CN114210275A - Method for preparing MOF/wood aerogel composite material - Google Patents
Method for preparing MOF/wood aerogel composite material Download PDFInfo
- Publication number
- CN114210275A CN114210275A CN202111229307.5A CN202111229307A CN114210275A CN 114210275 A CN114210275 A CN 114210275A CN 202111229307 A CN202111229307 A CN 202111229307A CN 114210275 A CN114210275 A CN 114210275A
- Authority
- CN
- China
- Prior art keywords
- wood
- aerogel
- mof
- composite material
- drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a method for preparing an MOF/wood aerogel composite material, which comprises the steps of carrying out delignification process on wood, freezing and drying to obtain a wood aerogel material, taking the wood aerogel, an organic ligand, an organic solvent and a metal salt solution as main raw materials, and successfully constructing the MOF/wood aerogel composite material by adopting an in-situ synthesis method or a hydrothermal synthesis method. The preparation method is simple in preparation process, easy to operate and low in cost. The problems of shrinkage of the structure, easy collapse of a fiber framework and the like of the wood aerogel are solved, and the wood aerogel has composite functional characteristics due to the introduction of the MOF nanoparticles. The composite material combines the structural characteristic advantages of the MOF reinforced phase and the wood aerogel matrix, so that the composite material has wide application prospects in the fields of flame retardance, adsorption, energy storage, electromagnetic shielding, gas separation and the like. The raw materials related by the invention are rich and wide in source, and an effective way is provided for developing the biomass composite material with high added value.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a method for preparing a MOF/wood aerogel composite material.
Background
The wood aerogel has the advantages of low density, large specific surface area, biocompatibility and the like, and provides an ideal carrier for preparing the biomass aerogel composite material with excellent functional characteristics. However, due to the hydrophilic action of abundant hydroxyl groups on a molecular chain, the wood aerogel is easy to generate structural shrinkage and pore cavity collapse in the solvent exchange and drying treatment processes, so that the application of the material in a plurality of leading-edge fields is limited. The Metal Organic Framework (MOF) is a porous hybrid nano material formed by self-assembling metal ions/metal clusters and organic ligands, has the characteristic advantages of high crystallization, inorganic-organic hybrid porous structure, large specific surface area, abundant porosity, a large number of active sites and the like, and is widely applied to the frontier fields of flame retardance, adsorption, energy storage, electromagnetic shielding, gas separation and the like. The invention aims to develop a preparation method of the wood aerogel composite material capable of successfully loading the MOF nano material, thereby having very important practical significance for realizing the development of high value-added functions of the biomass composite material.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for preparing MOF/wood aerogel composite material, which is used to solve the problems of the prior wood aerogel that the structure is easy to shrink, the cells collapse and the performance is greatly reduced. To achieve the above and other related objects, the present invention provides a method for preparing a MOF/wood aerogel composite, comprising the steps of:
and (1) putting wood into a sodium hypochlorite solution with a certain concentration ratio, placing the wood into a constant-temperature water bath for delignification process treatment for a period of time, after the wood is completely reacted by the delignification process, washing the wood, transferring the washed wood to a freeze dryer under a low-temperature environment for drying treatment, and obtaining the lightweight and porous wood aerogel material.
And (2) putting the wood aerogel prepared in the step (1) into the MOF precursor solution by adopting an in-situ synthesis method, stirring, fully stirring, mixing, reacting, washing and drying to obtain the MOF/wood aerogel composite material. Or putting the wood aerogel obtained in the step (1) into a precursor solution of the MOF by a hydrothermal synthesis method, transferring the wood aerogel into a polytetrafluoroethylene hydrothermal reaction kettle, putting the polytetrafluoroethylene hydrothermal reaction kettle into an oven, heating the wood aerogel to a certain temperature, preserving the heat for a period of time, washing a wood aerogel sample after the reaction is finished, and drying the wood aerogel sample to obtain the MOF/wood aerogel composite material.
Further, in the step (1), the wood is balsa wood, poplar wood, fir wood, pine wood, rubber wood, maple wood, birch wood, cedar wood, or the like.
Further, in the step (1), the concentration ratio of the sodium hypochlorite solution used in the delignification process is 1-10%, the reaction temperature of the water bath is 70-120 ℃, and the reaction time of the delignification process is 6-54 h.
Further, in the step (1), the wood sample treated by the complete delignification process is put into a freeze dryer for vacuum drying for 6-48h at the drying temperature of-50 to-70 ℃.
Further, in the step (2), the precursor solution for synthesizing the MOF material includes metal salt, organic ligand and organic solvent, wherein the metal salt is chloride, nitrate or sulfate of Zr, Cr, Co, Fe, Al, Mg, Ni or Zn; the organic ligand is terephthalic acid, trimesic acid, pyromellitic acid, dimethyl imidazole and the like, and the organic solvent is N, N-dimethylformamide, methanol and the like.
Further, in the step (2), the molar ratio of the metal salt to the organic ligand is (0.1-20): 1; the organic solvent is 10-100 mL.
Further, in the step (2), the stirring temperature of the in-situ synthesis method is 10-90 ℃, the stirring time of the wood aerogel immersed in the organic ligand solution for synthesizing the MOF is 1-48 h, and the stirring speed is 800-2000 r/min.
Further, in the step (2), the in-situ synthesis detergent is distilled water and methanol, and the washing is repeated for at least three times.
Further, in the step (2), the drying temperature of the sample in the in-situ synthesis method is 30-120 ℃, and the drying time is 1-48 h.
Further, in the step (2), the heating temperature of an oven in the hydrothermal synthesis method is 10-200 ℃, and the heat preservation time of the hydrothermal reaction is 1-48 h.
Further, in the step (2), the washing agents used for the sample after the reaction in the hydrothermal synthesis method are methanol and N, N-dimethylformamide, and the washing is repeated at least three times.
Further, in the step (2), the drying temperature of the sample after the reaction in the hydrothermal synthesis method is 30-120 ℃, and the drying time is 1-48 h.
As described above, the present invention provides a method for preparing MOF/wood aerogel composite material, which has the following beneficial effects: the method comprises the steps of performing delignification process and freeze drying process on natural wood raw materials, immersing the obtained light porous wood aerogel into a precursor solution for synthesizing MOF materials, stirring, and constructing the MOF/wood aerogel composite material by an in-situ synthesis method or a hydrothermal synthesis method. The preparation method is simple in preparation process, easy to operate and low in cost. The problems that the intrinsic structure of the wood aerogel is shrunk, the fiber framework is easy to collapse and the performance is reduced are solved, and the wood aerogel has functional characteristics due to the introduction of the MOF nano particles. The composite material combines the structural characteristic advantages of the MOF reinforced phase and the wood aerogel matrix, so that the composite material has wide application prospects in the leading-edge fields of flame retardance, adsorption, energy storage, electromagnetic shielding, gas separation and the like. The invention takes the wood aerogel, the organic ligand, the organic solvent and the metal salt solution as main raw materials, and the MOF synthesized by the in-situ synthesis method or the hydrothermal synthesis method uniformly grows on the surface of the fiber framework of the wood aerogel, thereby showing the effective load of the MOF inorganic-organic hybrid nano material in the wood aerogel matrix and successfully constructing the novel biomass aerogel composite material with good flame retardant and adsorption characteristics. The raw materials related by the invention are rich and wide in source, and an effective way is provided for developing the biomass composite material with high added value.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 shows a laminated structure of the light wood aerogel material of the present invention.
FIG. 2 shows that MOF nanoparticles are successfully loaded on the inner wall of the pore cavity of the MOF/light wood aerogel composite material.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the functions of the invention clearer and easier to understand, the invention is further explained by combining the drawings and the detailed implementation mode:
the present invention is described in terms of specific embodiments, and other advantages and benefits of the present invention will become apparent to those skilled in the art from the description herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
Referring to fig. 1 and 2, the present invention provides a method for preparing MOF/wood aerogel composite material, comprising the following steps:
and (1) putting wood into a sodium hypochlorite solution with a certain concentration ratio, placing the solution in a constant-temperature water bath kettle for delignification process treatment, washing the wood after the wood is completely reacted by the delignification process, and transferring the wood to a freeze dryer under a low-temperature environment for drying treatment to obtain the lightweight and porous wood aerogel material.
And (2) putting the wood aerogel prepared in the step (1) into the MOF precursor solution by adopting an in-situ synthesis method, stirring, fully stirring, mixing, reacting, washing and drying to obtain the MOF/wood aerogel composite material. Or putting the wood aerogel obtained in the step (1) into a precursor solution of the MOF by a hydrothermal synthesis method, transferring the wood aerogel into a polytetrafluoroethylene hydrothermal reaction kettle, putting the polytetrafluoroethylene hydrothermal reaction kettle into an oven, heating to a certain temperature, preserving heat for a period of time, washing a wood aerogel sample after the reaction is finished, and drying to obtain the MOF/wood aerogel composite material.
As an example, in the step (1), the wood raw material is balsa wood, poplar, cedar wood, rubber wood, pine wood, maple wood, birch wood, cedar wood, or the like. Putting wood into sodium hypochlorite solution with the corresponding concentration ratio of 1-10%, placing the wood in a constant-temperature water bath kettle at the temperature of 70-120 ℃ for delignification process reaction for 6-54 h, and transferring the wood to a freeze dryer at the temperature of-50-70 ℃ for vacuum drying for 6-48h after the wood is completely reacted by the delignification process.
As an example, in the step (2), the precursor solution for synthesizing the MOF material includes a metal salt, an organic ligand and an organic solvent, wherein the metal salt is a chloride, nitrate or sulfate of Zr, Cr, Co, Fe, Al, Mg, Ni or Zn, etc.; the organic ligand is terephthalic acid, trimesic acid, pyromellitic acid, dimethyl imidazole and the like, and the organic solvent is N, N-dimethylformamide, methanol and the like. The molar ratio of the metal salt to the organic ligand is (0.1-20): 1; the organic solvent is 10-100 mL. The stirring temperature of the in-situ synthesis method is 10-90 ℃, the stirring time is 1-48 h, and the stirring speed is 800-2000 r/min. The washing agent is distilled water and methanol, and is repeatedly washed for at least three times. In the in-situ synthesis method, the drying temperature is 30-120 ℃, and the drying time is 1-24 h. In the step (2), the heating temperature of the hydrothermal synthesis oven is 10-200 ℃, and the heat preservation time of the reaction kettle is 1-48 h. The washing agent is N, N-dimethylformamide and methanol, and is repeatedly washed for at least three times, the drying temperature is 30-120 ℃, and the drying time is 1-24 hours.
Specifically, example 1: putting the balsawood into a sodium hypochlorite solution with the concentration of 5%, placing the balsawood into a constant-temperature water bath kettle with the temperature of 70 ℃ for reaction for 48 hours, repeatedly washing the balsawood with distilled water for three times after the reaction of the wood delignification process is completed, transferring the balsawood into a freeze dryer for drying for 24 hours at the low temperature of 50 ℃ below zero, and adopting 0.307g of C4H6N2With 0.745g of Zn (NO)3)2.6H2Preparing 1mol of ZIF-8 precursor solution from O in 50mL of methanol solution, and stirring the obtained light wood aerogel in 1mol of ZIF-8 precursor solution for 48 hours at the stirring speed of 800 r/min. And (3) repeatedly cleaning the light wood aerogel after the reaction is finished for three times by adopting distilled water and methanol, and then drying the light wood aerogel in a vacuum drying oven at 30 ℃ for 3h to obtain the ZIF-8/light wood aerogel composite material.
The SEM of the light wood aerogel material after the complete delignification process is shown in figure 1, and the longitudinal section lamellar morphology in the wood can be clearly seen through figure 1. When the ZIF-8/light wood aerogel composite material is constructed, SEM under different magnifications is shown in figure 2, ZIF-8 is nano-scale polyhedral particles which are uniformly distributed in a wood pore channel. The test result shows that the ZIF-8/light wood aerogel composite material obtained in the embodiment has good flame retardant property, wherein the peak value of the heat release rate of the composite material is 20kJ-1(ii) a The adsorption rate to methylene blue reaches 90%, and the adsorption capacity is large.
Example 2: putting poplar into 6% sodium hypochlorite solution, reacting in a constant temperature water bath at 75 deg.C for 36 hr, and repeatedly washing poplar with distilled water after delignification reactionFour times, transferring to a freeze dryer for drying at-52 deg.C for 20h by using 0.462g of C4H6N2With 1.115g of Co (NO)3)2.6H2Preparing 1.5mol of ZIF-67 precursor solution from O in 50mL of methanol solution, putting the obtained poplar aerogel into 1.5mol of ZIF-67 precursor solution, stirring for 48h, repeatedly cleaning the poplar aerogel after the reaction is finished by adopting distilled water and methanol for three times, and then putting the poplar aerogel into a vacuum drying oven to dry for 3h at 40 ℃ to obtain the ZIF-67/poplar aerogel composite material. Test results show that the ZIF-67/poplar aerogel composite material obtained in the embodiment has good flame retardant property, wherein the peak value of the heat release rate of the composite material is 25kJ-1(ii) a The adsorption rate to methylene blue reaches 92%, and the adsorption capacity is large.
Example 3: putting the cedar into a sodium hypochlorite solution with the concentration of 7 percent, placing the cedar into a constant-temperature water bath kettle with the temperature of 80 ℃ for reaction for 36 hours, repeatedly washing the cedar with distilled water for three times after the delignification process is completely reacted, transferring the cedar into a freeze dryer for drying for 28 hours at the low temperature of-54 ℃, and adopting 0.615g of C4H6N2Preparing 2mol of UiO-66 precursor solution with 0.1.485g of zirconium chloride in 50mL of methanol solution, putting the obtained fir aerogel into 2mol of UiO-66 precursor solution for stirring for 36h, repeatedly cleaning the fir aerogel after the reaction is finished by adopting distilled water and methanol for three times, and then putting the fir aerogel into a vacuum drying oven for drying for 5h at 35 ℃ to obtain the UiO-66/fir aerogel composite material. The composite material has the advantages that the adsorption rate of methylene blue reaches 95%, and the composite material has large adsorption capacity.
Example 4: putting rubber wood into sodium hypochlorite solution with concentration of 8%, placing in a constant temperature water bath kettle with temperature of 85 deg.C for reaction for 32h, repeatedly washing wood with distilled water after delignification reaction is completed, transferring to a freeze dryer for drying at-56 deg.C for 18h, and drying with 0.765g C4H6N2With 1.860g of AlCl3.6H2O in 50mL methanol solutionPreparing 2.5mol of MIL-53 precursor solution, putting the obtained light wood aerogel into 2.5mol of MIL-53 precursor solution for stirring for 48h, repeatedly cleaning the reacted rubber wood aerogel by adopting distilled water and methanol, and then putting the cleaned rubber wood aerogel into a vacuum drying oven for drying for 8h at 20 ℃ to obtain the MIL-53/rubber wood aerogel composite material. Wherein the peak value of the heat release rate of the composite material is 26kJ-1And has better flame retardant property.
Example 5: putting pine into 9% sodium hypochlorite solution, reacting in 90 deg.C constant temperature water bath for 24 hr, repeatedly washing with distilled water for four times after delignification reaction is completed, transferring to freeze drier, drying at-58 deg.C for 24 hr, and adding 0.925g of C4H6N2With 2.231g of Fe2(SO4)3Preparing 3mol of MIL-100 precursor solution in 50mL of methanol solution, putting the obtained pine aerogel into 3mol of MIL-100 synthesis precursor solution, stirring for 48h, repeatedly cleaning the pine aerogel after the reaction is finished by adopting distilled water and methanol for three times, and then putting the pine aerogel into a vacuum drying oven to be dried for 4h at 35 ℃ to obtain the MIL-100/pine aerogel composite material. Wherein the peak value of the heat release rate of the composite material is 23kJ-1And has better flame retardant property.
Example 6: putting cypress into sodium hypochlorite solution with the concentration of 3%, placing the cypress into a constant-temperature water bath kettle with the temperature of 95 ℃ for reaction for 10h, repeatedly washing the wood with distilled water for five times after the delignification process is completely reacted, transferring the wood into a freeze dryer for drying for 12h at the temperature of-60 ℃, and adopting 0.1.228g of C4H6N2With 2.980g of Zn (NO)3)2.6H2Preparing 4mol of ZIF-8 precursor solution from O in 50mL of methanol solution, putting the obtained cedar aerogel into the 4mol of ZIF-8 synthesis precursor solution, stirring for 24h, repeatedly cleaning the pine aerogel after the reaction is finished by adopting distilled water and methanol for four times, and then putting the pine aerogel into a vacuum drying oven to dry for 8h at 18 ℃ to obtain the ZIF-8/cedar aerogel composite material. Wherein the composite material isPeak heat release rate of 21kJ.g-1(ii) a The adsorption rate of the methylene blue reaches 93 percent, and the adsorption capacity is larger.
Example 7: putting maple into 10% sodium hypochlorite solution, reacting in 100 deg.C constant temperature water bath for 18h, repeatedly washing wood with distilled water for five times after delignification reaction is completed, transferring to freeze drier, drying at-62 deg.C for 48h, and drying with 1.074g C4H6N2With 2.607g of Co (NO)3)2.6H2Preparing 3.5mol of ZIF-67 precursor solution from O in 50mL of methanol solution, putting the obtained maple aerogel into 3.5mol of ZIF-67 precursor solution, stirring for 48h, repeatedly cleaning the maple aerogel after the reaction is finished by adopting distilled water and methanol for four times, and then putting the maple aerogel into a vacuum drying oven to dry for 5h at 32 ℃ to obtain the ZIF-8/cedar aerogel composite material. Wherein the peak value of the heat release rate of the composite material is 23kJ-1(ii) a The adsorption rate to methylene blue reaches 91%, and the adsorption capacity is large.
Example 7: putting the balsawood into a sodium hypochlorite solution with the concentration of 10%, putting the balsawood into a constant-temperature water bath kettle with the temperature of 95 ℃ for reaction for 24 hours, repeatedly washing the balsawood with distilled water for four times after the delignification reaction is completed, and transferring the balsawood into a freeze dryer for vacuum drying for 48 hours at the temperature of-55 ℃; adding 0.125g of terephthalic acid and 0.116g of zirconium chloride into 15mLN, N-dimethylformamide, adding 1.34mL of glacial acetic acid, stirring for 20min to obtain a precursor solution of the UiO-66 material, transferring the dried wood aerogel and the UiO-66 precursor solution into a polytetrafluoroethylene hydrothermal reaction kettle, keeping the temperature in an oven at 110 ℃ for 28h, repeatedly cleaning the light wood aerogel by using methanol and N, N-dimethylformamide solution for three times after the hydrothermal reaction is finished, and then drying the light wood aerogel in a vacuum drying oven at 32 ℃ for 4h to obtain the UiO-66/light wood aerogel composite material. The test result shows that the UiO-66/light wood aerogel composite material obtained in the embodiment has good flame retardant property, wherein the adsorption rate of the composite material to methylene blue reaches 94%, and the composite material has large adsorption capacity.
Example 8: putting rubber wood into a sodium hypochlorite solution with the concentration of 10%, putting the rubber wood into a constant-temperature water bath kettle with the temperature of 100 ℃ for reaction for 24 hours, repeatedly washing the wood with distilled water for four times after the delignification reaction is completed, and transferring the wood into a freeze dryer for vacuum drying for 36 hours at the temperature of-60 ℃; 0.498g of trimesic acid and 0.466g of AlCl3.6H2Adding O into 60mLN, N-dimethylformamide, adding 5.36mL of glacial acetic acid, stirring at the stirring speed of 1000r/min for 10min to obtain a precursor solution of an MIL-53 material, transferring the dried wood aerogel and the MIL-53 precursor solution into a polytetrafluoroethylene hydrothermal reaction kettle, preserving heat in an oven at 130 ℃ for 20h, repeatedly cleaning the poplar aerogel by adopting methanol and N, N-dimethylformamide solution for four times after the hydrothermal reaction is finished, and then drying in a vacuum drying oven at 30 ℃ for 3h to obtain the MIL-53/rubber wood aerogel composite material. Wherein the peak value of the heat release rate of the composite material is 25kJ-1And has better flame retardant property.
In summary, the invention is characterized in that after the natural wood raw material is subjected to delignification process and freeze drying process, the obtained lightweight porous wood aerogel is immersed in a precursor solution for synthesizing the MOF material and stirred, and the MOF/wood aerogel composite material is constructed by an in-situ synthesis method or a hydrothermal synthesis method. The preparation method is simple in preparation process, easy to operate and low in cost. The problems of shrinkage of the structure and easy collapse of a fiber framework of the wood aerogel are solved, the mechanical property of the wood aerogel is obviously enhanced due to the existence of the MOF nanoparticles, and meanwhile, the flame retardance and the adsorption property of the wood aerogel are improved. In addition, the MOF/wood aerogel composite material also solves the problem of difficult recovery and processing of the nano MOF material. The composite material combines the structural characteristic advantages of the MOF reinforced phase and the wood aerogel matrix, so that the composite material has wide application prospects in the fields of flame retardance, adsorption, energy storage, electromagnetic shielding, gas separation and the like. The invention takes the wood aerogel, the organic ligand and the metal salt solution as main raw materials, and the MOF synthesized by the in-situ synthesis method or the hydrothermal synthesis method uniformly grows on the surface of the fiber framework of the wood aerogel, thereby showing the effective load of the MOF inorganic-organic hybrid nano material in the wood aerogel matrix and successfully constructing the novel biomass aerogel composite material with good flame retardant and adsorption characteristics. The raw materials related by the invention have rich and wide sources, and an effective way is provided for developing biomass materials with high added values. Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (11)
1. A method of making a MOF/wood aerogel composite comprising the steps of:
putting wood into sodium hypochlorite solution with a certain concentration ratio, placing the wood in a water bath kettle under a constant temperature condition for delignification process treatment, and then carrying out vacuum freeze drying on the wood after the delignification process reaction is completed in a low-temperature environment to obtain porous light wood aerogel;
step (2) putting the wood aerogel prepared in the step (1) into an MOF precursor solution by adopting an in-situ synthesis method for stirring, and washing and drying after fully stirring, mixing and reacting to obtain an MOF/wood aerogel composite material; or putting the wood aerogel obtained in the step (1) into a precursor solution of the MOF by a hydrothermal synthesis method, transferring the wood aerogel into a polytetrafluoroethylene hydrothermal reaction kettle, putting the wood aerogel into an oven, heating the wood aerogel to a certain temperature, preserving the heat for a period of time, washing a wood aerogel sample after the reaction is finished, and drying the wood aerogel sample to obtain the MOF/wood aerogel composite material.
2. The process of claim 1, wherein in step (1), the wood is balsa wood, poplar, fir wood, pine wood, rubber wood, maple wood, birch wood and/or cedar wood.
3. The method for preparing the MOF/wood aerogel composite material according to claim 1, wherein in the step (1), the concentration ratio of the sodium hypochlorite solution is 1-10%.
4. The method for preparing the MOF/wood aerogel composite material according to claim 1, wherein in the step (1), the reaction temperature of a constant-temperature water bath in the delignification process is 70-120 ℃, and the reaction time of the delignification process is 6-54 h.
5. The method for preparing the MOF/wood aerogel composite material according to claim 1, wherein in the step (1), the vacuum freeze-drying time of the wood aerogel in the freeze-drying process is 6-48h, and the vacuum freeze-drying temperature is-50 to-70 ℃.
6. A method of making a MOF/wood aerogel composite according to claim 1, wherein in step (2), the precursor solution of the synthetic MOF nanomaterial comprises a metal salt, an organic ligand and an organic solvent, wherein the metal salt is a chloride, nitrate or sulfate of Zr, Cr, Co, Fe, Al, Mg, Ni or Zn; the organic ligand is terephthalic acid, trimesic acid, pyromellitic acid and dimethyl imidazole; the organic solvent is N, N-dimethylformamide and methanol.
7. The method for preparing the MOF/wood aerogel composite material according to claim 1, wherein in the step (2), the molar ratio of the metal salt to the organic ligand is (0.1-20): 1; the organic solvent is 10-100 mL.
8. A method of making a MOF/wood aerogel composite according to claim 1, wherein in step (2) the washing agents are distilled water, methanol and N, N-dimethylformamide.
9. The method for preparing the MOF/wood aerogel composite material according to claim 1, wherein in the step (2), in the preparation process of the in-situ synthesis method, the stirring temperature of the in-situ synthesis reaction is 10-90 ℃, the stirring time of the wood aerogel immersed in the precursor solution for synthesizing the MOF is 1-48 h, and the stirring speed is 800-2000 r/min.
10. The method for preparing the MOF/wood aerogel composite material according to claim 1, wherein in the step (2), in the preparation process of the hydrothermal synthesis method, the hydrothermal reaction temperature is 10-200 ℃, and the temperature preservation time in an oven is 1-48 h.
11. The method for preparing the MOF/wood aerogel composite material according to claim 1, wherein in the step (2), the drying temperature of the sample after the reaction in the in-situ synthesis method and the hydrothermal synthesis method is 30-120 ℃, and the drying time is 1-48 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111229307.5A CN114210275A (en) | 2021-10-21 | 2021-10-21 | Method for preparing MOF/wood aerogel composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111229307.5A CN114210275A (en) | 2021-10-21 | 2021-10-21 | Method for preparing MOF/wood aerogel composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114210275A true CN114210275A (en) | 2022-03-22 |
Family
ID=80696089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111229307.5A Pending CN114210275A (en) | 2021-10-21 | 2021-10-21 | Method for preparing MOF/wood aerogel composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114210275A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114917887A (en) * | 2022-06-06 | 2022-08-19 | 南京林业大学 | Wood-based/MOF composite aerogel film and preparation method thereof |
| CN114957778A (en) * | 2022-06-02 | 2022-08-30 | 南京大学 | High-strength heat-insulation antibacterial aerogel and preparation method and application thereof |
| CN115025637A (en) * | 2022-05-25 | 2022-09-09 | 南京林业大学 | Preparation method and application of MOF/rattan composite material |
| CN115416125A (en) * | 2022-09-22 | 2022-12-02 | 陕西科技大学 | Method for reinforcing rotten wood by synthesizing nano MOF-5 under assistance of ultrasonic waves |
| CN115424876A (en) * | 2022-08-29 | 2022-12-02 | 中南林业科技大学 | Preparation method of wood-based composite electrode material |
| CN115501862A (en) * | 2022-09-20 | 2022-12-23 | 河南大学 | Preparation method of wheat bran/HKUST-1 aerogel in aqueous solution |
| CN115505130A (en) * | 2022-09-19 | 2022-12-23 | 中国林业科学研究院林产化学工业研究所 | Lignin-based metal organic complex and preparation method and application thereof |
| CN115505130B (en) * | 2022-09-19 | 2024-06-04 | 中国林业科学研究院林产化学工业研究所 | Lignin-based metal organic complex and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109663576A (en) * | 2019-02-02 | 2019-04-23 | 西北师范大学 | A kind of montmorillonite load molysite MOFs adsorbent and preparation method thereof |
| CN109999757A (en) * | 2019-04-16 | 2019-07-12 | 浙江农林大学 | A kind of Cr-MOF/ wood composite aeroge and preparation method and application capturing heavy metal ion |
| CN110484214A (en) * | 2019-08-19 | 2019-11-22 | 苏州阿德旺斯新材料有限公司 | A kind of sizing MOF base composite phase-change material and its preparation method and application |
| CN110483831A (en) * | 2019-08-19 | 2019-11-22 | 浙江大学 | A kind of MOF aeroge and preparation method thereof |
-
2021
- 2021-10-21 CN CN202111229307.5A patent/CN114210275A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109663576A (en) * | 2019-02-02 | 2019-04-23 | 西北师范大学 | A kind of montmorillonite load molysite MOFs adsorbent and preparation method thereof |
| CN109999757A (en) * | 2019-04-16 | 2019-07-12 | 浙江农林大学 | A kind of Cr-MOF/ wood composite aeroge and preparation method and application capturing heavy metal ion |
| CN110484214A (en) * | 2019-08-19 | 2019-11-22 | 苏州阿德旺斯新材料有限公司 | A kind of sizing MOF base composite phase-change material and its preparation method and application |
| CN110483831A (en) * | 2019-08-19 | 2019-11-22 | 浙江大学 | A kind of MOF aeroge and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115025637A (en) * | 2022-05-25 | 2022-09-09 | 南京林业大学 | Preparation method and application of MOF/rattan composite material |
| CN114957778A (en) * | 2022-06-02 | 2022-08-30 | 南京大学 | High-strength heat-insulation antibacterial aerogel and preparation method and application thereof |
| CN114917887A (en) * | 2022-06-06 | 2022-08-19 | 南京林业大学 | Wood-based/MOF composite aerogel film and preparation method thereof |
| CN114917887B (en) * | 2022-06-06 | 2023-08-18 | 南京林业大学 | Wood-based/MOF composite aerogel film and preparation method thereof |
| CN115424876A (en) * | 2022-08-29 | 2022-12-02 | 中南林业科技大学 | Preparation method of wood-based composite electrode material |
| CN115505130A (en) * | 2022-09-19 | 2022-12-23 | 中国林业科学研究院林产化学工业研究所 | Lignin-based metal organic complex and preparation method and application thereof |
| CN115505130B (en) * | 2022-09-19 | 2024-06-04 | 中国林业科学研究院林产化学工业研究所 | Lignin-based metal organic complex and preparation method and application thereof |
| CN115501862A (en) * | 2022-09-20 | 2022-12-23 | 河南大学 | Preparation method of wheat bran/HKUST-1 aerogel in aqueous solution |
| CN115501862B (en) * | 2022-09-20 | 2023-11-21 | 河南大学 | Preparation method of wheat bran/HKUST-1 aerogel in aqueous solution |
| CN115416125A (en) * | 2022-09-22 | 2022-12-02 | 陕西科技大学 | Method for reinforcing rotten wood by synthesizing nano MOF-5 under assistance of ultrasonic waves |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114210275A (en) | Method for preparing MOF/wood aerogel composite material | |
| Ding et al. | Bio-inspired synthesis of nanomaterials and smart structures for electrochemical energy storage and conversion | |
| CN107331865B (en) | Preparation method of cellulose nanofiber/silk fibroin-based porous nitrogen-doped 2D carbon nanosheet electrode material | |
| CN113183264A (en) | Method for preparing wood/MOF functional composite material | |
| CN109967099A (en) | A kind of Co with hollow nanostructures2P@C composite and its preparation method and application | |
| WO2022121594A1 (en) | Nanofiber/mofs-based preferential alcohol-permeable pervaporation membrane and preparation method thereof | |
| CN108686639A (en) | Three-dimensional netted carbon-based composite photo-catalyst of metal organic framework derived material-and preparation method thereof, purposes | |
| Liu et al. | Improved photocatalytic performance of covalent organic frameworks by nanostructure construction | |
| CN110105580A (en) | A kind of multi-stage porous class zeolitic imidazolate framework material and preparation method thereof | |
| CN106920696A (en) | Nano hybridization aeroge electrode material for super capacitor and its preparation method and application | |
| CN109972401A (en) | A kind of preparation method with the fire-retardant highly conductive fabric of super-amphiphobic | |
| CN107723284A (en) | A kind of method in situ for preparing nanometer enzyme membrane | |
| CN115069218A (en) | Preparation method of metal organic framework composite GO/waste spinning cellulose aerogel | |
| CN109706739B (en) | Synthesis method of Fe-MOF (Metal organic framework) loaded nano-array on carbon cloth | |
| CN114277576B (en) | Preparation method of multifunctional cotton fabric loaded with Cu-MOFs | |
| CN109503858A (en) | A kind of magnetism sandwich structure metal-organic framework materials and preparation method | |
| CN108097313A (en) | A kind of carbonitride/chitosan aeroge composite photo-catalyst and its preparation method and application | |
| CN113831749A (en) | Preparation method of double MOF/biomass-based multifunctional composite material | |
| Li et al. | Biopolymers for hygroscopic material development | |
| CN109872880A (en) | A kind of preparation method of humic acid synusia bimetallic MOFs composite granule | |
| Feng et al. | Facilitated propylene transport in mixed matrix membranes containing ZIF‐8@ Agmim core‐shell hybrid material | |
| KR102567347B1 (en) | Manufacturing method for development of organic-inorganic carbon materials with complex porosities through direct impregnation of metal-organic framework precursors in the presence of reduced graphene oxide aerogel and organic-inorganic carbon materials with complex porosities | |
| CN114907620A (en) | Preparation method of regenerated cellulose membrane with drug slow-release capability | |
| CN114082443A (en) | Preparation method and application of magnetic nano short fiber loaded with silver nanoparticles | |
| CN114522712A (en) | Amphiphilic CoP/g-C for degrading micro-plastic and synergistically producing hydrogen3N4Material and method for producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |