Influences of working pressure on properties for TiO2 films deposited by DC pulse magnetron sputtering

TiO2 films were deposited at room temperature by DC pulse magnetron sputtering system.The crystalline structures,morphological features and photocatalytic activity of TiO2 films were systematically investigated by X-ray diffraction (XRD),atomic force microscopy and ultraviolet spectrophotometer,respectively.The results indicated that the working pressure was the key deposition parameters influencing the TiO2 film phase composition at room temperature,which directly affected its photocatalytic activity.With increasing the working pressure,the target self-bias decreases monotonously.Therefore,low temperature TiO2 phase (anatase) could be deposited with high working pressure.The anatase TiO2 films deposited with 1.4 Pa working pressure displayed the highest photocatalytic activity by decomposition of Methyl Orange solution,which the degradation rate reached the maximum (35%) after irradiation by ultraviolet light for 1 h.     

非晶态TiO2-W薄膜的光催化性能研究

采用磁控溅射技术在玻璃基片上制备了W掺杂的非晶态TiO2薄膜,用XRD、XPS和椭圆偏光测厚仪等对薄膜进行了微观分析.结果表明,TiO2-W薄膜为非晶态结构.Ti以 4价存在;W以0价和 6价形式存在,并且6价和0价W的原子浓度比为6.4:1;薄膜中Ti和W的原子浓度比为2.6:1.对5 mg·L-1的亚甲基蓝溶液光催化脱色试验表明,随着膜厚的增加,光催化降解率递增,当膜厚达到141 nm时,所制备的TiO2-W薄膜对亚甲基蓝的脱色率在2 h达到90%;当膜厚大于141 nm时,光催化降解率不再增加.     

RGO改性介孔TiO2薄膜光催化同步去除Ni2+和SDBS

以钛酸四丁酯（TBT）、天然鳞片石墨为原料,聚乙烯吡咯烷酮（PVP）为介孔模板剂,通过浸渍-提拉法辅助热处理和紫外辐照还原制备介孔RGO-TiO₂薄膜,利用XRD、SEM、BET、UV-Vis DRS、FT-IR等对其结构、形貌及性能进行表征.以Ni²⁺和十二烷基苯磺酸钠（SDBS）为目标污染物,考察了介孔RGO-TiO₂薄膜光催化去除Ni²⁺和SDBS的反应性能,探讨了GO加入量及pH值对其催化性能的影响.在最佳条件下,进一步研究Ni²⁺/SDBS共存体系中Ni²⁺的光催化还原和SDBS的光催化氧化.结果表明：GO的加入量为1.0wt%时,介孔RGO-TiO₂薄膜对单一体系Ni²⁺和SDBS的光催化效率最高,在此条件下,pH=7.5时Ni²⁺还原效率最高,pH=6时SDBS降解效率最高.综合以上实验条件,设定GO加入量为1.0wt%,pH≈6时,Ni²⁺/SDBS共存体系中Ni²⁺和SDBS去除效率均优于Ni²⁺和SDBS单一体系,此时,Ni²⁺还原率为87.9%,SDBS氧化率为95.5%.分析协同光催化机制,TiO₂-SDBS表面复合物在紫外光激发下,SDBS被氧化同时,光生电子及SDBS氧化产物CO₂·^-自由基同步还原Ni²⁺.     

TiO_2薄膜光催化降解邻苯二甲酸乙酯的研究

采用solgel法制备TiO2薄膜。以该薄膜为催化剂,研究了在H2O2存在的条件下,对内分泌干扰物质邻苯二甲酸乙酯(DEP)的光催化降解反应。分别讨论了pH值、H2O2的加入量、DEP的初始浓度以及光照时间对降解反应的影响。结果表明在pH=2、50mg/L的H2O2中对初始浓度为50mg/L的DEP溶液光照150min有较好的降解效果。     

玻璃膜载Fe3+/TiO2的制备及其光催化活性研究

采用溶胶-凝胶法制备了稳定的涂膜Fe3+/TiO2溶胶,通过浸渍-提拉法分别制备了Fe3+/TiO2玻璃负载薄膜,讨论了分散剂加入量、提拉速度对成膜质量的影响,并对所制薄膜进行了结构分析,通过降解4-氟苯甲酸溶液初步研究了其光催化活性。     

漂珠为载体TiO_2/SiO_2膜的制备及性能研究

以漂珠为载体,探索采用液相沉积法制备TiO2/SiO2膜最佳条件。在自制的光催化反应器中,在相同的条件下,以酸性嫩黄和难处理的焦化废水为目标降解物,做了TiO2/SiO2和TiO2两种膜的光催化氧化对比试验。结果表明,与单一TiO2膜比较,以漂珠为载体,采用液相沉积法制备的TiO2/SiO2改性膜具有较高的光催化氧化性能。     

碳黑改性TiO_2薄膜光催化剂的稳定性研究

固定化光催化剂的稳定性一直是限制光催化氧化技术实用化的关键因素之一。通过环管型连续流反应器对所研制的碳黑改性TiO2薄膜光催化剂在长期使用中的稳定性进行了研究,探讨了光源、有机物负荷、阴离子对光催化剂稳定性的影响,并对不同负荷下光催化剂表现出的稳定性进行了动力学描述。试验结果表明,该催化剂在254 nm光源和低负荷条件下具有很好的稳定性,在活性艳红X-3B水溶液的光催化降解试验中,4个月内活性保持不变,并且不受水中的SO42-、NO3-以及硬度、碱度的影响。     

Fe~(3+)/TiO_2薄膜光催化降解UDMH废水的研究

研究Fe3+掺杂的TiO2薄膜对偏二甲肼废水光催化降解作用,考察了影响Fe3+掺杂的TiO2薄膜光催化降解偏二甲肼废水的效果的相关因素,结果表明最佳操作条件为:Fe3+掺杂TiO2薄膜的摩尔分数为0.5%,煅烧温度为500℃,煅烧时间为3h,催化降解反应时偏二甲肼废水为中性或弱碱性,催化降解温度为25℃。     

Study on the optical property and surface morphology of N doped TiO2 film deposited with different N2 flow rates by DCPMS

N doped TiO₂ films were deposited by direct current pulse magnetron sputtering system at room temperature. By using UV-Vis spectrophotometer and atomic force microscope, we studied the influence of N₂ flow rate on the optical property and surface morphology of films. The results indicate that the optical property and surface morphology of N doped TiO₂ film was dominated by the N₂ flow rate. The mean absorbency in visible range of pure TiO₂ films is near to 0%, which means that the pure TiO₂ could hardly display the photocatalytic property in visible range. When N₂ flow rate is 2 sccm, the mean absorbency in visible range of N doped TiO₂ film could reach at 24%. In this case, the film could be used as photocatalyst induced by visible light. While with increasing N₂ flow rate, the mean absorbency in visible range of N doped TiO₂ film decreased abruptly. Especially when N₂ flow rate exceeded 8 sccm, the mean absorbency in visible range of N doped TiO₂ film decreased to about 0%, which is like pure TiO₂ fimls.     

金属丝网负载TiO_2光催化降解染料废水

通过溶胶-凝胶法制备纳米二氧化钛,采用浸渍提拉的方法将TiO2固定在金属丝网上,通过掺杂碳黑获得高比表面的催化薄膜,用比表面仪、X-ray衍射仪进行表征。设计了光催化降解染料废水的反应装置,探讨了制备工艺和光催化反应条件对催化性能的影响。结果表明:在pH值为4.0、加入2.5mL/LH2O2的反应条件下,用400℃热处理温度、镀膜4次的催化薄膜对染料脱色率达92.4%,COD去除率达75.6%。     

碳黑改性TiO2薄膜光催化剂的结构性质

通过碳黑掺杂制备了改性的TiO₂薄膜光催化剂(CB-TiO₂),并采用液氮吸附、X射线衍射(XRD)和紫外-可见光漫反射光谱(DRS)对催化剂的比表面积、物相、晶粒度和最大激发波长等结构性质进行了表征.结果表明,CB-TiO₂的吸附性能大大改善,不同热处理温度下,BET比表面积增加50%～80%;同时碳黑掺杂能够减小催化剂的晶粒尺度,使相变温度降低.相应的光催化降解试验也表明,碳黑改性TiO₂的活性大大提高,其一级反应速率常数为普通TiO₂的1.5倍.     

SiO2纳米粉掺杂对薄膜光催化剂结构和活性的影响

针对固定膜光催化剂吸附能力差的缺陷,在催化剂的涂覆溶胶中掺杂具有较大比表面积的SiO₂纳米粉制备了一种新的TiO₂薄膜.通过X射线衍射(XRD)、扫描电镜(TEM)和红外光谱(FTIR)等手段对催化剂进行表征发现,催化剂的晶相以锐钛矿为主,并含有少量的金红石,平均晶粒尺寸为27nm左右.其中掺杂的SiO₂以十几到几十纳米的无定型团簇形式分散于薄膜中,除了能增大薄膜的表面积外,对TiO₂的晶体结构和表面基团等性质几乎没有影响.光催化降解试验表明,SiO₂掺杂后薄膜的活性大大改善,并受掺杂SiO₂的原始粒径和掺杂量影响很大.此外,该催化剂还具有很好的稳定性,在连续30多天的使用中,对活性艳红X-3B的去除率一直维持在80%左右,活性未见降低.     

酸雨中SO42-、NO3-、Ca2+、NH4+对红壤中重金属的影响

在实验室条件下连续浸泡污染红壤和黄红壤,研究模拟酸雨中阴离子、阳离子浓度对土壤中重金属解吸行为和化学形态分布的影响.结果表明,酸雨加速了土壤酸化,重金属活性增强.增加模拟酸雨中SO42-、NO3-或Ca2+、NH4+浓度对Cd、Zn解吸行为均产生明显促进作用,但对Cu影响不明显.增加模拟酸雨中SO42-、NO3-浓度,红壤和黄红壤交换态Cd、Zn百分率明显降低,交换态Cr百分率明显增加,交换态Cu百分率稍有提高,交换态Pb百分率变化不明显;增加模拟酸雨中Ca2+、NH4+浓度,红壤和黄红壤交换态Cd、Cu、Zn百分率明显降低,交换态Cr和活性形态Pb明显增加,但Cu的化学形态分布主要受模拟酸雨pH值的影响.     

纳米级TiO_2/粉煤灰/UV催化臭氧化去除水中苯胺的研究

采用溶胶-凝胶法制备了纳米TiO2/粉煤灰光催化剂,利用X射线衍射法对催化剂的物相和粒径进行了表征。通过苯胺光催化臭氧化降解实验,考察了pH、催化剂投加量、薄膜厚度等反应条件对苯胺降解效果的影响,并研究了苯胺光催化臭氧化降解的反应机理。实验结果表明,经550℃热处理后的TiO2主要以锐钛矿晶型存在,平均粒径为11.12 nm。降解反应遵循·OH机理,当催化剂投加量为5 g/1.5 L废水时,催化效果最好。     

地膜覆盖和生物炭添加对菜地N2O排放的影响

为研究生物炭添加(B0:0 t·hm^-2、 B20:20 t·hm^-2、 B40:40 t·hm^-2)和地膜覆盖（FM:覆膜、 NM:不覆膜）对菜地N₂O排放的影响,以西南大学农场内辣椒-萝卜轮作菜地为研究对象,采用静态暗箱/气相色谱法进行为期1 a的田间原位观测.共设置6个处理,分别为NMB0（CK）和FMB0、 NMB20和FMB20、 NMB40和FMB40.结果表明,FM显著提高辣椒季土壤中铵态氮和硝态氮含量（P<0.05）,而对萝卜季土壤环境因子均无显著影响.与NM相比,辣椒季FM分别对B0、 B20和B40处理下的N₂O排放提高了52.87%、 52.97%和52.49%（P<0.05）,但萝卜季FM对N₂O排放无显著影响.生物炭对辣椒和萝卜季土壤环境因子均无显著影响.萝卜季生物炭添加减少了28.76%～67.88%的N₂O排放（P<0.01）,辣椒季生物炭添加对N₂O排放无显著影响...     

地膜覆盖和施氮对菜地N2O排放的影响

为了探讨地膜覆盖和不同施氮处理对菜地N_2O排放的影响,以位于西南大学农业部重庆紫色土生态环境重点野外科学观测试验站内辣椒-萝卜轮作菜地为研究对象,采用静态暗箱/气相色谱法,进行为期2 a的田间原位观测.试验设置8个处理,分别为对照常规(NN0)、对照覆膜(FN0),低N常规(NN1)、低N覆膜(FN1),中N常规(NN2)、中N覆膜(FN2),高N常规(NN3)、高N覆膜(FN3),研究地膜覆盖和施氮对菜地N_2O的排放特征和影响因素.结果表明,覆膜与常规两种种植方式对于菜地N_2O的排放体现出明显差异,表现为辣椒季常规显著大于覆膜(P 0. 05),萝卜季为覆膜显著大于常规(P 0. 05). 2014年5月至2016年4月观测期间,覆膜种植下无氮、低氮、中氮和高氮菜地N_2O年均累积排放量分别为244. 91、730. 49、903. 32和1 867. 45 mg·m-2,常规种植下N_2O年均累积排放量为221. 48、840. 33、1 256. 50和1 469. 67 mg·m-2.不同施氮梯度对于菜地N_2O的排放呈现为随施氮量增加N_2O的排放随之增加.通过计算N_2O排放系数可知,覆膜可以一定程度上降低辣椒季N_2O的排放系数,而萝卜季则没有明显规律. 2014年5月至2015年4月,辣椒季常规和覆膜种植下均为低氮菜地的N_2O排放系数最高,在萝卜季则显示为高氮排放系数最高; 2015年5月至2016年4月,则显示辣椒季为高氮菜地N_2O排放系数最高,而萝卜季低氮菜地最高. N_2O的排放通量和土壤氮素含量以及土壤温度呈显著相关关系,而地膜覆盖可一定程度地增加土壤中氮素的含量,进而影响菜地N_2O的排放通量.     

Preparation and photocatalytic properties of porous C and N co-doped TiO2 deposited on brick by a fast, one-step microwave irradiation method

A one-step microwave irradiation method was used to deposit carbon and nitrogen co-doped TiO_2((C, N)-TiO_2) on commercial brick((C, N)-TiO_2/brick). The as-prepared samples were characterized by X-ray diffraction, ultraviolet–visible(UV–vis) diffuse reflectance spectroscopy, photoluminescence spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy(SEM). A selective technique was also used to investigate the concentration of hydroxyl radicals during UV–vis irradiation of the Methyl Orange solution with the as-prepared samples. The C and N dopants enhanced visible light absorption and provided a longer lifetime for the photo-generated electron–hole pairs. The SEM images showed that the as-prepared sample is porous. The dark adsorption and photodegradation test for(C, N)-TiO_2/brick showed good photodegradation and good recyclability. The best photodegradation rate was 94% after 2 hr. The maximum degradation rate was maintained even after the 6th cycle. The good photocatalytic properties are attributed to the enhanced visible light absorption, enhanced pollutant adsorption arising from the porous structure of the(C, N)-TiO_2 thin film, and longer lifetime of the photo-generated electron–hole pairs.(C, N)-TiO_2/brick should have potential commercial applications in photodegradation processes because of its low cost, good photodegradation, and excellent recyclability.     

地膜覆盖和施氮对菜地CO2通量的影响

为了探讨地膜覆盖和不同施氮处理对菜地生态系统CO₂净交换通量（Net CO₂ Ecosystem Exchange,简称NEE）、生态系统呼吸通量（Ecosystem Respiration,简称ER）及总初级生产力（Gross Primary Productivity,简称GPP）的影响,以辣椒-萝卜轮作菜地为研究对象,采用静态明/暗箱-气相色谱法,进行了为期1 a（2014年5月-2015年4月）的田间原位观测.试验设置8个处理,分别为常规无氮（CN0）、覆膜无氮（MN0）、常规低氮（CN1）、覆膜低氮（MN1）、常规中氮（CN2）、覆膜中氮（MN2）、常规高氮（CN3）、覆膜高氮（MN3）.结果表明,辣椒季累积NEE最大值分别为CN3和MN3处理下的-30.96和-29.83 t·hm^-2,累积ER排放量最大值分别为CN1和MN1处理下的40.18和39.16 t·hm^-2,累积GPP最大值分别为CN3和MN3处理下的70.60和68.61 t·hm^-2;萝卜季累积NEE最大值分别为CN3和MN3处理下的-22.25和-24.88 t·hm^-2,累积ER排放量最大值分别为CN2和MN2处理下的17.00和19.43 t·hm^-2,累积GPP最大值分别为CN3和MN3处理下的37.92和43.80 t·hm^-2.在两个生长季中,覆膜及覆膜和施氮的交互作用只对辣椒季中ER有显著影响,对于NEE和GPP均无显著影响（p>0.05）;施氮显著提高了菜地生态系统NEE和GPP而降低了辣椒季ER（p<0.05）,并且这种增加或降低效应随着施氮量的提高而逐渐增强.本研究中菜地呈现碳汇并随着施氮水平的提高碳汇逐渐增强,而覆膜对CO₂固定无显著影响,表明常规高氮的农田管理措施能够提高西南地区代表性的辣椒-萝卜轮作菜地的固碳潜力,对该地区农田生态系统碳的源/汇功能具有一定的参考意义.     

Effects of DOM characteristics from real wastewater on the degradation of pharmaceutically active compounds by the UV/H2O2 process

The characteristics of dissolved organic matter (DOM) can significantly affect the degradation of target compounds by the advanced oxidation processes. In this study, the effects of the different hydrophobicity/hydrophilicity fractions, molecular weight (MW) fractions, fluorescence components and molecular components of DOM extracted from municipal wastewater on the degradation of 4 pharmaceutically active compounds (PhACs), including carbamazepine, clofibric acid, atenolol and erythromycin by the UV/H₂O₂ process were investigated. The results showed that the degradation rate constants of 4 PhACs decreased dramatically in the presence of DOM. The linear regressions of 4 PhACs degradation as a function of specific fluorescence intensity (SFI) are exhibited during the degradation of 4 PhACs and the SFI may be used to evaluate effect of DOM on target compounds in wastewater. The hydrophobic acid (HPO-A) exhibited the strongest inhibitory effect on degradation of 4 PhACs during oxidation process. The small MW fractions of DOM significantly inhibited the degradation of 4 PhACs during oxidation process. Among three fluorescence components, hydrophobic humic-like substances may significantly inhibit the degradation of 4 PhACs during oxidation process. At the molecular level, the formulas may be derived from terrestrial sources. CHO compound may significantly inhibit the degradation of 4 PhACs during oxidation process on formula classes. The unsaturated hydrocarbons, carbohydrates and tannins compounds may significantly inhibit the effectiveness of the UV/H₂O₂ process on compound classes.     

HRT对A2O工艺中典型多环麝香迁移转化的影响

研究了不同水力停留时间(hydraulic retention time,HRT)条件下佳乐麝香(galaxolide,HHCB)与吐纳麝香(tonalide,AHTN)在A2O工艺各池水相和泥相中的变化情况.采用固相萃取与气相质谱联用的方法对水相与泥相中目标物的质量浓度进行检测.结果表明,HRT主要影响HHCB在A2O工艺中的生物降解和随剩余污泥排放的比重,影响AHTN随剩余污泥排放的比重.随着HRT的增大,HHCB、AHTN在厌氧池中的去除率与去除贡献率逐渐减小,而缺氧池与好氧池的去除率与去除贡献率相对增大.2种目标物在4个HRT工况(6、8、10、12 h)下的总去除率分别为73.93%、73.05%、75.14%、76.00%和48.76%、44.27%、57.17%、62.9%.A2O工艺对HHCB的去除效果较好,而对AHTN的去除效果较差.HRT的增大对HHCB的去除影响不大,而对AHTN的去除有促进作用.