Structural,morphological, optical and third order nonlinear optical response of spin-coated NiO thin films: An effect of N doping

The present work deals with the deposition of NiO and Nitrogen (N)-doped NiO thin films by sol-gel spin coating technique. Structural, morphological, linear and non-linear optical characteristics of undoped and N-doped (1–15 wt%) NiO films were studied. From XRD measurements, it is evident that single phase nano crystalline NiO is formed for all doping concentrations. Surface morphology study shows that higher concentration of N doped NiO thin films were of high quality and EDX mapping confirmed the doping of Nitrogen in films. The Raman spectra of the studied films were analyzed over the range of 1400-200 cm⁻¹. The optical studies confirm that as doping increases, transparency of the film decreases (except at 10% N doping) and the band gap narrows. Nonlinear parameters such as refractive index and susceptibilities also depend on N dopant concentration. Z-scan studies viz., absorption index, nonlinear refractive index were carried out on undoped and N doped NiO samples and the results were matched with theoretical calculated values.     

Effect of the composition and structure of titanosilicas on their photocatalytic activity in the decomposition of methylene blue

A comparison is made of the catalytic activity of the titanosilicas produced by pyrogenic synthesis and by the deposition of TiO₂ on pyrogenic SiO₂ in the photocatalytic decomposition of methylene blue (MB). The deposited titanosilicas exhibit high catalytic activity in the decomposition of MB as a result both of textural features and of the presence mainly of the anatase phase in the deposited TiO₂ compared with the pyrogenic titanosilicas. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 1, pp. 23–28, January–February, 2006.     

Low-temperature impedance and dielectric relaxation of NiO nanocrystals

Low-temperatures impedance and dielectric properties of NiO nanocrystals as a function of particle size were investigated by alternative current impedance spectra. It is found that NiO nanocrystals showed distinct bulk and grain boundary conductions at low temperatures, which were almost the same within the experimental error during the decreasing and the subsequent increasing temperature processes. This result indicated that no further protons are formed during these temperature cycles. The conductivities are also highly dependent on the particle size. As the particle size reduced, the conductivities of NiO nanocrystals increased to show a maximum. Further particle size reduction less than 8.9 nm led to a sudden decrease in conductivity. The corresponding activation energies showed a minimum with varying the particle size. These observations were most likely due to the balance between the concentration of charge carriers, holes and protons.     

Structural,optical and photocatalytic activity of cerium doped zinc aluminate

Zinc aluminate and cerium-doped zinc aluminate nanoparticles are synthesised by co-precipitation method. Ammonium hydroxide is used as a precipitating agent. The synthesised compounds are characterised by powder X-ray diffraction (XRD), Fourier transform Infrared spectroscopy (FT-IR), Ultraviolet diffuse reflectance spectroscopy (UV-DRS), Thermogravimetric analysis (TGA), Scanning electron microscopy (SEM) and Surface area measurements. The photocatalytic activity of zinc aluminate and cerium doped zinc aluminate nanoparticles are studied under the UV light and visible light taking methylene blue as a model pollutant. The amount of catalyst, concentration of dye solution and time are optimised under UV-light. Degradation of methylene blue under the UV-light is found to be 99% in 20 min with 10 mg of cerium doped catalyst. Compared to visible light degradation, the degradation of dye under UV-light is higher. Cerium doping in zinc aluminate (ZnAl₂O₄:Ce³⁺) increased the photocatalytic activity of zinc aluminate.     

Shape-dependent acidity and photocatalytic activity of Nb2O5 nanocrystals with an active TT (001) surface

Nb(2)O(5) nanorods and nanospheres were synthesized, and their photocatalytic activity for methylene blue decomposition in water compared. Nb(2)O(5) nanorods clearly displayed higher activity, despite their comparable surface area. With a shape-dependent surface acidity, hydrothermal stability, and high photoactivity, these Nb(2)O(5) nanorods are a unique and exciting nanomaterial for non-classical photocatalytic mineralization of organic compounds in water.     

溶液燃烧法一步合成纳米NiO和Ni

以硝酸镍为氧化剂,乙二醇为燃料,采用溶液燃烧法在300℃合成了纳米NiO和金属Ni.采用X射线衍射仪(XRD)和扫描电子显微镜(SEM)系统地研究了不同燃料、燃料/氧化剂比对合成产物的晶相组成和微观形貌的影响.结果表明:燃料种类和燃料/氧化剂比对合成产物晶相组成的影响显著.通过控制乙二醇/硝酸镍的比例,可以在空气气氛中...     

Facile synthesis of zirconia supported nanomaterials for efficient photocatalytic applications

The recent study enlightens the synthesis and characterization of zirconia (ZrO₂), Fe-doped ZrO₂ (Fe@ZrO₂), and Ni-doped ZrO₂ (Ni@ZrO₂) catalysts having new-fangled morphology with tuned band gap as photocatalysts for degradation of textile wastewater dyes methylene blue (MB), malachite green (MG), and their mixtures. SEM imaging of Fe@ZrO₂ and Ni@ZrO₂ is interestingly varied from ZrO₂ as well as doping of transition metals greatly affects the morphology of composites. The optimization study depicts that the pH, time (min) and catalyst amount (g) have a direct relation with degradation efficiency, while the dye concentration (mg/L) has an indirect relation as well. The photocatalytic studies depict that the degradation of MB and MG follows oxidation pathway via hydroxyl radicals (OH^•) and holes. Reusability of catalysts corresponds to a little decrease in degradation efficiency in the first two cycles and decreases to about ∼10% (Ni@ZrO₂) and ∼12% (Fe@ZrO₂) in next three cycles.     

Structural,optical, electrical,and photocatalytic properties of manganese doped zinc oxide nanocrystals

Manganese-doped and undoped ZnO nanocrystals were synthesized via wet-chemical methods. The structure, physico-chemical, electrical and optical properties of the as-prepared products were characterized by using the X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PLS) and electrochemical impedance spectroscopy (EIS) techniques. The photocatalytic activity of Mn-doped ZnO nanocrystal (mixed phases) has been examined under the visible-irradiation by using photocatalytic oxidation of rhodamine B (RhB) dye as a model reaction, and compared with that of known system such as pure ZnO nanocrystal (single-phase). The results showed that Mn doped ZnO nanocrystals bleaches RhB much faster than undoped ZnO upon its exposure to the visible light. The enhancement of the photocatalytic activity was discussed as an effect due to the Mn doping in the Mn-doped ZnO semiconductors, which shifts the optical absorption edge to the visible region and alters the electron-hole pair separation conditions. These factors are responsible for the higher photocatalytic performance of Mn/ZnO composites.     

无机离子对Ag_3PO_4可见光降解亚甲基蓝的影响

以亚甲基蓝(MB)为模拟废水污染物,Ag3PO4为光催化剂,固定污染物初始浓度、催化剂用量、光照强度和照射时间等,探讨不同浓度的无机阴、阳离子(NO-3、Cl-、SO2-4、Na+、Ca2+、Mg2+、Al 3+)对Ag3PO4光催化降解偶氮染料MB的影响.结果表明,Na+和NO-3对Ag3PO4光催化降解MB没有明显的影响;Cl-在一定程度上对MB的降解具有促进作用;SO2-4、Ca2+、Mg2+、Al3+在不同程度上抑制了该光催化反应的进行,且抑制顺序为SO2-4Ca2+Mg2+Al 3+.     

Synthesis,characterization, X-ray structure,electrochemistry, photocatalytic activity and DFT studies of heterotrinuclear Ni(II), Pd(II) and Zn(II) complexes containing a formylferrocene thiosemicarbazone ligand

Three complexes of the general formula M{CpFe(η⁵-C₅H₄CH=N–N=C(S)NH₂}₂ [where M = Ni^II ( 2a ), Pd^II ( 2b ) and Zn^II ( 2c )] were synthesized with formylferrocene thiosemicarbazone ( 1 ) as a bidentate ligand. All compounds were characterized using conventional spectroscopic and analytical techniques (infrared, ¹H and ¹³C NMR, mass spectrometry and elemental analysis). The molecular structure of 2b was confirmed by single-crystal X-ray analysis. To study the photocatalytic activity of the new complexes ( 2a–c ), methylene blue (MB) was selected as a model pollutant. After 180 min, the degradation efficiency of MB reached 87% for 2a , 76% for 2b and 85% for 2c , and all complexes showed a higher photocatalytic activity than the formylferrocene thiosemicarbazone free ligand 1 . Theoretical studies were used to characterize the geometry and electronic structure of the compounds and to provide a rational explanation for the measured photocatalytic activity.     

含季鏻阳离子的[Mo6O19]2-多酸化合物的合成、结构及光催化性能研究

通过使用季鏻盐与钼酸铵在常温条件下合成了含季鏻阳离子的(n-PentylPh₃P)₂[Mo₆O₁₉]多酸化合物,并通过X-射线单晶衍射、红外光谱、紫外光谱、热重分析和电化学对其进行了表征。产物中的季鏻配体上的氢原子通过与多酸阴离子端基氧原子形成氢键而构筑了一维链状结构,并且季鏻配体上的苯环与相邻季鏻配体上的苯环通过π-π作用形成三维层状结构。此外,对该多酸化合物的光催化降解亚甲基蓝的性能进行了研究。     

Synthesis of Ni-poor NiO nanoparticles for p-DSSC applications

To improve the performances of p-Dye Sensitized Solar Cell (p-DSSC) for the future, the synthesis of modified p-type nickel oxide semiconductor, commonly used as photocathode in such devices, was initiated with Ni₃O₂(OH)₄ as precursor. This specific nickel oxyhydroxide was first characterized by X-ray photo-electron spectroscopy and magnetic susceptibility measurements. Then its thermal decomposition was thoroughly studied in order to control the particles size of the as-prepared NiO nanopowders. Low temperature decomposition in air of this precursor allows the formation of Ni_1−xO nanoparticles with a large amount of Ni vacancies and specific surface areas up to 250 m² g⁻¹. Its ammonolysis at 250 °C leads to nanostructured N-doped NiO (NiO:N) materials.     

纳米氧化镍微粉的制备及光吸收谱

Uniform nanosized NiO particles were prepared by a chemical coprecipitation using NiCl2?6H2O as the starting material. The relationship between various annealing temperatures and grain size of NiO crystallite was investigated. Optical reflectivity spectra of Nanometer-sized NiO powders at room temperature were studied. The results show that seven optical absorption bands (P1、 P2、P3、P4、P5、P6 and P7) with the peak energies of 3.30, 2.99, 2.78, 2.25,1.92, 1.72 and 1.07eV, respectively, are located on a continuous refiectivity background. P1、 P2、P3 and P4 exhibit "blue shift", but P5、P6 and P7 present "red shift" in comparison with that of single crystal NiO. The continuous reflectivity background increases rapidly with increasing the annealing temperature from 500℃ to 600℃ to 700℃. The origins of P1 to P7 and the reasons of "blue shift", "red shift" and the increase of the reflectivity background with increasing the annealing temperature have been analyzed in detail.     

Synthesis and characterisation of mesoporous hybrid silica-polyoxometalate aerogels for photocatalytic degradation of rhodamine B and methylene blue

ABSTRACT

Mesoporous silica aerogel/polyoxometalate hybrids were successfully synthesised under mild conditions, and were investigated towards photocatalytic degradation of Rhodamine B and Methylene Blue dye models in aqueous media under ultraviolet irradiation. The materials were characterised, in the solid state, by various tools such as FTIR, TGA, and powder XRD, in order to gather information about their chemical and structural properties. Moreover, UV-Vis, AAS, BET, SEM, and EDX techniques were used to confirm the polyoxometalates’ loading and their distribution onto the silica aerogels’ surface. The most important analytical technique was the Nitrogen adsorption-desorption, which revealed a significant increase in the specific surface area and pore volume of the hybrid catalysts after immobilisation. The synthesised hybrid catalysts, TEOS/PW₁₂ and TEOS/SiW₁₂, have shown efficient photocatalytic activity towards Methylene Blue and Rhodamine B degradation within 120 min under ultraviolet illumination, thus reaching a degradation percentage of 81–98% and 55–90%, respectively. UV-Vis analysis was employed to scrutinise the formation of intermediate species and revealed that the photocatalytic degradation process proceeded to completion within a surprisingly short time of ~5 min.     

Visible‐light‐driven photocatalytic degradation using Mn‐doped SrMoO4 nanoparticles

Mn‐doped SrMoO₄ nanocrystals were synthesized by thermal decomposition of metal–organic salt in an organic solvent with the doping content in the range 0–12 mol%. The structures, morphologies and optical properties were characterized using various techniques. The results suggest that Mo sites in the SrMoO₄ lattice are substituted by the Mn dopant, the adsorption bands are found to be shifted toward the visible light region and the band gap becomes narrower correspondingly. The photocatalytic performance of the as‐synthesized product was determined using the degradation of methylene blue by visible light irradiation. The photocatalytic performance is enhanced with Mn doping, and the optimal degradation rate is 85% in 140 min for 5 mol% Mn doping. The enhanced photocatalytic activity with Mn doping may be ascribed to the energy band adjustment and effective photogenerated electron–hole separation caused by the Mn doping. A possible photocatalytic mechanism is also discussed.     

Photocatalytic Properties of Titanium Dioxide Heterostructures with Cyanine Dyes and Polyepoxy Propylcarbazole

We have obtained novel photosensitive materials containing a semiconductor photocatalyst and a dye sensitizer. We have studied the activity of the latter in the reaction of photoreduction of methylene blue, and we consider possible mechanisms for the photocatalytic effect.     

K_8[Cd(H_2O)NiW_(11)O_(39)]/PANI掺杂材料的制备、表征及光催化性能

采用化学氧化法将Keggin结构K8[CdNi(H2O)W11O39]掺杂到聚苯胺中制得K8[CdNi(H2O)W11O39]/PANI掺杂材料,并用UV,IR,XRD,SEM和EDM等测试方法对掺杂材料进行表征.并研究了所合成掺杂材料催化剂为对亚甲基蓝溶液光降解催化活性.通过控制不同的影响条件,寻找光降解的最适条件,实验结果表明:掺杂材料具有很高的催化活性,最适条件下,110min内对亚甲基蓝溶液的脱色率达到99%以上,因此,[CdNi(H2O)W11O39]/PANI掺杂材料是一种很好的光降解催化剂.     

Noble-metal nanocrystals with concave surfaces: synthesis and applications

Metal nanocrystals with concave surfaces are interesting for a wide variety of applications that are related to catalysis, plasmonics, and surface‐enhanced spectroscopy. This interest arises from their high‐index facets, surface cavities, and sharp corners/edges. Two major challenges are associated with this novel class of nanocrystals: 1) how to generate a concave surface with negative curvature, which is not favored by thermodynamics owing to its higher energy than the convex counterpart; and 2) how to stabilize the morphology of a nanocrystal with concave structures on the surface. Recently, a number of different procedures have been developed for the synthesis of noble‐metal nanocrystals with concave surfaces. This Review provides a brief account of these developments, with the aim of offering new insights into the growth mechanisms. We focus on methods based on two general strategies: 1) site‐specific dissolution through etching and galvanic replacement; and 2) directionally controlled overgrowth by facet‐selective capping, kinetic control, and template‐directed epitaxy. Their enhanced catalytic and electrocatalytic properties are also described.     

水相CdTe纳米晶的合成、生长机理和应用研究

纳米晶在生物检测、光电器件、光波导、可调激光器等领域有着广泛的应用前景．本文以CdTe为例,对近年来水相纳米品合成和生长机理方面的研究进展作了简要的归纳和论述．水相合成纳米晶具有操作简单、价格低廉、在水溶液中稳定性高等优点,并可以通过静电力、范德华力等弱相互作用实现一维、二维甚至三维结构的组装．对纳米晶的生长机理的研究涵盖了热力学主导的Ostwald熟化（Ostwaldripening）机理和动力学控制的聚集机理两个主要方面．文章最后对水相合成CdTe纳米晶的应用进行了总结和展望,     

Synthesis of W‐doped TiO2 by low‐temperature hydrolysis: Effects of annealing temperature and doping content on the surface microstructure and photocatalytic activity

A series of tungsten‐doped Titania photocatalysts were synthesized using a low‐temperature method. The effects of dopant concentration and annealing temperature on the phase transitions, crystallinity, electronic, optical, and photocatalytic properties of the resulting material were studied. The X‐ray patterns revealed that the doping delays the transition of anatase to rutile to a high temperature. A new phase W_yTi_1‐yO₂ appeared for 5.00 wt% W‐TiO₂ annealed at 900 °C. Raman and diffuse reflectance UV–Vis spectroscopy showed that band gap values decreased slightly up to 700 °C. X‐ray photoelectron spectroscopy showed that surface species viz. Ti³⁺, Ti⁴⁺, O^2?, oxygen‐vacancies, and adsorbed OH groups vary depending on the preparation conditions. The photocatalytic activity was evaluated via the degradation of methylene blue using LED white light. The degradation rate was affected by the percentage of dopants. The best photocatalytic activity was achieved with the sample labeled 5.00 wt% W‐TiO₂ annealed at 700 °C.