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Sublayer editing of covalent MAX phase for nanolaminated early transition metal compounds

Nature Synthesis volume 4, pages 1435–1441 (2025)Cite this article

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Abstract

Two-dimensional transition metal carbides/nitrides, known as MXenes, are interesting for energy applications. They are typically synthesized by etching the weak metallic M–A sublayer in MAX phases while the strong covalent M–X sublayer maintains the structure. However, certain MAX phases with non-metal A sites feature fully covalent M–A/M–X sublayers, preventing etching synthesis. Here we discovered that the covalent-bond-type M–A and M–X sublayers show different reactivities in a high-temperature molten state. By utilizing this difference in reactivity, we can structurally modify these covalent sublayers, enabling the substitution of elements at the X site, converting non-metal A-site atoms in non-van der Waals MAX phases into surface atoms in van der Waals layered materials. This results in a family of early transition metal Xide chalcogenides (TMXCs) with lattice characteristics of both MXenes and transition metal chalcogenides. Using electron-donor chemical scissors, these TMXC layered materials can be exfoliated into monolayer nanosheets. The atomic configurations of each atom in these monolayer TMXCs are the same as those of conventional MXenes, but the oxidation states of the M-site atoms can be regulated by both X-site atoms and intercalated cations. These materials may find applications in electrochemical energy storage and surface catalysis.

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Fig. 1: Topochemical transformations of MAX phases mediated by covalent chemical scissors.
Fig. 2: Structural evolution and chemical modification of Zr2Se2P through intercalation and ion exchange.
Fig. 3: Structural and chemical characterization of delaminated Zr2Se2P.
Fig. 4: Structural editing policy of covalent MAX phases and i-TMXC.

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Data availability

The authors declare that the data supporting this study are available within the published article, its Supplementary Information, and accompanying source data files. Source data are provided with this paper.

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Acknowledgements

This study was supported financially by the National Natural Science Foundation of China (grant numbers U23A2093 and 12375279) and the Ningbo Top-talent Team Program. Q.H. acknowledges support by the Ten-Thousand Talents Plan of Zhejiang Province (grant number 2022R51007). K.C. thanks the Youth Science and Technology Innovation Leading Talent Project of Ningbo (grant number 2024QL022), and the Leading and Top-notch Talent Training Project of Ningbo.

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Authors and Affiliations

  1. Zhejiang Key Laboratory of Data-Driven High-Safety Energy Materials and Applications, Ningbo Key Laboratory of Special Energy Materials and Chemistry, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, China

    Ziqian Li, Ke Chen, Xudong Wang, Kan Luo, Lei Lei, Mian Li, Kun Liang, Degao Wang, Shiyu Du, Zhifang Chai & Qing Huang

  2. University of Chinese Academy of Sciences, Beijing, China

    Ziqian Li & Xudong Wang

  3. Qianwan Institute of CNiTECH, Ningbo, China

    Ke Chen, Lei Lei, Mian Li, Kun Liang, Degao Wang, Zhifang Chai & Qing Huang

  4. School of Materials Science and Engineering, Xiangtan University, Xiangtan, China

    Xiaoping Ouyang

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  1. Ziqian Li
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Contributions

Q.H. initiated and supervised the experimental work. Z.L. and K.C. conducted the main experiment and analysed results. K.L. and S.D. calculated the bonding strength of MAX phases. L.L. and D.W. provided the XFAS analysis. M.L., K.L., X.W., Z.C. and X.O. participated in the analysis of the material structure. Z.L. and K.C. wrote the paper with contributions from all coauthors. All authors reviewed and commented on successive drafts of the paper.

Corresponding authors

Correspondence to Ke Chen or Qing Huang.

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Competing interests

Q.H., K.C., Z.L. and X.W. are inventors on a patent application (CN202211316587.8). The other authors declare no competing interests.

Peer review

Peer review information

Nature Synthesis thanks Varun Natu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information (download PDF )

Materials and methods, Supplementary Scheme 1, Text, Figs. 1–20, Tables 1–6, equations (1)–(25) and References.

Supplementary Data (download XLSX )

Source data for Supplementary Figs. 2–16 and 17–21.

Source data

Source Data Fig. 1 (download XLSX )

Source data of material XRD and enthalpy change of reaction equation.

Source Data Fig. 2 (download XLSX )

Source data of material XRD.

Source Data Fig. 3 (download XLSX )

Source data of material XRD, sAFM surface height and XFAS absorption edge.

Source Data Fig. 4 (download XLSX )

Source data of the variations in the binding state of the M element through XPS.

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Li, Z., Chen, K., Wang, X. et al. Sublayer editing of covalent MAX phase for nanolaminated early transition metal compounds. Nat. Synth 4, 1435–1441 (2025). https://doi.org/10.1038/s44160-025-00855-y

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