Evidence for bicarbonate formation on vacuum annealed TiO2(110) resulting from a precursor-mediated interaction between CO2 and H2O

The reaction of CO₂ and H₂O to form bicarbonate (HCO⁻₃) was examined on the nearly perfect and vacuum annealed surfaces of TiO₂(110) with temperature programmed desorption (TPD), static secondary ion mass spectrometry (SSIMS) and high resolution electron energy loss spectrometry (HREELS). The vacuum annealed TiO₂(110) surface possesses oxygen vacancy sites that are manifested in electronic EELS by a loss feature at 0.75 V. These oxygen vacancy sites bind CO₂ only slightly more strongly (TPD peak at 166 K) than do the five-coordinated Ti⁴⁺ sites (TPD peak at 137 K) typical of the nearly perfect TiO₂(110) surface. Vibrational HREELS indicates that CO₂ is linearly bound at the latter sites with a ν_a(OCO) frequency similar to the gas phase value. In contrast, oxygen vacancies dissociate H₂O to bridging OH groups which recombine to liberate H₂O in TPD at 490 K. No evidence for a reaction between CO₂ and H₂O is detected on the nearly perfect surface. In sequentially dosed experiments on the vacuum annealed surface at 110 K, CO₂ adsorption is blocked by the presence of preadsorbed H₂O, adsorbed CO₂ is displaced by postdosed H₂O, and there is little or no evidence for bicarbonate formation in either case. However, when CO₂ and H₂O are simultaneously dosed, a new CO₂ TPD state is observed at 213 K, and the 166 K state associated with CO₂ at the vacancies is absent. SSIMS was used to tentatively assign the 213 K CO₂ TPD state to a bicarbonate species. The 213 K CO₂ TPD state is not formed if the vacancy sites are filled with OH groups prior to simultaneous CO₂+H₂O exposure. Sticking coefficient measurements suggest that CO₂ adsorption at 110 K is precursor-mediated, as is known to be the case for H₂O adsorption on TiO₂(110). A model explaining the circumstances under which the proposed bicarbonate species is formed involves the surface catalyzed conversion of a precursor-bound H₂O–CO₂ van der Waals complex to carbonic acid, which then reacts at unoccupied oxygen vacancies to generate bicarbonate, but falls apart to CO₂ and H₂O in the absence of these sites. This model is consistent with the conditions under which bicarbonate is formed on powdered TiO₂, and is similar to the mechanism by which water catalyzes carbonic acid formation in aqueous solution.     

Characterization and chemical behavior of submonolayer coverages of titania on a Pt foil

The interaction between submonolayer titania coverages and Pt foil has been studied by Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), temperature programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). The submonolayer titania can be fully oxidized to TiO₂ at 923 K under 10⁻⁸ Torr O₂, and partially oxidized to TiO_x at lower oxidation temperatures. The oxidized surface can be reduced by annealing to 1000 K or higher, or by heating in H₂ at 823 K, or by interacting with surface carbon formed from acetone decomposition. Under certain conditions (e.g., hydrogen reduction at 923 K), the surface titania can be fully reduced to metallic Ti which diffuses into bulk Pt readily. The reduced metallic Ti can resurface when the surface is oxidized at 923 K. Both XPS and HREELS data indicate the existence of subsurface oxygen, which plays an important role for the diffusion of Ti into and out of the Pt foil. Although no special interfacial active sites were revealed by HREELS studies of adsorbed acetone and CO, some TPD and XPS data suggest the presence of sites active for acetone decomposition.     

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.     

The interaction of oxygen and potassium on the Ru(001) surface

The interaction of oxygen and different coverages of potassium on Ru(001) has been investigated by thermal desorption spectroscopy (TDS), metastable quenching spectroscopy (MQS), electron stimulated desorption spectroscopy (ESD), and work-function change measurements. The results show that this is a complex surface system with several different oxides forming, depending on the surface stoichiometry and temperature. While we cannot uniquely identify all the surface species, our interpretation of the present data combined with previous information is as follows. For potassium coverages up to about three monolayers (θ_K ≈ 1), exposure to oxygen initially gives oxygen atoms on the surface. Further exposure produces some surface monoxide ions O²⁻, which are converted with additional exposure to Superoxide ions O⁻₂ and possibly peroxide ions O²⁻₂. Thermal annealing causes strong changes in the surface oxide composition, and with potassium multilayers (θ_K ≈ 10) all the oxides diffuse beneath the K surface layer with annealing to only 300 K. K₂O and K₂O₂ are found to desorb together in the 600–700 K region.     

Elemental steps in the growth of thin β-Ga2O3 films on CoGa(1 0 0)

The oxidation of CoGa(1 0 0) at 700 K was studied by means of high resolution electron energy loss spectroscopy (EELS), scanning tunneling microscopy, low energy electron diffraction and Auger electron spectroscopy (AES). At 700 K, thin well-ordered β-Ga₂O₃ films grow on CoGa(1 0 0). The EEL spectrum of the Ga-oxide films exhibit Fuchs–Kliewer phonons at 305, 455, 645, and 785 cm⁻¹. For low oxygen exposure (<0.2 L), the growth of oxide-islands starts at step edges and on defects. The oxide films have the shape of long, rectangular islands and are oriented in the [1 0 0] and [0 1 0] directions of the substrate. For higher oxygen exposure, islands of β-Ga₂O₃ are found also on the terraces. After an exposure of 200 L O₂ at 700 K, the CoGa(1 0 0) surface is homogeneously covered with a thin film of β-Ga₂O₃.     

Effects of preadsorbed oxygen on the formation and decomposition of NCO on Rh(111) surfaces

The interaction of HNCO with oxygen dosed Rh(111) surface has been investigated by Auger electron, electron energy loss and thermal desorption spectroscopy. The presence of adsorbed oxygen exerted no apparent influence on the weakly adsorbed HNCO (T_p = 130 K). It promoted, however, the dissociative adsorption of HNCO by forming a strong O—H bond which prevented the associative desorption of HNCO. As a result no H₂ and NH₃ formation occurred, in contrast with the clean surface, and the surface concentration of irreversibly bonded NCO was also increased. New products of the surface reaction were H₂O and CO₂, in addition to CO and N₂ observed on a clean surface. From the behavior of the losses characteristic for the adsorbed NCO it appeared that the preadsorbed oxygen exerted a significant stabilizing effect on the NCO bonded to the Rh.     

Decomposition mechanism of triethylindium (TEI) on a GaP(0 0 1)-(2×1) surface studied by LEED, AES, TPD and HREELS

Adsorption and decomposition of triethylindium (TEI: (C₂H₅)₃In) on a GaP(0 0 1)-(2×1) surface have been studied by low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). It is found from the TPD result that ethyl radical and ethylene are evolved at about 300–400 and 450–550 K, respectively, as decomposition products of TEI on the surface. This result is quite different from that on the GaP(0 0 1)-(2×4) surface. The activation energy of desorption of ethyl radical is estimated to be about 93 kJ/mol. It is suggested that TEI is adsorbed molecularly on the surface at 100 K and that some of TEI molecules are dissociated into C₂H₅ to form P–C₂H₅ bonds at 300 K. The vibration modes related to ethyl group are decreased in intensity at about 300–400 and 450–550 K, which is consistent with the TPD result. The TEI molecules (including mono- and di-ethylindium) are not evolved from the surface. Based on the TPD and HREELS results, the decomposition mechanism of TEI on the GaP(0 0 1)-(2×1) surface is discussed and compared with that on the (2×4) surface.     

VO2薄膜表面氧缺陷的修复:F4TCNQ分子吸附反应

VO₂表面氧缺陷的存在对VO₂材料具有显著的电子掺杂效应, 极大地影响材料的本征电子结构和相变性质. 通过2, 3, 5, 6-四氟-7, 7', 8, 8'-四氰二甲基对苯醌(F₄TCNQ)分子表面吸附反应, 可以有效消除表面氧缺陷及其电子掺杂效应. 利用同步辐射光电子能谱和X射线吸收谱原位研究了修复过程中电子结构的变化以及界面的化学反应, 发现这种方式使得VO₂薄膜样品氩刻后得到的V³⁺失去电子成功地被氧化成原先的V⁴⁺, 同时F₄TCNQ分子吸附引起电子由衬底向分子层转移, 界面形成带负电荷的分子离子物种. 受电化学性质的制约, F₄TCNQ分子吸附反应修复氧缺陷较氧气氛退火更安全有效, 不会引起表面过度氧化形成V₂O₅.     

Adsorption and dissociation of Si2H6 on Ge(001)2 × 1

Adsorption and thermally-induced dissociation of disilane (Si₂H₆) on clean Ge(001)2 × 1 surfaces have been investigated using a combination of Auger electron spectroscopy (AES), electron energy loss spectroscopy (EELS), reflection high-energy electron diffraction (RHEED), and scanning tunneling microscopy (STM). With initial Si₂H₆ exposure at room temperature, the Si surface coverage increased monotonically, the EELS surface dangling bond peak intensities continuously decreased, and the intensity of half-order RHEED diffraction rods decreased. The low-coverage Si₂H₆ sticking probability at 300 K on Ge(001) was found to be 0.5 while the saturation coverage was 0.5 ML. A new EELS feature, GSH, involving Si-H and Ge-H bond states was observed at Si₂H₆ exposures φ 3.4 × 10¹³ cm⁻². In contrast to Si₂H₆ -saturated Si(001), the saturated Ge(001) surface significant fraction of dimerized bonds. Adsorbed overlayers were highly disordered with the primary species on saturated surfaces being SiH₂, GeH, and undissociated SiH₃· Si₂H₆-saturated Ge(001)2 × 1 substrates were annealed for l min at temperatures T_a between 425 and 825 K. Admolecules were mobile at T_a = 545 K giving rise to significant ordering in one-dimensional chains. By T_a = 605 K, essentially all of the admolecules were captured into coarsened islands. Dangling-bond EELS peaks reappeared by 625 K and the intensities of the half-order RHEED diffraction rods increased. Ge segregation to the surface, which began at T_a 625 K, occurred rapidly at T_a 675 K. All H was desorbed by 725 K.     

Auger electron spectroscopy and electron energy loss spectroscopy studies on carbonization of Si(100) and (111) surfaces with ethylene

The reactions of Si(100) and Si(111) surfaces at 700 °C (973 K) with ethylene (C₂H₄) at a pressure of 1.3×10⁻⁴ Pa for various periods of time were studied by using Auger electron spectroscopy (AES) and electron energy loss spectroscopy (ELS). For a C₂H₄ exposure level, the amount of C on the (111) surface was larger than that on the (100) surface. The formation of β-SiC grain was deduced by comparing the C_KLL spectra from the sample subjected to various C₂H₄ exposure levels, and from β-SiC crystal.     

Adsorbed state and vibrational excitation of N2 on Pd(110)

High-resolution vibrational electron energy loss spectroscopy, low-energy electron diffraction and Auger electron spectroscopy have been used to study the interactions of nitrogen with the Pd(110) surface. At 120 K, N₂ is chemisorbed molecularly on the Pd(110) surface, and the (2 × 1)-N₂ structure is formed. Most probably, the N₂ molecules are chemisorbed in the on-top sites of the bulk-like Pd(110) surface in the upright-linear structure. The Pd---N₂ bond energy is estimated to be ˜ 6 kcal/mol. The Pd---N₂ and N---N stretching vibrations of N₂ admolecules on Pd(110) are observed at 30 and 278 meV, respectively. The primary-energy dependence and angle dependence of their excitation cross sections agree reasonably well with the prediction of the dipole theory. The electron beam-induced effects are briefly discussed.     

Effects of potassium on the adsorption and dissociation of CH3Cl on Pd(100)

The effects of potassium on the adsorption and dissociation of CH₃Cl on a Pd(100) surface has been investigated by ultraviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES), electron energy loss spectroscopy (in the electronic range EELS), temperature-programmed desorption (TPD) and work function change. In contrast to the clean surface, the adsorption of CH₃Cl caused a significant work function increase, 0.9-1.4 eV, of potassium-dosed Pd. Preadsorbed K enhanced the binding energy of CH₃C1 to the surface and induced the dissociation of adsorbed molecules. The extent of the dissociation increased almost linearly with the potassium content. The appearance of a new emission in the UPS spectrum at 9.2 eV, attributed to adsorbed CH₃ species, and the low-temperature formation of ethane suggest that a fraction of adsorbed CH₃Cl dissociates even at 115–125 K on potassium-dosed Pd(100). At the same time, a significant part of adsorbed CH₃ radical is stabilized, the reaction of which occurs only at 250–300 K. By means of TPD measurements, H₂, CH₄, C₂H₆, C₂H₄, KCl and K were detected in the desorbing gases. The results are interpreted by assuming a through-metal electronic interaction at low potassium coverage and by a direct interaction of the Cl in the adsorbed CH₃Cl with potassium at high potassium coverage. The latter proposal is supported by the electron excited Auger fine structure of the Cl signal and by the formation of KCl in the desorbing gases.     

An examination of the initial oxidation of a uranium-base alloy (U–14.1 at.% Nb) by O2 and D2O using surface-sensitive techniques

The corrosion resistance of uranium is greatly enhanced by alloying with niobium. In this study the initial stages of corrosion of a specific uranium-base alloy (U–14.1 at.% Nb) by O₂ or D₂O have been examined using the surface specific techniques of X-ray photoelectron spectroscopy (XPS), thermal programmed desorption (TPD), static secondary-ion mass spectroscopy (SSIMS), and sputtered neutrals mass spectroscopy (SNMS). XPS studies of the U–14.1 at.% Nb surface following oxidation using O₂ at 300 K indicate production of a thin oxide overlayer of stoichiometric UO_2.0 intermixed with Nb₂O₅. The same stoichiometry is exhibited for uranium when the oxide is prepared at 500 K with O₂; although, niobium is much less oxidized exhibiting a mixture of NbO and Nb. Contrary to previous XPS literature, SNMS depth profiling studies reveal that oxidation by O₂ is much greater (as judged by oxide layer thickness) than that exhibited by D₂O. An oxide layer thickness of less than 20 Å was created using D₂O as an oxidant at 300 K with exposures >3500 L (oxide layers created from O₂ are significantly greater at much smaller exposures). Formation of a critical density of Nb₂O₅ is suggested to be responsible for the enhanced corrosion resistance by preventing diffusion of O⁻ (O²⁻) or OD⁻/OH⁻ into the oxide/metal interface region. The domains of stability of hydroxyl formation have also been followed using TPD, SSIMS and XPS. Maximal surface hydroxyl concentrations (Θ_rel=0.30) are obtained at a surface temperature of 175 K for these experimental conditions.     

Spin-polarized ion scattering spectroscopy of CCl4 adsorption on Fe(0 0 1) surfaces

The interaction of CCl₄ molecules with Fe(0 0 1) surfaces was investigated by spin-polarized ion scattering spectroscopy (SP-ISS). It was observed that CCl₄ molecules adsorb dissociatively on the surface at ambient temperature (290 K), and consequently, iron and chlorine were major surface constituents. It was found that the chlorine adatoms are located atop of iron atoms of the second surface layer (hollow sites of the surface). It is indicated that the spin state of iron atoms at the surface is not affected by exposure to a CCl₄ atmosphere, while almost no spin is induced in the chlorine adatoms. Similar behavior is observed in the spin states of iron and chlorine on an oxygen preadsorbed-Fe(0 0 1) surface. The difference in the spin states of iron and chlorine clarifies the local property of the incidence ion neutralization and element selectivity of SP-ISS in this CCl₄/Fe system.     

Promoter action of alkali in the activation of CO2 on Pd(111): A HREELS case study

We study the adsorption and reaction of CO₂ as a function of temperature between 100 and 700 K in the presence of Na on a Pd(111) surface using high resolution electron energy loss spectroscopy. While CO₂ does not react with a clean Pd(111) surface, we find various reaction channels on the Na precovered Pd(111) surface depending on the Na coverage. At intermediate coverage a bent CO₂⁸⁻ species with characteristic vibrational bands can be unambiguously identified. This species is stable up to 200 K, and dissociates into CO and oxygen similar to its behaviour on other surfaces, and as reported in a previous photoemission study [Wambach et al., Surface Sci. 209 (1989) 159]. In case the surface has been oxygen contaminated before Na and CO₂ exposure surface carbonates can be observed.     

Direct reaction of adsorbed molecular oxygen with hydrazine on a clean Pt(111) surface

The oxidation of hydrazine on the clean Pt(111) surface has been investigated by temperature-programmed reaction spectroscopy (TPRS) in the temperature range 130–800 K. Direct reaction of molecular oxygen is observed on the Pt(111) surface for the first time, as indicated by the desorption of nitrogen beginning at 130 K with a maximum rate at 145 K, below the molecular oxygen dissociation temperature. Direct reaction of hydrazine with adsorbed molecular oxygen results in the formation of water and nitrogen. With excess hydrazine, all surface oxygen is reacted, forming water. When only adsorbed atomic oxygen is present, the low-temperature nitrogen yield decreases by a factor of 3 and the peak nitrogen desorption temperature increases to 170 K. No high-temperature (450–650 K) nitrogen desorption characteristic of nitrogen atom recombination is seen, indicating that during oxidation the nitrogen-nitrogen bond in hydrazine remains intact, as observed previously for hydrazine decomposition on the Pt(111) surface and hydrazine oxidation on rhodium. Two water desorption peaks are observed, characteristic of desorption-limited (175 K) and reaction-limited (200 K) water evolution from the Pt(111) surface. For low coverages of hydrazine, only the reaction-limited water desorption is observed, previously attributed to water formed from adsorbed hydroxyl groups. When excess hydrazine is adsorbed, the usual hydrazine decomposition products, H₂, N₂ and NH₃, are also observed. No nitrogen oxide species (NO, NO₂ and N₂O) were observed in these experiments, even when excess oxygen was available on the surface.     

Co dissociation and recombination reactions on Ni(100)

The kinetics of atomic carbon and oxygen buildup on a Ni(100) surface exposed to carbon monoxide at high temperatures have been investigated by Auger electron spectroscopy. The experimental data, taken at different sample temperatures (453 , T 573 K) and at different CO partial pressures (3 ×10⁻⁷ , P_co , 3 ×10⁻¹ mbar) allowed the identification of the CO dissociation mechanism. By fitting the experimental data with a set of rate equations describing CO dissociation, CO reduction of surface oxygen, and C and O recombination, we have been able to determine the pre-exponential factors and the activation energies of these processes.     

Studies on the ZrO/W(100) surface by means of low-energy electron diffraction and X-ray photoelectron spectroscopy

The low work-function ZrO/W(100) surface was examined with the aim of understanding the reducing mechanism of the work function. Low-energy electron diffraction (LEED) was employed to analyze the surface atomic arrangement, and X-ray photoelectron spectroscopy (XPS) was used to identify the surface chemical condition. The ZrO/W(100) surface was made as follows: (i) around three monolayers of Zr were deposited on a clean W(100) surface, (ii) the sample was heat treated in an oxygen ambience of 1.3x10⁻⁵ Pa for several tens of minutes at 1500 K, and (iii) the sample was flash heated at 2000 K in ultrahigh vacuum (UHV). During heat treatment in O₂, the deposited Zr was oxidized to ZrO₂, and the LEED pattern formed was p(2×1). The work function increased to 5.3 eV. Subsequent flash heating in UHV changed the p(2×1) LEED pattern into a c(4×2) pattern, and transformed ZrO₂ into the so-called Zr–O complex, the oxidized level of which is between ZrO₂ and metallic Zr. A drastic decrease in the work function to 2.7 eV ensued. The angular dependence of XPS showed that the Zr–O complex segregated within a few monolayers 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.