CN114247305A - Two-dimensional nano island @ graphene heterojunction self-assembly hydrophobic nanofiltration membrane and preparation method thereof - Google Patents
Two-dimensional nano island @ graphene heterojunction self-assembly hydrophobic nanofiltration membrane and preparation method thereof Download PDFInfo
- Publication number
- CN114247305A CN114247305A CN202111571893.1A CN202111571893A CN114247305A CN 114247305 A CN114247305 A CN 114247305A CN 202111571893 A CN202111571893 A CN 202111571893A CN 114247305 A CN114247305 A CN 114247305A
- Authority
- CN
- China
- Prior art keywords
- hydrophobic
- dimensional nano
- graphene
- nano island
- island
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- B01D71/06—Organic material
-
- 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
- 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
-
- 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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention belongs to the technical field of nano-film materials, and particularly relates to a two-dimensional nano-island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane and a preparation method thereof. The invention also provides an application of the two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane in water treatment. According to the two-dimensional nano island @ graphene heterojunction self-assembly hydrophobic nanofiltration membrane, hydrophobic channels with the interlayer spacing of below 1nm and controllable angstrom level are constructed in the nanofiltration membrane, and the hydrophobic channels are not required to be arrangedCan only effectively block various hydrated ions (including K)+、Na+、Li+、Ca2+、Mg2+Etc.), can also obtain super high water flux through very big capillary force in the two-dimensional nanometer confinement to effectively promote ion barrier rate and water flux, improve water treatment efficiency greatly, reduce the energy consumption of water treatment membrane when occasion applications such as sea water desalination, municipal sewage treatment.
Description
Technical Field
The invention belongs to the technical field of nano-film materials, and particularly relates to a two-dimensional nano-island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane and a preparation method thereof.
Background
Compared with the traditional distillation method, the water treatment membrane technology is utilized for water purification treatment, has the advantages of high impurity separation efficiency, lower energy consumption in the treatment process, controllable cost and the like, and is widely applied to the fields of seawater desalination, household water purification, industrial wastewater treatment and the like. With the development of water treatment membrane technology, different application fields put higher demands on water treatment efficiency and reduction of energy loss in the water treatment process, and therefore, development of a novel water treatment membrane technology which can simultaneously have large water flux and high ion barrier property is urgently needed.
At present, water treatment membranes are mainly divided into four types, namely microfiltration membranes (0.1-10 μm), ultrafiltration membranes (10-100 nm), nanofiltration membranes (1-10 nm) and reverse osmosis membranes (0.1-1 nm), according to the size of the pore diameter in the membranes. As the pore size in the membrane decreases, the water is purified to a higher and higher degree. Specifically, the microfiltration membrane can be used for removing most suspended particles, microorganisms and the like; most of high molecules and viruses can be removed by using an ultrafiltration membrane; the nanofiltration membrane can be used for removing most of organic micromolecules and divalent ions; while substantially all ions, including monovalent alkali metal ions, can be removed using reverse osmosis membranes.
Meanwhile, the purification of the purified water to obtain high-purity water generally needs one or more reverse osmosis processes. Reverse osmosis membranes are generally made of polymeric materials, such as currently commercially available reverse osmosis membranes that generally employ thin film composite materials (TFC), e.g., polyamide membrane materials. Because reverse osmosis membrane utilizes minimum aperture size to block impurity such as monovalent ion, simultaneously, this minimum aperture also can produce the barrier action to the infiltration of hydrone simultaneously, consequently need exert great pressure (10 ~ 60bar generally) to the both sides of membrane, let the hydrone overcome osmotic pressure that the concentration difference produced and the resistance that the aperture produced and pass reverse osmosis membrane, leave impurity such as ion simultaneously, reach the effect of purified water. In this process, a higher additional applied pressure means a greater energy loss in the water treatment process, and a lower water flux (speed of water molecules passing through the membrane) means a lower efficiency of water treatment.
The difference is that the aperture of the nanofiltration membrane is slightly larger than that of the reverse osmosis membrane, the pressure required to be applied on two sides of the nanofiltration membrane is far smaller than that of the reverse osmosis membrane (about 5-10 bar), and the water flux is relatively larger, but the defect is that the aperture of the nanofiltration membrane is slightly larger, and the effect of blocking monovalent ions is poorer.
Therefore, how to compromise high flux and high ion separation and be the bottleneck problem in water treatment membrane field, based on this, this application provides a two-dimensional nanometer island @ graphite alkene heterojunction self-assembly hydrophobic nanofiltration membrane, through improving the structure of nanofiltration membrane to when realizing separation aquatic ion, can also obtain super high flux.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the two-dimensional nano island @ graphene heterojunction self-assembly hydrophobic nanofiltration membrane, and by constructing the hydrophobic pore channel with the interlayer spacing below 1nm and controllable angstrom level in the nanofiltration membrane, various hydrated ions (including K) can be effectively blocked+、Na+、Li+、Ca2+、Mg2+Etc.), can also obtain super high water flux through very big capillary force in the two-dimensional nanometer confinement, effectively solve ion barrier rate and water flux and can not improve the bottleneck problem simultaneously.
The application also provides a preparation method of the two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a hydrophobic two-dimensional nano-island @ graphene heterojunction material, wherein the two-dimensional nano-island structure can be, but is not limited to, Ni-p-phenylenediamine hydrochloride (Ni-pPD), Cu-p-phenylenediamine hydrochloride (Cu-pPD), Ni-hexa-aminobenzene (Ni-HAB), Cu-hexa-aminobenzene (Cu-HAB), Graphyne (GDY), Cu-hexa-mercaptobenzene (Cu-BHT), or a two-dimensional covalent organic framework.
Specifically, the two-dimensional nano island material grows on the surface of graphene through oxygen group catalytic reaction to prepare the hydrophobic two-dimensional nano island @ graphene heterojunction material, the two-dimensional nano island material in the prepared heterojunction material does not completely cover the surface of the graphene, the heterojunction material has certain porosity, and the area ratio of the two-dimensional nano island material to the graphene is 10-70%.
Preferably, the area ratio of the two-dimensional nano island to the graphene is 40-50%.
Specifically, in the prepared hydrophobic two-dimensional nano island @ graphene heterojunction material, the contact angle of a two-dimensional nano island is 60-120 degrees, and the contact angle of two-dimensional graphene is 60-90 degrees; preferably, the contact angle of the two-dimensional nano island is 80-90 degrees.
The preparation method comprises the steps of adding a graphene oxide suspension and soluble metal ions into a two-dimensional nano island precursor material aqueous solution, growing a two-dimensional nano island on the surface of a graphene oxide oxygen group in situ by utilizing the catalysis of the graphene oxide surface oxygen group, reducing the graphene oxide surface oxygen group, and keeping the original graphene shape in the area without the oxygen group on the surface of the graphene oxide, thereby preparing the two-dimensional nano island graphene heterojunction material.
The preparation method comprises the following steps:
(1) preparing a reaction solution: adding a Graphene Oxide (GO) suspension into a soluble metal salt solution, and introducing inert gas to remove oxygen to obtain a solution A;
(2) dissolving a two-dimensional nano island precursor material into water, and introducing inert gas to remove oxygen to obtain a solution B, so that the reaction of the two-dimensional nano island precursor material is only carried out on the surface of an oxygen group of Graphene Oxide (GO);
(3) and adding the solution B into the solution A, carrying out oxygen group catalytic reaction at the temperature of-30-150 ℃ for 0.5-96 h, carrying out suction filtration, and washing to prepare the hydrophobic two-dimensional nano island @ graphene heterojunction material.
Specifically, the soluble metal salt solution in the step (1) is a soluble metal salt solution of nickel or a soluble metal salt solution of copper.
Specifically, the concentration of the Graphene Oxide (GO) suspension in the step (1) is 0.1-5 mg/mL, preferably 0.2-1 mg/mL.
Specifically, the two-dimensional nano island precursor material in the step (2) is p-phenylenediamine hydrochloride, hexa-aminobenzene, graphdine or hexa-mercaptobenzene.
Specifically, the concentration of the solution B in the step (2) is 0.1-1 mol/L, preferably 0.1-0.5 mol/L.
Specifically, the inert gas used in the steps (1) and (2) is argon or nitrogen, and the inert gas is introduced for 0.1 to 24 hours, preferably 0.5 to 2 hours.
Specifically, the volume ratio of the solution B to the solution A in the step (3) is (0.1-10): 1.
specifically, in the step (3), the oxygen radical catalytic reaction is accelerated by stirring, preferably in a magnetic stirring mode, and the stirring speed is 10-1000 rpm, preferably 300-500 rpm.
Specifically, the temperature of the oxygen group catalytic reaction in the step (3) is preferably 10-110 ℃; the reaction time is preferably 5 to 20 hours.
Specifically, the suction filtration in the step (3) can adopt normal-pressure suction filtration or vacuum suction filtration, and the suction filtration time is 1-48 h; the washing solution used in washing is deionized water or an organic solvent including, but not limited to, ethanol, acetone or methanol.
Specifically, the two-dimensional nano-island obtained in step (3) may have a structure including, but not limited to, Ni-p-phenylenediamine hydrochloride (Ni-pPD), Cu-p-phenylenediamine hydrochloride (Cu-pPD), Ni-hexaaminobenzene (Ni-HAB), Cu-hexaaminobenzene (Cu-HAB), Graphyne (GDY), Cu-hexamercaptobenzene (Cu-BHT), or a two-dimensional covalent organic framework.
The invention further provides a substitution method for preparing the hydrophobic two-dimensional nano island @ graphene heterojunction material, and the specific steps of the preparation method are different from those of the preparation method in that only Graphene Oxide (GO) suspension is prepared in the step (1), and copper wires or silver wires are placed in the Graphene Oxide (GO) suspension for oxygen group catalytic reaction in the step (2).
Further, the invention also provides application of the hydrophobic two-dimensional nano island @ graphene heterojunction material in preparation of a self-assembled hydrophobic nanofiltration membrane.
Further preferably, the hydrophobic two-dimensional nano island @ graphene heterojunction material is prepared into a two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane in a suction filtration mode.
Further, the invention also discloses a preparation method of the two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane, which comprises the following steps:
a. preparing a filtrate: preparing the hydrophobic two-dimensional nano island @ graphene heterojunction material into a suspension;
b. suction filtration and drying: and (b) placing the suspension liquid obtained in the step a on a base membrane, performing suction filtration, then extruding the hydrophobic two-dimensional nano island @ graphene heterojunction material in the suspension liquid onto the base membrane under external pressure, and drying to obtain the two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane.
Further, in the step a, the concentration of the prepared hydrophobic two-dimensional nano island @ graphene heterojunction material suspension is 1-10 mg/mL, and preferably 2-5 mg/mL.
Further, in step b, the base film material includes, but is not limited to, Polyethersulfone (PES), Polystyrene (PS), Mixed Cellulose Ester (MCE), polyvinyl chloride (PVC), Polyacrylonitrile (PAN), Polycarbonate (PC), polypropylene (PP), polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), or porous alumina (AAO).
Furthermore, in the step b, the pressure applied during the extrusion is in the range of 1-100N, preferably 5-20N.
Further, in the step b, drying is carried out in a vacuum drying mode, wherein the drying temperature is 25-150 ℃, and preferably 60-70 ℃; the drying time is 0.5 to 96 hours, preferably 10 to 12 hours; the degree of vacuum used for drying is 1Pa to 1 atmosphere, preferably 1Pa to 10 Pa.
According to the two-dimensional nano island @ graphene heterojunction self-assembly hydrophobic nanofiltration membrane constructed by the hydrophobic two-dimensional nano island @ graphene heterojunction material in a self-assembly mode, in the construction process, due to the hydrophobic effect, the two-dimensional nano island @ graphene heterojunction material is self-assembled in an aqueous solution, so that the two-dimensional nano island is sandwiched between two layers of graphene to form a sub-nano interlayer, and therefore the nanofiltration membrane rich in the sub-nano hydrophobic pore inside is formed through bonding, specifically, the hydrophobic pore rich in the sub-nano hydrophobic pore inside the nanofiltration membrane is 0.1-1 nanometer in size.
According to the two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane prepared by the method, the inner part of the hydrophobic pore channel rich in sub-nano level is utilized, and the extremely small pore channel can be utilized to effectively block hydrated ions (including K) through the size effect+、Na+、Li+、Ca2+、Mg2+Etc.), and meanwhile, the extremely small hydrophobic pore channel can also obtain ultrahigh water flux through extremely large capillary force in the two-dimensional nano confinement.
Further, the invention also provides application of the two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane in water treatment, and specifically, the water treatment is seawater desalination treatment, industrial wastewater treatment or municipal sewage treatment.
Further, the invention also provides application of the two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane in adsorption and separation of anions and cations in sewage.
Compared with the prior art, the invention has the advantages that:
1) the invention provides a preparation method of a two-dimensional nano island @ graphene heterojunction self-assembly hydrophobic nanofiltration membrane, which is different from a sub-nanoscale hydrophilic pore channel or a larger-size hydrophobic pore channel in a traditional water treatment membrane, and the nano-filtration membrane prepared by the method is rich in the sub-nanoscale hydrophobic pore channel. Due to the extremely small interlayer spacing and the hydrophobic pore channels, the novel nanofiltration membrane can effectively block various hydrated ions (including K)+、Na+、Li+、Ca2+、Mg2+Etc.) while also being free of free radicalsThe ultra-high water flux can be obtained by utilizing the extremely large capillary force in the hydrophobic two-dimensional nano confinement, so that the ion barrier and the water flux can be effectively improved, the water treatment efficiency is greatly improved, and the energy consumption of the water treatment membrane technology in the applications of seawater desalination, industrial wastewater treatment, urban sewage treatment and the like is reduced.
2) Compared with the traditional reverse osmosis membrane prepared by adopting a Thin Film Composite (TFC) polyamide membrane material, the nanofiltration membrane has larger aperture and size which is just suitable for blocking various hydrated ions.
3) The internal pore channels of the water treatment membrane constructed by the two-dimensional Graphene Oxide (GO) or the composite material thereof are hydrophilic pore channels, a large number of hydrophilic oxygen groups have a barrier effect on the permeation of water molecules, and the smaller the pore diameter, the larger the resistance. Compared with a water treatment membrane constructed by two-dimensional Graphene Oxide (GO) or a composite material thereof, the nano-filtration membrane has the pore channel which is a sub-nano-scale hydrophobic pore channel.
4) Although the surface of the two-dimensional water treatment membrane prepared by Reducing Graphene Oxide (RGO) or a traditional composite material has fewer oxygen groups, and the water flux of the two-dimensional water treatment membrane is higher than that of a Graphene Oxide (GO) membrane in value, the two-dimensional RGO has the problem of re-stacking, so that the interlayer spacing between the water treatment membrane layers constructed by the RGO is difficult to accurately control to reach sub-nanometer level, and the ion blocking effect of the water treatment membrane is influenced. Compared with a water treatment membrane constructed by Reduced Graphene Oxide (RGO) or a traditional composite material thereof, the hydrophobic pore channel of the nanofiltration membrane is sub-nanometer and fine and adjustable.
Drawings
Fig. 1 is a schematic structural diagram of a two-dimensional nano island @ graphene heterojunction material prepared by the methods of embodiments 1, 3, and 5, where fig. 1a is a side structure and an atomic structure, and fig. 1b is a surface structure;
fig. 2 is a schematic structural diagram of a two-dimensional nano island @ graphene heterojunction self-assembled nanofiltration membrane prepared by the methods of embodiments 2, 4 and 6 of the present invention, and a part circled in fig. 2 is a sub-nano hydrophobic pore channel formed by a re-stacked suspended part;
FIG. 3 is a front transmission electron microscope atomic micrograph of the two-dimensional Ni-p-phenylenediamine hydrochloride nano-islands @ graphene heterojunction material obtained in example 1;
fig. 4 is a transmission electron microscope atomic micrograph of the cross section of the two-dimensional Ni-p-phenylenediamine hydrochloride nano island @ graphene heterojunction self-assembled nanofiltration membrane obtained in example 2, wherein fig. 4a is a partial view of the cross section of the heterojunction, fig. 4b is an enlarged view of the cross section of the heterojunction, a sub-nanometer hydrophobic pore channel can be seen, and an inset in fig. 4b is a cross-sectional atomic structure view of the heterojunction;
fig. 5 is a contact angle test chart of the two-dimensional Ni-p-phenylenediamine hydrochloride nano island @ graphene heterojunction self-contained nanofiltration membrane obtained in example 2, fig. 5a is a contact angle test result, and fig. 5b is a nanofiltration membrane photograph.
Detailed Description
The following examples will further illustrate the invention in conjunction with the accompanying drawings. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a process are given, but the scope of the present invention is not limited to the following embodiments.
In the following embodiment, a two-dimensional nano island @ graphene heterojunction material is constructed by adopting different two-dimensional nano island materials, and is self-assembled into a hydrophobic nanofiltration membrane. In the following examples, the experimental methods without specifying the specific conditions are generally carried out under the conventional conditions, and the starting materials and reagents used are all conventional commercially available products without specific description.
Example 1
In example 1, a two-dimensional nano island is a Ni-p-phenylenediamine hydrochloride (Ni-pPD) metal organic material, and a two-dimensional Ni-p-phenylenediamine hydrochloride nano island @ graphene heterojunction material is constructed, and based on this example 2, a two-dimensional Ni-p-phenylenediamine hydrochloride nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane is prepared.
A preparation method of a two-dimensional Ni-p-phenylenediamine hydrochloride (Ni-pPD) nano island @ graphene heterojunction material comprises the following specific steps:
(1) 1.9 g of nickel nitrate (NiNO)3) Adding into 16mL deionized water, stirring to dissolve, and adding 32mL GO suspension with concentration of 5mg/mL (GO suspension is prepared by conventional Hummer's Method, or is commercially availableProduct), introducing argon while stirring, and introducing the argon for 2 hours to remove air in the solution to obtain a solution A;
(2) adding 2.0 g of p-phenylenediamine hydrochloride (pPD) (the purity of the p-phenylenediamine hydrochloride (pPD) is more than 99 percent (chemical purity) by adopting a sigma medicament sold in the market) into 60ml of deionized water, stirring and dissolving by adopting a magnetic stirring mode, wherein the stirring speed is 400rpm, argon is introduced while stirring, and the air introduction time is 2h to remove air in the solution, so as to obtain a solution B (a two-dimensional nano island precursor material aqueous solution);
(3) adding the solution B into the solution A, gradually adding ammonia water with the total volume of 20ml, and carrying out oxygen group catalytic reaction at the reaction temperature of 40 ℃ for 20 h; and after the reaction is finished, pouring the reaction liquid into a filter flask for suction filtration, firstly carrying out suction filtration by using deionized water, then carrying out suction filtration by using ethanol, and finally carrying out suction filtration by using deionized water, wherein the total suction filtration time is 2 hours, and washing to obtain the two-dimensional Ni-p-phenylenediamine hydrochloride (Ni-pPD) nano island @ graphene heterojunction material. Wherein the area ratio of the two-dimensional Ni-p-phenylenediamine hydrochloride (Ni-pPD) nano island to the graphene is 40-50%.
Example 2
A preparation method of a two-dimensional Ni-p-phenylenediamine hydrochloride (Ni-pPD) nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane comprises the following specific steps:
a. weighing the two-dimensional Ni-p-phenylenediamine hydrochloride nano island @ graphene heterojunction material, dispersing the two-dimensional Ni-p-phenylenediamine hydrochloride nano island @ graphene heterojunction material into deionized water, preparing heterojunction suspension liquid with the dispersion degree of 2mg/mL, and then performing ultrasonic dispersion for 1 h;
b. according to the thickness of the nanofiltration membrane to be prepared, the suspension is dripped on a polyether sulfone (PES) basement membrane (the polyether sulfone (PES) basement membrane is a porous basement membrane prepared by PES materials, is also a standard material basement and can be purchased commercially, and the specification used in the implementation is that the diameter of a phi 50mm is 0.22um, and the membrane thickness is 110 micrometers), and the filtration is carried out for 2 hours; after the suction filtration is finished, the polyether sulfone containing the suspension is placed in two glass sheets, 20N pressure is applied to the two glass sheets for extrusion, then the two glass sheets are dried in vacuum at the temperature of 70 ℃, the vacuum degree is 10Pa, after the drying is finished, the glass sheets are opened at the normal temperature, and the two-dimensional Ni-p-phenylenediamine hydrochloride (Ni-pPD) nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane is obtained, wherein the mass of the nanofiltration membrane is 1-20 mg, and the thickness of the nanofiltration membrane is 5-50 micrometers.
The invention firstly provides a simple and effective method, and the method comprises the steps of generating another hydrophobic two-dimensional nano island material by an in-situ reaction at an oxygen group on the surface of two-dimensional graphene oxide through an oxygen group catalytic reaction, and simultaneously reducing the oxygen group on the two-dimensional graphene oxide to prepare the hydrophobic two-dimensional nano island @ graphene novel heterostructure material, wherein the structure of the material is shown in figure 1. The invention further utilizes the hydrophobic effect to enable the two-dimensional nano island @ graphene heterojunction material to be self-assembled in the water solution, so that a structure that the two-dimensional nano island is sandwiched by two layers of graphene is obtained, the two-dimensional nano island can be used as a sub-nano interlayer of the two-dimensional water treatment membrane, a nanofiltration membrane with an internal sub-nano hydrophobic pore passage is formed, and the structure is shown in figure 2.
Fig. 3 is a front transmission electron microscope atomic micrograph of the two-dimensional Ni-p-phenylenediamine hydrochloride nano-island @ graphene heterojunction material prepared in example 1. As can be seen from fig. 3, in the present embodiment, the two-dimensional Ni-p-phenylenediamine hydrochloride nano-islands are grown in situ on the graphene surface.
Fig. 4 is an atomic micrograph of a membrane interface transmission electron microscope of the heterojunction self-assembled hydrophobic nanofiltration membrane of example 2, and it can be seen from fig. 4 that two-dimensional Ni-p-phenylenediamine hydrochloride nano-islands are sandwiched by two layers of graphene to form sub-nanoscale channels.
Fig. 5 shows contact angle tests of the heterojunction self-assembled hydrophobic nanofiltration membrane of example 2 and a control group of Graphene Oxide nanofiltration Membranes, the Graphene Oxide nanofiltration membrane (GO) is prepared by vacuum-filtering GO suspension onto a substrate (such as PES substrate) and drying, and the method in the specific steps references (dr. mengchen Zhang, yang wing Mao, Guozhen Liu, prof. gongging Liu, prof. yiqun Fan, prof. wanq in jin. molecular Bridges dense Graphene Oxide Membranes in Water [ J ] angels angele, angelwan @ Chemie,2020,132(4): as can be seen from fig. 5, the contact angle of the two-dimensional Ni-p-phenylenediamine hydrochloride nano island @ Graphene heterojunction self-assembled hydrophobic nanofiltration membrane of example 2 is 84 °, and the contact angle of the Graphene Oxide nanofiltration membrane has good hydrophobicity. As can be seen from fig. 3-5, the nanofiltration membrane in example 2 is rich in sub-nanoscale hydrophobic channels inside.
Table 1 is a table of the water flux and ion barrier properties of the nanofiltration membrane prepared in example 2. Table 2 is a table of water flux and ion barrier properties of the Graphene Oxide (GO) water treatment membrane as a control.
The method for testing water flux and Ion barrier property is the method in the reference (Ion sizing in the graphene oxide membranes via the interfacial spacing [ J ]. Science Foundation in China,2017,25(04): 13.).
Table 1 example 2 permeation experiment results of two-dimensional Ni-pPD nano-island @ graphene heterojunction self-assembled nanofiltration membrane.
Table 2 permeation experiment results of control group two-dimensional graphene oxide nanofiltration membranes.
As can be seen from tables 1 and 2, the nanofiltration membrane prepared in example 2 has superior water flux and ion barrier property compared to the control group, and can achieve both high water flux and high ion barrier property.
Example 3
In example 3, the two-dimensional nano-island is a Ni-hexa-aminobenzene (Ni-HAB) metal organic material, and a two-dimensional Ni-hexa-aminobenzene nano-island @ graphene heterojunction material is constructed, so that the two-dimensional Ni-hexa-aminobenzene (Ni-HAB) nano-island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane is prepared based on this example 4.
A preparation method of a two-dimensional Ni-hexa-aminobenzene (Ni-HAB) nano island @ graphene heterojunction comprises the following specific steps:
(1) 2.2 g of nickel nitrate (NiNO)3) Adding into 20mL deionized water, stirring to dissolve, and adding 32mL GO with concentration of 5mg/mLStirring the suspension, introducing argon gas, and introducing the argon gas for 1h to remove air in the solution to obtain a solution A;
(2) adding 2.2 g of hexa-aminobenzene (HAB) (the hexa-aminobenzene (HAB) adopts a sigma medicine sold in the market, the purity is more than 99 percent (chemical purity)) into 50ml of deionized water, stirring and dissolving, introducing argon while stirring, and introducing air for 1h to remove air in the solution to obtain a solution B (a two-dimensional nano island precursor material aqueous solution);
(3) adding the solution B into the solution A, gradually adding ammonia water with the total volume of 30ml, and carrying out oxygen group catalytic reaction at the reaction temperature of 10 ℃ for 20 h; and after the reaction is finished, pouring the reaction liquid into a filter flask for suction filtration, firstly carrying out suction filtration by using deionized water, then carrying out suction filtration by using ethanol, and finally carrying out suction filtration by using deionized water, wherein the total suction filtration time is 4 hours, and washing to obtain the two-dimensional Ni-hexaaminobenzene (Ni-HAB) nano island @ graphene heterojunction material.
Example 4
A preparation method of a two-dimensional Ni-hexa-aminobenzene (Ni-HAB) nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane comprises the following specific steps:
a. weighing the two-dimensional Ni-hexa-aminobenzene (Ni-HAB) nano island @ graphene heterojunction material, dispersing the two-dimensional Ni-hexa-aminobenzene (Ni-HAB) nano island @ graphene heterojunction material into deionized water, preparing a heterojunction suspension with the dispersity of 2mg/mL, and then ultrasonically dispersing for 1 h;
b. according to the thickness of the nanofiltration membrane to be prepared, dropwise adding the suspension on a Polystyrene (PS) basement membrane (the Polystyrene (PS) basement membrane is a porous basement membrane prepared by adopting a PS material, is also a standard basement of a standard material and can be purchased commercially, and the specification used in the implementation is that the diameter of phi 50mm is 0.22um, and the membrane thickness is 110 micrometers), and carrying out suction filtration for 3 hours; after the filtration, the polyether sulfone containing the suspension is placed in two glass sheets, 20N pressure is applied for extrusion, then the vacuum drying is carried out at the temperature of 70 ℃, the vacuum degree is 10Pa, and after the drying, the glass sheets are opened at the normal temperature to obtain the two-dimensional Ni-hexaamino benzene (Ni-HAB) nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane.
Example 5
In example 5, the two-dimensional nano-island is a Graphyne (GDY) material, and a two-dimensional Graphyne (GDY) nano-island @ graphene heterojunction material is constructed, so that the two-dimensional Graphyne (GDY) nano-island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane is prepared based on this example 6.
A preparation method of a two-dimensional Graphdine (GDY) nano island @ graphene heterojunction comprises the following specific steps:
(1) adding 0.2 g of hexa (ethynyl) benzene (HEB) into 100ml of pyridine, stirring for dissolving, adding 5mg of GO powder, stirring (the GO powder is obtained by freeze-drying GO suspension, and the GO suspension is prepared by a traditional Hummer's Method or can be purchased from a commercially available finished product), stirring while introducing argon, and ventilating for 2 hours to remove air in the solution to obtain a solution A;
(2) heating the solution A to 110 ℃, adding copper wires, and carrying out oxygen group catalytic reaction at the reaction temperature of 110 ℃ for 20 hours; and after the reaction is finished, pouring the reaction liquid into a filter flask for suction filtration, firstly carrying out suction filtration by using ethanol, then carrying out suction filtration by using N, N-Dimethylformamide (DMF), and finally carrying out suction filtration by using deionized water, wherein the total suction filtration time is 6 hours, and washing to obtain the two-dimensional Graphdiyne (GDY) nano island @ graphene heterojunction material.
Example 6
A preparation method of a two-dimensional Graphdine (GDY) nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane specifically comprises the following steps:
a. weighing the two-dimensional Graphdine (GDY) nano island @ graphene heterojunction material, dispersing the two-dimensional Graphdine (GDY) nano island @ graphene heterojunction material into deionized water, preparing heterojunction suspension liquid with the dispersion degree of 2mg/mL, and then performing ultrasonic dispersion for 1 h;
b. according to the thickness of the nanofiltration membrane to be prepared, the suspension is dripped on a Polystyrene (PS) basement membrane (the Polystyrene (PS) basement membrane is a porous basement membrane prepared by adopting a PS material, is also a standard basement of a standard material and can be purchased commercially, and the specification used in the implementation is that the diameter of phi 50mm is 0.22um, and the membrane thickness is 110 micrometers), and the filtration is carried out for 4 hours; after the filtration, the polyether sulfone containing the suspension is placed in two glass sheets, the pressure of 20N is applied for extrusion, then the vacuum drying is carried out at the temperature of 70 ℃, the vacuum degree is 10Pa, and after the drying, the glass sheets are opened at the normal temperature to obtain the two-dimensional graphite alkyne (GDY) nano island @ graphene heterojunction self-assembly hydrophobic nanofiltration membrane.
The performances of high water flux and high ion barrier property of the two-dimensional Ni-hexa-aminobenzene (Ni-HAB) nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane obtained in the example 4 and the two-dimensional Grapyne (GDY) nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane obtained in the example 6 are equivalent to those of the two-dimensional Ni-p-phenylenediamine hydrochloride nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane obtained in the example 2.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The hydrophobic two-dimensional nano island @ graphene heterojunction material is characterized in that a two-dimensional nano island material grows on the surface of graphene through oxygen group catalytic reaction to prepare the hydrophobic two-dimensional nano island @ graphene heterojunction material, and the area ratio of the two-dimensional nano island material to the graphene is 10-70%.
2. The hydrophobic two-dimensional nano island @ graphene heterojunction material of claim 1, wherein in the prepared hydrophobic two-dimensional nano island @ graphene heterojunction material, the contact angle of a two-dimensional nano island is 60-120 degrees, and the contact angle of two-dimensional graphene is 60-90 degrees.
3. The preparation method of the hydrophobic two-dimensional nano island @ graphene heterojunction material as claimed in claim 1 or 2, characterized by comprising the following steps:
(1) adding the graphene oxide suspension into a soluble metal salt solution, and introducing inert gas to remove oxygen to obtain a solution A;
(2) dissolving a two-dimensional nano island precursor material into water, and introducing inert gas to remove oxygen to obtain a solution B;
(3) adding the solution B into the solution A, carrying out oxygen group catalytic reaction at the temperature of-30-150 ℃ for 0.5-96 h, carrying out suction filtration, and washing to prepare a hydrophobic two-dimensional nano island @ graphene heterojunction material;
the soluble metal salt solution in the step (1) is a soluble metal salt solution of nickel or a soluble metal salt solution of copper;
the two-dimensional nano island precursor material in the step (2) is p-phenylenediamine hydrochloride, hexa-aminobenzene, graphdiyne or hexa-mercaptobenzene.
4. The preparation method according to claim 3, wherein the concentration of the graphene oxide suspension in the step (1) is 0.1-5 mg/mL; the concentration of the solution B in the step (2) is 0.1-1 mol/L; the inert gas used in the steps (1) and (2) is argon or nitrogen, and the inert gas is introduced for 0.1-24 hours.
5. The preparation method according to claim 3, wherein in the step (3), the reaction temperature is 10 to 110 ℃ and the reaction time is 5 to 20 hours.
6. The use of the hydrophobic two-dimensional nano-island @ graphene heterojunction material as defined in claim 1 or 2 in the preparation of a self-assembled hydrophobic nanofiltration membrane.
7. The method for preparing the two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane by using the hydrophobic two-dimensional nano island @ graphene heterojunction material as claimed in claim 1 or 2, is characterized by comprising the following steps of:
a. preparing a filtrate: preparing the hydrophobic two-dimensional nano island @ graphene heterojunction material into a suspension;
b. suction filtration and drying: and (b) placing the suspension liquid obtained in the step a on a base membrane, performing suction filtration, then extruding the hydrophobic two-dimensional nano island @ graphene heterojunction material in the suspension liquid onto the base membrane under external pressure, and drying to obtain the two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane.
8. The method of claim 7, wherein in the step a, the concentration of the hydrophobic two-dimensional nano island @ graphene heterojunction material suspension is 1-10 mg/mL.
9. The method of claim 7, wherein in step b, the substrate membrane is made of polyethersulfone, polystyrene, mixed cellulose ester, polyvinyl chloride, polyacrylonitrile, polycarbonate, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, or porous alumina;
in the step b, the range of pressure applied during extrusion is 1-100N;
in the step b, drying is carried out in a vacuum drying mode, and the drying temperature is 25-150 ℃; the drying time is 0.5-96 hours; the vacuum degree adopted for drying is 1Pa to 1 atmospheric pressure.
10. The application of the two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane prepared according to claim 7 in water treatment, wherein the water treatment is seawater desalination treatment, industrial wastewater treatment or municipal sewage treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111571893.1A CN114247305B (en) | 2021-12-21 | 2021-12-21 | Two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111571893.1A CN114247305B (en) | 2021-12-21 | 2021-12-21 | Two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114247305A true CN114247305A (en) | 2022-03-29 |
| CN114247305B CN114247305B (en) | 2023-06-20 |
Family
ID=80796333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111571893.1A Active CN114247305B (en) | 2021-12-21 | 2021-12-21 | Two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114247305B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116061510A (en) * | 2022-12-07 | 2023-05-05 | 南通大学 | Multilayer self-adjusting composite non-woven material, preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989331A (en) * | 2012-12-20 | 2013-03-27 | 浙江工商大学 | Polymer/graphene hybridization nanofiltration composite membrane and preparation method thereof |
| US20140305864A1 (en) * | 2013-04-12 | 2014-10-16 | Delai Darren Sun | Inorganic fibrous membrane and a method of fabricating thereof |
| CN108321378A (en) * | 2018-03-05 | 2018-07-24 | 西北大学 | A kind of preparation method of metal oxide@metal composites/graphene nucleocapsid semi-conducting material with heterojunction boundary effect |
| CN109310954A (en) * | 2016-06-10 | 2019-02-05 | 苏黎世联邦理工学院 | The film for being used to prepare the method for porous graphene film and being prepared using this method |
| CN109950554A (en) * | 2019-01-09 | 2019-06-28 | 柯良节 | A kind of graphene-supported metal nano island catalyst and the preparation method and application thereof |
| WO2019195618A1 (en) * | 2018-04-04 | 2019-10-10 | The Regents Of The University Of California | Non-contact measurements of fluids, particles and bubbles |
| CN111774058A (en) * | 2020-07-17 | 2020-10-16 | 上海应用技术大学 | Heterojunction composite photocatalyst and preparation method and application thereof |
| CN112117445A (en) * | 2020-09-04 | 2020-12-22 | 四川大学 | Stannous oxide/graphene heterojunction composite material, preparation method and application thereof, and metal lithium cathode taking stannous oxide/graphene heterojunction composite material as host |
| CN113491955A (en) * | 2021-06-04 | 2021-10-12 | 中国石油大学(华东) | Composite membrane with heterostructure separation layer and preparation method thereof |
| CN113559841A (en) * | 2021-08-12 | 2021-10-29 | 台州学院 | Nano CuO/GO/BiVO4Heterogeneous heterojunction photocatalyst, preparation method and application thereof |
-
2021
- 2021-12-21 CN CN202111571893.1A patent/CN114247305B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989331A (en) * | 2012-12-20 | 2013-03-27 | 浙江工商大学 | Polymer/graphene hybridization nanofiltration composite membrane and preparation method thereof |
| US20140305864A1 (en) * | 2013-04-12 | 2014-10-16 | Delai Darren Sun | Inorganic fibrous membrane and a method of fabricating thereof |
| CN109310954A (en) * | 2016-06-10 | 2019-02-05 | 苏黎世联邦理工学院 | The film for being used to prepare the method for porous graphene film and being prepared using this method |
| CN108321378A (en) * | 2018-03-05 | 2018-07-24 | 西北大学 | A kind of preparation method of metal oxide@metal composites/graphene nucleocapsid semi-conducting material with heterojunction boundary effect |
| WO2019195618A1 (en) * | 2018-04-04 | 2019-10-10 | The Regents Of The University Of California | Non-contact measurements of fluids, particles and bubbles |
| CN109950554A (en) * | 2019-01-09 | 2019-06-28 | 柯良节 | A kind of graphene-supported metal nano island catalyst and the preparation method and application thereof |
| CN111774058A (en) * | 2020-07-17 | 2020-10-16 | 上海应用技术大学 | Heterojunction composite photocatalyst and preparation method and application thereof |
| CN112117445A (en) * | 2020-09-04 | 2020-12-22 | 四川大学 | Stannous oxide/graphene heterojunction composite material, preparation method and application thereof, and metal lithium cathode taking stannous oxide/graphene heterojunction composite material as host |
| CN113491955A (en) * | 2021-06-04 | 2021-10-12 | 中国石油大学(华东) | Composite membrane with heterostructure separation layer and preparation method thereof |
| CN113559841A (en) * | 2021-08-12 | 2021-10-29 | 台州学院 | Nano CuO/GO/BiVO4Heterogeneous heterojunction photocatalyst, preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116061510A (en) * | 2022-12-07 | 2023-05-05 | 南通大学 | Multilayer self-adjusting composite non-woven material, preparation method and application thereof |
| CN116061510B (en) * | 2022-12-07 | 2023-12-05 | 南通大学 | Multilayer self-adjusting composite non-woven material, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114247305B (en) | 2023-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | The rapid emergence of two-dimensional nanomaterials for high-performance separation membranes | |
| Emadzadeh et al. | Synthesis, modification and optimization of titanate nanotubes-polyamide thin film nanocomposite (TFN) membrane for forward osmosis (FO) application | |
| Fan et al. | A novel reduced graphene oxide/carbon nanotube hollow fiber membrane with high forward osmosis performance | |
| KR101421219B1 (en) | Composite Separation Membrane Containing Graphene Oxide Coating Layer and Manufacturing Method Thereof | |
| CN107158980A (en) | Utilized thin film composite membranes reacted based on air liquid interface and its preparation method and application | |
| Zhao et al. | Thermally reduced graphene oxide membrane with ultrahigh rejection of metal ions’ separation from water | |
| CN111282405A (en) | Modified metal organic framework nanosheet and preparation method thereof | |
| CN108993165B (en) | Layered inorganic material organic solvent nanofiltration composite membrane and preparation method thereof | |
| WO2022227838A1 (en) | Preparation method for hollow fiber inorganic membrane | |
| CN110694492A (en) | Mixed matrix polyamide membrane of ZIF type metal organic framework and preparation method thereof | |
| CN113648850B (en) | Preparation method of MXene/reduced porous graphene oxide (r-HGO) composite membrane with high flux and high removal rate | |
| Gui et al. | g-C3N4 nanofibers network reinforced polyamide nanofiltration membrane for fast desalination | |
| Lin et al. | Construction and application of two-dimensional MXene-based membranes for water treatment: A mini-review | |
| Xiao et al. | MOFs-mediated nanoscale Turing structure in polyamide membrane for enhanced nanofiltration | |
| CN114247305B (en) | Two-dimensional nano island @ graphene heterojunction self-assembled hydrophobic nanofiltration membrane and preparation method thereof | |
| Asghari et al. | Graphene oxide and its derivatives for gas separation membranes | |
| CN103212305B (en) | Preparation method of aligned carbon nano-tube nanofiltration membranes | |
| Tang et al. | A highly hydrophilic benzenesulfonic-grafted graphene oxide-based hybrid membrane for ethanol dehydration | |
| Liu et al. | Controllable synthesis of novel porous graphene-based sheets and design of ultrathin composite films by in-situ sealing technology | |
| Yu et al. | Graphene oxide nanofiltration membrane for efficient dyes separation by hexagonal boron nitride nanosheets intercalation and polyethyleneimine surface modification | |
| CN109012189A (en) | A method of graphene oxide composite nano filter membrane is prepared using Freeze Drying Technique | |
| Kanagaraj et al. | Effect of the different layered structural modification on the performances of the thin-film composite forward osmosis flat sheet membranes–A review | |
| CN111514856A (en) | Graphene oxide adsorption film, preparation method thereof and water treatment method | |
| CN113117525A (en) | Amino-functionalized single-walled carbon nanotube modified polyamide nanofiltration membrane as well as preparation method and application thereof | |
| CN115138220B (en) | Anionic covalent organic framework film and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |