CN-121649413-B - Method for preparing supported nano noble metal by introducing closed borane cluster into MXene matrix

Abstract

The invention provides a method for preparing supported nano noble metal by introducing closed borane clusters into an MXene matrix, and belongs to the technical field of nano noble metal materials. The method comprises the steps of preparing the supported nano noble metal by introducing a closed borane cluster into an MXene matrix, presetting the closed borane cluster (weak reducing agent) with weak reducing capability on the surface of the MXene in a mode of removing in-situ nucleation growth through a solvent, then introducing noble metal salt, realizing in-situ reduction of the noble metal salt on the surface of the MXene and attaching the noble metal salt on the surface of the MXene, realizing controllable reduction of noble metal ions, and stabilizing the structure of the material through high-temperature annealing treatment, thereby obtaining the supported nano noble metal material with small size and high dispersity.

Inventors

• ZHAO XUE
• YE QIAO
• LI RUCHUN

Assignees

• 云南师范大学

Dates

Publication Date

20260512

Application Date

20260205

Claims (5)

1. 1. The method for preparing the supported nano noble metal by introducing the closed borane cluster into the MXene matrix is characterized by comprising the following steps of: Mixing MXene and a closed borane cluster in an organic solvent, removing the organic solvent, and carrying out loading of the borane cluster to obtain a borane cluster-MXene; mixing the borane cluster-MXene with a noble metal salt solution, and carrying out a reduction reaction to obtain a compound; annealing the composite to obtain a load type nano noble metal material based on MXene; The anions of the closed borane cluster comprise dodecahydrododecaborane cluster anions, decahydrodecaborane cluster anions, hexahydrohexaborane cluster anions or heptahydrohexaborane cluster anions; The cation of the closed borane cluster comprises an organic ammonium positive ion, wherein the organic ammonium positive ion comprises a tetrabutylammonium positive ion or a tetraethylammonium positive ion; the temperature of the load of the borane cluster is room temperature, and the time is 0.5-4 hours; the temperature of the reduction reaction is 60-150 ℃ and the time is 0.5-4 h; the temperature of the annealing treatment is 400-1200 ℃ and the time is 1-4 hours.
2. 2. The method of claim 1, wherein the mass ratio of the MXene to the closed borane cluster is 1:0.5 to 1:5.
3. 3. The method according to claim 2, wherein the stirring speed of the load of the borane cluster is 500-2000 r/min.
4. 4. The method of claim 1, wherein the noble metal salt in the noble metal salt solution comprises one or more of chloroauric acid, chloroplatinic acid, sodium chloropalladate, potassium chloropalladate, silver nitrate, silver ammonia, ruthenium trichloride, ammonium hexachlororuthenate, iridium trichloride, hexairidium acid, and rhodium trichloride.
5. 5. The method according to claim 4, wherein the concentration of the noble metal salt solution is 1-100 mmol/L, and the molar ratio of the borane clusters to the noble metal salt in the borane cluster-MXene is 1:1-10:1.

Description

Method for preparing supported nano noble metal by introducing closed borane cluster into MXene matrix Technical Field The invention relates to the technical field of nano noble metal materials, in particular to a method for preparing supported nano noble metal by introducing closed borane clusters into an MXene matrix. Background Noble metals are widely used in fields including petrochemical industry, biological medicine, energy production/storage/conversion, environmental pollution treatment, etc., but cost problems caused by scarcity of noble metals prevent large-scale utilization of them. In most cases, noble metals are used in catalysts, and the process occurs at the surface of the noble metal, involving only a few atomic layers in thickness, with most of the noble metal atoms in the bulk phase not participating in the reaction. The nanocrystallization of noble metal materials has become an effective method for improving the atomic utilization rate and the activity of unit mass of noble metals, and has promotion effect on realizing green production. At present, the development of reliable noble metal nanocrystallization technology, particularly in the aspect of preparation of supported noble metals, is a focus of common attention in academia and industry. Conventionally, there are generally methods for introducing nano noble metals onto a specific carrier by (1) mixing a carrier, sodium borohydride, and a noble metal salt together, converting the noble metal salt into a zero-valent form by using the reducibility of sodium borohydride and attaching the noble metal salt to the carrier, which is simple but the strong reducibility of sodium borohydride easily causes aggregation of noble metal atoms to form nano noble metals of larger particles, (2) mixing a carrier, a noble metal salt, and some molecules having reducibility (such as ascorbic acid) together, and then reducing the noble metal to the carrier by a high-temperature hydrothermal method, which can obtain uniformly dispersed noble metal nanoparticles, but has problems of high energy consumption, difficult mass production, and the like, and (3) introducing the noble metal salt into the carrier by an immersion method or a coprecipitation method, and then converting the noble metal salt attached to the carrier into a zero-valent form by using hydrogen as a reducing agent in a high-temperature state, which is cumbersome to operate, high in energy consumption and has a safety risk. Under the background, the development and operation of the supported nano noble metal preparation technology which is simple in operation, low in cost, good in nano noble metal dispersity, small in scale and easy for large-scale mass production becomes an important direction of current research. MXene is a material with rich electrical properties, has a laminated structure, is favorable for exposing more metal sites, and is widely applied to the fields of chemical catalysis, new energy catalysis, environmental catalysis and the like. Therefore, the development of a new technology for controllably constructing the supported nano noble metal on the MXene is significant. Disclosure of Invention The invention aims to provide a method for preparing supported nano noble metal by introducing closed borane clusters into an MXene matrix, wherein the prepared nano noble metal has good dispersity and small scale and is easy to prepare in batches. In order to achieve the above object, the present invention provides the following technical solutions: The invention provides a method for preparing supported nano noble metal by introducing closed borane clusters into an MXene matrix, which comprises the following steps: Mixing MXene and a closed borane cluster in an organic solvent, removing the organic solvent, and carrying out loading of the borane cluster to obtain a borane cluster-MXene; mixing the borane cluster-MXene with a noble metal salt solution, and carrying out a reduction reaction to obtain a compound; And (3) annealing the composite to obtain the MXene-based supported nano noble metal material. Preferably, the anions of the closed borane cluster comprise dodecahydrododecaborane cluster anions, decahydrodecaborane cluster anions, hexahydrohexaborane cluster anions or heptahydrohexaborane cluster anions, and the cations of the closed borane cluster comprise organic ammonium cations. Preferably, the organic ammonium positive ions include tetrabutylammonium positive ions or tetraethylammonium positive ions. Preferably, the mass ratio of the MXene to the closed borane cluster is 1:0.5-1:5. Preferably, the temperature of the load of the borane cluster is room temperature, the time is 0.5-4 h, and the stirring speed is 500-2000 r/min. Preferably, the noble metal salt in the noble metal salt solution comprises one or more of chloroauric acid, chloroplatinic acid, sodium chloropalladate, potassium chloropalladate, silver nitrate, silver ammonia, ruthenium trichloride, ammonium hexachlo