CN-121244208-B - Metal ion doped amination graphene oxide film material for catalyzing CO2Use in the synthesis of cyclic carbonates

CN121244208BCN 121244208 BCN121244208 BCN 121244208BCN-121244208-B

Abstract

The invention provides an application of a metal ion doped amination graphene oxide film material in catalyzing CO 2 to synthesize cyclic carbonate. The metal ion doped amination graphene oxide film material simultaneously has an acidic catalytic site and an alkaline catalytic site, and a two-dimensional interlayer channel of the metal ion doped amination graphene oxide film material also has a domain limiting effect. In the process of catalyzing cycloaddition reaction of CO 2 /epoxy compound, epoxy compound molecules entering a two-dimensional interlayer limiting domain channel of the metal ion doped amination graphene oxide film material are efficiently opened under the combined action of organic amine molecules and metal ions and react with CO 2 , and finally, efficient synthesis of the cyclic carbonate by CO 2 is realized under the conditions of room temperature and low pressure (more than 0.1MPa and less than or equal to 1 MPa) (the reaction time is less than or equal to 5min, and the conversion rate of the epoxy compound is 75% -100%).

Inventors

JIANG LEI
SHEN XUYANG
ZHANG XIQI
Pang shuai

Assignees

中国科学院理化技术研究所

Dates

Publication Date: 20260508
Application Date: 20250905

Claims (12)

1. The application of the metal ion doped amination graphene oxide film material in synthesizing the cyclic carbonate by rapidly catalyzing the cycloaddition reaction of CO 2 /epoxy compound at room temperature, wherein the room temperature is a temperature range of 20-30 ℃, and the rapid reaction time is 30-300 s; The metal ion doped amination graphene oxide film material comprises graphene oxide, organic amine and metal ions, wherein the organic amine is modified on the surface and between layers of the graphene oxide; The metal ion is selected from at least one of Fe 3+ 、Co 2+ and Ni 2+ ; the organic amine is at least one selected from triethylene tetramine, tetraethylene pentamine, tri (2-aminoethyl) amine, 4-aminomethylpyridine and 1, 5-diaminopicoline.
2. The use according to claim 1, wherein the mass of metal ions in the metal ion doped aminated graphene oxide film material is 0.01-5wt% of the total mass of the film material, and/or the mass of organic amine in the metal ion doped aminated graphene oxide film material is 5-50wt% of the total mass of the film material.
3. Use according to claim 1, wherein the thickness of the metal ion doped aminated graphene oxide film material is 0.1-5 μm.
4. Use according to claim 1, wherein the metal ion doped aminated graphene oxide film material has an interlayer spacing of 1-2nm.
5. The use according to any one of claims 1 to 4, wherein the metal ion doped aminated graphene oxide film material is prepared by the following method: (1) Mixing graphene oxide dispersion liquid, organic amine and an activating agent, then reacting, and then performing dialysis treatment and ultrasonic treatment to prepare an amino graphene oxide dispersion liquid; (2) Adding metal salt into the amination graphene oxide dispersion liquid, and carrying out ultrasonic mixing to obtain metal ion doped amination graphene oxide dispersion liquid; (3) And (3) assembling the metal ion doped amination graphene oxide dispersion liquid obtained in the step (2) into a metal ion doped amination graphene oxide film by utilizing a vacuum filtration method, and then performing constant temperature and humidity standing treatment to obtain the metal ion doped amination graphene oxide film material.
6. The use according to claim 5, wherein in step (1) the activator is selected from 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide; And/or, in the step (1), the concentration of the graphene oxide dispersion liquid is 0.5-2mg/mL; And/or in the step (1), the mass ratio of the graphene oxide to the organic amine is 1:12-1:50; and/or in the step (1), the mass ratio of the graphene oxide to the activator is 1:8-1:25; and/or, in the step (1), the concentration of the amination graphene oxide dispersion liquid is 0.5-1.5mg/mL; And/or, in the step (3), the constant temperature and humidity standing treatment is carried out in a constant temperature and humidity box, and the constant temperature and humidity standing treatment is carried out at 20-30 ℃ and 10-20% RH for 12-24h.
7. The use according to claim 5, wherein in step (2), the molar mass ratio of the metal salt to the aminated graphene oxide is 2-30 μmol/2.25-6.75mg.
8. The use according to claim 5, wherein in step (2), the molar volume ratio of the metal salt and the aminated graphene oxide dispersion is 2-30 μmol/4.5mL.
9. Use according to any one of claims 1-4, wherein the method of catalyzing the synthesis of cyclic carbonates from CO 2 comprises the steps of: a) Mixing an epoxy compound, a cocatalyst and an optionally added or non-added organic solvent to obtain a reaction solution; b) And c, placing the metal ion doped amino graphene oxide film material at the bottom of a pressurizing device at room temperature, adding the reaction liquid in the step a) into the pressurizing device and placing the reaction liquid above the metal ion doped amino graphene oxide film material, introducing CO 2 to replace air in the pressurizing device, then continuously introducing CO 2 to raise the pressure in the pressurizing device, and driving the reaction liquid to pass through the metal ion doped amino graphene oxide film material under the pressure of CO 2 and carrying out cycloaddition reaction to prepare the cyclic carbonate.
10. A method of catalyzing CO 2 to synthesize a cyclic carbonate, the method comprising the steps of: a) Mixing an epoxy compound, a cocatalyst and an optionally added or non-added organic solvent to obtain a reaction solution; b) Placing a metal ion doped amination graphene oxide film material at room temperature at the bottom of a pressurizing device, adding the reaction liquid in the step a) into the pressurizing device and placing the pressurizing device above the metal ion doped amination graphene oxide film material, introducing CO 2 to replace air in the pressurizing device, then continuously introducing CO 2 to raise the pressure in the pressurizing device, and driving the reaction liquid to pass through the metal ion doped amination graphene oxide film material under the driving of the CO 2 pressure and carrying out cycloaddition reaction to prepare annular carbonic ester, wherein the room temperature is a temperature range of 20-30 ℃; The metal ion doped amination graphene oxide film material comprises graphene oxide, organic amine and metal ions, wherein the organic amine is modified on the surface and between layers of the graphene oxide; The metal ion is selected from at least one of Fe 3+ 、Co 2+ and Ni 2+ ; the organic amine is at least one selected from triethylene tetramine, tetraethylene pentamine, tri (2-aminoethyl) amine, 4-aminomethylpyridine and 1, 5-diaminopicoline.
11. The method according to claim 10, wherein in step a), the epoxy compound is selected from at least one of propylene oxide, epichlorohydrin, 1, 2-butylene oxide, 3, 4-epoxy-1, 2-butene, allyl glycidyl ether, and styrene oxide; And/or, in the step a), the organic solvent is selected from at least one of acetonitrile, acetone and dimethyl sulfoxide; and/or, in step a), the cocatalyst is selected from at least one of tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium chloride and tetrabutylammonium iodide; and/or, in the step a), the concentration of the epoxy compound in the reaction liquid is 0.2 mol/L-5 mol/L; and/or, in step a), the molar ratio of the cocatalyst to the epoxide compound is 1-5:100.
12. The method of claim 10, wherein in step b), the cycloaddition reaction is performed at room temperature; and/or, in the step b), the time required for the cycloaddition reaction is less than or equal to 5min; and/or, in step b), the pressure in the pressurizing device is >0.1MPa and is less than or equal to 1MPa.

Description

Application of metal ion doped amination graphene oxide film material in catalyzing CO 2 to synthesize cyclic carbonate Technical Field The invention belongs to the technical field of membrane catalysis, and mainly relates to application of a metal ion doped amination graphene oxide membrane material in synthesizing cyclic carbonate by rapidly and efficiently catalyzing cycloaddition reaction of CO 2/epoxy compounds at room temperature. Background Excessive human emission of CO 2 to the atmosphere is a recognized major cause of global warming, causing a series of environmental problems. Capturing, utilizing and sequestering carbon dioxide is widely accepted worldwide as an effective means of carbon abatement. However, the stable chemistry of CO 2 is a major challenge in achieving efficient utilization of CO 2 under mild conditions. Carbonates are compounds in which the hydroxyl hydrogens in the carbonate molecule are partially or fully substituted with alkyl groups. The cyclic carbonate can be used as solvent, battery electrolyte and polycarbonate monomer in chemical industry due to the characteristics of high dipole moment, good dielectric property, low toxicity and the like, and can also be used as an intermediate of other important compounds, such as pyrimidine and carbamate. The traditional cyclic carbonate production process using glycol and phosgene as raw materials is gradually eliminated due to low economical efficiency and unfriendly environment, and the cycloaddition reaction method using CO 2 and epoxy compounds as raw materials has the atom utilization rate of 100%, thereby not only meeting the principle of green chemistry, but also meeting the requirement of sustainable development strategy. Among them, the development of a novel high-efficiency catalyst is the research focus of the process for synthesizing cyclic carbonate by CO 2 cycloaddition reaction. Researchers have successfully developed a large number of different types of catalysts that catalyze the cycloaddition reaction of CO 2 and epoxy compounds, such as Porous Organic Polymers (POPs), ionic Liquids (IL), metal Organic Frameworks (MOFs), molecular sieves, and the like. However, these catalysts, which have been reported so far, have various drawbacks such as high reaction temperature (> 100 ℃) and high pressure of CO 2 (> 1 MPa) and long reaction time (> 72 hours) although they can achieve high conversion of epoxy compounds. These drawbacks are a great obstacle to the promotion of the CO 2 cycloaddition reaction. Therefore, the search for the realization of rapid and efficient synthesis of cyclic carbonates from CO 2 under low pressure conditions at room temperature is of great economic and environmental importance. Disclosure of Invention In order to overcome the defects in the prior art, the invention aims to provide an application of a metal ion doped amination graphene oxide film material in catalyzing CO 2 to synthesize cyclic carbonate. The metal ion doped amination graphene oxide film material is a Graphene Oxide (GO) film material with a multilayer layered structure, wherein organic amine molecules and metal ions are loaded on the surface and between layers of the graphene oxide film material, the metal ion doped amination graphene oxide film material simultaneously has an acid catalysis site and an alkaline catalysis site, and a two-dimensional interlayer channel of the metal ion doped amination graphene oxide film material also has a domain limiting effect. In the process of catalyzing cycloaddition reaction of CO 2/epoxy compound, a part of CO 2 is dissolved in a reaction solution to be used as a reaction raw material to participate in the cycloaddition reaction of CO 2/epoxy compound, the other part of CO 2 is used as a driving force to push the reaction solution to pass through the metal ion doped amination graphene oxide film material, epoxy compound molecules entering a two-dimensional interlayer limiting domain channel of the metal ion doped amination graphene oxide film material are subjected to efficient ring opening under the combined action of organic amine molecules and metal ions and react with CO 2, and finally, the efficient synthesis of the cyclic carbonate by CO 2 is realized under the conditions of room temperature and low pressure (more than 0.1MPa and less than or equal to 1MPa (preferably more than 0.1MPa and less than or equal to 0.5 MPa) (the reaction time is less than or equal to 5min, and the conversion rate of epoxy compound is 75% -100%). The invention aims at realizing the following technical scheme: The application of a metal ion doped amination graphene oxide film material in catalyzing CO 2 to synthesize cyclic carbonate is provided. According to the embodiment of the invention, the metal ion doped amination graphene oxide membrane material is used for rapidly catalyzing CO 2 to synthesize cyclic carbonate at room temperature. According to the embodiment of the invention, the metal ion doped a