Mechanistic insight into the controlled synthesis of metal phosphide catalysts from annealing of metal oxides with sodium hypophosphite
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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.
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Mechanistic insight into the controlled synthesis of metal phosphide catalysts from annealing of metal oxides with sodium hypophosphite
)
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.
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Acknowledgements
We acknowledge the National Natural Science Foundation of China (Nos. 21422104 and 21373149) for financial support.
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