Synthesis and application of Cu-BTC@ZSM-5 composites as effective adsorbents for removal of toluene gas under moist ambience: kinetics,thermodynamics, and mechanism studies

Metal organic frameworks (MOFs) are excellent adsorbents that provide abundant specific surface area, adjustable pore structure, and rich active sites. The purpose of this study was to prepare composites with hydrophobic and high microporous specific surface area and to adsorb toluene gas in moist ambience. An ethanol activation-assisted hydrothermal method was proposed to synthesize copper-benzene-1,3,5-tricarboxylic acid (Cu-BTC) metal-organic framework, Cu-BTC, and ZSM-5 molecular sieve composites (Cu-BTC@ZSM-5). The dynamic adsorption process of toluene on different adsorbents was investigated, and the results showed that the toluene adsorption capacity of Cu-BTC@ZSM-5 (158.6 mg/g) was 2.53 times higher than Cu-BTC (62.7 mg/g), when the ZSM-5 content is 5% and the humidity is 30%RH. Compared with other factors, the humidity inhibited the adsorption of toluene on Cu-BTC@ZSM-5. Langmuir model and the pseudo-second kinetics model can better describe the adsorption behavior of Cu-BTC@ZSM-5. The thermodynamic results showed the adsorption process was a spontaneous exothermic process at low temperature and mainly physical adsorption. The relative regenerability can still up to 80.4% after six cycles. The adsorption mechanisms of Cu-BTC@ZSM-5 were pore-filling adsorption, π-π interaction, cation-π bonding, and hydrophobic interactions. This study will help to design a systematic route to evaluate the adsorption performance of Cu-BTC@ZSM-5 for toluene.

     

Enhanced photocatalytic removal of amoxicillin with Ag/TiO2/mesoporous g-C3N4 under visible light: property and mechanistic studies

In present study, an efficient ternary Ag/TiO₂/mesoporous g-C₃N₄ (M-g-C₃N₄) photocatalyst was successfully synthesized through depositing Ag nanoparticles (NPs) on the surface of TiO₂/M-g-C₃N₄ heterojunction. Ag/TiO₂/M-g-C₃N₄ nanocomposite displayed the highest degradation efficiency for amoxicillin (AMX) compared to TiO₂/M-g-C₃N₄ heterojunction, M-g-C₃N₄, and bulk-g-C₃N₄ (B-g-C₃N₄). The removal efficiency of AMX in real situation, surface water (SW), hospital wastewater (HW), and waste water treatment plant (WWTP) also were studied to illustrate the effectiveness of Ag/TiO₂/M-g-C₃N₄ photocatalysts. The vulnerable atoms in AMX structure were revealed through DFT calculation. Additionally, the dominating active groups produced in time of the photocatalytic procedure were determined on account of free radical trapping experiments and ESR spectra. The mechanism of photocatalytic degradation was proposed and verified. The transfer of the electrons and the inhibition of the recombination of photogenerated electron-holes were enhanced effectively under the synergistic effect of the Ag NPs and TiO₂. As a consequence, the catalytic activity of the composite was improved under visible light.

     

La/Ce-codoped Bi2O3 composite photocatalysts with high photocatalytic performance in removal of high concentration dye

A series of La/Ce-codoped Bi_2O_3 composite photocatalysts were fabricated via hydrothermal–calcination process. The as-prepared products were intensively characterized by some physicochemical characterizations like N_2 physical adsorption, X-ray powder diffraction(XRD), scanning electron microscope(SEM), transmission electron microscope(TEM), UV–Vis diffuse reflectance(UV–Vis DRS), Fourier transform infrared spectroscopy(FT-IR),photoelectrochemical measurements, and photoluminescence(PL) spectroscopy. The characterization results indicated that La and Ce doping induced obvious crystal phase transformation in Bi_2O_3, from monoclinic to tetragonal phase. La and Ce codoping also gave rise to the obvious synergetic effects, e.g., the lattice contraction of Bi_2O_3, the decrease of crystal size and the increase of surface area. The photocatalytic performance of the prepared catalysts was evaluated by removal of dye acid orange II with high concentration under visible light irradiation. Results showed that La/Ce-codoped Bi_2O_3 displayed much higher photocatalytic performance than that of bare Bi_2O_3, single La or Ce doped Bi_2O_3 samples. The superior photocatalytic activity was mainly attributed to the improved texture and surface properties and the synergistic effects of La and Ce codoping on suppressing the recombination of photo-generated electrons(e~-) and holes(h~+).     

综采面高压注水联合高压喷雾二级防尘技术研究

综采工作面的粉尘防治一直是煤矿安全工作的重点和难题之一。结合双鸭山矿区新安矿综采工作面的实际状况,采用现场煤层高压注水实验方法,研究了高压注水条件下煤体增湿的规律;运用注水实验数据进行反演数值试验,优化煤层高压注水数学模型内部参数,利用注水数值模拟试验确定了综采工作面煤层高压注水减尘技术的最优参数;运用了高压喷雾降尘效率模型数值模拟方法,分析确定了综采工作面采煤机外置高压喷雾降尘的最优参数,研发了孔径为1.2 mm的7孔高压集成喷嘴。新安二矿、三矿煤层高压注水联合高压喷雾二级防尘技术应用效果表明:通过二级联合防尘措施,工作面全尘去除率高达96%,呼吸性粉尘去除率高达94%。     

成组生物毒性测试法综合评价典型工业废水毒性

为了更加准确地评估典型工业废水的综合生物毒性以及处理工艺对废水毒性的削减情况,采用发光细菌急性毒性实验、大型溞急性毒性实验和单细胞凝胶电泳实验,结合潜在生态毒性效应探测(potential ecotoxic effects probe,PEEP)指数对常州市7种典型工业废水的综合生物毒性进行了评价。结果表明,7种工业原水都表现出了急性毒性或遗传毒性,综合生物毒性强度的排序为电子厂>电镀厂>综合污水处理厂>印染厂>化工厂>食品厂>制药厂。而7种工业废水的处理后出水综合生物毒性强度的排序为印染厂>化工厂>电子厂>综合污水处理厂>食品厂>制药厂>电镀厂。其中,印染和化工厂出水综合生物毒性高于原水,分别增加了43.3%和38.7%,PEEP评价结果显示分别属于剧毒和高毒,而电镀、电子、综合污水处理和食品厂出水的综合生物毒性削减明显,分别比原水削减了76.9%、53.1%、48.3%和26.6%,PEEP结果表明基本无毒。建立在成组生物毒性实验基础上的PEEP评价方法可全面反映工业废水的综合生物毒性,进而更客观地评价废水对水生态系统乃至人类健康的潜在影响。     

α-二羰基化合物的结构-致突活性关系

采用ＡＭ１方法计算了６个α－二羰基化合物与ＤＮＡ碱基岛嘌呤环外Ｎ＾２发生紊电加成反应的速率控制步骤的活化能及分子结构和电子结构。研究其结构－知必凶线性回归结果表明;可用烷化反应活化能、ＬＵＭＯ能量、分子量表面积比和羰基面原子的正电性表示化合物的致突活性指数,获得很好的回归效果（Ｌ顺归系数Ｒ＝０．９９９８）。以本文提出的方程对这些化合物的估性进行计算,秘得到的结果与实验结果吻合得很好。     

稠油污水处理技术的应用及效果

锦州采油厂污水深度处理站自2002年10月投产以来,已连续处理污水并回用注汽锅炉2947×10~4m~3;污水常规处理站投产于2007年11月,连续处理污水回用注水443×10~4m~3。油田采出水的循环利用,节约了大量清水资源,避免了无效回注,同时充分利用了污水剩余热源,降低了湿蒸汽发生器的燃料消耗,产生了较好的经济效益、环境效益和社会效益。文章主要介绍了稠油污水处理技术,生产过程中遇到的问题及改进措施,取得的经济效益等。     

Effects of environmental factors on N2O emission from and CH4 uptake by the typical grasslands in the Inner Mongolia

The fluxes of N2O emission from and CH4 uptake by the typical semi-arid grasslands in the Inner Mongolia, China were measured in 1998-1999. Three steppes, i.e. the ungrazed Leymus chinensis (LC), the moderately grazed Leymus chinensis (LC) and the ungrazed Stipa grandis (SG), were investigated, at a measurement frequency of once per week in the growing seasons and once per month in the non-growing seasons of the LC steppes. In addition, four diurnal-cycles of the growing seasons of the LC steppes, each in an individual stage of grass growth, were measured. The investigated steppes play a role of source for the atmospheric N2O and sink for the atmospheric CH4, with a N2O emission flux of 0.06-0.21 kg N ha(-1) yr(-1) and a CH4 uptake flux of 1.8-2.3 kg C ha(-1) yr(-1). Soil moisture primarily and positively regulates the spatial and seasonal variability of N2O emission. The usual difference in soil moisture among various semi-arid steppes does not lead to significantly different CH4 uptake intensities. Soil moisture, however, negatively regulates the seasonal variability in CH4 uptake. Soil temperature of the most top layer might be the primary driving factor for CH4 uptake when soil moisture is relatively low. The annual net emission of N2O and CH4 from the ungrazed LC steppe, the moderately grazed LC steppe and the ungrazed SG steppe is at a CO2 equivalent rate of 7.7, 0.8 and -7.5 kg CO2-C ha(-1) yr(-1), respectively, which is at an ignorable level. This implies that the role of the semi-arid grasslands in the atmospheric greenhouse effect in terms of net emission of greenhouse gases (CO2, CH4 and N2O) may exclusively depend upon the net exchange of net ecosystem CO2 exchange.     

CO2浓度和光合光量子通量密度对叶用甘薯组培苗光合自养和过氧化物酶活力的影响

以新兴蔬菜叶用甘薯组织培养苗的茎节段作为外植体，用MS低糖、无激素培养基进行生根培养，设置不同的CO2浓度(Ci)和光合光量子通量密度(PPFD)对组培植株进行环境调控处理，获得小植株净光合速率最高的处理组合(Ci，PPFD)=(8720μmol mol^-1，250μmol m^-2 s^-1)，并在此组合下继续培养21d。结果表明：该调控系统可以有效地调节控制组培苗生长环境中的Ci和PPFD，提高组培苗的光合自养能力，实现低糖、无激素培养，处理组植株生长健壮，叶片数、株高、根鲜重和单株鲜重分别高出CK组57．7％，103．3％，131．6％和225．35％，叶片和根系过氧化物酶活力分别高出CK组26．3％和24．0％。图3表1参18。