A structural survey of the binary transition metal phosphides and arsenides of the d-block elements

Chen, Jinghan; Whitmire, Kenton H.

doi:10.1016/j.ccr.2017.08.029

Cited by 56 publications

(40 citation statements)

References 283 publications

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“…2 Fe(CO)4PH3  (-H)Fe2(CO)6(-CO)(-PH2) + PH3 (1) It was reasoned that with Compound 2, a t Bu group in place of a hydrogen could slow, and potentially stop, the release of phosphorus as PH 3 since PH 2 t Bu is a stronger donor and should be bound more tightly. 25 At 350 o C, Fe 2 P was again the product but decomposition of 2 at 450 o C gave phase-pure FeP.…”

Section: Mocvd Growth Of Phase Pure Thin Films Of Fep and Fe 2 Pmentioning

confidence: 99%

Effects of Catalyst Phase on the Hydrogen Evolution Reaction of Water Splitting: Preparation of Phase-Pure Films of FeP, Fe₂P, and Fe₃P and Their Relative Catalytic Activities

Schipper

Zhao

Thirumalai³

et al. 2018

Chem. Mater.

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132

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The comparative catalytic activities of iron phosphides, Fe x P (x = 1-3), have been established with phase-pure material grown by Chemical Vapor Deposition (CVD) from single-source organometallic precursors. This is the first report of the preparation of phase-pure thin films of FeP and Fe 2 P and their identity was established with scanning-electron microscopy, X-ray photoelectron spectroscopy, and powder X-ray diffraction. All materials were deposited on fluorine-doped tin oxide (FTO) for evaluation of their activities towards the hydrogen evolution reaction (HER) of water splitting in 0.5 M H 2 SO 4. HER activity follows the trend Fe 3 P > Fe 2 P > FeP, with Fe 3 P having the lowest overpotential of 49 mV at a current density of 10 mA cm-2. Density functional theory (DFT) calculations are congruent with the observed activity trend with hydrogen binding favoring the iron-rich terminating surfaces of Fe 3 P and Fe 2 P over the iron-poor terminating surfaces of FeP. The results present a clear trend of activity with iron-rich phosphide phases outperforming phosphorus rich phases for hydrogen evolution. The films of Fe 2 P were grown using Fe(CO) 4 PH 3 (1), while the films of FeP were prepared using either Fe(CO) 4 P t BuH 2 (2) or the new molecule {Fe(CO) 4 P(H) t Bu} 2 (3) on quartz and FTO. Compound 3 was prepared from the reaction of PCl 2 t Bu with a mixture of Na[HFe(CO) 4 ] and Na 2 [Fe(CO) 4 ] and characterized by single-crystal X-Ray diffraction, ESI-MS, elemental analysis, and 31 P/ 1 H NMR spectroscopies. Films of Fe 3 P were prepared as previously described from H 2 Fe 3 (CO) 9 P t Bu (4).

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Section: Mocvd Growth Of Phase Pure Thin Films Of Fep and Fe 2 Pmentioning

confidence: 99%

Effects of Catalyst Phase on the Hydrogen Evolution Reaction of Water Splitting: Preparation of Phase-Pure Films of FeP, Fe₂P, and Fe₃P and Their Relative Catalytic Activities

Schipper

Zhao

Thirumalai³

et al. 2018

Chem. Mater.

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132

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“…In particular, TMPs have been explored as highly efficient electrocatalysts toward the hydrogen evolution reaction (HER) in recent years . Due to the extraordinary richness of the phase space, TMPs offer great flexibility to tune their properties by controlling their phase . As ruthenium (Ru) is a low‐price noble metal (ca.…”

Section: Methodsmentioning

confidence: 99%

“…[5][6][7][8][9][10][11][12] Due to the extraordinary richness of the phase space,T MPs offer great flexibility to tune their properties by controlling their phase. [13] As ruthenium (Ru) is al ow-price noble metal (ca. 1/10 the price of Pt), Ru phosphides hold great promise as HER catalysts forp ractical application.…”

Section: Introductionmentioning

confidence: 99%

Benchmarking Three Ruthenium Phosphide Phases for Electrocatalysis of the Hydrogen Evolution Reaction: Experimental and Theoretical Insights

Liu

Wang

Zhong

et al. 2019

Chemistry A European J

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The outstanding electrocatalytic activityo f ruthenium (Ru) phosphides towardt he hydrogen evolution reaction( HER) has received wide attention.H owever, the effect of the Ru phosphide phase on the HER performance remains unclear.H erein, at wo-step methodw as developed to synthesize nanoparticles of three types of Ru phosphides, namely,R u 2 P, RuP,a nd RuP 2 ,w ith similar morphology,d imensions,l oading density,a nd electrochemical surface area on graphene nanosheets by simply controlling the dosageo fp hytic acida sPsource. Electrochemical tests revealed that Ru 2 P/graphene shows the highesti ntrinsic HER activity,f ollowedb yR uP/graphene and RuP 2 /graphene. Ru 2 P/graphene affords ac urrent density of 10 mA cm À2 at an overpotential of 18 mV in acid media.T heoretical calculationsf urthers howed that P-deficient Ru 2 Phas alower free energy of hydrogena dsorption on the surface than other two, P-rich Ru phosphides (RuP, RuP 2 ), which confirms the excellent intrinsic HER activity of Ru 2 Pa nd is consistent with experiment results. The work reveals for the first time ac lear trend of HER activity among three Ru phosphide phases.[a] T.

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“…As a class of materials, transition metal phosphides are unique in terms of both structure and reactivity. Such materials often have bulk physical and mechanical properties reminiscent of ceramics, while still exhibiting metal-like electronic characteristics, 1 allowing access to interesting structures 2 and reactivity not accessible via other materials such as metal nitrides or sulfides. Initially considered little more than "Chemist's Oddities", 3 transition metal phosphides have garnered significant attention in the literature as active catalysts for, among other things, hydrotreating and the hydrogen evolution reaction (HER).…”

Section: Introductionmentioning

confidence: 99%

In Situ Formation of a Sub-Nanometer Iridium Phosphide Catalyst from Supported Organometallic Species

Sheludko

Wegener

Çelik

et al. 2020

Preprint

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While several metal phosphides have attracted significant attention in the last several years due to their potential use as photocatalytic and hydrotreating catalysts, iridium phosphide has remained largely unexplored. In this work, silica-supported pincer-iridium species are thermolyzed, resulting in deconstruction of the tridentate ligand precursor and formation of a sub-nanometer iridium phosphide phase characterized by 31P magic angle spinning nuclear magnetic resonance (31P-MAS-NMR), X-ray absorption spectroscopy (XAS), and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). The support material was found to play an active role in determining the product of the surface thermolysis, with the silica supported material generating phosphorus rich iridium phosphide nanoparticles. The resulting silica-supported iridium phosphide phase is explored as a thermocatalyst for non-oxidative butane dehydrogenation, achieving high initial reaction rates up to 900 molbutenes molcatalyst-1 hr-1 and a terminal olefin selectivity of up to 70 %.

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A structural survey of the binary transition metal phosphides and arsenides of the d-block elements

Cited by 56 publications

References 283 publications

Effects of Catalyst Phase on the Hydrogen Evolution Reaction of Water Splitting: Preparation of Phase-Pure Films of FeP, Fe₂P, and Fe₃P and Their Relative Catalytic Activities

Effects of Catalyst Phase on the Hydrogen Evolution Reaction of Water Splitting: Preparation of Phase-Pure Films of FeP, Fe₂P, and Fe₃P and Their Relative Catalytic Activities

Benchmarking Three Ruthenium Phosphide Phases for Electrocatalysis of the Hydrogen Evolution Reaction: Experimental and Theoretical Insights

In Situ Formation of a Sub-Nanometer Iridium Phosphide Catalyst from Supported Organometallic Species

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A structural survey of the binary transition metal phosphides and arsenides of the d-block elements

Cited by 56 publications

References 283 publications

Effects of Catalyst Phase on the Hydrogen Evolution Reaction of Water Splitting: Preparation of Phase-Pure Films of FeP, Fe2P, and Fe3P and Their Relative Catalytic Activities

Effects of Catalyst Phase on the Hydrogen Evolution Reaction of Water Splitting: Preparation of Phase-Pure Films of FeP, Fe2P, and Fe3P and Their Relative Catalytic Activities

Benchmarking Three Ruthenium Phosphide Phases for Electrocatalysis of the Hydrogen Evolution Reaction: Experimental and Theoretical Insights

In Situ Formation of a Sub-Nanometer Iridium Phosphide Catalyst from Supported Organometallic Species

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Effects of Catalyst Phase on the Hydrogen Evolution Reaction of Water Splitting: Preparation of Phase-Pure Films of FeP, Fe₂P, and Fe₃P and Their Relative Catalytic Activities

Effects of Catalyst Phase on the Hydrogen Evolution Reaction of Water Splitting: Preparation of Phase-Pure Films of FeP, Fe₂P, and Fe₃P and Their Relative Catalytic Activities