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Title: Distinguishing electronic contributions of surface and sub-surface transition metal atoms in Ti-based MXenes

Abstract

MXenes are a rapidly-expanding family of 2D transition metal carbides and nitrides that have attracted attention due to their excellent performance in applications ranging from energy storage to electromagnetic interference shielding. Numerous other electronic and magnetic properties have been computationally predicted, but not yet realized due to the experimental difficulty in obtaining uniform surface terminations (Tx), necessitating new design approaches for MXenes that are independent of surface groups. In this study, we distinguished the contributions of surface and sub-surface Ti atoms to the electronic structure of four Ti-based MXenes (Ti2CTx, Ti3C2Tx, Cr2TiC2Tx, and Mo2TiC2Tx) using soft x-ray absorption spectroscopy, revealing minimal changes in the spectral features between the parent MAX phase and its MXene when no surface Ti atoms are present in the MXene, such as Mo2TiC2Tx and Cr2TiC2Tx. In contrast, for MXenes with surface Ti atoms, here Ti3C2Tx and Ti2CTx, the Ti L-edge spectra are significantly modified compared to their parent MAX phase compounds. First principles calculations provide similar trends in the partial density of states derived from surface and interior Ti atoms, corroborating the spectroscopic measurements. Furthermore, these results reveal that electronic states derived from sub-surface M-site layers are largely unperturbed by the surface groups, indicating a relativelymore » short length scale over which the Tx groups alter the nominal electron count associated with Ti atoms and suggesting that desired band features should be hosted by sub-surface M-sites that are electronically more robust than their surface M-site counterparts.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [3];  [4];  [1];  [5];  [5]; ORCiD logo [6];  [7];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Drexel Univ., Philadelphia, PA (United States)
  2. Univ. of Pennsylvania, Philadelphia, PA (United States)
  3. Drexel Univ., Philadelphia, PA (United States); Indiana Univ.—Purdue Univ. Indianapolis, IN (United States)
  4. Univ. of Saskatchewan, Saskatoon, SK (Canada); Univ. of British Columbia, Vancouver, BC (Canada)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Cornell Univ., Ithaca, NY (United States)
Publication Date:
Research Org.:
Drexel Univ., Philadelphia, PA (United States); Brookhaven National Lab. (BNL), Upton, NY (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation (NSF); Department of Defense (DoD); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1594224
Alternate Identifier(s):
OSTI ID: 1635482; OSTI ID: 1775362
Report Number(s):
BNL-216104-2020-JAAM
Journal ID: ISSN 2053-1583; TRN: US2100922
Grant/Contract Number:  
SC0018618; SC0012704; W911NF-16-1-0447; EFMA-542879; CMMI-1727717; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
2D Materials
Additional Journal Information:
Journal Volume: 7; Journal Issue: 2; Journal ID: ISSN 2053-1583
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; MXene; x-ray absorption spectroscopy; electronic structure; titanium

Citation Formats

Yang, Yizhou, Hantanasirisakul, Kanit, Frey, Nathan C., Anasori, Babak, Green, Robert J., Rogge, Paul C., Waluyo, Iradwikanari, Hunt, Adrian, Shafer, Padraic, Arenholz, Elke, Shenoy, Vivek B., Gogotsi, Yury, and May, Steven J. Distinguishing electronic contributions of surface and sub-surface transition metal atoms in Ti-based MXenes. United States: N. p., 2020. Web. doi:10.1088/2053-1583/ab68e7.
Yang, Yizhou, Hantanasirisakul, Kanit, Frey, Nathan C., Anasori, Babak, Green, Robert J., Rogge, Paul C., Waluyo, Iradwikanari, Hunt, Adrian, Shafer, Padraic, Arenholz, Elke, Shenoy, Vivek B., Gogotsi, Yury, & May, Steven J. Distinguishing electronic contributions of surface and sub-surface transition metal atoms in Ti-based MXenes. United States. https://doi.org/10.1088/2053-1583/ab68e7
Yang, Yizhou, Hantanasirisakul, Kanit, Frey, Nathan C., Anasori, Babak, Green, Robert J., Rogge, Paul C., Waluyo, Iradwikanari, Hunt, Adrian, Shafer, Padraic, Arenholz, Elke, Shenoy, Vivek B., Gogotsi, Yury, and May, Steven J. Wed . "Distinguishing electronic contributions of surface and sub-surface transition metal atoms in Ti-based MXenes". United States. https://doi.org/10.1088/2053-1583/ab68e7. https://www.osti.gov/servlets/purl/1594224.
@article{osti_1594224,
title = {Distinguishing electronic contributions of surface and sub-surface transition metal atoms in Ti-based MXenes},
author = {Yang, Yizhou and Hantanasirisakul, Kanit and Frey, Nathan C. and Anasori, Babak and Green, Robert J. and Rogge, Paul C. and Waluyo, Iradwikanari and Hunt, Adrian and Shafer, Padraic and Arenholz, Elke and Shenoy, Vivek B. and Gogotsi, Yury and May, Steven J.},
abstractNote = {MXenes are a rapidly-expanding family of 2D transition metal carbides and nitrides that have attracted attention due to their excellent performance in applications ranging from energy storage to electromagnetic interference shielding. Numerous other electronic and magnetic properties have been computationally predicted, but not yet realized due to the experimental difficulty in obtaining uniform surface terminations (Tx), necessitating new design approaches for MXenes that are independent of surface groups. In this study, we distinguished the contributions of surface and sub-surface Ti atoms to the electronic structure of four Ti-based MXenes (Ti2CTx, Ti3C2Tx, Cr2TiC2Tx, and Mo2TiC2Tx) using soft x-ray absorption spectroscopy, revealing minimal changes in the spectral features between the parent MAX phase and its MXene when no surface Ti atoms are present in the MXene, such as Mo2TiC2Tx and Cr2TiC2Tx. In contrast, for MXenes with surface Ti atoms, here Ti3C2Tx and Ti2CTx, the Ti L-edge spectra are significantly modified compared to their parent MAX phase compounds. First principles calculations provide similar trends in the partial density of states derived from surface and interior Ti atoms, corroborating the spectroscopic measurements. Furthermore, these results reveal that electronic states derived from sub-surface M-site layers are largely unperturbed by the surface groups, indicating a relatively short length scale over which the Tx groups alter the nominal electron count associated with Ti atoms and suggesting that desired band features should be hosted by sub-surface M-sites that are electronically more robust than their surface M-site counterparts.},
doi = {10.1088/2053-1583/ab68e7},
journal = {2D Materials},
number = 2,
volume = 7,
place = {United States},
year = {2020},
month = {2}
}

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