银-铜复合材料催化臭氧化降解苯酚及其机理研究

以HCHO为还原剂,使用2步法制备银-铜复合材料。以苯酚为探针,该催化剂在臭氧化降解苯酚过程中有极好的活性。臭氧分解实验结果表明,催化剂的活性与其分解臭氧的能力正相关,说明催化剂和臭氧之间的相互作用对臭氧臭氧化降解苯酚很关键。以原子吸收光谱、X射线衍射仪和催化活性测试结果表明,银-铜复合材料中还原态的Cu、Ag和Cu2O更易于与臭氧互相作用。在臭氧和催化剂相互作用过程中产生的铜氧化物和银氧化物可以氧化苯酚降解产物,这个过程会促进苯酚降解的程度。此外,合成原料中加入的HCHO溶液和银离子有利于催化剂的稳固,降低离子的沥出量。     

CeO_2-活性炭催化臭氧化降解水中草酸的研究

利用CeO_2的储氧和释氧能力,以高活性的活性炭作为催化剂载体,采用等体积浸渍法制备CeO_2-活性炭催化剂。分别用氮气低温吸附/脱附、XRD、XPS对CeO_2-活性炭催化剂进行表征。以CeO_2-活性炭作为催化剂,草酸作为模型化合物,催化臭氧化降解草酸的去除率达到77%。Ce组分的加入能显著提高草酸的去除率。Ce不仅能够提高反应体系中羟基自由基的浓度,还有利于O3分子直接氧化草酸。CeO_2-活性炭催化剂经过3次重复使用后,草酸去除率保持在70%以上,具有较好的稳定性。     

金属及其氧化物催化臭氧化反应的研究进展

介绍了金属及其氧化物催化臭氧化降解水中有机物的应用及其反应机理的研究进展；探讨了影响催化剂催化活性和催化臭氧化效率的因素及金属及其氧化物的催化性能；分析了催化臭氧化过程的反应途径。     

微波-载铜活性炭催化氧化降解腐殖酸

以粉末活性炭(PAC)和颗粒活性炭(GAC)为载体,采用浸渍焙烧法制备了负载铜氧化物的活性炭催化剂,考察了其表面结构、元素组成及BET参数;以腐殖酸模拟废水为对象,研究了微波?载铜活性炭催化氧化降解腐殖酸的效果和影响因素,探讨了微波?催化氧化协同H2O2降解腐殖酸的机理. 结果表明,载铜活性炭比未负载铜的活性炭对腐殖酸的降解率更高,且Cu/PAC的催化效果远优于Cu/GAC,两种催化剂最佳的微波?催化氧化条件分别为Cu/PAC投加量1 g/L, H2O2投加量0.9 mL/L, pH=3,微波功率400 W,微波时间4 min和Cu/GAC投加量8 g/L, H2O2投加量1.5 mL/L, pH=6,微波功率400 W,微波时间4 min,该条件下腐殖酸的去除率分别为93.91%和91.59%. 微波、H2O2和催化剂协同作用对腐殖酸高效降解有决定性作用.     

均相催化臭氧化反应的研究进展

综述了近年来水溶液和有机溶剂中均相催化臭氧化降解水中有机物的研究进展。介绍了水溶液中不同的有机污染物均相催化臭氧化过程中,各种催化剂的应用,它们的活性和影响催化体系效率的参数,及其催化氧化反应的机理。有机溶剂中的催化臭氧化具有更高的氧化效率和臭氧利用率,是一种可能的水处理的新方法。     

氧化锌纳米颗粒的简便合成及其臭氧化降解苯酚的催化性质

采用一种可控的直接沉淀法制得纳米级ZnO材料。结果表明,在不同合成条件下得到的纳米ZnO颗粒具有不同的表面性质,并且对苯酚的降解表现出不同的催化效率。其中,在原料加料速度为3.0 mL/min,前驱物煅烧温度为400℃时所得产物具有最高的催化活性。与单独臭氧化相比,加入该产物后,苯酚的降解率提高了85.38%。在优化的纳米ZnO存在的条件下,分别评估了臭氧的分解,叔丁醇对苯酚的臭氧化影响,表明在纳米ZnO存在时,苯酚直接被臭氧分子氧化而降解。     

不同形貌的纳米Mg(OH)2催化臭氧化降解甲硝唑

采用化学沉淀法分别以六水合氯化镁和取自察尔汗盐湖的天然水氯镁石为原料制备了不同形貌的纳米 Mg(OH)₂催化剂,通过扫描电子显微镜、X射线衍射、傅里叶变换红外光谱等手段对所合成的催化剂的表面形貌、晶体结构和表面官能团等性质进行了表征。将两种不同形貌的纳米Mg(OH)₂材料首次应用于催化臭氧化过程,研究了两种不同形貌的纳米Mg(OH)₂[Mg(OH)₂-1和Mg(OH)₂-2]催化剂对甲硝唑的降解和矿化能力。结果表明,在单独臭氧化过程中,反应10min时甲硝唑的降解和矿化效率均较低,分别为51.9%和17.4%,而在臭氧化系统中分别加入Mg(OH)₂-1和Mg(OH)₂-2,甲硝唑的去除效率和矿化效率均明显提高,且Mg(OH)₂-2的催化臭氧化性能要优于Mg(OH)₂-1。另外,单独臭氧化过程、Mg(OH)₂-1催化臭氧化以及Mg(OH)₂-2催化臭氧化过程中甲硝唑的降解均较好地符合伪一级动力学反应模型（R²>0.97）。除此之外,对这两种不同形貌的纳米Mg(OH)₂催化剂的稳定性进行了考察,结果表明,催化剂在循环使用六次后对甲硝唑仍有较高的催化臭氧化去除效率。因此,所合成的两种形貌的纳米Mg(OH)₂催化剂将是一种很有前景的、能用于去除抗生素的臭氧化催化剂。     

催化臭氧分离膜制备及去除腐殖酸机理分析

以微污染水为处理对象,考察了新型催化膜的过滤性能及抗污染行为。实验过程中采用溶胶凝胶法制备纳米TiO2粉体,将不同焙烧温度的纳米TiO2颗粒加入铸膜液中,利用相转换法制备催化膜。采用X射线衍射（XRD）及扫描电子显微镜（SEM）对膜进行表征,对膜的纯水通量、孔隙率、接触角、膜的催化性能及分离特性进行了系统地测定。实验结果表明,金红石型TiO2催化膜对腐殖酸（humic acid,HA）及总有机碳（total organic carbon,TOC）的去除效率分别为70%及65%以上,说明金红石型TiO2催化膜具有较高的污染物去除及抗污染特性。实验结果证实新型多功能膜对于水处理的实际应用具有较大的发展潜力。     

ACF催化臭氧化降解苯酚的反应参数影响

研究了活性碳纤维(ACF)催化臭氧化降解苯酚过程中各种参数的影响。结果表明,ACF能够显著提高臭氧化效率,当ACF为1g,反应10min时苯酚的去除率为96.8%,而同样条件下活性炭仅为68%;臭氧化效率在酸性下几乎相同并高于碱性下,而且在碱性下随pH值升高而降低;臭氧化空气流量从0.04m3/h增加到0.16m3/h,反应10min时的效率提高为17%;苯酚初始浓度升高到500mg/L仅使臭氧化效率下降不到10%。重复实验表明臭氧化过程中ACF的催化性能可以得到原位再生。     

光催化氧化去除水中腐殖酸

光催化氧化法对水中腐殖酸有很强的氧化能力，可将其完全氧化为ＣＯ２等简单无机物。该方法对ＰＨ和温度的适应范围广，无需曝气充氧也有很好的处理效果，很有希望实用于纯水的制备。     

纳米CuO粒子填充多壁碳纳米管复合材料的制备与表征

采用超声辅助的混酸处理方法对多壁碳纳米管(MWCNTs)进行酸化改性,用湿化学方法制备了填充CuO的MWCNTs复合材料(CuO@MWCNTs)。考察了MWCNTs直径、Cu(NO3)2溶液浓度及煅烧温度对CuO填充形貌的影响。借助FTIR、TEM、HRTEM、XRD测试手段对酸化MWCNTs(AMWCNTs)、CuO@MWCNTs进行了表征与分析。结果表明,直径40～60 nm的MWCNTs,在Cu(NO3)2浓度0.2 mol/L和600℃条件下,可得到CuO粒子均匀紧致分布的CuO@MWCNTs,CuO粒子粒径分布在10～15 nm。     

Effect of ozonation pretreatment on the surface properties and catalytic activity of multi-walled carbon nanotube

Multi-walled carbon nanotube (MWCNT) has been used in the catalytic ozonation of oxalic acid in aqueous solution, which was pretreated using ozone and was characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), nitrogen adsorption and Boehm titration. The effect of ozonation pretreatment on the catalytic activity of MWCNT and the ozonation mechanism of oxalic acid in the presence of MWCNT were investigated. The results indicate that with the increasing pretreatment time, the atom ratio of oxygen to carbon and the number of surface acid groups on MWCNT increase, while the catalytic activity of MWCNT on ozonation of oxalic acid decreases, suggesting that the chemical characteristics of MWCNT mainly determine its catalytic activity on oxalic acid mineralization. The inhibition of tert-butyl alcohol on the degradation of oxalic acid is slight for pristine MWCNT catalytic ozonation and this inhibition trend becomes more obvious when MWCNT was pretreated by ozone. A free radical mechanism was proposed which involves both surface reactions and bulk reactions between the oxalic acid and active species.     

Experimental and theoretical study on catalytic ozonation of humic acid by ZnO catalyst

Ozonation and catalytic ozonation of humic acid (HA) in the presence of ZnO were examined in a batch scale reactor. The degradation of HA by catalytic ozonation was found to be much more effective than ozonation alone. The quantum chemistry calculations showed that the reaction of the O₃ disproportionation on the surface of ZnO corresponds to the barrierless mechanism. The activation energy of the transition state formation was ?5.25 eV. The active oxygen atom formed on the surface of ZnO was found as interacting with both water molecules and dissolved organic molecules, which might lead to further oxidizing reactions.     

腐殖酸协同Mn2+催化臭氧氧化降解五氯苯酚

研究了向Mn2+催化臭氧氧化体系中添加少量腐殖酸对PCP去除效率的影响。结果表明:腐殖酸与Mn2+在催化臭氧氧化降解PCP过程中存在着明显的协同效应。在ρ(PCP)=30 mg/L,n(HA)∶n(PCP)值为3.18的条件下,氧化反应30 min,PCP去除率高达98.63%。分别向Mn(Ⅱ)/O3+HA、Mn(Ⅱ)/O3、O3+HA及单独臭氧氧化体系中加入.OH自由基抑制剂叔丁醇后,各个氧化体系中PCP的降解效率均受到了不同程度的抑制。实验结果表明,Mn(Ⅱ)/O3+HA氧化降解PCP以自由基的氧化为主,其拟一级反应表观速率常数为0.133 min-1,分别是Mn(Ⅱ)/O3及单独臭氧氧化体系的1.87、8.31倍。     

Gallic acid water ozonation using activated carbon

The ozonation of gallic acid in water in the presence of activated carbon has been studied at pH 5. Hydrogen peroxide, ketomalonic and oxalic acids were identified as by-products. The process involves two main periods of reaction. The first period, up to complete disappearance of gallic acid, during which ozonation rates are slightly improved by the presence of activated carbon. The second one, during which activated carbon plays an important role as promoter, and total mineralization of the organic content of the water is achieved. The organic matter removal is due to the sum of contributions of ozone direct reactions and adsorption during the first period and to a free radical mechanism likely involving surface reactions of ozone and hydrogen peroxide on the carbon surface during the second period. There is a third transition period where by-products concentration reach maximum values and ozonation is likely due to both direct and free radical mechanisms involving ozone and adsorption. Discussion on the mechanism and kinetics of the process is also presented both for single ozonation and activated carbon ozonation.     

Functionalization of carbon nanotube yarn by acid treatment

Carbon nanotube (CNT) yarn was functionalized using sulfuric and nitric acid solutions in 3:1 volumetric ratio. Successful functionalization of CNT yarn with carboxyl and hydroxyl groups (e.g., COOH, COO–, OH, etc.) was confirmed by attenuated total reflectance spectroscopy. X-ray diffraction revealed no significant change to the atomic in-plane alignment in the CNTs; however, the coherent length along the diameter was significantly reduced during functionalization. A morphology change of wavy extensions protruding from the surface was observed after the functionalization treatment. The force required to fracture the yarn remained the same after the functionalization process; however, the linear density was increased (310%). The increase in linear density after functionalization reduced the tenacity. However, the resistivity density product of the CNT yarn was reduced significantly (234%) after functionalization.     

Enhancement of electrochemiluminesence of lucigenin by ascorbic acid at single-wall carbon nanotube film-modified glassy carbon electrode

The electrochemiluminescent behavior of lucigenin on a single-wall carbon nanotube/DMF film-modified glassy carbon electrode was studied in this paper. Comparing with the bare glassy carbon electrode, the electrochemiluminescent of lucigenin at modified electrode is more stable and without tedious procedure for clean-up the surface of modified electrode. It has been found that ascorbic acid could enhance the electrochemiluminescent intensity of lucigenin greatly at this modified electrode. Based on which, a new sensitive and simple electrochemiluminescent method for determination of ascorbic acid could be developed. The condition for the determination of ascorbic acid was optimized. Under the optimized condition, the enhanced electrochemiluminescent intensity versus ascorbic acid concentration was linear in the range of 1.0 × 10⁻⁸ to 4.0 × 10⁻⁶ mol/L with a detection limit of 2.0 × 10⁻¹⁰ mol/L, and the relative standard derivation for 1.0 × 10⁻⁷ mol/L ascorbic acid was 3.8% (n = 8). The possible mechanism was also discussed.