Band gap modulation of nanostructured WO_(3) nanoplate film by Ti doping for enhanced photoelectrochemical performance

Despite being a promising photoanode material for water splitting,WO_(3) has low conductivity,high onset potential,and sluggish water oxidation kinetics.In this study,we designed Ti-doped WO_(3) nanoplate arrays on fluoride-doped tin oxide by a seed-free hydrothermal method,and the effects of doping on the photoelectrochemical performance were investigated.The optimal Ti-doped WO_(3) electrode achieved a photocurrent density of 0.53 mA/cm^(2) at 0.6 V(vs Ag/AgCl),110%higher than that of pure WO_(3) nanoplate arrays.Moreover,a significant cathodic shift in the onset potential was observed after doping.X-ray photoelectron spectroscopy valence band and ultraviolet–visible spectra revealed that the band positions of Ti-doped WO_(3) photoanodes moved upward,yielding a lower onset potential.Furthermore,electrochemical impedance spectroscopy measurements revealed that the conductivities of the WO_(3) photoanodes improved after doping,because of the rapid separation of photo-generated charge carriers.Thus,we report a new design route toward efficient and low-cost photoanodes for photoelectrochemical applications.

Density functional theory study of NO_2 -sensing mechanisms of pure and Ti-doped WO_3 (002) surfaces

Density functional theory （DFT） calculations are employed to explore the NO2-sensing mechanisms of pure and Ti-doped WO3 （002） surfaces. When Ti is doped into the WO3 surface, two substitution models are considered： substitution of Ti for W6c and substitution of Ti for Wsc. The results reveal that substitution of Ti for 5-fold W forms a stable doping structure, and doping induces some new electronic states in the band gap, which may lead to changes in the surface properties. Four top adsorption models of NO2 on pure and Ti-doped WO3 （002） surfaces are investigated： adsorptions on 5-fold W （Ti）, on 6-fold W, on bridging oxygen, and on plane oxygen. The most stable and likely NO2 adsorption structures are both N-end oriented to the surface bridge oxygen Olc site. By comparing the adsorption energy and the electronic population, it is found that Ti doping can enhance the adsorption of NO2, which theoretically proves the experimental observation that Ti doping can greatly increase the WO3 gas sensor sensitivity to NO2 gas.

Facile synthesis of S-doped reduced TiO_(2-x) with enhanced visible-light photocatalytic performance

A different approach to synthesize visible‐light‐active sulfur(S)‐doped reduced titania(S‐TiO2‐x)using thiourea dioxide as both the S source and reductant was developed.The structure,morphology,and optical and electronic properties of the as‐prepared S‐TiO2‐x samples were examined by multiple techniques,such as X‐ray diffraction,transmission electron microscopy,X‐ray photoelectron spectroscopy,ultraviolet‐visible diffuse reflectance spectroscopy,Brunauer‐Emmett‐Teller and photocurrent measurements,and electrochemical impedance spectroscopy.The photocatalytic activity of S‐TiO2‐x was evaluated by photodegradation of organic Rhodamine B under visible‐light irradiation.The degradation rate of Rhodamine B by S‐TiO2‐x obtained by calcination was about31,2.5,and3.6times higher than those of pure TiO2,pristine TiO2‐x,and S‐doped TiO2,respectively.In addition,the as‐prepared S‐TiO2‐x exhibited long‐term stable photocatalytic performance in the degradation of Rhodamine B under visible‐light illumination.This report reveals a new approach to prepare stable and highly efficient solar light‐driven photocatalysts for water purification.

Tuning anionic redox activity to boost high-performance sodium-storage in low-cost Na_(0.67)Fe_(0.5)Mn_(0.5)O_(2) cathode

Na-based layered iron-manganese oxide Na_(0.67)Fe_(0.5)Mn_(0.5)O_(2) containing only low-cost elements is a promising cathode for Na-ion batteries used in large-scale energy storage systems.However,the poor cycle stability restricts its practical application.The capacity decay of Na_(0.67)Fe_(0.6)Mn_(0.5)O_(2) mainly originates from the irreversible anionic redox reaction charge compensation due to the high-level hybridization between oxygen and iron.Herein,we rationally design a surface Ti doping strategy to tune the anionic redox reaction activity of Na_(0.67)Fe_(0.5)Mn_(0.5)O_(2) and improve its Na-storage properties.The doped Ti ions not only enlarge the Na migration spacing layer but also improve the structure stability thanks to the strong Ti-O bond.More importantly,the d0-shell electronic structure of Ti^(4+) can suppress the charge transfer from the oxidized anions to cations,thus reducing the anionic redox reaction activity and enhancing the reversibility of charge compensation.The modified Na_(0.67)Fe_(0.5)Mn_(0.5)O_(2) cathode shows a reversible capacity of 198 mA h g^(-1) and an increased capacity retention from 15% to 73% after about1 month of cycling.Meanwhile,a superior Na-ion diffusion kinetics and rate capability are also observed.This work advances the commercialization process of Na-based layered iron-manganese oxide cathodes;on the other hand,the proposed modification strategy paves the way for the design of high-performance electrode materials relying on anionic redox reactions.

One-pot topotactic synthesis of Ti^(3+) self-doped 3D TiO_2 hollow nanoboxes with enhanced visible light response

Ti^（3＋） self-doped anatase three-dimensional（3D） TiO_2 hollow nanoboxes were synthesized via a topological transformation process involving template participation by a facile one-pot hydrothermal treatment with an ethanol solution of zinc powder and TiOF_2. It is worth noting that the 3D TiO_2 hollow nanoboxes are assembled from six single-crystal nanosheets and have dominant exposure of the {001} facets. It is found from EPR spectra that adding zinc powder is an environment-friendly and effective strategy to introduce Ti^（3＋） and oxygen vacancy（Ov） into the bulk of 3D hollow nanoboxes rather than the surface, which is responsible for their enhanced visible photocatalytic properties.The photocatalytic activity was evaluated by measuring the formation rate of hydroxide free radicals using 7-hydroxycoumarin as a probe. The sample prepared with zinc/TiOF_2 mass ratio of0.25 exhibited the highest RhB photodegradation activity under visible-light irradiation with a degradation rate of 96%, which is 4.0-times higher than that of pure TiO_2. The results suggest a novel approach to construct in-situ 3D hierarchical TiO_2 hollow nanoboxes doped with Ti^（3＋） and Ov without introducing any impurity elements for superior visible-light photocatalytic activity.

Reactive DC Magnetron Sputter Deposited Titanium-Copper-Nitrogen Nano-Composite Thin Films with an Argon/Nitrogen Gas Mixture

A sintered Ti13Cus7 target was sputtered by reactive direct current （DC） magnetron sputtering with a gas mixture of argon/nitrogen for different sputtering powers. Titanium-coppernitrogen thin films were deposited on Si （111）, glass slide and potassium bromide （KBr） substrates. Phase analysis and structural properties of titanium-copper-nitrogen thin films were studied by X-ray diffraction （XRD）. The chemical bonding was characterized by Fourier transform infrared （FTIR） spectroscopy. The results from XRD show that the observed phases are nano-crystallite cubic anti rhenium oxide （anti ReO3） structures of titanium doped Cu3N （Ti：Cu3N） and nanocrystallite face centered cubic （fcc） structures of copper. Scanning electron microscopy and energy dispersive X-ray spectroscopy （SEM/EDX） were used to determine the film morphology and atomic titanium/copper ratio, respectively. The films possess continuous and agglomerated structure with an atomic titanium/copper ratio （-0.07） below that of the original target （- 0.15）. The transmittance spectra of the composite films were measured in the range of 360 nm to 1100 nm. Film thickness, refractive index and extinction coefficient were extracted from the measured transmittance using a reverse engineering method. In the visible range, the higher absorption coefficient of the films prepared at lower sputtering power indicates more nitrification in comparison to those prepared at higher sputtering power. This is consistent with the formation of larger Ti：Cu3N crystallites at lower sputtering power. The deposition rate vs. sputtering power shows an abrupt transition from metallic mode to poisoned mode. A complicated behavior of the films＇ resistivity upon sputtering power is shown.

Tunable Supercontinuum Generated in a Yb^3＋-Doped Microstructure Fiber Pumped by Ti：Sapphire Femtosecond Laser

We experimentally demonstrate that a tunable supercontinuum（SC） can be generated in a Yb3＋-doped microstructure fiber by the concept of wavelength conversion with a Ti：sapphire femtosecond（fs） laser as the pump.Experimental results show that an emission light around 1040 nm in an anomalous dispersion region is first generated and amplified by fs pulses in the normal dispersion region. Then, SC spectra from 1100 to 1380 nm and 630 to 840 nm can be achieved by combined effects of higher-order soliton fission and Raman soliton self-frequency shift in the anomalous dispersion region and self-phase modulation, dispersive wave, and four-wave mixing in the normal dispersion region. It is also demonstrated that the 20 nm change of pump results in a 280 nm broadband shift of soliton and the further red-shift of soliton is limited by OH-absorption at 1380 nm.

Mitigating the dissolution of V_(2)O_(5) in aqueous ZnSO_(4) electrolyte through Ti-doping for zinc storage

Aqueous zinc-ion batteries(AZIBs)have become a hotspot for electrochemical energy storage owing to the high safety,low cost,environmental friendliness,and favorable rate performance.However,the serious dissolution of cathode materials in aqueous electrolytes would lead to poor cyclability,which should be addressed before commercialization.Herein,we designed a Ti-doped V_(2)O_(5) with yolk-shell microspherical structure for AZIBs.The Ti doping stabilizes the crystal structure and relieves the dissolution of V_(2)O_(5) in aqueous ZnSO_(4) electrolyte.The optimized sample,Ti_(0.2)V_(1.8)O_(4.9),delivers a high capacity(355 mAh/g at 0.05 A/g)as well as good capacity retention(89%after 2500 cycles at 1.0 A/g).This work provides an effective strategy to mitigate the dissolution of cathode material in aqueous ZnSO_(4) electrolyte for cyclability enhancement.

Insights into the Ti^(4+) doping in P2-type Na_(0.67)Ni_(0.33)Mn_(0.52)Ti_(0.15)O_(2) for enhanced performance of sodium-ion batteries

Due to the sodium abundance and availability,sodium-ion batteries(SIBs)have the potential to meet the worldwide growing demand of electrical energy storage.P2-type sodium transition-metal layer oxides with a high energy density are considered as the most promising cathode materials for SIBs.We present here a detailed study of the enhanced rate capability and cyclic stability of the Ti-doped Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2)cathode material.The combined analysis of ex-situ X-ray absorption fine structure(XAFS)spectroscopy,aberration-corrected high resolution transmission electron microscopy(AB-HRTEM)and X-ray diffraction(XRD)show that the strong Ti–O bond in the transition metal layers stabilizes the local structure,destroy the Na+-vacancy ordering and arrest the irreversible multiphase transformation that occurs during the intercalation/deintercalation process.Actually,Na_(0.67)Ni_(0.33)Mn_(0.52)Ti_(0.15)O_(2)exhibits a reversible capacity of 89.6 mA h g^(-1)even at 5 C,an excellent cyclability with 88.78%capacity retention after 200 cycles at 0.5 C.This study provides a better understanding in optimization of the design of high-energy cathode materials based on titanium doped layered oxides for SIBs.

Double layered,one-pot hydrothermal synthesis of M-TiO_2(M=Fe^(3+),Ni^(2+),Cu^(2+)and Co^(2+)) and their application in photocatalysis

A double layered, one-pot hydrothermal method was adopted in this work to prepare transition metal ions （Fe3＋, Ni2＋, Cu2＋ and Co2＋） doped TiO〉 The morphology and chemical properties of TiO2 and the status of metal ions were characterized with XRD, TEM, BET, UV-Vis and XPS analysis. TEM images show that the obtained TiO2 was very uniform with an average particle size of 10.4 nm. XPS, TEM and XRD results show that transitional metals were doped onto TiO2 in the form of ions. Photocatalytic decomposition of oxalic acid under UV illumination and methylene blue degradation under visible light on these materials were conducted, respectively. The results reveal that Cu2＋-TiO2 and C02＋-TiO2 showed a highest activity under UV and visible light illumination, respectively, and they were both more active than commercial P25 TiO2. With this special design of double layers, the hydrolysis of titanium precursor in the system with water can be easily controlled and metal ions are simply doped. This strategy can be further applied to synthesize metal ion doped TiO2 using various metal precursors with controllable amounts, and thus lead to better optimization of highly active photocatalyst.

Study of the structural,ferroelectric,dielectric,and pyroelectric properties of the K0.5Na0.5NbO3 system doped with Li+,La3+,and Ti4+

Pure Ko.sNao sNbO3(KNN)and KNN doped with Lit(6%mole),Lat(1.66%,5%,6%mole),and Ti+t(10%mole)were prepared by mixture of oxides using high-energy milling and conventional solid-state reaction.The effects of the dopant on the physical properties of pure KNN have been evaluated based on the structural,ferroelectric,pyroelectric,and dielectric measurements.The XRD measurements show that KNN pure sample contains a mixture of monoclinic and orthorhombic crystalline phases,with a slightly higher concentration of monoclinic phase.In contrast,all doped samples show a higher concentration of the orthorhombic phase,as well as the presence of a secondary phase(K6Nb10.8O3o),also detected by Raman measurements.The samples with a higher concentration of this secondary phase,also present greater dielectric losses and lower values of remnant polarization.The dielectric measurements allowed us to detect temperatures of structural transitions(orthorhombic-tetragonal,O-T)previous to the ferroelectric paraelectric transition(tetragonal-cubic,T-C),and also in this set of samples,a direct correlation was found between the values of remnant polarization and the corresponding pyroelectric signal response.

The electron structure and photocatalytic activity of Ti(IV) doped Bi_2O_3

Density functional theory （DFT） plays a significant role in the development of visible light responsive photocatalysts. Based on the first-principles plane-wave ultrasoft pseudopotential （USPP） method, the crystal structures of α,β,γ, and 5-Bi2O3 were optimally calculated for the total density of states （TDOS） and the partial density of states （PDOS） of Bi, O atoms. The calculation for Ti（IV） doped Bi2O3 supercell was carried out. The effects of Ti（IV）-doping on the electron structures and light absorption properties of various Bi2O3 were analyzed. The results showed that Ti 3d orbital appeared in the forbidden band of Bi2O3 and hybridized with O 2p, Bi 6p orbitals. The narrowed band gap （Eg） and red-shift of light absorption edge are responsible for the enhanced photoeatalytic activity of Bi2O3. The Ⅱ-Bi2O3 and Ti-doped β-Bi2O3 were prepared by a hydrotherrnal synthesis method. The improvement of the photoeatalytic activity of Bi2O3 has also been verified by the characteristics of the UV-vis diffuse reflection spectrum and the experimental evaluation of the photocatalytic degradation of crystal violet in aqueous solution.

Insight into the influence of high temperature annealing on the onset potential of Ti-doped hematite photoanodes for solar water splitting

For Ti-doped hematite photoanodes, high temperature annealing drastically increases the water oxidation plateau photocurrent, but also induces an anodic shift of onset potential by about 100 m V, thus hindering the performance under low applied bias. To the best of our knowledge, the effects of high temperature annealing on the onset potential have been rarely studied. Herein, both X-ray photoelectron spectroscopy（XPS） measurements and theoretical calculations indicated that the increase of surface Ti/Fe atomic ratio after high temperature annealing decreased the adsorption capacity of hydroxide ions on the hematite surface. Subsequently, the flatband potential（i.e., the theoretical onset potential） of Ti doped hematite photoanodes positively shifted, which was supported by the Mott-Schottky measurements.

Electro-catalytic degradation properties of Ti/SnO_2–Sb electrodes doped with different rare earths

Ti/SnO2–Sb electrode has a good effect on the removal of organic pollutants. But its short service life limits its large-scale application in industry. Electro-catalytic degradation performances and service life of the electrode can be significantly improved by doping rare earth（RE） ions into the oxide coating of Ti/SnO2–Sb electrode. Ti/SnO2–Sb electrodes doped with different RE elements（Ce, Dy, La, and Eu） were prepared by the thermal decomposition method at 550 ℃. Electro-catalytic degradation performances of electrodes doped with different RE elements were evaluated by linear sweep voltammetry（LSV） and Tafel curves. During the electrolysis,the conversion of p-nitrophenol was performed with these electrodes as anodes under galvanostatic control. The structures and morphologies of the surface coating of the electrodes were characterized by scanning electron microscope（SEM）. The results demonstrate that the electro-catalytic degradation performances of Ti/SnO2–Sb electrodes are improved to different levels by doping different RE ions. Improved Ti/SnO2–Sb electrodes by the introduction of different RE have higher oxygen evolution potential, better electro-catalysis ability, better coverage,and longer electrode life.