Characterization of ZrO2-promoted Cu/ZnO/nano-Al2O3 methanol steam reforming catalysts

Three Cu/ZnO/ZrO₂/Al₂O₃ methanol reforming catalysts were investigated using X-ray photoelectron spectroscopy (XPS). The catalysts which contained ZrO₂ from a monoclinic nanoparticle ZrO₂ precursor exhibit both a higher activity toward the methanol steam reforming reaction and a lower CO production rate compared to catalysts composed of an XRD-amorphous ZrO₂ produced by impregnation using a Zr(NO₃)₂ precursor. The presence of a monoclinic phase appears to result in an increased charge transfer between the Zr and Cu species, as evidenced by a relatively electron-rich ZrO₂ phase and a partially oxidized Cu species on reduced catalysts. This electron deficient Cu species is more reactive toward the methanol reforming reaction and partially suppresses CO formation through the reverse water gas shift or methanol decomposition reactions.     

Methanol decomposition on platinum (111)

The interaction of methanol with clean and oxygen-covered Pt(111) surfaces has been examined with high resolution electron loss spectroscopy (EELS) and thermal desorption spectroscopy (TDS). On the clean Pt(111) surface, methanol dehydrogenated above 140 K to form adsorbed carbon monoxide and hydrogen. On a Pt(111)-p(2 × 2)O surface, methanol formed a methoxy species (CH₃O) and adsorbed water. The methoxy species was unstable above 170 K and decomposed to form adsorbed CO and hydrogen. Above room temperature, hydrogen and carbon monoxide desorbed near 360 and 470 K, respectively. The instability of methanol and methoxy groups on the Pt surface is in agreement with the dehydrogenation reaction observed on W, Ru, Pd and Ni surfaces at low pressures. This is in contrast with the higher stability of methoxy groups on silver and copper surfaces, where decomposition to formaldehyde and hydrogen occurs. The hypothesis is proposed that metals with low heats of adsorption of CO and H₂ (Ag, Cu) may selectively form formaldehyde via the methoxy intermediate, whereas other metals with high CO and H₂ chemisorption heats rapidly dehydrogenate methoxy species below room temperature.     

An electrochemical determination of oxygen adsorption on copper

The adsorption of oxygen on polycrystalline and thin film copper samples was studied with the solid state electrochemical cell: Cu,Cu₂O¦7.5wt%CaO/ZrO₂¦Cu in ultrahigh vacuum. The oxygen partial pressure in the bulk of the copper sample was controlled electrochemically by applying a voltage across the cell, while the oxygen coverage at the copper free surface was monitored by Auger Electron Spectroscopy (AES). This technique has enabled us to establish much lower oxygen partial pressures at high temperatures than normally attainable in ultrahigh vacuum. In this paper we report the results of reversible oxygen adsorption isotherms on polycrystalline copper at 928, 970 and 1093 K. The results agree reasonably well with the deductions of earlier surface energy measurements and indicate a surprising degree of stability for chemisorbed oxygen on polycrystalline copper. Isosteric heats of adsorption are calculated with and without the inclusion of the earlier surface energy measurements and are compared to previous differential heats of adsorption determined calorimetrically.     

Thermal spreading of WO3 onto zirconia support

This study focused on preparation of tungsten oxide supported on zirconia by thermal spreading. The prepared samples were characterized by infrared spectroscopy, UV-vis diffuse reflection spectroscopy, X-ray diffraction, and also by methanol dehydration reaction. It was observed that isolated octahedral tungsten dispersed species and dispersed polytungstate were formed on zirconia surface, although some WO₃ that remained after the thermal treatment could also be detected. The presence of these species led to an increase of the number of Lewis sites and the generation of Brönsted acid sites. High calcination temperatures promoted the creation of Brönsted sites as a consequence of polytungstate species formation. The activity on methanol dehydration was also determined by the concentration of these species, whereas the isolated WO_x species were found poorly active. The correlation observed between the catalytic performance and the tungsten dispersed species, as revealed by spectroscopic techniques, evidenced the occurrence of thermal spreading of WO₃ on ZrO₂. The results presented in this work show that WO₃ thermal spreading on ZrO₂ may be effectively accomplished as predicted by thermodynamics.     

The adsorption of hydrogen and the reaction of hydrogen with oxygen on Pt (100)

The adsorption of hydrogen on Pt (100) was investigated by utilizing LEED, Auger electron spectroscopy and flash desorption mass spectrometry. No new LEED structures were found during the adsorption of hydrogen. One desorption peak was detected by flash desorption with a desorption maximum at 160 °C. Quantitative evaluation of the flash desorption spectra yields a saturation coverage of 4.6 × 10¹⁴ atoms/cm² at room temperature with an initial sticking probability of 0.17. Second order desorption kinetics was observed and a desorption energy of 15–16 kcal/mole has been deduced. The shapes of the flash desorption spectra are discussed in terms of lateral interactions in the adsorbate and of the existence of two substates at the surface. The reaction between hydrogen and oxygen on Pt (100) has been investigated by monitoring the reaction product H₂O in a mass spectrometer. The temperature dependence of the reaction proved to be complex and different reaction mechanisms might be dominant at different temperatures. Oxygen excess in the gas phase inhibits the reaction by blocking reactive surface sites. At least two adsorption states of H₂O have to be considered on Pt (100). Desorption from the prevailing low energy state occurs below room temperature. Flash desorption spectra of strongly bound H₂O coadsorbed with hydrogen and oxygen have been obtained with desorption maxima at 190 °C and 340 °C.     

The role of copper species on Cu/γ-Al2O3 catalysts for NH3-SCO reaction

UV-vis spectra, XRD, H₂-TPR, TEM and ESR were used to characterize a series of Cu/γ-Al₂O₃ catalysts, which were prepared by incipient wetness impregnation using copper nitrate, copper acetate or copper sulfate as precursors, to study the role of Cu species on Cu/γ-Al₂O₃ catalysts for NH₃-SCO reaction. It was found that the mixture of CuO phase and CuAl₂O₄ phase formed on various Cu/γ-Al₂O₃ catalysts, and the Cu species and dispersion had significant influence on the Cu/γ-Al₂O₃ activity. Highly dispersed CuO phase on the support would be related with its high activity for the NH₃-SCO reaction.     

Preparation and characterization of SiO2/ZrO2/Ag multicoated microspheres

A new type of multicoated silica/zirconia/silver (SiO₂/ZrO₂/Ag) core-shell composite microspheres is synthesized in this paper. In the process, ZrO₂-decorated silica (SiO₂/ZrO₂) core-shell composites were firstly fabricated by the modification of zirconia on silica microspheres through the hydrolysis of zirconium precursor. Subsequently, on SiO₂/ZrO₂ composite cores, silver nanoparticles were introduced via ultrasonic irradiation and acted as “Ag seeds” for the formation of integrate silver shell by further reduction of silver ions using formaldehyde as reducer. The resulting samples were characterized by transmission electron microscopy, X-ray diffraction, Fourier-transform infrared, energy-dispersive X-ray, and UV-vis spectroscopy, indicating that zirconia and silver layers were successfully coated on the surfaces of silica microspheres.     

Characterization of the adsorption and decomposition of methanol on Ni(110)

The chemisorption, condensation, desorption, and decomposition of methanol, both CH₃OH and CH₃OD, on a clean Ni(110) surface have been characterized using high resolution electron energy loss spectroscopy, temperature programmed reaction spectroscopy, and low energy electron diffraction. The vibrational spectrum of the saturated chemisorbed layer, 7.4 × 10¹⁴ molecules cm^?2, is almost identical to the infrared spectrum of liquid or solid methanol. Condensation of multilayers of methanol is facile at 80 K. The only quasi-stable intermediate isolated during the decomposition is a methoxy species, CH₃O, which decomposes thermally to CO and H. The evolution of both CO and H₂ occurs in desorption limited processes.     

三甲基镓在Pd(111)表面吸附解离及表面预吸附H和O的影响

利用X-射线光电子能谱（XPS）和程序升温脱附谱（TPD）研究了三甲基镓在Pd（111）表面的吸附和解离行为,并考察了表面预吸附H和O的影响。结果表明,在吸附温度为140 K时,三甲基镓在Pd（111）上主要为解离吸附,此时表面物种为Ga（CH₃）_x （x=1,2,3）和CH_x物种。加热将导致Ga的甲基化合物中的Ga-C键发生分步断裂,在不同温度下产生CH₄和H₂从表面脱附。同时,XPS结果证实了在275~325 K的温度区间内存在Ga甲基化合物的分子脱附。退火至更高温度,表面只观察到积碳和金属Ga物种,这二者随着温度的继续升高逐渐向体相扩散。在Pd（111）表面预吸附O和H对上述吸附和解离行为存在显著的影响。当表面预吸附H时,脱附产物CH₄和H₂的脱附主要位于315 K,可归属为一甲基镓的解离脱附。当表面预吸附O时,只在258 K观察到CH₄和H₂的脱附峰,可能来自于Pd-O-Ga（CH₃）₂吸附结构的解离.     

Atomic oxygen erosion resistance of polyimide/ZrO2 hybrid films

A series of polyimide/zirconia (PI/ZrO₂) hybrid films were synthesized based on zirconium n-butoxide, pyromellitic acid dianhydride (PMDA) and 4,4′-oxydianiline (ODA) by a sol-gel process. The atomic oxygen (AO) exposure tests were carried out using a ground-based atomic oxygen effects simulation facility. The effects of ZrO₂ content on the morphology and structure evolvement of PI/ZrO₂ hybrid films were investigated using field emission scanning electron microscopy (FE-SEM) and X-ray photoelectron spectrometer (XPS), respectively. The results indicated that a zirconia-rich layer was formed on the polyimide film sourcing from the zirconium n-butoxide after AO exposure, which decreased the erosion rate and obviously improved the AO resistance of polyimide films.     

Adsorption and decomposition of HNCO on Cu(111) surface studied by auger electron,electron energy loss and thermal desorption spectroscopy

No detectable adsorbed species were observed after exposure of HNCO to a clean Cu(111) surface at 300 K. The presence of adsorbed oxygen, however, exerted a dramatic influence on the adsorptive properties of this surface and caused the dissociative adsorption of HNCO with concomitant release of water. The adsorption of HNCO at 300 K produced two new strong losses at 10.4 and 13.5 eV in electron energy loss spectra, which were not observed during the adsorption of either CO or atomic N. These loses can be attributed to surface NCO on Cu(111). The surface isocyanate was stable up to 400 K. The decomposition in the adsorbed phase began with the evolution of CO₂. The desorption of nitrogen started at 700 K. Above 800 K, the formation of C₂N₂ was observed. The characteristics of the CO₂ formation and the ratios of the products sensitively depended on the amount of preadsorbed oxygen. No HNCO was desorbed as such, and neither NCO nor (NCO)₂ were detected during the desorption. From the comparison of adsorption and desorption behaviours of HNCO, N, CO and CO₂ on copper surfaces it was concluded that NCO exists as such on a Cu(111) surface at 300 K. The interaction of HNCO with oxygen covered Cu(111) surface and the reactions of surface NCO with adsorbed oxygen are discussed in detail.     

DRIFTS study of different gas adsorption for CO selective oxidation on Cu-Zr-Ce-O catalysts

The adsorptions of different gases (CO, H₂ and O₂) in the hydrogen-rich gas on the co-precipitated Cu-Zr-Ce-O catalyst were discussed and the active sites were ascertained with infrared spectroscopy technique. It was shown that the adsorption strength of CO was stronger than that of O₂ or H₂. Hydrogen and CO were competitive adsorption and the coexistence H₂ and CO on the surface accelerated the rate of CO desorption. Adsorbed H₂ could convert into geminal OH groups on the ceria surface at high temperatures in the absence of oxygen, while it was easy to form surface hydroxyl groups at low temperatures and condensed to physical water with increasing desorption temperature in the existence of oxygen. The adsorption of CO₂ was strong and it could transform into thermal stable carbonate species even in the reaction conditions. The active sites of the Cu-Zr-Ce-O catalyst were Cu²⁺ and Cu⁺, mainly the latter. The oxygen defect sites could be formed on the Cu-Zr-Ce-O catalyst surface through dehydration and decarboxylation.     

Adsorption of ethylene on clean and oxygen precovered Cu(110) surfaces

UV photoemission spectroscopy (UPS) with He I and He II radiation is used to study the interaction of C₂H₄ with clean and oxygen precovered Cu(110) surfaces at 90 K. On the clean surface only-bonding of the C₂H₄ molecules is observed whereas preadsorbed oxygen causes a second molecular orbital to be involved in the chemisorption. This result is consistent with the differing behaviour of the work function change during thermal desorption of C₂H₄.     

Thermoluminescence (TL) of europium-doped ZrO2 obtained by sol–gel method

This article reports the preparation and characterization of europium-doped zirconium oxide (ZrO₂:Eu³⁺) formed by homogeneous precipitation from propoxyde of zirconium [Zr(OC₃H₇)₄]. The alkoxide sol gel process is an efficient method to prepare the zirconium oxide matrix by the hydrolysis of alkoxide precursors followed by condensation to yield a polymeric oxo-bridged ZrO₂ network. All compounds were characterized by thermal analysis and the X-ray diffractometry method. The thermoluminescence (TL) emission properties of ZrO₂:Eu³⁺ under beta radiation effects are studied. The europium-doped sintered zirconia powder presents a TL glow curve with two peaks (Tmax) centered at around 204 and around 292 ^°C, respectively. TL response of ZrO₂:Eu³⁺ as a function of beta-absorbed dose was linear from 2 Gy up to 90 Gy. The europium ion (Eu³⁺)-doped ZrO₂ was found to be more sensitive to beta radiation than undoped ZrO₂ obtained by the same method and presented a little fading of the TL signal compared with undoped zirconium oxide.     

Kinetics of oxygen desorption in Y Ba2Cu3O7-δ

In this paper the kinetics of oxygen desorption from Y Ba₂Cu₃O_7-δ has been investigated and measurements carried out in the temperature range 350–750 C. It is shown that the oxygen desorption is diffusion-controlled (and not surface-controlled), and characteristic of diffusion from small grains in a loosely coupled porous matrix. At every temperature a number of time constants with well-defined ratios appear and have been identified and measured. These time constants can be related to the average bulk diffusion constant which shows an Arrhenius behaviour with deviations around 750°C which are ascribed to the well-known orthorhombic to tetragonal transition. In this paper we establish the basic underlying physical mechanism of oxygen desorption in Y Ba₂Cu₃O_7-δ.     

Effect of the surface charge on the complexing and catalytic properties of Cu2+-containing composite materials based on zirconia and powdered cellulose

Composite materials (CMs) based on zirconia xerogels and powdered cellulose (PC) were synthesized. The effect of the CM surface charge on their complexing properties with respect to Cu²⁺ ions and on the catalytic activity of the samples in model reactions of the decomposition of H₂O₂ and the oxidative dehydrogenation of trimethylhydroquinone with atmospheric oxygen was analyzed. It was experimentally proved that the use of PC for the synthesis of ZrO₂-based CMs, as in the case of previously studied CMs based on SiO₂ and TiO₂, leads to an increase in the specific surface area S _sp and a decrease in the negative electric potential of their surface. The surface charge, sorption method, and the composition of the buffer solution used for sorption have a significant effect on the copper(II) content in the CM phase, the distribution pattern, and the composition of the sorbed copper(II) compounds and on the catalytic activity of the synthesized Cu²⁺-containing CMs.     

Lateral interactions in the thermal desorption of H2 from clean Cu/Ni(110) alloy surfaces

The adsorption of hydrogen on a clean Cu10%/Ni90% (110) alloy single crystal was studied using flash desorption spectroscopy (FDS), Auger electron spectroscopy (AES), and work function measurements. Surface compositions were varied from 100% Ni to 35% Ni. The hydrogen chemisorption on a-surface of 100% nickel revealed strong attractive interactions between the hydrogen atoms in accordance with previous work on Ni(100). Three desorption states (β₁, β₂ and α) appeared in the desorption spectra. The highest temperature (α) state was occupied only after the initial population of the β₂-state. As the amount of copper was increased in the nickel substrate, desorption from the higher energy binding α-state was reduced, indicating a decrease in the attractive interactions among hydrogen atoms. The hydrogen coverage at saturation was not affected by the addition of copper to the nickel substrate until the copper concentration was greater than 25% at which a sharp reduction in saturation coverage occurred. This phenomenon was apparently due to the adsorption of hydrogen on Ni atoms followed by occupation of NiNi and CuNi bridged adsorption sites, while occupation of CuCu sites was restricted due to an energy barrier to migration.     

Hydrogen absorption and re-emission characteristics of metal-oxide bi-layer composite materials measured by ion beam analysis

Hydrogen absorption and emission characteristics of Pt-Li₂ZrO₃ bi-layer materials exposed to normal air at room temperature have been studied by means of elastic recoil detection analysis(ERD), Rutherford backscattering spectroscopy (RBS), weight gain measurement (WGM) and thermal desorption spectroscopy (TDS). The Pt/Li₂ZrO₃/Pt sandwich specimens have been found to absorb H at the Pt surface from H₂O vapor, store it in Li₂ZrO₃, and emit 80% of it as H₂ gas, when they are heated at 100 °C for 10 min. Data obtained by WGM shows that the weight gain increases linearly with increasing the exposure time. TDS analysis also shows that the main species of gases re-emitted are H₂ and H₂O. Moreover, the hydrogen storage rate in Li₂ZrO₃ is shown to be controlled by the hydrogen absorption rate at the Pt surface, based on the hydrogen absorption and storage model proposed. The maximum storage capacity of Li₂ZrO₃ has been estimated to be 0.15 Nl/cm³ from the saturation hydrogen concentration, (1/2)H/Li₂ZrO₃, measured by means of the ERD technique.     

Interaction of PH3 coadsorbed with H2, D2, O2 and H2O on Rh(100)

The coadsorption of PH₃ with H₂, D₂, O₂ and H₂O on Rh(100) has been studied using temperature programmed desorption (TPD), Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). The adsorption and molecular desorption of PH₃ is not affected by preadsorbed H₂, D₂ and O₂. Preadsorbed PH₃ blocks H₂ desorption sites while postdosed PH₃ displaces H₂ (D₂₁) from the Rh(100). When D₂ and PH₃ are coadsorbed, no D appears in desorbed phosphine. Preadsorbed O₂ reduces the amount of H₂ desorption (from PH₃ decomposition) and increases the H₂ desorption temperature. There is also some reaction between O(a) and H(a) to form water. Preexposure to H₂O decreases the extent of PH₃ adsorption and of PH₃ decomposition.     

Formate stability and carbonate hydrogenation on strained Cu overlayers on Pt(1 1 1)

Formate (HCOO) synthesis, decomposition and the hydrogenation of carbonate (CO₃) on Cu overlayers deposited on a Pt(1 1 1) single crystal are investigated to examine the reactivity of a Cu surface under tensile strain with defects present.Formate is synthesized from a 0.5 bar mixture of 70% CO₂ and 30% H₂ at varying temperatures, and the evolution is followed with polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS). Subsequent TPD reveals decomposition of the formate species into CO₂ and H₂ at 420 ± 5 K for strained Cu at sub-monolayer to monolayer coverages. This is a significantly lower decomposition temperature than obtained earlier on pristine Cu(1 1 1) (460 K), as well as for thicker Cu layers where we assign an observed decomposition peak at 440 ± 5 K to relaxed, but defect-rich Cu(1 1 1). However, the thermal stability of formate on strained and defect-rich Cu is similar to previous results obtained for supported, and lattice-strained, Cu nanoparticles.The hydrogenation of carbonate produced by 0.3 bar CO₂ exposure at room temperature was monitored with XPS and TPD showing a significant loss of carbonate when subjected to 0.2 bar H₂ at room temperature. However, the presence of formate on the surface, or any other hydrogenation product, could not be established during or after H₂ exposure by PM-IRRAS, EELS or TPD. Even so, the results suggest that carbonate and its hydrogenation may constitute a relevant pathway to methanol production.