Multi-scale theoretical study of support effect on sintering dynamics of Pt

The capability of theoretical durability studies to offer an efficient alternative methodology for predicting the potential performance of catalysts has improved in recent years. In this regard, multi-scale theoretical methods for predicting sintering behavior of Pt on various catalyst supports are being developed. Various types of Pt diffusions depending on support were confirmed by the micro-scale ultra accelerated quantum chemical molecular dynamics (UA-QCMD) method. Moreover, macro-scale sintering behavior of Pt/γ-Al₂O₃, Pt/ZrO₂ and Pt/CeO₂ catalysts were studied using a developed 3D sintering simulator. Experimental results were well reproduced. While Pt on γ-Al₂O₃ sintered significantly, Pt on ZrO₂ sintered slightly and Pt on CeO₂ demonstrated the highest stability against sintering.     

Adsorption and dissociation of molecular hydrogen on Pt/CeO2 catalyst in the hydrogen spillover process: A quantum chemical molecular dynamics study

Ultra accelerated quantum chemical molecular dynamics method (UA-QCMD) was used to study the dynamics of the hydrogen spillover process on Pt/CeO₂ catalyst surface for the first time. The direct observation of dissociative adsorption of hydrogen on Pt/CeO₂ catalyst surface as well as the diffusion of dissociative hydrogen from the Pt/CeO₂ catalyst surface was simulated. The diffusion of the hydrogen atom in the gas phase explains the high reactivity observed in the hydrogen spillover process. Chemical changes, change of adsorption states and structural changes were investigated. It was observed that parallel adsorption of hydrogen facilitates the dissociative adsorption leading to hydrogen desorption. Impact with perpendicular adsorption of hydrogen causes the molecular adsorption on the surface, which decelerates the hydrogen spillover. The present study also indicates that the CeO₂ support has strong interaction with Pt catalyst, which may cause an increase in Pt activity as well as enhancement of the metal catalyst dispersions and hence increasing the rate of hydrogen spillover reaction.     

Pd与CeO2(111)面的相互作用的第一性原理研究

采用基于广义梯度近似的投影缀加平面波(projector augmented wave) 赝势和具有三维周期性边界条件的超晶胞模型，用第一性原理计算方法，计算并分析了Pd在CeO₂(111)面上不同覆盖度时的吸附能，价键结构和局域电子结构. 考虑了单层Pd和1/4单层Pd两种覆盖度吸附的情况. 结果表明：1)在单层吸附时，Pd的最佳吸附位置是O的顶位偏向Ce的桥位；在1/4单层吸附时，Pd最易在O的桥位偏向次层O的顶位吸附.2) 单层覆盖度吸附时，吸附原子Pd之间的作用较强；1/4单 关键词： 三元催化剂 Pd 2')" href="#">CeO₂ 吸附 密度泛函理论     

Effect of combination of noble metals and metal oxide supports on catalytic reduction of NO by H2

We investigated the effects of combination of noble metals M (Rh, Pd, Ir, Pt) and metal oxide supports S (Al₂O₃, SiO₂, ZrO₂, CeO₂) on the NO + H₂ reaction using planar catalysts with M/S two layered thin films on Si substrate. In this study, NO reduction ability per metal atom were evaluated with a specially designed apparatus employing pulse valves for the injection of reactant molecules onto catalysts and a time-of-flight mass spectrometer to measure multiple transient products: NH₃, N₂ and N₂O simultaneously as well as with an atomic force microscopy to observe the surface area of metal particles. The catalytic performances of Rh and Ir catalysts were hardly affected by a choice of a metal oxide support, while Pd and Pt catalysts showed different catalytic activity and selectivity depending on the metal oxide supports. This assortment is consistent with ability to dissociate NO depending on metals without the effect of any support materials. There, the metals to the left of Rh and Ir on the periodic table favor dissociation of NO and those to the right of Pd and Pt tend to show molecular adsorption of NO. Therefore, the catalytic property of noble metals could be assorted into two groups, i.e. Rh and Ir group whose own property would mainly dominate the catalytic performance, and Pd and Pt group whose interaction with metal oxides supports would clearly contribute to the reaction of NO with H₂. NO reduction activity of Pd and Pt was found to be promoted above that of Rh and Ir, provided that Pd and Pt were supported by CeO₂ and ZrO₂.     

Effect of lattice strain on the oxygen vacancy formation and hydrogen adsorption at CeO2(111) surface

Using first-principles calculation, the effect of lattice strain on the oxygen vacancy formation at CeO₂(111) surface has been investigated. The tensile strain facilitates the oxygen vacancy formation at the surface and the compressive strain hinders the process. This is in part due to the strengthening or weakening of the surface Ce–O bond under the lattice strain. On the other hand, a more open surface with a larger lattice constant can better accommodate the larger Ce³⁺ and thus facilitate the structural relaxation of the reduced surface. The studies on the strain effect on the atomic hydrogen adsorption at the defect-free CeO₂(111) surface show that the adsorption strength monotonously increases with the increase of the lattice strain, further confirming the tunable surface chemical activity by lattice strain.     

Preparation of Pt–CeO2/MWNT nano-composites by reverse micellar method for methanol oxidation

We report the preparation of Pt–CeO₂ nanoparticles on the multi-walled carbon nanotubes (MWNTs) by a reverse micellar method. Transmission electron microscopy (TEM) analysis indicated that well-dispersed small Pt–CeO₂ nanoparticles were formed on the MWCNTs. X-ray diffraction (XRD) analysis confirmed the formation of the Pt–CeO₂ nanoparticles on the MWNTs. Cyclic voltammetry (CV) results demonstrated that the Pt–CeO₂/MWNT exhibited a higher methanol oxidation than did the Pt/MWNT catalyst. The CO stripping test showed that CeO₂ can make CO stripped at a lower potential, which is helpful for CO and methanol electro-oxidation.     

Vibrational Spectroscopic Studies of Molybdena Dispersed on Ceria Support

Abstract

Diffuse Reflectance Infrared Fourier Transform (DRIFT) and FT-Raman spectra have been used to investigate the interactions between molybdena and ceria in MoO₃/CeO₂ samples with different Mo loadings. The spectra exhibit a weak Mo=O broad band of surface species at ca. 920–970 cm^?1, which reveals that the interaction between dispersed molybdena and ceria could be mainly ionic in nature. With the increasing of Mo loadings, the observed Mo=O band broadening and frequency shifting are due to the overlapping and condensation of different hydrated surface species. On the basis of the measured surface dispersion capacity of morybdena and the structure of the preferentially exposed (111) plane of ceria, it is reasonable to suggest that the Mo⁶⁺ cations and the accompanying O²- anions are incorporated into the surface available vacant sites of CeO₂, accordingly the dispersed molybdena species are interacted electrostatically with the support instead of only physically dispersed on the surface of it.     

Effect of 3.7 at% F doping on the atomic structure and reducibility of CeO2(111) surface: A first principles calculation

Density functional theory calculations was conducted to clarify effect of fluorination on the reducibility of CeO₂ polishing powder. The atomic structure and O vacancy formation energy of F-doped CeO₂(111) surface were systematically calculated, and electronic structure was also analyzed to understand the calculation results. It showed that the CeO_1.963(111) surface needs absorb 7.853 eV to be reduced further, so it is difficult to generate the second O vacancy (V₂). After fluorination, the first O vacancy (V₁) in CeO_1.926F_0.037(111) surface caused adjacent atoms to move significantly, and O vacancy formation energy decreased to 2.913 eV, which promoted the formation of V₂. Moreover, electronic structure calculation also showed that the interaction between O2p and Ce4f5d orbits was enhanced in reduced CeO_1.963(111) surface, which hindered the formation of V₂. The F2p orbit in CeO_1.926F_0.037(111) surface moved towards the low energy level, V₁ made the reduced surface stable and promoted the formation of V₂.     

Probing reoxidation sites by in situ Raman spectroscopy: differences between reduced CeO2 and Pt/CeO2

Raman spectroscopy is a powerful technique for detecting peroxo (O₂)^2– and superoxo (O₂)^– species adsorbed on defect sites of ceria. These sites are probed by reducing CeO₂ at high temperature and then chemisorbing oxygen species at low temperature. In the present study, it is shown for the first time that such Raman characterization has to be achieved at very low laser power to avoid formation of oxygen species by photolysis and analyze only the chemisorbed species. Respecting this requirement, the (O₂)^2– and (O₂)^– species formed on 0.7% Pt/CeO₂ compound, and the CeO₂ support used to prepare it were compared after reduction for various times and at various temperatures. Superoxo species were more stabilized on reduced 0.7% Pt/CeO₂ after short reduction at 773 K than on reduced CeO₂. Additionally, the distributions of peroxo species adsorbed on defect sites of Pt/CeO₂ and CeO₂ were significantly different after long reduction at 773 K in spite of similar amounts. Indeed, less stable species were formed during the reduction of 0.7% Pt/CeO_2. These two features revealed that new sites were created during the preparation and reduction of Pt/CeO₂ compared to its bare support. Copyright © 2012 John Wiley & Sons, Ltd.     

Low energy electron diffraction studies of the surfaces of molecular crystals (ice,ammonia, naphthalene,benzene)

Low Energy Electron Diffraction (LEED) has been used to study the surface structures of thin films of molecular crystals. The samples were grown epitaxially on metal single crystal substrates at low temperatures. Both Pt(111) and Ag(111) surfaces were used as substrates in order to identify the influence of the substrate on molecular film structure. Previous observations of ice (0001) and naphthalene (001) surfaces on films grown on Pt(111) substrates [Surface Sci. 55 (1976) 413], were confirmed using the Ag(111) substrate. The NH₃(111) and benzene (111) surfaces were also studied on films grown on either substrate. All observed molecular crystal surfaces showed no evidence of surface reconstruction. To minimize sample charging and electron beam induced damage, LEED experiments were performed on samples of thickness less than 10?10² nm, with low energy electron exposures less than 1 C cm^?2. The maximum thickness and exposure values were characteristic of the particular molecular crystal. The relationship between the structure of the initial adsorbed monolayer and the molecular crystal orientation is discussed.     

Synthesis and characterization of Sr2CeO4 phosphor: Positive features of sol-gel technique

Nano crystalline powder of Sr₂CeO₄ has been synthesized by sol-gel technique. The luminescence properties of the material were compared with the one synthesized by conventional solid state reaction technique. The homogeneity and uniformity of the particle prepared by this method is much better than that prepared by the solid state reaction technique. This blue emitting phosphor was characterized by X-ray diffraction, scanning electron microscopy images and luminescent measurements. The emission spectrum of the material exhibits a broad band around ∼480 nm. The photoluminescence spectra of the Sr₂CeO₄ reveals that the strong blue emission is assigned to the Ce⁴⁺-O²⁻ charge transfer transition (CTT) of Sr₂CeO₄ and not related to lattice defect. The Commission International de l’Eclairage coordinates are x=0.16 and y=0.25.     

ESR of adsorbates on single crystal metal surfaces under UHV conditions

Angular dependent electron spin resonance measurements were taken for paramagnetic molecules adsorbed on metallic single crystal surfaces in UHV. For the hydrated Cu(NO₃)₂ complex on a Cu[111] surface an angular dependent ESR signal is recorded. The plane ofthe molecule is found to lie preferentially out of the surface plane. Experiments on chemisorbed molecular O₂ on Ag[110] at 25 K and NO on Pt[111] at 110 K show no sharp ESR signal characteristic for well localized moments. If one assumes that NO on Pt (respectively Pd) carries an unpaired spin, one can estimate a lower limit for the spin flip rate of π^?1>2×10⁹s^?.     

Pt nanoparticles supported over Ce–Ti–O: the solvothermal and photochemical approaches for the preparation of catalytic materials

Ce–Ti–O supports with different Ce/Ti molar ratios were synthesized by the solvothermal method using hexadecyltrimethylammonium bromide. Pt nanoparticles were then supported by photochemical deposition. The shape, size, and structure of these materials were analyzed by high-resolution transmission electron microscopy. The single CeO₂ support was also prepared, consisting of agglomerated cubic particles ranging from ~3 to 8 nm. When titania was combined with ceria, a nanostructured architecture was produced, evidencing the strong influence of Ti in the support structure. Photodeposition of Pt nanoparticles is more efficient on Ce–Ti–O supports than in pristine CeO₂. Crystalline Pt nanoparticles (mainly of ~2 to 4 nm) were detected. The catalytic properties of the materials were tested in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol. It was observed that Pt supported on Ce–Ti–O is more active and selective than Pt on CeO₂ or TiO₂ separately. The catalyst with 40 mol% Ce leads to total conversion of cinnamaldehyde in a few minutes; however, higher selectivity toward the desired product (cinnamyl alcohol) was obtained with higher amounts of Ce (50 mol%).     

STM observation of the origin of electrochemical promotion on metal catalyst-electrodes interfaced with YSZ and β″-Al2O3

Scanning tunneling microscopy (STM) was used to investigate the surfaces of Pt(111) single crystals interfaced with YSZ and β″-Al₂O₃ at atmospheric pressure. In both cases the STM imaged the reversible electrochemically controlled dosing (backspillover) of O²⁻ species and of Na⁺ species on Pt(111) surface respectively, which both form a (12 × 12) hexagonal structure on the Pt(111) surface. On the mechanistic side, the STM has confirmed the backspillover mechanism of electrochemical promotion and metal support interactions.     

Effects of oxygen vacancies on the room-temperature ferromagnetism of Co-doped polycrystalline CeO2

Pure and Co-doped single-phase CeO₂ crystals were synthesized by a solid-state reaction method. Samples of different oxygen vacancy concentration were studied, including (1) as-sintered crystals, (2) powders ground from the same crystal, and (3) a cold-pressed pellet from the ground powder that was unannealed and annealed at 800 °C. By analyzing the magnetic behaviors, surface/volume ratio and O vacancy concentration, the effects of oxygen vacancies on the room-temperature ferromagnetism (RT-FM) of Co-doped CeO₂ were systematically investigated. The results confirm that the RT-FM observed in Co-doped CeO₂ has a direct relationship with the oxygen vacancy concentration, and support the oxygen vacancy mediated FM mechanism.     

Polishing behavior of PS/CeO2 hybrid microspheres with controlled shell thickness on silicon dioxide CMP

Organic-inorganic composite microspheres with PS as a core and CeO₂ nanoparticles as a shell were synthesized by in situ decomposition reaction of Ce(NO₃)₃ on the surfaces of PS microspheres prepared through soap-free emulsion polymerization. The shell thickness of the composite microspheres could be turned by varying the concentration of Ce(NO₃)₃ in the reaction solution. The whole process required neither surface treatment for PS microspheres nor additional surfactant or stabilizer. The as-synthesized PS/CeO₂ composite microsphere samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Oxide chemical mechanical polishing (CMP) performance of the PS/CeO₂ composite abrasives with different shell thickness was characterized by atomic force microscopy (AFM). The results indicated that the as-prepared core-shell structured composite microspheres (220-260 nm in diameter) possessed thin shell (10-30 nm) composed of CeO₂ nanoparticles (particle diameter of 5-10 nm), and the final CeO₂ contents of the composite microspheres ranged from 10 to 50 wt%. A possible mechanism for the formation of PS/CeO₂ composite microspheres was discussed also. The CMP test results confirmed that the novel core-shell structured composite abrasives are useful to improve oxide CMP performance. In addition, there is an obvious effect of shell thickness of the composite abrasives on oxide CMP performance.     

蓝宝石基片上制备大面积Tl2Ba2CaCu2O8超导薄膜

在2英寸双面蓝宝石基片上采用CeO₂作为缓冲层制备了高质量Tl₂Ba₂CaCu₂O₈(Tl-2212)超导薄膜.以金属铈作为溅射靶材,采用射频磁控反应溅射法生长了c轴织构的CeO₂缓冲薄膜,并研究了不同生长条件对于CeO₂缓冲层的晶体结构及表面形貌的影响.超导薄膜采用直流磁控溅射和后热处理的方法制备.扫描电子显微镜(SEM)图像显示,超     

Theoretical determination of the structure of acetylene on Pt(111)

An atom superposition and electron delocalization technique applied to acetylene chemisorption on small cluster models for the Pt(111) surface shows preference for the triangular site as deduced from electron energy loss analyses by Ibach and Lehwald. This confirms the applicability of Badger's and related rules in this instance. Calculations on CCH₃ produce a structure in agreement with a dynamic LEED analysis at 400 K by Kesmodel, Dubois and Somorjai. Structures of CCH₂ and CHCH₂ are calculated and these species are found to be less stable than acetylene and CCH₃, respectively, when chemisorbed on Pt(111).     

Surface chemistry studied by in situ X-ray photoelectron spectroscopy

Time-dependent X-ray photoelectron spectroscopy is used to study the kinetics and dynamics of simple surface reactions. Combining high-resolution core level spectroscopy with a supersonic molecular beam in one experimental setup, processes such as the dissociative adsorption of methane on both Pt(111) and Ni(111), the coadsorption of water and CO on Pt(111), and the oxidation of CO on Pt(111) have been studied. In the case of methane, the observed vibrational fine structure in C 1s spectra is used to identify the adsorbed species (CH₃) and further thermal dehydrogenation steps. While simple dehydrogenation via CH is observed on Pt(111), a C–C coupling reaction to acetylene is found on Ni(111). In the coadsorbate phase, CO is found to be able to replace predosed water from the bilayer into multilayers. Water, in turn, leads to a site change of the CO molecules, which are preferably adsorbed at bridge sites in the presence of water, as opposed to on-top adsorption on clean Pt(111). For the truly bimolecular surface reaction, the CO oxidation on Pt(111), the ability of the molecular beam to create a relatively high CO pressure was found essential to study the kinetics of the basic step (CO+OCO₂) without influence of adsorption or diffusion rate. An activation energy of 0.53 eV and a preexponential factor of 5×10⁶ s^-1 are found. PACS 68.43.Mn; 79.60.Dp; 82.20.Pm     

A new synthetic pathway of Sr2CeO4 phosphor and its characterization

A blue-white emitting Sr₂CeO₄ phosphor was synthesized via a simple sol-gel poly vinyl alcohol (PVA)-complexing process using strontium nitrate and cerium nitrate as raw materials. The samples were characterized by TG/DTA, XRD, FTIR, SEM and photoluminescence spectroscopy. The X-ray diffraction study confirms the structure of the system to be orthorhombic. The emission spectra when excited at 267 nm peaks at ∼470 nm. The emission band is assigned to the energy transfer between the molecular orbital of the ligand and charge transfer state of the Ce⁴⁺ ion. The Commission International de l'Eclairage (CIE) co-ordinates for the Sr₂CeO₄ sample were also calculated.