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Title: Structure-property relationships in NO x sensor materials composed of arrays of vanadium oxide nanoclusters

Here, the mixed-valent vanadium oxide based three-dimensional framework structure species [Cd 3(H 2O) 12V 16 IVV 2 VO 36(OH) 6(AO 4)]∙24H 2O, (A=V,S) (Cd 3(VO) o) represents a rare example of an interesting sensor material which exhibits NO x {NO+NO 2} semiconducting gas sensor properties under ambient conditions. The electrical resistance of the sensor material Cd 3(VO) o decreases in air. Combined characterization studies revealed that the building block, {V 18O 42(AO 4)} cluster, of 3-D framework undergoes oxidation and remains intact for at least 2 months. The decrease in resistance is attributable to the reactivity of molecular oxygen towards vanadium which results in an increase in the oxidation state as well as the coordination number of vanadium center and decrease in band gap of Cd 3(VO) o. Based on these results we propose that the changes in semiconducting properties of Cd 3(VO) o under ambient conditions are due to the greater overlap between the O 2p and V 3d orbitals occurring during the oxidation.
Authors:
ORCiD logo [1] ;  [2] ; ORCiD logo [1] ;  [1] ;  [1]
  1. Illinois Inst. of Technology, Chicago, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Chicago, Chicago, IL (United States)
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Solid State Sciences
Additional Journal Information:
Journal Volume: 74; Journal Issue: C; Journal ID: ISSN 1293-2558
Publisher:
Elsevier
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; vanadium oxide nanoclusters; NOx sensing; oxidation; XAFS
OSTI Identifier:
1429402

Putrevu, Naga Ravikanth, Darling, Seth B., Segre, Carlo U., Ganegoda, Hasitha, and Khan, M. Ishaque. Structure-property relationships in NOx sensor materials composed of arrays of vanadium oxide nanoclusters. United States: N. p., Web. doi:10.1016/j.solidstatesciences.2017.09.008.
Putrevu, Naga Ravikanth, Darling, Seth B., Segre, Carlo U., Ganegoda, Hasitha, & Khan, M. Ishaque. Structure-property relationships in NOx sensor materials composed of arrays of vanadium oxide nanoclusters. United States. doi:10.1016/j.solidstatesciences.2017.09.008.
Putrevu, Naga Ravikanth, Darling, Seth B., Segre, Carlo U., Ganegoda, Hasitha, and Khan, M. Ishaque. 2017. "Structure-property relationships in NOx sensor materials composed of arrays of vanadium oxide nanoclusters". United States. doi:10.1016/j.solidstatesciences.2017.09.008. https://www.osti.gov/servlets/purl/1429402.
@article{osti_1429402,
title = {Structure-property relationships in NOx sensor materials composed of arrays of vanadium oxide nanoclusters},
author = {Putrevu, Naga Ravikanth and Darling, Seth B. and Segre, Carlo U. and Ganegoda, Hasitha and Khan, M. Ishaque},
abstractNote = {Here, the mixed-valent vanadium oxide based three-dimensional framework structure species [Cd3(H2O)12V16IVV2VO36(OH)6(AO4)]∙24H2O, (A=V,S) (Cd3(VO)o) represents a rare example of an interesting sensor material which exhibits NOx {NO+NO2} semiconducting gas sensor properties under ambient conditions. The electrical resistance of the sensor material Cd3(VO)o decreases in air. Combined characterization studies revealed that the building block, {V18O42(AO4)} cluster, of 3-D framework undergoes oxidation and remains intact for at least 2 months. The decrease in resistance is attributable to the reactivity of molecular oxygen towards vanadium which results in an increase in the oxidation state as well as the coordination number of vanadium center and decrease in band gap of Cd3(VO)o. Based on these results we propose that the changes in semiconducting properties of Cd3(VO)o under ambient conditions are due to the greater overlap between the O 2p and V 3d orbitals occurring during the oxidation.},
doi = {10.1016/j.solidstatesciences.2017.09.008},
journal = {Solid State Sciences},
number = C,
volume = 74,
place = {United States},
year = {2017},
month = {10}
}