A Single Molecular Stoichiometric P-Source for Phase- Selective Synthesis of Crystalline and Amorphous Iron Phosphide Nanocatalysts - Sorbonne Université Access content directly
Journal Articles ChemNanoMat Year : 2020

A Single Molecular Stoichiometric P-Source for Phase- Selective Synthesis of Crystalline and Amorphous Iron Phosphide Nanocatalysts

Capucine Sassoye
Clément Sanchez
Sophie Carenco

Abstract

The formation of iron phosphide nanoparticles (FexP) is a well‐studied process. It usually uses air‐sensitive phosphorus precursors such as n‐trioctylphosphine or white phosphorus. In this study, we report the synthesis and characterization of a remarkably stable tetrakis(acyl)cyclotetraphosphane, P4(MesCO)4. We demonstrate that this compound can be used as a stoichiometric source of P(0) species in order to synthesize FeP and Fe2P nanoparticles at only 250 °C. This tunable process provides a route to monodisperse nanoparticles with different compositions and crystallinities. We combine X‐Ray photoelectron spectroscopy and atomic pair distribution function (PDF) to study the local order and bonding in the amorphous and crystalline materials. We show that crystalline FeP forms via an intermediate amorphous phase (obtained at a lower temperature) that presents local order similar to that of the crystalline sample. We explore their electrocatalytic properties for the hydrogen evolution reaction (HER) in acidic and neutral electrolytes. In both electrolytes, amorphous FeP is a more efficient catalyst than crystalline FeP, itself more efficient than crystalline Fe2P. Our study paves the way for a more systematic investigation of amorphous metal phosphide phases in electrocatalysis. It also shows the beneficial use of PDF on the highly challenging characterization of amorphous nanomaterials.
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Dates and versions

hal-02565354 , version 1 (06-05-2020)

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Florian D’accriscio, Erik Schrader, Capucine Sassoye, Mohamed Selmane, Rémi André, et al.. A Single Molecular Stoichiometric P-Source for Phase- Selective Synthesis of Crystalline and Amorphous Iron Phosphide Nanocatalysts. ChemNanoMat, 2020, ⟨10.1002/cnma.202000198⟩. ⟨hal-02565354⟩
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