Ce-promoted Mn/ZSM-5 catalysts for highly efficient decomposition of ozone

Manganese oxides supported by ZSM-5 zeolite (Mn/ZSM-5) as well as their further modified by Ce promoter were achieved by simple impregnation method for ozone catalytic decomposition. The yCe20Mn/ZSM-5–81 catalyst with 8% Ce loading showed the highest catalytic activity at relative humidity of 50% and a space velocity of 360 L/(g × hr), giving 93% conversion of 600 ppm O₃ after 5 hr. Moreover, this sample still maintained highly activity and stability in humid air with 50%–70% relative humidity. Series of physicochemical characterization including X-ray diffraction, temperature-programmed technology (NH₃-TPD and H₂-TPR), X-ray photoelectron spectroscopy and oxygen isotopic exchange were introduced to disclose the structure-performance relationship. The results indicated that moderate Si/Al ratio (81) of zeolite support was beneficial for ozone decomposition owing to the synergies of acidity and hydrophobicity. Furthermore, compared with 20Mn/ZSM-5-81, Ce doping could enhance the amount of low valance manganese (such as Mn²⁺ and Mn³⁺). Besides, the Ce³⁺/Ce⁴⁺ ratio of 8Ce20Mn/ZSM-5-81 sample was higher than that of 4Ce20Mn/ZSM-5-81. Additionally, the synergy between the MnO_x and CeO₂ could easily transfer electron via the redox cycle, thus resulting in an increased reducibility at low temperatures and high concentration of surface oxygen. This study provides important insights to the utilization of porous zeolite with high surface area to disperse active component of manganese for ozone decomposition.     

Glucose production from hydrolysis of cellulose over a novel silica catalyst under hydrothermal conditions

A novel silica catalyst was synthesized by evaporation-induced self-assembly (EISA) method and tested for the catalytic selective hydrolysis of cellulose to glucose. This silica catalyst exhibited a higher catalytic activity than other oxides prepared by the same method, such as ZrO₂, TiO₂, and Al₂O₃. Using silica as a catalyst, cellulose was selectively hydrolyzed into glucose with a glucose yield as high as 50% under hydrothermal conditions without hydrogen gas. The silica catalyst was characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results of temperature-programmed desorption of ammonia (NH₃-TPD) and textural properties indicated that the synergistic effect between strong acidity and a suitable pore diameter of the silica catalyst may be responsible for its high activity. In addition, the catalyst was recyclable and showed excellent stability during the recycle catalytic runs.     

Alkali/alkaline-earth metal-modified MnOx supported on three-dimensionally ordered macroporous–mesoporous TixSi1-xO2 catalysts: Preparation and catalytic performance for soot combustion

The performance of catalysts used in after-treatment systems is the key factor for the removal of diesel soot, which is an important component of atmospheric fine particle emissions. Herein, three-dimensionally ordered macroporous–mesoporous Ti_xSi_1-xO₂ (3DOM-m Ti_xSi_1-xO₂) and its supported MnO_x catalysts doped with different alkali/alkaline-earth metals (AMnO_x/3DOM-m Ti_0.7Si_0.3O₂ (A: Li, Na, K, Ru, Cs, Mg, Ca, Sr, Ba)) were prepared by mesoporous template (P123)-assisted colloidal crystal template (CCT) and incipient wetness impregnation methods, respectively. Physicochemical characterizations of the catalysts were performed using scanning electron microscopy, X-ray diffraction, N₂ adsorption–desorption, H₂ temperature-programmed reduction, O₂ temperature-programmed desorption, NO temperature-programmed oxidation, and Raman spectroscopy techniques; then, we evaluated their catalytic performances for the removal of diesel soot particles. The results show that the 3DOM-m Ti_0.7Si_0.3O₂ supports exhibited a well-defined 3DOM-m nanostructure, and AMnO_x nanoparticles with 10–50 nm were evenly dispersed on the inner walls of the uniform macropores. In addition, the as-prepared catalysts exhibited good catalytic performance for soot combustion. Among the prepared catalysts, CsMnO_x/3DOM-m Ti_0.7Si_0.3O₂ had the highest catalytic activity for soot combustion, with T₁₀, T₅₀, and T₉₀ (the temperatures corresponding to soot conversion rates of 10%, 50%, and 90%) values of 285, 355, and 393°C, respectively. The high catalytic activity of the CsMnO_x/3DOM-m Ti_0.7Si_0.3O₂ catalysts was attributed to their excellent low-temperature reducibility and homogeneous macroporous–mesoporous structure, as well as to the synergistic effects between Cs and Mn species and between CsMnO_x and the Ti_0.7Si_0.3O₂ support.     

Simultaneous removal of gaseous CO and elemental mercury over Cu-Co modified activated coke at low temperature

Cu-Co multiple-oxides modified on HNO₃-pretreated activated coke (AC_N) were optimized for the simultaneous removal of gaseous CO and elemental mercury (Hg⁰) at low temperature (< 200 °C). It was found that 2%CuOx-10%CoOx/AC_N catalyst calcined at 400°C resulted in the coexistence of complex oxides including CuO, Cu₂O, Co₃O₄, Co₂O₃ and CoO phases, which might be good for the simultaneous catalytic oxidation of CO by Co-species and removal of Hg⁰ by Cu-species, benefiting from the synergistic catalysis during the electro-interaction between Co and Cu cations (CoO ? Co₃O₄ and Cu₂O ? CuO). The catalysis removal of CO oxidation was obviously depended on the reaction temperature obtaining 94.7% at 200 °C, while no obvious promoting effect on the Hg⁰ removal (68.3%-78.7%). These materials were very substitute for the removal of CO and Hg° from the flue gas with the conditions of 8–20 vol.% O₂ and flue-gas temperature below 200 °C. The removal of Hg° followed the combination processes of adsorption and catalytic oxidation reaction via Langmuir-Hinshelwood mechanism, while the catalysis of CO abided by the Mars-van Krevelen mechanism with lattice oxygen species.     

Atmospheric Particle Hygroscopicity and the Influence by Oxidation State of Organic Aerosols in Urban Beijing

A hygroscopic tandem differential mobility analyser (H-TDMA) was used to observe the size-resolved hygroscopic characteristics of submicron particles in January and April 2018 in urban Beijing. The probability distribution of the hygroscopic growth factor (HGF-PDF) in winter and spring usually showed a bimodal pattern, with more hygroscopic mode (MH) being more dominant. The seasonal variation in particle hygroscopicity was related to the origin of air mass, which received polluted southerly air masses in spring and clean northwesterly air masses in winter. Particles showed stronger hygroscopic behaviour during heavy pollution episodes (HPEs) with elevated concentrations of secondary aerosols, especially higher mass fraction of nitrate, which were indicated using the PM_2.5 (particulate matter with diameter below 2.5 µm) mass concentration normalised by CO mass concentration. The hygroscopic parameter (κ) values were calculated using H-TDMA (κ_htdma) and chemical composition (κ_chem). The closure study showed that κ_chem was overestimated in winter afternoon when compared with κ_htdma, because the organic particle hygroscopic parameter (κ_org) was overestimated in the calculations. It was influenced by the presence of a high concentration of hydrocarbon-like organic aerosol (HOA) with a weak water uptake ability. A positive relationship was observed between κ_org and the ratio of oxygenated organic aerosol (OOA) and HOA, thereby indicating that the strong oxidation state enhanced the hygroscopicity of the particles. This study revealed the effect of local emission sources and secondary aerosol formation processes on particle hygroscopicity, which is of great significance for understanding the pollution formation mechanism in the North China Plain.     

Catalytic activity of porous manganese oxides for benzene oxidation improved via citric acid solution combustion synthesis

Various manganese oxides (MnO_x) prepared via citric acid solution combustion synthesis were applied for catalytic oxidation of benzene. The results showed the ratios of citric acid/manganese nitrate in synthesizing process positively affected the physicochemical properties of MnO_x, e.g., BET (Brunauer-Emmett-Teller) surface area, porous structure, reducibility and so on, which were in close relationship with their catalytic performance. Of all the catalysts, the sample prepared at a citric acid/manganese nitrate ratio of 2:1 (C2M1) displayed the best catalytic activity with T₉₀ (the temperature when 90% of benzene was catalytically oxidized) of 212℃. Further investigation showed that C2M1 was Mn₂O₃ with abundant nano-pores, the largest surface area and the proper ratio of surface Mn⁴⁺/Mn³⁺, resulting in preferable low-temperature reducibility and abundant surface active adsorbed oxygen species. The analysis results of the in-situ Fourier transform infrared spectroscopy (in-situ FTIR) revealed that the benzene was successively oxidized to phenolate, o-benzoquinone, small molecules (such as maleates, acetates, and vinyl), and finally transformed to CO₂ and H₂O.     

Promotional effect of cobalt doping on catalytic performance of cryptomelane-type manganese oxide in toluene oxidation

The cryptomelane-type manganese oxide (OMS-2)-supported Co (xCo/OMS-2; x = 5, 10, and 15 wt.%) catalysts were prepared via a pre-incorporation route. The as-prepared materials were used as catalysts for catalytic oxidation of toluene (2000 ppmV). Physical and chemical properties of the catalysts were measured using the X-ray diffraction (XRD), Fourier transform infrared spectroscopic (FT-IR), scanning electron microscopic (SEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H₂-TPR) techniques. Among all of the catalysts, 10Co/OMS-2 performed the best, with the T_90%, specific reaction rate at 245°C, and turnover frequency at 245°C (TOF_Co) being 245°C, 1.23 × 10⁻³ mol_toluene/(g_cat·sec), and 11.58 × 10⁻³ sec⁻¹ for toluene oxidation at a space velocity of 60,000 mL/(g·hr), respectively. The excellent catalytic performance of 10Co/OMS-2 were due to more oxygen vacancies, enhanced redox ability and oxygen mobility, and strong synergistic effect between Co species and OMS-2 support. Moreover, in the presence of poisoning gases CO₂, SO₂ or NH₃, the activity of 10Co/OMS-2 decreased for the carbonate, sulfate and ammonia species covered the active sites and oxygen vacancies, respectively. After the activation treatment, the catalytic activity was partly recovered. The good low-temperature reducibility of 10Co/OMS-2 could also facilitate the redox process accompanied by the consecutive electron transfer between the adsorbed O₂ and the cobalt or manganese ions. In the oxidation process of toluene, the benzoic and aldehydic intermediates were first generated, which were further oxidized to the benzoate intermediate that were eventually converted into H₂O and CO₂.     

Anaerobic oxidation of methane coupled to sulfate reduction: Consortium characteristics and application in co-removal of H2S and methane

Anaerobic sludge from a sewage treatment plant was used to acclimatize microbial colonies capable of anaerobic oxidation of methane (AOM) coupled to sulfate reduction. Clone libraries and fluorescence in situ hybridization were used to investigate the microbial population. Sulfate-reducing bacteria (SRB) (e.g., Desulfotomaculum arcticum and Desulfobulbus propionicus) and anaerobic methanotrophic archaea (ANME) (e.g., Methanosaeta sp. and Methanolinea sp.) coexisted in the enrichment. The archaeal and bacterial cells were randomly or evenly distributed throughout the consortia. Accompanied by sulfate reduction, methane was oxidized anaerobically by the consortia of methane-oxidizing archaea and SRB. Moreover, CH₄ and SO₄^2 ? were consumed by methanotrophs and sulfate reducers with CO₂ and H₂S as products. The H₃CSH produced by methanotrophy was an intermediate product during the process. The methanotrophic enrichment was inoculated in a down-flow biofilter for the treatment of methane and H₂S from a landfill site. On average, 93.33% of H₂S and 10.71% of methane was successfully reduced in the biofilter. This study tries to provide effective method for the synergistic treatment of waste gas containing sulfur compounds and CH₄.     

Biological methane production coupled with sulfur oxidation in a microbial electrosynthesis system without organic substrates

Methane is produced in a microbial electrosynthesis system (MES) without organic substrates. However, a relatively high applied voltage is required for the bioelectrical reactions. In this study, we demonstrated that electrotrophic methane production at the biocathode was achieved even at a very low voltage of 0.1 V in an MES, in which abiotic HS⁻ oxidized to SO₄²⁻ at the anodic carbon-cloth surface coated with platinum powder. In addition, microbial community analysis revealed the most probable pathway for methane production from electrons. First, electrotrophic H₂ was produced by syntrophic bacteria, such as Syntrophorhabdus, Syntrophobacter, Syntrophus, Leptolinea, and Aminicenantales, with the direct acceptance of electrons at the biocathode. Subsequently, most of the produced H₂ was converted to acetate by homoacetogens, such as Clostridium and Spirochaeta 2. In conclusion, the majority of the methane was indirectly produced by a large population of acetoclastic methanogens, namely Methanosaeta, via acetate. Further, hydrogenotrophic methanogens, including Methanobacterium and Methanolinea, produced methane via H₂.     

Effect of different reduction methods on Pd/Al2O3 for o-xylene oxidation at low temperature

Pd/Al₂O₃ was pretreated by CO, H₂ and NaBH₄ reduction, respectively. The reduced catalysts were tested for o-xylene oxidation and characterized by power X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and temperature-programmed decomposition of palladium hydride (TPDH). The characterizations indicate the pretreatments lead to distinct Pd particle sizes and amount of surface activated oxygen species, which are responsible for the catalytic performance. Compared with H₂ and NaBH₄ reduction methods, CO reduction shows a strong interaction between Pd and Al₂O₃ with smaller Pd particle size and more surface activated oxygen. It exhibited excellent catalytic performance, complete oxidation of 50 ppmV o-xylene at 85°C with a WHSV of 60,000 mL/(g∙hr).     

中国典型城市机动车排放演变趋势

选择中国12个典型城市建立1990~2009年机动车排放清单,分析各城市机动车排放历史演变趋势.结果显示,1990~2009年,研究各城市CO、VOCs、NOx和PM排放因子分别降低57%~81%、53%~78%、22%~74%和31%~76%.20年间,各城市CO和VOCs排放量总体在2000年后陆续达到增长峰值后开始下降,总量分别增长1.0倍和1.4倍;NOx和PM排放量总体保持持续增长,分别增长3.2倍和3.3倍.各城市汽油车是CO和VOCs排放主要贡献源,LDA-G、MDTB-G和HDTB-G对各城市机动车CO和VOCs排放的贡献和分别为约70%~90%和约50%~85%,其中LDA-G的排放贡献明显提高.LDA-G、MDTB-G、MDTB-D和HDTB-D贡献了80%~90%的NOx排放,其中MDTB-D和HDTB-D的排放贡献率从平均57.8%上升为72.7%.对于PM,MDTB-D和HDTB-D占排放的70%~90%.此外,部分城市摩托车排放的贡献不容忽视.     

国外保护矿业环境的矿业立法择优

勘探尤其是开采对环境的污染和破坏是比较典型的,为此,世界绝大多数国家制订了独立于矿产资源法的《矿业法》,从立法资源上保证保护矿业环境的法律构建.国外《矿业法》以源头控制、全过程控制、无过错和合力等立法原则,贯通于行政特许权授予为主并综合运用矿业主体激励、市场力量、公众参与等其他管理方式之中,构建成立体性保护矿业环境的法律制度.国外矿业法择优显得我国取代《矿业法》的《矿产资源法》关于矿业环境保护的规定过分“吝啬“.     

小兴安岭泥炭藓沼泽生态系统中的汞

研究了小兴安岭汤旺河流域中的泥炭、土壤和植物样品的汞,泥炭地总汞的平均含量为65.8～186.6ng/g;高于黑龙江土壤A层汞平均含量,也高于美国佛罗里达大沼泽国家公园和瑞典Birkeness湿地的含量.甲基汞平均含量为0.16～1.86ng/g;约占总汞的0.2%～1.4%,泥炭地总汞最高浓度出现在5～10cm深处,为186.6ng/g,甲基汞最高浓度出现在10～15cm处,为1.86ng/g,均随深度增加而减少.甲基汞含量与总汞没有很强的相关性(P=0.05,r=0.28)     

鸭绿江口潮滩沉积物间隙水中的营养盐

通过对鸭绿江口潮滩区2个采样点采集的柱状样分析、培养实验,测定了沉积物间隙水中的营养盐和沉积物中的S^2-结果表明,鸭绿江口潮滩区沉积物间隙水中的NO₃^-含量平均值为3.0μmol/L,垂直分布变化不大.PO₄^3-和SiO₃^2-的含量范围分别为0.8～70.4μmol/L,111.6～1054.3μmol/L,且两者垂直变化类似,随沉积物深度的增加先增加后下降.沉积物中硫化物的分布是随深度增加,含量升高.鸭绿江口潮滩区沉积物Eh、pH的测定结果显示,在13cm以下,Eh降为负值,沉积物还原性逐渐增强.而pH自上而下变化不大.由分子扩散公式计算结果表明,鸭绿江口潮滩区营养盐均由沉积物向上覆水扩散.     

我国四个港湾疏浚物石油污染

文中叙述了１９８８￣１９９０年间，我国４个港湾－大连湾、天津港、深圳湾及珠江河段各疏浚区疏浚物中油类污染调查及分布状况。文中介绍了站位布设原则，样品采集、样品处理、分析测试方法。进行了沾污疏浚物油类出溶出实验，认为油类溶出实验是估价疏浚物油类污染的程度的重要手段。讨论了４港湾疏浚物油类污染水平。大连湾海域疏浚物石油污染明显，珠江河段，深圳湾及天津港疏浚物稍受影响，基本上是清洁的。     

瑞丽城区一氧化碳污染的现状

经监测，瑞丽市城区街道空气中一氧化碳的日平均浓度己超过国家二级标准，其主要来源是汽车尾气排放，而且其浓度与汽车流量呈线性正相关。主导风与街道斜交，在街道峡谷内形成旋涡流场，使ＣＯ向背风面扩散并沿街道输送，导致局部测点浓度过高。目前控制ＣＯ浓度宜限制尾气超标汽车入城并合理分流入城汽车。     

上海城郊夏季大气VOCs在臭氧生成中的作用

为研究上海市夏季臭氧高发季节大气VOCs在臭氧生成中作用,选取2018年5～8月大气臭氧较高的时段,在淀山湖科学观测研究站对103种挥发性有机物、臭氧和氮氧化物等环境污染物进行观测.结果表明,上海臭氧高发季节大气平均φ(VOCs)为32.7×10-9,羰基化合物是VOCs的主要组分,所占质量分数达35.0％.羰基化合物...     

深圳市夏季臭氧污染研究

以2009年8月为例分析了深圳市夏季臭氧污染情况及污染气象特征,基于二维空气质量模式对臭氧污染控制进行数值模拟. 结果表明:深圳市８月各监测点均存在臭氧超标现象,污染形势严峻;副热带高压控制和热带气旋外围下沉气流是造成夏季出现高浓度臭氧的主要天气过程,此时大气边界层混合层高度在500～800 m,且近地面风速约在5 ms以内,不利于污染物扩散;臭氧的生成受前体物挥发性有机物(VOC)和氮氧化物(NO_x)排放的共同影响,其中VOC排放的影响较大,深圳市臭氧控制应以降低VOC排放量为重点,模拟得出对VOC和NO_x按25∶1～40∶1的比例协同减排可有效降低臭氧污染.      

水环境中微囊藻毒素分析技术进展

微囊藻毒素将成为衡量水质好坏的指标之一。水体中微囊藻毒素的检测是了解水体污染和毒素控制的基础,因此微囊藻毒素的检测变得尤其重要。文章综述了目前微囊藻毒素的来源、化学结构和性质的研究成果,重点评述国内外微囊藻毒素检测方法进展。     

中国海洋生态毒理学的研究进展

论述了海洋生态毒理学研究在中国的发展现状,结论为:污染物生物作用过程的研究主要进行了污染物在生物体内的累积与排放,在海洋食物链中的转移和潜在放大作用以及生物转化和生物降解方面的工作。污染物对海洋生物的影响,在急性毒性、慢性毒性方面进行了大量研究,另外对致畸和致突变现象以及海洋生物致毒和解毒的机制也进行了探讨。