Scaling Platinum-Catalyzed Hydrogen Dissociation on Corrugated Surfaces

We determine absolute reactivities for dissociation at low coordinated Pt sites. Two curved Pt(111) single-crystal surfaces allow us to probe either straight or highly kinked step edges with molecules impinging at a low impact energy. A model extracts the average reactivity of inner and outer kink atoms, which is compared to the reactivity of straight A- and B-type steps. Local surface coordination numbers do not adequately capture reactivity trends for H₂ dissociation. We utilize the increase of reactivity with step density to determine the area over which a step causes increased dissociation. This step-type specific reactive area extends beyond the step edge onto the (111) terrace. It defines the reaction cross-section for H₂ dissociation at the step, bypassing assumptions about contributions of individual types of surface atoms. Our results stress the non-local nature of H₂ interaction with a surface and provide insight into reactivity differences for nearly identical step sites.     

Evidence of stable high-temperature D(x)-CO intermediates on the Ru(0001) surface

We demonstrate the formation of complexes involving attractive interactions between D and CO on Ru(0001) that are stable at significantly higher temperatures than have previously been reported for such intermediate species on this surface. These complexes are evident by the appearance of new desorption features upon heating of the sample. They decompose in stages as the sample temperature is increased, with the most stable component desorbing at >500 K. The D:CO ratio remaining on the surface during the final stages of desorption tends towards 1:1. The new features are populated during normally incident molecular beam dosing of D(2) on to CO pre-covered Ru(0001) surfaces (180 K) when the CO coverage exceeds 50% of the saturation value. The amount of complex formed decreases somewhat with increasing CO pre-coverage. It is almost absent in the case of dosing on to the fully saturated surface. The results are interpreted in terms of both local and long-range rearrangements of the overlayer that give rise to the observed CO coverage dependence and limit the amount of complex that can be formed.     

Co-adsorption of water and hydrogen on Ni(111)

We have studied the surface coverage dependence of the co-adsorption of D and D(2)O on the Ni(111) surface under UHV conditions. We use detailed temperature-programmed desorption studies and high resolution electron energy loss spectroscopy to show how pre-covering the surface with various amounts of D affects adsorption and desorption of D(2)O. Our results show that the effects of co-adsorption are strongly dependent on D-coverage. In the deuterium pre-coverage range of 0-0.3 ML, adsorption of deuterium leaves a fraction of the available surface area bare for D(2)O adsorption, which shows no significant changes compared to adsorption on the bare surface. Our data indicate phase segregation of hydrogen and water into islands. At low post-coverages, D(2)O forms a two-phase system on the remaining bare surface that shows zero-order desorption kinetics. This two phase system likely consists of a 2-D solid phase of extended islands of hexamer rings and a 2-D water gas phase. Increasing the water post-dose leads at first to 'freezing' of the 2-D gas and is followed by formation of ordered, multilayered water islands in-between the deuterium islands. For deuterium pre-coverages between 0.3 and 0.5 ML, our data may be interpreted that the water hexamer ring structure, (D(2)O)(6), required for the formation of an ordered multilayer, does not form anymore. Instead, more disordered linear and branched chains of water molecules grow in-between the extended, hydrophobic deuterium islands. These deuterium islands have a D-atom density in agreement with a (2x2)-2D structure. The disordered water structures adsorbed in-between form nucleation sites for growth of 3-D water structures. Loss of regular lateral hydrogen bonding and weakened interaction with the substrate reduces the binding energy of water significantly in this regime and results in lowering of the desorption temperature. At deuterium pre-coverages greater than 0.5 ML, the saturated (2x2)-2D structure mixes with (1x1)-1D patches. The mixed structures are also hydrophobic. On such surfaces, submonolayer doses of water lead to formation of 3-D water structures well before wetting the entire hydrogen-covered surface.     

The interaction of water with Ni(111) and H/Ni(111) studied by TPD and HREELS

We have used temperature-programmed desorption in combination with specular and off-specular high resolution electron energy loss spectroscopy to study the interaction of H(2)O and D(2)O with the bare and hydrogen-covered Ni(111) surface. Our results for the bare metal surface agree with previous reports and we are able to relate two prominent features in vibrational spectra to nuclear motions at the surface. Pre-covering Ni(111) with hydrogen alters both adsorption and desorption of water significantly. The strong H-Ni bond does not allow for isotopic exchange with co-adsorbed D(2)O. Strong resemblance of desorption traces and vibrational spectra of submonolayer coverages on H-covered Ni(111) and multilayers on bare Ni(111) suggests that adsorption of hydrogen makes this nickel surface hydrophobic.     

Employing a cylindrical single crystal in gas-surface dynamics

We describe the use of a polished, hollow cylindrical nickel single crystal to study effects of step edges on adsorption and desorption of gas phase molecules. The crystal is held in an ultra-high vacuum apparatus by a crystal holder that provides axial rotation about a [100] direction, and a crystal temperature range of 89 to 1100 K. A microchannel plate-based low energy electron diffraction/retarding field Auger electron spectrometer (AES) apparatus identifies surface structures present on the outer surface of the cylinder, while a separate double pass cylindrical mirror analyzer AES verifies surface cleanliness. A supersonic molecular beam, skimmed by a rectangular slot, impinges molecules on a narrow longitudinal strip of the surface. Here, we use the King and Wells technique to demonstrate how surface structure influences the dissociation probability of deuterium at various kinetic energies. Finally, we introduce spatially-resolved temperature programmed desorption from areas exposed to the supersonic molecular beam to show how surface structures influence desorption features.     

CO and H2O adsorption and reaction on Au(310)

We have studied desorption of ¹³CO and H₂O and desorption and reaction of coadsorbed, ¹³CO and H₂O on Au(310). From the clean surface, CO desorbs mainly in, two peaks centered near 140 and 200 K. A complete analysis of desorption spectra, yields average binding energies of 21 ± 2 and 37 ± 4 kJ/mol, respectively. Additional desorption states are observed near 95 K and 110 K. Post-adsorption of H₂O displaces part of CO pre-adsorbed at step sites, but does not lead to CO oxidation or significant shifts in binding energies. However, in combination with electron irradiation, ¹³CO₂ is formed during H₂O desorption. Results suggest that electron-induced decomposition products of H₂O are sheltered by hydration from direct reaction with CO.     

Anomalous scaling in epitaxial growth on vicinal surfaces: meandering and mounding instabilities in a linear growth equation with spatiotemporally correlated noise

We have undertaken an extensive analytical and kinetic Monte Carlo study of the (2+1) dimensional discrete growth model on a vicinal surface. A non-local, phenomenological continuum equation describing surface growth in unstable systems with anomalous scaling is presented. The roughness produced by unstable growth is first studied considering various effects in surface diffusion processes (corresponding to temperature, flux, diffusion anisotropy). We found that the thermally activated roughness is well-described by a generalized Lai–Das Sarma–Villain model with non linear growth continuum equation and uncorrelated noise. The corresponding critical exponents are computed analytically for the first time and show a continuous variation in agreement with simulation results of a solid-on-solid model. However, the roughness related to the meandering instability is found, unexpectedly, to be well described by a linear continuum equation with spatiotemporally correlated noise.     

高效液相色谱法测定水体中的氯虫酰胺残留量

采用Kromasil C18不锈钢柱(250mm×4.6mm i.d..5μm),以甲醇-水混合溶剂(65:35,V/V)为流动相,流速1.0mL/min,光电二极管阵列检测器,检测波长236nm和柱温35C,建立了不同水体中氯虫酰胺残留的高效液相色谱分析方法.氯虫酰胺水样直接用二氯甲烷进行液-液分配萃取.在0.10-10mg/L的浓度范围内,氯虫酰胺峰面积(y)与质量浓度(x)呈现良好的相关性,其线性回归方程为y=2170.4x 2641.7,r2=0.9991.井水和池塘水中添加质量浓度为0.01-1.00mg/L时,其平均回收率分别为94.70%-100.37%和89.14%-100.22%,变异系数分别为0.81%-5.11%和1.81%-5.30%,水样中的氯虫酰胺最低检测质量浓度(LOQ)为7.5×10-3mg/L,方法快速、灵敏度高、重现性好,具有较好的准确度和精密度,可用于环境中水样和土壤样中氯虫酰胺的残留检测分析.