A laboratory X-ray emission spectrometer for phosphorus Kα and Kβ study of air-sensitive samples

Abramson, Jared; Holden, William M.; Rivera-Maldonado, Ricardo; Velian, Alexandra; Cossairt, Brandi M.; Seidler, Gerald T.

doi:10.1039/d3ja00053b

Cited by 6 publications

(5 citation statements)

References 46 publications

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“…In a recent detailed study, in which 5 nm Ni 2 P nanoparticles were synthesized under fully inert conditions and analyzed by P Kα X-ray emission spectroscopy (a bulk technique) after controlled air exposure, Seidler and co-workers demonstrated nearly complete oxidation to nickel phosphate after 1 week of air exposure. [37] The air-stability of Ni 2 P/Al 2 O 3 1-step , on the other hand, more closely resembles that of Pd/Al 2 O 3 . [27a] Crucially, thermal hydrogenation of nickel oxide and nickel phosphate, the common oxidation products of Ni 2 P, generally requires temperatures of ~450 °C and ~700 °C.…”

Section: Forschungsartikelmentioning

confidence: 99%

Expedited Synthesis of Metal Phosphides Maximizes Dispersion, Air Stability, and Catalytic Performance in Selective Hydrogenation

Karam,

Farès,

Weidenthaler

et al. 2024

Angewandte Chemie

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Metal phosphides have been hailed as potential replacements for scarce noble metal catalysts in many aspects of the hydrogen economy from hydrogen evolution to selective hydrogenation reactions. But the need for dangerous and costly phosphorus precursors, limited support dispersion, and low stability of the metal phosphide surface toward oxidation substantially lower the appeal and performance of metal phosphides in catalysis. We show here that a 1‐step procedure that relies on safe and cheap precursors can furnish an air‐stable Ni2P/Al2O3 catalyst containing 3.2 nm nanoparticles. Ni2P/Al2O3 1‐step is kinetically competitive with the palladium‐based Lindlar catalyst in selective hydrogenation catalysis, and a loading corresponding to 4 ppm Ni was sufficient to convert 0.1 mol alkyne. The 1‐step synthetic procedure alters the surface ligand speciation of Ni2P/Al2O3, which protects the nanoparticle surface from oxidation, and ensures that 85 % of the initial catalytic activity was retained after the catalyst was stored under air for 1.5 years. Preparation of Ni2P on a variety of supports (silica, TiO2, SBA‐15, ZrO2, C and HAP) as well as Co2P/Al2O3, Co2P/TiO2 and bimetallic NiCoP/TiO2 demonstrates the generality with which supported metal phosphides can be accessed in a safe and straightforward fashion with small sizes and high dispersion.

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Section: Forschungsartikelmentioning

confidence: 99%

Expedited Synthesis of Metal Phosphides Maximizes Dispersion, Air Stability, and Catalytic Performance in Selective Hydrogenation

Karam,

Farès,

Weidenthaler

et al. 2024

Angewandte Chemie

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“…X-ray Emission Spectroscopy. P Kα and Kβ XES measurements were performed on a laboratory spectrometer described in Abramson et al, 72 with a design similar to that of Holden et al, 73 and where the methodology of Stein et al 18 was used for estimating the oxidation state. The spectrometer is set up in a N 2 -filled glovebox and uses a low-power, unfocused X-ray tube (Varex VF-80, 100 W) to illuminate the sample, whose emitted X-rays are analyzed simultaneously by two 10 cm radius of curvature cylindrical crystal analyzer and coupled to homemade complementary metal oxide semiconductor (CMOS) direct-exposure color X-ray cameras.…”

Section: ■ Conclusionmentioning

confidence: 99%

“…The two multiplexed spectrometers are tuned to the P Kα and Kβ emission energies, respectively. Data collection followed the methodology from Abramson et al 72 InP QD samples were drop-cast onto Si wafer with a spot size of ∼5 mm diameter. The Kα emission spectra were analyzed using linear combination fitting with the nonlinear leastsquares fitting Python package LMFIT.36 (described in more detail in Stein et al 18 ).…”

Section: ■ Conclusionmentioning

confidence: 99%

Colloidal, Room-Temperature Growth of Metal Oxide Shells on InP Quantum Dots

et al. 2023

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We demonstrate colloidal, layer-by-layer growth of metal oxide shells on InP quantum dots (QDs) at room temperature. We show with computational modeling that native InP QD surface oxides give rise to nonradiative pathways due to the presence of surface-localized dark states near the band edges. Replacing surface indium with zinc to form a ZnO shell results in reduced nonradiative decay and a density of states at the valence band edge that resembles defect-free, stoichiometric InP. We then developed a synthetic strategy using stoichiometric amounts of common atomic layer deposition precursors in alternating cycles to achieve layer-by-layer growth. Metal-oxide-shelled InP QDs show bulk and local structural perturbations as determined by X-ray diffraction and extended X-ray absorption fine structure spectroscopy. Upon growing ZnSe shells of varying thickness on the oxide-shelled QDs, we observe increased photoluminescence (PL) quantum yields and narrowing of the emission linewidths that we attribute to decreased ion diffusion to the shell, as supported by phosphorus X-ray emission spectroscopy. These results present a versatile strategy to control QD interfaces for novel heterostructure design by leveraging surface oxides. This work also contributes to our understanding of the connections between structural complexity and PL properties in technologically relevant colloidal optoelectronic materials.

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“…Access to XES at synchrotron facilities in the tender X-ray region can be very limited and highly competitive (Mori et al, 2010;Rehanek et al, 2018;Butorin et al, 2018;Abraham et al, 2019;Rovezzi et al, 2020;Qureshi et al, 2021). Moreover, the availability of non-synchrotron based instruments for such experiments is also quite limited (Petric & Kavc ˇic ˇ, 2016;Malzer et al, 2018;Holden et al, 2017Holden et al, , 2018Abramson et al, 2023).…”

Section: Introductionmentioning

confidence: 99%

PINK: a tender X-ray beamline for X-ray emission spectroscopy

Peredkov,

Pereira,

Grötzsch

et al. 2024

J Synchrotron Rad

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A high-flux beamline optimized for non-resonant X-ray emission spectroscopy (XES) in the tender X-ray energy range has been constructed at the BESSY II synchrotron source. The beamline utilizes a cryogenically cooled undulator that provides X-rays over the energy range 2.1 keV to 9.5 keV. This energy range provides access to XES [and in the future X-ray absorption spectroscopy (XAS)] studies of transition metals ranging from Ti to Cu (Kα, Kβ lines) and Zr to Ag (Lα, Lβ), as well as light elements including P, S, Cl, K and Ca (Kα, Kβ). The beamline can be operated in two modes. In PINK mode, a multilayer monochromator (E/ΔE ≃ 30–80) provides a high photon flux (1014 photons s−1 at 6 keV and 300 mA ring current), allowing non-resonant XES measurements of dilute substances. This mode is currently available for general user operation. X-ray absorption near-edge structure and resonant XAS techniques will be available after the second stage of the PINK commissioning, when a high monochromatic mode (E/ΔE ≃ 10000–40000) will be facilitated by a double-crystal monochromator. At present, the beamline incorporates two von Hamos spectrometers, enabling time-resolved XES experiments with time scales down to 0.1 s and the possibility of two-color XES experiments. This paper describes the optical scheme of the PINK beamline and the endstation. The design of the two von Hamos dispersive spectrometers and sample environment are discussed here in detail. To illustrate, XES spectra of phosphorus complexes, KCl, TiO2 and Co3O4 measured using the PINK setup are presented.

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A laboratory X-ray emission spectrometer for phosphorus Kα and Kβ study of air-sensitive samples

Abstract: The analytical chemistry of phosphorus-containing materials is often impeded by the long measurement times and relatively large sample masses needed for 31P NMR spectroscopy, by the scarcity and access limitations...

Cited by 6 publications

References 46 publications

Expedited Synthesis of Metal Phosphides Maximizes Dispersion, Air Stability, and Catalytic Performance in Selective Hydrogenation

Expedited Synthesis of Metal Phosphides Maximizes Dispersion, Air Stability, and Catalytic Performance in Selective Hydrogenation

Colloidal, Room-Temperature Growth of Metal Oxide Shells on InP Quantum Dots

PINK: a tender X-ray beamline for X-ray emission spectroscopy

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