Electronic Conductivity in a Porous Vanadyl Prussian Blue Analogue upon Air Exposure

Published

November 6, 2017

Author(s)

Mary Anne Manumpil, Carmen Leal-Cervantes, Matthew R. Hudson, Craig Brown, Hemamala I. Karunadasa

Abstract

Exposure to humid oxygen or ambient air affords a 5-or-der-of-magnitude increase in the electronic conductivity of a new Prussian blue analog incorporation Co(II) and V(IV)-oxo units. Oxidation produces a mixed-valence framework, where the oxygen exposure time controls the V(IV)/V(V) ratio and thereby the material's conductivity. The oxidized framework shows an intervalence charge transfer band at ca. 4200 cm^-1, consistent with class II mixed-valence. Electronic conductivity measurements reveal semiconducting behavior in the mixed-valence frameworks with conductivity values of 10^-5^ S &#8226cm^-1 at room temperature and 10^-4S&#8226^-1 at 100 °C, and activation energies of ca. 03 eV. Nitrogen adsorption measurements at 77 K show that these materials posses permanent porosity before and ater oxidation with BET surface areas of 340 m²g^-1 and 370 m²g^-1, respectively.

Citation

Inorganic Chemistry

Volume

56

Issue

21

Pub Type

Journals

Download Paper

Local Download

Keywords

semiconductor, conductivity, Prussian blue, Crystallography

Citation

Manumpil, M. , Leal-Cervantes, C. , Hudson, M. , Brown, C. and Karunadasa, H. (2017), Electronic Conductivity in a Porous Vanadyl Prussian Blue Analogue upon Air Exposure, Inorganic Chemistry, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=923792 (Accessed October 15, 2024)