Tricrystalline TiO2 with enhanced photocatalytic activity and durability for removing volatile organic compounds from indoor air

It is important to develop efficient and economic techniques for removing volatile organic compounds(VOCs) in indoor air. Heterogeneous Ti O_2-based semiconductors are a promising technology for achieving this goal. Anatase/brookite/rutile tricrystalline Ti O_2 with mesoporous structure was synthesized by a low-temperature hydrothermal route in the presence of HNO_3.The obtained samples were characterized by X-ray diffraction and N_2 adsorption–desorption isotherm. The photocatalytic activity was evaluated by photocatalytic decomposition of toluene in air under UV light illumination. The results show that tricrystalline Ti O_2 exhibited higher photocatalytic activity and durability toward gaseous toluene than bicrystalline Ti O_2,due to the synergistic effects of high surface area, uniform mesoporous structure and junctions among mixed phases. The tricrystalline Ti O_2 prepared at R HNO_3= 0.8, containing80.7% anatase, 15.6% brookite and 3.7% rutile, exhibited the highest photocatalytic activity,about 3.85-fold higher than that of P25. The high activity did not significantly degrade even after five reuse cycles. In conclusion, it is expected that our study regarding gas-phase degradation of toluene over tricrystalline Ti O_2 will enrich the chemistry of the Ti O_2-based materials as photocatalysts for environmental remediation and stimulate further research interest on this intriguing topic.     

氧化锰八面体分子筛的合成及其对苯催化氧化性能

采用回流的方法,制备了氧化锰八面体分子筛（OMS-2）纳米棒.利用X射线衍射（XRD）、扫描电子显微镜（SEM）、氮气吸附-脱附、程序升温还原（H2-TPR）分别对产物进行晶型、形貌、孔径和H2还原性能进行分析,并考察不同煅烧温度下的催化剂对苯的催化氧化性能及300℃煅烧催化剂的稳定性.结果表明,煅烧温度对氧化锰八面体分子筛（OMS-2）的表面特征有显著的影响,煅烧温度越高,比表面积和孔容越小,平均孔径越大.同时随着煅烧温度的增加,催化剂对苯的催化氧化性能降低.经300℃煅烧的催化剂对苯的催化活性最佳,反应温度为200℃时,苯的转化率达到了50%;当反应温度为250℃时,苯的转化率达到90%.经300℃煅烧的催化剂在260℃下70 h内,对苯的催化氧化性能降低了5%,具有良好的稳定性.     

民用生物质燃烧挥发性有机化合物排放特征

民用生物质燃烧是我国人为源挥发性有机物（VOCs）排放的主要来源.采用罐采样-GC/MS和DNPH衍生-HPLC这2种方法联用采集和分析了5种主要民用生物质燃烧排放烟气中的VOCs组分,并利用碳平衡法确定其排放系数.研究表明,秸秆和木柴等民用生物质燃烧总的VOCs排放系数分别为（4.37±2.23）g·kg-1和（2.12±0.77）g·kg-1,秸秆燃烧排放高于木柴燃烧排放;民用生物质燃烧排放VOCs中,最为丰富的物种为芳香烃和醛类,含量均在25%以上;秸秆和木柴燃烧除卤代烃和腈类含量差异较大外,其余物种分布比较类似;秸秆和木柴燃烧VOCs排放总的臭氧生成潜势分别为（16.9±8.2）g·kg-1和（10.8±4.9）g·kg-1;臭氧生成潜势比较高的物种依次为：醛类、芳香烃和烯烃/炔烃,其中醛类贡献基本在50%以上.     

室内空气中挥发性有机化合物及多孔炭材料在其脱除中的应用

随着工业化进程的不断推进,室内空气中的挥发性有机化合物（ＶＯＣ） 对室内环境的污染日渐严重,对人体的健康也造成了危害。本文对此作了介绍,并综述了国内外室内空气污染物的监测、采样、分析手段及治理方法,着重叙述了多孔炭材料在环保中的应用开发。     

The Emissions of Major Aromatic Voc as Landfill Gas from Urban Landfill Sites in Korea

In this study, concentrations of major aromatic VOCs were determined from landfill gas (LFG) at a total of five municipal landfill sites in Korea including Nan Ji (NJ), Woon Jung (WJ), Sam Poong (SP), Hoei Chun (HC), and No Hyung (NH). The concentration levels of those VOC were found to be significantly different, mainly as a function of such a parameter as landfill aging. The VOC concentrations measured from the unclosed landfill sites (e.g., WJ) were characterized by exceedingly high values above a few tens of ppm. However, the results of the abandoned site (e.g., SP) were about three orders of magnitude lower than the others so as to merely exceed the typical ambient concentration levels. It was most striking to find a systematic dominance of toluene over other aromatic VOC under most circumstances. The LFG flux values of all aromatic VOC and the four specific major ones (termed as BTEX: benzene, toluene, ethylbenzene, and xylene) were also computed for each vent pipe from all study sites using their concentrations and the concurrently determined environmental parameters. The results, if calculated in terms of the average BTEX quantity emitted per vent pipe, showed that the magnitude of their emissions can vary substantially, with the values ranging from 0.05 (SP) to 49.2 kg yr⁻¹ (WJ in wintertime). The LFG flux values of aromatic VOC, when compared to the contribution of non-methane hydrocarbons (NMHC), were able to explain a constant, but minor, proportion of the LFG carbon budget.     

Study of the VOC emissions from a municipal solid waste storage pilot-scale cell: comparison with biogases from municipal waste landfill site

The emission of volatile organic compounds (VOCs) from municipal solid waste stored in a pilot-scale cell containing 6.4 tonnes of waste (storage facility which is left open during the first period (40 days) and then closed with recirculation of leachates during a second period (100 days)) was followed by dynamic sampling on activated carbon and analysed by GC–MS after solvent extraction. This was done in order to know the VOC emissions before the installation of a methanogenesis process for the entire waste mass. The results, expressed in reference to toluene, were exploited during the whole study on all the analyzable VOCs: alcohols, ketones and esters, alkanes, benzenic and cyclic compounds, chlorinated compounds, terpene, and organic sulphides.The results of this study on the pilot-scale cell are then compared with those concerning three biogases from a municipal waste landfill: biogas (1) coming from waste cells being filled or recently closed, biogas (2) from all the waste storage cells on site, and biogas (3) which is a residual gas from old storage cells without aspiration of the gas. The analysis of the results obtained revealed: (i) a high emission of VOCs, principally alcohols, ketones and esters during the acidogenesis; (ii) a decrease in the alkane content and an increase in the terpene content were observed in the VOCs emitted during the production of methane; (iii) the production of heavier alkanes and an increase in the average number of carbon atoms per molecule of alkane with the progression of the stabilisation/maturation process were also observed.Previous studies have concentrated almost on the analysis of biogases from landfills. Our research aimed at gaining a more complete understanding of the decomposition/degradation of municipal solid waste by measuring the VOCs emitted from the very start of the landfill process i.e. during the acidogenesis and acetogenesis phases.     

Investigation of volatile organic compounds and phthalates present in the cabin air of used private cars

The presence of selected volatile organic compounds (VOCs) including aromatic, aliphatic compounds and low molecular weight carbonyls, and a target set of phthalates were investigated in the interior of 23 used private cars during the summer and winter. VOC concentrations often exceeded levels typically found in residential indoor air, e.g. benzene concentrations reached values of up to 149.1 µg m^− 3. Overall concentrations were 40% higher in summer, with temperatures inside the cars reaching up to 70 °C. The most frequently detected phthalates were di-n-butyl-phthalate and bis-(2-ethylhexyl) phthalate in concentrations ranging from 196 to 3656 ng m^− 3.     

Effect of void structure of photocatalyst paper on VOC decomposition

TiO₂ powder-containing paper composites, called TiO₂ paper, were prepared by a papermaking technique, and their photocatalytic efficiency was investigated. The TiO₂ paper has a porous structure originating from the layered pulp fiber network, with TiO₂ powders scattered on the fiber matrix. Under UV irradiation, the TiO₂ paper decomposed gaseous acetaldehyde more effectively than powdery TiO₂ and a pulp/TiO₂ mixture not in paper form. Scanning electron microscopy and mercury intrusion analysis revealed that the TiO₂ paper had characteristic unique voids ca. 10 μm in diameter, which might have contributed to the improved photocatalytic performance. TiO₂ paper composites having different void structures were prepared by using beaten pulp fibers with different degrees of freeness and/or ceramic fibers. The photodecomposition efficiency was affected by the void structure of the photocatalyst paper, and the initial degradation rate of acetaldehyde increased with an increase in the total pore volume of TiO₂ paper. The paper voids presumably provided suitable conditions for TiO₂ catalysis, resulting in higher photocatalytic performance by TiO₂ paper than by TiO₂ powder and a pulp/TiO₂ mixture not in paper form.     

Inter-comparisons of VOC oxidation mechanisms based on box model: A focus on OH reactivity

Volatile organic compounds (VOCs) oxidation processes play a very important role in atmospheric chemistry, and the chemical reactions are expressed in various manners in chemical mechanisms. To gain an improved understanding of VOCs evolution during oxidation processes and evaluate the discrepancies of VOCs oxidation schemes among different mechanisms, we used the total VOC reactivity as a diagnostic and evaluated tool to explore the differences for six widely used chemical mechanisms. We compared the total VOC reactivity evolution under high-NO_x conditions for several sets of precursors, including n-pentane, toluene, ethene, isoprene and a mixture of 57 Photochemical Assessment Monitoring Stations (PAMS) species in a 0-D photochemical box model. Inter-comparison of total VOC reactivity of individual precursor simulations showed discrepancies to different extent of the oxidation schemes among the studied mechanisms, which are mainly attributed to the different lumping approaches for organic species. The PAMS simulation showed smaller discrepancy than individual precursor cases in terms of total VOC reactivity. SAPRC07 and RACM2 performances are found to better match the MCM for simulation of total VOC reactivity. Evidences suggest that the performance in simulating secondary organic products, OH concentrations and NO_x concentrations are related to the OH reactivity discrepancies among various chemical mechanisms. Information in this study can be used in selection of chemical mechanisms to better model OH reactivity in different environments. The results in this study also provide directions to further improve the ability in modelling total VOC reactivity with the chemical mechanisms.     

Chemical characterization of emissions from a municipal solid waste treatment plant

Gaseous emissions are an important problem in municipal solid waste (MSW) treatment plants. The sources points of emissions considered in the present work are: fresh compost, mature compost, landfill leaks and leachate ponds. Hydrogen sulphide, ammonia and volatile organic compounds (VOCs) were analysed in the emissions from these sources. Hydrogen sulphide and ammonia were important contributors to the total emission volume. Landfill leaks are significant source points of emissions of H₂S; the average concentration of H₂S in biogas from the landfill leaks is around 1700 ppmv. The fresh composting site was also an important contributor of H₂S to the total emission volume; its concentration varied between 3.2 and 1.7 ppmv and a decrease with time was observed. The mature composting site showed a reduction of H₂S concentration (<0.1 ppmv). Leachate pond showed a low concentration of H₂S (in order of ppbv). Regarding NH₃, composting sites and landfill leaks are notable source points of emissions (composting sites varied around 30–600 ppmv; biogas from landfill leaks varied from 160 to 640 ppmv).Regarding VOCs, the main compounds were: limonene, p-cymene, pinene, cyclohexane, reaching concentrations around 0.2–4.3 ppmv.H₂S/NH₃, limonene/p-cymene, limonene/cyclohexane ratios can be useful for analysing and identifying the emission sources.