Chelation-Based Route to Aluminum-Free Layered Transition Metal Carbides (MXenes). 2023

Luis R De Jesús Báez, and Alyssa S Rosas, and Pratibha Mahale, and Thomas E Mallouk
Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.

MXenes are of much interest because of their electrochemical, electronic, and surface chemical properties that arise from their structure and stoichiometry. The integrity and the nature of the terminal groups on the basal planes of MXene sheets depend strongly on the method used to etch the parent MAX (M = transition metal, A = Al, X = C, N, B) compound. Aluminum removal typically involves a high concentration of aqueous HF, HCl/LiF mixtures, or fluoride solutions of strong acids. HF etching is problematic because it leaves insoluble AlF3 in the product, degrades the crystallinity of the nanosheets, and results in the termination of the basal planes with F, O, or OH groups. Here, we demonstrate the use of HF at a low concentration in tandem with a chelating agent, N,N'-dihydroxyoctanediamide (suberohydroxamic acid), to selectively etch the archetypical MAX compound Ti3AlC2 at room temperature. X-ray absorption spectroscopy (XAS) of the etched materials shows that the carbide nature of bonding in the parent MAX structure is retained in the MXene layers. The stability of the MXene in aqueous suspensions is also significantly improved relative to MXene products made by etching in concentrated HF solutions.

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