CN112473642B - Graphene oxide modified attapulgite, preparation method and application thereof - Google Patents
Graphene oxide modified attapulgite, preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 123
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 110
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 229910002804 graphite Inorganic materials 0.000 claims description 19
- 239000010439 graphite Substances 0.000 claims description 19
- 239000010865 sewage Substances 0.000 claims description 17
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 7
- 239000004317 sodium nitrate Substances 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 5
- 238000011534 incubation Methods 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 description 22
- 238000001069 Raman spectroscopy Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000003911 water pollution Methods 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 235000019730 animal feed additive Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
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- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- -1 papermaking Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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Classifications
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B01J35/39—
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
-
- 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
A preparation method of graphene oxide modified attapulgite comprises the following steps of (1) mixing: uniformly mixing attapulgite and graphene oxide dispersion liquid in a mixer; (2) drying: heating and drying the mixture obtained in the step (1) in air or drying the mixture in vacuum; (3) crushing: and (3) grinding the mixture obtained in the step (2) to the required granularity by adopting a ball mill to obtain the graphene oxide modified attapulgite.
Description
Technical Field
The application belongs to the field of inorganic functional materials. In particular to graphene oxide modified attapulgite, a preparation method and application thereof.
Background
The problem of environmental pollution has become serious since the entrance of human society into industrial civilization. The environmental pollution which adversely affects human health mainly includes air pollution, water pollution, soil pollution, and the like. Water is a source of life, and water pollution control is also an important point in environmental control. At present, photocatalysis technology is widely used for treating water pollution. The principle of water pollution treatment by photocatalysis is as follows: the sunlight irradiates on the photocatalyst to induce various active components such as hydroxyl free radicals, superoxide free radicals and the like, and the active components can cooperatively degrade organic pollutants in polluted water, so that the problems of eutrophication of the polluted water and over-high chemical oxygen demand are solved, and the aim of purifying the polluted water is fulfilled.
Graphene is a new material with wide application, and in recent years, graphene composite materials are also used in the field of sewage treatment. The graphene material has good electron transmission performance, can be combined with a photocatalytic material in the process of degrading organic pollutants in water by photocatalysis, and can be used as an adsorbent and an electron acceptor in the photocatalysis process, so that the degradation efficiency of organic matters and heavy metal pollutants in the photocatalysis sewage treatment process can be greatly enhanced.
However, the graphene composite material for water treatment currently existing has the defects of high cost, difficulty in large-scale industrial production and the like.
An attapulgite crystalline hydrated magnesium aluminum silicate mineral has unique lamellar chain structural characteristics, lattice substitution exists in the structure of the mineral, and crystals are needle-shaped, fibrous or fiber-gathered. The attapulgite has unique good colloid properties of dispersion, high temperature resistance, salt and alkali resistance and the like, higher adsorption decolorization capability and an intermediate structure between a chain structure and a layered structure.
The unique crystal structure of the attapulgite enables the attapulgite to have a plurality of special physical and chemical properties and technological properties. The main physical and chemical properties and the technological properties are as follows: cation-exchangeable property, water-absorbing property, adsorption-decolorizing property, and large specific surface area (9.6-36 m 2 /g) gum price and expansion volume. These physicochemical properties are similar to those of montmorillonite.
The intermediate structure of the attapulgite between the chain structure and the layered structure is used as a carrier of Graphene Oxide (GO) to form the attapulgite@GO composite material, so that the technical bottlenecks of insufficient agglomeration and dispersion in the GO application process are skillfully solved. The application provides a sewage purification material with excellent performance based on the excellent performance of the composite material produced by combining attapulgite and graphene oxide.
Disclosure of Invention
In order to improve the prior art, the application aims to provide a preparation method of graphene oxide modified attapulgite, a product and application thereof. The application provides the following technical scheme:
a method for preparing graphene oxide modified attapulgite, the method comprising:
(1) Mixing: uniformly mixing attapulgite and graphene oxide dispersion liquid in a mixer;
(2) And (3) drying: heating and drying the mixture obtained in the step (1) in air or drying the mixture in vacuum;
(3) Crushing: and (3) grinding the mixture obtained in the step (2) to the required granularity by adopting a ball mill to obtain the graphene oxide modified attapulgite.
According to one embodiment of the present application, for example, in the step (1), the mixing mass ratio of the attapulgite to the Graphene Oxide dispersion liquid is 1:0.5-1:10, so that Graphene Oxide modified attapulgite with different Graphene Oxide contents can be obtained, the Graphene Oxide mass content is 0.25% -5%, and the Graphene Oxide modified attapulgite is marked as [email protected]% GO to attapulgite@5% GO, wherein GO is an abbreviation of Graphene Oxide, namely Graphene Oxide.
According to one embodiment of the present application, for example, in the step (2), the temperature of the drying in air is not more than 120 ℃, and the temperature of the vacuum drying is not more than 100 ℃; drying time is 2h to ultra
24h；
Preferably, in the step (3), the time for grinding by the ball mill is 2 to 8 hours.
The embodiment of the application provides a preparation method of graphene oxide modified attapulgite, which comprises the following steps:
(1) Mixing: uniformly mixing attapulgite and graphene oxide dispersion liquid in a mixer;
(2) Spray drying: and the temperature of the hot air is not more than 120 ℃, so that the graphene oxide modified attapulgite is obtained.
According to one embodiment of the application, for example, the mixing mass ratio of the attapulgite to the Graphene Oxide dispersion is 1:4-1:10, so as to obtain the attapulgite@GO composite material with different Graphene Oxide contents, wherein the mass content of GO is 2% -5%, and the attapulgite@2%GO-attapulgite@5%GO is marked as attapulgite@2%, wherein GO is an abbreviation of Graphene Oxide, namely Graphene Oxide.
The embodiment of the application provides graphene oxide modified attapulgite, which is prepared by adopting the preparation method.
According to one embodiment of the present application, for example, in the above-mentioned use, the graphene oxide modified attapulgite is mixed with sewage for purifying water;
preferably, in the graphene oxide modified attapulgite, the mass ratio of the attapulgite to the graphene oxide is between 100:2 and 100:5;
preferably, the mass ratio of the graphene oxide modified attapulgite to the sewage is 1:100000-1:100, more preferably 1:10000-1:1000.
according to one embodiment of the application, for example, the wastewater is running water or a stationary body of water;
preferably, the graphene oxide modified attapulgite is mixed with the sewage for at least 7 days, and more preferably, the graphene oxide modified attapulgite is mixed with the sewage for at least 14 days.
According to one embodiment of the present application, for example, the graphene oxide dispersion is prepared by the following method:
(a) Adding high-purity flake graphite and sodium nitrate into concentrated sulfuric acid, refrigerating to 0 ℃, stirring all the time, and preserving heat at 0 ℃ for a period of time;
(b) Slowly adding potassium permanganate, keeping the temperature at 0-5 ℃ in the process of potassium permanganate, and continuously stirring for a period of time;
(c) Heating to 30-50deg.C, and stirring for a while;
(d) Stopping heating, continuing stirring, slowly adding a certain amount of deionized water, and controlling the temperature of the system below 90 ℃;
(e) Adding a certain amount of 30% hydrogen peroxide by mass fraction under the condition that the temperature of the system is controlled to be not higher than 80 ℃, stirring for 5-20 minutes, and taking out;
(f) Washing graphene oxide, separating, measuring the content of graphene oxide in water, and adding metered pure water to prepare graphene oxide dispersion liquid with a certain concentration;
preferably, the high purity flake graphite has a size of 200 mesh to 1200 mesh, preferably 200 mesh to 1000 mesh, more preferably 300 mesh to 1000 mesh, more preferably 400 mesh to 800 mesh;
preferably, said incubation in step (a) is for a period of time >1h, preferably >2h; preferably, said incubation in step (a) is for a period of time ranging from 1h to 5h, preferably from 2h to 4h;
preferably, the system temperature in step (d) is controlled between 70℃and 90℃and preferably at 75℃for a period of time
85 ℃, more preferably from 77 ℃ to 82 ℃, most preferably from 80 ℃;
preferably, the washing graphene oxide in step (f) is: repeatedly washing graphene oxide with deionized water to neutrality;
preferably, the purity of the high purity flake graphite is >95%, preferably >97%, preferably >98%;
preferably, in step (a), the mass ratio of the high purity flake graphite to the sodium nitrate is 1:0.5-1.5, preferably 1:0.8-1.2, preferably 1:1;
preferably, in step (a), the ratio of the amount of the high-purity crystalline flake graphite to the concentrated sulfuric acid is 1g (30-80 mL), preferably 1g (40-60 mL), preferably 1g:50mL;
preferably, the mass of the potassium permanganate in step (b) is 3-10 times, preferably 4-8 times, preferably 6 times the mass of the high purity flake graphite in step (a);
preferably, the stirring continued in step (a) is continued for a period of time ranging from 30 to 120 minutes, preferably from 60 to 100 minutes, preferably 90 minutes;
preferably, the stirring is continued for a period of time in step (c) of from 1 to 3 hours, preferably 2 hours.
Preferably, the volume ratio of deionized water in step (d) to concentrated sulfuric acid in step (a) is (0.6-1.0): 1, preferably 0.8:1;
preferably, the volume ratio of the hydrogen peroxide with the mass fraction of 30% in the step (e) to the concentrated sulfuric acid in the step (a) is (0.05-0.2): 1, preferably 0.1:1;
preferably, step (c) is: heating to 40 ℃ and continuing stirring for a period of time;
preferably, step (e) is: adding a certain amount of 30% hydrogen peroxide by mass fraction under the condition that the temperature of the system is controlled to be not higher than 80 ℃, stirring for 10 minutes, and taking out.
Detailed Description
The electroluminescent material and the device according to the application will be further described with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the application. All techniques implemented based on the above description of the application are intended to be included within the scope of the application.
Preparation characterization example 1 preparation and characterization of an attapulgite @ GO composite
The raw materials for preparing the attapulgite@GO composite material mainly comprise two types: (1) Natural attapulgite with a particle size of less than 320 meshes (i.e. a particle size of less than 44 microns) is adopted, and the commercial specification is 500 meshes; (2) graphene oxide dispersion, concentration is 5mg/mL.
The preparation method of the graphene oxide dispersion liquid comprises the following steps:
(1) Adding 2g of 500-mesh high-purity crystalline flake graphite and 2g of sodium nitrate into 100mL of concentrated sulfuric acid, refrigerating to 0 ℃, stirring all the time, and preserving heat for 2h at 0 ℃;
(2) Slowly adding 12g of potassium permanganate, keeping the temperature at 0-5 ℃ in the process of adding the potassium permanganate, and continuously stirring for 90 minutes;
(3) Heating to 40 ℃ and continuously stirring for 2 hours;
(4) Stopping heating, continuing stirring, slowly adding 80mL of deionized water, and controlling the temperature of the system at 80 ℃;
(5) Adding 10mL of 30% hydrogen peroxide by mass fraction under the condition that the temperature of the system is controlled to be not more than 80 ℃, stirring for 10 minutes, and taking out;
(6) Repeatedly washing the obtained graphene oxide with deionized water to neutrality and separating, and then adding metered pure water to prepare a graphene oxide dispersion liquid with the concentration of 5mg/mL by measuring the content of the graphene oxide in the water.
The graphene oxide dispersion liquid is characterized by adopting means such as an atomic force microscope, an SEM (scanning electron microscope), a TEM (transmission electron microscope), an EDS (electron discharge spectroscopy), a Raman spectrum, a UV-Vis (ultraviolet and visible light) spectrum and the like, and the graphene oxide dispersion liquid comprises the following components: the graphene oxide sheet diameter is 400-1200 nm, the single-layer rate is more than 90%, the purity of the graphene oxide is more than 99%, the dispersion liquid is pure water, the graphene oxide concentration is 5mg/mL, and the graphene oxide sheet diameter does not contain any non-graphene substances such as dispersing agents; the forbidden bandwidth is 1.71-5.0 eV, and the corresponding intrinsic absorption wavelength limit is 245-725 nm, namely, the ultraviolet and visible light range has wide absorption.
The preparation methods of the attapulgite@GO composite material comprise two types, and any one preparation method can be selected according to different graphene oxide contents.
Method 1: mainly comprises the following steps of the method,
(1) Mixing: uniformly mixing attapulgite and graphene oxide dispersion liquid in a mixer, wherein the mixing ratio of the attapulgite to the graphene oxide dispersion liquid is 1:0.5-1:10, and the attapulgite@GO composite materials with different graphene oxide contents can be obtained, wherein the mass content of GO is 0.25% -5%, and the [email protected]% -attapulgite@5%GO is marked;
(2) And (3) drying: the material can be heated and dried in air or vacuum dried, the drying temperature in the air is not more than 120 ℃, and the vacuum drying temperature is not more than 100 ℃; the drying time is not equal to 2-24 hours; the vacuum degree is generally 50Pa or less, preferably 20Pa or less, preferably 15Pa or less, preferably 10Pa or less.
(3) Crushing: grinding to the required granularity by adopting a ball mill, and generally, 2-8 hours are needed;
(4) Raman spectroscopy test.
Method 2: mainly comprises the following steps of the method,
(1) Mixing: uniformly mixing attapulgite and graphene oxide dispersion liquid in a mixer, wherein the mixing ratio of the attapulgite to the graphene oxide dispersion liquid is 1:4-1:10, and the attapulgite@GO composite material with different graphene oxide contents can be obtained, wherein the mass content of GO is 2% -5%, and the attapulgite@2% -attapulgite@5%GO is marked;
(2) Spray drying: the temperature of the hot air is not more than 120 ℃;
(3) Raman spectroscopy test.
The method 1 is a general method; for the composite material with high graphene oxide content, as the fluidity of the mixture obtained by mixing is high, the spray drying method 2 can be adopted, the flow is shorter, and the efficiency is higher.
And carrying out test characterization on the prepared attapulgite@GO composite material by adopting Raman spectrum. The testing method comprises the following steps: adopts a light source asThe Raman spectrum of the graphene consists of a plurality of peaks, mainly a G peak, a D peak and a 2D peak; graphene oxide has only G and D peaks, and no 2D peak. The G peak is the main characteristic peak of graphene, and is composed of sp 2 Caused by in-plane vibrations of carbon atoms, which occur at 1580cm -1 Nearby, the peak can effectively reflect the number of layers of graphene, but is extremely susceptible to stress. The D peak is generally considered to be a disordered vibrational peak of graphene, the specific location of which appears as a function of the laser wavelength, due to lattice vibration away from the center of the brillouin zone, which is used to characterize structural defects or edges in graphene samples, which appear at 1350cm -1 Left and right. The 2D peak is a double phonon resonance second-order Raman peak used for representing an interlayer stacking mode of carbon atoms in a graphene sample, and the peak-out frequency of the 2D peak is also influenced by a laser wavelength and appears at 2700cm -1 Left and right. The graphene oxide in the graphene oxide dispersion liquid prepared according to the embodiment only has a D peak and a G peak, and if a 2D peak appears, it indicates that the graphene oxide has been partially reduced, and the special structure is changed.
Preparation examples 2 to 8
7 different attapulgite @ GO composites were prepared and Raman tested according to the preparation (method 1) and characterization method described in preparation characterization example 1 above, and the results are set forth in table 1 below.
TABLE 1 preparation of Attapulgite @ GO composite-composition and Process parameters (vacuum, temperature, time)
Note 1: a vacuum having a pressure of less than or equal to 20 Pa.
As can be seen from the results of table 1, the Raman test results of examples 2-4 and 6-7 all show no 2D peak, indicating that the structure of graphene oxide is well maintained; the Raman test results of examples 5, 8, however, found a 2D peak, indicating that graphene oxide has been partially reduced, i.e., the specific structure of the catalytically active graphene was altered by partial thermal reduction. The concentration of the graphene oxide dispersion used in examples was 5mg/mL, and it can be calculated that the mass ratio of attapulgite to graphene oxide in examples 2-8 was 100:0.25.
Preparation examples 9 to 16
According to the preparation (method 1) and characterization method described in preparation characterization example 1 above, 8 different attapulgite @ GO composites were prepared and Raman tested and the results are listed in table 2 below.
TABLE 2 preparation of Attapulgite @ GO composite-composition and Process parameters (vacuum, temperature, time)
Note 1: a vacuum having a pressure of less than or equal to 20 Pa.
As can be seen from the results of table 2 above, none of the Raman test results of examples 9-16 found a 2D peak, indicating that the structure of graphene oxide remained better. Comparing examples 9-16 with examples 2-8, the main difference is that the amount of the graphene oxide dispersion liquid in examples 9-16 is increased, and the concentration of the graphene oxide dispersion liquid used in examples is 5mg/mL, so that it can be calculated that the mass ratio of the attapulgite to the graphene oxide in examples 9-16 is between 100:2 and 100:5, and the results in Table 2 show that the product performance obtained in the above proportioning interval is better.
Preparation examples 17 to 23
7 different attapulgite @ GO composites were prepared and Raman tested according to the preparation (method 2) and characterization method described in preparation characterization example 1 above, and the results are set forth in table 3 below.
TABLE 3 preparation-composition and Process of Attapulgite @ GO composite Material
As can be seen from the results of Table 3 above, no 2D peak was found from the Raman test results of examples 17-23, indicating that the structure of graphene oxide remained better. Comparing examples 17-23 with examples 2-8, the main difference is that the amount of the graphene oxide dispersion liquid used in examples 17-23 is increased, and the concentration of the graphene oxide dispersion liquid used in examples is 5mg/mL, it can be calculated that the mass ratio of the attapulgite to the graphene oxide in examples 17-23 is three: from the results of Table 3, it can be seen that the above ratios gave good product properties, 100:2, 100:3.5 and 100:5.
Application examples 24 to 29
The products prepared in the above examples were used for water purification, and the results shown in Table 4 below were obtained.
TABLE 4 Attapulgite @ GO Water purification Effect
Note that: the attapulgite @0.25% go of example 26 was prepared using the method of example 2; the attapulgite @0.25% go of example 27 was prepared using the method of example 3 (examples 26 and 27 also achieve similar effects if the products of examples 4, 6-7 were used); the attapulgite @5% go of example 28 was prepared by the method of example 13; the attapulgite @5% go of example 29 was prepared using the method of example 14 (examples 28 and 29 also achieve a similar effect if other examples were used that produced attapulgite @5% go).
From the results of table 4 above, the following conclusions can be drawn:
(1) The results of example 24 show that the use of GO-unsupported attapulgite in one thousandth can rapidly purify sewage and can be maintained for about 7 days; the results of example 25 show that the water purifying capacity is greatly reduced and the water quality cannot be maintained when the usage amount is one ten thousandth;
(2) The results of example 26 show that the attapulgite @0.25% go is used in an amount of one thousandth to quickly purify the sewage and maintain the sewage for about 14d, and compared with the results of example 24, the water purification effect is better than that of the pure attapulgite, and the difference after 14d treatment is more obvious;
(3) The results of example 27 show that the sewage purification speed is slow when the attapulgite @ GO is used in one ten thousandth, but the water quality can be continuously purified and can be kept for 14d, and compared with the results of example 24, the water purification effect of example 27 after 14d treatment is obviously better than that of example 24 which uses attapulgite alone;
(4) The results of example 29 show that water quality can be purified and maintained for 14d using high GO attapulgite @5% GO in an amount of one tenth of ten million; whereas example 28 shows that the best water purification effect is achieved with high GO attapulgite @5% GO in one ten thousandth;
(5) The results of examples 24-29 show that maintaining water quality is actually related to the GO concentration used during treatment and also to treatment time; the effect of loading the GO on the attapulgite is not obvious after 4 hours of treatment, but the water purifying effect of the attapulgite@GO is close to or even exceeds that of pure attapulgite after 7 days of treatment; the treatment is carried out for 14 days, the timely dosage is only one tenth, even one thousandth, of that of pure attapulgite, and the water purifying effect of attapulgite@GO is comprehensively outweighed; the water purifying effect of the attapulgite@GO is long-acting, and the dosage of the GO-loaded water purifying agent can be greatly reduced, so that the cost is reduced on one hand, and the secondary pollution is also greatly reduced on the other hand.
The following conclusions can be drawn from the results of examples 1-29 above:
(1) The intermediate structure of the attapulgite between the chain structure and the layered structure is used as a carrier of the graphene to form the attapulgite@GO composite material, so that the technical bottleneck of insufficient agglomeration and dispersion in the GO application process is skillfully solved;
(2) Because of the special physical and chemical properties and technological properties of the attapulgite clay (namely the attapulgite clay), the attapulgite clay is widely applied to the fields of petroleum, chemical industry, building materials, papermaking, medicine, agriculture and the like; the largest domestic consumption is that paint, drilling mud and edible oil are decolorized; the attapulgite@GO composite material can be applied to the fields as well;
(3) The attapulgite@GO composite material has the characteristics of graphene oxide besides the characteristics of the attapulgite material;
(4) The graphene oxide dispersion liquid can be used for purifying the water quality of natural environment sewage, but the graphene oxide is lost in a flowing water body, so that the problem of graphene oxide concentration in the water body is difficult to maintain, the problem of graphene oxide loss can be effectively solved after the attapulgite@GO composite material is adopted, the attapulgite@GO composite material can remain at the bottom of the water body for a long time, experiments prove that the water quality can be obviously improved after the general treatment for 7-14 days, and the records in a laboratory show that the good water quality is maintained for 4 years all the time;
(5) The graphene oxide, the attapulgite and the composite materials thereof are evaluated through a third-party biosafety test, and the attapulgite can be used as an animal feed additive, so that new pollutants are not brought when the graphene oxide modified attapulgite is used for sewage treatment.
The embodiments of the present application have been described in detail above. However, the present application is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (11)
1. The preparation method of the graphene oxide modified attapulgite is characterized by comprising the following steps of:
(1) Mixing: uniformly mixing attapulgite and graphene oxide dispersion liquid in a mixer;
(2) And (3) drying: heating and drying the mixture obtained in the step (1) in air or drying the mixture in vacuum;
(3) Crushing: grinding the mixture obtained in the step (2) to a required granularity by adopting a ball mill to obtain the graphene oxide modified attapulgite;
the graphene oxide dispersion liquid is prepared by the following method:
(a) Adding high-purity flake graphite and sodium nitrate into concentrated sulfuric acid, refrigerating to 0 ℃, stirring all the time, and preserving heat at 0 ℃ for a period of time;
(b) Slowly adding potassium permanganate, keeping the temperature at 0-5 ℃ in the process of potassium permanganate, and continuously stirring for a period of time;
(c) Heating to 30-50deg.C, and stirring for a while;
(d) Stopping heating, continuing stirring, slowly adding a certain amount of deionized water, and controlling the temperature of the system at 70-90 ℃;
(e) Adding a certain amount of 30% hydrogen peroxide by mass fraction under the condition that the temperature of the system is controlled to be not higher than 80 ℃, stirring for 5-20 minutes, and taking out;
(f) Washing graphene oxide, separating, measuring the content of graphene oxide in water, and adding metered pure water to prepare graphene oxide dispersion liquid with a certain concentration;
the size of the high-purity flake graphite is 200-1200 meshes;
the incubation period in step (a) is >1h;
the temperature of the system in the step (d) is controlled to be 70-90 ℃;
the washing graphene oxide in step (f) is: repeatedly washing graphene oxide with deionized water to neutrality;
the purity of the high-purity flake graphite is more than 95%;
in the step (a), the mass ratio of the high-purity crystalline flake graphite to the sodium nitrate is 1:0.5-1.5;
in the step (a), the dosage ratio of the high-purity crystalline flake graphite to the concentrated sulfuric acid is 1g (30-80 mL);
the mass of the potassium permanganate in the step (b) is 3-10 times that of the high-purity flake graphite in the step (a);
the stirring is continued for a period of time in the step (a) of 30-120min;
the stirring is continued for a period of time in the step (c) of 1-3 hours;
the volume ratio of the deionized water in the step (d) to the concentrated sulfuric acid in the step (a) is (0.6-1.0): 1;
the volume ratio of the hydrogen peroxide with the mass fraction of 30% in the step (e) to the concentrated sulfuric acid in the step (a) is (0.05-0.2): 1;
the step (c) is as follows: heating to 40 ℃ and continuing stirring for a period of time;
the step (e) is as follows: adding a certain amount of 30% hydrogen peroxide by mass fraction under the condition that the temperature of the system is controlled to be not higher than 80 ℃, stirring for 10 minutes, and taking out.
2. The method according to claim 1, wherein in the step (2), the temperature of the drying in air is not more than 120 ℃, and the temperature of the vacuum drying is not more than 100 ℃; the drying time is 2-24 hours.
3. The method according to claim 1, wherein in the step (3), the time of grinding with a ball mill is 2h to 8h.
4. The preparation method of the graphene oxide modified attapulgite is characterized by comprising the following steps of:
(1) Mixing: uniformly mixing attapulgite and graphene oxide dispersion liquid in a mixer;
(2) Spray drying: the temperature of the hot air point is not more than 120 ℃, and the graphene oxide modified attapulgite is obtained;
the graphene oxide dispersion liquid is prepared by the following method:
(a) Adding high-purity flake graphite and sodium nitrate into concentrated sulfuric acid, refrigerating to 0 ℃, stirring all the time, and preserving heat at 0 ℃ for a period of time;
(b) Slowly adding potassium permanganate, keeping the temperature at 0-5 ℃ in the process of potassium permanganate, and continuously stirring for a period of time;
(c) Heating to 30-50deg.C, and stirring for a while;
(d) Stopping heating, continuing stirring, slowly adding a certain amount of deionized water, and controlling the temperature of the system at 70-90 ℃;
(e) Adding a certain amount of 30% hydrogen peroxide by mass fraction under the condition that the temperature of the system is controlled to be not higher than 80 ℃, stirring for 5-20 minutes, and taking out;
(f) Washing graphene oxide, separating, measuring the content of graphene oxide in water, and adding metered pure water to prepare graphene oxide dispersion liquid with a certain concentration;
the size of the high-purity flake graphite is 200-1200 meshes;
the incubation period in step (a) is >1h;
the temperature of the system in the step (d) is controlled to be 70-90 ℃;
the washing graphene oxide in step (f) is: repeatedly washing graphene oxide with deionized water to neutrality;
the purity of the high-purity flake graphite is more than 95%;
in the step (a), the mass ratio of the high-purity crystalline flake graphite to the sodium nitrate is 1:0.5-1.5;
in the step (a), the dosage ratio of the high-purity crystalline flake graphite to the concentrated sulfuric acid is 1g (30-80 mL);
the mass of the potassium permanganate in the step (b) is 3-10 times that of the high-purity flake graphite in the step (a);
the stirring is continued for a period of time in the step (a) of 30-120min;
the stirring is continued for a period of time in the step (c) of 1-3 hours;
the volume ratio of the deionized water in the step (d) to the concentrated sulfuric acid in the step (a) is (0.6-1.0): 1;
the volume ratio of the hydrogen peroxide with the mass fraction of 30% in the step (e) to the concentrated sulfuric acid in the step (a) is (0.05-0.2): 1;
the step (c) is as follows: heating to 40 ℃ and continuing stirring for a period of time;
the step (e) is as follows: adding a certain amount of 30% hydrogen peroxide by mass fraction under the condition that the temperature of the system is controlled to be not higher than 80 ℃, stirring for 10 minutes, and taking out.
5. A graphene oxide modified attapulgite clay, characterized in that the graphene oxide modified attapulgite clay is prepared by the method according to any one of claims 1-4.
6. Use of the graphene oxide modified attapulgite according to claim 5, wherein the graphene oxide modified attapulgite is mixed with sewage for purifying water.
7. Use of a graphene oxide modified attapulgite according to claim 6, wherein the mass ratio of the attapulgite to the graphene oxide in the graphene oxide modified attapulgite is between 100:2 and 100:5.
8. Use of the graphene oxide modified attapulgite according to claim 7, wherein the mass ratio of the graphene oxide modified attapulgite to the sewage is 1:100000-1:100.
9. the use according to claim 6, wherein the contaminated water is running water or a stationary body of water.
10. The use according to claim 9, wherein the graphene oxide modified attapulgite is mixed with sewage for at least 7 days.
11. The use according to claim 9, wherein the graphene oxide modified attapulgite is mixed with sewage for at least 14 days.
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| CN102225754A (en) * | 2011-05-11 | 2011-10-26 | 中国科学技术大学 | Preparation method of graphene oxide and preparation method of graphene |
| CN106902759A (en) * | 2017-03-29 | 2017-06-30 | 兰州石化职业技术学院 | A kind of preparation method of graphene oxide modified attapulgite composite adsorbing material |
| CN108993380A (en) * | 2018-07-31 | 2018-12-14 | 西安科技大学 | Graphene oxide/attapulgite magnetic composite material preparation method and applications |
| CN109179392A (en) * | 2018-09-05 | 2019-01-11 | 七台河宝泰隆石墨烯新材料有限公司 | A kind of technique of improved chemical method production graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102225754A (en) * | 2011-05-11 | 2011-10-26 | 中国科学技术大学 | Preparation method of graphene oxide and preparation method of graphene |
| CN106902759A (en) * | 2017-03-29 | 2017-06-30 | 兰州石化职业技术学院 | A kind of preparation method of graphene oxide modified attapulgite composite adsorbing material |
| CN108993380A (en) * | 2018-07-31 | 2018-12-14 | 西安科技大学 | Graphene oxide/attapulgite magnetic composite material preparation method and applications |
| CN109179392A (en) * | 2018-09-05 | 2019-01-11 | 七台河宝泰隆石墨烯新材料有限公司 | A kind of technique of improved chemical method production graphene |
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