CN111097481A - Preparation method of titanium and nitrogen-containing doped graphene quantum dot molecular sieve - Google Patents
Preparation method of titanium and nitrogen-containing doped graphene quantum dot molecular sieve Download PDFInfo
- Publication number
- CN111097481A CN111097481A CN201911391596.1A CN201911391596A CN111097481A CN 111097481 A CN111097481 A CN 111097481A CN 201911391596 A CN201911391596 A CN 201911391596A CN 111097481 A CN111097481 A CN 111097481A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- titanium
- graphene quantum
- doped graphene
- nitrogen
- 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.)
- Pending
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 98
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000010936 titanium Substances 0.000 title claims abstract description 38
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 38
- 239000002096 quantum dot Substances 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 229920002401 polyacrylamide Polymers 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 22
- 239000012498 ultrapure water Substances 0.000 claims description 22
- 238000009210 therapy by ultrasound Methods 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical group [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000862 absorption spectrum Methods 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 150000003608 titanium Chemical class 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000010865 sewage Substances 0.000 description 14
- 229910052785 arsenic Inorganic materials 0.000 description 10
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 238000005286 illumination Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
Abstract
The invention discloses a preparation method of a titanium and nitrogen-containing doped graphene quantum dot molecular sieve, which specifically comprises the steps of taking tetrabutyl titanate as a titanium source, compounding with N-doped graphene quantum dots, taking the molecular sieve as a carrier, and stably attaching modified titanium/nitrogen-doped graphene quantum dots to the molecular sieve through chemical bonds. By introducing the titanium and nitrogen doped graphene quantum dots, the absorption spectrum of titanium dioxide is expanded to a visible light region, so that the photocatalytic activity of the quantum dots in the visible light region is obviously improved, the organic matter degradation efficiency is improved, and the degradation time is reduced; the titanium nitrogen atoms promote charge transfer, inhibit the recombination of photoproduction electrons and holes and improve the photocatalytic efficiency of the quantum dots; the introduction of the molecular sieve can adsorb heavy metal ions and organic substances in a water body, and organic substances are directly degraded by the attached titanium/nitrogen hybridized graphene quantum, so that the degradation stability and efficiency of a system are ensured, the recovery of the photocatalyst is facilitated, and the cost is saved.
Description
Technical Field
The invention relates to the technical field of fine chemicals, in particular to a preparation method of a titanium and nitrogen-containing doped graphene quantum dot molecular sieve.
Background
China is a country with serious water shortage, is one of 13 water-deficient countries in the world, and fresh water resources are less than 1/4 of the per capita water quantity in the world. Since the innovation is open, the industry is rapidly developed, wastewater is discharged wantonly, more than 80% of surface water and underground water in China are polluted once, and the problem of water resource pollution in China is still serious so far, and needs to be solved urgently.
Substances which cause pollution to water bodies mainly comprise waste acid and alkali, solid impurities, organic pollutants, heavy metal ions and the like, and if water resource pollution control can be effectively carried out, the problem of pollutants is solved, the problem of water resources caused by industrial production can be effectively solved, and comprehensive cyclic utilization of the water resources is realized.
Titanium dioxide (TiO)2) The basic photocatalysis has attracted great attention because of its easy industrialization, good stability, abundant reserves, nontoxicity and high photoactivity. Graphene quantum dots serve as a novel zero-dimensional carbon nano material, and because excitons are bound to have a quantum confinement effect, an energy band of the graphene quantum dots is opened to form a semiconductor material with an adjustable bandwidth, organic pollutants can be effectively degraded by photocatalysis after the graphene quantum dots are modified by titanium-based hybrid graphene quantum dots, the molecular sieve serves as a carrier, impurities such as heavy metal ions in water can be adsorbed, the modified titanium nitrogen doped graphene quantum dots can be effectively recycled, and resources are saved.
Disclosure of Invention
The invention provides a preparation method of a titanium and nitrogen-containing doped graphene quantum dot molecular sieve.
A preparation method of a titanium and nitrogen-containing doped graphene quantum dot molecular sieve comprises the following steps:
(1) carrying out ultrasonic treatment on a molecular sieve in ultrapure water for 1-2 h, and drying the molecular sieve until no water exists for later use; adjusting the pH value of the polyacrylamide aqueous solution to 1-2, and uniformly mixing for later use;
(2) adding a polyacrylamide aqueous solution, tetrabutyl titanate and a molecular sieve into an organic solvent, performing ultrasonic treatment at normal temperature for 30min, transferring the materials and the molecular sieve into a reaction kettle, performing reaction at 180 ℃ for 10-12h in an acid environment, cooling to room temperature, performing ultrasonic treatment for 5-10min, filtering and separating titanium dioxide, washing the obtained molecular sieve with ultrapure water and ethanol, and performing vacuum drying; then putting the molecular sieve into a muffle furnace to anneal for 3 hours at the temperature of 450-500 ℃ to obtain a titanium-based molecular sieve;
(3) adding a titanium-based molecular sieve and N-doped graphene quantum dots into a reaction kettle, reacting for 6-8h at the temperature of 110-120 ℃ by using ultrapure water as a solvent, cooling to room temperature, carrying out ultrasonic treatment for 5-10min, filtering, washing the obtained molecular sieve with ultrapure water and ethanol, and drying to obtain the titanium-and nitrogen-doped graphene quantum dot molecular sieve.
Wherein the molecular sieve is a large-pore molecular sieve with the inner aperture size larger than 100nm and the diameter of 3-5 mm, the molecular sieve is a silicon-aluminum molecular sieve, and the molar ratio of the main components is nSiO2：nAl2O3=1：（50~100）：1。
Wherein the solid content of the polyacrylamide aqueous solution is 1.0-3.0%.
Wherein, in the step (1), the concrete steps are as follows: adding oxalic acid to adjust the pH of the polyacrylamide aqueous solution to 1-2.
Wherein the mass ratio of the tetrabutyl titanate to the polyacrylamide aqueous solution to the molecular sieve in the step (2) is 1: 200-300: 100-200.
Wherein the organic solvent is glycol, and the dosage of the organic solvent is 1-2 times of the volume of the polyacrylamide aqueous solution.
Wherein the acidic environment in step (2) is provided by an aqueous polyacrylamide solution and a molecular sieve.
The dosage of the N-doped graphene quantum dots in the step (3) is 1-10% of the mass of titanium dioxide in the titanium-based molecular sieve, and preferably 1-5%.
Wherein, the lining of the high-pressure reaction kettle in the step (2) is made of polytetrafluoroethylene.
According to the method, tetrabutyl titanate is used as a titanium source, ethylene glycol is used as a solvent, polyacrylamide and a molecular sieve provide an acid environment, the molecular sieve is used as a carrier, the polyacrylamide is used as a stabilizer and a dispersant, a titanium-based molecular sieve is obtained, and then the titanium-based molecular sieve reacts with nitrogen-doped graphene quantum dots (N-GQDs). The modified titanium/nitrogen-doped graphene quantum dots are stably attached to the molecular sieve through chemical bonds.
The invention has the beneficial effects
(1) By introducing the nitrogen-doped graphene quantum dots, the absorption spectrum of titanium dioxide is expanded to a visible light region, so that the photocatalytic activity of the quantum dots in the visible light region is obviously improved;
(2) the titanium nitrogen atoms promote charge transfer, inhibit the recombination of photoproduction electrons and holes and improve the photocatalytic efficiency of the quantum dots; improving the efficiency of degrading organic matters and reducing the degradation time
(3) The introduction of the molecular sieve can adsorb heavy metal ions and organic substances in a water body, and organic substances are directly degraded by the attached titanium/nitrogen hybridized graphene quantum, so that the degradation stability and efficiency of a system are ensured, the recovery of the photocatalyst is facilitated, and the cost is saved.
Detailed description of the invention
Example 1
The method comprises the following steps: carrying out ultrasonic treatment on 5 molecular sieves with the diameter of 3mm and the pore diameter of 100nm in ultrapure water for 1h, drying the molecular sieves until the molecular sieves are anhydrous for later use, and weighing 51.5g of the molecular sieves; adding oxalic acid into the polyacrylamide aqueous solution, wherein the pH value of the oxalic acid is 1.10, and uniformly mixing for later use;
step two: adding 100ml of ethylene glycol serving as an organic solvent into a clean beaker, sequentially adding 100g of polyacrylamide aqueous solution, 0.5g of tetrabutyl titanate and the 5 molecular sieves, uniformly mixing, performing ultrasonic treatment at normal temperature for 30min, transferring the mixed material and the molecular sieves into a high-pressure reaction kettle, reacting at the temperature of 171 +/-1 ℃ for 10h under the condition of pH value of 1.32, cooling to room temperature, performing ultrasonic treatment for 10min, filtering and separating 0.014g of dry titanium dioxide, leaching the obtained molecular sieves with ultrapure water and ethanol for 5 times respectively, performing vacuum drying at the temperature of 55 +/-1 ℃ for 6h, and then putting the molecular sieves into a muffle furnace at the temperature of 495 +/-5 ℃ for annealing for 3h to obtain the titanium-based molecular sieves;
step three: adding a titanium-based molecular sieve and 11.0mg of N-doped graphene quantum dots (N-GQDs) into a high-pressure reaction kettle, taking 150ml of ultrapure water as a solvent, reacting for 6 hours at 111 +/-1 ℃, cooling to room temperature, carrying out ultrasonic treatment for 8min, filtering, leaching the obtained molecular sieve with ultrapure water and ethanol for 5 times, and drying for 10 hours at 80 ℃ to obtain the titanium/nitrogen-doped graphene quantum dot molecular sieve, which is marked as T1-T5.
Example 2
The method comprises the following steps: carrying out ultrasonic treatment on 5 molecular sieves with the diameter of 5mm and the pore diameter of 100nm in ultrapure water for 2.01h, drying the molecular sieves until no water exists, and weighing 98.2 g; adding oxalic acid into the polyacrylamide aqueous solution to adjust the pH value to 1.89, and uniformly mixing for later use;
step two: adding 150ml of ethylene glycol serving as an organic solvent into a clean beaker, sequentially adding 150g of polyacrylamide aqueous solution, 0.5g of tetrabutyl titanate and the 5 molecular sieves, uniformly mixing, performing ultrasonic treatment at normal temperature for 30min, transferring the mixed material and the molecular sieves into a high-pressure reaction kettle, reacting at 179 +/-1 ℃ for 12h under the condition of pH value of 1.96, cooling to room temperature, performing ultrasonic treatment for 10min, filtering and separating 0.006g of dry titanium dioxide, leaching the obtained molecular sieves with ultrapure water and ethanol for 5 times, performing vacuum drying at 55 +/-1 ℃ for 6h, and then putting the molecular sieves into a muffle furnace to anneal at 455 +/-5 ℃ for 3h to obtain the titanium-based molecular sieves;
step three: adding 5 titanium-based molecular sieves and 6.6mg of N-doped graphene quantum dots (N-GQDs) into a high-pressure reaction kettle, taking 150ml of ultrapure water as a solvent, reacting for 8 hours at 119 +/-1 ℃, cooling to room temperature, carrying out ultrasonic treatment for 10min, filtering, leaching the obtained molecular sieve with ultrapure water and ethanol for 5 times, and drying for 12 hours at 70 ℃ to obtain the titanium/nitrogen-doped graphene quantum dot molecular sieve, wherein the molecular sieve is marked as F1-F5.
In comparative example 1 (acidifying with hydrochloric acid instead of oxalic acid), the pH value of the polyacrylamide aqueous solution is adjusted to be 1.15 by replacing oxalic acid with hydrochloric acid, other conditions are unchanged, and the titanium/nitrogen-doped graphene quantum dot molecular sieve obtained in the same way as in example 1 is marked as H1-H5.
Taking sewage after Fenton degradation treatment from an A2/0 sewage treatment system of a company, and detecting the following indexes after filtering: chemical oxygen demand COD: 78.4 mg/L; arsenic content: 5 ppm.
Application example 1
The titanium/nitrogen-doped graphene quantum dot molecular sieves T1, T2, T3, T4 and T5 prepared in the embodiment 1 are used as water treatment units to treat the sewage, and the specific steps are as follows:
slowly pouring 200g of the sewage into a clean 500ml beaker, adding titanium/nitrogen-doped graphene quantum dot molecular sieves T1-T5 into the beaker in advance, stirring for 1h under illumination, and detecting water quality indexes as follows: chemical oxygen demand COD: 18.9 mg/L; arsenic content: it was not detected.
Application example 2
The titanium/nitrogen-doped graphene quantum dot molecular sieves F1, F2, F3, F4 and F5 prepared in the embodiment 2 are used as water treatment units to treat the sewage, and the specific steps are as follows:
slowly pouring 200g of the sewage into a clean 500ml beaker, adding titanium/nitrogen-doped graphene quantum dot molecular sieves F1-F5 into the beaker in advance, stirring for 1h under illumination, and detecting water quality indexes as follows: chemical oxygen demand COD: 21.7 mg/L; arsenic content: it was not detected.
Application example 3
Treating the sewage by using the titanium/nitrogen-doped graphene quantum dot molecular sieves H1, H2, H3, H4 and H5 prepared in the comparative example 1 as water treatment units, and specifically comprising the following steps:
slowly pouring 200g of the sewage into a clean 500ml beaker, adding titanium/nitrogen-doped graphene quantum dot molecular sieves H1-H5 into the beaker in advance, stirring for 1H under illumination, and detecting water quality indexes as follows: chemical oxygen demand COD: 31.2 mg/L; arsenic content: it was not detected.
Comparative application example 1 (macroporous molecular sieve)
The method takes a large-pore molecular sieve with the diameter of 3mm and the pore diameter of 100nm as a water treatment unit to treat the sewage, and comprises the following specific steps: slowly pouring 200g of the sewage into a clean 500ml beaker, adding 5 macroporous molecular sieves into the beaker in advance, stirring for 1 hour under illumination, and detecting the water quality indexes as follows: chemical oxygen demand COD: 78.2 mg/L; arsenic content: it was not detected.
Application comparative example 2 (Nitrogen doped graphene quantum dots)
Slowly pouring 200g of the sewage into a clean 500ml beaker, adding nitrogen-doped graphene quantum dots with equivalent weight to that of the application example 1 into the beaker, and stirring for 3 hours under illumination, wherein the detected water quality indexes are as follows: chemical oxygen demand COD: 49.6 mg/L; arsenic content: 5 ppm.
Application comparative example 3 (titanium-doped graphene quantum dot molecular sieve prepared from titanium-based molecular sieve and graphene quantum dot)
Preparation: replacing the N-doped graphene quantum dots mixed with the titanium-based molecular sieve in the third step of the example 1 with common graphene quantum dots under the same other conditions, and treating the N-doped graphene quantum dots according to the conditions of the example 1 to obtain the titanium-doped graphene quantum dot molecular sieves D1-D5.
The application comprises the following steps: slowly pouring 200g of prepared sewage into a clean 500ml beaker, adding titanium-doped graphene quantum dot molecular sieves D1-D5 into the beaker in advance, stirring for 1h under illumination, and detecting water quality indexes as follows: chemical oxygen demand COD: 64.2 mg/L; arsenic content: it was not detected. Under the irradiation of ultraviolet light, Chemical Oxygen Demand (COD): 32.2 mg/L; arsenic content: it was not detected.
Application comparative example 4 (common macroporous molecular sieve + nitrogen doped graphene quantum dots)
Preparation: carrying out ultrasonic treatment on 5 molecular sieves with the diameter of 3mm and the pore diameter of 100nm in ultrapure water for 1h, drying the molecular sieves until the molecular sieves are anhydrous for later use, weighing 51.5g, adding the treated molecular sieves and 11.0mg of N-doped graphene quantum dots (N-GQDs) into a high-pressure reaction kettle, taking 150ml of ultrapure water as a solvent, reacting for 6h at 111 +/-1 ℃, cooling to room temperature, carrying out ultrasonic treatment for 8min, filtering, rinsing the obtained molecular sieves with ultrapure water and ethanol for 5 times, and drying for 10h at 80 ℃ to obtain the nitrogen-doped graphene quantum dot molecular sieves, wherein the molecular sieves are marked as D6-D10.
The application comprises the following steps: slowly pouring 200g of prepared sewage into a clean 500ml beaker, adding nitrogen-doped graphene quantum dot molecular sieves D6-D10 into the beaker in advance, stirring for 1h under illumination, and detecting water quality indexes as follows: chemical oxygen demand COD: 50.6 mg/L; arsenic content: it was not detected.
Comparative example 5 (titanium dioxide + nitrogen doped graphene quantum dots)
The method comprises the following steps: adding oxalic acid into the polyacrylamide aqueous solution to adjust the pH value to 1.21, and uniformly mixing for later use;
step two: adding 100ml of ethylene glycol serving as an organic solvent into a clean beaker, sequentially adding 100g of polyacrylamide aqueous solution and 0.5g of tetrabutyl titanate, uniformly mixing, performing ultrasound at normal temperature for 30min, transferring the mixed material into a high-pressure reaction kettle, reacting at 171 +/-1 ℃ for 10h under the condition that the pH value is 1.32, cooling to room temperature, performing ultrasound for 10min, performing suction filtration, rinsing with ultrapure water and ethanol for 3-5 times, collecting filtrate, performing vacuum drying at 55 +/-1 ℃ for 24h, putting the dried solid into a muffle furnace, and annealing at 495 +/-5 ℃ for 3h to obtain 0.11g of flower-shaped titanium dioxide;
step three: adding 0.11g of flower-like titanium dioxide and 11.0mg of N-doped graphene quantum dots (N-GQDs) into a high-pressure reaction kettle, taking 150ml of ultrapure water as a solvent, reacting for 6 hours at 111 +/-1 ℃, cooling to room temperature, carrying out ultrasonic treatment for 8min, filtering, rinsing for 3-5 times with ultrapure water and ethanol, and drying for 12 hours at 80 ℃ to obtain 0.111g of titanium/nitrogen-doped graphene quantum dots.
The application comprises the following steps: slowly pouring 200g of prepared sewage into a clean 500ml beaker, adding 0.111g of titanium/nitrogen doped graphene quantum dots into the beaker in advance, stirring for 2 hours under illumination, and detecting the water quality indexes as follows: chemical oxygen demand COD: 35.6 mg/L; arsenic content: 5 ppm.
Claims (8)
1. A preparation method of a titanium and nitrogen-containing doped graphene quantum dot molecular sieve is characterized by comprising the following steps:
(1) carrying out ultrasonic treatment on a molecular sieve in ultrapure water for 1-2 h, and drying the molecular sieve until no water exists for later use; adjusting the pH value of the polyacrylamide aqueous solution to 1-2, and uniformly mixing for later use;
(2) adding a polyacrylamide aqueous solution, tetrabutyl titanate and a molecular sieve into an organic solvent, performing ultrasonic treatment at normal temperature for 30min, transferring the materials and the molecular sieve into a reaction kettle, performing reaction at 180 ℃ for 10-12h in an acid environment, cooling to room temperature, performing ultrasonic treatment for 5-10min, filtering and separating titanium dioxide, washing the obtained molecular sieve with ultrapure water and ethanol, and performing vacuum drying; then putting the molecular sieve into a muffle furnace to anneal for 3 hours at the temperature of 450-500 ℃ to obtain a titanium-based molecular sieve;
(3) adding a titanium-based molecular sieve and N-doped graphene quantum dots into a reaction kettle, reacting for 6-8h at the temperature of 110-120 ℃ by using ultrapure water as a solvent, cooling to room temperature, carrying out ultrasonic treatment for 5-10min, filtering, washing the obtained molecular sieve with ultrapure water and ethanol, and drying to obtain the titanium-and nitrogen-doped graphene quantum dot molecular sieve.
2. The method of claim 1, wherein the molecular sieve is a large-pore molecular sieve with an inner pore size of more than 100nm and a diameter of 3-5 mm, the molecular sieve is a silicon-aluminum molecular sieve, and the molar ratio of the main components is nSiO2：nAl2O3=1：50~100：1。
3. The method of claim 1, wherein the solid content of the aqueous polyacrylamide solution is 1.0-3.0%.
4. The method according to claim 1, wherein in step (1), the method specifically comprises: adding oxalic acid to adjust the pH of the polyacrylamide aqueous solution to 1-2.
5. The method according to claim 1, wherein the mass ratio of the tetrabutyl titanate, the polyacrylamide aqueous solution and the molecular sieve in the step (2) is 1: 200-300: 100-200.
6. The method of claim 1, wherein the organic solvent is ethylene glycol and is used in an amount of 1 to 2 times the volume of the aqueous polyacrylamide solution.
7. The process of any one of claims 1 to 6, wherein the acidic environment in step (2) is provided by an aqueous polyacrylamide solution and a molecular sieve.
8. The method of claim 1, wherein the amount of the N-doped graphene quantum dots in the step (3) is 1-10% by mass of the titanium dioxide in the titanium-based molecular sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911391596.1A CN111097481A (en) | 2019-12-30 | 2019-12-30 | Preparation method of titanium and nitrogen-containing doped graphene quantum dot molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911391596.1A CN111097481A (en) | 2019-12-30 | 2019-12-30 | Preparation method of titanium and nitrogen-containing doped graphene quantum dot molecular sieve |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111097481A true CN111097481A (en) | 2020-05-05 |
Family
ID=70425014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911391596.1A Pending CN111097481A (en) | 2019-12-30 | 2019-12-30 | Preparation method of titanium and nitrogen-containing doped graphene quantum dot molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111097481A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385239A (en) * | 2021-07-15 | 2021-09-14 | 中科三清科技有限公司 | Modified catalyst carrier and preparation method thereof |
| CN114351274A (en) * | 2022-02-18 | 2022-04-15 | 台州东海塑料品制造有限公司 | High-light-fastness polyvinyl chloride composite material for textilene mesh cloth and preparation process of textilene mesh cloth |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205075A (en) * | 2006-12-22 | 2008-06-25 | 中国石油化工股份有限公司 | Method for synthesizing titanium-containing molecular sieve material |
| KR101420983B1 (en) * | 2013-07-24 | 2014-07-16 | 서울대학교산학협력단 | Fabrication of visible light photocatalyst containing graphene quantum dot and silver nanoparticles decorated titania nanoparticles |
| WO2016098127A1 (en) * | 2014-12-16 | 2016-06-23 | Council Of Scientific & Industrial Research | NOVEL TITANIUM DIOXIDE - GRAPHENE QUANTUM DOTS (TiO2-GQDS) HYBRID MULTIFUNCTIONAL MATERIAL AND PREPARATION THEREOF |
| CN106215920A (en) * | 2016-08-29 | 2016-12-14 | 佛山市高明区尚润盈科技有限公司 | A kind of porous graphene carried titanium dioxide composite and preparation method thereof |
| CN106423250A (en) * | 2016-01-21 | 2017-02-22 | 盐城工学院 | Preparation method of activated zeolite molecular sieve supported titanium dioxide photocatalysis material |
| CN109364992A (en) * | 2018-10-16 | 2019-02-22 | 中国科学院上海硅酸盐研究所 | A kind of nitrogen-doped graphene/nano titanium dioxide photocatalyst and its preparation method and application |
| CN110124724A (en) * | 2019-06-25 | 2019-08-16 | 西北师范大学 | A kind of preparation method of functionalization graphene quantum dot/composite titania material |
-
2019
- 2019-12-30 CN CN201911391596.1A patent/CN111097481A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205075A (en) * | 2006-12-22 | 2008-06-25 | 中国石油化工股份有限公司 | Method for synthesizing titanium-containing molecular sieve material |
| KR101420983B1 (en) * | 2013-07-24 | 2014-07-16 | 서울대학교산학협력단 | Fabrication of visible light photocatalyst containing graphene quantum dot and silver nanoparticles decorated titania nanoparticles |
| WO2016098127A1 (en) * | 2014-12-16 | 2016-06-23 | Council Of Scientific & Industrial Research | NOVEL TITANIUM DIOXIDE - GRAPHENE QUANTUM DOTS (TiO2-GQDS) HYBRID MULTIFUNCTIONAL MATERIAL AND PREPARATION THEREOF |
| CN106423250A (en) * | 2016-01-21 | 2017-02-22 | 盐城工学院 | Preparation method of activated zeolite molecular sieve supported titanium dioxide photocatalysis material |
| CN106215920A (en) * | 2016-08-29 | 2016-12-14 | 佛山市高明区尚润盈科技有限公司 | A kind of porous graphene carried titanium dioxide composite and preparation method thereof |
| CN109364992A (en) * | 2018-10-16 | 2019-02-22 | 中国科学院上海硅酸盐研究所 | A kind of nitrogen-doped graphene/nano titanium dioxide photocatalyst and its preparation method and application |
| CN110124724A (en) * | 2019-06-25 | 2019-08-16 | 西北师范大学 | A kind of preparation method of functionalization graphene quantum dot/composite titania material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385239A (en) * | 2021-07-15 | 2021-09-14 | 中科三清科技有限公司 | Modified catalyst carrier and preparation method thereof |
| CN114351274A (en) * | 2022-02-18 | 2022-04-15 | 台州东海塑料品制造有限公司 | High-light-fastness polyvinyl chloride composite material for textilene mesh cloth and preparation process of textilene mesh cloth |
| CN114351274B (en) * | 2022-02-18 | 2023-10-24 | 台州东海塑料品制造有限公司 | Polyvinyl chloride composite material for Testoslin mesh cloth with high light fastness and preparation process of Testoslin mesh cloth |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | The role of ozone and influence of band structure in WO3 photocatalysis and ozone integrated process for pharmaceutical wastewater treatment | |
| Wang et al. | Visible-light-driven photocatalytic degradation of dye and antibiotics by activated biochar composited with K+ doped g-C3N4: Effects, mechanisms, actual wastewater treatment and disinfection | |
| CN107285452B (en) | Method for rapidly degrading antibiotics | |
| CN113663693B (en) | Preparation method of indium zinc sulfide-titanium dioxide composite material and application of indium zinc sulfide-titanium dioxide composite material in production of hydrogen peroxide for wastewater treatment | |
| Lan et al. | Decomplexation of Cu (II)-EDTA over oxygen-doped g-C3N4: An available resource towards environmental sustainability | |
| CN110756215B (en) | CoP-HCCN composite photocatalyst and preparation method and application thereof | |
| CN111185216B (en) | Hollow tubular sulfur-doped carbon nitride/graphite phase carbon nitride homojunction photocatalyst, and preparation method and application thereof | |
| CN111097481A (en) | Preparation method of titanium and nitrogen-containing doped graphene quantum dot molecular sieve | |
| CN105251462A (en) | Garbage penetrating fluid efficient wastewater treating agent based on modified fly ash and preparation method | |
| CN113083344B (en) | Catalyst based on bismuth monoatomic anchoring carbon triazafion and preparation method and application thereof | |
| Zheng et al. | Sm2O3 nanoparticles coated with N-doped carbon for enhanced visible-light photocatalysis | |
| Yuan et al. | Efficient degradation of organic pollutants with a sewage sludge support and in situ doped TiO 2 under visible light irradiation conditions | |
| CN111592090A (en) | Application method of red mud-based heterogeneous Fenton catalyst for advanced wastewater treatment | |
| Bukhari et al. | Effects of Different Parameters on Photocatalytic Oxidation of Slaughterhouse Wastewater Using TiO | |
| CN109158117B (en) | Full-spectrum-response double-doped lanthanum fluoride/attapulgite up-conversion composite photocatalytic material and preparation method and application thereof | |
| CN113145158B (en) | Stripped tubular carbon nitride photocatalyst and preparation method and application thereof | |
| Rojviroon et al. | Removal of color and chemical oxygen demand from landfill leachate by photocatalytic process with AC/TiO2 | |
| Wang et al. | Efficient visible-light photocatalysis of chloramphenicol using novel engineered biochar-based Ti-doped Bi2WO6 composite: Mechanisms, degradation pathways, and applications | |
| CN106946312B (en) | Method for degrading drinking water disinfection by-product trichloroacetamide by utilizing photocatalytic cement-based material | |
| CN109482217B (en) | Titanium dioxide-iron-carbon nitride composite photocatalyst and preparation method thereof | |
| CN111558370A (en) | Oxygen-deficient ZnO nanosheet CDs composite photocatalyst and preparation method thereof | |
| CN105561969A (en) | Preparation and application of porous TixSn1-xO2 solid solution microspheres | |
| Wang et al. | Photocatalytic performance of biochar-modified TiO 2 (C/TiO 2) for ammonia–nitrogen removal | |
| Yang et al. | Review of N and metal co-doped TiO2 for water purification under visible light irradiation | |
| CN113578340A (en) | Iron-based metal catalytic material and preparation method 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200505 |
|
| RJ01 | Rejection of invention patent application after publication |