CN112915805A - Preparation and application of polydopamine-modified graphite-phase carbon nitride/cobalt iron tungstate composite membrane - Google Patents
Preparation and application of polydopamine-modified graphite-phase carbon nitride/cobalt iron tungstate composite membrane Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a polydopamine-modified graphite-phase carbon nitride/cobalt iron tungstate composite membranexFe1‑xWO4A solid solution; then preparing g-C by a strong alkali shearing method3N4Fragmenting; then preparing the product in a reduced pressure suction filtration mode to obtain g-C3N4/CoxFe1‑xWO4PDA composite membrane. The composite membrane of the invention is in g-C3N4g-C under the combined action of PDA3N4/CoxFe1‑xWO4The PDA composite membrane shows good stability and the ability of photocatalytically activating peroxymonosulfate to degrade rhodamine B.
Description
Technical Field
The invention belongs to the field of combination of advanced oxidation technology and membrane treatment, and particularly relates to preparation of a polydopamine-modified graphite-phase carbon nitride/cobalt iron tungstate composite membrane and application of the polydopamine-modified graphite-phase carbon nitride/cobalt iron tungstate composite membrane in degradation of organic pollutants.
Background
Under the current situation of water resource shortage, water pollution seriously affects the life style and body health of people. Various organic pollutants in water can exist in the environment for a long time, and are difficult to effectively remove by adopting a conventional method. Therefore, the development of a technology capable of efficiently removing organic pollutants in water is not slow.
Rhodamine B, as a water-soluble dye, has certain carcinogenic toxicity. There are many methods for removing residual colored dyes in water, including membrane separation and chemical degradation. The membrane separation operation is simple, but the membrane is easy to be polluted and loses the retention capacity, and the advanced oxidation technology in the chemical method is widely concerned due to the high degradation rate of organic matters. PMS is taken as an oxidant, sulfate radicals with strong oxidizing capability can be generated, Co (II) can effectively catalyze and activate PMS, and in recent years, a Co (II) -containing nano material is often used as a catalyst to deactivate PMS and degrade organic pollutants. However, the powdery solid catalyst has low recovery efficiency and is difficult to recycle, and cobalt ions in the material are dissolved out, thereby causing secondary pollution to the environment. In view of the defects, the invention enhances the removal efficiency of organic matters in the water body while improving the recovery and utilization rate of the catalyst material by combining the membrane treatment with the chemical degradation.
The inventor searches the relevant content of the application as follows:
chinese knowledge network retrieval results: (202/1/17)
The first retrieval method comprises the following steps:
the discourse is the preparation and application of the poly dopamine modified graphite phase carbon nitride/cobalt iron tungstate composite membrane 0.
Discourse-preparation and application of a polydopamine modified graphite phase carbon nitride composite membrane 0.
The discourse is the preparation and application of the graphite phase carbon nitride/cobalt iron tungstate composite film 0.
And a second retrieval mode:
all-round-a preparation and application 0 item of a polydopamine modified graphite phase carbon nitride/cobalt iron tungstate composite membrane.
Preparation and application of poly-dopamine modified graphite phase carbon nitride composite film 5 items, all of which are compatible with CoxFe1-xWO4The material is irrelevant.
The whole text-a preparation and application of a graphite phase carbon nitride/cobalt iron tungstate composite film 0.
And a third retrieval mode:
keyword- -polydopamine modification 0 item.
Key word-graphite phase carbon nitride/cobalt iron tungstate composite film 0 item.
Keyword- - -g-C3N4/CoxFe1-xWO4item/PDA 0.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method of a Polydopamine (PDA) -modified graphite-phase carbon nitride/cobalt iron tungstate composite film and an application thereof in degradation of organic pollutants. Under illumination, the composite membrane can effectively degrade organic pollutants in water by activating PMS to generate free radicals with strong oxidizing capability, and has higher circulation stability.
The invention relates to a polydopamine modified graphite phase carbon nitride/cobalt iron tungstate composite film (g-C)3N4/CoxFe1-xWO4PDA) preparation method, firstly Co is prepared by hydrothermal reactionxFe1-xWO4(3:1) solid solution, then preparing g-C by a strong alkali shearing method3N4The fragments are simultaneously prepared into g-C in a reduced pressure suction filtration mode3N4/CoxFe1-xWO4PDA composite membrane.
The preparation method of the polydopamine modified graphite phase carbon nitride/cobalt iron tungstate composite membrane comprises the following steps:
step 1: coxFe1-xWO4(3:1) preparation of
Preparation of Co by hydrothermal methodxFe1-xWO4(3:1) solid solution. 1.35mmol of CoCl2·6H2O and 0.45mmol FeCl2·4H2O is added into 50mL deionized water in turn, stirred for 10min at 70 ℃, and then 1.8mmol of NaWO is added dropwise4·2H2O, then placing the mixed solution in a hydrothermal kettle and heating and reacting for 24 hours at 180 ℃; after the reaction is finished, cooling to room temperature, and sequentially filtering, washing and drying to obtain CoxFe1-xWO4(3:1) materials.
Step 2: g-C3N4Preparation of the chips
2a, placing 15g of melamine in a muffle furnace, calcining at 550 ℃ for 5h, cooling and mashing to obtain g-C3N4；
2b, dissolving 12g NaOH in 100mL H2O, 2.5g of g-C from step 2a are added to the NaOH solution obtained3N4Stirring for 48h at 60 ℃; pouring the solution into a dialysis bag (36mm dialysis bag, molecular weight cut-off 3500D) after alkaline washing, placing the solution into a large beaker filled with deionized water, dialyzing until the solution is neutral, taking out the solution, freeze-drying the solution, and obtaining g-C after drying3N4Fragmenting;
and step 3: g-C3N4/CoxFe1-xWO4Preparation of/PDA composite membrane
3a, respectively taking 30mg of the mixture prepared in the step 1Obtained CoxFe1-xWO4Materials and g-C from step 23N4Fragmentation in 10mL H2Dispersing with ultrasound, adding 40mg Dopamine (DA) and stirring at room temperature for 1h, adding 100mL Tris-HCl buffer solution (pH 8.5), stirring at 80 deg.C for 24h, collecting precipitate, and drying to obtain C3N4/CoxFe1-xWO4PDA composite material;
3b, taking 10mg of C prepared in the step 3a3N4/CoxFe1-xWO4The g-C is prepared by placing the PDA composite material in deionized water, performing ultrasonic dispersion, then performing vacuum filtration on an acetate fiber membrane3N4/CoxFe1-xWO4PDA composite membrane.
The application of the polydopamine-modified graphite-phase carbon nitride/cobalt iron tungstate composite membrane prepared by the invention is to use the polydopamine-modified graphite-phase carbon nitride/cobalt iron tungstate composite membrane as a catalyst when organic pollutants in water are removed by catalytic degradation.
Further, the polydopamine-modified graphite-phase carbon nitride/cobalt iron tungstate composite membrane can effectively catalyze and activate PMS to generate free radicals with strong oxidation capacity, so that organic pollutants in a water body are effectively degraded, and meanwhile, the polydopamine-modified graphite-phase carbon nitride/cobalt iron tungstate composite membrane has high cycle stability.
Further, the organic contaminants include rhodamine B and the like.
In the specific catalytic degradation process, the volume of the reactor is 15mL, and the organic pollutant solution passes through the composite membrane at the flow rate of 0.6mL/min in the reaction process; during catalytic degradation, potassium hydrogen Persulfate (PMS) is used as an oxidant, and the concentration of PMS is 100 mg/L; the power of the xenon lamp is 500W, the luminous flux is 14200Lm, and the parallel illuminance is 5 multiplied by 105The output light power is 10W, and the distance between the reactor and the xenon lamp is 5-6 cm.
CoxFe1-xWO4(3:1) As a solid solution catalyst, it can activate PMS effectively by itself but has poor stability, and C after strong alkali shearing3N4In addition to enhancing the reactive active sites, can react with CoxFe1-xWO4Joined together to improve the stability of the materialAnd (5) performing qualitative determination. PDA has certain visible light absorption capacity, and is used as a coupling agent, so that the stability of the composite film is enhanced, the photocatalytic capacity of the material is improved, and the composite film is favorable for absorbing light energy to generate active free radicals. Under the illumination of visible light, the catalyst composite membrane formed by an acetate fiber touch mode is relied on, the smaller membrane aperture can improve the retention time of fluid and the retention rate of organic matters, the degradation of the organic matters by oxidation free radicals generated on the catalyst is facilitated, meanwhile, the membrane aperture can be prevented from being blocked by macromolecular organic matters, and the membrane flux is stabilized.
g-C obtained by the invention3N4/CoxFe1-xWO4The surface diameter of the PDA composite membrane is 3cm, and the area of the composite material loaded on the membrane is 7.5cm2The specific surface area is large, the solution can be contacted with the solution more fully, and the removal rate of target pollutants is improved.
g-C prepared by the invention3N4/CoxFe1-xWO4the/PDA composite membrane can activate Peroxymonosulfate (PMS) to generate sulfate radicals under the irradiation of visible light by utilizing a photocatalytic advanced oxidation technology, and target pollutants are degraded by the strong oxidation capability of the radicals.
Invention g-C3N4/CoxFe1-xWO4The PDA composite membrane has the capability of absorbing visible light, and can effectively absorb light energy to activate Peroxymonosulfate (PMS) under the condition of simulating sunlight irradiation, so that sulfate radicals are generated to degrade organic pollutants. The light source used for simulating sunlight is a 500W xenon lamp, and a 420nm cut-off filter is used at the same time.
Invention g-C3N4/CoxFe1-xWO4the/PDA composite material is a two-dimensional nano material, the aperture of the composite membrane is small, the contact time with a target pollutant can be prolonged while the retention rate is improved, so that the reaction time of free radicals generated by photocatalysis and the target pollutant is prolonged, and the removal rate of the target pollutant is improved.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the invention has the advantages of easy raw materialLow cost, simple synthesis steps, easy operation, g-C3N4/CoxFe1- xWO4the/PDA composite membrane has good stability, is easy to recover and can be recycled for multiple times.
2. The polydopamine modified g-C of the invention3N4/CoxFe1-xWO4the/PDA composite membrane has the capability of absorbing visible light, can effectively activate PMS to generate active free radicals, and can degrade organic matters by a photocatalytic advanced oxidation technology.
3、g-C3N4Can be reacted with CoxFe1-xWO4The materials are compounded, and simultaneously, the PDA is wrapped on the surface of the composite material to play a role in connection. The polydopamine modified g-C of the invention before and after the reaction3N4/CoxFe1-xWO4The PDA composite membrane can keep the stability of the structure thereof, thereby having higher and stable photocatalytic degradation efficiency.
Drawings
FIG. 1 is g-C3N4/CoxFe1-xWO4PDA composite membrane.
FIG. 2 is g-C3N4/CoxFe1-xWO4XRD pattern of/PDA composite material. Strong peaks exist at 18.98 °, 30.52 °, 36.22 ° and 53.92 ° of 2 θ, corresponding to crystal planes of (100), (-111), (021) and (-221), and diffraction peaks of these samples appear at positions corresponding to those of CoxFe1-xWO4The materials are similar. The diffraction peak intensity is higher, the peak shape is sharp, and the crystallization degree is higher. But in g-C3N4/CoxFe1-xWO4No g-C observed in the/PDA composite3N4Probably due to encapsulation of PDA, resulting in g-C3N4The crystallinity of (a) is decreased, so that its characteristic peak cannot be observed.
FIG. 3 is g-C3N4/CoxFe1-xWO4TEM image of/PDA composite. PDA is wrapped in g-C3N4And CoxFe1-xWO4The nanosheets have surfaces which are bonded together to form a composite. The stability of the composite material is enhanced while the visible light absorption capacity is improved.
FIG. 4 is g-C3N4/CoxFe1-xWO4Schematic diagram of equipment for performing photocatalytic membrane treatment on a PDA composite membrane.
FIG. 5 is g-C3N4/CoxFe1-xWO4The adsorption efficiency of the PDA film on RhB is shown. The RhB concentration is 10mg/L, the retention rate of the membrane to RhB is 55.6% at 10min, and then the retention rate begins to decrease, and the adsorption-desorption balance is achieved at 60min, and the retention rate reaches 7.5%. Before each photocatalytic degradation, the membrane needs to reach a state of adsorption saturation so as to explore the degradation effect of the membrane on organic matters. The membrane flux stabilized at 0.6mL/min over 1 h.
FIG. 6 is g-C3N4/CoxFe1-xWO4Time-removal rate diagram of degradation of RhB by PMS through chemical catalysis of PDA composite membrane. Adsorption-desorption balance is achieved before chemical catalysis, the average removal rate within 30min is 87.1%, the aim of completely removing RhB cannot be achieved, and the degradation capability of RhB can be improved by introducing illumination.
FIG. 7 is g-C3N4/CoxFe1-xWO4The removal efficiency of RhB when the/PDA composite membrane is subjected to photocatalytic membrane treatment is shown. The concentration of the oxidant PMS was 100 mg/L. The adsorption-desorption equilibrium is reached before photocatalysis, the removal rate in the first 5min is 88.6 percent, which is lower than the average removal rate of 98.6 percent in the last 25min, and the RhB which is saturated in adsorption on the filter is supposed to be desorbed in the first 5 min. Under illumination, the composite film activates PMS through absorbing light energy to generate more oxidation free radicals, so that the degradation efficiency of RhB is improved, and the RhB is almost completely removed.
FIG. 8 shows different ratios of CoxFe1-xWO4And (3) carrying out chemical catalysis on the material to activate the degradation efficiency diagram of PMS to RhB. The concentration of oxidant PMS is 100mg/L, 10mg of the materials with different proportions are added into 100mL of RhB solution with the concentration of 10mg/L to serve as a catalyst, and the reaction temperature is controlled at 30 ℃. As can be seen from the graph, when the reaction time was 10min,the degradation rate of RhB in the system with the cobalt-iron ratio of 3:1 is 91.8%, and the degradation rates in the systems with the cobalt-iron ratios of 2:1 and 1:1 are respectively 86.0% and 68.4%. From this, CoxFe1-xWO4(3:1) the ability of catalytic activation of PMS to degrade RhB is stronger than that of the other two mixture ratios.
FIG. 9 is a graph showing the efficiency of removing RhB from graphite phase carbon nitride composite films of different compositions. g-C alone3N4The average removal rate of the composite membrane in 30min is 28.9 percent, g-C3N4The average removal rate of the PDA composite membrane in 30min is 57.2%, but the removal rates of the PDA composite membrane and the PDA composite membrane are both lower than g-C3N4/CoxFe1-xWO4The average removal rate of the/PDA composite membrane in half an hour is 97.0%. Modification of PDA enhances g-C3N4Composite membrane catalytic activation of PMS, CoxFe1-xWO4The removal effect of the composite film on RhB is further enhanced by the doping of the material.
Detailed Description
Example 1: preparation of the target product
(1)CoxFe1-xWO4(3:1) preparation of
Preparation of Co by hydrothermal methodxFe1-xWO4(3:1) solid solution. 1.35mmol of CoCl2·6H2O and 0.45mmol FeCl2·4H2O is added into 50mL deionized water in turn, stirred for 10min at 70 ℃ and added dropwise with 1.8mmol NaWO4·2H2O, then placing the mixed solution in a hydrothermal kettle, heating for 24 hours at 180 ℃, cooling to room temperature, filtering, washing and drying to obtain CoxFe1-xWO4(3:1) materials.
(2)g-C3N4Preparation of the chips
Placing 15g of melamine in a muffle furnace, calcining at 550 ℃ for 5h, cooling and mashing to obtain g-C3N4。
Dissolve 12g NaOH in 100mL H2To the solution was added 2.5g g-C3N4And stirred at 60 ℃ for 48 h. After the completion of the alkaline washing, the solution was poured into a dialysis bag and placed in a bag containing deionized waterDialyzing in a big beaker until the solution is neutral, taking out, freeze-drying, and obtaining g-C after drying3N4And (4) fragmenting.
(3)g-C3N4/CoxFe1-xWO4Preparation of/PDA composite membrane
30mg of Co are respectively takenxFe1-xWO4(3:1)、g-C3N4Fragmentation in 10mL H2O, after ultrasonic dispersion, 40mg of Dopamine (DA) was added to the solution and stirred at room temperature for 1 hour, then 100mL of Tris-HCl buffer (pH 8.5) was added, the reaction was stirred at 80 ℃ for 24 hours, and the precipitate was collected and dried to obtain g-C3N4/CoxFe1-xWO4the/PDA composite material is prepared by placing 10mg of the material in deionized water, ultrasonically dispersing, vacuum filtering on acetate fiber membrane to obtain g-C3N4/CoxFe1-xWO4PDA composite membrane.
Example 2: g-C3N4/CoxFe1-xWO4Adsorption of PDA composite membrane to RhB
The concentration of RhB is 10mg/L, the mass of the material on the composite membrane is 10mg, the flow rate is stabilized at 0.6mL/min by adjusting the height difference of the liquid level, 1mL of effluent liquid is taken every 5min, and the absorbance is measured after the effluent liquid is diluted by 5 times. The RhB concentrations before and after adsorption were measured using an ultraviolet-visible spectrophotometer (754 PC).
Along with the adsorption process, the rejection rate of the composite membrane to RhB gradually decreases, and after 1h, the rejection rate is about 7.5%, so that the adsorption saturation state of the membrane is reached. To explore g-C next3N4/CoxFe1-xWO4The degradation efficiency of the PDA composite membrane activated PMS to degrade RhB is provided as a control.
Example 3: g-C3N4/CoxFe1-xWO4Chemical catalysis removal of RhB by PDA composite membrane
The concentration of PMS is 100mg/L, the concentration of RhB is 10mg/L, the mass of the material on the composite membrane is 10mg, 1mL of effluent liquid is taken every 5min, 1mL of methanol is added as a quenching agent, and the absorbance of the effluent liquid is measured after dilution. The RhB concentration was measured using an ultraviolet-visible spectrophotometer (754 PC).
g-C3N4/CoxFe1-xWO4the/PDA composite material can activate PMS to generate free radicals with strong oxidizing property, so that the oxidizing agent PMS is added to effectively degrade RhB, and the removal rate is improved. The average value of the removal rate of the composite membrane to RhB within 1h is 87.1%, and the degradation rate obtained by subtracting the adsorption rate of the composite membrane to RhB is about 79.6%. The chemical catalytic PMS of the composite film can not completely remove RhB, and the degradation capability of RhB is improved by considering the introduction of illumination.
Example 4: g-C3N4/CoxFe1-xWO4Method for removing RhB by treating/PDA composite membrane with photocatalytic membrane
The light source adopts a xenon lamp (500W, 420nm cut), the concentration of PMS is 100mg/L, the concentration of RhB is 10mg/L, the mass of the material on the composite film is 10mg, and the concentration of RhB is detected by an ultraviolet-visible spectrophotometer (754 PC).
Under photocatalysis, the removal rate reaches 99.7 percent once, the average value in 30min is 97.0 percent, the filtrate is colorless, and the RhB is nearly completely removed. g-C3N4/CoxFe1-xWO4The PDA composite material activates PMS to generate free radicals with strong oxidizing property by absorbing light energy, and the removal efficiency of RhB in an aqueous solution is improved.
Example 5: co of different proportionsxFe1-xWO4Material activation PMS degradation RhB
Preparation of Co with different Co-Fe molar ratiosxFe1-xWO4The activation capability of the powder material on PMS is researched in different proportions. Cobalt to iron ratio 2:1 Material 1.2mmol CoCl was used2·6H2O and 0.6mmol FeCl2·4H2O, cobalt to iron ratio 1:1 material 0.9mmol CoCl was used2·6H2O and 0.9mmol FeCl2·4H2O, preparation method is the same as CoxFe1-xWO4(3:1). The concentration of oxidant PMS is 100mg/L, 10mg of the materials with different proportions are added into 100mL of RhB solution with the concentration of 10mg/L to be used as a catalyst, and the reaction temperature is controlled at 30 ℃.
Reaction time is 15minThe degradation rate of RhB in a system with a cobalt-iron ratio of 3:1 is 97.4%, and the degradation rate is nearly completely removed, and at the moment, the degradation rate of RhB in a system with a cobalt-iron ratio of 2:1 is 94.9%. And when the reaction time is 25min, the RhB degradation rate in a system with the cobalt-iron ratio of 1:1 reaches 95.3%. From this, CoxFe1-xWO4(3:1) the ability of catalytic activation of PMS to degrade RhB is stronger than that of the other two mixture ratios.
Example 6: preparing graphite phase carbon nitride composite films with different compositions and activating PMS to degrade RhB
(1)g-C3N4Composite film and g-C3N4Preparation of/PDA composite membrane
Taking 10mg g-C3N4Putting the fragments into deionized water, performing ultrasonic dispersion, and performing vacuum filtration on an acetate fiber membrane to obtain g-C3N4A composite membrane.
Taking 30mg g-C3N4Fragmentation in 10mL H2O, adding 40mg of Dopamine (DA) after ultrasonic dispersion, stirring at room temperature for 1h, then adding 100mL of Tris-HCl buffer solution (pH 8.5), stirring at 80 ℃ for 24h, collecting precipitate, and drying to obtain g-C3N4the/PDA composite material is prepared by placing 10mg of the material in deionized water, ultrasonically dispersing, vacuum filtering on acetate fiber membrane to obtain g-C3N4PDA composite membrane.
(2)g-C3N4Composite film and g-C3N4PDA composite membrane activated PMS degradation RhB
The light source adopts a xenon lamp (500W, 420nm cut), the concentration of an oxidant PMS is 100mg/L, the concentration of RhB is 10mg/L, the flow rate of the solution is controlled at 0.6mL/min, and PDA and Co are exploredxFe1-xWO4The effect of incorporation on removal efficiency, the concentration of RhB was measured using an ultraviolet-visible spectrophotometer (754 PC).
g-C within 30min3N4Composite film and g-C3N4The average removal rate of the PDA composite film to RhB is respectively 28.9% and 57.2%, and the doping of PDA effectively improves the utilization of the composite film to light energy under illumination, but does not completely remove 10mg/L RhB solution. And g-C3N4/CoxFe1-xWO4The average removal rate of the PDA composite membrane in half an hour reaches 97.0 percent, the solution flowing out of the reactor is nearly colorless, and Co is removedxFe1-xWO4The incorporation of (2) improves the activation of the oxidant PMS, thereby generating a large number of active free radicals to enhance the removal capability of RhB.
Claims (7)
1. A preparation method of a polydopamine modified graphite phase carbon nitride/cobalt iron tungstate composite membrane is characterized by comprising the following steps: firstly, Co is prepared by hydrothermal reactionxFe1-xWO4A solid solution; then preparing g-C by a strong alkali shearing method3N4Fragmenting; then preparing the product in a reduced pressure suction filtration mode to obtain g-C3N4/CoxFe1-xWO4PDA composite membrane.
2. The method of claim 1, comprising the steps of:
step 1: coxFe1-xWO4Preparation of
Adding CoCl2·6H2O and FeCl2·4H2Sequentially adding O into deionized water, stirring at 70 deg.C for 10min, and dropwise adding NaWO4·2H2O, then placing the mixed solution in a hydrothermal kettle and heating and reacting for 24 hours at 180 ℃; after the reaction is finished, cooling to room temperature, and sequentially filtering, washing and drying to obtain CoxFe1-xWO4A material;
step 2: g-C3N4Preparation of the chips
2a, putting melamine into a muffle furnace, calcining at 550 ℃ for 5h, cooling and mashing to obtain g-C3N4；
2b, adding g-C prepared in the step 2a into NaOH solution3N4Stirring at 60 deg.C for 48 hr, pouring into dialysis bag after alkaline washing, placing into a beaker filled with deionized water, dialyzing until the solution is neutral, taking out, freeze drying, and drying to obtain g-C3N4Fragmenting;
and step 3: g-C3N4/CoxFe1-xWO4Preparation of/PDA composite membrane
3a, respectively taking the Co prepared in the step 1xFe1-xWO4Materials and g-C from step 23N4Fragment in H2Adding dopamine after uniform ultrasonic dispersion, stirring at room temperature for 1h, adding a Tris-HCl buffer solution with the pH of 8.5, stirring at 80 ℃ for 24h, collecting precipitates, and drying to obtain the compound C3N4/CoxFe1-xWO4PDA composite material;
3b, taking C prepared in the step 3a3N4/CoxFe1-xWO4The g-C is prepared by placing the PDA composite material in deionized water, performing ultrasonic dispersion, then performing vacuum filtration on an acetate fiber membrane3N4/CoxFe1-xWO4PDA composite membrane.
3. The method of claim 2, wherein:
in step 1, prepared CoxFe1-xWO4The molar ratio of cobalt to iron in the material was 3: 1.
4. The method of claim 2, wherein:
g-C in composite membranes3N4、CoxFe1-xWO4The mass ratio to PDA was 3:3: 4.
5. The application of the polydopamine-modified graphite-phase carbon nitride/cobalt iron tungstate composite film obtained by the preparation method according to claim 1, 2, 3 or 4 is characterized in that: the composite membrane is used as a catalyst when organic pollutants in a water body are removed through catalytic degradation.
6. Use according to claim 5, characterized in that:
the composite membrane can effectively catalyze and activate PMS to generate free radicals with strong oxidizing capability under the irradiation of visible light, so that organic pollutants in a water body are effectively degraded, and meanwhile, the composite membrane has high circulation stability.
7. Use according to claim 5 or 6, characterized in that:
the organic contaminant comprises rhodamine B.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114602531A (en) * | 2022-04-18 | 2022-06-10 | 郑州大学 | Carbon-dot-confinement quantum-dot-modified efficient graphite-phase carbon nitride-based photocatalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170232427A1 (en) * | 2016-02-16 | 2017-08-17 | The George Washington University | Doped graphitic carbon nitrides, methods of making and uses of the same |
| CN108283932A (en) * | 2017-12-21 | 2018-07-17 | 江苏大学 | A kind of C3N4@Ag3PO4The preparation and application thereof of/PDA@PVDF bionic composite catalyst films |
| CN108854588A (en) * | 2018-07-09 | 2018-11-23 | 河北工业大学 | A kind of preparation method and application of the hollow fiber ceramic membrane with dual persulfate mobilizing function |
-
2021
- 2021-01-21 CN CN202110079993.6A patent/CN112915805B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170232427A1 (en) * | 2016-02-16 | 2017-08-17 | The George Washington University | Doped graphitic carbon nitrides, methods of making and uses of the same |
| CN108283932A (en) * | 2017-12-21 | 2018-07-17 | 江苏大学 | A kind of C3N4@Ag3PO4The preparation and application thereof of/PDA@PVDF bionic composite catalyst films |
| CN108854588A (en) * | 2018-07-09 | 2018-11-23 | 河北工业大学 | A kind of preparation method and application of the hollow fiber ceramic membrane with dual persulfate mobilizing function |
Non-Patent Citations (4)
| Title |
|---|
| HAMED HEIDARPOUR ET AL.: "《Enhanced decolorization of rhodamine B solution through simultaneous photocatalysis and persulfate activation over Fe/C3N4 photocatalyst》", 《CHEMICAL ENGINEERING RESEARCH AND DESIGN》, vol. 153, 12 November 2019 (2019-11-12), pages 709 - 720 * |
| SHIZONG WANG ET AL.: "《Peroxymonosulfate Activation by Fe–Co–O-Codoped Graphite Carbon Nitride for Degradation of Sulfamethoxazole》", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY》, vol. 54, no. 16, 16 July 2020 (2020-07-16), pages 10361 - 10369 * |
| YUCHUAN LIU ET AL.: "《Super hydrophilic composite membrane with photocatalytic degradation and self-cleaning ability based on LDH and g-C3N4》", 《JOURNAL OFMEMBRANESCIENCE》, vol. 617, 6 August 2020 (2020-08-06), pages 118504, XP086272083, DOI: 10.1016/j.memsci.2020.118504 * |
| 李飞: "《多巴胺改性g-C3N4光催化剂的制备及其光催化石墨烯复合膜的性能研究》", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑(月刊)》, 15 July 2019 (2019-07-15), pages 31 - 51 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114602531A (en) * | 2022-04-18 | 2022-06-10 | 郑州大学 | Carbon-dot-confinement quantum-dot-modified efficient graphite-phase carbon nitride-based photocatalyst and preparation method and application thereof |
| CN114602531B (en) * | 2022-04-18 | 2023-06-23 | 郑州大学 | Efficient graphite-phase carbon nitride-based photocatalyst modified by carbon dot confinement quantum dots, and preparation method and application thereof |
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