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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.

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At least 973 records · Page 54
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Solution combustion synthesis of iron-based alumina catalysts for dehydrogenation of fossil fuels

Microwave-assisted thermocatalytic dehydrogenation of fossil fuels has been proposed as a method for hydrogen production with no CO2 emissions. The byproduct is carbon, which has a commercial value. Iron-based alumina nanocomposites are promising catalysts for this process as they both absorb microwave radiation and catalyze the dehydrogenation. In addition, they may have magnetic properties, which could be used for their separation from the carbon byproduct. Solution combustion synthesis (SCS) is an attractive technique for the fabrication of iron-based alumina nanocomposites because it can produce high specific surface area oxides in a facile manner. However, the effects of the heating mode, the fuel, and the iron/aluminum ratio on the combustion synthesis behavior and the product properties have not been studied yet. In the present work, the iron-based alumina nanocomposites were obtained by SCS using a hotplate, a muffle furnace, and a microwave oven. The initial mixtures were aqueous solutions of iron nitrate, aluminum nitrate, and an organic fuel. The concentrations of the two nitrates were varied in proportion to Fe:Al molar ratios of 1:2, 1:1, and 2:1. Two fuels were tested: citric acid and glycine. The combustion was less vigorous when citric acid was used as the fuel, which is explained by the lower exothermicity of the reaction. X-ray diffraction analysis of the products confirmed the formation of complex oxides of Fe and Al, specifically it detected hercynite and magnetite phases. Brunauer-Emmett-Teller surface area analysis has shown that the powders obtained using citric acid have specific surface areas as high as 276 m2/g, significantly higher than those obtained using glycine. Muffle furnace and hotplate heating led to comparable specific surface areas, while microwave heating resulted in significantly lower specific surface areas. The magnetic properties of the products increase with increasing the Fe/Al molar ratio from 1:2 (no response to a magnetic field) to 1:1 (weak response) and 2:1 (strong response).

solution combustion synthesis, nanoscale oxides, f↗
DOE OSTI2020

Nanomechanical sampling of material for nanoscale mass spectrometry chemical analysis

The ability to spatially resolve the chemical distribution of compounds on a surface is important in many applications ranging from biological to material science. To this extent, we have recently introduced a hybrid atomic force microscopy (AFM)-mass spectrometry (MS) system for direct thermal desorption and pyrolysis of material with nanoscale chemical resolution. However, spatially resolved direct surface heating using local thermal desorption becomes challenging on material surfaces with low melting points, because the material will undergo a melting phase transition due to heat dissipation prior to onset of thermal desorption. Therefore, here we developed an approach using mechanical sampling and collection of surface materials on an AFM cantilever probe tip for real-time analysis directly from the AFM tip. This approach allows for material to be concentrated directly onto the probe for subsequent MS analysis. We evaluate the performance metrics of the technique and demonstrate localized MS sampling from a candelilla wax matrix containing UV stabilizers avobenzone and oxinoxate from areas down to 250 nm × 250 nm. Overall, this approach removes heat dissipation into the bulk material allowing for a faster desorption and concentration of the gas phase analyte from a single heating pulse enabling higher signal levels from a given amount of material in a single sampling spot.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Targeted Dy intercalation under graphene/SiC for tuning its electronic band structure

Metal intercalation of graphene is a promising method to tune its electronic band structure and generate novel electronic and topological phases. The tuning depends critically on the ability to bond the intercalated atoms at predesigned, subsurface interlayer locations because the emerging band structure depends on metal location. In this work, we have studied Dy intercalation under single-layer graphene (SLG) on SiC using spot profile analysis–low-energy electron diffraction and scanning tunneling microscopy (STM). The experimental work is complemented with density-functional theory (DFT) analysis. Because different diffraction spots originate from different subsurface interlayer regions, it is possible to identify changes in the intercalation location by monitoring the spot intensity as a function of growth conditions. DFT calculations of the chemical potential as a function of intercalated Dy coverage support the variation of the stability of the intercalated phase at different intercalated locations. The preferred location is confirmed from STM studies showing the removal of the 6 × 6 moiré corrugation at the preferred location, observed at higher Dy coverage.

2-dimensional systems↗
DOE OSTI2020

Quantitatively accounting for the effects of surface topography on the oxidation kinetics of additive manufactured Hastelloy X processed by electron beam melting

In this work, the effects of surface roughness on the high-temperature corrosion of nickel-based superalloy X produced through electron-beam melting (EBM) additive manufacturing were studied. Surface area of samples in the rough, as-fabricated condition was measured using a 2D cross-section image analysis technique and a 3D image analysis technique. To verify the accuracy of surface area measurements, oxidation testing of samples in the as-fabricated and polished conditions was performed; polished sample oxidation curves were then compared to the as-fabricated sample oxidation curves before and after being adjusted using obtained surface area measurements. It was found that the 2D technique accurately measured surface area and accounted for the overlapping features present on EBM sample surfaces, whereas the 3D technique did not. Further, it was also observed that oxidation kinetics were moderately faster on the alloy X samples in the as-fabricated condition than for the polished condition.

36 MATERIALS SCIENCE↗
DOE OSTI2021

H 2 O-assisted O 2 reduction by H 2 on Pt and PtAu bimetallic nanoparticles: Influences of composition and reactant coverages on kinetic regimes, rates, and selectivities

Hydrogen peroxide (H 2 O 2 ) can replace hazardous oxidants in industrial processes but is currently too expensive for many such applications. While direct synthesis of H 2 O 2 (H 2 + O 2 → H 2 O 2 ) may reduce costs in comparison to incumbent technology, current catalysts lack the requisite stability and selectivity. Here, we examine the direct synthesis of H 2 O 2 on bimetallic Pt 1 Au x (0 ≤ x ≤ 230) and Pt catalysts at steady-state in pure water and relate kinetic parameters for H 2 O 2 and H 2 O formation to possible active site structures informed by complementary characterization methods. X-ray photoelectron spectra show significant Pt surface enrichment compared to the bulk composition. Analysis of infrared spectra of mixed monolayers of 12 CO* and 13 CO* indicate that Pt and Au form substitutional surface alloys. The Pt 1 Au x nanoparticles with the greatest mole fractions of Au predominantly expose Pt monomers (i.e., isolated Pt atoms), yet Pt atoms exposed upon all these nanoparticles possess electronic structures distinct from bulk Pt. Despite these differences, rate measurements are consistent with product formation through proton-electron transfer pathways for all Pt 1 Au x catalysts. In situ XAS indicate that Pt remains metallic during H 2 O 2 synthesis. Under the most oxidizing conditions, selectivities toward H 2 O 2 increase strongly with the Au to Pt ratio from 2% for monometallic Pt to 85% for Pt 1 Au 170 . However, selectivities are similar among all catalysts within reducing conditions. Comparisons of apparent activation enthalpies for the formation of H 2 O 2 and H 2 O across these catalysts and the range of conditions suggest that Pt monomers within Au provide the greatest selectivities for H 2 O 2 formation, because these active sites present high barriers for O-O bond rupture. Further, selectivities decrease with increasing ratios of H 2 to O 2 pressures, because Pt atoms aggregate and form oligomers that readily dissociate dioxygen intermediates. The combined use of spectroscopy, kinetics, and concepts employed in reaching these conclusions take inspiration from the legacy of Prof. Michel Boudart, and specifically his elegant methods for interrogating bimetallic catalysts.

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

A comprehensive analysis of the crop effect on the urban-rural differences in land surface phenology

The response of land surface phenology (LSP) to the urban heat island effect (UHI) is a useful biological indicator for understanding how vegetated ecosystems will be affected by future climate warming. However, vegetation cover in rural areas is often dominated by cultivated land, whose phenological timing is considerably influenced by agricultural managements (e.g., timing of sowing and harvesting), leading to biased conclusions derived from the urban-rural LSP differences. To demonstrate this problem, we investigated the crop influence on the phenological response to a warmer environment resulting from the UHI effect. We partitioned cities in the United States into cultivated and non-cultivated categories according to the proportion of crops in rural areas. We then built continuous buffer zones starting from the urban boundary to explore the urban-rural LSP differences considering the UHI effect on them. In this work, the results suggest crop inclusion is likely to lead to >14 days of urban-rural differences at both the start of the season (SOS) and the end of the season (EOS) between cultivated and non-cultivated cities. The temperature sensitivity (ST) of SOS is overestimated by approximately 2.7 days/°C, whereas the EOS is underestimated by 3.6 days/°C. Removing crop-dominated pixels (i.e., above 50 %) can minimize the influence of crop planting/harvesting on LSP and derive reliable results. We, therefore, suggest explicit consideration of crop impacts in future studies of phenological differences between urban and rural areas and the UHI effect on LSP in urban domains, as presented by this comprehensive study.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Amphiphilic Bottlebrush Block Copolymers: Analysis of Aqueous Self-Assembly by Small-Angle Neutron Scattering and Surface Tension Measurements

A systematic series of 16 amphiphilic bottlebrush block copolymers (BCPs) containing polystyrene and poly(N-acryloylmorpholine) (PACMO) side chains were prepared by a combination of atom-transfer radical polymerization (ATRP), photoiniferter polymerization, and ring-opening metathesis polymerization (ROMP). The grafting-through method used to prepare the polymers enabled a high degree of control over backbone and side-chain molar masses for each block. Surface tension measurements on the self-assembled amphiphilic bottlebrush BCPs in water revealed an ultralow critical micelle concentration (cmc), 1–2 orders of magnitude lower than linear BCP analogues on a molar basis, even for micelles with >90% PACMO content. Combined with coarse-grained molecular dynamics simulations, fitting of small-angle neutron scattering traces (SANS) allowed us to evaluate solution conformations for individual bottlebrush BCPs and micellar nanostructures for self-assembled macromolecules. Bottlebrush BCPs showed an increase in anisotropy with increasing PACMO content in toluene-d 8 , which is a good solvent for both blocks, reflecting an extended conformation for the PACMO block. SANS traces of bottlebrush BCPs assembled into micelles in D 2 O, a selective solvent for PACMO, were fitted to a core–shell–shell model, suggesting the presence of a partially hydrated inner shell. Here, results showed an average micelle diameter of 40 nm with combined shell diameters ranging from 16 to 18 nm. A general trend of increased stability of micelles (i.e., resistance to precipitation) was observed with increases in PACMO content. These results demonstrate the stability of bottlebrush polymer micelles, which self-assemble to form spherical micelles with ultralow (<70 nmol/L) cmc’s across a broad range of compositions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

The diversity of aluminum-based drinking water treatment residuals for use in environmental remediation

Drinking water treatment residuals (DWTRs) are complex mixtures of organic and inorganic phases generally disposed of as waste materials. However, their strong sorptive properties could be further exploited to immobilize contaminants. To characterize these materials, we applied a range of analytical techniques to a set of aluminum-based DWTRs. Here we determined surface areas, elemental compositions using CHNS analysis and X-ray fluorescence (XRF), performed thermogravimetric analyses paired with mass spectrometry (TGA-MS), and used synchrotron-based methods: X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Elemental analyses and specific surface area measurements – that vary between 7.23 ± 0.03 and 197.6 ± 0.9 m 2 g –1 – indicate that non-coagulant additives must play an important role in controlling sorption. High resolution powder XRD reveals the presence of only a few crystalline minerals mostly derived from source waters or additives. Fe was detected by XRF in all samples, whereas Mn was present in significant levels in samples with potassium permanganate as additive. The chemical speciation of these elements was characterized by performing spectral decompositions of XAS spectra. The spectral features of Fe are consistent with iron(III) oxides/hydroxides and structural iron in clays. On the other hand, Mn is predominantly present under its reduced form, Mn(II).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Potential energy savings benefits and limitations of radiative cooling coatings for U.S. residential buildings

We report radiative coatings are a promising strategy to implement passive cooling that provides an eco-friendly pathway to achieve energy efficiency in buildings. This study investigates the benefits and limitations of implementing radiative coatings on the building envelope, particularly the roof, of residential buildings in the United States. The analysis compares the performance of an ideal radiative coating with broadband surface properties to a realistic radiative coating with diffuse and semitransparent properties. To enhance the net energy efficiency of buildings, we carried out a comprehensive parametric analysis comprising key radiation surface properties to maximize cooling energy savings while minimizing heating energy penalties. A countrywide assessment for 68 locations across the United States showed that net energy savings are a strong function of the climatic and atmospheric conditions. Broadly, southern locations showed high overall energy savings whereas northern locations exhibited high overall energy penalties. Locations in International Energy Conservation Code (IECC) climate zones 1A, 2A, and 2B showed a net annual energy savings above 5%, whereas locations in IECC climate zones 5B, 6B, and 7 showed a net annual energy penalty greater than 3%. The hot and dry climate of Phoenix, Arizona, showed the highest overall energy savings of 426 kWh (6.2%). Additionally, the mathematical correlation reveals that the net energy savings of a location is positive only when its average cooling degree days is greater than 5.5 or its average heating degree days is less than 10.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2020

Updates to a Preliminary Probabilistic Performance Assessment Model for Radiological and Chemical Contamination at the West Valley Site, New York - 20420

The New York State Energy Research and Development Authority (NYSERDA) is the owner of the Western New York Nuclear Service Center (WNYNSC), a 1,351-ha site located approximately 48 km south of Buffalo, New York. In 1962, Nuclear Fuel Services, Inc. (NFS) entered into agreements with the Atomic Energy Commission and New York State to construct the first commercial reprocessing plant of nuclear fuel in the United States at the WNYNSC. NFS built and operated the spent fuel reprocessing plant and waste disposal facilities, processing 640 Mg (640 metric tons) of spent nuclear fuel from 1966 to 1972 under an Atomic Energy Commission license. Nuclear fuel reprocessing operations halted in 1972 and never restarted, leaving behind radioactive and chemical wastes. The U.S. Department of Energy (DOE) was required to complete certain waste management activities under the West Valley Demonstration Project (WVDP) Act of 1980 including decommissioning of WVDP facilities. As collaborating agencies, NYSERDA and the DOE are tasked with making decisions about decommissioning and risk reduction for the West Valley Site. Neptune and Company, Inc. (Neptune) was contracted to develop a probabilistic performance assessment (PPA) model to assist the agencies in their decision making process for decommissioning the WVDP and WNYNSC. One important tool that is needed in order to inform the decision-making process is a science-based model of the West Valley Site that evaluates potential future consequences for human health and the environment. This forms the core of the spatial domain of the West Valley PPA Model. The PPA Model, developed using the GoldSim system modeling software, is a tool intended to provide support for decision making that evaluates uncertainty, in a manner that is transparent, defensible, and robust. The PPA Model includes contaminant transport and health effects components, and is organized around geographically-grouped contaminated facilities. These include the waste disposal areas licensed by the U.S. Nuclear Regulatory Commission and the State of New York, a waste tank farm for storage of high level radioactive waste resulting from reprocessing operations, and several areas contaminated with radioactive and chemical constituents. The PPA Model evaluates contaminant transport from these sources to points of exposure across the site and into receiving surface waters and sediments. Hypothetical people and wildlife could be exposed to contamination at these locations, and the effects of these exposures are evaluated. Contaminant transport processes to be evaluated in the PPA Model include groundwater and surface water transport, contaminant translocation by plants and animals, diffusion, and erosion. The evaluation of exposures to people in this preliminary model is limited to a resident farmer scenario, and ecological assessment is performed at the level of a screening analysis. The results of these preliminary evaluations inform future model developments. PPA Model results are subjected to sensitivity analysis in order to determine those pathways and parameters that are most significant in influencing the results. This information allows analysts and decision makers to focus on those aspects of Site behavior and processes. With this information, the decision makers can drive informed, defensible decisions regarding decommissioning of the Site. This paper includes an update of the information presented at WM2019 [1]. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2019

Assessment of age, origin, and sustainability of fossil aquifers: A geochemical and remote sensing-based approach

An integrated approach was developed to assess the sustainability, origin, age, evolution, and groundwater potential of large fossil aquifers using the Mega Aquifer System (MAS) (area: 2 x 10(6) km(2)) in the Arabian Peninsula as a test site. A two-step exercise was adopted, the sustainability of the MAS was first investigated through the analysis of GRACE data and land surface model (LSM) outputs. Then, integrated geochemical, remote sensing, and field studies were conducted to address the age, origin, hydrogeological setting, and evolution of the southern sections of the MAS (Rub Al Khali Aquifer System (RAKAS)), the area identified from the analysis of GRACE and ISMs as being the most suited for sustainable development. Analysis of GRACE and ISMs revealed: (1) the MAS central and northern sections are experiencing high groundwater extraction (6.6 km(3)/yr) and depletion rates (-2.8 +/- 0.8 km(3)/yr) with minimum balancing potential through aquifer capture processes, yet sustainability could be achieved by reducing annual extraction by 2.8 km(3), and (2) the MAS southern sections (Rub Al Khali Aquifer System (RAKAS)) are experiencing low groundwater depletion rates (eastern RAKAS: -1.8 +/- 1.4 mm/yr) to steady-state conditions (western RAKAS: -0.73 +/- 1.4 mm/yr). Geochemical, remote sensing, and field investigations over the RAKAS revealed: (1) the presence of west to east trending drainage networks and large-scale groundwater flow systems consistent with a meteoric source (precipitation over Red Sea Hills); (2) increasing Cl-36 model ages along groundwater flow directions (up to 970,000 years), indicating aquifer recharge in wet Pleistocene periods; (3) progressive depletion in the O and H stable isotopic compositions of aquifers with increasing distance from the Red Sea Hills basement outcrops, indicating modest recharge during prevailing dry conditions; and (4) the presence of relatively fresh (TDS: 800-2800 mg/L) and nonradioactive (Ra-226 + Ra-228 < 0.185 Bq/kg) water in western RAKAS. Findings suggest that sustainable agricultural development is achievable at current extraction rates in western RAKAS and provide a replicable and cost-effective model.

Fossil aquifers↗
DOE OSTI2019

Microfluidic electrochemical cell for in situ structural characterization of amorphous thin-film catalysts using high-energy X-ray scattering

Porous, high-surface-area electrode architectures are described that allow structural characterization of interfacial amorphous thin films with high spatial resolution under device-relevant functional electrochemical conditions using high-energy X-ray (>50 keV) scattering and pair distribution function (PDF) analysis. Porous electrodes were fabricated from glass-capillary array membranes coated with conformal transparent conductive oxide layers, consisting of either a 40 nm–50 nm crystalline indium tin oxide or a 100 nm–150 nm-thick amorphous indium zinc oxide deposited by atomic layer deposition. These porous electrodes solve the problem of insufficient interaction volumes for catalyst thin films in two-dimensional working electrode designs and provide sufficiently low scattering backgrounds to enable high-resolution signal collection from interfacial thin-film catalysts. For example, PDF measurements were readily obtained with 0.2 Å spatial resolution for amorphous cobalt oxide films with thicknesses down to 60 nm when deposited on a porous electrode with 40 µm-diameter pores. This level of resolution resolves the cobaltate domain size and structure, the presence of defect sites assigned to the domain edges, and the changes in fine structure upon redox state change that are relevant to quantitative structure–function modeling. The results suggest the opportunity to leverage the porous, electrode architectures for PDF analysis of nanometre-scale surface-supported molecular catalysts. In addition, a compact 3D-printed electrochemical cell in a three-electrode configuration is described which is designed to allow for simultaneous X-ray transmission and electrolyte flow through the porous working electrode.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Long-Term Cycling of a Mn-Rich High-Voltage Spinel Cathode by Stabilizing the Surface with a Small Dose of Iron

The high-voltage, cobalt-free spinel cathode LiNi 0.5 Mn 1.5 O 4 (LNMO) is receiving extensive attention for lithium-ion batteries due to its low cost, high operating voltage and energy density, superior power density, and good thermal stability. However, its high operating voltage hampers its stability with commercial electrolytes and makes its practical viability challenging. We present here a Mn-rich LNMO cathode to encourage the disordering of Mn and Ni in the lattice and the incorporation of a small dose of Fe into Mn-rich LNMO (Fe-LNMO) to improve the cycling stability. The introduction of Fe further increases the cation disorder between Mn and Ni, thus enabling a better rate capability. Electron energy loss spectroscopy analysis indicates that Fe is concentrated on the surface, and X-ray photoelectron spectroscopy analysis shows that Fe-LNMO alleviates the aggressive reaction between the cathode surface and the electrolyte, thus stabilizing the interface and cycle life. Furthermore, a full cell assembled with a graphite anode with an areal capacity of 3 mA h cm –2 displays a capacity retention of 90% over 300 cycles. Furthermore, the present work demonstrates an effective way to promote cation disordering and lower the surface reactivity of LNMO with the electrolyte, thereby enhancing the conductivity, stabilizing the cathode–electrolyte interphase, and making LNMO promising for practical applications.

25 ENERGY STORAGE↗
DOE OSTI2020

Surface Design for Immobilization of an Antimicrobial Peptide Mimic for Efficient Anti-Biofouling

Microbial surface attachment negatively impacts a wide range of devices from water purification membranes to biomedical implants. Mimics of antimicrobial peptides (AMPs) constituted from poly(N-substituted glycine) „peptoids“ are of great interest as they resist proteolysis and can inhibit a wide spectrum of microbes. We investigate how terminal modification of a peptoid AMPmimic and its surface immobilization affect antimicrobial activity. We also demonstrate a convenient surface modification strategy for enabling alkyne–azide „click“ coupling on amino-functionalized surfaces. Our results verified that the N- and C-terminal peptoid structures are not required for antimicrobial activity. Moreover, our peptoid immobilization density and choice of PEG tether resulted in a „volumetric“ spatial separation between AMPs that, compared to past studies, enabled the highest AMP surface activity relative to bacterial attachment. Our analysis suggests the importance of spatial flexibility for membrane activity and that AMP separation may be a controlling parameter for optimizing surface anti-biofouling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Insights into the interaction of nitrobenzene and the Ag(111) surface: A DFT study

Here, this study explores the potential of nitrobenzene as an anolyte material for nonaqueous redox flow batteries (RFBs) by theoretically examining its low-coverage adsorption behavior on neutral and charged Ag(111) model electrode surfaces. At the low coverage limit, DFT calculations show a preference for nitrobenzene to adsorb parallel to the surface, with the benzene ring and nitro group centered over HCP sites. Interactions between nitrobenzene and the surface were analyzed using induced charge density analysis, Bader charge analysis, and projected density of states (PDOS). It was found that nitrobenzene adsorbs primarily through van der Waals interactions with the surface. As nitrobenzene accumulates negative charge, the strength of adsorption diminishes. Understanding the electrode-electrolyte interface is crucial for enhancing RFB electrochemical performance, and this study sheds light on nitrobenzene's interaction with a model Ag electrode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Simultaneous measurement of surface velocity and plasma density with interferometric velocimetry

The apparent velocity measured by an interferometric surface velocimeter is a function of both the surface velocity and the time derivative of the refractive index along the measurement path. We employed this dual sensitivity to simultaneously measure km/s surface velocities and 10 18 cm -3 average plasma densities with combined VISAR (velocity interferometer system for any reflector) and PDV (photonic Doppler velocimetry) measurements in experiments performed on the Z Pulsed Power Facility. We detail the governing equations, associated assumptions, and analysis specifics and show that the surface velocity can be extracted without knowledge of the specific plasma density profile.

47 OTHER INSTRUMENTATION↗
DOE OSTI2018

Quantum chemical analysis of mechanisms of phenylacetylene and styrene hydrogenation to ethylbenzene on the Pd{111} surface

The mechanisms of the hydrogenation of phenylacetylene and styrene to ethylbenzene on the Pd{111} surface, which are secondary reactions of the selective hydrogenation of phenylacetylene, were studied by the DFT-PBE method. The position of the Ph group of the styrene molecule with respect to the Pd surface is shown to exert a noticeable effect on the mechanism of the process. If the Ph group is adsorbed on the Pd surface, then the addition of the first H atom to the terminal C atom of the styrene molecule is most probable. If Ph does not contact the surface, then the most substituted C atom of the styrene molecule is first hydrogenated. On the whole, the interaction of the Ph group with the Pd{111} surface results in stable adsorption structures, the hydrogenation of which on the Pd{111} surface is strongly hindered. The Gibbs activation energy (ΔG{sup ≠}{sub 298}) is 22.9 and 27.1 kcal mol{sup –1} in the most probable reaction routes of styrene hydrogenation to ethylbenzene and direct hydrogenation of phenylacetylene to ethylbenzene, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗