Direct observation of subsurface oxygen on the defects of Pd(100)

Oxygen adsorption and desorption on a Pd(100) surface with a mesoscopic defect were studied by photoemission electron microscopy (PEEM). The defect surface, with an area of approximately 200 x 60 mu m(2), behaved differently from the perfect Pd(100) surface towards the adsorption of oxygen. When saturated, both surface oxygen and subsurface oxygen coexisted on the defect surface, whereas only surface oxygen was present on the Pd(100) surface. Upon heating, subsurface oxygen diffused back to the surface and desorbed with surface oxygen at the same time. The difference in oxygen adsorption ability between the defect surface and the perfect Pd(100) surface can be attributed to different structures of these two surfaces. (C) 1999 Elsevier Science B.V. All rights reserved.

Formation of subsurface oxygen species and its high activity toward CO oxidation over silver catalysts

Silver is well known to show peculiar catalytic activities in several oxidation reactions. In the present paper, we investigate the catalytic activity of silver catalysts toward CO-gelective oxidation in H-2. XRD, TEM, TPD, and in situ FTIR techniques were used to characterize the catalysts. The pretreatment of the catalysts was found to have great influence on their performance. The pretreatment in 02 improves the activity of the silver catalyst, whereas He pretreatment at 700 degreesC or direct hydrogen pretreatment shows an inverse effect. Silver catalysts undergo massive structural change during oxygen pretreatment at high temperatures (> 500 degreesC), and there is solid evidence for the formation of subsurface oxygen species. The existence of this silver-subsurface oxygen structure facilitates the formation of active sites on silver catalysts for CO oxidation, which are related to the size, morphology, and exposed crystal planes of the silver particles. Its formation requires a certain temperature, and a higher pretreatment temperature with oxygen is required for the silver catalyst with a smaller particle size. It is observed, for the first time, that adsorbed CO on the surface of silver particles can directly react with subsurface oxygen species at low temperatures (e.g., RT), and the surface oxygen can migrate into and refill these subsurface sites after the consumption of subsurface oxygen by the reaction with CO. This finding provides a new reaction pathway for CO oxidation on silver catalyst. (C) 2004 Published by Elsevier Inc.

Subsurface oxygen maximum anomaly found at depth in Muchalat Inlet

Senior thesis written for Oceanography 445

Observed oxygen concentrations and a possible implication behind the Muchalat inlet subsurface oxygen maximum

Senior thesis written for Oceanography 445

Dynamics of the Indian-Ocean oxygen minimum zones

In the Indian Ocean, mid-depth oxygen minimum zones (OMZs) occur in the Arabian Sea and the Bay of Bengal. The lower part of the Arabian-Sea OMZ (ASOMZ; below 400 m) intensifies northward across the basin; in contrast, its upper part (above 400 m) is located in the central/eastern basin, well east of the most productive regions along the western boundary. The Bay-of-Bengal OMZ (BBOMZ), although strong, is weaker than the ASOMZ. To investigate the processes that maintain the Indian-Ocean OMZs, we obtain a suite of solutions to a coupled biological/physical model. Its physical component is a variable-density, 6 1/2-layer model, in which each layer corresponds to a distinct dynamical regime or water-mass type. Its biological component has six compartments: nutrients, phytoplankton, zooplankton, two size classes of detritus, and oxygen. Because the model grid is non-eddy resolving (0.5 degrees), the biological model also includes a parameterization of enhanced mixing based on the eddy kinetic energy derived from satellite observations. To explore further the impact of local processes on OMZs, we also obtain analytic solutions to a one-dimensional, simplified version of the biological model. Our control run is able to simulate basic features of the oxygen, nutrient, and phytoplankton fields throughout the Indian Ocean. The model OMZs result from a balance, or lack thereof, between a sink of oxygen by remineralization and subsurface oxygen sources due primarily to northward spreading of oxygenated water from the Southern Hemisphere, with a contribution from Persian-Gulf water in the northern Arabian Sea. The northward intensification of the lower ASOMZ results mostly from horizontal mixing since advection is weak in its depth range. The eastward shift of the upper ASOMZ is due primarily to enhanced advection and vertical eddy mixing in the western Arabian Sea, which spread oxygenated waters both horizontally and vertically. Advection carries small detritus from the western boundary into the central/eastern Arabian Sea, where it provides an additional source of remineralization that drives the ASOMZ to suboxic levels. The model BBOMZ is weaker than the ASOMZ because the Bay lacks a remote source of detritus from the western boundary. Although detritus has a prominent annual cycle, the model OMZs do not because there is not enough time for significant remineralization to occur.

Circulation, eddies, oxygen and nutrient changes in the eastern tropical South Pacific Ocean

A large, subsurface oxygen deficiency zone is located in the eastern tropical South Pacific Ocean (ETSP). The large-scale circulation in the eastern equatorial Pacific and off Peru in November/December 2012 shows the influence of the equatorial current system, the eastern boundary currents, and the northern reaches of the subtropical gyre. In November 2012 the Equatorial Undercurrent is centered at 250 m depth, deeper than in earlier observations. In December 2012 the equatorial water is transported southeastward near the shelf in the Peru-Chile Undercurrent with a mean transport of 1.6 Sv. In the oxygen minimum zone (OMZ) the flow is overlaid with strong eddy activity on the poleward side of the OMZ. Floats with parking depth at 400 m show fast westward flow in the mid-depth equatorial channel and sluggish flow in the OMZ. Floats with oxygen sensors clearly show the passage of eddies with oxygen anomalies. The long-term float observations in the upper ocean lead to a net community production estimate at about 18° S of up to 16.7 mmol C m?3 yr1 extrapolated to an annual rate and 7.7 mmol C m?3 yr?1 for the time period below the mixed layer. Oxygen differences between repeated ship sections are influenced by the Interdecadal Pacific Oscillation, by the phase of El Niño, by seasonal changes, and by eddies and hence have to be interpreted with care. At and south of the equator the decrease in oxygen in the upper ocean since 1976 is related to an increase in nitrate, phosphate, and in part in silicate.

A combined environmental scanning electron microscopy and Raman microscopy study of methanol oxidation on silver(I) oxide

The techniques of environmental scanning electron microscopy (ESEM) and Raman microscopy have been used to respectively elucidate the morphological changes and nature of the adsorbed species on silver(I) oxide powder, during methanol oxidation conditions. Heating Ag2O in either water vapour or oxygen resulted firstly in the decomposition of silver(I) oxide to polycrystalline silver at 578 K followed by sintering of the particles at higher temperature. Raman spectroscopy revealed the presence of subsurface oxygen and hydroxyl species in addition to surface hydroxyl groups after interaction with water vapour. Similar species were identified following exposure to oxygen in an ambient atmosphere. This behaviour indicated that the polycrystalline silver formed from Ag2O decomposition was substantially more reactive than silver produced by electrochemical methods. The interaction of water at elevated temperatures subsequent to heating silver(I) oxide in oxygen resulted in a significantly enhanced concentration of subsurface hydroxyl species. The reaction of methanol with Ag2O at high temperatures was interesting in that an inhibition in silver grain growth was noted. Substantial structural modification of the silver(I) oxide material was induced by catalytic etching in a methanol/air mixture. In particular, "pin-hole" formation was observed to occur at temperatures in excess of 773 K, and it was also recorded that these "pin- holes" coalesced to form large-scale defects under typical industrial reaction conditions. Raman spectroscopy revealed that the working surface consisted mainly of subsurface oxygen and surface Ag=O species. The relative lack of sub-surface hydroxyl species suggested that it was the desorption of such moieties which was the cause of the "pin-hole" formation.

In situ imaging of catalytic etching on silver during methanol oxidation conditions by environmental scanning electron microscopy

Polycrystalline silver is used to catalytically oxidise methanol to formaldehyde. This paper reports the results of extensive investigations involving the use of environmental scanning electron microscopy (ESEM) to monitor structural changes in silver during simulated industrial reaction conditions. The interaction of oxygen, nitrogen, and water, either singly or in combination, with a silver catalyst at temperatures up to 973 K resulted in the appearance of a reconstructed silver surface. More spectacular was the effect an oxygen/methanol mixture had on the silver morphology. At a temperature of ca. 713 K pinholes were created in the vicinity of defects as a consequence of subsurface explosions. These holes gradually increased in size and large platelet features were created. Elevation of the catalyst temperature to 843 K facilitated the wholescale oxygen induced restructuring of the entire silver surface. Methanol reacted with subsurface oxygen to produce subsurface hydroxyl species which ultimately formed water in the subsurface layers of silver. The resultant hydrostatic pressure forced the silver surface to adopt a "hill and valley" conformation in order to minimise the surface free energy. Upon approaching typical industrial operating conditions widespread explosions occurred on the catalyst and it was also apparent that the silver surface was extremely mobile under the applied conditions. The interaction of methanol alone with silver resulted in the initial formation of pinholes primarily in the vicinity of defects, due to reaction with oxygen species incorporated in the catalyst during electrochemical synthesis. However, dramatic reduction in the hole concentration with time occurred as all the available oxygen became consumed. A remarkable correlation between formaldehyde production and hole concentration was found.

In situ Raman studies of the selective oxidation of methanol to formaldehyde and ethene to ethylene oxide on a polycrystalline silver catalyst

The combined techniques of in situ Raman microscopy and scanning electron microscopy (SEM) have been used to study the selective oxidation of methanol to formaldehyde and the ethene epoxidation reaction over polycrystalline silver catalysts. The nature of the oxygen species formed on silver was found to depend critically upon the exact morphology of the catalyst studied. Bands at 640, 780 and 960 cm-1 were identified only on silver catalysts containing a significant proportion of defects. These peaks were assigned to subsurface oxygen species situated in the vicinity of surface dislocations, AgIII=O sites formed on silver atoms modified by the presence of subsurface oxygen and O2 - species stabilized on subsurface oxygen-modified silver sites, respectively. The selective oxidation of methanol to formaldehyde was determined to occur at defect sites, where reaction of methanol with subsurface oxygen initially produced subsurface OH species (451 cm-1) and adsorbed methoxy species. Two distinct forms of adsorbed ethene were identified on oxidised silver sites. One of these was created on silver sites modified by the interaction of subsurface oxygen species, and the other on silver crystal planes containing a surface coverage of atomic oxygen species. The selective oxidation of ethene to ethylene oxide was achieved by the reaction between ethene adsorbed on modified silver sites and electrophilic AgIII=O species, whereas the combustion reaction was perceived to take place by the reaction of adsorbed ethene with nucleophilic surface atomic oxygen species. Defects were determined to play a critical role in the epoxidation reaction, as these sites allowed the rapid diffusion of oxygen into subsurface positions, and consequently facilitated the formation of the catalytically active AgIII=O sites.

Influence of oxidation and reduction conditions upon the morphology of silica-supported polycrystalline silver catalysts

The effect of oxidation and reduction conditions upon the morphology of polycrystalline silver catalysts has been investigated by means of in situ Fourier-transform infrared (FTIR) spectroscopy. Characterization of the sample was achieved by inspection of the νas(COO) band profile of adsorbed formate, recorded after dosing with formic acid at ambient temperature. Evidence was obtained for the existence of a silver surface reconstructed by the presence of subsurface oxygen in addition to the conventional family of Ag(111) and Ag(110) crystal faces. Oxidation at 773 K facilitated the reconstruction of silver planes due to the formation of subsurface oxygen species. Prolonged oxygen treatment at 773 K also caused particle fragmentation as a consequence of excessive oxygen penetration of the silver catalyst at defect sites. It was also deduced that the presence of oxygen in the gas phase stabilized the growth of silver planes which could form stronger bonds with oxygen. In contrast, high-temperature thermal treatment in vacuum induced significant sintering of the silver catalyst. Reduction at 773 K resulted in substantial quantities of dissolved hydrogen (and probably hydroxy species) in the bulk silver structure. Furthermore, enhanced defect formation in the catalyst was also noted, as evidenced by the increased concentration of formate species associated with oxygen-reconstructed silver faces.

ROLE OF CHLORINE AND ALKALI PROMOTERS IN ETHYLENE EPOXIDATION OVER SINGLE CRYSTAL SILVER SURFACES.

Experiments with N//2O were carried out with a view to obtaining additional information about the reactivity of oxygen surface species. On clean Ag, N//2O decomposition was found to be an activated process which led exclusively to the deposition of O(a) species. The presence of preadsorbed oxygen or subsurface oxygen served to enhance the deposition rate of O(a). Subsequent dosing with ethylene at 300 K of such an oxygen-populated surface followed by TPR examination showed it to be active for ethylene oxide formation. Control experiments established that adventitious decomposition of N//2O at the reactor walls or specimen supports followed by possible re-absorption of O//2(a) was an entirely negligible process. ) The oxidation activity of N//2O was also investigated at elevated pressures in the batch reactor.

Restructuring and redispersion of silver on SiO2 under oxidizing/reducing atmospheres and its activity toward CO oxidation

The effects of oxygen-hydrogen pretreatments of nanosilver catalysts in cycle mode on the structure and particle size of silver particles, and subsequently the activity of the catalyst toward CO oxidation (or CO selective oxidation in the presence of H-2) are reported in this paper. Ag/SiO2 catalyst with silver particle sizes of ca. 6 similar to 8 nm shows relatively high activity in the present reaction system. The adopting of a cycle of oxidation/reduction pretreatment has a marked influence on the activity of the catalyst. Oxygen pretreatment at 500 degrees C results in the formation of subsurface oxygen and activates the catalyst. As evidenced by in-situ XRD and TEM, the following H-2 treatment at low temperatures (100 similar to 300 degrees C) causes surface faceting and redispersing of the silver particles without destroying the subsurface oxygen species. The subsequent in-situ FTIR and catalytic reaction results show that CO oxidation occurs at -75 degrees C and complete CO conversion can be obtained at 40 degrees C over such a nanosilver catalyst pretreated with oxygen at 500 degrees C followed by H-2 at 100 degrees C. However, prolonged hydrogen treatment at high temperatures (> 300 degrees C) after oxygen pretreatment at 500 degrees C induces the aggregation of silver particles and also depletes so much subsurface oxygen species that the pathway of CO oxidation by the subsurface oxygen species is inhibited. Meanwhile, the ability of the catalyst to adsorb reactants is greatly depressed, resulting in a 20 similar to 30% decrease in the activity toward CO oxidation. However, the activity of the catalyst pretreated with oxygen at 500 degrees C followed by hydrogen treatment at high temperatures (> 300 degrees C) is still higher than that directly pretreated with H,. This kind of catalytic behavior of silver catalyst is associated with physical changes in the silver crystallites because of surface restructuring and crystallite redispersion during the course of oxygen-hydrogen pretreatment steps.

On the open-circuit interaction between methanol and oxidized platinum electrodes

In the present work, results of the interaction between methanol and oxidized platinum surfaces as studied via transients of open-circuit potentials are presented. The surface oxidation before the exposure to interaction with 0.5 M methanol was performed at different polarization times at 1.4 V vs reversible hydrogen electrode (RHE). In spite of the small changes in the initial oxide content, the increase of the pre-polarization time induces a considerable increase of the time needed for the oxide consumption during its interaction with methanol. The influence of the identity of the chemisorbing anion on the transients was also investigated in the following media: 0.1 M HClO4, 0.5 M H2SO4, and 0.5 M H2SO4 + 0.1 mM Cl-. It was observed that the transient time increases with the energy of anion chemisorption and, more importantly, without a change in the shape of the transient, meaning that free platinum sites are available at the topmost layer all over the transient and not only in the potential region of small oxide `coverage`. The impact of the pre-polarization time and the effect of anion chemisorption on the transients are rationalized in terms of the presence of surface and subsurface oxygen driven by place exchange.

Seasonal Climatology of Hydrographic Conditions in the Upwelling Region Off Northern Chile

Over 30 years of hydrographic data from the northern Chile (18 degreesS-24 degreesS) upwelling region are used to calculate the surface and subsurface seasonal climatology extending 400 km offshore. The data are interpolated to a grid with sufficient spatial resolution to preserve cross-shelf gradients and then presented as means within four seasons: austral winter (July-September), spring (October-December), summer (January-March), and fall (April-June). Climatological monthly wind forcing, surface temperature, and sea level from three coastal stations indicate equatorward (upwelling favorable) winds throughout the year, weakest in the north. Seasonal maximum alongshore wind stress is in late spring and summer (December-March). Major water masses of the region are identified in climatological T-S plots and their sources and implied circulation discussed. Surface fields and vertical transects of temperature and salinity confirm that upwelling occurs year-round, strongest in summer and weakest in winter, bringing relatively fresh water to the surface nearshore. Surface geostrophic flow nearshore is equatorward throughout the year. During summer, an anticyclonic circulation feature in the north which extends to at least 200 m depth is evident in geopotential anomaly and in both temperature and geopotential variance fields. Subsurface fields indicate generally poleward flow throughout the year, strongest in an undercurrent near the coast. This undercurrent is strongest in summer and most persistent and organized in the south (south of 21 degreesS), A subsurface oxygen minimum, centered at similar to 250 m, is strongest at lower latitudes. Low-salinity subsurface water intrudes into the study area near 100 m, predominantly in offshore regions, strongest during summer and fall and in the southernmost portion of the region. The climatological fields are compared to features off Baja within the somewhat analogous California Current and to measurements from higher latitudes within the Chile-Peru Current system.