IP Library Granted Patent US 12,649,665
Granted Patent B2
US 12,649,665 · App. 17/922,848 · Granted Jun 9, 2026

Covalent surface modification of two-dimensional metal carbides

Inventors: Vladislav Kamysbayev (Chicago, IL); Dmitri V. Talapin (La Grange Park, IL)
Assignee: The University of Chicago
C01B32/921C01B32/914C23F1/10C01P2004/20
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,649,665
App. No.
17/922,848
Granted
Jun 9, 2026
Kind
B2
Abstract

Methods for modifying the surface termination of two-dimensional (2D) transition metal carbides (MXenes) are provided. The methods, which allow for versatile chemical modification of the terminating anions via halide exchange or substitution and elimination reactions in molten inorganic salts, provide a processing approach that is widely applicable to MXenes as a broad class of functional materials.

Claims (23)

1 . A method of modifying a surface termination of an MXene, the method comprising:

providing particles of a first MXene represented by the formula M m+1 X m T n1 and having a layered structure in which the M m+1 X m form two-dimensional sheets, where M is a transition metal, X is carbon, m is 1, 2, or 3, and T n1 denotes surface terminating chloride anions, bromide anions, iodide anions or a combination thereof;

dispersing the particles of the first MXene in an alkali halide molten salt bath comprising an alkali chloride salt, an alkali bromide salt, an alkali iodide salt, or a eutectic thereof and containing solubilized non-halide anions, the solubilized non-halide anions characterized in that a bond formed between the non-halide anion and the transition metal of the first MXene is stronger than a bond formed between the surface terminating chloride anion, bromide anion, or iodide anion and the transition metal of the first MXene, whereby the non-halide anions replace surface terminating chloride anions, bromide anions, or iodide anions on the first MXene via a halide exchange reaction under temperature of 300° C.-700° C. to form a second MXene represented by the formula M m+1 X m T n2 and having a layered structure in which the M m+1 X m form two-dimensional sheets, where M is the transition metal, X is carbon, m is 1, 2, or 3, and T n2 comprises surface terminating non-halide anions.

2 . The method of claim 1 , wherein the transition metal of the first and second MXenes is titanium or niobium.

3 . The method of claim 1 , wherein the particles of the first MXene comprise the surface terminating bromide anions or the surface terminating chloride anions.

4 . The method of claim 1 , wherein the non-halide anions are chalcogenide anions.

5 . The method of claim 4 , wherein the chalcogenide anions are introduced into the alkali metal molten salt bath in the form of a lithium chalcogenide salt.

6 . The method of claim 1 , wherein the non-halide anions are amide anions.

7 . The method of claim 6 , wherein the amide anions are introduced into the alkali metal molten salt bath in the form of a NaNH 2 salt.

8 . The method of claim 1 , wherein the particles of the first MXene comprise the surface terminating bromide anions and the alkali halide molten salt bath is comprises an alkali bromide salt.

9 . The method of claim 1 , wherein the particles of the first MXene comprise the surface terminating chloride anions and the alkali halide molten salt bath comprises an alkali chloride salt.

10 . The method of claim 1 , wherein the second MXene is Ti 3 C 2 S, Ti 3 C 2 Se, Ti 3 C 2 Te, or Ti 3 C 2 O.

11 . The method of claim 1 , wherein the second MXene is Nb 2 CS 2 or Nb 2 CSe.

12 . The method of claim 1 , wherein the second MXene is Ti 3 C 2 (NH) or Nb 2 C(NH).

13 . The method of claim 5 , wherein the lithium chalcogenide salt is Li 2 O, Li 2 S, Li 2 Se, or Li 2 Te.

14 . The method of claim 2 , wherein the first MXene is Ti 3 C 2 Br 2 , Ti 3 C 2 Cl 2 , Ti 2 CCl 2 , or Ti 2 CBr 2 .

15 . The method of claim 2 , wherein the first MXene is Nb 2 CCl 2 .

16 . The method of claim 8 , wherein the alkali bromide molten salt bath comprises a mixture of CsBr, LiBr, and KBr.

17 . The method of claim 9 , wherein the alkali chloride molten salt bath comprises a mixture of KCl and LiCl.

18 . The method of claim 1 , wherein m is 1 or 2.

19 . The method of claim 1 , wherein the transition metal of the first and second MXenes is zirconium, vanadium, tantalum, chromium, molybdenum, or scandium.

20 . The method of claim 1 , wherein the transition metal of the first and second MXenes is titanium or niobium, m is 1 or 2, T n1 is chloride or bromide, and the non-halide anion is a chalcogenide or amide.

21 . The method of claim 20 , wherein the alkali halide molten salt bath comprises the alkali chloride salt or the alkali bromide salt.

Assignments (2)
CONFIRMATORY LICENSE Recorded Mar 12, 2025
From: UNIVERSITY OF CHICAGO
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 070485/0521 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 7, 2022
From: TALAPIN, DMITRI; KAMYSBAYEV, VLADISLAV
To: THE UNIVERSITY OF CHICAGO
Reel/Frame 061676/0320 →
Continuity (2)
Provisional Application 63020885 · May 6, 2020
Related Publication 20230159340A1 · May 25, 2023
References Cited (37)
US 3898096A · Heredy et al. · 1975 [cited by applicant]
US 10573768B2 · Ghidiu · 2020 [cited by examiner]
US 11040323B2 · Talapin et al. · 2021 [cited by applicant]
US 11247914B2 · Talapin et al. · 2022 [cited by applicant]
US 11296243B2 · Ghidiu · 2022 [cited by examiner]
US 12015092B2 · Ghidiu · 2024 [cited by examiner]
US 20040262163A1 · Nitta · 2004 [cited by examiner]
US 20210387857A1 · Nemeth · 2021 [cited by examiner]
CN 102544534A · 2012 [cited by applicant]
CN 107579235A · 2018 [cited by applicant]
CN 108863372A · 2018 [cited by examiner]
CN 110540236A · 2019 [cited by applicant]
CN 109437177B · 2019 [cited by applicant]
KR 20170106860A · 2017 [cited by examiner]
WO WO2021226221 · 2021 [cited by applicant]
Zhang et al. (Synthesis of two-dimensional Ti3C2Tx MXene using HCIφLiF etchant: Enhanced exfoliation and delamination, Journal of Alloys and Compounds 695 (2017) 818e826). [cited by examiner]
Mian Li et al., “Element Replacement Approach by Reaction with Lewis Acidic Molten Salts to Synthesize Nanolaminated MAX Phases and Mxenes,” Journal of the American Chemical Society, Mar. 1, 2019; pp. 1-19. DOI: 10.1021… [cited by applicant]
Youbing Li et al., Pre-publication of the article: “A general Lewis acidic etching route for preparing MXenes with enhanced electrochemical performance in non-aqueous electrolyte,” [cited by applicant]
Alexey Lipatov et al., “Elastic properties of 2D Ti3C2Tx MXene monolayers and bilayers,” [cited by applicant]
Joseph Halim et al., “Electronic and optical characterization of 2D Ti2C and Nb2C (MXene) thin films,” [cited by applicant]
Junyu Chen et al., “Recent progress and advances in the environmental applications of MXene related materials,” [cited by applicant]
Sina Abdolhosseinzadeh et al., “Perspectives on solution processing of two-dimensional Mxenes,” [cited by applicant]
Yury Gogotsi et al., “The Rise of Mxenes,” [cited by applicant]
Apurv Dash et al., Pre-publication of the article: “Molten Salt Shielded Synthesis (MS3) of oxidation prone materials in air,” [cited by applicant]
Ning Zhang et al., Pre-publication of the article: “Superior Structural, Elastic and Electronic Properties of 2D Titanium Nitride Mxenes Over Carbide MXenes: A Comprehensive First Principles Study,” 2D Materials publicl… [cited by applicant]
Justinas Palisaitis et al., “On the Structural Stability of MXene and the Role of Transition Metal Adatoms†,” [cited by applicant]
Ingemar Persson et al., “On the organization and thermal behavior of functional groups on Ti3C2 MXene surfaces in vacuum,” (2018), [cited by applicant]
Zaheer Ud Din Babar et al., Pre-publication of the article: “Novel highest-Tc superconductivity in two-dimensional Nb2C MXene.” [cited by applicant]
Tengfei Li et al., “Fluorine-Free Synthesis of High-Purity Ti3C2Tx (T=Oh, O) via Alkali Treatment,” [cited by applicant]
Pang, Sin-Yi, et al. “Universal strategy for HF-free facile and rapid synthesis of two-dimensional MXenes as multifunctional energy materials.” [cited by applicant]
Fu, Z. H., et al. “Stabilization and strengthening effects of functional groups in two-dimensional titanium carbide.” [cited by applicant]
Khazaei, Mohammad, et al. “Novel electronic and magnetic properties of two-dimensional transition metal carbides and nitrides.” [cited by applicant]
The International Search Report and the Written Opinion issued on Nov. 23, 2021 for international patent application No. PCT/US21/30860; pp. 1-10. [cited by applicant]
Y. Yoon et al., “Enhanced Electrocatalytic activity by chemical nitridation of two-dimensional titanium carbide MXene for Hydrogen Evolution,” [cited by applicant]
J. Zhu et al., “S-functionalized Mxenes as electrode materials for Li-ion batteries,” Sep. 27, 2017; pp. 1-16. [cited by applicant]
J. Zhu et al., “P and Si functionalized Mxenes for metal-ion battery applications,” [cited by applicant]
Zhongyue Zhang et al., “Molten Salt Synthesized MXene for catalytic applications: A review,” Chem. Phys. Rev. 5, 031311 (2024); pp. 1-20. https://doi.org/10.1063/5.0215613. [cited by applicant]