Synthesis method of Ti3C2Tx MXene and the effect of synthesis conditions on MXene

Abstract

With increasing industrialization, population growth, and rapidly rising consumption, the energy crisis and environmental pollution have become increasingly significant global concerns. Rapid industrial expansion, together with the industrial wastes it generates and the intensification of unplanned urbanization, has resulted in the contamination of existing surface and groundwater resources. In recent years, difficulties in accessing clean water and the emergence of water scarcity have begun to be felt worldwide. Therefore, new processes and novel materials are required both to prevent the pollution of current water resources and to remove contaminants from polluted water systems. Recent studies have shown a growing interest in nanomaterials. Among these, MXenes two-dimensional nanomaterials have been employed in various processes for the removal of toxic pollutants from aqueous environments due to their surface functional groups, high electrical conductivity, hydrophilic behavior, and large surface area. In this study, Ti₃C₂Tₓ MXene was synthesized from the Ti₃AlC₂ MAX phase through direct etching using HF and LiF+HCl solutions. The effects of synthesis conditions including temperature, etching duration, and etchant concentration on the surface terminations, morphological features, and chemical structure of the MXene were determined through SEM, EDS, XRD, and TGA analyses. Examination of the XRD data revealed that the 38.6° Al peak present in the MAX phase disappeared in the MXene structures synthesized by both routes, indicating the successful formation of the MXene phase. XPS results showed the presence of –F, –O, and –OH surface termination groups in MXenes synthesized via direct HF etching; together with the accordion-like morphology observed in SEM images, these features indicated the potential of the material to serve as an effective adsorbent for the removal of heavy metals and other pollutants. Contact angle measurements demonstrated that the MXene synthesized via HF (30 °C, 20% HF, 48 h) exhibited a contact angle of 40°, whereas MXene synthesized using LiF+HCl (33.13% HCl, 1.88 g LiF, 60 °C, 27 h) showed a contact angle of 26°, confirming a more hydrophilic behavior compared to the MAX phase (62°). TGA analysis further revealed that MXenes obtained through both synthesis routes remained stable without oxidation up to temperatures between 600 °C and 800 °C.

Keywords

• 2D nanomaterial
• MXene
• MAX
• etching solution

Supporting Institution

TÜBİTAK

Project Number

122Y006

Ethical Statement

I declare that all processes of the study are in accordance with research and publication ethics and that I comply with ethical rules and scientific citation principles.

Thanks

This study covers some of the results of the master's thesis titled "Synthesis of Ti3C2 MXene and the Effect of Synthesis Conditions on MXene Properties" and was carried out within the scope of TÜBİTAK project number 122Y006. We thank TÜBİTAK for their support.

Ti₃C₂Tₓ MXene sentez yöntemi ve sentez koşullarının MXene üzerindeki etkisi

Abstract

Artan endüstrileşme ve nüfüsun ve tüketimin hızla artmasıyla, enerji krizi ve çevre kirliliği giderek daha büyük bir sorun haline gelmektedir. Hızlıca büyüyen sanayileşme ve bunların oluşturduğu endüstriyel atıklar ve artan düzensiz şehirleşme sonucunda mevcut yüzeysel ve yer altı su kaynaklarını kirletmektedir. Son dönemlerde temiz su kaynaklarına erişim ve su kıtlığı tüm dünyada kendini hissettirmeye başlamıştır. Mevcut su kaynaklarının kirlenmesini önlemek yada kirlenen su kaynaklarındaki kirlikleri gidermek amacıyla yeni prosesler ve yeni malzemelere ihtiyaç duyulmaktadır. Son zamanlarda yapılan çalışmalarda nanomalzemelere olan ilgi giderek artmaktadır. Nanomalzemeler içerisinde 2D boyutlu nanomalzeme olan MXene yüzey grupları, yüksek elektriksel iletkenlik, hidrofilik davranışları ve büyük yüzey alanları sayesinde su ortamında toksik kirleticileri gidermek için çeşitli proseslerde kullanılmaktadır. Bu çalışmada, Ti3C2TX MXene, Ti3AlC2 MAX fazından HF ve LiF+HCl çözeltileri ile doğrudan aşındırılarak sentezlenmiştir. Sıcaklık, aşındırma süresi ve aşındırma çözeltisi konsantrasyonu gibi sentez koşullarının MXene'nin yüzey grupları, morfolojik yapısı ve kimyasal yapısı üzerindeki etkileri SEM, EDS, XRD ve TGA analizleri yapılarak belirlenmesi amaçlanmıştır. XRD sonuçları incelendiğinde MAX fazında bulunan 38.6o Al piki her iki yolla sentezlenen MXene’in yapısında gözlenmemiş olup başarılı bir şekilde MXene yapısının oluşturulduğu sonucuna varılmıştır. XPS Sonuçları incelendiğinde, doğrudan HF çözeltisi ile sentezlenen MXene'lerin yüzey sonlanma gruplarında -F, -O ve -OH gruplarının bulunması ağır metaller için, SEM görüntülerinde belirlenen akordiyonik yapıdan kaynaklı yüzey alanının artması kirleticilerin giderilmesi için etkin bir adsorbent olarak kullanılabileceğini göstermiştir. MAX fazıyla (62o ) kıyaslandığında doğrudan HF çözeltisi ile sentezlenen (30 oC, 20% HF ve 48 saat) MXene’in temas açısı 40o olduğu, LiF+HCl (33.13% HCl, 1.88 g LiF, 60 °C, and 27 saat) ile sentezlenen MXene’in 26o olduğu temas açısı analizi ile belirlenmiş MXene yapısı daha hidrofilik davranış sergilediği tespit edilmiştir. TGA analizleri sonucu her iki farklı yoldan sentezlenen MXene’in 600 oC -800 oC arasındaki sıcaklık değerlerine kadar oksitlenmeden stabil kaldığı belirlenmiştir.

Keywords

• 2D nanomalzeme
• MXene
• MAX
• aşındırma çözeltisi.

Project Number

122Y006

References

1. Park S, Kim S, Yea Y, Saravanakumar K, Lee E, Yoon Y, Park CM. Adsorptive and photocatalytic performance of cobalt-doped ZnTiO3/Ti3C2Tx MXene nanohybrids towards tetracycline: Kinetics and mechanistic insight. Journal of Hazardous Materials 2023;443:130165.https://doi.org/10.1016/j.jhazmat.2022.130165
2. Xu Y, Zhou Y, Li Y, Liu Y, Ding Z. Advances in cerium dioxide nanomaterials: Synthesis strategies, property modulation, and multifunctional applications. Journal of Environmental Chemical Engineering 2024;12(5):113719. https://doi.org/10.1016/j.jece.2024.113719
3. Kalaycı ÖA, Arslan H. Gümüş Nanoparçacık İçeren Polimer Hibrit Nanomalzemelerin Sentezi ve Metilen Mavisi İndirgenmesine Nanoparçacık Etkisi. Duzce University Journal of Science and Technology 2023;11(3):1349-1364. https://doi.org/10.29130/dubited.1124484
4. Yakut ŞM. Iron nanoparticle synthesis using waste banana peels and Maxilon Blue 5G sono-degradation. International Journal of Phytoremediation 2026;28(1):149-161. https://doi.org/10.1080/15226514.2025.2554171
5. Novoselov KS, Geim AK, Morozov SV, Jiang DE, Zhang Y, Dubonos SV, Firsov AA. Electric field effect in atomically thin carbon films. Science 2004;306(5696):666 669.https://doi.org/10.1126/science.1102896
6. Ramanathan AA, Aqra MW, Al-Rawajfeh AE. Recent advances in 2D nanopores for desalination. Environmental Chemistry Letters 2018;16(4):1217-1231.https://doi.org/10.1007/s10311-018-0745-4
7. Naguib M, Kurtoglu M, Presser V, Lu J, Niu J, Heon M, Barsoum MW. Two-dimensional nanocrystals produced by exfoliation of Ti3AlC2, MXenes. Jenny Stanford Publishing, 2023;15-29.
8. Zhu J, Ha E, Zhao G, Zhou Y, Huang D, Yue G, et al. Recent advance in MXenes: a promising 2D material for catalysis, sensor and chemical adsorption. Coordination Chemistry Reviews 2017;352:306-327. https://doi.org/10.1016/j.ccr.2017.09.012

9. Naguib M, Mochalin VN, Barsoum MW, Gogotsi Y. 25th anniversary article: MXenes: a new family of two‐dimensional materials. Advanced Materials 2014;26(7):992-1005. https://doi.org/10.1002/adma.201304138
10. Enyashin AN, Ivanovskii AL. Two-dimensional titanium carbonitrides and their hydroxylated derivatives: Structural, electronic properties and stability of MXenes Ti3C2−xNx(OH)2 from DFTB calculations. Journal of Solid State Chemistry 2013;207:42-48. https://doi.org/10.1016/j.jssc.2013.09.010
11. Chaudhari NK, Jin H, Kim B, San Baek D, Joo SH, Lee K. MXene: an emerging two-dimensional material for future energy conversion and storage applications. Journal of Materials Chemistry A 2017;5(47):24564-24579. https://doi.org/10.1039/C7TA09094C
12. Ganesh PS, Kim SY. Electrochemical sensing interfaces based on novel 2D-MXenes for monitoring environmental hazardous toxic compounds: A concise review. Journal of Industrial and Engineering Chemistry 2022;109:52-67. https://doi.org/10.1016/j.jiec.2022.02.006
13. Lukatskaya MR, Mashtalir O, Ren CE, Dall’Agnese Y, Rozier P, Taberna PL, Gogotsi Y. Cation intercalation and high volumetric capacitance of two-dimensional titanium carbide. Science 2013;341(6153):1502-1505. https://doi.org/10.1126/science.1241488
14. Yu F, Zhang X, Yang Z, Yang P, Ma J. Environmental applications of two-dimensional transition metal carbides and nitrides for water purification: a review. Environmental Chemistry Letters 2022;20(1):633-660. https://doi.org/10.1007/s10311-021-01325-5
15. Zhang S, Bilal M, Adeel M, Barceló D, Iqbal HM. MXene-based designer nanomaterials and their exploitation to mitigate hazardous pollutants from environmental matrices. Chemosphere 2021;283:131293. https://doi.org/10.1016/j.chemosphere.2021.131293
16. Maleski K, Mochalin VN, Gogotsi Y. Dispersions of two-dimensional titanium carbide MXene in organic solvents. Chemistry of Materials 2017;29(4):1632-1640. https://doi.org/10.1021/acs.chemmater.6b04830
17. Sun Y, Lu J, Li S, Dai C, Zou D, Jing W. MXene-based membranes in water treatment: Current status and future prospects. Separation and Purification Technology 2024;331:125640. https://doi.org/10.1016/j.seppur.2023.125640
18. Zha XJ, Zhao X, Pu JH, Tang LS, Ke K, Bao RY, Yang W. Flexible anti-biofouling MXene/cellulose fibrous membrane for sustainable solar-driven water purification. ACS Applied Materials & Interfaces 2019;11(40):36589-36597. https://doi.org/10.1021/acsami.9b10606
19. Çelik A, Yegin M, Köse Y, Hasar H. Advanced bipolar membranes incorporating Ti3CNTx MXene for improved BMED efficiency. Journal of Applied Electrochemistry 2025;1-20. https://doi.org/10.1007/s10800-025-02374-2
20. Suss ME, Presser V. Water desalination with energy storage electrode materials. Joule 2018;2(1):10-15.
21. Zou G, Guo J, Peng Q, Zhou A, Zhang Q, Liu B. Synthesis of urchin-like rutile titania carbon nanocomposites by iron-facilitated phase transformation of MXene for environmental remediation. Journal of Materials Chemistry A 2016;4(2):489-499. https://doi.org/10.1039/C5TA07343J
22. Feng A, Yu Y, Mi L, Yu Y, Song L. Comparative study on electrosorptive behavior of NH4HF2-etched Ti3C2 and HF-etched Ti3C2 for capacitive deionization. Ionics 2019;25(2):727-735. https://doi.org/10.1007/s11581-018-2787-9
23. Berdiyorov GR. Optical properties of functionalized Ti3C2T2 (T= F, O, OH) MXene: First-principles calculations. AIP Advances 2016;6(5). https://doi.org/10.1063/1.4948799
24. Gao Y, Wang L, Zhou A, Li Z, Chen J, Bala H, Cao X. Hydrothermal synthesis of TiO2/Ti3C2 nanocomposites with enhanced photocatalytic activity. Materials Letters 2015;150:62-64. https://doi.org/10.1016/j.matlet.2015.02.135
25. Ghidiu M, Lukatskaya MR, Zhao MQ, Gogotsi Y, Barsoum MW. Conductive two-dimensional titanium carbide ‘clay’with high volumetric capacitance. Nature 2014;516(7529):78-81.
26. Bashir T, Ismail SA, Wang J, Zhu W, Zhao J, Gao L. MXene Terminating Groups O,–F or–Oh,–F or O,–Oh,–F, or O,–Oh,–Cl?. Journal of Energy Chemistry 2023;76:90-104. https://doi.org/10.1016/j.jechem.2022.08.032
27. Alhabeb M, Maleski K, Anasori B, Lelyukh P, Clark L, Sin S, Gogotsi Y. Guidelines for synthesis and processing of two-dimensional titanium carbide (Ti3C2T x MXene). Chemistry of Materials 2017;29(18):7633-7644. https://doi.org/10.1021/acs.chemmater.7b02847
28. Lipatov A, Alhabeb M, Lukatskaya MR, Boson A, Gogotsi Y, Sinitskii A. Effect of synthesis on quality, electronic properties and environmental stability of individual monolayer Ti3C2 MXene flakes. Advanced Electronic Materials 2016;2(12):1600255. https://doi.org/10.1002/aelm.201600255
29. Zhang CJ, Pinilla S, McEvoy N, Cullen CP, Anasori B, Long E, Park SH, Nicolosi V. Oxidation stability of colloidal two-dimensional titanium carbides (MXenes). Chemistry of Materials 2017;29(11):4848-4856. https://doi.org/10.1021/acs.chemmater.7b00745
30. Anasori B, Lukatskaya MR, Gogotsi Y. 2D metal carbides and nitrides (MXenes) for energy storage, MXenes. Jenny Stanford Publishing, 2023;677-722.
31. Bilyk T, Benchakar M, Bugnet M, Loupias L, Chartier P, Pazniak H, Mauchamp V. Electronic structure sensitivity to surface disorder and nanometer-scale impurity of 2D titanium carbide MXene sheets as revealed by electron energy-loss spectroscopy. The Journal of Physical Chemistry C 2020;124(49):27071-27081. https://doi.org/10.1021/acs.jpcc.0c06798
32. Naguib M, Come J, Dyatkin B, Presser V, Taberna PL, Simon P, Gogotsi Y. MXene: a promising transition metal carbide anode for lithium-ion batteries. Electrochemistry Communications 2012;16(1):61-64. https://doi.org/10.1016/j.elecom.2012.01.002
33. Wang X, Shen X, Gao Y, Wang Z, Yu R, Chen L. Atomic-scale recognition of surface structure and intercalation mechanism of Ti3C2X. Journal of the American Chemical Society 2015;137(7):2715-2721. https://doi.org/10.1021/ja512820k
34. Shuck CE, Ventura-Martinez K, Goad A, Uzun S, Shekhirev M, Gogotsi Y. Safe synthesis of MAX and MXene: guidelines to reduce risk during synthesis. ACS Chemical Health & Safety 2021;28(5):326-338. https://doi.org/10.1021/acs.chas.1c00051
35. Naguib M, Mashtalir O, Carle J, Presser V, Lu J, Hultman L, Gogotsi Y, Barsoum MW. Two-dimensional transition metal carbides. ACS Nano 2012;6(2):1322-1331. https://doi.org/10.1021/nn204153h
36. Ronchi RM, Arantes JT, Santos SF. Synthesis, structure, properties and applications of MXenes: Current status and perspectives. Ceramics International 2019;45(15):18167-18188. https://doi.org/10.1016/j.ceramint.2019.06.114
37. Çelik A, Aksoy Y, Yegin M, Hanay Ö, Hasar H. An intermediate layer catalyst in bipolar membranes: Ti3CNTx MXene. Journal of Nanoparticle Research 2025;27(7):1-18. https://doi.org/10.1007/s11051-025-06380-5