TiO_2改性钛基SnO_2电极的制备及性能研究

采用热分解法制备了钛基SnO2(Ti/SnO2)电极和TiO2改性钛基SnO2(Ti/SnO2-TiO2)电极。利用扫描电子显微镜(SEM)和X射线衍射(XRD)仪,极化曲线和循环伏安测试等方法对改性前后的电极进行表征,并考察电极的电催化氧化能力。结果表明,Ti/SnO2-TiO2电极膜层中存在锐钛矿型TiO2粒子,引入的TiO2使Ti/SnO2-TiO2电极具有比Ti/SnO2电极更粗糙的表面和更大的比表面积,且使电极的析氧过电位由1.7V提高至2.0V。循环伏安测试结果和电催化氧化4-氯苯酚(4-CP)过程均表明,Ti/SnO2-TiO2电极具有比Ti/SnO2电极更高的电催化氧化能力。     

Ag~+-TiO_2/AC复合材料的可见光吸附-光催化协同作用

采用水热法制备活性炭负载银掺杂纳米Ti O2复合材料(Ag+-Ti O2/AC),对样品进行了TEM、XRD、FT-IR和UV-Vis表征,分析了Ag+-Ti O2/AC的微结构、吸收谱特性和掺杂银离子后的半导体带隙变化,并研究了其在可见光下对甲基橙溶液(MO)的降解性能。结果表明,水热法不需要高温处理即可得到高活性的锐钛矿相纳米Ti O2,Ag+掺杂和AC负载均明显提高Ti O2光催化剂的光催化活性,在可见光下光照180 min,0.2 g/L的Ag+-Ti O2/AC对10 mg/L的甲基橙溶液的降解率为73.7%,主要由于存在持续的活性炭局域强吸附-Ti O2光催化降解协同作用,明显提高了甲基橙的降解效率。     

附载型复合光催化剂TiO2·SiO2/beads降解有机磷农药

研究以四异丙醇钛 [Ti( iso- O C3 H7) 4]、硅酸乙酯为原料 ,以空心玻璃微球为载体 ,用溶胶—凝胶法制备可漂浮附载型复合光催化剂 Ti O2 · Si O2 / beads的过程 ,利用附载型复合光催化剂降解有机磷农药。结果表明 ,复合型光催化剂 Ti O2 · Si O2 摩尔比存在最佳值 ,n ( Ti O2 ) / m ( Si O2 ) =30 / 70时 ,光催化剂活性最高 ,其活性是同样降解条件下、同样含量 Degussa P- 2 5Ti O2 的 2倍左右。该光催化剂比表面大 ,吸附性强。并用 XRD和 SEM对附载型复合光催化剂进行表征     

不同种类金属离子改性椰壳活性炭吸附分离CO2/CH4的研究

分别用碱金属(K)、碱土金属(Ca、Mg)和重金属(Fe、Cu、Ag)对椰壳活性炭(AC)进行改性,对改性前后AC的理化性质及其对CO_2/CH_4的吸附分离效果进行了综合对比分析。结果表明,经金属离子改性后AC的比表面积、总孔体积和微孔体积下降,中孔体积变大;AC改性前后主要官能团基本相同,除Ag~+改性AC中出现了Ag的衍射峰外,其余的物相结构基本没有改变。经金属离子改性后,AC对CO_2的吸附量增大,这与负载的金属增加了AC的表面极性密切相关;而对CH_4的吸附则大体低于原AC。改性AC对CO_2/CH_4混合气的分离效果均优于原AC,其中以K~+改性效果最优。金属离子改性AC对CO_2吸附能力和对CO_2/CH_4混合气分离效果的优劣程度大体为:碱金属改性AC碱土金属改性AC重金属改性AC。     

氧化、还原改性对活性炭吸附草甘膦的影响

研究了氧化、还原改性对活性炭吸附草甘膦的影响.以傅立叶红外光谱定性表面官能团变化,以扫描电镜观察表面形貌,以化学吸附分析仪测定后再通过测定样品的氮气吸附/脱附等温线计算比表面积和孔径.结果表明:(1)氧化改性使活性炭比表面积增大;还原改性使活性炭比表面积减小.还原阶段使先前氧化阶段中产生的孔道以及原有孔道均发生塌陷,导致还原改性活性炭比表面积减小.(2)在静态吸附的条件下,氧化改性和还原改性活性炭对草甘膦的吸附均为吸热反应.还原改性在活性炭表面产生的还原性官能团有利于活性炭对草甘膦的吸附,而氧化改性产生的氧化性官能团并不利于活性炭对草甘膦的吸附.(3)热力学参数的计算进一步表明,改性活性炭对草甘膦的吸附为吸热反应.     

Fe_3O_4@改性悬铃木果毛复合中空纤维的制备及其吸附性能

选用对空气和人居环境具有污染的悬铃木果毛为基质,通过将四氧化三铁磁性纳米粒子在多巴胺改性悬铃木果毛表面的固载,制备得到具有中空结构的Fe_3O_4@改性悬铃木果毛复合吸附材料。用X射线衍射仪(XRD)、能谱(EDS)、电子扫描电镜(SEM)、红外光谱(FT-IR)和震动样品磁强计(VSM)等手段对样品进行了表征和分析,考察了Fe_3O_4@改性悬铃木果毛复合中空纤维对亚甲基蓝的吸附性能。结果表明:通过多巴胺对悬铃木果毛的化学改性,有效促进了反尖晶石型结构的四氧化三铁纳米粒子在其表面的固载,Fe_3O_4@改性悬铃木果毛复合中空纤维直径约为25.8μm,其饱和磁化强度为12.51 emu/g,Fe_3O_4@改性悬铃木果毛对亚甲基蓝的吸附在140 min达到平衡,吸附容量可达12.6 mg/g,吸附动力学符合准二级动力学。     

DSB+CPB复合改性膨润土对磷酸盐的吸附

为研究两性-阳离子表面活性剂复合改性膨润土的吸附除磷性能及其机理,采用不同比例两性表面活性剂——十二烷基二甲基磺丙基甜菜碱(DSB)和阳离子表面活性剂溴代十六烷基吡啶(CPB)对膨润土进行了有机复合改性,制得DSB+CPB复合改性膨润土,利用X射线衍射分析(XRD)、傅里叶红外分析(FT-IR)、扫描电子显微镜(SEM)、接触角(CA)以及热重分析(TGA)等手段对膨润土土样进行了表征,并用吸附等温模型和动力学方程拟合其吸附过程,探讨了改性比例、pH和温度等因素对吸附的影响。结果表明:DSB改性能提高膨润土对磷酸盐的吸附能力,当加入CPB复合改性后,可进一步促进DSB改性膨润土对磷酸盐的吸附能力,且吸附能力均随改性比例的增大而增强;对于0.5 DSB和1.0 DSB的改性膨润土,其与CPB最佳复合比例均为DSB+1.5CPB,最大吸附量分别为原土的7.81倍和8.19倍;改性膨润土对磷酸盐的吸附均符合Langmuir等温模型和伪二级吸附动力学方程,其吸附能力随pH的升高而降低,且吸附为物理和化学吸附同时存在的自发吸热熵增过程。上述研究结果可为两性-阳离子表面活性剂复合改性膨润土吸附除磷提供参考。     

TEMPO氧化微晶纤维素和马来酸酐接枝微晶纤维素的制备及对Cu~(2+)的吸附

通过马来酸酐(MA)固相接枝和四甲基哌啶(TEMPO)氧化体系改性微晶纤维素(MCC)制备了两种重金属离子吸附剂,对比了MA和TEMPO氧化体系对MCC的改性后对铜离子的吸附效果。结果表明:两者对MCC的改性都有效果,在铜离子浓度小于500 mg/L时,经TEMPO改性的MCC吸附容量和吸附率明显大于MA改性的MCC。经TEMPO改性后的MCC对铜离子的吸附性能提高,在室温条件下,0.22 g改性后MCC对pH=5.77,浓度为20 mg/L的铜离子溶液最大吸附率为90.56%,最大吸附容量为9.1 mg/g。     

Ag/AgCl改性碳纳米管薄膜连续流光催化去除水中亚甲基蓝

为了探究Ag/AgCl光催化薄膜在连续流状态下对有机污染物的光催化性能,采用连续沉积方法制备了Ag/AgCl改性碳纳米管(CNTs)薄膜,以亚甲基蓝为目标污染物,利用光化学过滤器对亚甲基蓝的光催化脱色效果进行了探究。结果表明,在900μW·cm-2光强下,Ag/AgCl-CNTs复合薄膜在连续流光催化体系中对10 mg·L-1的亚甲基蓝去除率可达90%,比传统序批式反应体系高出70%以上,说明连续流体系的对流传质效果明显优于序批式体系的扩散传质效果。同时,Ag/AgCl的沉积显著改善了CNTs薄膜的光催化脱色性能。在最佳实验条件下,Ag/AgCl改性后,复合薄膜的光催化脱色效果比CNTs薄膜提高了40%。Ag/AgCl-CNTs多功能复合薄膜体系具有光催化降解和膜分离以及减缓膜污染等多重特性。     

硫酸改性麻黄废渣对Cu~(2+)的吸附研究

用硫酸对麻黄废渣进行化学改性,制备改性麻黄废渣,并用于模拟废水中Cu2+的吸附。通过扫描电子显微镜、傅里叶红外光谱仪和官能团滴定等方法对改性麻黄废渣进行表征;采用静态吸附实验,考察了溶液pH、吸附剂用量、吸附时间等对吸附效果的影响。结果表明,麻黄废渣改性后,酸性基团数量明显增加,羟基和羧基也均有大幅度的增加,表面比改性前变得粗糙和疏松多孔,表面积增大,更有利于对Cu2+的吸附。室温(25℃)下改性麻黄废渣吸附Cu2+的较佳条件为:溶液pH 5.0、吸附时间60min、改性麻黄废渣用量4g/L。改性麻黄废渣对Cu2+的吸附可以用准二级动力学方程描述,Cu2+的饱和吸附量为2.20mmol/g,与改性前(1.49mmol/g)相比有明显提高。改性麻黄废渣吸附—解吸附循环使用5次中,Cu2+的平均解吸率达到83%左右,麻黄废渣平均再生率达到94%以上,经5次循环使用,Cu2+吸附率仍可达到99.46%,说明改性麻黄废渣具有良好的重复利用性能。     

Deodorization of dimethyl sulfide using a discharge approach at room temperature

The traditional technologies for odor removal of thiol usually create either secondary pollution for scrubbing, adsorption, and absorption processes, or sulfur (S) poisoning for catalytic incineration. This study applied a laboratory-scale radio-frequency plasma reactor to destructive percentage-grade concentrations of odorous dimethyl sulfide (CH3SCH3, or DMS). Odor was diminished effectively via reforming DMS into mainly carbon disulfide (CS2) or sulfur dioxide (SO2). The removal efficiencies of DMS elevated significantly with a lower feeding concentration of DMS or a higher applied rf power. A greater inlet oxygen (O2)/DMS molar ratio slightly improved the removal efficiency. In an O2-free environment, DMS was converted primarily to CS2, methane (CH4), acetylene (C2H2), ethylene (C2H4), and hydrogen (H2), with traces of hydrogen sulfide (H2S), methyl mercaptan (CH3SH), and dimethyl disulfide. In an O2-containing environment, the species detected were SO2, CS2, carbonyl sulfide, carbon dioxide (CO2), CH4, C2H4, C2H2, H2, formaldehyde, and methanol. Differences in yield of products were functions of the amounts of added O2 and the applied power. This study provided useful information for gaining insight into the reaction pathways for the DMS dissociation and the formation of products in the plasmolysis and conversion processes.     

Dimethylsulfide and its oxidation products in coastal atmospheres of Cheju Island

The concentrations of dimethylsulfide (DMS) in air and its oxidation products in aerosols were measured from the coastal atmospheres of Cheju Island, Korea, during three exploratory field experiments conducted over September 1997 through April 1998. According to our measurements, there were large fluctuations in the distribution of DMS and relevant species in the coastal atmospheres; the magnitude of variations was significant both within each measurement period and across different measurement periods. The mean mixing ratios of atmospheric DMS from the whole data sets were found within the range of 19 to 1140 pptv (n=84) with the grand mean value of 100 pptv. Like DMS, large variations in the data distribution were consistently seen from other species investigated concurrently. The concentrations of aerosol ions including non-seasalt sulfate (NSSS), seasalt sulfate (SSS), and methane sulfonate (MSA) spanned over two orders of magnitude such as 0.24-88 (mean 32), 0.08-17.2 (mean 3.70), and 0.01-0.78 (mean 0.16) nmol m(-3), respectively. The molar ratios of those ions were measured as: (1) NSSS/SSS in 1.26-95 (mean 44); (2) MSA/NSSS in 0.0002-0.063 (mean 0.009); and (3) NSSS/NO(3) in 0.21-9.5 (mean 2.35). Examinations of our measurement data indicated that the concentrations of DMS and relevant ions varied significantly across day/night periods and across different seasons. It was also seen that there are strong differences in seasonal distribution patterns between fall, winter, and spring. Detailed analysis of the data sets revealed that changes in their distribution patterns were in strong compliance with changes in meteorological conditions. Especially, large fluctuations in magnitudes and amplitudes of springtime DMS concentrations were coinciding with the intrusion of southeasterly winds, suggesting the possibility that the DMS-rich air masses were brought into the study area from the productive waters of the southeast coastal area of Cheju. Similarly to the case of DMS, the occurrence of unusual wind patterns during spring contributed to changes in the content and composition of aerosol ions. Although the introduction of southeasterly winds during spring helped maintain high DMS and MSA levels, the concentrations of aerosol ions dropped significantly because of depositional loss during the passage of air mass over land area. According to the procedures of Wylie and De Mora, we reached the conclusion that the magnitude of annual DMS emissions in the western Korean sea were in the range of 5 to 18 Gg S.     

OH-initiated oxidation of DMS/DMSO: reaction products at high NOx levels

Dimethylsulphide (DMS) gas phase oxidation with OH radicals was investigated by long path FT-IR spectroscopy and by ion chromatography (IC) and HPLC-MS2 to quantify the reaction products and evaluate heterogeneous processes. The experiments were performed considering two different NOx (NO2+NO) levels. The initial concentration of NO2 was varied from 24 ppbV (NOx=1 ppmV) to 953 ppbV (NOx=10 ppmV). Photolysis of H2O2 was used as the OH-radical source. SO2, dimethylsulphoxide (DMSO), dimethylsulphone (DMSO2), methanesulphonic acid (MSA), methanesulphinic acid (MSIA) and methane sulphonyl peroxynitrate (MSPN) were identified as the main sulphur-containing products. The results indicate that higher NOx levels play a significant role in the chemistry of CH3S(O)x radical, influencing both the SO2/MSPN ratio and the amount of the sulphur species in the condensed phase, and that the NO2/NO ratio could influence the trends in the molar yields of the different products. For this reason the NOx content results a limiting parameter when on measure DMS in atmospheric environment.     

Marine sulfur cycling and the atmospheric aerosol over the springtime North Atlantic

We investigated the distribution of phytoplankton species and the associated dimethyl sulfur species, dimethylsulfoniopropionate (DMSP) and dimethylsulfide (DMS) on a cruise into the spring bloom region of the northern North Atlantic (near 47 degrees N, 19 degrees W). The cruise was timed to characterize the relationship between plankton dynamics and sulfur species production during the spring plankton bloom period. At the same time, we measured the DMS concentrations in the atmospheric boundary layer and determined the abundance and composition of the atmospheric aerosol.The water column studies showed that the interplay of wind-driven mixing and stratification due to solar heating controlled the evolution of the plankton population, and consequently the abundance of particulate and dissolved DMSP and DMS. The sea-to-air transfer of DMS was modulated by strong variations in wind speed, and was found to be consistent with currently available transfer parameterizations. The atmospheric concentration of DMS was strongly dependent on the sea surface emission, the depth of the atmospheric boundary layer and the rate of photooxidation as inferred from UV irradiance. Sea-salt and anthropogenic sulfate were the most abundant components of the atmospheric aerosol. On two days, a strong dust episode was observed bringing mineral dust aerosol from the Sahara desert to our northerly study region. The background concentrations of marine biogenic sulfate aerosol were low, near 30-60 ppt. These values were consistent with the rate of sulfate production estimated from the abundance of DMS in the marine boundary layer.     

Effects of earthworms and effective microorganisms on the composting of sewage sludge with cassava dregs in the tropics

The present study revealed the role of earthworm-effective microorganisms (EM) in converting sewage sludge and cassava dregs into a valuable product. Sewage sludge was toxic to earthworm, therefore it was mixed with cassava dregs in 80:20 proportions (dry weight). Treatments included mixed substrate inoculated versus not inoculated with EM and treated with or without earthworms. The pH, total organic carbon, total nitrogen, and C:N ratio decreased from the initial measurements in the range of 17.43–18.46%, 25.48–33.82%, 19.60–25.37%, and 6.68–14.05% respectively; but electrical conductivity and available phosphorus increased in the range of 113.47–158.16% and 42.42–57.58%, respectively. In addition, they interactively increased total phosphorus from 19.84–63.01% and potassium from 16.41–50.78%, and decreased the polycyclic aromatic hydrocarbons content of substrate from 21.17% to 32.14% with an increase in earthworms from 51.71 to 57.69, respectively. Earthworms and EM could be used together as an efficient method for co-composting sewage sludge plus cassava dregs in the tropics. This could be expected to result in stabilization of waste, increase in nutrients, and reduction of pollutant content.

Implications: The first reports of interaction of earthworms and effective microorganisms in the treatment of sewage sludge and cassava dregs in the tropics. Co-composting was an efficient technology for treating sewage sludge and cassava dregs at the same time, in the tropics. The survival rate of the earthworms both> 95%, the highest number of cocoons (640.33) and hatchlings (4694.33) both in EW+EM (Earthworms added and EM inoculated) treatment. Earthworms and EM (Only EM inoculated) interactively increased total phosphorus and potassium content, and decreased the PAH content of substrate with increase in earthworms.     

Comparison of two micro-analytical methods for detecting the spatial distribution of sorbed Pu on geologic materials

Subsurface transport of groundwater contaminants is greatly influenced by chemical speciation, precipitation and sorption processes at the mineral-water interface. The retardation of contaminants is often greatest at boundaries between minerals and in fractures and pore spaces. The investigation of the spatial distribution of sorbed contaminants along these boundaries requires micro-analytical techniques. The sorption of dissolved Pu(V) on a natural zeolitic tuff from Yucca Mountain (NV, USA) was examined using microautoradiography (MAR), X-ray diffraction (XRD), electron microprobe (EM) techniques, and synchrotron-based micro-X-ray fluorescence (micro-SXRF). The tuff contained a heterogeneous distribution of zeolites and trace quantities of smectites, Fe oxides (hematite), and Mn oxides (rancieite), which are present as fracture fill and pore space materials. Micro-SXRF studies showed that Pu is mostly associated with bodies of smectite plus Mn oxides, which were typically elevated in Ce, Ga, Nb, Pb, Y, Ca, Ti, and Zn. Sorbed Pu was not associated with Fe-rich bodies, which were enriched in Cl and Rb. Results of the MAR studies were complementary to that of the micro-SXRF studies in that Pu was associated with similar elements in the tuff. Indirect detection of Pu by EM or micro-SXRF (by analyzing Ag developed on the MAR photoemulsion) was a more sensitive method for detecting lower levels of sorbed Pu than the direct detection of sorbed Pu via micro-SXRF in the absence of the photoemulsion.     

聚合硅酸钛铝复合絮凝剂的结构及性能

为了克服有机絮凝剂的二次投加及有毒性的缺点,以硅酸钠、硫酸钛、硫酸铝为原料,制备了聚合硅酸钛铝(PTAS)无机高分子复合絮凝剂处理模拟江水。结果表明,在n(Ti+Al)∶n(Si)=1∶3,n(Ti)∶n(Al)=1∶5,模拟江水pH值为5～9.3,絮凝剂投加量为0.3 mmol/L(以金属离子计)时,PTAS对模拟江水的混凝效果最好,除浊率达到92.5%以上。此外,通过X-射线衍射说明聚硅酸与硫酸铝、硫酸钛不是单纯的原料复合;红外吸收光谱显示钛、铝离子及其水解聚合产物可与共存的聚硅酸生成Si—O—Al键和Ti—O—Si键;激光粒度分析表明PTAS在聚合过程中粒度并没有明显变化,但均比聚硅酸粒径大。     

Deodorization of Dimethyl Sulfide Using a Discharge Approach at Room Temperature

Abstract

The traditional technologies for odor removal of thiol usually create either secondary pollution for scrubbing, adsorption, and absorption processes, or sulfur (S) poisoning for catalytic incineration. This study applied a laboratory-scale radio-frequency plasma reactor to destructive percentage-grade concentrations of odorous dimethyl sulfide (CH₃SCH₃, or DMS). Odor was diminished effectively via reforming DMS into mainly carbon disulfide (CS₂) or sulfur dioxide (SO₂). The removal efficiencies of DMS elevated significantly with a lower feeding concentration of DMS or a higher applied rf power. A greater inlet oxygen (O₂)/DMS molar ratio slightly improved the removal efficiency. In an O₂-free environment, DMS was converted primarily to CS₂, methane (CH₄), acetylene (C₂H₂), ethylene (C₂H₄), and hydrogen (H₂), with traces of hydrogen sulfide (H₂S), methyl mercaptan (CH₃SH), and dimethyl disulfide. In an O₂-containing environment, the species detected were SO₂, CS₂, carbonyl sulfide, carbon dioxide (CO₂), CH₄, C₂H₄, C₂H₂, H₂, formal-dehyde, and methanol. Differences in yield of products were functions of the amounts of added O₂ and the applied power. This study provided useful information for gaining insight into the reaction pathways for the DMS dissociation and the formation of products in the plasmolysis and conversion processes.     

聚硅酸锌铝的制备及其性能研究

以硅酸钠、硫酸锌、硫酸铝为原料，通过共聚法制备了无机高分子絮凝剂聚硅酸锌铝（PSZAS），研究了Na₂SiO₃的摩尔浓度、活化时间、Al/Si、Zn/Si 配比及絮凝剂的投加量对絮凝效果的影响，用X-射线衍射（XRD）和电子扫描电镜（SEM）对该絮凝剂的结构及形貌进行了表征。结果表明：当硅酸钠的浓度为0.4 mol/L，硅酸活化时间为2 h，Si∶Al∶Zn=1∶1∶1.5，絮凝剂投加量为20 mL/L废水时，絮凝剂的电中和能力和吸附架桥能力最强，絮凝剂对含H-酸染料模拟废水的絮凝效果最好。     

Environmental VOSCs--formation and degradation of dimethyl sulfide, methanethiol and related materials

Volatile organic sulfur compounds (VOSCs) play a major role in the global sulfur cycle. Two components, dimethyl sulfide (DMS) and methanethiol (MT) are formed in large amounts by living systems (e.g. algae, bacteria, plants), particularly in marine environments. A major route to DMS is by action of a lyase enzyme on dimethylsulfoniopropionate (DMSP). DMSP has other roles, for instance as an osmoprotectant and cryoprotectant. Demethiolation of DMSP and other materials leads to MT. A major transport process is release of DMS from the oceans to the atmosphere. Oxidation of DMS in the atmosphere by hydroxyl and nitrate radicals produces many degradation products including CO2, COS, dimethyl sulfoxide, dimethyl sulfone, organic oxyacids of sulfur, and sulfate. These materials also have roles in biotic processes and there are complex metabolic interrelationships between some of them. This review emphasizes the chemical reactions of the organic sulfur cycle. For biotic reactions, details of relevant enzymes are provided when possible.