微波辅助法合成纳米ReFeO3光催化剂

以稀土金属硝酸盐La（NO3）3、Sm（NO3）3、Eu（NO3）3、Gd（NO3）3和Fe（NO3）3.9H2O为原材料,以活性炭为模板剂,聚乙烯醇（PVA）和尿素分别用作阻聚剂和均相沉淀剂,在微波辐照下制得纳米钙钛矿型化合物ReFeO3（Re：La,Sm,Eu,Gd）。用X射线粉末衍射仪（XRD）、UV-vis漫反射仪（DRS）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）对产物组成、结构、颗粒大小、形貌等进行了表征,结果表明产物均为单一钙钛矿结构的纳米颗粒。以产物为光催化剂,在可见光照射下对罗丹明B水溶液进行光催化降解实验,发现该类化合物均具有较好的光催化活性,180 min内对罗丹明B的脱色率均达到85%以上。     

沉淀剂对稀土Gd掺杂SnO2/Ti涂层阳极性能的影响

实验采用共沉淀法,以无机盐SnCl₄·5H₂O、Sb₂O₃、Gd(NO₃)₃为前驱体,制备稀土Gd掺杂SnO2/Ti多组分涂层阳极。研究了用不同沉淀剂制备的电极以苯酚为目标有机物的电化学降解特性,以考察沉淀剂对稀土Gd掺杂SnO₂/Ti阳极性能的影响;并对所制备的涂层阳极进行了SEM、XRD、XPS等表征及阳极极化曲线、循环伏安曲线测试,分析并讨论了沉淀剂对稀土Gd掺杂SnO₂/Ti阳极性能的影响机理。结果表明,沉淀剂对稀土Gd掺杂SnO₂/Ti电极性能有较大的影响,在本实验条件,以氨水为沉淀剂所制备的电极电催化性能较好,稳定性能较高。     

铂铈共掺杂纳米TiO2的制备、表征及光催化性能

以钛酸四丁酯为前驱体,过氧化氢为氧化剂,采用简单易行的低温氧化法制备出晶粒尺寸较小(平均尺寸25 nm)的二氧化钛纳米粒子。通过贵金属Pt掺杂TiO₂(Pt-TiO₂)、稀土元素Ce掺杂TiO₂(Ce-TiO₂)和Pt、Ce共掺杂TiO₂(Pt/Ce-TiO₂)的掺杂的方法对二氧化钛进行改性。通过XRD,XPS,TEM,紫外漫反射等表征手段对制备的样品进行表征。通过可见光下降解罗丹明B来测试其光催化活性。实验结果表明,由Ce掺杂的TiO₂光催化剂对有机污染物的最大降解能力略大于Pt掺杂的TiO₂,2种元素进行共同掺杂时对应的TiO₂光催化剂降解能力最大。     

降低负荷以提高反硝化颗粒污泥的稳定性

在上流式污泥床反应器（USB）内,接种好氧活性污泥,以甲醇为碳源,NO-3为电子受体,经过40多d培养,得到良好的反硝化颗粒污泥,粒径2～3 mm,MLSS为36 g/L,氮去除速率和COD去除速率分别在0.15 g NO₃-N/(g VSS·d)和0.8 g COD/(g VSS·d)。当负荷提高至6.44 g NO₃-N/(L·d)继续运行1周后,观察到反应器内颗粒污泥出现上浮,浓度降低,颗粒粒径多数在3～5 mm,外观呈乳白色。为恢复反应器稳定运行,当负荷降至3.86 g NO₃-N/(L·d)时,上浮现象减轻,当负荷降至2.57 g NO₃-N/(L·d)时,上浮现象消失,颗粒污泥密度由不稳定时的1.0018 g/cm³提高到1.0126 g/cm³,颗粒粘连现象基本消失,污泥氮去除速率在0.19 g NO₃-N/(g VSS·d),连续运行30 d,系统保持稳定。分析认为,颗粒污泥表面微生物生长速度过快是导致不稳定的主要因素,较长的泥龄有利于系统稳定。     

几种试剂对硝酸根光催化脱色甲基橙的影响

以NO^-₃为光催化剂,在紫外灯照射下,对甲基橙溶液进行光催化脱色。结果表明,叔丁醇、甲醇和乙醇对催化脱色反应有抑制作用; KBr和Na₂SO₄对脱色反应均有促进作用;而且KBr的加入量存在最佳值; Na₂SO₄的促进作用随Na₂SO₄的量的增加逐渐增强。Na₂CO₃的存在对甲基橙的脱色反应没有影响。K₂S₃O₈和NO^-₃之间存在较强的协同作用;KIO₃和NO^-₃之间存在相加作用;KBrO₃和NO^-₃之间存在拮抗作用。     

微乳法制备Fe-TiO2纳米晶复合体及光催化性能

采用微乳法制备铁掺杂TiO₂纳米晶(Fe-TiO₂)复合体, 通过热重-差热(TG-DTA)、X射线衍射(XRD)、扫描电镜（SEM）和紫外漫反射光谱(DRS)等对其结构和形态进行表征; 以亚甲基蓝溶液(MB)为标准模拟降解物, 对Fe-TiO₂, 纯TiO₂和P25光催化降解性能进行评价。结果表明,Fe-TiO₂的光催化活性明显＞P25,原因是Fe掺杂不仅能抑制TiO₂晶粒     

纳米Bi2O3/TiO2复合光催化剂的制备及性能研究

以光催化效果为评价标准,采用超声波作用下水解法制备Bi₂O₃/TiO₂复合光催化剂,考察了水解条件和Bi₂O₃掺入量等制备条件对复合光催化剂性能的影响。结果表明,与传统制备方法相比,该方法操作简单、快速;当水和乙醇的比例为4∶1时所得样品的光催化活性最好;Bi₂O₃的掺入拓宽了TiO₂对光的吸收范围,提高了TiO₂的光催化活性,掺入量(Bi₂O₃)为0.25%复合光催化剂催化活性最高;复合光催化剂对多种水溶性染料均具有较好的处理效果。     

NO2对颗粒污泥甲烷化动力学特性的影响

采用间歇试验方法，以乙酸和乙酸盐混合物为基质，对取自EGSB反应器具有厌氧甲烷化反硝化与厌氧氨氧化活性的颗粒污泥的甲烷化动力学以及NO₂影响进行研究。无NO₂时，最大比基质降解速率为0.158 mg COD/mg VSS·h，半饱和常数为464 mg COD/L，甲烷的产率系数为0.254 mL CH₄/mg COD。添加微量NO₂对甲烷化有抑制作用，抑制程度随着微量NO₂浓度的增高而增大，在NO₂浓度为30.36 mg/m³、50.6 mg/m³、101.2 mg/m³、202.4 mg/m³和303.6 mg/m³条件下，甲烷化抑制程度分别为7.40％、11.87％、27.56％、39.75％和43.24％，外推得NO₂的甲烷化半抑制浓度IC₅₀值为383.8 mg/m³。NO₂气氛下甲烷化动力学可用反竞争性抑制动力学进行描述，最大比基质降解速率为0.148 mg COD/mg VSS·h，半饱和常数为396 mg COD/L，NO₂抑制系数为250 mg/m³。     

高铁酸盐对活性及分散染料的脱色研究

采用湿法制备了高铁酸钾(K₂FeO₄)氧化剂,研究了其对染料活性艳红X-3B(X-3B) 和分散蓝2BLN(2BLN)在不同pH条件下的脱色效果,并对Al₂ (SO₄)₃、K₂FeO₄及O₃对活性及分散染料的脱色效果进行了比较。结果表明：高铁酸钾对活性及分散染料的脱色效果明显, X-3B脱色率随pH的增加不断提高,2BLN脱色率在pH 6～10范围内无明显变化,在pH＝5时达到最大值。在X-3B及2BLN浓度同为100 mg／L,pH分别为10、5, K₂FeO₄浓度分别为100 mg／L和200 mg／L时,BLN及X-3B的脱色率分别达到92.3％和87.3％。在相同条件下,K₂FeO₄对活性艳红X-3B的脱色效果好于Al₂(SO₄)₃和O₃; 而K₂FeO₄对分散蓝2BLN的脱色效果虽比Al₂ (SO₄)₃稍差,但比臭氧的脱色效果要好。同时还研究了K₂FeO₄对活性及分散染料的脱色机理,结果表明： 高铁酸钾对X-3B的脱色依赖于K₂FeO₄的氧化作用,而对的2BLN的脱色则以絮凝为主。     

几种阴阳离子对磷钨酸光催化降解甲基橙的影响

以磷钨酸为光催化剂,在紫外灯照射下,对甲基橙溶液进行光催化降解,考察了几种阴阳离子对磷钨酸光催化降解甲基橙溶液的影响。结果表明：Mg²⁺、Ca²⁺、NO^-₃、SO^2-₄和CO^2-₃均对催化活性有促进作用,其中Mg²⁺和Ca²⁺仅有微弱的促进作用;NO^-₃和SO^2-₄随着浓度的增加促进作用也有所增加;CO^2-₃则随着浓度的增加促进作用呈下降趋势;Mn²⁺、Al³⁺和Cl^-对光解反应存在较强的抑制作用,且Al³⁺和Cl^-随着其浓度的增加,抑制作用增强。     

Preparation,characterization, and photocatalytic activity evaluation of Fe–N-codoped TiO2/fly ash cenospheres floating photocatalyst

Nitrogen-doped titanium dioxide (TiO₂) and Fe–N-codoped TiO₂ layers on fly ash cenospheres (FAC) as floating photocatalyst were successfully prepared through sol–gel method. Photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), ultraviolet (UV)–Vis diffuse reflectance spectroscopy (DRS), and nitrogen adsorption analyses for Brunauer–Emmett–Teller (BET) specific surface area. Photocatalytic efficiency of the prepared catalyst was evaluated through using the decomposition of Rhodamine B (RhB) as a model compound under visible light irradiation. Photocatalytic activity and kinetics of catalyst under visible light were detected in details from different Fe/Ti mole ratios by detecting photodegradation of RhB. Experimental results show that when the calcination temperature was 550 °C, the dosage of FAC was 3.0 g, and the mole ratio of Fe/Ti was 0.71 %; the synthesized Fe–N-TiO₂/FAC photocatalyst presented as anatase phase and that N and Fe ions were doped into TiO₂ lattice. The material’s specific surface area was 34.027 m²/g, and UV–Vis diffuse reflectance spectroscopy shows that the edge of the photon absorption has been red shifted up to 400–500 nm. Fe–N-codoped titanium dioxide on FAC had excellent photocatalytic activity during the process of photodegradation of RhB under visible light irradiation.

     

纳米TiO2-xNx催化剂的制备及其活性研究

以钛酸丁酯为前驱物、无水乙醇作溶剂、二乙醇胺作为抑制剂,采用溶胶-凝胶法制备TiO2溶胶,在NN3气流中直接进行热处理,制备一系列不同焙烧温度的淡黄色的掺氮纳米TiO2粉体。经XRD、UV-Vis和FTIR分析表明,实验制得的TiO2-xNx在350、400、450、500和550℃热处理3 h后仍为锐钛型;450℃保温3 h掺氮样品具有最佳的紫外-可见光响应,其吸收边红移至720 nm左右。罗丹明B的可见光降解实验及产物分析表明,掺氮样品具有良好的可见光催化活性。     

Synthesis and characterisation of transition metal sulphide-loaded fly ash–based mesoporous EU-12 photocatalysts for degradation of rhodamine B

Transition metal sulphide-loaded fly ash–based EU-12 photocatalysts were synthesized by sono-hydrothermal method followed by ion exchange. The composites were characterized by XRD, FESEM, DSC-TGA, Raman spectroscopy, and BET surface area analysis. The XRD results imply 76.39% crystallinity of EU-12 and morphological studies by FESEM, and TEM revealed the shape and size of EU-12, i.e. rod-shaped with size ranging from 5 to 200 nm. Band gap of all synthesized photocatalysts were found to be?≤?3.44 eV. The photoactivities of the photocatalysts were examined by degrading rhodamine B (RhB). The results indicated that metal sulphide/EU-12 composite had the strong photoactivity under visible light compared to dark environment. Furthermore, the efficiency of photocatalysts was determined in terms of degradation efficiency towards RhB which was found to be maximum of 98.62% for 0.2 M CdS/EU-12 at 2 gL^?1 of catalyst dosage and 10 ppm of dye concentration within 3 h under visible light source of 200 W.

     

Biomonitoring trace element atmospheric deposition using lichens in China

Concentrations of 32 elements, Ag, As, Au, Ba, Ca, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Mo, Na, Nd, Ni, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, U, W, Yb, and Zn were determined by instrumental neutron activation analysis (INAA) in the early preserved epiphytic lichens (Parmotrema recticulatum) from the remote southwestern China area in the 1960s, 1980s and 1990s. The concentrations of Ag, As, Ce, Cr, Cs, Eu, Fe, Hf, La, Nd, Ni, Sc, Se, Sm, Tb, U, Yb and Zn were dropped down by the temporal prolongation. The elemental concentration levels obtained from the organisms indicate that the extent of heavy metal atmospheric deposition among the sampling sites has been declining during the past decades.     

Preparation of a titanium dioxide photocatalyst codoped with cerium and iodine and its performance in the degradation of oxalic acid

A novel class of visible light-activated photocatalysts was prepared by codoping TiO(2) with cerium and iodine (Ce-I-TiO(2)). The particles were characterized using the Brunauer-Emmett-Teller method, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV-Visible light absorption. Particles of Ce-I-TiO(2) had greater photoabsorption in the 400-800 nm wavelength range than iodine-doped TiO(2) (I-TiO(2)). The effects on the photocatalytic degradation of oxalic acid under visible light or UV-Visible light irradiation were investigated. The photocatalytic activity of Ce-I-TiO(2) calcined at 673 K was significantly higher than that of Ce-I-TiO(2) calcined at 773 K and I-TiO(2) calcined at 673 K in aqueous oxalic acid solution under visible light or UV-Visible light irradiation. Under visible light irradiation, oxalic acid was first adsorbed on the surface of the catalysts rather than reacted with free radicals in the bulk solution, and then oxidized by (·)OH(ads) to CO(2), which was verified by studying the effects of nitrogen purging and scavengers, as well as by gas chromatography/mass spectrometry.     

以PEG为模板剂制备Bi2O2CO3及其可见光光催化性能

以聚乙二醇-6000（PEG-6000）为模板剂水热法制备碳酸氧铋（p-Bi2O2CO3）粉末,采用x射线衍射（XRD）、扫描电镜（SEM）、X射线光电子能谱（XPS）、透射电子显微镜（TEM）和紫外可见漫反射（DRS）对粉末进行了初步表征。在可见光（λ≥420nm）照射下,以罗丹明B（RbB）和水杨酸（SA）光催化降解实验为探针反应,实验结果表明,p-Bi2O2CO3具有较高的光催化活性,对RhB和SA有较好的降解效果。通过紫外-可见光谱（uV-Vis）、红外光谱（IR）和测定总有机碳（TOC）含量,光催化反应35h后RhB的矿化率为77％,同时对SA的降解率达到43％。同时,采用N,N-二乙基对苯二胺（DPD）分光光度法和对苯二甲酸荧光光度法分别测定了降解过程中H2O2和羟基自由基（·OH）的变化,表明p-Bi2O2CO3／Vis光催化降解机理涉及到·OH历程。     

UV–visible light-activated Ag-decorated,monodisperse TiO2 aggregates for treatment of the pharmaceutical oxytetracycline

Noble metal Ag-decorated, monodisperse TiO₂ aggregates were successfully synthesized by an ionic strength-assisted, simple sol–gel method and were used for the photocatalytic degradation of the antibiotic oxytetracycline (OTC) under both UV and visible light (UV–visible light) irradiation. The synthesized samples were characterized by X-ray diffraction analysis (XRD); UV–vis diffuse reflectance spectroscopy; environmental scanning electron microscopy (ESEM); transmission electron microscopy (TEM); high-resolution TEM (HR-TEM); micro-Raman, energy-dispersive X-ray spectroscopy (EDS); and inductively coupled plasma optical emission spectrometry (ICP-OES). The results showed that the uniformity of TiO₂ aggregates was finely tuned by the sol–gel method, and Ag was well decorated on the monodisperse TiO₂ aggregates. The absorption of the samples in the visible light region increased with increasing Ag loading that was proportional to the amount of Ag precursor added in the solution over the tested concentration range. The Brunauer, Emmett, and Teller (The BET) surface area slightly decreased with increasing Ag loading on the TiO₂ aggregates. Ag-decorated TiO₂ samples demonstrated enhanced photocatalytic activity for the degradation of OTC under UV–visible light illumination compared to that of pure TiO₂. The sample containing 1.9 wt% Ag showed the highest photocatalytic activity for the degradation of OTC under both UV–visible light and visible light illumination. During the experiments, the detected Ag leaching for the best TiO₂-Ag photocatalyst was much lower than the National Secondary Drinking Water Regulation for Ag limit (0.1 mg L^?1) issued by the US Environmental Protection Agency.     

Effects of redox potential and pH value on the release of rare earth elements from soil

Equilibrium release experiments were conducted under three different pH values of 3.5, 5.5 and 7.5 as well as three redox potentials of 400, 0 and -100 Mv to investigate the influence of redox potential and pH value on the La, Ce, Gd and Y release of from the simulated-REEs-accumulation (SRA) soil. Oxygen and nitrogen were allowed to flow into soil suspension to adjust redox potential to a preset value, and 1 mol/l HCl or 1 mol/l NaOH solutions were added into the soil suspension to keep pH at a preset value. Results indicated that La, Ce, Gd and Y release increased gradually with the decrease of pH value or Eh, and the influence of redox potential on Ce was more remarkable than on La, Gd and Y. At the same time. It was observed that La, Ce, Gd and Y releases were positively correlated with the release of Fe and Mn, indicating that La, Ce, Gd and Y releases might originate from dissolution of Fe-Mn oxyhydroxides under reduction and low pH conditions. Moreover, it was found that alteration of pH value and redox potential might affect the change of La, Ce, Gd and Y species in the soil. The contents of La, Ce, Gd and Y in exchangeable fraction and Fe-Mn oxide fraction in the solid phase from soil suspension separation decreased with the decline of pH value and redox potential. Multiple stepwise regression analysis showed that exchangeable fraction and Fe-Mn oxide fraction predominately contributed to the La, Ce, Gd and Y release. Low pH value and redox potential were more favorable to La, Ce, Gd and Y releases following the change of their species. The La, Ce, Gd and Y contents in exchangeable fraction and Fe-Mn oxide fraction are the main contributors to their release.     

Major to ultra trace elements in rainfall collected in suburban Tokyo

Major to ultra trace elements such as rare earth elements (REEs), platinum group elements (PGEs) in 20 rainfall events from suburban Tokyo were determined by inductively coupled plasma mass spectrometry (ICP-MS). Anion species were also determined by an ion chromatography (IC). The concentrations of PGEs were so low that only Pt was detected in some rainfall events. Enrichment factors (EFs), refer to soil and sea salt components, were calculated for the measured elements (with Al and Na as references). Be, (Na), Mg, (Al), Si, Cl, K, Fe, Rb, Sr, REEs (except La, Gd), Ta, and U were mostly originated from natural materials (soil and sea salt). For Li, B, Ca, Mn, Sr, Ba, and Cs, the contribution of natural materials was significant. EFs for Cu, Zn, As, Se, Sb, Cd, Pb, Bi, Ag, Te, Au, Pt, SO₄-S and NO₃-N exceeded 100 indicating non-crustal, non-sea salt origin, presumably anthropogenic; however, contribution of volcanic gases could not be excluded for As, Se, Te and Bi. Pt seemed to be uniformly distributed worldwide and a catalyst for automobile emission control may be the main source. Au also showed uniform distribution. On the other hand, EFs for Zr, Nb, Hf and Th were less than unity. Probably these elements resided in acid resistant refractory fine minerals that did not decompose with acid treatment, and did not evaporate and ionize in the ICP. An alternative explanation is that the concentration of these elements was lower in the soil of the sampling area than the average crust. In the crust normalized REE pattern plot, La, Eu and Gd showed clear positive anomalies. La and Gd could have anthropogenic components. A possible source of La and Gd is cracking catalyst for petrol refining, but this source does not fully explain the anomaly. The source of Gd may also be Gd-DTPA (Gadolinium (III) diethyltriaminepentaacetic acid) used for Magnetic Resonance Imaging (MRI) contrast agents. The Eu origin may be soil with higher concentration than the crust average.