CN114471186A - Graphene-based seawater desalination membrane and preparation method thereof - Google Patents

Graphene-based seawater desalination membrane and preparation method thereof Download PDF

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CN114471186A
CN114471186A CN202210332438.4A CN202210332438A CN114471186A CN 114471186 A CN114471186 A CN 114471186A CN 202210332438 A CN202210332438 A CN 202210332438A CN 114471186 A CN114471186 A CN 114471186A
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graphene
layer
seawater desalination
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desalination membrane
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武文杰
陈远富
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0076—Pretreatment of inorganic membrane material prior to membrane formation, e.g. coating of metal powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses a graphene-based seawater desalination membrane and a preparation method thereof, and belongs to the technical field of membrane materials. The graphene-based seawater desalination membrane comprises a supporting layer and at least one composite structure unit, wherein the composite structure unit comprises a graphene oxide layer and a porous graphene layer, and the supporting layer is located below the composite structure unit. According to the invention, the graphene oxide and the chemical vapor deposition graphene are combined, and the chemical vapor deposition porous graphene layer is covered on the graphene oxide layer, so that the problem of reduced desalination efficiency caused by expansion of the interlayer spacing of the graphene oxide after water absorption is solved, the service life of the porous graphene layer is greatly prolonged, and the graphene-based seawater desalination membrane with high mechanical property and good durability is prepared.

Description

Graphene-based seawater desalination membrane and preparation method thereof
Technical Field
The invention relates to the technical field of membrane materials, in particular to a graphene-based seawater desalination membrane and a preparation method thereof.
Background
Water is a life cradle, and the development of human society cannot utilize water resources; meanwhile, as a strategic resource, the shortage of water resource can seriously affect the development of economy and the stability of ecology. The high-performance nanofiltration membrane is an important means for solving the contradiction between water resource supply and demand, and the membrane material is the core of the membrane separation technology, so that the rise of two-dimensional materials in recent years further promotes the development of the membrane separation technology. Compared with the traditional separation membrane, the two-dimensional material is an atomic-scale thin film, so that a rapid transmission channel can be provided, low energy consumption is realized, the components and the structure are simpler, and the membrane has excellent mechanical strength and wide chemical adaptability.
The existing graphene-based seawater desalination membrane is mainly based on graphene oxide, the graphene oxide is relatively easy to prepare, but after the graphene oxide membrane is soaked in a solution, the inter-lamellar distance of the graphene oxide is slightly increased due to water absorption, so that the seawater desalination efficiency is reduced. The other type of graphene-based seawater desalination membrane is a polymer-supported nano-porous graphene membrane, and usually, sub-nano holes are introduced into graphene by directly adopting high-energy electron beam bombardment or oxygen plasma etching and other modes, but the desalination membrane is easy to block and needs to be cleaned frequently, and meanwhile, the desalination membrane lacks sufficient mechanical strength, so that the further development of the graphene-based seawater desalination membrane is limited.
Disclosure of Invention
In view of the above disadvantages, the present invention provides a graphene-based seawater desalination membrane and a preparation method thereof. According to the invention, the advantages of graphene oxide and chemical vapor deposition graphene are combined, the chemical vapor deposition porous graphene layer is covered on the graphene oxide layer, and the graphene oxide layer plays a role in secondary desalination while primary desalination, so that the problem of reduction of desalination efficiency caused by expansion of the interlayer spacing of the graphene oxide after water absorption is solved, the service life of the porous graphene layer is greatly prolonged, and the graphene-based seawater desalination membrane with high mechanical property and good durability is prepared.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a graphene-based seawater desalination membrane which comprises a supporting layer and at least one composite structure unit, wherein the composite structure unit comprises a graphene oxide layer and a porous graphene layer, and the supporting layer is positioned below the composite structure unit.
It should be noted that, the number of the composite structural units of the graphene-based seawater desalination membrane is not limited, and can be selected according to actual needs.
Further, the support layer is a polymer support layer; the polymer support layer may be a polymer commonly used in the art, such as polyethylene, polyimide, etc.
The invention also provides a preparation method of the graphene-based seawater desalination membrane, which comprises the following steps:
step (1): preparing porous graphene on a metal substrate by adopting a chemical vapor deposition method to prepare a metal substrate/porous graphene layer sample;
step (2): attaching one surface of porous graphene of the metal substrate/porous graphene sample obtained in the step (1) to a polymer, infiltrating an interface with a solvent, removing the metal substrate by adopting a chemical etching method, rinsing and drying to obtain a support layer/porous graphene layer sample;
and (3): and (3) depositing a graphene oxide layer on one surface of the porous graphene of the support layer/porous graphene sample obtained in the step (2), and then drying.
Further, in the step (1), the chemical vapor deposition method is used for preparing the porous graphene on the metal substrate, and comprises the following steps:
stage 1: heating to 800-1100 ℃ within 50-100min under the inert gas atmosphere, and introducing inert gas to carry out impurity removal treatment on the metal substrate;
and (2) stage: after the impurity removal treatment of the stage 1, introducing hydrogen or oxygen, and carrying out high-temperature annealing;
and (3) stage: after the high-temperature annealing in the stage 2, introducing carbon source gas, and growing the film for 10-300 min;
and (4) stage: and (3) after the stage 3 film growth, cooling and sampling to prepare a metal substrate/porous graphene layer sample.
Further, the inert gas is nitrogen or argon; the carbon source gas is organic carbon source gas or inorganic carbon source gas commonly used in the field, such as methane, ethane, acetylene, ethylene, ethanol or carbon dioxide; preferably methane.
Further, the oxygen gas, the hydrogen gas and the carbon source gas are respectively diluted by argon, the purity of the oxygen gas is 0.01-10 vol%, and the purity of the hydrogen gas and the carbon source gas is 0.1-10 vol%.
Further, in stage 1, the temperature is preferably raised to 1050 ℃ within 50 min.
Furthermore, the temperature of the high-temperature annealing in the stage 2 is 800-1060 ℃, and the time is 30-300 min.
Further, the specific cooling process in the stage 4 is as follows: cooling to room temperature within 15-40 min.
Further, the metal substrate includes, but is not limited to, Cu, Pt, Ni, Fe, Ru, Co, Rh, Ir, Pd, Au, Cu-Ni, Co-Ni, Au-Ni, Ni-Mo, or stainless steel; preferably a copper substrate.
Further, the solvent in the step (2) is an alcohol solvent, preferably absolute ethyl alcohol.
Further, the working parameters of the step (2) of removing the metal substrate by using a chemical etching method are as follows: the etching solution is a mixed solution of ferric chloride and hydrochloric acid with the concentration of 0.5-2mol/L, and the etching time is 10-120 min.
Further, the rinsing times are 1-7 times; preferably 5 rinses, each for 5 min.
Further, in the step (3), a Hummer method or a liquid surface tension mode is adopted to deposit a graphene oxide layer on one surface of the porous graphene of the support layer/porous graphene sample obtained in the step (2).
Further, the specific process of the step (3) is as follows: dispersing graphene oxide prepared by a Hummer method into water, forming graphene oxide suspension after ultrasonic vibration, then diluting the suspension, standing for 6-48 h, forming a layer of graphene oxide film at a gas/liquid interface, and fishing the graphene oxide film by using the sample obtained in the step (2).
In the present invention, the preparation method is not particularly limited, and can be performed by a conventional method in the art, for example, the process of preparing graphene oxide by the Hummer method can be performed by a conventional method in the art.
In summary, the invention has the following advantages:
1. the preparation method combines the advantages of the graphene oxide and the chemical vapor deposition graphene, covers the chemical vapor deposition porous graphene layer on the graphene oxide layer, improves the reduction of desalination efficiency caused by the expansion of the interlayer spacing of the graphene oxide after water absorption, and greatly prolongs the service life of the porous graphene layer, thereby preparing the graphene-based seawater desalination membrane with high mechanical property and good durability.
2. The preparation method further realizes the preparation of the graphene-based seawater desalination membrane by utilizing the characteristic that the chemical vapor deposition can prepare the graphene and the graphene oxide in a large area and is easy to synthesize; the chemical vapor deposition porous graphene layer coated graphene oxide layer structure is adopted, so that the problem of reduction of desalination efficiency caused by expansion of interlayer spacing of graphene oxide after water absorption is solved, and the mechanical property and durability of the seawater desalination membrane are improved.
3. The graphene-based seawater desalination membrane comprises a supporting layer and at least one composite structure unit, wherein the composite structure unit comprises a graphene oxide layer and a porous graphene layer, so that the problem that the seawater desalination efficiency is reduced due to the increase of the interlayer spacing after water absorption of graphene oxide is effectively solved, and the integral mechanical property and durability of the desalination membrane are improved; in addition, the number of the composite structural units in the invention can be expanded according to actual needs.
Drawings
Fig. 1 is a schematic view of a graphene-based seawater desalination membrane in embodiment 1 of the present invention;
fig. 2 is a schematic diagram of chemical vapor deposition of graphene in embodiment 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Examples
The embodiment provides a preparation method of a graphene-based seawater desalination membrane, which comprises the following steps:
s1: preparing porous graphene by chemical vapor deposition, as shown in fig. 2, heating to 1050 ℃ within 50min under the argon gas atmosphere, and introducing oxygen to remove impurities from the copper substrate (stage 1); then introducing hydrogen to carry out high-temperature annealing (stage 2); then introducing carbon source gas (methane, purity 5 vol%), and performing film growth for 200min (stage 3); cooling to room temperature within 30min, and sampling to obtain a copper/porous graphene sample (stage 4); preparing a metal substrate/porous graphene layer sample;
s2: the sample in S1 was placed on a polyethylene polymer substrate (support layer) with the graphene side in contact with the polyethylene polymer in S1; infiltrating the interface with absolute ethyl alcohol; removing the copper substrate of the sample obtained in the step S1 by using a mixed solution of ferric chloride and hydrochloric acid with the concentration of 1.5 mol/L; rinsing for 5 times, and drying for 5min each time; preparing a supporting layer/porous graphene layer sample;
s3: dispersing graphite oxide prepared by a Hummer method into water, forming a stable graphene oxide suspension after ultrasonic vibration, then properly diluting the suspension, standing for 6-48 h, forming a layer of paper-like graphene oxide film at a gas/liquid interface, and fishing out the graphene oxide film by using a sample obtained from S2 to obtain the graphene-grade seawater desalination film.
The schematic diagram of the graphene-based seawater desalination membrane prepared in the present example is shown in fig. 1, and it should be noted that the composite structural unit in the present example can be expanded according to actual needs, and the composite structural unit is repeatedly prepared according to S2-S3; in the embodiment, the supporting layer can be replaced by polymers such as polyimide and the like; the copper substrate in this example may be replaced with other metal substrates such as Pt, Ni, Fe, etc.
In conclusion, the method for combining graphene oxide with chemical vapor deposition graphene is adopted, and the chemical vapor deposition porous graphene layer is covered on the graphene oxide layer, so that the problem of reduction of desalination efficiency caused by expansion of interlayer spacing of graphene oxide after water absorption is effectively solved, and meanwhile, the mechanical property and durability of the seawater desalination membrane are improved, and the graphene-based seawater desalination membrane with high mechanical property and good durability is prepared.
The foregoing is merely exemplary and illustrative of the present invention and it is within the purview of one skilled in the art to modify or supplement the embodiments described or to substitute similar ones without the exercise of inventive faculty, and still fall within the scope of the claims.

Claims (9)

1. The graphene-based seawater desalination membrane is characterized by comprising a supporting layer and at least one composite structure unit, wherein the composite structure unit comprises a graphene oxide layer and a porous graphene layer, and the supporting layer is located below the composite structure unit.
2. The graphene-based seawater desalination membrane of claim 1, wherein the support layer is a polymeric support layer.
3. The preparation method of the graphene-based seawater desalination membrane as claimed in any one of claims 1 to 2, comprising the steps of:
step (1): preparing porous graphene on a metal substrate by adopting a chemical vapor deposition method to prepare a metal substrate/porous graphene layer sample;
step (2): attaching one surface of porous graphene of the metal substrate/porous graphene sample obtained in the step (1) to a polymer, infiltrating an interface with a solvent, removing the metal substrate by adopting a chemical etching method, rinsing and drying to obtain a support layer/porous graphene layer sample;
and (3): and (3) depositing a graphene oxide layer on one surface of the porous graphene of the support layer/porous graphene sample obtained in the step (2), and then drying.
4. The preparation method of the graphene-based seawater desalination membrane as claimed in claim 3, wherein the step (1) of preparing the porous graphene on the metal substrate by chemical vapor deposition comprises the following steps:
stage 1: heating to 800-1100 ℃ within 50-100min under the inert gas atmosphere, and introducing inert gas to carry out impurity removal treatment on the metal substrate;
and (2) stage: after the impurity removal treatment of the stage 1, introducing hydrogen or oxygen, and carrying out high-temperature annealing;
and (3) stage: after the high-temperature annealing in the stage 2, introducing carbon source gas, and growing the film for 10-300 min;
and (4) stage: and (3) after the stage 3 film growth, cooling and sampling to prepare a metal substrate/porous graphene layer sample.
5. The method for preparing the graphene-based seawater desalination membrane as claimed in claim 4, wherein the temperature of the high temperature annealing in the stage 2 is 800-1060 ℃ for 30-300 min.
6. The preparation method of the graphene-based seawater desalination membrane according to claim 4, wherein the specific cooling process in the stage 4 is as follows: cooling to room temperature within 15-40 min.
7. The method for preparing the graphene-based seawater desalination membrane of claim 4, wherein the inert gas is nitrogen or argon, and the carbon source gas is methane, ethane, acetylene, ethylene, ethanol or carbon dioxide.
8. The method for preparing the graphene-based seawater desalination membrane of claim 3, wherein the metal substrate is Cu, Pt, Ni, Fe, Ru, Co, Rh, Ir, Pd, Au, Cu-Ni, Co-Ni, Au-Ni, Ni-Mo or stainless steel.
9. The preparation method of the graphene-based seawater desalination membrane according to claim 3, wherein in the step (3), the graphene oxide layer is deposited on one surface of the porous graphene of the support layer/porous graphene sample obtained in the step (2) by a Hummer method or by using a liquid surface tension method.
CN202210332438.4A 2022-03-30 2022-03-30 Graphene-based seawater desalination membrane and preparation method thereof Pending CN114471186A (en)

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