CN107790074B - Halloysite clay doped graphene aerogel and preparation method thereof - Google Patents

Halloysite clay doped graphene aerogel and preparation method thereof Download PDF

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CN107790074B
CN107790074B CN201610779181.1A CN201610779181A CN107790074B CN 107790074 B CN107790074 B CN 107790074B CN 201610779181 A CN201610779181 A CN 201610779181A CN 107790074 B CN107790074 B CN 107790074B
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halloysite
doped graphene
aerogel
graphene aerogel
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刘洪丽
何翔
李洪彦
褚鹏
李婧
李亚静
***
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Tianjin Chengjian University
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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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention discloses a halloysite clay doped graphene aerogel and a preparation method thereof. According to the invention, the aerogel of a tent-like three-dimensional network system with controllable microscopic sizes is successfully prepared by using the halloysite as a framework supporting structure and the graphene as a flaky crosslinking structure through an ultrasonic dispersion and hydrothermal crosslinking method, so that the application of the graphene aerogel in the adsorption field is widened.

Description

Halloysite clay doped graphene aerogel and preparation method thereof
Technical Field
The invention relates to a graphene aerogel of a fibrous clay support system and a preparation method thereof, in particular to a halloysite nanotube doped graphene aerogel applicable to the field of adsorption and a preparation method thereof, and belongs to the research of the field of nano composite materials.
Background
The graphene aerogel serving as a novel nano porous carbon material has excellent performances of a unique porous nano network structure, a higher specific surface area, developed porosity, controllable pore distribution and the like, and has great potential in the field of adsorption. However, the two-dimensional graphene material is assembled into a three-dimensional aerogel material by stacking sheets and sheet parts, and the stacking mode often causes the problem of low specific surface area. At present, graphene oxide is taken as a precursor, and the interaction between a carbon nano tube and functional groups on the surface and the edge of the graphene is utilized, so that the interlayer spacing of graphene sheets is increased, and the graphene/carbon nano tube aerogel material with high specific surface area and good adsorption effect on harmful gases such as formaldehyde is prepared. However, the carbon nanotubes are expensive and the cost is high, which limits the wide application of the carbon nanotubes in the adsorption field to a certain extent. Therefore, the problem that the graphene aerogel needs to be solved urgently in the application field of adsorption is to find a fiber tubular material with low price and high specific surface area to replace the carbon nano tube. Halloysite (HNTs) is a fibrous tubular structured, multilayer coiled aluminosilicate material with a typical crystalline structure. Compared with other nano materials (such as carbon nano tubes), the HNTs have good ion exchange property, adsorptivity and higher specific surface area, and have wide application prospect in the adsorption field. The biggest defect of HNTs is that the surface active groups of the tube wall are few, and the bulk porous material is difficult to form.
Disclosure of Invention
The invention completely overcomes the defects of the existing material of the original graphene aerogel, and aims to provide the clay-doped graphene aerogel with low cost and high adsorption performance and the preparation method thereof. By using the ultrasonic dispersion and hydrothermal crosslinking method, the halloysite as a framework supporting structure and the graphene as a flaky crosslinking structure, the aerogel of a tent-shaped three-dimensional network system with controllable microscopic sizes is successfully prepared, and the application of the graphene aerogel in the field of adsorption is widened.
The technical purpose of the invention is realized by the following technical scheme:
a halloysite clay doped graphene aerogel and a preparation method thereof are prepared according to the following steps:
step 1, adding 1-10 parts by mass of modified halloysite into a graphene oxide suspension, and fully stirring to obtain a uniform mixed solution;
in step 1, a graphene oxide suspension is prepared using a modified hummers method: 4g of graphite and 2g of potassium nitrate are mixed uniformly, and then 80ml of concentrated sulfuric acid (96 wt%) is added and stirred for 40 min; then adding 12g of potassium permanganate, and stirring in a water bath at 35 ℃ for 1.5h to obtain a dark green paste; and then adding 50ml of deionized water, stirring in a water bath at 90 ℃ for 20min, washing with deionized water, and purifying to obtain 200ml of graphene oxide suspension.
In step 1, the modified halloysite is prepared as follows: uniformly dispersing 5-10 parts by mass of natural halloysite and 1-3 parts by mass of modifier isooctyltriethoxysilane in an ethanol aqueous solution, and magnetically stirring at 60-80 ℃ for at least 1 hour, preferably 70-75 ℃ for 3-5 hours, wherein the volume ratio of ethanol to water in the ethanol aqueous solution is (1-2): (8-10).
Step 2, performing ultrasonic dispersion on the mixed solution prepared in the step 1, sealing the mixed solution in a hydrothermal reaction kettle, performing hydrothermal reaction at 160-200 ℃ for at least 1 hour to obtain black blocky halloysite clay graphene hydrogel (namely wet gel);
in the step 2, the hydrothermal temperature is 180-200 ℃, and the reaction time is 2-3 hours.
In the step 2, when ultrasonic dispersion is carried out, 50-100% of ultrasonic power is selected for ultrasonic treatment for 30-60 min.
Step 3, carrying out supercritical drying on the halloysite clay graphene hydrogel obtained in the step 2 to obtain a target product, namely halloysite clay doped graphene aerogel; parameters of supercritical drying: the temperature is 40-50 ℃, the pressure is 5-12 MPa, and the time is at least 8 hours.
In step 3, parameters for supercritical drying: the temperature is 40-45 ℃, the pressure is 8-10 MPa, and the time is 8-12 hours.
According to the technical scheme, the halloysite nanotube is used for replacing the carbon nanotube as a framework supporting structure, the graphene is used as a sheet-shaped cross-linked structure, and the prepared clay-doped graphene aerogel can fully utilize the advantages of high activity of the graphene and good crystallinity and adsorbability of halloysite and make up for the inherent defects of the graphene and the halloysite; and the addition of halloysite greatly reduces the using amount of graphene, greatly reduces the production cost of the aerogel, and is beneficial to the wide application of the aerogel in the adsorption field.
Compared with the prior art, the invention has the characteristics and advantages that: (1) microscopic morphology and structure: the structure is characterized by comprising a nanoscale microstructure, wherein halloysite plays a supporting role to enhance the mechanical property of aerogel, a three-dimensional space network structure is formed by wrapping halloysite in a graphene sheet layer or inserting halloysite into graphene, as shown in the attached figures 1-4, the doping amount of halloysite is increased, the supporting role is increased, and the space network structure of aerogel is more perfect; (2) high porosity and low density. Due to the special microscopic three-dimensional network structure, the graphene aerogel has extremely high porosity of 90-98 percent and apparent density of 0.095-0.098 g/cm3(ii) a (3) High specific surface area. The fibrous halloysite clay limits the self-agglomeration of the graphene aerogel in the hydrothermal generation process, so that the graphene aerogel has a higher specific surface area than the conventional graphene aerogel, and the average specific surface area can reach 200-300 m2The volume of the pores is 0.5-0.8 ml/g, and the average diameter of the pores is 12-15 nm, so that the application of the material in the field of adsorption is facilitated; (4) the microscopic size is controllable, and the microscopic pore structure of the clay-doped graphene can be controlled by adjusting the dosage of the graphene, the halloysite and the subsequent solvent; (5) the adsorption capacity is extremely strong: the method comprises the steps of adding the aerogel into MB aqueous solution with the initial concentration of 10mg/L, detecting MB in the aqueous solution after soaking for a certain time (at intervals of 10min) through fluorescence intensity, wherein in Methylene Blue (MB) adsorption test, the average adsorption capacity is 500-520 mg/g, the maximum adsorption capacity is 523mg/g, and adsorption kinetics research shows that adsorption is a heat absorption and spontaneous process, and the adsorption mechanism is probably due to mutual electrostatic interaction between MB and graphene aerogel. In addition, the graphene aerogel can be easily washed and regenerated by using a dilute NaOH aqueous solution (0.01-0.1M), and 80% of adsorption capacity can be circularly reserved for three times, namely the application of the aerogel serving as an adsorption material in removing methylene blue in a water body.
Drawings
Fig. 1 is an SEM picture of graphene aerogel with low halloysite doping content according to the present invention.
Fig. 2 is an SEM picture of the graphene aerogel when the halloysite is highly doped according to the present invention.
Fig. 3 is an SEM picture of a composite mode of graphene and halloysite in the aerogel according to the present invention.
Fig. 4 is a schematic model diagram of a halloysite clay doped graphene aerogel according to the invention.
Fig. 5 is an infrared spectrum of a halloysite clay doped graphene aerogel according to the invention.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
Firstly, a graphene oxide suspension is prepared by a modified hummers method: 4g of graphite and 2g of potassium nitrate are mixed uniformly, and then 80ml of concentrated sulfuric acid (96 wt%) is added and stirred for 40 min; then adding 12g of potassium permanganate, and stirring in a water bath at 35 ℃ for 1.5h to obtain a dark green paste; then 50ml of deionized water is added, the mixture is stirred in a water bath at 90 ℃ for 20min, and the mixture is washed and purified by the deionized water to obtain 200ml of graphene oxide suspension which is used in the subsequent examples.
Secondly, the modified halloysite is prepared according to the following method: the natural halloysite is modified by selecting a nano powder final-stage material, 5g of natural halloysite and 1g of modifier isooctyltriethoxysilane are uniformly dispersed in an ethanol aqueous solution (the volume ratio of ethanol to water is 2: 8), and the mixture is magnetically stirred for 3 hours at 75 ℃ to obtain the modified halloysite which is used in the subsequent examples.
Example 1
Step 1, taking 10ml of graphene oxide for suspension, adding 1g of modified halloysite nanometer powder into the graphene oxide suspension, and fully stirring to obtain a uniform mixed solution;
step 2, performing ultrasonic dispersion on the mixed solution prepared in the step 1, and performing ultrasonic treatment for 30 minutes under the condition of 50% power; and then introducing the mixture into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 180 minutes at 180 ℃ to obtain the black blocky clay graphene hydrogel.
And 3, performing supercritical drying on the hydrogel obtained in the step 2 to obtain the target product, namely the clay-doped graphene aerogel, wherein the supercritical drying conditions are as follows: the temperature is 45 ℃; the pressure is 8.0 MPa; and (5) performing supercritical drying for 12h by using carbon dioxide. The halloysite clay doped graphene aerogel is good in blocking property, uniform in internal microstructure and excellent in adsorption performance.
Example 2
Step 1, taking 10ml of graphene oxide for suspension, adding 5g of modified halloysite nanometer powder into the graphene oxide suspension, and fully stirring to obtain a uniform mixed solution;
step 2, performing ultrasonic dispersion on the mixed solution prepared in the step 1, and performing ultrasonic treatment for 30 minutes under the condition of 100% power; and then introducing the mixture into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 180 minutes at 160 ℃ to obtain the black blocky clay graphene hydrogel.
And 3, performing supercritical drying on the hydrogel obtained in the step 2 to obtain the target product, namely the clay-doped graphene aerogel, wherein the supercritical drying conditions are as follows: the temperature is 45 ℃; the pressure is 10 MPa; and (5) performing supercritical drying for 10h by using carbon dioxide. The halloysite clay doped graphene aerogel is good in blocking property, uniform in internal microstructure and excellent in adsorption performance.
Example 3
Step 1, taking 10ml of graphene oxide for suspension, adding 10g of modified halloysite nanometer powder into the graphene oxide suspension, and fully stirring to obtain a uniform mixed solution;
step 2, performing ultrasonic dispersion on the mixed solution prepared in the step 1, and performing ultrasonic treatment for 60 minutes under the condition of 80% power; and then introducing the mixture into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 60 minutes at the temperature of 200 ℃ to obtain the black blocky clay graphene hydrogel.
And 3, performing supercritical drying on the hydrogel obtained in the step 2 to obtain the target product, namely the clay-doped graphene aerogel, wherein the supercritical drying conditions are as follows: the temperature is 40 ℃; the pressure is 12 MPa; and (5) performing supercritical drying for 8h by using carbon dioxide. The halloysite clay doped graphene aerogel is good in blocking property, uniform in internal microstructure and excellent in adsorption performance.
Example 4
Step 1, taking 10ml of graphene oxide for suspension, adding 3g of modified halloysite nanometer powder into the graphene oxide suspension, and fully stirring to obtain a uniform mixed solution;
step 2, performing ultrasonic dispersion on the mixed solution prepared in the step 1, and performing ultrasonic treatment for 50 minutes under the condition of 60% power; and then introducing the mixture into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 120 minutes at 160 ℃ to obtain the black blocky clay graphene hydrogel.
And 3, performing supercritical drying on the hydrogel obtained in the step 2 to obtain the target product, namely the clay-doped graphene aerogel, wherein the supercritical drying conditions are as follows: the temperature is 50 ℃; the pressure is 8.0 MPa; and (5) performing supercritical drying for 8h by using carbon dioxide. The halloysite clay doped graphene aerogel is good in blocking property, uniform in internal microstructure and excellent in adsorption performance.
Example 5
Step 1, taking 10ml of graphene oxide for suspension, adding 5g of modified halloysite nanometer powder into the graphene oxide suspension, and fully stirring to obtain a uniform mixed solution;
step 2, performing ultrasonic dispersion on the mixed solution prepared in the step 1, and performing ultrasonic treatment for 40 minutes under the condition of 50% power; and then introducing the mixture into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 120 minutes at 180 ℃ to obtain the black blocky clay graphene hydrogel.
And 3, performing supercritical drying on the hydrogel obtained in the step 2 to obtain the target product, namely the clay-doped graphene aerogel, wherein the supercritical drying conditions are as follows: the temperature is 50 ℃; the pressure is 5 MPa; and (5) performing supercritical drying for 12h by using carbon dioxide. The halloysite clay doped graphene aerogel is good in blocking property, uniform in internal microstructure and excellent in adsorption performance.
Observing the micro morphology of the aerogel by adopting a JEOL JSM-7800F type scanning electron microscope, and successfully preparing the aerogel of a tent-shaped three-dimensional network system with controllable micro size by taking halloysite as a framework supporting structure and graphene as a flaky cross-linked structure as shown in the attached drawing. The aerogel is characterized by using infrared spectroscopy (Nicolet 380 Fourier transform infrared spectrometer of Thermo company in the United states), and as shown in the attached drawing, the aerogel comprehensively shows the characteristics of all components, which indicates that the halloysite and the graphene are successfully compounded.
According to the inventionThe process is adjusted, halloysite clay aerogel can be prepared, a nitrogen adsorption specific surface area tester (3H-2000PS1) of Behcet instruments and technology Limited company is adopted to test the pore structure, the specific surface junction and the like, meanwhile, a TC3000E type thermal conductivity coefficient tester of Xian Xiajxi electronic technology Limited company is used to test the thermal conductivity coefficient of the prepared aerogel product, and the adsorption test is carried out aiming at Methylene Blue (MB). The halloysite clay doped graphene aerogel has extremely high porosity of 90-98 percent and apparent density of 0.095-0.098 g/cm3(ii) a Has higher specific surface area which can reach 200-300 m on average2The volume of the pores is 0.5-0.8 ml/g, and the average diameter of the pores is 12-15 nm, so that the application of the material in the field of adsorption is facilitated; adding aerogel into MB aqueous solution with the initial concentration of 10mg/L, detecting MB in the aqueous solution after soaking for a certain time (at an interval of 10min) by fluorescence intensity, wherein in Methylene Blue (MB) adsorption test, the average adsorption capacity is 500-520 mg/g, and the maximum adsorption capacity is up to 523 mg/g; the average thermal conductivity coefficient can reach 0.015-0.025W/mK, which shows that the aerogel of the invention is used as a thermal insulation material in the thermal insulation of buildings.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (10)

1. The halloysite clay doped graphene aerogel is characterized in that halloysite is used as a framework supporting structure, graphene is used as a flaky cross-linking structure, the whole halloysite clay doped graphene aerogel is an aerogel of a tent-shaped three-dimensional network system, the porosity is as high as 90-98%, and the apparent density is 0.095-0.098 g/cm3The average specific surface area can reach 200-300 m2Per gram, pore volume 0.5-0.8 mL/g, average pore diameter 12-15 nm, and average thermal conductivity of 0.015-0.025W/mK; and the preparation is carried out according to the following steps:
step 1, adding 1-10 parts by mass of modified halloysite into a graphene oxide suspension, and fully stirring to obtain a uniform mixed solution; in step 1, preparing a graphene oxide suspension by using an improved hummers method; the modified halloysite is prepared according to the following method: uniformly dispersing 5-10 parts by mass of natural halloysite and 1-3 parts by mass of modifier isooctyltriethoxysilane in an ethanol aqueous solution, and magnetically stirring at 60-80 ℃ for at least 1 hour, wherein the volume ratio of ethanol to water in the ethanol aqueous solution is (1-2): (8-10);
step 2, performing ultrasonic dispersion on the mixed solution prepared in the step 1, sealing the mixed solution in a hydrothermal reaction kettle, performing hydrothermal reaction at 160-200 ℃ for at least 1 hour to obtain black blocky halloysite clay graphene hydrogel;
step 3, carrying out supercritical drying on the halloysite clay graphene hydrogel obtained in the step 2 to obtain a target product, namely halloysite clay doped graphene aerogel; parameters of supercritical drying: the temperature is 40-50 ℃, the pressure is 5-12 MPa, and the time is at least 8 hours.
2. The halloysite clay doped graphene aerogel according to claim 1, wherein in step 1, the modified halloysite is prepared according to the following method: uniformly dispersing 5-10 parts by mass of natural halloysite and 1-3 parts by mass of modifier isooctyltriethoxysilane in an ethanol aqueous solution, and reacting at 70-75 ℃ for 3-5 hours, wherein the volume ratio of ethanol to water in the ethanol aqueous solution is (1-2): (8-10).
3. The halloysite clay doped graphene aerogel according to claim 1, wherein in step 2, the hydrothermal temperature is 180-200 ℃ and the reaction time is 2-3 hours; when ultrasonic dispersion is carried out, 50-100% of ultrasonic power is selected for ultrasonic treatment for 30-60 min.
4. The halloysite clay doped graphene aerogel according to claim 1, wherein in step 3, the parameters of supercritical drying are as follows: the temperature is 40-45 ℃, the pressure is 8-10 MPa, and the time is 8-12 hours.
5. The preparation method of the halloysite clay doped graphene aerogel is characterized by comprising the following steps:
step 1, adding 1-10 parts by mass of modified halloysite into a graphene oxide suspension, and fully stirring to obtain a uniform mixed solution; in step 1, preparing a graphene oxide suspension by using an improved hummers method; the modified halloysite is prepared according to the following method: uniformly dispersing 5-10 parts by mass of natural halloysite and 1-3 parts by mass of modifier isooctyltriethoxysilane in an ethanol aqueous solution, and magnetically stirring at 60-80 ℃ for at least 1 hour, wherein the volume ratio of ethanol to water in the ethanol aqueous solution is (1-2): (8-10);
step 2, performing ultrasonic dispersion on the mixed solution prepared in the step 1, sealing the mixed solution in a hydrothermal reaction kettle, performing hydrothermal reaction at 160-200 ℃ for at least 1 hour to obtain black blocky halloysite clay graphene hydrogel;
step 3, carrying out supercritical drying on the halloysite clay graphene hydrogel obtained in the step 2 to obtain a target product, namely halloysite clay doped graphene aerogel; parameters of supercritical drying: the temperature is 40-50 ℃, the pressure is 5-12 MPa, and the time is at least 8 hours.
6. The preparation method of the halloysite clay doped graphene aerogel according to claim 5, wherein in the step 1, the modified halloysite is prepared according to the following method: uniformly dispersing 5-10 parts by mass of natural halloysite and 1-3 parts by mass of modifier isooctyltriethoxysilane in an ethanol aqueous solution, and reacting at 70-75 ℃ for 3-5 hours, wherein the volume ratio of ethanol to water in the ethanol aqueous solution is (1-2): (8-10).
7. The preparation method of the halloysite clay doped graphene aerogel according to claim 5, wherein in the step 2, the hydrothermal temperature is 180-200 ℃, and the reaction time is 2-3 hours; when ultrasonic dispersion is carried out, 50-100% of ultrasonic power is selected for ultrasonic treatment for 30-60 min.
8. The preparation method of the halloysite clay doped graphene aerogel according to claim 5, wherein in the step 3, the parameters of supercritical drying are as follows: the temperature is 40-45 ℃, the pressure is 8-10 MPa, and the time is 8-12 hours.
9. The use of the halloysite clay doped graphene aerogel of claim 1 as an adsorbent material for the removal of methylene blue from a body of water.
10. Use of the halloysite clay doped graphene aerogel of claim 1 as an insulation material for building insulation.
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