Surface structure effects in the reactions of nitric oxide with hydrogen and carbon monoxide on rhodium: A comparison with the surface structure effects observed for the hydrogen-oxygen and carbon monoxide-oxygen reactions

Using field electron microscopy (FEM) and thermal desorption and reaction spectroscopy (TDS) the behaviour of various Rh single crystal surfaces towards reactions involving NO has been studied. If, after NO adsorption up to saturation at 77 K, the temperature is slowly raised the FEM results suggest that dissociation of NO starts at the (321), (331) and (533) surfaces. The reaction of NO_ads with hydrogen starts also at these surfaces (at about 360 K) suggesting that NO bond scission initiates the reaction. After initiation a surface explosion is observed. Depending on the heating rate either a clean surface or a N_ads covered surface is obtained after completion of the reaction. Apparently, the reduction of adsorbed N_ads by hydrogen can occur at a significant rate at this temperature. At a higher heating rate the formed N adatoms do not react with hydrogen and are readily desorbed as N₂ at 600 K. The reaction of NO_ads with CO starts again on the (321) and (331) surfaces. The rate of the reaction with CO is, however, much lower than that with hydrogen. For the reaction of CO_ads with NO, desorption of CO is the initiation step. The mechanisms of the reactions and the dependence of the reaction on the surface structure are discussed in relation to literature data.     

Adsorption and decomposition of formic acid on the NiO(111)-p(2 × 2) surface: TPD and steady state kinetics studies

The adsorption and decomposition of formic acid on NiO(111)-p(2 × 2) films grown on Ni(111) single crystal surface were studied by temperature-programmed desorption (TPD) spectroscopy. Exposure of formic acid at 163 K resulted in both molecular adsorption and dissociation to formate. The adsorbed formate underwent further dissociation to H₂, CO₂ and CO. H₂ and CO₂ desorbed at the same temperatures of 340, 390 and 520 K, while CO desorbed at 415 and 520 K. The desorption features varied with the formic acid exposure. Two reaction channels were identified for the decomposition of formate under equilibrium with gas-phase formic acid with a pressure of 2.5 × 10⁻⁴Pa, one preferentially producing H₂ and CO₂ with an activation energy of 22 ± 2 kJ mol⁻¹ and the other preferentially producing CO and H₂O with an activation energy of 16 ± 2 kJ mol⁻¹. The order of both reaction paths was 0.5 with respect to the pressure of formic acid.     

Elucidation of the nature of active oxygen in the reaction of low-temperature oxidation of CO on single crystal surfaces platinum and palladium

The temperature-programmed reaction (TPR) method, high-resolution electron energy loss spectroscopy (HREELS), and molecular beam method were used to elucidate the role surface reconstruction, subsurface oxygen (O_subs), and CO_ads concentration play in the low-temperature oxidation of CO on the Pt(100), Pt(410), Pd(111), and Pd(110) surfaces. The possibility of the formation of so-called hot oxygen atoms, which arise at the surface at the instant of dissociation of O_2ads molecules and can react with CO_ads at low temperatures (～150 K) to form CO₂, was examined. It was revealed that, when present in high concentration, CO_ads initiates the phase transition of the Pt(100)-(hex) reconstructed surface into the (1 × 1) non-reconstructed one and blocks fourfold hollow sites of oxygen adsorption (Pt₄-O_ads), thereby initiating the formation of weakly bound oxygen (Pt₂-O_ads), active in CO oxidation. For the Pt(410), Pd(111), and Pd(110) surfaces, the reactivity of O_ads with respect to CO was demonstrated to be dependent on the surface coverage of CO_ads. The ¹⁸O_ads isotope label was used to determine the nature of active oxygen reacting with CO at ～150–200 K. It was examined why a CO_ads layer produces a strong effect on the reactivity of atomic oxygen. The experimental results were confirmed by theoretical calculations based on the minimization of the Gibbs energy of the adsorption layer. According to these calculations, the CO_ads layer causes a decrease in the apparent activation energy E _act of the reaction due to changes in the type of coordination and in the energy of binding of O_ads atoms to the surface.     

The interaction of hydrazine with an Fe(111) surface

The interaction of hydrazine with a clean and nitrogen precovered Fe(111) surface was investigated in the temperature range of 126–600 K by means of UV and X-ray photoelectron spectroscopy (PES). At temperatures below 170 K the molecular adsorption of hydrazine is followed by multilayer condensation. In going from adsorbed to condensed hydrazine the valence and core levels shift in different directions relative to the vertical gas phase ionisation energies indicating strong interactions via hydrogen bonding in the condensed phase. Dissociative adsorption of N₂H₄ was observed at temperatures above 220 K. At room temperature no difference in the photoelectron spectra following the adsorption of N₂H₄ or NH₃ was observed indicating the presence of the same surface species, predominantly being -NH₂ radicals. Preadsorbed nitrogen stabilizes N₂H₄ against decomposition. The results will be discussed in view of possible intermediates in the ammonia-synthesis reaction on iron. Simple thermochemical arguments are presented to explain the observed difference in the heterogeneous dissociation mechanism of hydrazine on transition metals. General conclusions on the mechanism of ammonia synthesis on various transition metals can also be derived from these thermodynamic considerations.     

Adsorption of H2O on Al(111)

The adsorption of H₂O on Al(111) has been studied by ESDIAD (electron stimulated desorption ion angular distributions), LEED (low energy electron diffraction), AES (Auger electron spectroscopy) and thermal desorption in the temperature range 80–700 K. At 80 K, H₂O is adsorbed predominantly in molecular form, and the ESDIAD patterns indicate that bonding occurs through the O atom, with the molecular axis tilted away from the surface normal. Some of the H₂O adsorbed at 80 K on clean Al(111) can be desorbed in molecular form, but a considerable fraction dissociates upon heating into OH_ads and hydrogen, which leaves the surface as H₂. Following adsorption of H₂O onto oxygen-precovered Al(111), additional OH_ads is formed upon heating (perhaps via a hydrogen abstraction reaction), and H₂ desorbs at temperatures considerably higher than that seen for H₂O on clean Al(111). The general behavior of H₂O adsorption on clean and oxygen-precovered Al(111) (θ_O ? monolayer) is rather similar at low temperature, but much higher reactivity for dissociative adsorption of H₂O to form OH _adsis noted on the oxygen-dosed surface around room temperature.     

The mechanism of acetate oxidation on Ag(110)

The effects of coadsorbed oxygen atoms and gaseous O₂ at pressures up to 0.7 Torr on the stability of the surface acetate intermediate on Ag(110) were investigated. Under an O₂ pressure of 0.7 Torr acetate decomposes at temperatures as low as 400 K, which is 200 K lower than the decomposition temperature of acetate in vacuum. This destabilization is due to population of the surface with atomic oxygen when 0.7 Torr O₂ is present. Acetate reacts with coadsorbed oxygen atoms via an intermediate which decomposes at 340 K to CO₂, water and formate. The formate subsequently decomposes at 400 K to give CO₂ and H₂. Through the use of isotopic labelling, it was found that the carbon and hydrogen atoms in the formate originate from the methyl group of the acetate, while the two oxygen atoms come from surface atomic oxygen. A mechanism for the reaction of acetate with atomic oxygen is presented in which a surface oxygen atom abstracts a proton from the acetate, and the resulting CH₂COO_(a) species reacts further with another oxygen atom to form a glycolate (O₂CCH₂O_(a)) intermediate. Nucleophilic attack at the methylene carbon by an oxygen atom, followed by C-C bond scission releases CO₂ and forms H₂CO_2(a), which subsequently loses a hydrogen atom to make formate. The results presented here show that acetate will decompose under commercial ethylene oxidation conditions, and thus cannot be ruled out as an intermediate in the total oxidation of ethylene. Isomerization of ethylene oxide to acetaldehyde, followed by oxidation of the acetaldehyde is a plausible route to acetate formation during ethylene oxidation. In addition, this work demonstrates that phenomena which occur at high pressures can be observed in ultra high vacuum provided the relevant surface species can be formed in vacuum and remain on the surface up to the temperatures at which the high pressure phenomena occur.     

Interaction of H2O with a clean and oxygen precovered Ni(110) surface studied by XPS

The adsorption and reaction of H₂O on clean and oxygen precovered Ni(110) surfaces was studied by XPS from 100 to 520 K. At low temperature (T<150 K), a multilayer adsorption of H₂O on the clean surface with nearly constant sticking coefficient was observed. The O 1s binding energy shifted with coverage from 533.5 to 534.4 eV. H₂O adsorption on an oxygen precovered Ni(110) surface in the temperature range from 150 to 300 K leads to an O 1s double peak with maxima at 531.0 and 532.6 eV for T=150 K (530.8 and 532.8 eV at 300 K), proposed to be due to hydrogen bonded O_ads… HOH species on the surface. For T>350 K, only one sharp peak at 530.0 eV binding energy was detected, due to a dissociation of H₂O into O_ads and H₂. The s-shaped O 1s intensity-exposure curves are discussed on the basis of an autocatalytic process with a temperature dependent precursor state.     

A spectroscopic study of the adsorption and reactions of methanol,formaldehyde and methyl formate on clean and oxygenated Cu(110) surfaces

The adsorption and reaction of methanoi (CH₃OH), methyl formate (CH₃OCHO) and formaldehyde (H₂CO) on clean and oxygen-covered Cu(110) surfaces has been studied with EELS, UPS and thermal desorption spectroscopy (TDS). The clean surface is relatively unreactive but adsorbed oxygen readily attacks the hydroxyl proton and formyl carbon atoms to generate the intermediate methoxy (CH₃O) and formate (HCOO). Methyl formate is split into two intermediates, methoxy and formate. By correlating the three techniques we analyse (a) the condensed multilayer at 90 K; (b) the weakly bound molecular monolayer states prior to dissociation or reaction and (c) the reactive intermediates at higher temperatures. Formaldehyde forms the surface polymer polyoxymethylene [(CH₂O)_n] in the monolayer on Cu(110) which subsequently reacts with oxygen to generate formate. No molecular formaldehyde was observed above 120 K. Correlation of the EELS and UPS results for polyoxymethylene shows that an earlier interpretation by Rubloff et al. [Phys. Rev. B14 (1976) 1450] of anomalous shifts in the formaldehyde UPS spectrum on surfaces is incorrect, and due simply to the new polymeric structure of surface formaldehyde. Methyl formate coordinates to copper via the carbonyl lone pair orbital and methanol via the oxygen lone pair orbital. No evidence was found for methyl formate synthesis by dimerization of formaldehyde (the Tischenko reaction) or dehydrogenation of methanol on the clean Cu(110) surface. These latter reactions are facile over copper catalysts at atmospheric pressure. The success of the oxidation experiments and the failure of the synthesis reactions in UHV is a consequence of the pressure dependence of the equilibrium constants for the different reactions. As found previously in Fischer-Tropsch studies, condensation reaction equilibria are pressure dependent and product formation is considerably suppressed at UHV pressures.     

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.     

Reactivity of carbon dioxide at nickel (110)

Adsorption and reactivity of carbon dioxide at the clean and oxygen precovered Ni(110) surface has been studied by means of EELS and LEED. On the clean surface two different types of CO₂ molecules have been observed by EELS at 135 K, one being the undisturbed linear configuration. With increasing temperature the linear molecule changes into a different species which precedes dissociation at 220 K into CO and O. EELS and LEED data of the intermediate species support the assumption that it is a bent CO⁻₂ anion adsorbed in C_2v symmetry with twofold oxygen coordination to the surface. Oxygen preadsorption stabilizes the linear CO₂ molecule up to higher temperatures which does not convert into a bent species in this case. Instead, a reaction product of CO₂ and O is found and interpreted as a carbonate species.     

Electron energy loss spectroscopy of the decomposition of formic acid on Ru(001)

Electron energy loss spectroscopy has demonstrated the existence of both a monodentate and a symmetric bidentate bridging formate as stable intermediates in the decomposition of formic acid on the Ru(001) surface. The monodentate formate converts upon heating to the bidentate formate which decomposes via two pathways: CH bond cleavage to yield CO₂ and adsorbed hydrogen; and CO bond cleavage to yield adsorbed hydrogen, oxygen and CO. Thermal desorption spectra demonstrate the evolution of H₂,H₂O, CO and CO₂ as gaseous products of the decomposition reaction. The observation of this product distribution from Ru(100), Ni(100) and Ni(110) had prompted the proposal of a formic anhydride intermediate, the existence of which is rendered questionable by the spectroscopic results reported here.     

Low temperature decomposition of ethylene over Ni(100): Evidence for vinyl formation

Thermal programmed desorption (TPD), high resolution electron energy loss spectroscopy (HREELS), and time-resolved laser-induced desorption (LID) have been used to study the chemisorption and decomposition of ethylene over Ni(100). Ethylene adsorbs molecularly on this surface at temperatures below 150 K. The molecule is π bonded in this state, showing very little rehybridization. At coverages below half saturation, decomposition to vinyl plus a hydrogen atom occurs unimolecularly with a rate constant of (8.0 ± 2.0) × 10⁻² s⁻¹ at 170 K. A strong kinetic isotope effect was observed; vinyl formation from C₂D₄ does not occur until about 200 K. The proposal of vinyl as the intermediate is supported by studies with C₂H₄, 1,1− and 1,2−C₂D₂H₂, and C₂D₄. The reaction is slower at saturation coverages, where molecular desorption is still seen above 200 K. Vinyl decomposes further at 230 K to form an acetylenic fragment.     

Formate stability and carbonate hydrogenation on strained Cu overlayers on Pt(1 1 1)

Formate (HCOO) synthesis, decomposition and the hydrogenation of carbonate (CO₃) on Cu overlayers deposited on a Pt(1 1 1) single crystal are investigated to examine the reactivity of a Cu surface under tensile strain with defects present.Formate is synthesized from a 0.5 bar mixture of 70% CO₂ and 30% H₂ at varying temperatures, and the evolution is followed with polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS). Subsequent TPD reveals decomposition of the formate species into CO₂ and H₂ at 420 ± 5 K for strained Cu at sub-monolayer to monolayer coverages. This is a significantly lower decomposition temperature than obtained earlier on pristine Cu(1 1 1) (460 K), as well as for thicker Cu layers where we assign an observed decomposition peak at 440 ± 5 K to relaxed, but defect-rich Cu(1 1 1). However, the thermal stability of formate on strained and defect-rich Cu is similar to previous results obtained for supported, and lattice-strained, Cu nanoparticles.The hydrogenation of carbonate produced by 0.3 bar CO₂ exposure at room temperature was monitored with XPS and TPD showing a significant loss of carbonate when subjected to 0.2 bar H₂ at room temperature. However, the presence of formate on the surface, or any other hydrogenation product, could not be established during or after H₂ exposure by PM-IRRAS, EELS or TPD. Even so, the results suggest that carbonate and its hydrogenation may constitute a relevant pathway to methanol production.     

Dehydrogenation of acetylene and ethylene studied on clean and oxygen covered palladium surfaces

The interaction of acetylene and ethylene with a clean and oxygen covered Pd surface has been studied at a temperature of 473 K. The measurements were performed on a hydrogen sensitive Pd-MOS structure making it possible to obtain direct information on the dissociation of both hydrogen and oxygen containing species on a palladium surface. Desorption studies were also performed as well as ultraviolet photoelectron spectroscopy and work function measurements. The studies show that both acetylene and ethylene adsorb dissociatively at this temperature leaving mainly carbon on the surface. When an oxygen covered Pd surface is exposed to C₂H₂ or C₂H₄ carbon dioxide and water will be formed and desorb until the surface is oxygen free. In the case of acetylene the presence of preadsorbed oxygen does not block or prevent the C₂H₂ dissociation on the surface. For C₂H₄, a large preadsorbed oxygen coverage (⪆ 0.45) will have an impeding effect on the dissociation. The CO₂ desorption is oxygen coverage dependent contrary to the H₂O desorption. This is due to the fact that hydrogen has a large lateral mobility on the surface while carbon has not. Both the CO₂ and H₂O reactions are, however, due to the same type of mechanisms.     

Effect of surface temperature on the sorption of hydrogen by Pd(111)

Temperature programmed desorption (TPD) subsequent to various hydrogen exposure conditions indicates the formation of chemisorption, solid solution, and hydride phases of hydrogen in the near surface region of Pd(111). Variation of the sample exposure temperature (T_e) between 80 and 300 K has a strong effect on the subsequent TPD spectra. At T_e = 80 K a single desorption peak, β, appears at 310 K. Coverage variation of the β peak is consistent with second-order recombinative desorption of chemisorbed hydrogen. For T_e between 90 and 140 K a slight enhancement of the β peak occurs and a new peak, α, appears initially near 170 K. It does not saturate, exhibits near-zeroth-order desorption kinetics, and is assigned to the decomposition of a near surface palladium hydride phase. Population of the α peak is thermally activated with a maximum at T_e ≈ 115 K. For T_e, greater than 140 K, α disappears while the total amount of absorbed hydrogen increases significantly. At these temperatures, the concentration of absorbed hydrogen decreases significantly if the sample is held in vacuo at T_e after completion of the hydrogen exposure. At all exposure temperatures there is also a broad desorption feature near 800 K which is enhanced by higher T_e and is associated with hydrogen in solid solution.     

Acetic acid decomposition on a polycrystalline platinum surface

The decomposition of CH¹³₃COOH on a polycrystalline platinum surface has been examined at temperatures between 300 and 900 K during continuous exposure to CH¹³₃COOH at 7×10^-4 Torr. On an initially clean platinum surface ¹³CO, CO, ¹³CO₂, H₂ and adsorbed carbon-12 are the major reaction products. The adsorbed carbon eventually poisons completely the reactions that produce these products. For temperatures above approximately 800 K, the carbon overlayer that is formed is graphitic and saturates at a carbon adatom concentration of (2.6-3.5)×10¹⁵ cm^-2. The reaction quantities of ¹³CO and ¹³CO₂ that are produced depend both on the surface temperature and the carbon coverage. Lower temperatures and higher carbon coverages favor the production of ¹³CO. On the graphitized platinum surface, the catalytic dehydration of acetic acid to ketene and water proceeds at steady-state.     

The activation of FeTi for hydrogen absorption

FeTi is an interesting hydrogen storage material which has to be activated at ≈670 K for the absorption of hydrogen. We review critically the great number of previously published results and models on this activation process and emphasize the controversial points. To eliminate the controversy we analysed the variation of the surface composition of FeTi upon activation in the high-pressure cell of a photoelectron spectrometer. The initially passivating surface oxide is shown to be converted into a mixture of TiO₂ and Fe by surface segregation and chemical reduction. No evidence for the formation of Fe₂Ti₄O _x , FeTiO _x , and TiH _x is found. H₂/D₂ exchange reactions show that H₂ dissociates rapidly on Fe and FeTi, but not on TiO₂. The surface of FeTi is activated easily at 670 K. Difficulties encountered with the initial hydrogen absorption by virgin high purity FeTi are probably related to bulk (H diffusion, fracture toughness) rather than surface properties.     

Negative molecular ion formation and work function changes: Experimental results for CO and CO2 scattering from nickel (+potassium) surfaces

The scattering of CO⁺ and CO⁺₂ at grazing incidence from Ni(111)+K and clean Ni(111), Ni(110) surfaces produces CO, CO₂ and dissociated species. The observation of negative species O⁻ and CO⁻₂ is strongly dependent on the K coverage or work function of the surface. The dissociation of CO⁺ (CO) is weakly changed by the presence of K, whereas in the CO⁺₂ (CO₂) case dissociation via CO⁻₂ → CO + O⁻ is strongly increasing with K coverage.     

Formaldehyde decomposition and oxidation on Pt(110)

The decomposition reactions of formaldehyde on clean and oxygen dosed Pt(110) have been studied by LEED, XPS and TPRS. Formaldehyde is adsorbed in two states, a monolayer phase and a multilayer phase which were distinguishable by both TPRS and XPS. The saturated monolayer (corresponding to 8.06 × 10¹⁴ molecules cm⁻²) desorbed at 134 K and the multilayer phase (which could not be saturated) desorbed at 112 K. The only other reaction products observed at higher temperatures were CO and H₂ produced in desorption limited processes and these reached a maximum upon saturation of the formaldehyde monolayer. The desorption spectrum of hydrogen was found to be perturbed by the presence of CO as reported by Weinberg and coworkers. It is proposed that local lifting of the clean surface (1 × 2) reconstruction is responsible for this behaviour. Analysis of the TPRS and XPS peak areas demonstrated that on the clean surface approximately 50% of the adsorbed monolayer dissociated with the remainder desorbing intact. Reaction of formaldehyde with preadsorbed oxygen resulted in the formation of H₂O (hydroxyl recombination) and CO₂ (decomposition of formate) desorbing at 200 and 262 K, respectively. The CO and H₂ desorption peaks were both smaller relative to formaldehyde decomposition on the clean surface and in particular, H₂ desorbed in a reaction limited process associated with decomposition of the formate species. No evidence was found for methane or hydrocarbon evolution in the present study under any circumstances. The results of this investigation are discussed in the light of our earlier work on the decomposition of methanol on the same platinum surface.     

Evidence for non-thermalized vibrationally excited molecule production during azomethane pyrolysis in methane desorption from Cu(001)

A Cu(001) surface was exposed to products of an azomethane pyrolysis doser at varying temperatures. In addition to methyl radical adsorption, for certain doser conditions one or more doser emergent species can undergo an activated adsorption on the copper face. Directly after exposures, temperature programmed desorption between 170 K and 500 K was used to indicate the relative concentrations of adsorbed atomic hydrogen and methyl species, and thermally induced surface reactions. Two methane desorption features were invariably observed, indicating the presence of adsorbed methyl groups (CH₃) and transient adsorbed atomic hydrogen. The deduced relative surface concentrations levels of both H and CH₃ depend on the total exposures and the operating temperatures of the azomethane pyrolysis doser. The initial H concentrations apparent at surface temperatures between 275 K and 375 K are shown to arise from defect-related methyl decomposition and, at high operating doser temperatures, from the initial adsorption of one or more activated Cu incident species. It is proposed that the distributions of vibrational energies of emergent molecular hydrogen or methane species from higher temperature dosers are non-thermal. Hence, with doser temperatures of 800 °C or above, the effects of subsequent dissociative molecular adsorption on the copper surface can dominate over Cu defect chemistries.