Catalytic hydrolysis of CFC-12 over solid acid Ti(SO_4)_2

Due to increasing enthusiasm for environmental preservation, the synthesis ofchlorofluorocarbons (CFCs) alternatives and the decomposition of existing CFCs havebeen two hot topics since the production and utilization of CFCs are banned by manycountries. The former has been well carried out while the latter was rarely reported inChina. Among a dozen of decomposition approaches. catalytic hydrolysis is verypromising because of simple processes, requiring mild conditions, dioxins free and the…     

A kinetic study of ozone decomposition on illuminated oxide surfaces

The heterogeneous chemistry and photochemistry of ozone on oxide components of mineral dust aerosol, including α-Fe(2)O(3), TiO(2), and α-Al(2)O(3), at different relative humidities have been investigated using an environmental aerosol chamber. The rate and extent of ozone decomposition on these oxide surfaces are found to be a function of the nature of the surface as well as the presence of light and relative humidity. Under dark and dry conditions, only α-Fe(2)O(3) exhibits catalytic decomposition toward ozone, whereas the reactivity of TiO(2) and α-Al(2)O(3) is rapidly quenched upon ozone exposure. However, upon irradiation, TiO(2) is active toward O(3) decomposition and α-Al(2)O(3) remains inactive. In the presence of relative humidity, ozone decay on α-Fe(2)O(3) subject to irradiation or under dark conditions is found to decrease. In contrast, ozone decomposition is enhanced for irradiated TiO(2) as relative humidity initially increases but then begins to decrease at higher relative humidity levels. A kinetic model was used to obtain heterogeneous reaction rates for different homogeneous and heterogeneous reaction pathways taking place in the environmental aerosol chamber. The atmospheric implications of these results are discussed.     

Simultaneous determination of CFC-11, CFC-12 and CFC-113 in seawater samples using a purge and trap gas-chromatographic system

We have optimized the analytical parameters of a homemade instrument for the simultaneous measurement of the chlorofluorocarbons CCl₂F₂ (CFC-12), CCl₃F (CFC-11) and C₂Cl₃F₃ (CFC-113) in seawater. Seawater samples are flame sealed into 60 ml glass ampoules avoiding any contact with the atmosphere and stored in cold, dark condition until analysis. In the laboratory, after cracking the ampoule in an enclosed chamber filled with ultra-pure nitrogen, the seawater sample is transferred to a stripping chamber, where ultra-pure nitrogen is used to purge the dissolved CFCs from the seawater. The extracted gases are then cryogenically trapped, subsequently the trap is isolated and heated and the CFCs are transferred by a carrier gas stream into a precolumn and then are separated on a gaschromatographic packed column. To separate adequately CFC-12 from N₂O, during the early part of the chromatographic run, the gas stream passes through a molecular sieve, which is then isolated and backflushed. The CFCs are detected on an electron capture detector (⁶³Ni ECD). After a careful choice of the experimental conditions, the performances of the system were evaluated. The detection limits for seawater samples are: 0.0081 pmol kg⁻¹ for CFC-12, 0.0073 pmol kg⁻¹ for CFC-11 and 0.0043 pmol kg⁻¹ for CFC-113. The reproducibility of replicate samples lies within 5% for the three CFCs. The system has been successfully employed for CFC measurements in seawater samples collected in the Ross Sea (Antarctica) in the framework of the Italian Antarctic research project.     

A New Mechanism for the Formation of the Ozone Hole in the Earth Atmosphere

It is generally accepted that the Earth ozone layer is depleted by chlorine atoms produced via solar photolysis of chlorofluorocarbons (CFCs) in the upper stratosphere^[1]. This photodissociation model predicts an ozone depletion maximum at an altitude between 30 and 40 km and negligible ozone depletion below 20 km^[1]. However, the Antarctic/Arctic ozone hole appearing in each spring is observed to be located at an altitude of about 15 km^[2]. The formation of the ozone hole has been attributed to heterogeneous reactions on the surface of polar stratosphere clouds (PSCs) consisting mainly of condensed water ice:HCl+ClONO₂→Cl₂+HNO₃^[3,4]. Recently, it has been observed that dissociation of CFCs by capture of low-energy electrons is enhanced by several orders of magnitude when CFCs are adsorbed on the surfaces of ice films of polar molecules such as H₂O and NH₃^[5,6]. This enhancement is due to transfer of electrons in precursors of solvated states in polar molecular ice to CFCs that then dissociate^[7]. This effect should be most efficient in the lower stratosphere of about 15 km, where low-energy electrons can be produced by cosmic-ray ionization and localized in precursors of solvated electrons in PSCs^[8]. Strong and straightforward evidence of this new mechanism for ozone depletion has also been found in data obtained from field measurements (satellites, balloons, etc.)^[8]. In this talk, we will present the data from both field and laboratory measurements and discuss the new mechanism for the formation of the ozone hole.     

Trends of Atmospheric CCl 3 F,CCl 2 F 2 and CCl 2 FCClF 2 in Shanghai (China)

Atmospheric concentrations of CCl 3 F (CFC-11), CCl 2 F 2 (CFC-12), and CCl 2 FCClF 2 (CFC-113) in troposphere in Shanghai, China (31°1N) have been routinely monitored by using gas chromatography with electron capture detector from November 1997 to December 2000. The observation shows that there is a slowly declining trend of the three compounds. On the other hand, a comparison has been drawn between the concentrations observed and the ones calculated by 2-box model on the basis of the global statistical data of CFCs production and emission. Our observation agrees with the calculations. It shows that production and emission of chlorofluorocarbons (CFCs) in China are still at a low level and gradually decreasing.     

A Novel CFC-12 Hydrolysis Catalyst: WO3/SnO2

Thousands of studies have continuously confirmed that chlorofluorocarbons (CFCs) arekillers of the stratospheric ozone which protects life on earth against harmful ultravioletradiation from the sun'. Although many CFCs have been banned since the MontrealProtocol, there are still 2.25 million ton CFCs all over the world and numerous airconditioning systems still use them. These CFCs are leaking out of existing equipmentsand will not be degraded in nature for 50-100 years because of their c…     

室温水汽对Au/TiO2上光催化分解臭氧的影响

 采用沉积-沉淀法制备了Au/TiO2光催化剂,并用紫外-可见漫反射光谱和X射线光电子能谱对其进行了表征,详细考察了室温水汽的引入对Au/TiO2光催化分解臭氧活性的影响. 结果表明,同干燥状态时相比,室温引入水汽后催化剂活性较低,并且较快地达到了稳定值. 催化剂的O 1s和Au 4f的XPS分析结果表明,水汽的存在导致TiO2的表面结构发生变化,进而使金-载体之间的相互作用力减弱. 这是导致催化剂活性下降的主要原因.     

A method for carbon stable isotope analysis of methyl halides and chlorofluorocarbons at pptv concentrations

A pre-concentration system has been validated for use with a gas chromatography/mass spectrometry/isotope ratio mass spectrometer (GC/MS/IRMS) to determine ambient air (13)C/(12)C ratios for methyl halides (MeCl and MeBr) and chlorofluorocarbons (CFCs). The isotopic composition of specific compounds can provide useful information on their atmospheric budgets and biogeochemistry that cannot be ascertained from abundance measurements alone. Although pre-concentration systems have been previously used with a GC/MS/IRMS for atmospheric trace gas analysis, this is the first study also to report system validation tests. Validation results indicate that the pre-concentration system and subsequent separation technologies do not significantly alter the stable isotopic ratios of the target methyl halides, CFC-12 (CCl(2)F(2)) and CFC-113 (C(2)Cl(3)F(3)). Significant, but consistent, isotopic shifts of -27.5 per thousand to -25.6 per thousand do occur within the system for CFC-11 (CCl(3)F), although the shift is correctible. The method presented has the capacity to separate these target halocarbons from more than 50 other compounds in ambient air samples. Separation allows for the determination of stable carbon isotope ratios of five of these six target trace atmospheric constituents within ambient air for large volume samples (相似文献   

CoMo/TiO2-Al2O3催化剂的气相氟化改性

采用连续流动微型催化反应装置和氮气吸附等方法研究了气相预氟化和氟化铵溶液浸渍处理对CoMo/ TiO2-Al2O3噻吩加氢脱硫催化活性和物化性能的影响.通过对0.5 ％～7 ％ (φ)各种氟里昂浓度和473～773 K各种温度及不同时间氟化处理的样品进行详细考察,发现在623 K下由含氟里昂1％(φ)的湿空气氟化的载体制备的催化剂样品,其噻吩的加氢脱硫的活性有明显改善,相对于非氟化样品、BY-2工业催化剂以及氟化铵溶液浸渍处理的催化剂活性提高20％～30％,且非常稳定.初步表征还表明,氟里昂气相加氟与氟盐溶液浸渍加氟相比较,有不破坏催化剂结构和不降低催化剂比表面积的优点.     

Decomposition of Toluene in a Plasma Catalysis System with NiO, MnO2, CeO2, Fe2O3, and CuO Catalysts

The performance of NiO, MnO₂, CeO₂, Fe₂O₃, and CuO catalysts on alumina in removing toluene from a gas stream was studied in a plasma catalysis system. The NiO catalyst performed better than the other catalysts, generating more toluene-destroying oxygen species by decomposing ozone. The optimum nickel loading in the NiO/γ-Al₂O₃ catalyst was approximately 5 wt%, close to the monolayer dispersion threshold of NiO on γ-Al₂O₃. The presence of water vapor had a negative effect on catalytic performance due to its quenching of high speed electrons and its competition with toluene for adsorption sites. Water vapor also reduced the outlet ozone concentration by inhibiting the production of key intermediate in the ozone formation process.     

溴代甲烷在TiO2上的光催化降解研究

系统地研究了CH₃Br在溶胶-凝胶法制备的TiO₂催化剂上的气相光催化氧化行为,考察了催化剂煅烧温度、催化剂中残留NO-3、反应物料中的水份、反应温度等催化剂制备及反应条件对催化剂反应性能的影响,并结合XRD、BET比表面积和FTIR等表征结果对TiO₂催化剂的反应行为进行了解释.实验结果表明,CH₃Br在TiO₂上的气相光催化氧化是典型的一级反应,表观活化能为13.7kJ/mol.反应初始阶段存在显著的催化剂失活现象,催化剂高温煅烧,NO-3及水等对该反应活性都有明显的抑制作用,提高反应温度有利于改善催化剂的反应性能.     

Photocatalytic performance of Pt-loaded TiO2 in the decomposition of gaseous ozone

Gas-phase catalytic and photocatalytic decomposition of ozone (O₃) was investigated using TiO₂ and Pt-loaded TiO₂ (Pt/TiO₂) at room temperature and atmospheric pressure. The nominal weight loading of Pt was less than 1 wt.%. Results of this study indicate that both the overall conversion of O₃ to O₂ and other products with UV irradiation and without UV irradiation (dark reaction) can be improved by using Pt-loaded TiO₂. Photocatalytic conversion of O₃ on pure TiO₂ decreased with increasing water vapor. In contrast, Pt/TiO₂ was active for the decomposition of ozone under the humidity condition at room temperature.     

Y2O3纳米粒子/碳纳米管复合体的制备及其催化高氯酸铵热分解

采用化学液相沉淀法制备Y2O3纳米粒子/碳纳米管复合体(Y2O3/CNTC),利用扫描电镜(SEM)和X 射线光电子能谱(XPS)对其结构和成分进行了表征. 结果表明, Y2O3纳米粒子能负载在碳纳米管上,且负载效果较好. 采用差热分析研究了Y2O3/CNTC 对高氯酸铵热分解的催化性能, 结果表明, Y2O3 /CNTC 可显著降低高氯酸铵(AP)的高温分解峰温,表现出对AP 高温分解良好的催化性能. 相同量的Y2O3/CNTC 和纯Y2O3纳米粒子进行对比, Y2O3 /CNTC表现出更强的催化性能.当Y2O3/CNTC的质量分数为4%时,使AP的高温分解峰温提前131.14C[deg].     

A new mechanism for ozonolysis of unsaturated organics on solids: phosphocholines on NaCl as a model for sea salt particles

The ozonolysis of an approximately one monolayer film of 1-oleoyl-2-palmitoyl-sn-glycero-3-phosphocholine (OPPC) on NaCl was followed in real time using diffuse reflection infrared Fourier transform spectrometry (DRIFTS) at 23 degrees C. Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry and Auger electron spectroscopy were used to confirm the identification of the products. Ozone concentrations ranged from 1.7 x 10(12) to 7.0 x 10(13) molecules cm(-3) (70 ppb to 2.8 ppm). Upon exposure to O3, there was a loss of C[double bond, length as m-dash]C accompanied by the formation of a strong band at approximately 1110 cm(-1) due to the formation of a stable secondary ozonide (1,2,4-trioxolane, SOZ). The yield of the SOZ was smaller when the reaction was carried out in the presence of water vapor at concentrations corresponding to relative humidities between 2 and 25%. The dependencies of the rate of SOZ formation on the concentrations of ozone and water vapor are consistent with the initial formation of a primary ozonide (1,2,3-trioxolane, POZ) that can react with O3 or H2O in competition with its thermal decomposition to a Criegee intermediate and aldehyde. Estimates were obtained for the rate constants for the POZ thermal decomposition and for its reactions with O3 and H2O, as well as for the initial reaction of O3 with OPPC. The SOZ decomposed upon photolysis in the actinic region generating aldehydes, carboxylic acids and anhydrides. These studies show that the primary ozonide has a sufficiently long lifetime when formed on a solid substrate that direct reactions with O3 and H2O can compete with its thermal decomposition. In dry polluted atmospheres, ozone-alkene reactions may lead in part to the formation of stable secondary ozonides whose chemistry, photochemistry and toxicity should be taken into account in models of such regions.     

二氧化钛基固体超强酸的结构及其光催化氧化性能

采用溶胶－凝胶法制备了多孔性,大比表面积的ＳＯ４＾２－／ＴｉＯ２固体超强催化剂,运用ＸＲＤ,ＢＥＴ比表面积测定,ＸＰＳ和ＵＶ－Ｖｉｓ反射光谱等技术对该催化剂的结构,表面状态以及半导体特征进行了表征,并通过ＣＨ３Ｂｒ,Ｃ６Ｈ６和Ｃ２Ｈ４等典型有机物的气相光催化氧化反应。     

磁载WO3－TiO2／SiO2／Fe3O4复合光催化剂的制备及其光催化活性

 用溶胶－凝胶法在表面包覆了SiO2的磁基体Fe3O4上负载TiO2,从而得到了易于磁性固液分离的磁载WO3－TiO2／SiO2／Fe3O4复合光催化剂,并通过IR,XRD,SEM和XPS等测试手段对催化剂进行了表征．研究了磁载WO3－TiO2／SiO2／Fe3O4复合光催化剂对亚甲基蓝溶液脱色的性能,并考察了WO3掺杂量对样品催化活性的影响．结果表明,n（WO3）／n（TiO2）＝0．001时,磁载WO3－TiO2／SiO2／Fe3O4复合光催化剂的催化活性最高,循环使用3次时脱色率仍保持在98％．     

Physicochemical characterization of an anatase TiO2 surface and the adsorption of a nonionic surfactant: an atomic force microscopy study

Atomic force microscopy was used to characterize an anatase TiO2 surface, prepared by the helical vapor preparation method. The forces between two bare TiO2 surfaces were measured in the presence of water at various pH values. This TiO2 isoelectric point (iep) was characterized by the presence of only a van der Waals attraction and was measured at pH 5.8; this value is similar to that for a rutile TiO2 surface. The adsorption mechanism of a nonionic surfactant molecule to this anatase TiO2 surface was investigated by measuring the forces between two such TiO2 surfaces at their iep pH in the presence of linear dodecanol tetraethoxylate (C12E4), a poly(ethoxylene oxide) n-alkyl ether. C12E4 was seen by the presence of steric forces to adsorb to the uncharged TiO2 surface. For low surfactant concentrations, C12E4 adsorbed with its hydrophobic tail facing the TiO2 substrate, to reduce its entropically unfavorable contacts with water. Additional surfactant adsorption occurred at higher surfactant concentrations by the hydrophobic and hydrophilic interactions between the surfactant tails and heads, respectively, and gave sub-bilayers. A two-step adsorption isotherm was subsequently proposed with four regions: (1) submonolayer, (2) complete monolayer, (3) sub-bilayer, and (4) bilayer. The absence of a long-range repulsive force between the two TiO2 surfaces in the presence of the C12E4 surface aggregates indicated that a C12E4 nonionic surfactant aggregate did not possess charge.     

水面石油污染物的光催化降解

制备了漂浮负载型ＴｉＯ２光催化剂,并用ＸＲＤ,ＢＥＴ,ＴＥＭ和ＳＥＭ等方法进行了表征。研究了这类催化剂对水面石油污染物的光催化降解,实验结果表明,掺杂Ｆｅ＾３＋的ＴｉＯ２光催化剂具有高的光催化活性,经高压汞灯照射８ｈ,水面原油降解７５％。     

氟里昂催化分解研究进展

氟里昂分解已成为当今环保技术的热点之一,本文论述了氟里昂催化分解的必要性,优越性,介绍了氟里昂催化分解的概况和最新进展,并指出了今后的研究方向。     

Ligand-field photolysis of [Mo(CN)8]4- in aqueous hydrazine: trapped Mo(II) intermediate and catalytic disproportionation of hydrazine by cyano-ligated Mo(III,IV) complexes

The substitutional photolysis of K4[Mo(CN)8].2H2O in 98% N2H4.H2O has been investigated in detail. A molybdenum(II) intermediate, K5[Mo(CN)7].N2H4, is isolated in the primary stage of the reaction that involves the oxidation of N2H4 to N2, as evidenced by the analysis of evolving gases. The powder X-ray crystal structure of K5[Mo(CN)7].N2H4 indicates the pentagonal bipiramidal geometry of the anion and the presence of N2H4 in proximity to the CN(-) ligands. The salt is characterized by means of EDS, IR, UV-vis, and EPR spectroscopy as well as cyclic voltammetry measurements. The secondary stages of photolysis, involving the catalytic decomposition of N2H4 into NH3 and N2, lead to the formation of a molybdenum(IV) complex, [Mo(CN)4O(NH3)]2-. The monitoring of the amounts of evolving gases combined with UV-vis and EPR spectroscopic measurements at various stages of photolysis indicate that the molybdenum(III,IV) couple is catalytically active. The scheme of the catalytic decomposition of hydrazine is presented and discussed.