Olefin epoxidation with metal-based nanocatalysts

Alkene epoxidations are an important class of reactions carried out in industry; however, current methods are plagued by problems, including high cost, difficulty in recovering catalysts, and generation of large quantities of acidic and chlorinated waste. In recent years, nanocatalysts have been considered as robust, heterogeneous alternatives to homogeneous catalysts. This work evaluates silver- and base metal-containing nanocatalysts as olefin epoxidation catalysts, highlighting the industrial applicability and green aspects of these catalytic systems. The nanocatalysts discussed are mostly supported or composite materials that showed (generally) good activity and selectivity for various/multiple olefin epoxidation reactions.     

The Nanoscience Revolution: Merging of Colloid Science, Catalysis and Nanoelectronics

The incorporation of nanosciences into catalysis studies has become the most powerful approach to understanding reaction mechanisms of industrial catalysts and designing new-generation catalysts with high selectivity. Nanoparticle catalysts were synthesized via controlled colloid chemistry routes. Nanostructured catalysts such as nanodots and nanowires were fabricated with nanolithography techniques. Catalytic selectivity is dominated by several complex factors including the interface between active catalyst phase and oxide support, particle size and surface structure, and selective blocking of surface sites, etc. The advantage of incorporating nanosciences into the studies of catalytic selectivity is the capability of separating these complex factors and studying them one by one in different catalyst systems. The role of oxide–metal interfaces in catalytic reactions was investigated by detection of continuous hot electron flow in catalytic nanodiodes fabricated with shadow mask deposition technique. We found that the generation mechanism of hot electrons detected in Pt/TiO₂ nanodiode is closely correlated with the turnover rate under CO oxidation. The correlation suggests the possibility of promoting catalytic selectivity by precisely controlling hot electron flow at the oxide–metal interface. Catalytic activity of 1.7–7.2 nm monodispersed Pt nanoparticles exhibits particle size dependence, demonstrating the enhancement of catalytic selectivity via controlling the size of catalyst. Pt–Au alloys with different Au coverage grown on Pt(111) single crystal surface have different catalytic selectivity for four conversion channels of n-hexane, showing that selective blocking of catalytic sites is an approach to tuning catalytic selectivity. In addition, presence and absence of excess hydrogen lead to different catalytic selectivity for isomerization and dehydrocyclization of n-hexane on Pt(111) single crystal surface, suggesting that modification of reactive intermediates by the presence of coadsorbed hydrogen is one approach to shaping catalytic selectivity. Several challenges such as imaging the mobility of adsorbed molecules during catalytic reactions by high pressure STM and removing polymeric capping agents from metal nanoparticles remain.     

磺酸化碳材料负载Ru催化剂催化纤维素水解/加氢反应

采用纤维素衍生碳、活性炭和介孔碳材料CMK-3为不同碳源前驱体,在不同磺酸化条件下制备磺酸化碳材料负载Ru的双功能催化剂,并用FTIR光谱、XRD、元素分析、热重分析、N₂物理吸附 脱附进行了表征,考察了其对纤维素加氢反应的催化活性。结果表明：相比于纤维素衍生化碳,活性炭和介孔碳CMK-3为碳源经过磺酸化后制备的催化剂具有较强的结合-SO₃H的能力和较高的催化活性,对多元醇具有良好的选择性,170 ℃下反应10 h六元醇的收率可高达84.0%。在循环使用时,磺酸化活性炭负载Ru催化剂催化活性有所降低,但可以保持对多元醇的选择性;而磺酸化介孔碳负载Ru催化剂存在少量S流失,转化率基本不变,但产物的选择性有所降低。     

Catalytic decarboxylation of fatty acids to hydrocarbons over non-noble metal catalysts: the state of the art

The catalytic decarboxylation of fatty acids to yield hydrocarbons, for use as biofuel as a main target, is a topical reaction in which the main challenge is actually to control the selectivity while using the smallest amount of hydrogen possible (or even better, not using hydrogen at all) in order to optimize cost-efficiency of the process. Herein, the focus is on the non-noble mono-, bi- and tri-metallic catalysts used to carry out this reaction. Historically, several non-noble monometallic catalysts based on Cu, Co, Ni supported on different types of supports were first studied. Among such materials, the Co-based catalysts were not selective, while, Cu-based catalysts were more or less selective to hydrocarbons or to olefins, depending on the support used. Among these three metals, the Ni-based catalysts are the most widely described ones due to their specific ability to promote deoxygenation reactions. Combining Ni to a second metal yielded a synergistic effect toward better catalytic performances, with increases in both conversion and selectivity and also improvement of the resistance of the catalyst to carbon deposit, especially when adding non-noble metals. For future prospects, it appears that the main challenge will be to be able to maintain good catalytic performances under inert gas in solvent-free conditions, in order to yield a fully environmentally friendly and cost-effective process. © 2018 Society of Chemical Industry     

Selective Oxidations on Recoverable Catalysts Assembled in Emulsions

Catalysts assembled in emulsions are found to be potentially recoverable and efficient for a number of catalytic reactions. The catalysts composed of polyoxometalate anions and quaternary ammonium cations have been designed and synthesized according to the catalytic reactions and by optimizing the structures of cations and anions. The catalysts act essentially as surfactants, which are uniformly distributed in the interface of the emulsion droplets, and accordingly behave like homogeneous catalysts. The catalysts show remarkable selectivity and activity in the oxidation of sulfur-containing molecules to sulfones in diesel and the selective oxidation of alcohols to ketones, using H₂O₂ as oxidant. For an example, the catalyst demonstrated over 96% efficiency of H₂O₂ and ˜100% selectivity to sulfones for the selective oxidation of sulfur-containing molecules in real diesel. Moreover, the catalysts can be separated and recycled by a simple demulsification and re-emulsification.     

温和条件下水合肼催化分解制氢研究进展

水合肼（N2H4?H2O）的氢质量分数高达8.0%,完全分解时副产物仅为N2,且在温和条件下物理化学性质较为稳定,因此可以作为一种理想的移动氢源,在一些特殊场合为燃料电池提供氢气。本文概述了温和条件下水合肼分解制氢反应所使用的催化体系,具体包括金属纳米粒子、复合氧化物及负载型催化剂。简要介绍了肼分解过程的机理,并分析了影响水合肼分解制氢选择性的因素,包括催化剂中活性金属的特性、反应条件及助剂的性质对催化剂选择性的影响。总结了现阶段水合肼分解制氢催化剂的优缺点,为进一步开发高效、高选择性的水合肼分解制氢催化剂提供借鉴,并为涉及N—H键及N—N键断裂的其他反应催化剂设计提供参考。     

合成气直接或间接制乙醇非铑基催化剂研究进展

乙醇作为一种清洁绿色能源,具有环境友好的特点,在能源领域显现了广阔的应用前景,研制高活性和选择性并适合工业化的合成乙醇催化剂具有重要的战略意义,非铑基催化剂具有相对较高的催化活性和选择性,并具有工业化的前景,近年来得到广泛的研究。本文介绍了国内外由合成气直接或者间接制乙醇的非铑基催化剂最新研究进展,分析了催化剂的活性组分、载体、助剂以及制备方法对催化活性和选择性的影响,指出了存在的问题,提出了高活性和选择性并且适合工业化的非铑基催化剂的研制是未来的发展趋势。     

Selective Nanocatalysis of Organic Transformation by Metals: Concepts, Model Systems, and Instruments

Monodispersed transition metal (Pt, Rh, Pd) nanoparticles (NP) in the 0.8–15 nm range have been synthesized and are being used to probe catalytic selectivity in multipath organic transformation reactions. For NP systems, the turnover rates and product distributions depend on their size, shape, oxidation states, and their composition in case of bimetallic NP systems. Dendrimer-supported platinum and rhodium NPs of less than 2 nm diameter usually have high oxidation states and can be utilized for catalytic cyclization and hydroformylation reactions which previously were produced only by homogeneous catalysis. Transition metal nanoparticles in metal core (Pt, Co)––inorganic shell (SiO₂) structure exhibit exceptional thermal stability and are well-suited to perform catalytic reactions at high temperatures (>400 °C). Instruments developed in our laboratory permit the atomic and molecular level study of NPs under reaction conditions (SFG, ambient pressure XPS and high pressure STM). These studies indicate continuous restructuring of the metal substrate and the adsorbate molecules, changes of oxidation states with NP size and surface composition variations of bimetallic NPs with changes of reactant molecules. The facile rearrangement of NP catalysts required for catalytic turnover makes nanoparticle systems (heterogeneous, homogeneous and enzyme) excellent catalysts and provides opportunities to develop hybrid heterogeneous-homogeneous, heterogeneous-enzyme and homogeneous-enzyme catalyst systems.     

A highly efficient polymer‐anchored palladium(II) complex catalyst for hydrogenation,Heck cross‐coupling and cyanation reactions

BACKGROUND: Precise architectures of steric and electronic properties of palladium species play a crucial role in designing highly functionalized catalyst systems responsible for target organic transformations. Pd catalysts supported on polymer materials have been employed extensively as catalysts not only for hydrogenation but also for coupling reactions in the production of fine chemicals. RESULTS: A new polymer‐anchored Pd(II) complex has been synthesized and characterized. The catalyst shows high catalytic activity in the hydrogenation of styrene oxide, Heck cross‐coupling and cyanation reactions of aryl halides. The effect of various reaction parameters were investigated to optimize reaction conditions. The catalytic system shows good activity in the hydrogenation of styrene oxide (conversion 98%) with a selectivity to 2‐phenylethanol (93%) which is higher than its homogeneous analogues. The catalyst also exhibits excellent catalytic activity for the Heck cross‐coupling and cyanation reactions of various substituted and non‐substituted aryl halides. CONCLUSIONS: Results demonstrate that the catalyst is robust and stable and can be recovered quantitatively by simple filtration and reused several times without loss of activity. Copyright © 2010 Society of Chemical Industry     

Remarkable effect of ordered mesoporous carbon support in tantalum oxide-catalyzed selective epoxidation of cyclooctene

The olefin epoxidation is one of the most important reactions in chemical industry. Metal oxide supports often cause drawbacks in catalytic activity and selectivity, which has been overcome by introducing hydrophobic organic groups onto the oxide supports. The present study utilizes ordered mesoporous carbon (CMK-3 and CMK-1) as structurally defined hydrophobic catalyst support. Well-dispersed tantalum oxides supported on the ordered mesoporous carbon were prepared. Their application in catalytic epoxidation of cyclooctene demonstrates that the tantalum oxide catalysts on the ordered mesoporous carbon supports show higher performances than those of the catalysts supported on activated carbon and ordered mesoporous silica SBA-15.     

Production of Biomass-Derived Chemicals and Energy: Chemocatalytic Conversions of Glycerol

The growing production of biodiesel as a renewable source-based fuel leads to an increased amount of glycerol. Thus, it is a favorable starting material to obtain highly functionalized products. From a variety of catalytic reactions three examples, namely glycerol oxidation, glycerol hydrogenolysis and aqueous-phase reforming, were chosen for detailed studies in our group. The experimental focus for the oxidation of glycerol was set on preparation and detailed examination of supported Pt–Bi catalysts in batch reactions as well as in continuous experiments using a trickle bed reactor. For aqueous-phase reforming of glycerol to hydrogen the addition of tin to supported platinum catalysts was investigated. Ruthenium and copper based catalysts could be successfully applied in the hydrogenolysis of glycerol to 1,2-propanediol.     

Fischer-Tropsch synthesis on ruthenium supported ETS-10 titanium silicate catalysts

Titanium silicate ETS-10 was found to be a suitable metal catalyst support, having high surface area, high ion exchange capacity and no acidic functions. In this work, ETS-10 was used as a support in preparing ruthenium supported catalyst for Fischer-Tropsch synthesis. Ru/METS-10 catalytic systems (M standing for Na or K) showed some important characteristics, as good metal dispersion and shape selectivity. Moreover, no side reactions due to acidic functions were evidenced; indeed readsorption of olefins on active metal centers was found to control the activity of the catalysts.In part presented at 10th IZC, Garmisch-Partenkirchen, July 1994.     

精细化工中的催化加氢反应

介绍了精细化工中加氢催化剂的类型及其制备方法,以及精细化工中加氢反应的实际应用。     

Oxidative Heck Coupling Using Pd(II) Supported on Organosilane-Functionalized Silica Mesocellular Foam

Oxidative Heck couplings of arylboronic acids and olefins are carried out under air to facilitate reoxidation of palladium without the need for an added co-oxidant using Pd(II) supported on silica surface-tethered bipyridyl, iminopyridine, or 3-aminopropyl ligands. Use of silica-supported iminopyridine or bipyridine ligands gives active catalysts, with the bipyridine-based catalyst being most efficient. The Heck products are formed with high yields and selectivities over the 1,4-addition product, and the silica supported bipyridine-based catalyst is easily recovered via simple filtration. Unlike similar supported catalysts in traditional Heck reactions involving aryl halides and olefins, the catalysts presented here can be used for multiple catalytic cycles without activity or selectivity loss.     

Selectivity in heterogeneous catalytic processes

The selectivity of several catalytic systems was studied. Shape selectivity of Pt on carbon-fiber catalysts was demonstrated in the competitive hydrogenation of 1-hexene and cyclohexene and in the parallel dehydrogenation of cyclohexanol to cyclohexanone and phenol. Both reactions were carried out in a gas-phase fixed-bed reactor. Catalysts prepared on carbon fibers, containing pores with small constrictions (5 Å) yielded significantly higher rates of hydrogenation of 1-hexene compared to those of cyclohexene and selectively produced cyclohexanone from cyclohexanol. Other catalysts, supported on carbon fibers with large constrictions (7 Å) or activated carbon, displayed comparable rates of hydrogenation for both reactants and yielded cyclohexanone as well as phenol from cyclohexanol. Nitration of o-xylene with nitrogen dioxide was carried out in the gas phase over a series of solid acid catalysts packed in a fixed bed. Several zeolites, supported sulfuric acid, and sulfated zirconia were tested. Zeolite H-β was found to be the most active and selective catalyst for the production of 4-nitro-o-xylene. A preliminary kinetic model indicated that the selectivity to 4-nitro-o-xylene increased with decreasing concentration of nitrogen dioxide. Alkylation of phenol with methanol was performed on zeolites, supported sulfuric and phosphoric acids, and sulfated zirconia packed in a fixed-bed. The ratio of o- to c-alkylation, measured at 180°C and methanol to phenol feed molar ratio of unity, ranged from 4 with the supported acids to 2 with zeolite H-β. This ratio decreased with temperature. The ratio of o- to p-cresol changed from about 2 in zeolites in supported sulfuric acid and to 0.5 in phosphoric acid supported on carbon fibers.     

Oxidative dehydrogenation of ethane and propane: How far from commercial implementation?

This review examines the recent literature on the oxidative dehydrogenation (ODH) of ethane and propane, which aims for the synthesis of the corresponding alkenes. The following aspects are discussed: (a) the main features affecting the catalytic properties of systems based on supported vanadium oxide and molybdenum oxide; (b) the characteristics of catalysts producing outstanding olefin yields; (c) advantages in selectivity gained by means of either special reactor configurations or non-conventional conduction of the reaction; (d) the contribution of homogeneous reactions to the formation of olefins during the oxidation of alkanes.     

Zeolite catalysis studied by radiolysis/EPR. Transformations of cyclic olefins

The Brønsted acid-catalyzed transformations of cyclic olefins in zeolites HZSM5 and H-mordenite were elucidated by the radiolysis/EPR method. Products of catalytic reactions were spin- labeled by radiolytic means and identified by using EPR spectroscopy. Comparison of reactions on HZSM5 and H-mordenite reveals strong shape selectivity on reactions in these catalysts. The radiolysis/EPR method is a new in situ spectroscopy with excellent sensitivity and structural specificity for the study of reaction mechanisms in zeolite catalysts.     

The influence of non-uniform catalytic activity on the performance of a single spherical pellet

This work investigates the influence of a non-uniform distribution of the intrinsic catalytic activity of a single spherical pellet on its effectiveness factor, selectivity and deactivation. In most cases the performance of non-uniformly active catalysts is superior to that of uniformly active catalysts which have the same volume averaged activity. The specific deactivation mechanisms and rate as well as the diffusional resistance have an important influence on the most desired activity profile. Concentrating the catalytic activity in the exterior shell most often yields the maximal selectivity but it also yields minimal resistance to deactivation when compared with catalysts with the same volume averaged activity and different activity profiles. For this reason, when it is important to maintain the catalytic activity for long periods it may be desirable not to use catalysts in which the activity is concentrated in the exterior shell.It is also shown that the maximal temperature rise during regeneration of a catalyst, in which coke is deposited non-uniformly, may largely exceed that obtained for a uniformly coked pellet.     

Ullmann偶联反应催化剂研究进展

Ullmann偶联反应是典型的碳碳键偶联反应,反应合成的联苯类化合物是重要有机化工原料,应用前景广阔。初期采用均相Pd催化剂,不能重复利用,工业化生产受到限制。改用多相Pd催化剂催化反应,需要添加剂导致产物分离困难。多相Au催化剂适用性受到限制,反应底物局限于碘代芳烃,双金属催化剂在催化活性与选择性方面均有较好的优势。综述Ullmann-type偶联反应中均相Pd催化体系、多相Pd催化体系、多相Au催化体系以及多相双金属催化体系催化剂的研究进展,阐述反应机理,并对Ullmann偶联反应研究进行展望。     

CATALYST PRODUCT SEPARATION TECHNIQUES IN HECK REACTION

The Heck reaction finds several applications in industry because it is one of the effective tools for the formation of a new C─C bond. In addition to the catalytic activity and selectivity, catalyst-product separation strategies are very important for the industrial application. There are various methods of interest ranging from conventional heterogeneous catalysts to heterogenization of homogeneous catalysts. The heterogeneous catalysts are classified into supported metal catalysts, zeolite-encapsulated catalysts, colloids-nanoparticles, and intercalated metal compounds. The homogeneous metal complexes catalysts are heterogenized using modified silica catalysts, polymer-supported catalysts, biphasic catalysts, supported liquid-phase catalysts, nonionic liquids solvents, perfluorinated solvents, and reusable homogeneous complexes. In general, heterogeneous catalysts are effective and stable at higher temperatures, which may be important for the activation of less reactive but less expensive chloroaryls substrates. However, the heterogeneous catalysts have a major drawback of poor selectivity toward Heck coupling products. The heterogenized metal complexes catalysts operate under relatively mild conditions as compared with heterogeneous catalysts, and so they can be applied to the production of pharmaceuticals and fine chemicals. Catalysis using supercritical solvents with catalyst separation techniques is promising for the development of green chemistry processes. Although the concepts described in this article have been reviewed mainly for Heck reactions, they should be applicable to a wide range of other chemical transformations (hydrogenation, carbonylation, hydroformylation, and so on) that, currently, are homogeneously catalyzed reactions.