The role of atomic ensembles in the reactivity of bimetallic electrocatalysts

Bimetallic electrodes are used in a number of electrochemical processes, but the role of particular arrangements of surface metal atoms (ensembles) has not been studied directly. We have evaluated the electrochemical/catalytic properties of defined atomic ensembles in atomically flat PdAu(111) electrodes with variable surface stoichiometry that were prepared by controlled electrodeposition on Au(111). These properties are derived from infrared spectroscopic and voltammetric data obtained for electrode surfaces for which the concentration and distribution of the respective metal atoms are determined in situ by atomic resolution scanning tunneling microscopy with chemical contrast. Palladium monomers are identified as the smallest ensemble ("critical ensemble") for carbon monoxide adsorption and oxidation, whereas hydrogen adsorption requires at least palladium dimers.     

A microfluidic device for conducting gas-liquid-solid hydrogenation reactions

We have developed an efficient system for triphase reactions using a microchannel reactor. Using this system, we conducted hydrogenation reactions that proceeded smoothly to afford the desired products quantitatively within 2 minutes for a variety of substrates. The system could also be applied to deprotection reactions. We could achieve an effective interaction between hydrogen, substrates, and a palladium catalyst using extremely large interfacial areas and the short path required for molecular diffusion in the very narrow channel space. This concept could be extended to other multiphase reactions that use gas-phase reagents such as oxygen and carbon dioxide.     

Isolated metal atom geometries as a strategy for selective heterogeneous hydrogenations

Facile dissociation of reactants and weak binding of intermediates are key requirements for efficient and selective catalysis. However, these two variables are intimately linked in a way that does not generally allow the optimization of both properties simultaneously. By using desorption measurements in combination with high-resolution scanning tunneling microscopy, we show that individual, isolated Pd atoms in a Cu surface substantially lower the energy barrier to both hydrogen uptake on and subsequent desorption from the Cu metal surface. This facile hydrogen dissociation at Pd atom sites and weak binding to Cu allow for very selective hydrogenation of styrene and acetylene as compared with pure Cu or Pd metal alone.     

林地土壤中黑碳的出现及分布特点

黑碳是生物质不完全燃烧残留于自然界的碳形态,是土壤中高度稳定的有机碳,对土壤碳库形成具有重要贡献。为了解森林土壤中黑碳的分布特点,以浙江省为例,采样分析了亚热带林地土壤中黑碳的数量、对土壤碳库的贡献及其在土壤剖面中的分布特征。结果表明,林地土壤中普遍存在黑碳,枯枝落叶层、表土层（0-10cm）和亚表层（10-20cm）黑碳质量分数分别为0.27-67.63,0.83-22.42和0.27-8.72g·kg^-1,分别占有机碳总量的0.12%-13.14%,1.87%-21.40%和3.31%-27.13%。火灾发生对林地表层土壤黑碳数量有较大的影响,近期（40a内）发生过火灾的样区枯枝落叶层和表土层黑碳质量分数明显高于近期没有发生过火灾的土壤（P〈0.05）。因此,表层土壤中黑碳数量在一定程度上可反映林地火灾发生的情况。黑碳在地表可发生侧向迁移,但垂直迁移相对较小,土壤中黑碳的积累量在山坡坡脚区域明显高于坡顶和上坡。残积母质发育的土壤中,黑碳主要集中分布在表层土壤;但坡积母质发育的土壤中,剖面中下部也有较多的黑碳积累。土壤中黑碳颗粒大小呈随剖面深度增加而减小的趋势。     

Palladium: preparation and catalytic properties of particles of uniform size

A method has been developed for the preparation of uniform palladium particles of diameter from 55 to 450 angstroms. Uniform particles of gold layered on palladium were also synthesized. Hydrothermal treatment of aluminum hydroxide sol was used to prepare rods of alumina with uniform cross section from 100 to 500 angstroms and of varying lengths. The palladium was adsorbed as individual particles on alumina rods, both present in aqueous suspension. Then the suspension was dried to give a catalyst containing metal particles of uniform size dispersed in open pores produced by the intermeshing of the alumina rods. This procedure guaranteed the absence of diffusion control in the rate of reactions observed experimentally. All stages of the preparation were monitored with the electron microscope. The kinetics of the ethylene-hydrogen reaction were examined by means of a pulse technique. The number of active sites determined by carbon monoxide titration of the surface was equal to the number of surface atoms as determined by the calculation of the quantities of compounds involved in the synthesis and electron microscope examination. Furthermore, the activity per site depended on the method of preparation, being four times smaller when sodium formate was used as a reducing agent instead of sodium citrate. This may be due to the fact that the shape of particles makes certain crystallographic planes more favorable. Decrease in the size of particles to 56 angstroms produced no effect on catalytic activity beyond that due to the increase in the number of surface atoms. The activity of commercial 5 percent palladium on alumina diluted 100-fold with alumina gave 80.4 percent conversion with propylene and 82.7 percent conversion with ethylene. Thus there was little difference in the behavior of the two olefins.     

大温度区间氢在活性炭上的吸附平衡分析

分析温度变化对氢在活性炭上等量吸附热的影响,从而为构建活性炭低温吸附储氢系统提供技术支持.选用比表面积为2074 m2.g-1的椰壳型SAC-02活性炭,在低温区间77.15～113.15 K,压力范围0～8 MPa;较高温区间253.15～293.15 K,压力范围0～11 MPa,用Setaram PCT Pro E＆E测试氢在活性炭上的吸附等温线,并由Ozawa对吸附相作过热液体的假设确定绝对吸附等温线.根据绝对吸附平衡数据,在不同温度区间进行等量吸附线标绘,确定等量吸附热,并由亨利定律常数确定极限吸附热.结果表明：氢在SAC-02活性炭上低温区间、较高温区间和整个温度区间内的等量吸附热平均值分别为4.80,6.44,5.62 kJ.mol-1,极限吸附热平均值分别为6.89,8.38,7.64 kJ.mol-1,必须选用活性炭吸附储氢温度区域吸附数据的等量吸附线标绘,才能确定用于分析吸附过程热效应的等量吸附热.     

Seasonal variations in the stable carbon isotopic signature of biogenic methane in a coastal sediment

Systematic seasonal variations in the stable carbon isotopic signature of methane gas occur in the anoxic sediments of Cape Lookout Bight, a lagoonal basin on North Carolina's Outer Banks. Values for the carbon isotope ratio (delta 13C) of methane range from -57.3 per mil during summer to -68.5 per mil during winter in gas bubbles with an average methane content of 95%. The variations are hypothesized to result from changes in the pathways of microbial methane production and cycling of key substrates including acetate and hydrogen. The use of stable isotopic signatures to investigate the global methane cycle through mass balance calculations, involving various sediment and soil biogenic sources, appears to require seasonally averaged data from individual sites.     

河西内陆河不同流域盐碱土壤碳、氮、氢分布特征

利用元素分析仪测定了河西走廊不同地区盐碱土壤的碳、氮、氢含量,研究了其分布特征.结果表明,河西走廊内陆河不同流域地区盐碱土壤中的碳、氮、氢分布呈现出显著的地域特点.尤其是疏勒河流域,其碳、氮、氢总含量明显高于其它两个地区(黑河流域、石羊河流域),沿河西走廊从西向东,土壤中碳、氮、氢的总含量依次降低,土壤的肥沃程度也沿河...     

三聚氰胺甲醛树脂-钯络合物催化剂的表征及催化活性

报道了三聚氰胺甲醛树脂-Pd催化剂的表征。通过光电子能谱、电子探针、顺磁共振谱、X-射线衍射等测试结果证明新催化剂是载体与Pd(Ⅰ)络合,起催化作用的是零价钯。三聚氰胺甲醛树脂的聚和度不同其对硝基化合物的活性、选择性不同。该催化剂对蓖麻油有较强的催化氢化能力,其氢化蓖麻油的碘值可以达到3,对其他油也有较好的活性。     

Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene

The removal of trace acetylene from ethylene is performed industrially by palladium hydrogenation catalysts (often modified with silver) that avoid the hydrogenation of ethylene to ethane. In an effort to identify catalysts based on less expensive and more available metals, density functional calculations were performed that identified relations in heats of adsorption of hydrocarbon molecules and fragments on metal surfaces. This analysis not only verified the facility of known catalysts but identified nickel-zinc alloys as alternatives. Experimental studies demonstrated that these alloys dispersed on an oxide support were selective for acetylene hydrogenation at low pressures.     

Northern hemisphere controls on tropical southeast African climate during the past 60,000 years

The processes that control climate in the tropics are poorly understood. We applied compound-specific hydrogen isotopes (deltaD) and the TEX(86) (tetraether index of 86 carbon atoms) temperature proxy to sediment cores from Lake Tanganyika to independently reconstruct precipitation and temperature variations during the past 60,000 years. Tanganyika temperatures follow Northern Hemisphere insolation and indicate that warming in tropical southeast Africa during the last glacial termination began to increase approximately 3000 years before atmospheric carbon dioxide concentrations. deltaD data show that this region experienced abrupt changes in hydrology coeval with orbital and millennial-scale events recorded in Northern Hemisphere monsoonal climate records. This implies that precipitation in tropical southeast Africa is more strongly controlled by changes in Indian Ocean sea surface temperatures and the winter Indian monsoon than by migration of the Intertropical Convergence Zone.     

Hydrogen sensors and switches from electrodeposited palladium mesowire arrays

Hydrogen sensors and hydrogen-activated switches were fabricated from arrays of mesoscopic palladium wires. These palladium "mesowire" arrays were prepared by electrodeposition onto graphite surfaces and were transferred onto a cyanoacrylate film. Exposure to hydrogen gas caused a rapid (less than 75 milliseconds) reversible decrease in the resistance of the array that correlated with the hydrogen concentration over a range from 2 to 10%. The sensor response appears to involve the closing of nanoscopic gaps or "break junctions" in wires caused by the dilation of palladium grains undergoing hydrogen absorption. Wire arrays in which all wires possessed nanoscopic gaps reverted to open circuits in the absence of hydrogen gas.     

苹果缺钙对果实钙组分、亚细胞分布与超微结构的影响

 通过苹果幼果期果面喷钙获得试材,采用逐级提取法测定红富士和新红星两个品种贮藏过程中钙形态的变化;采用焦锑酸钾沉淀-透射电子显微镜观察方法,研究果实细胞中钙的亚细胞分布特点及其相应的超微结构变化。结果表明,随贮藏时间增加,红富士和新红星苹果果实水溶性钙和果胶钙含量下降,磷酸钙和草酸钙以及硅酸钙含量相应增加,与对照不喷钙比较,喷钙明显增加贮藏苹果果实各种形态钙的含量;品种间红富士苹果全钙及各种形态钙含量均显著高于新红星。钙均匀分布于细胞壁、细胞膜、液泡膜、核膜和核质,并在液泡内堆积;缺钙时核膜模糊或断裂,且钙颗     

Volatile-rich lunar soil: evidence of possible cometary impact

A subsurface Apollo 16 soil, 61221, is much richer in volatile compounds than soils from any other locations or sites as shown by thermal analysis-gas release measurements. A weight loss of 0.03 percent during the interval 175 degrees to 350 degrees C was associated with the release of water, carbon dioxide, methane, hydrogen cyanide, hydrogen, and minor amounts of hydrocarbons and other species. These volatile components may have been brought to this site by a comet, which may have formed North Ray crater.     

养殖场鸡粪废水碳氮质量比对厌氧发酵产氢的影响

以经过热处理的厌氧污泥为接种物,将鸡粪废水和米糠废水按不同体积比例混合进行发酵产氢研究,考察碳氮质量比对发酵产氢的影响;并对液相末端产物、COD去除率和产氢动力学进行分析。结果表明:初始pH5.0、发酵温度为36℃时,最佳碳氮质量比为40～50,最大累积生物气产量1.855L、H2产量1.128L,最大比产氢速率370.46mL/(g.d);COD去除率随发酵液碳氮质量比的增大先升高后降低,最大去除率为32.6%,液相末端产物主要转化为乙酸和丁酸等挥发性有机酸;利用Gompertz模型对鸡粪废水和米糠废水产氢过程进行模拟,实验曲线和拟合变化趋势一致,说明Gompertz模型可很好的模拟该产氢过程。     

Synthesis of Isocyanic Acid from Nitric Oxide over Palladium and Iridium Catalysts

A novel and convenient synthesis of isocyanic acid (HNCO) and its trimer isocyanuric acid has been obtained by the conversion of nitric oxide (NO). Nitric oxide, carbon monoxide, and hydrogen mixed in helium at the level of 0.3 to 5 percent reacted over iridium and palladium catalysts at 280 degrees to 450 degrees C to form HNCO in 60 to 75 percent yield. Major side products were ammonium cyanate at low temperature and ammonia or nitrogen at high temperature. Total conversion of nitrogen from NO to NCO reached 73 percent over palladium and 86 percent over iridium.     

碳纳米管的酸化处理对碳纳米管/聚氨酯复合材料微观结构及性能的影响

对多壁碳纳米管进行酸化处理,并采用原位聚合法制备了碳纳米管/聚氨酯复合材料。利用X射线光电子能谱分析(XPS)、电子扫描显微镜(SEM)、动态力学分析(DMA)研究了碳纳米管酸化与否对复合材料性能的影响。结果表明,碳纳米管经酸化处理后产生了羧基,碳纳米管的原位加入使得复合材料的储存模量和玻璃化转变温度都有所提高,而且经过酸化的碳纳米管对聚氨酯材料的改性要比未酸化碳纳米管对聚氨酯材料的改性效果更为显著。     

Production of liquid alkanes by aqueous-phase processing of biomass-derived carbohydrates

Liquid alkanes with the number of carbon atoms ranging from C7 to C15 were selectively produced from biomass-derived carbohydrates by acid-catalyzed dehydration, which was followed by aldol condensation over solid base catalysts to form large organic compounds. These molecules were then converted into alkanes by dehydration/hydrogenation over bifunctional catalysts that contained acid and metal sites in a four-phase reactor, in which the aqueous organic reactant becomes more hydrophobic and a hexadecane alkane stream removes hydrophobic species from the catalyst before they go on further to form coke. These liquid alkanes are of the appropriate molecular weight to be used as transportation fuel components, and they contain 90% of the energy of the carbohydrate and H2 feeds.     

低温季节西南亚高山森林土壤可溶性有机碳动态

作为生物有效性极高的土壤活性有机碳组分之一的土壤可溶性有机碳易受到地表覆被以及土壤水热动态等影响,其含量与动态在短期内可能产生较大变化,从而可作为土壤有机碳动态的短期指标。以我国敏感而重要土壤碳汇之一的西南亚高山森林生态系统为研究对象,通过测定不同地表覆盖处理下(积雪和凋落物)原位培养的土柱DOC含量,研究不同地表覆被下低温季节土壤DOC的动态变化。结果表明,不同处理下亚高山森林土壤DOC含量在低温季节的变化仍然显著;积雪与凋落物对土壤DOC含量的作用不同,凋落物覆盖有利于低温季节(尤其后期)土壤DOC含量升高,而积雪则抑制了凋落物对土壤DOC的增加效应。这表明对于亚高山森林生态系统,冬季积雪减少或消失,有利于土壤DOC含量升高,从而导致土壤有机碳库中的不稳定性碳库比例增加。     

In situ scanning tunneling microscopy of corrosion of silver-gold alloys

An in situ scanning tunneling microscope (STM) was used to observe the morphological changes accompanying the selective dissolution of Ag from low-Ag content Ag-Au alloys in dilute perchloric acid. This study was undertaken to explore the role of surface diffusion in alloy corrosion processes. These results are interpreted within the framework of the kink-ledge-terrace model of a crystal surface and a recent model of alloy corrosion based on a variant of percolation theory. The corrosion process leads to roughening of the surface by dissolution of Ag atoms from terrace sites. Annealing or smoothening of the surface occurs by vacancy migration through clusters and the subsequent annihilation of clusters at terrace ledges.