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Research Article

Mechanistic insight into the controlled synthesis of metal phosphide catalysts from annealing of metal oxides with sodium hypophosphite

Fanpeng Chen1,§, Bohang Zhao1,§, Mengyao Sun1, Cuibo Liu1, Yanmei Shi1, Yifu Yu1, Bin Zhang1,2( )
Department of Chemistry, School of Science, Institute of Molecular Plus, Tianjin University, Tianjin 300072, China
Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Tianjin 300072, China

§ Fanpeng Chen and Bohang Zhao contributed equally to this work.

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Graphical Abstract

The antagonism of the driven and impeded forces (time, P/O ratio, temperature, crystallinity, and oxophilicity) is reported to determine the composition of various products (e.g., metal oxide (MO), MOx−δ, MOx−δ–MPy, MPy, MP, and MPO) for the phosphorization synthesis of metal oxides. As a proof-of-concept application, the as-synthesized WO2.9/WP exhibits greatly improved photocatalytic oxidative performance toward the coupling of methane, outperforming WO3, WO2.9, and WP counterparts.

Abstract

Understanding and manipulating synthetic progress for precisely controlling the components and defects of nanomaterials is an important and challenging task in materials synthesis and nanocatalysis. Metal phosphides (MPs) have been explored as cheap advanced materials in various catalytic fields. MP materials are usually synthesized through gas-solid phosphorization reaction in a trial-to-error manner, but their formation mechanism and the origin of controlled synthesis remain unclear. Here, we combine in situ thermogravimetric analysis-mass spectrometry (TG-MS) and quasi-in situ X-ray powder diffraction (XRD) analysis to probe the transformation mechanism from metal oxides (MOs) to MPs during the phosphorization process mediated by hypophosphite. Temperature, time, and the amount of hypophosphite are revealed as the driven forces while oxophilicity and crystallinity as the impeded forces, simultaneously control the component and defect level of a series of MP (M = Ni, Co, W, Mo, and Nb). The as-obtained WO2.9/WP is proved to be an efficient Z-scheme photocatalyst for oxidative coupling of methane with the total C2+ production and C2H4 selectivity in C2+ products reaching 10.75 μmol·g−1 and 98.25%. Our work provides a fundamental understanding of the phosphorization treatment and thereby guides a viable synthetic route to the controlled synthesis of MOx−δ, MP, MOx−δ/MP, and MP/M heterostructured materials.

Keywords

phosphorization treatmentmetal phosphidesmethodologyheterostructureoxygen vacancyphotocatalysis

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Nano Research
Volume 15 Issue 12,
December 2022
Pages 10134-10141
DOI: 10.1007/s12274-022-4489-x
Cite this article:
Chen F, Zhao B, Sun M, et al. Mechanistic insight into the controlled synthesis of metal phosphide catalysts from annealing of metal oxides with sodium hypophosphite. Nano Research, 2022, 15(12): 10134-10141. https://doi.org/10.1007/s12274-022-4489-x
Topics:
Structural design
Part of a topical collection:
NR45 Awards in Nanocatalysis, 2022

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Received: 03 March 2022
Revised: 24 April 2022
Accepted: 02 May 2022
Published: 04 June 2022
© Tsinghua University Press 2022
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