Comparison between the adsorption properties of Pd(111) and PdCu(111) surfaces for carbon monoxide and hydrogen

Thermal desorption spectroscopy and LEED have been used to investigate the interaction of CO and hydrogen with a Pd_0.75Cu_0.25(111) single crystal surface with surface composition of about Pd_0.7Cu_0.3. The main objective was to make a comparison with the previously studied Pd_0.67Ag_0.33(111) (surface composition Pd_0.1Ag_0.9) and Pd(111) surfaces. In addition, the effect of preadsorbed H on subsequent CO dosage and the effect of adsorbed CO on postdosed hydrogen are described. Marked differences were found in the adsorption behaviour of the three surfaces towards CO and hydrogen. The maximum amount of H and CO that can be adsorbed at 250 K and pressures below 10⁻⁹ mbar is much lower on the PdCu surface than expected on the basis of the surface composition. This effect appears to be caused by a low heat of adsorption of hydrogen and CO and Pd singlet sites. Arguments are presented that singlet Pd sites or isolated Pd atoms in a Cu or Ag matrix are able to trap and dissociate the hydrogen molecule at 250 K. The CO desorption spectra are not influenced by pre- or postexposed hydrogen. Adsorbed CO hampers the uptake of hydrogen upon subsequent exposure to hydrogen. Postdosed CO causes adsorbed H adatoms to move to the bulk (adsorbed H). CO exposure at 250 K results in a very broad desorption plateau between 310 and 425 K with hardly discernable maxima. The results can be explained in terms of the size and relative concentration of the various Pd sites present on the surface (triplet, doublet and singlet sites). It can be concluded that for Pd (111) the heat of adsorption of both CO and H differ appreciably for the triplet, doublet and singlet sites. The effect of site has a larger contribution to the decrease of the heat of adsorption with coverage than the effect of lateral interaction in the adlayer. For Pd(111), PdCu(111) and PdAg(111) the effect of the available Pd sites is the major effect that determines the heat of adsorption, followed by the effect of lateral interaction and for the alloy surfaces the electronic or ligand effect.     

Static sims studies of adsorbate structure: II. CO adsorption on Pd(111); adsorbate-adsorbate interactions on Ru(001), Ni(111) and Pd(111)

In a study of CO adsorption on Pd(111) it is shown that the secondary ion mass spectrum contains information on both adsorbate site geometry and adsorbate coverage. The fractional yields of PdCO⁺, Pd₂CO⁺ and Pd₃CO⁺, as a function of CO coverage are correlated with the changing site geometries suggested by reflection IR data. A relationship between secondary ion emission and the adsorbate-adsorbate interactions revealed by IR and EELS is also demonstrated for CO adsorption on Ru(001), Ni(111) and Pd(111).     

EELS analysis of the low temperature phase of ethylene chemisorbed on Pd(111)

The chemisorption of C₂H₄ and C₂D₄ on Pd(111) at 150 K has been studied by high resolution electron energy loss spectroscopy. Analysis of the vibrational spectra indicates that (i) C₂H₄ is more weakly bound on Pd(111) than on Ni(111) and Pt(111) and (ii) softened and broadened CH stretching frequencies suggest hydrogen bond-like interactions between the molecule and the metal surface.     

Low energy electron loss spectroscopic study of Pd-Si(111) system

Effect of Pd deposition on a clean Si(111) surface was studied by ELS and AES methods for submonolayer [1 ML = 7.8 × 10¹⁴atomscm^-2forSi(111)] to several tens of monolayers. ELS spectra showed that the electronic nature of Pd-Si bonding for ? 1 ML of Pd coverage is different from Pd₂Si formed for ? 3 ML. Namely, it was shown that some critical thickness for Pd on Si(111) exist for inducing interfacial intermixing reaction at room temperature.     

The decay of111gPd and111mPd

The decays of 23·4 min^111gPd and 5·5 h^111mPd have been studied using high-resolution Ge(Li) singles -ray spectrometers and Ge(Li)-Ge(Li) coincidence system. About 140-rays were observed in the decays of both isomers. The half-life of^111gPd was remeasured and found to be 23·4±0·2 min. The¹¹¹Ag level scheme and the decay scheme of daughter 74 s^111mAg were examined.Authors are indebted to Prof. I.Úlehla and Dr. J.Adam for permanent support in this work and some usefull comments and to Drs. J.Frána and J.Jursík for preparing of computer programs and help in arrangement of experimental apparatus.     

Doping of sapphire single crystals with 111In and 111Cd detected by perturbed angular correlation

The electric hyperfine interaction of ion beam implanted ¹¹¹In and ¹¹¹Cd probe atoms in sapphire (Al₂O₃) single crystals has been investigated using perturbed angular correlation spectroscopy. For both probe atoms the same distinctive electric field gradient was found, indicating that nearly all the implanted probe atoms form a stable substitutional configuration in the temperature range between 77 K and 873 K on the aluminum sublattice. A comparative study between ¹¹¹In and ¹¹¹Cd-measurements points to a dynamic interaction initiated by the electron-capture of ¹¹¹In(EC)¹¹¹Cd similar to In₂O₃ and La₂O₃. Size and orientation of the EFG are discussed in comparison to experimental results in Cr₂O₃ single crystals. This revised version was published online in August 2006 with corrections to the Cover Date.     

Adsorption and coadsorption of carbon monoxide and hydrogen on Pd(111)

The adsorption and coadsorption of CO and H₂ have been studied by means of thermal desorption (TD) and electron stimulated desorption (ESD) at temperatures ranging from 250 to 400 K. Three CO TD states, labelled as β₂, β₁, and β₀ were detected after adsorption at 250 K. The population of β₂ and β₁ states which are the only ones observed upon adsorption at temperatures higher than 300 K was found to depend on adsorption temperature. The correlation between the binding states in the TD spectra and the ESD O⁺ and CO⁺ ions observed was discussed. Hydrogen is dissociatively adsorbed on Pd(111) and no ESD H⁺ signal was recorded following H₂ adsorption on a clean Pd surface. The presence of CO was found to cause an appearance of a H⁺ ESD signal, a decrease of hydrogen surface population and an arisement of a broad H₂ TD peak at about 450 K. An apparent influence of hydrogen on CO adsorption was detected at high hydrogen precoverages alone, leading to a decrease in the CO sticking coefficient and the relative population of CO β₂ state. The coadsorption results were interpreted assuming mutual interaction between CO and H at low and medium CO coverages, the “cooperative” species being responsible for the H⁺ ESD signal. Besides, the presence of CO was proved to favour hydrogen penetration into the bulk even at high CO coverage when H atoms were completely displaced from the surface.     

A leed-aes study of thin Pd films on Si(111) and (100) substrates

A system Pd (deposit)-Si (substrate) has been studied by LEED and AES. Pd₂Si formed on Si(111) became epitaxial after a short time of annealing at a temperature between 300 and 700°C, while the Pd₂Si formed on Si(100) did not, in both cases the surfaces of the Pd₂Si being covered with a very thin Si layer. A sequence of superstructures (3√3 × 3√3), (1 × 1), and (2√3 × 2√3) was observed successively in Pd/Si(111) as the annealing temperature was increased. A (√3 × √3) structure was obtained by sputtering the 3√3 surface slightly. It was found that the √3 structure corresponds to Pd²Si(0001)-(1 × 1) grown epitaxially on Si(111), and that the 3√3 structure comes from the thin Si layer accumulated over the silicide surface, while the 2√3 and 1 structures arise from a submonolayer of Pd adsorbed on Si(111). Superstructures observed on a Pd/Si(100) system are also studied.     

Phase transitions in the SrHfO3 perovskite measured with 111In/111Cd PAC

The temperature dependence of the hyperfine parameters in SrHfO₃ powder samples has been investigated by means of Perturbed Angular Correlation spectroscopy using implanted ¹¹¹In probes. Three quadrupole interactions have been established, with the largest fraction showing a pronounced dynamic interaction. We assign this fraction to ¹¹¹In / ¹¹¹Cd probe atoms on substitutional Hf sites. The temperature dependence of the dynamic interaction has been associated to the Pnma↔Imma phase transition at ∼700 K. We discuss the results in relation to those obtained for ¹⁸¹Hf / ¹¹¹Ta-probes in AHfO₃ (A=Ba, Sr, Ca) and for ¹¹¹In / ¹¹¹Cd-probes in PbZrO₃ and BaTiO₃. This revised version was published online in August 2006 with corrections to the Cover Date.     

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.     

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     

Benzene and thiophene formation from acetylene on sulfided Pd(111) studied by LITD/FTMS

We report the first laser-induced thermal desorption (LITD) studies of acetylene on Pd(111). LITD coupled with Fourier transform mass spectrometry (FTMS) probes the surface molecular composition. Our results show simultaneous formation of thiophene and benzene at 120 K after a 6 L dose of acetylene at 80 K on a Pd(111) surface with 0.06 ML of sulfur. Simultaneous formation implies that formation of the C₄H₄ intermediate is the slow step in the formation of both cyclic products. The relative amounts of thiophene and benzene observed with LITD/FTMS are comparable, while thermal desorption spectroscopy (TDS) yields integrated thiophene signals that are < 2% as intense as for benzene. This indicates that thiophene primarily decomposes upon heating. Low coverage (0.5 L) results confirm reports that the presence of sulfur enhances benzene production.     

Intrinsic point defects in niobium: Trapping at100Pd and111In impurities observed by PAC

Radiation-induced lattice defects in high-purity niobium have been investigated in the temperature range of 30K to 540 K by means of - perturbed angular correlation (PAC) measurements using the radioactive probes¹⁰⁰Pd/¹⁰⁰Rh and¹¹¹In/¹¹¹Cd. Both probes were produced within the niobium samples by means of heavy-ion nuclear reactions. At the Pd impurities trapping of defects occurred during heavy-ion irradiation at about 30 K in two defined configurations: defect 1(Pd) withv _Q1=e ² qQ/h=42(±2) MHz, ₁=0 and defect 2 (Pd) withv _Q2=(±2) MHz, ₂=1. Two defects were observed at the In impurities in annealing stage III (around 250 K) after heavy-ion as well as electron irradiations: defect 1(In) withv _Q1=87(±1) MHz, ₁=0 and defect 2(In) withv _Q2=105(±2) MHz, ₂=0.65(±0.02). A third defect (defect 3(In):v _Q3=177(±2) MHz, ₃0.2) appeared above 260 K after heavy-ion irradiation only. The data are interpreted in terms of interstitial trapping at the Pd impurities and vacancy trapping at the In impurities. Information on the microscopic structure of defect 1(In) and 2(In) is obtained from a PAC-single-crystal experiment. For defect 1(In) axial 111-symmetry is found, which leads us to identify this defect with a monovacancy as nearest neighbor with respect to the In probe. Defect 2(In) is the trapped divacancy for which an orientation is found that is consistent with both vacancies being nearest neighbor to the probe but second nearest neighbors to each other.     

Hyperfine interaction of111Cd in In-Pd intermetallic compounds

Perturbed - angular correlation (PAC) spectroscopy was applied to study the hyperfine parameters for¹¹¹In probes in In-Pd intermetallic compounds. The PAC spectra measured in In₃Pd, In₃Pd₂ and InPd₂ compounds reflect the number, population and symmetry of nonequivalent indium probe sites predicted by the crystallographic data. The temperature dependence of the observed electric field gradients was measured in the temperature range 80–873 K.     

The hydrogenation of CN on Pd(111) and Pd(100)

Adsorbed CN may be produced on Pd(111) and Pd(100) surfaces at RT by dissociative adsorption of cyanogen. HREELS measurements show that adsorbed CN forms adsorbed HCN or DCN on these Pd surfaces by reaction with H adsorbed from the residual gas or by dosing with H₂ or D₂. The reaction temperature is slighly lower for Pd(100) than for Pd(111), and the range of temperatures over which the reaction takes place much narrower. The reaction occurs on a time scale easily monitored with HREELS.     

Hyperfine interactions of111Cd impurities in Cr2O3

The electric and (antiferro-)magnetic hyperfine interaction of¹¹¹Cd in α-Cr₂O₃ after¹¹¹In implantation was studied via PAC. Two fractions with axially symmetric electric field gradients were observed having antishielding factors of V_zz/V_zz ^pc=79(12) and 106(16), respectively. From the line broadening of the Fourier components of the first fraction its supertransferred magnetic field was estimated as B_loc (20 K)≤0.41 T, about two orders of magnitude smaller than for substitutional¹¹¹Cd in NiO and CoO.     

Magnetic hyperfine fields on 111Cd in the Pd1+xMnSb heusler alloys

The time-differential perturbed angular correlation technique has been used to measure the magnetic hyperfine fields (mhf) acting on ¹¹¹Cd impurity on the series of alloys Pd_1+xMnSb with 0 ? x ? 1. We observe three diffrent mhf's which for small values of x are of the order of +250, ?250 and ?150 kOe, decreasing slowly for larger values of x. These three fields are associated with ¹¹¹Cd occupying the sites of Mn, Sb and Pd, respectively. In addition, magnetization measurements on three of the allows (x = 0, 0.4 and 0.8) gave magnetic moments on the Mn atoms of 3.88 ± 0.08, 4.18 ± 0.08, (4.14 ± 0.08)_μB and Curie temperatures of 470 ± 2,422 ± 5 and (288 ± 2) K, respectively. Our results together with the existing data for mhf's on various 5sp elements in the Pd₂MnSb Heusler alloy are compared with the Blandin-Campbell model and show an agreement which is only qualitative.     

Adsorption and reaction of nitric oxide and oxygen on Rh(111)

Adsorption of NO and O₂ on Rh(111) has been studied by TPD and XPS. Both gases adsorb molecularly at 120 K. At low coverages (θ_NO < 0.3) NO dissociates completely upon heating to form N₂ and O₂ which have peak desorption temperatures at 710 and 1310 K., respectively. At higher NO coverages NO desorbs at 455 K and a new N₂ state obeying first order kinetics appears at 470 K. At saturation, 55% of the adsorbed NO decomposes. Preadsorbed oxygen inhibits NO decomposition and produces new N₂ and NO desorption states, both at 400 K. The saturation coverage of NO on Rh(111) is approximately 0.67 of the surface atom density. Oxygen on Rh(111) has two strongly bound states with peak temperatures of 840 and 1125 K with a saturation coverage ratio of 1:2. Desorption parameters for the 1125 peak vary strongly with coverage and, assuming second-order kinetics, yield an activation energy of $\text{85 ± 5}\text{kcal}\text{mol}$ and a pre-exponential factor of 2.0 cm² s^?1 in the limit of zero coverage. A molecular state desorbing at 150 K and the 840 K state fill concurrently. The saturation coverage of atomic oxygen on Rh(111) is approximately 0.83 times the surface atom density. The behavior of NO on Rh and Pt low index planes is compared.     

Hyperfine interactions in intermetallic rare earth-gallium compounds studied by 111 Cd PAC

Magnetic and electric hyperfine interaction of the nuclear probe ¹¹¹In/¹¹¹Cd in intermetallic compounds of the rare earth-gallium system have been investigated by perturbed angular correlation (PAC) spectroscopy. The PAC measurements, supported by X-ray diffraction, provide evidence for a marked phase preference of ¹¹¹In for hexagonal RGa₂ over orthorhombic RGa and of RGa₃ with the L12 structure over RGa₂. In the case of SmGa₂, the magnetic hyperfine field B_hf, the electric quadrupole interaction and the angle β between B_hf and the symmetry axis of the electric field gradient have been determined as a function of temperature. The angle β?=?0 is consistent with the results of previous magnetization studies. Up to T?≤?17 K the magnetic hyperfine field has a constant value of B_hf?=?3.0(2) T. The rapid decrease at higher T gives the impression of a first-order transition with an order temperature of T_N?=?19.5 K. In the RKKY model of indirect 4f interaction the ratio T_C/B_hf(0) is a measure of the coupling constant. For ¹¹¹Cd:SmGa₂ (T_C/B_hf(0)~6.5 K/T) this ratio is significantly smaller than for the same probe in other R intermetallics (SmAl₂ ~9.5 K/T, Sm₂In ~13.5 K/T).     

Sign of the electric field gradient at111Cd in Zr and Sb

The Β-γ TDPAC technique was applied to¹¹¹Ag implanted in Zr and Sb metal single crystals in order to determine sign and magnitude of the quadrupole interaction at the site of¹¹¹Cd in these metals. An analysis of the data taken at 293K yielded Ν_Q=+15.4(6) MHz for¹¹¹Cd in Zr and Ν_Q=?107.5(20) MHz for¹¹¹Cd in Sb. From these values electric field gradients of +7.3(8)×10¹⁶ V/cm² and ?5.56(62)×10¹⁷ V/cm² for Cd in Zr and Sb are derived respectively.