Size effect of Pt nanoparticles in acid-assisted soot oxidation in the presence of NO

Pt/Al₂O₃ catalysts with mean Pt particle size ranged from 2.7 to 7.1 nm were synthesized by chemical reduction method, and the sulfated counterparts were prepared by impregnation of sulfuric acid. The turnover frequency of platinum for soot oxidation under loose contact conditions in a feed flow containing NO and O₂ are positively correlated with the size of platinum. The sulfated Pt/Al₂O₃ exhibits higher catalytic activity for soot oxidation in the presence of NO despite their reduced ability for NO₂ production. Such a contradiction is more significant for those catalysts with smaller platinum particles. Herein, the catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), transmission electron microscopy (TEM), inductive coupled plasma (ICP) emission spectrometry, CO chemisorption, thermogravimetric analysis (TGA), NH₃ temperature-programmed desorption (NH₃-TPD), NO temperature-programmed oxidation (TPO) and NO_x temperature-programmed desorption (TPD). Possible effect of Pt particle size for the catalytic oxidation of soot in the presence of NO was presented based primarily on the promoted NO₂ transfer efficiency onto the soot pushed by the acidic catalysts.     

阴霾天气PM_(10)的微观特征及生物活性研究

利用高分辨率场发射扫描电镜(FESEM)、图像分析技术(IA),对北京市2004年12月一次严重的阴霾天气条件下采集的PM10(指空气动力学直径小于10μm的颗粒物)的微观形貌、粒度分布、主要颗粒物类型进行了分析,并运用质粒DNA评价法对阴霾和非阴霾天气条件下的PM10样品的生物活性进行了对比研究。结果表明,阴霾天气时PM10样品中以粒度较小的烟尘及其集合体为主,且多呈湿状,含有较多的二次颗粒物,并发现了残余的有机液滴颗粒。质粒DNA实验的结果显示,阴霾天气PM10样品的水溶和全样样品的TD20值(造成20%DNA破坏时所需要的样品剂量)分别为93μg.ml-1和50μg.ml-1,而同一月份非阴霾天气条件下PM10样品的水溶和全样样品的TD20值分别为200μg.ml-1和160μg.ml-1,表明阴霾天气PM10样品比非阴霾天气样品具较强的生物活性,即对人体健康存在着潜在的危害。且无论是阴霾还是非阴霾天气条件下的PM10的全样样品均较水溶样品具更大的生物活性。     

贵州贫困农村室内不同燃料产生PM10的微观特征

应用高分辨率扫描电镜(SEM)和图像分析研究了贵州贫困农村不同燃料类型(拌泥煤、煤、蜂窝煤和柴)产生室内PM10的微观形貌和不同类型颗粒物的数量-粒度、体积-粒度分布.结果表明:不同类型燃料产生的PM10中颗粒物以烟尘及其集合体、矿物颗粒和飞灰为主,烟尘及其集合体均达到72.69%以上;在数量-粒度分布上,以煤和蜂窝煤燃烧产生的PM10中烟尘集合体和燃煤飞灰呈单峰分布;以拌泥煤为燃料产生的室内PM10中烟尘及其集合体呈单峰分布,燃煤飞灰呈双峰分布;以柴为燃料的室内PM10中烟尘及其集合体呈单峰分布.不同类型燃料产生的PM10中颗粒物体积-粒度分布基本呈单峰分布,主要分布在粒径>1.0μm.     

北京市冬季室内空气PM10微观形貌及粒度分布

探讨了北京市吸烟和非吸烟4户家庭室内外空气可吸入颗粒物(PM10)的质量浓度变化规律,利用高分辨场发射扫描电镜(FESEM)和图像分析技术研究了室内PM10的微观形貌特征及粒径分布特点.结果表明,吸烟室内PM10浓度一般高于非吸烟室内;室内PM10一般由烟尘集合体、燃煤飞灰、矿物颗粒、生物质颗粒及未知颗粒共5种颗粒物组成.吸烟和非吸烟室内PM10的粒径一般小于2.5祄,呈双峰分布,其中在吸烟室内,烟尘集合体和未知颗粒等的贡献比较大,而非吸烟室内PM10的数量-粒度分布也为双峰分布,烟尘集合体、燃煤飞灰的贡献比较大.吸烟和非吸烟室内PM10的体积-粒度分布均为单峰分布,并且集中在2.5~10祄范围,其中吸烟室内的烟尘集合体、矿物颗粒物占优势,而非吸烟的室内矿物颗粒占优势.虽然矿物颗粒对粒度粒径的贡献较小,但对体积的贡献比较大.     

2011年秋季广州城区大气PM2.5微观形貌和粒度分布

利用高分辨率扫描电镜加能谱仪(SEM-EDX)和图像数据分析技术对2011年秋季广州市中心大气PM2.5的微观形貌和粒度分布特征进行研究,系统获得3种典型颗粒(矿物、烟尘集合体和燃煤飞灰)和其它未知颗粒的数量-粒度分布和体积-粒度分布数据.结果表明,PM2.5颗粒数量-粒度分布峰值落在0.1~0.2μm之间,属于积聚模态中含有气相反应产物的凝结亚模态.3种典型颗粒对PM2.5的数量和体积贡献均为矿物>>烟尘集合体>飞灰.矿物主要分布在0.1~0.3μm范围内,所占数量百分比为41.97%,其中0.1~0.2μm范围内矿物占比高达26.42%,是影响PM2.5颗粒整体分布的主要因素.不同采样时段(上午、下午、晚上)和下雨前后PM2.5颗粒的粒度分布特征基本一致,但晚上和下雨后小于0.1μm的颗粒比例有明显减少趋势.     

EGR率对农用单缸柴油机燃用生物柴油的NOx与PM排放特性影响分析

单缸柴油机作为小型农用机械不可或缺的动力源,在使用过程中会产生大量污染物.其中氮氧化合物（NO_x）和颗粒（PM）是气溶胶的主要组成部分,对大气环境造成了严重污染.为有效改善农用单缸柴油机NO_x和PM排放,本研究通过添加生物柴油对柴油进行改质以及采用机内EGR净化技术两种方案,测量了柴油机分别燃用柴油B0,生物柴油调合燃料B20、B50在不同EGR率下的NO_x和PM排放.结果表明,采用EGR技术能够明显改善柴油机的NO_x排放,但同时会引起碳烟排放的增加.通过在柴油中添加生物柴油能够在一定程度上降低碳烟排放,其中高负荷、大EGR率条件下的改善最为明显.在2000 r·min^-1、75%负荷,EGR率为30%时,燃用B50的碳烟排放与燃用B0相比降低了47.3%.总体上柴油中添加生物柴油与EGR技术共同作用能够有效降低柴油机高负荷工况时的颗粒排放总数量.     

内蒙古乌达-乌斯太工业园环境单颗粒研究

2015年夏季在内蒙古乌达-乌斯太工业园布点采集了大气颗粒物核孔膜样品16件,采用扫描电镜（SEM-EDX）共表征了1600个单颗粒的形貌和化学组成,结果表明,研究区单颗粒主要为矿物颗粒、燃烧产生颗粒和含硫颗粒3大类,其中矿物颗粒不仅含有硅铝酸盐和碳酸盐这类常见颗粒,还有风化煤矸石和沙尘颗粒这两种特殊颗粒;燃烧产生颗粒不仅有通常的燃煤飞灰、烟尘集合体和絮状碳质颗粒,还有原煤尘颗粒.统计表明,烟尘聚合体、硅铝酸盐和沙尘这三者占颗粒物总数的64%,风化煤矸石尘和原煤尘主要呈现为可吸入颗粒（2.5~10μm）;烟尘聚合体和沙尘则主要为超细颗粒（<1.0μm）.总之,单颗粒分析揭示该典型煤炭工业园区大气颗粒物主要来源：园内燃煤排放和交通,上风向矿区煤炭生产和上风向沙漠自然活动.     

Thermal behaviors, combustion mechanisms, evolved gasses, and ash analysis of spent potlining for a hazardous waste management

An unavoidable but reusable waste so as to enhance a more circular waste utilization has been spent potlining (SPL) generated by the aluminum industry. The combustion mechanisms, evolved gasses, and ash properties of SPL were characterized dynamically in response to the elevated temperature and heating rates. Differential scanning calorimetric (DSC) results indicated an exothermic reaction behavior probably able to meet the energy needs of various industrial applications. The reaction mechanisms for the SPL combustion were best described using the 1.5-, 3- and 2.5-order reaction models. Fluoride volatilization rate of the flue gas was estimated at 2.24%. The SPL combustion emitted CO₂, HNCO, NO, and NO₂ but SO_x. The joint optimization of remaining mass, derivative thermogravimetry, and derivative DSC was achieved with the optimal temperature and heating rate combination of 783.5°C, and 5 °C/min, respectively. Interaction between temperature and heating rate exerted the strongest and weakest impact on DSC and remaining mass, respectively. The fluorine mainly as the formation of substantial NaF and CaF₂ in the residual ash. Besides, the composition and effect of environment of residual solid were evaluated. The ash slagging tendency and its mineral deposition mechanisms were elucidated in terms of turning SPL waste into a benign input to a circular waste utilization.     

Efficient nitrogen doped porous carbonaceous CO2 adsorbents based on lotus leaf

In this work, the waste biomass lotus leaf was converted into N-doped porous carbonaceous CO₂ adsorbents. The synthesis process includes carbonization of lotus leaf, melamine post-treatment and KOH activation. For the resultant sorbents, high nitrogen content can be contained due to the melamine modification and advanced porous structure were formed by KOH etching. These samples were carefully characterized by different techniques and their CO₂ adsorption properties were investigated in detail. These sorbents hold good CO₂ adsorption abilities, up to 3.87 and 5.89 mmol/g at 25 and 0°C under 1 bar, respectively. By thorough investigation, the combined interplay of N content and narrow microporous volume was found to be responsible for the CO₂ uptake for this series of sorbents. Together with the high CO₂ adsorption abilities, these carbons also display excellent reversibility, high CO₂/N₂ selectivity, applicable heat of adsorption, fast CO₂ adsorption kinetics and good dynamic CO₂ adsorption capacity. This study reveals a universal method of obtaining N-doped porous carbonaceous sorbents from leaves. The low cost of raw materials accompanied by easy synthesis procedure disclose the enormous potential of leaves-based carbons in CO₂ capture as well as many other applications.     

木质生物燃料与其半焦的混燃实验研究

生物质半焦作为生物质气化的副产物,其固定碳含量和热值均高于原生物质.若将生物质半焦充分利用将大幅提高生物质利用的能量效率,具有很大的经济和环境效益.在综合热分析基础上,考察了生物质半焦添加比例(掺烧比)对生物质微米燃料旋风炉燃烧炉膛温度、烟气及灰分的影响.试验研究发现掺烧比为20%(空气当量比为1.2,粉体粒径在0.177 mm以下,生物质含水率控制在8.1%以下),燃烧效果最好,燃烧效率高达98%,燃烧烟气中有害气体NOx和SO2的含量较少.     

Decoupling the adsorption mechanisms of arsenate at molecular level on modified cube-shaped sponge loaded superparamagnetic iron oxide nanoparticles

In this study, a commercial cube-shaped open-celled cellulose sponge adsorbent was modified by in-situ co-precipitation of superparamagnetic iron oxide nanoparticles (SPION) and used to remove As(V) from aqueous solutions. Fe K-edge X-ray absorption spectroscopy (XAS) and TEM identified maghemite as the main iron phase of the SPION nanoparticles with an average size 13 nm. Batch adsorption experiments at 800 mg/L showed a 63% increase of adsorption capacity when loading 2.6 wt.% mass fraction of SPION in the cube-sponge. Experimental determination of the adsorption thermodynamic parameters indicated that the As(V) adsorption on the composite material is a spontaneous and exothermic process. As K-edge XAS results confirmed that the adsorption enhancement on the composite can be attributed to the nanoparticles loaded. In addition, adsorbed As(V) did not get reduced to more toxic As(III) and formed a binuclear corner-sharing complex with SPION. The advantageous cube-shape of the sponge-loaded SPION composite together with its high affinity and good adsorption capacity for As(V), good regeneration capability and the enhanced-diffusion attributed to its open-celled structure make this adsorbent a good candidate for industrial applications.     

Primary and secondary organic aerosol in an urban/industrial site: Sources, health implications and the role of plastic enriched waste burning

PM10 samples were collected from an urban/industrial site nearby Athens, where uncontrolled burning activities occur. PAHs, monocarboxylic, dicarboxylic, hydroxycarboxylic and aromatic acids, tracers from BVOC oxidation, biomass burning tracers and bisphenol A were determined. PAH, monocarboxylic acids, biomass burning tracers and bisphenol A were increased during autumn/winter, while BSOA tracers, dicarboxylic- and hydroxycarboxylic acids during summer. Regarding aromatic acids, different sources and formation mechanisms were indicated as benzoic, phthalic and trimellitic acids were peaked during summer whereas p-toluic, isophthalic and terephthalic were more abundant during autumn/winter. The Benzo[a]pyrene-equivalent carcinogenic power, carcinogenic and mutagenic activities were calculated showing significant (p < 0.05) increases during the colder months. Palmitic, succinic and malic acids were the most abundant monocarboxylic, dicarboxylic and hydrocarboxylic acids during the entire sampling period. Isoprene oxidation was the most significant contributor to BSOA as the isoprene-SOA compounds were two times more abundant than the pinene-SOA (13.4 ± 12.3 and 6.1 ± 2.9 ng/m³, respectively). Ozone has significant impact on the formation of many studied compounds showing significant correlations with: isoprene-SOA (r = 0.77), hydrocarboxylic acids (r = 0.69), pinene-SOA (r = 0.63),dicarboxylic acids (r = 0.58), and the sum of phthalic, benzoic and trimellitic acids (r = 0.44). PCA demonstrated five factors that could explain sources including plastic enriched waste burning (30.8%), oxidation of unsaturated fatty acids (23.0%), vehicle missions and cooking (9.2%), biomass burning (7.7%) and oxidation of VOCs (5.8%). The results highlight the significant contribution of plastic waste uncontrolled burning to the overall air quality degradation.     

nZVI@SiO2-NH2对合成染料脱色效果及其对大肠杆菌生物毒性研究

采用液相还原法并使用氨基修饰的二氧化硅合成包覆型的纳米零价铁(nZVI@SiO_2-NH_2),同时,采用XRD、FT-IR及TEM等多种方法对所制备的材料进行表征.TEM表征结果表明,nZVI@SiO_2-NH_2粒径分布在10～50 nm之间,壳层厚度为15 nm.XRD和FTIR分析表明,复合颗粒具有Fe~0晶型结构的内核,表面SiO_2壳层存在氨基化修饰.使用nZVI@SiO_2-NH_2和nZVI对各类染料进行脱色处理,结果表明,nZVI@SiO_2-NH_2对上述染料的脱色效果都优于nZVI,且nZVI@SiO_2-NH_2具有对染料进行连续脱色的能力.大肠杆菌的存活情况和细胞内酶LDH和SOD的活性变化表明,nZVI@SiO_2-NH_2对生物的毒性更小.     

纳米TiO2在拟南芥中的富集、转运及对其生长和生理的影响

为了探讨纳米材料对植物的生理效应,以拟南芥(Arabidopsis thaliana)作为受试生物,研究了纳米TiO_2在拟南芥中的富集、转运及对其生长和生理的影响.本研究将拟南芥分别暴露于浓度为0、0.05、0.1、0.5、1.0、1.5 mg·L-1的纳米TiO_2中,通过ICP-MS测定纳米TiO_2在根和叶中的生物积累量,并采用TEM技术观察纳米TiO_2转运至叶片后对叶绿体结构的影响.在处理0、7和14 d后,测定拟南芥生物量、根系活力、叶片相对电导率和超氧化物歧化酶(SOD)、丙二醛(MDA)、谷胱甘肽(GSH)、活性氧自由基(ROS)等生长生理指标的变化.结果显示:拟南芥能吸收纳米TiO_2并向地上部转运,但转运系数较低;TEM切片观察到纳米TiO_2能进入拟南芥体内并造成叶绿体内囊体中质体小球数目增多、体积变大.与对照组相比,幼苗地上部生物量、叶片相对电导率、叶肉原生质体活力呈下降的趋势,地下部生物量及根系活力呈上升趋势;纳米TiO_2还可引起叶片及根部活性氧(ROS)含量的变化,进而导致MDA、SOD、GSH等抗氧化体系酶活性的应激变化,同时与根部相比,叶片引起的毒性效应更强.说明纳米TiO_2在拟南芥中富集并转运至地上部后,对拟南芥叶片的生长具有显著的抑制作用,诱导其产生氧化应激.同时,一定浓度的纳米TiO_2胁迫下,拟南芥根部与叶片对纳米TiO_2的响应不同,敏感度存在差异,叶生长受到抑制的同时却对根有促进作用.     

Engineering of responsive polymer based nano-reactors for facile mass transport and enhanced catalytic degradation of 4-nitrophenol

Silver nanoparticles with average diameter of 10 ± 3 nm were synthesized within the sieves of poly(N-isopropylacrylamide-2-hydroxyethylmethacrylate-acrylic acid)(p(NIPAAm-HEMA-AAc))polymer microgels. Free radial emulsion polymerization was employed for synthesis of p(NIPAAm-HEMA-AAc) polymer microgels. Silver nanoparticles were introduced within the microgels sphere by in situ reduction method. Microgels and hybrid microgels were characterized by Fourier transform infrared spectroscopy, ultra violet-visible spectroscopy,transmission electron microscopy and dynamic light scattering measurements. Catalytic activity of Ag-p(NIPAAm-HEMA-AAc) hybrid microgels was studied using catalytic reduction of 4-nitrophenol(4-NP) as a model reaction in aqueous media. The influence of sodium borohydride(Na BH4) concentration, catalyst dose and 4-NP concentration on catalytic reduction of 4-NP was investigated. A linear relationship was found between catalyst dose and apparent rate constant(kapp). The mechanism of catalysis by hybrid microgels was explored for further development in this area. The deep analysis of catalytic process reveals that the unique combination of NIPAAm, HEMA and AAc does not only stabilize silver nanoparticles in polymer network but it also enhances the mass transport of hydrophilic substrate like 4-NP from outside to inside the polymer network.     

提高柴油/甲醇组合燃烧尾气排放质量的研究

对原机、柴油/甲醇组合燃烧,以及带氧化催化转化器的柴油/甲醇组合燃烧3种情况下的尾气排放进行了比较和研究.针对柴油/甲醇组合燃烧可以使NOx、烟度大幅度下降,但同时PM、CO和HC的排放浓度与原机相比反而增加的现状,通过加装氧化催化转化器,对废气进行处理后,发现HC、CO和PM排放明显减少.与原机相比,不仅可以实现大幅度降低NOx,而且PM排放也有较大幅度下降.采用透射电子显微镜观察发现,与原机相比,柴油/甲醇组合燃烧的PM排放中干炭烟(DS)减少,但是可溶有机物(SOF)增加.经过氧化催化转化器处理后,尾气的PM中大量SOF和HC化合物被消除,致使PM的质量明显减少.     

纳米TiO2添加剂对DMDF发动机大负荷燃烧及PM排放影响的试验研究

在一台电控增压中冷四缸柴油机的进气道上加装一套电控喷射装置,使其运行柴油/甲醇双燃料(DMDF)模式.研究了甲醇中Ti O_2添加剂的添加量及同一添加剂添加量在不同甲醇分散系喷射量时对发动机大负荷工况的燃烧和颗粒物(PM)排放的影响.结果表明,在甲醇中添加适量(30和100 mg·kg~(-1))的纳米Ti O_2能够使爆发压力升高,对燃烧有一定的促进作用,但添加过量(100 mg·kg~(-1))会对燃烧产生不利影响.加入纳米Ti O_2后,干炭烟烟度排放和积聚态颗粒数明显降低,在添加剂添加量为1000 mg·kg~(-1)时,最大降幅分别达到26.8%和29.4%,而核态颗粒物排放变化不大.在相同添加剂添加量下,增加甲醇分散系替代率R_m会使放热始点后移,放热更加集中,爆发压力增大,干炭烟烟度和颗粒物排放均大幅度降低.在添加剂添加量为100 mg·kg~(-1)时,与R_m=10%相比,R_m=40%时爆发压力增加0.94 MPa,放热率峰值增加53.5%,烟度、核态颗粒数、积聚态颗粒数和颗粒物总数的降幅分别达66.9%、42.3%、67.0%和58.0%.     

The occurrence of per- and polyfluoroalkyl substances (PFASs) in fluoropolymer raw materials and products made in China

Perfluorooctanoic acid (PFOA), its salts, and related compounds were listed as new persistent organic pollutants by the Stockholm Convention in 2019. In this study, the occurrence of residues of PFOA and other per- and polyfluoroalkyl substances (PFASs) in raw materials and fluoropolymer products from the Chinese fluoropolymer industries are reported for the first time. The PFOA concentrations in raw materials and fluoropolymer products were in the range of 6.7 to 1.1 × 10⁶ ng/g, and <MDL (method detection limit) to 5.3 × 10³ ng/g, respectively. Generally, the levels of PFOA in raw materials were higher than in products, implying that PFOA in the emulsion/dispersion resin could be partly removed during the polymerization or post-processing steps. By tracking a company's polytetrafluoroethylene (PTFE) production line, it was found that over a 5 year period, the residual levels of PFOA in emulsion samples declined from 1.1 × 10⁶ to 28.4 ng/g, indicating that the contamination of PFOA in fluoropolymer products from production source gradually decreased after its use had been discontinued. High concentrations of HFPO-TrA (2.7 × 10⁵ to 8.2 × 10⁵ ng/g) were detected in some emulsion samples indicating this alternative has been widely applied in fluoropolymer manufacturing in China.     

哈尔滨春季大气PM_(2.5)物理化学特征及来源解析

应用场发射扫描电镜(FESEM)和带能谱的扫描电镜(SEM-EDX)对哈尔滨市春季市区大气PM2.5的物理和化学特征进行研究。微观图像表明PM2.5颗粒类型主要为矿物、烟尘集合体、飞灰和超细颗粒物;从各种颗粒的数量-粒度、体积-粒度分布及矿物元素分析表明,哈尔滨市大气PM2.5颗粒中,矿物、烟尘集合体、飞灰是颗粒的主要成分,分别来源于扬尘、燃煤燃烧和机动车尾气排放。     

Physicochemical and toxicological characteristics of nanoparticles in aerosols in southern Thailand during recent haze episodes in lower southeast Asia

Transboundary haze from biomass burning is one of the most important air pollutions in Southeast Asia. The most recent serious haze episode occurred in 2015. Southern Thailand was affected by the haze during September to October when the particulate matter concentration hit a record high. We investigated physical and chemical characteristics of aerosols, including concentration and aerosol size distribution down to sub-micron sizes during haze episodes in 2013 and 2015 and, for reference, an insignificant haze period in 2017. The highest total suspended particulates and PM₁₀ levels in Hat Yai city were 340.1 and 322.5 µg/m³. The mass fractions were nanoparticles (< 100 nm) 3.1%-14.8% and fine particles (< 1 µm) 54.6%-59.1%. Polycyclic aromatic hydrocarbon size distributions in haze periods peaked at 0.75 µm and the concentrations are 2-30 times higher than the normal period. High molecular weight (4-6 ring) PAHs during the haze episode contribute to about 56.7%-88.0% for nanoparticles. The average values of benzo(a)pyrene toxic equivalency quotient were 3.34±2.54ng/m³ in the 2015 haze period but only 0.89±0.17 ng/m³ in 2017. It is clear that particles smaller than 1 µm, were highly toxic. Nanoparticles contributed 19.4%-26.0% of total BaP-TEQ, whereas the mass fraction is 13.1%-14.8%. Thus the nanoparticles were more carcinogenic and can cause greater health effect than larger particles. The fraction of BaP-TEQ for nanoparticles during 2017 non-haze period was nearly the same, while the mass fraction was lower. This indicates that nanoparticles are the significant source of carcinogenic aerosols both during haze and non-haze periods.