Experimental and theoretical studies on NO selective catalytic oxidation over α-MnO2

Based on the experimental and theoretical methods, the NO selective catalytic oxidation process was proposed. The experimental results indicated that lattice oxygen was the active site for NO oxide over the $\mathrm{\alpha }$-MnO₂(110) surface. In the theoretical study, DFT (density functional theory) and periodic slab modeling were performed on an $\mathrm{\alpha }$-MnO₂(110) surface, and two possible NO oxidation mechanisms over the surface were proposed. The non-defect $\mathrm{\alpha }$-MnO₂(110) surface showed the highest stability, and the surface O_s (the second layer oxygen atoms) position was the most active and stable site. O₂ molecule enhanced the joint adsorption process of two NO molecules. The reaction process, including O₂ dissociation and O=N-O-O-N=O formation, was calculated to carry out the NO catalytic oxidation mechanism over $\mathrm{\alpha }$-MnO₂(110). The results showed that NO oxidation over the $\mathrm{\alpha }$-MnO₂(110) surface exhibited the greatest possibility following the route of O=N-O-O-N=O formation. Meanwhile, the formation of O=N-O-O-N=O was the rate-determining step.     

利用粉煤灰制备高纯超细氧化铝粉体的研究

利用粉煤灰为原料制备高纯超细氧化铝粉体。给出了采用硅酸二钙晶相转变自粉化、高效分散剂———碳化法从粉煤灰中制备氧化铝方法的工艺路线 ,确定了从粉煤灰制备高纯超细氧化铝粉体的最佳工艺条件 ,为粉煤灰的高价值利用开辟了一条新途径     

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。     

锰砂表面改性去除酚类化合物的研究

本文叙述了锰砂表面改性(以下简称旧锰砂)处理含酚饮用水的实验研究,陈酚率可达99％。本实验对除酚因素(温度、pH值、流速和接触时间等)进行了实验研究。当进水酚浓度≤2.0mg/l时,经旧锰砂的吸附,可使酚浓度≤0.002mg/l。     

Catalytic oxidation effect of MnSO4 on As(III) by air in alkaline solution

The catalytic oxidation effect of MnSO₄ on As(III) by air in an alkaline solution was investigated. According to the X-ray diffraction (XRD), scanning electron microscope-energy dispersive spectrometer (SEM-EDS) and X-ray photoelectron spectroscopy (XPS) analysis results of the product, it was shown that the introduction of MnSO₄ in the form of solution would generate Na_0.55Mn₂O₄·1.5H₂O with strong catalytic oxidation ability in the aerobic alkaline solution, whereas the catalytic effect of the other product MnOOH is not satisfactory. Under the optimal reaction conditions of temperature 90°C, As/Mn molar ratio 12.74:1, air flow rate 1.0 L/min, and stirring speed 300 r/min, As(III) can be completely oxidized after 2 hr reaction. The excellent catalytic oxidation ability of MnSO₄ on As(III) was mainly attributed to the indirect oxidation of As(III) by the product Na_0.55Mn₂O₄·1.5H₂O. This study shows a convenient and efficient process for the oxidation of As(III) in alkali solutions, which has potential application value for the pre-oxidation of arsenic-containing solution or the detoxification of As(III).     

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)％。     

长期暴露下纳米TiO2对厌氧颗粒污泥体系稳定性的影响

以厌氧颗粒污泥为研究对象,通过静态试验和连续流厌氧反应器,重点研究了长期暴露下纳米TiO_2在对厌氧产甲烷体系的影响及其在颗粒污泥中的归趋.结果表明,短期急性暴露于150 mg·g-1(以VSS计)的纳米TiO_2尽管会暂时减缓产甲烷速率,但产酸阶段及产甲烷阶段代谢产物总量不会明显受到影响,纳米TiO_2对厌氧颗粒污泥具有较低的急性毒性.反应器运行结果表明,纳米TiO_2的长期暴露可导致挥发性脂肪酸(VFAs)积累及生物气产量降低,产酸菌比产甲烷菌对纳米TiO_2的累积效应更加敏感,纳米TiO_2抑制机制可归因于"物理遮蔽"作用.出水中TiO_2的平均含量只有0.632 mg·L~(-1),绝大多数纳米TiO_2都被截留在了反应器中.FISH检测表明,厌氧颗粒污泥微生物的菌群结构有所变化,纳米TiO_2在反应器内的积累使得甲烷八叠球菌的丰度大幅增加了115.6%,其优势地位明显增强.长短期暴露试验的结果对比也说明,用短期暴露试验来说明纳米颗粒对厌氧体系的长期累积效应具有一定局限性,纳米TiO_2对厌氧颗粒污泥中微生物的负面影响需要较长时间的积累才会显现.本研究结果可为厌氧污水处理体系中纳米颗粒的潜在生态风险评价提供理论支持和参考依据.     

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.