TPD, HREELS and UPS study of the adsorption and reaction of methyl nitrite (CH3ONO) on Pt(111)

The adsorption and reaction of methyl nitrite (CH₃ONO, CD₃ONO) on Pt(111) was studied using HREELS, UPS, TPD, AES, and LEED. Adsorption of methyl nitrite on Pt(111) at 105 K forms a chemisorbed monolayer with a coverage of 0.25 ML, a physisorbed second layer with the same coverage that desorbs at 134 K, and a condensed multilayer that desorbs at 117 K. The Pt(111) surface is very reactive towards chemisorbed methyl nitrite; adsorption in the monolayer is completely irreversible. CH₃ONO dissociates to form NO and an intermediate which subsequently decomposes to yield CO and H₂ at low coverages and methanol for CH₃ONO coverages above one-half monolayer. We propose that a methoxy intermediate is formed. At least some C–O bond breaking occurs during decomposition to leave carbon on the surface after TPD. UPS and HREELS show that some methyl nitrite decomposition occurs below 110 K and all of the methyl nitrite in the monolayer is decomposed by 165 K. Intermediates from methyl nitrite decomposition are also relatively unstable on the Pt(111) surface since coadsorbed NO, CO and H are formed below 225 K.     

A LEED, TPD and HREELS investigation of NO adsorption on Sn/Pt(111) surface alloys

The adsorption of NO on Pt(111), and the (2 × 2)Sn/Pt(111) and (√3 × √3)R30°Sn/Pt(111) surface alloys has been studied using LEED, TPD and HREELS. NO adsorption produces a (2 × 2) LEED pattern on Pt(111) and a (2√3 × 2√3)R30° LEED pattern on the (2 × 2)Sn/Pt(111) surface. The initial sticking coefficient of NO on the (2 × 2)Sn/Pt(111) surface alloy at 100 K is the same as that on Pt(111), S₀ = 0.9, while the initial sticking coefficient of NO on the (√3 × √3)R30°Sn/Pt(111) surface decreases to 0.6. The presence of Sn in the surface layer of Pt(111) strongly reduces the binding energy of NO in contrast to the minor effect it has on CO. The binding energy of β-state NO is reduced by 8–10 kcal/mol on the Sn/Pt(111) surface alloys compared to Pt(111). HREELS data for saturation NO coverage on both surface alloys show two vibrational frequencies at 285 and 478 cm⁻¹ in the low frequency range and only one N-O stretching frequency at 1698 cm⁻¹. We assign this NO species as atop, bent-bonded NO. At small NO coverage, a species with a loss at 1455 cm⁻¹ was also observed on the (2 × 2)Sn/ Pt(111) surface alloy, similar to that observed on the Pt(111) surface. However, the atop, bent-bonded NO is the only species observed on the (√3 × √3)R30°Sn/Pt(111) surface alloy at any NO coverage studied.     

A temperature programmed desorption study of the reaction of methylacetylene on Pt(111) and Sn/Pt(111) surface alloys

The adsorption and reaction of methylacetylene (H₃CC≡CH) on Pt(111) and the p(2×2) and

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surface alloys were investigated with temperature programmed desorption, Auger electron spectroscopy and low energy electron diffraction. Hydrogenation of methylacetylene to form propylene is the most favored reaction pathway on all three surfaces accounting for ca 20% of the adsorbed monolayer. Addition of Sn to the Pt(111) surface to form these two ordered surface alloys suppresses the decomposition of methylacetylene to surface carbon. The alloy surfaces also greatly increase the amount of reversibly adsorbed methylacetylene, from none on Pt(111) to 60% of the adsorbed layer on the

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surface alloy. Methylacetylene reaction also leads to a small amount of desorption of benzene, along with butane, butene, isobutylene and ethylene. There is some difference in the yield of these other reaction products depending the Sn concentration, with the (2×2)-Sn/Pt(111) surface alloy having the highest selectivity for these. Despite previous experiments showing cyclotrimerization of acetylene to form benzene on the Pt–Sn surface alloys, the analogous reaction of methylacetylene on the alloy surfaces was not observed, that is, cyclotrimerization of methylacetylene to form trimethylbenzene. It is proposed that this and the high yield of propylene is due to facile dehydrogenation of methylacetylene because of the relatively weak H–CH₂CCH bond compared to acetylene. The desorption of several C₄ hydrocarbon products at low (<170 K) temperature indicates that some minor pathway involving C–C bond breaking is possible on these surfaces.     

The role of co-adsorbed metal atoms in the chemistry of methyl species on Pt(111) formed by the decomposition of dimethylmercury and dimethylzinc

The chemistry of methyl species resulting from the decomposition of dimethylmercury (DMM) and dimethylzinc (DMZ) on Pt(111) in the range 300–400 K has been investigated by temperature prograrnmed desorption (TPD) and Auger electron spectroscopy (AES). In each case at 300 K, dissociative adsorption of the precursor results in the formation of an adlayer of methylmetal (CH₃M) moieties. These species are thermally stable to around 350 K before decomposing to yield mainly gaseous products, methane and hydrogen, and surface bound metal atoms. For DMM, subsequent heating to 400 K or direct dissociative adsorption at 400 K results in the formation of ethylidyne species. Ethylidyne formation is not observed in the thermal chemistry of DMZ at temperatures below 400 K and only transiently in the chemistry at 400 K. Complementary TPD and AES data indicate that, for DMM, desorption of the mercury atoms produced by CH₃Hg decomposition is the limiting factor in allowing the prevailing C₁ species to couple to form ethylidyne. In contrast, AES evidence indicates that zinc atoms remain on the surface to temperatures in excess of 750 K and hence prevent C---C coupling by blocking surface sites.     

Adsorption of oxygen on Au(111) by exposure to ozone

Atomic oxygen coverages of up to 1.2 ML may be cleanly adsorbed on the Au(111) surface by exposure to O₃ at 300 K. We have studied the adsorbed oxygen layer by AES, XPS, HREELS, LEED, work function measurements and TPD. A plot of the O(519 eV)/Au(239 eV) AES ratio versus coverage is nearly linear, but a small change in slope occurs at Θ_O=0.9 ML. LEED observations show no ordered superlattice for the oxygen overlayer for any coverage studied. One-dimensional ordering of the adlayer occurs at low coverages, and disordering of the substrate occurs at higher coverages. Adsorption of 1.0 ML of oxygen on Au(111) increases the work function by +0.80 eV, indicating electron transfer from the Au substrate into an oxygen adlayer. The O(1s) peak in XPS has a binding energy of 530.1 eV, showing only a small (0.3 eV) shift to a higher binding energy with increasing oxygen coverage. No shift was detected for the Au 4f_7/2 peak due to adsorption. All oxygen is removed by thermal desorption of O₂ to leave a clean Au(111) surface after heating to 600 K. TPD spectra initially show an O₂ desorption peak at 520 K at low Θ_O, and the peak shifts to higher temperatures for increasing oxygen coverages up to Θ_O=0.22 ML. Above this coverage, the peak shifts very slightly to higher temperatures, resulting in a peak at 550 K at Θ_O=1.2 ML. Analysis of the TPD data indicates that the desorption of O₂ from Au(111) can be described by first-order kinetics with an activation energy for O₂ desorption of 30 kcal mol⁻¹ near saturation coverage. We estimate a value for the Au–O bond dissociation energy D(Au–O) to be 56 kcal mol⁻¹.     

Adsorption and reactions of CH2I2 on Ru(001) surface

The adsorption and dissociation of CH₂I₂ were studied at 110 K with the aim of generating CH₂ species on the Ru(001) surface. The methods used included X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), temperature programmed desorption (TPD), Auger electron spectroscopy (AES) and work function measurements. Adsorption of CH₂I₂ is characterized by a work function decrease (0.96 eV at monolayer), indicating that adsorbed CH₂I₂ has a positive outward dipole moment. Three adsorption states were distinguished: a multilayer (T_p=200 K), a weakly bonded state (T_p=220 K) and an irreversibly adsorbed state. A new feature is the formation of CH₃I, which desorbs with T_p=160 K. The adsorption of CH₂I₂ at 110 K is dissociative at submonolayer, but molecular at higher coverages. Dissociation of the monolayer to CH₂ and I proceeded at 198–230 K, as indicated by a shift in the I(3d_5/2) binding energy from 620.6 eV to 619.9 eV. A fraction of adsorbed CH₂ is self-hydrogenated into CH₄ (T_p=220 K), and another one is coupled to di-σ-bonded ethylene, which — instead of desorption — is converted to ethylidyne at 220–300 K. Illumination of the adsorbed CH₂I₂ initiated the dissociation of CH₂I₂ monolayer even at 110 K, and affected the reaction pathways of CH₂.     

Adsorption of ethene on Pt(1 1 1) and ordered PtxSn/Pt(1 1 1) surface alloys: A comparative HREELS and DFT investigation

The adsorption of ethene (C₂H₄) on Pt(1 1 1) and the Pt₃Sn/Pt(1 1 1) and Pt₂Sn/Pt(1 1 1) surface alloys has been investigated experimentally by high-resolution electron energy loss spectroscopy and temperature programmed desorption. The experimental results have been compared with density functional theory (DFT) calculations allowing us to perform a complete assignment of all vibration modes and loss features to the species present on the surfaces. On Pt(1 1 1) as well as on the Pt-Sn surface alloys an η² di-σ-bonded conformation of ethene has been found to be the most stable adsorbed form. In addition to this majority species a minor amount of π-bonded ethene has been identified, which is more abundant on the Pt₂Sn surface alloy than on the other surfaces. Additionally the HREELS spectra of ethene on Pt(1 1 1) and the Pt-Sn surface alloys differ only slightly in terms of the energetic positions of the loss peaks.     

Adsorption and reaction of bicyclic hydrocarbons at Pt(1 1 1) and Sn/Pt(1 1 1) surface alloys: trans-decahydronaphthalene (C10H18) and bicyclohexane (C12H22)

Adsorption and desorption of trans-decahydronaphthalene (C₁₀H₁₈) and bicyclohexane (C₁₂H₂₂) can be used to probe important aspects of non-specific dehydrogenation leading to surface carbon accumulation and establish better estimates of activation energies for C-H bond cleavage at Pt-Sn alloys. This chemistry was studied on Pt(1 1 1) and the (2 × 2)-Sn/Pt(1 1 1) and (√3 × √3)R30°-Sn/Pt(1 1 1) surface alloys by using temperature programmed desorption (TPD) mass spectroscopy and Auger electron spectroscopy (AES). These hydrocarbons are reactive on Pt(1 1 1) surfaces and fully dehydrogenate at low coverages to produce H₂ and surface carbon during TPD. At monolayer coverage, 87% of adsorbed C₁₀H₁₈ and 75% C₁₂H₂₂ on Pt(1 1 1) desorb with activation energies of 70 and 75 kJ/mol, respectively. Decomposition of C₁₀H₁₈ is totally inhibited during TPD on these Sn/Pt(1 1 1) alloys and decomposition of C₁₂H₂₂ is reduced to 10% of the monolayer coverage on the (2 × 2)-Sn/Pt(1 1 1) alloy and totally inhibited on the (√3 × √3)R30°-Sn/Pt(1 1 1) alloy. C₁₀H₁₈ and C₁₂H₂₂ are more weakly chemsorbed on these two alloys compared to Pt(1 1 1) and these molecules desorb in narrow peaks characteristic of each surface with activation energies of 65 and 73 kJ/mol on the (2 × 2) alloy and 60 and 70 kJ/mol on the (√3 × √3)R30°-Sn/Pt(1 1 1) alloy, respectively. Alloyed Sn has little influence on the monolayer saturation coverage of these two molecules, and this is decreased only slightly on these two Sn/Pt(1 1 1) alloys. The use of these two probe molecules enables an improved estimate of the activation energy barriers E* to break aliphatic C-H bonds in alkanes on Sn/Pt alloys; E* = 65-73 kJ/mol on the (2 × 2)-Sn/Pt(1 1 1) alloy and E* ? 70 kJ/mol on the (√3 × √3)R30°-Sn/Pt(1 1 1) alloy.     

Adsorption of hydrogen and carbon monoxide on Rh(1 1 1)/V surface alloys

A detailed study of the interaction of hydrogen and carbon monoxide with two different Rh(1 1 1)/V surface alloys (1/3 monolayer of V in the second atomic layer or 1/3 monolayer of V in form of islands on the surface) is presented in comparison to the clean Rh(1 1 1) surface. For hydrogen a decrease in the sticking coefficient is found for both alloy surfaces. The sticking coefficient of H₂ as a function of the translational energy is similar to the Rh(1 1 1) surface, showing a direct activated adsorption mechanism. For low translational energies hydrogen adsorption is dominated by dynamical steering on Rh(1 1 1) and by a precursor mechanism on the Rh(1 1 1)/V subsurface alloy. The H₂ TPD desorption peaks are shifted to lower temperatures on the alloy surfaces, caused by the downshift of the metal d-band due to V alloying. On all three surfaces the saturation coverage of hydrogen was measured, giving 1.2, 1.0 and 0.8 monolayer for Rh(1 1 1), the Rh(1 1 1)/V subsurface alloy and for the Rh(1 1 1)/V islands, respectively. For CO the sticking coefficients and the saturation coverages are basically the same on the Rh(1 1 1) and the alloy surfaces. There is an extrinsic precursor on the ordered CO (√3×√3) phase on the Rh(1 1 1) surface, but there is no evidence for such a precursor on the Rh(1 1 1)/V subsurface alloy. On the Rh(1 1 1)/V islands surface, the extrinsic precursor exists on the Rh(1 1 1) surface between the V islands. Apparently this precursor is only stable on the ordered CO layer on Rh(1 1 1).     

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.     

Adsorption of CH3Cl on clean and Cl-dosed Pd(100) surfaces

The adsorption of methyl chloride on a Pd(100) surface has been investigated by ultraviolet photoelectron spectroscopy (UPS), electron energy loss spectroscopy (in the electronic range, EELS), temperature-programmed desorption (TPD) and work function change. CH₃Cl adsorbs with high sticking probability at 80–100 K. UPS and TDS spectra suggest that the adsorption of CH₃Cl is molecular at 100 K, with a little distortion of the corresponding gas-phase molecular electronic structure. No dissociation of CH₃Cl was observed even up to 550 K. By means of TPD, we distinguished two adsorption states with desorption energies of 46.9 and 33.4 kJ/mol. The formation of a condensed layer at 105–110 K was also observed. Adsorption of CH₃Cl caused a significant work function decrease, Δ = −0.91 eV, indicating a dipole with positive end pointed away from the surface. The effects of electronegative additives, preadsorbed Cl and O were also examined. Preadsorbed Cl caused a slight destabilization of adsorbed CH₃Cl at lower concentration, prevented the adsorption of CH₃Cl at higher concentration and facilitated the formation of a condensed layer. No such effect was experienced in the presence of preadsorbed O.     

NO在Ag/Pt(110)-(1×2)双金属表面的吸附：亚硝酸盐/硝酸盐表面物种的生成

以俄歇电子能谱、X射线光电子能谱和热脱附谱研究了室温下NO在Ag/Pt(110)-(1×2)双金属表面的吸附. 在该双金属表面上观察到了可能的亚硝酸盐/硝酸盐表面物种,其在更高温度下分解生成N₂. 然而,室温下NO在清洁Pt(110)表面和Ag-Pt合金表面上并不会生成这种亚硝酸盐/硝酸盐表面物种. 亚硝酸盐/硝酸盐表面物种的形成归因于高度配位不饱和Ag粒子的高活性及其与Pt基底之间的协同作用.     

Tensor LEED analysis for the electrodeposited Pt(1 1 1)-(3×3)–Ag,I surface structure

A crystallographic analysis is reported using low-energy electron diffraction (LEED) in the tensor LEED approach for the electrodeposited coadsorption (3×3) structure with 4/9 monolayer (ML) of silver and 4/9 ML of iodine on the Pt(1 1 1) surface. The structure approximates a two-layer slice of bulk AgI cut parallel to its (1 1 1) plane and superimposed on the substrate with the Ag atoms in contact with the topmost Pt(1 1 1) layer, and the I atoms forming an overlayer on the Ag atoms. There are two types of Ag atoms in the (3×3) unit mesh; one type bonds to a single Pt atom, while the other type bonds to three Pt atoms. The average Ag–Pt bond distances are close to 2.48 and 2.82 Å respectively for the one and three-coordinate Ag atoms, but both types of Ag atoms bond to three I atoms with an average Ag–I distance of 2.67 Å. No significant corrugation is observed for either the I layer or the Ag layer.     

LEED structure determination of the Ni(1 1 1)(√3×√3)R30°-Sn surface

Quantitative low energy electron diffraction has been used to determine the structure of the Ni(1 1 1)(√3×√3)R30°-Sn surface phase. The results confirm that the surface layer comprises a substitutional alloy of composition Ni₂Sn as previously found by low energy ion scattering (LEIS), and also shows that there is no stacking fault at the substrate/alloy interface as has been found in (√3×√3)R30°-Sb surface alloys on Ag and Cu(1 1 1). The surface alloy layer is rumpled with the Sn atoms 0.45 ± 0.03 Å higher above the substrate than the surrounding Ni atoms. This rumpling amplitude is almost identical to that previously reported on the basis of the LEIS study. Comparison with similar results for Sn-induced surface alloy phases on Ni(1 0 0) and Ni(1 1 0) shows a clear trend to reduced rumpling with reduced surface atomic layer density, an effect which can be rationalised in terms of the different effects of valence electron charge smoothing at the surface.     

Investigation of the role of oxygen in NO reduction by C2H4 on the surface of stepped Pt(3 3 2)

The influence of pre-dosed oxygen on NO–C₂H₄ interactions on the surface of stepped Pt(3 3 2) has been investigated using Fourier transform infrared reflection–absorption spectroscopy (FTIR-RAS) and thermal desorption spectroscopy (TDS). The presence of oxygen significantly suppresses the adsorption of NO on the steps of Pt(3 3 2), leading to a very specific adsorption state for NO molecules when oxygen–NO co-adlayers are annealed to 350 K (assigned as atop NO on step edges). An oxygen-exchange reaction also takes place between these two kinds of adsorbed molecules, but there appears to be no other chemical reaction, which can result in the formation of higher-valence NOx.

C₂H₄ molecules which are post-dosed at 250 K to adlayers consisting of ¹⁸O and NO do not have strong interactions with either the NO or the ¹⁸O atoms. In particular, interactions which may result in the formation of new surface species that are intermediates for N₂ production appear to be absent. However, C₂H₄ is oxidized to C¹⁸O₂ by ¹⁸O atoms at higher annealing temperature. This reaction scavenges surface ¹⁸O atoms quickly, and the adsorption of NO molecules on step sites is therefore quickly restored. As a consequence, NO dissociation on steps proceeds very effectively, giving rise to N₂ desorption which closely resembles that following only NO exposure on a clean Pt(3 3 2), both in peak intensity and desorption temperature. It is concluded that the presence of ¹⁸O₂ in the selective catalytic reduction (SCR) of NO with C₂H₄ on the surface of Pt(3 3 2) does not play a role of activating reactants.     

NO adsorption and thermal behavior on Pd surfaces. A detailed comparative study

The adsorption and thermal behavior of NO on ‘flat’ Pd(111) and ‘stepped’ Pd(112) surfaces has been investigated by temperature programmed desorption (TPD), high resolution electron energy loss spectroscopy (HREELS), and electron stimulated desorption ion angular distribution (ESDIAD) techniques. NO is shown to molecularly adsorb on both Pd(111) and Pd(112) in the temperature range 100–373 K. NO thermally desorbs predominantly molecularly from Pd(111) near 500 K with an activation energy and pre-exponential factor of desorption which strongly depend on the initial NO surface coverage. In contrast, NO decomposes substantially on Pd(112) upon heating, with relatively large amounts of N₂ and N₂O desorbing near 500 K, in addition to NO. The fractional amount of NO dissociation on Pd(112) during heating is observed to be a strong function of the initial NO surface coverage. HREELS results indicate that the thermal dissociation of NO on both Pd(111) and Pd(112) occurs upon annealing to 490 K, forming surface-bound O on both surfaces. Evidence for the formation of sub-surface O via NO thermal dissociation is found only on Pd(112), and is verified by dissociative O₂ adsorption experiments. Both surface-bound O and sub-surface O dissolve into the Pd bulk upon annealing of both surfaces to 550 K. HREELS and ESDIAD data consistently indicate that NO preferentially adsorbs on the (111) terrace sites of Pd(112) at low coverages, filling the (001) step sites only at high coverage. This result was verified for adsorption temperatures in the range 100–373 K. In addition, the thermal dissociation of NO on Pd(112) is most prevalent at low coverages, where only terrace sites are occupied by NO. Thus, by direct comparison to NO/Pd(111), this study shows that the presence of steps on the Pd(112) surface enhances the thermal dissociation of NO, but that adsorption at the step sites is not the criterion for this decomposition.     

Oxidation of heated diamond C(100):H surfaces

This paper extends a previous study (Pehrsson and Mercer, submitted to Surf. Sci.) on unheated, hydrogenated, natural diamond (100) surfaces oxidized with thermally activated oxygen (O^*₂). In this paper, the oxidation is performed at substrate temperatures from T_sub=24 to 670°C. The diamond surface composition and structure were then investigated with high resolution electron energy loss spectroscopy (HREELS), Auger electron spectroscopy (AES), electron loss spectroscopy (ELS) and low energy electron diffraction (LEED).

The oxygen coverage (θ) increased in two stages, as it did during oxidation at T<80°C. However, there are fundamental differences between the oxidation of nominally unheated and heated diamond surfaces. This difference is attributed to simultaneous adsorption and rapid desorption of oxygen species at higher temperatures; the desorption step is much slower without heating. The initial oxidation rates were similar regardless of the substrate temperatures, but the peak coverage (θ) was lower at higher temperatures. For example, θ plateaued at 0.4±0.1 ML at 600°C. The lower saturation coverage is again attributed to oxygen desorption during oxidation. Consistent results were obtained on fully oxidized surfaces, which when heated in vacuum to T_sub=600°C, lost 60% of their adsorbed oxygen. ELS revealed few C=C dimers on the oxidized surfaces, and more graphitization than on unheated surfaces. Oxidation at elevated temperatures also increased the carbonyl to ether ratio, reflecting etching-induced changes in the types of surface sites. The carbonyl and C–H stretch frequencies increased with oxygen dose due to formation of higher oxidation states and/or hydrogen bonding between adjacent groups. The oxygen types did not interconvert when the oxidized surfaces were heated in vacuum. Oxygen desorption generated a much more reactive surface than heating-induced dehydrogenation of the smooth, hydrogenated surface.     

CO and O coadsorption on Pt3Sn studied by DFT: Changes in the adsorptive properties of the surface with alloying and coverage

Adsorption of CO and coadsorption of O and CO on Pt₃Sn(1 1 1) was studied using periodic DFT calculations. Calculations were performed on Pt(1 1 1) by using the same set of parameters and their results were used as reference basis. The calculations showed that the most stable configuration with the minimum energy for coadsorption of CO and O is CO adsorbed atop Pt and O adsorbed on fcc Pt2Sn hollow site and that the decrease in the adsorption strength of the system at a total surface coverage of 0.5 ML is by 0.063 eV as a result of coadsorption, with respect to the adsorption of one species individually. Results show that the interaction between the adsorbed CO and O is short range on PtSn alloy, contrary to that on pure Pt, and this is mainly related to stronger Sn–O bonds compared to Pt–O bonds which eventually reduce the surface strain at the coadsorption structure. There is a pronounced effect of total surface concentration on the adsorption energy of coadsorbed species; the adsorption strength is not directly proportional to the surface coverage but is also related to the distribution of the coadsorbed species on the surface.     

A theoretical analysis of adsorption and dissociation of CH3OH on the stoichiometric SnO2(110) surface

A theoretical analysis based on the Hartree–Fock pseudopotential method and a density-functional theory calculation using a hybrid combination of general gradient approximation with pseudopotential procedure has been carried out to study the adsorption and dissociation of methanol on the stoichiometric SnO₂(110) surface. The dependence of the results upon model system and computing method is discussed. An optimization procedure of adsorbate and substrate atom positions on a six-layer slab model has been selected to characterize the corresponding geometric parameters, adsorption energy and charge-transfer processes related with the molecularly adsorbed CH₃OH and dissociative channels to yield methoxy or methyl fragments. In the high-coverage limit (θ=1), we find that dissociation of the methanol molecule via the heterolytic cleavage of the C---O bond is favoured. At lower coverage (θ=1/2), this channel and the molecularly adsorbed methanol present similar adsorption energies.