TiO2光催化降解PFOA的反应动力学及机制研究

全氟辛酸(PFOA)是一种新的持久性有机污染物,其处置技术是研究的热点.以UV254 nm紫外灯为光源,采用商品TiO2(P25)对PFOA进行光催化降解实验,并考察pH、TiO2用量、初始浓度、反应气氛对降解的影响.结果表明,反应符合准一级动力学方程,pH对反应有重要影响,氧气存在下能提高反应效率.在pH为3,TiO2用量为1.5 g·L-1,通入空气条件下反应7 h实现基本降解,速率常数为0.4206 h-1.投加俘获剂实验表明,空穴(h+)是主要的活性物质,其对反应速率贡献率为66.1%;羟基自由基(·OH)也参与PFOA的降解过程;投加NaF实验表明,PFOA在TiO2上吸附是反应发生的首要条件.UPLC-QTOF/MS分析表明,PFOA光催化降解逐级生成短链全氟羧酸(PFCAs).     

3,5-二硝基水杨酸表面修饰纳米Ti2吸附对硝基苯酚

化学吸附法合成3,5-二硝基水杨酸表面修饰的TiO₂纳米粒子,TiO₂表面修饰后呈浅黄色,TiO₂表面羟基与3,5-二硝基水杨酸发生类似于醇和酸间的酯化反应.表层链接有苯环,极性减弱,非极性增强,在水、苯、乙醇中均分散性良好,与芳香族污染物的亲合力增强,有利于吸附去除芳香族污染物.表面修饰的TiO₂纳米粒子20mg,在最佳吸附pH值3、吸附时间10min,对100mL对硝基苯酚(3～10 mg/L)的吸附率可由改性前的43%增至99.9%.该法吸附效率高,可直接达到一级排放标准,提供了深度处理对硝基苯酚废水的新方法.     

Photocatalytic Treatment of RDX Wastewater with Nano-Sized Titanium Dioxide (5 pp)

Background, Aim and Scope The polynitramines, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), are important military explosives and regulated toxic hazardous compounds. Production, testing and use of the compounds has resulted in numerous acres of contaminated soils and groundwater near many munitions facilities. Economical and efficient methods for treatment of wastewater and cleanup of soils or groundwater containing RDX and HMX are needed. This study focuses on the photocatalytic treatment of RDX wastewater with nano-sized titanium dioxide (nano-TiO2) under simulated sunlight, whose intensity and wavelength are similar to that of the real sunlight in Xi'an at noon. The objective is to determine the potential for RDX destruction with nano-TiO2 in aqueous solution. Materials and Methods: An activated carbon fiber (ACF) cloth-loaded with nano-TiO2 was put into the RDX containing solution, and the concentration of RDX was measured (by HPLC–UV) at regular time intervals under simulated sunlight. Results: The RDX degradation percentage of the photocatalytic process is higher than that of Fenton oxidation before 80 min, equivalent after 80 min, and it reaches 95% or above after 120 min. The nano-TiO2 catalyst can be used repeatedly. Discussion: The photocatalytic degradation kinetics of RDX under simulated sunlight can be described by a first-order reaction kinetics equation. The possible degradation mechanism of RDX was presented and the degradation performance was compared with that of biological method. Conclusions: It was demonstrated that the degradation of RDX wastewater is very effective with nano-TiO2 as the photocatalytic catalyst under simulated sunlight. The efficiency of the nano-TiO2 catalyst for RDX degradation under simulated sunlight is nearly identical to that of Fenton oxidation. Recommendations and Perspectives: To date, a number of catalysts show poor absorption and utilization of sunlight, and still need ultraviolet light irradiation during wastewater degradation. The nano-TiO2 used in the described experiments features very good degradation of RDX under simulated sunlight, and the manufacturing costs are rather low (around 10 Euro/m2). Moreover, the degradation efficiency is higher compared to that of the biological method. This method exhibits great potential for practical applications owing to its easiness and low cost. If it can be applied extensively, the efficiency of wastewater treatment will be enhanced greatly.     

热盐腐蚀环境对TC11钛合金高温寿命影响规律试验研究

目的 针对发动机钛合金部件在热盐环境与工作载荷下的寿命衰减问题，开展TC11钛合金热盐腐蚀疲劳与应力腐蚀试验，研究腐蚀环境下TC11的高温寿命衰减规律与失效机理。方法 利用喷盐法制备TC11钛合金试验件，研究不同温度与应力水平对TC11腐蚀疲劳以及应力腐蚀的影响规律。利用SEM等观测手段，开展腐蚀疲劳以及应力腐蚀试样断口与表面的形貌分析，分析腐蚀环境下的失效机理。结果 热盐腐蚀环境导致TC11的寿命显著降低，对比450 ℃下无腐蚀寿命，腐蚀疲劳寿命下降了2个数量级，应力腐蚀寿命下降到不足1%，且分散性较大。观察腐蚀疲劳和应力腐蚀的试样可以发现，表面有明显的腐蚀坑，腐蚀坑底发现裂纹。结论 热盐环境下，TC11腐蚀疲劳寿命和应力腐蚀寿命都会明显下降。由于腐蚀导致钛合金试样表面产生许多腐蚀坑，在腐蚀坑局部形成近似缺口，缺口部位的应力集中是导致腐蚀疲劳寿命衰减的重要因素。腐蚀疲劳的寿命低于Kt=1的无腐蚀疲劳寿命，但是要大于Kt=3的无腐蚀疲劳寿命。     

TiO2薄膜超亲水性的研究进展

TiO2薄膜在紫外、光照射下所表现出来的超亲水性得到了国内外许多科学工作者的广泛关注。简要介绍了TiO2薄膜材料的超亲水机理、制备方法及应用发展等，指出了目前存在的问题并简单评述了今后的研究和发展方向。     

纳米二氧化钛粉体的制备及对染料脱色的研究

以钛酸四丁酯为原料,采用溶胶-凝胶法、水热沉淀法、水解法制备了纳米二氧化钛粉体。经XRD对三种方法制得粉体进行了表征,讨论了三种方法的优缺点。以水解法制得二氧化钛粉对六种染料进行了脱色研究,结果表明其有良好的光催化脱色性能。     

催化臭氧氧化法处理甲醛废水

用异丙醇钛盐表面改性法制备TiO2／SiO2催化剂，对甲醛废水进行催化臭氧氧化处理。通过比表面积的BET测定法、X射线衍射和拉曼光谱等分析方法对TiO2／SiO2催化剂进行了表征，考察了TiO2／SiO2催化剂加入量、臭氧流量及溶液pH等因素对甲醛催化臭氧氧化效果的影响。实验结果表明，在SiO2表面，TiO2微晶粒子以锐钛矿型高度分散；在甲醛质量浓度700mg／L、COD1000mg／L、TiO2／SiO2催化剂加入量2．0g、臭氧流量2．5mg／min、溶液pH8．5的条件下，催化臭氧氧化反应30min后，甲醛质量浓度由700mg／L降至39mg／L，COD去除率认到87．5％．     

介孔TiO2纤维的制备及其光催化性能

采用溶胶-凝胶和水蒸气活化热处理技术制备了介孔TiO2纤维,考察了各种因素对介孔TiO2纤维光催化活性的影响,并对介孔TiO2纤维结构进行了表征。介孔TiO2纤维的最佳制备条件：n（TBOT）∶n（C6H10O3）∶n（H2O）∶n（C3H8O）=1∶0.4∶2.0∶16,搅拌时间80min,Si与Ti的摩尔比为0.15,采用分段程序升温工艺,活化温度为700℃。所得介孔TiO2纤维比表面积为127.7m2/g,最可几孔径为7.3nm,具有极高的热稳定性及抗晶型转变能力,反应时间75min时活性艳红X-3B降解率为99.3%。     

负载型纳米TiO2光催化剂的制备及其光催化活性

采用悬浮聚合法制备粉煤灰-聚苯乙烯微珠载体，通过矿化接枝技术将水热法制备的纳米TiO2负载在粉煤灰-聚苯乙烯微珠载体上，制成负载型纳米TiO2光催化剂。用x射线衍射仪、扫描电子显微镜对负载型纳米TiO2光催化剂进行了表征；通过光催化降解甲醛实验评价了负载型纳米TiO2光催化剂的活性。实验结果表明，纳米TiO2在载体上分散良好，平均粒径为36．4nm；该催化剂活性较高，明显优于粉体纳米TiO2光催化剂，重复使用10次左右，该催化剂的活性无明显下降。     

纳米TiO2光电催化氧化法测定COD的影响因素

以纳米TiO2为光阳极，利用薄层微型反应器纳米TiO2光电催化氧化的方法测定COD，具有快速、准确、无二次污染的特点。研究了电解质类型、光源种类等对薄层微型反应器中光电催化测定COD的影响。研究结果表明：与NaNO，和KCl比较，NaH2PO4作电解质时的紫外光吸收低、电极表面氧化性能稳定，性能良好；与镓灯、碘镓灯比较，中压汞灯的紫外光谱丰富、辐射照度大，有利于TiO2光电催化反应的进行；通过热重分析，确定电极薄膜的烧结温度为520℃。