Synergetic effects of the Cu/Pt{110} surface alloy: enhanced reactivity of water and carbon monoxide

We have used synchrotron-based high-resolution X-ray photoelectron spectroscopy in combination with ab initio density functional theory calculations to investigate the characteristics of water and CO adsorption on the bimetallic Cu/Pt{110}-(2 x 1) surface at a Cu coverage near 0.5 ML. Cu fills the troughs of the reconstructed clean surface forming nanowires, which are stable up to 830 K. Their presence dramatically influences the adsorption of water and CO. Water adsorption changes from intact to partially dissociated while the desorption temperature of CO on this surface increases by up to 27 K with respect to the clean Pt{110} surface. Ab initio calculations and experimental valence band spectra reveal that the Cu 3d-band is narrowed and shifted upward with respect to bulk Cu surfaces. This and electron donation to surface Pt atoms cause the increase in the bond strength between CO and the Pt surface atoms. The pathway for water dissociation occurs via Cu surface atoms. The heat of adsorption of water bonding to Cu surface atoms was calculated to be 0.82 eV, which is significantly higher than on the clean Pt{110} surface; the activation energy for partial dissociation is 0.53 eV (not corrected for zero point energy).

Global and local expression of chirality in serine on the Cu{110} surface

Establishing a molecular-level understanding of enantioselectivity and chiral resolution at the organic−inorganic interfaces is a key challenge in the field of heterogeneous catalysis. As a model system, we investigate the adsorption geometry of serine on Cu{110} using a combination of low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The chirality of enantiopure chemisorbed layers, where serine is in its deprotonated (anionic) state, is expressed at three levels: (i) the molecules form dimers whose orientation with respect to the substrate depends on the molecular chirality, (ii) dimers of l- and d-enantiomers aggregate into superstructures with chiral (−1 2; 4 0) lattices, respectively, which are mirror images of each other, and (iii) small islands have elongated shapes with the dominant direction depending on the chirality of the molecules. Dimer and superlattice formation can be explained in terms of intra- and interdimer bonds involving carboxylate, amino, and β−OH groups. The stability of the layers increases with the size of ordered islands. In racemic mixtures, we observe chiral resolution into small ordered enantiopure islands, which appears to be driven by the formation of homochiral dimer subunits and the directionality of interdimer hydrogen bonds. These islands show the same enantiospecific elongated shapes those as in low-coverage enantiopure layers.

Enantiospecific adsorption of alanine on the chiral Cu{531} surface

We have studied enantiospecific differences in the adsorption of (S)- and (R)-alanine on Cu{531}R using low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy, and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. At saturation coverage, alanine adsorbs as alaninate forming a p(1 4) superstructure. LEED shows a significantly higher degree of long-range order for the S than for the R enantiomer. Also carbon K-edge NEXAFS spectra show differences between (S)- and (R)-alanine in the variations of the ð resonance when the linear polarization vector is rotated within the surface plane. This indicates differences in the local adsorption geometries of the molecules, most likely caused by the interaction between the methyl group and the metal surface and/or intermolecular hydrogen bonds. Comparison with model calculations and additional information from LEED and photoelectron spectroscopy suggest that both enantiomers of alaninate adsorb in two different orientations associated with triangular adsorption sites on {110} and {311} microfacets of the Cu{531} surface. The experimental data are ambiguous as to the exact difference between the local geometries of the two enantiomers. In one of two models that fit the data equally well, significantly more (R)-alaninate molecules are adsorbed on {110} sites than on {311} sites whereas for (S)-alaninate the numbers are equal. The enantiospecific differences found in these experiments are much more pronounced than those reported from other ultrahigh vacuum techniques applied to similar systems.

Water adsorption on O-covered Ru{0001}: coverage-dependent change from dissociation to molecular adsorption

When water is coadsorbed with oxygen at coverages above 0.25ML an intact water species is observed in high resolution X-ray photoelectron spectroscopy up to 220 K, which is significantly more stable than intact water on the clean surface. The presence of this species causes a shift in the O 1s binding energy of the pre-adsorbed oxygen, which indicates the formation of hydrogen bonds between the two adsorbates. Low coverages of oxygen induce partial dissociation and recombinative desorption in the same temperature range, which illustrates that desorption temperatures alone cannot be used to determine whether water is molecularly intact or not.

Model car-exhaust catalyst studied by TPD and TP-RAIRS: Surface reactions of NO on clean and O-covered Ir{100}

The adsorption of NO on Ir{100} has been studied as a function of NO coverage and temperature using temperature programmed reflection absorption infrared spectroscopy (TP-RAIRS), low energy electron diffraction (LEED) and temperature programmed desorption (TPD). After saturating the clean (1 x 5)-reconstructed surface with NO at 95 K. two N-2, desorption peaks are observed upon heating. The first N-2 peak at 346 K results from the decomposition of bridge-bonded NO, and the second at 475 K from the decomposition of atop-bonded NO molecules. NO decomposition is proposed to be the rate limiting step for both N-2 desorption states. For high NO coverages on the (1 x 5) surface, the narrow width of the first N-2 desorption peak is indicative of an autocatalytic process for which the parallel formation of N2O appears to be the crucial step. When NO is adsorbed on the metastable unreconstructed (1 x 1) phase of clean Ir{100} N-2 desorption starts at lower temperatures, indicating that this surface modification is more reactive. When a high coverage of oxygen, near 0.5 ML, is pre-adsorbed on the surface, the decomposition of NO is inhibited and mainly desorption of intact NO is observed.

Coverage-dependent molecular tilt of carbon monoxide chemisorbed on Pt{110}: A combined LEED and DFT structural analysis

The adsorption of carbon monoxide on the Pt{110} surface at coverages of 0.5 ML and 1.0 ML was investigated using quantitative low-energy electron diffraction (LEED IV) and density-functional theory (DFT). At 0.5 ML CO lifts the reconstruction of the clean surface but does not form an ordered overlayer. At the saturation coverage, 1.0 ML, a well-ordered p(2×1) superstructure with glide line symmetry is formed. It was confirmed that the CO molecules adsorb on top of the Pt atoms in the top-most substrate layer with the molecular axes tilted by ±22° with respect to the surface normal in alternating directions away from the close packed rows of Pt atoms. This is accompanied by significant lateral shifts of 0.55 Å away from the atop sites in the same direction as the tilt. The top-most substrate layer relaxes inwards by −4% with respect to the bulk-terminated atom positions, while the consecutive layers only show minor relaxations. Despite the lack of long-range order in the 0.5 ML CO layer it was possible to determine key structural parameters by LEED IV using only the intensities of the integer-order spots. At this coverage CO also adsorbs on atop sites with the molecular axis closer to the surface normal (b10°). The average substrate relaxations in each layer are similar for both coverages and consistent with DFT calculations performed for a variety of ordered structures with coverages of 1.0 ML and 0.5 ML.

The importance of attractive three-point interaction in enantioselective surface chemistry: stereospecific adsorption of serine on the intrinsically chiral Cu{531} surface

Both enantiomers of serine adsorb on the intrinsically chiral Cu{531} surface in two different adsorption geometries, depending on the coverage. At saturation, substrate bonds are formed through the two oxygen atoms of the carboxylate group and the amino group (μ3 coordination), whereas at lower coverage, an additional bond is formed through the deprotonated β−OH group (μ4 coordination). The latter adsorption geometry involves substrate bonds through three side groups of the chiral center, respectively, which leads to significantly larger enantiomeric differences in adsorption geometries and energies compared to the μ3 coordination, which involves only two side groups. This relatively simple model system demonstrates, in direct comparison, that attractive interactions of three side groups with the substrate are much more effective in inducing strong enantiomeric differences in heterogeneous chiral catalyst systems than hydrogen bonds or repulsive interactions.

Surface chemistry of glycine on Pt{111} in different aqueous environments

Adsorption of glycine on Ptf111g under UHV conditions and in different aqueous environments was studied by XPS (UHV and ambient pressure) and NEXAFS. Under UHV conditions, glycine adsorbs in its neutral molecular state up to about 0.15 ML. Further deposition leads to the formation of an additional zwitterionic species, which is in direct contact with the substrate surface, followed by the growth of multilayers, which also consist of zwitterions. The neutral surface species is most stable and decomposes at 360 K through a multi-step process which includes the formation of methylamine and carbon monoxide. When glycine and water are co-adsorbed in UHV at low temperatures (< 170 K) inter-layer diffusion is inhibited and the surface composition depends on the adsorption sequence. Water adsorbed on top of a glycine layer does not lead to significant changes in its chemical state. When glycine is adsorbed on top of a pre-adsorbed chemisorbed water layer or thick ice layer, however, it is found in its zwitterionic state, even at low coverage. No difference is seen in the chemical state of glycine when the layers are exposed to ambient water vapor pressure up to 0.2 Torr at temperatures above 300 K. Also the decomposition temperature stays the same, 360 K, irrespective of the water vapor pressure. Only the reaction path of the decomposition products is affected by ambient water vapor.

Interpreting Differential Temperature Trends at the Surface and in the Lower Troposphere

Estimated global-scale temperature trends at Earth's surface (as recorded by thermometers) and in the lower troposphere (as monitored by satellites) diverge by up to 0.14°C per decade over the period 1979 to 1998. Accounting for differences in the spatial coverage of satellite and surface measurements reduces this differential, but still leaves a statistically significant residual of roughly 0.1°C per decade. Natural internal climate variability alone, as simulated in three state-of-the-art coupled atmosphere-ocean models, cannot completely explain this residual trend difference. A model forced by a combination of anthropogenic factors and volcanic aerosols yields surface-troposphere temperature trend differences closest to those observed.

Surface water temperature observations of large lakes by optimal estimation

Optimal estimation (OE) and probabilistic cloud screening were developed to provide lake surface water temperature (LSWT) estimates from the series of (advanced) along-track scanning radiometers (ATSRs). Variations in physical properties such as elevation, salinity, and atmospheric conditions are accounted for through the forward modelling of observed radiances. Therefore, the OE retrieval scheme developed is generic (i.e., applicable to all lakes). LSWTs were obtained for 258 of Earth's largest lakes from ATSR-2 and AATSR imagery from 1995 to 2009. Comparison to in situ observations from several lakes yields satellite in situ differences of −0.2 ± 0.7 K for daytime and −0.1 ± 0.5 K for nighttime observations (mean ± standard deviation). This compares with −0.05 ± 0.8 K for daytime and −0.1 ± 0.9 K for nighttime observations for previous methods based on operational sea surface temperature algorithms. The new approach also increases coverage (reducing misclassification of clear sky as cloud) and exhibits greater consistency between retrievals using different channel–view combinations. Empirical orthogonal function (EOF) techniques were applied to the LSWT retrievals (which contain gaps due to cloud cover) to reconstruct spatially and temporally complete time series of LSWT. The new LSWT observations and the EOF-based reconstructions offer benefits to numerical weather prediction, lake model validation, and improve our knowledge of the climatology of lakes globally. Both observations and reconstructions are publically available from http://hdl.handle.net/10283/88.

NOAA's sea surface temperature products from operational geostationary satellites

NOAA's National Environmental Satellite, Data, and Information Service (NESDIS) has generated sea surface temperature (SST) products from Geostationary Operational Environmental Satellite (GOES)-East (E) and GOES-West (W) on an operational basis since December 2000. Since that time, a process of continual development has produced steady improvements in product accuracy. Recent improvements extended the capability to permit generation of operational SST retrievals from the Japanese Multifunction Transport Satellite (MTSAT)-1R and the European Meteosat Second Generation (MSG) satellite, thereby extending spatial coverage. The four geostationary satellites (at longitudes of 75°W, 135°W, 140°E, and 0°) provide high temporal SST retrievals for most of the tropics and midlatitudes, with the exception of a region between 60° and 80°E. Because of ongoing development, the quality of these retrievals now approaches that of SST products from the polar-orbiting Advanced Very High Resolution Radiometer (AVHRR). These products from GOES provide hourly regional imagery, 3-hourly hemispheric imagery, 24-h merged composites, a GOES SST level 2 preprocessed product every 1/2 h for each hemisphere, and a match-up data file for each product. The MTSAT and the MSG products include hourly, 3-hourly, and 24-h merged composites. These products provide the user community with a reliable source of SST observations, with improved accuracy and increased coverage in important oceanographic, meteorological, and climatic regions.

Objective determination of feature resolution in two sea surface temperature analyses

Considerable effort is presently being devoted to producing high-resolution sea surface temperature (SST) analyses with a goal of spatial grid resolutions as low as 1 km. Because grid resolution is not the same as feature resolution, a method is needed to objectively determine the resolution capability and accuracy of SST analysis products. Ocean model SST fields are used in this study as simulated “true” SST data and subsampled based on actual infrared and microwave satellite data coverage. The subsampled data are used to simulate sampling errors due to missing data. Two different SST analyses are considered and run using both the full and the subsampled model SST fields, with and without additional noise. The results are compared as a function of spatial scales of variability using wavenumber auto- and cross-spectral analysis. The spectral variance at high wavenumbers (smallest wavelengths) is shown to be attenuated relative to the true SST because of smoothing that is inherent to both analysis procedures. Comparisons of the two analyses (both having grid sizes of roughly ) show important differences. One analysis tends to reproduce small-scale features more accurately when the high-resolution data coverage is good but produces more spurious small-scale noise when the high-resolution data coverage is poor. Analysis procedures can thus generate small-scale features with and without data, but the small-scale features in an SST analysis may be just noise when high-resolution data are sparse. Users must therefore be skeptical of high-resolution SST products, especially in regions where high-resolution (~5 km) infrared satellite data are limited because of cloud cover.

An investigation into the impact of using various techniques to estimate Arctic surface air temperature anomalies

Time series of global and regional mean Surface Air Temperature (SAT) anomalies are a common metric used to estimate recent climate change. Various techniques can be used to create these time series from meteorological station data. The degree of difference arising from using five different techniques, based on existing temperature anomaly dataset techniques, to estimate Arctic SAT anomalies over land and sea ice were investigated using reanalysis data as a testbed. Techniques which interpolated anomalies were found to result in smaller errors than non-interpolating techniques relative to the reanalysis reference. Kriging techniques provided the smallest errors in estimates of Arctic anomalies and Simple Kriging was often the best kriging method in this study, especially over sea ice. A linear interpolation technique had, on average, Root Mean Square Errors (RMSEs) up to 0.55 K larger than the two kriging techniques tested. Non-interpolating techniques provided the least representative anomaly estimates. Nonetheless, they serve as useful checks for confirming whether estimates from interpolating techniques are reasonable. The interaction of meteorological station coverage with estimation techniques between 1850 and 2011 was simulated using an ensemble dataset comprising repeated individual years (1979-2011). All techniques were found to have larger RMSEs for earlier station coverages. This supports calls for increased data sharing and data rescue, especially in sparsely observed regions such as the Arctic.

Coverage-dependent structural evolution in the interaction of NO2 with Au{111}

We have used low-temperature STM, together with DFT calculations incorporating the effects of dispersion forces, to study from a structural point of view the interaction of NO2 with Au{111} surfaces. NO2 adsorbs molecularly on Au{111} at 80 K, initially as small, disordered clusters at the elbows of the type-x reconstruction lines of the clean-surface herringbone reconstruction, and then as larger, ordered islands on the fcc regions. Within the islands, the NO2 molecules define a (√3 × 2)rect. superlattice, for which we evaluate structural models. By around 0.25 ML coverage, the herringbone reconstruction has been lifted, accompanied by the formation of Au nanoclusters, and the islands have coalesced. At this stage, essentially the whole surface is covered with an overlayer consisting predominantly of domains of the (√3 × 2)rect. structure, but also containing less wellordered regions. With further exposure, the degree of disorder in the overlayer increases; saturation occurs close to 0.43 ML.

Stereochemistry and thermal stability of tartaric acid on the intrinsically chiral Cu{531} surface

Intrinsically chiral metal surfaces provide enantiospecific reaction environments without the need of coadsorbed modifiers. Amongst the intrinsically chiral copper surfaces, Cu{531} has the smallest unit cell and the highest density of chiral sites. XPS, NEXAFS and TPD were employed to investigate the adsorption and decomposition behaviour of the two chiral enantiomers of tartaric acid on this surface. The results obtained from XPS and NEXAFS show that at saturation coverage both enantiomers of tartaric acid adsorb in a μ4 configuration through the two carboxylic groups,which are rotatedwith respect to each other by 90°±≈15°within the surface plane. At intermediate coverage the R,R enantiomer adopts a similar configuration, but the S,S enantiomer is different and shows a high degree of dissociation. Growth of multilayers is observed at high exposures when the sample is kept at below 370 K. TPD experiments show that multilayers desorb between 390 K and 470 K and decomposition of the chemisorbed layer occurs between 470 K and 600 K. The desorption spectra support a two-step decomposition mechanism with a O_C_C_O or HO–HC_CH–OH intermediate that leads to production of CO2 and CO. Enantiomeric differences are observed in the desorption features related to the decomposition of the chemisorbed layer.