Preparation and photocatalytic performance of Cu-doped TiO_2 nanoparticles

Cu-doped TiO2 nanoparticles with different doping contents from 0 to 2.0% （mole fraction） were synthesized through sol-gel method. X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and field emission scanning electron microscope （FE-SEM） were used to characterize the crystalline structure, chemical valence states and morphology of TiO2 nanoparticles. UV-Vis absorption spectrum was used to measure the optical absorption property of the samples. The photocatalytic performance of the samples was characterized by degrading 20 mg/L methyl orange under UV-Vis irradiation. The results show that the Cu-doped TiO2 nanoparticles exhibit a significant increase in photocatalytic performance over the pure TiO2 nanoparticles, and the TiO2 nanoparticles doped with 1.0% Cu show the best photocatalytic performance. The improvement in photocatalytic performance is attributed to the enhanced light adsorption in UV-Vis range and the decrease of the recombination rate of photoinduced electron-hole oair of the Cu-doped TiO2 nanoparticles.

High room-temperature magnetization in Co-doped TiO_(2) nanoparticles promoted by vacuum annealing for different durations

To clarify the contribution of oxygen vacancies to room-temperature ferromagnetism(RTFM)in cobalt doped TiO_(2)(Co-TiO_(2)),and in order to obtain the high level of magnetization suitable for spintronic devices,in this work,Co-TiO_(2) nano-particles are prepared via the sol-gel route,followed by vacuum annealing for different durations,and the influence of vacu-um annealing duration on the structure and room-temperature magnetism of the compounds is examined.The results reveal that with an increase in annealing duration,the concentration of oxygen vacancies rises steadily,while the saturation magnetiza-tion(Ms)shows an initial gradual increase,followed by a sharp decline,and even disappearance.The maximum Ms is as high as 1.19 emu/g,which is promising with respect to the development of spintronic devices.Further analysis reveals that oxygen va-cancies,modulated by annealing duration,play a critical role in tuning room-temperature magnetism.An appropriate concentra-tion of oxygen vacancies is beneficial in terms of promoting RTFM in Co-TiO_(2).However,excessive oxygen vacancies will result in a negative impact on RTFM,due to antiferromagnetic superexchange interactions originating from nearest-neighbor Co^(2+)ions.

Nickel nanoparticles supported on nitrogen-doped carbon nanotubes are a highly active,selective and stable CO_(2) methanation catalyst

CO_(2) methanation using nickel-based catalysts has attracted large interest as a promising power-to-gas route.Ni nanoparticles supported on nitrogen-doped CNTs with Ni loadings in the range from 10 wt% to 50 wt% were synthesized by impregnation,calcination and reduction and characterized by elemental analysis,X-ray powder diffraction,H_(2) temperature-programmed reduction,CO pulse chemisorption and transmission electron microscopy.The Ni/NCNT catalysts were highly active in CO_(2) methanation at atmospheric pressure,reaching over 50% CO_(2) conversion and over 95% CH_(4) selectivity at 340℃ and a GHSV of50,000 mL g^(-1) h^(-1) under kinetically controlled conditions.The small Ni particle sizes below 10 nm despite the high Ni loading is ascribed to the efficient anchoring on the N-doped CNTs.The optimum loading of 30 wt%-40 wt% Ni was found to result in the highest Ni surface area,the highest degree of conversion and the highest selectivity to methane.A constant TOF of 0.3 s^(-1) was obtained indicating similar catalytic properties of the Ni nanoparticles in the range from 10 wt%to 50 wt% Ni loading.Long-term experiments showed that the Ni/NCNT catalyst with 30 wt% Ni was highly stable for 100 h time on stream.

Zn^(2+)和TiO_(2)合金化过程中不同成分占比对薄膜结构和光催化性能的影响

使用溶胶-凝胶法在单晶硅衬底上制备一批不同Zn^(2+)成分调节的TiO_(2)薄膜,观测Zn^(2+)和TiO_(2)合金化过程中光学和光催化性能的变化.X射线衍射光谱仪用于观测在合金化过程中薄膜的晶体结构变化并追踪ZnTiO_(3)化合物的形成.扫描电子显微镜、原子力显微镜用于观测合金化过程中因TiO_(2)晶格对Zn^(2+)溶解度有限而导致薄膜表面出现大量孔洞的现象.X射线光电子能谱和光学带隙用于观测Zn^(2+)与TiO_(2)合金化过程中电子结构层面的变化.最后,通过降解亚甲基蓝(MB)溶液,表明少量Zn^(2+)掺杂完全溶解在TiO_(2)中,并破坏TiO_(2)结晶质量.在Zn^(2+)的成分占比继续提高至15%的过程中,XPS峰形拟合结果验证了TiO_(2)对Zn^(2+)的溶解度有限,导致薄膜出现大量孔洞结构,薄膜的活性比表面积得以提升,同时Zn^(2+)可以有效地捕获光生e^(-)/h^(+).为了继续观察Zn^(2+)浓度对TiO_(2)的影响,将Zn^(2+)的浓度提升至40%,观察Zn^(2+)与TiO_(2)合金化过程中的现象.表明化合物ZnTiO_(3)的出现可以充当e^(-)/h^(+)的复合中心以及TiO_(2).占比的大幅下降导致合金化之后的薄膜光催化效率逐渐下降.

Antiferroelectricity in ZrO₂and Ferroelectricity in Zr, Al, La Doped HfO₂Nanoparticles

The dependence of the polarization P in Hf1-xZrxO2 nanoparticles on electric field, dopant concentration x, size and temperature are studied using the transverse Ising model and the Green’s function method. Pure ZrO2 shows at high electric fields an antiferroelectric behavior. Pure HfO2 is a linear dielectric in the monoclinic phase. With increasing ZrO2 content the of HZO shows a ferroelectric behavior. The composition dependence x of the remanent polarization Pr(x)?has a maximum for x = 0.5. For x = 0, pure HfO2, and x = 1, pure ZrO2, Pr=0.?P increases with decreasing HZO nanoparticle size. The influence of Al and La doping on Pr?in HfO2 nanoparticles is also studied. The exhibiting of the ferroelectricity in ion doped HfO2 is due to a phase transformation and to an internal strain effect. The observed results are in good qualitative agreement with the experimental data.

Photo-Electrochemical Studies on TiO₂-Doped Ce (III/IV) Oxides Nanoparticles in Aqueous Electrolytes

Photoelectrochemical studies on TiO2 doped with Ce2O3 or CeO2 took place in aqueous solutions of [Fe(CN)6]4- as the source of hydrated electrons. Our studies show that doping TiO2 with CeO2 gave better photocatalytic reduction of [Fe(CN)6]3- than TiO2 doped with Ce2O3. However the TiO2 assemblies doped with either Ce(III) or Ce(IV) oxides give less photochemical reduction of [Fe(CN)6]3- that the oxides of pure metals (Ti or Ce). In both cases a lowering of the band gaps of TiO2 was noticed. Immobilized TiO2 doped with Ce oxides on a FTO (Fluorine Ten Oxide) surface gave greater photocurrent with I2/I3– than that recorded for [Fe(CN)6]3-/4- redox systems. Our studies indicate that the TiO2 doped with Ce2O3 or CeO2 maintained photoactivity after being immobilized in thin solid sheets and can be used in all solid state photoelectron-chemical cells.

Effective photocatalytic conversion of formic acid using iron,copper and sulphate doped TiO_(2)

In this paper,the combined addition of copper or iron and sulphate ions onto TiO_(2) prepared by a simple sol-gel method is studied for formic acid photocatalytic conversion.A wide structural and morphological characterization of the different photocatalysts was performed by X-ray diffraction(XRD),N_(2)-physisorption for BET surface area measurements,scanning and transmission electronic microscopies(SEM and TEM),UV-Vis diffuse spectroscopy(DRS)and X-ray photoelectron spectroscopy(XPS),in order to correlate the physico-chemical properties of the materials to their photocatalytic efficiencies for formic acid oxidation.Results have shown important differences among the catalysts depending on the metal added.Sulphated TiO_(2)/Cu(1%Cu)was the best photocatalyst obtaining about 100% formic acid conversion in only 5 min.The appropriate physico-chemical features of this photocatalyst,given by the addition of combined copper and sulphate ions,explain its excellence in photocatalytic reaction.

La-doped TiO_(2) nanorods toward boosted electrocatalytic N_(2)-to-NH_(3)conversion at ambient conditions

Electrochemical N_(2) reduction provides a green and sustainable alternative to the Haber-Bosch technology for NH_(3 )synthesis.However,the extreme inertness of N_(2) molecules is a formidable challenge,which requires the development of an active electrocatalyst to drive the N_(2) reduction reaction(NRR)for NH_(3) production at ambient conditions.Herein,we demonstrate the development of La-doped TiO_(2) nanorods as an efficient NRR electrocatalyst for ambient NH3 synthesis.The optimized La-TiO_(2) catalyst offers a large NH_(3) yield of 23.06 pg h1 mgcat 1 and a high Faradaic efficiency of 14.54%at-0.70 V versus reversible hydrogen electrode in 0.1 M L1CIO_(4),outperforming most La-and Ti-based catalysts reported before.Significantly,it also demonstrates high electrochemical stability and its activity decay is negligible after 48 h test.The mechanism is further revealed by density functional theory calculations.

无定形TiO_(2)的F、La共掺杂及光催化脱硫性能

将钛酸四丁酯直接水解制备了无定形TiO_(2)〔TiO_(2)(Am)〕,将钛酸四丁酯在硝酸镧溶液或氟化铵溶液或其混合溶液中水解,分别制备了La掺杂型、F掺杂型以及F、La共掺杂型光催化剂,分别记为La-TiO_(2)(Am)、F-TiO_(2)(Am)和F-La-TiO_(2)(Am)。采用XRD、FTIR、XPS、UV-Vis DRS、SEM、PL及VB-XPS对其进行了表征,比较了其对模拟柴油〔二苯并噻吩(DBT)的正十二烷溶液〕的催化脱硫性能。结果表明,F、La共掺杂提升了TiO_(2)(Am)的吸光度和光吸收边缘红移程度,F的电负性使F-La-TiO_(2)(Am)的禁带宽度变窄,La—O键的生成为F-La-TiO_(2)(Am)提供了更多的氧空位,促进了杂质能级的生成,有效抑制了电子-空穴的复合。在以H_(2)O_(2)为氧化剂、无水甲醇为萃取剂、V(无水甲醇)∶V(模拟油)=1.0∶1、F-La-TiO_(2)(Am)用量为模拟柴油质量的1.0%、n(双氧水中O原子)∶n(DBT中S原子)=15∶1、反应时间3.0 h的条件下,模拟柴油脱硫率为94.10%。F-La-TiO_(2)(Am)使用4次后,脱硫率仍可达85.40%。在脱硫过程中,超氧自由基和空穴为主要活性物种,可将DBT转化成极性更强的亚砜和砜类物质,经由无水甲醇溶解后实现脱除。

Nitrogen and fluorine co-doped TiO_(2)/carbon microspheres for advanced anodes in sodium-ion batteries: High volumetric capacity, superior power density and large areal capacity

Fast charging and high volumetric capacity are two of the critical demands for sodium-ion batteries(SIBs).Although nanostructured materials achieve outstanding rate performance,they suffer from low tap density and small volumetric capacity.Therefore,how to realize large volumetric capacity and high tap density simultaneously is very challenging.Here,N/F co-doped TiO_(2)/carbon microspheres(NF- TiO_(2)/C)are synthesized to achieve both of them.Theoretical calculations reveal that N and F co-doping increases the contents of oxygen vacancies and narrows the bandgaps of TiO_(2) and C,improving the electronic conductivity of NF- TiO_(2)/C.Furthermore,NF- TiO_(2)/C exhibits the high binding energy and low diffusion energy barrier of Na+,significantly facilitating Na+storage and Na+diffusion.Therefore,NF- TiO_(2)/C offers a high tap density(1.51 g cm^(-3)),an outstanding rate performance(125.9 mAh g^(-1) at 100 C),a large volumetric capacity(190 mAh cm^(-3) at 100 C),a high areal capacity(4.8 mAh cm^(-2))and an ultra-long cycling performance(80.2%after 10,000 cycles at 10 C)simultaneously.In addition,NF- TiO_(2)/C||Na_(3)V_(2)(PO_(4))_(3) full cells achieve an ultrahigh power density of 25.2 kW kg^(-1).These results indicate the great promise of NF- TiO_(2)/C as a high-volumetric-capacity and high-power-density anode material of SIBs.

Ti^(3+)/C/N-TiO_(2)@NGQDs纳米复合光催化剂的制备及其可见光催化性能研究

采用两步水热法制备了Ti^(3+)、C和N共掺杂TiO_(2)@氮掺杂石墨烯量子点(Ti^(3+)/C/N-TiO_(2)@NGQDs)纳米复合光催化剂,通过X射线衍射、透射电子显微镜、X射线光电子能谱和紫外可见漫反射光谱对其进行了详细表征,且通过降解甲基橙溶液研究了其可见光催化性能。结果表明,Ti^(3+)、C和N成功地共掺杂了TiO_(2),纳米NGQDs附着在共掺杂的TiO_(2)上;Ti^(3+)/C/N-TiO_(2)@NGQDs降解甲基橙的动力学一阶速率常数分别是纯TiO_(2)、C/N-TiO_(2)和C/N-TiO_(2)@NGQDs的25.7倍、4.7倍和1.7倍,提升的可见光催化性能归因于其具有更强的可见光吸收、更快的光生电荷传输和分离效率。超氧自由基和光生空穴是Ti^(3+)/C/N-TiO_(2)@NGQDs可见光降解甲基橙过程中的主要活性物质。此外,Ti^(3+)/C/N-TiO_(2)@NGQDs具有非常高的稳定性。这种TiO_(2)基的复合光催化剂可适用于实际废水处理过程。

Preparation and Properties of Lanthanum Trivalent Ion Doped TiO_2 Nanopowders by Liquid Plasma Spray

The lanthanum trivalent ion doped TiO2 nanopowders were prepared by liquid plasma spray with solution of titanium tetra-tert-butoxide and alcohol as feedstock and La(NO3)3·6H2O as doping component. The photocatalytic activity of samples at different doping concentrations in photocatalytic degradation of methyl orange was discussed. The powders were characterized by Transmission Electron Microscopy (TEM) and X-Ray Diffraction (XRD), and the effect of doped ion on the pattern, phase composition and crystallite sizes were analyzed. The results indicated that lanthanum trivalent ion doped TiO2 nanopowders could be prepared by liquid plasma spray. Lanthanum trivalent ion doping increased the photocatalytic activity of TiO2 greatly, the optimal doping concentration was 0.5%. The doped powders were the mixture of anatase phase and rutile phase. The contents of anatase phase decreased firstly and then increased with an increase in the contents of lanthanum trivalent ion. Doping lanthanum trivalent ion could make the TiO2 nanopowders uniform and reduced its particle size.

Humidity sensing properties of spray deposited Fe doped TiO_(2)thin film

In the present work,ferrite(Fe)doped TiO_(2)thin films with different volume percentage(vol%)were synthesized using a spray pyrolysis technique.The effect of Fe doping on structural properties such as crystallite size,texture coefficient,microstrain,dislocation densities etc.were evaluated from the X ray diffratometry(XRD)data.XRD data revealed a polycrystalline anatase TiO_(2)phase for sample synthesized up to 2 vol%and mixed anatase and rutile crystalline phase for sample synthesized at 4 vol%Fe doped TiO_(2).The crystalline size was observed to decrease with increase in Fe dopant vol%and also other structural parameters changes with Fe dopant percentage.In the present work,electrical resistance was observed to decrease with a rise in Fe dopant vol%and temperature of the sample.Thermal properties like temperature coefficient of resistance and activation energy also showed strong correlation with Fe dopant vol%.Humidity sensing properties of the synthesized sample altered with a change in Fe dopant vol%.In the present paper,maximum sensitivity of about 88.7%for the sample synthesized with 2 vol%Fe doped TiO_(2)and also the lowest response and recovery time of about 52 and 3 s were reported for the same sample.

INFLUENCE OF THE ALIGNMENT OF TiO_2 NANOPARTICLES ON OPTICAL AND STRUCTURAL PROPERTIES OF POLY(PHENYLENEVINYLENE) FILMS

A series of poly(phenylenevinylene) (PPV)/titanium oxide (TiO_2)nanocomposites with different contents of TiO_2 nanoparticles were prepared from mixtures of PPVprecursor and titanium butoxide ethanol solution in a sol- gel process. TEM images showed theformation of the connected network of TiO_2 nanoparticles with a higher content of TiO_2, whichresulted in the titanium butoxide hydrolyzed to form Ti organic compound. Meanwhile, the conjugationof PPV polymer chains can be interrupted by the TiO_2 network structure. The PL spectra revealedthat the emitted light of the PPV/TiO_2 nanocomposites blue shifted without fine structure and thePL intensity enhanced when the TiO_2 network formed. In the lifetime spectroscopy of positronannihilation, the structural properties of the PPV dominated the character of the nanocomposites, inwhich the formation of the omicron -Ps was presented in free volume polymer, when the content ofTiO_2 was below 10 percent. Further increasing the content of TiO_2 nanoparticle introduced muchmore vacancies, vacancy clusters and grain boundaries at their interfaces, which led to thecorresponding lifetime and intensity close to that of the nano- TiO_2 bulk materials. With the TiO_2content of 50 percent of long lifetime. These phenomena suggested that the optical and structuralproperties of the PPV/TiO_2 nanocomposites are dependent on the interfacial structure between PPVand TiO_2 nanoparticles.

Li-Ce共掺杂TiO_(2)纳米材料制备及光催化性能的研究

选用六水合硝酸铈(Ce(NO_(3))_(3)·6H_(2)O)为掺杂剂,以钛酸四丁酯(TBOT)为原料,采用溶胶-凝胶法制备出铈掺杂改性的TiO_(2)光催化剂,并利用XRD、SEM、Uv-vis等表征方法研究Ce/TiO_(2)催化剂的结构、形貌和其对亚甲基蓝的光催化降解性能。结果表明:在500℃退火2 h,Ti与Ce物质的量比为1∶0.01(TiO_(2):0.01Ce)时,样品光催化效率最高,对亚甲基蓝降解率可达93.8%。同时还对TiO_(2):0.01Ce进行Li共掺改良,其光降解率可达95.4%,大于相同条件下单掺杂Ce的光降解率。

Hydrothermal preparation of TiO_(2)-Ag nanoparticles and its antimicrobial performance against human pathogenic microbial cells in water

Water contaminated with pathogenic microbes is considered as one of the most common routes for transmitting diseases in human beings.Different methods have been applied for the decontamination of microbes in contaminated water.In the current study,an easy to do hydrothermal method has been used for the preparation of TiO_(2)-Ag nanoparticles.The obtained material was characterised using a scanning electron microscope(SEM)and fourier transform infra-red spectroscopy(FTIR).The morphological appearance of the obtained nanoparticles was in the shape of a sphere with a size range of 60-90 nm.The antimicrobial activity of the prepared nanoparticles was tested against several pathogenic bacteria and fungi.The obtained results proved that the nanoparticles succeeded to affect all the tested microbes in the following order:Bacillus cereus ATCC6633>Pseudomonas aeruginosa ATCC9027=Klebsiella pneumoniae ATCC13883>Vibrio cholera ATCC700=Candida albicans ATCC 700=Escherichia coli NCTC10418>Staphylococcus aureus ATCC6538.The minimum inhibitory concentration(MIC)of the prepared nanoparticles varied among the tested microbes at range of 12 mg/ml and 25 mg/ml.These results encourage the application of prepared TiO_(2)-Ag nanoparticles for treatment of microbe-contaminated waters.

纳米TiO_(2)对NH_(3)-H_(2)O-LiBr工质降膜吸收性能的影响

为了探讨纳米TiO_(2)对三元NH_(3)-H_(2)O-LiBr工质降膜吸收的影响,本文利用数值分析建立了三元工作流体薄膜吸收的连续方程、能量方程和组分质量平衡方程,采用Matlab软件进行编程和计算纳米流体的降膜吸收性能,将其与实验数据进行对比验证,并进一步分析了纳米TiO_(2)质量分数、初始氨浓度、初始温度、冷却水进口温度、吸收压力和下降薄膜管长度对薄膜吸收性能的影响。研究表明:添加纳米TiO_(2)可以增强降膜吸收的传质速率,主要原因为液膜中氨的扩散系数增加。当纳米TiO_(2)质量分数从0%增加到0.1%、0.3%和0.5%时,扩散系数分别增加了3.44倍、6.42倍和11.76倍。此外,增加初始氨浓度、降低初始温度、提高冷却水进口温度或降低吸收压力都可以提高最终溶液的饱和度。

Theory of multiphoton photoemission disclosing excited states in conduction band of individual TiO_(2) nanoparticles

A theory of multiphoton photoemission is derived to explain the experimentally observed monotonic decrease with the wavelength in the electron yield of TiO_(2) nanoparticles(NPs)by as large as four orders of magnitude.It is found that the fitting parameter corresponds to the energy position of Ti3d e_(g) and t_(2g) states,and the derived theory is a novel diagnostic of excited states in the conduction band,very importantly,applicable to individual NPs.The difference between four-photon slope NPs and three-photon slope NPs is attributed to the difference in defect density.The success of the theory in solving the puzzling result shows that thermal emission from high-lying levels may dominate over direct multiphoton ionization in solids when the photon number larger than four is required.

Preparation and characterization of TiO_(2) photoelectrode codoped with aluminum and boron and its application in dye-sensitized solar cell

Nanocrystalline titania films codoped with aluminum and boron were prepared by cathodic vacuum arc deposition.In the process,titanium alloy target was used under an O_(2) /Ar atmosphere,and sensitization of films were carried out by natural dye-sensitized complex in anhydrous ethanol.The structure,surface morphology and UV-vis spectra of titania films codoped were measured by X-ray diffraction analysis,scanning electron microscopy and ultraviolet-visible spectrometer.The as-deposited films are found to be amorphous.The films annealed were examined to be of anatase structure with orientation along the(101)planes,the average crystal size is in the range between 41 and 45 nm.SEM results show that there are some pores in the codoped titania films,the optical properties of the dye-sensitized films were also measured which reveals that the spectral responses of films shift to the visible region.Under simulated sunlight illumination,the overall energy conversion efficiency of dye-sensitized nanocrystalline solar cell is 0.9%.

NaH doped TiO_(2)as a high-performance catalyst for Mg/MgH_(2)cycling stability and room temperature absorption

This paper presents the catalytic effect of NaH doped nanocrystalline TiO_(2)(designated as NaTiOxH)in the improvement of MgH_(2)hydrogen storage properties.The catalyst preparation involves ball milling NaH with TiO_(2)for 3 hr.The addition of 5 wt%NaTiOxH powder into MgH_(2)reduces its operating temperature to∼185℃,which is∼110℃lower than the additive-free as-milled MgH_(2).The composite remarkably desorbs∼7.2 wt%H_(2)within 15 min at∼290℃and reabsorbs∼4.5 wt%H_(2)in 45 min at room temperature under 50 bar H_(2).MgH_(2)dehydrogenation is activated at 57 kJ/mol by the catalyst.More importantly,the addition of 2.5 wt%NaTiOxH catalyst aids MgH_(2)to reversibly produce∼6.1 wt%H_(2)upon 100 cycles within 475 hr at 300℃.Microstructural investigation into the catalyzed MgH_(2)composite reveals a firm contact existing between NaTiOxH and MgH_(2)particles.Meanwhile,the NaTiOxH catalyst consists of catalytically active Ti_(3)O_(5),and“rod-like”Na_(2)Ti_(3)O_(7)species liberated in-situ during preparation;these active species could provide multiple hydrogen diffusion pathways for an improved MgH_(2)sorption process.Furthermore,the elemental characterization identifies the reduced valence states of titanium(Ti<4+)which show some sort of reversibility consistent with H_(2)insertion and removal.This phenomenon is believed to enhance the mobility of Mg/MgH_(2)electrons by the creation and elimination of oxygen vacancies in the defective(TiO_(2-x))catalyst.Our findings have therefore moved MgH_(2)closer to practical applications.