Journal article
Molybdenum Oxide Precursors that Promote the Low-Temperature Formation of High-Surface-Area Cubic Molybdenum (Oxy)nitride
Inorganic chemistry, v 61(42), pp 16760-16769
24 Oct 2022
PMID: 36219544
Abstract
Molybdenum nitrides and oxynitrides have been increasingly realized as (electro)catalysts for a variety of reactions. In this context, the cubic "gamma-Mo2N", also known to contain oxygen in the bulk, is of particular interest. The gamma phase is typically derived from ammonolysis of MoO3, and a high temperature is needed to fully react the stable MoO2 intermediate that often forms along the reaction pathway. In this study, ammonolysis of atypical bronze (HxMoO(3)) and peroxo (H2MoO5) precursors was undertaken to avoid the formation of this undesired intermediate with the aim of synthesizing "gamma-Mo2N" at reduced temperatures and thus with a high surface area. It was found, using in situ powder diffraction, that, when the phase I bronze (x approximate to 0.3) served as the precursor, MoO2 formed as an intermediate and was retained in the reaction product until 700 degrees C. In contrast, ammonolysis of the phase III bronze (x approximate to 1.7) and of H2MoO5 circumvented the MoO2 intermediate. From these latter two precursors, "gamma-Mo2N" was formed at the lowest maximum reaction temperatures reported in the literature, namely, 480 degrees C in the case of HxMoO(3)-III and 380 degrees C for H2MoO5. The resulting products displayed extremely high surface areas of 206 and 152 m(2)/g, respectively, presumably as a consequence of the low synthesis temperatures. While the HxMoO(3)-III precursor showed evidence of a topotactic transformation pathway, with morphological similarity between precursor and product phases, H2MoO5 transformed via amorphization. Electrochemical characterization showed moderate activity for the hydrogen evolution reaction (HER), which increased after exposure to reducing potentials and loosely scaled with the catalystspecific surface area. This work points toward new low-temperature synthesis pathways for accessing molybdenum (oxy)nitrides with high surface areas.
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Details
- Title
- Molybdenum Oxide Precursors that Promote the Low-Temperature Formation of High-Surface-Area Cubic Molybdenum (Oxy)nitride
- Creators
- Elise A. Goldfine - Northwestern UniversityJill K. Wenderott - Northwestern UniversityMatthew E. Sweers - Northwestern UniversityShobhit Pandey - Northwestern UniversityLinsey C. Seitz - Northwestern UniversityMichael J. Bedzyk - Northwestern UniversitySossina M. Haile - Northwestern University
- Publication Details
- Inorganic chemistry, v 61(42), pp 16760-16769
- Publisher
- Amer Chemical Soc
- Number of pages
- 10
- Grant note
- DMR-1720139 / MRSEC-IRG2 (NSF) ECCS-2025633 / Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF) IIN
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Materials Science and Engineering
- Web of Science ID
- WOS:000877042400001
- Scopus ID
- 2-s2.0-85140418072
- Other Identifier
- 991022132052904721