CN114534699B - Preparation and application of UiO-66/nanocellulose composite aerogel - Google Patents
Preparation and application of UiO-66/nanocellulose composite aerogel Download PDFInfo
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Abstract
The invention discloses a preparation method of UiO-66/nano cellulose composite aerogel and an application of the UiO-66/nano cellulose composite aerogel in adsorption of small molecular compounds. Carboxymethyl cellulose and cellulose nanocrystals are respectively subjected to hydrazide group modification and aldehyde group modification, and then the carboxymethyl cellulose and the cellulose nanocrystals are subjected to self-crosslinking with UiO-66 to prepare the UiO-66/nanocellulose composite aerogel with layered pores and low density. The preparation method is simple and convenient, and the economic cost is low. The composite aerogel is used for extracting small molecular compounds through adsorption, has high adsorption rate and elution rate, is short in extraction time and can be repeatedly used. Can be used for preparing adsorption materials and filtering materials in the fields of chemical analysis materials, chromatographic materials, environmental protection materials and food materials.
Description
Technical Field
The invention belongs to the field of chemical analysis, and particularly relates to preparation and application of UiO-66/nano cellulose composite aerogel.
Background
The extraction technology plays a vital role in purifying and detecting small molecular substances for a long time, and complicated pretreatment methods such as solid phase extraction, liquid phase extraction, micro solid phase extraction, serial solvent extraction and the like are needed before the detection of the small molecular substances due to the interference of complex matrixes. However, most of these pretreatment methods have disadvantages of long time consumption, limited diffusion, low mass transfer rate, and the like. Therefore, it is particularly important to design a simple and effective pretreatment method for extracting small molecular substances from complex substrates.
Metal organic frameworks are a class of crystalline porous materials composed of organic bonds connected by metal nodes and coordination bonds. The metal organic framework has the characteristics of adjustable pore structure, large surface area and easy surface functionalization, so the metal organic framework is considered to be a good substitute for the traditional solid-phase extraction. UiO-66 is a chemically stable metal organic framework material that was first synthesized by Lillerud et al in the form of reciprocal crystals, and subsequent work by Behrens et al showed that the shape of the UiO-66 crystals could be effectively tuned from reciprocal morphology to well-defined octahedra by the addition of benzoic acid or acetic acid. However, due to the crystalline nature of UiO-66, it is mostly obtained in powder or form, which hinders its processability and practicality. To clear this obstacle, uiO-66 is integrated into various support structures to form a moldable, cost-effective product to expand the potential applications of UiO-66 as a functional material.
In recent years nanocellulose has shown great promise as a support material for metal organic frameworks, especially in the form of cellulose aerogels. The nanocellulose has the excellent characteristics of high strength, light weight, no toxicity, easy processing and the like. In addition, cellulose nanocrystals can help suspend unstable colloidal nanoparticles (e.g., carbon nanotubes, manganese dioxide, or boron nitride, etc.) uniformly in water, and thus can be processed into uniformly mixed nanocomposites. The li et al synthesized MOF crystals in situ around the nanocellulose template of 2, 6-tetramethylpiperidine nitroxide, which had higher adsorption capacity than conventional MOF powders. Xu Dengren Flexible MOF aerogels with practical macroscopic shape and graded porosity were prepared by in situ growth of MOF nanoparticles (e.g., ZIF-8 and UiO-66) on bacterial cellulose and applied for water purification. However, complex manufacturing processes of chemical modification, seed growth, and additional cross-linking agents also result in poor interfacial interactions and higher costs.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation and application of a UiO-66/nanocellulose composite aerogel, wherein functional groups (hydrazide groups and aldehyde groups) are introduced into carboxymethyl cellulose and cellulose nanocrystals through molecular design, and the UiO-66 is embedded into the aerogel through a self-crosslinking method to obtain more excellent adsorption performance, so that a simple, rapid, stable and effective pretreatment method for extracting compounds from complex matrixes is designed on the basis of the composite aerogel.
The invention provides a preparation method of UiO-66/nano cellulose composite aerogel, which comprises the following specific steps:
s1, preparing hydrazide modified carboxymethyl cellulose: dripping N-hydroxysuccinimide solution and ethyl dimethyl amine propyl carbodiimide solution into carboxymethyl cellulose mixed solution, uniformly mixing (5-10 min), regulating the pH value of the hydrazide modified carboxymethyl cellulose to 5-9 (preferably 6-8) by sodium hydroxide or hydrochloric acid, and finally dialyzing the solution, and freeze-drying the solution after dialysis to obtain the hydrazide modified carboxymethyl cellulose until further use; wherein the volume ratio of the N-hydroxysuccinimide solution to the mixed solution of the ethyl dimethyl amine propyl carbodiimide solution to the carboxymethyl cellulose is 1:1:1; the preparation method of the carboxymethyl cellulose mixed solution comprises the following steps: dissolving carboxymethyl cellulose and oxalic acid dihydrazide in water to obtain carboxymethyl cellulose mixed solution, wherein the ratio of carboxymethyl cellulose, oxalic acid diacyl and water is 1-5 g: 2-6 g:100 to 500mL, preferably 1 to 2g: 4-6 g: 300-400 mL; the preparation method of the N-hydroxysuccinimide solution comprises the following steps: dissolving N-hydroxysuccinimide in a mixed solution of dimethyl sulfoxide and water to obtain an N-hydroxysuccinimide solution, wherein the ratio of the N-hydroxysuccinimide to the mixed solution of dimethyl sulfoxide and water is 0.10-0.50 g:5 to 10mL, preferably 0.11 to 0.14g: 1-2 ml; the preparation method of the ethyl dimethyl amine propyl carbodiimide solution comprises the following steps: dissolving ethyl dimethyl amine propyl carbodiimide in a mixed solution of dimethyl sulfoxide and water to obtain an ethyl dimethyl amine propyl carbodiimide solution, wherein the ratio of the ethyl dimethyl amine propyl carbodiimide to the mixed solution of dimethyl sulfoxide and water is 0.1-0.8 g:1 to 5ml, preferably 0.4 to 0.6g: 1-2 ml;
s2, preparing aldehyde group modified cellulose nanocrystals: dissolving sodium periodate in a suspension of cellulose nanocrystals in an amount of 1-5 wt% (preferably 1-2 wt%) and stirring in a dark place at room temperature for 8-15 h (preferably 10-12 h), after the completion of the reaction, rapidly adding ethylene glycol into the suspension to terminate the reaction, dialyzing the suspension, and finally storing the suspension in the form of a suspension at 4-8 ℃; wherein, the proportion of the suspension of the sodium periodate and the cellulose nanocrystalline is 0.2-0.8 g: 80-120 mL, preferably 0.4-0.6 g: 80-120 mL;
s3, preparing the UiO-66/nano cellulose composite aerogel: suspending UiO-66 nano particles in 1-5 wt% (preferably 1-2 wt%) aldehyde-modified cellulose nano crystal solution, carrying out ultrasonic treatment for 1-15 min (preferably 10-15 min), then mixing the obtained suspension with an equal volume of 1-5 wt% (preferably 1-2 wt%) hydrazide-modified carboxymethyl cellulose solution for 1-10 min (preferably 1-2 min) by using a vortex mixer, transferring the final cross-linked mass suspension into a plastic tray, storing for 5-20 min (preferably 5-10 min) in a refrigerator at-60-80 ℃ (preferably-70-80 ℃), and finally carrying out freeze-drying to obtain the UiO-66/nano cellulose composite aerogel; wherein, the ratio of the UiO-66 nano particles to the aldehyde group modified cellulose nano crystal solution is 5-50 mg:1 to 5mL, preferably 10 to 20mg: 1-3 mL.
Further, the volume ratio of the dimethyl sulfoxide to the water in the mixed solution of the dimethyl sulfoxide and the water is 1:1-1:5.
Further, the condition of freeze-drying is that the freeze-drying is carried out for 15-24 hours at the temperature of-70 to-80 ℃.
Further, the molecular weight cut-off for dialysis is 5000-14000Da.
Further, the particle size of the UiO-66 nano particles is 300-1000 nm.
Further, the plastic disc is a cylindrical plastic disc with a diameter of 10mm.
In another aspect, the invention provides a UiO-66/nanocellulose composite aerogel prepared by the method described above, said composite aerogel having recyclability.
In a further aspect, the invention provides the application of the UiO-66/nanocellulose composite aerogel, wherein the composite aerogel is applied to the fields of chemical analysis materials, chromatographic treatment materials, environment-friendly materials and food materials and is used as an adsorption material and a filtering material.
Further, the application method of the UiO-66/nano cellulose composite aerogel comprises the following steps:
s1, adsorption of small molecular compounds (heterocyclic amines) by UiO-66/nano cellulose composite aerogel: the UiO-66/nanocellulose composite aerogel is immersed in a solution of 100-300 ng/mL (preferably 150-200 ng/mL) of 14 heterocyclic amines in water for 5-20 min (preferably 10-20 min) to adsorb analytes.
S2, eluting small molecular compounds by utilizing UiO-66/nano cellulose composite aerogel: cleaning the UiO-66/nano cellulose composite aerogel by adopting ultrapure water, and immersing the UiO-66/nano cellulose composite aerogel in acetonitrile containing amine hydroxide or acetic acid for 1-20 min (preferably 5-10 min) to elute small molecular compounds; wherein, the volume ratio of the amine hydroxide or the acetic acid in the acetonitrile containing the amine hydroxide or the acetic acid to the acetonitrile is 1-4: 10 to 100, preferably 1 to 2:10 to 20.
Further, the ratio of the UiO-66/nano-cellulose to the 14 heterocyclic amine aqueous solutions is 5-25 mg:1 to 5mL, preferably 20 to 25mg: 1-2 mL.
Further, the ratio of the UiO-66/nano cellulose composite aerogel to acetonitrile is 5-25 mg:1 to 10mL, preferably 20 to 25mg: 1-2 mL.
Further, when the UiO-66/nano cellulose composite aerogel is cleaned, the ratio of the UiO-66/nano cellulose composite aerogel to the ultrapure water is 5-25 mg:1 to 5mL, preferably 20 to 25mg: 1-2 mL.
The invention has the beneficial effects that:
1. the invention prepares the composite aerogel with layered pores and low density by using carboxymethyl cellulose, cellulose nanocrystalline and UiO-66 through a self-crosslinking method. Compared with the common solid phase extraction column, the composite aerogel has the advantages of simple and convenient preparation method and low economic cost.
The UiO-66/nano cellulose composite aerogel is used for extracting small molecular compounds through adsorption, has high adsorption rate and elution rate, is short in extraction time and can be repeatedly used.
Drawings
FIG. 1 is a physical photograph of UiO-66/nanocellulose composite aerogel of example 1.
FIG. 2 is a scanning electron microscope image of the UiO-66/nanocellulose composite aerogel of example 2.
FIG. 3 is a graph of nitrogen desorption from the UiO-66/nanocellulose composite aerogel of example 3.
FIG. 4 is the adsorption and desorption efficiency of the UiO-66/nanocellulose composite aerogel of example 1 at different application times.
FIG. 5 is a pore size distribution plot of the UiO-66/nanocellulose composite aerogel of example 1.
Detailed Description
The invention will be further illustrated by the following examples of embodiments
Example 1 preparation of UiO-66/nanocellulose composite aerogel 1
1. Preparation of hydrazide modified carboxymethyl cellulose: sequentially dissolving 2g of carboxymethyl cellulose and 6g of oxalic acid dihydrazide in 400mL of deionized water to obtain a carboxymethyl cellulose mixed solution; simultaneously dissolving 0.14g of N-hydroxysuccinimide in 8ml of 1:1 dimethyl sulfoxide/water solution to obtain N-hydroxysuccinimide solution; 0.6g of ethyl dimethyl amine propyl carbodiimide was dissolved in 2ml of a 1:1 dimethyl sulfoxide/water solution to give an ethyl dimethyl amine propyl carbodiimide solution. Then dripping the N-hydroxysuccinimide solution and the ethyl dimethyl amine propyl carbodiimide solution into the carboxymethyl cellulose mixed solution, uniformly mixing for 5min, and adjusting the pH value of the hydrazide modified carboxymethyl cellulose to 6.8 by hydrochloric acid. Finally, the solution was dialyzed (12000 Da). The dialyzed solution was lyophilized at-70℃for 18h to give 1wt% hydrazide-modified carboxymethyl cellulose.
2. Preparing aldehyde group modified cellulose nanocrystals: 0.6g of sodium periodate is dissolved in 100mL of a suspension of 1wt% cellulose nanocrystals, stirred at room temperature in the absence of light for 12 hours, ethylene glycol is rapidly added to the suspension after completion to terminate the reaction, the suspension is dialyzed (12000 Da), and finally the suspension is stored as a suspension at 4℃to obtain a suspension of 1wt% aldehyde-modified cellulose nanocrystals.
3. Preparation of UiO-66/nanocellulose composite aerogel: 800nmUiO-66 nanoparticles were suspended in 1wt% aldehyde modified cellulose nanocrystals, sonicated for 15min, and the resulting suspension was then mixed with an equal volume of 1wt% hydrazide modified carboxymethyl cellulose with a vortex mixer for 2min. The final crosslinked pellet suspension was transferred to a cylindrical plastic tray (diameter 10 mm) and stored in a-80 ℃ refrigerator for 10min. Finally, freeze-drying is carried out for 15 hours at the temperature of minus 72 ℃ to obtain the UiO-66/nano cellulose composite aerogel.
4. According to the pore size distribution diagram of fig. 5, the UiO-66/nanocellulose composite aerogel has the characteristics of layered voids: consists of micropores (0.7 nm) of UiO-66, mesopores (2.4 nm) of aerogel and macropores (12.8 nm) of ice sublimation during lyophilization.
Example 2 preparation of UiO-66/nanocellulose composite aerogel 2
1. Preparation of hydrazide modified carboxymethyl cellulose: sequentially dissolving 5g of carboxymethyl cellulose and 2g of oxalic acid dihydrazide in 200mL of deionized water to obtain a carboxymethyl cellulose mixed solution; simultaneously, 0.5g of N-hydroxysuccinimide is dissolved in 5mL of 1:1 dimethyl sulfoxide/water solution to obtain N-hydroxysuccinimide solution; 0.8g of ethyl dimethyl amine propyl carbodiimide was dissolved in 5ml of a 1:1 dimethyl sulfoxide/water solution to give an ethyl dimethyl amine propyl carbodiimide solution. Then dripping the N-hydroxysuccinimide solution and the ethyl dimethyl amine propyl carbodiimide solution into the carboxymethyl cellulose mixed solution, uniformly mixing for 10min, and adjusting the pH value of the hydrazide modified carboxymethyl cellulose to 9.0 by hydrochloric acid. Finally, the solution was dialyzed (12000 Da). The dialyzed solution was lyophilized at-80℃for 24 hours to give 5wt% hydrazide-modified carboxymethyl cellulose.
2. Preparing aldehyde group modified cellulose nanocrystals: 0.8g of sodium periodate is dissolved in 110ml of a suspension of 3wt% cellulose nanocrystals, stirred at room temperature in the absence of light for 15 hours, ethylene glycol is rapidly added to the suspension after the completion of the reaction to terminate the reaction, the suspension is dialyzed (12000 Da), and finally stored as a suspension at 7℃to give a suspension of 5wt% aldehyde-modified cellulose nanocrystals.
3. Preparation of UiO-66/nanocellulose composite aerogel: 300nmUiO-66 nanoparticles were suspended in 5wt% aldehyde modified cellulose nanocrystals, sonicated for 15min, and the resulting suspension was then mixed with an equal volume of 5wt% hydrazide modified carboxymethyl cellulose with a vortex mixer for 10min. The final crosslinked pellet suspension was transferred to a cylindrical plastic tray (diameter 10 mm) and stored in a-80 ℃ refrigerator for 20min. Finally, freeze-drying is carried out for 18 hours at the temperature of minus 80 ℃ to obtain the UiO-66/nano cellulose composite aerogel.
4. According to the scanning electron microscope image of the UiO-66/nanocellulose composite aerogel of FIG. 2, the UiO-66 particles are tightly and uniformly wrapped on the fiber network, not just attached to the surface of the cellulose.
EXAMPLE 3 preparation of UiO-66/nanocellulose composite aerogel 3
1. Preparation of hydrazide modified carboxymethyl cellulose: sequentially dissolving 1g of carboxymethyl cellulose and 2g of oxalic acid dihydrazide in 100mL of deionized water to obtain a carboxymethyl cellulose mixed solution; simultaneously, 0.1g of N-hydroxysuccinimide is dissolved in 5mL of 1:1 dimethyl sulfoxide/water solution to obtain N-hydroxysuccinimide solution; 0.1g of ethyl dimethyl amine propyl carbodiimide was dissolved in 1ml of a 1:1 dimethyl sulfoxide/water solution to give an ethyl dimethyl amine propyl carbodiimide solution. Then dripping the N-hydroxysuccinimide solution and the ethyl dimethyl amine propyl carbodiimide solution into the carboxymethyl cellulose mixed solution, uniformly mixing for 8min, and adjusting the pH value of the hydrazide modified carboxymethyl cellulose to 5 by hydrochloric acid. Finally, the solution was dialyzed (12000 Da). The post-dialysis solution was lyophilized at-72℃for 22h to give 2wt% hydrazide-modified carboxymethyl cellulose.
2. Preparing aldehyde group modified cellulose nanocrystals: 0.2g of sodium periodate is dissolved in 90ml of a suspension of 2wt% cellulose nanocrystals, stirred at room temperature in the absence of light for 13h, ethylene glycol is rapidly added to the suspension after the completion of the reaction to terminate the reaction, the suspension is dialyzed (12000 Da), and finally stored as a suspension at 8℃to give a suspension of 3wt% aldehyde-modified cellulose nanocrystals.
3. Preparation of UiO-66/nanocellulose composite aerogel: 700nmUiO-66 nanoparticles were suspended in 3wt% aldehyde modified cellulose nanocrystals, sonicated for 8min, and the resulting suspension was then mixed with an equal volume of 2wt% hydrazide modified carboxymethyl cellulose with a vortex mixer for 7min. The final crosslinked pellet suspension was transferred to a cylindrical plastic tray (diameter 10 mm) and stored in a-70 ℃ refrigerator for 7min. Finally, freeze-drying is carried out for 24 hours at the temperature of minus 76 ℃ to obtain the UiO-66/nano cellulose composite aerogel.
4. According to the nitrogen desorption curve of the UiO-66/nanocellulose composite aerogel in FIG. 3, the UiO-66/nanocellulose composite aerogel shows type I N 2 Adsorption-desorption isotherms, and at P/P 0 <A sharp increase at 0.1 occurred, indicating that the aerogel had good adsorption properties.
Example 4: adsorption and elution of 14 heterocyclic amines by UiO-66/nano-cellulose composite aerogel
14 aqueous heterocyclic amine solutions (10, 100, 200 ng/mL) were used for three concentration gradients. 25mg of the composite aerogel of example 1 was immersed in 2mL of 200ng/mL aqueous solution of 14 heterocyclic amines for 20min, the heterocyclic amine types including: 1-methyl-9H-pyridine [4,3-b ] indole (Harman), 9H-pyridine [4,3-b ] indole (Norharman), 2-amino-9H-pyridine [2,3-b ] indole (AαC), 2-amino-3-methyl-9H-pyridine [2,3-b ] indole (MeAαC), 3-amino-1-methyl-5H-pyridine [4,3-b ] indole (Trp-P-2), 2-amino-1, 6-dimethylimidazole- [4,5-b ] pyridine (DMIP), 2-amino-3, 4-dimethylimidazole- [4,5-b ] quinoline (MeIQ), 2-amino-3, 7, 8-trimethylimidazole- [4,5-f ] quinoxaline (7, 8-DiMeIQx), 2-amino-3, 4, 8-trimethylimidazole- [4,5-f ] quinoxaline (4, 8-DiQx), 2-amino-3, 3-b ] indole (Trp-2), 2-amino-1, 6-dimethylimidazole- [4,5-b ] quinoline (MeIQ), 2-amino-3, 4-dimethylimidazole- [4,5-b ] quinoline (MeIQ), 2-amino-3, 8-trimethylimidazole- [4,5-f ] quinoxaline (MeIQ), 5-b ] pyridine (PhIP), 2-amino-1-methylimidazole [4,5-b ] -quinoline (IQ [4,5-b ]). After adsorption, the composite aerogel was rinsed with 2mL of ultra pure water. The composite aerogel was then immersed in 2mL of acetonitrile containing 1% amine hydroxide for 10min to desorb the heterocyclic amine. Finally, the solution was filtered through a 0.22 μm nylon filter and analyzed by UPLC-MS/MS. The above experimental procedure was repeated four times to determine whether the composite aerogel could be reused.
Taking the purified sample preparation liquid obtained in the embodiment, and measuring heterocyclic amine, wherein the method comprises the following steps:
1. and (3) introducing the purified sample into a high performance liquid chromatography tandem triple quadrupole mass spectrometry for determination: chromatographic conditions: chromatographic column: c182.1x100mm analytical column; mobile phase a:10mM ammonium acetate solution, mobile phase B: acetonitrile, gradient elution conditions: 0-0.1min,5% B;0.1-7min,70% B;7-11min,95% B;11-16min,95% B;16-20min,5% B;20-25min,5% B; flow rate: 0.3mL/min; column temperature: 40 ℃; sample injection amount: 1 μl; mass spectrometry conditions: see table 1.
TABLE 1 Mass Spectrometry conditions for heterocyclic amines
* The ion is used for quantification and the other ion is used for confirmation
2. According to the peak area value of the purified sample preparation liquid measured in the step 1 as an ordinate, heterocyclic amine mixed labels (1, 10, 50, 100, 150, 200 ng/mL) with different concentration gradients are taken as an abscissa, and a linear equation and R are obtained through fitting 2 Values.
TABLE 2 Linear Range of Standard curves, regression scheme and correlation coefficients
3. According to the peak area value of the purified sample preparation liquid measured in the step 1, referring to the working curve of the heterocyclic amine standard solution in table 2 (in the regression equation, x represents the concentration of the heterocyclic amine, and y represents the chromatographic peak area of the heterocyclic amine), calculating the content of the heterocyclic amine corresponding to the peak area value, and calculating the recovery rate of the sample to be measured according to the following formula:
wherein, cs is the standard concentration, ca and Cb are the measured concentrations before and after the standard solution is added.
TABLE 3 actual analysis results and recovery of UiO-66/nanocellulose composite aerogel
a 10ng/mL； b 100ng/mL； c 200ng/mL.
4. The adsorption and desorption efficiencies of the UiO-66/nanocellulose composite aerogel according to fig. 4 at different times of use show that the adsorption efficiency is higher for 14 heterocyclic amines, and the average value is 99.49%. In addition, the average adsorption and analysis efficiency for heterocyclic amines can be maintained at 90% or more in the second repeated use.
In summary, the invention discloses preparation and application of UiO-66/nano cellulose composite aerogel. Carboxymethyl cellulose, cellulose nanocrystalline and UiO-66 are prepared into composite aerogel with layered pores and low density through a self-crosslinking method. Compared with the common solid phase extraction column, the composite aerogel has the advantages of simple and convenient preparation method and low economic cost. The composite aerogel is used for extracting small molecular compounds through adsorption, has high adsorption rate and elution rate, is short in extraction time and can be repeatedly used. Can be used for preparing adsorption materials and filtering materials in the fields of chemical analysis materials, chromatographic materials, environmental protection materials and food materials.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art who is within the scope of the present invention shall cover the scope of the present invention by equivalent substitution or modification according to the technical scheme of the present invention and the inventive concept thereof.
Claims (6)
1. The application of the UiO-66/nano cellulose composite aerogel in an adsorption material and a filter material is characterized in that the preparation method of the UiO-66/nano cellulose composite aerogel comprises the following steps:
s1, preparing hydrazide modified carboxymethyl cellulose:
dripping the N-hydroxysuccinimide solution and the ethyl dimethyl amine propyl carbodiimide solution into a carboxymethyl cellulose mixed solution, uniformly mixing, regulating the pH value to 5-9 by using sodium hydroxide or hydrochloric acid, finally dialyzing, and freeze-drying the solution after dialysis;
wherein the volume ratio of the N-hydroxysuccinimide solution to the mixed solution of the ethyl dimethyl amine propyl carbodiimide solution to the carboxymethyl cellulose is 1:1:1; the preparation method of the carboxymethyl cellulose mixed solution comprises the following steps: dissolving carboxymethyl cellulose and oxalic acid dihydrazide in water to obtain carboxymethyl cellulose mixed solution, wherein the ratio of carboxymethyl cellulose, oxalic acid diacyl and water is 1-5 g: 2-6 g: 100-500 mL;
the preparation method of the N-hydroxysuccinimide solution comprises the following steps: dissolving N-hydroxysuccinimide in a mixed solution of dimethyl sulfoxide and water to obtain an N-hydroxysuccinimide solution, wherein the ratio of the N-hydroxysuccinimide to the mixed solution of dimethyl sulfoxide and water is 0.10-0.50 g: 5-10 mL;
the preparation method of the ethyl dimethyl amine propyl carbodiimide solution comprises the following steps: dissolving ethyl dimethyl amine propyl carbodiimide in a mixed solution of dimethyl sulfoxide and water to obtain an ethyl dimethyl amine propyl carbodiimide solution, wherein the ratio of the ethyl dimethyl amine propyl carbodiimide to the mixed solution of dimethyl sulfoxide and water is 0.1-0.8 g: 1-5 ml;
s2, preparing aldehyde group modified cellulose nanocrystals:
dissolving sodium periodate in a suspension of cellulose nanocrystals in an amount of 1-5 wt%, stirring the mixture at room temperature in a dark place for 8-15 hours, adding ethylene glycol into the suspension after the completion of the reaction to terminate the reaction, dialyzing the suspension, and finally storing the suspension at 4-8 ℃ in the form of a suspension;
wherein, the proportion of the suspension of the sodium periodate and the cellulose nanocrystalline is 0.2-0.8 g: 80-120 mL;
s3, preparing the UiO-66/nano cellulose composite aerogel: suspending UiO-66 nano particles in an aldehyde group modified cellulose nanocrystalline solution with the weight percentage of 1-5%, carrying out ultrasonic treatment for 1-15 min, then mixing the obtained suspension with an equal volume of a hydrazide modified carboxymethyl cellulose solution with the weight percentage of 1-5% by using a vortex mixer for 1-10 min, transferring the final cross-linked mass suspension into a plastic tray, storing for 5-20 min in a refrigerator with the temperature of minus 60-80 ℃, and finally carrying out freeze-drying to obtain the UiO-66/nano cellulose composite aerogel;
wherein, the ratio of the UiO-66 nano particles to the aldehyde group modified cellulose nano crystal solution is 5-50 mg: 1-5 mL;
the application method comprises the following steps:
s1, adsorption of small molecular compounds by UiO-66/nano cellulose composite aerogel: immersing the UiO-66/nano cellulose composite aerogel in 100-300 ng/mL heterocyclic amine aqueous solution for 5-20 min to adsorb analytes;
s2, eluting small molecular compounds by utilizing UiO-66/nano cellulose composite aerogel: cleaning the composite UiO-66/nano cellulose aerogel by adopting ultrapure water, and immersing the UiO-66/nano cellulose composite aerogel in acetonitrile containing amine hydroxide or acetic acid for 1-20 min so as to elute small molecular compounds; wherein, the volume ratio of the amine hydroxide or the acetic acid in the acetonitrile containing the amine hydroxide or the acetic acid to the acetonitrile is 1-4: 10 to 100.
2. The use according to claim 1, wherein the volume ratio of dimethyl sulfoxide to water in the mixed solution of dimethyl sulfoxide and water is 1:1-1:5.
3. The use according to claim 1, the lyophilization conditions being: freeze-drying at-70-80 deg.C for 15-24 hr.
4. The use according to claim 1, characterized in that the dialysis has a molecular weight cut-off of 5000-14000Da.
5. Use according to claim 1, characterized in that the plastic disc is a cylindrical plastic disc with a diameter of 10mm.
6. Use according to claim 1, characterized in that the ratio of UiO-66/nanocellulose to heterocyclic amine aqueous solution is 5-25 mg: 1-5 mL; the ratio of the UiO-66/nano cellulose composite aerogel to the acetonitrile is 5-25 mg: 1-10 mL.
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