CN113509907A - Preparation of lignin-based composite hydrogel and application of lignin-based composite hydrogel in heavy metal ion adsorption and luminescent materials - Google Patents
Preparation of lignin-based composite hydrogel and application of lignin-based composite hydrogel in heavy metal ion adsorption and luminescent materials Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 57
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000002500 ions Chemical class 0.000 claims abstract description 79
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- 238000000034 method Methods 0.000 claims abstract description 16
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- 238000004108 freeze drying Methods 0.000 claims abstract description 11
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- 238000003756 stirring Methods 0.000 claims abstract description 8
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
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- 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
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Abstract
The invention discloses preparation of lignin-based composite hydrogel and application of the lignin-based composite hydrogel in heavy metal ion adsorption and luminescent materials, and belongs to the field of functional materials. The preparation method of the hydrogel comprises the following steps: 1) mixing the sodium hydroxide aqueous solution and acrylic acid uniformly under the condition of ice-water bath, then adding lignosulfonate, N-methylene bisacrylamide and potassium persulfate in sequence, and stirring uniformly. 2) And carrying out free radical polymerization reaction on the obtained mixed solution under the ultrasonic-assisted condition, soaking the obtained product in absolute ethyl alcohol overnight, and freeze-drying to obtain the lignin-based composite hydrogel. The invention not only can fully utilize the lignin which is an industrial waste and provide a new way for high-value utilization of the lignin, but also the prepared hydrogel has strong adsorption capacity to heavy metal ions in water. In addition, the hydrogel after absorbing the heavy metal ions can be applied to the preparation of luminescent materials. Therefore, the method has good application prospect.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to preparation of lignin-based composite hydrogel and application of the lignin-based composite hydrogel in heavy metal ion adsorption and luminescent materials.
Background
With the advance of industrialization, industries such as mining, smelting, electronics, electroplating, petroleum, fertilizer manufacturing and the like can generate a large amount of wastewater rich in heavy metal ions. The discharge of these waste waters has resulted in the enrichment of heavy metal ions in natural water bodies. Since heavy metal ions cannot be degraded, the heavy metal ions are easy to enter human bodies through food chains, and further seriously harm human health, such as cadmium pollution events in Guangxi, Jiangsu blood lead events, Shanxi lead poisoning events and the like. Therefore, how to rapidly and efficiently remove heavy metal ions in water has become a major issue in the research field of water pollution control at present.
At present, the methods for removing heavy metal ions in water are mainly divided into chemical methods, biological methods and physical adsorption methods. In contrast, the physical adsorption method is highly concerned by broad scholars due to its advantages of simple operation, low cost, no secondary pollution, etc. The key to the utilization of physical adsorption is the development of an inexpensive and efficient adsorbent. Currently, adsorbent materials have been developed that mainly include activated carbon, zeolites, resins and hydrogels. The hydrogel is a novel three-dimensional network structure material, contains a large number of functional groups such as hydroxyl, amino or carboxyl, and the like, and can be effectively chelated with heavy metal ions in a water body, so that the hydrogel has excellent adsorption performance. However, most current hydrogel materials are prepared from non-renewable chemicals, and a large amount of organic solvents, such as dimethyl sulfoxide, glycerol ether and the like, are required to be used in the preparation process. This not only increases the cost of hydrogel preparation, but also causes severe environmental pollution, which is not conducive to its industrial application. In addition, in the current research, the hydrogel after adsorbing heavy metal ions is often directly treated as solid waste, which causes a serious waste of resources.
Disclosure of Invention
The invention provides preparation of lignin-based composite hydrogel and application of the lignin-based composite hydrogel in heavy metal ion adsorption and luminescent materials, aiming at the defects in preparation and application of the existing heavy metal ion adsorption materials. The invention takes industrial lignin and acrylic acid monomers as raw materials, prepares lignin-based composite hydrogel by an ultrasonic-assisted free radical polymerization method, and then applies the lignin-based composite hydrogel to the fields of heavy metal ion adsorption and luminescent materials. The invention not only provides a new way for the high-value utilization of industrial lignin, but also the prepared adsorbent has strong adsorption capacity to heavy metal ions in water. In addition, the hydrogel after absorbing the heavy metal ions can be developed into a luminescent material with high luminous intensity and long duration. Therefore, the invention has good application prospect.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of lignin-based composite hydrogel comprises the following steps:
1) mixing the sodium hydroxide aqueous solution and acrylic acid uniformly under the condition of ice-water bath, then adding lignosulfonate, N-methylene bisacrylamide and potassium persulfate in sequence, and stirring uniformly.
2) Carrying out free radical polymerization reaction on the mixed solution obtained in the step 1) under the ultrasonic-assisted condition, soaking the obtained product in absolute ethyl alcohol overnight, and then freeze-drying to obtain the lignin-based composite hydrogel.
According to the above technical solution, preferably, in step 1), the lignosulfonate is sodium lignosulfonate.
According to the technical scheme, preferably, in the step 1), the concentration of the sodium hydroxide aqueous solution is 5-10 mol/L, and preferably 7-8 mol/L; the volume ratio of the sodium hydroxide aqueous solution to the acrylic acid is 1: 1.
according to the above technical solution, in step 1), the ratio of acrylic acid, lignosulfonate, N-methylenebisacrylamide and potassium persulfate is preferably 3 mL: 0.1-1.5 g: 0.01-0.03 g: 0.1-0.3 g, preferably 3 mL: 0.5-1.0 g: 0.01-0.02 g: 0.1 to 0.2 g.
According to the above technical scheme, preferably, in the step 2), the temperature of the radical polymerization reaction is 40-80 ℃, preferably 50-60 ℃; the time is 1-3 h, preferably 1-2 h.
According to the above technical solution, preferably, in the step 2), the temperature of the freeze drying is-50 to-60 ℃, preferably-50 ℃; the time is 20-40 h, preferably 24 h.
According to the technical scheme, preferably, in the step 2), the ultrasonic auxiliary conditions are 200-300W and 30-50 kHz.
The invention also relates to protection of the lignin-based composite hydrogel prepared by the method.
The application of the lignin-based composite hydrogel in heavy metal ion adsorption comprises the following steps: mixing the lignin-based composite hydrogel with a heavy metal ion aqueous solution, and adsorbing for 10-30 h in a shaking table at the temperature of 20-40 ℃ and the rpm of 50-150; after adsorption, carrying out suction filtration, and measuring the concentration of heavy metal ions in the filtrate by an atomic absorption method; the obtained solid sample is the lignin-based composite hydrogel after the heavy metal ions are adsorbed.
According to the above technical solution, preferably, the heavy metal ion aqueous solution is one or more of a cobalt chloride solution, a cobalt nitrate solution, a copper chloride solution, a copper nitrate solution, a nickel chloride solution, a nickel nitrate solution, a cadmium chloride solution, a cadmium nitrate solution, and a lead nitrate solution, and preferably is a cobalt chloride solution, a nickel nitrate solution, or a cadmium nitrate solution. The concentration of the heavy metal ion aqueous solution is 10-400 mg/L.
According to the above technical solution, preferably, the ratio of the lignin-based composite hydrogel to the heavy metal ion aqueous solution is 0.1 g: 50-100 mL, preferably 0.1 g: 50 mL.
The application of the lignin-based composite hydrogel in the field of luminescent materials is that the lignin-based composite hydrogel obtained by the method is subjected to heavy metal ion adsorption, and the application process of the lignin-based composite hydrogel subjected to heavy metal ion adsorption in the field of luminescent materials is as follows: and mixing the lignin-based composite hydrogel after heavy metal ion adsorption with an N- (4-aminobutyl) -N-ethyl isoluminol solution, uniformly stirring, and adding a hydrogen peroxide solution to obtain the chemiluminescent hydrogel with high luminous intensity and long duration.
According to the above technical solution, preferably, the lignin-based composite hydrogel after absorbing heavy metal ions is fully crushed, ground or mashed and then mixed with N- (4-aminobutyl) -N-ethyl isoluminol solution.
According to the technical scheme, preferably, the concentration of the N- (4-aminobutyl) -N-ethyl isoluminol solution is 1.0-25.0 mmol/L, and preferably 5.0-10.0 mmol/L; the concentration of the hydrogen peroxide solution is 0.01-0.2 mol/L, preferably 0.05-0.1 mol/L; the ratio of the lignin-based composite hydrogel after heavy metal ion adsorption, the N- (4-aminobutyl) -N-ethyl isoluminol solution and the hydrogen peroxide solution is 0.1 g: 0.1-0.3 mL: 0.1-0.3 mL, preferably 0.1 g: 0.2-0.3 mL: 0.2-0.3 mL.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) the raw material used in the invention is lignosulfonate which is a byproduct in the pulping and papermaking process, but is not limited to lignin, so the raw material used in the invention has rich sources and low price, and is suitable for large-scale industrial utilization.
2) The preparation method of the hydrogel is simple and green, does not use any organic solvent, and can be used for large-scale production.
3) The hydrogel prepared by the invention contains abundant heavy metal ion adsorption sites, so that the hydrogel has strong adsorption capacity on various heavy metal ions.
4) The invention applies the hydrogel absorbing heavy metal ions to the preparation of luminescent materials for the first time, and the obtained luminescent hydrogel has the advantages of high luminous intensity, long luminous time and the like, and can be applied to cold light sources, decorative entertainment and underwater illumination in emergency.
5) The invention utilizes the industrial lignin to prepare the hydrogel and applies the hydrogel to the field of heavy metal ion adsorption and luminescent materials, which not only can fully utilize the industrial waste lignin and provide a new way for high-value utilization of the industrial waste lignin, but also the prepared hydrogel has strong adsorption capacity to the heavy metal ions in the water body. In addition, the hydrogel after absorbing the heavy metal ions can be applied to the preparation of luminescent materials. Therefore, the method has good application prospect.
Drawings
FIG. 1 is a lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 of the present invention1、SL-g-PAA2、SL-g-PAA3And SL-g-PAA4) Co of (A)2+Ion adsorption capacity data.
FIG. 2 is a lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 of the present invention1、SL-g-PAA2、SL-g-PAA3And SL-g-PAA4) Cu of (2)2+Ion adsorption capacity data.
FIG. 3 is a lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 of the present invention3) Co of (A)2+、Cu2+、Ni2 +、Pb2+And Cd2+Ion adsorption capacity data.
FIG. 4 is a graph showing the luminescence intensity and the luminescence kinetics of the lignin-based composite luminescent hydrogel prepared in example 7 of the present invention.
FIG. 5 is a graph showing the luminescence intensity and the luminescence kinetics of the lignin-based composite luminescent hydrogel prepared in example 8 of the present invention.
FIG. 6 is a graph showing the luminescence intensity and the luminescence kinetics of the lignin-based composite luminescent hydrogel prepared in example 9 of the present invention.
FIG. 7 is a digital photograph of the lignin-based composite luminescent hydrogel prepared in example 10 of the present invention under different luminescent times in dark.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, but the scope of the present invention is not limited by the following embodiments.
Example 1
A preparation method of lignin-based composite hydrogel comprises the following steps:
1) 3mL of an aqueous sodium hydroxide solution (10mol/L) and 3mL of acrylic acid were mixed uniformly in an ice-water bath, and then 0.3g, 0.6g, 0.9g, 1.2g of sodium lignosulfonate (Shanghai Michelin Biochemical technology Co., Ltd.), 0.02g of N, N-methylenebisacrylamide and 0.2g of potassium persulfate were added, respectively, and were magnetically stirred at 300rpm for 5 minutes to be completely dissolved.
2) Putting the mixed solution obtained in the step 1) into an ultrasonic cleaner (250W and 40kHz) at 50 ℃ for carrying out free radical polymerization reaction for 1 h. After the reaction is finished, the obtained product is soaked in absolute ethyl alcohol overnight.
3) Filtering the product obtained in step 2), placing in an ultra-low temperature refrigerator at (-52 deg.C), taking out after 6h, placing in a freeze-drying machine at (-50 deg.C), taking out after 24h, and freeze-drying to obtain lignin-based composite hydrogel (the dosage of lignosulfonate is 0.3g, 0.6g, 0.9g and 1.2g respectively as SL-g-PAA)1、SL-g-PAA2、SL-g-PAA3And SL-g-PAA4)。
Example 2
A preparation method of lignin-based composite hydrogel comprises the following steps:
1) 3mL of an aqueous solution of sodium hydroxide (7.5mol/L) and 3mL of acrylic acid were mixed uniformly in an ice-water bath, and then 0.9g of sodium lignosulfonate (Shanghai Michelin Biochemical technology Co., Ltd.), 0.01g of N, N-methylenebisacrylamide and 0.2g of potassium persulfate were sequentially added thereto, and were magnetically stirred at 300rpm for 5 minutes to be completely dissolved.
2) Putting the mixed solution obtained in the step 1) into ultrasonic cleaners (250W and 40kHz) at 50 ℃, 60 ℃, 70 ℃ and 80 ℃ respectively, and carrying out free radical polymerization reaction for 1 h. After the reaction is finished, the obtained product is soaked in absolute ethyl alcohol overnight.
3) Filtering the product obtained in step 2), placing into an ultra-low temperature refrigerator at (-52 deg.C), taking out after 6h, placing into a freeze-drying machine at (-50 deg.C), taking out after 24h, and freeze-drying to obtain lignin-based composite hydrogel (the free radical polymerization reaction temperature is 50 deg.C, 60 deg.C, 70 deg.C and 80 deg.C is respectively marked as SL-g-PAA5、SL-g-PAA6、SL-g-PAA7And SL-g-PAA8)。
Example 3
A preparation method of lignin-based composite hydrogel comprises the following steps:
1) 3mL of an aqueous solution of sodium hydroxide (7.5mol/L) and 3mL of acrylic acid were mixed uniformly in an ice-water bath, and then 0.6g of sodium lignosulfonate (Shanghai Michelin Biochemical technology Co., Ltd.), 0.01g of N, N-methylenebisacrylamide and 0.2g of potassium persulfate were sequentially added thereto, and were magnetically stirred at 300rpm for 5 minutes to be completely dissolved.
2) Putting the mixed solution obtained in the step 1) into an ultrasonic cleaner (250W and 40kHz) at 50 ℃, and respectively carrying out free radical polymerization reactions for 1h, 2h and 3 h. After the reaction is finished, the obtained product is soaked in absolute ethyl alcohol overnight.
3) Filtering the product obtained in step 2), placing in an ultra-low temperature refrigerator at (-52 deg.C), taking out after 6h, placing in a freeze-drying machine at (-50 deg.C), taking out after 24h, and freeze-drying to obtain lignin-based composite hydrogel (the free radical polymerization reaction time is 1h, 2h and 3h respectively marked as SL-g-PAA)9、SL-g-PAA10And SL-g-PAA11)。
Example 4
Lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 was used1、SL-g-PAA2、SL-g-PAA3And SL-g-PAA4) Carrying out Co in water2+An ion adsorption experiment, comprising the following steps:
1) 0.1g of SL-g-PAA prepared in example 1 was weighed out separately1、SL-g-PAA2、SL-g-PAA3And SL-g-PAA4The hydrogel was placed in a 100mL Erlenmeyer flask, then 50mL cobalt chloride solution (200mg Co/L) was added, and finally the Erlenmeyer flask was sealed.
2) Placing the conical flask obtained in the step 1) into a constant temperature shaking table, oscillating at 25 ℃ and 150rpm for 24h, filtering with a 0.22 mu m filter membrane, and measuring Co in the filtrate by an atomic absorption method2+The ion concentration. The obtained solid sample is the lignin-based composite hydrogel after ion adsorption, and is respectively recorded as: co2+@SL-g-PAA1、Co2+@SL-g-PAA2、Co2+@SL-g-PAA3And Co2+@SL-g-PAA4。
3) According to Co in aqueous solution before and after adsorption2+Calculating Co of adsorbent by ion concentration2+The amount of ion adsorption (as shown in fig. 1).
Example 5
Lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 was used1、SL-g-PAA2、SL-g-PAA3And SL-g-PAA4) Carrying out Cu in water2+An ion adsorption experiment, comprising the following steps:
1) 0.1g of SL-g-PAA prepared in example 1 was weighed out separately1、SL-g-PAA2、SL-g-PAA3And SL-g-PAA4The hydrogel was placed in a 100mL Erlenmeyer flask, then 50mL of copper nitrate solution (200mg Cu/L) was added, and finally the Erlenmeyer flask was sealed.
2) Placing the conical flask obtained in the step 1) into a constant temperature shaking table, oscillating at 25 ℃ and 150rpm for 24h, filtering with a 0.22 mu m filter membrane, and measuring Cu in the filtrate by an atomic absorption method2+The ion concentration. The obtained solid sample is the adsorbed Cu2+The ionized lignin-based composite hydrogel is respectively marked as: cu2+@SL-g-PAA1、Cu2+@SL-g-PAA2、Cu2+@SL-g-PAA3And Cu2+@SL-g-PAA4。
3) According to Cu in the aqueous solution before and after adsorption2+Calculation of ion concentration of Cu of adsorbent2+The amount of ion adsorption (as shown in fig. 2).
Example 6
Lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 was used3) Respectively carrying out Co in water2+、Cu2+、Ni2+、Pb2+And Cd2+An ion adsorption experiment, comprising the following steps:
1) 0.1g of SL-g-PAA prepared in example 1 was weighed3The hydrogel was placed in a 100mL Erlenmeyer flask, and then 50mL cobalt chloride solution (400mg Co/L) was added separately50mL of a copper nitrate solution (400mg of Cu/L), 50mL of a nickel nitrate solution (400mg of Ni/L), 50mL of a lead nitrate solution (400mg of Pb/L) and 50mL of a cadmium nitrate solution (400mg of Cd/L), and finally the Erlenmeyer flask was sealed.
2) Placing the conical flask obtained in the step 1) into a constant temperature shaking table, oscillating at 25 ℃ and 150rpm for 24h, filtering with a 0.22 mu m filter membrane, and respectively measuring Co in the filtrate by an atomic absorption method2+、Cu2+、Ni2+、Pb2+And Cd2+The ion concentration. The obtained solid samples are respectively adsorbed Co2+、Cu2+、Ni2+、Pb2+And Cd2+The ionized lignin-based composite hydrogel is respectively marked as: co2+@SL-g-PAA3、Cu2+@SL-g-PAA3、Ni2+@SL-g-PAA3、Pb2+@SL-g-PAA3And Cd2+@SL-g-PAA3。
3) SL-g-PAA is obtained by calculation according to the change of the concentration of heavy metal ions in the aqueous solution before and after adsorption3The amount of adsorption of each heavy metal ion (as shown in FIG. 3).
Example 7
Using the adsorbed Co obtained in example 42+Ionized lignin-based composite hydrogel (Co)2+@SL-g-PAA3) Preparing a luminescent hydrogel material, comprising the following steps:
1) 0.1g of Co obtained in example 4 was weighed2+@SL-g-PAA3And putting the mixture into a mortar for fully grinding. The resulting solid was then mixed with 0.1mL of N- (4-aminobutyl) -N-ethyliisoluminol solutions at different concentrations (1mmol/L, 2.5mmol/L, 5mmol/L, 10mmol/L and 15mmol/L), respectively.
2) Magnetically stirring the mixture obtained in the step 1) for 5 hours, and then slowly adding 0.3mL of hydrogen peroxide solution (0.1mol/L) to obtain a series of chemiluminescent hydrogel materials. Finally, the obtained luminescent gel material was put into a BPCL weak luminescence analyzer (PMT voltage of 800V), and the luminescence intensity and the luminescence kinetics were measured (as shown in fig. 4).
Example 8
Using the adsorbed Co obtained in example 42+Ionized lignin-based composite hydrogel (Co)2+@SL-g-PAA3) Preparing a luminescent hydrogel material, comprising the following steps:
1) 0.1g of Co obtained in example 4 was weighed2+@SL-g-PAA3And putting the mixture into a mortar for fully grinding. The resulting solid was then mixed with 0.1mL of N- (4-aminobutyl) -N-ethylisobutol solution (5 mmol/L).
2) Magnetically stirring the mixture obtained in the step 1) for 3 hours, and then respectively adding 0.3mL of hydrogen peroxide solutions with different concentrations (0.025mol/L, 0.05mol/L, 0.075mol/L, 0.1mol/L and 0.125mol/L) to obtain a series of chemiluminescent hydrogel materials. Finally, the obtained luminescent gel material was put into a BPCL weak luminescence analyzer (PMT voltage of 800V), and the luminescence intensity and the luminescence kinetics were measured (as shown in fig. 5).
Example 9
Using the lignin-based composite hydrogel (SL-g-PAA) before and after heavy metal ion adsorption in example 63、Co2+@SL-g-PAA3、Cu2+@SL-g-PAA3、Ni2+@SL-g-PAA3、Pb2+@SL-g-PAA3And Cd2+@SL-g-PAA3) Preparing a luminescent hydrogel material, comprising the following steps:
1) 0.1g of SL-g-PAA from example 6 was weighed out separately3(control), Co2+@SL-g-PAA3、Cu2+@SL-g-PAA3、Ni2+@SL-g-PAA3、Pb2+@SL-g-PAA3And Cd2+@SL-g-PAA3And putting the mixture into a mortar for fully grinding. The resulting solid was then mixed with 0.1mL of N- (4-aminobutyl) -N-ethylisobutol solution (5 mmol/L).
2) Magnetically stirring the mixture obtained in the step 1) for 3 hours, and then adding 0.3mL of hydrogen peroxide solution (0.1mol/L) to obtain a series of chemiluminescent hydrogel materials. Finally, the obtained luminescent gel material was put into a BPCL weak luminescence analyzer (PMT voltage of 800V), and the luminescence intensity and the luminescence kinetics were measured (as shown in fig. 6).
Example 10
Using a seedAdsorbed Co obtained in example 42+Ionized lignin-based composite hydrogel (Co)2+@SL-g-PAA3) Preparing a luminescent hydrogel material, comprising the following steps:
1) 1g of Co obtained in example 4 was weighed2+@SL-g-PAA3And putting the mixture into a mortar for fully grinding. The resulting solid was then mixed with 1mL of N- (4-aminobutyl) -N-ethylisobutol solution (15 mmol/L).
2) Magnetically stirring the mixture obtained in the step 1) for 3 hours, and then adding 3mL of hydrogen peroxide solution (0.1mol/L) to obtain a chemiluminescent hydrogel material. Finally, the chemiluminescence duration of the luminescent hydrogel material was observed in a dark environment (as shown in FIG. 7).
FIG. 1 is a lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 of the present invention1、SL-g-PAA2、SL-g-PAA3And SL-g-PAA4) Co of (A)2+Ion adsorption capacity data. From the figure, it can be seen that the composite hydrogel is applied to Co along with the increase of the dosage of the lignosulfonate2+The amount of ion adsorption gradually decreases. However, when the addition amount of the lignosulfonate reaches 0.9g, the composite hydrogel still has high Co2+Ion adsorption capacity.
FIG. 2 is a lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 of the present invention1、SL-g-PAA2、SL-g-PAA3And SL-g-PAA4) Cu of (2)2+Ion adsorption capacity data. From the figure, it can be seen that the composite hydrogel is applied to Cu along with the increase of the dosage of the lignosulfonate2+The amount of ion adsorption gradually decreases. However, when the addition amount of the lignosulfonate reaches 0.9g, the composite hydrogel still has high Cu2+Ion adsorption capacity.
FIG. 3 is a lignin-based composite hydrogel (SL-g-PAA) prepared in example 1 of the present invention3) Co of (A)2+、Cu2+、Ni2 +、Pb2+And Cd2+Ion adsorption capacity data. As can be seen from the figure, SL-g-PAA3To Co in water body2+、Cu2+、Ni2+、Pb2+And Cd2+The ions all haveBetter adsorption capacity to Pb2+The adsorption amount of ions is the largest.
FIG. 4 is a graph showing the luminescence intensity and the luminescence kinetics of the lignin-based composite luminescent hydrogel prepared in example 7 of the present invention. As can be seen from the figure, the concentration of the N- (4-aminobutyl) -N-ethyl isoluminol solution has a large influence on the luminous intensity of the obtained luminous hydrogel. With the increase of the concentration of the N- (4-aminobutyl) -N-ethyl isoluminol solution, the luminous intensity of the obtained luminous hydrogel is obviously enhanced.
FIG. 5 is a graph showing the luminescence intensity and the luminescence kinetics of the lignin-based composite luminescent hydrogel prepared in example 8 of the present invention. As can be seen from the figure, the concentration of the hydrogen peroxide solution has a large influence on the luminescence intensity of the obtained luminescent hydrogel. The luminous intensity of the obtained luminous hydrogel is obviously enhanced along with the increase of the concentration of the hydrogen peroxide solution. However, when the concentration of the hydrogen peroxide solution exceeds 0.1M, the increase of the concentration of the hydrogen peroxide solution can cause the rapid decay of the luminous intensity of the luminescent hydrogel, which is not favorable for the long-term continuous chemiluminescence.
FIG. 6 is a graph showing the luminescence intensity and the luminescence kinetics of the lignin-based composite luminescent hydrogel prepared in example 9 of the present invention. As can be seen from the figure, compared with the control group, the chemiluminescence intensity of all the luminescent hydrogels after absorbing heavy metal ions is significantly enhanced, which indicates that the existence of heavy metal ions in the hydrogel system can enhance the luminescent performance of the luminescent hydrogel. Furthermore, with Cu2+、Ni2+、Pb2+And Cd2+Adsorption of Co by ionic phase2+The luminous hydrogel after ionization has obviously higher chemiluminescence intensity, and the luminous intensity can still be kept above 75% of the maximum value after 50 min.
FIG. 7 is a digital photograph of the lignin-based composite luminescent hydrogel prepared in example 10 of the present invention under different luminescent times in dark. As can be seen from the graph, the luminescence intensity of the hydrogel gradually decreased as the luminescence duration increased. After 24 hours, the luminescence intensity of the luminescent hydrogel was still visible to the naked eye. The result shows that the luminescent hydrogel has the characteristics of high luminescent intensity and long duration.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Accordingly, it should be understood that various other modifications, substitutions and simplifications may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. The preparation method of the lignin-based composite hydrogel is characterized by comprising the following steps:
1) uniformly mixing a sodium hydroxide aqueous solution and acrylic acid under the ice-water bath condition, then sequentially adding lignosulfonate, N-methylene bisacrylamide and potassium persulfate, and uniformly stirring;
2) carrying out free radical polymerization reaction on the mixed solution obtained in the step 1) under the ultrasonic-assisted condition, soaking the obtained product in absolute ethyl alcohol overnight, and freeze-drying to obtain the lignin-based composite hydrogel.
2. The preparation method according to claim 1, wherein in the step 1), the concentration of the sodium hydroxide aqueous solution is 5-10 mol/L, and the volume ratio of the sodium hydroxide aqueous solution to the acrylic acid is 1: 1; the ratio of the acrylic acid, the lignosulfonate, the N, N-methylene bisacrylamide and the potassium persulfate is 3 mL: 0.1-1.5 g: 0.01-0.03 g: 0.1-0.3 g; the lignosulfonate is sodium lignosulfonate.
3. The preparation method according to claim 1, wherein in the step 2), the temperature of the free radical polymerization reaction is 40-80 ℃ and the time is 1-3 h;
the temperature of the freeze drying is-50 to-60 ℃, and the time is 20 to 40 hours; the ultrasonic auxiliary conditions are as follows: 200 to 300W, 30 to 50 kHz.
4. The lignin-based composite hydrogel obtained by the production method according to any one of claims 1 to 3.
5. The use of the lignin-based composite hydrogel according to claim 4 for heavy metal ion adsorption.
6. The application of the lignin-based composite hydrogel as claimed in claim 5, wherein the lignin-based composite hydrogel is mixed with a heavy metal ion aqueous solution, the mixture is adsorbed for 10-30 hours in a shaking table with the temperature of 20-40 ℃ and the speed of 50-150 rpm, and after adsorption is finished, suction filtration is carried out, and the obtained solid sample is the lignin-based composite hydrogel after heavy metal ions are adsorbed;
the heavy metal ion aqueous solution is more than one of cobalt chloride solution, cobalt nitrate solution, copper chloride solution, copper nitrate solution, nickel chloride solution, nickel nitrate solution, cadmium chloride solution, cadmium nitrate solution and lead nitrate solution; the concentration of the heavy metal ion aqueous solution is 10-400 mg/L; the ratio of the lignin-based composite hydrogel to the heavy metal ion aqueous solution is 0.1 g: 50-100 mL.
7. Use of the lignin-based composite hydrogel according to claim 4 in a luminescent material.
8. The use according to claim 7, wherein the lignin-based composite hydrogel after heavy metal ion adsorption is prepared by a method comprising: mixing the lignin-based composite hydrogel with a heavy metal ion aqueous solution, adsorbing for 10-30 h in a shaking table at 20-40 ℃ and 50-150 rpm, and after adsorption, performing suction filtration to obtain a solid sample, namely the lignin-based composite hydrogel after heavy metal ions are adsorbed;
the heavy metal ion aqueous solution is more than one of cobalt chloride solution, cobalt nitrate solution, copper chloride solution, copper nitrate solution, nickel chloride solution, nickel nitrate solution, cadmium chloride solution, cadmium nitrate solution and lead nitrate solution; the concentration of the heavy metal ion aqueous solution is 10-400 mg/L; the ratio of the lignin-based composite hydrogel to the heavy metal ion aqueous solution is 0.1 g: 50-100 mL.
9. The application of claim 8, wherein the lignin-based composite hydrogel after absorbing heavy metal ions is mixed with an N- (4-aminobutyl) -N-ethyl isoluminol solution, and after the mixture is uniformly stirred, a hydrogen peroxide solution is added to obtain the chemiluminescent hydrogel.
10. The use of claim 9, wherein the lignin-based composite hydrogel after adsorbing heavy metal ions is fully crushed, crushed or mashed and then mixed with N- (4-aminobutyl) -N-ethyl isoluminol solution; the concentration of the N- (4-aminobutyl) -N-ethyl isoluminol solution is 1.0-25.0 mmol/L, the concentration of the hydrogen peroxide solution is 0.01-0.2 mol/L, and the ratio of the lignin-based composite hydrogel after heavy metal ion adsorption, the N- (4-aminobutyl) -N-ethyl isoluminol solution and the hydrogen peroxide solution is 0.1 g: 0.1-0.3 mL: 0.1-0.3 mL.
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