Unusually low stretching frequency for CO adsorbed on Fe(100)

For CO adsorption on Fe(100) different adsorption species are detected with high resolution EELS (electron energy loss spectroscopy) which sequentially fill in with increasing coverage. Up to ～ 350 K and low CO exposure (≦1 L), a predominant molecular species with an unusually low stretching frequency, 1180–1245 cm^?1, is detected. This unusual CO bond weakening is consistent with a “lying down” binding configuration of CO. For higher CO coverages at 110 K, further CO adsorption states with vibrational frequencies of 1900–2055 cm^?1 are populated which are due to CO bound with the molecular axis perpendicular to the surface.     

The adsorption of CO on evaporated iridium films,studied with infrared reflection-absorption spectroscopy

The adsorption of ^12CO on Ir films evaporated under ultrahigh vacuum (UHV) conditions was studied using infrared reflection-absorption spectroscopy (IRAS). Only a single absorption band was observed at 300 K, shifting continuously from the “singleton” value ~2010 cm^?1 at very low coverages to 2093 cm^?1 at saturation coverage. This band is attributed to CO adsorbed on top of the surface atoms. Synchronously with this shift the bandwidth at half maximum intensity $\text{Δv}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ decreases from ~30 to 8 cm^?1. The integrated peak area increases linearly with coverage up to a relative coverage (θ_r) of approximately 0.4, then the increase levels off and a maximum is observed. Upon continuing adsorption the intensity decreases slightly. In addition results are presented on adsorption at 300 K of ¹²CO?¹³CO isotopic mixtures. The coverage induced frequency shift is discussed in terms of a dipole-dipole coupling mechanism and it is concluded that intermolecular coupling can explain the shift (~83 cm^?1) observed. The decrease in intensity at coverages > 0.4 is attributed to the formation of a compressed overlayer with part of the CO molecules adsorbed in a multicentre position with different spectral properties. No infrared bands of nitrogen adsorbed at 78 K could be detected at pressures up to 6.7 kPa (1 Pa = 0.0075 Torr, 1 Torr = 133.32 Pa).     

Absolute coverages of CO and O on Pt(111); Comparison of saturation CO coverages on Pt(100), (110) and (111) surfaces

Nuclear microanalysis (NMA) has been used to determine the absolute coverages of oxygen and CO adsorbed on Pt(111). The saturation oxygen coverage at 300 K is 3.9 ± 0.4 × 10¹⁴ O atoms cm^?2 (θ = 0.26 ± 0.03), confirming the assignment of the LEED pattern as p(2 × 2). The saturation CO coverage at 300 K is 7.4 ± 0.3 × 10¹⁴ CO cm^?2 (θ = 0.49 ± 0.02). The low temperature saturation CO coverages on Pt(100), (110) and (111) surfaces are compared.     

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.     

Adsorption of oxygen on Pt(111)

Oxygen adsorbed on Pt(111) has been studied by means of temperature programmed thermal desorption spectroscopy (TPDS). high resolution electron energy loss spectroscopy (EELS) and LEED. At about 100 K oxygen is found to be adsorbed in a molecular form with the axis of the molecule parallel to the surface as a peroxo-like species, that is, the OO bond order is about 1. At saturation coverage (θ_mol= 0.44) a $\text{(}\text{3}\text{2}\text{×}\text{3}\text{2}\text{)R15°}$ diffraction pattern is observed. The sticking probability S at 100 K as a function of coverage passes through a maximum at θ = 0.11 with S = 0.68. The shape of the coverage dependence is characteristic for adsorption in islands. Two coexisting types of adsorbed oxygen molecules with different OO stretching vibrations are distinguished. At higher coverages units with v-OO = 875 cm^?1 are dominant. With decreasing oxygen coverages the concentration of a type with v-OO = 700 cm^?1 is increased. The dissociation energy of the OO bond in the speices with v-OO = 875 cm^?1 is estimated from the frequency shift of the first overtone to be ~ 0.5 eV. When the sample is annealed oxygen partially desorbs at ~ 160K, partially dissociates and orders into a p(2×2) overlayer. Below saturation coverage of molecular oxygen, dissociation takes place already at92 K. Atomically adsorbed oxygen occupies threefold hollow sites, with a fundamental stretching frequency of 480 cm^?1. In the non-fundamental spectrum of atomic oxygen the overtone of the E-type vibration is observed, which is “dipole forbidden” as a fundamental in EELS.     

Chemisorption of carbon monoxide on platinum {111}: Reflection-absorption infrared spectroscopy

Reflection-adsorption infrared spectroscopy has been combined with thermal desorption and surface stoichiometry measurements to study the structure of CO chemisorbed on a {111}- oriented platinum ribbon under uhv conditions. Desorption spectra show a single peak at coverages > 10¹⁴ molecules cm^?2, with the desorption energy decreasing with increasing coverage up to 0.4 of a monolayer, and then remaining constant at ≈135 kJ mol^?1 until saturation. The “saturation” coverage at 300 K is 7 × 10¹⁴ molecules cm^?2, and no new low temperatures state is formed after adsorption at 120 K. Infrared spectra show a single very intense, sharp band over the spectral range investigated (1500 to 2100 cm^?1), which first appears at low coverages at 2065 cm^?1 and shifts continuously with increasing coverage to 2101 cm^?1 at 7 × 10¹⁴ molecules cm^?2. The halfwidth of the band at 2101 cm^?1 is 9.0 cm^?1, independent of temperature and only slightly dependent on coverage. The band intensity does not increase uniformly with increasing coverage, and hysteresis is observed between adsorption and desorption sequences in the variation of both the band intensity and frequency as a function of coverage. The frequency shift and the virtual invariance of the absorption band halfwidt with increasing coverage (Jespite recent LEED evidence for overlayer compression in this system) are attributed to strong dipole-dipole coupling in the overlayer.     

The adsorption of carbon monoxide on Cu(110)-Ni surfaces prepared by dissociation of nickel carbonyl

Cu(110)-Ni surface alloys were prepared by dissociation of nickel carbonyl on clean Cu(110). The adsorption of CO is reversible in the temperature region of 22–200°C and the pressure range of 5 × 10^?8-0.7 Torr, as monitored with ellipsometry and AES. The amount of adsorbed CO depends on the amount of preadsorbed oxygen but not on the amount of carbon present at the surface. The isosteric heat of adsorption decreases from 31 ± 3kcal/mole to 18 ± 2 kcal/mole with increasing CO coverage (up to θ = 0.14θ_max) but is constant for higher coverages (up to θ = 0.4θ _max).     

The adsorption of CO on Cu(110)

The adsorption of CO on Cu(110) has been studied by LEED, surface potentials and infrared spectroscopy. With increasing surface coverage the s.p. passes through a maximum value of 0.29 V and than falls to 0.17 V at saturation. The heat of adsorption is nearly constant (~55 kJ mol^?1) up to the maximum s.p. but then falls rapidly. A ( 2× 1) structure is formed near the s.p. maximum, followed by a structure which is compressed in the [11?0] direction and poorly ordered in the [001] direction but tending towards c(1.3 × 2). At low coverage two infrared bands appear at 2088 and 2104 cm^?1; their relative intensity is similar at 77, 195 and 295 K. As the coverage increases, the bands shift in frequency and merge into a single band at 2094 cm^?1. The origin of the two bands is discussed in relation to the overlayer structure. Strong interaction between CO molecules is shown by the spectra of mixtures of ¹³CO and ¹²CO.     

Adsorption and decomposition of methyl iso-cyanide on Pt(111)

CH₃NC adsorption and thermal decomposition on a Pt(111) surface has been studied by high resolution EEL and TD spectroscopies. At 90 K, CH₃NC adsorbs initially in a terminal-bonded configuration characterized by a blue-shifted iso-cyanide stretch at 2265-2240 cm^?1. At higher coverages this form co-exists with a second form characterized by an imine-like stretch at 1600–1770 cm^?1, increasing with coverage. This form is associated with bridge bonding to adjacent surface platinum atoms. Adsorption is irreversible and. except for multilayer desorption at 135 K, only reaction-limited H₂ (T_p = 440–460 K) andHCN (T_p = 420–610 K) desorption and. at high coverages, isomerization to CH₃CN (T_p = 430 K) was seen. EEL spectra recorded after heating the adsorbed layer indicated that at lower coverages, the molecular integrity of the adsorbed CH₃NC was completely lost before dehydrogenation occurred. On the other hand, at saturation structural changes in the adsorbed layer corresponded firstly to the onset of dehydrogenation and then. at higher temperatures, to HCN evolution. No spectroscopic evidence for an η²-bonding configuration was found either at low temperatures or during thermal decomposition. The terminal- and bridged-bonded configurations adopted by CH₃NC have been compared and contrasted with those found with the isoelectronic CO and the isomeric CH₃CN by reference to the chemically important frontier orbitals of these ligand molecules.     

Thermal desorption of carbon monoxide from Mo(110)

Adsorption and desorption of carbon monoxide (CO) from Mo(110) have been investigated by temperature programmed desorption (TPD). The TPD spectra exhibit peaks in two temperature regions: 250-400 and 850-1100 K. The first region correspond to adsorption in molecular form, whereas the latter region corresponds to desorption of CO that has been dissociatively adsorbed. When the surface was saturated by CO, about 35% of the desorption intensity originates from the high-temperature region (recombinative desorption) and the remaining desorption signal is from the low-temperature region (molecular adsorption). Desorption parameters for molecular adsorbed CO were obtained using several different heating rates. Desorption energies were estimated to range from 0.9 eV for low coverages of CO to about 0.65 eV for high coverages. Corresponding prefactors were estimated to be in the range from 1 210¹¹ to 1 210⁹ s^{m 1}. The experimental data have been compared with Monte Carlo simulations of first-order TPD from a bcc (110) lattice, in which partial poisoning of adsorption sites by dissociated carbon and oxygen was modelled. Repulsive near-neighbour interactions were used.     

The chemisorption of nitrogen on the (001) surface of ruthenium

High resolution electron energy loss spectroscopy (EELS), thermal desorption mass spectrometry (TDMS) and low energy electron diffraction (LEED) have been used to investigate the molecular chemisorption of N₂ on Ru(001) at 75 K and 95 K. Adsorption at 95 K produces a single chemisorbed state, and, at saturation, a (√3x√3) R30° LEED pattern is observed. Adsorption at 75 K produces an additional chemisorbed state of lower binding energy, and the probability of adsorption increases by a factor of two from its zero coverage value when the second chemisorbed state begins to populate. EEL spectra recorded for all coverages at 75 K show only two dipolar modes — ν(RuN₂) at 280–300 cm^?1 and ν(NN) at 2200–2250 cm^?1 — indicating adsorption at on-top sites with the axis of the molecular standing perpendicular to the surface. The intensities of these loss features increase and ν(NN) decreases with increasing surface coverage of both chemisorbed states.     

Electron impact desorption of Xe from the tungsten (110) plane

The electron stimulated desorption of Xe adsorbed on the clean and on oxygen and CO covered tungsten (110) surfaces has been investigated. Only neutral Xe desorption was observed; for Xe on clean W a very small initial regime with cross section 10^?17cm² is followed by a slow decay with cross section 3×10^?19cm². The Xe yield varies nonlinearly with coverage, suggesting desorption from edges of islands or from sites with less than their full complement of nearest neighbor Xe atoms. Desorption from oxygen or CO covered surfaces results in an apparent desorption cross section identical to that of the underlying adsorbate. This results from a kicking off of Xe by electron desorbed O or CO. The true cross sections for these processes are ～10^?14cm² for Xe-0 and ～10^?15 cm² for Xe-CO. Some speculations about the mechanism, particularly the absence of ions are presented.     

Absolute coverages for the various surface phases of CO and O adsorbed on Pd(110)

The absolute surface coverages of CO and O on Pd(110) have been measured by nuclear reaction analysis (NRA) using the ¹²C(d, p)¹³C and ¹⁶O(d, p₁)¹⁷O¹ reactions. The CO coverages of the (2 × 1) and (4 × 2) phases of CO on Pd(110) are 1.00 ±0.05 and 0.73 ±0.05 ML (1 ML = 1 monolayer = 9.4 × 10¹⁴ CO molecules cm⁻²) respectively. The oxygen coverage in the c(4 × 2) phase of O on Pd(110) is 0.50 ±0.05 ML.     

Vibrational excitations and structure of oxygen on Fe(110)

Vibrational spectra of oxygen adsorbed on a clean Fe(110) surface at 300 K have been measured by high resolution electron energy loss spectroscopy (EELS). In the exposure range up to 6 L a single loss around 500 cm^-1 is observed which is interpreted to be due to the stretching vibration of atomic oxygen adsorbed at a 2-fold long-bridge site. Above exposures of 6 L a second loss around 400 cm^-1 appears which is attributed to the formation of a disordered oxide layer. Subsequent heating of the sample leads to the observation of a (5×12) LEED pattern which is explained by a mixed oxygen-iron surface structure which is nearly identical to the (111) face of bulk FeO. A weak loss around 910 cm^-1 appears after oxygen exposures at elevated sample temperatures. This loss is attributed to the formation of bulk oxide.     

Adsorption von wasserstoff an platin: II. Adsorptionsentropien

Differential and integral molar entropies of the adsorbed layer are calculated from the dependence of the coverage on pressure and temperature published in part I. The experimental entropies correspond up to coverages of 2 × 10¹⁴ molecules cm^?2 with entropies of the localized adsorption and an additional vibration entropy of about 20 cal deg^?1 mole^?1 caused by vibrations of the adsorbed atoms in the order of magnitude of 10¹² sec^?1. At higher coverages the entropy increases and passes through a maximum. This is explained by the formation of a second adsorption state (γ state) probably consisting of molecular hydrogen.     

The coadsorption of potassium and co on the pt(111) crystal surface: A TDS,HREELS and UPS study

The interaction of CO with a potassium covered Pt(111) surface is investigated using thermal desorption (TDS), high resolution electron energy loss (HREELS) and ultraviolet photoelectron (UPS) spectroscopies. When submonolayer amounts of potassium are preadsorbed, the adsorption energy of CO increases from 25 to 36 kcal/mole, while substantial shifts in the site occupancy from the linear to the bridged site are observed. The CO stretching vibrational frequencies are shown to decrease continuously with either increasing potassium coverage or decreasing CO coverage. A minimum CO stretching frequency of 1400 cm^?1 is observed, indicative of a CO bond order of 1.5. The work function decreases by up to 4.5 eV at submonolayer potassium coverages, but then increases by 1.5 eV upon CO co-adsorption. The results indicate that the large adsorption energy, vibrational frequency and work function changes are due to molecular CO adsorption with a substantial charge donation from potassium through the platinum substrate and into the 2π¹_CO orbital.     

Evidence for two different adsorption sites of CO on Pt(111) from infrared reflection spectroscopy

The adsorption of CO on Pt(111) surfaces has been studied under clean conditions by a highly surface sensitive double-beam infrared reflection spectroscopy (IRS). In contrast to results of other authors two stretching vibrations of adsorbed CO rather than one are detected near 2100cm⁻¹ and 1870cm⁻¹. This is in agreement with recent findings in high-resolution electron energy loss spectroscopy (ELS). The results are discussed in terms of two adsorption sites: CO adsorbed in on-top positions and double coordinated on bridging sites, respectively. Furthermore, a precursor state and a preferential adsorption in islands at low coverage is taken into account.     

The adsorption of CO,H2, H2, CO2 and H2O on carburized and graphitized Ni(110)

A study of the adsorption/desorption behavior of CO, H₂O, CO₂ and H₂ on Ni(110)(4 × 5)-C and Ni(110)-graphite was made in order to assess the importance of desorption as a rate-limiting step for the decomposition of formic acid and to identify available reaction channels for the decomposition. The carbide surface adsorbed CO and H₂O in amounts comparable to the clean surface, whereas this surface, unlike clean Ni(110), did not appreciably adsorb H₂. The binding energy of CO on the carbide was coverage sensitive, decreasing from 21 to 12 $\text{kcal}\text{mol}$ as the CO coverage approached 1.1 × 10¹⁵ molecules cm^?2 at 200K. The initial sticking probability and maximum coverage of CO on the carbide surface were close to that observed for clean Ni(110). The amount of H₂, CO, CO₂ and H₂O adsorbed on the graphitized surface was insignificant relative to the clean surface. The kinetics of adsorption/desorption of the states observed are discussed.     

The adsorption of ethylene oxide on Ag(110) and Pt(111): Relevance to selective olefin oxidation

The interactions of ethylene oxide (EtO) with the Ag(110) and Pt(111) surfaces have been studied using XPS, TDS, AES and EELS. On Ag(110), the interaction is very weak, with only molecular desorption observable. The heat of adsorption is ≈ 10.1 kcal mole⁻¹. In contrast, decomposition reactions strongly predominate on Pt(111) at low coverage. Molecular desorption is only seen at high coverages. The heat of adsorption decreases from > 11.9 to 10 kcal mole⁻¹ with increasing coverage. Condensed multilayers desorb at ≈ 140 K. Ultimate decomposition products on Pt(111) include H₂ and CO gas, and carbon residue on the surface. Evidence suggests that adsorbed decomposition intermediates may include atomic hydrogen, CO, acetyl and ethylidyne species, with at least one other, yet unidentified, species. These results imply that, if produced, adsorbed ethylene oxide would be unlikely to escape a reactor containing Pt catalyst without further decomposition reactions. This may help explain the uniqueness of Ag catalysts in ethylene epoxidation.     

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 [011&#x0304;] direction. Additional CO adsorption causes the heat of adsorption to decrease further and the overlayer structure to be compressed in the [011&#x0304;] 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.