Photocatalytic oil-water separation material and preparation method thereof
11413609 · 2022-08-16
Assignee
Inventors
- Yucheng LIU (Chengdu, CN)
- Meng ZHU (Chengdu, CN)
- Mingyan CHEN (Chengdu, CN)
- Zhicheng PAN (Chengdu, CN)
- Maoren WANG (Chengdu, CN)
- Lian QIU (Chengdu, CN)
- Maoqi LIAO (Chengdu, CN)
- Bing Yang (Chengdu, CN)
- Dong GAN (Chengdu, CN)
Cpc classification
C02F1/40
CHEMISTRY; METALLURGY
B01J31/2239
PERFORMING OPERATIONS; TRANSPORTING
C02F1/288
CHEMISTRY; METALLURGY
B01J37/10
PERFORMING OPERATIONS; TRANSPORTING
B01J31/1691
PERFORMING OPERATIONS; TRANSPORTING
International classification
C02F1/40
CHEMISTRY; METALLURGY
B01J35/00
PERFORMING OPERATIONS; TRANSPORTING
B01J31/16
PERFORMING OPERATIONS; TRANSPORTING
B01J37/10
PERFORMING OPERATIONS; TRANSPORTING
B01J37/34
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The invention relates to a photocatalytic oil-water separation material and a preparation method thereof, the method including the following steps: cleaning a base material and a metal-doped material, and drying for later use; preparing a mixed solution of an amine monomer and an acid-alkali buffer reagent, soaking the base material in the mixed solution, and reacting under an oscillation condition, to obtain the base material attached with amine monomer polymer; dissolving a soluble metal additive and an organic ligand reagent into an organic solvent, and performing ultrasonic stirring uniformly, to obtain a metal organic framework material (MOF) reaction solution with photocatalytic performance; and placing the metal-doped material, the base material attached with the amine and the MOF reaction solution into a reaction kettle for performing hydrothermal reaction, cleaning and drying the reacted base material, to obtain the photocatalytic oil-water separation material.
Claims
1. A preparation method of a photocatalytic oil-water separation material comprising the following steps: step S1, sequentially cleaning a base material and a metal-doped material by using an alcohol solvent, a dilute acid solution and deionized water, and drying for later use; step S2, preparing a mixed solution of an amine monomer and an acid-alkali buffer reagent, soaking the base material in the mixed solution, and reacting under an oscillation condition, to obtain the base material attached with amine monomer polymer; step S3, dissolving a soluble metal additive and an organic ligand reagent comprising carboxylic acid or pyridine into an organic solvent, and uniformly performing ultrasonic stirring, to obtain a photocatalytic Metal-Organic Frameworks (MOFs) reaction solution; step S4, placing the metal-doped material in the step S1, the base material that has been reacted in the step S2 and the MOFs reaction solution obtained in the step S3 into a reaction kettle for performing hydrothermal reaction; and step S5, cleaning excess impurities on surfaces of the base material that has been reacted in the step S4 by using anhydrous methanol or anhydrous ethanol and then drying, to obtain the photocatalytic oil-water separation material; and wherein a metal element comprised in the soluble metal additive is different from that of the metal-doped material, and a main metal component comprised in the base material is different from the metal element of the metal-doped material wherein the base material in the step S1 is a stainless steel wire mesh; the metal-doped material is a copper mesh; the soluble metal additive in the step S3 is zirconium chloride.
2. The preparation method as claimed in claim 1, wherein the alcoholic solvent in the step S1 is the anhydrous methanol, with a mass fraction of 95%-99.9%; the diluted acid solution is diluted hydrochloric acid, with a concentration of 0.25-1.0 M.
3. The preparation method as claimed in claim 1, wherein the amine monomer in the step S2 is dopamine hydrochloride, with a concentration of 0.5-2.5 mg/mL; the acid-alkali buffer reagent is a tris (hydroxymethyl) aminomethane hydrochloride reagent, with a concentration of 0.05-0.2 mg/L; and a pH value of the mixed solution is 8-9.
4. The preparation method as claimed in claim 3, wherein a specific operation of the step S2 is as follows: preparing an amine monomer solution, and then adjusting a pH value of the amine monomer solution to 8.5 by using a buffer solution and a sodium hydroxide solution, adding the base material obtained in the step S1 within 10 seconds, and reacting for 12-24 hours at a constant temperature under conditions that a temperature is 20-80° C. and a stirring speed is 60-180 r/min, to obtain the base material attached with amine monomer polymer.
5. The preparation method as claimed in claim 1, wherein in the step S3, a concentration of the soluble metal additive in the MOFs reaction solution is 10-30 mM; the organic ligand reagent comprising the carboxylic acid or the pyridine is 2-aminoterephthalic acid, with a concentration of 10-30 mM; the organic solvent is N, N-dimethylformamide.
6. The preparation method as claimed in claim 1, wherein in the step S4, a quantity ratio of the base material to the metal-doped material is 2:1-10:1, both the base material and the metal-doped material soaked in the MOFs reaction solution; a time of the hydrothermal reaction is 6-24 hours, and a reaction temperature of the hydrothermal reaction is 100-180° C.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(10) In order to more clearly understand and implement the technical features, objects, and advantages of the present disclosure for one of ordinary skilled in the related art, the principles and characteristics of the present disclosure are described on the basis of these drawings and embodiments; the examples cited are provided only to interpret the present disclosure, but not to limit the scope of the present disclosure.
(11) Chemical raw materials used in the present disclosure are chemically pure unless otherwise specified.
A First Embodiment
(12) Step S1, material pretreatment: cutting a stainless steel wire mesh taken as a base material and a copper mesh taken as a metal-doped material into circles with a diameter of 4 cm, soaking the circles in anhydrous ethanol, hydrochloric acid and pure water, ultrasonically cleaning the circles for 30 minutes to remove surface oxides and grease, and drying the circles for later use. A pore size of the base material is 400 meshes.
(13) Step S2, Further treatment of the base material: preparing a tris (hydroxymethyl) aminomethane hydrochloride buffer solution with a concentration of 0.1 mg/L, a dopamine hydrochloride solution with a concentration of 2 mg/L, and a sodium hydroxide solution with a concentration of 0.5 M, adjusting a pH value of the dopamine hydrochloride solution by using the buffer solution and the sodium hydroxide solution, to obtain a mixed solution with the pH value of 8.5, soaking the stainless steel wire mesh obtained in the step S1 in the mixed solution, oscillating and reacting for 24 hours in a constant-temperature gas bath at a temperature of 60° C., cleaning the stainless steel wire mesh after the above reaction until the water is clear, and drying at the temperature of 60° C. for later use.
(14) Step S3, preparation of MOFs reaction solution: adding zirconium chloride and 2-aminoterephthalic acid into an N,N-dimethylformamide solvent, respectively, performing ultrasonic full dissolution, and uniformly mixing the two solutions to obtain the MOFs reaction solution, wherein a concentration of the zirconium chloride is 25 mM, and a concentration of the 2-aminoterephthalic acid is 30 mM.
(15) Step S4, preparation of the oil-water separation material: placing the copper mesh in the step S1 and the stainless steel wire mesh in the step S2 into a polytetrafluoroethylene reaction kettle, adding 50 ml MOFs reaction solution in the step S3, and reacting at 180° C. for 12 hours.
(16) Step S5, cleaning the stainless steel wire mesh obtained in the step S4 by using the anhydrous ethanol for 3-5 times, and drying at 60° C. to obtain the photocatalytic oil-water separation material of the present disclosure.
(17) In the first embodiment of the present disclosure, the copper mesh taken as the metal-doped material can be reused after being cleaned by the anhydrous ethanol, a diluted acid solution and pure water, so as to reduce the waste of resources, and the production cost.
A Second Embodiment
(18) A preparation method of the photocatalytic oil-water separation material of the embodiment is as follows:
(19) step S1, material pretreatment: cutting a base material and a metal-doped material into circles with a diameter of 4 cm, ultrasonically cleaning the base material and the metal-doped material in the anhydrous ethanol, hydrochloric acid and pure water for 30 minutes, to remove surface oxides and grease, and drying the base material and the metal-doped material in a vacuum drying oven for later use; the base material is cotton cloth, and the metal-doped material is a copper mesh; preparing tris (hydroxymethyl) aminomethane hydrochloride into a buffer solution with a concentration of 0.1 mg/L, and sodium hydroxide into a solution with a concentration of 0.5 M.
(20) step S2, adjusting a pH value of a dopamine hydrochloride solution (2.0 mg/mL) to 8.5 by using the buffer solution and the sodium hydroxide solution obtained in the step S1, placing the cotton cloth obtained in the step S1 therein, oscillating and reacting for 24 hours in a constant-temperature gas bath at a temperature of 60° C., cleaning the cotton cloth after the reaction until the water is clear, and drying at the temperature of 60° C. for later use.
(21) step S3, preparation of the MOFs reaction solution: adding zirconium chloride and 2-aminoterephthalic acid into an N,N-dimethylformamide solvent, respectively, performing ultrasonic dissolution, and uniformly mixing and stirring the two solutions for 30 minutes; wherein a concentration of the zirconium chloride is 10 mM, and a concentration of the 2-aminoterephthalic acid is 15 mM.
(22) step S4, placing the cotton cloth in the step S2 and the copper mesh in the step S1 into a polytetrafluoroethylene reaction kettle, adding 40 mL MOFs reaction solution obtained in the step S3, and performing hydrothermal reaction at a temperature of 120° C. for 12 hours.
(23) step S5, cleaning the base material obtained in the step S4 by using the anhydrous methanol for 3-5 times, and drying at 60° C. to obtain the photocatalytic oil-water separation material of the present disclosure.
(24) In the second embodiment of the present disclosure, the copper mesh taken as the metal-doped material can be reused after being cleaned by the anhydrous ethanol, a diluted acid solution and pure water, so as to reduce the waste of resources, and the production cost.
A Third Embodiment
(25) A preparation method of the photocatalytic oil-water separation material of the embodiment is as follows:
(26) step S1, material pretreatment and preparation of acid-alkali buffer solution: cutting an iron mesh and a foam copper into squares of 4×4 cm, and ultrasonically cleaning the squares in anhydrous ethanol, diluted sulfuric acid and pure water for 30 minutes for later use; preparing a tris (hydroxymethyl) aminomethane hydrochloride buffer solution with a concentration of 0.1 mg/L, and a sodium hydroxide solution (0.5 M).
(27) step S2, placing the iron mesh obtained in the step S1 in a dopamine hydrochloride solution with a concentration of 1 mg/L, adjusting a pH value of the dopamine hydrochloride solution to 8.5 by using the buffer solution and the sodium hydroxide solution prepared in the step S1, oscillating and reacting for 24 hours at 60° C., cleaning with pure water, and drying at 60° C. for later use.
(28) step S3, preparation of the MOFs reaction solution: adding ferric trichloride and terephthalic acid into a mixed solution of DMF and anhydrous methanol, respectively, performing ultrasonic dissolution, and uniformly mixing and stirring for 30 minutes; wherein a concentration of the ferric trichloride is 20 mM, and a concentration of the terephthalic acid is 25 mM.
(29) step S4, placing the iron mesh in the step S2 and the foam copper in the step S1 into a polytetrafluoroethylene reaction kettle, adding 40 mL MOFs reaction solution obtained in the step S3, and performing hydrothermal reaction at the temperature of 120° C. for 8 hours.
(30) step S5, cleaning the iron mesh obtained in the step S4 with the anhydrous methanol for 3-5 times, and drying at 60° C. to obtain the photocatalytic oil-water separation material of the present disclosure.
(31) In the third embodiment of the present disclosure, the foam copper taken as the metal-doped material can be reused after being cleaned by the anhydrous ethanol, a diluted acid solution and pure water, so as to reduce the waste of resources, and the production cost.
A Fourth Embodiment
(32) A preparation method of the photocatalytic oil-water separation material of the embodiment is as follows:
(33) step S1, material pretreatment and preparation of acid-alkali buffer solution: cutting a titanium mesh and a copper mesh into squares of 4×4 cm, and ultrasonically cleaning the squares in anhydrous ethanol, diluted hydrochloric acid and pure water for 30 minutes for later use; preparing a sodium dihydrogen phosphate-citric acid buffer reagent with a concentration of 0.1 mg/L and a sodium hydroxide solution with a concentration of 0.5M.
(34) step S2, preparing a dopamine hydrochloride solution with a concentration of 2 mg/mL, adjusting a pH value to 8.5 by using the buffer reagent and the sodium hydroxide solution obtained in the step S1, placing the titanium mesh obtained in the step S1 in the mixed solution with the pH value of 8.5, oscillating and reacting for 20 hours at 60° C., cleaning with pure water, and drying at 60° C. for later use.
(35) step S3, preparation of the MOFs reaction solution: adding titanic acid and 2,5-dihydroxy terephthalic acid into a mixed solution of DMF and anhydrous methanol, respectively, uniformly mixing by ultrasonic waves and stirring for 30 minutes, wherein a concentration of the titanic acid is 20 mM, and a concentration of the 2,5-dihydroxy terephthalic acid is 25 mM.
(36) step S4, placing the titanium mesh in the step S2 and the copper mesh in the step S1 into a polytetrafluoroethylene reaction kettle, adding 40 mL MOFs reaction solution obtained in the step S3, and performing hydrothermal reaction at the temperature of 120° C. for 8 hours.
(37) step S5, cleaning the titanium mesh obtained in the step S4 with the anhydrous methanol for 3-5 times, and drying at 60° C. to obtain the photocatalytic oil-water separation material of the present disclosure.
(38) In the fourth embodiment of the present disclosure, the copper mesh taken as the metal-doped material can be reused after being cleaned by the anhydrous ethanol, a diluted acid solution and pure water, so as to reduce the waste of resources, and the production cost.
A Fifth Embodiment
(39) A preparation method of the photocatalytic oil-water separation material of the embodiment is as follows:
(40) step S1, material pretreatment and preparation of buffer solution: cutting a stainless steel wire mesh and a titanium mesh into squares of 4×4 cm, and ultrasonically cleaning the squares in anhydrous ethanol, diluted hydrochloric acid and pure water for 30 minutes, and drying the stainless steel wire mesh and the titanium mesh for later use; preparing a sodium dihydrogen phosphate-citric acid buffer reagent with a concentration of 0.1 mg/L and a sodium hydroxide solution with a concentration of 0.5 M.
(41) step S2, adjusting a pH value of a dopamine hydrochloride solution to 8.5 by using the buffer reagent and the sodium hydroxide solution obtained in the step S1, soaking the stainless steel wire mesh obtained in the step S1 therein, oscillating and reacting for 24 hours in a constant-temperature gas bath at a temperature of 30° C., cleaning and drying the stainless steel wire mesh, to obtain the polydopamine modified stainless steel wire mesh.
(42) step S3, preparation of the MOFs reaction solution: respectively adding bismuth nitrate pentahydrate and trimesic acid into 20 mL mixed solvent of DMF and anhydrous ethanol, performing ultrasonic dissolution, mixing the two solutions, and stirring for 30 minutes, wherein a concentration of the bismuth nitrate pentahydrate is 20 mM, and a concentration of the trimesic acid is 25 mM.
(43) step S4, placing the stainless steel wire mesh in the step S2 and the titanium mesh in the step S1 into a polytetrafluoroethylene reaction kettle, adding 50 mL MOFs reaction solution obtained in the step S3, and performing hydrothermal reaction at a temperature of 120° C. for 12 hours.
(44) step S5, cleaning the stainless steel wire mesh obtained in the step S4 with the anhydrous methanol for 3-5 times, and drying at 60° C. to obtain the photocatalytic oil-water separation material of the present disclosure.
(45) In the fifth embodiment of the present disclosure, the titanium mesh taken as the metal-doped material can be reused after being cleaned by the anhydrous ethanol, a diluted acid solution and pure water, so as to reduce the waste of resources, and the production cost.
A Sixth Embodiment
(46) A preparation method of the photocatalytic oil-water separation material of the embodiment is as follows:
(47) step S1, material pretreatment and preparation of acid-alkali buffer solution: cutting a foam iron and a titanium mesh into squares of 4×4 cm, and ultrasonically cleaning the squares in anhydrous ethanol, diluted hydrochloric acid and pure water for later use; preparing a tris (hydroxymethyl) aminomethane hydrochloride buffer solution with a concentration of 0.1 mg/L, and a sodium hydroxide solution with a concentration of 0.5 M.
(48) step S2, adjusting a pH value of a dopamine hydrochloride solution to 8.5 by using the buffer solution and the sodium hydroxide solution obtained in the step S1 in advance, placing the foam iron taken as the base material in the step S1 in the dopamine hydrochloride solution with a concentration of 1 mg/mL, reacting at 60° C. for 20 hours, cleaning the foam iron with pure water, and drying at 60° C. for later use.
(49) step S3, preparation of the MOFs reaction solution: adding ferric trichloride and terephthalic acid into a mixed solution of N,N-dimethylacetamide and anhydrous ethanol, respectively, performing ultrasonic accelerated dissolution, and mixing and stirring for 30 minutes; wherein a concentration of the ferric trichloride is 10 mM, and a concentration of the terephthalic acid is 15 mM.
(50) step S4, placing the foam iron in the step S2 and the titanium mesh in the step S1 into a polytetrafluoroethylene reaction kettle, adding 40 mL MOFs reaction solution obtained in the step S3, performing hydrothermal reaction at a temperature of 120° C. for 12 hours; and cleaning the foam iron for a plurality of times after performing hydrothermal reaction by using anhydrous methanol, and drying at 60° C. to obtain the photocatalytic oil-water separation material of the present disclosure.
(51) A difference between the sixth embodiment and the fifth embodiment is that: the concentration of the dopamine hydrochloride is adjusted to be 1 mg/mL, the base material and the metal-doped material are respectively changed to be the foam iron and the titanium copper, the MOFs is changed to be iron-MOFs from bismuth-MOFs, the concentrations of the MOFs preparation material are changed to be 10 mM and 15 mM, and the organic solvent is changed to be the mixed solution of the N,N-dimethylacetamide and the anhydrous ethanol.
(52) In the sixth embodiment of the present disclosure, the titanium mesh taken as the metal-doped material can be reused after being cleaned by the anhydrous ethanol, a diluted acid solution and pure water, so as to reduce the waste of resources, and the production cost.
(53) In order to further illustrate the technical effect of the present disclosure, the following performance tests are performed on the oil-water separation material of the first embodiment.
(54) 1. SEM test:
(55) 2. Contact angle test:
(56) 3. XRD diagram of MOFs with a bimetallic central structure: as can be seen from the XRD diagram of Cu-doped MOFs and un-doped modified MOFs, a diffraction peak of the Cu-doped MOFs with about 5-10° is obviously enhanced when comparing with that of the un-doped modified MOFs, Cu.sup.2+ with a smaller particle size replaces Zr.sup.4+ with a greater particle size to form the MOFs with a bimetallic center. The doping of Cu.sup.2+ will cause crystal lattices of the MOFs to generate micro deformation, so that the crystal lattices of the MOFs contract to form structural defects, which represents the phenomenon that intensity of the diffraction peak is increased and an angle of the diffraction peak is changed, and further explains a successful doping of the MOFs material by copper ions.
(57) 4. Oil-water separation test: as shown in
(58) 5. Separation and test of different kinds of heavy oil, light oil and high-salt-content oily wastewater: it can be seen from FIG. (a) of
(59) 6. Acid-alkali resistance and high/low temperature resistance test:
(60) 7. Photocatalytic degradation test of organic dyes:
(61) 8. Chemical stability test:
(62) 9. Recyclable test:
(63) It should be understood by one of ordinary skilled in the related art that the above embodiments are only a description of the present disclosure and the foregoing description is not in any form a limitation to the present disclosure. Any variation or replacement made by one of ordinary skilled in the related art without departing from the spirit of the present disclosure shall fall within the protection scope of the present disclosure.