Elucidation of CO2 Formation Mechanism in CO + NO Reaction on Pd(111) and Pd(110) Surfaces Using IR Chemiluminescence Method

The infrared (IR) chemiluminescence technique was applied to steady-state CO oxidation by NO on Pd(111) and Pd(110). From a comparison of IR emission spectra of CO₂ between the CO + NO and CO + O₂ reactions, it was found that the vibrational energy states of CO₂ in the CO + NO reaction were similar to those in the CO + O₂ reaction. This indicates that the reaction path of CO₂ formation in CO + NO is the same as that in CO + O₂, although the vibrational states are very dependent on the surface structure.     

Vibrationally Excited CO2 Formed in CO + NO Reaction on Pd(110) Surface in High Surface Temperature Range

The infrared chemiluminescence spectra of CO₂ formed during steady-state CO+NO reaction over Pd(110) indicated that the temperature of the bending vibrational mode was much higher than that of the antisymmetric one at higher surface temperatures such as 800–850 K. Especially, in the high temperature range, more vibrationally excited CO₂ was formed from CO+NO reaction than CO+O₂ reaction. On the basis of the result, we propose the model structure of reaction intermediates for CO₂ formation in CO+NO reaction, which is different from that in CO+O₂ reaction.     

Understanding Automotive Exhaust Catalysts Using a Surface Science Approach: Model NOx Storage Materials

The structure–reactivity relationships of model BaO-based NO_x storage/reduction catalysts were investigated under well controlled experimental conditions using surface science analysis techniques. The reactivity of BaO toward NO₂, CO₂, and H₂O was studied as a function of BaO layer thickness [0 < θ_BaO < 30 monolayer (ML)], sample temperature, reactant partial pressure, and the nature of the substrate the NO_x storage material was deposited onto. Most of the efforts focused on understanding the mechanism of NO₂ storage either on pure BaO, or on BaO exposed to CO₂ or H₂O prior to NO₂ exposure. The interaction of NO₂ with a pure BaO film results in the initial formation of nitrite/nitrate ion pairs by a cooperative adsorption mechanism predicted by prior theoretical calculations. The nitrites are then further oxidized to nitrates to produce a fully nitrated surface. The mechanism of NO₂ uptake on thin BaO films (<4 ML), BaO clusters (<1 ML) and mixed BaO/Al₂O₃ layers are fundamentally different: in these systems initially nitrites are formed only, and then converted to nitrates at longer NO₂ exposure times. These results clarify the contradicting mechanisms presented in prior studies in the literature. After the formation of a nitrate layer the further conversion of the underlying BaO is slow, and strongly depends on both the sample temperature and the NO₂ partial pressure. At 300 K sample temperature amorphous Ba(NO₃)₂ forms that then can be converted to crystalline nitrates at elevated temperatures. The reaction between BaO and H₂O is facile, a series of Ba(OH)₂ phases form under the temperature and H₂O partial pressure regimes studied. Both amorphous and crystalline Ba(OH)₂ phases react with NO₂, and initially form nitrites only that can be converted to nitrates. The NO₂ adsorption capacities of BaO and Ba(OH)₂ are identical, i.e., both of these phases can completely be converted to Ba(NO₃)₂. In contrast, the interaction of CO₂ with pure BaO results in the formation of a BaCO₃ layer that prevents to complete carbonation of the entire BaO film under the experimental conditions applied in these studies. However, these “carbonated” BaO layers readily react with NO₂, and at elevated sample temperature even the carbonate layer is converted to nitrates. The importance of the metal oxide/metal interface in the chemistry on NO_x storage-reduction catalysts was studied on BaO(<1 ML)/Pt(111) reverse model catalysts. In comparison to the clean Pt(111), new oxygen adsorption phases were identified on the BaO/Pt(111) surface that can be associated with oxygen atoms strongly adsorbed on Pt atoms at the peripheries of BaO particles. A simple kinetic model developed helped explain the observed thermal desorption results. The role of the oxide/metal interface in the reduction of Ba(NO₃)₂ was also substantiated in experiments where Ba(NO₃)₂/O/Pt(111) samples were exposed to CO at elevated sample temperature. The catalytic decomposition of the nitrate phase occurred as soon as metal sites opened up by the removal of interfacial oxygen via CO oxidation from the O/Pt(111) surface. The temperature for catalytic nitrate reduction was found to be significantly lower than the onset temperature of thermal nitrate decomposition.     

Reaction of Formic Acid on Zn-Modified Pd(111)

The decomposition of formic acid on Zn/Pd(111) was studied using Temperature Programmed Desorption and High Resolution Electron Energy Loss Spectroscopy. On Pd(111), HCOOH decomposes via both dehydration and dehydrogenation pathways to produce CO, CO₂, H₂ and H₂O. Small amounts of Zn (<0.1 mL) incorporated the Pd(111) surface were found to increase the stability of formate species and alter their decomposition selectivity to favor dehydrogenation, resulting in an increase in CO₂ production. This difference in reactivity appears to be caused by relatively long range electronic interactions between surface Pd and Zn atoms and may be important in Pd/ZnO methanol steam reforming catalysts which exhibit high selectivities to CO₂ and H₂.     

CO Oxidation and the CO/NO Reaction on Pd(110) Studied Using “Fast” XPS and a Molecular Beam Reactor

We have combined the use of a molecular beam reactor and in situ spectroscopy (XPS) in order to correlate changes in the rate of CO oxidation and the CO–NO reaction with the coverages of the adsorbates and intermediates on the surface. In the reactor, both reactions exhibit an isothermal “light-off” phenomenon in which the rate autocatalytically increases with time. In the case of the CO oxidation reaction this is due to the desorption of CO which releases extra sites for O₂ dissociation which, in turn, removes more CO, and hence the acceleration. In effect the reaction can be written as 2CO_a + O_2g + 2S → 2CO_2g + 4S, the acceleration coming from the release of extra adsorption sites S, which are involved in the reaction itself. “Fast XPS”, carried out in situ during the course of the reaction, shows domination of the surface by CO_a below 390 K and domination by O_a above that temperature, with a rapid change in surface coverage over a very narrow temperature window. On high surface area samples this acceleration is further reinforced due to a rapid temperature increase because of the highly exothermic nature of the overall reaction. The situation for the CO–NO reaction is broadly similar, except that the surface is dominated by NO at low temperature, not CO which tends to be displaced from the surface by NO. “Light-off” is dictated by the onset of the dissociation of NO_a, which occurs at ～400 K. Once N_a and O_a are formed, N₂O production is immediate and accelerates due to the creation of vacant sites for both NO and CO adsorption, the latter removing O_a as CO_2g. Again, the reaction self-accelerates and there is a rapid change of surface coverage from NO_a to O_a at ～450 K. The overall self acceleration is due to the following overall reaction, 2NO_a + CO_g + S → N₂O_g + CO_2g + 3S, again producing more adsorption sites (S) in carrying out the reaction step. The rate is reduced at high temperature due to domination of the surface by O_a and to the reduced coverages of the molecular species.     

Fabrication of an Effusive Molecular Beam Instrument for Surface Reaction Kinetics—CO Oxidation and NO Reduction on Pd(111) Surfaces

A simple molecular beam instrument (MBI) was fabricated for measuring the fundamental parameters in catalysis such as, sticking coefficient, transient and steady state kinetics and reaction mechanism of gas/vapor phase reactions on metal surfaces. Important aspects of MBI fabrication are given in detail. Nitric oxide (NO) decomposition and NO reduction with carbon monoxide (CO) on Pd(111) surfaces were studied. Interesting results were observed for the above reactions and they support the efficiency of the MBI to derive the fundamental parameters of adsorption and catalysis. Sustenance of CO oxidation at 400 K is dependent mostly on the absence of CO-poisoning; apparently, CO + O recombination is the rate determining step ≤400 K. NO adsorption measurements on Pd(111) surface clearly indicating a typical precursor kinetics. Displacement of the chemisorbed CO by NO on Pd(111) surfaces was observed directly with NO + CO beams in the transient kinetics. It is also relatively easy to identify the rate-determining step directly from the MBI data and the same was demonstrated for the above reactions.     

Catalytic Conversion of NO and C3H6 in Exhaust Gases Over Silver Catalysts Under Stoichiometric or Excess Oxygen

The role of Ag in simultaneously catalyzing NO reduction and C₃H₆ oxidation was shown to be strongly dependent on the redox properties of its local environment. Under an atmosphere of 1,000 ppm NO, 3,000 ppm C₃H₆, and 1% O₂ and a GHSV of 30,000 h⁻¹, a perovskite La_0.88Ag_0.12FeO₃ prepared by reactive grinding is active giving a complete NO conversion and 92% C₃H₆ conversion at 500 °C. These values are much higher than the NO conversion of 55% and C₃H₆ conversion of 45% obtained over a 3 wt.% Ag/Al₂O₃ catalyst under the same conditions. Under an excess of oxygen (10% O₂) a good SCR performance with a plateau of N₂ yield above 97% over a wide temperature window of 350–500 °C along with C₃H₆ conversion of 90% at 500 °C was observed over Ag/Al₂O₃, while minor N₂ yields (∼10% at 250–350 °C) and high C₃H₆ conversions (reaching ∼100% at 450 °C) were obtained over La_0.88Ag_0.12FeO₃. Abundant molecular oxygen is desorbed from Ag substituted perovskite after 10% O₂ adsorption as verified by O₂- temperature programmed desorption (TPD). This reflects the strongly oxidative properties of La_0.88Ag_0.12FeO₃, which lead to a satisfactory NO reduction at 1% O₂ due to the ease of nitrate formation but to a significant C₃H₆ combustion above that value. The formation of nitrate species over the less oxidizing Ag/Al₂O₃ was accelerated under an excess of oxygen resulting in an excellent lean NO reduction behavior. The redox properties of silver catalysts could be adjusted via mixing perovskite with alumina for an optimal elimination of both NO and C₃H₆ over the whole range of oxygen concentration between 0 to 10%.     

汽车尾气催化净化技术进展

催化剂是当前控制汽车尾气的主要手段。本文介绍了汽车尾气净化 发展过程、净化应用、组成原理、制备工艺以及表征评价方法等。     

Decomposition of Furan on Pd(111)

Periodic density functional theory calculations (GGA-PBE) have been performed to investigate the mechanism for the decomposition of furan up to CO formation on the Pd(111) surface. At 1/9 ML coverage, furan adsorbs with its molecular plane parallel to the surface in several states with nearly identical adsorption energies of ?1.0?eV. The decomposition of furan begins with the opening of the ring at the C?CO position with an activation barrier of E _a ?=?0.82?eV, which yields a C₄H₄O aldehyde species that rapidly loses the ?? H to form C₄H₃O (E _a ?=?0.40?eV). C₄H₃O further dehydrogenates at the ?? position to form C₄H₂O (E _a ?=?0.83?eV), before the ???C?? C?CC bond dissociates (E _a ?=?1.08?eV) to form CO. Each step is the lowest-barrier dissociation step in the respective species. A simple kinetic analysis suggests that furan decomposition begins at 240?C270?K and is mostly complete by 320?K, in close agreement with previous experiments. It is suggested that the C₄H₂O intermediate delays the decarbonylation step up to 350?K.     

Effects of Ring Structure on the Reaction Pathways of Cyclic Esters and Ethers on Pd(111)

A combination of experimental surface science techniques and density functional theory calculations has been employed to understand the adsorption and surface chemistry of a variety of C₄ cyclic oxygenates on the (111) surface of Pd. These C₄ cyclic oxygenates represent important probe molecules for production of chemicals from biomass-derived carbohydrates. The surface level studies of these intermediates reveal that adsorption and reactivity trends are determined by ring size/strain, degree of unsaturation, nature of the oxygenate function, and composition of the metal surface.     

Catalytic disruption and volatilization of rhodium particles on silica in NO + CO

Initially reduced 100 Å diameter Rh metal particles on SiO₂ are found by TEM to be dispersed into an amorphous metal film by treatment in 5% NO + 5% CO in He at 260 °C, leaving thin rings around the perimeter of the original particles. Electron diffraction shows that Rh is amorphous while XPS shows that the Rh is approximately zero valent in the dispersed state. Continued heating in this mixture resulted in irreversible volatilization of the Rh even at these low temperatures. Subsequent heating in H₂ at 650 °C caused sintering and the reformation of crystalline Rh particles, but with a lower loading than observed initially. Treatment of Rh particles in 5% NO at 260 °C causes Rh particles to shrink in diameter and to form thin shells around their perimeters. The only change observed after treatment in 5% CO alone at 260 °C was slight sintering of adjacent Rh particles.This research was sponsored by NSF under Grant CBT-882745 and by a grant from Ford Motor Company.     

An overview: Comparative kinetic behaviour of Pt, Rh and Pd in the NO + CO and NO + H2 reactions

This paper reports a comparative kinetic investigation of the overall reduction of NO in the presence of CO or H₂ over supported Pt-, Rh- and Pd-based catalysts. Different activity sequences have been established for the NO+H₂ reaction Pt/Al₂O₃>Pd/Al₂O₃>Rh/Al₂O₃ and for the NO+CO reaction Rh/Al₂O₃>Pd/Al₂O₃> Pt/Al₂O₃. It was found that both reactions differ from the rate determining step usually ascribed to the dissociation of chemisorbed NO molecules. The rate enhancement observed for the NO+H₂ reaction has been mainly related to the involvement of a dissociation step of chemisorbed NO molecules assisted by adjacent chemisorbed H atoms. The calculation of the kinetic and thermodynamic constants from steady-state rate measurements and subsequent comparisons show that Pd and Rh are predominantly covered by chemisorbed NO molecules in our operating conditions which could explain either changes in activity or in selectivity with the lack of ammonia formation on Rh/Al₂O₃ during the NO+H₂ reaction. Interestingly, Pd and Rh exhibit similar selectivity behaviour towards the production of nitrous oxide (N₂O) irrespective of the nature of the reducing agent (CO or H₂). A weak partial pressure dependency of the selectivity is observed which can be related to the predominant formation of N₂ via a reaction between chemisorbed NO molecules and N atoms, while over Pt-based catalysts the associative desorption of two adjacent N atoms would occur simultaneously. Such tendencies are still observed under lean conditions in the presence of an excess of oxygen. However, a detrimental effect is observed on the selectivity with an enhancement of the competitive H₂+O₂ reaction, and on the activity behaviour with a strong oxygen inhibiting effect on the rate of NO conversion, particularly on Rh.     

Catalytic properties of La2CuO4 in the CO + NO reaction

La₂CuO₄ is an active catalyst for the reduction of NO by CO. Under reaction conditions, the catalyst exhibits an activation which results in a lowering of the light‐off temperature by 80°C. XRD, TEM and EDX analysis carried out after the catalytic test indicate that the mixed oxide has been reduced to form a La₂O₃, Cu binary system. It seems that metallic copper species are the most active sites in the CO + NO reaction. This revised version was published online in July 2006 with corrections to the Cover Date.     

Pd/Al2O3催化剂上低浓度CO氧化的研究

采用共沉淀法和浸渍法制备了2%Pd-Al2O3催化剂,在固定反应器中评价不同制备方法(共沉淀和浸渍)、助剂(1%K和1%Mg)、预处理方法(快速氧化和缓慢还原)、空速(726h-1、1638h-1和5274h-1)情况下2%Pd-Al2O3催化剂对CO氧化的催化活性。结果表明,共沉淀法制备的2%Pd50%Zr-Al2O3催化剂有较高的反应活性,该催化剂经缓慢还原预处理活化,在温度为70℃时就可以使低浓度的CO完全氧化。     

汽车尾气净化催化剂的净化原理与作用机理分析

文章阐述了汽车尾气净化催化剂的净化原理,并以含稀土钙钛矿(ABO3)型催化剂为例,对其作用机理进行了分析,为研究开发符合我国国情的汽车尾气净化催化剂奠定了理论基础。     

Structure and Reactivity of Alkyl Ethers Adsorbed on CeO2(111) Model Catalysts

The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO₂(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tilt away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO₂) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C?CO bond from ethers requires the presence of ??-hydrogen.     

甲醛在Pd(111)与Pd(100)晶面上氧化的计算化学研究

使用密度泛函理论对甲醛分子在Pd(111)晶面与Pd(100)晶面的氧化反应机理进行研究,结果表明,Pd(100)晶面相比于Pd(111)晶面更有利于甲醛分子的氧化,为进一步合理设计甲醛氧化贵金属催化剂提供了理论依据。     

Modelling Study of the Temperature-Programmed Conversion Curves of NO Reduction by CO over Supported Pt- and Rh-Based Catalysts

We have attempted to model the rate of NO transformation on a sintered Pt–Rh/Al₂O₃ three-way catalyst (TWC) in various temperature and conversion conditions close to the actual ones in TWCs. For this purpose a rate expression, previously established from kinetic measurements performed at a single temperature of 300°C, was used. The temperature dependency of the kinetic and thermodynamic parameters, using a non-linear optimisation, has been previously determined. Then, temperature-programmed experiments, performed in a fixed-bed flow reactor at atmospheric pressure under differential conditions, have been modelled using such parameters. A similar procedure has been achieved for modelling the TP experiments on Rh/Al₂O₃. Both results have been compared and discussed in the light of previous surface characterisations.