CN109569311B - Surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane and preparation method thereof - Google Patents
Surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
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- 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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- 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
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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
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- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane and a preparation method thereof, belonging to the field of water treatment membrane materials and preparation processes thereof. The invention selects the carbon nitride photocatalyst which has plasticity of polymer molecules and chemical stability of carbonaceous materials, and prepares the multifunctional water treatment membrane by methods of surface modification, chemical modification, Fenton-like reagent compounding and the like. On one hand, triangular nano holes among carbon nitride composition elements are utilized to provide a stable natural channel for water molecules to pass through quickly, on the other hand, the in-situ degradation of nano filtration trapped pollutants is realized by adopting catalytic degradation under illumination and Fenton oxidation of iron-containing reagents, and a novel way is provided for solving the problem of membrane pollution which is difficult to surmount by the traditional nano filtration membrane material. The nanofiltration membrane prepared by the invention has the advantages of simple preparation method, low cost, pollution resistance, small water mass transfer resistance and the like, and is expected to be applied in the field of water purification.
Description
Technical Field
The invention relates to a water quality purification membrane material and a preparation process technology thereof, in particular to a surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane and a preparation method thereof.
Background
Nanofiltration is used as a novel membrane separation process between ultrafiltration and reverse osmosis, and can effectively intercept divalent and high-valent ions, dyes, organic small molecules, antibiotics and the like under lower pressure, so that the method has great application prospect in the field of water treatment. However, nanofiltration membrane water treatment technology still faces the problems of high cost, flux reduction caused by membrane pollution, water quality deterioration of produced water and the like, and it is very important to find a feasible way for solving the problem of membrane pollution while developing novel membrane materials [ energy environs.sci.2011, 4,1946 ]. Research shows that NOM, organic pollutants, microorganisms and inorganic salts in water are main factors causing membrane pollution, and although membrane pollution can be slowed down through surface modification of the nanofiltration membrane and optimal control of the membrane process, the pollutants causing the membrane pollution cannot be fundamentally eliminated. The advanced oxidation technology is also a commonly used method in advanced wastewater treatment, various pollutants and microorganisms can be directly degraded through a free radical chain reaction, and therefore, an effective method can be provided for separating trapped pollutant molecules by an in-situ mineralized membrane. Among them, photocatalysis and fenton-like are considered as novel advanced oxidation technologies with high efficiency, low consumption, cleanness, no secondary pollution and environmental friendliness, and become research hotspots in the field of environmental pollutant treatment. The membrane separation technology is ingeniously combined with Fenton-like and photocatalytic processes, advanced oxidation reaction can not only carry out deep oxidation reduction treatment on small molecular pollutants or heavy metal ions which are difficult to intercept during nanofiltration, but also can realize in-situ degradation of physically intercepted pollutants, and therefore a powerful way is hopefully provided for enhancing water quality purification efficiency and solving the membrane pollution problem. [ Water Res.2013,47,5647 ].
At present, the research of the membrane separation-photocatalysis coupling technology is mainly realized by combining a separation membrane and a suspension type photocatalysis reactor or adding photocatalysis nano particles into a filter membrane. For example, mixing TiO2The photocatalyst is loaded or embedded into the separation membrane, and hydroxyl groups formed by oxygen vacancy induction under illumination enable the separation membrane to have unique photoinduced hydrophilic performance, so that the anti-pollution capacity of the surface of the membrane can be obviously enhanced, and the pollutant removal performance of the system is also enhanced. A significant problem faced by such research is TiO2The spectrum utilization range is narrow, non-optical active organic matters influence the optical catalytic activity, and catalyst nano particles are difficult to form a film compactly, and the like. Seeking to have visible light catalytic activity and physicochemical stabilityThe material capable of forming a compact laminated structure is used for preparing the photocatalytic nanofiltration membrane, and is an important direction for the research of a membrane separation-photocatalytic coupling technology in the future [ adv.funct.mater.2017,27,1700251 ]. The graphite phase carbon nitride (g-C) has the characteristics of cheap and easily obtained raw materials, simple and convenient synthesis method, easy large-scale preparation, high stability and the like3N4) The material becomes a hotspot material researched in recent years, and the capability of catalyzing and degrading pollutants under illumination makes the material become an excellent choice for developing a novel photocatalytic water purification film. In particular, carbon nitride with triazine C3N3Or 3-s-triazine C6N7The basic units are periodically arranged to form a graphene-like two-dimensional conjugated structure, so that the graphene-like two-dimensional conjugated structure has polymer molecule tailorability and chemical stability of a carbonaceous material, and meanwhile, a rapid channel is provided for water molecule transmission by using triangular nano holes between elements [ Angew. Therefore, compared with the carbon nanotube array which is difficult to prepare in a large scale and the graphene oxide which has low water permeability and poor structural stability, the g-C3N4The multifunctional water purifying film has more advantages in the development of the multifunctional water purifying film.
Although the development of a photocatalytic water purification membrane with high rejection rate, high water flux and pollution resistance on the surface based on carbon nitride has a huge application prospect, a bulk phase material prepared by a thermal polymerization method generally has a larger size, limited surface active functional groups and poor dispersibility in a solvent, and the characteristics bring new challenges to the fine structure regulation of polymer molecules and the formation of a homogeneous membrane. Therefore, a new process for preparing the carbon nitride-based nanofiltration membrane in a large scale through surface modification and exploration of carbon nitride molecules in future research is urgently needed.
Disclosure of Invention
The invention aims to solve the difficult problems that the traditional nanofiltration membrane is difficult to eliminate membrane pollution and a carbon nitride photocatalyst is difficult to form a homogeneous membrane, and provides a multifunctional nanofiltration membrane for realizing photocatalysis and Fenton-like reaction coupling oxidation based on transition metal-containing Fenton reagent modification and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the invention provides a surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane and a preparation method thereof.
The surface self-cleaning carbon nitride Fenton-like photocatalytic nanofiltration membrane provided by the invention consists of a graphite phase carbon nitride film forming material and a Fenton-like catalyst loaded on the surface of the graphite phase carbon nitride film forming material.
The surface self-cleaning type carbon nitride Fenton-photocatalytic nanofiltration membrane is prepared by the following steps:
1) preparing graphite-phase carbon nitride by using a nitrogen-containing compound as a nitrogen-containing precursor;
2) preparing a carbon nitride sol membrane preparation solution from the graphite-phase carbon nitride obtained in the step 1);
3) mixing the carbon nitride sol membrane-forming solution obtained in the step 2) with a precursor solution containing Fenton-like active metal ions, and loading a Fenton-like catalyst on the surface of a carbon nitride photocatalyst to obtain a mixed membrane-forming solution containing carbon nitride and the Fenton-like catalyst;
or 3') preparing a Fenton-like catalyst from a precursor containing Fenton-like active metal ions, and then mixing the carbon nitride sol membrane-forming solution obtained in the step 2) with the Fenton-like catalyst to obtain a mixed membrane-forming solution containing carbon nitride and the Fenton-like catalyst;
4) and preparing the surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane.
In step 1) of the above method, the nitrogen-containing compound includes, but is not limited to: nitrogen-containing organic compounds such as cyanamide, dicyandiamide, melamine, urea, thiourea, hexamethylenetetramine and the like.
The nitrogen-containing compound is used as a precursor, and the graphite-phase carbon nitride is prepared by methods such as high-temperature thermal polymerization, dissolution thermal synthesis and the like.
Wherein the thermal polymerization may specifically be: the nitrogen-containing compound is put into a high temperature furnace to carry out thermal polymerization reaction for 1 to 10 hours at the temperature of 400-700 ℃.
In step 2) of the above method, the operation of preparing the carbon nitride sol film-forming solution from the graphite-phase carbon nitride obtained in step 1) is a) or b) as follows:
a) the carbon nitride nanosheets are obtained by ultrasonic liquid phase stripping, and the size of the stripped carbon nitride nanosheets is screened by means of high-speed centrifugation, so that carbon nitride sol with good dispersibility is obtained and used as membrane preparation liquid.
Wherein the ultrasonic liquid phase stripping operation comprises the following steps: dispersing the graphite-phase carbon nitride obtained in the step 1) in a solvent, and carrying out liquid phase stripping under the assistance of ultrasonic waves.
b) Treating the graphite-phase carbon nitride obtained in the step 1) in an acid or alkali solution, and obtaining carbon nitride sol with good dispersibility as a membrane preparation solution through molecular cutting and high-speed centrifugation.
In step 3), the fenton-like active metal may be: iron, manganese, copper, cobalt, nickel and the like, and specifically can be iron or copper;
ferric salt can be used as a precursor containing Fenton-like active metal ions, and cupric salt can be used as a precursor containing Fenton-like active metal ions;
the fenton-like catalyst may be: metals having fenton-like activity, oxides, hydroxides, organic complexes of said metals.
When an iron salt is used as a precursor containing a fenton-like active metal ion, the fenton-like catalyst can be: nano-iron, iron-containing oxides, hydroxides, polyoxometallates, and the like.
When a copper salt is used as a precursor containing a fenton-like active metal ion, the fenton-like catalyst may be: copper-containing oxides, hydroxides, polyoxometallates, and the like.
In the step 3), the Fenton-like catalyst can be loaded on the surface of the carbon nitride photocatalyst by methods such as physical mixing, chemical precipitation, solvothermal reaction, calcination and the like.
The load capacity of the Fenton-like catalyst can be 1-20% of the mass of the carbon nitride.
And 4) taking the polymer or ceramic microfiltration membrane as a support substrate, and performing suction filtration on the mixed membrane preparation solution by using a filter under a negative pressure condition to obtain the surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane.
The surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane prepared by the method also belongs to the protection scope of the invention.
The application of the surface self-cleaning type carbon nitride Fenton-photocatalytic nanofiltration membrane in water treatment also belongs to the protection scope of the invention.
The invention also provides a method for treating water by using the nanofiltration membrane, which comprises the following steps: under the condition of illumination, the water body to be treated and H are mixed2O2And (3) mixing the solution and then passing the mixed solution through the surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane.
The nanofiltration membrane physically intercepts pollutant molecules and degrades and removes the pollutants through photocatalysis and Fenton-like oxidation.
The illumination conditions include various ultraviolet light sources, simulated or actual sunlight.
And the self-cleaning performance of the membrane surface can be obtained by respectively selecting photocatalysis, Fenton-like oxidation and photocatalysis coupling Fenton-like oxidation according to the types and degradation removal effects of the pollutants.
The invention has the following beneficial effects:
the nanometer holes periodically distributed in the carbon nitride conjugated molecular structure can provide a separation pore passage through which water molecules pass with low resistance, and the photocatalysis and Fenton-like reaction can effectively degrade pollutants intercepted by nanofiltration, so that the effective combination of high-flux separation and pollution resistance is obtained.
The invention uses Fenton reagent containing transition metal and g-C3N4The hybridization compound is used for functionally modifying the surface of polymer molecules, and the coupling of photocatalysis and Fenton-like reaction is obtained on the basis of improving the film forming property of carbon nitride molecules, so that the surface self-cleaning carbon nitride nanofiltration membrane is obtained.
The preparation method disclosed by the invention has the advantages of simple required experimental equipment, mild operation conditions, simplicity, convenience, feasibility and capabilities of effectively improving the anti-pollution performance of the nanofiltration membrane and reducing the preparation and operation costs of the water treatment membrane material.
The nanofiltration membrane prepared by the invention has the advantages of simple preparation method, low cost, pollution resistance, small water mass transfer resistance and the like, thereby having important application prospect.
Drawings
Fig. 1 is a scanning electron microscope photograph of the surface of a carbon nitride-based fenton-photocatalytic nanofiltration membrane in example 1 of the present invention;
FIG. 2 is a graph showing the molecular rejection and membrane flux of different dyes for a carbon nitride-based Fenton-photocatalytic nanofiltration membrane in example 2 of the present invention;
FIG. 3 shows the performance of carbon nitride Fenton-based photocatalytic nanofiltration membrane for continuous interception of methyl blue dye in water in example 4 of the present invention;
fig. 4 shows the photocatalytic degradation effect of the trapped contaminants under the illumination of the carbon nitride-based fenton-photocatalytic nanofiltration membrane in example 4 of the present invention.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of Fenton-like photocatalytic nanofiltration membranes based on carbon nitride and iron-containing Fenton-like reagents
A Fenton-like photocatalytic nanofiltration membrane preparation method based on carbon nitride and an iron-containing Fenton-like reagent comprises the following steps:
step 1: melamine is used as a nitrogen-containing precursor, and thermal polymerization reaction is carried out for 4 hours at 550 ℃ in a high-temperature furnace to prepare the graphite-phase carbon nitride.
Step 2: and (2) dispersing the graphene carbon nitride in the isopropanol solvent in the step (1), carrying out liquid phase stripping by using an ultrasonic device, carrying out high-speed centrifugation for 10 minutes at 5000 r/min, and removing the bulk-phase carbon nitride which is not fully stripped to obtain carbon nitride nanosheets with good dispersibility as membrane preparation liquid.
And step 3: ferric chloride and phosphotungstic acid are adopted to prepare a Fenton-like reaction precursor solution, the pH value of the solution is adjusted to 1.0, and then the solution is stirred to react for 12 hours to obtain the iron-containing polyoxometallate serving as a Fenton-like reagent dispersion liquid. The polyoxometallate Fenton reagent is prepared by coprecipitation and compounding.
And 4, step 4: and (3) mixing the carbon nitride membrane-forming solution obtained in the step (2) with the Fenton-like reagent dispersion solution obtained in the step (3) according to a certain proportion to obtain a nanofiltration membrane-forming solution containing carbon nitride and Fenton-like nano materials.
And 5: and (3) taking the ceramic microfiltration membrane as a support substrate, and carrying out suction filtration on the mixed membrane preparation solution obtained in the step (4) to form a membrane on the surface of the substrate by using a filter under a negative pressure condition to obtain the carbon nitride-based Fenton-photocatalytic nanofiltration membrane.
Fig. 1 is a surface scanning electron microscope photograph of the prepared carbon nitride fenton-photocatalytic nanofiltration membrane.
As can be seen from fig. 1: the carbon nitride modified by the polyacid molecule Fenton reagent can form a uniform and compact membrane structure on the surface of the support microfiltration membrane.
Example 2 preparation of Fenton-like photocatalytic nanofiltration membranes based on carbon nitride and iron-containing Fenton-like reagents
A Fenton-like photocatalytic nanofiltration membrane preparation method based on carbon nitride and an iron-containing Fenton-like reagent comprises the following steps:
step 1: urea is used as a nitrogen-containing precursor, and thermal polymerization reaction is carried out for 4 hours at 550 ℃ in a high-temperature furnace to prepare the graphite-phase carbon nitride.
Step 2: and (2) performing molecular cutting treatment on the graphene carbon nitride in the step (1) in a sodium hydroxide concentrated solution, treating the reaction solution through dialysis to remove impurity ions, and centrifuging the dialyzed solution at 1500 rpm for 10 minutes to obtain carbon nitride sol with good dispersibility as a membrane preparation solution.
And step 3: preparing a Fenton-like reaction precursor solution by adopting ferric chloride and phosphotungstic acid, adjusting the pH value of the solution to 1.0, and then stirring for reaction for 12 hours to obtain iron-containing polyoxometallate serving as a Fenton-like reagent dispersion solution;
and 4, step 4: and (3) mixing the carbon nitride membrane-forming solution obtained in the step (2) with the Fenton-like reagent dispersion solution obtained in the step (3) according to a certain proportion to obtain a nanofiltration membrane-forming solution containing carbon nitride and Fenton-like nano materials.
And 5: and (3) taking the poly sulfoxide microfiltration membrane as a support substrate, and performing suction filtration on the mixed membrane-making solution obtained in the step (4) to form a membrane on the surface of the substrate by using a filter under a negative pressure condition to obtain the carbon nitride Fenton-based photocatalytic nanofiltration membrane (Fenton-based photocatalytic nanofiltration membrane containing 1% of iron phosphotungstate).
In fig. 2, a and b are respectively the comparison of the rejection rate and water flux of urea carbon nitride/iron phosphotungstate nanofiltration membrane treatment simulation of different dye wastewater.
The carbon nitride/iron phosphotungstate loaded by the poly sulfoxide is taken as a Fenton-like photocatalytic nanofiltration membrane, and different dye aqueous solutions flow through the nanofiltration membrane under the vacuum filtration condition. The nanofiltration membranes showed the highest retention for Methyl Blue (MB) and congo Red (Cango Red) and retention for Methyl Orange (MO) and rhodamine (RhB) of 51.8% and 53.1%, respectively, as determined by the concentration of dye in the draw filtrate in panel a. The flux of congo red solution penetrating the nanofiltration membrane is up to 80L m-2h-1bar-1。
Example 3 preparation of Fenton-like photocatalytic nanofiltration membranes based on carbon nitride and iron-containing Fenton-like reagents
A Fenton-like photocatalytic nanofiltration membrane preparation method based on carbon nitride and an iron-containing Fenton-like reagent comprises the following steps:
step 1: melamine is used as a nitrogen-containing precursor, and thermal polymerization reaction is carried out for 4 hours at 550 ℃ in a high-temperature furnace to prepare the graphite-phase carbon nitride.
Step 2: and (2) performing molecular cutting treatment on the graphene carbon nitride in the step (1) in a sodium hydroxide concentrated solution, treating the reaction solution through dialysis to remove impurity ions, and centrifuging the dialyzed solution at 1500 rpm for 10 minutes to obtain carbon nitride sol with good dispersibility as a membrane preparation solution.
And step 3: and (3) taking ferric chloride as a Fenton-like reagent precursor, mixing the carbon nitride sol solution obtained in the step (2) with a certain amount of ferric chloride solution, adding ammonium bicarbonate, stirring and reacting for 8 hours to obtain the nano-hydroxyl iron modified carbon nitride dispersion liquid serving as a nanofiltration membrane preparation liquid.
And 5: and (3) taking a micro-filtration membrane such as poly sulfoxide and ceramic as a supporting substrate, and carrying out suction filtration on the mixed membrane-making solution obtained in the step (2) to form a membrane on the surface of the substrate by using a filter under a negative pressure condition to obtain the carbon nitride based Fenton-photocatalytic nanofiltration membrane.
Example 4, Fenton-like photocatalytic nanofiltration membrane water purification performance test, including the following steps: .
Step 1: a simulated wastewater containing 10ppm of dye molecules and H at a concentration of 1mL/L was subjected to a negative pressure condition by using a Fenton-like photocatalytic nanofiltration membrane containing 1% iron phosphotungstate prepared in example 2 above, and then the simulated wastewater containing the dye molecules was subjected to a negative pressure condition2O2Through a nanofiltration membrane, through H2O2And (3) carrying out in-situ degradation on the pollutants by the synergistic action between the in-situ degradation product and the Fenton-like reagent.
Step 2: physical interception and H in nanofiltration membrane2O2Based on Fenton-like oxidation dye, the light intensity density is 100mWcm-2The simulated sunlight irradiates the surface of the membrane, and the removal capacity of pollutants is enhanced by means of Fenton-like reaction and photocatalysis, so that the surface self-cleaning of the nanofiltration membrane is realized.
FIG. 3 shows the carbon nitride Fenton-photocatalytic nanofiltration membrane prepared in example 2 under illumination and H conditions2O2In the presence of the catalyst, the reaction time is 0.5mL min-1The MB solution continuously flowing through the nanofiltration membrane has the performance of intercepting, degrading and oxidizing for 8 hours, and therefore, the nanofiltration membrane keeps the removal rate of MB molecules close to 100 percent and good membrane flux in a continuous operation period.
Fig. 4 shows the catalytic degradation effect of the carbon nitride fenton-photocatalytic nanofiltration membrane on trapped pollutants under simulated solar illumination, and the decolorization and degradation of MB molecules fully show that the catalytic oxidation process can well realize the self-cleaning effect of the surface of the nanofiltration membrane.
Claims (8)
1. A surface self-cleaning carbon nitride Fenton-like photocatalytic nanofiltration membrane consists of a graphite phase carbon nitride film forming material and a Fenton-like catalyst loaded on the surface of the graphite phase carbon nitride film forming material;
the method for preparing the surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane comprises the following steps:
1) preparing graphite-phase carbon nitride by using a nitrogen-containing compound as a nitrogen-containing precursor;
2) preparing a carbon nitride sol membrane preparation solution from the graphite-phase carbon nitride obtained in the step 1);
3) mixing the carbon nitride sol membrane-forming solution obtained in the step 2) with a precursor solution containing Fenton-like active metal ions, and loading a Fenton-like catalyst on the surface of a carbon nitride photocatalyst to obtain a mixed membrane-forming solution containing carbon nitride and the Fenton-like catalyst;
or 3') preparing a Fenton-like catalyst from a precursor containing Fenton-like active metal ions, and then mixing the carbon nitride sol membrane-forming solution obtained in the step 2) with the Fenton-like catalyst to obtain a mixed membrane-forming solution containing carbon nitride and the Fenton-like catalyst;
4) preparing a surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane;
in the step 2), the operation of preparing the carbon nitride sol membrane-forming solution from the graphite-phase carbon nitride obtained in the step 1) is a) or b) as follows:
a) obtaining carbon nitride nanosheets by ultrasonic liquid phase stripping, and screening the size of the stripped carbon nitride nanosheets by means of high-speed centrifugation to obtain carbon nitride sol with good dispersibility as membrane preparation liquid;
b) treating the graphite-phase carbon nitride obtained in the step 1) in an acid or alkali solution, and obtaining carbon nitride sol with good dispersibility as a membrane preparation solution through molecular cutting and high-speed centrifugation.
2. The method for preparing the surface self-cleaning type carbon nitride Fenton-photocatalytic nanofiltration membrane as claimed in claim 1, comprises the following steps:
1) preparing graphite-phase carbon nitride by using a nitrogen-containing compound as a nitrogen-containing precursor;
2) preparing a carbon nitride sol membrane preparation solution from the graphite-phase carbon nitride obtained in the step 1);
3) mixing the carbon nitride sol membrane-forming solution obtained in the step 2) with a precursor solution containing Fenton-like active metal ions, and loading a Fenton-like catalyst on the surface of a carbon nitride photocatalyst to obtain a mixed membrane-forming solution containing carbon nitride and the Fenton-like catalyst;
or 3') preparing a Fenton-like catalyst from a precursor containing Fenton-like active metal ions, and then mixing the carbon nitride sol membrane-forming solution obtained in the step 2) with the Fenton-like catalyst to obtain a mixed membrane-forming solution containing carbon nitride and the Fenton-like catalyst;
4) preparing a surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane;
in the step 2), the operation of preparing the carbon nitride sol membrane-forming solution from the graphite-phase carbon nitride obtained in the step 1) is a) or b) as follows:
a) obtaining carbon nitride nanosheets by ultrasonic liquid phase stripping, and screening the size of the stripped carbon nitride nanosheets by means of high-speed centrifugation to obtain carbon nitride sol with good dispersibility as membrane preparation liquid;
b) treating the graphite-phase carbon nitride obtained in the step 1) in an acid or alkali solution, and obtaining carbon nitride sol with good dispersibility as a membrane preparation solution through molecular cutting and high-speed centrifugation.
3. The method of claim 2, wherein: in step 1), the nitrogen-containing compound is: one or more of cyanamide, dicyandiamide, melamine, urea, thiourea and hexamethylenetetramine;
the nitrogen-containing compound is used as a precursor, and the graphite-phase carbon nitride is prepared by adopting high-temperature thermal polymerization or solution thermal synthesis.
4. The method of claim 2, wherein: in step 3), the Fenton-like catalyst is: metals having fenton-like activity, oxides, hydroxides, organic complexes of said metals;
wherein the metal having fenton-like activity is: one or more of iron, manganese, copper, cobalt and nickel.
5. The method of claim 2, wherein: and 4) taking the polymer or ceramic microfiltration membrane as a support substrate, and performing suction filtration on the mixed membrane preparation solution by using a filter under a negative pressure condition to obtain the surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane.
6. The use of the surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane as claimed in claim 1 in water treatment.
7. A method for water treatment by using the surface self-cleaning type carbon nitride Fenton-photocatalytic nanofiltration membrane as claimed in claim 1, which comprises the following steps: under the condition of illumination, the water body to be treated and H are mixed2O2And (3) mixing the solution and then passing the mixed solution through the surface self-cleaning carbon nitride Fenton-photocatalytic nanofiltration membrane.
8. The method of claim 7, wherein: the illumination conditions include an ultraviolet light source, simulated or actual sunlight.
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