Impact of Solution Chemistry on Growth and Structural Features of Mo-Substituted Spinel Iron Oxides

Haouari, Chérazade; Squires, Alexander G.; Berthelot, Romain; Stievano, Lorenzo; Sougrati, Moulay Tahar; Morgan, Benjamin J.; Lebedev, Oleg I.; Iadecola, Antonella; Borkiewicz, Olaf J.; Dambournet, Damien

doi:10.1021/acs.inorgchem.1c00278

Impact of Solution Chemistry on Growth and Structural Features of Mo-Substituted Spinel Iron Oxides

Journal Article · Thu May 06 00:00:00 EDT 2021 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.1c00278· OSTI ID:1833554

Haouari, Chérazade ^[1]; Squires, Alexander G. ^[2]; Berthelot, Romain ^[3]; ^[3]; ^[3]; ^[2]; Lebedev, Oleg I. ^[4]; Iadecola, Antonella ^[5]; Borkiewicz, Olaf J. ^[6]; ^[3]

Centre National de la Recherche Scientifique (CNRS) (France); Sorbonne Univ., Paris (France); Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amiens (France)
University of Bath (United Kingdom); Faraday Institution, Didcot (United Kingdom)
Centre National de la Recherche Scientifique (CNRS) (France); Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amiens (France)
Centre National de la Recherche Scientifique (CNRS) (France)
Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amiens (France)
Argonne National Lab. (ANL), Argonne, IL (United States)

The effect of crystallizing solution chemistry on the chemistry of subsequently as-grown materials was investigated for Mo-substituted iron oxides prepared by thermally activated co-precipitation. In the presence of Mo ions, we find that varying the oxidation state of the iron precursor from Fe(II) to Fe(III) causes a progressive loss of atomic long-range order with the stabilization of 2-4 nm particles for the sample prepared with Fe(III). The oxidation state of the Fe precursor also affects the distribution of Fe and Mo cations within the spinel structure. Increasing the Fe precursor oxidation state gives decreased Fe-ion occupation and increased Mo-ion occupation of tetrahedral sites, as revealed by the extended X-ray absorption fine structure. The stabilization of Mo within tetrahedral sites appears to be unexpected, considering the octahedral preferred coordination number of Mo(VI). The analysis of the atomic structure of the sample prepared with Fe(III) indicates a local ordering of vacancies and that the occupation of tetrahedral sites by Mo induces a contraction of the interatomic distances within the polyhedra as compared to Fe atoms. Moreover, the occupancy of Mo into the thermodynamic site preference of a Mo dopant in Fe₂O₃ assessed by density functional theory calculations points to a stronger preference for Mo substitution at octahedral sites. Hence, we suggest that the synthetized compound is thermodynamically metastable, that is, kinetically trapped. Such a state is suggested to be a consequence of the tetrahedral site occupation by Mo ions. The population of these sites, known to be reactive sites enabling particle growth, is concomitant with the stabilization of very small particles. Furthermore, we confirmed our hypothesis by using a blank experiment without Mo ions, further supporting the impact of tetrahedral Mo ions on the growth of iron oxide nanoparticles. Our findings provide new insights into the relationships between the Fechemistry of the crystallizing solution and the structural features of the as-grown Mo-substituted Fe-oxide materials.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: Reseau sur le Stockage Electrochimique de l'Energie (RS2E); Royal Society United Kingdom; The Faraday Institution; Agence Nationale de la recherche (ANR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1833554

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 10 Vol. 60; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Cationic vacancies
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Disordered structure
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Metal oxide nanoparticles
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Nanoparticles growth
Precursors
Spinel

Impact of Solution Chemistry on Growth and Structural Features of Mo-Substituted Spinel Iron Oxides

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