Identification and hydrogenation of C2 on Pt(111)

Reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) were used to identify the molecular species formed upon the reaction of hydrogen with surface carbon that is deposited by exposing acetylene to a Pt(111) surface held at 750 K. At this temperature, the acetylene is completely dehydrogenated and all hydrogen is desorbed from the surface. Upon subsequent hydrogen exposure at 85 K followed by sequential annealing to higher temperatures, ethylidyne (CCH3), ethynyl (CCH), and methylidyne (CH) are formed. The observation of these species indicates that carbon atoms and C2 molecules exist as stable species on the surface over a wide range of temperatures. Through a combination of RAIRS intensities, hydrogen TPD peak areas, and Auger electron spectroscopy, quantitative estimates of the coverages of the various species were obtained. It was found that 79% of the acetylene-derived carbon was in the form of C2 molecules, with the remainder in the form of carbon atoms. Essentially all of the acetylene-derived carbon could be hydrogenated. In contrast, 85% of an equivalent coverage of carbon deposited by ethylene exposure at 750 K was found to be inert toward hydrogenation.     

Formation of C=C and Si-Cl adstructures by insertion reactions of cis-dichloroethylene and perchloroethylene on Si(100)2 x 1

The room-temperature adsorption and thermal evolution of cis-dichloroethylene (DCE) and perchloroethylene (PCE) on Si(100)2 x 1 have been studied by X-ray photoelectron spectroscopy and temperature programmed desorption (TPD) mass spectrometry. Unlike ethylene that is found to adsorb on Si(100)2 x 1 through a [2+2] cycloaddition reaction, cis-DCE and PCE appear to dechlorinate upon adsorption on the 2 x 1 surface through an insertion reaction preserving the C=C bond. Our C 1s XPS spectra are consistent with the existence of mono-sigma-bonded and di-sigma bonded dechlorinated adstructures for both cis-DCE and PCE. The presence of the XPS C 1s feature at 283.9 eV, characteristic of the (=C<(Si)(Si)) component, supports the formation of a unique tetra-sigma-bonded C(2) dimer (i.e., by full dechlorination) for PCE, which is found to be stable to 800 K. In marked contrast to PCE for which no organic desorption fragments are observed, m/z 26 TPD features at 590 and 750 K have been observed for cis-DCE. These features could be attributed to the formation of acetylene resulting from Cl beta-elimination of 2-chlorovinyl adspecies and to direct desorption of vinylene, respectively. Further annealing the cis-DCE and PCE samples to above 800 K produces SiC and/or carbon clusters. The TPD data also show HCl evolution over 810-850 K for both cis-DCE and PCE, the latter of which also exhibits an additional SiCl(2) evolution above 850 K. The present work illustrates that the insertion mechanism could be quite common in the surface chemistry of chlorinated ethylenes on the 2 x 1 surface.     

Ionization and solvation of HCl adsorbed on the D2O-ice surface

The interaction of HCl with the D(2)O-ice surface has been investigated in the temperature range 15-200 K by utilizing time-of-flight secondary ion mass spectroscopy, temperature-programmed desorption, and x-ray photoelectron spectroscopy. The intensities of sputtered H(+)(D(2)O) and Cl(-) ions (the H(+) ions) are increased (decreased) markedly above 40 K due to the hydrogen bond formation between the HCl and D(2)O molecules. The HCl molecules which form ionic hydrates undergo H/D exchange at 110-140 K and a considerable fraction of them dissolves into the bulk above 140 K. The neutral hydrates of HCl should coexist as evidenced by the desorption of HCl above 170 K. They are incorporated completely in the D(2)O layer up to 140 K. The HCl molecules embedded in the thick D(2)O layer dissolve into the bulk, and the ionic hydrate tends to segregate to the surface above 150 K.     

The influence of substrate temperature on the surface chemistry of ketene on Pt(111)

Processes occurring during dosing of ketene on a heated Pt(111) surface were investigated using high-resolution electron energy loss spectroscopy and temperature-programmed desorption. During dosing at 400 K, CO and H₂ are evolved and ethylidyne accumulates on the surface. In contrast, at 350 K a C_xH_y species, not ethylidyne, is formed and some CO accumulates. It is postulated that small amounts of adsorbed carbon monoxide stabilize the C_xH_y species and inhibit ethylidyne formation.     

The application of diffuse reflectance infrared spectroscopy and temperature-programmed desorption to investigate the interaction of methanol on eta-alumina

The adsorption of methanol and its subsequent transformation to form dimethyl ether (DME) on a commercial grade eta-alumina catalyst has been investigated using a combination of mass selective temperature-programmed desorption (TPD) and diffuse reflectance infrared spectroscopy (DRIFTS). The infrared spectrum of a saturated overlayer of methanol on eta-alumina shows the surface to be comprised of associatively adsorbed methanol and chemisorbed methoxy species. TPD shows methanol and DME to desorb with respective maxima at 380 and 480 K, with desorption detectable for both molecules up to ca. 700 K. At 673 K, infrared spectroscopy reveals the formation of a formate species; the spectral line width of the antisymmetric C-O stretch indicates the adoption of a high symmetry adsorbed state. Conventional TPD using a tubular reactor, combined with mass spectrometric analysis of the gas stream exiting the IR cell, indicate hydrogen and methane evolution to be associated with formation of the surface formate group and CO evolution with its decomposition. A reaction scheme is proposed for the generation and decomposition of this important reaction intermediate. The overall processes involved in (i) the adsorption/desorption of methanol, (ii) the transformation of methanol to DME, and (iii) the formation and decomposition of formate species are discussed within the context of a recently developed four-site model for the Lewis acidity of eta-alumina.     

Surface chemistry of isopropoxy tetramethyl dioxaborolane on Cu(111)

The surface chemistry of isopropoxy tetramethyl dioxaborolane (ITDB), tetramethyl dioxaborolane (TDB), and 2-propanol is studied on a clean Cu(111) single crystal using temperature-programmed desorption (TPD). 2-Propanol is found to have two competing reactions on the copper surface. Dehydration results in water and propene formation, and dehydrogenation results in the formation of acetone and hydrogen. ITDB directly adsorbed on the surface reacts completely and does not molecularly desorb. TDB and 2-propanol decompose desorbing mainly 2,3-dimethyl 2-butene and acetone, respectively. Both of those products desorb above room temperature and are present in TPDs of ITDB. An additional acetone desorption peak was observed for ITDB at higher temperatures than acetone desorption from 2-propanol. This higher temperature peak at ～391 K was attributed to two acetone molecules forming from the tetramethyl end group resulting from a stronger bound surface species in ITDB compared to TDB despite their identical end groups. The copper surface seems to be reactive enough toward ITDB at room temperature that a potential boron-containing tribofilm could be produced for copper-copper sliding contacts. Despite their similarities, ITDB and TDB have different surface species present at room temperature, so their tribological properties will be investigated in the future.     

Adsorption, ionization, and migration of hydrogen chloride on ice films at temperatures between 100 and 140 K

Adsorption of hydrogen chloride (HCl) on water ice films is studied in the temperature range of 100-140 K by using Cs+ reactive ion scattering (Cs+ RIS), low energy sputtering (LES), and temperature-programmed-desorption mass spectrometry (TPDMS). At 100 K, HCl on ice partially dissociates to hydronium and chloride ions and the undissociated HCl exists in two distinct molecular states (alpha- and beta-states). Upon heating of the ice films, HCl molecules in the alpha-state desorb at 135-150 K, whereas those in the beta-state first become ionized and then desorb via recombinative reaction of ions at 170 K. An adsorption kinetics study reveals that HCl adsorption into the ionized state is slightly favored over adsorption into the molecular states at 100 K, leading to earlier saturation of the ionized state. Between the two molecular states, the beta-state is formed first, and the alpha-state appears only at high HCl coverage. At 140 K, ionic dissociation of HCl is completed. The resulting hydronium ion can migrate into the underlying sublayer to a depth <4 bilayers, suggesting that the migration is assisted by self-diffusion of water molecules near the surface. When HCl is covered by a water overlayer at 100 K, its ionization efficiency is enhanced, but a substantial portion of HCl remains undissociated as molecules or contact ion pairs. The observation suggests that three-dimensional surrounding by water molecules does not guarantee ionic dissociation of HCl. Complete ionization of HCl requires additional thermal energy to separate the hydronium and chloride ions.     

Adsorption of HCl on the water ice surface studied by X-ray absorption spectroscopy

The adsorption state of HCl at 20 and 90 K on crystalline water ice films deposited under ultrahigh vacuum at 150 K has been studied by X-ray absorption spectroscopy at the O1s K-edge and Cl2p L-edge. We show that HCl dissociates at temperatures as low as 20 K, in agreement with the prediction of a spontaneous ionization of HCl on ice. Comparison between the rate of saturation of the "dangling" hydrogen bonds and the chlorine uptake indicates that hydrogen bonding of HCl with the surface native water "dangling" groups only accounts for a small part of the ionization events (20% at 90 K). A further mechanism drives the rest of the dissociation/solvation process. We suggest that the weakening of the ice surface hydrogen-bond network after the initial HCl adsorption phase facilitates the generation of new dissociation/solvation sites, which increases the uptake capacity of ice. These results also emphasize the necessity to take into account not only a single dissociation event but its catalyzing effect on the subsequent events when modeling the uptake of hydrogen-bonding molecules on the ice surface.     

Room-temperature kinetics of short-chain alkanethiol film growth on Ag(111) from the vapor phase

We have used time-of-flight (TOF) direct recoiling spectroscopy (DRS) to follow propanethiol adsorption at 300 K from the vapor phase on an Ag(111) surface, for exposures ranging from 10(-1) to 10(5) L. Results show that the adsorption proceeds with changes in the sticking coefficient, consistent with at least three phases. At low exposures, the alkanethiol molecules adsorb with high probability at defect sites, followed by a slower growth mode that essentially covers the whole surface. A third change in the sticking coefficient is associated with the final saturation stage, corresponding to a thicker layer related to molecules in a more upright orientation. The adsorption kinetics for hexanethiol is similar to that of propanethiol but taking place at higher rates, stressing the importance of the hydrocarbon chain length in the growth process. ISS-TOF measurements during thermal desorption show that most of the C, H, and S go away together, suggesting that the molecules adsorb and desorb from flat regions without S-C bond cleavage. Fitting the desorption maximum at 450 K with a first-order desorption curve gives a desorption energy of 1.43 eV. A small final S content that is correlated with the initial Ag(111) surface roughness is observed after desorption.     

Collisions of DCl with pure and salty glycerol: enhancement of interfacial D --> H exchange by dissolved NaI

The fate of DCl molecules striking pure glycerol and a 2.6 M NaI-glycerol solution is investigated using scattering, uptake, and residence time measurements. We find that dissolved Na+ and I- ions alter every gas-liquid pathway from the moment of contact of DCl with the surface to its eventual emergence as HCl. In particular, the salt enhances both trapping-desorption of DCl and interfacial DCl --> HCl exchange at the expense of DCl entry into the bulk solution. The reduced entry and enhanced desorption of thermalized DCl molecules are interpreted by assuming that Na+ and I- ions bind to interfacial OH groups and tie up surface sites that would otherwise capture incoming DCl molecules. These ion-glycerol interactions may also be responsible for enhancing interfacial D --> H exchange by disrupting the interfacial hydrogen bond network that carries the newly formed H+ ion away from its Cl- pair. This disruption may increase the fraction of interfacial Cl- and H+ that recombine and desorb immediately as HCl before the ions separate and diffuse deeply into the bulk.     

Methane dissociative adsorption on the Pt(111) surface over the 300-500 K temperature and 1-10 Torr pressure ranges

The dissociative adsorption of methane on the Pt(111) surface has been investigated and characterized over the 1-10 Torr pressure and 300-500 K temperature ranges using sum frequency generation (SFG) vibrational spectroscopy and Auger electron spectroscopy (AES). At a reaction temperature of 300 K and a pressure of 1 Torr, C-H bond dissociation occurs in methane on the Pt(111) surface to produce adsorbed methyl (CH(3)) groups, carbon, and hydrogen. SFG results suggest that C-C coupling occurs at higher reaction temperatures and pressures. At 400 K, methyl groups react with adsorbed C to form ethylidyne (C(2)H(3)), which dehydrogenates at 500 K to form ethynyl (C(2)H) and methylidyne (CH) species, as shown by SFG. By 600 K, all of the ethylidyne has reacted to form the dissociation products ethynyl and methylidyne. Calculated C-H bond dissociation probabilities for methane, determined by carbon deposition measured by AES, are in the 10(-8) range and increase with increasing reaction temperature. A mechanism has been developed and is compared with conclusions from other experimental and theoretical studies using single crystals.     

Nondissociative chemisorption of short chain alkanethiols on Au(111)

The adsorption of methanethiol and n-propanethiol on the Au(111) surface has been studied by temperature-programmed desorption (TPD), Auger electron spectroscopy (AES), and low-temperature scanning tunneling microscopy (LT-STM). Methanethiol desorbs molecularly from the chemisorbed monolayer at temperatures below 220 K in three overlapping desorption processes. No evidence for S-H or C-S bond cleavage has been found on the basis of three types of observations: (1) A mixture of chemisorbed CH3SD and CD3SH does not yield CD3SD, (2) no sulfur remains after desorption, and (3) no residual surface species remain when the adsorbed layer is heated to 300 K as measured by STM. On the other hand, when defects are introduced on the surface by ion bombardment, the desorption temperature of CH3SH is extended to 300 K and a small amount of dimethyl disulfide is observed to desorb at 410 K, indicating that S-H bond scission occurs on defect sites on Au(111) followed by dimerization of CH3S(a) species. Propanethiol also adsorbs nondissociatively on the Au(111) surface and desorbs from the surface below 250 K.     

FTIR spectroscopic studies of the stabilities and reactivities of hydrogen-terminated surfaces of silicon nanowires

Attenuated total reflection Fourier transform infrared (FTIR) spectroscopy was used to characterize the surface species on oxide-free silicon nanowires (SiNWs) after etching with aqueous HF solution. The HF-etched SiNW surfaces were found to be hydrogen-terminated; in particular, three types of silicon hydride species, the monohydride (SiH), the dihydride (SiH(2)), and the trihydride (SiH(3)), had been observed. The thermal stability of the hydrogen-passivated surfaces of SiNWs was investigated by measuring the FTIR spectra after annealing at different elevated temperatures. It was found that hydrogen desorption of the trihydrides occurred at approximately 550 K, and that of the dihydrides occurred at approximately 650 K. At or above 750 K, all silicon hydride species began to desorb from the surfaces of the SiNWs. At around 850 K, the SiNW surfaces were free of silicon hydride species. The stabilities and reactivities of HF-etched SiNWs in air and water were also studied. The hydrogen-passivated surfaces of SiNWs showed good stability in air (under ambient conditions) but relatively poor stability in water. The stabilities and reactivities of the SiNWs are also compared with those of silicon wafers.     

Interaction of petroleum-relevant organosulfur compounds with TiO2(110)

The interaction of two sets of structurally related molecules, thiophenol/thioanisole, and thiophene/tetrahydrothiophene, with vacuum-annealed and ion-bombarded TiO(2)(110) surfaces has been studied using a combination of temperature-programmed reaction spectroscopy (TPRS) and X-ray photoelectron spectroscopy (XPS). All thioethers studied were observed to adsorb and desorb from both surfaces without producing reaction products, while thiophenol, the only species studied containing a S-H bond, reacted with both surfaces. Approximately 25% of surface bound thiophenol decomposed over the vacuum-annealed surface. On the bombarded surface, thiophenol both decomposed into surface-bound C(x)H(y)/S fragments, and reacted to form benzene, which desorbed from the surface at 400 K. We propose that phenylthiolate formation on the bombarded surface leads to the observed production of benzene. These results highlight the importance of defects in the reactivity of titania, and lay the foundation for the study of larger, refractory sulfur compounds present in fuel.     

Enhanced reactivity of Pt nanoparticles supported on ceria thin films during ethylene dehydrogenation

The adsorption and reaction of ethylene on Pt/CeO(2-x)/Cu(111) model catalysts were studied by means of high resolution photoelectron spectroscopy (HR-PES) in conjunction with resonant photoemission spectroscopy (RPES). The dehydrogenation mechanism is compared to the HR-PES data obtained on a Pt(111) single crystal under identical conditions. It was found that the Pt nanoparticle system shows a substantially enhanced reactivity and several additional reaction pathways. In sharp contrast to Pt(111), partial dehydrogenation of ethylene on the supported Pt nanoparticles already starts at temperatures as low as 100 K. Similar to the single crystal surface, dehydrogenation occurs via the isomer ethylidene (CHCH(3)) and then mainly via ethylidyne (CCH(3)). In the temperature region between 100 and 250 K there is strong evidence for spillover of hydrocarbon fragments to the ceria support. In addition, splitting of ethylene to C(1) fragments is more facile than on Pt(111), giving rise to the formation of CH species and CO in the temperature region between 250 and 400 K. Upon further annealing, carbonaceous deposits are formed at 450 K. By heating to 700 K, these carbon deposits are completely removed from the surface by reaction with oxygen, provided by reverse spillover of oxygen from the ceria support.     

Decomposition of 1,1-dichloroethene on Pd(111)

The decomposition of 1,1-dichloroethene on Pd(111) is investigated using conventional thermal desorption, laser-induced thermal desorption (LITD), and FT reflection absorption infrared spectroscopy (FT-RAIRS). The decomposition mechanism produces at least three hydrocarbon surface intermediates, including ethylidyne. Thermal desorption results differ between high and low coverages because of relative surface concentrations of Cl and H in combination with kinetic effects.     

A variable temperature infrared spectroscopy study of NaA zeolite dehydration

Variable temperature diffuse reflectance infrared spectroscopy is used to monitor the dehydration of sodium Linde type A zeolite (NaA). Between ambient temperature and 423 K, water desorbs from NaA α-cages. At 423 K, remaining NaA water molecules are primarily confined to β-cages. Variable temperature infrared difference spectra band shape and intensity trends reflect the influence of water-Na⁺ interactions and hydrogen bonding on α-cage water desorption mechanisms. Difference spectrum variations suggest that water loss is accompanied by rearrangement of the remaining NaA water molecules to establish new interactions and minimize potential energies. Water molecules that do not interact with Na⁺ form multiple water-water hydrogen bonds and attain near bulk water configurations. These waters desorb at the lowest temperatures. Most α-cage waters are involved in Na⁺ interactions. These water molecules participate in hydrogen bonding with neighboring water molecules, but opportunities diminish with increased dehydration, resulting in systematic temperature-dependent vibrational spectrum changes.     

Molecular beam studies of HCl dissolution and dissociation in cold salty water

Gas-liquid scattering experiments are used to explore collisions and reactions of HCl and DCl with 12 mol% LiBr solutions of H(2)O and D(2)O at 208-218 K. These ～6 M aqueous salt solutions have vapor pressures just below 0.01 Torr, requiring special consideration of the effects of gas-vapor collisions. We find that impinging HCl molecules readily equilibrate on the surface of the solution even at incident energies of 90 kJ mol(-1). Approximately 90% of the thermalized HCl molecules dissolve and dissociate for long times in the cold salty solution, while the remaining 10% desorb from the surface intact. There is no evidence for rapid, interfacial conversion of HCl into DCl, in striking contrast to previous observations of distinct submicrosecond DCl→HCl exchange in collisions of DCl with salty glycerol at 292 K. These results indicate that cold salty water efficiently captures impinging HCl molecules and suppresses interfacial proton exchange, most likely because of the long interaction times of the HCl molecules in contact with the cold surface and because of facile transport of H(+) and Cl(-) from the interfacial region into the bulk solution.     

The chemistry of trimethylamine on Ru(001) and O/Ru(001)

The interaction and reactivity of trimethylamine (TMA) has been studied over clean and oxygen-covered Ru(001) under UHV conditions, as a model for the chemistry of high-density hydrocarbons on a catalytic surface. The molecule adsorbs intact at surface temperature below 100 K with the nitrogen end directed toward the surface, as indicated from work function change measurements. At coverage less than 0.05 ML (relative to the Ru substrate atoms), TMA fully dissociates upon surface heating, with hydrogen as the only evolving molecule following temperature-programmed reaction/desorption (TPR/TPD). At higher coverage, the parent molecule desorbs, and its desorption peak shifts down from 270 K to 115 K upon completion of the first monolayer, indicating a strong repulsion among neighbor molecules. The dipole moment of an adsorbed TMA molecule has been estimated from work function study to be 1.4 D. Oxygen precoverage on the ruthenium surface has shown efficient reactivity with TMA. It shifts the surface chemistry toward the production of various oxygen-containing stable molecules such as H2CO, CO2, and CO that desorb between 200 and 600 K, respectively. TMA at a coverage of 0.5 ML practically cleans off the surface from its oxygen atoms as a result of TPR up to 1650 K, in contrast to CO oxidation on the O/Ru(001) surface. The overall reactivity of TMA on the oxidized ruthenium surface has been described as a multistep reaction mechanism.     

Scattering, accommodation, and trapping of HCl in collisions with a hydroxylated self-assembled monolayer

Time-of-flight molecular beam scattering techniques are used to explore the energy exchange, thermal accommodation, and residence time of HCl in collisions with an OH-terminated self-assembled monolayer. The monolayer, consisting of 16-mercapto-1-hexadecanol (HS(CH(2))(16)OH) self-assembled on gold, provides a well-characterized surface containing hydroxyl groups located at the gas-solid interface. Upon colliding with the hydroxylated surface, the gas-phase HCl is found to follow one of three pathways: direct impulsive scattering, thermal accommodation followed by prompt desorption, and temporary trapping through HO--- HCl hydrogen bond formation. For an incident energy of 85 kJ/mol, the HCl transfers the majority, >80%, of its translational energy to the surface. The extensive energy exchange facilitates thermalization, leading to very large accommodation probabilities on the surface. Under the experimental conditions used in this work, over 75% of the HCl approaches thermal equilibrium with the surface before desorption and, for a 6 kJ/mol HCl beam, nearly 100% of the molecules that recoil from the surface can be described by a thermal distribution at the temperature of the surface. For the molecules that reach thermal equilibrium with the surface prior to desorption, a significant fraction appear to form hydrogen bonds with surface hydroxyl groups. The adsorption energy, determined by measuring the HCl residence time as a function of surface temperature, is 24 +/- 2 kJ/mol.