Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “surface transformation”

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 1,027 records · Page 57
All sourcesNASA NTRSDOE OSTI
NASA NTRS2006

The Application of Satellite-Derived, High-Resolution Land Use/Land Cover Data to Improve Urban Air Quality Model Forecasts

Local and state agencies are responsible for developing state implementation plans to meet National Ambient Air Quality Standards. Numerical models used for this purpose simulate the transport and transformation of criteria pollutants and their precursors. The specification of land use/land cover (LULC) plays an important role in controlling modeled surface meteorology and emissions. NASA researchers have worked with partners and Atlanta stakeholders to incorporate an improved high-resolution LULC dataset for the Atlanta area within their modeling system and to assess meteorological and air quality impacts of Urban Heat Island (UHI) mitigation strategies. The new LULC dataset provides a more accurate representation of land use, has the potential to improve model accuracy, and facilitates prediction of LULC changes. Use of the new LULC dataset for two summertime episodes improved meteorological forecasts, with an existing daytime cold bias of approx. equal to 3 C reduced by 30%. Model performance for ozone prediction did not show improvement. In addition, LULC changes due to Atlanta area urbanization were predicted through 2030, for which model simulations predict higher urban air temperatures. The incorporation of UHI mitigation strategies partially offset this warming trend. The data and modeling methods used are generally applicable to other U.S. cities.

Quattrochi, D. A.↗
NASA NTRS1987

General technique for the integration of MIC/MMIC'S with waveguides

A technique for packaging and integrating of a microwave integrated circuit (MIC) or monolithic microwave integrated circuit (MMIC) with a waveguide uses a printed conductive circuit pattern on a dielectric substrate to transform impedance and mode of propagation between the MIC/MMIC and the waveguide. The virtually coplanar circuit pattern lies on an equipotential surface within the waveguide and therefore makes possible single or dual polarized mode structures.

Geller, Bernard D.↗
NASA NTRS2009

Heavy Ion Formation in Titan's Ionosphere: Magnetospheric Introduction of Free Oxygen and a Source of Titan's Aerosols?

Discovery by Cassini's plasma instrument of heavy positive and negative ions within Titan's upper atmosphere and ionosphere has advanced our understanding of ion neutral chemistry within Titan's upper atmosphere, primarily composed of molecular nitrogen, with approx.2.5% methane. The external energy flux transforms Titan's upper atmosphere and ionosphere into a medium rich in complex hydrocarbons, nitriles and haze particles extending from the surface to 1200 km altitudes. The energy sources are solar UV, solar X-rays, Saturn's magnetospheric ions and electrons, solar wind and shocked magnetosheath ions and electrons, galactic cosmic rays (CCR) and the ablation of incident meteoritic dust from Enceladus' E-ring and interplanetary medium. Here it is proposed that the heavy atmospheric ions detected in situ by Cassini for heights >950 km, are the likely seed particles for aerosols detected by the Huygens probe for altitudes <100km. These seed particles may be in the form of polycyclic aromatic hydrocarbons (PAH) containing both carbon and hydrogen atoms CnHx. There could also be hollow shells of carbon atoms, such as C60, called fullerenes which contain no hydrogen. The fullerenes may compose a significant fraction of the seed particles with PAHs contributing the rest. As shown by Cassini, the upper atmosphere is bombarded by magnetospheric plasma composed of protons, H(2+) and water group ions. The latter provide keV oxygen, hydroxyl and water ions to Titan's upper atmosphere and can become trapped within the fullerene molecules and ions. Pickup keV N(2+), N(+) and CH(4+) can also be implanted inside of fullerenes. Attachment of oxygen ions to PAH molecules is uncertain, but following thermalization O(+) can interact with abundant CH4 contributing to the CO and CO2 observed in Titan's atmosphere. If an exogenic keV O(+) ion is implanted into the haze particles, it could become free oxygen within those aerosols that eventually fall onto Titan's surface. The process of freeing oxygen within aerosols could be driven by cosmic ray interactions with aerosols at all heights. This process could drive pre-biotic chemistry within the descending aerosols. Cosmic ray interactions with grains at the surface, including water frost depositing on grains from cryovolcanism, would further add to abundance of trapped free oxygen. Pre-biotic chemistry could arise within surface microcosms of the composite organic-ice grains, in part driven by free oxygen in the presence of organics and any heat sources, thereby raising the astrobiological potential for microscopic equivalents of Darwin's "warm ponds" on Titan.

Sittler, E. C., Jr.↗
DOE OSTI2026

Chemical and Radiological Compatibility Testing of 3D Printed Materials

To dramatically increase the adaptability, performance, and safety of processes in support of the Defense Waste Processing Facility (DWPF), Savannah River National Lab (SRNL) plans to perform chemical and radiological compatibility testing on a wide variety of 3D printed materials of interest. The 3D printing process provides numerous strategic operational benefits such as rapid prototyping of complex designs and geometry specific to the needs of the nuclear waste disposition process, as well as on-demand rapid prototyping and iteration with materials that aren’t as accessible through traditional manufacturing methods. Reaction chemistry in simulated waste batches can be matched closely to its radioactive counterpart, but glass reactor vessels have limitations. Vessel geometry can play a big factor in mixing transport limitations, process chemistry, and degradation reaction kinetics. In addition, additive manufacturing allows for much more detailed vessel design than traditional alternatives. Waste processing techniques in DWPF also encounter extreme chemical environments including high pH, strong acids, abrasive slurries, and significant irradiation. To meet these challenges, a matrix of various polymer, ceramic, and metal additive manufacturing materials have been exposed to a suite of chemical environments of interest as well as radioactive dose (such as gamma radiation from 60 Co) to properly test their durability under these conditions. Mass change has been monitored over a period of up to a week in these conditions, as well as added characterization for surface modification through Scanning Electron Microscopy/Electron Dispersive X-ray analysis (SEM/EDX). Further chemical characterization has been monitored through Fourier-Transform InfraRed Spectroscopy (FTIR), with planned investigation via thermal and tensile strength degradation. While the direct product of this research is identification of material(s) that can withstand specific hazardous environments encountered by the mercury water wash tank in DWPF process simulation experiments, the reference base of materials will be used for many other nuclear processes in the pursuit of rapidly developed, cost-efficient, and highly specific devices for environmental remediation and much more.

Wilson, Nathan W. [Savannah River National Laborat↗
DOE OSTI2022

Improving Non-Destructive Detection Technology Through SAVY Feature Detection

Surveillance of special nuclear material (SNM) storage containers is required by the DOE to assess their integrity across the Complex. This work aims to improve the task of container inspections by leveraging automation through machine learning (ML) tools to reduce the human-intensive effort and expert-level knowledge needed to assess container status. A field-deployable, non-destructive technology was designed using off-the-shelf components to collect multiple images from different perspectives of containers in storage to detect both spatial features of interest and anomalies of concern. Nine ML models were generated using unique training datasets and parameters. Learned features include SAVY surface regions including the body side wall, collar, lid, filter, and printed/etched information. Average Precision (AP) is used to calculate detection performance when both viewing previously seen environments and previously unseen environments. The application of image transformations and resolution scaling while training greatly improved the detection performance in unseen environments, and significantly increasing the number of computation iterations improved detection performance on previously seen environments. Additional capabilities were developed including the novel detection of procedural non-compliance and the ability to localize anomalies relative to SAVY surface features.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Surface Oxidation Behavior of FeNi-based Metal Amorphous Nanocomposite (MANC) Alloys for High-Speed Motor Applications

New interest in high performance soft magnetic materials (SMMs) have been fueled by the need to lower losses at higher operating frequencies while maintaining high flux density and tunable permeability in electrical motors, transformer, and generator applications. Conventional SMMs like electrical steels and Fe-based metal amorphous nanocomposite (MANC) alloys are dominated by eddy current losses at high frequencies. Recent breakthrough in high-performance FeNi MANC have shown promise in reducing eddy current losses as compared to electrical steels. Their intrinsic adherent native surface oxide layer provides sufficient electrical insulation to reduce interlaminate eddy current losses. However, notwithstanding advances in MANCs, there exists a gap in literature on investigations of the surface oxide layer responsible for significant reduction of interlaminate eddy current losses in magnetic cores. This work presents a detailed characterization of the surface oxide, oxidation behavior, and relationship between oxide thickness and resistivity of a new FeNi MANC alloy (Fe70Ni30)80Nb4B14Si2.

Egbu, James↗
DOE OSTI2020

Consequences of long-term water exposure for bulk crystal structure and surface composition/chemistry of nickel-rich layered oxide materials for Li-ion batteries

Water exposure of layered nickel-rich transition metal oxide electrodes, widely used in high-energy lithium-ion batteries, has detrimental effects on the electrochemical performance, which complicates electrode handling and prevents implementation of environmentally benign aqueous processing procedures. Elucidating the degradation mechanisms in play may help rationally mitigate/circumvent key challenges. Here, the bulk structural consequences of long-term (>2.5 years) deuterated water (D2O) exposure of intercalation materials with compositions Li x Ni 0.5 Co 0.2 Mn 0.3 O 2 (NCM523) and Li x Ni 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) are studied by neutron powder diffraction (NPD). Detailed inspection of the NPD data reveals gradual formation of a secondary crystalline phase in all exposed samples, not previously reported for this system. This unknown phase forms faster in liquid- compared to vapor-exposed compounds. Structural modelling of the NPD data shows a stable level of Li/Ni anti-site defects and does not indicate any significant changes in lattice parameters or hydrogen-lithium (D + /Li + ) exchange in the structure. Consequently, the secondary phase formation must take place via transformation rather than modification of the parent material. X-ray photoelectron spectroscopy data indicate formation of LiHCO 3 /Li 2 CO 3 at the surface and a Li-deficient oxide in the sub-surface region of the pristine compounds, and the presence of adsorbed water and transition metal hydroxides at the exposed sample surfaces.

25 ENERGY STORAGE↗
DOE OSTI2021

Iron(II) monosulfide (FeS) minerals reductively transform the insensitive munitions compounds 2,4-dinitroanisole (DNAN) and 3-nitro-1,2,4-triazol-5-one (NTO)

As military applications of the insensitive munitions compounds (IMCs) 2,4-dinitroanisole (DNAN) and 3-nitro-1,2,4-triazol-5-one (NTO) increase, there is a growing need to understand their environmental fate and to develop remediation strategies to mitigate their impacts. Iron (II) monosulfide (FeS) minerals are abundant in freshwater and marine sediments, marshes, and hydrothermal environments. Here, this study shows that FeS solids can reduce DNAN and NTO to their corresponding amines under anoxic ambient conditions. The reactions between IMCs and the FeS minerals were surface-mediated since they did not occur when only dissolved Fe 2+ (aq) and S 2– (aq) were present. Mackinawite, a tetragonal FeS with a layered structure, reduced DNAN mainly to 2-methoxy-5-nitroaniline (MENA), which in turn was partially reduced to 2-4-diaminoanisole (DAAN). The layered structure of mackinawite provided intercalation sites likely responsible for partial adsorption of MENA and DAAN. Mackinawite entirely reduced NTO to 3-amino-1,2,4-triazol-5-one (ATO). The reduction of IMCs showed concurrent oxidation of mackinawite to goethite and elemental sulfur. A commercial FeS product, composed mainly of pyrrhotite and troilite, reduced DNAN to DAAN and NTO to ATO. At pH 6.5, DNAN and NTO transformation rates were 667 and 912 μmol h –1 m –2 , respectively, on the mackinawite surface and 417 and 1344 μmol h –1 m –2 , respectively, on the commercial FeS surface. This is the first report of the reduction of a nitro-heterocyclic compound (NTO) by FeS minerals. The evidence indicates that DNAN and NTO can be rapidly transformed to their succeeding amines in anoxic subsurface environments and aquatic sediments rich in FeS minerals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Effect of amine type on acidic toxic gas adsorption at ambient conditions on modified CuBTC

We report two amine-modified copper-based Metal Organic Frameworks (MOF (CuBTC)) of different surface chemical and textural features were synthesized and used as adsorbents of acidic toxic gases (NO 2 and H 2 S) in both moist (71% relative humidity (R.H.)) and dry conditions. The initial and exhausted samples were characterized by nitrogen adsorption, powder X-ray diffraction, scanning electron microscopy, thermal gravimetric analysis and Fourier transform infrared spectroscopy. The addition of melamine prevented full growth of CuBTC crystals and resulted in amorphous-like particles with sizes less than 200 nm. The material was non-porous with a small surface area. When urea was used as an amine source, the resulting particles maintained the overall octahedral shape of the parent CuBTC MOF and the material was more porous than the parent MOF. While the urea-modified CuBTC sample performed well as an NO 2 adsorbent in the presence of moisture, the reactivity of the melamine-modified sample and its physical properties provided a favorable environment for the removal of H 2 S. The incorporation of amines into the MOF structure also resulted in surface defects /open copper sites that favored the removal of toxic gases in dry conditions. The reactivity of the adsorbents with toxic gases was demonstrated by the changes in the adsorbent colors, in texture, and in surface chemistry (organic salts, complexes, sulfides and nitrates were formed).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

The aerodynamics of an oscillating cascade in a compressible flow field

Fundamental experiments are performed in the NASA Lewis Research Center Transonic Oscillating Cascade Facility to investigate and quantify the aerodynamics of a cascade of bioconvex airfoils executing torsion mode oscillations at realistic reduced frequency values. Both steady and unsteady airfoil surface pressures are measured at two inlet Mach numbers, 0.65 and 0.80, and two incidence angles, 0 and 7 deg, with the harmonic torsional airfoil cascade oscillations at realistic high reduced frequency and unsteady data obtained at several interblade phase angle values. The time-variant pressures are analyzed by means of discrete Fourier transform techniques, with these unique data compared with predictions from a linearized unsteady cascade model. The experimental results indicate that the interblade phase angle has a major effect on the chordwise distributions of the airfoil surface unsteady pressure, with the effect of reduced frequency, incidence angle, and Mach numbers somewhat less significant.

Buffum, D. H.↗
NASA NTRS2006

Direct Imaging of Stellar Surfaces: Results from the Stellar Imager (SI) Vision Mission Study

The Stellar Imager (SI) is a UV-Optical, Space-Based Interferometer designed to enable 0.1 milli-arcsecond (mas) spectral imaging of stellar surfaces and stellar interiors (via asteroseismology) and of the Universe in general. SI is identified as a "Flagship and Landmark Discovery Mission'' in the 2005 Sun Solar System Connection (SSSC) Roadmap and as a candidate for a "Pathways to Life Observatory'' in the Exploration of the Universe Division (EUD) Roadmap (May, 2005). The ultra-sharp images of the Stellar Imager will revolutionize our view of many dynamic astrophysical processes: The 0.1 mas resolution of this deep-space telescope will transform point sources into extended sources, and snapshots into evolving views. SI's science focuses on the role of magnetism in the Universe, particularly on magnetic activity on the surfaces of stars like the Sun. SI's prime goal is to enable long-term forecasting of solar activity and the space weather that it drives in support of the Living With a Star program in the Exploration Era. SI will also revolutionize our understanding of the formation of planetary systems, of the habitability and climatology of distant planets, and of many magneto-hydrodynamically controlled processes in the Universe. In this paper we will discuss the results of the SI Vision Mission Study, elaborating on the science goals of the SI Mission and a mission architecture that could meet those goals.

Carpenter, Kenneth↗
NASA NTRS2006

Stellar Imager (SI) Space Mission: Stellar Magnetic Activity

The Stellar Imager (SI) is a UV-Optical, Space-Based interferometer designed to enable 0.1 milli-arcsecond (mas) spectral imaging of stellar surfaces and stellar interiors (via asteroseismology) and of the Universe in general. SI is identified as a "Flagship and Landmark Discovery Mission" in the 2005 Sun Solar System Connection (SSSC) Roadmap and as a candidate for a "Pathways to Life Observatory" in the Exploration of the Universe Division (EUD) Roadmap (May, 2005). The ultra-sharp images of the Stellar Imager will revolutionize our view of many dynamic astrophysical processes: The 0.1 mas resolution of this deep-space telescope will transform point sources into extended sources, and snapshots into evolving views. SI'S science focuses on the role of magnetism in the Universe, particularly on magnetic activity on the surfaces of stars like the Sun. SI'S prime goal is to enable long-term forecasting of solar activity and the space weather that it drives in support of the Living With a Star program in the Exploration Era. SI will also revolutionize our understanding of the formation of planetary systems, of the habitability and climatology of distant planets, and of many magneto-hydrodynamically controlled processes in the Universe. In this paper we will discuss the science goals of the SI Mission and a mission architecture that could meet those goals.

Carpenter, K. G.↗
DOE OSTI2023

Revolutionizing Porous Liquids: Stabilization and Structural Engineering Achieved by a Surface Deposition Strategy

Facile approaches capable of constructing stable and structurally diverse porous liquids (PLs) that can deliver high-performance applications are a long-standing, captivating, and challenging research area that requires significant attention. Here, in this work, a facile surface deposition strategy is demonstrated to afford diverse type III-PLs possessing ultra-stable dispersion, external structure modification, and enhanced performance in gas storage and transformation by leveraging the expeditious and uniform precipitation of selected metal salts. The Ag(I) species-modified zeolite nanosheets are deployed as the porous host to construct type III-PLs with ionic liquids (ILs) containing bromide anion , leading to stable dispersion driven by the formation of AgBr nanoparticles. The as-afforded type-III PLs display promising performance in CO 2 capture/conversion and ethylene/ethane separation. Property and performance of the as-produced PLs can be tuned by the cation structure of the ILs, which can be harnessed to achieve polarity reversal of the porous host via ionic exchange. The surface deposition procedure can be further extended to produce PLs from Ba(II)-functionalized zeolite and ILs containing [SO 4 ] 2– anion driven by the formation of BaSO 4 salts. The as-produced PLs are featured by well-maintained crystallinity of the porous host, good fluidity and stability, enhanced gas uptake capacity, and attractive performance in small gas molecule utilization.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Chemo-Mechanical Instabilities in Lithium Cobalt Oxide at Higher State-Of-Charge in Li-Ion Batteries

Transition metal oxide cathodes are widely used in commercial Li-ion batteries. However, their practical charge capacity is limited due to severe chemo-mechanical instabilities at higher charge voltage, and state-of-charge condition. Here, in situ stress and strain measurements were synchronized to probe mechanical deformations in the lithium cobalt oxide (LCO) cathode via a multi-beam stress sensor and digital image correlation, respectively. In situ mechanical measurements revealed how Li removal from the electrode structure induces deformations on the LCO composite cathodes during cycling. The structure and morphology of the LCO cathodes were further investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies. Two distinct electrochemical and mechanical behaviors were identified when the LCO was charged up to 4.65 V. The LCO undergoes a compressive stress generation when charged up to 4.2 V and surface fractures on the LCO particles were detected by SEM. LCO cathode experienced significantly large contractions (negative strains) when charged up to 4.65 V, where intergranular crack formation and phase transformation were detected on the LCO particles via SEM and XRD, respectively. Overall, the study bridges complicated structural deformations with in situ analysis of mechanical degradations in LCO cathodes charged at higher voltages. The correlation is vital to understanding instability mechanisms in transition metal oxides at high voltages for alkali metal ion batteries.

higher state-of-charge↗
DOE OSTI2023

α-Quartz Phase Stabilization, Surface Texturing, and Tunable Optical Properties of Nanocrystalline GeO 2 Films Made by Pulsed-Laser Deposition: Implications for Optical and Optoelectronic Applications

Germanium oxide (GeO 2 ) has great potential in multifunctional devices and next-generation power electronics due to its high thermal conductivity and ambipolar doping capability. However, the complexity of synthesizing the desirable polymorph with a controlled phase, surface/interface quality, microstructure, and functional properties is the main barrier to GeO 2 utilization in advanced applications. Here, in this regard, we present a method to realize the hexagonal (h) or a-quartz type GeO 2 with nano-textured surface morphology on sapphire substrates using a hybrid synthesis strategy that comprises pulsed laser deposition (PLD) and post-deposition thermal annealing. We performed a comprehensive study to investigate the effect of annealing temperature, which was varied in a wide range (600-1100 °C), on the crystal structure, phase, surface morphology, chemical stoichiometry, defect states, and optical properties of PLD-grown GeO 2 films. As-deposited GeO 2 films at 500 °C were amorphous. Upon annealing, the GeO 2 films induced an amorphous-to-crystalline phase transformation; GeO 2 films annealed at higher annealing temperatures (≥900 °C) stabilized in the hexagonal phase and demonstrated excellent crystal quality and chemical stability. Thermally activated growth process showed increased average crystallite size, which was varied in the range of 20-130 (±2) nm, while the surface roughness followed a similar trend. The spectral transmittance and band gap also increased with increasing annealing temperature. The resulting h-GeO 2 films, particularly those obtained at annealing temperatures in the 900-1100 °C range, had a higher band gap of 6.2-6.3 eV and displayed excellent optical transmittance in the visible region. Moreover, the absence of extended valence band maxima and reduced optical defect density support the quality improvement upon annealing. When considering phase-pure bulk and nanostructured GeO 2 as a possible candidate for ultra wide band gap semiconductors in cutting-edge technological applications, the results of the current work can be beneficial to realize high structural and optical quality a-quartz structured GeO 2 films.

GeO2↗
NASA NTRS2011

Hyperspectral Remote Sensing of Atmosphere and Surface Properties

Atmospheric Infrared Sounder (AIRS), Infrared Atmospheric Sounding Interferometer (IASI), and Cross-track Infrared Sounder (CrIS) are all hyper-spectral satellite sensors with thousands of spectral channels. Top of atmospheric radiance spectra measured by these sensors contain high information content on atmospheric, cloud, and surface properties. Exploring high information content contained in these high spectral resolution spectra is a challenging task due to computation e ort involved in modeling thousands of spectral channels. Usually, only very small fractions (4{10 percent) of the available channels are included in physical retrieval systems or numerical weather forecast (NWP) satellite data assimilations. We will describe a method of simultaneously retrieving atmospheric temperature, moisture, cloud, and surface properties using all available spectral channels without sacrificing computational speed. The essence of the method is to convert channel radiance spectra into super-channels by an Empirical Orthogonal Function (EOF) transformation. Because the EOFs are orthogonal to each other, about 100 super-channels are adequate to capture the information content of the radiance spectra. A Principal Component-based Radiative Transfer Model (PCRTM) developed at NASA Langley Research Center is used to calculate both the super-channel magnitudes and derivatives with respect to atmospheric profiles and other properties. There is no need to perform EOF transformations to convert super channels back to spectral space at each iteration step for a one-dimensional variational retrieval or a NWP data assimilation system. The PCRTM forward model is also capable of calculating radiative contributions due to multiple-layer clouds. The multiple scattering effects of the clouds are efficiently parameterized. A physical retrieval algorithm then performs an inversion of atmospheric, cloud, and surface properties in super channel domain directly therefore both reducing the computational need and preserving the information content of the IASI measurements. The inversion algorithm is based on a non-linear Levenberg-Marquardt method with climatology covariance matrices and a priori information as constraints. One advantage of this approach is that it uses all information content from the hyper-spectral data so that the retrieval is less sensitive to instrument noise and eliminates the need for selecting a sub-set of the channels.

Liu, Xu↗
DOE OSTI2021

Mechanistic Investigation of Dimethylmercury Formation Mediated by a Sulfide Mineral Surface

Mercury (Hg) pollution is a global environmental problem, but many key transformations among 29 various Hg species are not well understood. Although anaerobic microorganisms are the primary 30 producers of monomethylmercury (MMeHg), the abiotic formation of dimethylmercury (DMeHg) 31 from MMeHg have been suggested to account for a large portion of DMeHg in the ocean. It has 32 been shown that abiotic formation of DMeHg from MMeHg can be facilitated by reduced sulfur 33 groups on mineral surfaces. However, a detailed mechanistic understanding of this reaction is 34 lacking. Here we perform density functional theory (DFT) calculations to explore mechanisms of 35 DMeHg formation on the 110 surface of a CdS(s) (hawleyite) nanoparticle. We show that 36 coordination of MMeHg substituents to adjacent reduced sulfur groups protruding from the surface 37 facilitate DMeHg formation and that the reaction proceeds through direct transmethylation from 38 one MMeHg substituent to another. Solvation effects were found to play an important role in the 39 surface reconstruction of the nanoparticle and in decreasing the energetic barrier for DMeHg 40 formation. We also investigate DMeHg formation from MMeHg mediated by organic dithiols and 41 compare the results to those mediated by the mineral surface. In contrast to the surface reaction, 42 the calculations suggest that dithiol-mediated formation of DMeHg instead proceeds through a 43 mechanism in which Hg–Hg interactions activate a methyl group from one MMeHg substituent 44 for intramolecular transfer to the adjacent MMeHg substituent. These findings refine previously 45 proposed mechanisms of abiotic DMeHg formation and fill gaps in our understanding of global 46 Hg cycling in the environment.

Lian, Peng↗
DOE OSTI2022

Elucidation of the Roles of Water on the Reactivity of Surface Intermediates in Carboxylic Acid Ketonization on TiO 2

The effects of water on the carboxylic acid ketonization reaction over solid Lewis-acid catalysts were examined by nuclear magnetic resonance (NMR) spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), temperature-programmed desorption (TPD), and kinetic measurements. Acetic acid and propanoic acid were used as model compounds, and P25 TiO 2 was used as a model catalyst to represent the anatase TiO 2 since the rutile phase only contributes to <2.5% of the overall ketonization activity of P25 TiO 2 . The kinetic measurement showed that introducing H 2 O vapor in gaseous feed decreases the ketonization reaction rate by increasing the intrinsic activation barrier of gas-phase acetic acid on anatase TiO 2 . Quantitative TPD of acetic acid indicated that H 2 O does not compete with acetic acid for Lewis sites. Instead, as indicated by combined approaches of NMR and DRIFTS, H 2 O associates with the adsorbed acetate or acetic acid intermediates on the catalyst surface and alters their reactivities for the ketonization reaction. There are multiple species present on the anatase TiO 2 surface upon carboxylic acid adsorption, including molecular carboxylic acid, monodentate carboxylate, and chelating/bridging bidentate carboxylates. The presence of H 2 O vapor increases the coverage of the less reactive bridging bidentate carboxylate associated with adsorbed H 2 O, leading to lower ketonization activity on hydrated anatase TiO 2 . In conclusion, surface hydroxyl groups, which are consumed by interaction with carboxylic acid upon the formation of surface acetate species, do not impact the ketonization reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗