Dynamic Behavior of Intermediate Adsorbates to Control Activity and Product Selectivity in Heterogeneous Catalysis: Methanol Decomposition on Pt/TiO2(110).

Dynamic behavior of intermediate adsorbates, such as diffusion, spillover, and reverse spillover, has a strong influence on the catalytic performance in oxide-supported metal catalysts. However, it is challenging to elucidate how the intermediate adsorbates move on the catalyst surface and find active sites to give the corresponding products. In this study, the effect of the dynamic behavior of methoxy intermediate on methanol decomposition on a Pt/TiO2(110) surface has been clarified by combination of scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), and density functional theory (DFT) calculations. The methoxy intermediates were formed by the dissociative adsorption of methanol molecules on Pt nanoparticles at room temperature followed by spillover to the TiO2(110) support surface. TPD results showed that the methoxy intermediates were thermally decomposed at >350 K on the Pt sites to produce CO (dehydrogenation) and CH4 (C-O bond scission). A decrease of the Pt nanoparticle density lowered the activity for the decomposition reaction and increased the selectivity toward CH4, which indicates that the reaction is controlled by diffusion and reverse spillover of the methoxy intermediates. Time-lapse STM imaging and DFT calculations revealed that the methoxy intermediates migrate on the five-fold coordinated Ti (Ti5c) sites along the [001] or [11¯0] direction with the aid of hydrogen adatoms bonded to the bridging oxygens (Obr) and can move over the entire surface to seek and find active Pt sites. This work offers an in-depth understanding of the important role of intermediate adsorbate migration in the control of the catalytic performance in oxide-supported metal catalysts.

Acceleration of hydrogen absorption by palladium through surface alloying with gold.

Enhancement of hydrogen (H) absorption kinetics improves the performance of hydrogen-purifying membranes and hydrogen-storage materials, which is necessary for utilizing hydrogen as a carbon-free energy carrier. Pd-Au alloys are known to show higher hydrogen solubility than pure Pd. However, the effect of Au on the hydrogen penetration from the surface into the subsurface region has not been clarified so far. Here, we investigate the hydrogen absorption at Pd-Au surface alloys on Pd(110) by means of thermal desorption spectroscopy (TDS) and hydrogen depth profiling with nuclear reaction analysis (NRA). We demonstrate that alloying the Pd(110) surface with submonolayer amounts of Au dramatically accelerates the hydrogen absorption. The degree of acceleration shows a volcano-shaped form against Au coverage. This kinetic enhancement is explained by a reduced penetration barrier mainly caused by a destabilization of chemisorbed surface hydrogen, which is supported by density-functional-theory (DFT) calculations. The destabilization of chemisorbed surface hydrogen is attributed to the change of the surface electronic states as observed by angle-resolved photoemission spectroscopy (ARPES). If generalized, these discoveries may lead to improving and controlling the hydrogen transport across the surfaces of hydrogen-absorbing materials.

Two charged states of hydrogen on the SrTiO3(001) surface.

The effects of hydrogen exposure on the electronic structure of two types of SrTiO3(001) surfaces, oxygen-deficient (OD) and nearly-vacancy-free (NVF) surfaces, were investigated with ultraviolet photoemission spectroscopy and nuclear reaction analysis. Upon molecular hydrogen exposure to the OD surface which reveals in-gap states at 1.3 eV below the Fermi level, the in-gap state intensity was reduced to half the initial value at a hydrogen coverage of 0.9 ± 0.7 × 10(14) cm(-2). On the NVF surface which has no in-gap state, on the other hand, atomic-hydrogen exposure induced in-gap states, and the hydrogen saturation coverage was evaluated to be 3.1 ± 0.8 × 10(14) cm(-2). We argue that H is positively charged as H(∼0.3 +) on the NVF surface by being coordinated to the O atom, whereas H is negatively charged as H(-) on the OD surface by occupying the oxygen vacancy site. The stability of H(-) at the oxygen vacancy site is discussed.

Knudsen layer formation in laser induced thermal desorption.

Laser induced thermal desorption of Xe atoms into vacuum from a metal surface following the nano-second pulsed laser heating was investigated by the time-of-flight (TOF) measurement. The desorption flow was studied at a wide range of desorption flux by varying the initially prepared Xe coverage Θ (1 ML = 4.5 × 10(18) atoms/m(2)). At Θ = 0.3 ML, the TOF of Xe was well represented by a Maxwell-Boltzmann velocity distribution, which is in good agreement with thermal desorption followed by collision-free flow. At Θ > 0.3 ML, the peak positions of the TOF spectra were shifted towards the smaller values and became constant at large Θ, which were well fitted with a shifted Maxwell-Boltzmann velocity distribution with a temperature TD and a stream velocity u. With TD fixed at 165 K, u was found to increase from 80 to 125 m/s with increasing Θ from 1.2 to 4 ML. At Θ > 4 ML, the value of u becomes constant at 125 m/s. The converging feature of u was found to be consistent with analytical predictions and simulated results based on the Knudsen layer formation theory. We found that the Knudsen layer formation in laser desorption is completed at Knudsen number Kn <0.39.

Quantification of Hydrogen Concentrations in Surface and Interface Layers and Bulk Materials through Depth Profiling with Nuclear Reaction Analysis.

Nuclear reaction analysis (NRA) via the resonant (1)H((15)N,αγ)(12)C reaction is a highly effective method of depth profiling that quantitatively and non-destructively reveals the hydrogen density distribution at surfaces, at interfaces, and in the volume of solid materials with high depth resolution. The technique applies a (15)N ion beam of 6.385 MeV provided by an electrostatic accelerator and specifically detects the (1)H isotope in depths up to about 2 µm from the target surface. Surface H coverages are measured with a sensitivity in the order of ~10(13) cm(-2) (~1% of a typical atomic monolayer density) and H volume concentrations with a detection limit of ~10(18) cm(-3) (~100 at. ppm). The near-surface depth resolution is 2-5 nm for surface-normal (15)N ion incidence onto the target and can be enhanced to values below 1 nm for very flat targets by adopting a surface-grazing incidence geometry. The method is versatile and readily applied to any high vacuum compatible homogeneous material with a smooth surface (no pores). Electrically conductive targets usually tolerate the ion beam irradiation with negligible degradation. Hydrogen quantitation and correct depth analysis require knowledge of the elementary composition (besides hydrogen) and mass density of the target material. Especially in combination with ultra-high vacuum methods for in-situ target preparation and characterization, (1)H((15)N,αγ)(12)C NRA is ideally suited for hydrogen analysis at atomically controlled surfaces and nanostructured interfaces. We exemplarily demonstrate here the application of (15)N NRA at the MALT Tandem accelerator facility of the University of Tokyo to (1) quantitatively measure the surface coverage and the bulk concentration of hydrogen in the near-surface region of a H2 exposed Pd(110) single crystal, and (2) to determine the depth location and layer density of hydrogen near the interfaces of thin SiO2 films on Si(100).

Interlayer diffusion of Au atoms in a heteroepitaxial system.

In heteroepitaxy, thin-film growth proceeds in two-dimensional layer-by-layer, three-dimensional island, or layer-plus-island modes depending on the growth conditions. Interlayer mass transport plays a crucial role in determining the growth mode. We investigate interlayer diffusion of Au atoms from Au islands grown on Ir(111) by scanning tunneling microscopy (STM) and kinetic Monte Carlo (KMC) simulations. STM measurements reveal that the first Au layer on Ir(111) grows in a complete layer at 100 K, whereas the Au layer grows in a three-dimensional fashion from the second Au layer at this temperature. Annealing these surfaces to 300 K reduces the higher-layer islands, indicating that Au atoms undergo step-down diffusion. By measuring the density of the top-layer islands and comparing them with the KMC simulation results, the additional step-down diffusion barrier for Au atoms to descend from the Au islands is estimated to be 0.02 eV on the first Au layer and 0.04 eV on the second Au layer. The layer dependence of the additional step-down diffusion barrier is explained in terms of the lattice mismatch between Au and underlying layers.