Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “SURFACES”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Texture Analysis of Inconel 718 with Different Modes During Single-Track Laser Surface Re-Melting

An in-depth understanding of the texture formation in melt pools allows for the modification of the surface layer microstructure and corresponding material properties, providing an opportunity to integrate laser surface re-melting into metal additive manufacturing. This study investigates crystallographic texture formation at different cooling rates in single melting tracks on the Inconel 718 (IN718) plate produced by laser surface re-melting. The cooling rate varies from 2.31 × 10 5 °C/s to 9.56 × 10 5 °C/s with the increase in scanning rates from 400 mm/s to 1200 mm/s, measured by recently developed real-time temperature monitoring of melt pools. Columnar grains are dominant, with distinct crystallographic textures forming in the melt pools. At a slower scanning speed, the keyhole mode shows three different textures forming at different depths (crystallographically layered structure), while, at a faster scanning speed, the conduction mode shows only random grain orientation. There are no pores/voids detected, and the columnar grain morphology and columnar grain width (8.6 μm to 12.4 μm) follow the analysis framework in terms of thermal gradient and solidification rate analysis. This implies that laser surface re-melting provides the potential to modify the surface structure from a random grain orientation to a crystallographically layered structure.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Formation of Nano- and Micro-Scale Surface Features Induced by Long-Range Femtosecond Filament Laser Ablation

In this work, we study the characteristics of femtosecond-filament-laser–matter interactions and laser-induced periodic surface structures (LIPSS) at a beam-propagation distance up to 55 m. The quantification of the periodicity of filament-induced self-organized surface structures was accomplished by SEM and AFM measurements combined with the use of discrete two-dimensional fast Fourier transform (2D-FFT) analysis, at different filament propagation distances. The results show that the size of the nano-scale surface features increased with ongoing laser filament processing and, further, periodic ripples started to form in the ablation-spot center after irradiation with five spatially overlapping pulses. The effective number of irradiating filament pulses per spot area affected the developing surface texture, with the period of the low spatial frequency LIPSS reducing notably at a high pulse number. The high regularity of the filament-induced ripples was verified by the demonstration of the angle-of-incidence-dependent diffraction of sunlight. This work underlines the potential of long-range femtosecond filamentation for energy delivery at remote distances, with suppressed diffraction and long depth focus, which can be used in biomimetic laser surface engineering and remote-sensing applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Statistical Tool Size Study for Computer-Controlled Optical Surfacing

Over the past few decades, computer-controlled optical surfacing (CCOS) systems have become more deterministic. A target surface profile can be predictably achieved with a combination of tools of different sizes. However, deciding the optimal set of tool sizes that will achieve the target residual error in the shortest run time is difficult, and no general guidance has been proposed in the literature. In this paper, we present a computer-assisted study on choosing the proper tool size for a given surface error map. First, we propose that the characteristic frequency ratio (CFR) can be used as a general measure of the correction capability of a tool over a surface map. Second, the performance of different CFRs is quantitatively studied with a computer simulation by applying them to guide the tool size selection for polishing a large number of randomly generated surface maps with similar initial spatial frequencies and root mean square errors. Finally, we find that CFR = 0.75 achieves the most stable trade-off between the total run time and the number of iterations and thus can be used as a general criterion in tool size selection for CCOS processes. To the best of our knowledge, the CFR is the first criterion that ties tool size selection to overall efficiency.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Environmental Quenching of Low-surface-brightness Galaxies Near Hosts from Large Magellanic Cloud to Milky Way Mass Scales

Low-surface-brightness galaxies (LSBGs) are excellent probes of quenching and other environmental processes near massive galaxies. We study an extensive sample of LSBGs near massive hosts in the local universe that are distributed across a diverse range of environments. The LSBGs with surface-brightness ${\mu }_{\mathrm{eff},{g}}\gt 24.2\,\mathrm{mag}\,{\mathrm{arcsec}}^{-2}$ are drawn from the Dark Energy Survey Year 3 catalog while the hosts with masses $9.0\lt \mathrm{log}({{ \mathcal M }}_{\star }/{M}_{\odot })\lt 11.0$ comparable to the Milky Way and the Large Magellanic Cloud are selected from the z0MGS sample. We study the projected radial density profiles of LSBGs as a function of their color and surface brightness around hosts in both the rich Fornax–Eridanus cluster environment and the low-density field. We detect an overdensity with respect to the background density, out to 2.5 times the virial radius for both hosts in the cluster environment and the isolated field galaxies. When the LSBG sample is split by g − i color or surface brightness μ eff, g , we find the LSBGs closer to their hosts are significantly redder and brighter, like their high-surface-brightness counterparts. The LSBGs form a clear “red sequence” in both the cluster and isolated environments that is visible beyond the virial radius of the hosts. This suggests preprocessing of infalling LSBGs and a quenched backsplash population around both host samples. More so, the relative prominence of the “blue cloud” feature implies that preprocessing is ongoing near the isolated hosts compared to the cluster environment where the LSBGs are already well processed.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

A globally sampled high-resolution hand-labeled validation dataset for evaluating surface water extent maps

Effective monitoring of global water resources is increasingly critical due to climate change and population growth. Advancements in remote sensing technology, specifically in spatial, spectral, and temporal resolutions, are revolutionizing water resource monitoring, leading to more frequent and high-quality surface water extent maps using various techniques such as traditional image processing and machine learning algorithms. However, satellite imagery datasets contain trade-offs that result in inconsistencies in performance, such as disparities in measurement principles between optical (e.g., Sentinel-2) and radar (e.g., Sentinel-1) sensors and differences in spatial and spectral resolutions among optical sensors. Therefore, developing accurate and robust surface water mapping solutions requires independent validations from multiple datasets to identify potential biases within the imagery and algorithms. However, high-quality validation datasets are expensive to build, and few contain information on water resources. For this purpose, we introduce a globally sampled, high-spatial-resolution dataset labeled using 3 m PlanetScope imagery. Our surface water extent dataset comprises 100 images, each with a size of 1024×1024 pixels, which were sampled using a stratified random sampling strategy covering all 14 biomes. We highlighted urban and rural regions, lakes, and rivers, including braided rivers and coastal regions. We evaluated two surface water extent mapping methods using our dataset – Dynamic World, based on Sentinel-2, and the NASA IMPACT model, based on Sentinel-1. Dynamic World achieved a mean intersection over union (IoU) of 72.16 % and F1 score of 79.70 %, while the NASA IMPACT model had a mean IoU of 57.61 % and F1 score of 65.79 %. Performance varied substantially across biomes, highlighting the importance of evaluating models on diverse landscapes to assess their generalizability and robustness. Our dataset can be used to analyze satellite products and methods, providing insights into their advantages and drawbacks. Our dataset offers a unique tool for analyzing satellite products, aiding the development of more accurate and robust surface water monitoring solutions. The dataset can be accessed via https://doi.org/10.25739/03nt-4f29.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Quantifying the impacts of atmospheric rivers on the surface energy budget of the Arctic based on reanalysis

We present a comprehensive analysis of Arctic surface energy budget (SEB) components during atmospheric river (AR) events identified by integrated water vapor transport exceeding the monthly 85th-percentile climatological threshold in 3-hourly ERA5 reanalysis data from January 1980 to December 2019. Analysis of average anomalies in SEB components, net SEB, and the overall AR contribution to both the seasonal SEB components and net SEB climatology reveals clear seasonality and distinct land–sea–sea ice contrast patterns. Over the sea-ice-covered central Arctic Ocean, ARs significantly impact net SEB, inducing substantial surface warming in fall, winter, and spring. This warming is primarily driven by large anomalies in surface downward longwave radiation (LWD), which average 29–45 W m −2 during the cold seasons. In contrast, AR-related LWD anomalies are smaller in summer, averaging around 15 W m −2 , indicating a reduced impact during this season. Over sub-polar oceans, ARs have the most substantial positive impact on net SEB in cold seasons, mainly attributed to significant positive turbulent heat flux anomalies. AR-related turbulent heat anomalies reduce the upward turbulent flux, contributing up to −11 % relative to its seasonal climatology. In summer, ARs induce negative impacts on net SEB, primarily due to reduced shortwave radiation from increased cloud cover during AR events. Over continents, ARs generate smaller absolute impacts on net SEB because the large LWD anomalies are largely offset by corresponding increases in upward longwave radiation, particularly during cold seasons. Additionally, the seemingly large relative contributions of ARs to the net SEB over land primarily reflects the small magnitude of the climatological net SEB over continents. Greenland, especially western Greenland, exhibits significant downward longwave radiation anomalies associated with ARs, which drive large net SEB anomalies and contribute >54 % to mean SEB and induce amplified surface warming year-round. This holds significance for melt events, particularly during summer. Additionally, results of AR-related SEB impacts strongly depend on detection methods, as restrictive AR detection algorithms that emphasize extreme AR events, with large AR-related anomalies, do not necessarily indicate a large overall contribution to the SEB climatology due to the low occurrence frequency of these events. This study quantifies the role of ARs in the surface energy budget, contributing to our understanding of the Arctic warming and sea ice decline in ongoing Arctic amplification.

Arctic Sea ice change↗
DOE OSTI2021

Processed Surface Imagery & Raster Imagery taken onboard TigerShark (U3) UAS

Land-surface orthomosaic imagery derived from the images collected using the Micasense Altum Imager on board the UAS TigerShark (U3) on March 11th, 2021 at an altitude of 2000 ft. The Altum takes images of the land surface across five visible bands and one long wave infrared thermal band. The photogrametry software Agisoft PhotoScan v 1.4 is used to align and stitch the images into a larger composet image using the technique of structure from motion image capture to construct a dense cloud and 3-D model of the surface, which is used to produce a digital elevation model of the terraine surveyed and orthomosaic imagery. This dataset contains the raster calculated orthomosaics of various vegetative indicies, which are used to indicate plant health and land surface characteristics, including Normalized Difference Vegetation Index (NDVI), Green Normalized Difference Vegetation Index (GNDVI), Normalized Difference Water Index (NDWI), surface temperature, and Enhanced_vegetation_index (EVI). These orthomosaics were collected west of the Starkville, MS, airport, and include natural, agricultural, and industrial land coverage. The images have a resolution of 0.2 m/pix.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Technoeconomic Benefits of Film-Forming Amine Products Applied to Steam Surface Condensers

In a conventional Rankine cycle, the majority of power plants employ surface condensers that use pumped cooling water to reject heat from the cycle. In such cases, heat rejection occurs in a shell and tube heat exchanger by film-wise condensation of low-pressure steam on stainless steel, titanium, brass, or copper-nickel tubing. To improve the thermal performance of steam surface condensers, a replenishable film-forming substance (FFS) can be ap-plied to the condenser tubing to promote efficient dropwise condensation. Conventionally, film-forming amine prod-uct (FFAP) coatings protect boiler surfaces from oxidative corrosion, which substantially reduces the operation and maintenance costs. To quantify the technical and economic benefits of FFAP coatings applied to condenser tubing due to the promotion of dropwise condensation, a thermal resistance network model was established. Using a rep-resentative steam surface condenser, the improvements in thermal performance (overall heat transfer coefficient) and process parameters (net plant efficiency, cooling water flowrate, and turbine backpressure) were determined due to the enhancement in the condensation heat transfer coefficient. Experimentally measured condensation heat transfer coefficients for common condenser materials were compared with the modeling results and were found to be within attainable bounds. Lastly, the trend in total heat exchanger cost reduction is generalized to understand the trade-off between reduced surface area for heat rejection and increase in coating application costs for a re-plenishable coating system.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2026

WHONDRS Surface Water and Sediment Geochemistry and Organic Matter Characterization Data from Streams across HJ Andrews Experimental Forest, Oregon (v2)

This dataset supports a broader study developing conceptual models for river corridor critical zone processes across spatial scales and was generated in collaboration with the HJ Andrews River Corridor Critical Zone Workshop in 2025. The dataset provides surface water geochemistry (dissolved organic carbon, total dissolved nitrogen) from 48 sites across the HJ Andrews Experimental Forest, Oregon (https://andrewsforest.oregonstate.edu). Some of the sites have been impacted by the Holiday Farm Fire and the Lookout Fire in 2020 and 2023, respectively. Related data were collected as part of the workshop and will be published separately in collaboration with other workshop attendees and available at http://www.hydroshare.org/resource/b274c4a234bf4b12b7cb8a54a696c629. Related genomic data can be found on the National Center for Biotechnology Information (NCBI) under BioProject PRJNA1503030 (see critical details section below for more information). Additional related data collected in 2016 from a similar effort can be found at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/3377027 and http://www.hydroshare.org/resource/ea6c0832885a46c3939e7bb22e48e754 and are described within https://doi.org/10.5194/essd-11-1-2019 (Ward et al., 2019). This data package was originally published in March 2026. It was updated in August 2026 (v2; new and modified files). See the change history section in the readme for more details. For details on how to navigate data packages generated by this project, see https://data.ess-dive.lbl.gov/portals/PNNLRiverCorridorSFA/About. In addition to a readme, this data package also includes a file-level metadata (FLMD) file that describes each file and a data dictionary (DD) that describes all column/row headers and variable definitions. This dataset is comprised of (1) a folder of field photos, (2) a folder of raw Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) data, (3) a data checks report, (4) a folder of sample data, (5) file-level metadata, (6) data dictionary, (7) field metadata, (8) readme, (9) international generic sample number (IGSN) mapping file; and (10) field protocol. The sample data subfolder contains surface water and sediment (1) dissolved organic carbon (DOC, measured as non-purgeable organic carbon, NPOC) data and averages, (2) total dissolved nitrogen data and averages, (3) methods codes, (4) FTICR-MS methods; and (5) a subfolder of 9.4 Tesla (9.4T) FTICR-MS data. This folder contains the CoreMS processed data and seven subfolders, thee containing .xml files for each sample type (sediment, surface water and blank samples), three containing the sediment CoreMS output files for each sample type (sediment, surface water and blank samples), and the other containing instructions and scripts for processing the files in CoreMS (https://github.com/EMSL-Computing/CoreMS). All files are .csv, .pdf, .R, .xml, .Rmd, .py, .cal, .json, .jpg, or .jpeg.

Biogeochemistry↗
DOE OSTI2021

The Role of Titania Surface Coating by Atomic Layer Deposition in Improving Osteogenic Differentiation and Hard Tissue Formation of Dental Pulp Stem Cells

Recent studies have focused on modifying implant surface properties to improve bone regeneration and osseointegration. Herein, the role of titania surface coating in enabling dental pulp stem cells (DPSCs) differentiation and hard tissue formation is studied. Atomic layer deposition is applied at lower temperature to coat a nanolayer of titania onto hard and soft polybutadiene substrates without altering their moduli, to probe the effects of surface chemistry and substrate modulus. In the absence of titania, DPSCs prefer to attach and proliferate on the hard substrate, where particle-like biomineralization is present after 28 days in culture, whereas no biomineralization is observed on the soft substrate. Applying titania surface coating results in the improvement of adhesion and proliferation, regardless of substrate modulus, whereas cell and substrate moduli remain the same as control without titania coating. Furthermore, templated biomineralization is observed given the bone-like tissue composition by Raman analysis, in consistent with real time-polymerase chain reaction (RT-PCR) results showing upregulation of osteopontin (OPN) and bone sialoprotein (BSP), representing osteogenic differentiation. Furthermore, the results indicate that titania surface coating improved the ability to nucleate banded collagen fibers which in turn templated mineral deposits, and further induced the osteogenesis of DPSCs, regardless of its substrate modulus.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Surface Ligand Management Aided by a Secondary Amine Enables Increased Synthesis Yield of CsPbI 3 Perovskite Quantum Dots and High Photovoltaic Performance

Lead-halide perovskite quantum dots (PQDs) or more broadly, nanocrystals possess advantageous features for solution-processed photovoltaic devices. The nanocrystal surface ligands play a crucial role in the transport of photogenerated carriers and ultimately affect the overall performance of PQD solar cells. Here, significantly improved CsPbI 3 PQD synthetic yield and solar-cell performance through surface ligand management are demonstrated. The treatment of a secondary amine, di- n -propylamine (DPA), provides a mild and efficient approach to control the surface ligand density of PQDs, which has an apparently different working mechanism compared to previously reported surface treatments. Using an optimal DPA concentration, the treatment can simultaneously remove both long-chain insulating surface ligands of oleic acid and oleylamine, even for unpurified PQDs with high ligand density. As a result, the electrical coupling between PQDs is enhanced, leading to improved charge transport, reduced carrier recombination, and a high power conversion efficiency approaching 15% for CsPbI 3 -PQD-based solar cells. In addition, the production yield of CsPbI 3 PQDs can be increased by a factor of 8. These results highlight the importance of developing new ligand-management strategies, specifically for emerging PQDs to achieve scalable and high-performance perovskite-based optoelectronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Mechanistic Insights into the Surface Instabilities of TiNb 2 O 7, a High‐Power Li‐Ion Anode

TiNb 2 O 7 (TNO) is a promising Li-ion battery anode for high-power applications, such as implantable medical devices and heavy-duty equipment. Hailed as being safe due to its elevated operating potential near 1.6 V, TNO has long been assumed to be highly stable in the carbonate-based electrolytes used in Li-ion batteries. Herein, all mechanisms occurring at the surface of both TNO and Nd-doped TNO are identified, and both materials in fact show significant gassing. CO 2 is even released at open circuit conditions, demonstrating the poor chemical stability of the material in the electrolyte even prior to battery operation. Such extreme instability is a critical safety concern. In addition, it was found that Ti dissolves from the surface of TNO particles at low voltage (below 1.4 V vs Li), and in fact deposits on the counter electrode. Ti further inside TNO particles then diffuses to the Ti-poor surface during discharge. Partial carbon-coating as a mitigating measure has also been tested and found to exacerbate these processes. The findings identify novel reactions occurring within TNO, and clearly highlight the need to stabilize the surfaces of TNO in order to prevent such aggressive deterioration at the surface of the particles.

25 ENERGY STORAGE↗
DOE OSTI2021

Facilitating Large‐Scale Snow Shedding from In‐Field Solar Arrays using Icephobic Surfaces with Low‐Interfacial Toughness

Abstract Large‐scale accrual of snow and ice on solar arrays in northern latitudes can cause significant power generation losses during winter. Depending on environmental conditions, snow can encompass a wide range in physical characteristics from dry snow (modulus ≈100 kPa and density ≈0.1 g cm −3 ) to bulk ice (modulus ≈8 GPa and density ≈0.9 g cm −3 ). This variation in snow morphology has made the development of a passive, broad‐spectrum, snow and ice‐shedding surface challenging. Here, the authors develop one of the first surfaces that simultaneously possesses both low‐interfacial strength ( τ˄ ice < 50 kPa) and toughness (Γ ice < 0.5 J m −2 ) with ice. These surfaces, fabricated via the addition of mobile polymer chains/oils to a thin polymeric coating, require extremely low detachment forces for ice, enabling its passive shedding at virtually any accretion length scale. Preliminary evidence that the new surfaces can shed different forms of snow and ice from field‐deployed solar arrays, over a range of subzero temperatures for several weeks, leading to significant increases in power generation is provided. The optically transparent surfaces are easily scalable and can be widely deployed by the solar industry in areas that see persistent snow. Other applications include automotive windshields, LIDAR covers for autonomous vehicles, and cold climate optical sensors.

Dhyani, Abhishek↗
DOE OSTI2020

Squeezing a Prism into a Surface: Emulating Bulk Optics with Achromatic Metasurfaces

Metasurfaces promise to replace bulky prisms and lenses with 2D surfaces, revolutionizing wavefront control with technologically significant advantages in size, weight, and planar fabrication. However, conventional implementations suffer from large chromatic aberrations and cannot sustain performance over practical bandwidths of real-world signals because of the limited phase modulation margin available in a surface. How can an infinitely thin surface generate the arbitrarily large, broadband phase delay that bulk phase accumulation can provide? Here, equivalence between bulk optics and certain multiresonant metasurfaces is demonstrated, where phase delay arises from trains of multiple resonances in the effective sheet conductivities of the surface itself instead of accumulation of propagation phase. The fundamentally required electromagnetic surface conductivities of a purely achromatic metasurface are derived and general design rules for arbitrarily broadband beam steering and lensing are obtained. Both operation in transmission and reflection can be achieved in a unified way by proper alignment of the resonances, enabling 360° directionality. The arbitrary spectral bandwidth, dual reflection/transmission operation, and complete dispensability of propagation phase constitute a major advance in the state of the art of achromatic metasurfaces for wavefront manipulation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

An In Situ Formed Surface Coating Layer Enabling LiCoO 2 with Stable 4.6 V High‐Voltage Cycle Performances

Abstract The development of high‐voltage LiCoO 2 is essential for achieving lithium‐ion batteries with high volumetric energy density, however, it faces a great deal of challenges owing to the materials, structure and interfacial instability issues. In this work, a strategy is developed, through heat annealing a precoated surface layer to in situ form a high‐voltage‐stable surface coating layer, which is demonstrated to be highly effective to improve the high‐voltage performance of LiCoO 2 . It is discovered that LiCoO 2 reacts with Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 (LATP) at 700 °C to form exclusively spinel phases in addition to Li 3 PO 4 , which are structurally coherent to the layered lattice of LiCoO 2 . The heat annealing of the precoated thin layer of LATP enables the formation of a high‐quality surface layer. Spinel phases possess high‐voltage‐stable structures with much weaker oxidizing ability of lattice oxygen than layered structure. In addition, the Li 3 PO 4 is a good lithium‐ion conductor with excellent chemical stability at high voltages. All these benefits contribute to the construction of a uniform and conformal high‐voltage‐stable surface layer with favorable lithium conducting kinetics at the LiCoO 2 surface. The modified LiCoO 2 shows excellent 4.6 V high‐voltage cycle performance at both room temperature and 45 °C. The thermal stability is greatly enhanced as well.

Wang, Yi↗
DOE OSTI2021

Effects of surface species and homogeneous reactions on rates and selectivity in ethane oxidation on oxide catalysts

Selective alkane oxidations on metal oxide catalysts involve complex mechanisms with multiple reactions in series and parallel, different types of reduced and oxidized surface species, and potential contributions from gas-phase reactions. We report kinetics and thermodynamics of elementary steps involved in C 2 H 6 -O 2 reactions on SiO 2 -supported small vanadium oxide domains are determined using density functional theory. These surface reactions together with gas-phase mechanisms are incorporated in kinetic simulations to determine how surface and gaseous reactions interact and contribute to rates and selectivity. The results show that gas-phase reactions within pore volumes in contact with the catalyst contribute significantly to C 2 H 6 activation rates, even at conditions where gas-phase reactions in empty volumes without catalyst are negligible. The majority of C 2 H 6 activations occur on the surface, via H abstraction by vanadium oxo species present at terminal lattice oxygens. The gas-phase activations via H-abstraction by OH radicals also exhibit significant contributions. The reduced centers formed by reactions at vanadium oxo species are re-oxidized rapidly and, therefore, are present in very small concentrations at reaction conditions. The re-oxidation steps lead to the formation of HO 2 radicals and surface peroxo species that are also rapidly consumed and are present in small concentrations. The peroxo species preferentially convert C 2 H 4 to its epoxide product and influence selectivity even at low concentrations. The gas-phase reactions decrease the concentrations of peroxo species and improve selectivity slightly. The effects of reaction conditions and catalyst site density provide further insights into how factors beyond conversions at lattice oxygens influence rates and selectivity in alkane oxidation reactions of significant industrial importance.

42 ENGINEERING↗
DOE OSTI2020

Real-time Atomic-scale Visualization of Reversible Copper Surface Activation during the CO Oxidation Reaction

Dynamic structural and chemical information of catalyst surface during a catalytic reaction is critical for deciphering the mechanisms governing the properties of catalysts. Transition-metal based catalysts have emerged as an important alternative to noble metal catalysts, but their catalytic mechanism remains largely elusive, complicated by dynamic structure and valence evolution. Herein, by using in situ aberration-corrected environmental transmission electron microscopy, we capture, for the first time at atomic level, the dynamic evolution of Cu surface during CO oxidation reaction. We discovered that, under reaction condition, the Cu surface is activated, typically involving 2-3 atomic layers with the formation of a reversible meta-stable phase that only exists during catalytic reactions. Further, we reveal the distinctive role of CO and O2 in the surface activation, featuring CO exposure to lead to surface roughening and consequently formation of low-coordinated Cu atoms, while O2 exposure to induce quasi-crystalline CuOx phase. Corrugated by DFT calculations, we rationalize crystalline CuOx reversibly transforms into the amorphous phase, acting as an active species to facilitate the interaction of gas reactants and catalyzing CO oxidation.

Luo, Langli↗
DOE OSTI2023

Resolving the Heat Generated from ZrO 2 Atomic Layer Deposition Surface Reactions

Abstract In situ pyroelectric calorimetry and spectroscopic ellipsometry were used to investigate surface reactions in atomic layer deposition (ALD) of zirconium oxide (ZrO 2 ). Calibrated and time‐resolved in situ ALD calorimetry provides new insights into the thermodynamics and kinetics of saturating surface reactions for tetrakis(dimethylamino)zirconium(IV) (TDMAZr) and water. The net ALD reaction heat ranged from 0.197 mJ cm −2 at 76 °C to 0.155 mJ cm −2 at 158 °C, corresponding to an average of 4.0 eV/Zr at all temperatures. A temperature dependence for reaction kinetics was not resolved over the range investigated. The temperature dependence of net reaction heat and distribution among metalorganic and oxygen source exposure is attributed to factors including growth rate, equilibrium surface hydroxylation, and the extent of the reaction. ZrO 2 ‐forming surface reactions were investigated computationally using DFT methods to better understand the influence of surface hydration on reaction thermodynamics.

Bielinski, Ashley R.↗