Correlation between structural and electronic changes during the oxidation of clean germanium surfaces
LEED pattern and germanium surface conductivity during oxidation indicating electron states annihilation
Feinstein, L. G.↗
SEARCH · Engineering Papers
Results for “surface oxidation”
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The surface energy of certain oxides, sulfides and selenides <poverkhnostnaya energiva nerotorykh okislov, sul'fidov i selenidov<
Surface energy of oxides, sulfides, and selenides
SELENIDE↗
Kinetics of the Heterogeneous Reaction CO + O = CO(sub 2) on Inorganic Oxide and Water Ice Surfaces: Implications for the Martian Atmosphere
The heterogeneous reaction CO + O - CO(sub 2) on water ice and varios inorganic oxide surfaces has been investigated in order to evaluate the proposition that this heterogeneous reaction may contribute to the CO(sub 2) stability in the Martian atmosphere.
heterogeneous reaction inorganic oxide martian atm↗
Mutual modulation between surface chemistry and bulk microstructure within secondary particles of nickel-rich layered oxides
Abstract Surface lattice reconstruction is commonly observed in nickel-rich layered oxide battery cathode materials, causing unsatisfactory high-voltage cycling performance. However, the interplay of the surface chemistry and the bulk microstructure remains largely unexplored due to the intrinsic structural complexity and the lack of integrated diagnostic tools for a thorough investigation at complementary length scales. Herein, by combining nano-resolution X-ray probes in both soft and hard X-ray regimes, we demonstrate correlative surface chemical mapping and bulk microstructure imaging over a single charged LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) secondary particle. We reveal that the sub-particle regions with more micro cracks are associated with more severe surface degradation. A mechanism of mutual modulation between the surface chemistry and the bulk microstructure is formulated based on our experimental observations and finite element modeling. Such a surface-to-bulk reaction coupling effect is fundamentally important for the design of the next generation battery cathode materials.
25 ENERGY STORAGE↗
Surface Integrity and Oxidation of a Powder Metallurgy Ni-Based Superalloy Treated by Laser Shock Peening
Laser shock peening is a mechanical surface treatment which can induce large compressive residual stresses and microstructural changes in the material by using repetitive shocks from laser pulses. In this work, the surface integrity (surface microstructure, topography, hardness and residual stress) of a laser shock peening treated powder metallurgy Ni-based superalloy was investigated. Laser shock peening treatment introduces large plastic deformation especially at a depth of about 100 μm from the surface, which increases the local hardness. The residual stress from the surface to the interior of the sample was investigated by synchrotron X-ray diffraction. The maximum compressive stress reaches 400 MPa at the surface, while the depth of the compressive stress is about 0.7 mm. Lastly, the oxidation behavior of the treated and untreated samples was evaluated by thermal exposure at 700°C for 312 h. The LSP treatment decreased the thickness of oxide layer, thereby showing improved oxidation resistance.
36 MATERIALS SCIENCE↗
Decadal Changes in Summertime Reactive Oxidized Nitrogen and Surface Ozone over the Southeast United States
Widespread efforts to abate ozone (O3) smog have significantly reduced emissions of nitrogen oxides (NOx) over the past 2 decades in the Southeast US, a place heavily influenced by both anthropogenic and biogenic emissions. How reactive nitrogen speciation responds to the reduction in NOx emissions in this region remains to be elucidated. Here we exploit aircraft measurements from ICARTT (International Consortium for Atmospheric Research on Transport and Transformation - July-August 2004), SENEX (Southeast Nexus - June-July 2013), and SEAC4RS (Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys - August-September 2013) and long-term ground measurement networks alongside a global chemistry-climate model to examine decadal changes in summertime reactive oxidized nitrogen (RON) and ozone over the Southeast US. We show that our model can reproduce the mean vertical profiles of major RON species and the total (NO (sub y)) in both 2004 and 2013. Among the major RON species, nitric acid (HNO3) is dominant (approximately 42-45 percent), followed by NOx (31 percent), total peroxy nitrates (Sigma PNs; 14 percent), and total alkyl nitrates (Sigma ANs; 9-12 percent) on a regional scale. We find that most RON species, including NOx, Sigma PNs, and HNO3, decline proportionally with decreasing NOx emissions in this region, leading to a similar decline in NO (sub y). This linear response might be in part due to the nearly constant summertime supply of biogenic VOC (Volatile Organic Compounds) emissions in this region. Our model captures the observed relative change in RON and surface ozone from 2004 to 2013. Model sensitivity tests indicate that further reductions of NOx emissions will lead to a continued decline in surface ozone and less frequent high-ozone events.
Li, Jingyi↗
Dynamic structural evolution of MgO-supported palladium catalysts: from metal to metal oxide nanoparticles to surface then subsurface atomically dispersed cations
Supported noble metal catalysts, ubiquitous in chemical technology, often undergo dynamic transformations between reduced and oxidized states—which influence the metal nuclearities, oxidation states, and catalytic properties.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Density Functional Theory Investigation of Oxidation Intermediates on Gold and Gold–Silver Surfaces
Gold and gold-silver alloys can be active and selective oxidation catalysts. Previous work has suggested that O 2 dissociation occurs at bimetallic step sites on gold-silver alloys, but the site responsible for the rest of the reaction steps has not been studied. As a first step in gaining insight into this issue, in this work we investigated the adsorption of oxygen and other oxidation intermediates on the (111) and (211) facets of gold-silver alloys using density functional theory. Oxygen and silver coverage effects were analyzed, and different model structures were compared. We also examined the energy barriers for the diffusion of atomic oxygen to gain insight into O migration and spillover. On (111) surfaces, O adsorption is much stronger at low O coverage (less than 0.22 ML), while on (211) surfaces O is strongly bound at both high and low O coverage. O diffusion across the step is faster than diffusion along the step. Ag stabilizes O, both when directly bound to it and when in an adjacent site. Ag also reduces repulsive O-O interactions at low O coverage. Our calculated reaction barriers for O-assisted CH 3 O dehydrogenation suggest that reaction is faster on steps than on terraces. Overall, our findings suggest that spillover of O from Ag-rich steps to Au-rich terraces does not occur, and that oxidation reactions on gold-silver alloys occurs on step sites. More specifically, oxidation likely occurs either on Ag-rich step sites or on Au-rich step sites that are adjacent to Ag-rich step sites.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Surface Area, and Oxidation Effects on Nitridation Kinetics of Silicon Powder Compacts
Commercially available silicon powders were wet-attrition-milled from 2 to 48 hr to achieve surface areas (SA's) ranging from 1.3 to 70 sq m/g. The surface area effects on the nitridation kinetics of silicon powder compacts were determined at 1250 or 1350 C for 4 hr. In addition, the influence of nitridation environment, and preoxidation on nitridation kinetics of a silicon powder of high surface area (approximately equals 63 sq m/g) was investigated. As the surface area increased, so did the percentage nitridation after 4 hr in N2 at 1250 or 1350 C. Silicon powders of high surface area (greater than 40 sq m/g) can be nitrided to greater than 70% at 1250 C in 4 hr. The nitridation kinetics of the high-surface-area powder compacts were significantly delayed by preoxidation treatment. Conversely, the nitridation environment had no significant influence on the nitridation kinetics of the same powder. Impurities present in the starting powder, and those accumulated during attrition milling, appeared to react with the silica layer on the surface of silicon particles to form a molten silicate layer, which provided a path for rapid diffusion of nitrogen and enhanced the nitridation kinetics of high surface area silicon powder.
Bhatt, R. T.↗
Amphilic Water-Lean Carbon Capture Solvent Wetting Behavior through Decomposition by Stainless-Steel Interfaces
In this work, we report on a combined experimental and theoretical study of the wetting and reactivity of water-lean carbon capture solvents on the surface of common column packing materials. Paradoxically, we find that these solvents are equally able to wet hydrophobic and hydrophilic surfaces. The solvents are amphiphilic and are able to adapt to any interfacial environment due to their inherent heterogeneous molecular structure. Ab initio molecular dynamics indicates that these structures enable the formation of a strong adlayer on the surface of hydrophilic surfaces like oxidized steel which promotes solvent decomposition akin to hydrolysis from surface oxides and hydroxides. This decomposition passivates the surface, making it effectively hydrophobic, and the decomposed solvent promotes leaching of the iron into the bulk fluid. This study links the wetting behavior to the observed corrosion of the steels via decomposition of solvent at steel interfaces. The overall affect is strongly dependent on the chemical composition of the solvent, in that amines are stable, whereas imines and alcohols are not. We also observed that plastic packing shows little to no solvent degradation, but an equal degree of wetting.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Surface engineering with oxidized Ti 3 C 2 T x MXene enables efficient and stable p-i-n-structured CsPbI 3 perovskite solar cells
All-inorganic CsPbI 3 perovskite has a near-ideal band gap, high thermal stability, and simple material composition, thus presenting a promising option for developing perovskite/Si tandem solar cells. However, CsPbI 3 undergoes a rapid phase transition under exposure to moisture and exhibits a significant performance gap relative to other perovskite compounds, particularly in the p-i-n structure favored for perovskite/Si tandems. In this work, we demonstrate highly efficient and stable p-i-n-structured CsPbI 3 perovskite solar cells by surface engineering the CsPbI 3 layer with oxidized Ti 3 C 2 T x MXene (OMXene) nanoplates via spray coatings. OMXene provides a physical barrier against moisture and improves charge separation at the perovskite-electron transporting layer interface via an enhanced electric field. Consequently, we demonstrated CsPbI 3 /OMXene-based p-i-n devices with efficiencies of 19.69% for 0.096-cm 2 cells and 14.64% for 25-cm 2 minimodules. The encapsulated minimodule showed good stability, retaining ~85% of the initial efficiency under simultaneous damp heat (85°C/85% relative humidity) and 1-sun light soaking for over 1,000 h.
14 SOLAR ENERGY↗
Prebiotic Oxidative Polymerization of 2,3 Dimercaptopropanol on the Surface of Iron(III) Hydroxide Oxide
The oxidation of 2,3-Dimercapto-1-propanol by ferric ions on the surface of iron (III) hydroxide oxide yielded polydisulfide polymers. This polymerization occured readily at low dithiol concentration under mild aqueous conditions. Polydisulfide polymers up to the 15-mer were synthesized from 1 mM dithiol in 5 ml water reacted with iron (III) hydroxide oxide (20 mg, 160 micro mole Fe) for 3 days under anaerobic conditions at 40 C and pH 4. About 91% of the dithiol was converted to short soluble oligomers and 9% to insoluble larger oligomers that were isolated with the mineral phase. Reactions at higher dithiol concentrations with the same ratio of dithiol to mineral gave a higher yield of the larger insoluble oligomers. The relationship of these results to prebiotic polymer synthesis will be discussed.
Weber, Arthur L.↗
Effects of size of an oxide layer on the surface properties of lithium irradiated by deuterium plasma
We investigate how growth of an oxide film will influence the deuterium recycling properties of Li on plasma facing surfaces. Lithium films on the walls or plasma-facing material surfaces of a fusion vacuum vessel improves plasma performance in part by removing residual impurity atoms from the plasma. Oxygen atoms, from residual water vapor or eroded oxide surfaces, are a prominent ubiquitous impurity that can create a layer of oxide on lithium films. The results of the work herein also indicate a possibility for determining the thickness of the oxide layer on such Li films by measuring the reflection probability of incident deuterium particles from the surface.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Enhancing the Carbon Monoxide Oxidation Performance through Surface Defect Enrichment of Ceria-Based Supports for Platinum Catalyst
Effective synthesis and application of single-atom catalysts on supports lacking enough defects remain a significant challenge in environmental catalysis. Herein, we present a universal defect-enrichment strategy to increase the surface defects of CeO 2 -based supports through H 2 reduction pretreatment. The Pt catalysts supported by defective CeO 2 -based supports, including CeO 2 , CeZrO x , and CeO 2 /Al 2 O 3 (CA), exhibit much higher Pt dispersion and CO oxidation activity upon reduction activation compared to their counterpart catalysts without defect enrichment. Specifically, Pt is present as embedded single atoms on the CA support with enriched surface defects (CA-HD) based on which the highly active catalyst showing embedded Pt clusters (Pt C ) with the bottom layer of Pt atoms substituting the Ce cations in the CeO 2 surface lattice can be obtained through reduction activation. Embedded PtC can better facilitate CO adsorption and promote O 2 activation at Pt C –CeO 2 interfaces, thereby contributing to the superior low-temperature CO oxidation activity of the Pt/CA-HD catalyst after activation.
36 MATERIALS SCIENCE↗
Tailoring the Surface of Metal Halide Perovskites to Enable the Atomic Layer Deposition of Metal Oxide Contacts
Replacing organic contact layers with inorganic counterparts, such as metal oxides, is one strategy for improving long-term device stability in metal halide perovskite solar cells. Often, the methods used to deposit metal oxide thin films are incompatible with metal halide perovskites, creating challenges for the fabrication of contacts above the perovskite absorber layer. In this study, we utilize a one-step, solution treatment of the top surface of Cs 0.25 FA 0.75 Pb(Br 0.20 I 0.80 ) 3 to create a thin (~1 nm) overlayer of lead sulfide (PbS) to protect the underlying perovskite during subsequent deposition. X-ray characterization of the surface region shows that the PbS overlayer limits undesirable changes to the perovskite structure and stoichiometry during atomic layer deposition (ALD) of SnO 2 . This protection enables ALD growth of SnO 2 electron contacts on top of the perovskite without an organic transport layer (e.g., C 60 ), resulting in a solar cell with a power conversion efficiency of 5.8%. This result is a marked improvement over devices with ALD SnO 2 grown directly on the perovskite without a PbS overlayer, which produce no power output. Furthermore, the interface characterization and device results in this study highlight some of the key challenges associated with ALD metal oxide growth on perovskite materials and can help inform the future design of inorganic contact layer deposition in solar photovoltaic technologies.
36 MATERIALS SCIENCE↗
Atomic Layer Deposition (ALD) of Metal and Metal Oxide Films: A Surface Science Study (Final Report)
This is the final report for this project. The long-term objective of our project is to develop a general molecular-level picture of the surface chemistry associated with ALD processes. Our central hypothesis is that the chemistry of ALD precursors can differ significantly from that seen in solution. Awareness of such differences should provide general guidelines on what to watch for when synthesizing new ALD precursors and designing and optimizing new ALD processes, especially in terms of minimizing the incorporation of impurities in the growing films and of carrying out depositions under mild pressure and temperature conditions. The main objective of our research project has been to advance the fundamental knowledge of the surface chemistry of ALD precursors needed for the design and optimization of film deposition processes. A modern surface-science approach has been implemented to both elucidate the mechanism of the reactions of the precursors on the surface and characterize the composition and morphology of the growing films. In general, emphasis is being placed on: • Identifying the primary reactions that may lead to the deposition of clean films; •Identifying the secondary reactions that may help the ALD process, by, for instance, helping with the reduction (or oxidation) of the metal atom; • Identifying the secondary reactions that may lead to the deposition of undesirable impurities in the growing films; • Determining the kinetic parameters of the relevant surface reactions in order to define the optimum conditions for film deposition and to minimize impurity deposition. • Characterizing the nature of the resulting films, with focus on their stoichiometry and on the final oxidation states of the constituent elements; and • Using the information obtained to propose better precursors for given ALD processes.
36 MATERIALS SCIENCE↗
Friction-induced surface activity of some hydrocarbons with clean and oxide-covered iron
Sliding friction studies were conducted on a clean and oxide-covered iron surface with exposure of that surface to various hydrocarbons. The hydrocarbons included ethane, ethylene ethyl chloride, methyl chloride, and vinyl chloride. Auger cylindrical mirror analysis was used to follow interactions of the hydrocarbon with the iron surface. Results with vinyl chloride indicate friction induced surface reactivity, adsorption to surface oxides, friction sensitivity to concentration and polymerization. Variation in the loads employed influence adsorption and accordingly friction. In contrast with ethyl and vinyl chloride, friction induced surface reactivity was not observed with ethane and ethylene.
Buckley, D. H.↗
Sputtering and native oxide formation on (110) surfaces of Cd(1-x)Mn(x)Te
Native oxides on the surface of Cd(1-x)Mn(x)Te (X between 0 and 0.7) have been analyzed on the basis of X-ray photoemission spectroscopy measurements. Depth profile analysis revealed a significant increase in the thickness at higher Mn concentrations and a strong Mn segregation to the surface, respectively. Sputter-induced damage on cleaved (110)-oriented surfaces was analyzed by photoreflectance and photoluminescence measurements. The damage was found to be larger on CdTe than on the alloy. Thermal annealing showed nearly complete restoration for the surface of the alloy, while CdTe revealed irreversible modifications in the near-surface regime upon sputtering and post annealing.
Neff, H.↗