Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Published Version

Publication Date

2015

Journal or Book Title

Inorganic Chemistry

Volume

54

Issue

13

First Page

6356

Last Page

6362

DOI

10.1021/acs.inorgchem.5b00679

Abstract

Low-dimensional cuprous nitride (Cu3N) was synthesized by nitridation (ammonolysis) of cuprous oxide (Cu2O) nanocrystals using either ammonia (NH3) or urea (H2NCONH2) as the nitrogen source. The resulting nanocrystalline Cu3N spontaneously decomposes to nanocrystalline CuO in the presence of both water and oxygen from air at room temperature. Ammonia was produced in 60% chemical yield during Cu3N decomposition, as measured using the colorimetric indophenol method. Because Cu3N decomposition requires H2O and produces substoichiometric amounts of NH3>, we conclude that this reaction proceeds through a complex stoichiometry that involves the concomitant release of both N2 and NH3. This is a thermodynamically unfavorable outcome, strongly indicating that H2O (and thus NH3 production) facilitate the kinetics of the reaction by lowering the energy barrier for Cu3N decomposition. The three different Cu2O, Cu3N, and CuO nanocrystalline phases were characterized by a combination of optical absorption, powder X-ray diffraction, transmission electron microscopy, and electronic density of states obtained from electronic structure calculations on the bulk solids. The relative ease of interconversion between these interesting and inexpensive materials bears possible implications for catalytic and optoelectronic applications.

Comments

Reprinted (adapted) with permission from Inorganic Chemistry 54 (2015): 6356, doi: 10.1021/acs.inorgchem.5b00679. Copyright 2015 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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