CN111977729B - Polyurethane foam-based seawater desalination material and preparation method thereof - Google Patents
Polyurethane foam-based seawater desalination material and preparation method thereof Download PDFInfo
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- CN111977729B CN111977729B CN202010826234.7A CN202010826234A CN111977729B CN 111977729 B CN111977729 B CN 111977729B CN 202010826234 A CN202010826234 A CN 202010826234A CN 111977729 B CN111977729 B CN 111977729B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
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Abstract
The invention discloses a polyurethane foam-based seawater desalination material and a preparation method thereof, belonging to the technical field of seawater desalination. The preparation method of the material comprises the following steps: (1) reducing low-cost graphene oxide into reduced graphene oxide and connecting the reduced graphene oxide on polyurethane sponge; (2) the iron urushiol conjugate is assembled on the sponge through self-assembly to prepare sponge with super-heat absorption performance and hydrophobic performance. The heat-absorbing hydrophobic sponge designed and synthesized by the invention has a porous structure, and is beneficial to moisture transportation; the black hydrophobic sponge surface greatly reduces heat loss caused by heat transfer to a water body, and the material has good solar energy utilization rate and evaporation rate, shows good salt resistance and has wide application prospect in the field of seawater desalination.
Description
Technical Field
The invention relates to the technical field of seawater desalination, in particular to a polyurethane foam-based seawater desalination material and a preparation method thereof.
Background
With the increase of energy demand and the aggravation of shortage of fresh water resources, the effective utilization of solar energy is an urgent problem to be solved. Because solar energy is sustainable, additional energy input is not needed for evaporating water by using the heat of the sun, and a simple solution is provided for water purification and desalination. At present, the seawater desalination projects mainly comprise a distillation method, an electrodialysis method, a freezing crystallization method and a reverse osmosis method. The distillation method can achieve good seawater desalination effect by enhancing heat absorption efficiency through heat transfer. The photothermal conversion technology can effectively reduce energy consumption and treatment cost, and becomes a research hotspot in the field of seawater desalination. At the present stage, due to the technical limitation, the photo-thermal conversion efficiency is low, and a good seawater desalination material is lacked, so that the solar energy cannot be effectively utilized.
Raw lacquer is a milky white juice collected from the lacquer tree and has been used in asia for thousands of years as a durable and aesthetically pleasing coating. The main component of the compound is urushiol, and urushiol molecules are natural amphoteric compounds, have polar hydroxyl groups and nonpolar long aliphatic chains, and have the property of low surface energy.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a polyurethane foam-based seawater desalination material and a preparation method thereof. The material performance is further improved by utilizing the heat absorption property of the reduced graphene oxide, matching with the hydrophobic surface manufactured by the lacquer iron chelating high polymer and the heat absorption enhancement effect. The seawater desalination material provides a sponge material with good weather resistance and strong salt discharge aiming at the problems of low evaporation efficiency, poor desalination effect and the like, and provides a technical solution for the problems faced by the existing seawater desalination material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a seawater desalination material based on polyurethane foam comprises the following steps:
1) reducing graphene oxide by hydrazine hydrate and grafting the reduced graphene oxide onto polyurethane sponge to obtain reduced graphene oxide grafted polyurethane sponge;
2) adding urushiol into a ferric salt-ethanol solution, performing ultrasonic dispersion to obtain a mixed solution, then adding the polyurethane sponge grafted with reduced graphene oxide into the mixed solution, assembling a urushiol iron conjugated polymer on the polyurethane sponge through self-assembly, and then drying to obtain a modified sponge, namely the seawater desalination material.
Further, the steps 1) and 2) are specifically as follows:
1-1) adding graphene oxide into deionized water, and performing ultrasonic dispersion to obtain a solution A;
1-2) adding the pretreated polyurethane sponge into the solution A, and stirring in a constant-temperature water bath for coagulation;
1-3) heating a constant-temperature water bath, and adding hydrazine hydrate for reduction;
1-4) taking out and drying the polyurethane sponge to obtain the reduced graphene oxide grafted polyurethane sponge;
2-1) dropwise adding urushiol into a ferric salt-ethanol solution, and performing ultrasonic dispersion;
2-2) placing the solution subjected to ultrasonic dispersion in a magnetic stirrer, stirring for 30-40min, adding the reduced graphene oxide grafted polyurethane sponge, and continuing stirring;
2-3) taking out the polyurethane sponge and drying to obtain the modified sponge, namely the seawater desalination material.
Further, the pretreatment in the step 1-2) is to place polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, place the polyurethane sponge in deionized water for ultrasonic treatment after drying, and then dry the polyurethane sponge; the temperature of the constant temperature water bath kettle is 30-32 ℃, and the stirring time is 30-40 min.
In the step 1-3), the temperature of a constant-temperature water bath is raised to 95-105 ℃, and the graphene oxide is reduced in situ for 1-1.2h according to the proportion of adding 20 mul of hydrazine hydrate into each mg of graphene oxide.
In the step 1-4), the drying temperature is 50-55 ℃ and the time is 24-30 h.
In the step 2-1), the ferric salt is ferrous chloride, ferric sulfate, copperas, ferric nitrate, ferrous nitrate, ferric hydroxide, ferric acetate, ferrous acetate or ferrocene and other ferrous salts or ferric salts.
In the step 2-1), the molar ratio of the urushiol to the ferric salt is 1-3:1, and the ultrasonic dispersion time is 5-10 min.
In the step 2-2), the stirring is continued for 12-14 h.
In the step 2-3), the drying temperature is 75-85 ℃.
The invention has the following advantages: 1. the reduced graphene oxide is an excellent heat-absorbing material, the graphene is a carbon material with the highest heat conductivity coefficient, and has excellent heat conduction performance and particularly outstanding optical characteristics. 2. According to the invention, the urushiol iron is used as a reinforcing material, the urushiol structure of the raw lacquer contains an o-diphenol hydroxyl structure, and lone electron pairs on the urushiol structure form coordination bonds with metal iron ions, so that the heat absorption performance of the sponge is greatly improved. 3. According to the invention, the polyurethane sponge is used as a substrate, and the surface of the polyurethane sponge is subjected to hydrophobic treatment, so that the material can float on the water surface, the sponge has a loose and porous structure, the water transportation can be promoted, the polyurethane sponge has a special structure, the heat stored inside the polyurethane sponge is not easy to dissipate into the water, and the polyurethane sponge has a good heat preservation and heat storage function.
Drawings
FIG. 1 is an infrared thermal display image of a sponge irradiated under an artificial seawater infrared lamp for 6min, wherein a is a modified sponge and b is an unmodified sponge.
FIG. 2 is a graph showing the temperature change with time of the modified sponge and the common sponge after being irradiated under an infrared lamp for 5 min.
Fig. 3 is a photograph of an outdoor evaporation experiment of artificial seawater in a sealed room using a modified sponge and a blank control.
Detailed Description
A preparation method of a seawater desalination material based on polyurethane foam comprises the following steps:
1) preparing polyurethane sponge grafted with reduced graphene oxide;
1-1) adding graphene oxide into a three-neck flask, adding deionized water, and performing ultrasonic dispersion to obtain a solution A;
1-2) placing polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, drying, then placing in deionized water for ultrasonic treatment, and then drying; adding the pretreated polyurethane sponge into the solution A, and stirring for 30-40min in a constant-temperature water bath kettle at 30-32 ℃ for coagulation;
1-3) heating a constant-temperature water bath to 95-105 ℃, and reducing in situ for 1-1.2h according to the proportion of adding 20 mu l of hydrazine hydrate into each mg of graphene oxide;
1-4) taking out the polyurethane sponge, and drying at 50-55 ℃ for 24-30 to obtain the reduced graphene oxide grafted polyurethane sponge;
2) preparing the seawater desalination material.
2-1) dropwise adding urushiol into the ferric salt-ethanol solution, and performing ultrasonic dispersion for 5-10 min; the ferric salt is ferrous chloride, ferric sulfate, copperas, ferric nitrate, ferrous nitrate, ferric hydroxide, ferric acetate, ferrous acetate or ferrocene and other ferrous salts or ferric salts; the molar ratio of the urushiol to the ferric salt is 1-3: 1;
2-2) placing the solution subjected to ultrasonic dispersion in a magnetic stirrer, stirring for 30-40min, adding the reduced graphene oxide grafted polyurethane sponge, and continuing to stir for 12-14 h;
2-3) taking out the polyurethane sponge, and drying at 75-85 ℃ to obtain the modified sponge, namely the seawater desalination material.
The polyurethane sponge has the characteristics of heat preservation, heat insulation, good air permeability and the like, is a high-molecular polymer formed by a foaming technology, and has good heat preservation, heat insulation, air permeability and the like, so that the heat stored inside is not easy to dissipate into water; due to hydrophobic modification, the water-soluble polymer can float on the water surface, and the porous structure of the water-soluble polymer provides a good transportation channel for moisture. The polyurethane sponge has better photo-thermal conversion capability through the treatment of iron urushiol and multilayer reduced graphene oxide, so that the water evaporation rate is increased.
The seawater desalination material prepared by the invention adopts polyurethane sponge as a matrix, and adopts reduced graphene oxide and urushiol iron chelate as hydrophobic light absorption materials, so that the preparation cost is low, and large-scale production can be realized.
Example 1
A preparation method of a seawater desalination material based on polyurethane foam comprises the following steps:
step 1, adding 0.1g of graphene oxide into a 250mL three-neck flask, adding 80 mL of deionized water, and ultrasonically dispersing the mixed solution for 10min to obtain a solution A;
placing polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, drying, placing the polyurethane sponge in deionized water for ultrasonic treatment, and drying;
adding three pieces of dried sponge (about 0.5 g) into the solution A, and stirring in 30 deg.C constant temperature water bath for 30min for coagulation;
heating a constant-temperature water bath to 100 ℃, and adding 20 mu l of hydrazine hydrate into each mg of graphene oxide to carry out in-situ reduction for 1 h;
taking out the polyurethane sponge, and drying the polyurethane sponge in a low-temperature drying oven at 50 ℃ for 24 hours to obtain the reduced graphene oxide grafted polyurethane sponge;
step 2, dissolving 0.254g of anhydrous ferrous chloride particles in 100mL of industrial alcohol, and placing the prepared ferrous chloride-ethanol solution in a 250mL three-neck flask;
0.628g of urushiol is added into the prepared ferrous chloride-ethanol solution drop by drop, and ultrasonic dispersion is carried out for 5 min;
placing the three-necked flask subjected to ultrasonic treatment in a magnetic stirrer, adding the polyurethane sponge grafted with the reduced graphene oxide into the three-necked flask after 30min, and continuously stirring for 12 h;
and (3) drying the black sponge taken out in a vacuum oven at 80 ℃ to obtain the modified sponge, namely the seawater desalination material.
Example 2
A preparation method of a seawater desalination material based on polyurethane foam comprises the following steps:
step 1, adding 0.1g of graphene oxide into a 250mL three-neck flask, adding 80 mL of deionized water, and ultrasonically dispersing the mixed solution for 10min to obtain a solution A;
placing polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, drying, placing the polyurethane sponge in deionized water for ultrasonic treatment, and drying;
adding three pieces of dried sponge (about 0.5 g) into the solution A, and stirring in 30 deg.C constant temperature water bath for 30min for coagulation;
heating a constant-temperature water bath to 100 ℃, and adding 20 mu l of hydrazine hydrate into each mg of graphene oxide to carry out in-situ reduction for 1 h;
taking out the sponge, and drying the sponge in a low-temperature drying oven at 50 ℃ for 24h to obtain the reduced graphene oxide grafted polyurethane sponge;
step 2, dissolving 0.254g of anhydrous ferrous chloride particles in 100mL of industrial alcohol, and placing the prepared ferrous chloride-ethanol solution in a 250mL three-neck flask;
1.256g of urushiol is added into the prepared ferrous chloride-ethanol solution drop by drop, and ultrasonic dispersion is carried out for 5 min;
placing the three-neck flask which is filled with the ultrasonic waves into a magnetic stirrer; after 30min, adding the polyurethane sponge grafted with the reduced graphene oxide into a three-neck flask, and continuously stirring for 12 h;
and (3) drying the black sponge taken out in a vacuum oven at 80 ℃ to obtain the modified sponge, namely the seawater desalination material.
Example 3
A preparation method of a seawater desalination material based on polyurethane foam specifically comprises the following steps:
step 1, adding 0.1g of graphene oxide into a 250mL three-neck flask, adding 80 mL of deionized water, and ultrasonically dispersing the mixed solution for 10min to obtain a solution A;
placing polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, drying, placing the polyurethane sponge in deionized water for ultrasonic treatment, and drying;
adding three pieces of dried sponge (about 0.5 g) into the solution A, and stirring in 30 deg.C constant temperature water bath for 30min for coagulation;
heating a constant-temperature water bath to 100 ℃, and adding 20 mu l of hydrazine hydrate into each mg of graphene oxide to reduce in situ for 1 h;
taking out the sponge, and drying the sponge in a low-temperature drying oven at 50 ℃ for 24h to obtain the reduced graphene oxide grafted polyurethane sponge;
step 2, dissolving 0.254g of anhydrous ferrous chloride particles in 100mL of industrial alcohol, and placing the prepared ferrous chloride-ethanol solution in a 250mL three-neck flask;
1.884g of urushiol is added into the prepared ferrous chloride-ethanol solution drop by drop, and ultrasonic dispersion is carried out for 5 min;
placing the three-neck flask with the ultrasonic wave in a magnetic stirrer, adding the polyurethane sponge grafted with the reduced graphene oxide into the three-neck flask after 30min, and continuously stirring for 12 h;
and (3) drying the black sponge taken out in a vacuum oven at 80 ℃ to obtain the modified sponge, namely the seawater desalination material.
Example 4
A preparation method of a seawater desalination material based on polyurethane foam specifically comprises the following steps:
step 1, adding 0.1g of graphene oxide into a 250mL three-neck flask, adding 80 mL of deionized water, and ultrasonically dispersing the mixed solution for 10min to obtain a solution A;
placing polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, drying, placing the polyurethane sponge in deionized water for ultrasonic treatment, and drying;
adding three pieces of dried sponge (about 0.5 g) into the solution A, and stirring in 30 deg.C constant temperature water bath for 30min for coagulation;
heating a constant-temperature water bath to 100 ℃, and adding 20 mu l of hydrazine hydrate into each mg of graphene oxide to carry out in-situ reduction for 1 h;
taking out the sponge, and drying the sponge in a low-temperature drying oven at 50 ℃ for 24h to obtain the reduced graphene oxide grafted polyurethane sponge;
step 2, dissolving 0.324g of anhydrous ferric chloride particles into 100mL of industrial alcohol, and placing the prepared ferric chloride-ethanol solution into a 250mL three-neck flask;
1.884g of urushiol is added into the prepared ferric chloride-ethanol solution drop by drop, and ultrasonic dispersion is carried out for 5 min;
placing the three-necked flask subjected to ultrasonic treatment in a magnetic stirrer, adding the polyurethane sponge grafted with the reduced graphene oxide into the three-necked flask after 30min, and continuously stirring for 12 h;
and (3) drying the black sponge taken out in a vacuum oven at 80 ℃ to obtain the modified sponge, namely the seawater desalination material.
Example 5
A preparation method of a seawater desalination material based on polyurethane foam specifically comprises the following steps:
step 1, adding 0.1g of graphene oxide into a 250mL three-neck flask, adding 80 mL of deionized water, and ultrasonically dispersing the mixed solution for 10min to obtain a solution A;
placing polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, drying, placing the polyurethane sponge in deionized water for ultrasonic treatment, and drying;
adding three pieces of dried sponge (about 0.5 g) into the solution A, and stirring in 30 deg.C constant temperature water bath for 30min for coagulation;
heating a constant-temperature water bath to 100 ℃, and adding 20 mu l of hydrazine hydrate into each mg of graphene oxide to carry out in-situ reduction for 1 h;
taking out the sponge, and drying the sponge in a low-temperature drying oven at 50 ℃ for 24h to obtain the reduced graphene oxide grafted polyurethane sponge;
step 2, dissolving 0.254g of anhydrous ferrous chloride particles in 100mL of industrial alcohol, and placing the prepared ferrous chloride-ethanol solution in a 250mL three-neck flask;
1.884g of raw lacquer is added into the prepared ferrous chloride-ethanol solution drop by drop, and ultrasonic dispersion is carried out for 5 min;
placing the three-neck flask subjected to ultrasonic treatment in a magnetic stirrer; after 30min, adding the polyurethane sponge grafted with the reduced graphene oxide into a three-neck flask, and continuously stirring for 12 h;
and (3) drying the black sponge taken out in a vacuum oven at 80 ℃ to obtain the modified sponge, namely the seawater desalination material.
Example 6
A preparation method of a seawater desalination material based on polyurethane foam specifically comprises the following steps:
step 1, adding 0.1g of graphene oxide into a 250mL three-neck flask, adding 80 mL of deionized water, and ultrasonically dispersing the mixed solution for 10min to obtain a solution A;
placing polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, drying, placing the polyurethane sponge in deionized water for ultrasonic treatment, and drying;
adding three pieces of dried sponge (about 0.5 g) into the solution A, and stirring in 30 deg.C constant temperature water bath for 30min for coagulation;
heating a constant-temperature water bath to 100 ℃, and adding 20 mu l of hydrazine hydrate into each mg of graphene oxide to carry out in-situ reduction for 1 h;
taking out the sponge, and drying the sponge in a low-temperature drying oven at 50 ℃ for 24h to obtain the reduced graphene oxide grafted polyurethane sponge;
step 2, dissolving 0.800g of ferric sulfate in 100mL of industrial alcohol, and placing the prepared ferric sulfate-ethanol solution in a 250mL three-neck flask;
1.884g of urushiol is added into the prepared ferric sulfate-ethanol solution drop by drop, and ultrasonic dispersion is carried out for 5 min;
placing the three-necked flask subjected to ultrasonic treatment in a magnetic stirrer, adding the polyurethane sponge grafted with the reduced graphene oxide into the three-necked flask after 30min, and continuously stirring for 12 h;
and (3) drying the black sponge taken out in a vacuum oven at 80 ℃ to obtain the modified sponge, namely the seawater desalination material.
Example 7
A preparation method of a seawater desalination material based on polyurethane foam specifically comprises the following steps:
step 1, adding 0.1g of graphene oxide into a 250mL three-neck flask, adding 80 mL of deionized water, and ultrasonically dispersing the mixed solution for 10min to obtain a solution A;
placing polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, drying, placing the polyurethane sponge in deionized water for ultrasonic treatment, and drying;
adding three pieces of dried sponge (about 0.5 g) into the solution A, and stirring in 30 deg.C constant temperature water bath for 30min for coagulation;
heating a constant-temperature water bath to 100 ℃, and adding 20 mu l of hydrazine hydrate into each mg of graphene oxide to carry out in-situ reduction for 1 h;
taking out the sponge, and drying the sponge in a low-temperature drying oven at 50 ℃ for 24h to obtain the reduced graphene oxide grafted polyurethane sponge;
step 2, dissolving 0.556g of copperas particles in 100mL of industrial alcohol, and placing the prepared copperas-ethanol solution in a 250mL three-neck flask;
1.884g of urushiol is added into the prepared copperas-ethanol solution drop by drop, and ultrasonic dispersion is carried out for 5 min;
placing the three-necked flask subjected to ultrasonic treatment in a magnetic stirrer, adding the polyurethane sponge grafted with the reduced graphene oxide into the three-necked flask after 30min, and continuously stirring for 12 h;
and (3) drying the black sponge taken out in a vacuum oven at 80 ℃ to obtain the modified sponge, namely the seawater desalination material.
Example 8
A preparation method of a seawater desalination material based on polyurethane foam specifically comprises the following steps:
step 1, adding 0.1g of graphene oxide into a 250mL three-neck flask, adding 80 mL of deionized water, and ultrasonically dispersing the mixed solution for 10min to obtain a solution A;
placing polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, drying, placing the polyurethane sponge in deionized water for ultrasonic treatment, and drying;
adding three pieces of dried sponge (about 0.5 g) into the solution A, and stirring in 30 deg.C constant temperature water bath for 30min for coagulation;
heating a constant-temperature water bath to 100 ℃, and adding 20 mu l of hydrazine hydrate into each mg of graphene oxide to carry out in-situ reduction for 1 h;
taking out the sponge, and drying the sponge in a low-temperature drying oven at 50 ℃ for 24h to obtain the reduced graphene oxide grafted polyurethane sponge;
step 2, dissolving 0.484g of ferric nitrate granules in 100mL of industrial alcohol, and placing the prepared ferric nitrate-ethanol solution in a 250mL three-neck flask;
1.884g of urushiol is added into the prepared ferric nitrate-ethanol solution drop by drop, and ultrasonic dispersion is carried out for 5 min;
placing the three-neck flask with the ultrasonic wave in a magnetic stirrer, adding the polyurethane sponge grafted with the reduced graphene oxide into the three-neck flask after 30min, and continuously stirring for 12 h;
and (3) drying the black sponge taken out in a vacuum oven at 80 ℃ to obtain the modified sponge, namely the seawater desalination material.
Example 9
A preparation method of a seawater desalination material based on polyurethane foam specifically comprises the following steps:
step 1, adding 0.1g of graphene oxide into a 250mL three-neck flask, adding 80 mL of deionized water, and ultrasonically dispersing the mixed solution for 10min to obtain a solution A;
placing polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, drying, placing the polyurethane sponge in deionized water for ultrasonic treatment, and drying;
adding three pieces of dried sponge (about 0.5 g) into the solution A, and stirring in 30 deg.C constant temperature water bath for 30min for coagulation;
heating a constant-temperature water bath to 100 ℃, and adding 20 mu l of hydrazine hydrate into each mg of graphene oxide to carry out in-situ reduction for 1 h;
taking out the sponge, and drying in a low-temperature drying oven at 50 deg.C for 24 h. Obtaining polyurethane sponge grafted with reduced graphene oxide;
step 2, dissolving 0.360g of ferrous nitrate particles in 100mL of industrial alcohol, and placing the prepared ferrous nitrate-ethanol solution in a 250mL three-neck flask;
1.884g of urushiol is added into the prepared ferrous nitrate-ethanol solution drop by drop, and ultrasonic dispersion is carried out for 5 min;
placing the three-necked flask subjected to ultrasonic treatment in a magnetic stirrer, adding the polyurethane sponge grafted with the reduced graphene oxide into the three-necked flask after 30min, and continuously stirring for 12 h;
and (3) drying the black sponge taken out in a vacuum oven at 80 ℃ to obtain the modified sponge, namely the seawater desalination material.
Example 10
A preparation method of a seawater desalination material based on polyurethane foam specifically comprises the following steps:
step 1, adding 0.1g of graphene oxide into a 250mL three-neck flask, adding 80 mL of deionized water, and ultrasonically dispersing the mixed solution for 10min to obtain a solution A;
placing polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, drying, placing the polyurethane sponge in deionized water for ultrasonic treatment, and drying;
adding three pieces of dried sponge (about 0.5 g) into the solution A, and stirring in 30 deg.C constant temperature water bath for 30min for coagulation;
heating a constant-temperature water bath to 100 ℃, and adding 20 mu l of hydrazine hydrate into each mg of graphene oxide to carry out in-situ reduction for 1 h;
taking out the sponge, and drying the sponge in a low-temperature drying oven at 50 ℃ for 24h to obtain the reduced graphene oxide grafted polyurethane sponge;
step 2, dissolving 0.214g of iron hydroxide powder into 100mL of industrial alcohol, and placing the prepared iron hydroxide-ethanol solution into a 250mL three-neck flask;
1.884g of urushiol is added into the prepared ferric hydroxide-ethanol solution drop by drop, and ultrasonic dispersion is carried out for 5 min;
placing the three-necked flask subjected to ultrasonic treatment in a magnetic stirrer, adding the polyurethane sponge grafted with the reduced graphene oxide into the three-necked flask after 30min, and continuously stirring for 12 h;
and (3) drying the black sponge taken out in a vacuum oven at 80 ℃ to obtain the modified sponge, namely the seawater desalination material.
Example 11
A preparation method of a seawater desalination material based on polyurethane foam specifically comprises the following steps:
step 1, adding 0.1g of graphene oxide into a 250mL three-neck flask, adding 80 mL of deionized water, and ultrasonically dispersing the mixed solution for 10min to obtain a solution A;
placing polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, drying, placing the polyurethane sponge in deionized water for ultrasonic treatment, and drying;
adding three pieces of dried sponge (about 0.5 g) into the solution A, and stirring in 30 deg.C constant temperature water bath for 30min for coagulation;
heating a constant-temperature water bath to 100 ℃, and adding 20 mu l of hydrazine hydrate into each mg of graphene oxide to reduce in situ for 1 h;
taking out the sponge, and drying the sponge in a low-temperature drying oven at 50 ℃ for 24h to obtain the reduced graphene oxide grafted polyurethane sponge;
step 2, dissolving 0.382g of iron acetate powder in 100mL of industrial alcohol, and placing the prepared iron acetate-ethanol solution in a 250mL three-neck flask;
1.884g of urushiol is added into the prepared ferric acetate-ethanol solution drop by drop, and ultrasonic dispersion is carried out for 5 min;
placing the three-neck flask subjected to the ultrasonic treatment in a magnetic stirrer, adding the polyurethane sponge grafted with the reduced graphene oxide into the three-neck flask after 30min, and continuously stirring for 12 h;
and (3) drying the black sponge taken out in a vacuum oven at 80 ℃ to obtain the modified sponge, namely the seawater desalination material.
Example 12
A preparation method of a seawater desalination material based on polyurethane foam specifically comprises the following steps:
step 1, adding 0.1g of graphene oxide into a 250mL three-neck flask, adding 80 mL of deionized water, and ultrasonically dispersing the mixed solution for 10min to obtain a solution A;
placing polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, drying, placing the polyurethane sponge in deionized water for ultrasonic treatment, and drying;
adding three pieces of dried sponge (about 0.5 g) into the solution A, and stirring in 30 deg.C constant temperature water bath for 30min for coagulation;
heating a constant-temperature water bath to 100 ℃, and adding 20 mu l of hydrazine hydrate into each mg of graphene oxide to carry out in-situ reduction for 1 h;
taking out the sponge, and drying the sponge in a low-temperature drying oven at 50 ℃ for 24h to obtain the reduced graphene oxide grafted polyurethane sponge;
step 2, dissolving 0.348g of ferrous acetate powder in 100mL of industrial alcohol, and placing the prepared ferrous acetate-ethanol solution in a 250mL three-neck flask;
1.884g of urushiol is added into the prepared ferrous acetate-ethanol solution drop by drop, and ultrasonic dispersion is carried out for 5 min;
placing the three-necked flask subjected to ultrasonic treatment in a magnetic stirrer, adding the polyurethane sponge grafted with the reduced graphene oxide into the three-necked flask after 30min, and continuously stirring for 12 h;
and (3) drying the black sponge taken out in a vacuum oven at 80 ℃ to obtain the modified sponge, namely the seawater desalination material.
Example 13
A preparation method of a seawater desalination material based on polyurethane foam specifically comprises the following steps:
step 1, adding 0.1g of graphene oxide into a 250mL three-neck flask, adding 80 mL of deionized water, and ultrasonically dispersing the mixed solution for 10min to obtain a solution A;
placing polyurethane sponge in absolute ethyl alcohol for ultrasonic treatment, drying, placing the polyurethane sponge in deionized water for ultrasonic treatment, and drying;
adding three pieces of dried sponge (about 0.5 g) into the solution A, and stirring in 30 deg.C constant temperature water bath for 30min for coagulation;
heating a constant-temperature water bath to 100 ℃, and adding 20 mu l of hydrazine hydrate (2 ml) into each mg of graphene oxide for in-situ reduction for 1 h;
taking out the sponge, and drying the sponge in a low-temperature drying oven at 50 ℃ for 24h to obtain the reduced graphene oxide grafted polyurethane sponge;
step 2, dissolving 0.372g of ferrocene powder in 100mL of industrial alcohol, and placing the prepared ferrocene-ethanol solution in a 250mL three-neck flask;
1.884g of urushiol is added into the prepared ferrocene-ethanol solution drop by drop, and ultrasonic dispersion is carried out for 5 min;
placing the three-necked flask subjected to ultrasonic treatment in a magnetic stirrer, adding the polyurethane sponge grafted with the reduced graphene oxide into the three-necked flask after 30min, and continuously stirring for 12 h;
and (3) drying the black sponge taken out in a vacuum oven at 80 ℃ to obtain the modified sponge, namely the seawater desalination material.
Examples of the experiments
The polyurethane foam-based seawater desalination material of example 3 was tested.
1. Water contact Angle test
The modified sponge has a water contact angle of above 117 ° as measured by DSA25 contact angle measuring instrument (KRUSS, germany), which satisfies the definition of hydrophobic, wherein the contact angle can reach 138 ° at the maximum.
2. Heat absorption Performance test
When an RX400 infrared thermal imager is used for carrying out endothermic test, the temperature of the modified sponge can reach 83 ℃ under the irradiation of natural light, and the temperature can be kept at 48 ℃ in the process of seawater evaporation.
3. Test of Evaporation Performance
When the ordinary sponge and the modified sponge are subjected to seawater evaporation in the sun, the evaporation capacity of the added modified sponge is 4.72 times of that of normal evaporation.
FIG. 1 is an infrared thermal display image of a sponge irradiated under an artificial seawater infrared lamp for 6min, wherein a is a modified sponge and b is an unmodified sponge. FIG. 2 is a graph showing the temperature change with time of the modified sponge and the common sponge after being irradiated under an infrared lamp for 5 min. Fig. 3 is a photograph of an outdoor evaporation experiment of artificial seawater in a sealed room using a modified sponge and a blank control.
Fig. 1 clearly shows that the temperature of the artificial seawater with the modified sponge is higher than that of the seawater without the modified sponge, because the super heat absorption sponge absorbs more heat than the artificial seawater under the same environment, and the sponge transfers the absorbed heat to the artificial seawater in the cup, so that the temperature of the seawater is higher than that of the seawater without the modified sponge. As shown in FIG. 2, a significant temperature difference can be seen, and the modified sponge can be heated up to 83 ℃ at most, which is much higher than that of the common sponge.
In summary, according to the preparation method of the seawater desalination material based on polyurethane foam provided by the invention, the hydrophobic sponge is prepared by assembling and reducing graphene oxide on the polyurethane sponge by using the reduction effect of hydrazine hydrate on the graphene oxide. The roughness of the surface of the polyurethane sponge and the covered reduced graphene oxide microparticles further increase the roughness of the surface of the polyurethane sponge, so that the modified polyurethane sponge has a certain hydrophobic effect. Meanwhile, the reduced graphene oxide assembled on the polyurethane sponge has excellent optical performance, so that the modified polyurethane sponge has certain light absorption and heat absorption properties. Secondly, a urushiol iron chelating high polymer is loaded on the modified polyurethane sponge by self-assembly through a hydrothermal method, urushiol iron nanoparticles are hydrophobic particles, and the addition of the hydrophobic nanoparticles can improve the evaporation rate of water; the urushiol iron chelate high polymer has excellent thermal properties, and can improve the heat absorption efficiency of the sponge. Based on these advantages, the material can be widely used.
Claims (7)
1. A preparation method of a seawater desalination material based on polyurethane foam is characterized by comprising the following steps:
1) preparation of reduced graphene oxide grafted polyurethane sponge
1-1) adding graphene oxide into deionized water, and performing ultrasonic dispersion to obtain a solution A;
1-2) adding the pretreated polyurethane sponge into the solution A, and stirring in a constant-temperature water bath for coagulation;
1-3) heating a constant-temperature water bath, and adding hydrazine hydrate for reduction;
1-4) taking out and drying the polyurethane sponge to obtain the reduced graphene oxide grafted polyurethane sponge;
2) preparation of seawater desalination material
2-1) dropwise adding urushiol into an iron salt-ethanol solution, wherein the molar ratio of the urushiol to the iron salt is 1-3:1, and then carrying out ultrasonic dispersion for 5-10 min;
2-2) placing the solution subjected to ultrasonic dispersion in a magnetic stirrer, stirring for 30-40min, adding the reduced graphene oxide grafted polyurethane sponge, continuing stirring, and assembling the iron urushiol conjugated polymer on the polyurethane sponge through self-assembly;
2-3) taking out the polyurethane sponge and drying to obtain the modified sponge, namely the seawater desalination material.
2. The method for preparing a polyurethane foam-based seawater desalination material as claimed in claim 1, wherein the pretreatment in step 1-2) is performed by placing polyurethane sponge in absolute ethanol for ultrasonic treatment, drying, placing in deionized water for ultrasonic treatment, and drying; the temperature of the constant temperature water bath is 30-32 ℃, and the stirring time is 30-40 min.
3. The method for preparing a polyurethane foam-based seawater desalination material as claimed in claim 1, wherein in step 1-3), the temperature of the thermostat water bath is raised to 95-105 ℃, and the in-situ reduction is carried out for 1-1.2h at a rate of adding 20 μ l hydrazine hydrate per mg of graphene oxide.
4. The method for preparing a polyurethane foam-based seawater desalination material as claimed in claim 1, wherein the drying temperature in step 1-4) is 50-55 ℃ and the drying time is 24-30 h.
5. The method for preparing a polyurethane foam-based seawater desalination material as claimed in claim 1, wherein in step 2-1), the iron salt is one of ferrous chloride, ferric sulfate, copperas, ferric nitrate, ferrous nitrate, ferric hydroxide, ferric acetate, ferrous acetate or ferrocene.
6. The method for preparing a polyurethane foam-based seawater desalination material as claimed in claim 1, wherein in the step 2-2), the stirring is continued for 12-14 h; in the step 2-3), the drying temperature is 75-85 ℃.
7. A seawater desalination material obtained by the production method as claimed in any one of claims 1 to 6.
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| CN113174083A (en) * | 2021-04-29 | 2021-07-27 | 西安交通大学 | Preparation method and application of green super-hydrophobic magnetic sponge |
| CN114479171B (en) * | 2021-12-29 | 2023-02-28 | 东华大学 | Porphyrin-based conjugated microporous polymer photothermal conversion sponge and preparation and application thereof |
| CN115262135B (en) * | 2022-08-03 | 2023-12-29 | 福建师范大学 | Janus cotton cloth for sea water desalination and preparation method thereof |
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