Synthesis and Optical Properties of 2D Carbides MXenes

UDC 542;546;62

O.O. HONCHARUK 1, V. YU. BALITSKIY1, 2, R. V. VORON1, M.P. BRODNIKOVSKIY2, O.G. GOGOTSI2, V.V. ZAHORODNA2,

Y. I. ZOZULYA2, M. ALHABEEB3, B. ANASORI3, K. MALESKY3, Y. G. GOGOTSI3

1 National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, Institute of Mechanical Engineering, Department of Laser Systems and Physical Technologies, Polytechnichna st., 37, Kyiv 03055, Ukraine

2 Materials Research Centre, 3, Krzhyzhanovs'koho st, Kyiv 03680, Ukraine

3A.J. Drexel Nanomaterials Institute and Department of Materials Science and Engineering, Drexel University, 3141 Chestnut Street, Philadelphia, Pennsylvania 19104, United States

SYNTHESIS AND OPTICAL PROPERTIES OF 2D CARBIDES MXENES

Keywords: MXenes, 2D carbides, nanomaterials, optical properties, electromagnetic shielding, photothermal therapy, reactor, laboratory line

The family of two-dimensional (2D) transition metal carbides and nitrides, MXenes, has been expanding rapidly since the discovery of Ti3C2 MXene in 2011 [1]. More than 20 different MXenes have been synthesized, and the structure and properties of numerous other MXenes have been predicted using density functional theory calculations [2]. Two-dimensional (2D) materials with a thickness of a few nanometers or less can be used as single sheets due to their unique properties or as building blocks, to assemble a variety of structures. MXenes properties can be tunable for a large variety of applications [3] that directly lead to their use for electromagnetic shielding [4], transparent conductors, light-to-heat energy conversion [5], new advanced lasers and photothermal therapy [6].

The 2D structure, combined with high electrical conductivity and good electronic coupling between the layers, resulted very high electromagnetic interference shielding efficiency of MXenes [4].

Research results showed that MXenes demonstrates an outstanding internal light-to-heat conversion efficiency (∼100%) and show much more higher light absorption capability than other materials [5]. The 2D titanium carbide sheets show strong optical absorption in the near-infrared (NIR) around 800 nm. The performance of this material is comparable or even superior to that of stateof- the-art photo absorption materials, including gold-based nanostructures, carbon nanomaterials, and transition-metal dichalcogenides.

Unique optical and plasmonic properties have also been demonstrated, making the materials promising for photothermal therapy applications. Preliminary studies show that the titanium carbide sheets serve as an efficient photothermal agent against tumor cells [6].

Synthesis of MXene begins with etching with 10% wt. HF solution and/or a mixture of salts and acids at room temperature or slightly higher temperature the A-element atomic layers (for example, aluminum) in a MAX phase (for example, Ti3AlC2). After the etching is finished (complete removal of the A-element layers), washing must be applied to remove residual acid and reaction products (salts) and achieve a safe pH (∼6). After the pH is increased to ∼6, and intercalation of large organic molecules and subsequent delamination completed, the multilayered MXene flakes or single nanosheets can be collected via vacuum-assisted filtration and then dried in vacuum [7].

Fig. 1. Pilot laboratory line with controlled parameters for MXene synthesis (up to 100 g per batch): 1 – computer control system; 2- Etching reactor for MXene synthesis; 3 – additional equipment for laboratory technological line.

Fig. 1. Pilot laboratory line with controlled parameters for MXene synthesis (up to 100 g per batch): 1 – computer control system; 2- Etching reactor for MXene synthesis; 3 – additional equipment for laboratory technological line.

 MXenes can be deposited by spin, spray, or dip coating, painted or printed, or fabricated in a variety of ways. Synthesis conditions used to produce MXenes influence the resulting properties and thus are directly related to the performance of MXenes in their applications [7].

In the laboratory, researchers synthesize MXene in very small quantity (milligramms), and it is very difficult to repeat the synthesis conditions in order to obtain a material with the same repeatable properties.

For scaling up laboratory process and to obtain the material in larger quantities (up to 100 g per batch) of good quality with repeatable properties, a pilot laboratory line was developed [7] (Fig. 1), which allows to control the etching process and adjust its basic parameters - temperature, mixing speed, recording and storing all necessary data for analysis or to repeat the conditions during subsequent syntheses to obtain a MXxene with repeatable properties.

In addition, since the acidic etching process is accompanied by the release of heat, a specially developed sealed reactor allows more secure synthesis, and also the computer control system provides the desired optimal synthesis temperature.

ACKNOWLEDGMENTS The publication was supported by the EU MSCA RISE NANO2DAY project №777810 under the Horizon-2020 program

 References:

[1] Two-Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2. M. Naguib, et al., Advanced Materials, 23, 4248 (2011)
[2] Synthesis and Biomedical Applications Of 2D Carbides (MXenes). Gogotsi O. G., Zahorodna V. V., Balitskiy V. Y., Zozulya Y. I., Gogotsi H. G., Brodnikovskiy M. P., Gubynskyi M. V., Fedorov S. S., Alhabeb M., Meng F., Anasori B., Gogotsi Y. G. Abstract Book of 5th International Conference Nanobiophysics: Fundamental and Applied Aspects, October 2-5, 2017, Kharkiv, Ukraine
[3] Organic-Base-Driven Intercalation and Delamination for the Production of Functionalized Titanium Carbide Nanosheets with Superior Photothermal Therapeutic Performance. J. Xuan, et al., Angew. Chem. Int. Ed. 55, 1 – 7 (2016)
[4] F. Shahzad, M. Alhabeb, C.B. Hatter, B, Anasori, S.M. Hong, C. M. Koo, Y. Gogotsi, Electromagnetic Interference Shielding with 2D Transition Metal Carbides (MXenes), Science, 353 (6304) 1137-1140 (2016)
[5] MXene Ti3C2: an Effective 2D Light-to-Heat Conversion Material. Renyuan Li, Lianbin Zhang, Le Shi, Peng Wang. March 2017, ACS Nano 11(4) DOI10.1021/acsnano.6b08415
[6] Organic-Base-Driven Intercalation and Delamination for the Production of Functionalized Titanium Carbide Nanosheets with Superior Photothermal Therapeutic Performance. J. Xuan, et al., Angew. Chem. Int. Ed. 55, 1 – 7 (2016)
[7] M. Alhabeb, K. Maleski, B. Anasori, P. Lelyukh, L. Clark, S. Sin, Y. Gogotsi, Guidelines for Synthesis and Processing of 2D Titanium Carbide (Ti3C2Tx MXene), Chemistry of Materials, 29 (18) 7633-7644 (2017)

O.O. Honcharuk, V. YU. Balitskiy, R. V. Voron, M.P. Brodnikovskiy, O.G. Gogotsi, V.V. Zahorodna, Y. I. Zozulya, M. Alhabeeb, B. Anasori, K. Malesky, Y. G. Gogotsi. Synthesis and Optical Properties of 2D Carbides MXenes, Book of Abstracts for 11th International Scientific-Technical Conference "Composite Materials", National Technical University of Ukraine "Igor Sikorsky Kyiv Polytechnic Institute", April 2018, рр.118-120. UDC 542;546;62.

Conference Links:

ХI International Science and Technology Web Conference «COMPOSITION MATERIALS»

Book of Abstract for ХI International Science and Technology Web Conference «COMPOSITION MATERIALS»

 

 

News from MRC.ORG.UA

2024 MRS Fall Meeting & Exhibit, Boston, Massachusetts, from December 1-6, 2024

2024 MRS Fall Meeting & Exhibit, Poster Session, from left to right: Prof. Yury Gogotsi, Prof. Maksym Pogorielov, Prof. Goknur Buke, Dr. Babak Anasori and Dr. Oleksiy GogotsiDr. Oleksiy Gogotsi, director of MRC and Carbon-Ukraine, innovative companies that are among the leaders on the world MXene market, visited 2024 MRS Fall Meeting & Exhibit. together with Dr. Maksym Pogorielov, Head of Advanced Biomaterials and Biophysics Laboratory, University of Latvia.

 
Our team participated in the 3rd International Conference at Drexel University "MXene: Changing the World", August 5-7, 2024

3rd international MXene Confernce at Drexel University, August 5-7, 2024, Philadelphia, USAMRC and Carbon-Ukraine team visited the 3rd International MXene conference held at Drexel University on August 5-8, 2024. Conference brought together the best reserchers and leading experts on MXene field. 

 
Visit to our project partners from Worcester Polytechnic Institute that joined to ESCULAPE research project consortium

Visiting Functional Biomaterials Lab at Worcester Polytechnic Institute led by Dr. Jeannine Coburne

Looking forward to work together with Dr. Lyubov Titova and Dr. Jeannine Coubourne from Worcester Polytechnic Institute on structural and biomedical applications of MXenes and study of their properties within HORIZON EUROPE MSCA RISE ESCULAPE project!

 
MXenes for biomedical applications: MXene-Polydopamine-antiCEACAM1 Antibody Complex as a Strategy for Targeted Ablation of Melanoma

MXene-Polydopamine-antiCEACAM1 Antibody Complex fro cancer therapyTogether with colleagues from the University of Latvia, MRC/Carbone Ukraine, Adam Mickiewicz University, University Clinic Essen, and others, we have developed a novel concept involving the binding of antibodies to MXenes. In our research, we utilized anti-CEACAM1 antibodies to develop targeted photo-thermal therapy for melanoma (in vitro), paving the way for future in vivo studies and clinical trials. For the first time, we demonstrate the feasibility of delivering MXenes specifically targeted to melanoma cells, enabling the effective ablation of cancer cells under near-infrared (NIR) light. This new technique opens up vast potential for the application of MXenes in cancer treatment, diagnostics, drug delivery, and many other medical purposes.

 
Looking forward our collaboration with Dr. Vladimir Tsukruk's team from Georgia Tech University in trilateral research project IMPRESS-U on MXene-Based Composite Bio-membranes with Tailored Properties

SSU, MRC and Carbon-Ukraine team visited research group led by Prof. Vladimir Tsukruk from Georgia Tech University, Atlanta, USA

Looking forward our collaboration with Dr. Vladimir Tsukruk's team from Georgia Tech University in trilateral research project IMPRESS-U, involving teams from Ukraine, Latvia, and the United States funded by National Science Foundation (NSF). project is focused on MXene-Based Composite Bio-membranes with Tailored Properties. Can't wait our Kick-off meeting that will be held at Latvias University in Riga with all project participants.

 

 
Our new collaborative research paper with Drexel team on Porous Ti3AlC2 MAX phase enables efficient synthesis of Ti3C2Tx MXene

porous MAX phase technologyIn this study, we have optimized the synthesis of MAX phases for MXene manufacturing. The main purpose of this study is to develop a porous Ti3AlC2MAX phase that can be easily ground into individual grains manually without time-consuming eliminating the need for drilling and intenseball-milling before MXene synthesis. Moreover, we also demonstrate the synthesis of highly porous Ti3AlC2 (about 70%) from an inexpensive raw materials.

 
Novel electrically conductive electrospun PCL‑MXene scaffolds for cardiac tissue regeneration

Scanning electron microscopy image of PCLMXene membranes crosssection (left side) with the representation of EDX line (dotted line) and example of cross-sectional EDX elements line scan (right side)Here we demonstrate a new developed method for depositing Ti3C2Tx MXenes onto hydrophobic electrospun PCL membranes using oxygen plasma treatment. These novel patches hold tremendous potential for providing mechanical support to damaged heart tissue and enabling electrical signal transmission,thereby mimicking the crucial electroconductivity required for normal cardiac function. After a detailed investigation of scaffold-to-cell interplay, including electrical stimulation, novel technology has the potential for clinical application not only for cardiac regeneration, but also as neural and muscular tissue substitutes.

 
Read recently published paper about our collaborative work: MXene Functionalized Kevlar Yarn via Automated, Continuous Dip Coating

MXene Functionalized Kevlar Yarn via Automated,Continuous Dip CoatingThe rise of the Internet of Things has spurred extensive research on integrating conductive materials into textiles to turn them into sensors, antennas, energy storage devices, and heaters. MXenes, owing to their high electrical conductivity and solution processability, offer an efficient way to add conductivity and electronic functions to textiles. Here, a versatile automated yarn dip coater tailored for producing continuously high-quality MXene-coated yarns and conducted the most comprehensive MXene-yarn dip coating study to date is developed. 

 
MX-MAP project secondment visit of Dr. Oleksiy Gogotsi and Veronika Zahorodna from MRC to University of Padova, Italy, October 2023

altMX-MAP project participants from MRC Dr. Oleksiy Gogotsi and Veronika Zahorodna performed split secondment visit to project partner organization University of Padova (Italy). MX-MAP project works on development of the key strategies for MXene medical applications. 

 
CanbioSe Project Meeting and Project Workshop, September 26-27, 2023, Montpellier, France

altCanbioSe Project Meeting and Project Workshop was held  at European Institute of Membranes (IEM), University of Montpellier, France on September 26-27, 2023. The workshop was focused on the theme of "Commercializing Biosensors, Intellectual Property, and Knowledge Transfer from Academia to Industry.

 
IEEE NAP 2023: 2023 IEEE 13th International Conference “Nanomaterials: Applications & Properties” Sep 10, 2023 - Sep 15, 2023, Bratislava, Slovakia

altDr. Oleksiy Gogotsi and Veronika Zahorodna visited IEEE NAP 2023 conference held in Bratislava on September 10-15, 2023. The prime focus of the IEEE NAP-2023 was on nanoscale materials with emphasis on interdisciplinary research exploring and exploiting their unique physical and chemical proprieties for practical applications.

 
Visit to CEST labs in Wiener Neustadt (Low Energy Ion Scattering, Batteries development) and TU Vienna (ELSA, SFA)

altDirector of MRC and Carbon-Ukraine Dr. Oleksiy Gogotsi visited CEST labs in Wiener Neustadt (Low Energy Ion Scattering, Batteries development) and TU Vienna (ELSA, SFA). He meet with Dr. Pierluigi Bilotto, Dr. Chriatian Pichler and their colleagues, discussing novel materials and r&d activities for new technologies.

 
MX-MAP Session at YUCOMAT Conference 2023 "Towards MXenes’ biomedical applications by high-dimensional immune MAPping", HORIZON-MSCA-2021-SE-01 project MX-MAP.

altMX-MAP Session was held during the YUCOMAT Conference 2023 titled: "Towards MXenes’ biomedical applications by high-dimensional immune MAPping", HORIZON-MSCA-2021-SE-01 project MX-MAP.

 
THE TWENTY-FOURTH ANNUAL CONFERENCE YUCOMAT 2023, HERCEG NOVI, MONTENEGRO, September 04-08, 2023

altThe conference was organised by the Materials Research Society of Sebia and supported by MRS-Singapore with the participation of a pleiad of distinguished scientists.

 
CANBIOSE secondment visit of Dr. Oleksiy Gogotsi and Veronika Zahorodna from MRC to European Institute of Membranes in Montpellier, France

altCANBIOSE project participants from MRC Dr. Oleksiy Gogotsi and Veronika Zahorodna performed secondment visit to project partner organization European Institute of Membranes in Montpellier (France) on August -September 2023.