Niobium Precursor Research Articles

High-electrophilic (SiO)2Nb(OH)(=O) sites confined in silanol defects over Nb-Beta zeolite for efficient cyclic alkene epoxidation reactions

Dealuminated Beta zeolite has a large amount of silanol defects on its interface, which provides an ideal place for embedding metal species and creating metal active sites in a confined microenvironment. The confined metal sites as well as their surroundings are closely related to the reactant activation and transient state achievement. Hence, unraveling the confined metal sites is of great significance for the catalytic reaction process. Herein, niobium species were incorporated into the silanol defects over dealuminated Beta zeolite with a facile dry impregnation method, co-grinding the niobium precursor with dealuminated Beta zeolite support. The successful incorporation of niobium into the silanol defects for 30Nb-Beta zeolite was verified by DRIFT, 1H MAS NMR, UV–Vis and UV-Raman characterizations. XAS characterization and DFT calculations further disclosed that the confined Nb species existed as (SiO)2Nb(OH)(=O), containing two Si−O−Nb bonds, one Nb=O bond as well as one Nb−OH bond. The synthesized 30Nb-Beta zeolite catalyst displayed a superior cyclohexene conversion of 51.1%, cyclohexene oxide selectivity of 83.1% as well as TOF value of 188.2 h−1 ascribed to the inherent electrophilicity of Nb(V) for confined (SiO)2Nb(OH)(=O) species as well as the low oxygen transfer energy barrier for NbV−OOH species. Furthermore, the prepared 30Nb-Beta zeolite can be effectively employed to other cyclic alkene epoxidation reactions.

LiNbO3 Thin Films through a Sol-Gel/Spin-Coating Approach Using a Novel Heterobimetallic Lithium-Niobium Precursor.

Lithium niobate is a lead-free material which has attracted considerable attention due to its excellent optical, piezoelectric, and ferroelectric properties. This research is devoted to the synthesis through an innovative sol-gel/spin-coating approach of polycrystalline LiNbO3 films on Si substrates. A novel single-source hetero-bimetallic precursor containing lithium and niobium was synthesized and applied to the sol-gel synthesis. The structural, compositional, and thermal characteristics of the precursor have been tested through attenuated total reflection, X-ray photoelectron spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The LiNbO3 films have been characterized from a structural point of view with combined X-ray diffraction and Raman spectroscopy. Field-emission scanning electron microscopy, energy dispersive X-ray analysis, and X-ray photoelectron spectroscopy have been used to study the morphological and compositional properties of the deposited films.

Silyl‐Substituted ortho‐Terphenoxide Group 3–5 Complexes: Synthesis, Structure and Applications in Catalysis

AbstractThe complexation behavior of 3,3’‐silyl‐substituted ortho‐terphenoxide ligands o‐C6H4(C6H2‐2‐OH‐3‐SiR3‐5‐Me)2 (SiR3= SiPh3, SiMePh2, SiMe3, Sit‐BuMe2) with a range of yttrium, titanium, niobium and tantalum precursors was examined. The complexation of the ligands with [Y(N(SiHMe2)2)3(THF)2] yielded monomeric complexes, as confirmed by NMR spectroscopy and X‐ray crystallography for the methyldiphenylsilyl‐ and tert‐butyldimethylsilyl‐substituted complex. The triphenylsilyl‐substituted yttrium bis(dimethylsilyl)amido complex showed good activity in the intramolecular hydroamination reaction of aminoalkenes. Complexation with Ti(NMe2)4 yielded a mixture of products, depending on the silyl substituents and the solvent used for complexation. A mono‐ligated bimetallic titanium complex and a bisligated titanium complex were analyzed by X‐ray crystallography. Complexation with M(NMe2)5 (M=Nb, Ta) produced the corresponding monomeric ortho‐terphenoxide complexes as confirmed by NMR spectroscopy and X‐ray structure analysis of a niobium complex and 3 tantalum complexes.

Study of Nb2O5 High-k Dielectric Material Deposited By Atomic Layer Deposition for Metal-Insulator-Metal Capacitor

Metal-Insulator-Metal (MIM) capacitors are important components in many electronic devices, including memory devices, filters, and oscillators. The performance of these devices depends strongly on the electrical properties of the dielectric layer. The application of new high-k materials can improve the properties of modern capacitors such as leakage current and capacitance density. However, it is necessary to understand the deposition conditions of both electrode and dielectric materials in order to master the dielectric properties in future MIM capacitors.One potentially interesting high-k material is niobium pentoxide (Nb2O5) with a wide band gap (3.6 eV) and high refractive index (n=2.3 @633 nm) deposited by Atomic Layer Deposition (ALD) using niobium (V) ethoxide as niobium precursor at 180°C and H2O as reaction agent and oxygen source. Nb2O5 films were deposited directly on a silicon (Si 100) substrate or on a 10nm of titanium nitride (deposited by ALD on Si substrate, n=1.4@633 nm). The Nb2O5 films were deposited with a good film thickness uniformity on the 6-inches of the wafers with a thickness ranging from 20 to 60 nm on each sample. The deposition was done under a suitable ALD temperature of 200-300 °C. In order to investigate the film growth, structure, morphology and optical properties, the samples were characterized by spectroscopic ellipsometry (SE), scanning electron microscopy (SEM), X-Ray diffraction (XRD) and atomic force microscopy (AFM). The as-deposited films were then annealed in a furnace at temperature ranging from 500 to 650°C under N2 atmosphere.Subsequently, a MIM structure (Al/Nb2O5/TiN) was produced by adding a second aluminum layer deposited at 250°C on a Nb2O5/TiN/Si stack by the sputtering method. The surface of the second electrodes was aimed to have 0.1-1.0 mm2 to confirm the surface dependency of the capacitance value. The electrical properties of Nb2O5 dielectric layer such as dielectric constant, breakdown voltage and leakage current at possible user voltage were measured on this last structure. The low leakage current density is desirable for MIM capacitors as it helps to minimize energy loss and increase the energy storage capabilities of the capacitors. The obtained J-E curve was compared to some electrical conduction mechanisms to identify its electrical conduction behaviors. The barrier height of the F-N tunneling mechanism was determined by fitting the experimental data to the F-N equation. These measurements indicate that the electrical properties of the Nb2O5 material produced by ALD with specific settings are promising for the application in capacitors. These results provide new insight into our understanding of the application of Nb2O5 realized by ALD for the MIM capacitor.

Wet-impregnated niobosilicate catalysts for glycerol conversion into solketal

Novel mesoporous niobosilicate materials with a homogeneous dispersion of niobium species were synthesized via impregnation of (NH4)3[Nb(O2)2(edtaO2)]·H2O·H2O2 on different hydrophilic surfaces of porous siliceous supports: extra small silica nanoparticles (XS-SiO2) and silica nanotubes (NTs-SiO2) bearing three different Si/Nb molar ratios of 74, 37 and 18. The Nb-silica catalysts obtained were calcined at 600 °C and then fully characterized by different physico-chemical techniques. The niobium precursor was found to be successfully loaded on the two silica support surfaces without noticeable modification of the silicate structural integrity. The Nb-containing catalysts were applied as active and selective heterogeneous catalysts for acid-catalyzed condensation of glycerol with acetone yielding solketal (2,2-dimethyl-1,3-dioxolane-4-methanol). The catalytic performance of these materials is ascribed to the enhanced accessibility of their active sites given by their morphology and to the suitable combination of acid sites. Moreover, no leaching of active sites was evidenced and the catalyst reusability studies indicated that the Nb-XS-74 and Nb-NTs-74 catalysts were successfully recyclable and highly stable in the acetalization of glycerol. The robustness and stability of the mesoporous Nb-silicate materials were also supported via characterization of the spent catalysts after the fifth recycling.

Isolation of a Dodecanuclear Polyoxo Cluster {Nb12O21} Showing a Rare Case of Five‐fold Coordinated Niobium(V) Centers with a Square Pyramidal Geometry

AbstractThe reactivity of the complexing anthracene‐9‐carboxylate ligand has been investigated with a niobium(IV) tetrachloride precursor (NbCl4 ⋅ 2THF) in isopropanol solvent. This resulted in the crystallization of a molecular assembly containing two distinct {Nb12O21} cores surrounded by multiple isopropanolate and anthracenoate ligands. The compound is formulated [Nb12((μ3‐O)3(μ‐O)18(C15H9O2)8(OiPr)10] ⋅ [Nb12(μ3‐O)2(μ‐O)19(C15H9O2)8(OiPr)10] illustrating the two different dodecameric oxo‐clusters, for which the niobium(IV) precursor was oxidized in the niobium(V) state during the reactional process. The two distinct {Nb12O21} units mainly differs by the environment of the niobium centers, which exhibits unexpected five‐fold coordination (square pyramid) for some of them, together with the classical six‐fold coordination (octahedron) as usually found for niobium(V). In the crystallization process, the. IR spectroscopy was used to analyze the esterification reaction occurring between the anthracene acid an isopropanolate ligands responsible of the production of water used in the oxo‐condensation of the niobium centers. 93Nb Solid state NMR was tentatively used to assess the occurrence of the different niobium environments.

Alumina Coatings Containing Niobium Pentoxide Polymorphs Prepared by Plasma Electrolytic Oxidation of Aluminum

This study explores the experimental parameters related to the production of Nb2O5 over alumina coatings produced by plasma electrolytic oxidation (PEO) and evaluates its use in photocatalytic applications. The influence of niobium precursor concentration and the electrolyte temperature on the electrochemical, morphological, and compositional responses are investigated using chemometric tools. The experimental design provides a geometrical representation of experimental parameters and shows the effect of the anodizing conditions on the pore density and the anodization curves. The samples are prepared at a constant current (10 mA cm−2) under the PEO regime. The coatings reveal a porous structure and crystalline phases of Nb2O5 and γ‐Al2O3. A preliminary photodegradation test under UV radiation and utilizing Rhodamine B (RhB) solution shows the best photocatalytic performance for the sample produced by the highest Nb salt concentration (16.0 g L−1) and highest temperature (18.7 °C). These results are attributed to a higher niobium content in this sample and crystalline phases of Nb2O5 over the Al substrate.

Surface stability of SrNbO3+δ grown by hybrid molecular beam epitaxy

4d transition metal oxides have emerged as promising materials for numerous applications including high mobility electronics. SrNbO3 is one such candidate material, serving as a good donor material in interfacial oxide systems and exhibiting high electron mobility in ultrathin films. However, its synthesis is challenging due to the metastable nature of the d1 Nb4+ cation and the limitations in the delivery of refractory Nb. To date, films have been grown primarily by pulsed laser deposition (PLD), but development of a means to grow and stabilize the material via molecular beam epitaxy (MBE) would enable studies of interfacial phenomena and multilayer structures that may be challenging by PLD. To that end, SrNbO3 thin films were grown using hybrid MBE for the first time using a tris(diethylamido)(tert-butylimido) niobium precursor for Nb and an elemental Sr source on GdScO3 substrates. Varying thicknesses of insulating SrHfO3 capping layers were deposited using a hafnium tert-butoxide precursor for Hf on top of SrNbO3 films to preserve the metastable surface. Grown films were transferred in vacuo for x-ray photoelectron spectroscopy to quantify elemental composition, density of states at the Fermi energy, and Nb oxidation state. Ex situ studies by x-ray absorption near edge spectroscopy and scanning transmission electron microscopy illustrate that the SrHfO3 capping plays an important role in preserving the crystalline quality of the material and the Nb 4d1 metastable charge state under atmospheric conditions.

Niobium- and titanium-based coating for the protection of carbon steel SAE 1020 against corrosion

PurposeThe purpose of this paper is to evaluate the protection against corrosion of carbon steel SAE 1020 promoted by a niobium- and titanium-based coating produced from a resin obtained by the Pechini method.Design/methodology/approachA resin was prepared with ammonium niobium oxalate as niobium precursor and K2TiF6 as titanium precursor. Carbon Steel SAE 1020 plates were dip coated in the resin and calcinated for 1 h at 600 ºC. Scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction were used to characterize the coating morphologically and structurally. Open circuit potential, electrochemical impedance spectroscopy, anodic potentiodynamic polarization and scanning vibrating electrode technique were used to evaluate the corrosion protection of the coating.FindingsThe electrochemical analyses evidence slight protection against corrosion of the coating by itself; however, the needle-like crystal structure obtained may potentially provide a good anchorage site, suggesting the coating could be used as a pretreatment that may present similar application to phosphating processes, generating lower environmental impacts.Originality/valueDue to increasingly restrictive environmental laws, new environmentally friendlier surface treatments must be researched. This paper approaches this matter using a combination of niobium- and titanium-based coating, produced by a cleaner process, the Pechini method.

Synthesis of niobium pentoxide from bis(cyclopentadienyl) niobium(IV) dichloride using the spin coating process

In this research study, the optical, electrical and structural properties of synthesized niobium pentoxide (Nb2O5) thin films using bis(cyclopentadienyl)niobium(IV)dichloride(C10H10Cl2Nb) as the organometallic niobium precursor have been reported. The samples were formed via the sol-gel spin coating deposition process and calcined at varying temperatures to produce Nb2O5 thin films. The fabricated thin films were then subjected to Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray (EDX) spectroscopy, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Ultraviolet-visible spectroscopy and electrical tests. The XRD showed the films to have an orthorhombic structure, while the EDX indicated the presence of niobium oxide in the thin films. The SEM analysis revealed that the films consisted of nanometric spheres, with the FTIR spectroscopy illustrating the formation of an Nb-O-Nb bond. Also, the thin films showed a high absorbance coefficient in the UV region, with 3.61 eV as the lowest optical energy bandgap at 700 °C. The conductivity and resistivity tests confirmed that the synthesized thin films were good semiconductors. The correlation between the different analyses with respect to the annealing temperatures of the Nb2O5 thin films was also discussed.

Production of Niobium Nitride Via Nitrogen-Based Solid-Gas Reaction

Nanostructured niobium nitride was synthesized through a solid-gas reaction in an atmosphere of nitrogen and hydrogen using an oxalic niobium precursor. Crystal phases evolution throughout the reactive processes were evaluated using X-Ray Diffraction, reaction parameters modifications were performed in isotherm time, gas flow, and precursors’ mass. It was verified the synthesis of a stable NbN material with a hexagonal structure under the following conditions: 1g of precursor, 300 min of isotherm at 1100 °C and, the gas flow of N2 = 40% (v/v), and H2 = 60% (v/v). The increase in gas phase flow and the decrease of solid load favored the process, and a pure and single-phase powder was obtained. This set indicates the importance of physical resistance in the fluid-particle interaction process. Under these conditions, the solid obtained had a crystallite size of 30 - 50 nm.

Photocatalytic degradation of rhodamine B using Nb2O5 synthesized with different niobium precursors: Factorial design of experiments

Niobium pentoxide (Nb2O5) was synthesized by the microwave-assisted hydrothermal method using two different niobium precursors: niobium ammoniacal oxalate (P1) and niobium chloride (P2). The XRD result confirms the presence of Nb2O5 with low crystallinity for both precursor samples. The SEM images show differences between the material morphologies but with the same aggregation particle characteristics. Photocatalytic degradation of the rhodamine B (RhB) dye was performed using both samples of Nb2O5 as a photocatalyst under UVC illumination using a 24 factorial design experimental method. The studied variables were the type of precursor (P1 and P2), the RhB concentration (1 × 10−5 and 3 × 10−5 M), the Nb2O5 photocatalyst dosage (25 and 50 mg), and the time of the photocatalysis analysis (30 and 60 min), verifying the influence on the RhB dye removal efficiency. The factorial design showed that all variables had a significant effect on the process, but the variables with the most influence were RhB concentration and photocatalysis time. For both precursors, the samples that showed greater removal efficiency were those under conditions 1 × 10−5 M, 50 mg, and 60 min, obtaining 92.87% and 98.99%, respectively. The high rate of RhB removal suggests that the Nb2O5 obtained by microwave-assisted hydrothermal synthesis has the potential to be used in photocatalytic processes to remove organic pollutants from effluents.

Synthesis of novel volatile niobium precursors containing carboxamide for Nb2O5 thin films

A series of novel Nb(V) tBu-imido/N-alkoxy carboxamide complexes, NbCl2(NtBu)(pyridine)(edpa) (1), NbCl2(NtBu)(pyridine)(mdpa) (2), and Nb(NtBu)(mdpa)3 (3), were successfully synthesized by metathesis reaction between Nb(NtBu)Cl3(py)2 and several equivalents of Na(edpa) (edpaH = Nethoxy-2,2-dimethylpropanamide) and Na(mdpa) (mdpaH = N-methoxy-2,2-dimethylpropanamide). These complexes could potentially serve as precursors for Nb-containing thin films. Compounds 1–3 were characterized by FT-IR and 1H and 13C NMR spectroscopies, elemental analysis, and thermogravimetric analysis (TGA). Single crystal X-ray diffraction analysis suggested that complex 3 has a distorted pentagonal bipyramidal geometry around the central Nb atom, with three bidentate mdpa ligands and one tBu imido group saturating the coordination. TGA analysis revealed that the thermal characteristics of 3 were superior to those of 1 and 2. All prepared complexes were able to be distilled or sublimed and expected potential precursors for the fabrication of thin films.

Magnetic and Mesoporous Silica-Niobia Material as Modifier of Carbon Paste Electrode for p-Nitrophenol Electrochemical Determination

In the present work, the sol-gel synthesis method was employed as strategy to obtain a magnetic and mesoporous silica-niobia material. The planned synthesis was based on the heterocondensation of niobium and silicon alkoxide precursors, in the presence of spherical magnetite particles. The resulting material presented interesting characteristics such as magnetism, large mesopores, in the range from 20 to 50 nm, and 68 m2 g−1 of surface area. These features allowed its use as modifier of carbon paste electrode for p-nitrophenol determination, since niobia has never been used in electrochemical sensors for the determination of nitrophenol compounds. By using differential pulse voltammetry technique, the electrode can be applied in a wide range of p-nitrophenol concentration, from 10 to 490 μmol L−1, with a limit of detection of 1.2 µmol L−1 and sensitivity up to 0.60 µA L µmol−1. The proposed electrode presented good sensitivity and selectivity and it was applied in real water samples.

Improved critical temperature of superconducting plasma-enhanced atomic layer deposition of niobium nitride thin films by thermal annealing

The efficiency of the superconducting radio frequency cavities composed of Nb required the deposition of thickness-controlled multilayer coatings of superconductor-insulator-superconductor (S-I-S) on the internal surfaces of the cavities. Herein, we report the plasma-enhanced atomic layer deposition of carbon-free NbN (50 µm thick), followed by a thermal treatment, to obtain the superconducting layer in the S-I-S structure. Using (tert-butylimido)-tris(diethylamino)-niobium as the niobium precursor and H2 and NH3 plasma as reactive gasses, the deposition and annealing parameters were optimized by studying their effects on the film properties (crystallinity, density, and composition). We demonstrated that the superconducting critical temperature (Tc) can be improved after thermal annealing up to 13.8 K, a value compatible with the targeted application. In addition to the expected densified layers and increased grain size, we observed a partial transformation of the oxide present in the as-deposited layer into niobium oxynitride, which could indicate the origin of the improvement of the superconducting properties. With low carbon and oxygen impurity concentrations in the films, this study contributes to the understanding of the relationship between the structure, composition, and superconductivity in NbN.

Entrapped NbOx clusters in MFI zeolite for sustainable acid catalysis

Abstract Entrapping the small NbOx clusters into MFI zeolite crystals was directly prepared via a facile hydrothermal method, assisting with the sodium citrate and EDTA-2Na to dissolve and chelate the niobium precursors. The existing states and configurations of Nb species in the zeolites were carefully characterized by a series of techniques including XRD, FTIR, SEM, TEM, UV–Vis, XPS and Raman. These results clearly indicated that the entrapped oligomeric NbOx clusters in MFI zeolite crystals contained Nb-OH, Nb=O and Nb-O-Si bonds. These characters were the origin of both Lewis and Bronsted acid sites for these Nb-MFI samples, which was vividly confirmed by FTIR spectroscopy with pyridine absorption and solid-state NMR spectroscopy with ammonia and TMPO as probing molecules techniques. The as-prepared Nb-MFI zeolites were employed as sustainable Lewis acids in several catalytic reactions. Especially, Nb-MFI zeolites exhibited remarkable catalytic performance in the cross-aldol condensation between furfural and acetone for biomass upgrading, surpassing traditional Lewis acidic zeolites Sn-MFI and Sn-BEA in terms of activity and selectivity, respectively. The 2.6%Nb-MFI also showed very good stability during reaction and it could be recycled for six times without loss in activity. Finally, 2.6%Nb-MFI was verified as a general catalyst for the cross-aldol condensation reaction between small-molecule aldehydes and ketones. All these results demonstrate the great potential of Nb-MFI as a robust catalyst for the shape-selective Lewis acid catalysis. The synthesis strategy developed herein could be readily extended to the construction of zeolite entrapped high-valence transition metal clusters for catalytic applications.

SiO2 supported niobium oxides with active acid sites for the catalytic acetalization of glycerol

The silica supported niobium oxide catalysts with abundant acid active sites were successfully fabricated and demonstrated catalytic activity in the acetalization of glycerol with acetone to produce solketal. Although Niobium pentachloride which was used as the niobium precursor preferred to aggregate on the surface, the chemical vapor deposition method was introduced to remove the surface chloride. The synthesis parameter of the material affects the structure and the type of the supported niobium oxide on the carrier, and directly changes the amounts of catalytic sites. The effect of calcination temperature/time and loading amount of hydrated niobium oxide on the catalytic performance was investigated. The properties of acid sites on catalysts were characterized, and the catalytic process was directly observed by operando Raman. These in-situ experimental trials could provide deep insight to understand the catalytic mechanism.

Facile Synthesis of Nb2O5 as a Visible Light-Sensitive Photocatalyst

Niobium pentoxide (Nb2O5) is a promising semiconductor in catalysis due to its chemical and physical properties, availability, and non-toxicity. However, because of its large bandgap energy (Eg= 3.1 – 4.0 eV), Nb2O5 does not work as a photocatalyst under visible light, which makes its use of solar light limited. Even though Nb2O5 presents this drawback, its photocatalytic activity under visible light radiation can be enhanced due to the presence of surface groups, known as niobium peroxo complexes, formed by the treatment with hydrogen peroxide. In general, the modified niobia is synthetized in multi-step processes which allow the generation of strongly reactive oxygen species (ROS) (i.e. peroxo and superoxo) on its surface. In contrast, in this study, the peroxo-niobium oxide was prepared by a facile combination of the oxidant peroxide method (OPM) and hydrothermal treatment. The ability of Nb2O5 to form the ROS using this method was investigated in respect to the different Nb:H2O2 molar ratio (1:2 or 1:10) added in the metal oxide synthesis. For this purpose, ammonium niobium oxalate was dissolved in distilled water and hydrogen peroxide was then added to the reaction medium. The niobium precursor in contact with H2O2 forms instantaneously the niobium peroxo complex that was crystallized at 120 ⁰C with a heating ramp of 1 oC/min, for 12h in a home-made teflon lined autoclave. When the desired temperature was reached, the internal pressure of the reactor varied from ca. 10 to 27 atm, depending upon the amount of hydrogen peroxide used to prepare each material. The oxidative properties of the reactive oxygen species formed on the surface of metal oxides were tested in photodegradation of caffeic acid (CA) under visible light. In addition, reuse tests were performed in order to investigate the loss of photoactivity of the best photocatalyst in the CA degradation. XRD patterns revealed that the crystallographic structures of the samples Nb2H and Nb10H contain the Nb2O5 pseudohexagonal-type phase (JCPDS 28-317) and hydrated niobium oxide. Although no changes in the crystalline structure of both materials were observed, the presence of peroxo and superoxo species in the photocatalysts was confirmed by XPS and FTIR. The composites Nb2H and Nb10H presented band gap energies of 3.20 and 3.16 eV, respectively. However, Nb10H sample absorbs visible light at more than 400 nm, suggesting that the synthesis of the Nb2O5 with excess of H2O2 shifts the absorption edge of this material to the visible range, as well as reduces the energy required to the photoactivation of the catalyst. It was found that the photocatalytic activity increased with increasing oxidant concentration in the synthesis medium due to formation of a higher amount of oxygen reactive species on the surface of niobia. The peroxo-niobium groups on the Nb2O5 surface allowed the photocatalysts to be activated by visible light, and the superoxo groups formed can be also be responsible to improve its photocatalytic efficiency. The reuse tests of the Nb10H oxide indicated that the CA removal capacity remained practically constant even after four consecutive cycles. Therefore, the possibility of using solar irradiation to supply energy to active the photocatalyst make this material promising for use in low-cost photocatalytic systems for treatment of wastewater.

Structure Engineering and Structure-Property Study of TiNb2O7 Nanofibers As Anode for Safer Lithium Ion Batteries

Lithium ion batteries (LIBs) have been the dominant energy storage technology for a wide range of applications including portable electronic, electrical vehicles, and grid-scale energy storage. Recently with safety and performance in mind, TiNb2O7 (TNO) has been studied as a promising anode material. It offers a theoretical capacity of 387.6 mA h g-1, which is comparable to that of graphite (372 mA h g-1) and two times that of Li4Ti5O12 (175 mA h g-1). TNO also exhibits an operational voltage larger than 1.0 V (vs Li+/Li0), which helps to avoid formation of dendritic lithium and ensure safe operation. TNO with various morphology and size has been studied intensely since its discovery by Goodenough et. al. in 2011 including mesoporous microspheres, solid or porous nanoparticles, and solid or hollow 1D fibers. However, no comprehensive study which studies the structure-property-aspect of TNO has been completed. Here, we are trying to prepare TNO with various morphology, size, and porosity as well as to study the correlation of TNO properties with electrochemical performance. Electrospinning technology is used to synthesize target materials, which are formulated from using poly(lactic acid) as a carrier polymer in various solvents (dimethylformamide, acetone, and dichloromethane) and adding titanium and niobium precursors. Parameters that affect the morphology of spun fibers are concentration, flow rate, applied voltage, collector plate distance, viscosity, and surface tension. Those parameters, especially solution chemistry, are carefully tuned to control the resulting fiber morphology and other properties. For example, solid, hollow, and porous (surface porous, inner porous, or highly porous) TNO fibers can be obtained by careful solvent selection as solvents have been proven to strongly affect evaporation and phase separation processes. All prepared TNO are further tested as anode materials in lithium ion battery and the property-performance correlation is carefully analyzed.

Gyroidal Niobium Sulfide/Carbon Hybrid Monoliths for Electrochemical Energy Storage

AbstractTransition metal dichalcogenides are attractive two‐dimensional electrode materials for electrochemical energy storage devices due to their high reversible charge storage capacity. Hybridization of these materials with carbon promises enhanced performance by facilitating the access to reactive sites and extended mechanical stabilization. Herein, we introduce a NbS2/C hybrid material exhibiting a gyroidal microstructure synthesized through macromolecular co‐assembly of a tailored block copolymer and an organometallic niobium precursor and subsequent sulfidation. Our synthesis allows the preparation of mechanically stable monoliths with NbS2 nanocrystals engulfed in a highly porous carbon shell. Due to the curvature of the gyroidal structure, abundant reactive sites are exposed that lead to an attractive performance in a lithium‐containing electrolyte with a capacity of up to 400 mAh/g.