Search NASA⌕ Search

SEARCH · Search NASA

Results for “PHOSPHIDES”

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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Method of synthesizing bulk transition metal carbide, nitride and phosphide catalysts

A method for synthesizing catalyst beads of bulk transmission metal carbides, nitrides and phosphides is provided. The method includes providing an aqueous suspension of transition metal oxide particles in a gel forming base, dropping the suspension into an aqueous solution to form a gel bead matrix, heating the bead to remove the binder, and carburizing, nitriding or phosphiding the bead to form a transition metal carbide, nitride, or phosphide catalyst bead. The method can be tuned for control of porosity, mechanical strength, and dopant content of the beads. The produced catalyst beads are catalytically active, mechanically robust, and suitable for packed-bed reactor applications. The produced catalyst beads are suitable for biomass conversion, petrochemistry, petroleum refining, electrocatalysis, and other applications.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Crystal and electronic structures of CaAl{sub 2}Si{sub 2}-type rare-earth copper zinc phosphides RECuZnP{sub 2} (RE=Pr, Nd, Gd-Tm, Lu)

The quaternary rare-earth phosphides RECuZnP{sub 2} (RE=Pr, Nd, Gd-Tm, Lu) have been prepared by reaction of the elements at 900 {sup o}C, completing this versatile series which forms for nearly all RE metals. They adopt the trigonal CaAl{sub 2}Si{sub 2}-type structure (Pearson symbol hP5, space group P3-bar m1, Z=1), as confirmed by single-crystal X-ray diffraction analysis on ErCuZnP{sub 2} and powder X-ray diffraction analysis on the remaining members. The Cu and Zn atoms are assumed to be disordered over the single transition-metal site. Band structure calculations on a hypothetically ordered YCuZnP{sub 2} model suggest a semimetal, with a zero band gap between the valence and conduction bands. This electronic structure is supported by XPS valence band spectra for RECuZnP{sub 2} (RE=Gd-Er), in which the intensity drops off smoothly at the Fermi edge. The absence of a band gap permits the electron count to deviate from the precise value of 16 e{sup -} per formula unit, as demonstrated by the formation of a solid solution in GdCu{sub x}Zn{sub 2-x}P{sub 2} (1.0{<=}x{<=}1.3), while still retaining the CaAl{sub 2}Si{sub 2}-type structure. Because the Cu 2p XPS spectra indicate that the Cu atoms are always monovalent, the substitution of Cu for Zn leads to a decrease in electron count and a lowering of the Fermi level in the valence band. The magnetic susceptibility of RECuZnP{sub 2} (RE=Gd-Er), which obeys the Curie-Weiss law, confirms the presence of trivalent RE atoms. -- Graphical abstract: The absence of a band gap in the semimetallic quaternary rare-earth phosphides RECuZnP{sub 2} permits the formation of a solid solution such as GdCu{sub x}Zn{sub 2-x}P{sub 2} through hole-doping of the valence band. Display Omitted

36 MATERIALS SCIENCE↗
DOE OSTI2014

Materials Development for Boron Phosphide Based Neutron Detectors: Final Technical Report

The project goal was to improve the quality of boron phosphide (BP) by optimizing its epitaxial growth on single crystal substrates and by producing bulk BP single crystals with low dislocation densities. BP is potentially a good semiconductor for high efficiency solid state neutron detectors by combining neutron capture and charge creation within the same volume. The project strategy was to use newly available single crystal substrates, silicon carbide and aluminum nitride, engineered to produce the best film properties. Substrate variables included the SiC polytype, crystallographic planes, misorientation of the substrate surface (tilt direction and magnitude) from the major crystallographic plane, and surface polarity (Si and C). The best films were (111)BP on silicon-face (0001) 4H-SiC misoriented 4° in the [1-100] direction, and BP on (100) and (111) 3C-SiC/Si; these substrates resulted in films that were free of in-plane twin defects, as determined by x-ray topography. The impact of the deposition temperature was also assessed: increasing the temperature from 1000 °C to 1200 °C produced films that were more ordered and more uniform, and the size of individual grains increased by more than a factor of twenty. The BP films were free of other compounds such as icosahedral boron phosphide (B 12 P 2 ) over the entire temperature range, as established by Raman spectroscopy. The roughness of the BP films was reduced by increasing the phosphine to diborane ratio from 50 to 200. Bulk crystals were grown by reacting boron dissolved in nickel with phosphorus vapor to precipitate BP. Crystals with dimensions up to 2 mm were produced.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2018

Colloidal Cobalt Phosphide Nanocrystals as Trifunctional Electrocatalysts for Overall Water Splitting Powered by a Zinc–Air Battery

Highly efficient and stable electrocatalysts, particularly those that are capable of multifunctionality in the same electrolyte, are in high demand for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). In this paper, highly monodisperse CoP and Co 2 P nanocrystals (NCs) are synthesized using a robust solution-phase method. The highly exposed (211) crystal plane and abundant surface phosphide atoms make the CoP NCs efficient catalysts toward ORR and HER, while metal-rich Co 2 P NCs show higher OER performance owing to easier formation of plentiful Co 2 P@COOH heterojunctions. Density functional theory calculation results indicate that the desorption of OH* from cobalt sites is the rate-limiting step for both CoP and Co 2 P in ORR and that the high content of phosphide can lower the reaction barrier. A water electrolyzer constructed with a CoP NC cathode and a Co 2 P NC anode can achieve a current density of 10 mA cm -2 at 1.56 V, comparable even to the noble metal-based Pt/C and RuO 2 /C pair. Finally and furthermore, the CoP NCs are employed as an air cathode in a primary zinc–air battery, exhibiting a high power density of 62 mW cm -2 and good stability.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Metal Phosphide Nanoparticles Generated via a Molecular Precursor Route for Hydrotreatment of Methyl Laurate

Transition metal phosphide nanoparticles supported on silica were used as catalysts to investigate the hydrodeoxygenation of methyl laurate (used as a model compound for vegetable oils). Ni 2 P, Ni 1 Mo 1 P, and Ni 1.6 Mo 0.4 P were synthesized using a molecular precursor route. The nanoparticles were added to the silica support without any changes in their structure or particle size. As a reference and for comparison, MoP/SiO 2 was also prepared by the phosphite method. The prepared catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and chemical analysis. A higher conversion is reached with the MoP/SiO 2 monometallic catalyst, close to that with Ni 1 Mo 1 P/SiO 2 . However, this observation is misleading because the differences in dispersion obscure the result that the intrinsic activity (turnover frequency) of the bimetallic catalyst, prepared by a molecular precursor route, is significantly higher than that of the monometallic catalyst, prepared by the phosphite route, revealing a synergistic effect on the catalytic activity due to the formation of the bimetallic phosphide.

09 BIOMASS FUELS↗
DOE OSTI2015

Evaluation of Silica-Supported Metal and Metal Phosphide Nanoparticle Catalysts for the Hydrodeoxygenation of Guaiacol Under Ex Situ Catalytic Fast Pyrolysis Conditions

A series of metal and metal phosphide catalysts were investigated for the hydrodeoxygenation of guaiacol under ex situ catalytic fast pyrolysis (CFP) conditions (350 °C, 0.5 MPa, 12 H 2 :1 guaiacol, weight hourly space velocity 5 h $-$1 ). Ligand-capped Ni, Pt, Rh, Ni 2 P, and Rh 2 P nanoparticles (NPs) were prepared using solution-phase synthesis techniques and dispersed on a silica support. For the metal phosphide NP-catalysts, a synthetic route that relies on the decomposition of a single molecular precursor was employed. The reactivity of the NP-catalysts was compared to a series of reference materials including Ni/SiO 2 and Pt/SiO 2 prepared using incipient wetness (IW) impregnation and a commercial (com) Pt/SiO 2 catalyst. The NP-Ni/SiO 2 catalyst exhibited the largest reduction in the oxygen mol% of the organic phase and outperformed the IW-Ni/SiO 2 material. Although it was less active for guaiacol conversion than NP-Ni/SiO 2 , NP-Rh2P/SiO 2 demonstrated the largest production of completely deoxygenated products and the highest selectivity to anisole, benzene, and cyclohexane, suggesting that it is a promising catalyst for deoxygenation of aryl-OH bonds. Finally, the com-Pt/SiO 2 and IW-Pt/SiO 2 catalyst exhibited the highest normalized rate of guaiacol conversion per m 2 and per gram of active phase, respectively, but did not produce any completely deoxygenated products.

09 BIOMASS FUELS↗
DOE OSTI2019

Application of phase-pure nickel phosphide nanoparticles as cathode catalysts for hydrogen production in microbial electrolysis cells

Transition metal phosphide catalysts such as nickel phosphide (Ni 2 P) have demonstrated excellent activities for the hydrogen evolution reaction, but they have primarily been studied in strongly acidic or alkaline electrolytes. In microbial electrolysis cells (MECs), yet, the electrolyte is usually a neutral pH to support the bacteria. Carbon-supported phase-pure Ni 2 P nanoparticle catalysts (Ni 2 P/C) were synthesized using solution-phase methods and their performance was compared to Pt/C and Ni/C catalysts in MECs. The Ni 2 P/C produced a similar quantity of hydrogen over a 24 h cycle (0.29 ± 0.04 L-H 2 /L-reactor) as that obtained using Pt/C (0.32 ± 0.03 L-H 2 /L) or Ni/C (0.29 ± 0.02 L-H2/L). The mass normalized current density of the Ni 2 P/C was 14 times higher than that of the Ni/C, and the Ni 2 P/C exhibited stable performance over 11 days. Ni 2 P/C may therefore be a useful alternative to Pt/C or other Ni-based catalysts in MECs due to its chemical stability over time.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Deoxygenation of Palmitic Acid on Unsupported Transition-Metal Phosphides

Abstract Highly active bulk transition metal phosphides (WP, MoP, and Ni2P) were synthesized for the catalytic hydrodeoxygenation of palmitic acid, hexadecanol, hexadecanal, and microalgae oil. The specific activities positively correlated with the concentration of exposed metal sites, although the relative rates changed with temperature due to activation energies varying from 57 kJ·mol-1 for MoP to 142 kJ·mol-1 for WP. The reduction of the fatty acid to the aldehyde occurs through a Langmuir-Hinshelwood mechanism, where the rate-determining step is the addition of the second H to the hydrocarbon. On WP, the conversion of palmitic acid proceeds via R-CH2COOH R-CH2CHO R-CH2CH2OH R-CHCH2 R-CH2CH3 (hydrodeoxygenation). Decarbonylation of the intermittently formed aldehyde (R-CH2COOH R-CH2CHO R-CH3) was an important pathway on MoP and Ni2P. Conversion via dehydration to a ketene, followed by its decarbonylation occurred only on Ni2P. The rates of alcohol dehydration (R-CH2CH2OH R-CHCH2) correlate with the concentration of Lewis acid sites of the phosphides. Acknowledgements The authors would like to thank Roel Prins for the critical discussion of the results. We are also grateful to Xaver Hecht for technical support. Funding by the German Federal Ministry of Food and Agriculture in the framework of the Advanced Biomass Value project (03SF0446A) is gratefully acknowledged. J.A.L. acknowledges support for his contribution by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences for exploring non-oxidic supports for deoxygenation reactions.

Bio-oil↗
DOE OSTI2016

Bimetallic Cobalt-Based Phosphide Zeolitic Imidazolate Framework: CoP x Phase-Dependent Electrical Conductivity and Hydrogen Atom Adsorption Energy for Efficient Overall Water Splitting

Cobalt-based bimetallic phosphide encapsulated in carbonized zeolitic imadazolate frameworks has been successfully synthesized and showed excellent activities toward both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Density functional theory calculation and electrochemical measurements reveal that the electrical conductivity and electrochemical activity are closely associated with the Co2P/CoP mixed phase behaviors upon Cu metal doping. This relationship is found to be the decisive factor for enhanced electrocatalytic performance. Moreover, the precise control of Cu content in Co-host lattice effectively alters the Gibbs free energy for H* adsorption, which is favorable for facilitating reaction kinetics. Impressively, an optimized performance has been achieved with mild Cu doping in Cu0.3Co2.7P/nitrogen-doped carbon (NC) which exhibits an ultralow overpotential of 0.19 V at 10 mA cm–2 and satisfying stability for OER. Cu0.3Co2.7P/NC also shows excellent HER activity, affording a current density of 10 mA cm–2 at a low overpotential of 0.22 V. In addition, a homemade electrolyzer with Cu0.3Co2.7P/NC paired electrodes shows 60% larger current density than Pt/ RuO2 couple at 1.74 V, along with negligible catalytic deactivation after 50 h operation. The manipulation of electronic structure by controlled incorporation of second metal sheds light on understanding and synthesizing bimetallic transition metal phosphides for electrolysis-based energy conversion.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2011

Structural stability and mutual transformations of molybdenum carbide, nitride and phosphide

Graphical abstract: Both Mo{sub 2}C and Mo{sub 2}N can be transformed to MoP, whereas the reverse changes are inviable, which is used to develop a promising and practical pathway for preparing MoP nanoparticles. Highlights: {yields} Mo carbide, nitride and phosphide are prepared. {yields} The structural stability increases in the order of Mo{sub 2}N < Mo{sub 2}C < MoP. {yields} Both Mo{sub 2}C and Mo{sub 2}N can be transformed to MoP, whereas the reverse changes are inviable. {yields} This study develops a promising and practical pathway for preparing MoP nanoparticles. -- Abstract: The structural stability and transformations of Mo carbide, nitride and phosphide were investigated under various atmosphere conditions by X-ray diffraction (XRD). The results indicated that the order of structural stability of these Mo-based compounds was as follows: Mo{sub 2}N < Mo{sub 2}C < MoP. Both Mo{sub 2}C and Mo{sub 2}N can be transformed to MoP, whereas the reverse transformations did not occur. Noticeably, compared with those Mo sources containing oxygen, the use of Mo{sub 2}C/Mo{sub 2}N as Mo-source can produce finely dispersed MoP nanoparticles by the temperature-programmed reaction (TPR) method. The result was probably due to the fact that lower-levels H{sub 2}O generated during synthesis process can avoid strong hydrothermal sintering. The influence of formation energy had been considered and was found to relate to the structural stability and transformations of these Mo-based compounds.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Three-dimensional interconnected nickel phosphide networks with hollow microstructures and desulfurization performance

Graphical abstract: Three-dimensional interconnected nickel phosphide networks with hollow microstructures and desulfurization performance. - Highlights: • Three-dimensional Ni{sub 2}P has been prepared using foam nickel as a template. • The microstructures interconnected and formed sponge-like porous networks. • Three-dimensional Ni{sub 2}P shows superior hydrodesulfurization activity. - Abstract: Three-dimensional microstructured nickel phosphide (Ni{sub 2}P) was fabricated by the reaction between foam nickel (Ni) and phosphorus red. The as-prepared Ni{sub 2}P samples, as interconnected networks, maintained the original mesh structure of foamed nickel. The crystal structure and morphology of the as-synthesized Ni{sub 2}P were characterized by X-ray diffraction, scanning electron microscopy, automatic mercury porosimetry and X-ray photoelectron spectroscopy. The SEM study showed adjacent hollow branches were mutually interconnected to form sponge-like networks. The investigation on pore structure provided detailed information for the hollow microstructures. The growth mechanism for the three-dimensionally structured Ni{sub 2}P was postulated and discussed in detail. To investigate its catalytic properties, SiO{sub 2} supported three-dimensional Ni{sub 2}P was prepared successfully and evaluated for the hydrodesulfurization (HDS) of dibenzothiophene (DBT). DBT molecules were mostly hydrogenated and then desulfurized by Ni{sub 2}P/SiO{sub 2}.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Revealing Structural Evolution of Nickel Phosphide-Iron Oxide Core–Shell Nanocatalysts in Alkaline Medium for the Oxygen Evolution Reaction

Metal phosphide-containing materials have emerged as a potential candidate of non-precious metal-based catalysts for alkaline oxygen evolution reaction (OER). While it is known that metal phosphide undergoes structural evolution, considerable debate persists regarding the effects of dynamics on the surface activation and morphological stability of the catalysts. In this study, we synthesize NiP x -FeO x core-shell nanocatalysts with an amorphous NiP x core designed for enhanced OER activity. Using ex-situ X-ray absorption spectroscopy, we elucidate the local structural changes as a function of cyclic voltammetry cycles. Our studies suggest that the presence of corner-sharing octahedra in the FeO x shell improves structural rigidity through interlayer cross-linking, thereby inhibiting the diffusion of OH - /H 2 O. Thus, the FeO x shell preserves the amorphous NiP x core from rapid oxidation to Ni 3 (PO 4 ) 2 and Ni(OH) 2 . On the other hand, the incorporation of Ni from the core into the FeO x shell facilitates absorption of hydroxide ions for OER. As a result, the Ni/Fe(OH) x at the surface oxidizes to the active γ-(oxy)hydroxide phase under the applied potentials, promoting OER. This intriguing synergistic behavior holds significance as such synthetic route involving the FeO x shell can be extended to other systems, enabling manipulation of surface adsorption and diffusion of hydroxide ions. These findings also demonstrate that nanomaterials with core-shell morphology can be tuned to leverage the strength of each metallic component for improved electrochemical activities.

25 ENERGY STORAGE↗
DOE OSTI2016

Highly Ordered Mesoporous Bimetallic Phosphides as Efficient Oxygen Evolution Electrocatalysts

Oxygen evolution from water using earth abundant transition metal based catalysts is of importance for the commercialization of water electrolyzer. Herein, we report a novel hard templating method to synthesize transition metal phosphides with uniform shape and size. By virtue of the structural feature, synergistic effect among metals and the in situ formed active species, the as-prepared phosphides with optimized composition present enhanced electrocatalytic performance towards oxygen evolution reaction in alkaline solution. In details, the most efficient catalyst reaches a current density of 10 mA/cm2 at a potential of 1.511 V vs reversible hydrogen electrode, which is much lower than that of commercial RuO2 catalyst. Our work offers a new strategy to optimize the catalysts for water splitting by controlling the morphology and composition.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2018

The Predominance of Hydrogen Evolution on Transition Metal Sulfides and Phosphides under CO 2 Reduction Conditions: An Experimental and Theoretical Study

Here, a combination of experiment and theory has been used to understand the relationship between the hydrogen evolution reaction (HER) and CO 2 reduction (CO 2 R) on transition metal phosphide and transition metal sulfide catalysts. Although multifunctional active sites in these materials could potentially improve their CO 2 R activity relative to pure transition metal electrocatalysts, under aqueous testing conditions, these materials showed a high selectivity for the HER relative to CO 2 R. Computational results supported these findings, indicating that a limitation of the metal phosphide catalysts is that the HER is favored thermodynamically over CO 2 R. On Ni-MoS2, a limitation is the kinetic barrier for the proton–electron transfer to *CO. These theoretical and experimental results demonstrate that selective CO 2 R requires electrocatalysts that possess both favorable thermodynamic pathways and surmountable kinetic barriers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

High-performance light-driven heterogeneous CO 2 catalysis with near-unity selectivity on metal phosphides

Akin to single-site homogeneous catalysis, a long sought-after goal is to achieve reaction site precision in heterogeneous catalysis for chemical control over patterns of activity, selectivity and stability. Herein, we report on metal phosphides as a class of material capable of realizing these attributes and unlock their potential in solar-driven CO 2 hydrogenation. Selected as an archetype, Ni 12 P 5 affords a structure based upon highly dispersed nickel nanoclusters integrated into a phosphorus lattice that harvest light intensely across the entire solar spectral range. Motivated by its panchromatic absorption and unique linearly bonded nickel-carbonyl-dominated reaction route, Ni 12 P 5 is found to be a photothermal catalyst for the reverse water gas shift reaction, offering a CO production rate of 960 ± 12 mmol g cat –1 h –1 , near 100% selectivity and long-term stability. Successful extension of this idea to Co2P analogs implies that metal phosphide materials are poised as a universal platform for high-rate and highly selective photothermal CO 2 catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Fabrication of Single Crystal Gallium Phosphide Thin Films on Glass

Due to its high refractive index and low absorption coefficient, gallium phosphide is an ideal material for photonic structures targeted at the visible wavelengths. However, these properties are only realized with high quality epitaxial growth, which limits substrate choice and thus possible photonic applications. In this work, we report the fabrication of single crystal gallium phosphide thin films on transparent glass substrates via transfer bonding. GaP thin films on Si (001) and (112) grown by MOCVD are bonded to glass, and then the growth substrate is removed with a XeF 2 vapor etch. The resulting GaP films have surface roughnesses below 1 nm RMS and exhibit room temperature band edge photoluminescence. Magnesium doping yielded p-type films with a carrier density of 1.6 × 10 17 cm -3 that exhibited mobilities as high as 16 cm 2 V -1 s -1 . Therefore, due to their unique optical properties, these films hold much promise for use in advanced optical devices.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Engineering absorption and blackbody radiation in the far-infrared with surface phonon polaritons on gallium phosphide

We demonstrate excitation of surface phonon polaritons on patterned gallium phosphide surfaces. Control over the light-polariton coupling frequencies is demonstrated by changing the pattern periodicity and used to experimentally determine the gallium phosphide surface phonon polariton dispersion curve. Selective emission via out-coupling of thermally excited surface phonon polaritons is experimentally demonstrated. Samples are characterized experimentally by Fourier transform infrared reflection and emission spectroscopy, and modeled using finite element techniques and rigorous coupled wave analysis. The use of phonon resonances for control of emissivity and excitation of bound surface waves offers a potential tool for the exploration of long-wavelength Reststrahlen band frequencies.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗