静电纺制备TiO2/PVA复合纳米纤维及其光催化性能研究

通过静电纺丝的方法制备一种以二氧化钛(TiO2)为催化剂,聚乙烯醇(PVA)为载体的TiO2/PVA复合纳米纤维光催化材料。使用FE-SEM,XRD,Tg,FTIR对制备的TiO2/PVA复合纳米纤维膜进行了表征,并考察了其紫外光照射下光催化降解罗丹明B(Rh B)的能力。结果表明:制备的TiO2/PVA复合纳米纤维具有较高的光催化活性。     

室温固相法制备纳米Fe2O3

以FeSO4·7H2O和NH4HCO3为原料,聚乙二醇辛基苯基醚(OP-10)为分散剂,在室温下通过固相反应制备前驱物,然后灼烧前驱物制得纳米氧化铁;研究了反应时间和灼烧温度对产物的影响;利用XRD和SEM对制备的纳米氧化物进行表征.结果表明:反应物转化率高,灼烧温度对产物的晶型和粒径均有影响,300℃灼烧得到产物为γ-Fe2O3纳米粒子;在500℃、550℃、800℃灼烧得产物均为α-Fe2O3纳米粒子;随着温度的升高,纳米Fe2O3的粒径增大.     

Review: Ferromagnetism in Undoped ZrO2 Thin Films

未掺杂氧化锆薄膜的铁磁性研究

宁帅,张政军（清华大学材料学院）

创新点说明：1,通过不同的物理气相沉积方法,实现了对未掺杂氧化锆薄膜的物相调控;2,发现了未掺杂氧化锆薄膜室温铁磁性对物相结构的依赖性;3,通过缺陷分析表征,发现四方相氧化锆的室温铁磁性主要由氧空位缺陷调控。

目的：未掺杂氧化锆薄膜的制备、物相和缺陷调控以及室温铁磁性研究。

方法：脉冲电子束沉积、直流反应磁控溅射、电子束蒸镀。

结果：1,通过不同的物理气相沉积方法,实现了未掺杂氧化锆薄膜的物相调控;2,发现了未掺杂氧化锆薄膜室温铁磁性的物相依赖性;3,通过缺陷分析表征,发现四方相氧化锆的室温铁磁性主要由氧空位缺陷调控。

结论： 1,制备了不同物相结构的未掺杂的氧化锆薄膜;2,发现了四方相氧化锆薄膜可以在室温下呈现铁磁性;3,四方相氧化锆薄膜中的室温铁磁性主要由氧空位缺陷引起。

关键词：氧化锆薄膜,物相调控,室温铁磁性,氧空位缺陷

     

Simulated Sunlight Irradiation Based Photocatalytic Degradation of Acrylonitrile by Sn-F Co-doped TiO2/SiO2 Nano Powder Catalyst

模拟阳光照射下Sn-F共掺杂TiO2/SiO2纳米粉体催化剂对丙烯腈的光催化降解

李翰良¹,苗诗雨²,邱露¹,Bandna Bharti¹,欧阳峰¹

（1．哈尔滨工业大学（深圳） 土木与环境工程学院, 深圳 518055;

2． 大连理工大学（盘锦） 生命科学与医学学院,辽宁 盘锦 124000）

创新点说明：

光催化降解污染物是一种绿色环保技术,其中F-TiO2/SiO2是本课题组研究比较成熟的技术,现通过进一步Sn-F共掺杂方式使得催化剂活性进一步提升,对光的吸收能力更强。

研究目的：

本研究致力于解决丙烯腈生产废水的光催化降解问题,由于丙烯腈存在碳氮三键,很难被生物降解,且丙烯腈生物毒性很强,常规方法很难达到彻底降解的目的。故本研究通过光催化技术产生强氧化能力的空穴将其氧化。

研究方法：

通过Sn-F共掺杂方式改性F-TiO2/SiO2催化剂,研究不同煅烧温度对其表面特性的影响,并进行XRD,SEM,EDS,XPS,BET,UV-Vis,PL等表征手段研究。

研究结果：

实验结果表明：通过Sn-F共掺杂,提升了光的吸收能力,增大了催化剂的比表面积,不同温度下煅烧均为锐钛矿相,且催化剂的分散性良好,电子-空穴对的分离得到改善,降解丙烯腈的能力比未掺杂前有很大的提高。

结论：

采用溶胶-凝胶法制备了Sn-F-TiO2/SiO2催化剂。在模拟光照条件下降解丙烯腈,评价其光催化活性。系统研究了Sn-F-TiO2/SiO2催化剂对丙烯腈降解的催化活性。Sn-F-TiO2 /SiO2催化剂对丙烯腈的降解率为67.7%。表征结果表明,Sn-F-TiO2/SiO2催化剂晶体尺寸小,颗粒表面小,颗粒疏松,有利于催化剂粉末在反应体系中均匀分散。PL也略有减弱,这意味着光生电子和空穴的复合受到抑制。吸收边发生红移,提高了光的利用率,并提高了光催化活性。XPS结果表明,催化剂晶格中成功掺杂了锡。在反应体系中加入牺牲剂表明,空穴是光催化活性中最重要的活性组分。

关键词：光催化,丙烯腈降解,Sn掺杂,F-TiO2/SiO2

     

Temperature dependence on reaction of CaCO3 and SO2 in O2/CO2 coal combustion

The temperature dependence on the reaction of desulfurization reagent CaCO₃ and SO₂ in O₂/CO₂ coal combustion was investigated by thermogravimetric analysis, X-ray diffraction measurement and pore structure analysis. The results show that the conversion of the reaction of CaCO₃ and SO₂ in air is higher at 500–1 100 °C and lower at 1 200 °C compared with that in O₂/CO₂ atmosphere. The conversion can be increased by increasing the concentration of SO₂, which causes the inhibition of CaSO₄ decomposition and shifting of the reaction equilibrium toward the products. XRD analysis of the product shows that the reaction mechanism of CaCO₃ and SO₂ differs with temperature in O₂/CO₂ atmosphere, i.e. CaCO₃ directly reacts with SO₂ at 500 °C and CaO from CaCO₃ decomposition reacts with SO₂ at 1 000 °C. The pore analysis of the products indicates that the maximum specific surface area of the products accounts for the highest conversion at 1 100 °C in O₂/CO₂ atmosphere. The results reveal that the effect of the atmosphere on the conversion is temperature dependence.     

Ni3Fe/Ni4S3/Ni/C Mixed Crystal Composite Nanofibers Prepared by Electrospinning and Heat Treatment Methods for Oxygen Evolution Reaction

OER catalyst of Ni₃Fe/Ni₄S₃/Ni/C (NiFeSC series) mixed crystal composite nanofibers was prepared by electrospinning and atmospheric heat treatment process.The testing results indicate that the diameters of Ni₃Fe/Ni₄S₃/Ni/C composite nanofibers is about 200 nm,the grains size is about 1-3 nm,and the fiber surface is rough.The electrochemical test results show that the heterojunction of the prepared Ni₃Fe/Ni₄S<...     

电纺法制备壳聚糖/聚乙烯醇纳米纤维

采用电纺法制备了壳聚糖/聚乙烯醇纳米纤维.考察了纺丝液配比和挤出速度对电纺纤维形貌的影响.结果表明当壳聚糖质量比小于70%时,共混溶液的可纺性较好,纤维直径随着壳聚糖含量的增大而减小;随着挤出速度的增大,电纺纤维直径有逐渐增大趋势,挤出速度为0.5～0.8 mL/h时得到的纤维形貌最佳.     

Modification of nano-TiO2 by Al2O3 in-situ coating

A novel technology of in-situ coating Al₂O₃ on the surface of H₄TiO₄ was developed to prevent the aggregation of nano-TiO₂ powders and improve the dispersibility and thermal stability in the way of forming a uniform coating layer. The heterogeneous nucleation was conducted to prepare the precursor of nano-TiO₂ and then Al₂O₃ was coated on the surface of precursor. The effects of Al₂O₃ in-situ coating on the properties of nano-TiO₂ were investigated. The results show that H₄TiO₄ can be dispersed well under alkaline condition (pH 8.5) and the heterogeneous nucleation can be controlled easily. The optimized uniform coating layer is obtained by adding 5% (mass fraction) and 10% of Al₂O₃ and the aggregation of nano-TiO₂ powders is effectively inhibited and the dispersibility is obviously improved. The crystal sizes of TiO₂ powders are 12.3, 11.4 and 8.7 nm after coating 0,5% and 10% of Al₂O₃ respectively. Al₂O₃ on the surface of particulates in amorphous phase could increase the thermal stability of nano-particles after calcined at 550 °C. Foundation item: Project(04GK2007) supported by Hunan Industrial Key Project of Science and Technology     

氧化铝增强的PdSe2/Si异质结光电探测器

为了降低暗电流,通过原子层沉积(ALD)生长了一层氧化铝(Al₂O₃)隧穿层,制备了PdSe₂/Al₂O₃/Si异质结光电探测器.通过优化Al₂O₃层的厚度,使得该探测器实现了高速和宽光谱响应.研究结果表明,在波长为808 nm的光照射和-2 V偏压下,所制备的光电探测器与未生长Al₂O₃的器件相比,暗电流降低了约3个数量级,器件的光响应度达到了约为0.31 A/W,对应的比探测率约为2.5×10¹² Jones,器件在零偏压下表现出明显的自驱动效应.经过循环测试1 200次后,器件保持良好的光响应.器件响应的上升时间和下降时间分别为7.1和15.6μs.结果表明,在二维层状半导体材料与Si之间引入Al₂O₃隧穿层,可以有效地降低器件的暗电流,有利于高性能的Si基光电探测器的制备.     

SnO2及SnO2／Fe2O3复合微米材料的合成及表征

本文首先以SnCl2·2H2O为主要原料,无水乙醇为溶剂,利用溶剂热法于180℃反应24h得到了SnO2微球;再以所制备的SnO2微球为前驱体,FeCl3·6H2O为主要原料,通过水热法得到SnO2／Fe2O3复合材料．利用X射线粉末衍射仪（XRD）和扫描电子显微镜（SEM）对所得产物进行了表征．结果表明：所得的SnO2为四方锡石型,形貌为微球,平均直径约为2．0μm;复合后得到的SnO2／Fe2O3微球平均直径约为2．5μm．其中,Fe2O3为六方赤铁矿型,在复合物的表面以小颗粒的形式存在,尺寸约为200nm．另外,也对SnO3与SnO2／Fe2O3微球的形成过程进行了讨论．     

Degradation of p-nitrotoluene by O3/H2O2 process and oxidation mechanism

The degradation of p-nitrotoluene by O3/H2O2 process in a bubble contact column was investigated. Effects of the molar ratio of hydrogen peroxide to ozone,pH value and t-butanol on the oxidation process were discussed. It was found that the proper H2O2/O3 molar ratio for the degradation of p-nitrotoluene was around 0.6, different pH values and the presence of t-butanol highly influenced the removal efficiency of p-nitrotoluene. 5-methyl-2-nitrophenol, 2-methyl-5-nitrophenol, (4-nitrophenyl) methanol, 5-(hydroxymethyl)-2-nitro phenol, acetic acid, 2-methylpropane diacid and 2-(hydroxylmethyl)propane diacid were identified as degradation intermediates and products through GC-MS. Radical reaction mechanism and degradation pathway were proposed based on the results of experiments. It is deduced that the benzene ring of p-nitrotoluene can be only destroyed by hydroxyl radicals through a polyhydroxy intermediate pathway. Then unstable polyhydroxy intermediates can be oxidized to different acids with low molecular weight rapidly.     

Preparation of TiO2 photocatalyst loaded with V2O5 for O2 evolution

TiO₂ photocatalysts loaded with V₂O₅ were prepared via a modified hydrolysis process, and characterized by X-ray diffraction, transmission electron microscopy, Raman spectra and diffuse reflectance UV-Vis spectra measurements. The photocatalytic activity of V₂O₅/TiO₂ was investigated by employing splitting of water for O₂ evolution. The results indicate that V₂O₅ loading can pronouncedly improve the photocatalytic activity of TiO₂ with Fe³⁺ as an electron acceptor under UV or visible light irradiation. The optimum mass fraction of the loaded V₂O₅ is 8%, and the largest speed of O₂ evolution for 8%V₂O₅ (mass fraction) loaded TiO₂ catalyst is 118.2 μmol/(L·h) under UV irradiation, and 83.7 μmol/(L·h) under visible light irradiation.     

介质填充材料对低温等离子体分解CO2的研究

低温等离子体内部存在很多高活性粒子可以促进CO₂气体在常温下分解。为了提高CO₂的分解效率,探索CO₂减排的新途径。研究了介质材料（γ-Al₂O₃、石英棉、CaO）加入时,等离子体与CO₂的反应情况及不同填充材料对该反应的影响。研究表明,加入介质填充材料会显著提高CO₂的分解效率,且加入石英棉时对CO₂的分解效率最高;填充材料粒径在250 μm时,CO₂转化率最高。     

N-Fe共掺杂BiVO_4的制备及其光催化活性的研究

采用溶胶凝胶法制备了N和Fe共掺杂的Bi VO4可见光光催化剂,并用X射线衍射(XRD)、比表面积测试(BET)和紫外-可见漫反射谱(UV-Vis DRS)对其进行了表征.结果显示,N-Fe共掺杂对Bi VO4晶型没有产生影响,掺杂前后均为单斜晶系,但晶粒粒径有所减小,BET比表面积相对增大.由UV-Vis可知,N-Fe共掺杂的Bi VO4的吸光强度明显增强,禁带宽度变窄.以可见光降解甲基橙(MO)考察催化剂的光催化活性,N-Fe共掺杂的Bi VO4对MO的降解速率明显高于纯Bi VO4,证明N-Fe共掺杂产生的协同效应提高了Bi VO4在可见光照射下的光催化活性.     

Fe~0/H_2O_2类Fenton体系降解水中对氯硝基苯

为解决传统Fenton过程中Fe3＋返回Fe2＋速率慢致使反应过程中铁离子循环受阻的瓶颈问题,对Fe0/H2O2-类Fenton降解对氯硝基苯（pCNB）的效果与机理进行研究.考察H2O2和铁的投加量、初始pH值等因素对pCNB降解效果的影响,对体系TOC和Cl-、NO3-浓度以及一些中间产物进行鉴定和分析.当pH值为...     

H2O2—Br2溴化对甲苯腈制备对腈基苄溴

研究了在过氧化氢的存在下,用液溴和过氧化氢溴化对甲苯腈制备对腈基苄溴的方法,在回流状态下,把86．4液溴慢性滴加到58．5g对甲苯腈和200g环已烷的混合物中,并分次加入质量分数30％过氧化氢68．2g,反应2h,过滤出沉淀物,用质量分数95％乙醇重结晶,得到腈基苄溴80．3g,收率81．6％。     

三氧化二铝是导致建筑物火灾的严重隐患

建筑物供电线路中的铜线与铝线连接处常常生成一种灰白物质－－三氧化二铝,极易引发建筑物火灾。着重介绍和分析这种灰白物质的成分、生成原因、危害以及防止其生成的主要措施。     

氢（氘、氚）分子与低能氦原子（E=0.1eV）碰撞研究

对H2,D2,T2碰撞体系,采用Tang-Toennies势,用密耦方法求解散射方程,计算了E＝0.1eV时00－00,00－02,00－04分子转动激发分截面和角分布,并研究了原子与分子碰撞弹性分波截面和非弹性激发截面随量子数增加的变化规律。     

Preparation of ZrO2 nano-particles by the hydrolysis of ZrOCl2 solution in the reverse micelles

Zirconia nano-particles have been produced by the hydrolysis of ZrOCl2 solution in the reverse micelles of a liquid-liquid two-phase system, in which sodium bis（2-ethylhexyl） sulfosuccinite （AOT） and toluene were chosen as the surfactant and organic phase, respectively. The reverse micelles prevented the aggregation of primary particles and reduced the diameters of zirconia nanoparticles. Superfine zirconia powders soft-aggregated by the zirconia nano-particles were obtained. The diameters of zirconia nanoparticles were influenced by the quantity of the surfactant.     

负载型催化剂MnOx-CeO2/TiO2去除甲苯

为了考察铈掺杂对金属氧化物催化剂催化燃烧处理有机废气的影响,采用蜂窝状TiO2丝网作为催化燃烧催化剂的载体,以MnOx、CeO2作为活性组分,用浸渍法负载制备出催化燃烧催化剂,考察了活性组分负载量及配比、焙烧温度、焙烧时间对催化剂降解甲苯的影响.实验确定了催化剂的最佳制备工艺:Mn的负载量(质量分数)约为15%,Mn与Ce物质的量比为3∶1,催化剂的焙烧温度为500℃,焙烧时间为5h.结果表明:与催化剂MnOx/TiO2相比,掺杂Ce后的催化剂MnOx-CeO2/TiO2对甲苯催化燃烧的起燃温度和完全转化温度均有明显降低,催化剂表面燃烧物颗粒的粒径有所减小,分散均匀,更有利于甲苯的降解处理.