酞菁钴/MCM-41的制备及其可见光催化性能

以MCM-41分子筛为载体,采用浸渍法将酞菁钴负载到分子筛上以氙灯为光源降解甲基橙溶液。对负载型酞菁钴催化剂进行FT-IR、XRD、SEM表征,结果表明所制催化剂负载效果良好,且分子筛结构未发生改变。以甲基橙溶液为模拟处理对象,研究催化剂的催化性能,考察了光照、酞菁钴负载、催化剂用量等因素对催化效果的影响。结果表明,氧气充足时,在光照条件下、0.04g负载型酞菁钴催化剂处理200mL的0.05g/L甲基橙溶液能够有很好的处理效果,2h降解率能够达到98.3%,且重复利用4次后降解率仍能达到90%。     

蚕丝纤维/金属酞菁活化双氧水催化氧化酸性橙的研究

合成了四磺酸基钴酞菁(CoPcS),采用基质辅助激光解析电离飞行时间质谱(MALDI-TOF-MS)、紫外-可见光谱(UV-Vis)和傅里叶变换红外光谱(FT-IR)对其进行表征,然后通过三聚氯氰改性将其负载到蚕丝纤维(SF)上,制得了新型蚕丝纤维负载钴酞菁催化剂(CoPcS-SF)。以H2O2为氧化剂,考察了CoPcS-SF对酸性橙Ⅱ(AO2)的催化氧化性能,结果表明,在中性条件下,CoPcS-SF能高效催化氧化AO2,反应60min后AO2的去除率可达97%以上,并且具有较好的重复使用性。考察了pH值、电解质NaCl和温度对CoPcS-SF催化性能的影响,结果表明,CoPcS-SF在pH值3～9较宽范围内均具有较高催化活性;NaCl对催化AO2有促进作用;催化活性随反应温度升高而增强。FT-IR和气质联用(GC-MS)对AO2的降解产物分析表明,AO2的主要产物为顺丁烯二酸、反丁烯二酸和丁二酸等小分子可生物降解脂肪酸。     

镁酞菁/PHBV催化薄膜的制备及光催化性能研究

将四氨基镁酞菁(MgPc)负载到PHBV上制备复合催化薄膜(MgPc/PHBV)。采用XRD、FT-IR、TGDTA和UV-Vis DRS等表征技术对MgPc/PHBV的结构和性质进行表征。结果表明,MgPc和PHBV之间可能通过物理作用结合;MgPc的加入降低PHBV的结晶度;并且将PHBV的分解温度提高20℃。基于UV-Vis DRS的测试表明MgPc/PHBV薄膜具有可见光催化活性。此外,MgPc/PHBV光催化降解有机污染物甲基橙的结果表明,光照、MgPc/PHBV和H_2O_2同时存在时才能催化氧化甲基橙;光照160 min后,甲基橙剩余率为0.0%,甲基橙完全被降解。光催化氧化反应中羟基自由基发挥着关键作用。     

电化学阳极氧化条件对多孔硅及其光催化性能的影响研究

在HF/乙醇电解液中,采用恒电压电化学阳极氧化法,将P型硅片制备成了多孔硅催化剂。以甲基橙模拟废水为目标物,分析了电化学阳极氧化条件对多孔硅光催化甲基橙脱色率的影响。结果表明:随着HF浓度、阳极氧化时间、电流密度和光照时间的增加,甲基橙的脱色率逐渐增大。当V(HF)∶V(乙醇)=1∶1、阳极氧化时间为30min、电流密度为10mA/cm2以及光照时间为60min时,对甲基橙废水的脱色率较好。用十二烷基苯磺酸钠修饰的多孔硅对甲基橙废水有更高的脱色率。同直接催化相比,光催化甲基橙废水的脱色率提高到45.32%。同时对多孔硅表面形貌进行了表征。     

微弧氧化技术在制备纳米TiO2光催化剂中的应用

进行了微弧氧化法在制备TiO2光催化剂中的应用研究,考察了各工艺条件对制备的TiO2光催化剂降解甲基橙的活性影响,发现以0.11 mol/L磷酸为电解液,放电5min制备的催化剂活性最佳,120min内使甲基橙脱色率达49%.通过超声处理和重复使用对催化剂进行考察,发现其表现出良好的稳定性.表征结果表明文中以钛为阳极进行微弧氧化,其表面形成的陶瓷层为多孔的、纳米级的锐钛矿型的TiO2.     

SDS-Mg_nAl-LDO对亚甲基蓝的脱色研究

采用低饱和态共沉淀法,辅助微波手段,快速制备了十二烷基磺酸钠(SDS)改性水滑石SDS-MgnAl-LDHs,将其煅烧产物SDS-MgnAl-LDO用于亚甲基蓝的脱色研究,考察了SDS-MgnAl-LDHs制备条件和亚甲基蓝的脱色条件对脱色率的影响。结果表明,在最佳的条件下可达到完全脱色;SDS-MgnAl-LDO可重复利用,平均脱色率为92.01%,重复使用4次后,SDS-MgnAl-LDO的脱色性能基本稳定。     

金属酞菁负载纤维对空气中含硫化合物的催化氧化

合成了八羧基钴酞菁(Co-oaPc)和八羧基铁酞菁(Fe-oaPc) 两种水溶性酞菁,将这两种酞菁及两者按摩尔比为1:1混合的酞菁分别负载到阳离子改性的粘胶纤维上,制得3种金属酞菁负载纤维.测试其在溶液中对巯基乙醇的催化氧化性能发现这些负载纤维均具有催化氧化能力,而混合金属酞菁负载纤维的催化活性最高;通过在空气中对甲硫醇和H2S的消除实验,得到的结论相同.ESR测试表明,混合酞菁负载纤维可以观测到10个Co2 和Fe3 的超精细分裂线,表明其聚集的趋势较两种酞菁单独负载时弱,有利于甲硫醇和硫化氢分子与酞菁发生轴向配位,从而提高其催化活性.     

负载新型酞菁纤维素纤维的制备及催化氧化性能

首先采用丁二酸酐和顺丁烯二酸酐改性氨基钴酞菁制得两种新型水溶性钴酞菁,然后将这两种新型水溶性钴酞菁负载到纤维素纤维上,制得新型高分子催化剂,并选用巯基乙醇和H2O2作为底物来考察负载酞菁纤维素纤维的催化氧化活性。实验结果表明,两种高分子催化剂对巯基乙醇具有良好的催化氧化活性和催化分解H2O2的能力。     

纳米TiO2/聚酯织物的制备及光催化性能

基于聚合物溶剂诱导结晶(SINC)原理,制得了纳米TiO2/聚酯光催化织物。利用X射线衍射(XRD)、热重分析(TG)和扫描电镜(SEM)对表面成分和形貌进行了表征,通过甲基橙的降解脱色试验考察了纳米TiO2/聚酯织物的光催化性能,研究了浸渍时间、悬浮液中TiO2含量对光催化性能的影响。结果表明,聚酯织物利用溶剂诱导结晶负载纳米TiO2比直接浸渍负载纳米TiO2的分散性好、活性高,且重复使用性好。溶解时间5s、悬浮液中TiO2浓度0.035 g/mL为最佳实验条件,制得的光催化织物对甲基橙的8h降解率可达95.1%。     

活性碳纤维负载钴酞菁催化氧化2-巯基乙醇的研究

将四（2,4-二氯-1,3,5-三嗪基）氨基钴酞菁以共价键形式键合在活性碳纤维（ACF）载体上,制得了活性碳纤维负载钴酞菁催化剂（ACF-CoPc）,采用热重分析、原子吸收光谱和氮气等温吸附法对其进行了表征。原子吸收光谱测得金属酞菁的负载量为5.26μmol/g。氮气等温吸附法测得ACF-CoPc的比表面积为1235.9m2/g,孔径分布以2nm左右的小孔为主。以2-巯基乙醇为催化对象,采用超高效液相色谱研究了ACF-CoPc的催化氧化性能。结果表明ACF-CoPc对2-巯基乙醇具有很好的催化氧化性能,反应4h时对2-巯基乙醇的去除率高达100%,氧化产物为2,2’-二硫二乙醇。而且催化剂ACF-CoPc经6次循环使用后,对2-巯基乙醇的去除率没有持续下降,这表明该催化剂具有良好的重复使用性。     

Decolorization of molasses fermentation wastewater by SnO(2)-catalyzed ozonation

In the presence of O(3), the oxidative decolorization reaction on molasses fermentation wastewater with SnO(2) as a catalyst was studied. The results showed that SnO(2) accelerated the ozone oxidation reaction and the oxidative decolorization of molasses fermentation wastewater was accelerated. Influences on SnO(2) catalytic ozonation activity by precipitants and the calcination temperature were studied by XRD, IR and TG-DSC. SnO(2) prepared by ammonia as the precipitant had higher catalytic activity and a stronger dehydroxylation. The IR spectra of adsorbed pyridine showed that there were Lewis acid sites on the surface of this SnO(2) catalyst. The main factors influencing molasses fermentation wastewater oxidative decolorization were the wastewater concentration, the O(3) concentration, the pH value and the catalyst dosage. The decolorization of wastewater was improved with the increase of the wastewater dilution ratio, the ozone concentration and the catalyst dosage. High activity *OH was found to be existing with less amount and low concentration in the process of SnO(2) catalyzed ozonation decolorization.     

Degradation of methyl orange through synergistic effect of zirconia nanotubes and ultrasonic wave

Zirconia nanotubes with a length of 25 μm, inner diameter of 80 nm, and wall thickness of 35 nm were prepared by anodization method in mixture of formamide and glycerol (volume ratio = 1:1) containing 1 wt% NH(4)F and 1 wt% H(2)O. Experiments showed that zirconia nanotubes and ultrasonic wave had synergistic degradation effect for methyl orange and the efficiency of ultrasonic wave increased by more than 7 times. The decolorization percentage was influenced by pH value of the solution. Methyl orange was easy to be degraded in acidic solution. The decolorization percentage of methyl orange reached 97.6% when degraded for 8h in 20mg/L methyl orange solution with optimal pH value 2. The reason of synergistic degradation effect for methyl orange might be that adsorption of methyl orange onto zirconia nanotubes resulted in the easy degradation of the methyl orange through ultrasonic wave.     

ZnO/Al_2O_3复合纳米颗粒的制备与表征

为研究ZnO/Al2O3复合纳米颗粒在涂料、化妆品等领域的应用,采用直接沉淀法制备了纳米ZnO,用硫酸铝水解生成的Al2O3对纳米ZnO进行了表面改性。采用IR、TEM、SEM、XRD等手段对改性前后的粉体进行表征。分析结果表明,改性后粉体颗粒的团聚现象减轻。粉体的光催化降解甲基橙的实验研究表明,改性后ZnO粉体的光催化活性明显下降,进一步证明纳米ZnO颗粒表面存在Al2O3的包覆层。     

Magnetic Fe(2)MO(4) (M:Fe, Mn) activated carbons: fabrication, characterization and heterogeneous Fenton oxidation of methyl orange

We present a simple and efficient method for the fabrication of magnetic Fe(2)MO(4) (M:Fe and Mn) activated carbons (Fe(2)MO(4)/AC-H, M:Fe and Mn) by impregnating the activated carbon with simultaneous magnetic precursor and carbon modifying agent followed by calcination. The obtained samples were characterized by nitrogen adsorption isotherms, X-ray diffraction (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM), and the catalytic activity in heterogeneous Fenton oxidation of methyl orange (MO) was evaluated. The resulting Fe(2)MnO(4)/AC-H showed higher catalytic activity in the methyl orange oxidation than Fe(3)O(4)/AC-H. The effect of operational parameters (pH, catalyst loading H(2)O(2) dosage and initial MO concentration) on degradation performance of the oxidation process was investigated. Stability and reusability of selected catalyst were also tested.     

Decolorization of methyl orange by ozonation in combination with ultrasonic irradiation

The combination of ultrasound and ozone for the decolorization of azo dye, methyl orange, was studied. The effect of ultrasonic power, ozone gas flow rate, gaseous ozone concentration, initial dye concentration, pH and hydroxyl radical scavenger on the decolorization of methyl orange was investigated. The results showed that the synergistic effect was achieved by combining ozone with ultrasonic irradiation for the decolorization of methyl orange. The synergistic effect was more significant when the system temperature was raised due to the heat effect of ultrasonic irradiation. The decolorization of methyl orange fits the pseudo first order kinetic model. The decolorization rate increased with the increase of ultrasonic power, ozone gas flow rate, gaseous ozone concentration. However, the decolorization rate decreased with the increasing initial dye concentration. Either pH or sodium carbonate has little effect on the decolorization rate, indicating that the low frequency ultrasound enhanced ozonation process for the decolorization of methyl orange is mainly a direct reaction rather than radical reaction.     

Homogeneous catalytic ozonation of C.I. Reactive Red 2 by metallic ions in a bubble column reactor

This study elucidates the decolorization of C.I. Reactive Red 2 (RR2) by homogeneous catalytic ozonation. The effects of pH and catalyst dosage were evaluated in O3/Mn(II), O3/Fe(II), O3/Fe(III), O3/Zn(II), O3/Co(II) and O3/Ni(II) systems. In O3/Mn(II), O3/Fe(II) and O3/Fe(III) systems, increasing the catalyst concentration increased the rate of RR2 decolorization; however, further increasing the catalyst concentration caused no further significant increase. When 0.6 mM catalyst was added, the decolorization rates of O3/Mn(II), O3/Fe(II), O3/Fe(III), O3/Zn(II), O3/Co(II) and O3/Ni(II) systems at pH 2 were 3.295, 1.299, 1.278, 1.015, 0.843 and 0.822 min(-1), respectively. Under all of the experimental conditions, the decolorization efficiency of catalytic ozonation exceeded that of ozonation alone. The decolorization rate markedly exceeds the TOC removal rate in all tested systems. The effect of the radical scavenger on the catalytic ozonation processes suggests that the decolorization reaction in catalytic ozonation systems proceeds by mainly radical-type mechanisms, except in the O3/Mn(II) system.     

Photocatalytic degradation of methyl orange: influence of H2O2 in the TiO2-based system

The purpose of this study was to investigate the photocatalytic oxidation of a reactive azo dye. The photocatalytic activity of the TiO2 was studied using a reactor equipped with UV-A sources, with maximum emission at 365 nm. The photocatalytic activity of the TiO2 powder (99.9% anatase) and thin films has been measured through the decomposition of methyl orange solutions. The thin film was prepared by doctor blade and spray pyrolysis deposition (SPD). The TiO2 suspensions were prepared at 1 g/L concentration, and the initial methyl orange concentration was fixed at 7.8125 mg/L. The influence of the TiO2 (powder or thin films) and/or O2 and H2O2 on the photobleaching rate, was tested under different experiments, at pH = 5. Thin films (doctor blade) of TiO2 formed of mezo-sized aggregates formed of nanosized anatase crystallites show better photobleaching efficiency than thin film (SPD) due to their large internal surface. The rate is even higher in H2O2 compared to oxygen environment.     

MgAl-LDH吸附甲基橙性能研究

在水热反应温度为180℃,反应溶液pH值=9～10,反应时间为4h,反应总物质浓度为0.1mol/L的实验条件下,探索Mg/Al的摩尔比对MgAl-LDH吸附甲基橙性能的影响,并考察了材料再生后的吸附性能。研究结果表明,Mg/Al摩尔比为2.5∶1时的MgAl-LDH吸附甲基橙性能最优;在最佳吸附条件下,MgAl-LDH对甲基橙吸附量高达83.33mg/g;并对吸附材料循环利用焙烧温度进行探讨,可再生循环焙烧温度在400℃达到最佳,循环使用3次吸附性能保持良好。此外,对Mg/Al-LDH及其各个温度焙烧产物进行TG-DTA和SEM表征,显示其片状构型及对甲基橙进行的离子交换吸附和表面静电吸附作用。     

纳米TiO2／Al2O3复合薄膜光催化特性研究

以电化学方法合成的Al2O3多孔膜为基体，采用交流电沉积的方法在膜孔中沉积纳米TiO2，制备出纳米TiO2／Al2O3复合薄膜。对TiO2／Al2O3复合薄膜的形貌、结构和组成进行了表征；对TiO2／Al2O3复合薄膜光催化甲基橙溶液进行了研究。结果表明Al2O3／TiO2复合薄膜呈现出较好的光催化活性，电沉积TiO2的时间、热处理温度、选择不同光源照射均对TiO2／Al2O3复合薄膜光催化活性有一定的影响。     

Decolorization of alkaline TNT hydrolysis effluents using UV/H(2)O(2)

Effects of H(2)O(2) dosage (0, 10, 50, 100 and 300 mg/l), reaction pH (11.9, 6.5 and 2.5) and initial color intensity (85, 80 and 60 color unit) on decolorization of alkaline 2,4,6-trinitrotoluene (TNT) hydrolysis effluents were investigated at a fixed UV strength (40 W/m(2)). Results indicated that UV/H(2)O(2) oxidation could efficiently achieve decolorization and further mineralization. Pseudo first-order decolorization rate constants, k, ranged between 2.9 and 5.4 h(-1) with higher values for lower H(2)O(2) dosage (i.e., 10 mg/l H(2)O(2)) when the decolorization occurred at the reaction pH of 11.9, whereas a faster decolorization was achieved with increase in H(2)O(2) dosage at both pH 6.5 and 2.5, resulting in the values of k as fast as 15.4 and 26.6 h(-1) with 300 mg/l H(2)O(2) at pH 6.5 and 2.5, respectively. Difference in decolorization rates was attributed to the reaction pH rather than to the initial color intensity, resulting from the scavenging of hydroxyl radical by carbonate ion. About 40% of spontaneous mineralization was achieved with addition of 10 mg/l H(2)O(2) at pH 6.5. Efficient decolorization and extension of H(2)O(2) longevity were observed at pH 6.5 conditions. It is recommended that the colored effluents from alkaline TNT hydrolysis be neutralized prior to a decolorization step.