increased and has a critical point at 5% A1203 （volume fraction）. In the machining accuracy, many tangles of CNT in A1203/CNTs composites cause violent spark. Thus, it causes the poor dimensional accuracy and circularity. The results show that conductivity of the materials and homogeneous distribution of CNTs in the matrix are important factors for micro-EDM of A1203/CNTs hybrid composites.

Syntheses and Structures of Three Hybrid Materials Using Vanadium Polyoxoanions and Macrocyclic Copper Complex as Building Blocks

The reactions of the four-coordinated macrocyclic copper complex [CuL]（ClO4）2（L = 1,4,8,11-tetraazacyclotetradecane） with NH4VO3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO3]2·2.33H2O（1）, [CuL]3[V（10）O（28）]·8H2O（2） and [Cu L]3[V6O（18）]·8H2O（3）. Single-crystal X-ray diffraction analyses reveal that three diverse vanadium polyoxoanions, [V6O（18）]6- ring, [V（10）O（28）]6- cluster, and [V（12）O（35）]^10- ring, were isolated from the same reactant NH4VO3 under different conditions. The [CuL]^2＋ bridges the [V10O28]6- clusters to form a two-dimensional sheet in 2, and link the [V6O（18）]^6- rings in 1 and [V（12）O（35）]^10- rings in 3 into three-dimensional frameworks, respectively.

Syntheses,Structures and Electrochemical Investigation of a New Dawson-based Hybrid Material with Cd-BTA Coordination Polymers

A new organic-inorganic hybrid based on tungstophosphate anions and benzotria- zole cations, [Na（BTA）E（H2O）2]2[{Cd（BTA）4（H2O）}2（P2W18O62）]·6H2O （1） （BTA = benzotriazole） has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. X-ray analysis showed that both {Na（BTA）2} and {Cd（BTA）4} units are supported on the a-Dawson polyoxoanion [P2W18062]6- via the surface bridging oxygen atoms. The electrochemical properties of 1 in aqueous solution are studied at room temperature. It was found that 1 presents good electrocatalytic activities for the reduction of NO2^-.

Ball-milling MoS_2/carbon black hybrid material for catalyzing hydrogen evolution reaction in acidic medium

Replacing platinum for catalyzing hydrogen evolution reaction （HER） in acidic medium remains great chal- lenges. Herein, we prepared few-layered MoS2 by ball milling as an efficient catalyst for HER in acidic medium, The activity of as-prepared MoS2 had a strong dependence on the ball milling time, Furthermore, Ketjen Black EC 300J was added into the ball-milled MoS2 followed by a second ball milling, and the resultant MoS2/carbon black hybrid material showed a much higher HER activity than MoS2 and carbon black alone. The enhanced activity of the MoS2/carbon black hybrid material was attributed to the increased abundance of catalytic edge sites of MoS） and excellent electrical coupling to the underlving carbon network.

Synthesis and Characterization of Two New Photochromic Inorganic-organic Hybrid Materials Based on Keggin-type Polyoxometalates

Two new photochromic inorganic-organic hybrid materials formed from Keggin-type polyoxometalates（POMs） and metronidazole （C6H9N3O3, MNZ）, formulated as H3PMo12OaO-3MNZ·3H2O （1） and H3PW12O40.3MNZ·3H2O（2）, were synthesized and characterized by elemental analysis, IR spectra, electronic spectra, electron spin resonance （ESR） spectra and thermogravi-metry-differential thermal analysis （TG-DTA）. Reflectance spectra show the presence of weak intermolecular charge transfer between the organic and inorganic moieties in the solid state. The photochromic properties were studied by solid diffuse reflectance spectra and ESR spectra, and the photochromic reactions were found to exhibit first-order kinetics. TG-DTA showed that two hybrid materials have similar thermal behavior.

Hydrothermal synthesis and characterization of two novel inorganic-organic hybrid materials

By using different organic ligands, two 3D inorganic-organic hybrid compounds Co（C4H4N2）（VO3）2 1 and Co（C12H12N2）（VO3）2 2 were synthesized by hydrothermal reaction and characterized by X-ray crystallography. Crystal data： 1. crystal system orthorhombic, space group Pnna, a=1 0.188（2） A, b=1 1.497（2） A, c=7.3975（15） A, V=866.5（3） A^3, Z=4, Dcalcd= 2.705 g/cm^3; 2. crystal system triclinic, space group P1^- （No. 2）, a=8.3190（17） A, b=8.4764（17） A, c=1 1.183（2） A, a=95.48（3）°, β=92.03（3）°, γ=107.24（3）°,V=748.0（3） A^3, Z=2, Dcalcd= 1.958 g/cm^3. The framework of compound 1 contains both {Co（C4H4N2）} and infinite metavanadate chains. Crystal structure of compound 2 is constructed with inorganic {CoV2O6} layers across-linked by organic 1,2-bis（4-pyridyl） ethane ligands. The two compounds are thermally stable to approximately 410 ℃ and 350 ℃, respectively. Their optical band gaps are determined to be 2.13 eV and 2.12 eV by UV-VIS-NIR diffuse reflectance spectra, which revealed their nature of semiconductor and optical absorption features.

A new inorganic-organic hybrid material as consolidation material for Jinsha archaeological site of Chengdu

An organic-inorganic epoxy-silica-acrylate(ESA) hybrid material was used for the consolidation of Jinsha archaeological site of Chengdu in China.The hybrid materials have multiple functional groups,such as anhydride,epoxy,hydroxyl and carboxyl,which can form networks at room temperature and result in an enhanced chemical and water resistance of the consolidated soil.With increasing of TEOS content,the hybrid materials keep colorless with only some reduction of transparency,while the hybrid materials obviously turn from moderate yellowish to brown yellow with the increase of the epoxy resin(EOR) content after 120 min UV irradiation.SEM observation indicates that the hybrid soil consolidation materials can effectively penetrate into the soil substrate,fill up most of the pores,decrease the area porosity and consolidate the Jinsha archaeological soil.The consolidation performances are in the sequence:ESA > K2SiO4(PS) > tetraethyl orthosilicate(TEOS).

pH-Dependent Assembly of Hybrid Materials Based on Molybdates and Copper/imidazole Complexes

Three novel inorganic-organic hybrid materials, [Cu（imi）2（H2O）（MoO4）]n 1, [Cuz（imi）3（MoO4）E]n.nH2O 2 and [Cu3（imi）2（OH）2（MoO4）2]n 3 （imi = imidazole）, were synthesized and characterized by X-ray single-crystal structure determination. 1 crystallizes in orthorhombic, space group Pca21 with a = 13.382（4）, b = 8.527（2）, c = 9.622（3）A, V = 1098.0（5） A^3 Z = 4, C6H10CuMoN4O5, Mr = 377.66, Dc = 2.285 g/cm^3, F（000） = 740,μ（MoKa） = 3.095 mm^-1, the final R = 0.0256 and wR = 0.0722 for 1896 observed reflections with I 〉 2σ（I）. 2 crystallizes in monoclinic, space group P2t/c with a= 11.170（2）, b = 7.8244（15）, c = 22.631（4）A, β = 115.790（7）°, V = 1780.9（6）A^3 Z = 4, C9H14Cu2Mo2N6O9, Mr = 669.24, Dc= 2.496 g/cm^3, F（000）=1295,μ（MoKa） = 3.792 mm^-1, the final R = 0.0225 and wR = 0.0615 for 3838 observed reflections with I 〉 2σ（I）. 3 crystallizes in monoclinic, space group P21/c with a = 5.5599（19）, b = 23.771（8）, c = 7.3044（18）A , β = 129.356（16）°, V = 746.5（4）A^3, Z = 2, C6H10Cu3Mo2N4O10, Mr = 680.71, Dc = 3.029 g/cm^3, F（000） = 650,μ（MoKa） = 5.900 mm^-1, the final R = 0.0215 and wR = 0.0524 for 1620 observed reflections with I 〉 2σ（I）.

A New Method to Study the Sol-gel Transition Process of Organic/Inorganic Hybrid Materials

The sol-gel transition process of PMMA/SiO2 hybrid materials was first studied by means of the dynamic torsional vibration method. The different stages of the transition can be described by the change of torque. The temperature-dependent measurement of the gel time（ tg ） gives the possibility to determine the apparent activation energy.（ Ea ） of this transition according to Flory＇s gelation theory. The non-equilibrium thermodynamic fluctuation theory was used to predict the transition behavior. The isothermal transition experiments on hybrid sols with different TEOS（tetraethyl orthosilicate） contents were carried out. The results show that the Ea of a hybrid sol is higher than that of a non- hybrid sol of a TEOS-water-ethanol system. The increasing of TEOS content in a hybrid sol has no obvious effect on the Ea value, but it can enhance the sol-gel .reaction rate.

Organic-inorganic hybrid materials and architectures in optoelectronic devices: Recent advancements

Organic-inorganic hybrids are next-generation materials for use in high-performance optoelectronic devices owing to their adaptabilities in terms of design and properties.This article reviews the application of hybrid materials and layers in several widely used optoelectronic devices,i.e.,light amplification by stimulated emission of radiation(LASER),solar cells,and light-emitting diodes(LEDs).The effects of the incorporation of inorganic particles on photostability and optical gain are analyzed in the first section with reference to dye and perovskite lasers.Second,the strategies used in blending inorganic nanostructures into organic solar cells and bulk heterojunctions are analyzed.The use of various organic layers as electron-and hole-transport materials in Si heterojunction solar cells is reviewed in detail.Finally,the benefits of the presence of organic components in quantum-dot-and perovskite-based LEDs are derived from the analysis.The integration of organic and inorganic components with optimal interfaces and morphologies is a challenge in developing hybrid materials with improved efficiencies.

Luminescence properties of rare earth complexes bonded to novel mesoporous spherical hybrid materials

YVO_(4):Eu^(3+) phosphors have been widely used in optoelectronic integration fields of its chemical and thermal stability.However,the excitation spectrum band of VO_(4)^(3-) is too narrow for high-efficiency luminescence,restricting its further development.Herein,flower-like and linear-like YVO_(4):Eu^(3+) hollow mesoporous spheres were synthesized and connected with Eu organic ligand,to obtain a new hybrid luminescent material.The characterization shows that the pores of microspheres are in size of about 2-50 nm,sticked with regular morphology,well crystallized,and in uniform distribution.The emission intensity of hybrid luminescent material is higher than that of single YVO_(4):Eu^(3+) and single Eu co mplexes realizing the purpose of mutually reinforcing luminesce nce.This paper provides a new idea to connect rare earth complexes for a new non-silicon-based mesoporous spherical matrix.

Polymer-based hybrid materials and their application in personal health

With unprecedented properties and functions,polymer-based hybrid materials hold extremely important position in many fields.Here in this review,we summarized applications of polymer-based hybrid materials toward personal health.Firstly,theoretical calculation and in-situ visualization used to explore the interfacial interaction and formation of hybrid materials are introduced.Secondly,applications of polymer-based hybrid materials in personal health from proactive protection(anti-bacteria and harmful gas removal),health condition monitoring(breathing and sleep)to disease diagnosis(magnetic resonance imaging),and tissue therapy(dental restoration)are discussed.Additionally,aggregation-induced emission(AIE)organic molecules based optical sensors for personal security and polymer semiconductor for organic thin film transistors are simply discussed.Finally,we present the future tendency for preparing polymer-based hybrid materials that related with personal health.

Fabrication of branch-like Aph@LDH-MgO material through organic-inorganic hybrid conjugation for excellent anti-corrosion performance

Layered double hydroxides(LDH)frameworks have shown significant enhancement in stability and reusability,and their tailorable architecture brings new insight into the development of the next generation of hybrid materials,which attracted considerable attention in many fields over the years.One of the factors contributing to the widespread applicability of layered double hydroxides is their adaptable composition,which can accommodate a wide spectrum of potential anionic guests.This exceptional property makes the LDH system simple to adjust for various applications.However,most LDH systems are synthesized in situ in an autoclave at high temperatures and pressures that severely restrict the industrial use of such coating systems.In this study,LDH was directly synthesized on a magnesium alloy that had undergone plasma electrolytic oxidation(PEO)treatment in the presence of ethylenediaminetetraacetic acid,thereby avoiding the use of hydrothermal autoclave conditions.This LDH system was compared with a hybrid architecture consisting of organic-inorganic self-assembly.An organic layer was fabricated on top of the LDH film using 4-Aminophenol(Aph)compound,resulting in a smart hierarchical structure that can provide a robust Aph@LDH film with excellent anti-corrosion performance.At the molecular level,the conjugation characteristics and adsorption mechanism of Aph molecule were studied using two levels of theory as follows.First,Localized orbit locator(LOL)-πisosurface,electrostatic potential(ESP)distribution,and average local ionization energy(ALIE)on the molecular surface were used to highlight localization region,reveal the favorable electrophilic and nucleophilic attacks,and clearly explore the type of interactions that occurred around interesting regions.Second,first-principles based on density functional theory(DFT)was applied to study the hybrid mechanism of Aph on LDH system and elucidate their mutual interactions.The experimental and computational analyses suggest that the highπ-electron density and delocalization characteristics of the functional groups and benzene ring in the Aph molecule played a leading role in the synergistic effects arising from the combination of organic and inorganic coatings.This work provides a promising approach to design advanced hybrid materials with exceptional electrochemical performance.

Synthesis and characterization of hybrid organic-inorganic materials based on EA-MAn-APTES and silica

Poly (EA-MAn-APTES)/silica hybrid materials were successfully prepared fromEthyl acrylate (EA), maleic anhydride (MAn) and tetraethoxysilane (TEOS) in the presence of acoupling agent 3-aminopropyltriethoxysilane (APTES),by free-radical solution polymerization and insitu sol-gel process. The mass fraction of TEOS varied from 0 to 25%. The hybrid materials werecharacterized by the methods of FT-IR spectra, solvent extraction, scanning electron microscope (SEM), transmission electron microscope (TEM), differential scanning calorimetry (DSC) andthermogravimetric analysis (TGA) measuring apparatus to get their structures, gel contents,morphologies, particle sizes and thermal performances. The results show that the covalent bonds arebetween organic and inorganic phases, gel contents in the hybrid materials are much higher, theSiO_2 phase is well dispersed in the polymer matrix, silicon dioxide exist at nanoscale in thecomposites and have excellent thermal stability.

Nanocellulose-Graphene Hybrids: Advanced Functional Materials as Multifunctional Sensing Platform

Naturally derived nanocellulose with unique physiochemical properties and giant potentials as renewable smart nanomaterials opens up endless novel advanced functional materials for multi-sensing applications.However,integrating inorganic functional two-dimensional carbon materials such as graphene has realized hybrid organic-inorganic nanocomposite materials with precisely tailored properties and multi-sensing abilities.Altogether,the affinity,stability,dispersibility,modification,and functionalization are some of the key merits permitting their synergistic interfacial interactions,which exhibited highly advanced multifunctional hybrid nanocomposites with desirable properties.Moreover,the high performance of such hybrids could be achievable through green and straightforward approaches.In this context,the review covered the most advanced nanocellulose-graphene hybrids,focusing on their synthetization,functionalization,fabrication,and multi-sensing applications.These hybrid films exhibited great potentials as a multifunctional sensing platform for numerous mechanical,environmental,and human bio-signals detections,mimicking,and in-situ monitoring.

Hierarchical porous cellulose/lanthanide hybrid materials as luminescent sensor

Photoluminescent hybrid materials containing carboxymethyl cellulose and lanthanide ions（Eu3＋, Tb3＋）were prepared by a facile method under ambient conditions. Lanthanide ions were covalently grafted to the cellulose framework through coordination with the carboxylic groups of the cellulose. Hybrid materials were fabricated as hydrogel and aerogel. As shown by SEM and pore parameters, aerogel materials which were obtained by supercritical CO2 drying show hierarchical porous structure. The photoluminescence spectrum of the hybrid materials shows the characteristic red emission of Eu3＋ ion and green emission of Tb3＋. Further luminescent investigations reveal that these hybrid materials can detect Fe3＋ with relative selectivity and high sensitivity, which suggests that the hybrid materials could be a promising luminescent probe for selectively sensing Fe3＋ ion.

Novel Hybrid Nanoparticles of Vanadium Nitride/Porous Carbon as an Anode Material for Symmetrical Supercapacitor

Hybrid materials of vanadium nitride and porous carbon nanoparticles(VN/PCNPs) were fabricated by a facile pyrolysis process of vanadium pentoxide(V_2O_5) xerogel and melamine at relatively low temperature of 800 °C for supercapacitor application. The effects of the feed ratio of V_2O_5 to melamine(r), and nitrogen flow rate on the microstructure and electrochemical performance were also investigated. It was found that the size of the as-synthesized nanoparticles is about 20 nm. Both r value and N_2 flow rate have enormous impacts on morphology and microstructure of the nanoparticle, which correspondingly determined the electrochemical performance of the material. The VN/C hybrid nanoparticles exhibited high capacitive properties, and a maximum specific capacitance of 255.0 Fg^(-1) was achieved at a current density of 1.0 Ag^(-1) in 2 M KOH aqueous electrolyte and the potential range from 0 to -1.15 V. In addition,symmetrical supercapacitor fabricated with the as-synthesized VN/PCNPs presents a high specific capacitance of 43.5 F g^(-1) at 0.5 A g^(-1) based on the entire cell, and an energy density of 8.0 Wh kg^(-1) when the power density was 575 W kg^(-1). Even when the power density increased to 2831.5 W kg^(-1), the energy density still remained 6.1 Wh kg^(-1).

Organic-inorganic Hybrid Materials Based on Molybdophosphate and Organic Polyammonium

A new organic-inorganic hybrid compound （dienHs）2（P2Mo5O23） （1） [dien=NH（CH2CH2NH2）2] has been hydrothermally synthesized and characterized by elemental analyses, IR spectrum, thermogravimetric analysis, and the single crystal X-ray diffraction technique. Compound 1 crystallizes in the triclinic system with space group P1 and a=0.9790（2） nm, b=0.9922（2） nm, c= 1.4644（3） nm, α=95.510（10）°, β=98.860（10）°, γ=95.700（10）°, V=1.3895（5） nm^3, Z=2, R=0.0465. The results show that the compound consists of dienH3^3＋＋ and P2Mo5O23^6-, and the heteropoly anion P2Mo5O23^6- is connected to a 1-D chain structure with the protonated dien by hydrogen bonds.