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CN-122006725-A - Gallium-based liquid metal microsphere and preparation method and application thereof

CN122006725ACN 122006725 ACN122006725 ACN 122006725ACN-122006725-A

Abstract

The invention discloses a gallium-based liquid metal microsphere and a preparation method and application thereof, and belongs to the field of catalytic materials. The gallium-based liquid metal microsphere has a core-shell structure, wherein the core is a liquid alloy, the shell is a crystalline alloy, the crystalline alloy is uniformly coated on the surface of the liquid alloy, and the average particle size of the microsphere is 100 nm-1000 nm. The preparation method comprises the following steps of (1) interfacial activation and system construction, namely adding a liquid alloy into a solvent and acidifying the liquid alloy, (2) adding a metal salt precursor, (3) ultrasonic induction synthesis, namely carrying out pulse ultrasonic treatment on a mixture obtained in the step (2) under the protection of inert atmosphere, and (4) post-treatment, namely separating, washing and drying a product obtained in the step (3) to obtain the gallium-based liquid microsphere. The gallium-based liquid metal microsphere provided by the invention can achieve the effects of high catalytic activity, uniform and stable core-shell structure and long cycle service life.

Inventors

  • CHEN XIAO
  • LIU JU
  • LIU JIACHENG
  • WEN HONGLIN
  • YU CHAO

Assignees

  • 江苏科技大学

Dates

Publication Date
20260512
Application Date
20260416

Claims (7)

  1. 1. The gallium-based liquid metal microsphere is characterized by having a core-shell structure, wherein an inner core is a liquid alloy, an outer shell is a crystalline alloy, the crystalline alloy is uniformly coated on the surface of the liquid alloy, the average particle size of the microsphere is 100 nm-1000 nm, the liquid alloy is gallium-indium liquid alloy with the mass ratio of gallium to indium being 3-20:1, the crystalline alloy is selected from copper-gallium alloy, and the preparation method of the gallium-based liquid metal microsphere comprises the following steps: (1) Interface activation and system construction, namely adding the liquid alloy into an organic solvent and acidifying the liquid alloy; (2) Adding copper sulfate pentahydrate, and uniformly mixing; (3) Performing ultrasonic induction synthesis, namely performing pulse ultrasonic treatment on the mixture obtained in the step (2) under the protection of inert atmosphere; (4) Post-treatment, namely separating, washing and drying the product obtained in the step (3) to obtain the gallium-based liquid microsphere; The molar ratio of the liquid alloy in the step (1) to the copper sulfate pentahydrate in the step (2) is 10-35:1.
  2. 2. The gallium-based liquid metal microsphere according to claim 1, wherein the organic solvent in the step (1) is one or more of N, N-dimethylformamide, ethanol, ethylene glycol, and glycerol, and the acid used for acidification is one or more of hydrochloric acid, sulfuric acid, nitric acid, and acetic acid.
  3. 3. The gallium-based liquid metal microsphere according to claim 1, wherein in the step (3), the condition of pulsed ultrasonic treatment is that ultrasonic power is 300W-500W, a pulse mode of 5-15 seconds of operation and 1-5 seconds of pause is adopted, the total treatment time is 10-60 minutes, the inert atmosphere is nitrogen, argon or helium atmosphere, in the step (4), centrifugal separation is adopted, the centrifugal rotation speed is 5000-15000 rpm, the centrifugal time is 5-30 minutes, the washing is carried out by using an organic solvent, the drying is carried out under a vacuum condition, the drying temperature is 20-60 ℃, and the drying time is 6-24 hours.
  4. 4. Use of a microsphere according to any one of claims 1-3 for catalyzing a carbon dioxide reduction reaction to produce a solid carbon material.
  5. 5. The process according to claim 4, wherein the reaction is carried out in a mixed medium comprising an organic solvent and an amine promoter at a temperature of from 25℃to 80℃and a reaction pressure of from 0.1 to 1.0 MPa.
  6. 6. The method according to claim 5, wherein the organic solvent is selected from one or more of N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, methanol, and ethanol, and the amine promoter is selected from one or more of ethanolamine, diethanolamine, triethanolamine, and diethylenetriamine.
  7. 7. The method according to claim 6, wherein the mixed medium is DMF-ETA mixed solvent formed by adding 5% ethanol amine by volume fraction to N, N-dimethylformamide.

Description

Gallium-based liquid metal microsphere and preparation method and application thereof Technical Field The invention relates to a catalytic material, in particular to a gallium-based liquid metal microsphere, a preparation method and application thereof. Background The global climate change problem caused by artificially discharged carbon dioxide is increasingly serious, and the development of efficient and low-energy-consumption carbon dioxide capturing and recycling conversion technology is of great importance. The direct catalytic conversion of carbon dioxide into a solid carbon material with high added value is a potential negative carbon technology path. However, the conventional carbon dioxide conversion technology generally requires high-temperature and high-pressure conditions, and has huge energy consumption and limits the large-scale application thereof. Copper-based catalysts are widely studied in the field of carbon dioxide reduction due to their unique affinity for carbon dioxide molecules, moderate adsorption energy and stabilization for key intermediates. Research shows that the 4s electronic layer of copper is easy to form a stable intermediate with carbon dioxide, has proper adsorption energy for the CO intermediate, and the d orbit of copper atoms can be hybridized with oxygen atoms in the carbon dioxide to form intermediate species with proper energy level and stability, so that various high-value chemicals such as methane, methanol, formaldehyde, ethanol and the like are efficiently generated in a catalytic mode. However, conventional solid copper-based catalysts generally face challenges such as easy sintering deactivation, active site coverage caused by product carbon deposition, difficulty in product selectivity control caused by complex reaction paths, and the like. The introduction of transition metal may lead to wide product distribution and lower target product selectivity, while alkali metal has high activity and covers active site easily, noble metal has high cost and difficult regulation and control of reaction path. Liquid metals, such as gallium and its alloys, bring new opportunities for catalytic science with their unique room temperature fluidity, high surface energy, dynamically reconfigurable interfaces, and excellent electron conduction properties. Gallium-based liquid metals have the unique advantages of providing a rich active site on the dynamic surface, high surface energy giving it excellent carbon absorption capacity, self-healing properties making it resistant to deactivation, and excellent electron conduction capacity facilitating charge transfer. Research shows that carbon dioxide thermal conversion can be realized at 500 ℃ by doping lithium metal into gallium to form a shell-like carbon material, gaSnNi ternary alloy can catalyze hydrocarbon to propylene at 150 ℃, and Ga-Ag system can realize carbon dioxide conversion efficiency as high as 92% under the condition of mechanical induction. These studies lay the foundation for the development of high-value carbon products, but still require the exploration of efficient conversion systems under milder conditions. Combining liquid metal with high activity metal, such as copper, is expected to constitute one kind of composite catalyst system with high catalytic activity, excellent stability and unique dynamic interface characteristic. However, the methods for preparing the liquid metal composite catalyst in the prior art, such as high-temperature molten alloy, electrochemical deposition or simple mechanical mixing, generally have the defects of complex process, high energy consumption, difficulty in accurately controlling the morphology and microstructure of the catalyst, and particularly difficulty in realizing the large-scale preparation of the catalyst with a uniform and stable core-shell structure, so that the full play of the potential performance of the catalyst is limited. Disclosure of Invention The invention aims to provide a gallium-based liquid metal microsphere which has high catalytic activity, uniform and stable core-shell structure and long cycle service life, and the preparation method of the gallium-based liquid metal microsphere has mild conditions and controllable process, and the third aim of the invention is to provide an application of the gallium-based liquid metal microsphere in catalyzing carbon dioxide reduction reaction. The gallium-based liquid metal microsphere has a core-shell structure, wherein the core is a liquid alloy, the shell is a crystalline alloy, the crystalline alloy is uniformly coated on the surface of the liquid alloy, and the average particle size of the microsphere is 100 nm-1000 nm. The liquid alloy is gallium-indium liquid alloy rich in indium elements, the gallium-based liquid metal comprises gallium-indium (GaIn) alloy and gallium-indium-tin (GaInSn) alloy, and the enrichment of indium elements in the core is beneficial to maintaining the liquid property of the alloy