Abstract
Two-dimensional transition metal carbides and nitrides (MXenes) are a class of materials that have drawn substantial attention for their diverse application, particularly in the field of energy storage. These materials are commonly derived from layered ternary solids, MAX phases, through etching processes. Efforts have been made to expand the scope of MXene synthesis beyond these top-down approaches to include bottom-up synthesis. Here we demonstrate a general direct synthetic route for scalable and atom-economic synthesis of various MXenes using different organohalide compounds as precursors for both carbon and surface termination groups. By reacting organochlorides (such as C2Cl4, C2Cl6 and CH2Cl2) or organobromides (CBr4 and CH2Br2) with transition metals, we synthesized a variety of MXenes (Ti2CCl2, Ti2CBr2, Zr2CCl2, Zr2CBr2 and Nb2CCl2), including a Nb2CBr2 MXene phase not accessed by other routes. The use of molecular precursors enables precise control of their reactivity, which allows the direct synthesis of MXene nanostructures. We demonstrate that nanometre-scale MXenes show higher surface reactivity compared with MXenes with micrometre-size flakes.
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The data supporting the findings of this study are provided in the Supplementary Information. Source data are published with this paper.
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Acknowledgements
We thank A. Thakur and B. Anasori for exploring the electrochemical reactivity of directly synthesized MXene and M. Downes for the mechanistic studies of direct MXene synthesis. The authors are thankful J. S. Anderson and J. C. Ondry for helpful discussions. We are also grateful to A. Nelson for critical reading and editing of the manuscript. The work on direct MXene synthesis was supported by funding from the US National Science Foundation under grant no. CHE-2318105 (M-STAR CCI). N.L.M. acknowledges support by the National Science Foundation Graduate Research Fellowship Program under grant no. 2140001. The in-depth characterization of MXenes was supported by the Department of Defense Air Force Office of Scientific Research under grant no. FA9550-22-1-0283. F.K. and R.F.K. at UIC were supported by a grant from the National Science Foundation (grant no. NSF-DMR 2309396). Acquisition of UIC JEOL ARM200CF was supported by an MRI-R2 grant from the National Science Foundation (grant no. DMR-0959470). The Gatan Continuum GIF acquisition at UIC was supported by an MRI grant from the National Science Foundation (grant no. DMR-1626065). The work also used resources of the Center for Nanoscale Materials, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357.
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D.W. conceived, designed and performed direct synthesis, CVD and solution processing of MXenes; analysed data; and cowrote the paper. N.L.M. conceived, designed and performed parametric studies and synthesis of MXenes using methylene halides, analysed data, and cowrote the paper. F.K. and R.F.K. performed high-resolution STEM studies and image analysis. Y.Y. and D.J. performed DFT calculations. A.S.F. contributed to X-ray measurements and data analysis. Y.H.K contributed to calculations and data analysis. C.Z. carried out data analysis. D.V.T. conceived and designed experiments, analysed data, cowrote the paper, acquired funding and supervised the project. All authors discussed the results and commented on the paper.
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D.W. and D.V.T. are inventors on patent application PCT/US2023/072474 submitted by the University of Chicago, which covers direct synthesis and CVD of MXenes using organohalides. D.W., N.L.M. and D.V.T. are inventors on patent application US 63/777,897 submitted by the University of Chicago, which covers the direct synthesis of MXenes using CH2X2, where X is halogen. The other authors declare no competing interests.
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Wang, D., Mason, N.L., Karimi, F. et al. Molecular organohalides as general precursors for direct synthesis of two-dimensional transition metal carbide MXenes. Nat. Synth (2025). https://doi.org/10.1038/s44160-025-00946-w
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DOI: https://doi.org/10.1038/s44160-025-00946-w
