The influence of crystallographic steps on coadsorption: CO---O/Ni(119)

On low index nickel surfaces, repulsive interactions between atomic oxygen and CO drive the phase separation of these species into oxygen-rich and CO-rich islands. Because these adsorbates interact differently with crystallographic steps, the size and the structure of these islands are modified on stepped surfaces. We have monitored coadsorption-induced changes in the distribution of CO with IRRAS, observing six different CO stretching bands which are assigned to distinct local chemisorption environments. When oxygen fully saturates sites along the step edge, the steps are completely blocked from CO adsorption and virtually all the CO population on the terraces shifts from atop to bridge sites. This terrace site shift is similarly accomplished by atomic oxygen chemisorbed at terrace sites. From these coadsorption-induced changes in CO site distributions, constrained by the 10 Å terrace width, we conclude the through-metal O---CO interaction responsible for this CO site shift must be operative over a range of 5 Å. At θ_o = 0.18 ML, when oxygen occupies, but does not fully saturate the step edge, a new CO adsorption site is created, with a characteristic frequency of 1750 cm⁻¹. This new site is assigned to CO bonded to kinks along the step edge based upon its low intensity ( geometric kink density), enhanced binding strength and sensitivity to oxygen coverage. At higher oxygen coverages, compression of the CO adlayer is observed, with CO shifting to asymmetric bridge sites. As saturation coverage is approached, CO occupies weakly bound sites in close proximity ( 3 Å) to O adatoms, with high characteristic frequencies of 2100 cm⁻¹.     

CO adsorption on Ni(1 0 0): Evidences for a weakly bound phase by HREELS measurements

The vibrational properties of CO on Ni(1 0 0) were investigated by high resolution electron energy loss spectroscopy. Loss measurements were performed as a function of temperature and CO exposures. At room temperature, regardless of CO coverage, we found stretching energies at 250 meV and 240 meV, assigned to CO at atop and bridge sites, respectively. At low temperature and for CO exposures lower than 0.6 L, the loss spectra showed a single stretching peak at 240 meV which is assigned to CO at bridge sites. For higher doses, a new intense peak at 260 meV appeared in the loss spectra. The rise of this new loss strongly influenced the intensity of the peak at 240 meV suggesting the occurrence of dipole couplings between adjacent CO molecules. This unusual high stretching frequency leads us to assign the peak at 260 meV to the stretching vibration of CO molecules which are weakly bonded to the Ni surface. We suggest that the formation of this phase is due to an electronic effect arising from a reduced back donation of electrons into the empty π orbital of CO.     

Adsorption of CO on Ni-promoted TiO2(110)

The valence-band structure and the vibrational modes of CO adsorbed on nickel-promoted TiO₂(110) surfaces as a function of CO exposure have been studied by means of ultraviolet photoelectron spectroscopy (UPS) and high-resolution electron energy-loss spectroscopy (HREELS). It is found that CO exists in molecular form at room temperature on the nickel-promoted TiO₂(110) surfaces and most likely binds to the Ni atoms or nickel-affected sites rather than to the substrate atoms. At saturation coverage, CO molecules adsorb simultaneously on the 2-fold bridge sites and terminal sites on the (111)-oriented Ni islands deposited upon TiO₂(110). The occupation of the edge sites of Ni islands gives rise to an anomalously low frequency of the C---O stretching vibration. This frequency, indicative of a weakened C---O bond, suggests existence of a precursor to the dissociated state.     

Vibrational characterization of carbon monoxide oxidation on the Pt(111) surface

The surface reaction between coadsorbed carbon monoxide and atomic oxygen has been characterized using high resolution electron energy loss spectroscopy, coupled with temperature programmed reaction spectroscopy on a Pt(111) surface characterized using Auger electron spectroscopy and low energy electron diffraction. Preferential oxidation of bridge bonded CO is not observed despite the fact that bridge bonded CO is adsorbed less vigorously than linearly bound CO. Saturation of the Pt(111) surface with one quarter of a monolayer of atomic oxygen completely suppresses the adsorption of bridge bonded CO. However, substantial coverages of bridge bonded CO can be coadsorbed if the Pt(111) surface is only partially saturated with atomic oxygen. The vibrational data for reaction of coadsorbed CO and atomic oxygen is consistent with a reaction mechanism involving reaction of mobile CO along oxygen island perimeters.     

Adsorption sites of CO on Pt (111)

The surface vibrations of CO adsorbed on Pt(111) single crystal surfaces at 320 K have been studied by electron-energy-loss spectroscopy. At low coverages two vibration modes at 58 and ∼260 meV are observed. For exposures >0.2 Langmuir two additional modes at 45 and 232 meV develop. Considering also the observed LEED structures these vibrations are attributed to CO molecules being adsorbed upright in on-top and bridge sites, respectively.     

ATR-SEIRAS--an approach to probe the reactivity of Pd-modified quasi-single crystal gold film electrodes

Quasi-single crystalline gold films of 20 nm thickness and preferential (1 1 1) orientation on Si hemispheres were modified by controlled potentiostatic deposition of Pd (sub-ML, ML, multi-L) from sulphate and/or chloride-containing electrolyte. The electrochemical properties of these model electrodes were characterised for hydrogen and (hydrogen-) sulphate adsorption as well as for surface oxide formation by cyclic voltammetry. Conditions were developed to fabricate defined and stable Pd monolayers. In situ ATR-SEIRAS (Attenuated Total Reflection Surface Enhanced Infrared Reflection Absorption Spectroscopy) experiments were carried out to describe the electrochemical double layer of Pd modified gold film electrodes in contact with aqueous 0.1 M H₂SO₄ with focus on interfacial water and anion adsorption. Based on an analysis of the non-resonant IR background signal the potential of zero charge is estimated to 0.10-0.20 V (vs. RHE). CO was found to be weakly physisorbed in atop sites on Au(1 1 1-20 nm)/0.1 M H₂SO₄ only in CO saturated electrolyte. CO, deposited on a quasi-single crystal gold film modified with 1 ML Pd, is chemisorbed with preferential occupation of bridge sites and atop positions at step edges. Saturated CO adlayers, as obtained by deposition at 0.10 V, contain isolated water species and are covered by a second layer of hydrogen bonded water. Potentiodynamic SEIRAS experiments of CO electro-oxidation on Pd-modified gold film electrodes demonstrate clearly the existence of a “pre-oxidation” region. They also provide spectroscopic evidence that isolated water and weakly hydrogen bonded water are consumed during the reaction and that atop CO on defect sites is a preferential reactant. The simultaneous in situ monitoring of the potential- and time-dependent evolution of characteristic vibrational modes in the OH- and CO-stretching regions are in agreement with the Gilman (“reactant pair”) mechanism of CO oxidation.     

Vibrational EELS,XPS and UPS study of CO chemisorbed on Pt10Ni90(111): Evidence for the existence of different sites

CO adsorption on the (111) face of a Pt₁₀Ni₉₀ alloy single crystal has been investigated at room temperature by vibrational electron energy loss spectroscopy (EELS) and photoelectron spectroscopy (XPS and UPS). Two well separated CO stretching modes develop at 2070 and 1820 ± 10 cm^?1, with their intensities reaching 64 and 36% respectively of the total intensity at saturation coverage. They are attributed to CO adspecies in terminal and bridge bonded configuration respectively. The UPS spectra of 4σ, 5σ and 1π molecular orbitais of adsorbed CO show complex features which may be resolved into two components having the main characteristics of CO adsorbed on pure Pt(111) and Ni(111) respectively. Such behaviour is also observed by XPS on C 1s on O 1s peaks. Their respective contributions, in both XPS and UPS spectra are about 64 and 36% of the whole spectrum. Finally compared to Ni(111) — on which CO adsorbs mainly in bridge configuration — the alloying with 10% Pt has generated the appearance of a large number of new sites for CO chemisorption associated with the presence of Pt atoms at the surface. The large amount of terminal CO adspecies is interpreted in terms of considerable surface enrichment of the alloy in platinum.     

Entropy-controlled site occupation of CO adsorbed on Ni(100)

The adsorption of CO on a Ni(100) surface has been studied by FT-IRAS in the temperature range from 85 K to 300 K. At 300 K and for =0.5, the CO molecules are predominantly adsorbed in on-top sites with only a minor fraction located at two-fold bridge sites. Measurements on a Ni(100) surface pre-covered with sulphur, oxygen and carbon indicate that the occupation of bridge sites may be caused by small amounts of surface impurities. The relative broadness of the infrared bands is explained by CO molecules occupying intermediate positions at domain walls. Upon lowering the temperature, the bridge sites are increasingly occupied at the expense of terminal sites. This process is completely reversible and is explained by a contribution of the hindered translations of the adsorbed CO molecules to the entropy. At 85 K and for low initial coverages, we observe an unusual high CO stretching frequency at 2205 cm^–1 which cannot be explained at present.     

The role of electrodynamic interactions on energy loss intensities of adsorbed molecules

The effect on energy loss intensities of the electrodynamic interactions with the substrate and neighboring adsorbed molecules is discussed. The experimentally observed large variations in the loss intensity from molecules adsorbed on various sites are considered. A simple dipole model of the molecule interacting with its image in the substrate and its neighbors on equivalent and inequivalent sites is used. Good agreement with experiment for a well characterized surface coverage of bridge and on-top bonded CO molecules on Ni(111) is found.     

CO stretching vibrations on Pt(111) and Pt(110) studied by sumfrequency generation

Optical sum-frequency generation (SFG) is used to characterize CO stretching vibrations on Pt(111) and Pt(110) surfaces. Different adsorption sites (terminal, bridge and step sites) are identified in the SFG spectra of CO on Pt(111), in good quantitative agreement with previous infrared reflection-absorption experiments on this system. For CO on Pt(110) we only observe CO molecules on terminal sites. The measured CO stretching vibration frequencies on Pt(110), both for low and high coverages, are at variance with the results of previous infrared studies. Our SFG results for CO on Pt(110) are confirmed by independent EELS measurements which, in addition, also reveal the frustrated rotational mode and the metal-CO vibration. The measured frequency of 2065 cm⁻¹ for low CO coverage on Pt(110)-(1 × 2) is consistent with a previously proposed empirical relation between the frequency of an isolated adsorbed CO molecule and the coordination number of the binding Pt surface atom.     

Site-specific core level spectroscopy of CO and NO adsorption on Pt(110)(1×2) and (1×1) surfaces

The adsorption of CO and NO on the (1×2) and (1×1) modifications of the Pt(110) surface was studied by x-ray photoemission spectroscopy, LEED and work-function change measurements. The O(1s) binding energy of adsorbed CO is site-specific and differentiates between on-top and bridge adsorbed species. CO adsorption on Pt(110)(1×2) at 120 K occurred sequentially into on-top and bridge sites yielding an orderedc(8×4) layer at the maximum coverage. At 300 K only on-top bonded CO was present after CO adsorption on the (1×2) surface. CO adsorption on the (1×1) surface at 120 K showed a transient bridge adsorbed CO and on-top CO at saturation, with an ordered (2×1)p1g1 LEED pattern. Heating the (2×1)p1g1 CO layer to 400 K also showed this transient bridge CO species. Work function changes generally correlated with the appearance of different CO species but were complex in detail. The findings for CO adsorption are consistent with the missing row model of the (1×2) surface.Parallel data for NO adsorption on (1×2) and (1×1) surfaces at 120 K were less informative than those for CO because O(1s) spectra showed single broad peaks. Peak contributions due to bridge and on-top bonded NO could be estimated.     

CO在表面有序合金Cu{001}c(2×2)-Pd上的吸附

用高分辨电子能量损失谱研究CO在有序表面合金Cu{001}c(2×2)-Pd上的吸附位置,在240K,CO仅直立地吸附在Pd原子的顶位;在135K,低覆盖度时,CO仅直立地吸附于Pd原子顶住,覆盖度增加后,CO同时直立地也吸附于Pd和Cu原子的顶位。     

Surface interaction between H2 and CO2 over silicalite-supported platinum

Infrared spectroscopic evidence is presented for the formation of linearly bonded CO species, as a result of surface interaction between H₂ and CO₂ at room temperature over silicalite-supported Pt. Comparison with direct CO adsorption results suggests that the active sites for this CO₂ reaction are the corner or step sites on platinum particles. The CO formed on these active sites then migrates to other sites on the surface of Pt particles. Co-adsorbed hydrogen and water make the linearly bonded CO species more strongly adsorbed on Pt particles. However, exposure to oxygen or air at room temperature effectively removes these CO species.     

An IRAS study of CO bonding on Sn/Pt(1 1 1) surface alloys at maximal pressures of 10 Torr

The adsorption of CO on Pt(1 1 1), (2 × 2) and (√3 × √3)R30° Sn/Pt(1 1 1) surface alloys has been studied using temperature programmed desorption (TPD), low energy electron diffraction (LEED) and infrared reflection adsorption spectroscopy (IRAS). The presence of Sn in the surface layer of Pt(1 1 1) reduces the binding energy of CO by a few kcal/mol. IRAS data show two C-O stretching frequencies, ∼2100 and ∼1860 cm⁻¹, corresponding to atop and bridge bonded species, respectively. Bridge bonded stretching frequencies are only observed for Pt(1 1 1) and (2 × 2) Sn/Pt(1 1 1) alloy surfaces. A slight coverage dependence of the vibrational frequencies is observed for the three surfaces. High pressure IRAS experiments over a broad temperature range show no indication of bridge bonded CO on any of the three surfaces. Direct CO adsorption on Sn sites is not observed over the measured temperature and pressure ranges.     

Chemisorption of isocyanate (NCO) on the Pd(1 0 0) surface at different coverages

The chemisorption of isocyanate (NCO) species on Pd(1 0 0) was studied within the density functional formalism (DFT) using a periodic slab model. The NCO was adsorbed on top, bridge and hollow sites of the metal surface at different coverages. At low coverages, the adsorption energies are in the range of ?2.5/?3.0 eV, indicating an important adsorbate–substrate interaction for the three sites studied. The lateral repulsive interaction between neighboring NCO species is almost negligible or weak at lower and intermediate coverages, and very strong at complete monolayer. At low coverages, both bridge and hollow sites are energetically preferred; yet the bridge site becomes the only favoured site at intermediate and complete coverages. Work function and dipole moment calculations can be interpreted by an important charge transfer from the metal surface to NCO. Interestingly, while on hollow site the charge taken by NCO is essentially the same over all the range of coverage, an increasing depolarization is observed on bridge and top sites as the coverage increases. Symmetric and asymmetric NCO stretching modes were also calculated and compared with recent infrared spectroscopy measurements.     

The adsorption sites of CO on Ni(111) as determined by infrared reflection-absorption spectroscopy

The adsorption of CO on Ni(111) has been studied using infrared reflection-absorption spectroscopy combined with LEED, Auger electron spectroscopy, thermal desorption spectroscopy and work function measurements. At low CO coverage (θ = 0.05) CO adsorbs on threefold sites with a strecthing frequency given by ω_CO = 1817 cm^?1. At θ = 0.30 all molecules have shifted to two-fold sites, and θ = 0.50, where a c(4 × 2) structure is observed, ω_CO = 1910 cm^?1. At θ = 0.57, with a (√7/2) × √7/2)R19.1° structure, one quarter of the molecules are adsorbed on top of the nickel atoms with the others in two-fold sites. Molecules bonded on the top sites give rise to a band at 2045 cm^?1. The frequency shift due to dipole-dipole interactions is small compared with the shift resulting from bonding to different crystallographic sites.     

表面缺陷对一氧化碳和甲基基团在金红石TiO2(110)表面吸附的影响

本文利用程序升温脱附技术研究了氧空位浓度对甲基基团和CO在R-TiO₂(110)表面吸附的影响. 结果表明,随着氧空位浓度的变化,吸附在桥氧位的甲基基团和吸附在五配位Ti⁴⁺位点上的CO分子的脱附温度呈现了不同的趋势,揭示了表面缺陷可能对R-TiO₂(110)不同位点上的物质吸附具有重要影响.     

Vibrational EELS studies of CO chemisorption on clean and carbided (111), (100) and (110) nickel surfaces

Room temperature adsorption of CO on bare and carbided (111), (100) and (110) nickel surfaces has been studied by vibrational electron energy loss spectroscopy (EELS) and thermal desorption. On the clean (100) and (110) surfaces two configurations of CO adsorbed species, namely “terminal” and bridge bonded CO, are observed simultaneously. On Ni(111), only two-fold sites are involved. The presence of superficial carbon lowers markedly the bond strength of CO on Ni(111)C and Ni(110)C surfaces, while no adsorption has been detected on the Ni(100)C surface. Moreover, on the carbided Ni(110)C surface, the adsorption mode for adsorbed CO is changed with respect to the clean surface; only “terminal” CO is then observed.     

Normal modes of CO adsorbed on metal surfaces

A normal mode analysis of experimental data from helium atom scattering (HAS) and electron energy loss spectroscopy (EELS) for vibrations of CO molecules adsorbed in on-top and bridge sites on Ni(100) is presented, using a refined force-constant analysis. The similar case of CO adsorbed on Pt(111) is reinvestigated, revealing a misassignment of normal modes in previous work. Finally, available experimental data for CO on Pt(111) is used to construct a trial potential energy surface.     

Parametric plate-bridge dynamic filter model of violin radiativity

A hybrid, deterministic-statistical, parametric "dynamic filter" model of the violin's radiativity profile [characterized by an averaged-over-sphere, mean-square radiativity (R(ω)(2))] is developed based on the premise that acoustic radiation depends on (1) how strongly it vibrates [characterized by the averaged-over-corpus, mean-square mobility (Y(ω)(2))] and (2) how effectively these vibrations are turned into sound, characterized by the radiation efficiency, which is proportional to (R(ω)(2))/(Y(ω)(2)). Two plate mode frequencies were used to compute 1st corpus bending mode frequencies using empirical trend lines; these corpus bending modes in turn drive cavity volume flows to excite the two lowest cavity modes A0 and A1. All widely-separated, strongly-radiating corpus and cavity modes in the low frequency deterministic region are then parameterized in a dual-Helmholtz resonator model. Mid-high frequency statistical regions are parameterized with the aid of a distributed-excitation statistical mobility function (no bridge) to help extract bridge filter effects associated with (a) bridge rocking mode frequency changes and (b) bridge-corpus interactions from 14-violin-average, excited-via-bridge (Y(ω)(2)) and (R(ω)(2)). Deterministic-statistical regions are rejoined at ~630 Hz in a mobility-radiativity "trough" where all violin quality classes had a common radiativity. Simulations indicate that typical plate tuning has a significantly weaker effect on radiativity profile trends than bridge tuning.