Stoichiometry-controlled FeP nanoparticles synthesized from a single source precursor

Hunger, Cornelia; Ojo, Wilfried-Solo; Bauer, Susanne E.; Xu, Shu; Zabel, Manfred; Chaudret, Bruno; Lacroix, Lise‐Marie; Scheer, Manfred; Nayral, Céline; Delpech, Fabien

doi:10.1039/c3cc46863a

Cited by 17 publications

(15 citation statements)

References 37 publications

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“…Compound 1 has been previously demonstrated to yield nanoparticles of FeP by solution-based decomposition 24 and was explored as a CVD precursor; however, it was found that Fe 2 P was the only material that deposited on a quartz substrate in our apparatus at 350 °C (Table S1) . The 31 P and 1 H NMR spectra of the off-gases from the decomposition of 1 under CVD conditions confirmed the elimination of PH 3 (Figures S2−S5).…”

Section: ■ Results and Discussionmentioning

confidence: 96%

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.

134

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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: ■ Results and Discussionmentioning

confidence: 96%

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.

134

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“…Recently, we investigated the usage of single‐source precursors for the synthesis of transition metal phosphide nanoparticles and could show that complexes containing only labile CO ligands and hydrogen substituents on phosphorus are suitable precursors for the synthesis of size‐ and stoichiometry‐controlled nanoparticles . This was demonstrated by the synthesis of FeP nanoparticles with a precise stoichiometry control by starting from the single‐source precursor [Fe(CO) 4 (PH 3 )] or [{Fe(CO) 3 } 2 (μ‐PH 2 )] 2 . Targeting the corresponding As‐containing complexes, we realized that the synthetic pathway for this kind of compounds goes totally different ways and, to our surprise, we achieved the synthesis of the unprecedented diarsene iron carbonyl complex [Fe(CO) 4 (η 2 ‐As 2 H 2 )] ( 2 )—a complex without sterically demanding ligands—in which the diarsene ligand is only stabilized in the coordination sphere of one transition metal.…”

Section: Methodsmentioning

confidence: 99%

“…Interestingly, under similar reaction conditions, the methanolysis of [{Fe(CO) 4 }P(SiMe 3 ) 3 ] leads to [{Fe(CO) 4 }(PH 3 )] in good yields. Thermolysis or photolysis of [{Fe(CO) 4 }(PH 3 )] lead to the formation of the dinuclear complex [{Fe(CO) 3 } 2 (μ‐PH 2 )] 2 , indicating that the hypothetical complex [Fe(CO) 4 (AsH 3 )] might form as an intermediate, which, however, is unstable and decomposes to 2 and other unidentified products.…”

Section: Methodsmentioning

confidence: 99%

The Parent Diarsene HAs=AsH as Side‐on Bound Ligand in an Iron Carbonyl Complex

et al. 2019

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The terminal diarsene HAs=AsH ligand attracts special interest concerning its bonding relation in comparison to its isolable relative, ethene. Herein, by the methanolysis of [{Fe(CO)4}As(SiMe3)3] (1) the synthesis of [{Fe(CO)4}(η2‐As2H2)] (2) is reported, containing a parent diarsene as unprecedented side‐on coordinated ligand. Following this synthetic route, also the D‐labeled complex [{Fe(CO)4}(η2‐As2D2)] (2D) could be isolated. The electronic structure and bonding situation of 2 was elucidated by DFT calculations revealing that 2 is best described as an olefin‐like complex. Moreover, the reactivity of 2 towards the Lewis acids [{M(CO)5}(thf)] (M=Cr, W) was investigated, leading to the complexes [Fe(CO)4AsHW(CO)5]2 (3) and [{Fe(CO)4}2AsH{Cr(CO)5}] (4), respectively.

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“…Cd 3 P 2 NCs could be synthesized by TOP (Khanna et al, 2010), PH 3 (Miao et al, 2012), P(SiMe 3 ) 3 (Miao et al, 2010), and MSCs (Li et al, 2014) acting as single source precursors. FeP could be synthesized by TOP (Henkes and Schaak, 2007) and (CO) 4 Fe(PH 3 ) (Hunger et al, 2013) acting as single source precursors. Copper phosphides could be synthesized by TOP (Henkes and Schaak, 2007), PH 3 (Manna et al, 2013), P(SiMe 3 ) 3 (Liu et al, 2016), and P 4 (Bichat et al, 2004a).…”

Section: Introductionmentioning

confidence: 99%

Chemical Synthesis and Applications of Colloidal Metal Phosphide Nanocrystals

Jia

Meng

et al. 2019

Front. Chem.

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Colloidal nanocrystals (NCs) have emerged as promising materials in optoelectronic devices and biological imaging application due to their tailorable properties through size, shape, and composition. Among these NCs, metal phosphide is an important class, in parallel with metal chalcogenide. In this review, we summarize the recent progress regarding the chemical synthesis and applications of colloidal metal phosphide NCs. As the most important metal phosphide NCs, indium phosphide (InP) NCs have been intensively investigated because of their low toxicity, wide and tunable emission range from visible to the near-infrared region. Firstly, we give a brief overview of synthetic strategies to InP NCs, highlighting the benefit of employing zinc precursors as reaction additive and the importance of different phosphorus precursors to improve the quality of the InP NCs, in terms of size distribution, quantum yield, colloidal stability, and non-blinking behavior. Next, we discuss additional synthetic techniques to overcome the issues of lattice mismatch in the synthesis of core/shell metal phosphide NCs, by constructing an intermediate layer between core/shell or designing a shell with gradient composition in a radial direction. We also envision future research directions of InP NCs. The chemical synthesis of other metal phosphide NCs, such as II–V metal phosphide NCs (Cd3P2, Zn3P2) and transition metal phosphides NCs (Cu3P, FeP) is subsequently introduced. We finally discuss the potential applications of colloidal metal phosphide NCs in photovoltaics, light-emitting diodes, and lithium ion battery. An overview of several key applications based on colloidal metal phosphide NCs is provided at the end.

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Stoichiometry-controlled FeP nanoparticles synthesized from a single source precursor

Cited by 17 publications

References 37 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

The Parent Diarsene HAs=AsH as Side‐on Bound Ligand in an Iron Carbonyl Complex

Chemical Synthesis and Applications of Colloidal Metal Phosphide Nanocrystals

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Stoichiometry-controlled FeP nanoparticles synthesized from a single source precursor

Cited by 17 publications

References 37 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

The Parent Diarsene HAs=AsH as Side‐on Bound Ligand in an Iron Carbonyl Complex

Chemical Synthesis and Applications of Colloidal Metal Phosphide Nanocrystals

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Product

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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