TDS and EELS observations for CO,O2, and CH3OH bound to Ru(0001)/Cu

The electronic properties of monolayers of copper atoms adsorbed onto a Ru(0001) single crystal surface have been studied with thermal desorption spectroscopy (TDS) and high resolution electron energy loss spectroscopy (EELS) utilizing carbon monoxide (CO), dioxygen (O₂), methanol (CH₃OH), and to some extent water (H₂O) as chemical probes. Whereas a three-monolayer-thick film exhibits most properties of a Cu(111) crystal distinct deviations are found at lower Cu coverages. TDS as well as EELS show a weakened RuCO bond and a strengthened CuCO bond as a result of metal-metal interaction. The stronger CuCO bond is accompanied by a higher probability for O₂ dissociation. The mobilities of copper and oxygen atoms are such that annealing to 650 K produces an overlayer structure which is independent of adsorption sequence: Cu/O₂ or O₂/Cu, but where RuO as well as CuO vibrations can be identified. Methanol adsorbs reversibly on a monolayer of copper atoms. Metal bound methoxy species are formed in the presence of oxygen atoms. The decomposition paths of such methoxy intermediates alter towards more formaldehyde (CH₂O) relative to CO with increasing copper and methoxy coverages.     

A study of the infrared spectra of carbon monoxide adsorbed on metals of the copper subgroup and on cobalt,ruthenium, rhodium,and palladium

A study has been made of the infrared spectra of carbon monoxide CO, adsorbed on Cu, Ag, Au, Co, Ru, Rh and Pd at temperatures from –160° C to 200° C and pressures from 10^–5 to 1–10 mm Hg. The spectra of CO adsorbed on Cu, Ag, and Au show one absorption band, characteristic of a surface compound of carbon monoxide, with linear structure. It has been found that in the stable chemosorption of CO on Co, Ru, Rh, and Pd in the range of temperatures and pressures studied, two types of surface compound-linear and bridged-are produced.     

A molecular beam study of the adsorption dynamics of CO on Ru(0001), Cu(111) and a pseudomorphic Cu monolayer on Ru(0001)

We have investigated the sticking coefficient of CO on Ru(0001), a pseudomorphic Cu monolayer on Ru(0001), and a fully relaxed Cu(111) multilayer as function of kinetic energy, surface coverage, and surface temperature. At a low kinetic energy of 0.09 eV, the initial sticking coefficients, S₀, on these surfaces are determined to be 0.92, 0.96 and 0.87, respectively. In all cases, a decrease of S₀ with increasing beam energy was observed, yielding values of 0.58, 0.14 and 0.07, respectively, at a kinetic energy of 2.0 eV. For all three surfaces the coverage dependent sticking coefficients, S(Θ), display very characteristic behavior at low kinetic energies: S(Θ) remains more or less constant up to coverages close to saturation, indicative of precursor adsorption kinetics. However, characteristic minima at intermediate coverages are observed, which are correlated to the formation of well ordered adsorbate phases. For high kinetic energies we observe a transition towards a linear decrease of S(Θ) for Ru(0001). In contrast, for the pseudomorphic Cu monolayer and for Cu(111) we find an increase in the sticking coefficients at low coverages, followed by a decrease close to saturation. This behavior is attributed to adsorbate assisted sticking, that is, to a higher sticking coefficient on adsorbate covered regions than on the bare surface. The comparison between the pseudomorphic monolayer and Cu(111) reveals that the CO bond strength to the former is larger by 40%. The initial sticking coefficients for both surfaces are very similar at low kinetic energies; at high kinetic energies, S₀ for the pseudomorphic Cu monolayer is, however, larger by a factor of two.     

Geometric structure and electronic states of copper films on a ruthenium (0001) surface

Auger electron spectroscopy (AES), combined with thermal desorption mass spectroscopy (TDS), work function (Δφ) measurements and energy-dependent angular resolved UV photoemission using synchrotron radiation were used to investigate the geometric and electronic properties of submonolayer and monolayer copper films grown by vapor deposition on a clean Ru(0001) substrate. A pronounced influence of the deposition temperature on the morphology of the Cu films was established in that lower temperatures favor an island growth mechanism (Stranski-Krastanov or Volmer-Weber type), whereas higher deposition temperatures lead to a more uniform spreading and a layer-by-layer growth (Frank-van der Merwe type). For Cu films grown under the latter conditions angular resolved photoemission reveals the existence of two-dimensional Cu bands even before the monolayer has reached completion; the experimentally determined band dispersions agree quite well with recent theoretical calculations.     

Experimental development of reflection-absorption spectroscopy: Infrared spectrum of carbon monoxide adsorbed on copper and copper oxide

The reflection-adsorption technique is used to obtain the infrared spectrum of a monolayer or less of carbon monoxide adsorbed on an evaporated copper film. The band is located at 2105 cm⁻¹ and is obtained with a signal-to-noise ratio in the range 5 to 15. In this technique, the infrared beam is multiply reflected between two closely-spaced parallel metal surfaces covered with the adsorbed layer. The CO band is used to investigate the dependence of the signal-to-noise ratio on the spacing of the metal surfaces. The existence of an optimum value of the spacing is demonstrated. The contribution to the absorption band of infrared rays with different angles of incidence is investigated and explained in terms of an optimum number of reflections and its variations with angle of incidence. After the copper surface is progressively exposed to oxygen, a slight shifting of the CO band to 2113 cm⁻¹ is observed. Further exposure gives rise to a new band of adsorbed CO at 2135 cm⁻¹, interpreted as CO adsorbed on copper oxide.     

Reflection-absorption infrared spectroscopy of adsorbates on a Cu(111) single crystal surface

A Fourier Transform infrared spectrometer has been attached to an ultrahigh vacuum (UHV) apparatus in order to perform reflection-absorption infrared Spectroscopy (RAIRS) of adsorbed species on well-defined surfaces.An infrared spectrum of carbon monoxide (CO) adsorbed at 90 K on Cu(111) has been measured using a resolution of 2 cm⁻¹ and a measuring time of 60 s. Coverages below 1 % of a monolayer are easily detectable.Tetracyanoethylene (TCNE) has been adsorbed at various coverages at 100 K on Cu(111). Strongly red-shifted CN stretchings modes due to charged TCNE adspecies are observed at low coverage. The RAIRS spectrum of the condensed phase is characteristic of crystalline TCNE.Finally, isotopically labeled ¹²C and ¹³C acetonitrile (CH₃CN) has been adsorbed on Cu(111) as multilayers. Shifts caused by isotopic labeling as small as 3 cm⁻¹ are easily detected.     

Band structure of Au layers on the Ru(0001) and graphene/Ru(0001) surfaces

The electronic structures of Au monolayers on the Ru(0001) and graphene-coated Ru(0001) surfaces have been calculated by DFT method using the supercell (repeated-slab) approach. The local densities of states (LDOS) and band structures of the monolayer and bilayer Au films adsorbed on the graphene/Ru(0001) and those of free hexagonal Au layers are found to be very similar. This result indicates that the monolayer graphene almost completely screens the Au layers from the Ru(0001) substrate surface, so that electronic properties of Au films adsorbed on graphene are determined predominantly by the electronic structure of the Au adlayers, essentially independent on the electronic structure of the substrate surface.     

Pd修饰Cu电极的电化学CO2还原

利用微分电化学质谱和电化学原位衰减全反射红外光谱技术探究了Cu和CuPd催化剂上CO₂和CO的电化学还原行为. 红外光谱观察到了生成甲醇、甲烷与乙烯的CH_x中间物种. 在CuPd电极CO₂还原过程中,红外光谱的CO吸附峰起始电位比Cu正移大约300 mV,说明CuPd能够有效促进CO₂还原;CO饱和溶液中,Cu和CuPd电极CO起始吸附电位基本相同;两电极上CO谱带出现的电位与CO₃^2-的谱带降低的电位基本相同,说明CO的吸附需要CO₃^2-的脱附. 利用电化学在线质谱发现在CuPd电极上CO还原产生CH₄和CH₃OH的起始电位比Cu电极正移约200 mV. 推测催化活性的提升可能是由于Pd的引入改变了Cu的d能带,且Pd吸附更多的H,从而促进CO₂还原,使CO能够与H结合并被深度还原.     

Formation of graphene on Ru（0001） surface

We report on the formation of a graphene monolayer on a Ru(0001) surface by annealing the Ru(0001) crystal. The samples are characterized by scanning tunnelling microscopy (STM) and Auger electron spectroscopy (AES). STM images show that the Moir\'{e} pattern is caused by the graphene layer mismatched with the underlying Ru(0001) surface and has an $N\times N$ superlattice. It is further found that the graphene monolayer on a Ru(0001) surface is very stable at high temperatures. Our results provide a simple and convenient method to produce a graphene monolayer on the Ru(0001) surface, which is used as a template for fabricating functional nanostructures needed in future nano devices and catalysis.     

Cluster-model calculation of Raman intensity for vibration of CO adsorbed on copper

We calculate the derivative of the static polarizability of CO with respect to the carbon-oxygen distance, for the system HCuCO. This models crudely a system of interest in surface enhanced Raman spectroscopy, namely CO adsorbed on a Cu atom which in turn is adsorbed on a single crystal Cu surface. The electronic structure calculation is done by using the ab initio Hartree-Fock method. Some of the calculations are aimed at showing that CO bound to HCu has properties similar to those of adsorbed CO. The derivative of the polarizability allows us to estimate the enhancement of the Raman signal caused by the formation of a chemical bond between CO and the Cu ad-atom. We find that this is a minor enhancement, of at most an order of magnitude.     

The adsorption of Xe and CO on a Cu (311) single crystal surface

LEED, electron energy loss spectroscopy and surface potential measurements have been used to study the adsorption of Xe and CO on Cu (311). Xe is adsorbed with a heat of 19 ± 2 kJ mol^/t-1. The complete monolayer has a surface potential of 0.58 V and a hexagonal close-packed structure with an interatomic distance of 4.45 ± 0.05 Å. CO gives a positive surface potential increasing with coverage to a maximum of 0.34 V and then falling to 0.22 V at saturation. The heat of adsorption is initially 61 ± 2 kJ mol^?1, falling as the surface potential maximum is approached to about 45 kJ mol^?1. At this coverage streaks appear in the LEED pattern corresponding to an overlayer which is one-dimensionally ordered in the [011̄] direction. Additional CO adsorption causes the heat of adsorption to decrease further and the overlayer structure to be compressed in the [011̄] direction. At saturation the LEED pattern shows extra spots which are tentatively attributed to domains of a new overlayer structure coexisting with the first. Electron energy loss spectra (EELS) of adsorbed CO show two characteristic peaks at 4.5 and 13.5 eV probably arising from transitions between the electronic levels of chemisorbed CO.     

Molecular orbital study of the interaction of carbon monoxide and carbon dioxide with copper (100)

A molecular orbital study is made of the structures and energy levels of CO and CO₂ on Cu(100). The importance of self-consistency is discussed. CO is found to occupy fourfold indentations, in agreement with the semiempirical results of Doyden and Ertl. The C-surface distance is 1.0 Å and the CO bond stretches less than 0.1 Å. Large models of the surface show convergence of the electronic structure with four CO molecules on a twelve Cu atom cluster model of the surface. At coverages up to c(2 × 2) half monolayer, calculated energy levels match Demuth and Eastman's phase I photoemission spectrum. Phase II, as observed by them, has no analog in the calculations. No evidence is found for CO deviating from perpendicular to the surface when tightly bound. CO₂ is found to adsorb more weakly to the surface. This molecule rests in a μ bridging position, bonded through mixing of Cu d with CO₂ π¹ orbitals. It bends, with an angle of 120°, which is significantly similar to 122° for the ¹B₂ excited state of free CO₂, which has an electron promoted to the π¹ orbital. On the basis of this molecular orbital study, extrapolations to Ni and Zn surfaces and OCS, CS₂, CSe₂ and CTe₂ are made.     

Adsorption of CO and C2H4 on Rh-loaded thin-film dysprosium oxide

A dysprosium oxide thin film was deposited on Ru(0 0 0 1) by vapor depositing Dy in 2 × 10⁻⁷ torr O₂ while the Ru was at 700 K. The film was ca. 5 nm thick and produced a p(1.4 × 1.4) LEED pattern relative to the Ru(0 0 0 1) substrate. The adsorption and reaction of CO and C₂H₄ adsorbed on Rh supported on the Dy₂O₃ film were studied by TPD and SXPS. The CO initially reacted with loosely bound oxygen in the substrate to produce CO₂. After the loosely bound oxygen was removed, the CO adsorbed non-dissociatively in a manner similar to what is seen on Rh(1 1 1). C₂H₄ adsorbed on the Rh particles and underwent progressive dehydrogenation to produce H₂ during TPD. The C from the C₂H₄ reacted with the O in Dy₂O₃ to produce CO. CO dissociation on the Rh particles could be promoted by treating the Dy₂O₃ with C₂H₄ before CO exposure.     

Electron induced dissociation of CO on Ru(001): A study by thermal desorption and electron spectroscopies

CO adsorbed on Ru cannot convert thermally into a β-state of the kind observed on W and Mo — which is most probably dissociated CO — under CO pressures below 10^?5 Torr. Such a state can, however, be produced by electron impact onto a virgin CO layer adsorbed on Ru. This is shown using temperature-programmed desorption, UPS, XPS, XPS satellites, and XAES. A comparative discussion of the β-states on W and Ru yields rough estimates of the energies for desorption and conversion of CO on these metals; possible implications for catalytic reactions are mentioned.     

Raman study of photo‐induced degradation of the Ru(II) complex adsorbed on nanocrystalline TiO2 films

Photo‐induced degradation of a monolayer of the Ru(II) complex adsorbed on anatase TiO₂ thin films was studied by using resonant micro‐Raman spectroscopy. We developed two contrastive experiments to analyze the degradation mechanism. An exponential decay law was found when the dye was irradiated in the absence of a reducing agent. While the sensitized TiO₂ thin film electrode was covered by the I^–/I₃^– redox couple, the dye degradation exhibited a slowed linear decay. The experimental result was compared and the degradation mechanism was analyzed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Chemisorption studies on cobalt single crystal surfaces: I. Carbon monoxide on Co(0001)

The chemisorption of CO on Co(0001) and on a polycrystalline specimen has been studied by LEED, Auger spectroscopy, and thermal desorption measurements. Annealing of the polycrystal was found to result in a surface dominated by crystallites of (0001) orientation in the surface plane, along with a few (101̄2) oriented crystallites. CO adsorbs on the clean surface at 300 K with an initial sticking probability of 0.9 and the system follows precursor state kinetics. The saturation coverage under UHV conditions corresponds to a well-ordered (√3 × √3)R30° structure; with P_CO>5 × 10^-9 a uniform compression of the adlayer takes place and a (√7 × √7)R19.2° structure begins to form. Models are proposed for these two ordered phases which are in agreement with the observed relative coverage data and the appearance of the corresponding desorption spectra. The desorption enthalpy of CO at low coverages is 103 ± 8 kJmol^-1, and a fairly sharp fall in this enthalpy occurs for coverages $\text{>}\text{1}\text{3}$. In many respects, the system's behaviour closely resembles that of Ni(111)-CO. Oxygen contamination leads to the appearance of a strongly adsorbed CO state with a desorption enthalpy of ~170 kJmol^-1. This is reminiscent of a strongly adsorbed non-dissociated state of CO on Ru(101̄1) which occurs under similar conditions.     

Structures of the O/Cu top layer in O-mediated film growth of Cu on Ru(0001)

In order to characterize the disordered O/Cu surfactant layer causing layer-by-layer growth of Cu on O-precovered Ru(0001), an ordered O/Cu structure is used as substrate to study further Cu growth. The O/Cu structure develops during Cu deposition on O-saturated Ru(0001) at growth temperatures of ca 520 K. It was recently interpreted as being composed of separated wave-like O–Cu–O chains forming a disrupted ‘Cu₂O’ surface layer. Scanning tunneling microscopy (STM) is used to characterize domains and defects of the O/Cu structure and the morphology of the Cu film growing on-top. For temperatures ca 400 K, again an O-mediated layer-by-layer growth of Cu is observed. The post-deposited Cu films display a similar island shape and island density as found for the Cu film growth on O-saturated Ru(0001) where a disordered O/Cu surfactant layer is present. Initially, domains of the ordered O/Cu structure are revealed on-top of the growing Cu film which are rotated by 120° to each other and separated by boundaries where the ordering is disturbed. The domain size drastically decreases with film thickness. As a result, the ordering of the O/Cu top-layer is extinguished already after the deposition of a few Cu monolayers. Finally, the surface displays the same disordered corrugation pattern as the O/Cu surfactant layer. The STM investigations indicate a strong correlation between the O/Cu structure and the disordered O/Cu surfactant layer. This leads to the conclusion that the O/Cu surfactant layer is composed of a random-like arrangement of O–Cu–O strings which locally form disrupted ‘Cu₂O’ fragments.     

Self-assembled monolayer and multilayer formation using redox-active Ru complex with phosphonic acids on silicon oxide surface

The formation of self-assembled monolayer and multilayer using redox-active Ru complex molecules with phosphonic acids on SiO₂ surface has been examined using X-ray photoelectron spectroscopy (XPS), ellipsometry, and time of flight secondary mass-ion spectroscopy (TOF-SIMS). We found that an introduction of a Zr adlayer leads to higher surface molecular density of Ru complex SAMs on the SiO₂ surface, compared to that of obtained from the direct adsorption of Ru complex monolayer on the SiO₂ surface. We further tried to fabricate a multilayer film using this molecule with Zr(IV) ion acting as a chemical glue by a successive immersion process. The XPS data revealed that the molecular densities of the multilayers were also higher for the immobilization with Zr adlayer between Ru complex and SiO₂ surface than those without the Zr adlayer, suggesting that Zr adlayer is effective in forming highly packed molecular layer of phosphonic acids on SiO₂ surface. We found the film growth reached a saturation point after 6 layers on the SiO₂ surface. The film growth saturation can be explained by a molecular domain boundary effect encountered due to the large tilt angle of the molecular layer.     

Electronic structure of a cobalt monolayer on Cu(100)

Angular resolved photoemission spectra using synchrotron radiation have been measured for different amounts of cobalt evaporated on Cu(100). At room temperature cobalt grows layer-bylayer forming well-ordered layers in registry with the substrate, as judged by AES, LEED and UPS measurements. The energy position and linewidth of the Cu peaks remain unchanged when cobalt is deposited onto the surface, suggesting a rather weak interaction between the d-bands of Co and Cu. The two-dimensional band structure of the monolayer of cobalt has been determined. We have obtained a value for the magnetic exchange splitting of ΔE_exch = 0.80 ± 0.15 eV, which is nearly identical to the bulk value. A shift in the energy positions of the critical points for the monolayer versus bulk of cobalt is interpreted in terms of a narrower 2D density of states in the monolayer as compared to the bulk. A resonant valence-band two-electron satellite has been found. The correlation energy and screening effects of the two d-holes are very similar to the corresponding bulk values, while the decreased intensity of the satellite at resonance compared to the one for Co(0001) suggests that there are more d-states relative to s-states in the monolayer than in a bulk cobalt single crystal, in agreement with recent models of the valence band electronic structure at surfaces.     

Decomposition pathways of C1C4 alcohols adsorbed on platinum (111)

The adsorption and decomposition of methanol, ethanol, propan-1-ol, propan-2-ol and butan-1-ol has been studied on clean, and oxygen pre-covered Pt(111) surfaces. Temperature Programmed Reaction Spectroscopy (TPRS), Surface Potential Measurements (ΔV), UPS and XPS were used to characterise the adsorbed layer as a function of temperature. Each alcohol adsorbed into two states, a monolayer phase and a multilayer phase which were distinguishable by TPRS and Spectroscopy measurements. The monolayer alcohol adsorption heats increased sequentially from methanol to n-butanol (11.5–15 kcal mole^?1). On the clean surface, less than 10% of the adsorbed monolayer dissociated, with 90% of the alcohol desorbing intact. Two competing dissociative pathways were observed: complete dissociation to adsorbed CO, H and C, and with propan-1-ol and butan-1-ol, scission of the CC bond nearest the CO group to form adsorbed CO, H and ethylidyne and propylidyne species respectively. The latter reaction probability was constant at 30% for n-propanol and n-butanol. In all cases the final desorption products were the parent alcohol, CO and H₂ with carbon remaining on the surface for the higher alcohols. Atomic oxygen removed hydrogen from the alcohols as water but did not change the final reaction products.