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At least 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Tuning Pt-CeO 2 interactions by high-temperature vapor-phase synthesis for improved reducibility of lattice oxygen

In this work, we compare the CO oxidation performance of Pt single atom catalysts (SACs) prepared via two methods: (1) conventional wet chemical synthesis (strong electrostatic adsorption–SEA) with calcination at 350 °C in air; and (2) high temperature vapor phase synthesis (atom trapping–AT) with calcination in air at 800 °C leading to ionic Pt being trapped on the CeO 2 in a thermally stable form. As-synthesized, both SACs are inactive for low temperature (<150 °C) CO oxidation. After treatment in CO at 275 °C, both catalysts show enhanced reactivity. Despite similar Pt metal particle size, the AT catalyst is significantly more active, with onset of CO oxidation near room temperature. A combination of near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and CO temperature-programmed reduction (CO-TPR) shows that the high reactivity at low temperatures can be related to the improved reducibility of lattice oxygen on the CeO 2 support.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Single-atom Zr promoter boosts oxygen activation on ceria-supported Pt catalysts

Activation of surface lattice oxygen and chemisorbed oxygen on catalyst surfaces constitutes a pivotal step in heterogeneous oxidative catalysis. Herein, we report a strategy for enhancing oxygen activation by rational design of catalysts with single-atom promoters. Single-site Zr species in CeO 2 (Zr 1 -CeO 2 ) are synthesized using the atom-trapping method. The Zr 1 -CeO 2 -supported Pt catalyst exhibits enhanced catalytic performance over the CeO 2 -supported Pt catalyst in the oxidation of CO, C 3 H 8 , and C 3 H 6 , achieving significantly lower T 50 values (temperature required to reach 50% conversion). This enhanced catalytic activity is attributed to the formation of an asymmetric Zr 1 -O-Pt 1 structure, which favors the activation of the adjacent surface lattice oxygen and chemisorbed molecular oxygen. This work exemplifies that incorporating single-site atoms into oxide support facilitates oxygen activation, providing new insights into the role of atomically dispersed promoters in heterogeneous catalysis.

Science & Technology - Other Topics↗
DOE OSTI2019

Structural evolution of atomically dispersed Pt catalysts dictates reactivity

The use of oxide-supported isolated Pt-group metal atoms as catalytic active sites is of interest due to their unique reactivity and efficient metal utilization. However, relationships between the structure of these active sites, their dynamic response to environments and catalytic functionality have proved difficult to experimentally establish. Here, sinter-resistant catalysts where Pt was deposited uniformly as isolated atoms in well-defined locations on anatase TiO 2 nanoparticle supports were used to develop such relationships. Through a combination of in situ atomic-resolution microscopy- and spectroscopy-based characterization supported by first-principles calculations it was demonstrated that isolated Pt species can adopt a range of local coordination environments and oxidation states, which evolve in response to varied environmental conditions. In conclusion, the variation in local coordination showed a strong influence on the chemical reactivity and could be exploited to control the catalytic performance.

36 MATERIALS SCIENCE↗
DOE OSTI2018

An atomic-scale view of single-site Pt catalysis for low-temperature CO oxidation

Single-atom catalysts have attracted great attention in recent years due to their high efficiencies and cost savings. However, there is debate concerning the nature of the active site, interaction with the support, and mechanism by which single-atom catalysts operate. Here, using a combined surface science and theory approach, we designed a model system in which we unambiguously show that individual Pt atoms on a well-defined Cu 2 O film are able to perform CO oxidation at low temperatures. Isotopic labelling studies reveal that oxygen is supplied by the support. Density functional theory rationalizes the reaction mechanism and confirms X-ray photoelectron spectroscopy measurements of the neutral charge state of Pt. Scanning tunneling microscopy enables visualization of the active site as the reaction progresses, and infrared measurements of the CO stretch frequency are consistent with atomically dispersed Pt atoms. These results serve as a benchmark for characterizing, understanding and designing other single-atom catalysts.

Therrien, Andrew J.↗
DOE OSTI2016

Heteroepitaxial growth of Pt and Au thin films on MgO single crystals by bias-assisted sputtering

The crystallographic orientation of a metal affects its surface energy and structure, and has profound implications for surface chemical reactions and interface engineering, which are important in areas ranging from optoelectronic device fabrication to catalysis. However, it can be very difficult and expensive to manufacture, orient, and cut single crystal metals along different crystallographic orientations, especially in the case of precious metals. One approach is to grow thin metal films epitaxially on dielectric substrates. In this work, we report on growth of Pt and Au films on MgO single crystal substrates of (100) and (110) surface orientation for use as epitaxial templates for thin film photovoltaic devices. We develop bias-assisted sputtering for deposition of oriented Pt and Au films with sub-nanometer roughness. We show that biasing the substrate decreases the substrate temperature necessary to achieve epitaxial orientation, with temperature reduction from 600 to 350 °C for Au, and from 750 to 550 °C for Pt, without use of transition metal seed layers. Additionally, this temperature can be further reduced by reducing the growth rate. Biased deposition with varying substrate bias power and working pressure also enables control of the film morphology and surface roughness.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Hydrogen adsorption and desorption at the Pt(110)-(1×2) surface: experimental and theoretical study

The interaction of hydrogen with the Pt(110)-(1×2) surface is studied using temperature programmed desorption (TPD) measurements and density functional theory (DFT) calculations. The ridges in this surface resemble edges between micro-facets of Pt nano-particle catalysts used for hydrogen evolution (HER) and hydrogen oxidation reactions (HOR). The binding energy and activation energy for desorption are found to depend strongly on hydrogen coverage. At low coverage, the strongest binding sites are found to be the low coordination bridge sites at the edge and this is shown to agree well with the He-atom interaction and work function change which have been reported previously. At higher hydrogen coverage, the higher coordination sites on the micro-facet and in the trough get populated. The simulated TPD spectra based on the DFT results are in close agreement with our experimental spectra and provide microscopic interpretation of the three measured peaks. The lowest temperature peak obtained from the surface with highest hydrogen coverage does not correspond to desorption directly from the weakest binding sites, the trough sites, but is due to desorption from the ridge sites, followed by subsequent, thermally activated rearrangement of the H-adatoms. The reason is low catalytic activity of the Pt-atoms at the trough sites and large reduction in the binding energy at the ridge sites at high coverage. The intermediate temperature peak corresponds to desorption from the micro-facet. The highest temperature peak again corresponds to desorption from the ridge sites, giving rise to a re-entrant mechanism for the thermal desorption.

Gudmundsdóttir, Sigrídur↗
DOE OSTI2014

Structural disordering of de-alloyed Pt bimetallic nanocatalysts: the effect on oxygen reduction reaction activity and stability

Platinum bimetallic alloys are well-known for their ability to catalyze the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). In this work, Pt x Co 1-x colloidal nanoparticles were synthesized with varying initial Pt : Co ratios, but constant size to investigate how the initial metal composition affects their electrocatalytic performance. The results show that upon contact with acid environment the Co leaches out of the particles leading to almost identical compositions, independent of the initial differences. Surprisingly the data show a clear trend in ORR activity, although the Pt x Co 1-x nanoparticles almost completely de-alloy during acid leaching, i.e. under reaction conditions in a fuel cell. To scrutinize the resulting particle structure after de-alloying we used pair distribution function (PDF) analysis and X-ray diffraction (XRD) gaining insight into the structural disorder and its dependence on the initial metal composition. Our results suggest that not only the ORR activity, but also the corrosion resistance of the synthesized NPs, are dependent on the structural disorder resulting from the de-alloying process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Structurally ordered Pt–Zn/C series nanoparticles as efficient anode catalysts for formic acid electrooxidation

Controlling the size, composition, and structure of bimetallic nanoparticles is of particular interest in the field of electrocatalysts for fuel cells. In the present work, structurally ordered nanoparticles with intermetallic phases of Pt 3 Zn and PtZn have been successfully synthesized via an impregnation reduction method, followed by post heat-treatment. The Pt 3 Zn and PtZn ordered intermetallic nanoparticles are well dispersed on a carbon support with ultrasmall mean particle sizes of ~5 nm and ~3 nm in diameter, respectively, which are credited to the evaporation of the zinc element at high temperature. These catalysts are less susceptible to CO poisoning relative to Pt/C and exhibited enhanced catalytic activity and stability toward formic acid electrooxidation. The mass activities of the as-prepared catalysts were approximately 2 to 3 times that of commercial Pt at 0.5 V (vs. RHE). As a result, this facile synthetic strategy is scalable for mass production of catalytic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Electron injection study of photoexcitation effects on supported subnanometer Pt clusters for CO 2 photoreduction

In this paper, using density functional theory, we study the effect of injected electrons (simulating photoexcited electrons) on the energetics, structures, and binding sites available to CO 2 molecules on subnanometer Pt clusters decorated onto anatase TiO 2 (101) surfaces, shedding light on the first and key step of CO 2 photoreduction. Upon the addition of one, two, or three electrons, the O–C–O angles of adsorbed CO 2 become progressively smaller in binding sites that directly contact Pt clusters, while no significant change is found in the intra bond length of the adsorbed CO 2 and in the bonding distances between the adsorbed CO 2 and supported clusters. The extra electrons lead to the stabilization of adsorption sites identified on neutral slabs, including previously metastable configurations, suggesting the enhancement of accessible CO 2 binding sites. Furthermore, supported clusters are able to populate the electronic states of adsorbed CO 2 species, facilitating the formation of the CO 2 - anion. To help interpret experimentally observed frequencies, conversion factors are proposed to gain insight into the charge state and O–C–O angle of the adsorbed CO 2 . Interestingly, upon electron addition, cluster reconstruction may exist due to the bonding inclination between CO 2 and atoms in the Pt cluster, further stabilizing the intermediate complexes. In conclusion, the rate-limiting step (C–O bond cleavage) in the CO 2 dissociation to CO is slightly reduced by the introduction of an extra electron. Our results show that subnanometer metal cluster based photocatalysts are good candidates for CO 2 photoreduction.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2019

In situ , operando studies on the size and structure of supported Pt catalysts under supercritical conditions by simultaneous synchrotron-based X-ray techniques

To control the size and structure of supported Pt catalysts, the influence of additional metal particles and the effect of supports were elucidated during the cracking reaction of n-dodecane under supercritical reaction conditions. The dynamical changes in nanocatalysts and catalytic activity are studied under realistic reaction conditions by using a combination of simultaneous temperature-programmed heating, in situ Small Angle X-ray Scattering (SAXS) and X-ray Absorption Near Edge Structure (XANES). In situ SAXS results indicate that the stability of the catalysts increases with Sn concentration. In situ XANES analysis reveals that the degree of oxidation and the electronic states of catalysts are dependent on the amount of Sn. Carbonaceous deposits over spent catalysts were characterized by Raman spectroscopy, suggesting that the highest Sn loading inhibits the formation of disordered graphitic lattices, which leads to an increased catalytic activity. SiO 2 , γ-Al 2 O 3 and Mg(Al)Ox were employed as supports to investigate the support effect on the stability of Pt catalysts. In situ SAXS and XANES findings clearly reflect the improved stability of catalysts on γ-Al 2 O 3 and Mg(Al)Ox supports compared to Pt catalysts on SiO 2 and the electronic states of catalysts are strongly influenced by support materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Evidence for interfacial geometric interactions at metal–support interfaces and their influence on the electroactivity and stability of Pt nanoparticles

Supported metals are widely used as industrial catalysts wherein the supports affect catalytic performances remarkably through either electronic and/or geometric interactions with the metals, and/or providing interfacial synergistic sites. Herein, we observed evidence for interfacial geometric interactions (IGIs) at Pt–C interfaces through a combination of atomic-scale structural analysis, in situ X-ray absorption fine structure, and electrochemical measurements for Pt/C model systems. The IGI has a long-range attribute and affects Pt surface atoms not only at interfacial perimeters but also adjacent to interfaces. The affected Pt surface atoms are proposed to contribute enhanced activity and stability for the oxygen reduction reaction through retarding the formation of strongly adsorbed oxygenated intermediates. Our work provides some necessary information for a better understanding of support effects and catalytically active surface sites.

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

Magnetic coupling between Fe(NO) spin probe ligands through diamagnetic Ni II , Pd II and Pt II tetrathiolate bridges

Reaction of the nitrosylated-iron metallodithiolate ligand, paramagnetic (NO)Fe(N 2 S 2 ), with [M(CH 3 CN) n ][BF 4 ] 2 salts (M = Ni II , Pd II , and Pt II ; n = 4 or 6) affords di-radical tri-metallic complexes in a stairstep type arrangement ([FeMFe] 2+ , M = Ni, Pd, and Pt), with the central group 10 metal held in a MS 4 square plane. These isostructural compounds have nearly identical ν(NO) stretching values, isomer shifts, and electrochemical properties, but vary in their magnetic properties. Despite the intramolecular Fe∙∙∙Fe distances of ca. 6 Å, antiferromagnetic coupling is observed between {Fe(NO)} 7 units as established by magnetic susceptibility, EPR, and DFT studies. The superexchange interaction through the thiolate sulfur and central metal atoms is on the order of Ni II < Pd II $\ll$ Pt II with exchange coupling constants (J) of -3, -23, and -124 cm -1 , consistent with increased covalency of the M–S bonds (3d < 4d < 5d). This trend is reproduced by DFT calculations with molecular orbital analysis providing insight into the origin of the enhancement in the exchange interaction. Specifically, the magnitude of the exchange interaction correlates surprisingly well with the energy difference between the HOMO and HOMO-1 orbitals of the triplet states, which is reflected in the central metal's contribution to these orbitals. These results demonstrate the ability of sulfur-dense metallodithiolate ligands to engender strong magnetic communication by virtue of their enhanced covalency and polarizability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Topological perturbation to a standard dehydrogenation catalyst, Pt 3 Sn

Topological materials, which exhibit protected topological surface states (TSS) near the Fermi level, have been proposed to be good catalysts. Topological catalysis may be more prevalent than we suspect, and not limited to exotic new materials. Here we study a known dehydrogenation catalyst, Pt 3 Sn alloy, which happens to be a topological semimetal, and probe the participation of TSSs in catalytic dehydrogenation of methane catalyzed by this material. Through first principle modeling and detailed analysis of the electronic structure for topological and non-topological surfaces of Pt 3 Sn, we find that TSS get significantly altered by the binding of reaction intermediates, particularly H. However, this effect of TSS on the binding of the reagents is merely perturbative, as the majority of the adsorbate binding is achieved by not-surface-focused electronic states, located much deeper below the Fermi level. Therefore, the reaction energetics and selectivity are predominantly determined by electronic states other than TSS. The fact that TSS are available for the reagent binding does not alone guarantee that the catalysis is strongly driven by TSS. However, TSS are not to be ignored, as small changes in the energetics along the reaction profile can translate into substantial differences in the reaction rate. Hence, in our view, Pt 3 Sn – a topological material – is first and foremost a standard catalyst, with added topological features, and not purely a topological catalyst. Our results point at the need to carefully consider all the bonding effects at the topological material interface.

Chemistry↗
DOE OSTI2011

Magnetic properties of pulsed laser deposition-fabricated isotropic Fe-Pt film magnets

A high-speed pulsed laser deposition method with the deposition rate of several tens of microns per 1 h enabled us to obtain isotropic Fe-Pt thick film magnets. Increase in the laser power enabled us to obtain as-deposited films with L1{sub 0} ordered phase due to the heat radiation from a target, which means that a substrate heating system and a post-annealing process are not required to achieve hard magnetic properties in the process. Use of an Fe-rich target enhanced the magnetic properties, and as a result (BH){sub max} value exceeded 100 kJ/m{sup 3} in an isotropic Fe-Pt film fabricated at the power of 3 W, which was comparable to those of isotropic Fe-Pt thick film magnets prepared by a sputtering method.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Surface Relaxation and Electronic States of Pt(111) Surface with Varying Slab Thickness

Surface relaxation and electronic DOS's of Pt(111) surface have been studied with varying slab thickness using ab-initio SIESTA method. We found the expansion in the top layer and contraction in the subsurface layers of Pt(111) surface. Our results match with the experimental results. Also observing electronic density of states we found that as we increase the thickness of slab, the PDOS of Pt(111) surface goes towards the bulk density of states and Fermi energy shifts towards the bulk fermi energy.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Thermally induced nanoscale structural and morphological changes for atomic-layer-deposited Pt on SrTiO{sub 3}(001).

Platinum grown by atomic layer deposition (ALD) on SrTiO{sub 3}(001) surfaces was studied as a function of Pt coverage and post-deposition thermal treatment. The combination of atomic-force microscopy, scanning electron microscopy, x-ray fluorescence, x-ray reflectivity, and grazing-incidence small-angle x-ray scattering reveals significant changes in the nanoscale surface morphology and crystallinity for the differently prepared films. Surfaces with Pt coverages from 1 to 40 monolayers (ML) show different initial morphologies that evolve into different final Pt microstructures after annealing to 800 C. These distinct nanoscale structural changes are explained by surface diffusion and the surface and interface energies for noble metals on oxides.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2012

Dual phase transformation and resultant magnetic properties in Fe{sub 3}Pt thin films

Fifty-nm-thick Fe{sub 75}Pt{sub 25} thin films have been made on glass substrates by rf magnetron sputtering at room temperature, and subsequently annealed at 300 -700 deg. C (T{sub a}) for 1 h. The as-deposited Fe{sub 3}Pt film exhibits high magnetization of 1530 emu/cm{sup 3} and a disordered bcc structure, confirmed by high-resolution synchrotron radiation x-ray diffractometry. First-phase transformation from the bcc to disorder fcc structure occurs for samples annealed at 300 deg. C. With increasing of T{sub a} up to 375 deg. C, the film displays a nearly disordered fcc phase with low magnetization of 1083 emu/cm{sup 3}. The fcc phase changes to ordered L1{sub 2} structure for samples with T{sub a} {>=} 400 deg. C. The highly ordered L1{sub 2} phase with magnetization of 1270 emu/cm{sup 3} and coercivity of 66 Oe was obtained in Fe{sub 3}Pt film at 700 deg. C-annealing.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Magnetism of dilute Co(Hf) and Co(Pt) nanoclusters

An investigation of the magnetic properties of Co-rich nanoparticles alloyed with a small fraction of Pt and Hf is presented. Co(Hf) and Co(Pt) nanoparticles with less than 15 at% of dopants were produced using a cluster-deposition method. The nanoparticles have sizes of less than 10 nm and show improved magnetic properties upon doping. Maximum coercivities of 900 Oe (at 300 K) and 2000 Oe (at 10 K) were observed for Co nanoparticles alloyed with 14.1 at% of Hf. Doped nanoparticles also exhibit high anisotropies, such as K-1 = 9.98 Mergs/cm(3) (14.1 at% of Hf) and K-1 = 8.24 Mergs/cm(3) (9.5 at% of Pt), as compared to Co nanoparticles (K-1 = 6.21 Mergs/cm(3)). (C) 2012 American Institute of Physics. [doi:10.1063/1.3678582]

Balamurugan, B↗