Shifts in valence states in bimetallic MXenes revealed by electron energy-loss spectroscopy (EELS)

Foucher, Alexandre C.; Han, Meikang; Shuck, Christopher E.; Maleski, Kathleen; Gogotsi, Yury; Stach, Eric Andrew

doi:10.1088/2053-1583/ac4ba2

Shifts in valence states in bimetallic MXenes revealed by electron energy-loss spectroscopy (EELS)

Journal Article · Sun Jan 30 23:00:00 EST 2022 · 2D Materials

DOI:https://doi.org/10.1088/2053-1583/ac4ba2· OSTI ID:1979455

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Univ. of Pennsylvania, Philadelphia, PA (United States); OSTI
Drexel Univ., Philadelphia, PA (United States)
Univ. of Pennsylvania, Philadelphia, PA (United States)

MXenes are an emergent class of two-dimensional materials with a very wide spectrum of promising applications. The synthesis of multiple MXenes, specifically solid-solution MXenes, allows fine tuning of their properties, expands their range of applications, and leads to enhanced performance. The functionality of solid-solution MXenes is closely related to the valence state of their constituents: transition metals, oxygen, carbon, and nitrogen. However, the impact of changes in the oxidation state of elements in MXenes is not well understood. In this work, three interrelated solid-solution MXene systems (Ti$$_{2–y}$$Nb$$_y$$CT$$_x$$, Nb$$_{2–y}$$V$$_y$$CT$$_x$$, and Ti$$_{2–y}$$V$$_y$$CT$$_x$$) were investigated with scanning transmission electron microscopy and electron energy-loss spectroscopy to determine the localized valence states of metals at the nanoscale. The analysis demonstrates changes in the electronic configuration of V upon modification of the overall composition and within individual MXene flakes. These shifts of oxidation state can explain the nonlinear optical and electronic features of solid-solution MXenes. Vanadium appears to be particularly sensitive to modification of the valence state, while titanium maintains the same oxidation state in Ti–Nb and Ti–V MXenes, regardless of stoichiometry. Here, the study also explains Nb's influential role in the previously observed electronic properties in the Nb–V and Nb–Ti systems.

View Accepted Manuscript (DOE)

Research Organization:: Harvard Univ., Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0012573

OSTI ID:: 1979455

Journal Information:: 2D Materials, Journal Name: 2D Materials Journal Issue: 2 Vol. 9; ISSN 2053-1583

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

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