Effect of Mechanochemical Activation on the Catalytic Properties of Ferrites with the Spinel Structure

It was found experimentally that stacking defects formed in the mechanochemical activation of zinc ferrite enhanced the specific catalytic activity in the reaction of CO oxidation. The specific rate of CO oxidation was a linear function of defect concentration, which was determined using Mössbauer spectroscopy and X-ray diffraction. A conclusion was drawn that the same centers are responsible for an increase in the catalytic activity, the sorption capacity for hydrogen sulfide, and the reactivity of zinc ferrite in the interaction with hydrochloric acid. It was assumed that analogous factors caused an increase in the catalytic activity and reactivity of magnesium ferrite.     

MnO x -Al2O3 catalysts for deep oxidation prepared with the use of mechanochemical activation: The effect of synthesis conditions on the phase composition and catalytic properties

The catalytic activity of alumina-manganese catalysts in the oxidation of CO was studied. The MnO _x -Al₂O₃ catalysts were prepared by an extrusion method with the introduction of mechanically activated components (manganese oxide and its mixtures with aluminum oxide, aluminum hydroxide, and a mixture of a manganese salt with aluminum hydroxide) into a paste of aluminum hydroxide followed by thermal treatment in air or argon at 1000°C. In the majority of cases, the catalysts contained a mixture of the phases of β-Mn₃O₄ (Mn₂O₃), α-Al₂O₃, and δ-Al₂O₃. The presence of low-temperature δ-Al₂O₃ suggested the incomplete interaction of manganese and aluminum oxides. It was found that the catalytic activity of MnO _x -Al₂O₃ depends on the degree of interaction of the initial reactants, and its value is correlated with the amount of β-Mn₃O₄ in the active constituent. The intermediate thermal treatment of components at 700°C negatively affects the catalytic activity as a result of the formation of Mn₂O₃ and the coarsening of particles, which levels the results of mechanochemical activation. The greatest degree of interaction between Al- and Mn-containing components was reached in the selection of mechanochemical activation conditions by decreasing the size of grinding bodies, optimizing the time of mechanochemical activation, and using the mechanochemical activation of precursor mixtures. As a result of mechanochemical activation, the initial reactants were dispersed, the amounts of MnO₂ and Mn₂O₃ changed, and defects were formed; this strengthened the interaction of components and increased catalytic activity.     

Preferential Carbon Monoxide Oxidation over Copper‐Based Catalysts under In Situ Ball Milling

In situ ball milling of solid catalysts is a promising yet almost unexplored concept for boosting catalytic performance. The continuous preferential oxidation of CO (CO‐PROX) under in situ ball milling of Cu‐based catalysts such as Cu/Cr₂O₃ is presented. At temperatures as low as −40 °C, considerable activity and more than 95 % selectivity were achieved. A negative apparent activation energy was observed, which is attributed to the mechanically induced generation and subsequent thermal healing of short‐lived surface defects. In situ ball milling at sub‐zero temperatures resulted in an increase of the CO oxidation rate by roughly 4 orders of magnitude. This drastic and highly selective enhancement of CO oxidation showcases the potential of in situ ball milling in heterogeneous catalysis.     

Enhanced low-temperature CO oxidation on a stepped platinum surface for oxygen pressures above 10(-5) Torr

The rate of CO oxidation has been characterized on the stepped Pt(411) surface for oxygen pressures up to 0.002 Torr, over the 100-1000 K temperature range. CO oxidation was characterized using both temperature-programmed reaction spectroscopy (TPRS) and in situ soft X-ray fluorescence yield near-edge spectroscopy (FYNES). New understanding of the important role surface defects play in accelerating CO oxidation for oxygen pressure above 10(-5) Torr is presented in this paper for the first time. For saturated monolayers of CO, the oxidation rate increases and the activation energy decreases significantly for oxygen pressures above 10(-5) Torr. This enhanced CO oxidation rate is caused by a change in the rate-limiting step to a surface reaction limited process above 10(-5) Torr oxygen from a CO desorption limited process at lower oxygen pressure. For example, in oxygen pressures above 0.002 Torr, CO(2) formation begins at 275 K even for the CO saturated monolayer, which is well below the 350 K onset temperature for CO desorption. Isothermal kinetic measurements in flowing oxygen for this stepped surface indicate that activation energies and preexponential factors depend strongly on oxygen pressure, a factor that has not previously been considered critical for CO oxidation on platinum. As oxygen pressure is increased from 10(-6) to 0.002 Torr, the oxidation activation energies for the saturated CO monolayer decrease from 24.1 to 13.5 kcal/mol for reaction over the 0.95-0.90 ML CO coverage range. This dramatic decrease in activation energy is associated with a simple increase in oxygen pressure from 10(-5) to 10(-3) Torr. Activation energies as low as 7.8 kcal/mol were observed for oxidation of an initially saturated CO layer reacting over the 0.4-0.25 ML coverage range in oxygen pressure of 0.002 Torr. These dramatic changes in reaction mechanism with oxygen pressure for stepped surfaces are consistent with mechanistic models involving transient low activation energy dissociation sites for oxygen associated with step sites. Taken together these experimental results clearly indicate that surface defects play a key role in increasing the sensitivity of CO oxidation to oxygen pressure.     

Reactivity of La1 ? xSrxFeO3 ? y (x = 0–1) Perovskites in Oxidation Reactions

Oxygen species and their reactivity in La_{1 − x} Sr _x FeO_{3 − y} perovskites prepared using mechanochemical activation were studied by temperature-programmed reduction (TPR) with hydrogen and methane. The experimental data were compared with data on the catalytic activity in oxidation reactions. It was found that the rates of CO and methane oxidation on the perovskites in the presence of gas-phase oxygen correlated (k = 0.8) with the amount of reactive surface oxygen species that were removed by TPR with hydrogen up to 250°C. Maximum amounts of this oxygen species were released from two-phase samples (x = 0.3, 0.4, and 0.8), which exhibited an enhanced activity in the reaction of CO oxidation. In the absence of oxygen in the gas phase, methane is oxidized by lattice oxygen. In this case, the process activity and selectivity depend on the mobility of lattice oxygen, which is determined by the temperature, the degree of substitution, the degree of reduction, and the microstructure of the oxide. Thus, the high mobility of oxygen, which is reached at high concentrations of point defects or interphase/domain boundaries, is of importance for the process of deep oxidation. However, the process of partial oxidation occurs in single-phase samples at low degrees of substitution (x = 0.1–0.2). __________ Translated from Kinetika i Kataliz, Vol. 46, No. 5, 2005, pp. 773–779. Original Russian Text Copyright ? 2005 by Isupova, Yakovleva, Alikina, Rogov, Sadykov.     

The effect of the particle size on the kinetics of CO electrooxidation on high surface area Pt catalysts

Using high-resolution transmission electron microscopy (TEM), infrared reflection-absorption spectroscopy (IRAS), and electrochemical (EC) measurements, platinum nanoparticles ranging in size from 1 to 30 nm are characterized and their catalytic activity for CO electrooxidation is evaluated. TEM analysis reveals that Pt crystallites are not perfect cubooctahedrons, and that large particles have "rougher" surfaces than small particles, which have some fairly smooth (111) facets. The importance of "defect" sites for the catalytic properties of nanoparticles is probed in IRAS experiments by monitoring how the vibrational frequencies of atop CO (nu(CO)) as well as the concomitant development of dissolved CO(2) are affected by the number of defects on the Pt nanoparticles. It is found that defects play a significant role in CO "clustering"on nanoparticles, causing CO to decrease/increase in local coverage, which yields to anomalous redshift/blueshift nu(CO) frequency deviations from the normal Stark-tuning behavior. The observed deviations are accompanied by CO(2) production, which increases by increasing the number of defects on the nanoparticles, that is, 1 < or = 2 < 5 < 30 nm. We suggest that the catalytic activity for CO adlayer oxidation is predominantly influenced by the ability of the surface to dissociate water and to form OH(ad) on defect sites rather than by CO energetics. These results are complemented by chronoamperometric and rotating disk electrode (RDE) data. In contrast to CO stripping experiments, we found that in the backsweep of CO bulk oxidation, the activity increases with decreasing particle size, that is, with increasing oxophilicity of the particles.     

Scientific Grounds for the Application of Mechanochemistry to Catalyst Preparation

It is shown that mechanochemical activation is efficient in creating waste-free energy-saving methods for the preparation of hydride catalysts, heteropoly acid catalysts, and catalysts for hydrocarbon decomposition into hydrogen and carbon materials, as well for the syntheses of earlier unknown catalytic systems. The capabilities of the mechanochemical methods are demonstrated on modifying the catalytic properties of catalysts and supports: an increase in the strength and catalytic activity, sorption properties, etc. Adhesion theory applied to melts helps to describe the mechanism of mechanochemical synthesis of catalytic systems.     

La—Cu—Mn系钙钛矿型（ABO3）催化剂性能

采用共沉淀法制得了Ｃｕ２＋部分取代Ｌａ３＋的Ｌａ１－ｘＣｕｘＭｎＯ３钙钛矿型催化剂，通过ＸＲＤ、ＴＰＲ、电镜分析及活性评价，研究了Ｃｕ２＋的部分取代对Ｌａ１－ｘＣｕｘＭｎＯ３系催化剂性能的影响．结果表明，Ｃｕ２＋部分取代Ｌａ３＋后，使催化剂易被还原，活化能降低，对ＣＨ４、ＣＯ氧化反应，均有最佳取代量使催化剂的活性最佳，其值分别为０．２和０．４，这是由于随ｘ值的增大，催化剂晶格缺陷增多，晶格氧的化学势增大的缘故     

在Pd(Ⅱ)-Cu(Ⅱ)/活性炭催化剂上水汽对CO氧化的影响

研究了ＣＯ在Ｐｄ（ Ⅱ） － Ｃｕ（ Ⅱ）／ 活性炭催化剂上的催化氧化反应，发现当空气中含有水汽时催化活性大大提高。并对ＣＯ 络合催化机理进行了讨论，求得总包反应级数约为１ ．３，表观活化能为５０ ．４６ｋＪ·ｍｏｌ－ １ 。     

Efficient CO oxidation at low temperature on Au(111)

The rate of CO oxidation to CO2 depends strongly on the reaction temperature and characteristics of the oxygen overlayer on Au(111). The factors that contribute to the temperature dependence in the oxidation rate are (1) the residence time of CO on the surface, (2) the island size containing Au-O complexes, and (3) the local properties, including the degree of order of the oxygen layer. Three different types of oxygen--defined as chemisorbed oxygen, a surface oxide, and a bulk oxide--are identified and shown to have different reactivity. The relative populations of the various oxygen species depend on the preparation temperature and the oxygen coverage. The highest rate of CO oxidation was observed for an initial oxygen coverage of 0.5 monolayers that was deposited at 200 K where the density of chemisorbed oxygen is maximized. The rate decreases when two-dimensional islands of the surface oxide are populated and further decreases when three-dimensional bulk gold oxide forms. Our results are significant for designing catalytic processes that use Au for CO oxidation, because they suggest that the most efficient oxidation of CO occurs at low temperature--even below room temperature--as long as oxygen could be adsorbed on the surface.     

Self-sustained oscillations within the temperature hysteresis in CO oxidation over Pd: Mathematical model of a cascade of continuous stirred-tank reactors

The results of temperature-programmed reaction experimental studies and mathematical modeling of self-sustained oscillations within an inverse temperature hysteresis in CO oxidation over Pd catalyst are presented. The experimental data demonstrate the influence of the reaction medium on the catalyst activity under reaction conditions. Under oxygen excess in the feeding gas mixture and high temperature, the defects appeared on the initially flat surface of metallic palladium due to deep oxidation of palladium (three-dimensional PdO nanoparticles were observed). The palladium oxide reduced under cooling of the catalytic system, and the catalyst surface became flat again. To take into account these variations of the palladium surface structure, we consider the piecewise-constant dependence of the rate constant of some reaction step on the concentrations of oxygen species, namely, the dissolved oxygen or oxide in the palladium bulk. The proposed model of the process in the cascade of continuous stirred-tank reactors that account for these dependences qualitatively describes the inverse temperature hysteresis as well as the oscillatory dynamics within the hysteresis loop which were obtained experimentally.     

Inhibition at perimeter sites of Au/TiO2 oxidation catalyst by reactant oxygen

TiO(2)-supported gold nanoparticles exhibit surprising catalytic activity for oxidation reactions compared to noble bulk gold which is inactive. The catalytic activity is localized at the perimeter of the Au nanoparticles where Au atoms are atomically adjacent to the TiO(2) support. At these dual-catalytic sites an oxygen molecule is efficiently activated through chemical bonding to both Au and Ti(4+) sites. A significant inhibition by a factor of 22 in the CO oxidation reaction rate is observed at 120 K when the Au is preoxidized, caused by the oxygen-induced positive charge produced on the perimeter Au atoms. Theoretical calculations indicate that induced positive charge occurs in the Au atoms which are adjacent to chemisorbed oxygen atoms, almost doubling the activation energy for CO oxidation at the dual-catalytic sites in agreement with experiments. This is an example of self-inhibition in catalysis by a reactant species.     

铂、钯负载型活性催化剂的制备及其对一氧化碳的催化氧化活性

用浸渍法分别将铂、钯负载在铝柱撑蒙脱石载体上,制备了铂、钯负载铝柱撑蒙脱石催化剂。运用X射线衍射(XRD)、原子吸收光谱(AAS)、透射电镜(TEM)等分析方法对样品的性能和结构进行了表征,并考察了不同铂、钯负载量的催化剂对一氧化碳的催化氧化性能。结果表明,铂、钯均以高度分散的纳米粒子状态均匀分布在载体表面,并表现出良好的CO催化氧化活性。铂、钯在铝柱撑蒙脱石载体表面的有效负载率在70%~76%之间,在相同的设计负载量条件下,铂的实际负载量和有效负载率均略大于钯。CO催化氧化试验结果表明,相对于负载前,负载后催化剂的催化活性明显增加,且其催化活性随着铂、钯负载量的增加而不断增强。在相同温度和负载量条件下,钯负载型催化剂的催化活性明显高于铂负载型催化剂。     

Effects of reduction temperature and metal-support interactions on the catalytic activity of Pt/gamma-Al2O3 and Pt/TiO2 for the oxidation of CO in the presence and absence of H2

TiO2- and gamma-Al2O3-supported Pt catalysts were characterized by HRTEM, XPS, EXAFS, and in situ FTIR spectroscopy after activation at various conditions, and their catalytic properties were examined for the oxidation of CO in the absence and presence of H2 (PROX). When gamma-Al2O3 was used as the support, the catalytic, electronic, and structural properties of the Pt particles formed were not affected substantially by the pretreatment conditions. In contrast, the surface properties and catalytic activity of Pt/TiO2 were strongly influenced by the pretreatment conditions. In this case, an increase in the reduction temperature led to higher electron density on Pt, altering its chemisorptive properties, weakening the Pt-CO bonds, and increasing its activity for the oxidation of CO. The in situ FTIR data suggest that both the terminal and bridging CO species adsorbed on fully reduced Pt are active for this reaction. The high activity of Pt/TiO2 for the oxidation of CO can also be attributed to the ability of TiO2 to provide or stabilize highly reactive oxygen species at the metal-support interface. However, such species appear to be more reactive toward H2 than CO. Consequently, Pt/TiO2 shows substantially lower selectivities toward CO oxidation under PROX conditions than Pt/gamma-Al2O3.     

Does enhanced oxygen activation always facilitate CO oxidation on gold clusters?

We investigate the catalytic activity of the subnanometer‐sized bimetallic Au₁₉Pt cluster for oxidation of CO via first‐principles density functional theory calculations. For this purpose we consider two structurally similar and energetically close homotops of the Au₁₉Pt cluster with the Pt atom occupying an edge (Td‐E) or a facet (Td‐S) site of a 20‐atom tetrahedron. Using these homotops as catalysts we calculate the complete reaction paths and the thermodynamic functions corresponding to the oxidation of CO to CO₂. It is found that the oxidation of CO on the Td‐S isomer occurs through a smaller reaction barrier (0.38 eV) as compared with that on the Td‐E isomer (0.70 eV), although the activation of O₂ on the latter is much higher than that on the former. Therefore, a clear conclusion is that a higher O₂ activation, which is generally believed to be the key factor for CO oxidation, solely cannot determine the catalytic efficiency of the Au‐Pt bimetallic clusters. In addition, we find a stronger CO adsorption on the Td‐E isomer (2.06 eV) as compared with that on the Td‐S isomer (1.68 eV). Although stronger CO adsorption on the Td‐E isomer leads to a higher O₂ activation; however, high value of CO adsorption energy deteriorates the catalytic activity of the Td‐E isomer towards the CO oxidation reaction. © 2015 Wiley Periodicals, Inc.     

High catalytic activity for CO oxidation of gold nanoparticles confined in acidic support Al-SBA-15 at low temperatures

While there is a large number of recent studies of Au nanocatalysts supported on metal oxides, low-temperature CO oxidation under an acidic environment has not yet been accomplished. Over a novel acidic Al-SBA-15 support, uniformly distributed gold nanoparticles with sizes approximately 2.7 nm were obtained by a successive procedure of aminosilane grafting, gold adsorption-reduction, and then high-temperature hydrogen treatment. The catalyst system, Au@Al-SBA-15, exhibits extraordinarily high activity for CO oxidation at 80 degrees C. By varying the Si/Al ratio of the support, the dependence of the catalytic activity on the support Si/Al ratio was found in the CO oxidation reaction.     

纳米金催化剂上CO低（常）温氧化的研究

金历来被认为是催化惰性的,但近年来有关金催化剂的研究与开发引起人们的兴趣与关注。负载纳米金催化剂显示了良好的催化性能,尤其对一氧化碳氧化反应,能够在低（常）温下将CO氧化为CO₂。和其他CO氧化催化剂相比,金催化剂具有高的催化活性、稳定性和抗潮湿的性能,预示着更加广泛的应用前景。本文从制备方法、载体的性质、微粒粒径的大小、预处理、活性机理和催化反应机理等方面进行综合与评述。     

纳米级ZnO/MgO固体的合成及其对CO的氧化活性

The ZnO/MgO solid samples containing the ZnO nanoparticles of controllable size were prepared using colloidal technique. The catalytic performance of the ZnO/MgO samples for the CO oxidation was measured. It was revealed that the rate of the CO oxidation reaction on the ZnO nanoparticles with variable average radius (2.01-2.29 nm) shows nonmonotonic dependence caused by the quantum-confinement effect.     

Oxidation of CO on Mn-Containing Catalysts Prepared by Pyrolysis of Metal β-Diketonates on Synthetic Ceramic Foam

New catalytic systems for oxidation of CO to CO₂ were developed. These systems are based on composite Mn, Mn-Ni, and Mn-Cu coatings and are prepared by gas-phase thermolysis of metal β-diketonates on a ceramic foam support. The relative activity of the new catalytic systems was examined. The kinetic and activation parameters of the oxidation of CO on these catalysts were determined.     

Defect-mediated reactivity of Pt/TiO2 catalysts: the different role of titanium and oxygen vacancies

Defects are ubiquitous in oxide supports and can often tune the catalytic property of supported metal catalysts. This work describes the distinct role of titanium and oxygen vacancies of TiO_2 supports in the catalytic performance of supported Pt catalysts for CO oxidation. Pt was loaded on the TiO_2 supports with oxygen vacancies(VO-TiO_2) and titanium vacancies(VTiTiO_2). It was found that different defects of TiO_2 could distinctively modify the electron property of Pt and thereby CO adsorption strength. The strength of CO adsorption on Pt/VTi-TiO_2 is enhanced, while that of Pt/VO-TiO_2 becomes weaker.Additionally, the presence of defects would also promote the reducibility of catalysts. On the account of the superior redox ability, both Pt/VTi-TiO_2 and Pt/VO-TiO_2 exhibit a higher activity than Pt supported on normal TiO_2 for CO oxidation.