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Title: Assessing Stability of Transition Metal Nitrides in Aqueous Environments: The Case of Molybdenum, Iron, Vanadium and Nickel Nitride

Abstract

Analysis of the MoN, Mo2N, VN, Fe2N, Fe4N, Ni3N stability in the aqueous media was performed based on the thermodynamic data available in HSC Chemistry software. Our analysis show that among all the studied nitrides, cubic Mo2N is the most resistant while cubic VN is the least resistant to oxidation and decomposition. The change in temperature up to 100 °C does not significantly influence the formation potentials of transition metal oxides from nitrides; however, pH significantly affects the stability of the studied transition metal nitrides. In the case of Mo2N, MoN, and VN changing pH from acidic to neutral and alkaline decreases the stability of the nitrides and the oxide formation potentials shift to more negative values. Additionally, based on thermodynamics, orthorhombic Fe2N should be stable only in alkaline conditions, while cubic Fe4N and hexagonal Ni3N should be the most stable at pH ~ 7 and pH ~ 9. Changing pH from these values decreases the stability of both Fe4N and Ni3N and the formation of oxy-, hydroxy- species becomes thermodynamically more favorable. Overall, the limited stability of the metal nitrides places severe constraints for their use in aqueous electrocatalytic applications.

Authors:
ORCiD logo [1];  [2]
  1. Univ. of New Mexico, Albuquerque, NM (United States). Center for Micro-Engineered Materials (CMEM); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Univ. of New Mexico, Albuquerque, NM (United States). Center for Micro-Engineered Materials (CMEM)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E)
OSTI Identifier:
1671088
Report Number(s):
LA-UR-19-31548
Journal ID: ISSN 1945-7111
Grant/Contract Number:  
89233218CNA000001; AR0000687
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society (Online)
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society (Online); Journal Volume: 167; Journal Issue: 4; Journal ID: ISSN 1945-7111
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; transition metal nitrides; thermodynamic stability; molybdenum nitride; nickel nitride; iron nitride; vanadium nitride

Citation Formats

Matanovic, Ivana, and Garzon, Fernando H. Assessing Stability of Transition Metal Nitrides in Aqueous Environments: The Case of Molybdenum, Iron, Vanadium and Nickel Nitride. United States: N. p., 2020. Web. doi:10.1149/1945-7111/ab7a8b.
Matanovic, Ivana, & Garzon, Fernando H. Assessing Stability of Transition Metal Nitrides in Aqueous Environments: The Case of Molybdenum, Iron, Vanadium and Nickel Nitride. United States. doi:10.1149/1945-7111/ab7a8b.
Matanovic, Ivana, and Garzon, Fernando H. Fri . "Assessing Stability of Transition Metal Nitrides in Aqueous Environments: The Case of Molybdenum, Iron, Vanadium and Nickel Nitride". United States. doi:10.1149/1945-7111/ab7a8b.
@article{osti_1671088,
title = {Assessing Stability of Transition Metal Nitrides in Aqueous Environments: The Case of Molybdenum, Iron, Vanadium and Nickel Nitride},
author = {Matanovic, Ivana and Garzon, Fernando H.},
abstractNote = {Analysis of the MoN, Mo2N, VN, Fe2N, Fe4N, Ni3N stability in the aqueous media was performed based on the thermodynamic data available in HSC Chemistry software. Our analysis show that among all the studied nitrides, cubic Mo2N is the most resistant while cubic VN is the least resistant to oxidation and decomposition. The change in temperature up to 100 °C does not significantly influence the formation potentials of transition metal oxides from nitrides; however, pH significantly affects the stability of the studied transition metal nitrides. In the case of Mo2N, MoN, and VN changing pH from acidic to neutral and alkaline decreases the stability of the nitrides and the oxide formation potentials shift to more negative values. Additionally, based on thermodynamics, orthorhombic Fe2N should be stable only in alkaline conditions, while cubic Fe4N and hexagonal Ni3N should be the most stable at pH ~ 7 and pH ~ 9. Changing pH from these values decreases the stability of both Fe4N and Ni3N and the formation of oxy-, hydroxy- species becomes thermodynamically more favorable. Overall, the limited stability of the metal nitrides places severe constraints for their use in aqueous electrocatalytic applications.},
doi = {10.1149/1945-7111/ab7a8b},
journal = {Journal of the Electrochemical Society (Online)},
number = 4,
volume = 167,
place = {United States},
year = {2020},
month = {3}
}

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