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CN108948380B - Cellulose proton type ionic liquid gel/nano metal composite material and preparation method and application thereof - Google Patents

Cellulose proton type ionic liquid gel/nano metal composite material and preparation method and application thereof Download PDF

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CN108948380B
CN108948380B CN201810788315.5A CN201810788315A CN108948380B CN 108948380 B CN108948380 B CN 108948380B CN 201810788315 A CN201810788315 A CN 201810788315A CN 108948380 B CN108948380 B CN 108948380B
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谢海波
李想
董福平
张丽华
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Guizhou University
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Abstract

本发明公开了一种纤维素聚质子型离子液体凝胶/纳米金属复合材料及其制备方法及应用。本发明所制备的纤维素聚质子型离子液体凝胶形状可控，分子结构上具有羧基和羟基以及含氮的质子型离子液体基团，能够稳定负载大量纳米金属颗粒；金属颗粒在凝胶内部均匀分散，粒径在0.1‑100nm范围内可调；本发明适用于钯、银、金、铂、镍、钴、铜等金属及两种或两种以上金属的合金，可有效避免纳米金属制备过程中的团聚问题；本发明具有工艺简单、操作方便、成本低廉等优点，可应用在催化、环境保护、抗菌和制药等领域。

Figure 201810788315

The invention discloses a cellulose polyproton type ionic liquid gel/nano metal composite material and a preparation method and application thereof. The cellulose polyprotic ionic liquid gel prepared by the invention has a controllable shape, and has carboxyl and hydroxyl groups and nitrogen-containing proton ionic liquid groups on its molecular structure, and can stably support a large number of nano-metal particles; the metal particles are inside the gel. It is uniformly dispersed, and the particle size is adjustable within the range of 0.1-100nm; the invention is suitable for metals such as palladium, silver, gold, platinum, nickel, cobalt, copper and alloys of two or more metals, and can effectively avoid the preparation of nano-metals The problem of agglomeration in the process is solved; the invention has the advantages of simple process, convenient operation, low cost and the like, and can be applied in the fields of catalysis, environmental protection, antibacterial and pharmacy.

Figure 201810788315

Description

Cellulose proton type ionic liquid gel/nano metal composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of materials, in particular to a cellulose proton type ionic liquid gel/nano metal composite material and a preparation method and application thereof.
Background
The polymer gel is a polymer material with a three-dimensional network structure, and comprises polymer hydrogel, aerogel and organic solvent gel, wherein the three gels respectively use water, gas and organic solvent as dispersion media. The polymer gel contains hydrophilic groups and hydrophobic groups, the hydrophilic groups can be coupled with water molecules, and the hydrophobic groups can be expanded when meeting water. Therefore, the polymer gel can absorb a large amount of water in water to swell itself but not dissolve. The water in the polymer gel after absorbing water molecules exists in various forms such as free water, bound water and bonded water, so that the polymer gel can maintain the fixed shape of the polymer gel and can also allow the water in the environment to be transmitted inside the polymer gel (Macromolecules,2012,45(8): 3523-3530.). In addition, the abundance of functional groups in polymeric gels allows them to be tailored to a variety of specific tasks, with specific functionality. Therefore, polymer gel becomes an indispensable functional material in the design of many advanced materials (polymer science (English edition), 2017,35(10): 1165-1180.).
Proton-type ionic liquids (Protic liquids) are ionic liquids prepared by the neutralization reaction of a bronsted base and a bronsted acid, and have important applications in many fields because of their simple preparation and strong structure designability (Chemical Reviews 2015,115(20): 11379-. Polymer ionic liquids (Poly (ionic liquid) s) refer to polymers having both anionic and cationic electrolyte groups in the repeat unit, and have the excellent properties of both ionic liquids and polymers (Polymer Reviews,2009,49(4): 339-. The development of the proton type ionic liquid introduces a proton type ionic liquid group on a polymer structure innovatively, thereby greatly expanding the application of the polymer ionic liquid, simplifying the preparation process of the polymer ionic liquid and having important significance.
Cellulose is a natural polymer material with a wide source. Chinese patent CN201210374955.4 protects a CO-based catalyst2The cellulose dissolving method of switch type solvent is mainly characterized by utilizing CO2Organic base and aprotic polar organic solvent are used for realizing derivatization or non-derivatization dissolution of the cellulose. Based on our previous work (chinese patent CN201710887689.8), the above dissolution method can be used to conveniently dissolve cellulose and further add a derivatization reagent to perform derivatization, so as to obtain a series of cellulose derivatives with different structures. In the process, because the presence of the organic base can catalyze the chemical reaction of hydroxyl and acid anhydride, the addition of the compound containing 2 or more than 2 cyclic acid anhydride functional groups can obtain the cellulose deprotonated ionic liquid gel with a crosslinking structure.
The metal material, especially the noble metal material, has very wide application in the fields of catalysis, functional materials and the like because of the unique properties (Rsc Advances,2014,4(103): 59562) 59570). Generally, the preparation of metal particles requires the reduction of high-valence metal salt ions to elemental zero-valence metal. In the reduction process, the phenomenon of agglomeration often occurs, so that the specific surface area of the metal particles is greatly reduced, and the use efficiency of the metal particles is reduced. Therefore, it is necessary to load the metal ions onto a certain carrier and then perform the reduction process to avoid the occurrence of "agglomeration" (Progress in Polymer Science,2013,38(9): 1329-.
Nanocomposites are mixtures of two or more phases, with at least one phase being a material with a particle size within 100nm, and have unique functions and properties due to their unique structure. In recent years, polymer/nano-metal composite materials have attracted more and more attention. In 2016, zhang et al (Industrial & Engineering Chemistry Research,2016,55(48): 12398) -12406) reported that Ag NPs @ PGMA-PAM composite materials were prepared by loading Ag nanoparticles (Ag NP) on Polyacrylamide (PAM) modified poly (glycidyl methacrylate) (PGMA) microspheres, the average diameter of the Ag nanoparticles being 9.7 +/-2.7 nm and good dispersion; in the same year, Wu et al (Acs Sustainable Chemistry,2016,4(11): 5929-; in 2018, Pei et al (Nano Research,2018:1-9.) supported palladium nanoparticles with an average particle size of 1.3nm on chitosan nanowires and applied to the field of catalysis. Compared with common polymer materials, the polymer hydrogel has a regular three-dimensional network structure and has the advantage of being unique when used as a carrier of nano metal. In 2002, Haraguchi firstly prepares the nano-composite hydrogel with a unique network structure, and firstly establishes the concept of nano-composite in the hydrogel material. The polymer gel and the nano metal particles are compounded, the advantages of the polymer gel and the nano metal particles can be combined, the functions of the polymer gel are increased, the metal exists in a nano particle form with extremely high specific surface area, the metal is convenient to recycle, and the use efficiency of the metal is greatly improved. In 2013, a hydrogel of poly (ethylene oxide propyl phosphonamide) (PEOPPA) is synthesized by Zhang et al (Rsc Advances,2013,3(14):4692-4703.), and the gel is used for trying to load metal nanoparticles such as gold, silver, palladium, platinum and ruthenium, so that the generated metal nanoparticles are uniformly dispersed in the gel and have good catalytic performance; in 2014, Gema et al (Macromolecules,2014,47(17): 6028-; in 2017, Massome et al (Applied organic Chemistry,2017,32: e3917.) reported that poly (acrylic acid) hydrogel/nano silver composites can be used to catalyze the oxidation and reduction reactions of specific organic compounds.
In summary, although new polymer gel/nano-metal composite materials are continuously developed, related researches and products still have the disadvantages of high cost, environmentally-friendly raw materials, complicated production steps, serious leakage of nano-metal in the use process and the like.
Disclosure of Invention
The invention aims to provide a cellulose proton type ionic liquid gel/nano metal composite material as well as a preparation method and application thereof, the preparation is convenient, the process is green, the composite material has the advantages of cheap and easily obtained raw materials, good biocompatibility and biodegradability, can stably load a large amount of nano metal particles, and has important application prospect so as to overcome the defects of the prior art.
The invention is based on the reaction of cellulose with CO in the presence of an organic base2Reaction to achieve CO thereof2And after reversible derivatization and dissolution, directly adding a compound containing a cyclic anhydride functional group for in-situ derivatization to generate cellulose proton type ionic liquid gel, and then loading metal nano particles on the gel to prepare the cellulose proton type ionic liquid gel/nano metal composite material. By means of CO2The method solves the problem that the existing material is not available to a certain extentAnd (4) a foot. Compared with the similar materials, the composite material has the obvious advantages that the prepared composite material takes cellulose proton type ionic liquid gel as a matrix, nano metal particles are uniformly dispersed in the matrix, the particle size is adjustable within the range of 0.1-100nm, and the composite material has unique structural advantages; the cellulose proton type ionic liquid gel is convenient and rapid to prepare, controllable in size and shape, and capable of stably loading a large number of nano metal particles, and a molecular structure of the cellulose proton type ionic liquid gel is provided with a nitrogen-containing proton type ionic liquid group, a carboxyl group and a hydroxyl group; the invention is suitable for metals such as palladium, silver, gold, platinum, nickel, cobalt, copper and the like and alloys of two or more metals, and can effectively avoid the agglomeration problem in the preparation process of nano-metals; the composite material prepared by the invention can be applied to the fields of catalysis, environmental protection, antibacterial materials, pharmacy and the like, for example, the composite material can be used for catalyzing and degrading common pollutants in water such as nitrobenzene derivatives, organic dyes, chlorohydrocarbons and the like, can be used for resisting microorganisms such as Escherichia coli, Candida albicans and the like, and can be used for producing medical intermediates such as 4-aminophenol and the like; the invention has the advantages of simple process, convenient operation, low cost and the like.
The invention is realized by the following steps: the cellulose proton type ionic liquid gel/nano metal composite material takes the cellulose proton type ionic liquid gel as a matrix, and metal particles with the particle size of 0.1-100nm are uniformly dispersed in the matrix; the molecular structure of the cellulose proton type ionic liquid gel has a nitrogen-containing proton type ionic liquid group and carboxyl and hydroxyl.
The preparation method of the cellulose proton type ionic liquid gel/nano metal composite material comprises the following steps:
1) mixing cellulose, organic base and aprotic polar organic solvent, and introducing CO into the mixed system2Carrying out a reaction to obtain cellulose-based CO2A solution of a reversible polyionic compound;
2) adding a compound containing anhydride functional groups into the solution prepared in the step 1), wherein the added compound is a combination of more than one compound, and at least one of the added compounds has 2 or more than 2 cyclic anhydride functional groups, and reacting at 20-200 ℃ for 1-240h to obtain gel A;
3) soaking the gel A in pure water for 1-10 days, and changing water every 4h to obtain gel B;
4) placing the gel B in a solution containing target metal ions, and oscillating for 1-48h at normal temperature to obtain a gel C;
5) placing the gel C in pure water, and oscillating for 1-48h at normal temperature to obtain a gel D;
6) placing the gel D in a reducing agent solution, and oscillating for 1-48h at normal temperature to obtain a gel E;
7) placing the gel E in pure water, and oscillating for 1-48h at normal temperature to obtain gel F;
8) freeze drying gel F for 5-72 hr, or supercritical CO2Drying for 1-10 times, each time for 0.1-5 hr to obtain gel G;
9) and soaking the gel F or the gel G in an organic solvent for 1-10 days to obtain the cellulose deprotonated ionic liquid organic solvent gel/nano metal composite material.
The cellulose raw material in the step 1) is one or any combination of more of microcrystalline cellulose, alpha-cellulose, cotton, wood pulp, bamboo pulp or plant cellulose separated from agricultural and forestry lignocellulose waste; the uniform chemical structure of the cellulose contained in the raw materials is shown as the formula (I):
Figure BDA0001734210280000061
where 50< p < 1000.
The acid-base dissociation constant of the organic base in the step 1) is more than 20, and the organic base has the following structural characteristics:
Figure BDA0001734210280000062
wherein:
a series, R1Is alkyl with 1-6 carbon atoms, R2, R3, and R4 are independent methyl or ethyl;
b series, n-1 or n-2; m is 1-6; r isIndependently hydrogen, methyl or ethyl; r1Is independent hydrogen or alkyl with 1-6 carbon atoms; r2,R3,R4And R5Is independently hydrogen, methyl or ethyl;
the chemical structural formula of the organic base in the step 1) is shown as formulas (II), (III), (IV) and (V)
Or (VI):
Figure BDA0001734210280000071
wherein: n is 1 or 2; r1Is independent hydrogen or alkyl with 1-6 carbon atoms;
the aprotic polar organic solvent in the step 1) is one or any combination of more of dimethyl sulfoxide, N-methyl pyrrolidone, tetramethylurea, tetraethylurea, N-dimethyl imidazolidinone, N-dimethylformamide, N-diethylacetamide, pyrrolidone, 2-azacyclohexanone, epsilon-caprolactam, N-dimethyl propylene urea or sulfolane.
In the mixed system in the step 1), the mass concentration of the organic alkali is 0.1-50%; the mass concentration of the cellulose is 0.1-30%.
Step 1) charging CO into the mixed system2The pressure of the reaction is 0.1MPa to 15MPa, the reaction temperature is 50 ℃ to 150 ℃, and the reaction time is 1h to 24 h.
Step 2) adding one or more compounds containing anhydride functional groups in a total amount of the total substances with the cellulose-based CO2The molar ratio of glucose units in the solution of the reversible polyionic compound is from 0.5:1 to 5: 1.
The compound containing the anhydride functional group in the step 2) comprises one of the following structural formulas:
Figure BDA0001734210280000081
cellulose-based CO obtained in step 1)2The cation of the reversible polyionic compound has the following structure:
Figure BDA0001734210280000082
wherein:
a series, R1Is an alkyl group having 1 to 6 carbon atoms, R2,R3And R4Is independently methyl or ethyl;
b series, n-1 or n-2; m is 1-6; r is independently hydrogen, methyl or ethyl; r1Is independent hydrogen or alkyl with 1-6 carbon atoms; r2,R3,R4And R5Is independently hydrogen, methyl or ethyl;
cellulose-based CO2The anion structure of the reversible polyionic compound has the following structural features:
Figure BDA0001734210280000091
where 50< p < 1000.
The cellulose deprotonated ionic liquid gel A, B, C, D, E, F, G described in step 2), step 3), step 4), step 5), step 6), step 7), step 8) and step 9) all has the following structure:
Figure BDA0001734210280000092
where 50< p < 1000.
Wherein R1 is H or a protic ionic liquid; wherein, when the ionic liquid is a proton type ionic liquid, the anion of the proton type ionic liquid is one or more than one of the following structures:
Figure BDA0001734210280000101
the cation of the proton type ionic liquid is one or a mixture of more than one of the following structures:
Figure BDA0001734210280000102
wherein:
a series, R1Is alkyl with 1-6 carbon atoms, R2,R3,R4Is independently methyl or ethyl;
b series, n-1 or n-2; m is 1-6; r is independently hydrogen, methyl or ethyl; r1Is independent hydrogen or alkyl with 1-6 carbon atoms; r2,R3,R4And R5Is independently hydrogen, methyl or ethyl;
the volume ratio of the gel A in the step 3) to the pure water is 5:1-100: 1;
the concentration of the metal ions in the solution containing the target metal ions in the step 4) is 0.01-100mg/ml, and the volume ratio of the gel B to the solution containing the target metal ions is 1:1-100: 1;
the volume ratio of the pure water to the gel C in the step 5) is 1:1-100: 1;
the concentration of the reducing agent solution in the step 6) is 0.01-10mol/L, and the volume ratio of the reducing agent solution to the gel D is 1:1-100: 1;
the volume ratio of the pure water to the gel E in the step 7) is 1:1-100: 1;
freeze-drying the gel F for 24-48h in the step 8); supercritical CO2Drying for 3-5 times, each time for 0.5-2 hr;
the volume ratio of the organic solvent to the gel F or the gel G in the step 9) is 1:1-100: 1.
Advantageous effects
Compared with the prior art, the invention is based on the fact that cellulose reacts with CO in the presence of organic alkali2Reaction to achieve CO thereof2And after reversible derivatization and dissolution, directly adding a derivatization reagent containing a cyclic anhydride functional group for in-situ derivatization to generate cellulose proton type ionic liquid gel, and then loading metal nano particles on the gel to prepare the cellulose proton type ionic liquid gel/nano metal composite material. By means of CO2Switch type solvent dissolving fiberThe cellulose is subjected to in-situ derivatization and then loaded with nano metal particles to prepare the cellulose proton type ionic liquid gel/nano metal composite material, thereby solving the defects of the existing material to a certain extent. Compared with the similar materials, the composite material has the obvious advantages that the prepared composite material takes cellulose proton type ionic liquid gel as a matrix, nano metal particles are uniformly dispersed in the matrix, the particle size is adjustable within the range of 0.1-100nm, and the composite material has unique structural advantages; the cellulose proton type ionic liquid gel is convenient and rapid to prepare, controllable in size and shape, and capable of stably loading a large number of nano metal particles, and a molecular structure of the cellulose proton type ionic liquid gel is provided with a nitrogen-containing proton type ionic liquid group, a carboxyl group and a hydroxyl group; the invention is suitable for metals such as palladium, silver, gold, platinum, nickel, cobalt, copper and the like and alloys of two or more metals, and can effectively avoid the agglomeration problem in the preparation process of nano-metals; the cellulose proton type ionic liquid gel/nano metal composite material prepared by the invention can be applied to the fields of catalysis, environmental protection, antibacterial materials, pharmacy and the like, for example, can be used for catalyzing and degrading common pollutants in water such as nitrobenzene derivatives, organic dyes, chlorohydrocarbons and the like, can be used for resisting microorganisms such as Escherichia coli, Candida albicans and the like, and can be used for producing medical intermediates such as 4-aminophenol and the like; the invention has the advantages of simple process, convenient operation, low cost and the like.
Drawings
FIG. 1: the invention discloses a flow chart of patent steps;
FIG. 2: performing Fourier transform infrared spectroscopy (FTIR) comparison on cotton pulp cellulose and cellulose proton type ionic liquid gel;
from the FTIR data of fig. 2, it can be seen that the cellulose deprotonated ionic liquid gel has a peak of ester group stretching vibration at line 1733, a peak of carbon-nitrogen double bond (C ═ N) stretching vibration at line 1655, a peak of carboxyl group stretching vibration at line 1587, and peaks of 1405 and 1261 of methylene group stretching vibration linked to carboxyl group and its salt, thus proving the synthesis of the cellulose deprotonated ionic liquid gel;
FIG. 3: a Transmission Electron Microscope (TEM) picture of the cellulose proton type ionic liquid gel/nano palladium composite material;
as can be seen from FIG. 3, Pd in the composite catalyst is in nanometer level, and has uniform particle size and uniform dispersion;
FIG. 4: the particle size distribution diagram of the nano metal particles in the cellulose proton type ionic liquid gel/nano palladium composite material is shown;
from FIG. 4, it can be seen that most of the Pd nanoparticles have a particle size below 5nm, and most are concentrated in the range of 2-4 nm;
FIG. 5: the ultraviolet-visible spectrophotometer monitored the 4-nitrophenol reduction process.
Detailed Description
Example 1 of the invention: the preparation method of the cellulose proton type ionic liquid gel/nano metal composite material comprises the following steps:
1) weighing about 0.8 g of wheat straw cellulose, 1.723 g of tetramethylguanidine and about 23 g of DMSO (the molar ratio of the tetramethylguanidine to the hydroxyl in the cellulose is 1:1), adding the wheat straw cellulose, the tetramethylguanidine and the DMSO into a high-pressure reaction kettle, covering the reaction kettle, and introducing 0.4MPa CO2And the temperature is 50 ℃, the mixture is sealed and stirred by strong magnetic force for 3 hours, and a one-pot reaction is carried out to dissolve cellulose, so as to obtain a clear and transparent cellulose solution, wherein the mass fraction of the cellulose is about 3%.
2) Pouring the cellulose solution into a 100ml two-neck round-bottom flask, adding succinic anhydride (the molar ratio of the succinic anhydride to the cellulose glucose unit is 1) and pyromellitic anhydride (the molar ratio of the pyromellitic anhydride to the cellulose glucose unit is 1), uniformly stirring, and reacting the mixed solution at 80 ℃ for 5 hours to obtain the gel A with the cross-linked structure.
3) And (3) placing the gel A in 100ml of pure water, changing water every 4 hours, and soaking for 3 days to obtain the cellulose proton type ionic liquid hydrogel B.
4) Immersing cellulose proton type ionic liquid hydrogel into 25ml palladium chloride (PdCl) with concentration of 0.5mg/ml2) Oscillating in water solution at normal temperature for 12h to obtain Pd supported on the solution2+The cellulose deprotonated ionic liquid hydrogel C.
5) Will load Pd2+The cellulose proton type ionic liquid hydrogel is placed in 25ml of pure water and oscillated at normal temperature for 12h to obtain gel D.
6) Placing the gel D in 25ml of 0.1mol/L sodium borohydride aqueous solution, and oscillating at normal temperature for 12h to obtain gel E;
7) and (3) placing the gel E in 25ml of pure water, and oscillating at normal temperature for 12h to obtain a gel F, wherein the gel F is the cellulose proton type ionic liquid hydrogel/nano palladium composite material.
8) And freezing the gel F by using liquid nitrogen, and then carrying out freeze drying for 48 hours to obtain a gel G, wherein the gel G is the cellulose proton type ionic liquid aerogel/nano palladium composite material.
9) And (3) soaking 0.1G of the gel G in 100ml of ethanol for 48 hours to obtain a gel H, wherein the gel H is the cellulose proton type ionic liquid organic solvent (ethanol) gel/nano palladium composite material.
Example 2 of the invention: the application of the cellulose proton type ionic liquid gel/nano metal composite material, which catalyzes the reduction reaction of 4-nitrophenol to prepare 4-aminophenol, comprises the following experimental steps:
1) preparing 0.3Mm 4-nitrophenol aqueous solution;
2) preparing 30Mm NaBH4An aqueous solution of (a);
3) taking 1ml of NaBH4The solution and 1ml of 4-nitrophenol solution were mixed in a single-neck bottle, 8ml of pure water was added, 2.5g of the cellulose deprotonated ionic liquid hydrogel/nano palladium metal composite prepared in step 7) of example 1 was added, the reaction was carried out at room temperature, and the reaction process was monitored using an ultraviolet-visible spectrophotometer, the results of which are shown in fig. 5.
Example 3 of the invention: the preparation method of the cellulose proton type ionic liquid gel/nano metal composite material comprises the following steps:
1) weighing about 1.3 g of cotton pulp cellulose, 2.886 g of tetramethylguanidine and about 22 g of DMSO (the molar ratio of the tetramethylguanidine to the hydroxyl in the cellulose is 1:1), adding into a high-pressure reaction kettle, covering the reaction kettle, and introducing 0.6MPa CO2And the temperature is 50 ℃, the mixture is sealed and stirred by strong magnetic force for 3 hours, and a one-pot reaction is carried out to dissolve cellulose, so as to obtain a clear and transparent cellulose solution, wherein the mass fraction of the cellulose is about 5%.
2) Pouring the cellulose solution into a 100ml two-neck round-bottom flask, adding succinic anhydride (the molar ratio of the succinic anhydride to the cellulose glucose unit is 1) and pyromellitic anhydride (the molar ratio of the pyromellitic anhydride to the cellulose glucose unit is 1), uniformly stirring, and reacting the mixed solution at 100 ℃ for 10 hours to obtain the gel A with the cross-linked structure.
3) And (3) placing the gel A in 100ml of pure water, changing water every 4 hours, and soaking for 3 days to obtain the cellulose proton type ionic liquid hydrogel B.
4) Gel B was immersed in 25ml silver nitrate (AgNO) at a concentration of 0.3mg/ml3) Oscillating for 15h at normal temperature in the aqueous solution to obtain the Ag-loaded material+The cellulose deprotonated ionic liquid hydrogel C.
5) Will load Ag+The cellulose proton type ionic liquid hydrogel C is placed in 25ml of pure water and oscillated for 15 hours at normal temperature to obtain gel D.
6) And placing the gel D in 25ml of 0.1mol/L aqueous solution of sodium borohydride, and oscillating for 5 hours at normal temperature to obtain gel E.
7) And (3) placing the gel E in 25ml of pure water, and oscillating for 5h at normal temperature to obtain a gel F, wherein the gel F is the cellulose proton type ionic liquid hydrogel/nano silver composite material.
8) And freezing and drying the gel F for 36h after freezing the gel F by using liquid nitrogen to obtain a gel G, wherein the gel G is the cellulose proton-polymerized ionic liquid aerogel/nano-silver composite material.
Example 4 of the invention: the preparation method of the cellulose proton type ionic liquid gel/nano metal composite material comprises the following steps:
1) weighing about 0.8 g of bamboo pulp cellulose, 1.723 g of tetramethylguanidine and about 23 g of DMSO (the molar ratio of the tetramethylguanidine to the hydroxyl in the cellulose is 1:1), adding into a high-pressure reaction kettle, covering the reaction kettle, and introducing 0.4MPa CO2And the temperature is 50 ℃, the mixture is sealed and stirred by strong magnetic force for 3 hours, and a one-pot reaction is carried out to dissolve cellulose, so as to obtain a clear and transparent cellulose solution, wherein the mass fraction of the cellulose is 3%.
2) Pouring the cellulose solution into a 100ml two-neck round-bottom flask, adding succinic anhydride (the molar ratio of the succinic anhydride to the cellulose glucose unit is 1) and pyromellitic anhydride (the molar ratio of the pyromellitic anhydride to the cellulose glucose unit is 1), uniformly stirring, and reacting the mixed solution at 120 ℃ for 3h to obtain the gel A with the cross-linked structure.
3) And (3) placing the gel in 150ml of pure water, changing water every 4 hours, and soaking for 3 days to obtain the cellulose proton type ionic liquid hydrogel B.
4) Immersing cellulose proton type ionic liquid hydrogel into 25ml cobalt nitrate (Co (NO) with concentration of 0.1mg/ml3)2) Oscillating in water solution at normal temperature for 24h to obtain the Co-loaded material2+The cellulose deprotonated ionic liquid hydrogel C.
5) Will be loaded with Co2+The cellulose proton type ionic liquid hydrogel is placed in 25ml of pure water and oscillated at normal temperature for 24h to obtain gel D.
6) And placing the gel D in 25ml of 0.1mol/L aqueous solution of sodium borohydride, and oscillating at normal temperature for 12h to obtain gel E.
7) And (3) placing the gel E in 25ml of pure water, and oscillating at normal temperature for 12h to obtain a gel F, wherein the gel F is the cellulose proton type ionic liquid hydrogel/nano cobalt composite material.
8) Subjecting gel F to supercritical CO2Drying for 3 times and 1h each time to obtain gel G, wherein the gel G is the cellulose proton type ionic liquid aerogel/nano cobalt composite material.
Example 5 of the invention: the preparation method of the cellulose proton type ionic liquid gel/nano metal composite material comprises the following steps:
1) weighing about 0.8 g of wood pulp cellulose, 1.723 g of tetramethylguanidine and about 23 g of DMSO (the molar ratio of the tetramethylguanidine to the hydroxyl in the cellulose is 1:1), adding into a high-pressure reaction kettle, covering the reaction kettle, and introducing 0.4MPa CO2And the temperature is 50 ℃, the mixture is sealed and stirred by strong magnetic force for 3 hours, and a one-pot reaction is carried out to dissolve cellulose, so as to obtain a clear and transparent cellulose solution, wherein the mass fraction of the cellulose is 3%.
2) Pouring the cellulose solution into a 100ml two-neck round-bottom flask, adding succinic anhydride (the molar ratio of the succinic anhydride to the cellulose glucose unit is 1) and pyromellitic anhydride (the molar ratio of the pyromellitic anhydride to the cellulose glucose unit is 0.75), uniformly stirring, and reacting the mixed solution at 80 ℃ for 5 hours to obtain the gel A with the cross-linked structure.
3) And (3) placing the gel in 200ml of pure water, changing water every 4 hours, and soaking for 3 days to obtain the cellulose proton type ionic liquid hydrogel B.
4) Immersing cellulose proton type ionic liquid hydrogel into 25ml palladium chloride (PdCl) with concentration of 0.1mg/ml2) Oscillating in water solution at normal temperature for 24h to obtain Pd supported on the solution2+The cellulose deprotonated ionic liquid hydrogel C.
5) Will load Pd2+The cellulose proton type ionic liquid hydrogel C is placed in 25ml of pure water and oscillated at normal temperature for 24h to obtain gel D.
6) And placing the gel D in 25ml of 0.1mol/L aqueous solution of sodium borohydride, and oscillating at normal temperature for 12h to obtain gel E.
7) And (3) placing the gel E in 25ml of pure water, and oscillating at normal temperature for 12h to obtain a gel F, wherein the gel F is the cellulose proton type ionic liquid hydrogel/nano palladium composite material.
8) And freezing the gel F by using liquid nitrogen, and then carrying out freeze drying for 48 hours to obtain a gel G, wherein the gel G is the cellulose proton type ionic liquid aerogel/nano palladium composite material.
Example 6 of the invention: the preparation method of the cellulose proton type ionic liquid gel/nano metal composite material comprises the following steps:
1) weighing about 0.8 g of cotton pulp cellulose, 1.723 g of tetramethylguanidine and about 23 g of DMSO (the molar ratio of the tetramethylguanidine to the hydroxyl in the cellulose is 1:1), adding into a high-pressure reaction kettle, covering the reaction kettle, and introducing 0.4MPa CO2And the temperature is 50 ℃, the mixture is sealed and stirred by strong magnetic force for 3 hours, and a one-pot reaction is carried out to dissolve cellulose, so as to obtain a clear and transparent cellulose solution, wherein the mass fraction of the cellulose is 3%.
2) Pouring the cellulose solution into a 100ml two-neck round-bottom flask, adding succinic anhydride (the molar ratio of the succinic anhydride to the cellulose glucose unit is 1) and 3,3,4, 4-biphenyltetracarboxylic dianhydride (the molar ratio of the succinic anhydride to the cellulose glucose unit is 1.25), uniformly stirring, and reacting the mixed solution at 80 ℃ for 5 hours to obtain the gel A with the cross-linked structure.
3) And (3) placing the gel A in 300ml of pure water, changing water every 4 hours, and soaking for 3 days to obtain the cellulose proton type ionic liquid hydrogel B.
4) Immersing cellulose proton type ionic liquid hydrogel into 25ml palladium chloride (PdCl) with concentration of 0.1mg/ml2) Oscillating in water solution at normal temperature for 24h to obtain Pd supported on the solution2+The cellulose deprotonated ionic liquid hydrogel C.
5) Will load Pd2+The cellulose proton type ionic liquid hydrogel C is placed in 25ml of pure water and oscillated at normal temperature for 24h to obtain gel D.
6) And placing the gel D in 25ml of 0.1mol/L aqueous solution of sodium borohydride, and oscillating at normal temperature for 12h to obtain gel E.
7) And (3) placing the gel E in 25ml of pure water, and oscillating at normal temperature for 12h to obtain a gel F, wherein the gel F is the cellulose proton type ionic liquid hydrogel/nano palladium composite material.
8) And freezing the gel F by using liquid nitrogen, and then carrying out freeze drying for 48 hours to obtain a gel G, wherein the gel G is the cellulose proton type ionic liquid aerogel/nano palladium composite material.
Example 7 of the invention: the application of the cellulose proton type ionic liquid gel/nano metal composite material, which catalyzes the reduction reaction of 4-nitrophenol to prepare 4-aminophenol, comprises the following experimental steps:
1) preparing 0.6Mm 4-nitrophenol aqueous solution;
2) preparing 60Mm NaBH4An aqueous solution of (a);
3) 5ml of NaBH are taken4Mixing the solution and 5ml of 4-nitrophenol solution in a single-mouth bottle, adding 5g of cellulose proton type ionic liquid hydrogel/nano palladium composite material, reacting at normal temperature, and monitoring the reaction process by using an ultraviolet-visible spectrophotometer.

Claims (8)

1.一种纤维素聚质子型离子液体凝胶/纳米金属复合材料，其特征在于：以纤维素聚质子型离子液体凝胶为基体，在基体内设有均匀分散的粒径在0.1-100nm纳米之间的金属颗粒；纤维素聚质子型离子液体凝胶中的纤维素聚质子型离子的分子结构上具有含氮的质子型离子液体基团以及羧基和羟基；1. a cellulose polyproton type ionic liquid gel/nano metal composite material is characterized in that: take the cellulose polyproton type ionic liquid gel as a matrix, in the matrix, be provided with a uniformly dispersed particle size at 0.1-100nm Metal particles between nanometers; the molecular structure of cellulose polyprotic ions in the cellulose polyprotic ionic liquid gel has nitrogen-containing protic ionic liquid groups, carboxyl groups and hydroxyl groups; 其制备方法包括如下步骤：Its preparation method comprises the following steps: 1)将纤维素、有机碱与非质子型极性有机溶剂进行混合，并向混合体系中充入CO2进行反应，得到纤维素基CO2可逆聚离子化合物的溶液；1) mixing cellulose, organic base and aprotic polar organic solvent, and charging CO into the mixed system to react to obtain a solution of cellulose-based CO reversible polyionic compound; 2)向步骤1)制备获得的溶液中加入含有酸酐官能团的化合物，所加入的化合物为一种以上的组合、且加入的化合物中至少有一种具有2个以上环状酸酐官能团，在20-200℃下反应1-240h，得到凝胶A；2) Add a compound containing an acid anhydride functional group to the solution prepared in step 1), the added compound is a combination of more than one, and at least one of the added compounds has more than 2 cyclic acid anhydride functional groups, at 20-200 React at ℃ for 1-240h to obtain gel A; 3)将凝胶A置于纯水中浸泡1-10天，且每隔4h换一次水，得到凝胶B；3) Soak gel A in pure water for 1-10 days, and change the water every 4h to obtain gel B; 4)将凝胶B置于含有目标金属离子的溶液中，常温振荡1-48h，得到凝胶C；4) Place gel B in a solution containing target metal ions, and shake at room temperature for 1-48 h to obtain gel C; 5)将凝胶C置于纯水中常温振荡1-48h，得到凝胶D；5) Place gel C in pure water and shake at room temperature for 1-48h to obtain gel D; 6)将凝胶D置于还原剂溶液中常温振荡1-48h，得到凝胶E；6) Place gel D in a reducing agent solution and shake at room temperature for 1-48h to obtain gel E; 7)将凝胶E置于纯水中常温振荡1-48h，得到凝胶F；7) Place gel E in pure water and shake at room temperature for 1-48h to obtain gel F; 8)将凝胶F进行冷冻干燥5-72h，或超临界CO2干燥1-10次，每次0.1-5h，得到凝胶G；8) freeze-drying gel F for 5-72 h, or drying with supercritical CO 2 for 1-10 times, each time for 0.1-5 h, to obtain gel G; 9)将凝胶F或凝胶G浸泡于有机溶剂中1-10天，获得纤维素聚质子型离子液体有机溶剂凝胶/纳米金属复合材料；9) soaking gel F or gel G in an organic solvent for 1-10 days to obtain a cellulose polyprotic ionic liquid organic solvent gel/nano-metal composite material; 步骤1)所述的有机碱的酸碱离解常数大于20，且有机碱具有如下结构特征：The acid-base dissociation constant of the organic base described in step 1) is greater than 20, and the organic base has the following structural characteristics:
Figure FDA0003210782910000021
Figure FDA0003210782910000021
 其中：in: A系列，R1为碳原子数为1-6的烷基，R2,R3,及R4为独立的甲基或乙基；A series, R 1 is an alkyl group with 1-6 carbon atoms, R 2 , R 3 , and R 4 are independent methyl or ethyl groups; B系列，n＝1或n＝2；m＝1-6；R为独立的氢、甲基或乙基；R1为独立的氢或碳原子数为1-6的烷基；R2,R3,R4,及R5为独立的氢、甲基或乙基；B series, n=1 or n=2; m=1-6; R is independent hydrogen, methyl or ethyl; R 1 is independent hydrogen or an alkyl group with 1-6 carbon atoms; R 2 , R 3 , R 4 , and R 5 are independently hydrogen, methyl or ethyl; 步骤1)所述非质子型极性有机溶剂为二甲基亚砜、N-甲基吡咯烷酮、四甲基脲、四乙基脲、N，N-二甲基咪唑啉酮、N,N-二甲基甲酰胺、N,N-二乙基乙酰胺、吡咯烷酮、2-氮己环酮、ε-己内酰胺、N,N-二甲基丙烯基脲或环丁砜中的一种或几种的任意组合；Step 1) The aprotic polar organic solvent is dimethyl sulfoxide, N-methylpyrrolidone, tetramethylurea, tetraethylurea, N,N-dimethylimidazolidinone, N,N- Any of one or more of dimethylformamide, N,N-diethylacetamide, pyrrolidone, 2-azexanone, ε-caprolactam, N,N-dimethylpropenylurea or sulfolane combination; 步骤1)所述的混合体系中，有机碱的质量浓度为0.1-50％；纤维素的质量浓度为0.1％-30％；In the mixing system described in step 1), the mass concentration of the organic base is 0.1-50%; the mass concentration of the cellulose is 0.1%-30%; 步骤1)所述向混合体系中充入CO2的压力为0.1MPa-15 MPa，反应温度为50-150℃，反应时间为1-24h；In step 1), the pressure of filling CO into the mixing system is 0.1MPa-15MPa, the reaction temperature is 50-150°C, and the reaction time is 1-24h; 步骤2)所述加入的一种以上含有酸酐官能团的化合物，其总的物质的量与所述的纤维素基CO2可逆聚离子化合物的溶液中葡萄糖单元的摩尔比为0.5:1-5:1；步骤2)所述的含有酸酐官能团的化合物包括如下结构式之一：Step 2) described adding more than one compound containing acid anhydride functional group, the amount of its total substance and the described cellulose-based CO The mol ratio of the glucose unit in the solution of the reversible polyionic compound is 0.5:1-5: 1; Step 2) the described compound containing an acid anhydride functional group includes one of the following structural formulas:
Figure FDA0003210782910000031
Figure FDA0003210782910000031
 2.一种如权利要求1所述的纤维素聚质子型离子液体凝胶/纳米金属复合材料的制备方法，其特征在于，包括如下步骤：2. a preparation method of cellulose polyprotic ionic liquid gel/nano metal composite material as claimed in claim 1, is characterized in that, comprises the steps: 1)将纤维素、有机碱与非质子型极性有机溶剂进行混合，并向混合体系中充入CO2进行反应，得到纤维素基CO2可逆聚离子化合物的溶液；1) mixing cellulose, organic base and aprotic polar organic solvent, and charging CO into the mixed system to react to obtain a solution of cellulose-based CO reversible polyionic compound; 2)向步骤1)制备获得的溶液中加入含有酸酐官能团的化合物，所加入的化合物为一种以上的组合、且加入的化合物中至少有一种具有2个以上环状酸酐官能团，在20-200℃下反应1-240h，得到凝胶A；2) Add a compound containing an acid anhydride functional group to the solution prepared in step 1), the added compound is a combination of more than one, and at least one of the added compounds has more than 2 cyclic acid anhydride functional groups, at 20-200 React at ℃ for 1-240h to obtain gel A; 3)将凝胶A置于纯水中浸泡1-10天，且每隔4h换一次水，得到凝胶B；3) Soak gel A in pure water for 1-10 days, and change the water every 4h to obtain gel B; 4)将凝胶B置于含有目标金属离子的溶液中，常温振荡1-48h，得到凝胶C；4) Place gel B in a solution containing target metal ions, and shake at room temperature for 1-48 h to obtain gel C; 5)将凝胶C置于纯水中常温振荡1-48h，得到凝胶D；5) Place gel C in pure water and shake at room temperature for 1-48h to obtain gel D; 6)将凝胶D置于还原剂溶液中常温振荡1-48h，得到凝胶E；6) Place gel D in a reducing agent solution and shake at room temperature for 1-48h to obtain gel E; 7)将凝胶E置于纯水中常温振荡1-48h，得到凝胶F；7) Place gel E in pure water and shake at room temperature for 1-48h to obtain gel F; 8)将凝胶F进行冷冻干燥5-72h，或超临界CO2干燥1-10次，每次0.1-5h，得到凝胶G；8) freeze-drying gel F for 5-72 h, or drying with supercritical CO 2 for 1-10 times, each time for 0.1-5 h, to obtain gel G; 9)将凝胶F或凝胶G浸泡于有机溶剂中1-10天，获得纤维素聚质子型离子液体有机溶剂凝胶/纳米金属复合材料。9) Immerse the gel F or the gel G in an organic solvent for 1-10 days to obtain a cellulose polyprotic ionic liquid organic solvent gel/nano-metal composite material. 3.根据权利要求2所述的制备方法，其特征在于：步骤1)所述的纤维素原料为微晶纤维素、α-纤维素、棉花、木浆粕、竹子浆粕或农林木质纤维素废弃物中分离的植物纤维素的一种或几种任意组合；此类原料所含纤维素的统一化学结构均如式(I)所示：3. preparation method according to claim 2 is characterized in that: the cellulose raw material described in step 1) is microcrystalline cellulose, α-cellulose, cotton, wood pulp, bamboo pulp or agricultural and forestry lignocellulose One or any combination of plant cellulose separated from waste; the unified chemical structure of cellulose contained in such raw materials is shown in formula (I):
Figure FDA0003210782910000041
Figure FDA0003210782910000041
 其中50<p<1000。where 50<p<1000. 4.根据权利要求2所述的制备方法，其特征在于：步骤1)所述的有机碱的化学结构式为式(II)、(III)、(IV)、(V)或(VI)：4. preparation method according to claim 2 is characterized in that: the chemical structural formula of the described organic base of step 1) is formula (II), (III), (IV), (V) or (VI):
Figure FDA0003210782910000042
Figure FDA0003210782910000042
Figure FDA0003210782910000051
Figure FDA0003210782910000051
 其中：n＝1或2；R1为独立的氢或碳原子数为1-6的烷基。Wherein: n=1 or 2; R 1 is independent hydrogen or an alkyl group having 1-6 carbon atoms. 5.根据权利要求2所述的制备方法，其特征在于：5. preparation method according to claim 2, is characterized in that: 步骤1)获得的纤维素基CO2可逆聚离子化合物的阳离子具有如下结构：The cation of the cellulose-based CO2 reversible polyionic compound obtained in step 1) has the following structure: A：
Figure FDA0003210782910000052
A:
Figure FDA0003210782910000052
 B：
Figure FDA0003210782910000053
B:
Figure FDA0003210782910000053
 其中：in: A系列,R1,为碳原子数为1-6的烷基，R2,R3及R4为独立的甲基或乙基；A series, R 1 , is an alkyl group with 1-6 carbon atoms, R 2 , R 3 and R 4 are independent methyl or ethyl groups; B系列，n＝1或n＝2；m＝1-6；R为独立的氢、甲基或乙基；R1为独立的氢或碳原子数为1-6的烷基；R2,R3,R4及R5为独立的氢、甲基或乙基；B series, n=1 or n=2; m=1-6; R is independent hydrogen, methyl or ethyl; R 1 is independent hydrogen or an alkyl group with 1-6 carbon atoms; R 2 , R 3 , R 4 and R 5 are independently hydrogen, methyl or ethyl; 纤维素基CO2可逆聚离子化合物的阴离子结构具有如下结构特征：The anionic structures of cellulose-based CO2 reversible polyionic compounds have the following structural features:
Figure FDA0003210782910000061
Figure FDA0003210782910000061
 其中50<p<1000。where 50<p<1000. 6.根据权利要求2所述的制备方法，其特征在于：步骤2)、步骤3)、步骤4)、步骤5)、步骤6)、步骤7)、步骤8)和步骤9)中所述的的纤维素聚质子型离子液体凝胶A、B、C、D、E、F、G均具有如下结构：6. preparation method according to claim 2 is characterized in that: described in step 2), step 3), step 4), step 5), step 6), step 7), step 8) and step 9) The cellulose polyprotic ionic liquid gels A, B, C, D, E, F, G all have the following structures:
Figure FDA0003210782910000062
Figure FDA0003210782910000062
 其中50<p<1000；where 50<p<1000; 其中R1为H或质子型离子液体；其中，为质子型离子液体时，质子型离子液体的阴离子为如下结构中的一种或两种以上的混合物：Wherein R1 is H or a proton ionic liquid; wherein, when it is a proton ionic liquid, the anion of the proton ionic liquid is one or a mixture of two or more of the following structures:
Figure FDA0003210782910000071
Figure FDA0003210782910000071
 质子型离子液体的阳离子为如下结构中的一种或两种以上的混合物：The cation of the proton ionic liquid is one or a mixture of two or more of the following structures: A：
Figure FDA0003210782910000072
A:
Figure FDA0003210782910000072
 B：
Figure FDA0003210782910000073
B:
Figure FDA0003210782910000073
 其中：in: A系列,R1为碳原子数为1-6的烷基，R2,R3,R4为独立的甲基或乙基；A series, R 1 is an alkyl group with 1-6 carbon atoms, R 2 , R 3 , R 4 are independent methyl or ethyl; B系列，n＝1或n＝2；m＝1-6；R为独立的氢、甲基或乙基；R1为独立的氢或碳原子数为1-6的烷基；R2,R3,R4及R5为独立的氢、甲基或乙基。B series, n=1 or n=2; m=1-6; R is independent hydrogen, methyl or ethyl; R 1 is independent hydrogen or an alkyl group with 1-6 carbon atoms; R 2 , R 3 , R 4 and R 5 are independently hydrogen, methyl or ethyl. 7.根据权利要求2所述的制备方法，其特征在于：7. preparation method according to claim 2, is characterized in that: 步骤3)所述的凝胶A与的纯水体积比为5:1-100:1；步骤4)所述的含有目标金属离子的溶液中的金属离子的浓度为0.01-100mg/ml，凝胶B与含有目标金属离子的溶液的体积比为1:1-100:1；步骤5)所述的纯水与凝胶C的体积比为1:1-100:1；步骤6)所述的还原剂溶液浓度为0.01-10mol/L，还原剂溶液与凝胶D的体积比为1:1-100:1；步骤7)所述的纯水与凝胶E的体积比为1:1-100:1；步骤8)所述的将凝胶F进行冷冻干燥时间为24-48h；超临界CO2干燥3-5次，每次0.5-2h；步骤9)所述的有机溶剂与凝胶F或凝胶G的体积比为1:1-100:1。The volume ratio of gel A to pure water described in step 3) is 5:1-100:1; the concentration of metal ions in the solution containing target metal ions described in step 4) is 0.01-100 mg/ml, and the condensation The volume ratio of gel B to the solution containing target metal ions is 1:1-100:1; the volume ratio of pure water and gel C described in step 5) is 1:1-100:1; step 6) described The concentration of the reducing agent solution is 0.01-10mol/L, and the volume ratio of the reducing agent solution and the gel D is 1:1-100:1; the volume ratio of the pure water and the gel E described in step 7) is 1:1 -100:1; the freeze-drying time of gel F in step 8) is 24-48h; supercritical CO 2 drying 3-5 times, each 0.5-2h; the organic solvent described in step 9) is mixed with coagulation The volume ratio of gel F or gel G is 1:1-100:1. 8.一种如权利要求1所述的纤维素聚质子型离子液体凝胶/纳米金属复合材料在制备抗菌、催化、环保或制药材料中的应用。8. The application of the cellulose polyprotic ionic liquid gel/nano-metal composite material as claimed in claim 1 in the preparation of antibacterial, catalysis, environmental protection or pharmaceutical materials.
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