Unexpected high binding energy of CO2 on CH3NH3PbI3 lead-halide organic-inorganic perovskites via bicarbonate formation.

The adsorption kinetics of CO2 was experimentally characterized in ultra-high vacuum (UHV). Unexpectedly, high desorption temperatures (640 K, 170 kJ mol-1) were seen. Density functional theory (DFT) calculations suggest the stabilization mechanism: bicarbonate formation in the defected perovskite film due to CO2 and H2O coadsorption.

Support effects in the adsorption of water on CVD graphene: an ultra-high vacuum adsorption study.

Experimental data for water adsorption on CVD (chemical vapor deposition) graphene/SiO2 and graphene/Cu studied under ultra-high vacuum (UHV) conditions are discussed, focusing on support effects and hydrophobicity. Under UHV, it seems that graphene wettability is inversely related to wetting properties of the support. Graphene is not transparent to water wetting on the supports studied here.

Adsorption of water on graphene/Ru(0001)-an experimental ultra-high vacuum study.

Data for water adsorption on epitaxial graphene grown on Ru(0001) at ultra-high vacuum (clean conditions) are discussed. Accordingly, water adsorption was not affected by the support. The interaction is not strictly hydrophobic. We propose simple rules based on ultra-high vacuum kinetics to classify the water-graphene-support interactions.

Unexpected bond activation of small organic molecules on a metal oxide-butane/CaO(100).

We present the first example of bond activation of small alkanes (n-/iso-butane) on a metal oxide surface--CaO(100)--at ultra-high vacuum (UHV) conditions and at low surface temperatures studied by molecular beam scattering and thermal desorption spectroscopy.

Unexpected adsorption of oxygen on TiO2 nanotube arrays: influence of crystal structure.

We present kinetics data of O2, n/iso-butane, CO2, and CO adsorbed at ultrahigh vacuum conditions on TiO2 nanotube (TiNTs) arrays produced by electrochemical anodization; amorphous and polycrystalline (anatase and mixed anatase/rutile) TiNTs have been studied addressing structure-activity relationships. Oxygen distinctly interacts with the TiNTs, whereas this process is not observed on fully oxidized TiO2 single crystals. Both molecularly and atomically bonded oxygen have been observed. Variations in the binding energies of alkanes were also detected.

Adsorption of CO2 on oxidized, defected, hydrogen and oxygen covered rutile (1 x 1)-TiO2(110).

Presented are initial, S(0) and coverage, Theta, dependent S(Theta), adsorption probability measurements of CO(2) as a function of impact energy, E(i) = 0.12-1.3 eV, adsorption temperature, T(s) = 85-300 K, hydrogen and oxygen pre-exposure, as well as density of defects, Gamma, as varied by annealing (T = 600-900 K) and Ar(+) ion sputtering (dose chi(Ar) at 600 eV at 85 K) of a rutile (1 x 1) TiO(2)(110) surface. The defect densities were qualitatively characterized by thermal desorption spectroscopy (TDS) of CO(2). The CO(2) TDS curves consisted of two structures that can be assigned to adsorption on pristine and oxygen vacancy sites, in agreement with earlier studies. S(0) decreased linearly with E(i) and was independent of T(s). The adsorption dynamics were dominated by the effect of precursor states leading to Kisliuk-like shapes over the E(i) and T(s) range studied. Oxygen vacancy sites reduced S(0) of CO(2). Preadsorbed oxygen blocked preferentially defect sites, which led to an increase in S(0). Hydrogen preadsorption results in physical site blocking with decreased S(0) as H-preexposure increased, while the shape of S(Theta) curves was conserved. In contrast to oxygen, hydrogen does not adsorb preferentially on defect sites. The adsorption probability data were parameterized by analytic functions (Kisliuk model) and by Monte Carlo simulations (MCSs).

Adsorption dynamics of CO2 on copper-precovered ZnO(0001)-Zn: a molecular-beam scattering and thermal-desorption spectroscopy study.

Initial, S(0), as well as coverage-dependent adsorption probability measurements, S(Theta), have been conducted at normal impact angle and as a function of the impact energy of CO(2), E(i), adsorption temperature, T(s), and copper precoverage, Theta(Cu) (at 300 K). S(0), which decreased from approximately 0.4 exponentially to approximately 0.05 with E(i) was independent of Theta(Cu). Astonishingly, S(0) for Cu on ZnO(0001)-Zn is smaller than for the clean support which indicates a chemical modification of the support by the Cu deposits. S(Theta) curves consist of two regimes, a Kisliuk-type and Langmuirian-type section. The first is consistent with capture zone models; the second may indicate direct adsorption of CO(2) on the Cu cluster. The thermal-desorption (TDS) curves for Cu on ZnO(0001)-Zn consist of two structures with binding energies of 26 and approximately 40 kJmol (nu=1 x 10(13) ls). The TDS results indicate that CO(2) populates predominantly the Cu deposits and the rim along the Cu nanoparticles. No indications for CO(2) dissociation could be obtained with Auger electron spectroscopy.

Adsorption of CO on the copper-precovered ZnO(0001) surface: a molecular-beam scattering study.

Auger electron spectroscopy (AES), thermal-desorption spectroscopy (TDS), and, in particular, molecular-beam scattering techniques have been combined to address particle size effects in the adsorption of CO on Cu-on-ZnO(0001). AES and TDS lead to a Cu coverage, theta(Cu), calibration. The TDS curves, as a function of theta(Cu) and CO exposure, revealed three structures at 150, 220, and 260-280 K, in agreement with prior studies. However, a unique assignment of the TDS structures to a particular Cu face was not possible. An enhancement of the initial adsorption probability, S0, with respect to the support indicates the effect of the Cu nanoparticles. Despite that the shape of S0 versus impact energy curves was independent of theta(Cu) and agreed with Cu single-crystal reference systems, distinct particle size effects were present with regard to the adsorption mechanism. It was possible to observe a crossover from Langmuir-type adsorption dynamics to more precursor-assisted adsorption dynamics with increasing theta(Cu). Thus, a dynamic structure-activity relationship was evident, i.e., the energy-transfer mechanism depends on the Cu morphology.

Adsorption dynamics of CO2 on Zn-ZnO(0001): a molecular beam study.

Presented are initial S(0) and coverage Theta dependent, S(Theta), adsorption probability measurements, respectively, of CO(2) adsorption on the polar Zn-terminated surface of ZnO, parametric in the impact energy E(i), the surface temperature T(s), the impact angle alpha(i), varied along the [001] azimuth, the CO(2) flux, and the density of defects, chi(Ar(+)), as varied by rare gas ion sputtering. S(0) decreases linearly from 0.72 to 0.25 within E(i)=0.12-1.33 eV and is independent of T(s). Above E(i)=0.56 eV, S(0) decreases by approximately 0.2 with increasing alpha(i). The shape of S(Theta) curves is consistent with precursor-mediated adsorption (Kisliuk shape, i.e., S approximately const) for low E(i); above E(i)=0.56 eV, however, a turnover to adsorbate-assisted adsorption (S increases with Theta) has been observed. The initial slope of S(Theta) curves decreases thereby with increasing alpha(i), chi(Ar(+)), and T(s), i.e., the adsorbate-assisted adsorption is most distinct for normal impact on the pristine surface at low T(s) and is independent of the CO(2) flux. The S(Theta) curves have been parametrized by analytic precursor models and Monte Carlo simulations have been conducted as well. The temperature dependence of the saturation coverage shows two structures which could be assigned to adsorption on pristine and intrinsic defect sites, respectively, in agreement with a prior thermal desorption spectroscopy study. The heat of adsorption E(d) for the pristine sites amounts to 34.0-5.4Theta, whereas for adsorption on the intrinsic defect sites E(d) of approximately 43.6 kJ/mol could be estimated. Thus, a kinetic structure-activity relationship was present.

Stabilization of polar ZnO surfaces: validating microscopic models by using CO as a probe molecule.

The determination of the structure of inhomogeneous metal-oxide surfaces represents a formidable task. With the present study, we demonstrate that using the binding energy of a probe molecule, CO, is a reliable tool to validate structural models for such complex surfaces. Combining several types of first-principles calculations with advanced molecular beam methods, we are able to provide conclusive evidence that the polar O-terminated surface of ZnO is either reconstructed or hydrogen covered. This finding has important consequences for the ongoing discussion regarding the stabilization mechanism of the electrostatically unstable ("Tasker type 3") polar ZnO surfaces.