Solvent-free oxidation of primary carbon-hydrogen bonds in toluene using Au-Pd alloy nanoparticles

Selective oxidation of primary carbon-hydrogen bonds with oxygen is of crucial importance for the sustainable exploitation of available feedstocks. To date, heterogeneous catalysts have either shown low activity and/or selectivity or have required activated oxygen donors. We report here that supported gold-palladium (Au-Pd) nanoparticles on carbon or TiO(2) are active for the oxidation of the primary carbon-hydrogen bonds in toluene and related molecules, giving high selectivities to benzyl benzoate under mild solvent-free conditions. Differences between the catalytic activity of the Au-Pd nanoparticles on carbon and TiO(2) supports are rationalized in terms of the particle/support wetting behavior and the availability of exposed corner/edge sites.     

(111)晶面暴露的NiO纳米催化剂的制备及其CO催化氧化性能

采用溶剂热法,以Ni(NO_3)_3·6H_2O、均苯三甲酸以及N,N-二甲基甲酰胺(DMF)为原料快速合成金属有机骨架材料Ni_3(BTC)_2·12H_2O晶体。以Ni_3(BTC)_2·12H_2O为前体,通过焙烧得到具有(111)面的NiO颗粒用于CO催化氧化反应,并与由硝酸镍热解得到的NiO(R)催化剂进行对比。通过X射线衍射(XRD)、N_2物理吸附-脱附、透射电子显微镜(TEM)以及X射线光电子能谱(XPS)等方法对具有(111)面的NiO颗粒的组成、结构和形貌进行表征。CO催化氧化结果表明,具有(111)面的NiO颗粒的催化活性优于普通NiO催化剂的催化活性。     

Solvent-free oxidation of primary alcohols to aldehydes using Au-Pd/TiO2 catalysts

The oxidation of alcohols to aldehydes with O2 in place of stoichiometric oxygen donors is a crucial process for the synthesis of fine chemicals. However, the catalysts that have been identified so far are relatively inactive with primary alkyl alcohols. We showed that Au/Pd-TiO2 catalysts give very high turnover frequencies (up to 270,000 turnovers per hour) for the oxidation of alcohols, including primary alkyl alcohols. The addition of Au to Pd nanocrystals improved the overall selectivity and, using scanning transmission electron microscopy combined with x-ray photoelectron spectroscopy, we showed that the Au-Pd nanocrystals were made up of a Au-rich core with a Pd-rich shell, indicating that the Au electronically influences the catalytic properties of Pd.     

Enhanced ethylene and ethane production with free-radical cracking catalysts

A series of free-radical catalysts have been discovered that increase the yield of highly valuable olefins from the cracking of low molecular weight paraffins. For example, catalytic cracking of n-butane, isobutane, and propane over manganese or iron supported on magnesium oxide (MgO) gave product distributions different from those given by thermal (free-radical) cracking or cracking over traditional acid catalysts. With n-butane and propane feeds, the products from catalytic cracking included large amounts of ethylene and ethane; with isobutane feed, propylene was the major product. Physical characterization of the MgO-supported catalyst showed the manganese to be in a 2+ oxidation state in the reduced catalyst and a 4+ oxidation state in the fully oxidized catalyst. Manganese was also shown to be uniformly distributed in the support material with very little enrichment at the surface. Matrix isolation of the gasphase radicals from n-butane feed showed that ethyl and methyl radicals were produced over the active catalysts. In the thermal process, only methyl radicals were produced. The mechanism of the catalytic reaction appears to be selective formation of primary carbanions at the catalyst surface followed by electron transfer and release of primary hydrocarbon radicals to the gas phase.     

A functional model for O-O bond formation by the O2-evolving complex in photosystem II

The formation of molecular oxygen from water in photosynthesis is catalyzed by photosystem II at an active site containing four manganese ions that are arranged in di-mu-oxo dimanganese units (where mu is a bridging mode). The complex [H2O(terpy)Mn(O)2Mn(terpy)OH2](NO3)3 (terpy is 2,2':6', 2"-terpyridine), which was synthesized and structurally characterized, contains a di-mu-oxo manganese dimer and catalyzes the conversion of sodium hypochlorite to molecular oxygen. Oxygen-18 isotope labeling showed that water is the source of the oxygen atoms in the molecular oxygen evolved, and so this system is a functional model for photosynthetic water oxidation.     

催化湿式二氧化氯氧化法处理高浓度有机农药废水的研究

通过浸渍法制备了4类主活性组分的负载型催化剂,用于二氧化氯催化湿式氧化(CWCDO)法处理有机农药废水的研究,并确定了催化湿式氧化的条件。结果表明:4元组合MnO2-CuO-CeO2-V2O(5 24∶1∶1∶)催化剂性能较好;当反应在常温常压下,维持pH值为3～5,反应时间为30 min时,COD的去除率大于85%,色度去除率大于90%。     

Spectroscopic observation of dual catalytic sites during oxidation of CO on a Au/TiO₂ catalyst

The prevailing view of CO oxidation on gold-titanium oxide (Au/TiO(2)) catalysts is that the reaction occurs on metal sites at the Au/TiO(2) interface. We observed dual catalytic sites at the perimeter of 3-nanometer Au particles supported on TiO(2) during CO oxidation. Infrared-kinetic measurements indicate that O-O bond scission is activated by the formation of a CO-O(2) complex at dual Ti-Au sites at the Au/TiO(2) interface. Density functional theory calculations, which provide the activation barriers for the formation and bond scission of the CO-O(2) complex, confirm this model as well as the measured apparent activation energy of 0.16 electron volt. The observation of sequential delivery and reaction of CO first from TiO(2) sites and then from Au sites indicates that catalytic activity occurs at the perimeter of Au nanoparticles.     

X-ray diffraction study of the ultrathin Al2O3 layer on NiAl110

Ultrathin Al2O3 layers on alloys are used as templates for model catalysts, tunneling barriers in electronic devices, or corrosion-resistant layers. The complex atomic structure of well-ordered alumina overlayers on NiAl110 was solved by surface x-ray diffraction. The oxide layer is composed of a double layer of strongly distorted hexagonal oxygen ions that hosts aluminum ions on both octahedral and tetrahedral sites with equal probability. The alumina overlayer exhibits a domain structure that can be related to characteristic growth defects and is generated during the growth of a hexagonally ordered overlayer (Al2O3) on a body-centered cubic (110) substrate (NiAl).     

Cu-Zn/ZSM-5催化剂催化湿式氧化H-酸

以萘系染料中间体中具有代表性的H-酸(1-氨基-8-萘酚-3,6-二磺酸,分子式为C10H9O7S2N)的水溶液为研究对象,分别采用以等体积浸渍法制备的不同负载量的Cu-Zn/ZSM-5催化剂、以共沉淀法制得的Cu-Zn-Al催化剂对H-酸水溶液进行湿空气催化氧化降解。研究结果表明:对于处理H-酸水溶液,Cu-Zn/ZSM-5系列催化剂的COD去除率更高,这主要是由于催化活性中心在分子筛上获得了更优的分散性;最佳的CuO负载量为3.41%,ZnO负载量为1.16%,此时H-酸COD去除率为88.18%。     

Efficient oxidative dechlorination and aromatic ring cleavage of chlorinated phenols catalyzed by iron sulfophthalocyanine

An efficient method has been developed for the catalytic oxidation of pollutants that are not easily degraded. The products of the hydrogen peroxide (H(2)O(2)) oxidation of 2,4,6,-trichlorophenol (TCP) catalyzed by the iron complex 2,9,16,23-tetrasulfophthalocyanine (FePcS) were observed to be chloromaleic, chlorofumaric, maleic, and fumaric acids from dechlorination and aromatic cycle cleavage, as well as additional products that resulted from oxidative coupling. Quantitative analysis of the TCP oxidation reaction revealed that up to two chloride ions were released per TCP molecule. This chemical system, consisting of an environmentally safe oxidant (H(2)O(2)) and an easily accessible catalyst (FePcS), can perform several key steps in the oxidative mineralization of TCP, a paradigm of recalcitrant pollutants.     

A mercury-catalyzed, high-yield system for the oxidation of methane to methanol

A homogeneous system for the selective, catalytic oxidation of methane to methanol via methyl bisulfate is reported. The net reaction catalyzed by mercuric ions, Hg(II), is the oxidation of methane by concentrated sulfuric acid to produce methyl bisulfate, water, and sulfur dioxide. The reaction is efficient. At a methane conversion of 50 percent, 85 percent selectivity to methyl bisulfate ( approximately 43 percent yield; the major side product is carbon dioxide) was achieved at a molar productivity of 10(-7) mole per cubic centimeter per second and Hg(II) turnover frequency of 10(-3) per second. Separate hydrolysis of methyl bisulfate and reoxidation of the sulfur dioxide with air provides a potentially practical scheme for the oxidation of methane to methanol with molecular oxygen. The primary steps of the Hg(II)-catalyzed reaction were individually examined and the essential elements of the mechanism were identified. The Hg(II) ion reacts with methane by an electrophilic displacement mechanism to produce an observable species, CH(3)HgOSO(3)H, 1. Under the reaction conditions, 1 readily decomposes to CH(3)OSO(3)H and the reduced mercurous species, Hg(2)(2+) The catalytic cycle is completed by the reoxidation of Hg(2)(2+) with H(2)SO(4) to regenerate Hg(II) and byproducts SO(2) and H(2)O. Thallium(III), palladium(II), and the cations of platinum and gold also oxidize methane to methyl bisulfate in sulfuric acid.     

Mixed-phase oxide catalyst based on Mn-mullite (Sm, Gd)Mn2O5 for NO oxidation in diesel exhaust

Oxidation of nitric oxide (NO) for subsequent efficient reduction in selective catalytic reduction or lean NO(x) trap devices continues to be a challenge in diesel engines because of the low efficiency and high cost of the currently used platinum (Pt)-based catalysts. We show that mixed-phase oxide materials based on Mn-mullite (Sm, Gd)Mn(2)O(5) are an efficient substitute for the current commercial Pt-based catalysts. Under laboratory-simulated diesel exhaust conditions, this mixed-phase oxide material was superior to Pt in terms of cost, thermal durability, and catalytic activity for NO oxidation. This oxide material is active at temperatures as low as 120°C with conversion maxima of ~45% higher than that achieved with Pt. Density functional theory and diffuse reflectance infrared Fourier transform spectroscopy provide insights into the NO-to-NO(2) reaction mechanism on catalytically active Mn-Mn sites via the intermediate nitrate species.     

金属掺杂TiO_2对中药渣裂解油特性的影响

以Ni、Fe、Co等3种不同金属掺杂的TiO2介孔材料作催化剂对中药渣进行催化裂解,研究不同催化剂对生物油产率及油品的影响,采用热值分析和气质联用(GC-MS)分析裂解油的特性,利用N2吸附-脱附对催化剂进行表征。研究表明,Ni/TiO2的催化效果优于Fe/TiO2和Co/TiO2,Ni/TiO2作催化剂时,裂解油中脂肪烃和烷基苯的种数最多,且其中与汽油或柴油相近的组分占大多数,而芳香族化合物数量明显较少。在Ni/TiO2的催化作用下,大分子中的氧多以H2O分子的形式脱去,因而生物油中含水率较高,导致其热值降低。     

On atmospheric loss of oxygen ions from earth through magnetospheric processes

In Earth's environment, the observed polar outflow rate for O(+) ions, the main source of oxygen above gravitational escape energy, corresponds to the loss of approximately 18% of the present-day atmospheric oxygen over 3 billion years. However, part of this apparent loss can actually be returned to the atmosphere. Examining loss rates of four escape routes with high-altitude spacecraft observations, we show that the total oxygen loss rate inferred from current knowledge is about one order of magnitude smaller than the polar O(+) outflow rate. This disagreement suggests that there may be a substantial return flux from the magnetosphere to the low-latitude ionosphere. Then the net oxygen loss over 3 billion years drops to approximately 2% of the current atmospheric oxygen content.     

Molecular recognition in the selective oxygenation of saturated C-H bonds by a dimanganese catalyst

Although enzymes often incorporate molecular recognition elements to orient substrates selectively, such strategies are rarely achieved by synthetic catalysts. We combined molecular recognition through hydrogen bonding with C-H activation to obtain high-turnover catalytic regioselective functionalization of sp3 C-H bonds remote from the -COOH recognition group. The catalyst contains a Mn(mu-O)2Mn reactive center and a ligand based on Kemp's triacid that directs a -COOH group to anchor the carboxylic acid group of the substrate and thus modify the usual selectivity for oxidation. Control experiments supported the role of hydrogen bonding in orienting the substrate to achieve high selectivity.     

Mechanism of the selective catalytic reduction of nitric oxide by ammonia elucidated by in situ on-line fourier transform infrared spectroscopy

The selective catalytic reduction reaction of nitric oxide bv ammonia over vanadia-titania catalysts is one of the methods of removing NOx pollution. In the present study, it has been possible to identify the reaction mechanism and the nature of the active sites in these catalysts by combining transient or steady-state in situ (Fourier transform infrared spectroscopy) experiments directly with on-line activity studies. The results suggest a catalytic cycle that consists of both acid and redox reactions and involves both surface V-OH (Br?nsted acid sites) and V=O species. A fundamental microkinetic model is proposed, which accounts for the observed industrial kinetics performance.     

离子液体[BMIM]Cl与H5PV2Mo10O40双效催化降解麦草碱木质素的研究

采用常规合成法制备了杂多酸H₅PV₂Mo₁₀O₄₀,并通过FT-IR、XRD、SEM对其进行表征。研究了[BMIM]Cl单催化与{H₅PV₂Mo₁₀O₄₀+[BMIM]Cl}双效催化体系中,反应时间、温度以及H₅PV₂Mo₁₀O₄₀用量对麦草碱木质素降解的影响,并初步探讨了木质素的降解机理。结果表明:H₅PV₂Mo₁₀O₄₀中P、V、Mo相对原子质量满足1:2:10关系,并具有典型的Keggin结构;木质素降解反应中,仅离子液体[BMIM]Cl降解木质素的最佳条件为140 ℃下反应3 h,降解后固体产物中总羟基由3.49 mol/kg增加到10.92 mol/kg,液体产物中有香草醛与丁香醛生成,分别占2.00%和2.15%;{H₅PV₂Mo₁₀O₄₀+[BMIM]Cl}双效催化体系中,最佳反应条件为加入20%的H₅PV₂Mo₁₀O₄₀ 120 ℃下反应6 h,降解后固体产物中总羟基由3.49 mol/kg增加到14.12 mol/kg,摩尔质量由7.691 kg/mol降为1.589 kg/mol;液体产物中无丁香醛生成,香草醛占6.97%。初步认为:当单独[BMIM]Cl催化木质素时,H+首先进攻木质素中β-O-4键上的氧原子,正电荷转移到β位,然后水分子中氧原子向带有正电荷的β位进攻,从而催化剂的H+被消除,最后实现了β-O-4键水解断裂,生成愈创木酚,进而侧链发生氧化生成香草醛与丁香醛;当添加H₅PV₂Mo₁₀O₄₀时,[PV₂Mo₁₀O₄₀]5-中的VO₂+由V(V)→V(IV),故使模型化合物得以单电子的氧化,使木质素脱甲氧基,由紫丁香基木质素转变成愈创木基木质素,液体产物中无丁香醛生成,且香草醛质量分数升高。      

Surface-modified carbon nanotubes catalyze oxidative dehydrogenation of n-butane

Butenes and butadiene, which are useful intermediates for the synthesis of polymers and other compounds, are synthesized traditionally by oxidative dehydrogenation (ODH) of n-butane over complex metal oxides. Such catalysts require high O2/butane ratios to maintain the activity, which leads to unwanted product oxidation. We show that carbon nanotubes with modified surface functionality efficiently catalyze the oxidative dehydrogenation of n-butane to butenes, especially butadiene. For low O2/butane ratios, a high selectivity to alkenes was achieved for periods as long as 100 hours. This process is mildly catalyzed by ketonic CO groups and occurs via a combination of parallel and sequential oxidation steps. A small amount of phosphorus greatly improved the selectivity by suppressing the combustion of hydrocarbons.     

金属氧化物/吸附树脂催化分子氧氧化巴豆醛的研究

考察了金属氧化物／吸附树脂催化剂催化分子氧氧化巴豆醛的性能与催化氧化反应条件。结果表明,催化剂有较高活性和选择性,在优化反应条件下,巴豆酸产率为８７．１％。     

Activity of CeOx and TiOx nanoparticles grown on Au(111) in the water-gas shift reaction

The high performance of Au-CeO2 and Au-TiO2 catalysts in the water-gas shift (WGS) reaction (H2O + CO-->H2 + CO2) relies heavily on the direct participation of the oxide in the catalytic process. Although clean Au(111) is not catalytically active for the WGS, gold surfaces that are 20 to 30% covered by ceria or titania nanoparticles have activities comparable to those of good WGS catalysts such as Cu(111) or Cu(100). In TiO(2-x)/Au(111) and CeO(2-x)/Au(111), water dissociates on O vacancies of the oxide nanoparticles, CO adsorbs on Au sites located nearby, and subsequent reaction steps take place at the metal-oxide interface. In these inverse catalysts, the moderate chemical activity of bulk gold is coupled to that of a more reactive oxide.