PL239048B1 - Two-dimensional crystalline surface-modified titanium carbide Ti₃C₂ and method for obtaining two-dimensional crystalline surface-modified titanium carbide Ti₃C₂ - Google Patents

Abstract

The subject of the application is crystalline two-dimensional titanium carbide Ti3C2 surface modified with metal oxides of group 13 of the periodic table. The application also includes a method for obtaining crystalline two-dimensional titanium carbide Ti3C2 surface-modified with metal oxides of group 13 of the periodic table, which consists in adding titanium carbide and an organometallic compound R3M to an organic solvent in an atmosphere of nitrogen or argon, where R is an alkyl substituent and/or aromatic with the number of carbon atoms from 1 to 15 and M is a metal of group 13 of the periodic table, heated for several hours and then the solvent with the unreacted organometallic compound is removed and the modified titanium carbide in the form of a precipitate is exposed to air with a relative humidity of up to 100% or oxygen. The obtained modified titanium carbide is subjected to thermal treatment and then the titanium carbide with a solution of the organometallic compound is heated at a temperature of 20-200°C for 0.5-24 hours and after the reaction the solvent is removed. The remaining solvent is removed from the precipitate in a vacuum and exposed to air or oxygen, and the material thus obtained is thermally treated in a dryer or oven.

Description

The present invention relates to a method of obtaining surface-modified two-dimensional crystalline titanium carbide Ti3C2 for potential applications in catalysis, photocatalysis and medicine.

The discovery of graphene and the study of its unusual properties resulted in a huge interest in 2D materials in the world [K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva, and A. A. Firsov, Electric field effect in atomically thin carbon films, Science 306 (2004), 666]. A new family of 2D materials has been under investigation for several years, including transition metal carbides, nitrides and carbide nitrides. These new materials are produced by removing metallic element layers from crystalline 3D layered materials called MAX phases. The name of these phases comes from their composition expressed by the formula Mn + 1AXn, where M is a light transition metal (e.g. titanium), A is a metal of main groups 13 and 14 in the table of elements (e.g. aluminum), n = 1,2, 3. .., while X represents carbon and nitrogen [MW Barsoum, Mn + 1AXn phases: a new class of solids; thermodynamically stable nanolaminates, Prog. Solid State Chem. 28 (2000) 201-281]. In the MAX phases, the Mn + 1Xn layers alternate with the metal A layers. A characteristic feature are strong covalent-metal-ionic M-X bonds and much weaker M-A bonds. The presence of weaker M-A bonds enables the selective removal of the layers of element A and the preparation of two-dimensional materials with the composition Mn + 1Xn [M. Naguib, M. Kurtoglu, V. Presser, J. Lu, J. Niu, M. Heon, L. Hultman, Y. Gogotsi, and M. W. Barsoum, Two-dimensional nanocrystals produced by exfoliation of Ti3AIC2, Adv. Mater. 23 (2011) 4248; I. R. Shein and A. L. Ivanovskii, Graphene-like nanocarbides and nanonitrides of d metals (MXenes): synthesis, properties and simulation, Micro & Nano Lett. 8 (2013) 59]. MAX phase exfoliation is carried out under the influence of hydrofluoric acid HF of various concentrations and also in the presence of lithium fluoride LiF in hydrochloric acid HCl [M. Ghidu, M. R. Lukatskaya, M.-Q. Zhao, Y. Gogotsi, M. W. Barsoum, Conductive Two-Dimensional Titanium Carbide Clay with High Volumetric Capacitance, Nature 516 (2014) 78.]. After breaking the M-A bonds, the surface of the two-dimensional Mn + 1Xn materials is saturated by the attachment of OH, F and O groups. The presence of these terminal groups allows for further functionalisation of the surface of the materials by covalently or coordinatively attaching other atoms of organic, inorganic and organometallic compounds. The functionalization is carried out in order to change the properties of the two-dimensional Mn + 1Xn materials.

Although the first information about the synthesis of 2D titanium carbides appeared in 2011, the research showed a great potential application of these materials as capacitors [M. R. Lukatskaya, O. Mashtalir, CE Ren, Y. Dall'Agnese, P. Rozier, PL Taberna, M. Naguib, P. Simon, MW Barsoum, Y. Gogotsi, Cation Intercalation and High Volumetric Capacitance of Two-Dimensional Titanium Carbide. Science 341 (2013) 1502], batteries [X. Wang, S. Kajiyama, H. linuma, E. Hosono, S. Oro, I. Moriguchi, M. Okubo, A. Yamada, Pseudocapacitance of MXene Nanosheets for High-Power SodiumIon Hybrid Capacitors. Nat. Commun. 6 (2015) 6544], water filters [C. E. Ren, K. B. Hatzell, M. Alhabeb, Z. Ling, K. A. Mahmoud, Y. Gogotsi, Charge- and Size-Selective Ion Sieving Through Ti3C2Tx MXene Membranes, J. Phys. Chem. Lett. 6 (2015) 4026], catalysts [Z. W. Seh, K. D. Fredrickson, B. Anasori, J. Kibsgaard, A. L. Strickler, M. R. Lukatskaya, Y. Gogotsi, T. F. Jaramillo, A. Vojvodic, Two-Dimensional Molybdenum Carbide (MXene) as an Efficient Electrocatalyst for Hydrogen Evolution. ACS Energy Lett. 1 (2016) 589], antibacterial coatings [K. Rasool, M. Helal, A. Ali, C. E. Ren, Y. Gogotsi, K. A. Mahmoud, Antibacterial Activity of Ti3C2Tx MXene. ACS Nano 10 (2016) 3674] and transparent conductive electrodes [K. Hantanasirisakul, M.-Q. Zhao, P. Urbankowski, J. Halim, B. Anasori, S. Kota, C. E. Ren, M. W. Barsoum, Y. Gogotsi, Fabrication of Ti3C2Tx MXene Transparent Thin Films with Tunable Optoelectronic Properties. Adv. Electron. Mater. (2) 2016, 1600050].

The simplest modification is the introduction of metal ions, organic compounds or even polymers between the titanium carbide layers. This process is called intercalation and involves physically placing ions or particles between the flakes of 2D titanium carbides. Intercalating particles, molecules of compounds and ions can interact with the OH, F and O functional groups on the surface of Ti3C2 layers, but they do not form strong covalent and coordination bonds with these groups, but rather they are much weaker long-range interactions. It was found that intercalation with metal ions significantly increases the volumetric capacity of the electrode [M. R. Lukatskaya, O. Mashtalir, CE Ren, Y. Dall'Agnese, P. Rozier, PL Taberna, M. Naguib, P. Simon, MW Barsoum, Y. Gogotsi, Cation Intercalation and High Volumetric Capacitance of Two-Dimensional Titanium Carbide. Science 341 (2013)

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1502]. In turn, the introduction of carbon nanotubes between the T13C2 layers protects them against thickening of the layers [M.-Q. Zhao, C. E. Ren, Z. Ling, M. R. Lukatskaya, C. Zhang, K. L. Van Aken, M. W. Barsoum, Y. Gogotsi, Flexible MXene / Carbon Nanotube Composite Paper with High Volumetric Capacitance. Adv. Mater. 27 (2015) 339]. Intercalation of the two-dimensional Ti3C2 material with organic compounds such as urea, hydrazine, DMF, DMSO allowed for delamination of layers and obtaining two-dimensional Ti3C2 structures in the form of flakes, which when used in lithium-ion batteries improved their performance [O. Mashtalir, M. Naguib, V. N. Mochalin, Y. Dall'Agnese, M. Heon, M. W. Barsoum, Y. Gogotsi, Intercalation and Delamination of Layered Carbides and Carbonitrides. Nat. Commun. 4 (2013) 1716. O. Mashtalir, M. R. Lukatskaya, A. Kolesnikov, E. Raymundo-Pinero, M. Naguib, M. W. Barsoum, Y. Gogotsi, Effect of Hydrazine Intercalation on Structure and Capacitance of 2D Titanium Carbide (MXene). Nanoscale 8 (2016) 9128]. Ti3C2 served as a precursor to hybrid C / TiO2 materials consisting of thin carbon layers coated with titanium nanoxide. This material was obtained during the thermal treatment of Ti3C2 in a CO2 atmosphere. It was found that it absorbs microwave radiation very well and therefore other 2D titanium carbides may also be precursors of similar absorbing materials [M. Han, X. Yin, X. Li, B. Anasori, L. Zhang, L. Cheng, Y. Gogotsi, Laminated and Two-Dimensional Carbon-Supported Microwave Absorbers Derived from MXenes, ACS Appl. Mater. Interfaces 9 (2017) 20038].

Gogotsi and colleagues [M. Boota, M. Pasini, F. Galeotti, W. Porzio, M.-Q. Zhao, J. Halim, Y. Gogotsi, Interaction of Polar and Nonpolar Polyfluorenes with Layers of Two-Dimensional Titanium Carbide (MXene): Intercalation and Pseudocapacitance, Chem. Mater. 29 (2017) 2731] carried out the process of intercalation of polymers between the titanium carbide layers. They chose three types of polymers: non-polar poly (9,9-dioctylfluorene, polar nitrogen-containing poly ({9,9'-bis [3 ”- (N, N-dimethylamino) propyl] -2,7-fluorene] -alt-2) , 7- (9,9'-dioctylfluorene and ionic poly ([2,7- (9,9'-dioctyl) fluorene] -alt- {2,7- [9,9'-bis (5 ”-trimethylammonium bromide) ) hexyl] fluorene. Studies have shown that the interaction of intercalating particles with the surface of titanium carbide directly affects the amount of intercalated substance.Due to the weak interaction of the non-polar polymer with the surface, titanium carbide contained only 2% of the incorporated polymer between the layers of the material, while the polar polymer had a better interaction with the surface constituted as much as 10% in the polymer / carbide composite. It should be expected that the strong bonding of chemical compounds and particles by covalent and coordination bonds with OH, F and O groups on the titanium carbide surface will allow for permanent surface functionalization. functionalities on the surface of the carbide guarantee their uniform surface functionalisation. Direct doping of titanium carbide with doping nanoparticles will not ensure even coverage of its surface, because the finished nanoparticles join the surface with weaker long-range forces. Poorly bonded nanoparticles can be easily washed off.

A characteristic feature of metal compounds from group 13 of the periodic table R3M (where R = alkyl or aromatic substituent, M = Al, Ga, In) is the reaction with compounds containing active hydrogen functional groups such as OH and COOH. As a result of the reaction, covalent M -O bonds are formed and an alkane is released. In addition, R3M compounds coordinate with groups lacking active hydrogen such as C = O ketone, epoxy -O-, and ether oxygen atoms, and no alkane is evolved. Both covalent and coordination bonds are the strongest known chemical bonds. The characteristic reactions of R3M compounds presented above can be used to permanently attach Group 13 metals to the surface of functional materials. Jastrzębska and colleagues [A. Jastrzębska, J. Jureczko, J. Karcz, A. Kunicki, W. Ziemkowska, A. Olszyna, Controlled synthesis of graphene oxide / alumina nanocomposites using a new dry sol-gel method of synthesis, Chem. Papers 71 (2017) 579] showed that the organoaluminum compound Et3AI reacts with OH and COOH groups present on the surface of two-dimensional graphene oxide flakes to form Al-O covalent bonds and release ethane. Et3AI also attaches to the surface of graphene oxide through coordination bonds, connecting with oxygen atoms of ketone and epoxy groups. The aluminum compound thus attached was then subjected to oxidation and hydrolysis, and thermally treated at 280 ° C to obtain graphene oxide with a surface modified with nanaluminum.

It was found that doping nanomaterials with aluminum ions changes the properties of these materials. Xiang et al. [J.-l. Luo, S.-f. Wang, W. Liu, C.-x. Tian, J.-w. Wu, X.-t. Zu, W.-l. Zhou, X.-d. Yuan, X. Xiang, Influence of different aluminum salts on the photocatalytic properties of AI doped TO nanoparticles towards the degradation of AO7 dye, Sci. Rep. 7 (2017) 8108] describe the synthesis of nano

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TiO2 doped with aluminum ions, where Ti (SO4) 2 was used as the TiO2 precursor, while the aluminum ions precursors were various aluminum salts. The addition of aluminum significantly improved the photocatalytic properties of TiO2 in the reaction of decomposition of the orange yellow dye, reducing the high value of anatase energy gap, which allows for better use of visible light energy. The addition of aluminum ions inhibited the growth of TiO2 grains and the agglomeration process, increased the phase purity of anatase and increased the temperature of anatase transformation into rutile, which is favorable from the point of view of the photocatalytic properties of the material. Jastrzębska and colleagues [A. M. Jastrzębska, J. Karcz, R. Letmanowski, D. Zabost, E. Ciecierska, J. Zdunek, E. Karwowska, M. Siekierski, A. Olszyna, A. Kunicki, Synthesis of the RGO / AI2O3 core-shell nanocomposite flakes and characterization of their unique electrostatic properties using zeta potential measurements, Appl. Surface Sci. 362 (2016) 577] noted that the deposition of AI2O3 nanoparticles on the surface of RGO reduced graphene oxide flakes changes the electrostatic properties of graphene oxide. In a neutral environment in distilled water, the zeta potential curves obtained for the composite RGO / Al2O3 differ from the curves for GO and Al2O3. Despite the complete coverage of the surface of RGO flakes with Al2O3 nanoparticles, the electrostatic properties of the RGO / Al2O3 composite are not the same as those of Al2O3. It should be expected that also the Ti3C2 / Al2O3 composite may have different properties than its constituent materials.

Gallium and indium oxides are widely used in electronics, cells, catalysis and medicine, and the literature on their applications is very rich. The addition of these oxides to other materials changes the properties of these materials and their applicability. Some recently published examples of nanomaterial modification with gallium and indium nanoxides are given below. Titanium oxide TO2 doped with Ga2O3 obtained by flame pyrolysis of the precursors of both oxides turned out to be a good catalyst for the oxidative dehydrogenation of ethane to ethylene, which is a much better method of obtaining ethylene from ethane than thermal dehydrogenation due to the possibility of process control, reduction of side reactions and lower process temperature. The authors [R. Koirala, R. Buechel, F. Krumeich, S. E. Pratsinis, A. Baiker, Oxidative Dehydrogenation of Ethane with CO2 over Flame-Made Ga-Loaded TiO2, ACS Catal. 5 (2015) 690] found that the efficiency of the ethylene production from ethane depends on the gallium content in the TiO2 / Ga2O3 composite and is best if this content is 10% by weight. Moreover, the gallium content influences other properties of the catalyst. The higher the gallium content, the more resistant the catalyst is to sintering and, at the same time, the faster it undergoes coking due to the greater number of strong acid centers.

Research on the improvement of electrodes in lithium-ion cells led to the discovery that it is possible to control the phase composition of gallium nanoxide by exfoliating this oxide on RGO flakes by the wet sol-gel method [S. B. Patii, I. Y. Kim, J. L. Gunjakar, S. M. Oh, T. Eom, H. Kim, S.-J. Hwang, Phase Tuning of Nanostructured Gallium Oxide via Hybridization with Reduced Graphene Oxide for Superior Anode Performance in Li-Ion Battery: An Experimental and Theoretical Study, ACS Appl. Mater. Interfaces 7 (2015) 18679]. The crystal structure and morphology of nano Ga2O3 depend on the RGO / Ga2O3 ratio. The authors found that the composite obtained by them containing mixed phases of α, β and γ gallium oxide and used in the electrodes of lithium ion cells shows a very good discharge capacity and has good cyclic and speed characteristics. The control of electrode composition obtained by interaction with the RGOs is therefore important for optimizing the activity of these electrodes.

Due to the wide energy gap of approx. 5 eV, gallium oxide is transparent in the UV range and is therefore a desirable material in electronics, optoelectronics and magnetoelectronics. Kumar et al. [S. S. Kumar, E. J. Rubio, M. Noor-A-Alam, G. Martinez, S. Manandhar, V. Shutthanandan, S. Thevuthasan, C.V. Ramana, Structure, Morphology, and Optical Properties of Amorphous and Nanocrystalline Gallium Oxide Thin Films, J. Phys. Chem. C 117 (2013), 4194] investigated that the structure and optical properties of thin gallium oxide films deposited by sputtering depend on the sputtering temperature. At lower temperatures, up to 300 ° C, amorphous Ga2O3 is deposited with a lower energy gap of about 4.66 eV, while above 500 ° C, nanocrystalline Ga2O3 is formed with a band gap of up to 5.17 eV. Thus, changing the deposition temperature makes it possible to control the structure and properties of Ga2O3 thin layers.

Gallium compounds have an affinity for certain tissues, in particular they aid in bone renewal and removal of tumors. Ganguly and colleagues [B. N. Ganguly, V. Verma, D. Chatterjee, B. Satpati, S. Debnath, P. Saha, Study of Gallium Oxide Nanoparticles Conjugated with e-Cyclodextrin: An Application To Combat Cancer, ACS Appl. Mater. Interfaces 8 (2016) 17127] combined these gallium properties with those of cyclodextrins to obtain Ga (OH) O / cyclodextrin conjugated nanoparticles forming aqueous dispersions. On the one hand, cyclodextrins are a complexing agent for the molecules

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Ga (OH) O and, on the other hand, provide good solubility in water and are therefore a good drug carrier. The authors investigated in vitro the biological activity of these conjugated nanoparticles on malignant cells of the HeLa lineage, observing the effect of complete inhibition of cell proliferation after 72 hours. The resulting nanomaterial has great potential as a diagnostic tool as well as a drug in the removal of certain types of cancer cells in the body.

Currently, an intensive search for materials for the so-called green electronics based on oxide semiconducting materials. These materials must have a wide range of applications and be obtained at low temperatures, which will greatly reduce costs. Gallium and indium oxides fit perfectly into the green electronics concept. Xu et al. [W. Xu, H. Cao, L. Liang, J.-B. Xu, Aqueous SolutionDeposited Gallium Oxide Dielectric for Low-Temperature, Low-Operating-Voltage Indium Oxide ThinFilm Transistors: A Facile Route to Green Oxide Electronics, ACS Appl. Mater. Interfaces 7 (2015) 14720] have developed a method for obtaining Ga2O3 thin-film insulators and thin-film dielectrics from mixed Ga2O3 and In2O3 oxides. The method is cheap because the annealing temperature is a maximum of 250 ° C and the materials obtained can be widely used in the construction of thin-film transistors.

Indium oxide is often included in materials that are catalysts or photocatalysts of organic reactions. In2O3 nanocubes covered with a 5 nm thick carbon layer are photocatalysts for the reduction of carbon dioxide CO2 to carbon monoxide CO and methane CH4 [Y.-X. Pan, Y. You, S. Xin, Y. Li, G. Fu, Z. Cui, Y.-L. Men, F.-F. Cao, S.-H. Yu, J. B. Goodenough, Photocatalytic CO2 Reduction by Carbon-Coated Indium-Oxide Nanobelts, J. Am. Chem. Soc. 139 (2017) 4123]. The carbon coating facilitates the absorption of visible light, improves the separation of the induced electron-hole pairs and CO2 chemisorption, increases the number of protons from the splitting of water molecules involved in CO2 reduction and facilitates the photocatalytic reduction of CO2 to CO and CH4. This is an example of a material in which the components synergistically enhance each other's catalytic effect.

Indium oxide nanoparticles impregnated with scandium were used as a catalyst in the reaction of ethanol to propene, acetaldehyde, ethyl acetate, crotonaldehyde, acetic acid, acetone and 2-propanol [M. Iwamoto, M. Tanaka, S. Hirakawa, S. Mizuno, M. Kurosawa, Pulse and IR Study on the Reaction Pathways for the Conversion of Ethanol to Propene over Scandium-Loaded Indium Oxide Catalysts, ACS Catal. 4 (2014) 3463].

Indium nanoxide is often used in chemical sensors, biosensors and optical detectors. Recently, nano In2O3 in the form of nano-ribbons has been used in highly sensitive biosensors for the biomolecular detection of the human HIV-1 p24 antigen [N. Aroonyadet, X. Wang, Y. Song, H. Chen, RJ Cote, ME Thompson, RH Datar, C. Zhou, Highly Scalable, Uniform, and Sensitive Biosensors Based on Top-Down Indium Oxide Nanoribbons and Electronic Enzyme-Linked Immunosorbent Assay , Nano Lett. 15 (2015) 1943].

2D titanium carbides have been modified so far only with nanoparticles and nanomaterials such as: SnO2 [W. Zheng, P. Zhang, W. Tian, Y. Wang, Y. Zhang, J. Chen, ZM. Sun, Microwave-assisted synthesis of SnO2-Ti3C2 nanocomposite for enhanced supercapacitive performance, Mater. Lett. 209 (2017) 122-125, F. Wang, Z. Wang, J. Zhu, H. Yang, X. Chen, L. Wang, C. Yang, Facile synthesis SnO2 nanoparticle-modified Ti3C2 MXene nanocomposites for enhanced lithium storage application, J Mater Sci 52 (2017) 3556-3565], TiO2 [C. Peng, H. Wang, H. Yu F. Peng, (111) TiO2-x / Ti3C2: Synergy of active facets, interfacial charge transfer and Ti ³⁺ doping for enhance photocatalytic activity, Mater. Res. Bull., 89 (2017) 16-25, M. Xue, Z. Wang, F. Yuan, X. Zhang, W. Wei, H. Tang, C. Lid, Preparation of TiO2 / Ti3C2Tx hybrid nanocomposites and their tribological properties as base oil lubricant additives, RSC Adv., 7 (2017), 4312-4319, C. (J.) Zhang, SJ Kim, M. Ghidiu, M.-Q. Zhao, MW Barsoum, V. Nicolosi, Y. Gogotsi, Layered Orthorhombic Nb2O5 @ Nb4C3Tx and TiO2 @ Ti3C2Tx Hierarchical Composites for High Performance Li-ion Batteries, Adv. Funct. Mater. 26 (2016) 4143-4151; H. Tang, S. Zhuang, Z. Bao, C. Lao, Y. Mei, Two-Step oxidation of Mxene in the synthesis of layer-stacked anatase titania with enhanced lithium-storage performance, ChemElectroChem, 3 (2016) 871- 876; C. Peng, X. Yang, Y. Li, H. Yu, H. Wang, F. Peng, Hybrids of two-dimensional Ti3C2 and TO2 exposing {001} facets toward enhanced photocatalytic activity, ACS Appl. Mater. Interfaces 8 (2016) 6051-6060; F. Wang, CH Yang, M. Duan, Y. Tang, JF Zhu, TiO2 nanoparticle modified organ-likeTi3C2 MXene nanocomposite encapsulating hemoglobin for a mediator-free biosensor with excellent performances, Biosens Bioelectron. 74 (2015) 1022-1028; Y. Gao, L. Wang, A. Zhou, Z. Li, J. Chen, H. Bala, Q. Hu, X. Cao, Hydrothermal synthesis of TiO2 / Ti3C2 nanocomposites with enhanced photocatalytic activity, Mater. Lett. 150 (2015) 62-64; H. Ghassemi, W. Harlow, O. Mashtalir, M. Beidaghi, MR Lukatskaya, Y. Gogotsi ML

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Taheri, In situ environmental transmission electron microscopy study of oxidation of two-dimensional Ti3C2 and formation of carbon-supported TO2, J. Mater. Chem. A., 35 (2014) 14339-14343.] Nb2Os [C. (J.) Zhang, S. J. Kim, M. Ghidiu, M.-Q. Zhao, M. W. Barsoum, V. Nicolosi, Y. Gogotsi, Layered Orthorhombic Nb2O5 @ Nb4C3Tx and TiO2 @ Ti3C2Tx Hierarchical Composites for High Performance Li-ion Batteries, Adv. Funct. Mater. 26 (2016) 4143-4151.], CU2O [H. Zhang, H. Dong, X. Zhang, Y. Xu, J. Fransaer, Cu2O Hybridized Titanium Carbide with Open Conductive Frameworks for Lithium-ion Batteries, Electrochimica Acta 202 (2016) 24-31; Y. Gao, L. Wang, Z. Li, A. Zhou, Q. Hu, X. Cao, Preparation of MXene-Cu2O nanocomposite and effect on thermal decomposition of ammonium perchlorate, Solid State Sci. 35 (2014) 62-65.] Rhodium [M. Ming, Y. Ren, M. Hu, Y. Zhang, T. Sun, Y. Ma, X. Li, W. Jiang, D. Gao, J. Bi, G. Fan, Promoted effect of alkalization on the catalytic performance of Rh / alk-Ti3C2X2 (X = O, F) for the hydrodechlorination of chlorophenols in base-free aqueous medium, Appl. Catal. B: Environ. 210 (2017) 462-469] ruthenium [X. Li, G. Fan, C. Zeng, Synthesis of ruthenium nanoparticles deposited on graphene-like transition metal carbide as an effective catalyst for the hydrolysis of sodium borohydride, Internat. J. Hydrogen Energy 39 (2014) 14927-14934], ruthenium / nickel bimetallic system [X. Li, C. Zeng, G. Fan, Ultrafast hydrogen generation from the hydrolysis of ammonia borane catalyzed by highly efficient bimetallic RuNi nanoparticles stabilized on Ti3C2X2 (X = OH and / or F), Internat. J. Hydrogen Energy 40 (2015) 3883-3891.] Mn3O4 [Q. Xue, Z. Pei, Y. Huang, M. Zhu, Z. Tang, H. Li, Y. Huang, N. Li, H. Zhang, C. Zhi, Mn3O4 nanoparticles on layer-structured Ti3C2 MXene towards the oxygen reduction reaction and zinc-air batteries, J. Mater. Chem. A, 5 (2017) 20818-20823.] MnO2 [R. B. Rakhi, B. Ahmed, D. Anjum, H. N. Alshareef, Direct Chemical Synthesis of MnO2 Nanowhiskers on Transition-Metal Carbide Surfaces for Supercapacitor Applications, ACS Appl. Mater. Interfaces 8 (2016) 18806-18814.] Sb2O3 [X. Guo, X. Xie, S. Choi, Y. Zhao, H. Liu, C. Wang, S. Chang, G. Wang, Sb2O3 / MXene (Ti3C2Tx) hybrid anode materials with enhanced performance for sodium-ion batteries, J. Mater. Chem. A, 5 (2017) 12445-12452] NiO2 [Q. X. Xia, J. Fu, JM Yun, RS Mane, KH Kim, High volumetric energy density annealed-MXene nickel oxide / MXene asymmetric supercapacitor, RSC Adv., 7 (2017) 11000-11011] MXene V2CO2 modified with Fe transition metals, What nothing. Ling, L. Shi, Y. Ouyang, Q. Chen, J. Wang, Transition Metal-Promoted V2CO2 (MXenes): A New and Highly Active Catalyst for Hydrogen Evolution Reaction, Adv. Sci. 3 (2016) 1600 180-1600187.] Ni / Al hydroxide [Y. Wang, H. Dou, J. Wang, B. Ding, Y. Xu, Z. Chang, X. Hao, Three-dimensional porous MXene / layered double hydroxide composite for high performance supercapacitors, J. Power Sources 327 (2016) 221 -228], carbon nanotubes [Y. Liu, W. Wang, Y. Ying, Y. Wang, X. Peng, Binder-free layered Ti3C2 / CNTs nanocomposite anodes with enhanced capacity and long-cycle life for lithium-ion batteries, Dalton Trans., 44 (2015) 7123 .], blue phosphate [Z. Guo, N. Miao, J. Zhou, B. Sa, Z. Sun, Strain-mediated type-I / type-II transition in MXene / Blue phosphorene van der Waals heterostructures for flexible optical / electronic devices, J. Mater. Chem. C, 5 (2017) 978-984.

There are many composites known, in which aluminum, gallium and indium oxides were used for modification, obtaining materials with new properties. However, the current state of knowledge indicates that there is no method for obtaining 2D titanium carbides surface-modified with nanoparticles of metal oxides from group 13 of the periodic table.

The subject of the invention is a method of obtaining a crystalline two-dimensional titanium carbide Ti3C2 surface-modified with a metal oxide of group 13 of the periodic table selected from the group of aluminum, gallium and indium, characterized in that under nitrogen or argon atmosphere to a liquid organic solvent selected from the group of hydrocarbons containing from 5 to 18 carbon atoms or ethers containing from 4 to 16 carbon atoms or halogen hydrocarbons containing from 1 to 18 carbon atoms, titanium carbide and organometallic compound R3M are added, where R is an alkyl and / or aromatic substituent with carbon atoms from 1 to 15 and M is metal group 13 of the periodic table selected from the group of aluminum, gallium and indium, the organometallic compound used R3M, where R and M are as defined above, has the ability to react with the OH groups and form coordination bonds with the F and O groups, and the solvent used is dehydrated and deoxygenated then titanium carbide with a solution of a metal-metal compound The organic solvent is heated in the temperature range from room to 200 ° C for 0.5-24 hours, and after the reaction, the solvent is removed by decanting the modified titanium carbide sediment and washed with the same solvent, which was used for the reaction or another solvent, and the sediment was removed from the sediment. the rest of the solvent is removed in vacuo and exposed to air or oxygen, and the material thus obtained is either used without further treatment or is thermally treated in an oven or oven, the compounds being used in the following weight ratios to one another:

PL 239 048 Β1 crystalline two-dimensional titanium carbide Ti3C2: aluminum organometallic compound from 1: 1 to 1: 1.66, crystalline two-dimensional titanium carbide Ti3C2: gallium organometallic compound from 1: 1 to 1: 2.26, crystalline two-dimensional titanium carbide Ti3C2: organometallic compound indium from 1: 1 to 1: 3.14. Preferably, the alkyl group is a methyl or ethyl group.

Preferably, toluene is used as the solvent, preferably by heating the titanium carbide with an organometallic compound at the toluene boiling point of about 110 ° C, preferably for 2 hours.

Preferably, the oxidation / hydrolysis of the organometallic compound attached to the titanium carbide surface is carried out by exposing the sample to air having a relative humidity of 30-70%, and is preferably subjected to a thermal treatment at 100 ° C for 0.5 h.

By carrying out the process according to the invention, titanium carbide layers uniformly coated with metal oxide nanoparticles are obtained. For such a material, the notation T13C2 / M2O3 can be taken (M = group 13 metal of the periodic table selected from the aluminum, gallium and indium group. Exemplary SEM photos show titanium carbide layers before modification (Fig. 1a) and photos of Ti3C2 / Al2O3 materials (Fig. 1 b) Ti3C2 / Ga2O3 (Fig. 1 c), Ti3C2 / ln2O3 (Fig. 1 d). Photos of Ti3C2 / Al2O3 and Ti3C2 / ln2O3 composites show titanium carbide layers evenly covered with AI2O3 and Ιη2θ3 nanoparticles, while Ga2Os nanoparticles are on the surface titanium carbide in a small amount. is that they tend to exist in monomeric form, while aluminum and indium compounds always exist in associated form or in complexes with electron donors. u with surface groups cause removal of gallium compounds from the surface during solvent washout.

EDS studies showed a significant increase in the number of aluminum atoms on the surface of the T13C2 layers modified with aluminum nanoxide compared to the unmodified T13C2 (Figs. 2 and 3, Tables 1 and 2).

Table 1 EDS results obtained from the surface area measurement of unmodified T13C2

element series C [at%] C [wt%] C error [wt%] titanium K-series 40.48 66.09 6.34 Fluorine K-series 23.96 15.52 7.31 oxygen K-series 16.57 9.04 5.08 coal K-series 15.93 6.53 3.43 aluminum K-series 3.06 2.81 0.53

Table 2 EDS results obtained from surface area measurements of unmodified T13C2 / Al2O3

element series C [at%] C [wt%] C error [wt%] titanium K-series 16.23 35.89 1.29 Fluorine K-series 25.04 21.97 3.42 oxygen K-series 30.69 20.68 3.62 coal K-series 12.45 22.44. 3.43 aluminum K-series 5.03 6.27 0.38 silicon K-series 0.51 0.66 0.06 chlorine k-series 0.05 0.08 0.03

This proves that the T13C2 surface has been modified with aluminum compounds. EDS tests confirmed the presence of gallium on the Ti3C2 / Ga2O3 surface, however, it is present in the amount of 2.08 wt.%. (Fig. 4, Table 3).

PL 239 048 Β1

Table 3. EDS results obtained from the measurement of the surface of T13O2 layers modified with Ti3C2 / Ga2O3 gallium nanoxide

element series C [at%] C [wt%] C error [wt%] titanium K-series 29.30 56.30 6.86 Fluorine K-series 17.36 13.23 7.91 oxygen K-series 14.29 9.17 6.33 coal K-series 37.07 17.87 9.90 aluminum K-series 1.24 1.35 0.36 gai K-series 0.74 2.08 0.65

all elements on the surface. The Indium is present on the TisCz / 3O2 surface in an amount of 5.92 wt% (Fig. 5, Table 4).

Table 4. EDS results obtained from the measurement of the surface of T13O2 layers modified with indium nanoxide TisCz / InzOs

element series C [at%] C [wt%] C error [weight%] titanium K-series 37.95 56.30 1.29 Fluorine K-series 15.11 10.50 1.79 oxygen K-series 31.52 17.31 2.89 coal K-series 20.88 8.61 1.43 aluminum K-series 1.70 1.57 0.12 indium K-series 23.32 5.92 0.84 magnesium K-series 0.41 0.34 0.05 silicon K-series 0.23 0.22 0.04 chlorine K-series 0.14 0.17 0.04

Thermogravimetric tests on T13C2 indicate a weight loss of 8.6% to 200 ° C and the total weight loss in the range from room temperature to 1000 ° C is 26.8%, while for T13C2 / Al2O3 the weight loss is smaller and amounts to 6.9%, respectively % and 23.6% by weight, which proves that aluminum permanently binds the surface groups and protects them against detachment from the titanium carbide surface. Alumina is non-volatile and therefore the weight loss for T13C2 / Al2O3 is lower compared to the loss for T13C. For Ti3C2 / Ga2O3, as for T13C2 / Al2O3, the weight loss up to 200 ° C is lower than for T13C2 and amounts to 3.7%, and at 1000 ° C it reaches a value of 23.2%, almost the same as for T13C2 / Al2O3. On the other hand, for TisCz / I ^ Os, the thermogravimetric curve has a different course. In the range up to 1000 ° C, at least 4 weight losses can be distinguished and the total weight loss at 1000 ° C is 45.9 wt.%. Such a large loss of mass indicates the existence of a large number of organic groups on the Ti3C2 / ln2O3 surface, which did not react with moisture and oxygen from the air. This is consistent with the observation that indium alkyl compounds are less reactive than aluminum and gallium compounds.

The essence of the invention is explained in the following examples:

EXAMPLE 1 To a suspension of 0.50 g T13C2 in 5 cm ³ of toluene was added at room temperature EtsAl (1 cm ^3, 0.83 g) and heated for 2 hours under reflux of toluene to 110 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} toluene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to air humidity and oxygen for 7 days. TisCz / AbOs were obtained in the form of a black solid.

Example 2 To a suspension of 0.50 g T13C2 in 5 cm ³ of toluene was added at room temperature ETSG (1 cm ^3, 1.07 g) and heated for 2 hours under reflux of toluene to 110 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} toluene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to air humidity and oxygen for 7 days. TisC2 / Ga2O3 was obtained in the form of a black solid.

PL 239 048 B1

EXAMPLE 3 To a suspension of 0.50 g Ti3C2 in 5 cm ³ of toluene was added at room temperature Mesale (1 cm ^3, 0.75 g) and heated for 2 hours under reflux of toluene to 110 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} toluene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to air humidity and oxygen for 7 days. Ti3C2 / Inl2O3 was obtained in the form of a black solid.

Example 4. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of toluene was added Me3Al (1 cm ^3, 0.75 g) and heated for 2 hours under reflux of toluene to 110 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} toluene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to air humidity and oxygen for 7 days. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

EXAMPLE 5 To a suspension of 0.50 g Ti3C2 in 5 cm ³ of toluene was added at room temperature Me3Ga (1 cm ^3, 1.13 g) and heated for 2 hours under reflux of toluene to 110 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} toluene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to air humidity and oxygen for 7 days. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

Example 6. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of toluene was added at room temperature Me3ln (1 cm ^3, 1.57 g) and heated for 2 hours under reflux of toluene to 110 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed, and then the precipitate was washed with 5 cm ^{3 of} toluene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to air humidity and oxygen for 7 days. Ti3C2 / In2O3 was obtained in the form of a black solid.

Example 7. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of hexane was added at room temperature Et3AI (1 cm ^3, 0.83 g) and heated for 2 hours under reflux of hexane of 68 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} hexane. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to air humidity and oxygen for 7 days. Ti3C2 / Al2O3 was obtained in the form of a black solid.

Example 8 To a suspension of 0.50 g Ti3C2 in 5 cm ³ of hexane was added at room temperature Et3Ga (1 cm ^3, 1.07 g) and heated for 2 hours under reflux of hexane of 68 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} hexane. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to air humidity and oxygen for 7 days. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

Example 9 To a suspension of 0.50 g of Ti ^{3 Cl 2 in 5 cm 3 of hexane, Et 3} Al (1 cm 3, 0.83 g) was added at room temperature and heated for 2 hours at the reflux temperature of hexane at 68 ° C. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} hexane. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to air humidity and oxygen for 7 days. Ti3C2 / Al2O3 was obtained in the form of a black solid.

Example 10. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of chloroform was added at room temperature Et3AI (1 cm ^3, 0.83 g) and heated for 2 hours under reflux of chloroform, 61 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} chloroform. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to air humidity and oxygen for 7 days. Ti3C2 / AhO3 was obtained in the form of a black solid.

Example 11. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of chloroform was added at room temperature Et3Ga (1 cm ^3, 1.07 g) and heated for 2 hours under reflux of chloroform, 61 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} chloroform. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to air humidity and oxygen for 7 days. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

PL 239 048 B1

Example 12 To a suspension of 0.50 g of TisCz in 5 cm ^{3 of chloroform, Et 3} In (1 cm 3, 1.38 g) was added at room temperature and heated for 2 hours at the reflux temperature of the chloroform at 61 ° C. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} chloroform. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to air humidity and oxygen for 7 days. Ti3C2 / In2O3 was obtained in the form of a black solid.

Example 13. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of toluene was added at room temperature Et3AI (1 cm ^3, 0.83 g) and heated for 2 hours under reflux of toluene to 110 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} toluene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / AbO3 was obtained in the form of a black solid.

Example 14. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of toluene was added at room temperature Et3Ga (1 cm ^3, 1.07 g) and heated for 2 hours under reflux of toluene to 110 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} toluene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

Example 15 To a suspension of 0.50 g of Ti 3 Cl 2 in 5 cm ^{3 of toluene, Et 3} In (1 cm 3, 1.38 g) was added at room temperature and heated for 2 hours at the reflux temperature of toluene at 110 ° C. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} toluene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / In2O3 was obtained in the form of a black solid.

Example 16. To a suspension of 0.50 g Ti3C2 in 5 cm ^{3 of} diethyl ether were added at room temperature Et3AI (1 cm ^3, 0.83 g) and heated for 2 hours at reflux temperature of ether 36 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and discarded and then washed with 5 cm ^{3 of} ether. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / AbO3 was obtained in the form of a black solid.

Example 17. To a suspension of 0.50 g Ti3C2 in 5 cm ^{3 of} diethyl ether were added at room temperature Et3Ga (1 cm ^3, 1.07 g) and heated for 2 hours at reflux temperature of ether 36 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and discarded and then washed with 5 cm ^{3 of} ether. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

Example 18. To a suspension of 0.50 g Ti3C2 in 5 cm ^{3 of} diethyl ether were added at room temperature Et3ln (1 cm ^3, 1.38 g) and heated for 2 hours at reflux temperature of ether 36 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and discarded and then washed with 5 cm ^{3 of} ether. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 2-7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / In2O3 was obtained in the form of a black solid.

Example 19. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of tetrahydrofuran at room temperature and-Bu3AI (1 cm ^3, 0.79 g) and heated for 2 hours at the reflux temperature of tetrahydrofuran, 66 ° C to reflux . After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ^{3 of} tetrahydrofuran. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2lAl2O3 was obtained in the form of a black solid.

PL 239 048 B1

Example 20. To a suspension of 0.50 g TisCz in 5 cm ³ of tetrahydrofuran was added 0.50 g of i-Bu3Ga and heated for 2 hours at the reflux temperature of tetrahydrofuran, 66 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ^{3 of} tetrahydrofuran. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

Example 21 To a suspension of 0.50 g of Ti ^{3 Cl 2 in 5 ml of tetrahydrofuran, 0.50 g of i-Bu 3 In} was added at room temperature and heated for 2 hours at the reflux temperature of tetrahydrofuran at 66 ° C. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ^{3 of} tetrahydrofuran. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / In2O3 was obtained in the form of a black solid.

Example 22. To a suspension of 0.50 g Ti3C2 in 5 cm ^{3 of} cyclo-hexane was added at room temperature 0.50 g of i-Pr3AI and heated for 2 hours at reflux cyclo-hexane of 81 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} cyclohexane. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / Al2O3 was obtained in the form of a black solid.

Example 23. To a suspension of 0.50 g Ti3C2 in 5 cm ^{3 of} cyclo-hexane was added at room temperature 0.50 g of i-Pr3Ga and heated for 2 hours at reflux cyclo-hexane of 81 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} cyclohexane. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

Example 24. To a suspension of 0.50 g Ti3C2 in 5 cm ^{3 of} cyclo-hexane was added at room temperature 0.50 g of i-Pr3In and heated for 2 hours at reflux cyclo-hexane of 81 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ^{3 of} cyclohexane. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / In2O3 was obtained in the form of a black solid.

Example 25. To a suspension of 0.50 g Ti3C in 5 cm ^{3 of} n-decane was added at room temperature 0.50 g of t-Bu3AI and heated for 2 hours at 100 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and discarded and then washed with 5 cm ^{3 of} n-decane. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / AbO3 was obtained in the form of a black solid.

Example 26. To a suspension of 0.50 g Ti3C2 in 5 cm ^{3 of} n-decane was added at room temperature 0.50 g of t-Bu3Ga and heated for 2 hours at 100 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and discarded and then washed with 5 cm ^{3 of} n-decane. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

Example 27. To a suspension of 0.50 g Ti3C2 in 5 cm ^{3 of} n-decane was added at room temperature 0.50 g of t-Bu3ln and heated for 2 hours at 100 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and discarded and then washed with 5 cm ^{3 of} n-decane. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / In2O3 was obtained in the form of a black solid.

PL 239 048 B1

Example 28 To a suspension of 0.50 g of TisCz in 5 cm ³ of dibutyl ether was added Et ³ Al (1 cm 3, 0.83 g) at room temperature and heated for 2 hours at the reflux temperature of 140 ° C in dibutyl ether. . After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ³ of dibutyl ether. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / Al2O3 was obtained in the form of a black solid.

Example 29. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of dibutyl ether was added Et3Ga (1 cm ^3, 1.07 g) and heated for 2 hours at reflux dibutyl ether 140 ° C under reflux . After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ³ of dibutyl ether. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to air humidity and oxygen for 7 days. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

Example 30. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of dibutyl ether was added Et3ln (1 cm ^3, 1.38 g) and heated for 2 hours at reflux dibutyl ether 140 ° C under reflux . After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ³ of dibutyl ether. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to air humidity and oxygen for 7 days. Ti3C2 / In2O3 was obtained in the form of a black solid.

Example 31. To a suspension of 0.50 g Ti3C2 in 5 cm ^{3 of} methylene chloride is added at room temperature Et3AI (1 cm ^3, 0.83 g) and heated for 2 hours at the boiling point of methylene chloride is 39 ° C to reflux . After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ³ of methylene chloride. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 70 ° C for 0.5 hours. Ti3C2 / Al2O3 was obtained in the form of a black solid.

Example 32. To a suspension of 0.50 g Ti3C2 in 5 cm ^{3 of} methylene chloride is added at room temperature Et3Ga (1 cm ^3, 1.07 g) and heated for 2 hours at the boiling point of methylene chloride is 39 ° C to reflux . After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ³ of methylene chloride. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 70 ° C for 0.5 hours. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

Example 33. To a suspension of 0.50 g Ti3C2 in 5 cm ^{3 of} methylene chloride is added at room temperature Et3ln (1 cm ^3, 1.38 g) and heated for 2 hours at the boiling point of methylene chloride is 39 ° C to reflux . After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm ³ of methylene chloride. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 70 ° C for 0.5 hours. Ti3C2 / In2O3 was obtained in the form of a black solid.

Example 34. To a suspension of 0.50 g Ti3C2 / A 5 cm ³ of methyl iodide Mel was added Et3AI (1 cm ^3, 0.83 g) and heated for 2 hours at reflux temperature methyl iodide Mel 42 ° C under reflux condenser. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ³ of methyl iodide. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 50 ° C for 1 hour. Ti3C2 / Al2O3 was obtained in the form of a black solid.

Example 35. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of methyl iodide were added at room temperature Et3Ga (1 cm ^3, 1.07 g) and heated for 2 hours at reflux temperature methyl iodide of 42 ° C to reflux . After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ³ of methyl iodide. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 50 ° C for 1 hour. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

PL 239 048 B1

Example 36. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of methyl iodide were added at room temperature Et3ln (1 cm ^3, 1.38 g) and heated for 2 hours at reflux temperature methyl iodide of 42 ° C to reflux . After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ³ of methyl iodide. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 50 ° C for 1 hour. Ti3C2 / In2O3 was obtained in the form of a black solid.

Example 37. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of chlorobenzene was added at room temperature Et3AI (1 cm ^3, 0.83 g) and heated for 2 hours at the reflux temperature of chlorobenzene of 131 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ^{3 of} chlorobenzene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 50 ° C for 1 hour. Ti3C2 / AhO3 was obtained in the form of a black solid.

Example 38. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of chlorobenzene was added at room temperature Et3Ga (1 cm ^3, 1.07 g) and heated for 2 hours at the reflux temperature of chlorobenzene of 131 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ^{3 of} chlorobenzene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 50 ° C for 1 hour. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

Example 39 To a suspension of 0.50 g of Ti ^{3 Cl 2 in 5 cm 3 of chlorobenzene, Et 3} In (1 cm 3, 1.38 g) was added at room temperature and heated for 2 hours at the reflux temperature of chlorobenzene at 131 ° C. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ³ of methyl iodide. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 50 ° C for 1 hour. Ti3C2 / In2O3 was obtained in the form of a black solid.

Example 40. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of toluene was added at room temperature Et3AI (1 cm ^3, 0.83 g) and allowed to stand 24 hours at room temperature with stirring. The liquid was then decanted and the precipitate was removed and washed with 5 cm ^{3 of} toluene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 70 ° C for 0.5 hours. Ti3C2 / AhO3 was obtained in the form of a black solid.

Example 41. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of toluene was added at room temperature Et3Ga (1 cm ^3, 1.07 g) and allowed to stand 24 hours at room temperature with stirring. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and washed with 5 cm ^{3 of} toluene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 70 ° C for 0.5 hours. Ti3C2 / GaO3 was obtained in the form of a black solid.

Example 42. To a suspension of 0.50 g of Ti ^{3 Cl 2 in 5 cm 3 of} toluene was added Et ³ In (1 cm 3, 1.38 g) at room temperature and left for 24 hours at room temperature with stirring. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and washed with 5 cm ^{3 of} toluene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 70 ° C for 0.5 hours. Ti3C2 / In2O3 was obtained in the form of a black solid.

Example 43 To a suspension of 0.50 g of Ti ^{3 Cl 2 in 5 cm 3 of} chlorobenzene, 0.50 g of (C 6 H 5) 3 Al was added at room temperature and heated for 1 hour at the reflux temperature of chlorobenzene at 131 ° C. After cooling the reaction mixture to room temperature, the liquid was decanted and removed and then washed with 5 cm <3> of chlorobenzene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 50 ° C for 1 hour. Ti3C2 / Al2O3 was obtained in the form of a black solid.

Example 44. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of chlorobenzene was added 0.50 g of (C6H5) 3ga and heated for 1 hour at the boiling point of chlorobenzene of 131 ° C under reflux. After cooling the reaction mixture to room temperature, decantation was carried out

The liquid was removed and the precipitate was washed with 5 cm ^{3 of} chlorobenzene and then washed. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 50 ° C for 1 hour. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

Example 45 To a suspension of 0.50 g of Ti ^{3 Cl 2 in 5 ml of chlorobenzene, 0.50 g of (C 6 H 5) 3 In} was added at room temperature and heated for 1 hour at the reflux temperature of chlorobenzene at 131 ° C. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ^{3 of} chlorobenzene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 50 ° C for 1 hour. Ti3C2 / In2O3 was obtained in the form of a black solid.

Example 46. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of tetrahydrofuran was added 0.50 g (C6HsCH2) 3AI and heated for 2 hours at the reflux temperature of tetrahydrofuran, 66 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ^{3 of} tetrahydrofuran. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / AhO3 was obtained in the form of a black solid.

Example 47. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of tetrahydrofuran was added 0.50 g (C6HsCH2) 3ga and heated for 2 hours at the reflux temperature of tetrahydrofuran, 66 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ^{3 of} tetrahydrofuran. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

Example 48. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of tetrahydrofuran was added 0.50 g (C6HsCH2) 3in and heated for 2 hours at the reflux temperature of tetrahydrofuran, 66 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ^{3 of} tetrahydrofuran. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / In2O3 was obtained in the form of a black solid.

Example 49. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of bromobenzene was added at room temperature 0.50 g (C6HsCH2) 3AI and heated for 2 hours at reflux bromobenzene 156 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ^{3 of} bromobenzene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / AhO3 was obtained in the form of a black solid.

Example 50. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of bromobenzene was added at room temperature 0.50 g (C6HsCH2) 3ga and heated for 2 hours at reflux bromobenzene 156 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ^{3 of} bromobenzene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / Ga2O3 was obtained in the form of a black solid.

Example 51. To a suspension of 0.50 g Ti3C2 in 5 cm ³ of bromobenzene was added at room temperature 0.50 g (C6HsCH2) 3in and heated for 2 hours at reflux bromobenzene 156 ° C under reflux. After cooling the reaction mixture to room temperature, the liquid was decanted and the precipitate was removed and then washed with 5 cm ^{3 of} bromobenzene. The operations were performed under an inert gas atmosphere. The pellet was dried in vacuo and exposed to moisture and oxygen from the air for 7 days and then heated in an oven at 100 ° C for 0.5 hours. Ti3C2 / In2O3 was obtained in the form of a black solid.

Claims (4)

1: 3.14. 1: 2.26, crystalline two-dimensional titanium carbide Ti3C2: indium organometallic compound from 1: 1 to 1. A method of obtaining crystalline two-dimensional titanium carbide T13C2 surface-modified with a metal oxide of group 13 of the periodic table selected from the group of aluminum, gallium and indium, characterized in that under nitrogen or argon atmosphere to a liquid organic solvent selected from the group of hydrocarbons containing from 5 to 18 carbon atoms or ethers containing from 4 to 16 carbon atoms or halogen hydrocarbons containing from 1 to 18 carbon atoms, titanium carbide and organometallic compound R3M are added, where R is an alkyl and / or aromatic substituent with carbon atoms from 1 to 15 and M is a group 13 metal of the Periodic Table selected from the group of aluminum, gallium and indium, the used organometallic compound R3M, where R and M are as defined above, has the ability to react with the OH groups and form coordination bonds with the F and O groups, and the solvent used is dehydrated and deoxygenated, then The titanium carbide with the organometallic compound solution is heated in the te range room temperature from room temperature to 200 ° C for 0.5-24 hours and after the reaction, the solvent is removed by decanting the modified titanium carbide sediment and washed with the same solvent used for the reaction or otherwise, the rest of the solvent is removed from the sediment in vacuo and exposed to air or oxygen and the material so obtained is either used without further treatment, or is thermally treated in an oven or oven, the compounds being used in the following proportions by weight to one another: crystalline two-dimensional titanium carbide Ti3C2: aluminum organometallic compound from 1: 1 to 1: 1.66, crystalline two-dimensional titanium carbide Ti3C2: gallium organometallic compound from 1: 1 to 2. The method according to p. The process of claim 1, wherein the alkyl group is a methyl or ethyl group. 3. The method according to p. The process of claim 1, wherein the solvent is toluene and the heating of the titanium carbide with the organometallic compound is carried out at the boiling point of toluene for 2 hours. 4. The method according to p. The method of claim 1, characterized in that the oxidation / hydrolysis of the organometallic compound attached to the titanium carbide surface is carried out by exposing the sample to air with a relative humidity of 30-70% and subjecting to a thermal treatment at 100 ° C for 0.5 h.