Structure sensitivity in the oxidation of CO on Ir surfaces

We report results on the catalytic oxidation of carbon monoxide (CO) over clean Ir surfaces that are prepared reversibly from the same crystal in situ with different surface morphologies, from planar to nanometer-scale facets of specific crystal orientations and various sizes. Our temperature-programmed desorption (TPD) data show that both planar Ir(210) and faceted Ir(210) are very active for CO oxidation to form CO2. Preadsorbed oxygen promotes the oxidation of CO, whereas high coverages of preadsorbed CO poison the reaction by blocking the surface sites for oxygen adsorption. At low coverages of preadsorbed oxygen (< or = 0.3 ML of O), the temperature Ti for the onset of CO2 desorption decreases with increasing CO coverage. At high coverages of preadsorbed oxygen (> 0.5 ML of O), T(i) is < 330 K and is independent of CO coverage. Moreover, we find clear evidence for structure sensitivity in CO oxidation over clean planar Ir(210) versus that over clean faceted Ir(210): the CO2 desorption rate is sensitive to the surface morphological differences. However, no evidence has been found for size effects in CO oxidation over faceted Ir(210) for average facet size ranging from 5 to 14 nm. Energetically favorable binding sites for O/Ir(210) are characterized using density functional theory (DFT) calculations.     

Active surfaces for CO oxidation on palladium in the hyperactive state

Hyperactivity was previously observed for CO oxidation over palladium, rhodium, and platinum surfaces under oxygen-rich conditions, characterized by reaction rates 2-3 orders higher than those observed under stoichiometric reaction conditions [Chen et al. Surf. Sci. 2007, 601, 5326]. In the present study, the formation of large amounts of CO(2) and the depletion of CO at the hyperactive state on both Pd(100) and polycrystalline Pd foil were evidenced by the infrared intensities of the gas phase CO(2) and CO, respectively. The active surfaces at the hyperactive state for palladium were characterized using infrared reflection absorption spectroscopy (IRAS, 450-4000 cm(-1)) under the realistic catalytic reaction condition. Palladium oxide on a Pd(100) surface was reduced eventually by CO at 450 K, and also under CO oxidation conditions at 450 K. In situ IRAS combined with isotopic (18)O(2) revealed that the active surfaces for CO oxidation on Pd(100) and Pd foil are not a palladium oxide at the hyperactive state and under oxygen-rich reaction conditions. The results demonstrate that a chemisorbed oxygen-rich surface of Pd is the active surface corresponding to the hyperactivity for CO oxidation on Pd. In the hyperactive region, the CO(2) formation rate is limited by the mass transfer of CO to the surface.     

CO oxidation on Ir(111) surfaces under large non-Gaussian noise

In this article we consider the CO oxidation on Ir(111) surfaces under large external noise with large autocorrelation imposed on the composition of the feed gas, both in experiments and in theory. We report new experimental results that show how the fluctuations force the reaction rate to jump between two well defined states. The statistics of the reaction rate depend on those of the external noise, and neither of them have a Gaussian distribution, and thus they cannot be modeled by white or colored noise. A continuous-time discrete-state Markov process is proposed as a suitable model for the observed phenomena. The model captures the main features of the observed fluctuations and can be modified to accommodate other surface reactions and other systems under non-Gaussian external noise.     

Effects of internal noise for rate oscillations during CO oxidation on platinum surfaces

We have studied the influence of internal noise on the reaction rate oscillation during carbon-monoxide oxidation on single crystal platinum surfaces using chemical Langevin equations. Considering that the surface is divided into small well-mixed cells, we have focused on the dynamic behavior inside a single cell. Internal noise can induce rate oscillations and the performance of the stochastic rate oscillations shows double maxima with the variation of the internal noise intensity, demonstrating the occurrence of internal noise coherent biresonance. The relationship between such a phenomenon with the deterministic bifurcation features of the system is also discussed.     

Theoretical analysis of internal fluctuations and bistability in CO oxidation on nanoscale surfaces

The bistable CO oxidation on a nanoscale surface is characterized by a limited number of reacting molecules on the catalytic area. Internal fluctuations due to finite-size effects are studied by the master equation with a Langmuir-Hinshelwood mechanism for CO oxidation. Analytical solutions can be found in a reduced one-component model after the adiabatic elimination of one variable which in our case is the oxygen coverage. It is shown that near the critical point, with decreasing surface area, one cannot distinguish between two macroscopically stable stationary states. This is a consequence of the large fluctuations in the coverage which occur on a fast time scale. Under these conditions, the transition times between the macroscopic states also are no longer separated from the short-time scale of the coverage fluctuations as is the case for large surface areas and far away from the critical point. The corresponding stationary solutions of the probability distribution and the mean first passage times calculated in the reduced model are supported by numerics of the full two-component model.     

Pt-表层限域的表面FeOx结构用于低温CO氧化反应

通过简单的浸渍-还原并随后在酸性溶液中处理制备了Pt-Cu双金属催化剂. 利用电感耦合等离子体发射光谱、X射线衍射和X射线光电子能谱对不同处理条件下的Pt-Cu纳米粒子的结构和组成进行了表征. 研究发现, Pt-Cu催化剂在高温H₂中还原形成了PtCu₃合金结构, 酸洗处理后形成了包含Pt-骨架(Pt-skeleton)的表面结构和PtCu₃合金核的纳米粒子. 而Pt-骨架结构又可通过在H₂中退火转变为规整的Pt-表层(Pt-skin)结构. Pt-表层表面修饰Fe氧化物后在CO选择氧化反应中表现出较好的催化性能. 通过此方法制备的三金属Pt-Cu-Fe催化剂可达到与Pt-Fe相近的高活性, 并且催化剂中Pt的用量大大降低.     

Co3O4纳米晶表面晶格氧催化氧化CO的理论研究

近年来,纳米科学技术的迅速发展给催化领域,特别是多相催化带来了新的机遇和挑战.科学家们开始着眼于在纳米尺度上对催化剂结构和催化性能进行表征、控制和设计.Co3O4作为一种重要的半导体金属氧化物材料,由于其优异的氧化还原性质,在锂电池、气体传感器以及多相催化领域得到了十分广泛的应用.最近,研究者发现Co3O4纳米晶在催化CO低温氧化和CH4活化等一系列重要反应中表现出显著的反应活性和晶面效应,表明有效设计和合成特定的高活性、高选择性的纳米晶面,对催化领域的发展将具有十分重要的意义.因而,从原子层面对纳米晶所表现出的这种高活性和晶面效应进行深入解释,将为高效催化剂设计提供重要指导.低温CO氧化作为一种重要的催化反应在燃料电池、空气净化与汽车尾气处理中具有重要的应用价值.本文采用密度泛函理论对Co3O4纳米晶催化CO氧化反应的机理、晶面效应以及结构敏感性进行了理论研究.首先,研究了CO在Co3O4(001)和(011)表面Co,CoOo和Co-Ot三种不同位点的吸附扩散行为,发现CO在Co位点表现出较强的吸附行为,但这种吸附构型需要克服很高的能垒(～1 eV)才能转变到Co-O离子对位点,在低温下这种转变将不可能发生,因此我们推断CO在Co位点的吸附对Co3O4催化CO氧化的晶面效应没有显著影响.接着,对CO在Co-O离子对位点抽提晶格氧生成CO2的反应机理进行了研究.我们发现,(011)表面Co-Ot位点可以较强地吸附CO(吸附能-1.15 eV),并十分容易夺取晶格氧离子(能垒0.26 eV),具有很低的势能面,因而其CO氧化活性明显大于(001)面.为了更清楚地理解这种晶面效应和结构敏感效应的本质,我们提出将CO2形成步的过渡态在反应路径上的能级作为反应活性指标.这种活性指标兼顾考虑了CO在Co-O氧位点的吸附覆盖度和CO2形成步的反应能垒,可以近似理解为反应的表观活化能.据此我们得出,Co3O4不同表面不同品格位点催化CO氧化的反应活性顺序为:(011)-Co-Ot＞＞(001)-Co-Oo＞(011)-Co-Oo＞(001)-Co-Ot.由于CO吸附和CO2形成步都涉及到表面被还原的过程,我们因此发现CO催化氧化活性的高低与表面晶格氧位点的可还原性具有正相关性.这种表面不同位点的还原性可以直接通过对空穴形成能的计算获得,降低表面氧空穴的生成能将有利于提高CO氧化的活性.催化设计的终极目标是在对催化活性位点的本质及反应机理深入认识的基础上在原子层面上对催化剂进行可控设计,从而实现催化剂材料的高效、经济的利用.本文研究表明离子对活性位点是Co3O4纳米晶催化CO氧化反应的活性位点,其中阳离子负责对CO的吸附,阴离子则负责CO2的形成过程,这种协同作用实现了Co3O4纳米晶的高反应活性.我们相信,寻找有效的方法在催化剂表面增加离子对位点活性中心的数目是一种实现高性能催化剂设计的途径.     

Catalytic spatiotemporal thermal patterns during CO oxidation on cylindrical surfaces: experiments and simulations

Dynamics of spatiotemporal thermal patterns during the catalytic CO oxidation over Pd supported on a glass-fiber catalytic cloth rolled into a tube of 20 mm diameter and 80 mm length has been studied in a continuous flow reactor by IR thermography. A specially designed aluminum mirror built in the reactor provided image of the entire surface of the horizontally held catalytic tube. With flow in the main axial direction and through the tube surface, we observed periodic motions of a pulse, which was born downstream and propagated upstream. The temperature pulse motion was accompanied by conversion oscillations of CO2. With flow in the main axial direction, parallel to the surface, we observed a stationary hot zone after an oscillatory transient. These patterns can be simulated with a plug-flow-reactor-like heterogeneous reactor model that incorporates previously determined kinetic and transport parameters.     

载体对负载PdO催化剂的CO氧化活性的影响

由于催化燃烧比传统的热力燃烧法有反应温度低和能量消耗低的优点，因而广泛用于挥发性有机物和CO的消除．把和铂是最常用的催化剂，但是载体对催化性能的影响很大【‘’‘］．本文制备了系列负载把催化剂，发现载体的性质对催化剂的CO氧化活性影响很大．本文所用载体为CeO。，TIO。，SnO。，AI。O。，ZAI。，ZSM－5和SIO。催化剂制备采用浸渍法，把负载量为5％（质量分数）．催化剂经120C烘干后，于650’C空气气氛焙烧4h制成．在常压固定床流动反应装置上考察催化剂的CO氧化活性，反应气组成为CO2．4％，O。1．2％，N。96．4…     

First-principles study on the effect of arsenic impurity on oxidation of pyrite surfaces

Arsenic (As) frequently exists in pyrite (FeS₂) in the form of impurities. The oxidation behavior of As in FeS₂ is important in environmental science, mineral processing, and other related fields. The adsorption behaviors of H₂O and O₂ molecules on the As-bearing pyrite (100) surface (As FeS₂(100)) are studied using the density functional theory (DFT). The results show that As prefers the S site on the pyrite (100) surface (FeS₂(100)). In the absence of O₂, an isolated H₂O molecule does not dissociate when adsorbed at an iron (Fe) site and is repelled at an As site. Furthermore, the surface area around the As atoms exhibits a hydrophobic behavior. Adsorption energy analysis reveals that the presence of As atoms is unfavorable for the adsorption of H₂O molecules on the pure FeS₂ surface, and that the adsorption of H₂O molecules on the As FeS₂(100) is physical adsorption. In the absence of H₂O, it is suggested that the O₂ molecule easily dissociates on both the pure FeS₂(100) and As FeS₂(100). The adsorption of O₂ on the As-bearing surface is weaker than that on the pure FeS₂(100). For the co-adsorption of H₂O and O₂, the adsorption energy on the As-bearing surface is more negative than that on the pure surface. This indicates that the presence of As promotes surface oxidation. Additionally, two  OH and O (AsO or SO) or  O (Fe O) species are formed on the surface of pyrite when the H₂O molecule is dissociated.     

On the effect of tungsten on CO oxidation at Pt electrodes

The co-catalytic effect of W on the oxidation of CO and methanol is investigated by using differential electrochemical mass spectrometry (DEMS). DEMS reveals that CO oxidation starts at 120 mV, overlapping with W oxidation. The action of W consists in shifting the pre-peak from 450 mV (as observed on pure Pt) to 200 mV. In this shifted pre-peak only 2% of the total adsorbed CO is oxidized independently from the W coverage, as compared to 10% on pure Pt. A correlation between the surface coverage of W as determined by XPS with the W oxidation peak charge in cyclic voltammetry suggests that the oxidation is a six-electron process.Dedicated to Prof. Wolf Vielstich on the occasion of his 80th birthday in recognition of his numerous contributions to interfacial electrochemistry.     

Study of Ce0.7Sn0.3O2 supported PdO catalysts for CO oxidation

Palladium supported by Ce_0.7Sn_0.3O₂ has been prepared by an impregnation method, and used for low temperature carbon monoxide oxidation. They were characterized by means of XRD and H₂-TPR techniques. For PdO/Ce_0.7Sn_0.3O₂ catalyst, three reduction peaks (α, β and γ) are observed. The β peak contributes to the reduction of PdO species and Sn⁴⁺ species on the surface of Ce_0.7Sn_0.3O₂; β peak to the reduction of bulk SnO₂ and surface Ce⁴⁺and the γ peak to the reduction of bulk CeO₂. The increase of Pd loading from 0 to 0.75% enhances oxidation of CO, further increase of the Pd content affects the catalytic activity but slightly. XRD and TPR results show that highly dispersed Pd on the surface of the support is the active species for CO oxidation. This revised version was published online in June 2006 with corrections to the Cover Date.     

A DFT study of the CO adsorption and oxidation at ZnO surfaces and its implication for CO detection

Recently,ZnO-based gas sensors have been successfully fabricated and widely studied for their excellent sensitivity and selectivity,especially in CO detection.However,detailed explorations of their mechanisms are rather limited.Herein,aiming at clarifying the sensing mechanism,we carried out density functional theory(DFT) calculations to track down the CO adsorption and oxidation on the ZnO(101 0) and(1120) surfaces.The calculated results show that the lattice O of ZnO(1010) is more reactive than that of ZnO(1120) for CO oxidation.From the calculated energetics and structures,the main reaction product on both surfaces can be determined to be CO_2 rather than carbonate.Moreover,the surface conductivity changes during the adsorption and reaction processes of CO were also studied.For both ZnO(1010) and(1120),the conductivity would increase upon CO adsorption and decrease following CO oxidation,in consistence with the reported experimental results.This work can help understand the origins of ZnO-based sensors' performances and the development of novel gas sensors with higher sensitivity and selectivity.     

Promoter effect on the CO2-H2O formation during Fischer-Tropsch synthesis on iron-based catalysts

The effects of Mg, La and Ca promoters on primary and secondary CO_2 and H_2O formation pathways during Fischer-Tropsch synthesis on precipitated Fe/Cu/SiO_2 catalysts are investigated. The chemisorbed oxygen atoms in the primary pathway formed in the CO dissociation steps reacted with co-adsorbed hydrogen or carbon monoxide to produce H_2O and CO_2 , respectively. The secondary pathway was the water-gas shift reaction. The results indicated that the CO_2 production led to an increase in both primary and secondary pathways, and H_2 O production decreased when surface basicity of the catalyst increased in the order Ca >Mg >La.     

Promotion effect of Au single-atom support graphene for CO oxidation

CO oxidation is a vital catalytic reaction for environmental purification, facing challenges due to the catalysts applied to oxidize CO are mainly rare and expensive noble catalysts. Since the high atomic availability, catalytic efficiency, and selectivity of single-atom catalysis, it has been widely studied and proven to be brilliant in CO oxidation. Au single-atom catalysts are regarded as excellent single-atom catalysts in oxidizing CO, whose progress is limited by the indistinct understanding of the reaction mechanism and role of the active atom. Hence, DFT calculation was used to investigate CO oxidation processes, active mechanisms, and the role of Au single-atom. Graphene involving prominent physical and chemical properties was selected as a model supporter. The single-atom support graphene materials exhibit better CO oxidation activities than pristine graphene, among which CO oxidation property on Au/GP is the highest with a 0.38 eV rate-determining barrier following ER mechanism. The outstanding performances including excellent electronic structures, adsorption properties, and strong activation of intermediate products contribute to the high CO oxidation activity of Au/GP, and the Au single-atom is the active center. Our work provides a novel guide for single-atom catalytic CO oxidation, accelerating the development of single-atom catalysis.     

金催化一氧化碳氧化反应中锌锡复合氧化物的载体效应

氧化物负载的纳米金催化剂对CO氧化反应具有极高的活性,这不仅依赖于金的结构特性,也取决于氧化物载体的结构.近年来,除了氧化硅、氧化铝等惰性载体以及氧化钛、氧化铈、氧化铁等可还原性载体外,人们还致力于探索各类新型氧化物载体.另一方面,锡酸锌是具有反尖晶石结构的化合物,并且在透明导电氧化物、锂离子电池阳极材料、光电转换装置以及传感器等方面应用广泛.然而,迄今为止,锡酸锌仍未被用于负载纳米金催化剂,因此相关的构效关系作用研究也十分有限.基于此,本文采用氮气吸附-脱附实验、电感耦合等离子体原子发射光谱(ICP-AES)、X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)和高分辨电镜(HRTEM)、高角环形暗场像-扫描透射电子显微镜(HAADF-STEM)、X射线吸收精细结构谱(XAFS)和氢气程序升温脱附(H2-TPD)等手段,系统研究了锡酸锌负载的纳米金催化剂在CO氧化反应中催化性能差异的原因.首先,利用水热法制备了锡酸锌(ZTO)载体,而其织构性质可由碱(N2H4·H2O)与金属离子(Zn2+)的比例在4/1(ZTO_1)、8/1(ZTO_2)和16/1(ZTO_3)之间进行调节.结果发现, ZTO_2具有最大的孔体积(0.223 cm3/g)和最窄的孔径分布.再采用沉积沉淀法将0.7 wt% Au负载于其上,得到金-锡酸锌(Au_ZTO)催化剂. ICP-AES测得样品中Au含量在0.57-0.59 wt%,与投料比接近. CO氧化反应结果显示, Au_ZTO_1和Au_ZTO_2的表观活化能相同,但后者的活性更高;而Au_ZTO_3在220°C以下没有活性,催化性能最差,与纯锡酸锌载体相当. XRD结果显示,反应过程中ZTO晶相、晶胞参数及晶粒尺寸变化不明显; TEM和HRTEM分析表明,载体ZTO在反应前后均为多面体形貌,平均颗粒尺寸在12-16 nm; XPS结果验证了Zn2+和Sn4+离子是新鲜和反应后样品中载体金属的存在形式; HAADF-STEM探测到所有样品中均含有1-2 nm的Au粒子; XAFS结果表明, Au以Au0形式存在,并且在Au_ZTO_3中Au平均粒径大于4 nm,而其它两样品约为2 nm. H2-TPR结果表明,金的引入对ZTO载体耗氢量影响不大,但还原峰温度向低温移动;金属-载体相互作用强弱与催化活性高低具有正相关性,即Au_ZTO_2> Au_ZTO_1>> Au_ZTO_3.这是由于不同织构性质的锡酸锌载体对于纳米金活性物种的稳定作用不同所致,具有最大孔体积和最窄孔径分布的ZTO_2负载的金纳米颗粒表现出最高活性.     

Catalytic oxidation of CO on platinum

Using concepts recently developed in thermal decompositions of solids and reduction of bulk oxides by gases and (re)analysis of experimental literature data, a novel mechanism for the catalytic oxidation of CO by PtO₂ is proposed. Instead of the conventional Mars–van Krevelen scheme, the reactions proposed are: PtO₂(s) + 2CO ? Pt(g) + 2CO₂ and Pt(g) + O₂ ? PtO₂(g) → PtO₂(s). The first reaction determines the kinetics of CO oxidation and the second determines the kinetics of restoration of the PtO₂ layer. Thermochemical consideration of the kinetic features of this model, based on Langmuir’s quasi-equilibrium equations for evaporation of simple substances, allowed calculation of the reaction enthalpy and the absolute rate of CO oxidation. These results are in good agreement with experimental data. The proposed mechanism explains the origin of the surface-retexturing effect, the limited loss of Pt metal from the catalyst, the mechanism of PtO₂ regeneration by oxygen, the strong effect of CO₂ in reducing the CO oxidation rate and the three-fold variation of the Arrhenius E parameter with temperature.     

The effect of Bi adsorption on CO oxidation inside 1.8 nm Pt pores

Modification of the surface of H(1)-e Pt with Bi causes significant changes in the CO stripping voltammetry; the pre-wave disappears and CO and Bi oxidation peaks appear. The absence of the pre-wave suggests that Bi preferentially adsorbs on the trough sites of the concave 1.8 nm diameter pore walls preventing oxygenated species from nucleating there.     

Chemisorption of CO2 on nickel surfaces

CO2 chemisorption on the Ni(111), Ni(100), and Ni(110) surfaces was investigated at the level of density functional theory. It was found that the ability of CO2 chemisorption is in the order of Ni(110) > Ni(100) > Ni(111). CO2 has exothermic chemisorption on Ni(110) and endothermic chemisorption on Ni(111), while it is thermally neutral on Ni(100). It is also found that there is no significant lateral interaction between the adsorbed CO2 at 1/4 monolayer (ML) coverage, while there is stronger repulsive interaction at 1/2 ML. On all surfaces, the chemisorbed CO2 is partially negatively charged, indicating the enhanced electron transfer, and the stronger the electron transfer, the stronger the C=O bond elongation. The bonding nature of the adsorbed CO2 on nickel surfaces has been analyzed. The thermodynamics of CO2 dissociative chemisorption, compared with CO and O adsorption, has been discussed, and the thermodynamic preference is in the sequence Ni(100) > Ni(111) > Ni(110).     

氧化镁载体和氧化钡助剂对钌基氨合成催化剂结构和性能的影响

采用不同来源氧化镁(市售MgO-1,合成MgO-2)作为钌基氨合成催化剂载体,浸渍法制备了添加不同BaO助剂含量的Ba-Ru/MgO催化剂,通过X射线衍射(XRD)、热重-量热扫描分析(TG/DSC)、N2-低温物理吸附、透射电镜(TEM)、H2程序升温还原(H2-TPR)和CO2程序升温脱附(CO2-TPD)等手段对其进行了表征,考察了不同来源的MgO和BaO助剂含量对负载型钌基氨合成催化剂的物相结构、织构性质、微观形貌、Ru物种的还原性质和体系酸碱性质以及催化剂的氨合成活性等方面的影响。结果表明,MgO的理化性质对所制备的钌基氨合成催化剂的结构以及氨合成活性有较大影响。MgO-2比表面较大,总碱性位数量较多,负载在其表面的Ru粒子粒径在2 nm左右,nBa∶nRu为1.0时,Ba-Ru(1∶1)/MgO-2催化剂表面的Ru物种易于还原,表面存在的弱碱性位极大地促进了氨合成活性,在400°C时活性达到15.40 L.g-1Ru.h-1(3.0 MPa,5 000 h-1),在相同反应条件下比Ba-Ru/MgO-1催化剂活性更高。