微波/Fenton试剂/钛掺杂笼型八聚倍半硅氧烷体系降解苯胺宏观反应动力学研究

建立了以颗粒钛掺杂笼型八聚倍半硅氧烷为催化剂的微波诱导氧化工艺处理苯胺废水,并深入开展了相关基础研究。基于钛掺杂笼型八聚倍半硅氧烷对有机污染物的吸附能力和对微波的强吸收能力,利用微波能量实现对有机物的分解和炭化。考察了微波辅助催化氧化剂处理苯胺废水过程中各种参数对处理效果的影响,建立了微波辅助催化氧化降解苯胺废水过程的宏观动力学模型。     

微波/Fenton试剂/钛掺杂笼型八聚倍半硅氧烷协同处理苯胺模拟废水研究

以自行合成的一种新型的钛硅固体材料——钛掺杂笼型八聚倍半硅氧烷进行吸附处理苯胺废水。实验中对各条件下体系中苯胺去除率的影响进行了考察;同时,对该体系下苯胺中氨基生成N2的选择性和微波/Fenton试剂条件下催化剂的再生损失和使用寿命作了相应研究。     

钛杂化笼型聚倍半硅氧烷吸附苯胺废水的动/热力学以及吸附机理研究

采用自行合成的一种新型钛硅固体材料——钛杂化笼型聚倍半硅氧烷,吸附处理质量浓度50 mg/L的苯胺废水。结果表明,当钛杂化笼型聚倍半硅氧烷用量2 g/L,pH值4.0,常温吸附20 min时,其吸附率达到64%。吸附符合Freundlich模型,属于优惠吸附等温线。通过计算获取ΔG0,ΔH0,ΔS0等吸附参数数据,证实了钛杂化笼型聚倍半硅氧烷吸附苯胺的趋势;同时依据参数值推测了苯胺分子在催化剂表面被吸附的机理。     

含活性氢基的八聚笼型倍半硅氧烷的合成与表征

笼形倍半硅氧烷具有较低的介电常数。采用正硅酸乙酯和季铵碱为原材料,合成了八聚四甲基铵基笼型倍半硅氧烷,并采用二甲基氯硅烷对其进行烷基取代,得到了含活性氢基的八聚笼型倍半硅氧烷。采用核磁共振29Si、13C、1H谱和凝胶渗透色谱GPC对其结构进行了表征和确认。     

含POSS的纳米杂化物对环氧树脂改性研究

将笼型八聚倍半硅氧烷(POSS)与对-甲苯基缩水甘油醚(TGE)反应,合成了顶角含有苯环的笼形八聚倍半硅氧烷无机/有机纳米杂化物(PTGE),将该杂化物添加到双酚A型环氧树脂(E44)中对其改性,测定固化后改性环氧树脂复合材料的力学性能和热稳定性能。结果表明,改性后环氧树脂的冲击强度、拉伸强度和断裂伸长率较改性前有了明显的提高,热稳定性大大增强。     

笼型八聚倍半硅氧烷与聚苯胺复合物的合成与表征

由笼型八聚倍半硅氧烷(POSS)与顺丁烯二酸在水中进行复合,形成离子形式的POSS/COOH复合物,再与聚苯胺(PAn)进行掺杂,将POSS基团引入聚苯胺,合成了掺杂态聚苯胺(PAn-POSS)。结果表明,POSS作为掺杂剂被成功的引入聚苯胺之中,POSS掺杂后的聚苯胺高温稳定性增强,电化学活性得以显著提高。     

不同硝基苯基POSS的合成及热性能研究

以八苯基笼型低聚倍半硅氧烷(OPS)和十二苯基笼型低聚倍半硅氧烷(DPS)为原料,经发烟硝酸和发烟硝酸/浓硫酸的混合酸硝化反应,分别合成了八硝基苯基笼型低聚倍半硅氧烷(ONPS),十二硝基苯基笼型低聚倍半硅氧烷(DNPS),十六硝基八苯基笼型低聚倍半硅氧烷(HDNPS)。利用傅里叶红外光谱、核磁共振光谱、XRD分析测试手段对其结构进行了表征。重点考察了笼子体积和硝基取代数对化合物热稳定性的影响,经TGA测试表明:三者质量损失为5%时的温度分别为349℃、292℃、187℃,最大热分解速度对应的温度分别是430℃、428℃、410℃,在1 190℃处,三者的残留质量分数分别是53.4%、50.25%、36.69%。三者都具有良好的热稳定性,其中以硝基取代数最少和笼子体积最小的ONPS热稳定最佳。     

微波／催化氧化法对废水中苯胺降解的研究

采用微波催化氧化法对苯胺模拟水的处理进行了初步的探讨分析;考察了微波时间、微波功率、pH值、H2O2浓度、高分子负载型催化荆质量对废水中苯胺降解的影响,确定了最佳工艺条件.在最佳工艺条件下,CODcr的去除率达到98%以上.     

P（POSS-IA）纳米复合材料的制备及其鞣制性能

以八乙烯基笼型倍半硅氧烷（POSS-Vi）和衣康酸（IA）为原料，通过自由基聚合制得聚（笼型倍半硅氧烷-衣康酸）〔P（POSS-IA）〕纳米复合材料。通过FT-IR、1H-NMR、XRD、TEM对其结构进行了表征，POSS-Vi均匀分散在聚合物基体中，直径在50nm左右。将P（POSS-IA）应用于坯革鞣制工序中，与聚（衣康酸）〔P（IA）〕、聚（丙烯酸）〔P（AA）〕、聚（笼型倍半硅氧烷-丙烯酸）〔P（POSS-AA）〕、聚（甲基丙烯酸）〔P（MAA）〕、聚（笼型倍半硅氧烷-甲基丙烯酸）〔P（POSS-MAA）〕鞣制坯革进行了性能对比。结果表明，P（POSS-IA）鞣制坯革具有较高的收缩温度，达到68.2 ℃；P（POSS-MAA）鞣制坯革增厚率最大，可达到53.3%；P（POSS-AA）鞣制坯革的抗张强度和撕裂强度最高，分别达到31.6 MPa、59.3 N/mm。坯革的SEM和EDS结果表明，P（POSS-IA）纳米复合材料在鞣制坯革中分散更均匀。     

聚醚硅氧烷/ 聚倍半硅氧烷双重改性蓖麻油基水性聚氨酯

以蓖麻油与聚醚硅氧烷（PEPSO）互混作为多元醇原料制备出植物油基水性聚氨酯。在预聚体合成过程中,加入不同含量的四羟基八苯基双层笼型倍半硅氧烷,通过醇羟基与异氰酸酯基的反应,将聚倍半硅氧烷（POSS）引入到植物油聚氨酯基体中,制备出聚氨酯纳米复合材料,并探讨纳米粒子-聚倍半硅氧烷对聚氨酯材料热稳定性,表面疏水性及力学性能的影响。热重分析（TGA）结果表明,复合材料的初始降解温度 T5% 和最终稳定温度 Tf 都会提高;静态接触角测试结果表明随 POSS 含量的增加,材料表面的疏水性随之增大。同时从扫描电镜图中可以看到,随着 POSS 含量的增加,断面的不平整度增大,粒子间的团聚愈发严重;拉伸测试结果表明 POSS 的引入能在一定程度上提高材料的拉伸强度。     

溶胶-凝胶-微波法制备银掺杂TiO_2光催化剂及其光催化性能

用硝酸银和钛酸正丁酯为原料,采用溶胶-凝胶-微波辐射干燥法合成银掺杂TiO_2光催化剂TiO_2-Ag。为了提高催化剂的光催化活性和降解有机污染物的速率,用微波辅助Ti O2-Ag光催化剂降解有机污染物。通过扫描电子显微镜、红外光谱法、紫外可见光谱法和荧光光谱法对TiO_2-Ag催化剂进行测试和表征。以甲基橙为有机污染物,分别在太阳光照射和微波、紫外、紫外-微波条件下降解甲基橙以考察催化剂的光催化活性。结果表明,TiO_2-Ag光催化剂最佳制备条件为:银掺杂量n(Ag+)∶n(Ti~(4+))=0.003,离子液体用量3.0 m L,微波干燥功率210 W,微波干燥时间20 min,焙烧温度650℃,焙烧时间3 h,此条件下制备的TiO_2-Ag光催化剂在太阳光照射4 h下,紫外光照、微波辐射和紫外光照-微波辐射分别辐射55 min后,甲基橙降解率分别为98.70%、98.79%和99.05%。     

用于环境净化的TiO2/AC复合材料的制备及其改性研究进展

二氧化钛（TiO₂）在光照下可以产生具有强氧化性能的活性基团,活性炭（AC）具有良好的吸附性能。将TiO₂负载在AC上制备的TiO₂/AC复合材料可以有效去除大部分难降解的有机污染物,因此在环境净化领域具有良好的应用前景。本文综述了TiO₂/AC复合材料的研究现状,介绍了目前TiO₂/AC复合材料的三种主要制备工艺：溶胶-凝胶法、溶剂热法和微波合成法。其中溶胶-凝胶法所制备的材料稳定性好、溶剂热法制备条件温和、微波合成法制备周期短。针对TiO₂/AC复合材料可见光吸收率低和量子利用率低等问题,介绍了离子掺杂、半导体复合、贵金属沉积等现有的TiO₂/AC复合材料改性方法。之后,概述了所制备的TiO₂/AC复合材料在去除难降解有机污染物（染料废水、药物类、酚类、挥发性有机物）中的应用。最后展望了TiO₂/AC复合材料在改性研究与实际应用过程中存在的挑战性问题及可行的解决方法,为TiO₂/AC复合材料深入研究和大规模工业生产应用提供参考。     

吸附剂再生技术的研究进展

吸附法是废水处理技术中最有效的物化方法,吸附剂可以有效的去除废水中各种污染物,尤其是采用其他方法难以有效处理的有毒和难降解的污染物.吸附剂吸附了大量吸附质会逐渐趋向饱和并失去继续吸附的能力,需要对其进行再生处理.本文总结热再生法、化学再生法、生物再生法、溶剂再生法、以及微波辐射再生法等目前常用的再生方法,并对这几种方法的优缺点进行了概述.     

Assessment of Microwave/UV/O<Subscript>3</Subscript> in the Photo-Catalytic Degradation of Bromothymol Blue in Aqueous Nano TiO<Subscript>2</Subscript> Particles Dispersions

In this study, a microwave/UV/TiO₂/ozone/H₂O₂ hybrid process system, in which various techniques that have been used for water treatment are combined, is evaluated to develop an advanced technology to treat non-biodegradable water pollutants efficiently. In particular, the objective of this study is to develop a novel advanced oxidation process that overcomes the limitations of existing single-process water treatment methods by adding microwave irradiation to maximize the formation of active intermediate products, e.g., OH radicals, with the aid of UV irradiation by microwave discharge electrodeless lamp, photo-catalysts, and auxiliary oxidants. The results of photo-catalytic degradation of BTB showed that the decomposition rate increased with the TiO₂ particle dosages and microwave intensity. When an auxiliary oxidant such as ozone or hydrogen peroxide was added to the microwave-assisted photo-catalysis, however, a synergy effect that enhanced the reaction rate considerably was observed.     

Ultrasound assisted synthesis of heterostructured TiO2/ZnFe2O4 and TiO2/ZnFe1.98La0.02O4 systems as tunable photocatalysts for efficient organic pollutants removal

As a response to the everyday growing concern about wastewater treatment, some new mesoporous TiO₂/ZnFe₂O₄ and TiO₂/ZnFe_1.98La_0.02O₄ catalysts were synthesized during this research. The ultrasound template-assisted sol-gel method was employed in the synthesis, using conventional calcination and microwave treatment for pore directing agent removal. The as-prepared samples were characterized from the structural, optical, morphological and textural points of view, confirming the presence of spinel ferrites and TiO₂ anatase crystals in the nanocomposites. The synthetized powders exhibit promising characteristics for their use in adsorption and light activated degradation of organic pollutants. The photodegradation experiments of model pollutant basic blue 9 (methylene blue) dye were performed at laboratory scale and the optimum experimental parameters were determined as 0.4 g/L catalyst and 30 mg/L initial dye concentration, under UV light irradiation, visible irradiation and natural sun light irradiation. The conventionally calcined lanthanum doped TiO₂/ZnFe_1.98La_0.02O₄ system exhibited the highest efficiencies of 97%, 70% and 91% for dye removal from the solution, under UV light, visible light and natural sun light irradiation, respectively. Moreover, the catalytic activity was similar for up to four consecutive cycles. A lower yield of organic pollutant removal was observed in wastewater treatment plant (WWTP) effluent. The obtained results show that the newly synthesized catalysts are good candidates for the removal of water pollutants through adsorption and photocatalysis.     

微波辐射-均相Fenton氧化耦合混凝法处理印染废水

将微波污水处理技术、均相Fenton氧化和传统混凝工艺结合起来对成分复杂的印染废水进行了强化处理。结果表明,微波辐射-均相Fenton氧化耦合混凝法特别适合于处理复杂印染废水,在H2O2和FeSO4.7H2O的质量浓度分别为4.8 g/L和0.08 g/L,微波功率为500 W,辐射处理1 min的最佳条件下,色度和CODCr去除率分别高达98%和95.96%,出水主要水质指标均达到纺织染整工业水污染物排放Ⅰ级标准(GB4287-92)。初步的机理探讨表明,该法充分体现了微波辐射、Fenton氧化与混凝过程之间的协同效应,复杂染料分子降解反应历程的提出使得这种协同效应更为直观。     

One-pot synthesis and modification of silica nanoparticles with 3-chloropropyl-trimethoxysilane assisted by microwave irradiation

Industry and academia have shown great interest in the synthesis of organic–inorganic hybrid material because the modification of inorganic supports with organic groups increases the options for using these materials. Microwave irradiation as a heat source is an alternative tool compared with conventional heating (oil bath or furnace) to reduce the reaction times during the synthesis of these materials. Thus, the purpose of this work was to synthesize an organic–inorganic hybrid material, more specifically silica nanoparticles modified with 3-chloropropyl-trimethoxysilane, using microwave irradiation as the heat source. The hybrid materials were synthesized using the sol–gel method, with microwave irradiation for 10, 25, and 40?min, at 300?W of power and temperature of 40, 60, and 80°C. Elemental analyses, FTIR, and N₂ adsorption–desorption isotherms were developed to characterize the materials. It can be concluded that when microwave irradiation is used as a heat source, the reaction rate is accelerated and the surface area of hybrid materials increases considerably.