CN113772667A - Graphene oxide-based porous photothermal material capable of efficiently generating solar steam, and preparation method and application thereof - Google Patents
Graphene oxide-based porous photothermal material capable of efficiently generating solar steam, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a graphene oxide-based porous photothermal material capable of efficiently generating solar steam, which comprises the following steps: s1, preparing graphene oxide by a hummers method; s2, preparing the graphene oxide-based porous photothermal material in an oriented arrangement manner; s3, preparing the hydrophilic oleophobic oxidized graphene-based porous photo-thermal material. The invention firstly introduces a synthesis method of a graphene oxide-based porous photothermal material which can efficiently generate solar steam and has an aligned channel and oleophobicity by taking directional freezing and simple carbonization as main means. The application of the method in seawater desalination and wastewater purification treatment (containing oil or dye) is introduced secondly. The graphene oxide-based porous photothermal material has high solar energy conversion efficiency and excellent salt resistance and stain resistance, and has certain practical application value in the aspects of seawater desalination and (oil-containing and dye-containing) wastewater purification treatment in the future.
Description
Technical Field
The invention relates to a graphene oxide-based porous photothermal material capable of efficiently generating solar steam, a preparation method and application thereof, and also relates to application of the material in seawater desalination and wastewater (containing oil and dye) purification treatment.
Background
Nowadays, global warming and industrial pollution are getting more and more serious, and the conventional seawater desalination technologies, such as Reverse Osmosis (RO), microfiltration, ultrafiltration, multi-effect distillation, multi-stage flash evaporation, adsorption, etc., have limitations of low efficiency, high cost, redundant operation and huge energy consumption, which aggravate the greenhouse effect and environmental pollution, thereby hindering their large-scale application. Therefore, it is very slow to produce fresh water efficiently by using clean energy as input in a more practical way. Solar energy is an inexhaustible renewable energy source. Recently, solar steam desalination (SSG) has received increasing attention due to its high evaporation rate and solar conversion efficiency, simplicity and ease of operation, and the use of only clean solar radiation as an energy input. The conventional water evaporation has a disadvantage of low conversion efficiency due to ineffective conversion of most solar energy into a large amount of water or loss to the external environment, compared to the conventional water evaporation using solar radiation as a heat source, and the high solar conversion efficiency of the SSG is attributed to its unique interfacial evaporation mode, i.e., solar radiation is collected and located only at a water-air interface, heating a thin air-water surface layer, so that heat loss can be effectively reduced. Based on these advantages, SSG is considered to be one of the most efficient methods for desalination and production of fresh water. Ideal interface heating means for SSG production have the following advantages: wide solar absorption range, high photothermal conversion efficiency, low thermal conductivity, directional porosity, and rich porosity for water molecule transport. Materials used to date for efficient solar interface evaporation include carbon-based materials, conjugated microporous polymers, composites, biomass materials, and metal nanomaterials. It is well known that petroleum is ubiquitous in water, and most photothermal materials are hydrophilic and oleophilic. Once the oil pollutes the pores, water molecules cannot be normally conveyed to the surface of the sample, and the photothermal conversion efficiency of the photothermal material is greatly reduced. Fortunately, the development of oleophobic and hydrophilic materials addresses these issues, further building into the oleophobic performance. The practical application of the photo-thermal material in the aspect of solar interface evaporation, particularly in the field of oily wastewater, enlarges the application range of interface evaporation. Therefore, development and research of novel high-performance photo-thermal materials will become a main direction of future research.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a graphene oxide-based porous photothermal material which can efficiently generate solar steam and has an aligned channel and oleophobic property, a preparation method thereof and application thereof in seawater desalination and (oil-containing and dye-containing) wastewater purification treatment.
The invention provides a preparation method of a graphene oxide-based porous photothermal material capable of efficiently generating solar steam, which comprises the following steps:
s1, preparing graphene oxide by a hummers method;
s2, preparing the oriented graphene oxide-based porous photothermal material: respectively dispersing or dissolving graphene oxide and polyvinyl alcohol by using deionized water, then uniformly mixing, wherein the mass ratio of the graphene oxide to the polyvinyl alcohol is 0.5-1.5:1, removing bubbles by adopting an ultrasonic method, then putting the mixture into liquid nitrogen at a constant speed for freezing to obtain a solidified product, then freeze-drying the solidified product in a freeze dryer to obtain a graphene oxide precursor, and carbonizing the graphene oxide precursor to obtain an oriented graphene oxide-based porous photothermal material, which is named as GO-1;
s3, preparing the hydrophilic oleophobic oxidized graphene-based porous photothermal material: mixing GO with-1 is immersed in a polydiallyldimethylammonium chloride solution to obtain PDDA modified GO-1; soaking PDDA modified GO-1 in sodium alginate solution and calcium chloride solution in sequence to obtain Ca2+Alginate hydrogel coating; then adding Ca2+Immersing the surface of the alginate hydrogel coating into poly (diallyldimethylammonium chloride), finally immersing into sodium perfluorooctanoate for oleophobic modification, taking out and drying to obtain the hydrophilic oleophobic oxidized graphene-based porous photothermal material.
Preferably, in step S2, the mass ratio of the graphene oxide to the polyvinyl alcohol is 1: 1.
Preferably, in step S2, the mixture is frozen at a constant speed of 3-5mm/min when being put into liquid nitrogen for freezing.
Preferably, in step S2, the freeze-drying is specifically: freeze-drying at-50 deg.C for 3 days.
Preferably, in step S2, the carbonization is specifically: and (3) raising the temperature of the graphene oxide precursor to 200 ℃ at a constant speed, carbonizing for 2h, and then cooling at a constant speed.
Preferably, in step S2, the carbonization is specifically: and (3) uniformly heating the graphene oxide precursor to 200 ℃ at the speed of 2 ℃/min, carbonizing for 2h, and then uniformly cooling at the speed of 2 ℃/min.
In step S3, the GO-1 is immersed in the poly (diallyldimethylammonium chloride) solution for 18-22 min; soaking PDDA modified GO-1 in sodium alginate solution for 2min and in calcium chloride solution for 18-22 min; adding Ca2+The surface of the alginate hydrogel coating is immersed in the PDDA solution for 2min and in the sodium perfluorooctanoate solution for 18-22 min.
The invention also provides the graphene oxide-based porous photothermal material capable of efficiently generating solar steam, which is prepared by applying the method.
The invention also provides application of the graphene oxide-based porous photothermal material capable of efficiently generating solar steam in seawater desalination or purification treatment of oil-containing and dye-containing wastewater.
Preferably, the graphene oxide-based porous photothermal material capable of efficiently generating solar steam is placed in seawater or wastewater containing oil and dye, and subjected to solar irradiation.
The invention firstly introduces a synthesis method of a graphene oxide-based porous photothermal material which can efficiently generate solar steam and has an aligned channel and oleophobicity by taking directional freezing and simple carbonization as main means. The application of the method in seawater desalination and wastewater purification treatment (containing oil or dye) is introduced secondly. In addition, the ordered structure is obtained by directional freezing of liquid nitrogen, so that the material has good salt resistance, and then the oil-repellent layer is prepared by surface oil-repellent modification, so that the oil-repellent property of the material is improved. The super-oleophobic property and the high-efficiency salt resistance enable the solar energy steam desalination device to show excellent solar energy steam desalination performance. Through research on the application of the graphene oxide-based porous photothermal material, the graphene oxide-based porous photothermal material which can efficiently generate solar steam and has an alignment channel and oleophobicity is preliminarily considered to have high solar energy conversion efficiency and excellent salt resistance and stain resistance, and has a certain practical application value in the aspects of seawater desalination and (oil-containing and dye-containing) wastewater purification treatment in the future.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic diagram of the preparation route of the graphene oxide-based porous photothermal material with aligned channels and oleophobic property, which can efficiently generate solar steam.
In FIG. 2, a, d are optical photographs of GO-1, and b, c, e, f are scanning electron microscope images of GO-1 and GO-2.
In FIG. 3, a is the mercury intrusion/extrusion curve of GO-1 and b is the macro-pore diameter distribution of GO-1.
FIG. 4 shows the wettability and contact angle of GO-1, GO-2 in pure water and the oleophobicity and contact angle in n-hexadecane with red oil-O dye.
In FIG. 5, a is a graph showing the change of the mass of GO-1 in pure water, GO-2 in 20% sodium chloride, GO-2 in 10% n-hexadecane oily water and GO-1 in 10% n-hexadecane oily water with time in the pure water condition of one sun and no photo-thermal substances, and b is a graph showing the evaporation rate (●) and the evaporation efficiency (|) of GO-1 in 10% n-hexadecane oily water in pure water, GO-1 in 20% sodium chloride, GO-2 in 10% n-hexadecane oily water and pure water condition of 1 sun and no photo-thermal substances.
FIG. 6 is an evaporation efficiency test of GO-1 for 10 cycles in 1 sun.
FIG. 7 is a comparison graph before and after GO-2 evaporation simulation seawater ion concentration.
FIG. 8 is a comparison graph of UV absorption spectra of GO-2 evaporated methylene blue aqueous solution.
Detailed Description
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples are commercially available unless otherwise specified.
The preparation method of the graphene oxide-based porous photothermal material capable of efficiently generating solar steam and having the aligned channels and the oleophobic property is shown in figure 1.
Fig. 1 is a preparation route diagram of the graphene oxide-based porous photothermal material capable of efficiently generating solar steam according to the present invention.
The preparation method of the graphene oxide-based porous photothermal material capable of efficiently generating solar steam comprises the following steps:
preparation of graphene oxide by hummers method
(1) Pre-oxidation of graphite
7.5mL of concentrated sulfuric acid, 1.5g of potassium peroxodisulfate, and 1.5g of phosphorus pentoxide were put in a 50mL three-necked flask, heated to 90 ℃ and stirred for 15min, and then cooled to 80 ℃. 1.8g of graphite powder was slowly added thereto, and stirred at 80 ℃ for 4.5 hours to form a black precipitate mixture. After the reaction is finished, the mixture is cooled to room temperature, diluted by 300mL of deionized water, kept stand for one night, the treated graphite is washed to be neutral by distilled water, and dried for 24 hours at room temperature to obtain pre-oxidized graphite.
Wherein, concentrated sulfuric acid and phosphorus pentoxide: an intercalating agent; potassium peroxodisulfate: an oxidizing agent. After pre-oxidation, the solubility of graphite in water increases.
(2) Preparation of graphene oxide
19mL of concentrated sulfuric acid was weighed into a 250mL three-necked flask, and cooled to about 0 ℃ in an ice water bath. And (3) adding the graphite subjected to preoxidation treatment in the step (1) under stirring, and quickly stirring until the graphite powder is completely dissolved. Slowly adding 9.0g of potassium permanganate, controlling the temperature not to exceed 10 ℃, continuing stirring for 2 hours after the addition is finished, and curling the edge part of the graphene at the moment, wherein the stage is a low-temperature reaction stage. The mixture is heated to 35 ℃ +/-3 ℃ for 2h, and the mixture becomes viscous and brown as the reaction proceeds, and the reaction stage is a low-temperature reaction stage. After the medium-temperature reaction is finished, 138mL of deionized water is slowly added into a three-neck flask, the temperature is greatly increased, the graphite oxide layer can be separated into single layers under the action of thermal tension, the dissociated sheet layers can be polymerized into multi-layer carbon particles again at high temperature, the yield of GO is reduced, the temperature is required to be controlled to be not more than 60 ℃, a large amount of bubbles can be generated in the mixture along with the addition of distilled water, the color is deepened, after the deionized water is added, the temperature is increased to 96 +/-2 ℃, the temperature is kept for 30min, and the stage is a high-temperature dehydration reaction stage. Adding 420mL of deionized water and 7.5mL of hydrogen peroxide into the reaction system, wherein the weight ratio of the deionized water: causing the graphite to expand. Hydrogen peroxide: excess potassium permanganate was removed, oxidized to 2-valent manganese ions and removed, the solution turned brown to bright yellow, and the reaction mixture was allowed to stand overnight. Washing with pre-prepared 3% HCl solution until free of SO4 2-(with BaCl)2Solution detection), washing with distilled water to neutrality, pouring the washed colloid into a clean surface dish, drying at 55 ℃ for 48h, grinding, sealing and storing to obtain graphene oxide named as GO.
Wherein, concentrated sulfuric acid: strong proton acid enters the graphite layer; potassium permanganate: strong oxidant oxidation, and strong concentrated sulfuric acid oxidation. The obtained graphite oxide has high solubility in water and high stability.
Preparation of directionally arranged graphene oxide-based porous photothermal material
Putting GO into deionized water, and preparing into dispersion with concentration of 8-12mg/mL according to m by ultrasonicGO:mPVAPolyvinyl alcohol (PVA with a molecular weight of 80000-120000, acting as a crosslinking agent) was weighed at a mass ratio of 1:1, then dissolved in deionized water, and heated to 96 ℃ to completely dissolve the PVA. Then cooling the polyvinyl alcohol solution to room temperature to obtain the polyvinyl alcohol solution with the concentration of 8-12 mg/mL. Adding GO dispersion to polyvinyl alcohol solution, where mGO:mPVAThe solution was stirred rapidly with a mass ratio of 1:1 to mix the GO dispersion and polyvinyl alcohol solution evenly and the bubbles were removed by ultrasound for 15 min. And then pouring the mixture into a glass bottle, slowly and vertically putting the glass bottle into liquid nitrogen at a constant speed of 3-4mm/min for freezing, wherein the constant speed is used for forming hole directional arrangement, and freezing control holes which are directionally arranged from bottom to top are formed through the liquid nitrogen, so that the holes of the GO aerogel precursor are orderly and vertically arranged. After the solution is completely solidified, freeze-drying in a freeze dryer, for example, freeze-drying at-48-52 ℃ for 3 days, taking out and placing at room temperature, wherein after 2min, the appearance of anhydrous beads is complete freeze-drying, and a GO-1 precursor is obtained; after the liquid nitrogen is frozen, ice crystals are generated in the material, and the ice crystals in the material are sublimated by freeze drying the material through a freeze dryer, so that holes are left in the material. And finally, heating the GO-1 precursor to 200 ℃ at a constant speed of 2 ℃/min for example in a nitrogen atmosphere, carbonizing for 2h, and cooling at a speed of 2 ℃/min to obtain the directionally arranged graphene oxide-based porous photothermal material, which is named as GO-1. The prepared GO-1 is an oriented porous black cylinder.
The purpose of carbonizing the GO-1 precursor in a nitrogen atmosphere is to make the material black and easy to absorb light, and the graphitization degree is increased. The carbonization temperature is selected because the material blackens to a large extent and has good light absorption properties.
The prepared oriented graphene oxide-based porous photothermal material is beneficial to the transmission of water molecules, and the photothermal conversion efficiency of an interface evaporation system is improved.
The optimization process of the amount ratio of the polyvinyl alcohol and GO dispersions is as follows:
GO and PVA mass ratio 0.5 respectively: 1. 1: 1. 1: 1.5 according to the test result of the scanning electron microscope, the mass ratio of the two is 1:1 the pores of the resulting material are relatively dense.
Preparation of hydrophilic oleophobic graphene oxide-based porous photothermal material
And (2) immersing GO-1 into a polydiallyldimethylammonium chloride (PDDA, 1.0mg/L) solution for 18-22min to enable the surface to be positively charged, so as to obtain the PDDA modified GO-1. Then soaking PDDA modified GO-1 in sodium alginate solution (0.4 wt%) for 2min, and then soaking in calcium chloride solution (0.1M) for 18-22min to obtain Ca2+Alginate hydrogel coating. Then, Ca is added2 +Immersing the surface of the alginate hydrogel coating into a PDDA solution (1.0mg/L) for 2min, finally immersing into a sodium perfluorooctanoate (PFO, 0.1M) solution for 18-22min, and drying at room temperature to obtain the hydrophilic oleophobic graphene oxide based porous photothermal material named as GO-2.
Wherein, PDDA: positively charging the GO-1 surface; sodium alginate and calcium chloride: calcium ions and sodium alginate are crosslinked to form a hydrogel coating, so that the GO-1 material is hydrophilic; PFO: and (4) oleophobic modification.
Example 1 preparation of oriented graphene oxide-based porous photothermal material
Preparation of graphene oxide by hummers method
(1) Pre-oxidation of graphite
7.5mL of concentrated sulfuric acid, 1.5g of potassium peroxodisulfate, and 1.5g of phosphorus pentoxide were put in a 50mL three-necked flask, heated to 90 ℃ and stirred for 15min, and then cooled to 80 ℃. 1.8g of graphite powder was slowly added thereto, and stirred at 80 ℃ for 4.5 hours to form a black precipitate mixture. After the reaction is finished, the mixture is cooled to room temperature, diluted by 300mL of deionized water, kept stand for one night, the treated graphite is washed to be neutral by distilled water, and dried for 24 hours at room temperature to obtain pre-oxidized graphite.
(2) Preparation of graphene oxide
19mL of concentrated sulfuric acid was weighed into a 250mL three-necked flask, and cooled to about 0 ℃ in an ice water bath. And (3) adding the graphite subjected to preoxidation treatment in the step (1) under stirring, and quickly stirring until the graphite powder is completely dissolved. Slowly adding 9.0g of potassium permanganate, controlling the temperature not to exceed 10 ℃, and continuously stirring for 2 hours after the addition is finished, wherein at the momentThe edge part of the graphene is curled, and the stage is a low-temperature reaction stage. The mixture was heated to 35 ℃ for 2h, and as the reaction proceeded, the mixture became viscous and brown in color, which was a medium temperature reaction stage. After the medium-temperature reaction is finished, 138mL of deionized water is slowly added into a three-neck flask, the temperature is greatly increased, the graphite oxide layer can be separated into single layers under the action of thermal tension, the dissociated sheet layers can be polymerized into multi-layer carbon particles again at high temperature, the yield of GO is reduced, the temperature is required to be controlled to be not more than 60 ℃, a large amount of bubbles can be generated in the mixture along with the addition of distilled water, the color is deepened, after the deionized water is added, the temperature is increased to 96 +/-2 ℃, the temperature is kept for 30min, and the stage is a high-temperature dehydration reaction stage. 420mL of deionized water and 7.5mL of hydrogen peroxide were added to the reaction system, the solution turned brown to light yellow, and the reacted mixture was allowed to stand overnight. Washing with pre-prepared 3% HCl solution until free of SO4 2-(with BaCl)2Solution detection), washing with distilled water to neutrality, pouring the washed colloid into a clean surface dish, drying at 55 ℃ for 48h, grinding, sealing and storing to obtain graphene oxide named as GO.
Preparation of directionally arranged graphene oxide-based porous photo-thermal material (GO-1)
Placing GO into deionized water, and preparing into 10mg/mL dispersion by ultrasonic treatment according to mGO:mPVAPolyvinyl alcohol (PVA, molecular weight 100000, function: crosslinker) was weighed in a mass ratio of 1:1, then dissolved in deionized water and heated to 96 ℃ to completely dissolve the PVA. Then, the polyvinyl alcohol solution is cooled to room temperature, and the polyvinyl alcohol solution with the concentration of 10mg/mL is obtained. Adding equal volume of GO dispersoid into polyvinyl alcohol solution, rapidly stirring the solution to uniformly mix the GO dispersoid and the polyvinyl alcohol solution, and removing bubbles by ultrasound for 15 min. And then pouring the mixture into a glass bottle, slowly putting the glass bottle into liquid nitrogen at a speed of 4mm/min for freezing, and forming freezing control holes which are directionally arranged from bottom to top through the liquid nitrogen to enable the pores of the GO aerogel precursor to be orderly and vertically arranged. After the solution is completely solidified, freeze-drying at-50 deg.C for 3 days in a freeze-drying machine, taking out, and placingAnd (3) standing at room temperature, and completely freeze-drying after anhydrous beads appear after 2min to obtain the GO-1 precursor. And finally, heating the GO-1 precursor to 200 ℃ at the speed of 2 ℃/min in a nitrogen atmosphere for carbonization for 2h, and then cooling at the speed of 2 ℃/min to obtain the oriented graphene oxide-based porous photothermal material, which is named as GO-1.
The prepared GO-1 is an oriented porous black cylinder with the height of 1cm and the diameter of 2.3 cm.
In FIG. 2, a, d are optical photographs of GO-1, and b, c, e, f are scanning electron microscope images of GO-1 and GO-2.
As shown in FIG. 2b, which is a scanning electron microscope image of the cross section of GO-1, it can be seen that GO-1 has a dense pore structure with uniform size and shape.
As shown in FIGS. 2e-f, scanning electron micrographs of GO-1 in longitudinal section, ordered orientation of the pores can be seen. The structure is more beneficial to the transfer of water molecules, and the photo-thermal conversion efficiency of the interface evaporation system is improved.
The pore size of GO-1 and the pore size distribution of mesopores and macropores are tested by using a mercury intrusion Method (MIP), and the specific test method comprises the following steps: the method adopts an automatic pore9520 type high-performance full-automatic mercury intrusion instrument of the American Mike instrument company and adopts a computer to control point type measurement. Cutting several 1cm from different regions on GO-13The cut small blocks are put in a vacuum oven to be heated to 110 ℃ for treatment for 4 h. Then it was placed in a clean, dry volume of 1cm3The sample dilatometer of (1) is evacuated for testing. The test results are shown in FIG. 3.
In FIG. 3, a is the mercury intrusion/extrusion curve of GO-1 and b is the macro-pore diameter distribution of GO-1.
As shown in FIGS. 3a-b, the pore size of GO-1 and the pore size distribution of mesopores and macropores were measured using Mercury Intrusion Porosimetry (MIP), and when the pore size was around 300nm, the mercury intrusion volume tended to be flat, the porosity was 84.2%, and the average pore size was 338.5nm, indicating that GO-1 consisted mainly of macropores.
Example 2 preparation of hydrophilic oleophobic graphene oxide-based porous photothermal Material
(1) Preparing a directional arrangement graphene oxide-based porous photo-thermal material (GO-1): the same as in example 1.
(2) Soaking GO-1 in polydiallyldimethylammonium chloride (PDDA, 1.0mg/L) solution for 20min to make the surface positively charged, soaking PDDA modified GO-1 in sodium alginate solution (0.4 wt%) for 2min, and soaking in calcium chloride solution (0.1M) for 20min to obtain Ca2+Alginate hydrogel coating. Finally, Ca is added2+Soaking the alginate hydrogel-covered surface in PDDA solution (1.0mg/L) for 2min, then soaking in PFO (PFO, 0.1M) solution for 20min, and drying at room temperature to obtain the hydrophilic oleophobic graphene oxide-based porous photothermal material named GO-2.
As shown in FIG. 2c, which is a scanning electron microscope image of the cross-section of GO-2, the pore structure becomes denser than that of GO-1.
The wettability of GO-1 and GO-2 in pure water and the oleophobicity in n-hexadecane with red oil-O dye were tested as follows:
two toilet papers were placed on dry GO-1 and GO-2, respectively, and then placed in pure water to test for wettability, with the two toilet papers fully penetrating at 28s and 180s, respectively. Two toilet papers are respectively placed on dry GO-1 and GO-2, the whole toilet paper is placed into n-hexadecane containing red oil-O dye for an oleophobic test, the toilet paper on GO-1 is completely soaked by n-hexadecane within 58s, GO-2 can float on liquid due to the oleophobic property, and the toilet paper can still keep dry after 5 min.
FIG. 4 shows the wettability and contact angle of GO-1, GO-2 in pure water and the oleophobicity and contact angle in n-hexadecane with red oil-O dye.
As shown in a of fig. 4, the contact angle of GO-1 prepared in example 1 with pure water is 0 °. The contact angle of GO-2 prepared in example 2 with pure water, shown as b in figure 4, is less than 30 deg., this result is due to the fact that the surface of GOP-2 is attached with a PFO-containing hydrogel coating, which has reduced hydrophilicity and therefore a slightly longer soaking time. The contact angle of GO-1 prepared in example 1 with n-hexadecane containing red oil-O dye was 0 ° as shown in c in fig. 4, and the contact angle of GO-2 prepared in example 2 with n-hexadecane containing red oil-O dye was 105 ° and greater than 90 ° as shown in d in fig. 4, indicating that: the oleophobic modified GO-2 shows excellent oil resistance.
Example 3 application of the graphene oxide-based porous photothermal material capable of efficiently generating solar steam and having aligned channels and oleophobic properties of the present invention to simulated seawater desalination and (oil-containing, dye-containing) wastewater purification treatment.
Firstly, the GO-1 prepared in example 1 and the GO-2 prepared in example 2 are respectively placed in different environments (pure water, 20% NaCl and 10% hexadecane oily water) under 1 sun (1 kW/m)2) The irradiation was carried out for 5 minutes, 30 minutes and 60 minutes, respectively. The evaporation performance of the test sample is tested by using a simulated solar test device system in a laboratory. Wherein, the mass change of water in the system is monitored in real time by an electronic analytical balance, and the temperature change at the top of the material is monitored by an infrared photography technology. The evaporation rate and evaporation efficiency of GO-SSG can be obtained according to the slope of the curve of the change of mass with time. And GO-1 was tested for evaporation efficiency 10 times in one sun.
In FIG. 5, a is a graph showing the change of the mass of GO-1 in pure water, GO-2 in 20% sodium chloride, GO-2 in 10% n-hexadecane oily water and GO-1 in 10% n-hexadecane oily water in the condition of pure water containing no photothermal substances in one sun, and b is a graph showing the evaporation rate (|) and the evaporation efficiency (●) of GO-1 in 10% n-hexadecane oily water in the condition of pure water containing no photothermal substances in 1 sun, GO-1 in 20% sodium chloride, GO-2 in 10% n-hexadecane oily water and GO-1 in 10% n-hexadecane oily water.
As shown in a-b in figure 5, after one sun irradiation for 60 minutes, the surface temperature of GO-1 in pure water rises from 21.9 ℃ to 45.1 ℃, the surface temperature of GO-2 in 20% sodium chloride solution rises from 19.5 ℃ to 40.5 ℃, and the surface temperature of GO-2 in 10% n-hexadecane oily water rises from 20.0 ℃ to 40.2 ℃. The evaporation rate of GO-1 in pure water is 1.63kw/m2H, evaporation efficiency of 92%; while the evaporation rate of pure water without the photothermal material is 0.4114kW/m2The evaporation efficiency was 8.197%. The value of the light-emitting diode is far smaller than that of GO-1 under the same illumination, which shows that the directional arrangement channel of GO-1 is beneficial to the transmission of water molecules and has high-efficiency solar energy conversion performance.
The evaporation rate of GO-2 in 10% n-hexadecane oily water is 1.48kw/m2H, evaporation efficiency of 84% of the total weight of the composition. The evaporation rate of GO-1 in 10% n-hexadecane oily water is 1.10kw/m2And h, the evaporation efficiency is 55%, which shows that GO-2 has excellent oleophobic property and good evaporation efficiency in oily wastewater. The evaporation rate of GO-2 in a 20% sodium chloride solution is 1.52kw/m2/h, the evaporation efficiency is 86%, and the GO-2 has good salt tolerance.
FIG. 6 is an evaporation efficiency test of GO-1 in pure water for 10 cycles in 1 sun.
As shown in FIG. 6, GO-1 was tested for evaporation efficiency over 10 cycles under 1 sun exposure, with an average efficiency of 92%.
And secondly, placing the GO-2 in simulated seawater for heating and evaporation, and collecting evaporated condensate for ion concentration test. Simulating the ions in seawater and the initial concentration of Na+(10473.6mg/L)，Mg2+(6723.2mg/L)，Ca2+(396.4mg/L)，K+(382.7mg/L)。
FIG. 7 is a comparison graph before and after GO-2 evaporation simulation seawater ion concentration.
As shown in FIG. 7, GO-2 was heated and evaporated in simulated seawater, and the evaporated condensate was collected for ion concentration test, where the ions present in the simulated seawater and their initial concentrations were Na, respectively+(10473.6mg/L)，Mg2+(6723.2mg/L)，Ca2+(396.4mg/L)，K+(382.7 mg/L); the ions present in the evaporation water and their concentrations are respectively Na+(25.199mg/L)，Mg2+(6.814mg/L)，Ca2+(1.462mg/L)，K+(1.401 mg/L). The GO-2 has obvious filtering effect, and the concentration of each ion is lower than the membrane or distilled seawater desalination value and is far lower than the standard value of drinking water.
And thirdly, placing the GO-2 in a methylene blue aqueous solution, heating and evaporating, collecting evaporated condensate water, and detecting whether a high-intensity peak of the methylene blue exists or not by using an ultraviolet-visible spectrophotometer.
FIG. 8 is a comparison graph of UV absorption spectra of GO-2 evaporated methylene blue aqueous solution.
As shown in figure 8, GO-2 is placed in a methylene blue aqueous solution, heated and evaporated, evaporated condensed water is collected, the liquid can be clearly seen to be filtered into colorless and transparent liquid from blue evaporation, and an ultraviolet-visible spectrophotometer is used for detecting, the methylene blue aqueous solution detects a high intensity peak at 660nm, the high intensity peak detected by evaporated water disappears, which proves that GO-2 successfully filters out methylene blue, and the GO-2 can filter colored dyes.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the graphene oxide-based porous photothermal material capable of efficiently generating solar steam is characterized by comprising the following steps of: the method comprises the following steps:
s1, preparing graphene oxide by a hummers method;
s2, preparing the oriented graphene oxide-based porous photothermal material: respectively dispersing or dissolving graphene oxide and polyvinyl alcohol by using deionized water, then uniformly mixing, wherein the mass ratio of the graphene oxide to the polyvinyl alcohol is 0.5-1.5:1, removing bubbles by adopting an ultrasonic method, then putting the mixture into liquid nitrogen at a constant speed for freezing to obtain a solidified product, then freeze-drying the solidified product in a freeze dryer to obtain a graphene oxide precursor, and carbonizing the graphene oxide precursor to obtain an oriented graphene oxide-based porous photothermal material, which is named as GO-1;
s3, preparing the hydrophilic oleophobic oxidized graphene-based porous photothermal material: immersing GO-1 into a poly (diallyldimethylammonium chloride) solution to obtain PDDA modified GO-1; soaking PDDA modified GO-1 in sodium alginate solution and calcium chloride solution in sequence to obtain Ca2+Alginate hydrogel coating; then adding Ca2+Surface immersion of alginate hydrogel coating in polydiallyldimethyl chlorideAnd finally immersing the porous graphene oxide-based porous photothermal material into ammonium chloride for oleophobic modification, taking out and drying to obtain the hydrophilic oleophobic oxidized graphene porous photothermal material.
2. The method of claim 1, wherein: in step S2, the mass ratio of the graphene oxide to the polyvinyl alcohol is 1: 1.
3. The method of claim 1, wherein: in step S2, when the mixture is frozen in liquid nitrogen at a constant speed, the speed is 3-5 mm/min.
4. The method of claim 1, wherein: in step S2, the freeze-drying specifically includes: freeze-drying at-50 deg.C for 3 days.
5. The method of claim 1, wherein: in step S2, the carbonization specifically includes: and (3) raising the temperature of the graphene oxide precursor to 200 ℃ at a constant speed, carbonizing for 2h, and then cooling at a constant speed.
6. The method of claim 1, wherein: in step S2, the carbonization specifically includes: and (3) uniformly heating the graphene oxide precursor to 200 ℃ at the speed of 2 ℃/min, carbonizing for 2h, and then uniformly cooling at the speed of 2 ℃/min.
7. The graphene oxide-based porous photothermal material capable of efficiently generating solar steam is prepared by applying the method of any one of claims 1 to 6.
8. The graphene oxide-based porous photothermal material capable of efficiently generating solar steam according to claim 7 is applied to seawater desalination or purification treatment of wastewater containing oil and dye.
9. Use according to claim 8, characterized in that: the graphene oxide-based porous photothermal material capable of efficiently generating solar steam is placed in seawater or wastewater containing oil and dye for sunlight irradiation.
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| CN115092982B (en) * | 2022-07-05 | 2023-09-22 | 中山大学 | Interception-evaporation interface separation type photo-thermal evaporation device and preparation method and application thereof |
| CN115092983A (en) * | 2022-07-28 | 2022-09-23 | 福建农林大学 | Solar evaporator with photovoltaic power generation function |
| CN115092983B (en) * | 2022-07-28 | 2023-08-11 | 福建农林大学 | Solar evaporator with photovoltaic power generation function |
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