Mg0.5NixZn0.5-xFe2O4 spinel as a sustainable magnetic nano-photocatalyst with dopant driven band shifting and reduced recombination for visible and solar degradation of Reactive Blue-19

Focussing on visible light active ferrites for high performance removal of noxious pollutants, we report the synthesis of Mg_0.5Ni_xZn_0.5-xFe₂O₄ (x = 0.1, 0.2, 0.3, 0.4, & 0.5) ferrite nanoparticle for degradation of reactive blue-19 (RB-19). Lattice parameters calculated using intense X-ray diffraction (XRD) peaks and Nelson-Riley plots (N-R plot) are in well agreement with each other. The sample Mg_0.5Ni_0.4Zn_0.1Fe₂O₄ (M5N4) exhibits best performance with 99.5% RB-19 degradation in 90 min under visible light. Photoluminescence (PL) results confirm that recombination of charge carriers is highly reduced in the photocatalyst. Scavenging experiments suggest that O₂⁻ radicals were the dominant species responsible for photocatalytic performance. The photocatalytic mechanism was explained in terms of dopant driven shifting of conduction bands and valence bands (calculated by Mott-Schottky plots). The thermodynamic probability of radical generation along with role of redox cycles of metal ions has been discussed in the mechanism. The dye degradation was ascertained by detection of intermediates via mass spectrometry analysis and a possible degradation route was also predicted. The findings in this work provide intriguing opportunities to modify the electronic band structure of spinel ferrites for visible and solar light photocatalytic activity for environmental detoxification.     

Pool boiling on a superhydrophilic surface

Titanium Dioxide, TiO₂, is a photocatalyst with a unique characteristic. A surface coated with TiO₂ exhibits an extremely high affinity for water when exposed to UV light and the contact angle decreases nearly to zero. Inversely, the contact angle increases when the surface is shielded from UV. This superhydrophilic nature gives a self-cleaning effect to the coated surface and has already been applied to some construction materials, car coatings and so on. We applied this property to the enhancement of boiling heat transfer. An experiment involving the pool boiling of pure water has been performed to make clear the effect of high wettability on heat transfer characteristics. The heat transfer surface is a vertical copper cylinder of 17 mm in diameter and the measurement has been done at saturated temperature and in a steady state. Both TiO₂-coated and non-coated surfaces were used for comparison. In the case of the TiO₂-coated surface, it is exposed to UV light for a few hours before experiment and it is found that the maximum heat flux (CHF) is about two times larger than that of the uncoated surface. The temperature at minimum heat flux (MHF) for the superhydrophilic surface is higher by 100 K than that for the normal one. The superhydrophilic surface can be an ideal heat transfer surface. Copyright © 2002 John Wiley & Sons, Ltd.     

Mg-doped LiNi0.5Mn1.5O4 spinel for cathode materials

Lithium-ion batteries are becoming more and more important not only for portable electronic devices, but also in prevision of high power electric vehicles. In such an optic, deep studies regarding all the components of a secondary battery are in development. In this study, high voltage cathode materials have been selected. Crystals with spinel structure have a 3D vacancy pathway suitable for Li-ions transport. The material under study was LiNi_0.5Mn_1.5O₄ doped with magnesium replacing the nickel. Various samples were synthesized via three different routes: a solid-state method, a modified sol–gel method and a xerogel method. The structure and morphology of the powders were analyzed with HRTEM and XRD. Electrochemical tests were also performed. A wide range of particle sizes (from micro to nanosize) was the result of the different synthesis routes. Unfortunately pure materials were not always obtained. The electrochemical tests showed improvement of the material's cyclability, by reducing the particle size. The electrochemical tests further confirmed the existence of a Li_1+dMn_2−dO₄ impurity. The results are quite promising, however, further improvement of the purity of the electrode composition are needed.     

Surface structural change of ZnO-coated LiNi0.5Mn1.5O4 spinel as 5 V cathode materials at elevated temperatures

LiNi_0.5Mn_1.5O₄ powder was synthesized via sol-gel method and coated with ZnO in order to test the electrochemical cyclability of the material as a cathode for the secondary Li battery in the 5 V range at 55 °C. The ZnO-coated LiNi_0.5Mn_1.5O₄ powder nearly maintained its initial capacity of 137 mA h g⁻¹ after 50 cycles whereas the uncoated powder was able to retain no more than 10% of the initial capacity after 30 cycles. TEM analysis of the cycled cathodes suggests that the formation of the graphitic surface phase, hindering the Li migration, may be responsible for the rapid capacity loss of the uncoated material while no such phase was observed on the surface of the ZnO coated LiNi_0.5Mn_1.5O₄ powder.     

Promising alloys for intermediate-temperature solid oxide fuel cell interconnect application

The formation of a low Cr-volatility and electrically conductive oxide outer layer atop an inner chromia layer via thermal oxidation is highly desirable for preventing chromium evaporation from solid oxide fuel cell (SOFC) metallic interconnects at the SOFC operation temperatures. In this paper, a number of ferritic Fe–22Cr alloys with different levels of Mn and Ti as well as a Ni-based alloy Haynes 242 were cyclically oxidized in air at 800 °C for twenty 100-h cycles. No oxide scale spallation was observed during thermal cycling for any of these alloys. A mixed Mn₂O₃/TiO₂ surface layer and/or a (Mn, Cr)₃O₄ spinel outer layer atop a Cr₂O₃ inner layer was formed for the Fe–22Cr series alloys, while an NiO outer layer with a Cr₂O₃ inner layer was developed for Haynes 242 after cyclic oxidation. For the Fe–22Cr series alloys, the effects of Mn and Ti contents as well as alloy purity on the oxidation resistance and scale area specific resistance were evaluated. The performance of the ferritic alloys was compared with that of Haynes 242. The mismatch in thermal expansion coefficient between the different layers in the oxide scale was identified as a potential concern for these otherwise promising alloys.     

Synthesis of nano particle of inorganic oxides by polymer matrix

Ultrafine (⩽ 150 nm) powders of spinels [MFe₂O₄ where M = Ni(II), Co(II) and Zn(II)]; rare-earth orthoferrites [RFeO₃ where R = Sm, Nd and Gd], and rare-earth garnets [R₃Fe₃O₁₂ where R = Sm, Nd and Gd] with good purity and chemical homogeneity were prepared through two new versatile chemical routes. The first route involved the coprecipitation of the desired metal nitrates from their aqueous solution, in presence of a water soluble polymer-polyvinyl alcohol (PVA), by triethyl ammonium carbonate solution. The other process involved complete evaporation of a mixture of optimum amounts of PVA and the desired aqueous metal nitrate solutions, with and without the addition of optimum amounts of urea when the mixture was evaporated to a pasty mass. In addition, detailed study on the reported potassium ferricyanide route was also carried out for the production of the rare-earth orthoferrite powders. The various precursor as well as the heat-treated mixed-oxide powders, prepared through each of the routes, were compared by the physical characterization studies involving thermal gravimetry and differential scanning calorimetry, infrared spectroscopy, X-ray powder diffraction, transmission electron microscopy, and room temperature magnetic measurements.     

纳米掺钼二氧化钛光催化剂研究发展

介绍了纳米掺钼二氧化钛光催化剂的制备、特性及应用     

Fe(Ⅲ)改性膨润土光催化降解水溶液中的4-氯苯酚

以Fe（Ⅲ）离子交换改性膨润土,制得一种多相Fenton催化剂;以4-氯苯酚为模型污染物,研究不同反应条件的影响。结果表明,复合催化剂主要含SiO2及α-Fe2O3两种晶型,Fe是以高催化活性的α-Fe2O3形式存在。复合催化剂在H2O2及紫外光的协同作用下,经60 min反应后对4-氯苯酚的降解率约100%,TOC去除率约70%,且其循环使用性能较好。在实际操作过程中,控制溶液体系的pH值为6以及H2O2与4-氯苯酚浓度比约15较为适宜;在4-氯苯酚的降解过程中,C—Cl键持续断裂,Cl-被释放出来,降解过程生成了一些不含氯的中间产物。     

可见光响应的"Cu核- Cu2O壳"型光催化剂性能的研究

以碱性染料结晶紫为目标污染物,金属卤化物灯为可见光光源,研究了自制的"Cu核-Cu20壳"微粒的光催化性能.实验结果表明,该催化剂对可见光有良好的响应,当固液比为1500,光照120min,质量浓度为60mg/L的结晶紫溶液色度和COD去除率分别达98%和92%.检测结果表明,光催化过程中有氢氧自由基产生,染料发生了彻底的降解.     

纳米氧化锆/氧化锌光催化降解酸性红B的研究

以醋酸锌和氯氧化锆为原料，采用化学沉淀法制备了纳米氧化锆／氧化锌光催化剂。在中性条件下研究了催化剂煅烧温度，锆复合量，催化剂用量，染料初始质量浓度，过氧化氢质量浓度，各种阴、阳离子等条件对酸性红B脱色反应的影响。结果表明，该催化剂最佳制备条件为煅烧温度350℃，锆复合量2．5％（物质的量分数）。催化剂最佳用量0．9g／L。提高染料初始质量浓度会降低反应脱色率。适量过氧化氢可提高反应脱色率，当其质量浓度超过300mg／L会起负作用。NO3^-对反应影响不大；Fe^3＋和Ag^＋对反应起促进作用；SO4^2-，Cl^-，NO2^-等阴离子和Fe^2＋，Mn^2＋等阳离子对反应起抑制作用。