Oxidation Stability of Colloidal Two-Dimensional Titanium Carbides (MXenes)

Two-dimensional (2D) transition metal carbides and nitrides (MXenes) have shown outstanding performances in electrochemical energy storage and many other applications. Delamination of MXene flakes in water produces colloidal solutions that are used to manufacture all kinds of products (thin films, c...

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Published in	Chemistry of materials Vol. 29; no. 11; pp. 4848 - 4856
Main Authors	Zhang, Chuanfang John, Pinilla, Sergio, McEvoy, Niall, Cullen, Conor P, Anasori, Babak, Long, Edmund, Park, Sang-Hoon, Seral-Ascaso, Andrés, Shmeliov, Aleksey, Krishnan, Dileep, Morant, Carmen, Liu, Xinhua, Duesberg, Georg S, Gogotsi, Yury, Nicolosi, Valeria
Format	Journal Article
Language	English
Published	American Chemical Society 13.06.2017
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Abstract	Two-dimensional (2D) transition metal carbides and nitrides (MXenes) have shown outstanding performances in electrochemical energy storage and many other applications. Delamination of MXene flakes in water produces colloidal solutions that are used to manufacture all kinds of products (thin films, coatings, and electrodes, etc.). However, the stability of MXene colloidal solutions, which is of critical importance to their application, remains largely unexplored. Here we report on the degradation of delaminated-Ti3C2T x colloidal solutions (T represents the surface functionalities) and outline protocols to improve their stability. Ti3C2T x MXene solutions in open vials degraded by 42%, 85%, and 100% after 5, 10, and 15 days, respectively, leading to the formation of cloudy-white colloidal solutionss containing primarily anatase (TiO2). On the other hand, the solution could be well-preserved when Ti3C2T x MXene colloidal solutionss were stored in hermetic Ar-filled bottles at 5 °C, because dissolved oxygen, the main oxidant of the MXene flakes, was eliminated. Under such a recipe, the time constant of the solution was dramatically increased. We have found that the degradation starts at the edges and its kinetics follows the single-exponential decay quite well. Moreover, we performed size selection of the MXene solution via a cascade technique and showed that the degradation process is also size-dependent, with the small flakes being the least stable. Furthermore, a dependence between the degradation time constants and the flake size allows us to determine the size of the nanosheets in situ from UV–vis spectra and vice versa. Finally, the proposed method of storing the MXene colloidal solution in Ar-filled vials was applied to Ti2CT x to improve its stability and time constant, demonstrating the validity of this protocol in improving the lifetime of different MXene solutions.
AbstractList	Two-dimensional (2D) transition metal carbides and nitrides (MXenes) have shown outstanding performances in electrochemical energy storage and many other applications. Delamination of MXene flakes in water produces colloidal solutions that are used to manufacture all kinds of products (thin films, coatings, and electrodes, etc.). However, the stability of MXene colloidal solutions, which is of critical importance to their application, remains largely unexplored. Here we report on the degradation of delaminated-Ti3C2T x colloidal solutions (T represents the surface functionalities) and outline protocols to improve their stability. Ti3C2T x MXene solutions in open vials degraded by 42%, 85%, and 100% after 5, 10, and 15 days, respectively, leading to the formation of cloudy-white colloidal solutionss containing primarily anatase (TiO2). On the other hand, the solution could be well-preserved when Ti3C2T x MXene colloidal solutionss were stored in hermetic Ar-filled bottles at 5 °C, because dissolved oxygen, the main oxidant of the MXene flakes, was eliminated. Under such a recipe, the time constant of the solution was dramatically increased. We have found that the degradation starts at the edges and its kinetics follows the single-exponential decay quite well. Moreover, we performed size selection of the MXene solution via a cascade technique and showed that the degradation process is also size-dependent, with the small flakes being the least stable. Furthermore, a dependence between the degradation time constants and the flake size allows us to determine the size of the nanosheets in situ from UV–vis spectra and vice versa. Finally, the proposed method of storing the MXene colloidal solution in Ar-filled vials was applied to Ti2CT x to improve its stability and time constant, demonstrating the validity of this protocol in improving the lifetime of different MXene solutions.
Author	Anasori, Babak Shmeliov, Aleksey Duesberg, Georg S Gogotsi, Yury Long, Edmund Cullen, Conor P Krishnan, Dileep Zhang, Chuanfang John Seral-Ascaso, Andrés Liu, Xinhua Park, Sang-Hoon Pinilla, Sergio Morant, Carmen Nicolosi, Valeria McEvoy, Niall
AuthorAffiliation	Universidad Autónoma de Madrid School of Physics CRANN and AMBER Research Centers Drexel University Department of Materials Science and Engineering, and A. J. Drexel Nanomaterials Institute Applied Physics Department School of Chemistry
AuthorAffiliation_xml	– name: Universidad Autónoma de Madrid – name: Department of Materials Science and Engineering, and A. J. Drexel Nanomaterials Institute – name: Drexel University – name: School of Physics – name: CRANN and AMBER Research Centers – name: School of Chemistry – name: Applied Physics Department
Author_xml	– sequence: 1 givenname: Chuanfang John orcidid: 0000-0001-8663-3674 surname: Zhang fullname: Zhang, Chuanfang John organization: School of Chemistry – sequence: 2 givenname: Sergio surname: Pinilla fullname: Pinilla, Sergio organization: Universidad Autónoma de Madrid – sequence: 3 givenname: Niall surname: McEvoy fullname: McEvoy, Niall organization: School of Chemistry – sequence: 4 givenname: Conor P surname: Cullen fullname: Cullen, Conor P organization: School of Chemistry – sequence: 5 givenname: Babak surname: Anasori fullname: Anasori, Babak organization: Drexel University – sequence: 6 givenname: Edmund surname: Long fullname: Long, Edmund organization: School of Physics – sequence: 7 givenname: Sang-Hoon surname: Park fullname: Park, Sang-Hoon organization: School of Chemistry – sequence: 8 givenname: Andrés surname: Seral-Ascaso fullname: Seral-Ascaso, Andrés organization: School of Chemistry – sequence: 9 givenname: Aleksey surname: Shmeliov fullname: Shmeliov, Aleksey organization: School of Chemistry – sequence: 10 givenname: Dileep surname: Krishnan fullname: Krishnan, Dileep organization: School of Chemistry – sequence: 11 givenname: Carmen surname: Morant fullname: Morant, Carmen organization: Universidad Autónoma de Madrid – sequence: 12 givenname: Xinhua surname: Liu fullname: Liu, Xinhua organization: School of Chemistry – sequence: 13 givenname: Georg S surname: Duesberg fullname: Duesberg, Georg S organization: School of Chemistry – sequence: 14 givenname: Yury orcidid: 0000-0001-9423-4032 surname: Gogotsi fullname: Gogotsi, Yury email: gogotsi@drexel.edu organization: Drexel University – sequence: 15 givenname: Valeria surname: Nicolosi fullname: Nicolosi, Valeria email: nicolov@tcd.ie organization: School of Physics
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