CN111617705A - Metal organic framework/graphene aerogel composite material and preparation method thereof - Google Patents
Metal organic framework/graphene aerogel composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of novel composite functional materials, and discloses a metal organic framework/graphene aerogel composite material and a preparation method thereof, wherein the method comprises the steps of dissolving an ionic liquid into a metal salt solution, and fully stirring to obtain a metal salt-ionic liquid solution; placing the graphene aerogel in a metal salt-ionic liquid solution and standing for a period of time to obtain a solid-liquid mixture; adding an alkaline ligand salt solution into the solid-liquid mixture, fully stirring, and then centrifuging to obtain a lower-layer precipitate; and adding the precipitate into a solvent, fully stirring and standing for a period of time, then filtering to obtain a solid product, and heating and drying to obtain the metal organic framework/graphene aerogel composite material. The invention promotes the nucleation and growth of the metal organic framework by adding the ionic liquid; the ligand is provided by the alkaline ligand salt solution, so that the full contact and reaction of the organic ligand and the metal salt are facilitated; meanwhile, the adjustment of the load capacity of the metal organic framework in the composite material is realized.
Description
Technical Field
The invention belongs to the field of novel composite functional materials, and particularly relates to a metal organic framework/graphene aerogel composite material and a preparation method thereof.
Background
With the rapid development of global economy in recent years, the demand for conventional fossil fuels such as coal, oil, natural gas, etc. has been increasing. However, the random use of fossil fuels, resulting in CO2The global emissions of (b) show a trend of rising year by year, making people have no time to bear the threats of global warming, extreme weather, species extinction, acid rain and other environmental problems. Therefore, there is an urgent need for adsorbents with superior performance to mitigate CO in life and industrial production2The discharge brings influence to life.
CO commonly used in industrial production at present2The gas adsorbent mainly comprises active carbon, zeolite, porous molecular sieve and the like, and the gas adsorbent has the defects of low adsorption quantity, poor selectivity, long adsorption time, complex preparation process and the like in the using process, so that scientific researchers aim at the metal organic framework material to solve the defects of the traditional adsorbent. The metal organic framework material is a crystal material which has a periodic network structure generated by self-assembly of metal ions or metal clusters and ligands and has the advantages of organic polymers and inorganic compounds. The metal organic framework material is known as CO due to the advantages of high specific surface area, adjustable pore channel size, designable structure and function, high porosity, low density, good mechanical and chemical stability and the like2One of the most promising nanomaterials in the field of adsorption. However, although the metal organic framework material has many advantages, the problems of difficult molding, slow adsorption speed, complicated preparation process, harsh conditions and the like restrict the application of the metal organic framework material in CO2Application prospect in the field of adsorption.
How to select a proper carrier and compound the carrier and the metal organic framework is one of effective ways for solving the problems. At present, graphene or carbon nanotubes and the like are mainly adopted to be compounded with a metal organic framework material, and although part of problems of the metal organic framework material in practical application are solved, the metal organic framework material still faces the limitations of difficult forming, low adsorption rate, insufficient adsorption capacity and the like.
Disclosure of Invention
In view of the above-mentioned disadvantages and/or needs for improvement of the prior art, the present invention provides a metal-organic framework/graphene aerogel composite material and a method for preparing the same, wherein the ligand is provided by using a basic ligand salt solution, and the ionic liquid is added to facilitate the nucleation and growth of the metal-organic framework material, so as to improve the performance of the composite material, thereby being particularly suitable for preparing CO2Adsorbent, and the like.
In order to achieve the above object, according to one aspect of the present invention, a method for preparing a metal organic framework/graphene aerogel composite material is provided, wherein the method comprises the following steps:
(a) dissolving ionic liquid into a metal salt solution, and fully stirring to uniformly mix the ionic liquid and the metal salt solution to obtain a metal salt-ionic liquid solution;
(b) placing the graphene aerogel in the metal salt-ionic liquid solution and standing for a period of time to fully diffuse the metal salt-ionic liquid solution into the graphene aerogel so as to obtain a solid-liquid mixture;
(c) adding an alkaline ligand salt solution into the solid-liquid mixture, fully stirring, and then centrifuging to obtain a lower-layer precipitate;
(d) and adding the precipitate into a solvent, fully stirring and standing for a period of time, then filtering to obtain a solid product, and heating and drying to obtain the metal organic framework/graphene aerogel composite material.
As a further preference, the ionic liquid in step (a) is preferably [ BMIM][PF6]Or [ BMIM][BF4]The metal salt solution is preferably a copper nitrate solution, a copper chloride solution, a zinc nitrate solution, a zinc chloride solution, a ferrous chloride solution, a zirconium hypochlorite solution or a zirconium dichloride solutionThe concentration of the metal salt solution is preferably 0.1mol/L to 0.2 mol/L.
Further preferably, the molar ratio of the metal salt to the ionic liquid in the metal salt-ionic liquid solution in the step (a) is preferably 1: 0.1-1: 2.
More preferably, the graphene aerogel in the step (b) has a mass of preferably 0.025g to 100g, the volume of the metal salt solution is preferably 10mL to 200mL, and the standing time is preferably 2h to 24 h.
More preferably, in the step (c), the basic ligand salt solution is preferably a sodium trimesate solution, a potassium trimesate solution, a sodium terephthalate solution, a potassium terephthalate solution, an isobasic potassium carboxylate solution or an isobasic sodium carboxylate solution, the concentration of the basic ligand salt solution is preferably 0.05mol/L to 0.2mol/L, and the molar ratio of the metal salt to the basic ligand salt in the solid-liquid mixture is preferably 3:2 to 1: 2.
More preferably, the centrifugation time in the step (c) is preferably 3min to 15min, the centrifugation temperature is preferably 10 ℃ to 35 ℃, and the centrifugation rotation speed is preferably 500r/min to 8000 r/min.
More preferably, the stirring time in the step (a), the step (c) and the step (d) is preferably 1min to 10min, the stirring temperature is preferably 10 ℃ to 35 ℃, and the stirring speed is preferably 500r/min to 3000 r/min.
As a further preference, the solvent in step (d) is preferably ethanol, methanol, acetone, dichloromethane or N, N-dimethylformamide.
More preferably, in the step (d), the standing temperature is preferably 10 to 35 ℃, the standing time is preferably 1 to 3 hours, the heating temperature is preferably 60 to 120 ℃, and the heating time is preferably 12 to 24 hours.
According to another aspect of the present invention, there is provided a metal organic framework/graphene aerogel composite prepared by the above method.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
1.the ionic liquid has good thermal stability and chemical stability, and has good intersolubility with organic matters and inorganic matters, so the invention adds the ionic liquid such as [ BMIM ] into the metal salt solution][PF6]Or [ BMIM][BF4]And the molar ratio of the metal salt to the ionic liquid is controlled within the range of 1: 0.1-1: 2, so that the nucleation and growth of the metal organic framework can be promoted, and the CO of the metal organic framework is improved2The amount of adsorption;
2. meanwhile, the alkaline ligand salt solution with the concentration of 0.05-0.2 mol/L is used for providing the ligand, the solubility of the organic ligand can be increased, and the molar ratio of the metal salt to the alkaline ligand salt is controlled within the range of 3: 2-1: 2, so that the organic ligand and the metal salt can be in full contact and reaction, and the reaction rate and the raw material utilization rate are improved;
3. particularly, the mass of the graphene aerogel serving as a carrier in the preparation process is controlled within the range of 0.025 g-100 g, and the volume of the metal salt solution is adjusted within the range of 10 mL-200 mL, so that the adjustment of the load capacity of the metal organic framework in the composite material is realized, the adjustment and control of the performance of the composite material are facilitated, and the specific surface area of the prepared metal organic framework/graphene aerogel composite material can be ensured to reach 1281.806m by controlling each reaction condition in the preparation process2The absorption capacity can reach 3.71cm3/g。
Drawings
Fig. 1 is a flow chart of the preparation of the metal organic framework/graphene aerogel composite material provided by the present invention;
FIG. 2 is a CuBTC/graphene aerogel composite- [ BMIM ] prepared in example 1 of the present invention][BF4]N at 77K2Adsorption isotherms;
FIG. 3 is a CuBTC/graphene aerogel composite- [ BMIM ] prepared in example 1 of the present invention][BF4]The XRD pattern of (A) and the XRD pattern of theoretical CuBTC;
FIG. 4 is a CuBTC/graphene aerogel composite- [ BMIM ] prepared in example 1 of the present invention][BF4]CO at 298K2An adsorption curve;
FIG. 5 is N of the CuBTC/graphene aerogel composite prepared in comparative example 1 of the present invention under 77K conditions2Adsorption isotherms;
FIG. 6 is an XRD pattern of the CuBTC/graphene aerogel composite prepared in comparative example 1 of the present invention;
FIG. 7 is a CO of the CuBTC/graphene aerogel composite prepared in comparative example 1 of the present invention under the condition of 298K2Adsorption profile.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in fig. 1, according to an aspect of the present invention, a method for preparing a metal organic framework/graphene aerogel composite is provided, the method comprising the following steps:
(a) dissolving ionic liquid into metal salt solution, stirring thoroughly to mix uniformly to obtain metal salt-ionic liquid solution, wherein the ionic liquid is preferably 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid ([ BMIM ]][PF6]) Or 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid ([ BMIM ]][BF4]) The metal salt solution is preferably a copper nitrate solution, a copper chloride solution, a zinc nitrate solution, a zinc chloride solution, a ferrous chloride solution, a zirconium hypochlorite solution or a cobalt dichloride solution, the concentration of the metal salt solution is preferably 0.1-0.2 mol/L, and the molar ratio of metal salt to ionic liquid in the metal salt-ionic liquid solution is preferably 1: 0.1-1: 2;
(b) placing 0.025g to 100g of graphene aerogel into 10mL to 200mL of metal salt-ionic liquid solution, and standing for 2h to 24h to fully diffuse the metal salt-ionic liquid solution into the graphene aerogel so as to obtain a solid-liquid mixture;
(c) adding an alkaline ligand salt solution into the solid-liquid mixture, fully stirring, and centrifuging to obtain a precipitate at a lower layer, wherein the alkaline ligand salt solution is preferably a sodium trimesate solution, a potassium trimesate solution, a sodium terephthalate solution, a potassium terephthalate solution, an alkaline potassium carboxylate solution or an alkaline sodium carboxylate solution, the concentration of the alkaline ligand salt solution is preferably 0.05 mol/L-0.2 mol/L, the molar ratio of metal salt to alkaline ligand salt in the solid-liquid mixture is preferably 3: 2-1: 2, the centrifuging time is preferably 3 min-15 min, the centrifuging temperature is preferably 10-35 ℃, and the centrifuging speed is preferably 500 r/min-8000 r/min;
(d) and adding the precipitate into a solvent such as ethanol, methanol, acetone, dichloromethane or N, N-dimethylformamide for solvent exchange, fully stirring, standing for 1-3 h at 10-35 ℃, filtering to obtain a solid product, heating for 12-24 h at 60-120 ℃, and drying to obtain the metal organic framework/graphene aerogel composite material.
Further, the stirring time in the step (a), the step (c) and the step (d) is preferably 1min to 10min, the stirring temperature is preferably 10 ℃ to 35 ℃, and the stirring speed is preferably 500r/min to 3000 r/min.
Further, the preparation process of the graphene aerogel comprises the following steps: firstly, mixing graphite powder, potassium permanganate, concentrated sulfuric acid and hydrogen peroxide to prepare graphene oxide, wherein the graphite powder and the potassium permanganate are mixed according to the mass ratio of 1: 3; and then adding 1-ascorbic acid into a 4mg/L graphene oxide solution, stirring and heating to obtain the graphene aerogel, wherein the mass ratio of the graphene oxide to the 1-ascorbic acid is 1: 2.
Further, the preparation process of the alkaline ligand salt solution is as follows: dissolving sodium hydroxide or potassium hydroxide in pure water, performing ultrasonic dissolution to obtain a sodium hydroxide solution or a potassium hydroxide solution, adding a ligand into the prepared sodium hydroxide or potassium hydroxide solution, performing ultrasonic treatment and fully stirring to obtain a uniformly mixed alkaline ligand salt solution.
According to another aspect of the present invention, there is provided a metal organic framework/graphene aerogel composite prepared by the above method.
The present invention will now be described in further detail by taking a specific metal organic framework/graphene aerogel composite material and a preparation method thereof as an example.
Example 1
(a) 0.452g of ionic liquid [ BMIM ]][BF4]Dissolving the mixture into 10mL of 0.1mol/L copper nitrate solution, and stirring the mixture for 10min at the temperature of 35 ℃, wherein the stirring speed is 500 r/min;
(b) placing 0.035g of graphene aerogel in 10mL of metal salt-ionic liquid solution, and standing for 2h at 35 ℃ to obtain a solid-liquid mixture;
(c) adding 10ml of 0.2mol/L sodium trimesate solution into the solid-liquid mixture, stirring at 35 ℃ for 10min at a stirring speed of 500r/min, centrifuging at 35 ℃ for 15min at a centrifugation speed of 500r/min, and pouring out the supernatant to obtain a lower-layer precipitate;
(d) adding the precipitate into absolute ethyl alcohol, stirring for 10min at 35 ℃, with the stirring speed of 500r/min, standing the stirred product for 1h at 35 ℃, then filtering to obtain a solid product, washing for 3 times with absolute ethyl alcohol, heating for 12h at 120 ℃, and drying to obtain the CuBTC/graphene aerogel composite material- [ BMIM ]][BF4]。
For the prepared CuBTC/graphene aerogel composite material- [ BMIM][BF4]The analysis was carried out:
(1) the CuBTC/graphene aerogel composite material- [ BMIM ] prepared by the invention is subjected to an Autosorb-iQ full-automatic gas adsorption analyzer produced by Kangta instruments][BF4]The samples were analyzed and the pore structure and specific surface area are shown in Table 1, which shows N at 77K2The adsorption isotherms are shown in figure 2;
TABLE 2 specific surface area and pore Structure of CuBTC/graphene aerogel composite- [ BMIM ] [ BF4]
(2) The CuBTC/graphene aerogel composite material- [ BMIM ] is subjected to X-ray diffractometer of X' Pert3Powder model manufactured by Pasacaceae, the Netherlands][BF4]The operating conditions are as follows: 60KV and 60mA, step length is 0.02 degrees, a measured XRD spectrum is shown in figure 3, and the CuBTC/graphene aerogel composite material- [ BMIM ] prepared by the method][BF4]The characteristic peak of the composite material is completely corresponding to the theoretical CuBTC peak value, which indicates that the prepared CuBTC/graphene aerogel composite material- [ BMIM][BF4]The phase is uniform, and the crystal structure is intact;
(3) prepared CuBTC/graphene aerogel composite material- [ BMIM ] is subjected to automatic gas adsorption analyzer produced by Kangta instruments of America][BF4]CO at Room temperature (298K)2The adsorption experiment shows that the obtained adsorption curve is shown in FIG. 4, and it can be seen from FIG. 4 that the CuBTC/graphene aerogel composite material- [ BMIM ] is increased along with the increase of the relative pressure][BF4]CO of2The adsorption capacity is increased continuously, and the maximum adsorption capacity is 3.71cm3/g。
Example 2
(a) 6.78g of ionic liquid [ BMIM ]][PF6]Dissolving into 200mL of 0.15mol/L copper chloride solution, and stirring at 25 deg.C for 5min at 1500 r/min;
(b) placing 100g of graphene aerogel in 200mL of metal salt-ionic liquid solution, and standing for 12h at 25 ℃ to obtain a solid-liquid mixture;
(c) adding 200ml of 0.15mol/L potassium trimesate solution into the solid-liquid mixture, stirring at 25 ℃ for 5min at the stirring speed of 1500r/min, centrifuging at 25 ℃ for 10min at the centrifugation speed of 8000r/min, and pouring out the supernatant to obtain the lower-layer precipitate;
(d) adding the precipitate into acetone, stirring at 25 ℃ for 5min at a stirring speed of 1500r/min, standing the stirred product at 25 ℃ for 2h, filtering to obtain a solid product, washing with acetone for 3 times, heating at 80 ℃ for 18h, and drying to obtain the CuBTC/graphene aerogel composite material- [ BMIM [ ]][PF6]。
Example 3
(a) 0.8525g of ionic liquid [ BMIM ]][PF6]Dissolving in 150mL of 0.2mol/L zinc chloride solutionStirring for 1min at 10 ℃ and the stirring speed is 3000 r/min;
(b) placing 0.025g of graphene aerogel in 150mL of metal salt-ionic liquid solution, and standing for 24h at 10 ℃ to obtain a solid-liquid mixture;
(c) adding 400ml of 0.05mol/L sodium terephthalate solution into the solid-liquid mixture, stirring at 10 ℃ for 1min at the stirring speed of 3000r/min, centrifuging at 10 ℃ for 1min at the centrifugation speed of 3000r/min, and pouring out the supernatant to obtain the precipitate of the lower layer;
(d) adding the precipitate into dichloromethane, stirring at 10 ℃ for 1min at the stirring speed of 3000r/min, standing the stirred product at 10 ℃ for 3h, filtering to obtain a solid product, washing with dichloromethane for 3 times, heating at 60 ℃ for 24h, and drying to obtain the ZnBDC/graphene aerogel composite material- [ BMIM ]][PF6]。
Comparative example 1
(b) Placing 0.035g of graphene aerogel in 10mL of 0.1mol/L copper nitrate solution, and standing for 2h at 35 ℃ to obtain a solid-liquid mixture;
(c) adding 10ml of 0.2mol/L sodium trimesate solution into the solid-liquid mixture, stirring at 35 ℃ for 10min at a stirring speed of 500r/min, centrifuging at 35 ℃ for 15min at a centrifugation speed of 500r/min, and pouring out the supernatant to obtain a lower-layer precipitate;
(d) adding the precipitate into absolute ethyl alcohol, stirring for 10min at 35 ℃, with the stirring speed of 500r/min, standing the stirred product for 1h at 35 ℃, then filtering to obtain a solid product, washing for 3 times with absolute ethyl alcohol, heating for 12h at 120 ℃, and drying to obtain the CuBTC/graphene aerogel composite material.
Analyzing the prepared CuBTC/graphene aerogel composite material:
(1) the CuBTC/graphene aerogel composite material sample prepared by the invention is analyzed by adopting an Autosorb-iQ full-automatic gas adsorption analyzer produced by Kangta instruments, the pore structure and the specific surface area are shown in Table 2, and N is obtained under the condition of 77K2The adsorption isotherms are shown in fig. 5;
TABLE 2 specific surface area and pore structure of CuBTC/graphene aerogel composites
(2) Nature of crystal structure
The crystal structure of the CuBTC/graphene aerogel composite material is characterized by adopting an X' Pert3Powder model X-ray diffractometer produced by the Parnacaceae company in the Netherlands, and the operation conditions are as follows: 60KV and 60mA, the step length is 0.02 degrees, and the measured XRD spectrum is shown in figure 6, and as can be seen from figure 6, the characteristic peak and the theoretical peak of the CuBTC/graphene aerogel composite material prepared by the method are well corresponded, which indicates that the prepared CuBTC/graphene aerogel composite material has uniform phase and good crystal structure;
(3)CO2adsorption analysis
The CO adsorption analysis of the CuBTC/graphene aerogel composite material prepared by the invention at room temperature (298K) is carried out by adopting an Autosorb-iQ full-automatic gas adsorption analyzer produced by Kangta instruments2The adsorption experiment, the resulting adsorption curve is shown in fig. 7. As can be seen from FIG. 7, the CO of the CuBTC/graphene aerogel composite increases with the relative pressure2The adsorption capacity is continuously increased, and the maximum adsorption capacity is 3.26cm3/g。
The CuBTC/graphene aerogel composite- [ BMIM ] prepared in example 1][BF4]Compared with the CuBTC/graphene aerogel composite material prepared in the comparative example 1, the composite material prepared by adding the ionic liquid has larger micropore specific surface area and higher maximum adsorption capacity, and the ionic liquid can promote the nucleation and growth of the metal-organic framework material, thereby being beneficial to improving the quality and performance of the metal-organic framework material.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the metal organic framework/graphene aerogel composite material is characterized by comprising the following steps:
(a) dissolving ionic liquid into a metal salt solution, and fully stirring to uniformly mix the ionic liquid and the metal salt solution to obtain a metal salt-ionic liquid solution;
(b) placing the graphene aerogel in the metal salt-ionic liquid solution and standing for a period of time to fully diffuse the metal salt-ionic liquid solution into the graphene aerogel so as to obtain a solid-liquid mixture;
(c) adding an alkaline ligand salt solution into the solid-liquid mixture, fully stirring, and then centrifuging to obtain a lower-layer precipitate;
(d) and adding the precipitate into a solvent, fully stirring and standing for a period of time, then filtering to obtain a solid product, and heating and drying to obtain the metal organic framework/graphene aerogel composite material.
2. The method of preparing a metal-organic framework/graphene aerogel composite according to claim 1, wherein the ionic liquid in step (a) is preferably [ BMIM ]][PF6]Or [ BMIM][BF4]The metal salt solution is preferably a copper nitrate solution, a copper chloride solution, a zinc nitrate solution, a zinc chloride solution, a ferrous chloride solution, a zirconium hypochlorite solution or a cobalt dichloride solution, and the concentration of the metal salt solution is preferably 0.1 mol/L-0.2 mol/L.
3. The method for preparing a metal-organic framework/graphene aerogel composite material according to claim 1 or 2, wherein the molar ratio of the metal salt to the ionic liquid in the metal salt-ionic liquid solution in the step (a) is preferably 1: 0.1-1: 2.
4. The method for preparing a metal-organic framework/graphene aerogel composite material according to any one of claims 1 to 3, wherein the graphene aerogel in the step (b) has a mass of preferably 0.025g to 100g, the volume of the metal salt solution is preferably 10mL to 200mL, and the standing time is preferably 2h to 24 h.
5. The method for preparing a metal-organic framework/graphene aerogel composite material according to any one of claims 1 to 4, wherein in the step (c), the alkaline ligand salt solution is preferably sodium trimesate solution, potassium trimesate solution, sodium terephthalate solution, potassium carboxylate solution or sodium carboxylate solution, the concentration of the alkaline ligand salt solution is preferably 0.05mol/L to 0.2mol/L, and the molar ratio of the metal salt to the alkaline ligand salt in the solid-liquid mixture is preferably 3:2 to 1: 2.
6. The method for preparing a metal organic framework/graphene aerogel composite material according to any one of claims 1 to 5, wherein the centrifugation time in the step (c) is preferably 3min to 15min, the centrifugation temperature is preferably 10 ℃ to 35 ℃, and the centrifugation rotation speed is preferably 500r/min to 8000 r/min.
7. The preparation method of the metal organic framework/graphene aerogel composite material according to any one of claims 1 to 6, wherein the stirring time in the step (a), the step (c) and the step (d) is preferably 1min to 10min, the stirring temperature is preferably 10 ℃ to 35 ℃, and the stirring speed is preferably 500r/min to 3000 r/min.
8. The method for preparing a metal-organic framework/graphene aerogel composite material according to any one of claims 1 to 7, wherein the solvent in the step (d) is preferably ethanol, methanol, acetone, dichloromethane or N, N-dimethylformamide.
9. The method for preparing a metal organic framework/graphene aerogel composite material according to any one of claims 1 to 8, wherein the standing temperature in the step (d) is preferably 10 ℃ to 35 ℃, the standing time is preferably 1h to 3h, the heating temperature is preferably 60 ℃ to 120 ℃, and the heating time is preferably 12h to 24 h.
10. A metal organic framework/graphene aerogel composite prepared by the method of any one of claims 1-9.
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