Surface sensitive study to determine the reactivity of soot with the focus on the European emission standards IV and VI

Diesel soot (Euro IV and Euro VI) was investigated with spectroscopic methods such as near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoemission spectroscopy (XPS). C and O K-edge NEXAFS show that structural disorder on the surface is accompanied by a higher amount of oxygen functional groups. O K-edge NEXAFS and O1s XPS results are discussed with the aim to elucidate the nature of the oxygen surface species. The analysis of the data presented here allows the postulation of a hypothetical structure for soot samples emitted by diesel engines.     

Impact of the Pt catalyst on the oxygen electroreduction reaction kinetics on various carbon supports

Micro- and mesoporous carbide-derived carbons synthesized from molybdenum and tungsten carbides were used as porous supports for a platinum catalyst. Synthesized materials were compared with commercial Vulcan XC72R conducting furnace black. The scanning electron microscopy, X-ray diffraction, Raman spectroscopy, high-resolution transmission electron microscopy, and low-temperature N₂ adsorption methods were applied to characterize the structure of catalysts prepared. The kinetics of oxygen electroreduction in 0.5 M H₂SO₄ solution was studied using cyclic voltammetry and rotating disk electrode methods. The synthesized carbide-derived carbons exhibited high specific surface area and narrow pore size distribution. The platinum catalyst was deposited onto the surface of a carbon support in the form of nanoparticles or agglomerates of nanoparticles. Comparison of carbide-derived carbons and Vulcan XC72R as a support showed that the catalysts prepared using carbide-derived carbons are more active towards oxygen electroreduction. It was shown that the structure of the carbon support has a great influence on the activity of the catalyst towards oxygen electroreduction.     

Development and characterization of a mobile photoacoustic sensor for on-line soot emission monitoring in diesel exhaust gas

Upcoming regulations for vehicle exhaust emission demand substantial reduction of particle emission in diesel exhaust. To achieve these emission levels, the car manufacturing industry is developing new combustion concepts and exhaust after-treatment techniques such as the use of catalysts and particle filters. Many of the state-of-the-art analytical instruments do not meet the required detection limits, in combination with a high temporal resolution necessary for engine optimization. This paper reports a new detection system and the first results of its application to on-line diesel exhaust soot measurements on a engine test bench (MAN diesel engine facility Nürnberg, Germany). The instrument is based on differential photoacoustic (PA) spectroscopy of black carbon aerosol. It contains two identical PA cells, one for the measurement of the aerosol particles and one which analyses the particle-free gas. Thus, a potential cross-sensitivity to gaseous absorbers in the exhaust gas can be excluded. The PA cells were characterized in a laboratory set-up, with water vapor as reference gas and artificial soot generated by a spark discharge generator. The detection limit was found to be 2 microg m(-3) BC (for diesel soot) with a sampling rate of 3 Hz. The temporal response of the system was found to be in the order of 1 s. After full characterization of the cells, the system was transferred into a mobile 19"-rack. Characterization of the mobile sensor system under real-world conditions was performed during several measurement campaigns at an engine test bench for heavy-duty diesel engines. Results for the limit of detection, the time resolution, accuracy, repeatability, and robustness of the sensor system are very promising with regards to a routine application of the system in engine development.     

CeO2纳米层对多层载体x-CeO2/3DOM Al2O3负载纳米Au催化剂催化柴油炭烟燃烧活性的影响

与汽油车相比,柴油车具有CO2排放低、寿命长和经济性好等优点,所以近年来受到广泛关注并被大量使用.但是,柴油车在使用过程中会产生大量炭烟颗粒物(PM),对大气环境和人类健康造成很大威胁.因此,开展这方面的基础研究具有重要的科学意义及环境保护意义.催化柴油炭烟燃烧反应是一个气-固-固多相深度氧化反应,由于PM的粒径远大于传统催化剂,导致PM不能进入催化剂孔道内部,造成催化剂活性比表面积利用率较低.设计并制备大孔径的三维有序大孔结构(3DOM)的催化剂,能够减小反应扩散阻力,增加催化剂与炭烟颗粒物的有效接触,加快反应进行.另外,可以通过在3DOM氧化物表面担载其它活性组分,提高催化剂的氧化还原性能,进而提高其活性.CeO2有很好的储放氧性能,在柴油车尾气净化催化剂中较为常见,但是单一的CeO2热稳定性较差,高温下容易烧结,使得比表面积减小,并且失去储氧能力,造成催化剂失活.文献中较常见的解决办法是在CeO2中掺杂其它阳离子,如Zr4+,Pr3+,Al3+,La3+及Y3+等离子,以提高CeO2的抗高温烧结能力.此外,研究报道的催化剂对催化柴油炭烟颗粒物燃烧的峰值温度已经远低于炭烟颗粒物的自燃温度,但是对颗粒物的起燃温度仍普遍较高.我们前期研究结果表明,担载纳米Au颗粒催化剂能够显著降低炭烟燃烧的起燃温度.本文采用胶体晶体模板法制备了3DOM Al2O3载体,利用微孔膜-氨沉淀法担载不同量的活性组分CeO2,制备出一种负载型x-CeO2/3DOM Al2O3催化剂,它既可减少稀土元素用量,降低成本,又因为Al2O3的机械强度较高,还能保证催化剂的机械强度足够好.为了进一步降低催化剂催化炭烟燃烧的起燃温度,利用还原沉积法在多层载体x-CeO2/3DOM Al2O3上负载纳米Au催化剂,制备出不同厚度的CeO2纳米层负载Au催化剂(Au/x-CeO2/3DOM Al2O3).利用X射线衍射、扫描电镜、透射电镜、H2程序升温还原和O2程序升温脱附等方法研究了催化剂的结构及物化性质与催化剂活性之间的关系,提出了消除PM反应的可能机理.结果表明,Al3+离子能够部分进入到CeO2中,形成Al-Ce固溶体.由于Al离子半径小于Ce离子,Al3+掺杂后能引起CeO2晶格发生畸变,产生大量缺陷,形成大量氧空位,促进晶格氧的移动,从而使催化剂具有更大的储放氧能力.在Au/x-CeO2/3DOM Al2O3催化剂中,CeO2担载量过高时,氧化铈纳米层较厚,活性组分容易烧结,不利于催化剂活性提高;而CeO2担载量过低,则CeO2纳米层较稀薄,催化剂的氧化还原性能受限,催化剂活性也不高.因此,CeO2的担载量应适当.此外,Au和CeO2之间的强相互作用能够增加Au纳米颗粒表面活性氧物种的数量,从而促进柴油炭烟燃烧反应.活性测试结果表明,担载纳米Au颗粒后,催化剂催化柴油炭烟燃烧的起燃温度均明显降低,在所制备的系列催化剂中Au/20％CeO2/3DOM Al2O3催化剂展示了最高的催化活性,T10,T50和T90分别为267,372和426 oC.     

有机金属化合物降低柴油机炭烟排放及其机理的研究

在直喷式柴油机上按自由加速法进行了柴油机炭烟排放试验，考察了8种有机金属化合物降低炭烟排放的效果，并对其作用机理进行了研究。实验表明，8种有机金属化合物均能有效降低炭烟排放，降烟效果顺序为二壬基萘磺酸钡>二茂铁>环烷酸铁>石油磺酸钡>环烷酸锰>环烷酸铜>环烷酸钡>环烷酸铈。在纯柴油中添加4‰二壬基萘磺酸钡时，降低炭烟排放40.7%；添加1‰二茂铁时，降低炭烟排放35.3%。试验还表明，有机结构影响有机金属化合物的降烟效果，同时影响着它在添加量上的感受性。炭烟的生成，主要与生成的乙炔（C2H2）和多环芳香烃（PAH）有关，而炭烟的氧化则与炭烟周围氧浓度和炭烟颗粒表面积有关。多数有机金属化合物本身携氧，能使燃油迅速分解生成CO，CO的增加使PAH明显减少，从而抑止炭烟的生成。茂型金属有机物能活化CO分子，进而有效抑止炭烟先导物的生成。     

xK/MgAlO型催化剂催化碳烟燃烧的机理研究

通过等体积浸渍法制备了不同K掺杂量的镁铝水滑石复合氧化物(xK/MgAlO),利用X射线衍射光谱及暂态响应、扫描电子显微镜、傅里叶变换红外光谱、X射线光电子能谱及程序升温等技术比较了焙烧和未焙烧的MgAlO形貌结构和晶型的异同,在含硫气氛中研究了K对镁铝水滑石复合氧化物形貌结构和催化碳烟燃烧性能的影响,阐明了反应过程中K掺杂的xK/MgAlO型催化剂降低碳烟起燃温度的关键机制。结果表明,焙烧后的镁铝水滑石3R层状结构消失,出现了尖晶石相,层状结构坍塌变为球形颗粒状;掺杂钾后的催化剂(K/MgAlO)表面活性氧与晶格氧的比例增大,使得氧空位的数量增多,有效提高了催化剂的催化反应活性。在模拟烟气实验中发现掺杂量x=7的(7K/MgAlO)催化剂在含SO_2的混合气中使碳烟的起燃温度降低了127℃,且对NO_x的转化率显著增强。     

Pore Development during the Carbonization Process of Lignin Microparticles Investigated by Small Angle X-ray Scattering

Application of low-cost carbon black from lignin highly depends on the materials properties, which might by determined by raw material and processing conditions. Four different technical lignins were subjected to thermostabilization followed by stepwise heat treatment up to a temperature of 2000 °C in order to obtain micro-sized carbon particles. The development of the pore structure, graphitization and inner surfaces were investigated by X-ray scattering complemented by scanning electron microscopy and FTIR spectroscopy. Lignosulfonate-based carbons exhibit a complex pore structure with nanopores and mesopores that evolve by heat treatment. Organosolv, kraft and soda lignin-based samples exhibit distinct pores growing steadily with heat treatment temperature. All carbons exhibit increasing pore size of about 0.5–2 nm and increasing inner surface, with a strong increase between 1200 °C and 1600 °C. The chemistry and bonding nature shifts from basic organic material towards pure graphite. The crystallite size was found to increase with the increasing degree of graphitization. Heat treatment of just 1600 °C might be sufficient for many applications, allowing to reduce production energy while maintaining materials properties.     

Photocatalytic Removal of Soot: Unravelling of the Reaction Mechanism by EPR and in situ FTIR Spectroscopy

Photocatalytic soot oxidation is studied on P25 TiO₂ as an important model reaction for self‐cleaning processes by means of electron paramagnetic resonance (EPR) and Fourier transform infrared (FTIR) spectroscopy. Contacting of carbon black with P25 leads on the one hand to a reduction of the local dioxygen concentration in the powder. On the other hand, the weakly adsorbed radicals on the carbon particles are likely to act as alternative traps for the photogenerated conduction‐band electrons. We find furthermore that the presence of dioxygen and oxygen‐related radicals is vital for the photocatalytic soot degradation. The complete oxidation of soot to CO₂ is evidenced by in situ FTIR spectroscopy, no intermediate CO is detected during the photocatalytic process.     

Ce0.5+xZr0.4-xLa0.1O2-Al2O3催化剂催化燃烧柴油车碳烟

采用共沉淀法制备了系列Ce_0.5+xZr_0.4-xLa_0.1O₂-Al₂O₃催化剂, 其中0≤x≤0.4且Ce_0.5+xZr_0.4-xLa_0.1O₂与Al₂O₃的质量比为1:1. 考察了该系列催化剂对柴油车排放碳烟的催化燃烧性能, 并用低温N2吸附-脱附、X射线衍射(XRD)、X射线光电子能谱(XPS)、氢气程序升温还原(H₂-TPR)和氧气程序升温脱附(O₂-TPD)等手段对催化剂进行了表征. 研究结果表明该系列催化剂均形成了具有立方萤石结构的固溶体. 当x=0.2时, Ce³⁺离子在催化剂表面有一定的富集, 此时催化剂具有最大的β氧脱附峰和最好的表面还原性能, 同时具有良好的催化碳烟氧化活性, 碳烟在该催化剂的起燃温度为360 °C, 具有较好的应用前景.     

Anisotropic structure and transport in self-assembled layered polymer-clay nanocomposites

Using the layer-by-layer (LbL) assembly technique, we create a polymer-clay structure from a unique combination of LbL materials: poly(ethylene imine), Laponite clay, and poly(ethylene oxide). This trilayer LbL structure is assembled using a combination of hydrogen bonding and electrostatic interactions. The films were characterized using ellipsometry, profilometry, X-ray photon spectroscopy, atomic force microscopy, scanning electron microscopy, wide-angle X-ray diffraction, grazing-incidence small-angle X-ray scattering, and electrochemical impedance spectroscopy (EIS). We observe a layered, anisotropic structure, which resulted in in-plane ion transport 100 times faster than cross-plane at 0% relative humidity. This study represents a first application of EIS in determining anisotropic ion transport in LbL assemblies and its correlation to structural anisotropy.     

Detonation nanodiamonds as catalysts of steam reforming of ethanol

Physicochemical properties and catalytic performance of detonation nanodiamonds were studied. Original samples of nanodiamonds and nanodiamonds modified by hydrogen, oxygen, and nitric acid with hydrogen peroxide and infrared-treated were investigated. The catalyst structure and morphology were examined by transmission electron microscopy and IR spectroscopy. All the investigated catalysts were active in the steam reforming of ethanol. The correlation of catalytic properties with composition and structure of the described systems is discussed. The specific surface area of nanodiamonds is changed insignificantly upon modification.     

Application of anodized edge-plane pyrolytic graphite electrode for analysis of clindamycin in pharmaceutical formulations and human urine samples

Different graphitic carbon-based electrode materials were evaluated for direct electro-oxidation of clindamycin and electroanalytical parameters such as sensitivity, residual background current, and signal-tobackground current ratio were compared to select the best one for the clindamycin electroanalysis. Such electrode materials include glassy carbon, carbon paste, pyrolytic graphite (edge-plane and basal-plane), carbon nanotube, reduced graphene oxide, and carbon black. The edge-plane pyrolytic graphite electrode after a simple and fast electrochemical pretreatment showed superior performance compared with the other carbon electrodes. Raman and Fourier transform infrared spectroscopy were employed to analyze the surface microstructure and chemical bonding of the carbon materials and scanning electron microscopy was used to study their surface morphologic features. The applicability of the electrochemically activated edge-plane pyrolytic graphite electrode for the determination of clindamycin in pharmaceutical formulations and human urine samples was evaluated.     

Density functional theory study of the hydrogen bond interaction between lactones, lactams, and methanol

The structure and relative stability of methanol complexes with various cyclic ketones, lactones, lactams, and N-methyl lactams from three- to seven-membered rings have been investigated using the density functional theory method. The geometries, harmonic frequencies, and energies were calculated at the B3LYP/6-311+G(d,p) level. Three stable structures, cis-a, cis-b, and trans, with respect to the ring oxygen (nitrogen) atom, were found to be local minima of the potential energy surface. For lactones and N-methyl lactams, the most stable structure is trans; it is stabilized, as in cyclic ketones, through the conventional hydrogen bond (HB) interaction between the basic carbonyl oxygen and the acidic methanolic hydrogen and an unconventional HB interaction between the methanolic oxygen and the CH hydrogen, in the alpha position of the carbonyl group. For unsubstituted lactams, the cis-a structure, stabilized through a HB interaction between the NH group and the methanol oxygen in addition to the conventional HB interaction, is the most stable. The topological properties of the electron density ratify the existence of conventional (N,O-H. . .O) and unconventional (C-H. . .O) hydrogen bonding. A good correlation was found between the HB distances and the electron density at the HB critical point. The unsubstituted lactams yield more stable complexes with methanol than N-methyl lactams, lactones, and cyclic ketones. In the most stable complexes, both components behave simultaneously as a HB donor and as a HB acceptor.     

Facile synthesis of the structural hierarchy in chrysanthemum–snowball-like self-organized polyaniline

A facile synthesis of the “chrysanthemum–snowball”-shaped polyaniline (PAni) has been prepared by using self-assembly polymerization of the host–guest monomeric inclusion complex of β-cyclodextrin (β-CD) with aniline. The amount of the monomer complex plays a role as a structural regulator during fabrication of the inclusion polymer as chrysanthemum–snowball structure/nanorods via intermolecular interactions such as: hydrogen bonding between β-CD and PAni, π–π interactions and cooperative interaction between PAni with FeCl₃ in an aqueous medium. The microstructure and morphology of the resulting materials were investigated by using various analytical techniques such as Fourier transform infrared, wide-angle X-ray diffraction, small-angle X-ray scattering, field emission scanning electron microscopy and transmission electron microscopy. After observing the growth process, a tentative mechanism is proposed to elucidate the formation of the PAni hierarchical structures.     

Simultaneous catalytic removal of NOϰ and diesel soot particulates

The simultaneous removal of NO_? and soot particulates in an oxidizing atmosphere is desirable for the aftertreatment of diesel exhausts. After briefly reviewing the development of catalysts for reactions involving carbons, our recent studies on the simultaneous NO_?–soot removal using perovskite-related and spinel-type oxides are described.     

Adsorption of NH3 onto activated carbon prepared from palm shells impregnated with H2SO4

Adsorption of ammonia (NH3) onto activated carbons prepared from palm shells impregnated with sulfuric acid (H2SO4) was investigated. The effects of activation temperature and acid concentration on pore surface area development were studied. The relatively large micropore surface areas of the palm-shell activated carbons prepared by H2SO4 activation suggest their potential applications in gas adsorption. Adsorption experiments at a fixed temperature showed that the amounts of NH3 adsorbed onto the chemically activated carbons, unlike those prepared by CO2 thermal activation, were not solely dependent on the specific pore surface areas of the adsorbents. Further adsorption tests for a wide range of temperatures suggested combined physisorption and chemisorption of NH3. Desorption tests at the same temperature as adsorption and at an elevated temperature were carried out to confirm the occurrence of chemisorption due to the interaction between NH3 and some oxygen functional groups via hydrogen bonding. The surface functional groups on the adsorbent surface were detected by Fourier transform infrared spectroscopy. The amounts of NH3 adsorbed by chemisorption were correlated with the contents of elemental oxygen present in the adsorbents. Mechanisms for chemical activation and adsorption processes are proposed based on the observed phenomena.     

松散接触下 Au-Ce强相互作用对 Au/CeO2/3DOM Al2O3催化剂催化柴油炭烟燃烧活性的影响

与汽油发动机相比,柴油发动机具有热效率高、CO2排放低、寿命长、续航距离远和经济性好等优点,可大大缓解能源短缺,降低 CO2排放量.因此,机动车柴油化是当前发展趋势.然而,柴油发动机在使用过程中会排放大量炭烟颗粒物,对人体危害极大.因此,控制炭烟颗粒排放成为环境催化研究的重点之一.
　　炭烟颗粒物催化燃烧反应是典型的固(炭烟颗粒)-固(催化剂)-气(O2)多相催化反应.三维有序大孔氧化物(3DOM)具有大孔径和内部贯通的孔道结构,能有效提高炭烟颗粒与催化活性中心的接触性能.同时,纳米 Au颗粒在大孔氧化物表面的负载可有效提高催化剂本征活性,但纳米 Au颗粒催化剂热稳定性较差. CeO2具有较好的储放氧性能,可与贵金属活性组分发生相互作用,从而提高贵金属纳米颗粒的分散度和稳定性.因此,本文从柴油炭烟颗粒物催化燃烧反应本质出发,设计制备了高炭烟燃烧催化活性的3DOM氧化物担载 Au基催化剂,研究了 Au与 CeO2强相互作用对炭烟燃烧活性的影响.
　　采用胶体晶体模板法制备3DOM Al2O3载体,由微孔膜氨沉淀法制备 CeO2/3DOM Al2O3催化剂,以还原-沉积法制备 Au/3DOM Al2O3和 Au/CeO2/3DOM Al2O3催化剂,并利用扫描电镜、N2物理吸附-脱附、X射线衍射、透射电镜、紫外漫反射光谱、H2程序升温还原和 X射线光电子能谱等手段对催化剂形貌、比表面积、物理化学性质和氧化还原性进行了表征.结果表明,在 CeO2/3DOM Al2O3中, Al3+可进入到氧化铈晶格内,形成 Al-Ce-O固溶体,产生氧空位,这有利于氧物种转移.此外, Au/CeO2/3DOM Al2O3催化剂中 Au和 CeO2之间的强相互作用能增加 Au纳米颗粒表面活性氧物种数量,从而促进柴油炭烟燃烧反应.纳米颗粒 Au的担载使得催化柴油炭烟燃烧的起燃温度明显降低,其中 Au/CeO2/3DOM Al2O3催化剂表现出最高的催化活性,T10,T50和T90分别为273,364和412oC.     

Diesel Soot Combustion over Mn2O3 Catalysts with Different Morphologies: Elucidating the Role of Active Oxygen Species in Soot Combustion

Catalytic diesel soot combustion was examined using a series of Mn₂O₃ catalysts with different morphologies, including plate, prism, hollow spheres and powders. The plate‐shaped Mn₂O₃ (Mn₂O₃‐plate) exhibited superior carbon soot combustion activity compared to the prism‐shaped, hollow‐structured and powdery Mn₂O₃ under both tight and loose contact modes at soot combustion temperatures (T₅₀) of 327 °C and 457 °C, respectively. Comprehensive characterization studies using scanning electron microscopy, scanning transmission electron microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, temperature‐programmed reduction and oxygen release measurements, revealed that the improved activity of Mn₂O₃‐plate was mainly attributed to the high oxygen release rate of surface‐adsorbed active oxygen species, which originated from oxygen vacancy sites introduced during the catalyst preparation, rather than specific surface‐exposed planes. The study provides new insights for the design and synthesis of efficient oxidation catalysts for carbon soot combustion as well as for other oxidation reactions of harmful hydrocarbon compounds.     

柴油机尾气净化催化剂的最新研究进展

柴油机尾气排放的污染物已经引起了严重的环境污染问题,催化净化技术是柴油机尾气污染治理必不可少和最有效的处理技术之一,而高效催化剂的研制和开发是催化净化技术的核心.本文以柴油机尾气中最难处理的两种污染物NOx和碳烟颗粒(PM)的催化处理技术为主线,综述了NOx的催化还原(选择性催化还原(SCR)和贮存还原(NSR))催化剂、碳烟的催化燃烧催化剂、NOx和碳烟颗粒同时消除的催化剂及柴油机尾气四效催化剂的最新研究进展,并总结性地提出了目前该研究方向存在的主要问题和发展方向.     

The hydrogen bond and free volume property of poly(ether‐urethane) irradiated by neutron

Poly(ether‐urethane) (PEU) was irradiated by neutron in different atmospheres. The hydrogen bonding interaction was analyzed by Fourier transform infrared (FTIR), and the microstructure of PEU had been investigated by positron annihilation lifetime spectroscopy (PALS). The gas products were detected by gas chromatography after irradiation. The results demonstrated that the irradiation led to more hydrogen bonded carbonyl in PEU, smaller relative free volume fraction, and narrower free volume distribution. It suggested that increasing hydrogen bonds would result in the collapse of free volume. The irradiation induced micro‐phase merging together and the presence of oxygen would accelerate this tendency, which was revealed by PALS. All the results indicated that the chain relaxation led to more hydrogen bonds, and the hydrogen bonding interaction suppressed the free volume. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 381–388, 2010