Combined in situ QXAFS and FTIR analysis of a Ni phosphide catalyst under hydrodesulfurization conditions

Bando, Kyoko K.; Wada, Takahiro; Miyamoto, Takeshi; Miyazaki, Kei; Takakusagi, Satoru; Koike, Yuichiro; Inada, Yuji; Nomura, Masaharu; Yamaguchi, Aritomo; Gott, Travis; Oyama, S. Ted; Asakura, Kiyotaka

doi:10.1016/j.jcat.2011.10.025

Cited by 50 publications

(32 citation statements)

References 32 publications

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“…This feature can be attributed to metal-to-ligand charge transfer, and resembles the pre-edge feature observed for Ni Kedge XANES spectra of Ni2P. 28,29 The ex-situ spectrum also exhibited a white line feature at 7727 eV similar to that observed for the CoO standard material, indicating the presence of oxidized Co in the as-prepared material that was not detectable by XANES in the active electrocatalyst. Figure 3f-j presents Fourier-transformed Co K-edge extended X-ray absorption fine structure (EXAFS) data analogous to the XANES data presented in Figure 3a-e. Due to the phase shift, the apparent distance in the Fourier-transformed data is ~0.5 Å shorter than the real distance.…”

Section: Supporting Information Placeholdermentioning

confidence: 57%

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction

Saadi¹,

Carim²,

Drisdell

et al. 2017

J. Am. Chem. Soc.

133

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Transition metal phosphides exhibit high catalytic activity toward the electrochemical hydrogenevolution reaction (HER) and resist chemical corrosion in acidic solutions. For example, an electrodeposited CoP catalyst exhibited an overpotential, η, of −η < 100 mV at a current density of −10 mA cm −2 in 0.500 M H 2 SO 4 (aq). To obtain a chemical description of the material asprepared and also while effecting the HER in acidic media, such electrocatalyst films were investigated using Raman spectroscopy and X-ray absorption spectroscopy both ex situ as well as under in situ and operando conditions in 0.500 M H 2 SO 4 (aq). Ex situ analysis using the tandem spectroscopies indicated the presence of multiple ordered and disordered phases that contained both near-zerovalent and oxidized Co species, in addition to reduced and oxygenated P species. Operando analysis indicated that the active electrocatalyst was primarily amorphous and predominantly consisted of near-zerovalent Co as well as reduced P.

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Section: Supporting Information Placeholdermentioning

confidence: 57%

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction

Saadi¹,

Carim²,

Drisdell

et al. 2017

J. Am. Chem. Soc.

133

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“…[8][9][10] Moreover, recent in situ XAFS studies show that the adsorption of sulfur on the Ni 2 P creates the active phase. [11][12][13] Therefore the chemically modified Ni 2 P surface is interesting not only the fundamental problem but also the catalysis applications.In the present study we have explored the density functional theoretical (DFT) work on the Ni 3 PP surface to reveal the mechanism of P-covered surface formation and its hydrogen adsorption properties in comparison with the Ni 3 P 2 .DFT calculations were performed using the Vienna abinitio Simulation Package code (VASP 5.2.12). [14-16] The Perdew-Burke-Ernzerh exchange-correlation functional with a generalized gradient approximation [17,18] was used.…”

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Density Function Theoretical Investigation on the Ni3PP Structure and the Hydrogen Adsorption Property of the Ni2P(0001) Surface

et al. 2013

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Electronic and structural properties of phosphorus terminated structure of Ni 2 P(0001) surface(Ni 3 PP) are investigated by density functional theoretical (DFT) calculation. Phosphorus adsorption largely stabilizes the Ni 2 P(0001) surface by creating Ni-P bonds on the Ni trimer. Atomic hydrogen can adsorb on the topmost P site but its adsorption energy is much lower than its adsorption energy on the Ni trimer site of Ni 3 P 2 surface. Our results suggest that the Ni trimer is the key factor for high catalytic activity.Nickel phosphide (Ni 2 P) shows a high catalytic activity for the hydrodesulfurization[1] and other hydrotreatment catalyses towards hydrodenitrogenation and hydrodeoxidation and so on.[2] The key issue to understand the hydrogenation reactions is interaction between hydrogen with Ni 2 P surface in an atomic level. The bulk structure of Ni 2 P is composed of two different layers with different composition, Ni 3 P 2 and Ni 3 P 1 , aligning alternately along the [0001] direction as shown in Figure 1(a). Rodriguez et al. showed that Ni 3 P 2 surface was more stable surface than Ni 3 P 1 surface and they discussed the hydrogen adsorption properties on the Ni 3 P 2 surface.[3] However, scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) studies on the Ni 2 P(0001) have revealed that the Ni 2 P(0001) surface is mainly (about 80 %) covered with phosphorus on the Ni three fold site of Ni 3 P 2 surface after 953 K annealing under UHV conditions with minor amount of uncovered Ni 3 P 2 surface. [4][5][6] This new phosphorus covered surface is called as Ni 3 PP surface. Similar phosphorus terminated surface was reported on the reconstructed (10-10) surface by STM observation [7]. The phosphorus termination of the surfaces were supported by photoemission spectroscope (PES) study. [8][9][10] Moreover, recent in situ XAFS studies show that the adsorption of sulfur on the Ni 2 P creates the active phase. [11][12][13] Therefore the chemically modified Ni 2 P surface is interesting not only the fundamental problem but also the catalysis applications.In the present study we have explored the density functional theoretical (DFT) work on the Ni 3 PP surface to reveal the mechanism of P-covered surface formation and its hydrogen adsorption properties in comparison with the Ni 3 P 2 .DFT calculations were performed using the Vienna abinitio Simulation Package code (VASP 5.2.12).[14-16] The Perdew-Burke-Ernzerh exchange-correlation functional with a generalized gradient approximation [17,18] was used. Projector-augmented wave approach (PAW) [19,20] have been used together with plane wave basis sets. The optimized bulk Ni 2 P lattice constants were a = b = 0.5876 nm, c = 0.3365 nm, α = β = 90°, γ = 120°. The Ni 2 P(0001) surface was modeled with 12 atomic-layers periodic slab with a ca. 3.5 nm vacuum layer. The chemical formula of Ni 3 P 2 and Ni 3 PP are Ni 36 P 18 and Ni 36 P 19 , respectively. The kinetic energy cutoff of 300 eV was used and the Brillouin zone was sampled by a 4 × 4 × 1 Monk...

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“…In addition Oyama et al found that the NiPS phase are active for 6 hydrodesulfurization reaction and they suggested the Ni(2) provides active site. [16][17][18][19][20][21] Despite these current insights, a thorough understanding of the high activity of Ni2P 8 at the atomic level requires us to investigate the structures and properties of Ni2P single 9 crystals. Many efforts have been made to date to elucidate the surface properties of Ni2P 10 single crystal surfaces, using X-ray photoelectron spectroscopy (XPS) [22,23], scanning 11 tunneling microscopy (STM) [24][25][26][27][28], low-energy electron diffraction (LEED) [24][25][26][27][28][29][30], 12 photoemission electron microscopy (PEEM) [25], photoelectron diffraction [31] and 13 photoemission spectroscopy (PES) [30,[32][33][34][35].…”

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confidence: 99%

An Investigation of Ni2P Single Crystal Surfaces: Structure, Electronic State and Reactivity

2015

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8Ni2P has demonstrated high catalytic activity for hydrodesulfurization and has 9 recently been employed as a catalyst in a variety of other reactions. We have thoroughly 10 reviewed the literature concerning Ni2P single crystal surfaces, with the aim of 11 determining the relationship between surface structure and catalytic properties. 12Published results to date indicate that Ni2P single crystal surfaces exhibit reconstructed 13 structures, and so the bulk terminated structure may not be stable. We have also 14 reviewed the surface structures and electronic states of (1×1) and reconstructed Ni2P

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Combined in situ QXAFS and FTIR analysis of a Ni phosphide catalyst under hydrodesulfurization conditions

Cited by 50 publications

References 32 publications

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction

Density Function Theoretical Investigation on the Ni3PP Structure and the Hydrogen Adsorption Property of the Ni2P(0001) Surface

An Investigation of Ni2P Single Crystal Surfaces: Structure, Electronic State and Reactivity

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