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Title: 2D molybdenum and vanadium nitrides synthesized by ammoniation of 2D transition metal carbides (MXenes)

MXenes are a rapidly growing class of 2D transition metal carbides and nitrides, finding applications in fields ranging from energy storage to electromagnetic interference shielding and transparent conductive coatings. However, while more than 20 carbide MXenes have already been synthesized, Ti 4N 3 and Ti 2N are the only nitride MXenes reported so far. Here by ammoniation of Mo 2CT x and V 2CT x MXenes at 600 °C, we report on their transformation to 2D metal nitrides. Carbon atoms in the precursor MXenes are replaced with N atoms, resulting from the decomposition of ammonia molecules. The crystal structures of the resulting Mo 2N and V 2N were determined with transmission electron microscopy and X-ray pair distribution function analysis. Our results indicate that Mo 2N retains the MXene structure and V 2C transforms to a mixed layered structure of trigonal V 2N and cubic VN. Temperature-dependent resistivity measurements of the nitrides reveal that they exhibit metallic conductivity, as opposed to semiconductor-like behavior of their parent carbides. As important, room-temperature electrical conductivity values of Mo2N and V2N are three and one order of magnitude larger than those of the Mo 2CT x and V 2CT x precursors, respectively. In conclusion, thismore » study shows how gas treatment synthesis such as ammoniation can transform carbide MXenes into 2D nitrides with higher electrical conductivities and metallic behavior, opening a new avenue in 2D materials synthesis.« less
Authors:
ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [1] ; ORCiD logo [2] ;  [3] ;  [1] ; ORCiD logo [1] ; ORCiD logo [4] ; ORCiD logo [1]
  1. Drexel Univ., Philadelphia, PA (United States). A. J. Drexel Nanotechnology Inst., and Dept. of Materials Science & Engineering
  2. Columbia Univ., New York, NY (United States). Dept. of Applied Physics and Applied Mathematics
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  4. Columbia Univ., New York, NY (United States). Dept. of Applied Physics and Applied Mathematics; Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
Publication Date:
Report Number(s):
BNL-203531-2018-JAAM
Journal ID: ISSN 2040-3364; NANOHL
Grant/Contract Number:
SC0012704; DMR-1310245; DMR-1420634
Type:
Accepted Manuscript
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 9; Journal Issue: 45; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY
OSTI Identifier:
1433989

Urbankowski, Patrick, Anasori, Babak, Hantanasirisakul, Kanit, Yang, Long, Zhang, Lihua, Haines, Bernard, May, Steven J., Billinge, Simon J. L., and Gogotsi, Yury. 2D molybdenum and vanadium nitrides synthesized by ammoniation of 2D transition metal carbides (MXenes). United States: N. p., Web. doi:10.1039/C7NR06721F.
Urbankowski, Patrick, Anasori, Babak, Hantanasirisakul, Kanit, Yang, Long, Zhang, Lihua, Haines, Bernard, May, Steven J., Billinge, Simon J. L., & Gogotsi, Yury. 2D molybdenum and vanadium nitrides synthesized by ammoniation of 2D transition metal carbides (MXenes). United States. doi:10.1039/C7NR06721F.
Urbankowski, Patrick, Anasori, Babak, Hantanasirisakul, Kanit, Yang, Long, Zhang, Lihua, Haines, Bernard, May, Steven J., Billinge, Simon J. L., and Gogotsi, Yury. 2017. "2D molybdenum and vanadium nitrides synthesized by ammoniation of 2D transition metal carbides (MXenes)". United States. doi:10.1039/C7NR06721F. https://www.osti.gov/servlets/purl/1433989.
@article{osti_1433989,
title = {2D molybdenum and vanadium nitrides synthesized by ammoniation of 2D transition metal carbides (MXenes)},
author = {Urbankowski, Patrick and Anasori, Babak and Hantanasirisakul, Kanit and Yang, Long and Zhang, Lihua and Haines, Bernard and May, Steven J. and Billinge, Simon J. L. and Gogotsi, Yury},
abstractNote = {MXenes are a rapidly growing class of 2D transition metal carbides and nitrides, finding applications in fields ranging from energy storage to electromagnetic interference shielding and transparent conductive coatings. However, while more than 20 carbide MXenes have already been synthesized, Ti4N3 and Ti2N are the only nitride MXenes reported so far. Here by ammoniation of Mo2CTx and V2CTx MXenes at 600 °C, we report on their transformation to 2D metal nitrides. Carbon atoms in the precursor MXenes are replaced with N atoms, resulting from the decomposition of ammonia molecules. The crystal structures of the resulting Mo2N and V2N were determined with transmission electron microscopy and X-ray pair distribution function analysis. Our results indicate that Mo2N retains the MXene structure and V2C transforms to a mixed layered structure of trigonal V2N and cubic VN. Temperature-dependent resistivity measurements of the nitrides reveal that they exhibit metallic conductivity, as opposed to semiconductor-like behavior of their parent carbides. As important, room-temperature electrical conductivity values of Mo2N and V2N are three and one order of magnitude larger than those of the Mo2CTx and V2CTx precursors, respectively. In conclusion, this study shows how gas treatment synthesis such as ammoniation can transform carbide MXenes into 2D nitrides with higher electrical conductivities and metallic behavior, opening a new avenue in 2D materials synthesis.},
doi = {10.1039/C7NR06721F},
journal = {Nanoscale},
number = 45,
volume = 9,
place = {United States},
year = {2017},
month = {11}
}

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