银、钕掺杂TiO_2催化光解甲基橙的实验研究

实验用水热合成法制备出银、钕掺杂TiO2催化剂粉体,然后以高压汞灯为光源,掺杂TiO2催化剂粉体为光化降解催化剂,探究对甲基橙模拟印染废水光催化分解的效果。光解实验研究采用正交设计法,以模拟废水浓度、催化剂用量、光照时间以及pH为因素,各因素选取4个水平,对催化光解甲基橙染料的降解率进行评价。分析结果表明:银、钕掺杂TiO2催化剂对甲基橙光化降解有良好的效果,最佳实验条件为:溶液pH为5,甲基橙的初始质量浓度为2 mg/L,催化剂投加量60 mg/L和光照时间80 min。在最佳条件下,连续光照8 h后甲基橙的降解率达到92%以上。     

Na_2CO_3对回填材料膨润土的改型效果分析

以新疆柯尔碱膨润土为原料,加入不同比例的Na2CO3改型剂,研究改型剂添加对膨润土胶质价、膨胀容和pH值的影响。另外,考虑到压实膨润土的非饱和渗透特性对于评价缓冲回填材料性能具有重要意义,故采用压力膜仪测量压实Na2CO3改型膨润土和原土的土水特征曲线,分析研究二者基质吸力随体积含水率变化的相关关系。实验结果显示,添加Na2CO3改型剂可以增大膨润土的胶质价、膨胀容和pH值,成功地将膨润土中的钙蒙脱石转化为钠蒙脱石,其对柯尔碱膨润土pH值的作用效果满足地质处置库对缓冲回填材料的要求;改型后膨润土的持水能力明显大于原土。     

Soil warming effect on net ecosystem exchange of carbon dioxide during the transition from winter carbon source to spring carbon sink in a temperate urban lawn

The significant warming in urban environment caused by the combined effects of global warming and heat island has stimulated widely development of urban vegetations. However, it is less known of the climate feedback of urban lawn in warmed environment. Soil warming effect on net ecosystem exchange (NEE) of carbon dioxide during the transition period from winter to spring was investigated in a temperate urban lawn in Beijing, China. The NEE (negative for uptake) under soil warming treatment (temperature was about 5℃ higher than the ambient treatment as a control) was -0.71 μmol/(m².sec), the ecosytem was a CO₂ sink under soil warming treatment, the lawn ecosystem under the control was a CO₂ source (0.13 μmol/(m².sec)), indicating that the lawn ecosystem would provide a negative feedback to global warming. There was no significant effect of soil warming on nocturnal NEE (i.e., ecosystem respiration), although the soil temperature sensitivity (Q₁₀) of ecosystem respiration under soil warming treatment was 3.86, much lower than that in the control (7.03). The CO₂ uptake was significantly increased by soil warming treatment that was attributed to about 100% increase of α (apparent quantum yield) and A_max (maximum rate of photosynthesis). Our results indicated that the response of photosynthesis in urban lawn is much more sensitive to global warming than respiration in the transition period.     

Preparation, characterization and application of CuCrO2/ZnO photocatalysts for the reduction of Cr(VI)

The delafossite CuCrO₂ elaborated by sol-gel from 40 nm diameter colloid is optically active in the visible region. It is characterized physically and photoelectrochemically. The microstructure is fairly homogenous with a mean crystallite size of ca. 2 μm. The optical gap (1.30 eV), determined from the diffuse reflectance, is well suited to the sunlight spectrum. The Mott Schottky plot is characteristic of P-type conductivity with a flat band potential of -0.26 V_SCE. As application, the photoreduction of chromate is successfully achieved in air-equilibrated suspension CuCrO₂/ZnO (1/1). CuCrO₂ is photoactivated by visible light and the electrons in the conduction band (-1.34 V_SCE) are injected to ZnO. In the presence of salicylic acid, a conversion of Cr(VI) to Cr(III) of 57% is obtained under optimal conditions (pH 3 at 25℃, 5×10^-4 mol/L) because of the HCrO₄^- dark adsorption onto ZnO (4HCrO₄^- + 3C₇H₆O₃ + 18O₂ + 16H⁺ → 4Cr³⁺ + 21CO₂ + 19H₂O, ΔG⁰ = -557 kcal/mol). Prolonged illumination is accompanied by a deceleration in the photoactivity owing to the competitive water reduction, an issue of energetic concern. The hetero-system exhibits self sensitization for hydrogen production with an evolution rate of 149 μmol/(hr·g).     

Transverse approach between real world concentrations of SO2, NO2, BTEX, aldehyde emissions and corrosion in the Grand Mare tunnel

With regard to automotive traffic, a tunnel-type semi enclosed atmosphere is characterized by a higher concentration of gaseous pollutants than on urban traffic roads and highlights the gaseous effluent species having an impact on material degradation. Therefore, a transverse approach between air quality and its consequences upon the longevity of materials is necessary, implying better knowledge of tunnel atmosphere and a better understanding of material degradation inside a tunnel for operating administration. Gaseous pollutant measurements carried out in a road tunnel in Rouen (Normandy) give the real world traffic concentrations of experimental exposure conditions. The sampling campaigns, achieved in summer and winter include SO₂, NO₂, BTEX and aldehyde analyses. Effluent profiles in the upward and downward tubes have been established. The current work shows that SO₂, NO₂, formaldehyde, acetaldehyde, propanal and butanal must be considered in the degradation process of materials in a stuffy environment. As regards NO₂, its concentration depends on the modification of the automotive fleet. The total aldehyde concentrations indicate no particular trend between the two bores. Formaldehyde, acetaldehyde, propanal, butanal and acrolein species are the most abundant species emitted by vehicles and represent 90% to 95% of the total aldehyde emissions.     

Characterizing the optimal operation of photocatalytic degradation of BDE-209 by nano-sized TiO2

Brominated flame retardants have been widely used in industry. There is a rapid growing public concern for their availabilities in the environment. Advanced oxidation process (AOP) is a promising and efficient technology which may be used to remove emerging chemicals such as brominated flame retardants. This project aims at investigating optimal operational conditions for the removal of BDE-209 using nano-scaled titanium(IV) oxide. The residual PBDE congeners after photocatalytical degradation of BDE-209 by TiO₂ were analysed by gas chromatography-mass spectrometry (GC-MS). It was found that the degradability of BDE-209 by TiO₂ was attributed to its photocatalytic activity but not the small size of the particles. The half-life of removing BDE-209 by TiO₂ was 3.05 days under visible light. Tetra- and penta-BDEs were the major degraded products of BDE-209. Optimum conditions for photocatalytical degradation of BDE-209 was found to be at pH 12 (93% ± 1%), 5, 10, 20 mg/L (93.0% ± 1.70%, 91.6% ± 3.21%, 91.9% ± 0.952%, respectively), respectively of humic acid and in the form of anatase/rutile TiO₂ (82% ± 3%). Hence, the efficiency of removing BDE-209 can be maximized while being cost effective at the said operating conditions.     

Effects of WOx modification on the activity, adsorption and redox properties of CeO2 catalyst for NOx reduction with ammonia

A series of WO₃/CeO₂ (WOx/CeO₂) catalysts were synthesized by wet impregnation of ammonium metatungstate on a CeO₂ support. The resulting solid acid catalysts were characterized by X-ray diffraction (XRD), UV-Vis spectroscopy (UV-Vis), Raman spectroscopy (Raman), in-situ Fourier transform infrared spectroscopy (in-situ FT-IR) of ammonia adsorption, NH₃-TPD, H₂ temperature-programmed reduction (H₂-TPR), NH₃/NO oxidation and activity measurements for NOx reduction by NH₃ (NH₃-SCR). The results show that polytungstate (WOx) species are the main species of tungsten oxide on the surface of ceria. The addition of tungsten oxide enhances the Brönsted acidity of ceria catalysts remarkably and decreases the amount of surface oxygen on ceria, with strong interaction between CeO₂ and WOx. As a result, the N₂ selectivity of NH₃ oxidation and NH₃-SCR at high temperatures (> 300℃) is enhanced. Therefore, a wide working temperature window in which NOx conversion exceeds 80% (NOx conversion > 80%) from 200 to 450℃, is achieved over 10 wt.% WOx/CeO₂ catalyst. A tentative model of the NH₃-SCR reaction route on WOx/CeO₂ catalysts is presented.     

Effect of CeO2 and Al2O3 on the activity of Pd/Co_3O_4/cordierite catalyst in the three-way catalysis reactions (CO/NO/CnHm)

The present article studies the effect of CeO₂ and Al₂O₃ on the activity of Pd/Co₃O₄/cordierite catalyst in conversion of NO, CO, C_nH_m. The catalysts were characterized by temperature programmed reduction with hydrogen, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. It is shown that the effect of CeO₂ on the properties of Pd/Co₃O₄/cordierite catalyst depends on preparation method. The catalyst obtained by co-deposition of cerium and cobalt oxides has higher activity in CO oxidation (CO + O₂ and CO + NO) and total hexane oxidation (C₆H₁₄ + O₂). Such phenomenon is probably caused by more than stoichiometric amount of formed oxygen vacancies, an increase in both mobility of surface oxygen and dispersity of components in the catalytic composition. It is demonstrated that CeO₂ addition promotes the SO₂ resistance of Pd/Co₃O₄/cordierite. The second support decreases the activity of Pd/Co₃O₄/cordierite catalyst in the reactions of CO and C₆H₁₄ with oxygen because of CoAl₂O₄ formation.     

Aminobenzenesulfonamide functionalized SBA-15 nanoporous molecular sieve: A new and promising adsorbent for preconcentration of lead and copper ions

A rapid method for the extraction and monitoring of nanogram level of Pb²⁺ and Cu²⁺ ions using uniform silanized mesopor (SBA-15) functionalized with aminobenzenesulfonamide groups and flame atomic absorption spectrometry (FAAS) is presented. Aminobenzenesulfonamide functionalized SBA-15 was synthesized according to procedure in the literature and the presence of organic groups in the silica framework was demonstrated by FT-IR spectra. The functionalized product showed the BET surface area 110 m²/g and pore diameter 5.1 nm, based on adsorption-desorption of N₂ at 77 K. The effect of several variables such as (amount of adsorbent, stirring time, pH and presence of other ions in the medium) has been studied. Lead and copper were completely extracted at pH greater than 3 after stirring for 10 min. The maximum capacity of the adsorbent was found to be 191.3 ± 1.4 and 155.0 ± 1.0 μg of lead and copper ions/mg functionalized SBA-15, respectively. The preconcentration factor of the method was found to be 200. The detection limit of the technique was 3.4 and 0.4 ng/mL for Pb²⁺ and Cu²⁺, respectively. The applications of this methodology for real samples were examined by various water type, black tea and pepper samples.     

Measurement of air exchange rates in different indoor environments using continuous CO2 sensors

A new air exchange rate (AER) monitoring method using continuous CO₂ sensors was developed and validated through both laboratory experiments and field studies. Controlled laboratory simulation tests were conducted in a 1-m³ environmental chamber at different AERs (0.1-10.0 hr^-1). AERs were determined using the decay method based on box model assumptions. Field tests were conducted in classrooms, dormitories, meeting rooms and apartments during 2-5 weekdays using CO₂ sensors coupled with data loggers. Indoor temperature, relative humidity (RH), and CO₂ concentrations were continuously monitored while outdoor parameters combined with on-site climate conditions were recorded. Statistical results indicated that good laboratory performance was achieved: duplicate precision was within 10%, and the measured AERs were 90%-120% of the real AERs. Average AERs were 1.22, 1.37, 1.10, 1.91 and 0.73 hr^-1 in dormitories, air-conditioned classrooms, classrooms with an air circulation cooling system, reading rooms, and meeting rooms, respectively. In an elderly particulate matter exposure study, all the homes had AER values ranging from 0.29 to 3.46 hr??1 in fall, and 0.12 to 1.39 hr^-1 in winter with a median AER of 1.15.