CN113877631B - Preparation method of graphene quantum dot-supported bismuth vanadate nanocomposite capable of efficiently degrading heavy metal ions - Google Patents
Preparation method of graphene quantum dot-supported bismuth vanadate nanocomposite capable of efficiently degrading heavy metal ions Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 33
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 150000002500 ions Chemical class 0.000 title claims abstract description 26
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 15
- 230000000593 degrading effect Effects 0.000 title abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002096 quantum dot Substances 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 85
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 22
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000007853 buffer solution Substances 0.000 claims description 12
- 230000015556 catabolic process Effects 0.000 claims description 12
- 238000006731 degradation reaction Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 239000000872 buffer Substances 0.000 claims description 8
- 239000012456 homogeneous solution Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims 3
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 4
- 244000005700 microbiome Species 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 30
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 14
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 14
- CWGFSQJQIHRAAE-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol tetrahydrochloride Chemical compound Cl.Cl.Cl.Cl.OCC(N)(CO)CO CWGFSQJQIHRAAE-UHFFFAOYSA-N 0.000 description 11
- 229920001690 polydopamine Polymers 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000002135 nanosheet Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000002336 sorption--desorption measurement Methods 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- 150000001621 bismuth Chemical class 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical group O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical group NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/396—Distribution of the active metal ingredient
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention belongs to the field of preparation of organic-inorganic nanocomposite materials, and relates to a preparation method of a graphene quantum dot supported bismuth vanadate nanocomposite material for efficiently degrading heavy metal ions. The bismuth vanadate nanocomposite prepared by the method can efficiently degrade heavy metal ions, and can be widely applied to purification of dye, heavy metal and microorganism polluted water.
Description
Technical Field
The invention belongs to the field of preparation of organic-inorganic nanocomposite materials, and relates to a preparation method of a graphene quantum dot supported bismuth vanadate nanocomposite material for efficiently degrading heavy metal ions.
Background
The two-dimensional bismuth-based material integrates the advantages of the two-dimensional structural material and the bismuth-based compound, has both visible light absorption and higher catalytic activity, provides an important foundation for developing high-efficiency visible light photocatalytic materials, and in recent years, more two-dimensional bismuth-based materials are studied mainly including bismuth tungstate, bismuth vanadate, bismuth oxyhalide and the like. Bismuth vanadate (BiVO) 4 ) From 1998The Kudo et al reported for the first time that the oxygen can be generated by photolysis of water under visible light, and the development of the oxygen can be realized in the field of visible light photocatalysis for twenty years. Although two-dimensional bismuth vanadate can have certain degradation capability under visible light, the problems of low quantum efficiency and low solar energy utilization efficiency still exist. Patent CN103962146a discloses a preparation method of an iron oxide modified porous bismuth vanadate nanosheet photocatalyst, and the composite photocatalyst prepared by the technology has better activity than porous bismuth vanadate nanosheets which are not modified by iron oxide when being used for degrading rhodamine B and phenol under visible light.
Due to the excellent adhesion performance, polydopamine (PDA) has attracted more and more researches in recent years as a material surface modification material, and the surface of the Polydopamine (PDA) contains various functional groups such as o-benzoquinone, carboxyl, amino, phenol, imine and the like, has extremely high adsorption performance on metal ions, and can be used in the fields of sewage treatment, environmental protection and the like. Patent CN110042407A discloses a preparation method of a cobalt phosphate-polydopamine-bismuth vanadate ternary composite photoelectrode, and the composite photoelectrode prepared by the method has good chemical stability and photoelectrochemical property, and the photoelectric conversion efficiency is as high as 27%.
Disclosure of Invention
The invention aims to provide a simple, energy-saving, green and pollution-free preparation method of a graphene quantum dot supported bismuth vanadate nanocomposite material for efficiently degrading heavy metal ions, which uses two-dimensional BiVO 4 The nano sheet is taken as a substrate, the surface is uniformly coated with the PDA shell layer and GQDs are loaded, thus greatly improving the BiVO 4 Is used in the application range of (a). The technology has the advantages of simple method, energy conservation, green pollution-free property and the like, and the obtained material has the large specific surface area of a two-dimensional material, the open structure at two sides of a 2D plane, good adhesion, excellent fluorescence performance and good biocompatibility, and can be used in the fields of catalysis, adsorption, biological medicine and the like. There is no report about the technology, which explores a new way for the development of new materials.
The invention aims at realizing the following steps: preparation of graphene quantum dot-supported bismuth vanadate nanocomposite capable of efficiently degrading heavy metal ionsThe key point of the method is that dopamine hydrochloride and GQDs/BiVO are mixed 4 The mass ratio of the sample is as follows: dopamine hydrochloride GQDs/BiVO 4 And (2) adding the mixture in a reaction container in a ratio of (1:10) - (50), adding the mixture into a 20mL Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl) buffer solution, and stirring the mixture at 60 ℃ for 6-24 hours to obtain the target product GQDs-loaded bismuth vanadate nanocomposite.
More specifically, the specific steps are as follows:
step 1: 30mg of Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl) was dissolved in 20mL of deionized water and prepared as 10mM, pH=8.5 Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl) buffer;
step 2: weighing 40mg of dopamine hydrochloride powder, adding the dopamine hydrochloride powder into the solution, and performing ultrasonic oscillation to form 2mg/mL of dopamine hydrochloride Tris-HCl buffer solution;
step 3: weighing 0.4-2 g of GQDs/BiVO 4 The sample is dissolved in the buffer solution obtained in the step 2 and placed in an oil bath pot, and the sample is stirred for 6-24 hours at the temperature of 60 ℃;
step 4: cooling the solution obtained in the step 3 to room temperature, separating, washing and drying the obtained product to obtain the target product GQDs-loaded bismuth vanadate nanocomposite (marked as GQDs/BiVO) 4 @PDA）。
More specifically, GQDs/BiVO 4 The preparation steps of (a) are as follows:
step A: 1mmol of Bi (NO) 3 ) 3 •5H 2 O (0.485, g) and 0.72mmol SDBS (0.250, g) were dissolved in 10mL of 4M nitric acid to give a homogeneous solution;
and (B) step (B): 1mmol of NH 4 VO 3 (0.117, g) in 10mL of 2M aqueous NaOH;
step C: adding the solution obtained in the step B into the solution obtained in the step A, then slowly adding a proper amount of 2M NaOH aqueous solution, adjusting the pH value to 6.5, and stirring to obtain uniform suspension;
and D, according to the mass ratio: GQDs: biVO (BiVO) 4 C, taking 0.162-0.972 mL of graphene quantum dot solution with concentration of 1mg/mL, and adding the graphene quantum dot solution into the solution obtained in the step C, wherein the concentration is 1-3:100;
step E: step D is carried outAdding the obtained solution into a 50mL stainless steel reaction kettle with polytetrafluoroethylene lining, maintaining at 160deg.C for 3h, separating, washing and drying the obtained product to obtain the target product GQDs/BiVO 4 And (3) a sample.
More specifically, two-dimensional BiVO 4 The preparation steps of the nano-sheet are as follows:
step a: the molar ratio of bismuth salt to Sodium Dodecyl Benzene Sulfonate (SDBS) is as follows: bismuth salt Sodium Dodecyl Benzene Sulfonate (SDBS) =1:0.72 is dissolved in nitric acid solution to obtain solution A, and the solution A is stirred for 2 hours;
step b: the molar ratio of the vanadium-containing compound to the bismuth salt is as follows: vanadium-containing compounds: bismuth salt=1:1, adding a vanadium-containing compound to an aqueous NaOH solution to obtain solution B;
step c: b, adding the solution B obtained in the step B into the solution A obtained in the step a, then slowly adding a proper amount of 2M NaOH aqueous solution, adjusting the pH value to 6.5, and stirring for 2 hours to obtain a uniform suspension;
step d: adding the solution obtained in the step c into a 50mL stainless steel reaction kettle with polytetrafluoroethylene lining, maintaining at 160 ℃ for 3 hours, separating, washing and drying the obtained product to obtain the two-dimensional BiVO 4 A nanoplatelet sample.
The bismuth salt in the step a is Bi (NO 3 ) 3 •5H 2 O or BiCl 3 。
The vanadium-containing compound in the step a is NH 4 VO 3 Or Na (or) 3 VO 4 。
The purity of the drug used in the above steps is not lower than the analytical purity.
And (3) after separating the solid matters in the step (4) and the step (E), alternately washing with deionized water and absolute ethyl alcohol, and drying to obtain the target product.
In the step d, deionized water and absolute ethyl alcohol are adopted for washing for 4-6 times; the drying temperature is 60-100 ℃, and the drying time is 6-12 hours.
The invention has the beneficial effects that:
the invention realizes BiVO loaded by graphene quantum dots 4 Composite material with @ PDA core-shell structure, benefiting from poly dopaThe composite material can efficiently degrade heavy metal ions, and can be widely applied to purification of dye, heavy metal and microorganism polluted water.
Drawings
FIG. 1 shows the X-ray powder diffraction pattern (XRD) of the product obtained in example 5 of the present invention.
FIG. 2 shows a transmission electron micrograph and a high resolution transmission electron micrograph (TEM and HRTEM) of the product obtained in example 5 of the present invention.
Detailed Description
The invention is illustrated in further detail below in connection with examples.
The preparation method of the graphene quantum dot supported bismuth vanadate nanocomposite for efficiently degrading heavy metal ions comprises the following specific steps:
step 1: 30mg of Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl) was dissolved in 20mL of deionized water and prepared as 10mM, pH=8.5 Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl) buffer;
step 2: weighing 40mg of dopamine hydrochloride powder, adding the dopamine hydrochloride powder into the solution, and performing ultrasonic oscillation to form 2mg/mL of dopamine hydrochloride Tris-HCl buffer solution;
step 3: weighing 0.4-2 g of GQDs/BiVO 4 The sample is dissolved in the buffer solution obtained in the step 2 and placed in an oil bath pot, and the sample is stirred for 6-24 hours at the temperature of 60 ℃;
step 4: cooling the solution obtained in the step 3 to room temperature, separating the obtained product, alternately washing with deionized water and absolute ethyl alcohol, and drying to obtain the target product GQDs-loaded bismuth vanadate nanocomposite (marked as GQDs/BiVO) 4 @PDA）。
Wherein GQDs/BiVO 4 The preparation steps of (a) are as follows:
step A: 1mmol of Bi (NO) 3 ) 3 •5H 2 O (0.485, g) and 0.72mmol SDBS (0.250, g) were dissolved in 10mL of 4M nitric acid to give a homogeneous solution;
and (B) step (B): 1mmol of NH 4 VO 3 (0.117 g) in 10mL of 2M aqueous NaOH solutionIn (a) and (b);
step C: adding the solution obtained in the step B into the solution obtained in the step A, then slowly adding a proper amount of 2M NaOH aqueous solution, adjusting the pH value to 6.5, and stirring to obtain uniform suspension;
and D, according to the mass ratio: GQDs: biVO (BiVO) 4 C, taking 0.162-0.972 mL of graphene quantum dot solution with concentration of 1mg/mL, and adding the graphene quantum dot solution into the solution obtained in the step C, wherein the concentration is 1-3:100;
step E: adding the solution obtained in the step D into a 50mL stainless steel reaction kettle with polytetrafluoroethylene lining, maintaining at 160 ℃ for 3 hours, separating the obtained product, alternately washing with deionized water and absolute ethyl alcohol, and drying to obtain the target product GQDs/BiVO 4 And (3) a sample.
Wherein, two-dimensional BiVO 4 The preparation steps of the nano-sheet are as follows:
step a: bismuth salt (Bi (NO) 3 ) 3 •5H 2 O or BiCl 3 ) The molar ratio of the Sodium Dodecyl Benzene Sulfonate (SDBS) to the Sodium Dodecyl Benzene Sulfonate (SDBS) is as follows: bismuth salt Sodium Dodecyl Benzene Sulfonate (SDBS) =1:0.72 is dissolved in nitric acid solution to obtain solution A, and the solution A is stirred for 2 hours;
step b: according to the vanadium-containing compound (NH) 4 VO 3 Or Na (or) 3 VO 4 ) The molar ratio of the bismuth salt to the bismuth salt is as follows: vanadium-containing compounds: bismuth salt=1:1, adding a vanadium-containing compound to an aqueous NaOH solution to obtain solution B;
step c: b, adding the solution B obtained in the step B into the solution A obtained in the step a, then slowly adding a proper amount of 2M NaOH aqueous solution, adjusting the pH value to 6.5, and stirring for 2 hours to obtain a uniform suspension;
step d: c, adding the solution obtained in the step c into a 50mL stainless steel reaction kettle with polytetrafluoroethylene lining, keeping at 160 ℃ for 3 hours, separating the obtained product, and adopting deionized water and absolute ethyl alcohol to wash for 4-6 times; the drying temperature is 60-100 ℃, the drying time is 6-12 hours, and the two-dimensional BiVO is obtained 4 A nanoplatelet sample.
Example 1
Two-dimensional BiVO 4 The preparation steps of the nano-sheet are as follows:
step A: taking 1mmol Bi%NO 3 ) 3 •5H 2 O (0.485, g) and 0.72mmol SDBS (0.250, g) were dissolved in 10mL of 4M nitric acid to give a homogeneous solution;
and (B) step (B): 1mmol of NH 4 VO 3 (0.117, g) in 10mL of 2M aqueous NaOH;
step C: adding the solution obtained in the step B into the solution obtained in the step A, then slowly adding a proper amount of 2M NaOH aqueous solution, adjusting the pH value to 6.5, and stirring to obtain uniform suspension;
step D: adding the solution obtained in the step C into a 50mL stainless steel reaction kettle with polytetrafluoroethylene lining, keeping at 160 ℃ for 3 hours, alternately washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol for multiple times, and then drying at 100 ℃ for 8 hours to obtain the two-dimensional BiVO 4 A nanoplatelet sample.
50mg of two-dimensional BiVO is added into 50mL of lead ion solution with the concentration of 70mg/L 4 And stirring the nano sheet sample for 2 hours in a dark place to ensure that lead ions reach adsorption-desorption balance on the surface of the sample. Then the light source is started, 10ml reaction solutions are taken every time at fixed intervals, high-speed centrifugal separation is carried out, and the supernatant is taken for analysis. Inductively coupled plasma mass spectrometer (ICP-MS) results indicate two-dimensional BiVO 4 The degradation rate of the nano sheet sample to lead ions is 25.7%.
Example 2
GQDs/BiVO 4 The preparation steps of (a) are as follows:
step A: 1mmol of Bi (NO) 3 ) 3 •5H 2 O (0.485, g) and 0.72mmol SDBS (0.250, g) were dissolved in 10mL of 4M nitric acid to give a homogeneous solution;
and (B) step (B): 1mmol of NH 4 VO 3 (0.117, g) in 10mL of 2M aqueous NaOH;
step C: adding the solution obtained in the step B into the solution obtained in the step A, then slowly adding a proper amount of 2M NaOH aqueous solution, adjusting the pH value to 6.5, and stirring to obtain uniform suspension;
and D, according to the mass ratio: GQDs: biVO (BiVO) 4 =1:100 taking graphene quantum dot solution with concentration of 0.324 mL being 1mg/mL, adding the solution obtained in step CIn the liquid;
step E: adding the solution obtained in the step D into a 50mL stainless steel reaction kettle with polytetrafluoroethylene lining, keeping at 160 ℃ for 3 hours, alternately washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol for multiple times, and then drying at 100 ℃ for 8 hours to obtain the target product 1%GQDs/BiVO 4 And (3) a sample.
50mg of 1% GQDs/BiVO was added to 50mL of a lead ion solution having a concentration of 70mg/L 4 The sample is stirred for 2 hours in a dark place, so that lead ions reach adsorption-desorption equilibrium on the surface of the sample. Then the light source is started, 10ml reaction solutions are taken every time at fixed intervals, high-speed centrifugal separation is carried out, and the supernatant is taken for analysis. ICP-MS results showed 1% GQDs/BiVO 4 The degradation rate of the sample to lead ions is 40%.
Example 3
GQDs/BiVO 4 The preparation steps of (a) are as follows:
step A: 1mmol of Bi (NO) 3 ) 3 •5H 2 O (0.485, g) and 0.72mmol SDBS (0.250, g) were dissolved in 10mL of 4M nitric acid to give a homogeneous solution;
and (B) step (B): 1mmol of NH 4 VO 3 (0.117, g) in 10mL of 2M aqueous NaOH;
step C: adding the solution obtained in the step B into the solution obtained in the step A, then slowly adding a proper amount of 2M NaOH aqueous solution, adjusting the pH value to 6.5, and stirring to obtain uniform suspension;
and D, according to the mass ratio: GQDs: biVO (BiVO) 4 2:100 graphene quantum dot solution with concentration of 0.648 mL being 1mg/mL is taken and added into the solution obtained in the step C;
step E: adding the solution obtained in the step D into a 50mL stainless steel reaction kettle with polytetrafluoroethylene lining, keeping at 160 ℃ for 3 hours, alternately washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol for multiple times, and then drying at 100 ℃ for 8 hours to obtain the target product 2%GQDs/BiVO 4 And (3) a sample.
50mg of 2% GQDs/BiVO was added to 50mL of a lead ion solution having a concentration of 70mg/L 4 Stirring the sample in a dark place for 2 hours to ensure that lead ions reach adsorption-desorption equilibrium on the surface of the sample. Then the light source is started, 10ml reaction solutions are taken every time at fixed intervals, high-speed centrifugal separation is carried out, and the supernatant is taken for analysis. ICP-MS results showed 2% GQDs/BiVO 4 The degradation rate of the sample to lead ions is 50%.
Example 4
GQDs/BiVO 4 The preparation steps of (a) are as follows:
step A: 1mmol of Bi (NO) 3 ) 3 •5H 2 O (0.485, g) and 0.72mmol SDBS (0.250, g) were dissolved in 10mL of 4M nitric acid to give a homogeneous solution;
and (B) step (B): 1mmol of NH 4 VO 3 (0.117, g) in 10mL of 2M aqueous NaOH;
step C: adding the solution obtained in the step B into the solution obtained in the step A, then slowly adding a proper amount of 2M NaOH aqueous solution, adjusting the pH value to 6.5, and stirring to obtain uniform suspension;
and D, according to the mass ratio: GQDs: biVO (BiVO) 4 C, taking a graphene quantum dot solution with the concentration of 0.972mL of 1mg/mL, and adding the graphene quantum dot solution into the solution obtained in the step C, wherein the concentration is=3:100;
step E: adding the solution obtained in the step D into a 50mL stainless steel reaction kettle with polytetrafluoroethylene lining, keeping at 160 ℃ for 3 hours, alternately washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol for multiple times, and then drying at 100 ℃ for 8 hours to obtain the target product 3%GQDs/BiVO 4 And (3) a sample.
50mg of 3% GQDs/BiVO was added to 50mL of a lead ion solution having a concentration of 70mg/L 4 The sample is stirred for 2 hours in a dark place, so that lead ions reach adsorption-desorption equilibrium on the surface of the sample. Then the light source is started, 10ml reaction solutions are taken every time at fixed intervals, high-speed centrifugal separation is carried out, and the supernatant is taken for analysis. ICP-MS results showed 3% GQDs/BiVO 4 The degradation rate of the sample to lead ions is 75.5%.
Example 5
30mg of Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl) was weighed into 20mL of deionized water and formulated as 10mM Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl) buffer at pH=8.5. 40mg of dopamine hydrochloride powder is weighed and added into the aboveIn the solution, 2mg/mL dopamine hydrochloride Tris-HCl buffer solution is formed by ultrasonic oscillation. 0.4g of 1% GQDs/BiVO obtained in example 2 was weighed out 4 Dissolving a sample in a dopamine hydrochloride Tris-HCl buffer solution, placing the solution in an oil bath kettle, stirring the solution at 60 ℃ for 24 hours, cooling the obtained solution to room temperature, alternately washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol for multiple times, and drying the product at 60 ℃ for 12 hours to obtain a target product of 1% GQDs-loaded bismuth vanadate nanocomposite (marked as 1% GQDs/BiVO) 4 @10 PDA). FIG. 1 shows the synthesized 1% GQDs/BiVO 4 XRD spectrum of @10PDA sample, corresponding to monoclinic scheelite phase BiVO 4 (JCPDS No. 14-0688). FIGS. 2a, 2b and 2c are, respectively, 1% GQDs/BiVO synthesized in this example 4 Transmission electron microscopy and high resolution transmission electron microscopy of @10PDA samples, 2D BiVO can be seen 4 The amorphous PDA shell layer is wrapped around, the thickness of the shell layer is 5-17nm, and in figure 2b, the interplanar spacing is 0.31nm corresponding to BiVO 4 (-121) crystal plane of GQD, figure 2c with a 0.24nm interplanar spacing.
50mg of 1% GQDs/BiVO was added to 50mL of a lead ion solution having a concentration of 70mg/L 4 Stirring the sample @ PDA for 2 hours in a dark place to ensure that lead ions reach adsorption-desorption equilibrium on the surface of the sample. Then the light source is started, 10ml reaction solutions are taken every time at fixed intervals, high-speed centrifugal separation is carried out, and the supernatant is taken for analysis. ICP-MS results showed 1% GQDs/BiVO 4 The degradation rate of the sample at 10PDA to lead ions was 81%.
Example 6
30mg of Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl) was weighed into 20mL of deionized water and formulated as 10mM Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl) buffer at pH=8.5. 40mg of dopamine hydrochloride powder was weighed into the above solution, and sonicated to form 2mg/mL dopamine hydrochloride Tris-HCl buffer. 0.4g of 2% GQDs/BiVO obtained in example 3 was weighed out 4 Dissolving a sample in a dopamine hydrochloride Tris-HCl buffer solution, placing the solution in an oil bath kettle, stirring the solution at 60 ℃ for 24 hours, cooling the obtained solution to room temperature, alternately washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol for multiple times, and drying the product at 60 ℃ for 12 hours to obtain the target product 2% GQDs-loaded vanadiumBismuth acid nanocomposite (labeled 2% GQDs/BiVO 4 @10PDA）。
50mg of 2% GQDs/BiVO was added to 50mL of a lead ion solution having a concentration of 70mg/L 4 Stirring the sample at 10PDA for 2 hours in a dark place to ensure that lead ions reach adsorption-desorption equilibrium on the surface of the sample. Then the light source is started, 10ml reaction solutions are taken every time at fixed intervals, high-speed centrifugal separation is carried out, and the supernatant is taken for analysis. ICP-MS results showed 2% GQDs/BiVO 4 The degradation rate of lead ions by the sample @10PDA was 90%.
Example 7
30mg of Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl) was weighed into 20mL of deionized water and formulated as 10mM Tris (hydroxymethyl) aminomethane hydrochloride (Tris-HCl) buffer at pH=8.5. 40mg of dopamine hydrochloride powder was weighed into the above solution, and sonicated to form 2mg/mL dopamine hydrochloride Tris-HCl buffer. 0.4g of the 3% GQDs/BiVO obtained in example 4 was weighed out 4 Dissolving a sample in a dopamine hydrochloride Tris-HCl buffer solution, placing the solution in an oil bath kettle, stirring the solution at 60 ℃ for 24 hours, cooling the obtained solution to room temperature, alternately washing and centrifuging the obtained product with deionized water and absolute ethyl alcohol for multiple times, and drying the product at 60 ℃ for 12 hours to obtain a target product of 3% GQDs-loaded bismuth vanadate nanocomposite (marked as 3% GQDs/BiVO) 4 @10PDA）。
50mg of 3% GQDs/BiVO was added to 50mL of a lead ion solution having a concentration of 70mg/L 4 Stirring the sample at 10PDA for 2 hours in a dark place to ensure that lead ions reach adsorption-desorption equilibrium on the surface of the sample. Then the light source is started, 10ml reaction solutions are taken every time at fixed intervals, high-speed centrifugal separation is carried out, and the supernatant is taken for analysis. ICP-MS results showed 3% GQDs/BiVO 4 The degradation rate of lead ions by the sample @10PDA was 96%.
Although embodiments of the present invention have been described herein, it will be appreciated by those of ordinary skill in the art that changes can be made to the embodiments herein without departing from the spirit of the invention. The above-described embodiments are exemplary only, and should not be taken as limiting the scope of the claims herein.
Claims (4)
1. The application of the graphene quantum dot supported bismuth vanadate nanocomposite in high-efficiency degradation of heavy metal ions is characterized in that dopamine hydrochloride and GQDs/BiVO are subjected to 4 The mass ratio of the sample is as follows: dopamine hydrochloride: GQDs/BiVO 4 =1: 10-50% of the bismuth vanadate nanocomposite is added into a reaction container, and added into a tris hydrochloride buffer solution, heated and stirred to obtain a target product GQDs-loaded bismuth vanadate nanocomposite;
GQDs/BiVO 4 the preparation steps of (a) are as follows:
step A: 1mmol of Bi (NO) 3 ) 3 ·5H 2 O (0.485 g) and 0.72mmol SDBS (0.250 g) were dissolved in 10mL 4M nitric acid to give a homogeneous solution;
and (B) step (B): 1mmol of NH 4 VO 3 (0.117 g) in 10mL of 2M aqueous NaOH solution;
step C: adding the solution obtained in the step B into the solution obtained in the step A, then slowly adding a proper amount of 2M NaOH aqueous solution, adjusting the pH value to 6.5, and stirring to obtain uniform suspension;
step D: the mass ratio is as follows: GQDs: biVO (BiVO) 4 =1 to 3: c, 100, adding 0.162-0.972 mL of graphene quantum dot solution with the concentration of 1mg/mL into the solution obtained in the step C;
step E: adding the solution obtained in the step D into a 50mL stainless steel reaction kettle with polytetrafluoroethylene lining, maintaining at 160 ℃ for 3 hours, separating, washing and drying the obtained product to obtain a target product GQDs/BiVO 4 And (3) a sample.
2. The application of the graphene quantum dot supported bismuth vanadate nanocomposite in high-efficiency degradation of heavy metal ions as claimed in claim 1, which is characterized by comprising the following specific steps:
step 1: 30mg of tris hydrochloride was weighed into 20mL of deionized water and formulated as 10mm tris hydrochloride buffer at ph=8.5;
step 2: weighing 40mg of dopamine hydrochloride powder, adding the dopamine hydrochloride powder into the solution, and performing ultrasonic oscillation to form 2mg/mL of dopamine hydrochloride Tris-HCl buffer solution;
step 3: weighing 0.4-2 g of GQDs/BiVO 4 The sample is dissolved in the buffer solution obtained in the step 2 and placed in an oil bath pot, and the sample is stirred for 6-24 hours at the temperature of 60 ℃;
step 4: and (3) cooling the solution obtained in the step (3) to room temperature, and then separating, washing and drying the obtained product to obtain the target product GQDs-loaded bismuth vanadate nanocomposite.
3. The application of the graphene quantum dot supported bismuth vanadate nanocomposite in high-efficiency degradation of heavy metal ions as claimed in claim 2, wherein after solid substances are separated in the step 4, deionized water and absolute ethyl alcohol are used for alternately washing, and a target product is obtained after drying.
4. The application of the graphene quantum dot supported bismuth vanadate nanocomposite in high-efficiency degradation of heavy metal ions as claimed in claim 1, wherein after solid substances are separated in the step E, deionized water and absolute ethyl alcohol are used for alternately washing, and a target product is obtained after drying.
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