CN113815072A - Wood-based composite material for photo-thermal sewage purification and preparation method and application thereof - Google Patents
Wood-based composite material for photo-thermal sewage purification and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/025—Controlling the process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/20—Compounds of alkali metals or ammonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
- B27K3/22—Compounds of zinc or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/343—Heterocyclic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/36—Aliphatic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
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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
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- B27K2240/00—Purpose of the treatment
- B27K2240/15—Decontamination of previously treated wood
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- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
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- Y02A20/138—Water desalination using renewable energy
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Abstract
The invention discloses a wood-based composite material for photothermal sewage purification and a preparation method and application thereof, and belongs to the technical field of photothermal conversion. The method comprises the steps of growing a metal organic framework material in a wood pore channel after wood is subjected to vacuum impregnation by an MOF precursor solution, and preparing the wood-based composite material for photo-thermal evaporation and heavy metal ion removal. The poly-dopamine photo-thermal material in the composite material can convert solar spectrum into heat energy, so that purified water evaporation is efficiently carried out; the wood substrate can effectively reduce heat conduction loss, realize heat concentration and improve the photo-thermal conversion efficiency; in addition, the hydrophobic property of the wood accelerates the transmission and evaporation of water; the porous MOF nanomaterials can adsorb contaminant ions. The purpose of removing the sewage ions is realized. The composite material has the advantages of low preparation raw material cost, simple and convenient process, high repeatability, easy mass production and wide application prospect in the interdisciplinary fields of seawater desalination, sewage purification and the like.
Description
Technical Field
The invention belongs to the technical field of photo-thermal conversion, and particularly relates to a wood-based composite material for photo-thermal sewage purification, and a preparation method and application thereof.
Background
The shortage of fresh water is one of the major challenges facing the world, and researchers developed many water collection technologies, including desalination of sea water and rainwater collection, in order to solve the water shortage problem in the world. However, most of the regions which suffer from water resource pressure are inland and arid regions, and natural liquid water cannot be obtained, and on the other hand, the moisture and water droplets in the air cannot fully meet the requirements of people in the arid regions. In recent years, solar heat conversion related technologies have received much attention in terms of economical, sustainable water collection and purification. The solar photo-thermal interface evaporation technology is characterized in that clean solar energy is used for photo-thermal conversion, so that seawater and sewage are evaporated by using heat energy, and pure water collection is realized.
Wood is a sustainable and renewable environment-friendly material, and the main components of the wood are cellulose, hemicellulose and lignin. The unique physical and chemical properties of wood and its derivatives make it have great potential in bioengineering, flexible electronics, clean energy and other fields. By utilizing the characteristic of the hierarchical porous structure of the wood, various functional materials are compounded among the wood-based pore channels, and the multifunctional application of the wood-based material is expanded.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a photothermal wood-based composite material. The invention aims to solve another technical problem and provides a preparation method of the photothermal wood-based composite material. The invention also aims to solve the technical problem of providing the application of the photothermal wood-based composite material in efficient photothermal seawater desalination and water purification.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
after wood is subjected to vacuum impregnation by MOF precursor solution, a metal organic framework material grows in pore channels of the wood, and the wood-based composite material for photo-thermal evaporation and heavy metal ion removal is prepared. The method comprises the following steps:
(1) respectively preparing sodium chloroacetate, sodium hydroxide aqueous solution, zinc nitrate hexahydrate solution, 2-methylimidazole solution and PDA (personal digital Assistant) wrapping solution, wherein the PDA wrapping solution is tetramethylpiperidine oxynitride and dopamine hydrochloride aqueous solution;
(2) placing wood in the sodium chloroacetate and sodium hydroxide aqueous solution, carrying out hydrothermal reaction, and washing the wood by using deionized water after the reaction is finished so as to remove lignin and hemicellulose in the wood;
(3) vacuum impregnation is carried out on the wood treated in the step (2) in the zinc nitrate hexahydrate solution, then the 2-methylimidazole solution is added for continuous vacuum impregnation, and vacuum drying is carried out after the vacuum impregnation is finished so as to grow the ZIF-8 nano material in situ in a wood pore channel, so that the dried wood loaded with the functional material for the first time is obtained;
(4) and (5) repeating the step (3) to obtain the again-loaded ZIF-8 composite wood, and drying and forming.
(5) And (4) stirring the wood treated in the step (4) in the PDA solution, and performing vacuum drying to wrap a PDA black coating on the surface of the wood.
According to the preparation method of the wood-based composite material for photothermal purification of sewage, the mass concentration of the sodium chloroacetate is 11.8 wt%, and the mass concentration of the sodium hydroxide is 1.5 wt%; the hydrothermal reaction temperature is 80 ℃, and the time is 1 h; stirring and cleaning the mixture for 24 hours by using deionized water after the hydrothermal reaction.
According to the preparation method of the wood-based composite material for photo-thermal sewage purification, zinc nitrate hexahydrate, methanol and water in a zinc nitrate hexahydrate solution are in a mass ratio of 2.38-9.52: 20:3, and vacuum impregnation is carried out for 1-2 hours; and (3) continuing vacuum impregnation for 1-2h, wherein the mass ratio of the 2-methylimidazole to the methanol to the water in the 2-methylimidazole solution is 3.35-13.4: 20: 3.
According to the preparation method of the wood-based composite material for photo-thermal sewage purification, the zinc nitrate hexahydrate solution is obtained by dissolving 0.008mol, 0.016mol, 0.024mol and 0.032mol of zinc nitrate hexahydrate in 20g of methanol and 3g of deionized water and uniformly stirring; the 2-methylimidazole solution is prepared by dissolving 0.04mol, 0.08mol, 0.12mol and 0.16mol of 2-methylimidazole in 20g of methanol and 3g of deionized water and uniformly stirring.
According to the preparation method of the wood-based composite material for photo-thermal purification of sewage, the mass concentration of the tetramethylpiperidine nitrogen oxide is 0.4 wt%, and the mass concentration of the dopamine hydrochloride is 0.2 wt%.
According to the preparation method of the wood-based composite material for photo-thermal sewage purification, the wood is balsa or cedar.
The wood-based composite material for photo-thermal sewage purification prepared by the method.
The wood-based composite material is applied to photo-thermal evaporation and purification of seawater, heavy metals, dyes and strong acid-base wastewater.
The wood-based composite material is applied to high-efficiency adsorption of heavy metal ions.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) the Metal Organic Framework (MOF) derived carbon material, zinc-2-methylimidazole (ZIF-8) shows stronger adsorption property due to the microporous structure with large surface area. The ZIF-8 nano material is compounded with the porous wood-based material, so that the adsorption of the wood-based composite material on heavy metal ions can be realized, and the aim of purifying water is fulfilled. In addition, polydopamine with high light absorption rate is wrapped on the surface of the wood, so that the hydrophilicity and the light absorption characteristics of the wood are effectively improved, and efficient photo-thermal steam conversion is realized.
(2) The poly-dopamine photo-thermal material in the composite material can convert solar spectrum into heat energy, so that purified water evaporation is efficiently carried out; the wood substrate can effectively reduce heat conduction loss, realize heat concentration and improve the photo-thermal conversion efficiency; in addition, the hydrophobic property of the wood accelerates the transmission and evaporation of water; the porous MOF nanomaterials can adsorb contaminant ions. The purpose of removing the sewage ions is realized. The composite material has the advantages of low preparation raw material cost, simple and convenient process, high repeatability, easy mass production and wide application prospect in the interdisciplinary fields of seawater desalination, sewage purification and the like.
Drawings
Fig. 1 is a graph of wood evaporation efficiency (fig. 1a) and wood evaporation rate (fig. 1 b). Wherein BZ1-BZ4 respectively represent ZIF/PDA composite balsawood with ZIF-8 content of 1, 2, 3, 4 concentration, and SZ1-SZ4 respectively represent ZIF/PDA composite cedarwood with 1, 2, 3, 4 concentration;
FIG. 2 is various photo-thermal test graphs of BZ4-PDA, wherein FIG. 2a is a graph showing the photo-thermal evaporation rate and photo-thermal conversion rate results of the photo-thermal evaporation of BZ4-PDA under 1, 3, 5 illumination intensities respectively, FIG. 2b is a graph showing the results of the cyclic stability test of the evaporation performance of BZ4-PDA in seawater under sunlight irradiation, FIG. 2c is a graph showing the results of the mass loss of the photo-thermal evaporation of BZ4-PDA under 1, 3, 5 illumination intensities respectively, and FIG. 2d is a graph showing the ion concentration changes in seawater and wastewater before and after the photo-thermal evaporation of BZ 4-PDA;
FIG. 3 is the performance of different wood-based composites in removing organic contaminants, FIG. 3a is the performance of different wood-based composites in removing phenol, the square curve is the absorbance curve of unfiltered phenol solution, the circular curve is the absorbance curve of filtered solution, FIG. 3b is the performance of different wood-based composites in removing methylene blue, the square curve is the absorbance curve of unfiltered methylene blue solution, the circular curve is the absorbance curve of filtered solution, and the photograph on the left shows a comparison of the color before and after filtration;
FIG. 4 is an X-ray diffraction pattern of Basambucus chinensis (B), carboxylated Basambucus chinensis (B + S), ZIF-8 loaded Basambucus chinensis (B + Z), ZIF/PDA wrapped Basambucus chinensis (B + Z + PDA);
FIG. 5 is a scanning electron microscope image of a ZIF-8 nanopowder and a ZIF-8/PDA composite nanomaterial, FIGS. 5a-5c are respectively the morphology of the ZIF-8 nanopowder at different magnifications, and FIGS. 5d-5f are respectively the morphology of the ZIF-8/PDA composite nanopowder at different magnifications;
FIG. 6 is a scanning electron microscope image of a balsawood composite ZIF-8/PDA material, and FIGS. 6a-6d are the internal appearance of the pore channels of the composite wood-based material synthesized with 1 time, 2 times, 3 times and 4 times of ZIF-8 loading, respectively;
FIG. 7 is a scanning electron microscope image of a fir composite ZIF-8/PDA material, and FIGS. 7a-7d are the internal features of the channels of the composite wood-based material synthesized with 1, 2, 3 and 4 times of ZIF-8 loading, respectively.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Example 1
A preparation method of a wood-based composite material for photo-thermal sewage purification comprises the following steps:
(1) 9.5g of sodium chloroacetate and 1.2g of sodium hydroxide were added to 70mL of deionized water, stirred uniformly, added to Basasa having a size of 1X 0.5cm, and heated in a water bath at 80 ℃ for 1 hour in a reaction kettle. Then taking out the wood, putting the wood into deionized water, stirring and cleaning for 24h, comparing the pH value of the cleaned solution with that of the pure water by using a pH meter after cleaning is finished, wherein the difference is not more than +/-0.1, putting the wood into a freeze dryer, freezing for 4h, and then drying for 8h to obtain dry carboxylated treated wood for later use;
(2) dissolving 9.52g (0.032mol, 4 concentration) of zinc nitrate hexahydrate in 20g of methanol and 3g of deionized water, uniformly stirring, putting the dried wood subjected to carboxylation treatment into the solution, putting the solution into a closed container, vacuumizing the closed container by using a vacuum pump, and performing vacuum impregnation for 1 to 2 hours. 13.4g (0.16mol, 4 concentration) of 2-methylimidazole (2-MeIm) are dissolved in 20g of methanol and 3g of deionized water, the mixture is stirred uniformly, the solution and wood are placed in a closed container, vacuum pumping is carried out, and vacuum impregnation is carried out for 1-2 h. The impregnated wood was then washed three times with 50mL of methanol, each time with stirring for 5 min. And after the washing is finished, putting the wood into a vacuum drying oven, and carrying out vacuum drying for 24 hours at the temperature of 60 ℃ to obtain the first load-treated dried wood. Repeating the steps once to obtain a secondary-loaded ZIF-8 composite wood;
(3) dissolving 0.4g of tetramethylpiperidine nitroxide (TEMPO) in 80mL of deionized water, stirring for 20min, adding 0.2g of dopamine hydrochloride and 20mL of deionized water, stirring uniformly, putting the dried wood loaded with ZIF-8 into the prepared solution, and stirring for 8 h. The wood was then removed from the solution and washed three times with 50mL methanol with agitation, each for about 5 min. And after the wood is cleaned, putting the wood into a vacuum drying oven for drying for 24 hours at the temperature of 60 ℃ to obtain the dried ZIF/PDA composite wood which is recorded as BZ 4-PDA.
Through photothermal evaporation tests, the BZ4-PDA evaporator has good photothermal evaporation performance under the irradiation of standard sunlight, and the evaporation rate can reach 2.72kg m-2h-1(FIG. 1b), the photothermal conversion efficiency was 82.5% (FIG. 1b), and the photothermal conversion efficiency was the highest at one light intensity (FIG. 2 a). Compared with other bazaar loaded with ZIF at a lower concentration, the 4-concentration ZIF-loaded PDA-wrapped BZ4 sample has a significant advantage in photothermal evaporation performance under standard solar radiation (fig. 1a) and is significantly better than the steam conversion performance of a non-photothermal evaporator.
Through a cycle stability test (figure 2b) of the evaporation performance of the BZ4-PDA photo-thermal evaporator in seawater under the irradiation of sunlight, the BZ4-PDA photo-thermal evaporator has more stable photo-thermal steam conversion performance in seawater. Through a photo-thermal evaporation test (fig. 2d) of a heavy metal ion polluted water body, the BZ4-PDA photo-thermal evaporator can be obtained to effectively adsorb heavy metal ions, and the purpose of removing heavy metal ion pollutants is achieved.
Example 2
A preparation method of a wood-based composite material for photo-thermal sewage purification comprises the following steps:
(1) adding 9.5g sodium chloroacetate and 1.2g sodium hydroxide into 70mL deionized water, stirring, adding 1X 0.5cm fir, and heating in water bath at 80 deg.C for 1 hr. Then taking out the wood, putting the wood into deionized water, stirring and cleaning for 24h, comparing the pH value of the cleaned solution with that of the pure water by using a pH meter after cleaning is finished, wherein the difference is not more than +/-0.1, putting the wood into a freeze dryer, freezing for 4h, and then drying for 8h to obtain dry carboxylated treated wood for later use;
(2) dissolving 7.15g (0.024mol, 3 concentration) of zinc nitrate hexahydrate in 20g of methanol and 3g of deionized water, stirring uniformly, putting the dried wood subjected to carboxylation treatment into the solution, putting the solution into a closed container, vacuumizing the closed container by using a vacuum pump, and performing vacuum impregnation for 1-2 hours. Then 10.1g (0.12mol, 3 concentration) of 2-methylimidazole (2-MeIm) is dissolved in 20g of methanol and 3g of deionized water, the mixture is stirred uniformly, the solution and wood are placed in a closed container for vacuumizing, and vacuum impregnation is carried out for 1-2 h. The impregnated wood was then washed three times with about 50mL of methanol, each time with 5min of stirring. And after the washing is finished, putting the wood into a vacuum drying oven, and carrying out vacuum drying for 24 hours at the temperature of 60 ℃ to obtain the first load-treated dried wood. Repeating the steps once to obtain a second ZIF-8-loaded composite wood;
(3) dissolving 0.4g of tetramethylpiperidine nitroxide (TEMPO) in 80mL of deionized water, stirring for 20min, adding 0.2g of dopamine hydrochloride and 20mL of deionized water, stirring uniformly, putting the dried ZIF-8-loaded composite wood into the prepared solution, and stirring for 8 h. The wood was then removed from the solution and washed three times with 50mL methanol with agitation, each for about 5 min. And after cleaning, putting the wood into a vacuum drying oven at the temperature of 60 ℃ for drying for 24 hours to obtain dry ZIF/PDA composite fir, which is recorded as SZ 3-PDA.
Through photothermal evaporation tests, the SZ3 photothermal evaporator has good photothermal evaporation performance under the irradiation of standard sunlight, and the evaporation rate can reach 2.46kg m-2h-1(FIG. 1b), the photothermal conversion efficiency was 73.78% (FIG. 1 b). 3 concentration of ZIF-Compared with other concentration ZIF-8 loaded fir evaporators, the 8-composite SZ3 photo-thermal evaporator has the advantages that the photo-thermal evaporation performance is obviously improved under the irradiation of standard sunlight (figure 1a), and the steam conversion efficiency is obviously higher than that of the evaporator without the photo-thermal evaporator.
Example 3
A preparation method of a wood-based composite material for photo-thermal sewage purification comprises the following steps:
(1) 9.5g of sodium chloroacetate and 1.2g of sodium hydroxide were added to 70mL of deionized water, stirred uniformly, added to Basasa having a size of 1X 0.5cm, and heated in a water bath at 80 ℃ for 1 hour in a reaction kettle. Then taking out the wood, putting the wood into deionized water, stirring and cleaning for 24h, comparing the pH value of the cleaned solution with that of the pure water by using a pH meter after cleaning is finished, wherein the difference is not more than +/-0.1, putting the wood into a freeze dryer, freezing for 4h, and then drying for 8h to obtain dry carboxylated treated wood, and marking as B + S;
(2) 2.38g (0.008mol, 1 concentration) of zinc nitrate hexahydrate is dissolved in 20g of methanol and 3g of deionized water, the mixture is stirred uniformly, dried wood after carboxylation treatment is placed in the solution, the solution is placed in a closed container, the sealed container is vacuumized by a vacuum pump, and the vacuum impregnation is carried out for 1 to 2 hours. Then 3.35g (0.04mol, 1 concentration) of 2-methylimidazole (2-MeIm) are dissolved in 20g of methanol and 3g of deionized water, the mixture is stirred uniformly, the solution and wood are placed in a closed container, vacuum pumping is carried out, and vacuum impregnation is carried out for 1-2 h. The impregnated wood was then washed three times with 50mL of methanol, each time with stirring for 5 min. And after the washing is finished, putting the wood into a vacuum drying oven, and carrying out vacuum drying for 24 hours at the temperature of 60 ℃ to obtain the first load-treated dried wood. Repeating the steps once to obtain a second-time loaded hot zinc carbide-2-methylimidazole (ZIF-8) wood which is marked as B + Z;
(3) dissolving 0.4g of tetramethylpiperidine nitroxide (TEMPO) in 80mL of deionized water, stirring for 20min, adding 0.2g of dopamine hydrochloride and 20mL of deionized water, stirring uniformly, putting the dried ZIF-8-loaded composite wood into the prepared solution, and stirring for 8 h. The wood was then removed from the solution and washed three times with 50mL methanol with agitation, each for about 5 min. And after the wood is cleaned, putting the wood into a vacuum drying oven for drying for 24 hours at the temperature of 60 ℃ to obtain dry ZIF + PDA wrapped balsawood, which is recorded as S + Z-PDA.
A piece of pausal without any treatment was taken and marked as B. By means of an X-ray diffraction pattern (figure 4) and a phase spectrogram of an analyte, after carboxylation treatment is carried out, zinc nitrate and 2-methylimidazole medicines are added for vacuum impregnation, and ZIF-8 can be well loaded in pores of the balsa wood.
Example 4
A preparation method of a wood-based composite material for photo-thermal sewage purification comprises the following steps:
(1) 9.5g of sodium chloroacetate and 1.2g of sodium hydroxide were added to 70mL of deionized water, stirred uniformly, added to Basasa having a size of 1X 0.5cm, and heated in a water bath at 80 ℃ for 1 hour in a reaction kettle. Then taking out the wood, putting the wood into deionized water, stirring and cleaning for 24h, comparing the pH value of the cleaned solution with that of the pure water by using a pH meter after cleaning is finished, wherein the difference is not more than +/-0.1, putting the wood into a freeze dryer, freezing for 4h, and then drying for 8h to obtain dry carboxylated treated wood for later use;
(2) respectively dissolving 0.008mol (1 concentration), 0.016mol (2 concentration), 0.024mol (3 concentration) and 0.032mol (4 concentration) of zinc nitrate hexahydrate in 20g of methanol and 3g of deionized water, uniformly stirring, respectively putting the dried wood subjected to carboxylation treatment into the above solution, putting the solution into a closed container, vacuumizing by using a vacuum pump, and carrying out vacuum impregnation for 1-2 h. And then respectively dissolving 0.04mol (1 concentration), 0.08mol (2 concentration), 0.12mol (3 concentration) and 0.16mol (4 concentration) of 2-methylimidazole in 20g of methanol and 3g of deionized water, uniformly stirring, adding the wood with the corresponding composite zinc nitrate hexahydrate concentration processed from low to high into a 2-methylimidazole solution with the concentration processed from low to high, placing the wood into a closed container, vacuumizing, and carrying out vacuum impregnation for 1-2 hours. The impregnated wood was then washed three times with 50mL of methanol, each time with stirring for 5 min. And after the washing is finished, putting the wood into a vacuum drying oven, and carrying out vacuum drying for 24 hours at the temperature of 60 ℃ to obtain the first load-treated dried wood. Repeating the steps once to obtain a secondary-loaded ZIF-8 composite wood;
(3) dissolving 0.4g of tetramethylpiperidine nitroxide (TEMPO) in 80mL of deionized water, stirring for 20min, adding 0.2g of dopamine hydrochloride and 20mL of deionized water, stirring uniformly, putting dried wood loaded with 4 ZIF-8 with different concentrations into the solution, and stirring for 8 h. Subsequently, the wood was removed from the solution and washed three times with 50mL methanol with stirring, each time for about 5 min. After the wood is cleaned, the wood is placed in a vacuum drying oven to be dried for 24 hours at the temperature of 60 ℃ to obtain the dried ZIF/PDA composite wood, and the concentration of the treatment solution is recorded as BZ1-PDA, BZ2-PDA, BZ3-PDA and BZ4-PDA from low to high.
From SEM scanning images (FIG. 6), it can be seen that as the concentration of the solution for loading ZIF-8 is increased, the amount of ZIF-8 growing in the pore channels of the wood-based composite material is increased. As shown in the figure, a small amount of ZIF-8 is distributed in the pore channels of the wood-based composite material loaded with the concentration of 1, and a large amount of flaky ZIF-8 nano materials grow in the pore channels of the wood-based composite material loaded with the concentration of 4. This example illustrates that the amount of crystals of the ZIF-8 nanomaterial growing in the pore channels of wood can be controlled by adjusting the concentration of the solution, and the wood-based composite material loaded with a specific amount of crystals can be obtained by the preparation method of the present invention. The specific morphology of the loaded ZIF-8 can be known through SEM scanning images (figure 5), the ZIF-8 nano material grows in a regular cube in a Basha wood pore passage, and after the wood is wrapped by PDA, the regularity of the ZIF-8 nano material is reduced, and the flaky crystal form ZIF-8 nano material is stacked.
10mg of L is prepared-1Phenol solution and 10mg L-1And (3) preparing a filter by using 4 composite wood-based materials with different concentrations in the methylene blue solution to perform organic pollutant removal performance test. And (3) passing the organic pollutant solution through a composite wood-based material filter, collecting the filtered solution, and measuring the absorbance of the filtered solution. Through testing the absorbance C of organic pollutants before and after filtration0And C, the removal rate (1-C/C) of the organic pollutants by the 4 composite wood-based materials with different concentrations can be obtained after calculation0)。
Through 4 composite wood-based materials with different concentrations to remove organic pollutants (phenol and methylene blue), the removal rate of the organic pollutants (phenol and methylene blue) of the wood-based composite materials is improved along with the increase of the concentration of the loaded ZIF (figure 3). The removal rate of the BZ4-PDA to phenol can reach 96%, and the removal rate of the BZ4-PDA to methylene blue can reach 99%, which shows that the composite wood-based material has good adsorption capacity to organic pollutants, has larger adsorption capacity, and can remove the organic pollutants (phenol and methylene blue).
Example 5
A preparation method of a wood-based composite material for photo-thermal sewage purification comprises the following steps:
(1) adding 9.5g sodium chloroacetate and 1.2g sodium hydroxide into 70mL deionized water, stirring, adding 1X 0.5cm fir, and heating in water bath at 80 deg.C for 1 hr. Then taking out the wood, putting the wood into deionized water, stirring and cleaning for 24h, comparing the pH value of the cleaned solution with that of the pure water by using a pH meter after cleaning is finished, wherein the difference is not more than +/-0.1, putting the wood into a freeze dryer, freezing for 4h, and drying for 8h to obtain dry carboxylated treated wood;
(2) respectively dissolving 0.008mol (1 concentration), 0.016mol (2 concentration), 0.024mol (3 concentration) and 0.032mol (4 concentration) of zinc nitrate hexahydrate in 20g of methanol and 3g of deionized water, uniformly stirring, respectively putting the dried wood subjected to carboxylation treatment into the above solution, putting the solution into a closed container, vacuumizing by using a vacuum pump, and carrying out vacuum impregnation for 1-2 h. And then dissolving 0.04mol (1 concentration), 0.08mol (2 concentration), 0.12mol (3 concentration) and 0.16mol (4 concentration) of 2-methylimidazole in 20g of methanol and 3g of deionized water, uniformly stirring, adding the wood treated by the corresponding zinc nitrate hexahydrate from low to high in concentration into a 2-methylimidazole solution from low to high in concentration, placing the wood into a closed container, vacuumizing, and carrying out vacuum impregnation for 1-2 hours. The impregnated wood was then washed three times with 50mL of methanol, each time with stirring for 5 min. And after the washing is finished, putting the wood into a vacuum drying oven, and carrying out vacuum drying for 24 hours at the temperature of 60 ℃ to obtain the first load-treated dried wood. Then, repeating the steps once to obtain a secondary-loaded ZIF-8 composite wood;
(3) dissolving 0.4g of tetramethylpiperidine nitroxide (TEMPO) in 80mL of deionized water, stirring for 20min, adding 0.2g of dopamine hydrochloride and 20mL of deionized water, stirring uniformly, putting dried wood loaded with 4 ZIF-8 with different concentrations into the solution, and stirring for 8 h. Subsequently, the wood was removed from the solution and washed three times with 50mL methanol with stirring, each time for about 5 min. And after cleaning, putting the wood into a vacuum drying chamber at 60 ℃ for 24h to obtain the dried ZIF/PDA composite wood. According to the number of the composite wood added with ZIF-8, the composite wood is marked as SZ1-PDA, SZ2-PDA, SZ3-PDA and SZ4-PDA from low to high.
From SEM scanning images (FIG. 7), it can be seen that as the concentration of the solution used for loading ZIF-8 is increased, the amount of ZIF-8 growing in the pore channels of the wood-based composite material is increased. As shown in the figure, only a small amount of ZIF-8 grows in the pore channels of the wood-based composite material loaded with the concentration of 1, and a large amount of ZIF-8 grows in the pore channels of the wood-based composite material loaded with the concentration of 4. And the comparison with the Bassa wood SEM scanning image (figure 6) shows that the ZIF-8 nano materials growing in the channels of the fir wood and the Bassa wood have different shapes. Comparing the SEM image (FIG. 6b) of the ZIF-8 nanomaterial loaded in the balsa pore canal with the 2-fold concentration and the SEM image (FIG. 7b) of the ZIF-8 nanomaterial loaded in the fir pore canal with the 2-fold concentration, it can be seen that the ZIF-8 nanomaterial grows in the balsa pore canal as granular crystals and rod-shaped crystals.
Claims (10)
1. A preparation method of a wood-based composite material for photo-thermal purification of sewage is characterized in that wood is subjected to vacuum impregnation by an MOF precursor solution, and then a metal organic framework material grows in pore channels of the wood, so that the wood-based composite material for photo-thermal evaporation and removal of heavy metal ions is prepared.
2. The method for preparing the wood-based composite material for photothermal purification of wastewater according to claim 1, comprising the steps of:
(1) respectively preparing sodium chloroacetate, sodium hydroxide aqueous solution, zinc nitrate hexahydrate solution, 2-methylimidazole solution and PDA (personal digital Assistant) wrapping solution, wherein the PDA wrapping solution is tetramethylpiperidine oxynitride and dopamine hydrochloride aqueous solution;
(2) placing wood in the sodium chloroacetate and sodium hydroxide aqueous solution, carrying out hydrothermal reaction, and washing the wood by using deionized water after the reaction is finished so as to remove lignin and hemicellulose in the wood;
(3) vacuum impregnation is carried out on the wood treated in the step (2) in the zinc nitrate hexahydrate solution, then the 2-methylimidazole solution is added for continuous vacuum impregnation, and vacuum drying is carried out after the vacuum impregnation is finished so as to grow the ZIF-8 nano material in situ in a wood pore channel, so that the dried wood loaded with the functional material for the first time is obtained;
(4) repeating the step (3) to obtain the again-loaded ZIF-8 composite wood, and drying and forming;
(5) and (4) stirring the wood treated in the step (4) in the PDA solution, and performing vacuum drying to wrap a PDA black coating on the surface of the wood.
3. The method for preparing the wood-based composite material for photothermal purification of sewage according to claim 2, wherein the sodium chloroacetate mass concentration is 11.8 wt%, and the sodium hydroxide mass concentration is 1.5 wt%; the hydrothermal reaction temperature is 80 ℃, and the time is 1 h; stirring and cleaning the mixture for 24 hours by using deionized water after the hydrothermal reaction.
4. The preparation method of the wood-based composite material for photothermal purification of sewage according to claim 2, wherein the zinc nitrate hexahydrate solution comprises zinc nitrate hexahydrate, methanol and water in a mass ratio of 2.38-9.52: 20:3, and the wood-based composite material is vacuum-impregnated for 1-2 hours; and (3) continuing vacuum impregnation for 1-2h, wherein the mass ratio of the 2-methylimidazole to the methanol to the water in the 2-methylimidazole solution is 3.35-13.4: 20: 3.
5. The method for preparing a wood-based composite material for photothermal purification of sewage according to claim 2, wherein the zinc nitrate hexahydrate solution is prepared by dissolving 0.008mol, 0.016mol, 0.024mol and 0.032mol of zinc nitrate hexahydrate in 20g of methanol and 3g of deionized water, and uniformly stirring; the 2-methylimidazole solution is prepared by dissolving 0.04mol, 0.08mol, 0.12mol and 0.16mol of 2-methylimidazole in 20g of methanol and 3g of deionized water and uniformly stirring.
6. The method of claim 2, wherein the concentration of the tetramethylpiperidine nitroxide is 0.4 wt% and the concentration of the dopamine hydrochloride is 0.2 wt%.
7. The method of preparing a wood-based composite material for photothermal purification of wastewater according to claim 1 or 2, wherein the wood is balsa wood or cedar wood.
8. The photothermal wood-based composite material prepared by the method of claim 1.
9. Use of the photothermal wood based composite material according to claim 8 for photothermal evaporation purification of seawater and heavy metals, dyes, strongly acidic and alkaline wastewater.
10. Use of the photothermal wood-based composite material according to claim 8 for highly efficient adsorption of heavy metal ions.
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