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CN-121974345-A - High-entropy MXene material, preparation method and application thereof in SERS substrate

CN121974345ACN 121974345 ACN121974345 ACN 121974345ACN-121974345-A

Abstract

The invention discloses a high-entropy MXene material, a preparation method and application thereof in an SERS substrate, and relates to the technical field of functional materials. The method comprises the steps of adding high-entropy MAX phase raw material powder into mixed solution containing LiF and HCl, performing chemical etching, centrifuging to obtain a precipitate, repeatedly washing the precipitate until the pH value of supernatant is 6-7, dispersing the precipitate into deionized water, performing ultrasonic treatment to obtain high-entropy MXene solution, centrifuging the high-entropy MXene solution, and collecting an upper layer solution to obtain a single-layer high-entropy MXene colloidal solution serving as a high-entropy MXene material. The invention adopts a mild wet chemical etching process to prepare a single-layer high-entropy MXene colloidal solution with high yield, and the single-layer high-entropy MXene colloidal solution is dripped on a glass substrate, thereby providing a solution for constructing a stable and sensitive MXene-based SERS substrate.

Inventors

  • Dang Alei
  • LIU YUHUI
  • CHEN JIAHE
  • HAN YONGKANG

Assignees

  • 西北工业大学

Dates

Publication Date
20260505
Application Date
20260107

Claims (10)

  1. 1. The preparation method of the high-entropy MXene material is characterized by comprising the following steps of: adding high-entropy MAX phase raw material powder into mixed solution containing LiF and HCl, performing chemical etching, and centrifuging to obtain precipitate; Repeatedly washing the precipitate until the pH value of the supernatant is 6-7, dispersing the precipitate in deionized water, and performing ultrasonic treatment to obtain a high-entropy MXene solution; and centrifuging the high-entropy MXene solution, and collecting an upper layer solution to obtain a single-layer high-entropy MXene colloid solution serving as a high-entropy MXene material.
  2. 2. The method for preparing the high-entropy MXene material according to claim 1, wherein in the chemical etching process, the magnetic stirring reaction is carried out at 45-60 ℃ for 48-72 h; The mixed solution of LiF and HCl is prepared from LiF and 8-12M HCl, wherein the dosage ratio of LiF to HCl is 1.6-4.0 g:10-30 mL; The mass ratio of the high-entropy MAX phase raw material powder to LiF is (0.5-2.0) to (1.6-4.0).
  3. 3. The method for preparing the high-entropy MXene material according to claim 1, wherein the precipitate is repeatedly washed by hydrochloric acid and deionized water when the precipitate is repeatedly washed.
  4. 4. The method for preparing the high-entropy MXene material according to claim 1, wherein in the ultrasonic treatment process, an ultrasonic cell crusher is used, the solution is crushed to 30-60 min under the ultrasonic power of 200-500W, and the centrifugal speed is 5000-8000 rpm and the centrifugal time is 5-15 min during the centrifugation.
  5. 5. The method of claim 1, wherein the high-entropy MAX phase raw material powder is a high-entropy MAX phase (Ti 1/5 V 1/5 Nb 1/5 Ta 1/5 Zr 1/5 ) 2 AlC raw material powder).
  6. 6. A high entropy MXene material made by the method of any one of claims 1-5.
  7. 7. Use of the high entropy MXene material of claim 6in a SERS substrate.
  8. 8. A method for preparing a SERS substrate, comprising the steps of: uniformly coating the high-entropy MXene material in claim 6 on a glass substrate by adopting a dripping method, and naturally airing to obtain a SERS substrate of the high-entropy MXene; the concentration of the high-entropy MXene material is 2-10 mg/mL.
  9. 9. A SERS substrate made by the method of claim 8 wherein the SERS substrate has a detection limit of 10 -8 M when subjected to 532 nm laser excitation, and a raman signal intensity retention of not less than 50% of an initial value after 60 days of air exposure.
  10. 10. Use of a SERS substrate according to claim 9 in trace detection.

Description

High-entropy MXene material, preparation method and application thereof in SERS substrate Technical Field The invention relates to the technical field of functional materials, in particular to a high-entropy MXene material, a preparation method and application thereof in a SERS substrate. Background As a rapid, accurate and nondestructive spectrum analysis technology, the Surface enhanced Raman scattering (Surface-ENHANCED RAMAN SCATTERING, SERS) technology can accurately identify the molecules of the object to be detected with the concentration as low as nanomole in extremely short time (1 s-1 min) mainly by detecting the unique Raman signal of the target molecules, so that the Surface enhanced Raman scattering (Surface-ENHANCED RAMAN SCATTERING, SERS) technology has been widely applied to the fields of environmental protection, clinical diagnosis, biomedical treatment, food safety, anti-counterfeiting and the like. Although two-dimensional MXene materials have made certain progress in the SERS field, the development and application of MXene-based SERS substrate materials are still restricted by the following two key factors, namely (1) the Raman activity of MXene is mainly generated through the charge transfer effect between MXene and probe molecules (chemical enhancement), the SERS activity is far lower than that of a traditional noble metal substrate based on electromagnetic enhancement, the sensitivity (lower enhancement factor) of the SERS technology is greatly reduced, and (2) the stability of the two-dimensional MXene nano-sheet in the environment is poor, and colloid solution of an aqueous medium is oxidized after being stored for about 15 days, so that the service life, the detection stability and the application field of the MXene-based SERS substrate are greatly restricted. Thus, the potential of MXene in the SERS field has not been fully exploited. High-entropy MXene is a novel quaternary transition metal carbon or nitride developed based on the concept of conventional MXene borrowing high-entropy alloys, and generally 5 or more elements are combined to form a stable single phase with nearly equal atomic concentrations. The high entropy MXene has the special properties of highly exposed surface, rich surface chemical property, adjustable electronic structure, tunable light response in visible light range and the like, so that the application of the MXene material in the fields of energy storage, catalysis, electromagnetic shielding and the like is greatly expanded. However, the field of high-entropy MXene is still in the initial stage of exploration, so far only a few researches have been reported, and research and application of the field of high-entropy MXene in SERS are not reported. The prior art discloses a high-entropy MXene material, a high-entropy MAX phase material, a preparation method thereof, an electrode and a battery, wherein the high-entropy MAX phase (Ti 0.2Nb0.2Ta0.2Zr0.2V0.2)2 AlC) is placed in an etchant and reacts at 50 ℃ for 24h, centrifugal separation, water washing and drying treatment are carried out after the reaction is finished to obtain a high-entropy two-dimensional material (Ti 0.2Nb0.2Ta0.2Zr0.2V0.2)2CTx, and then the material is used as a metal lithium electrode. The prior art also discloses the high-entropy MXene material, the nitrogen-containing high-entropy MAX phase (Ti 1/3Nb1/6Ta1/6Zr1/6V1/6)2AlC0.5N0.5) is placed in the etchant and reacts at 50 ℃ for 24h, centrifugal separation, water washing and drying treatment are carried out after the reaction is finished to obtain the nitrogen-containing high-entropy two-dimensional material (Ti 1/3Nb1/6Ta1/6Zr1/6V1/6)2AlC0.5N0.5Tx. It is seen that the prior art can only be used after the MXene is obtained by etching, and the reduction of the MXene layer spacing and the loss of surface functional groups are easily caused, so that the performance is reduced. Disclosure of Invention Aiming at the defects in the background technology, the invention mainly solves the problem that the SERS sensitivity is not high because the MXene material only depends on chemical enhancement. The invention provides a high-entropy MXene material, a preparation method and application thereof in a SERS substrate. The method adopts a mild wet chemical etching process, HF is generated in situ through a mixed solution of LiF and HCl, a high-entropy MAX phase precursor is etched, a single-layer high-entropy MXene ((Ti 1/5V1/5Nb1/5Ta1/5Zr1/5)2CTx) colloid solution with high yield is prepared, and the single-layer high-entropy MXene (Ti 1/5V1/5Nb1/5Ta1/5Zr1/5)2CTx) colloid solution is dripped on a glass substrate to obtain a high-sensitivity high-entropy MXene SRES substrate. The first object of the invention is to provide a preparation method of a high-entropy MXene material, which comprises the following steps: adding high-entropy MAX phase raw material powder into mixed solution containing LiF and HCl, performing chemical etching, and centrifugi