Heterogeneous catalysis: some recent developments

In recent years major progress has been made in the area of heterogeneous catalysis by metals. Much has been learned about the nature of metal catalysts and of catalytic phenomena on metals. Characteristic patterns of catalytic behavior among the metallic elements have been established for certain classes of reactions, and these patterns provide a first step toward a more comprehensive understanding of catalytic specificity. Studies on metal alloys and related bimetallic catalysts have revived interest in a geometric factor in surface catalysis to complement the traditional electronic factor. Closely related to this geometric factor is the discovery that selectivity, rather than activity alone, is a major factor in reactions on bimetallic catalysts. Concurrent with progress in understanding how catalysts work, advances are also being made in the development of new catalyst systems, examples of which are the bimetallic (or polymetallic) cluster catalysts. Research in this area provides an example of how advances in catalyst technology can be realized within a framework of fundamental research on catalytic phenomena (38).     

Identification of active gold nanoclusters on iron oxide supports for CO oxidation

Gold nanocrystals absorbed on metal oxides have exceptional properties in oxidation catalysis, including the oxidation of carbon monoxide at ambient temperatures, but the identification of the active catalytic gold species among the many present on real catalysts is challenging. We have used aberration-corrected scanning transmission electron microscopy to analyze several iron oxide-supported catalyst samples, ranging from those with little or no activity to others with high activities. High catalytic activity for carbon monoxide oxidation is correlated with the presence of bilayer clusters that are approximately 0.5 nanometer in diameter and contain only approximately 10 gold atoms. The activity of these bilayer clusters is consistent with that demonstrated previously with the use of model catalyst systems.     

Iron catalysts for selective anti-Markovnikov alkene hydrosilylation using tertiary silanes

Alkene hydrosilylation, the addition of a silicon hydride (Si-H) across a carbon-carbon double bond, is one of the largest-scale industrial applications of homogeneous catalysis and is used in the commercial production of numerous consumer goods. For decades, precious metals, principally compounds of platinum and rhodium, have been used as catalysts for this reaction class. Despite their widespread application, limitations such as high and volatile catalyst costs and competing side reactions have persisted. Here, we report that well-characterized molecular iron coordination compounds promote the selective anti-Markovnikov addition of sterically hindered, tertiary silanes to alkenes under mild conditions. These Earth-abundant base-metal catalysts, coordinated by optimized bis(imino)pyridine ligands, show promise for industrial application.     

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。     

The interplay between chemistry and biology in the design of enzymatic catalysts

Chemists and biologists are focusing considerable effort on the development of efficient, highly selective catalysts for the synthesis or modification of complex molecules. Two approaches are described here, the generation of catalytic antibodies and hybrid enzymes, which exploit the binding and catalytic machinery of nature in catalyst design. Characterization of these systems is providing additional insight into the mechanisms of molecular recognition and catalysis which may, in turn, lead to the design of tailor-made catalysts for applications in chemistry, biology, and medicine.     

At the crossroads of chemistry and immunology: catalytic antibodies

Immunochemistry has historically focused on the nature of antigenicity and antibody-antigen recognition. However, in the last 5 years, the field of immunochemistry has taken a new direction. With the aid of mechanistic and synthetic chemistry, the vast network of molecules and cells of the immune system has been tapped to produce antibodies with a new function--catalytic antibodies. Because antibodies can be generated that selectively bind almost any molecule of interest, this new technology offers the potential to tailor-make highly selective catalysts for applications in biology, chemistry, and medicine. In addition, catalytic antibodies provide fundamental insight into important aspects of biological catalysis, including the importance of transition-state stabilization, proximity effects, general acid and base catalysts, electrophilic and nucleophilic catalysis, and strain.     

Surface science and catalysis

During the last 20 years, surface scientists have developed a variety of techniques that make it possible to study, on the molecular level, the structure, composition, and chemical bonding in the surface monolayer. Both single-crystal model catalysts and real catalyst systems that are active in important chemical processes have been investigated by a combination of ultrahigh-vacuum surface science techniques and high-pressure kinetic techniques in an effort to determine the relation between the structure and composition of the surface and the rates of reaction and selectivities. The structure of the atomic surface, a strongly adsorbed overlayer, and the oxidation states of surface atoms are the important molecular features of an active catalyst. As a consequence of modern surface science, the design and preparation of catalysts has developed from an art into a high technology.     

Linear metal nanostructures and size effects of supported metal catalysts

Nickel metal catalysts composed of nanometer by micrometer strips have been produced with solid-state microfabrication techniques. The strips are actually the edges of nickelcatalyst thin films, which are sandwiched between separating support layers, which are also nanometers thick. These linear nanostructures constitute well-defined and well-controlled catalytic entities that reproduce the size of traditional supported metal clusters in one dimension, thus separating size from total number of atoms in the catalyst. Examination of their catalytic activity showed that they duplicate the behavior of conventional supported clusters. A specific rate maximum was observed for the hydrogenolysis of ethane at a nanoscale dimension similar to the cluster size at which the rate is maximum in the case of the supported cluster studies, whereas the hydrogenation of ethylene shows no such size dependency. The results suggest that the surface-to-volume ratio or the number of atoms in the catalytic entity cannot be the source of these size effects and that either support effects or nonequilibrium surface structures are the determining factors.     

Catalytic processes in the atmospheres of Earth and venus

Photochemical processes in planetary atmospheres are strongly influenced by catalytic effects of minor constituents. Catalytic cycles in the atmospheres of Earth and Venus are closely related. For example, chlorine oxides (CIOx) act as catalysts in the two atmospheres. On Earth, they serve to convert odd oxygen (atomic oxygen and ozone) to molecular oxygen. On Venus they have a similar effect, but in addition they accelerate the reactions of atomic and molecular oxygen with carbon monoxide. The latter process occurs by a unique combination of CIOx catalysis and sulfur dioxide photosensitization. The mechanism provides an explanation for the very low extent of carbon dioxide decomposition by sunlight in the Venus atmosphere.     

The active site of methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts

One of the main stumbling blocks in developing rational design strategies for heterogeneous catalysis is that the complexity of the catalysts impairs efforts to characterize their active sites. We show how to identify the crucial atomic structure motif for the industrial Cu/ZnO/Al(2)O(3) methanol synthesis catalyst by using a combination of experimental evidence from bulk, surface-sensitive, and imaging methods collected on real high-performance catalytic systems in combination with density functional theory calculations. The active site consists of Cu steps decorated with Zn atoms, all stabilized by a series of well-defined bulk defects and surface species that need to be present jointly for the system to work.     

Conducting Layered Organic-inorganic Halides Containing <110>-Oriented Perovskite Sheets

Single crystals of the layered organic-inorganic perovskites, [NH(2)C(I=NH(2)](2)(CH(3)NH(3))m SnmI3m+2, were prepared by an aqueous solution growth technique. In contrast to the recently discovered family, (C(4)H(9)NH(3))(2)(CH(3)NH(3))n-1SnnI3n+1, which consists of (100)-terminated perovskite layers, structure determination reveals an unusual structural class with sets of m <110>-oriented CH(3)NH(3)SnI(3) perovskite sheets separated by iodoformamidinium cations. Whereas the m = 2 compound is semiconducting with a band gap of 0.33 +/- 0.05 electron volt, increasing m leads to more metallic character. The ability to control perovskite sheet orientation through the choice of organic cation demonstrates the flexibility provided by organic-inorganic perovskites and adds an important handle for tailoring and understanding lower dimensional transport in layered perovskites.     

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.     

分子筛改性催化乳酸丁酯制备农药中间体丙烯酸酯的合成研究

[目的]在改性分子筛的作用下,研究了以乳酸丁酯为原料催化制备农药中间体丙烯酸酯的工艺。[方法]考察了K、Ca、La等金属离子改性的NaX、NaY、ZSM-6、ZSM-8等沸石分子筛对乳酸丁酯脱水制备丙烯酸酯的影响。[结果]K/ZSM-6改性分子筛对该脱水过程具有较高的选择性和转化率。最佳反应温度为380℃,空速为3h-1,甲醇与乳酸丁酯的摩尔比为2.0,转化率达到100%,丙烯酸及其酯的总选择性达到了64.3%。     

Fine particles produced from automotive emissions-control catalysts

High concentrations of metal-containing condensation nuclei have been thermally induced from stabilized catalysts containing chromium, copper, and nickel under conditions closely resembling those found in automobile exhaust. Commercial and developmental catalyst formulations have been found to emit fine particles under a broad range of controlled conditions at temperatures ranging from 185 degrees to 800 degrees C, in filtered air, in a mixture of 3 percent carbon monoxide in molecular nitrogen, and in the product stream of a pulsed flame combustor.     

Isocyanate Intermediates in Ammonia Formation over Noble Metal Catalysts for Automobile Exhaust Reactions

Isocyanate species have been detected on the surface of noble metal catalysts during the reactions of carbon monoxide with nitric oxide. The intensity of the surface isocyanate infrared band correlates with the known ammonia-forming tendencies among the noble metals. The discovery of this isocyanate species suggests a new mechanistic pathway to the ammonia formed during catalytic reduction of nitrogen oxides in automobile exhaust.     

A dynamic knockout reveals that conformational fluctuations influence the chemical step of enzyme catalysis

Conformational dynamics play a key role in enzyme catalysis. Although protein motions have clear implications for ligand flux, a role for dynamics in the chemical step of enzyme catalysis has not been clearly established. We generated a mutant of Escherichia coli dihydrofolate reductase that abrogates millisecond-time-scale fluctuations in the enzyme active site without perturbing its structural and electrostatic preorganization. This dynamic knockout severely impairs hydride transfer. Thus, we have found a link between conformational fluctuations on the millisecond time scale and the chemical step of an enzymatic reaction, with broad implications for our understanding of enzyme mechanisms and for design of novel protein catalysts.     

Electron localization determines defect formation on ceria substrates

The high performance of ceria (CeO2) as an oxygen buffer and active support for noble metals in catalysis relies on an efficient supply of lattice oxygen at reaction sites governed by oxygen vacancy formation. We used high-resolution scanning tunneling microscopy and density functional calculations to unravel the local structure of surface and subsurface oxygen vacancies on the (111) surface. Electrons left behind by released oxygen localize on cerium ions. Clusters of more than two vacancies exclusively expose these reduced cerium ions, primarily by including subsurface vacancies, which therefore play a crucial role in the process of vacancy cluster formation. These results have implications for our understanding of oxidation processes on reducible rare-earth oxides.     

Ferroelectricity at the nanoscale: local polarization in oxide thin films and heterostructures

Ferroelectric oxide materials have offered a tantalizing potential for applications since the discovery of ferroelectric perovskites more than 50 years ago. Their switchable electric polarization is ideal for use in devices for memory storage and integrated microelectronics, but progress has long been hampered by difficulties in materials processing. Recent breakthroughs in the synthesis of complex oxides have brought the field to an entirely new level, in which complex artificial oxide structures can be realized with an atomic-level precision comparable to that well known for semiconductor heterostructures. Not only can the necessary high-quality ferroelectric films now be grown for new device capabilities, but ferroelectrics can be combined with other functional oxides, such as high-temperature superconductors and magnetic oxides, to create multifunctional materials and devices. Moreover, the shrinking of the relevant lengths to the nanoscale produces new physical phenomena. Real-space characterization and manipulation of the structure and properties at atomic scales involves new kinds of local probes and a key role for first-principles theory.     

Phosphorus: an elemental catalyst for diamond synthesis and growth

As diamond-producing catalysts, 12 transition metals such as iron, cobalt, and nickel were first reported by General Electric researchers more than 30 years ago. Since then, no additional elemental catalyst has been reported. An investigation of the catalytic action of group V elements is of great interest from the viewpoint of producing an n-type semiconducting diamond crystal. In the present study, diamond was synthesized from graphite in the presence of elemental phosphorus at high pressure and temperature (7.7 gigapascals and 1800 degrees C). Furthermore, single-crystal diamond was grown on a diamond seed crystal.     

Thermographic selection of effective catalysts from an encoded polymer-bound library

A general method is introduced for the rapid and simultaneous evaluation of each member of large encoded catalyst libraries for the ability to catalyze a reaction in solution. The procedure was used to select active catalysts from a library of potential polymer-bound multifunctional catalysts. From approximately 7000 beads screened (3150 distinct catalysts), 23 beads were selected for catalysis of an acylation reaction. Kinetic experiments indicate that the most strongly selected beads are also the most efficient catalysts.