Photocatalysis of sprayed nitrogen-containing Fe2O3–ZnO and WO3–ZnO composite powders in gas-phase acetaldehyde decomposition

Two series of nano-sized N-containing MO_x–ZnO (M: Fe, W) composite powders were synthesized by spray pyrolysis. The nitrogen content was controlled from 500 to 2100 ppm by changing the powder ingredients and spray pyrolysis temperature. Ultraviolet-visible (UV-Vis) spectra indicated that the N-containing MO_x–ZnO powders absorbed not only ultraviolet light (λ<387 nm) like pure ZnO powder, but also part of visible light (λ<650 nm). Acetaldehyde decomposition was used as a probe reaction to evaluate the photocatalysis of these composite powders. The photocatalytic activity of the N-containing ZnO powder was pronouncedly enhanced by the WO₃ addition under both UV and visible-light irradiation. However, that of the N-containing ZnO powder was suppressed by the Fe₂O₃ addition. A model of the semiconductor energy-band structure is proposed to explain the enhancement and suppression of photocatalytic activity.     

Fluorine-doped TiO2 powders prepared by spray pyrolysis and their improved photocatalytic activity for decomposition of gas-phase acetaldehyde

F-doped TiO₂ (FTO) powders were synthesized by spray pyrolysis (SP) from an aqueous solution of H₂TiF₆. The resulting FTO powders possessed spherical particles with a rough surface morphology and a strong surface acidity. The fluorine concentrations in the FTO powders calculated from XPS spectra significantly depended on SP temperature and ranged from 2.76 to 9.40 at.%. The FTO powder prepared at SP temperature of 1173 K demonstrated the highest photocatalytic activity for the decomposition of gas-phase acetaldehyde under both ultraviolet (UV) and visible light (vis) irradiations, and it was higher than that of commercial P 25. This high photocatalytic activity was ascribed to several beneficial effects produced by F-doping: enhancement of surface acidity, creation of oxygen vacancies, and increase of active sites. It was interesting to point out that the vis photocatalytic activity of FTO powders was achieved by the creation of surface oxygen vacancies rather than the improvement of optical absorption property of bulk TiO₂ in vis region.     

Thermal decomposition of surface compounds for the generation of small quantities of acetaldehyde: Calibration of a thermal desorption-gas chromatography-flame ionization detection

The paper presents a new method for the generation of acetaldehyde in the amounts that allow to calibrate the measuring system. The method is based on thermal decomposition of surface compounds at the range 130-190 °C, in which an acetaldehyde as the decomposition product is released. The synthetic pathway leading to the desired surface compounds is described. Investigations demonstrated that the synthesis of the compounds on the surface of the support material (silica gel) was carried out homogeneously. The technique proposed was used for the generation of gaseous standard mixtures containing acetaldehyde for the calibration of a thermal desorber-gas chromatograph-flame ionization detector system.     

Acetaldehyde adsorption and catalytic decomposition on Pd(1 1 0) and the dissolution of carbon

The reaction of acetaldehyde with the Pd(1 1 0) surface has been studied using a molecular beam reactor, TPD and LEED. Below 270 K acetaldehyde sticks to the surface with a high initial probability (∼0.8), but no gas phase products evolve. When the reaction is run at >270 K, hydrogen evolves into the gas phase early in the reaction together with methane in a non-steady-state fashion, but above 300 K there is a very efficient steady-state catalytic reaction at the surface; this reaction is the decarbonylation of acetaldehyde to produce methane and carbon monoxide in the gas phase. This behaviour continues up to about 400 K. However, when acetaldehyde is dosed at 423 K, the reaction rate slowly evolves through a maximum to a very low catalytic rate. Upon carrying out reactor experiments at 473 K and above, the reaction mechanism changes to total dehydrogenation, and CO and H₂ are produced at high steady-state rate, not withstanding the fact that carbon is continually being deposited onto the surface. This carbon does not appear to affect the reaction, which takes place on a surface with a c(2 × 2)-C layer present, since the extra carbon is lost from the reaction zone by diffusion into the bulk of the crystal.     

AlOOH结构对甲醇和一氧化碳反应性能的影响

利用水热法制备了3种AlOOH催化剂,对其进行了表征,并用于催化甲醇和一氧化碳反应.结果表明,适宜的AlOOH结构有利于催化甲醇和一氧化碳反应生成高选择性(≥97.28%)的乙醛,且AlOOH结构的差异会导致反应产物分布出现明显区别.其中,结晶度高、孔径较大、能提供CO解离吸附中心且表面具有适宜酸碱性的AlOOH催化剂表现出高的乙醛选择性,推测乙醛的生成是通过中间体CH_3与HCO的偶联实现的.     

TiO_2/Mn-ZSM-5复合催化剂的光催化-臭氧耦合降解乙醛

采用离子交换法制备了Mn-ZSM-5系列催化剂,并利用浸渍法制备了TiO2/Mn-ZSM-5系列复合催化剂.通过Uv-Vis、BET、X射线衍射等手段对催化剂进行了表征,考察了臭氧存在下乙醛的降解性能.结果表明:臭氧能显著促进乙醛的光催化降解,在所制备的催化剂中TiO2/Mn-ZSM-5(1:2)对乙醛降解具有最好的活性,这归功于这种复合催化剂对臭氧和乙醛的吸附和催化协同效应.     

醛类分子的拉曼光谱研究

应用便携式拉曼光谱仪,采集了四种醛类分子(GnH2nO,n=1,2,3,4)的拉曼光谱,并通过量子化学中密度泛函理论(DFT)对四种醛类分子进行了分子模型构建和理论拉曼光谱模拟计算.通过实验拉曼光谱和DFT模拟计算结果的对比,对四种醛类分子的特征振动峰进行了指认.同时对四种醛类分子的实验光谱进行了分析比较.应用便携式拉...     

纸质包装材料中甲醛、乙醛向食品模拟物改性聚苯醚的迁移行为

为了解纸质包装材料中甲醛、乙醛向食品模拟物改性聚苯醚( Tenax)中的迁移行为,建立了一步提取衍生化、超高效液相色谱测定纸质包装材料和Tenax中的甲醛和乙醛的方法。本方法在甲醛和乙醛的测定范围内,线性相关系数R2>0.9999,甲醛检出限为0.03 mg/m2,乙醛检出限为0.04 mg/m2,测定纸样和Tenax的加标回收率为90.1%~108.6%。采用本方法研究不同温度和时间下两种纸质包装材料中甲醛、乙醛向Tenax中的迁移规律。研究表明,甲醛、乙醛迁移行为随时间变化趋势大致相同,均呈现迁移率随迁移时间延长先迅速增大,后又减小达到一个常数;甲醛和乙醛迁移率受温度的影响不同,达到平衡后,甲醛在30℃下迁移率最高,乙醛在70℃和50℃下迁移率高;甲醛和乙醛向Tenax中的迁移率差异较大,达到平衡后,乙醛的迁移率远高于甲醛。     

气相色谱-质谱法测定聚对苯二甲酸乙二醇酯瓶装水中乙醛的迁移量

提出了测定聚对苯二甲酸乙二醇酯(PEGTP)瓶装纯水中乙醛迁移量的气相色谱质谱法。水样(100mL)中乙醛用2,4-二硝基苯肼在pH 3柠檬酸盐缓冲溶液10mL中,于40℃水浴上振荡1h加热使之衍生化。冷却后用二氯甲烷萃取3次,每次10mL。萃取液于40℃旋转蒸发至1.0mL,分取1分L进样分析。采用DB-5MS毛细管柱及在70℃～280℃范围内程序升温进行分离。线性范围在300μg·L~(-1)以内,检出限(3S/N)为1μg·L~(-1),加入50μg·L~(-1)及100μg·L~(-1)标准溶液做回收试验及精密度试验,测得平均回收率为88%,相对标准偏差(n=5)依次为5.4%及4.5%。     

Quantification of oxygenated volatile organic compounds in seawater by membrane inlet-proton transfer reaction/mass spectrometry

The role of the ocean in the cycling of oxygenated volatile organic compounds (OVOCs) remains largely unanswered due to a paucity of datasets. We describe the method development of a membrane inlet-proton transfer reaction/mass spectrometer (MI-PTR/MS) as an efficient method of analysing methanol, acetaldehyde and acetone in seawater. Validation of the technique with water standards shows that the optimised responses are linear and reproducible. Limits of detection are 27 nM for methanol, 0.7 nM for acetaldehyde and 0.3 nM for acetone. Acetone and acetaldehyde concentrations generated by MI-PTR/MS are compared to a second, independent method based on purge and trap-gas chromatography/flame ionisation detection (P&T-GC/FID) and show excellent agreement. Chromatographic separation of isomeric species acetone and propanal permits correction to mass 59 signal generated by the PTR/MS and overcomes a known uncertainty in reporting acetone concentrations via mass spectrometry. A third bioassay technique using radiolabelled acetone further supported the result generated by this method. We present the development and optimisation of the MI-PTR/MS technique as a reliable and convenient tool for analysing seawater samples for these trace gases. We compare this method with other analytical techniques and discuss its potential use in improving the current understanding of the cycling of oceanic OVOCs.