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

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.

doi:10.1088/2053-1583/ab68e7

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

Journal Article · Wed Feb 05 00:00:00 EST 2020 · 2D Materials

DOI:https://doi.org/10.1088/2053-1583/ab68e7· OSTI ID:1594224

^[1]; Hantanasirisakul, Kanit ^[2]; ^[3]; ^[4]; Green, Robert J. ^[5]; Rogge, Paul C. ^[2]; Waluyo, Iradwikanari ^[6]; Hunt, Adrian ^[6]; ^[7]; Arenholz, Elke ^[8]; Shenoy, Vivek B. ^[3]; ^[2]; ^[2]

Drexel Univ., Philadelphia, PA (United States); Drexel University
Drexel Univ., Philadelphia, PA (United States)
Univ. of Pennsylvania, Philadelphia, PA (United States)
Drexel Univ., Philadelphia, PA (United States); Indiana Univ.—Purdue Univ. Indianapolis, IN (United States)
Univ. of Saskatchewan, Saskatoon, SK (Canada); Univ. of British Columbia, Vancouver, BC (Canada)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Cornell Univ., Ithaca, NY (United States)

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 (T_x), 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 (Ti₂CT_x, Ti₃C₂T_x, Cr₂TiC₂T_x, and Mo₂TiC₂T_x) 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 Mo₂TiC₂T_x and Cr₂TiC₂T_x. In contrast, for MXenes with surface Ti atoms, here Ti₃C₂T_x and Ti₂CT_x, 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 T_x 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.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Drexel Univ., Philadelphia, PA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: Department of Defense (DoD); National Science Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; 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

Grant/Contract Number:: AC02-05CH11231; SC0012704; SC0018618

OSTI ID:: 1594224

Alternate ID(s):: OSTI ID: 1635482
OSTI ID: 1775362
OSTI ID: 23020431

Report Number(s):: BNL--216104-2020-JAAM

Journal Information:: 2D Materials, Journal Name: 2D Materials Journal Issue: 2 Vol. 7; ISSN 2053-1583

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

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