CN-122006661-A - Novel graphene oxide adsorption film and application thereof

Abstract

A novel graphene oxide adsorption membrane and application thereof belong to the technical field of membrane separation. The preparation method comprises the steps of mixing graphene oxide ethanol dispersion liquid with RCC3 molecular cage aqueous solution, carrying out ultrasonic dispersion and constant-temperature stirring reaction to enable secondary amine groups in the molecular cage and epoxy groups on the surface of graphene oxide to carry out nucleophilic ring-opening reaction to realize covalent connection, coating functionalized suspension liquid on a porous membrane substrate to form an adsorption layer, carrying out protonation treatment through vacuum filtration of hydrochloric acid solution, and finally drying and curing to obtain a finished product. The membrane can efficiently and selectively adsorb haloacetic acid disinfection byproducts (the retention rate is more than or equal to 90 percent) in drinking water, and simultaneously allows beneficial inorganic salt ions such as calcium, magnesium, sodium and the like to permeate (the permeability is more than or equal to 80 percent), thereby effectively taking into account high flux, high selectivity and anti-swelling stability. The preparation process is simple and controllable, is suitable for various scenes such as water works, underground water purification, industrial wastewater treatment and the like, and has remarkable industrialization potential.

Inventors

• CHEN TIANLE
• YU LONGQIANG
• HU HAIFANG
• XU BITAO
• WU YINGHUA
• Jin Hangliang
• HU JUNHUI
• FANG CHUANJIE

Assignees

• 杭州和达能源有限公司

Dates

Publication Date

20260512

Application Date

20260129

Claims (8)

1. 1. The novel graphene oxide adsorption film is characterized by being prepared by adopting the following method: 1) Taking graphene oxide ethanol dispersion liquid, carrying out ultrasonic dispersion uniformly, and adding RCC3 molecular cages into the graphene oxide ethanol dispersion liquid, wherein the concentration of the graphene oxide ethanol dispersion liquid is 0.05-0.1mg/mL, and the concentration of the RCC3 molecular cages is 0.125-0.25mg/mL; 2) Ultrasonically dispersing the mixed solution at room temperature for 30-60 minutes until a stable and uniform mixed suspension is formed; 3) Transferring the mixed suspension into a reaction vessel, stirring at a constant temperature of 60-70 ℃ for reaction for 18-24 hours, and carrying out nucleophilic ring-opening reaction on secondary amine groups in RCC3 molecular cages and epoxy groups on the surface of graphene oxide to realize covalent functional modification of the RCC3 molecular cages on the surface of graphene oxide to prepare a functionalized graphene oxide suspension; 4) Uniformly coating the functionalized graphene oxide suspension on a porous membrane substrate to form a functional adsorption layer, wherein the thickness of the adsorption layer is 500-2000 nm; 5) The composite membrane obtained in the step 4) is subjected to protonation treatment of a molecular cage in the membrane by vacuum filtration of hydrochloric acid solution, and the filtration time is 30-60 minutes; 6) And drying and curing the prepared composite film to obtain the novel graphene oxide adsorption film.
2. 2. The novel graphene oxide adsorption membrane according to claim 1, wherein in the step 1), the concentration of the graphene oxide ethanol dispersion liquid is 0.06-0.07mg/mL, and the concentration of the RCC3 molecular cage is 0.15-0.175mg/mL.
3. 3. The novel graphene oxide adsorption film according to claim 1, wherein in the step 2), the ultrasonic dispersion time is 40-50 minutes.
4. 4. The novel graphene oxide adsorption film according to claim 1, wherein in the step 3), the reaction temperature is 65-68 ℃ and the reaction time is 20-22 hours.
5. 5. The novel graphene oxide adsorption film according to claim 1, wherein in the step 4), the film is formed on a porous substrate by vacuum filtration or spin coating, and the film thickness is 800-1200 nm.
6. 6. The novel graphene oxide adsorption film according to claim 1, wherein in the step 6), the drying temperature is 50-80 ℃, and the drying and curing time is 6-10 hours.
7. 7. Use of an adsorption membrane according to any one of claims 1-6 for the removal of drinking water disinfection by-products, in particular for haloacetic acids.
8. 8. The use according to claim 7, wherein the adsorption film has a retention rate of 90% or more for haloacetic acid disinfection byproducts and a transmittance of 80% or more for at least one of calcium, magnesium and sodium ions.

Description

Novel graphene oxide adsorption film and application thereof Technical Field The invention belongs to the technical field of membrane separation, and particularly relates to a novel graphene oxide adsorption membrane and application thereof. Background In recent years, with the acceleration of industrialization progress and urban treatment, the problem of water source pollution is increasingly severe, and various novel pollutants are continuously emerging, particularly the problem of Disinfection Byproducts (DBPs) in drinking water is attracting a great deal of attention. Disinfection byproducts such as haloacetic acid (HAAs) and the like are an important organic pollutant generated in the tap water disinfection process, have potential cancerogenic, teratogenic and mutagenic risks, and seriously threaten human health. Therefore, how to efficiently remove disinfection byproducts in water is a hot spot of current drinking water treatment research. The membrane separation technology is widely applied to the deep purification treatment of drinking water due to the advantages of high efficiency, energy conservation, environmental protection and the like. The adsorption membrane has proper pore size range and charge rejection characteristic, so that organic matters and micromolecular pollutants in water can be effectively removed, and the adsorption membrane becomes an important technical means in the field of drinking water treatment. In particular, graphene Oxide (GO) films are attracting attention as a novel two-dimensional film material with high specific surface area, excellent mechanical properties, chemical stability and abundant surface functional groups. The GO membrane not only can realize accurate screening of molecular level, but also has certain adsorption and charge rejection functions, and theoretically shows great potential in the aspect of DBPs removal. However, the existing GO membrane still has obvious defects in practical application, such as reduced selectivity caused by membrane expansion during long-term use, difficult compromise between water flux and interception efficiency, weak selective removal capability of a membrane material on specific pollutants, and poor effect on short-chain DBPs which are difficult to remove. In addition, the conventional GO membrane is easily influenced by Natural Organic Matters (NOM) and inorganic salts in water in the actual water treatment application process, so that the membrane is seriously polluted, and the treatment efficiency and the service life are reduced. Therefore, a novel efficient and stable graphene oxide adsorption film is developed, and the action mechanism between a film material and pollutant molecules is deeply explored, so that the graphene oxide adsorption film has important theoretical significance and practical application value. Disclosure of Invention Aiming at the problems in the prior art, the invention aims to design and provide a novel graphene oxide adsorption film and a technical scheme of application thereof, wherein the adsorption film remarkably improves the selective adsorption performance of haloacetic acid disinfection byproducts through the cooperative regulation and control of a molecular structure and interface chemistry, realizes the cooperative enhancement of adsorption efficiency and selectivity while maintaining high water flux, and is suitable for the deep purification treatment of drinking water. The adsorption film has the advantages of simple preparation process, strong controllability, good repeatability and large-scale preparation potential. The novel graphene oxide adsorption film is characterized by being prepared by the following method: 1) Taking graphene oxide ethanol dispersion liquid, carrying out ultrasonic dispersion uniformly, and adding RCC3 molecular cages into the graphene oxide ethanol dispersion liquid, wherein the concentration of the graphene oxide ethanol dispersion liquid is 0.05-0.1mg/mL, and the concentration of the RCC3 molecular cages is 0.125-0.25mg/mL; 2) Ultrasonically dispersing the mixed solution at room temperature for 30-60 minutes until a stable and uniform mixed suspension is formed; 3) Transferring the mixed suspension into a reaction vessel, stirring at a constant temperature of 60-70 ℃ for reaction for 18-24 hours, and carrying out nucleophilic ring-opening reaction on secondary amine groups in RCC3 molecular cages and epoxy groups on the surface of graphene oxide to realize covalent functional modification of the RCC3 molecular cages on the surface of graphene oxide to prepare a functionalized graphene oxide suspension; 4) Uniformly coating the functionalized graphene oxide suspension on a porous membrane substrate to form a functional adsorption layer, wherein the thickness of the adsorption layer is 500-2000 nm; 5) The composite membrane obtained in the step 4) is subjected to protonation treatment of a molecular cage in the membrane by vacuum filtration of hydrochloric