利用XPS研究复合氧化物催化剂在汽车尾气净化中硫中毒及抗硫中毒机理

运用ＸＰＳ分析方法研究一系列复合氧化物催化剂中毒前后硫在其表面的各种形态及催化剂活性组分中毒前后的组成，价态，化学机理及其变化。结果表明，ＳＯ２在催化剂活性中心进行化学吸附，然后一部分ＳＯ２与活性组分生成相应的亚硫酸盐和硫酸盐，从而使催化剂失活。     

Promotional effect of cobalt doping on catalytic performance of cryptomelane-type manganese oxide in toluene oxidation

The cryptomelane-type manganese oxide (OMS-2)-supported Co (xCo/OMS-2; x = 5, 10, and 15 wt.%) catalysts were prepared via a pre-incorporation route. The as-prepared materials were used as catalysts for catalytic oxidation of toluene (2000 ppmV). Physical and chemical properties of the catalysts were measured using the X-ray diffraction (XRD), Fourier transform infrared spectroscopic (FT-IR), scanning electron microscopic (SEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H₂-TPR) techniques. Among all of the catalysts, 10Co/OMS-2 performed the best, with the T_90%, specific reaction rate at 245°C, and turnover frequency at 245°C (TOF_Co) being 245°C, 1.23 × 10⁻³ mol_toluene/(g_cat·sec), and 11.58 × 10⁻³ sec⁻¹ for toluene oxidation at a space velocity of 60,000 mL/(g·hr), respectively. The excellent catalytic performance of 10Co/OMS-2 were due to more oxygen vacancies, enhanced redox ability and oxygen mobility, and strong synergistic effect between Co species and OMS-2 support. Moreover, in the presence of poisoning gases CO₂, SO₂ or NH₃, the activity of 10Co/OMS-2 decreased for the carbonate, sulfate and ammonia species covered the active sites and oxygen vacancies, respectively. After the activation treatment, the catalytic activity was partly recovered. The good low-temperature reducibility of 10Co/OMS-2 could also facilitate the redox process accompanied by the consecutive electron transfer between the adsorbed O₂ and the cobalt or manganese ions. In the oxidation process of toluene, the benzoic and aldehydic intermediates were first generated, which were further oxidized to the benzoate intermediate that were eventually converted into H₂O and CO₂.     

Greenhouse impacts of anthropogenic CH4 and N2O emissions in Finland

The Finnish anthropogenic CH₄ emissions in 1990 are estimated to be about 250 Gg, with an uncertainty range extending from 160 to 440 Gg. The most important sources are landfills and animal husbandry. The N₂O emissions, which come mainly from agriculture and the nitric acid industry are about 20 Gg in 1990 (uncertainty range 10–30 Gg). The development of the emissions to the year 2010 is reviewed in two scenarios: the base and the reduction scenarios.According to the base scenario, the Finnish CH₄ emissions will decrease in the near future. Emissions from landfills, energy production, and transportation will decrease because of already decided and partly realized volume and technical changes in these sectors. The average reduction potential of 50%, as assumed in the reduction scenario, is considered achievable.N₂O emissions, on the other hand, are expected to increase as emissions from energy production and transportation will grow due to an increasing use of fluidized bed boilers and catalytic converters in cars. The average reduction potential of 50%, as assumed in the reduction scenario, is optimistic.Anthropogenic CH₄ and N₂O emissions presently cause about 30% of the direct radiative forcing due to Finnish anthropogenic greenhouse gas emissions. This share would be even larger if the indirect impacts of CH₄ were included. The contribution of CH₄ can be controlled due to its relatively short atmospheric lifetime and due to the existing emission reduction potential. Nitrous oxide has a long atmospheric lifetime and its emission control possiblities are limited consequently, the greenhouse impact of N₂O seems to be increasing even if the emissions were limited somehow.     

尿中氚水和总氚的分析测定

用蒸馏-液闪法和氧化蒸馏-液闪法分别测量了氚污染人员尿中的氚水浓度和总氚(氚水和有机氚)浓度。根据72个高于本底水平的尿中氚水和总氚浓度分析比较，认为在氚内污染工作人员的尿中，有机氚与氚水的浓度比值为(5.4 3.7)％。     

两种有机锌络合物处理棉花的霉变及热解行为研究

棉花是纺织业的重要原料,是人民群众生活不可或缺的必需品,同时也是我国进出口重要的商品。研究如何安全有效地进行棉花的储备具有十分重要的现实意义。棉纤维本身含有脂肪、蜡质和果胶等适合微生物生长繁殖的营养物质。在棉花储备中,高的回潮率会加速微生物的繁殖,进而产生热量。热量的累积会引起温度升高以及棉花霉变,不利于棉花的安全有效储存。因此,通过静电吸附法将安全无毒的有机锌络合物附着在棉纤维表面,研究表明,相同条件下,处理棉的霉变状况明显得到抑制。加速发霉条件下,未处理棉的相对于白纸的平均色差值为28.10,而双乙酸锌以及苯甲酸锌防霉处理棉的色差值分别为5.16和5.86,下降了81.6%和79.1%。自然发霉条件下,双乙酸锌以及苯甲酸锌防霉处理棉的色差值分别下降了53.8%和50.7%。同时研究了纯棉以及处理棉氮气下的热分解动力学,相比于未处理棉,双乙酸锌防霉处理后活化能下降了15.8%,而苯甲酸锌防霉处理后活化能下降了10.9%。此外,利用实时红外和热重红外联用技术得到了样品在热解过程中固相以及气相的裂解产物的红外谱图,发现防霉处理能一定程度上抑制棉花热解。     

氧化镁基生物质炭高效去除水体中磷的特性

利用花生壳为前驱体,在高温限氧条件下,将氧化镁(MgO)负载于生物质炭(BC)表面制备出氧化镁基生物质炭(MgOBC)复合材料.系统研究了MgO-BC对水体中P的吸附特性,并探讨了溶液pH值、接触时间、竞争离子等因素对P的吸附效果的影响.结果表明,P的最佳吸附初始pH为7~9,过酸过碱的环境均不利于P的吸附;P的吸附过程可在540 min内达到平衡,且动力学曲线较好地符合伪一级和伪二级动力学模型,拟合系数可达97.3%和99.0%;当Cl~-、HCO_3~-、NO_3~-等共存离子的量浓度达到P的10倍时,MgO-BC对P仍具有较强的吸附能力;P的吸附过程较好地符合Langmuir等温模型,拟合系数达99%,理论最大吸附容量为138.07 mg·g~(-1),远高于其它未经改性或改性的生物质炭和几种典型P吸附剂的吸附容量.此外,吸附P后的复合材料可作为肥料施入土壤,可有效实现P的再利用.综上所述,该MgO-BC复合材料在净化实际P污染水体中有着广阔的应用前景.     

Nano-sized Fe2O3/Fe3O4 facilitate anaerobic transformation of hexavalent chromium in soil–water systems

The purpose of this study is to investigate the effects of nano-sized or submicro Fe_2O_3/Fe_3O_4 on the bioreduction of hexavalent chromium(Cr(VI)) and to evaluate the effects of nano-sized Fe_2O_3/Fe_3O_4 on the microbial communities from the anaerobic flooding soil.The results indicated that the net decreases upon Cr(VI) concentration from biotic soil samples amended with nano-sized Fe_2O_3(317.1 ± 2.1 mg/L) and Fe_3O_4(324.0 ± 22.2 mg/L) within21 days,which were approximately 2-fold of Cr(VI) concentration released from blank control assays(117.1 ± 5.6 mg/L).Furthermore,the results of denaturing gradient gel electrophoresis(DGGE) and high-throughput sequencing indicated a greater variety of microbes within the microbial community in amendments with nano-sized Fe_2O_3/Fe_3O_4 than the control assays.Especially,Proteobacteria occupied a predominant status on the phylum level within the indigenous microbial communities from chromium-contaminated soils.Besides,some partial decrease of soluble Cr(VI) in abiotic nano-sized Fe_2O_3/Fe_3O_4 amendments was responsible for the adsorption of nano-sized Fe_2O_3/Fe_3O_4 to soluble Cr(VI).Hence,the presence of nano-sized Fe_2O_3/Fe_3O_4 could largely facilitate the mobilization and biotransformation of Cr(VI) from flooding soils by adsorption and bio-mediated processes.     

碳酸钙改性硅藻土处理电解锌漂洗废水实验研究

铅锌矿在我国储存量大,电解法生产锌过程中可产生含Zn~(2+)、Pb~(2+)、Cd~(2+)、As5+和Cu~(2+)等重金属离子的漂洗废水。以硅藻土精土为基体,用碳酸钙作为改性剂制备改性硅藻土,对电解锌漂洗废水进行吸附实验研究。结果表明:在反应时间为150 min,碳酸钙改性硅藻土用量为3 g/L,pH为5.46,温度为25℃条件下,对废水进行吸附实验,吸附后废水中的Cu~(2+)和As5+离子浓度低于仪器检测线(0.01 mg/L和0.09 mg/L),Pb~(2+)浓度为0.16 mg/L,吸附后废水中Cu~(2+)、As5+和Pb~(2+)离子浓度均满足GB 25466—2010《铅锌工业污染物排放标准》的排放要求。同时,采用SEM、FTIR、XRD等对碳酸钙改性硅藻土进行表征,进一步探讨了碳酸钙改性硅藻土对重金属的吸附机理。     

铁锰氧化物/坡缕石复合材料吸附磷的性能

将铁锰氧化物与坡缕石黏土结合制备了复合材料FO/P、MO/P和FMO/P,由静态吸附实验研究了复合材料吸附磷的性能,考察了氧化物与坡缕石质量比、焙烧温度、溶液p H值、离子强度和振荡时间对吸附量的影响,探讨了吸附动力学、吸附平衡和机理。结果表明,FMO/P的吸附性能优于FO/P和MO/P,铁锰氧化物与坡缕石黏土的质量比为0.1的FMO/P对20mg/L的磷溶液去除率可达95%,吸附量明显受溶液p H的影响,离子强度对吸附量影响较小,磷吸附在复合材料表面主要形成内层络合物,60 min可基本达吸附平衡,过程符合pseudo-second-order方程,具有化学吸附的性质,FMO/P吸附等温线符合Freundlich方程,有不均匀吸附的性质,饱和吸附量达49 mg/g。     

铁锰复合氧化物/壳聚糖珠:一种环境友好型除磷吸附剂

采用两步法制备了一种环境友好型除磷基吸附剂——铁锰复合氧化物/壳聚糖珠(FMCB),对其进行了表征,并对其磷吸附行为进行了系统研究.表征结果表明,该吸附剂为多孔纤维结构,比表面积为248 m~2·g~(-1),孔容为0.37 m~3·g~(-1).吸附实验结果表明,FMCB对磷的吸附容量远高于纯的壳聚糖颗粒,且Langmuir模型能更好地拟合FMCB对磷的吸附,最大吸附量为13.3 mg·g~(-1)(pH 7.0);准二级动力学模型能更好地拟合FMCB对磷吸附的动力学实验数据;溶液pH对磷的吸附影响较大,随着pH的增大,磷的吸附量逐渐降低;共存的Ca~(2+)和Mg~(2+)对磷吸附略有促进,而共存阴离子对磷吸附具有抑制作用,影响大小顺序为:SiO_3~(2-)CO_3~(2-)SO_4~(2-)≥Cl~-.吸附磷后的FMCB可用NaOH溶液进行脱附再生,并可重复使用.在进水磷初始浓度为3 mg·L~(-1)条件下,吸附达到穿透时(出水磷浓度达0.5 mg·L~(-1)),可处理约800个柱体积的模拟含磷废水.