CN109092251B - Preparation method of low-concentration high-specific-surface-area metal organogel - Google Patents
Preparation method of low-concentration high-specific-surface-area metal organogel Download PDFInfo
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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Abstract
The invention discloses a preparation method of a low-concentration high-specific-surface-area metal organic gel, belonging to the technical field of preparation of soft material in a gel form. The method takes (E) -4,4'- (azobenzene) diacyl (N, N' - (salicyloyl hydrazine) and zinc acetate dihydrate as raw materials and dimethyl sulfoxide as a solvent to prepare the metal organic gel with low concentration and high specific surface area, the preparation of the gel has the characteristics of low raw material cost, mild synthesis conditions, high yield and the like, and the prepared gel has low gelling concentration (0.073 wt%) and higher specific surface area (3412 m)2g‑1) And good selective adsorption function of dye.
Description
Technical Field
The invention belongs to the technical field of preparation of soft material in a gel form, and particularly relates to a preparation method of a low-concentration metal organic gel with high specific surface area.
Background
The gel is a substance with both solid and liquid characteristics, and plays an important role in production application and basic research. The metal organic gel is one of gels, and the gelation is caused by introducing metal ions to participate in small molecule coordination. Compared with high molecular gel and organic small molecular gel, the rich metal ions and the designability of small molecular structures lead the metal organic gel to have more excellent and rich performances, such as catalysis, molecular recognition, gas storage separation, magnetism and other applications. Meanwhile, the metal organic gel has various performances due to various interactions such as hydrogen bonds, coordination and the like, and can respond to multiple external stimuli. Therefore, the design and development of novel metal organogels are of great significance in searching multifunctional stimulus-responsive materials.
The molecules of the traditional polymer gel and organic gel materials are generally higher in molecular weight, which not only brings difficulties in synthesis, but also leads to higher gel concentration, and causes the increase of production cost. For metal organic gel, the selectivity of metal ions is wide, the design diversity of small molecules is realized, and the utilization rate of gel raw materials can be greatly reduced through the coupling of the metal ions and the small molecules, so that the cost is reduced. However, the introduction of small molecules often leads to a gel system with a large minimum gel formation concentration, and the formation of an invertible gel at a low concentration cannot be realized. Meanwhile, due to the high gelling concentration, the structure of the obtained gel is easy to collapse when the gel is freeze-dried to prepare xerogel, and the low specific surface area is also a prominent problem of related researches. From the angle of molecular design, the invention uses a chelating coordination mode, on one hand, shortens the gelling and aging time of the gel, on the other hand, improves the stability of the gel framework structure, enables the obtained gel to have low gelling concentration and high specific surface area, and preliminarily discusses the selective adsorption capacity of the xerogel to the dye.
Disclosure of Invention
The invention aims to provide a preparation method of a metal organogel with low gelling concentration and high specific surface area, aiming at the problems of high gelling concentration and few types of metal organogels with high specific surface area of organic micromolecule gel. The invention uses simple and easily obtained micromolecular hydrazide to prepare the metal organic gel, and the prepared gel has low gelling concentration, higher specific surface area and good dye selective adsorption function. In addition, the raw materials of the invention are easy to obtain, the price is low, and the method is simple and convenient.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a low-concentration high-specific-surface-area metal organic gel is prepared by taking (E) -4,4'- (azobenzene) diacyl (N, N' - (salicyloyl hydrazine) (L for short) and zinc acetate dihydrate as raw materials and dimethyl sulfoxide (DMSO) as a solvent, and specifically comprises the following steps:
(1) respectively dissolving L and zinc acetate dihydrate in DMSO, uniformly mixing the two solutions to obtain an orange-red mixed solution, and sealing and standing at room temperature for 2 min-24 h to obtain wet gel; the molar ratio of the L to the zinc acetate dihydrate is 1: 2;
(2) and (2) freeze-drying the wet gel obtained in the step (1) to obtain the gel (Zn-L).
The wet gel obtained in the step (1) has a gel mass fraction of 0.073-1.13 wt%.
The structural formula of the (E) -4,4'- (azobenzene) diacyl (N, N' - (salicyloyl hydrazide) is as follows:
The preparation method of the (E) -4,4'- (azobenzene) diacyl (N, N' - (salicyloyl hydrazide) comprises the following steps:
1) carrying out reflux reaction on methyl salicylate and hydrazine hydrate in an absolute ethyl alcohol solvent, and cooling at room temperature to separate out salicyloyl hydrazine;
2) reacting p-nitrobenzoic acid in an alkaline solution containing glucose for 2 days, adding acetic acid until no gas is generated, and filtering and washing to obtain earthy yellow powder, namely 4,4' -azobenzene dicarboxylic acid;
3) 4,4 '-azobenzene dicarboxylic acid and thionyl chloride are subjected to acyl chlorination by taking DMF as a catalyst to obtain 4,4' -azobenzene diacid chloride;
4) using the salicyloyl hydrazine prepared in the step 1) and the 4,4' -azobenzene diacid chloride prepared in the step 3) as reactants, using triethylamine as a catalyst, using DMF as a solvent, carrying out heating reflux reaction, removing the solvent, washing the precipitate with absolute ethyl alcohol, and obtaining orange-red powder, namely (E) -4,4' - (azobenzene) diacyl (N, N ' - (salicyloyl hydrazine).
The invention has the beneficial effects that:
(1) the raw materials are simple and convenient to prepare and low in price; the preparation method of the metal organic gel is simple, the conditions are mild, and the prepared gel has good stability;
(2) compared with the metal organic gel of the same type, the gelling concentration is reduced by 1-2 orders of magnitude; the specific surface area reaches 3412 m2g-1Much larger than most of the reported metal organogels;
(3) the prepared metal organogel has better thermal stability and dye selective adsorption function.
Drawings
FIG. 1: (E) -high resolution mass spectrum of 4,4'- (azobenzene) diacyl (N, N' - (salicyloyl hydrazide);
FIG. 2: (E) -nuclear magnetic hydrogen spectrum of 4,4'- (azobenzene) diacyl (N, N' - (salicyloyl hydrazide);
FIG. 3: the ultraviolet-visible absorption spectrum of the gel Zn-L;
FIG. 4: infrared spectrogram of gel Zn-L;
FIG. 5: dynamic rheology of gel Zn-L;
FIG. 6: scanning electron microscopy of gel Zn-L;
FIG. 7: thermogravimetric plot of gel Zn-L;
FIG. 8: the nitrogen of the gel Zn-L is absorbed and removed from the attached figure;
FIG. 9: the dye of gel Zn-L absorbs the figure.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Synthesis of 4,4' -azobenzene dicarboxylic acid: completely dissolving 10.0 g (60 mmol) of p-nitrobenzoic acid in 200 mL of aqueous solution containing 30.0 g (0.75 mol) of sodium hydroxide, and keeping the temperature at 50 ℃ for standby; then, 150 mL of an aqueous solution containing 63.0 g (0.32 mol) of glucose monohydrate was slowly dropped into the above solution, and the whole reaction was maintained at 50 ℃ for about 2 hours. Naturally cooling to room temperature after the glucose solution is dripped; stirring for 2 days, adding a proper amount of acetic acid until no gas is generated, performing suction filtration, washing a filter cake with a large amount of deionized water, performing vacuum drying at 60 ℃, and weighing to obtain a khaki product with the yield of 5.6 g being about 70%.
Synthesis of 4,4' -azobenzene diacid chloride: 1.0-2.0 g of 4,4' -azobenzene dicarboxylic acid was taken in a 100 mL round-bottomed flask, 1 drop of DMF was added as a catalyst, excess thionyl chloride was added, and the mixture was refluxed at 75 ℃ for 9 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain 4,4' -azobiscarbonyl chloride as a red crystalline powder.
(E) -synthesis of 4,4'- (azobenzene) diacyl (N, N' - (salicyloyl hydrazide): 2.2 g (14.5 mmol) of salicylhydrazide and 0.66 g (6.5 mmol) of triethylamine are first dissolved in 25 mL of dry DMF (which is not further treated here), then 25 mL of DMF solution containing 2.0 g (6.5 mmol) of 4,4' -azobiscarbonyl dichloride is slowly dripped into the solution in the ice bath, when the dripping is finished, the round bottom flask is transferred into an oil bath pot and heated at 90 ℃ for 9 h, after the reaction is finished, cooling to room temperature, vacuum filtering, repeatedly washing the filter cake with ethanol and deionized water, drying at 60 deg.C to obtain 2.3 g of orange red powder with yield of 65.8%, subjecting the product to mass spectrum characterization (see FIG. 1), wherein FIG. 1 shows m/Z peak 537.1529 in negative ion mode, the ratio of the charge to the mass of the target product is 537.1523 in DMSO-d.6The product is subjected to hydrogen spectrum nuclear magnetism characterization in a reagent (400 MHz, DMSO-d)6Fig. 2), the following (/ ppm) was assigned to each group of peaks: 11.90 (s, 1H), 10.91 (s, 1H), 10.75 (s, 1H), 8.18 (d,J = 8.2 Hz, 2H), 8.08 (d, J = 8.2 Hz, 2H), 7.96 (d, J = 7.5 Hz, 1H), 7.48 (t, J = 7.6 Hz, 1H), 6.99 (dd, J = 11.7, 7.9 Hz, 2H) 。
example 1
Preparation of Metal organogel (Zn-L) (example gelling concentration 0.073 wt.)
(1) Preparation of Wet gels
5mL of 1.66X 10-3DMSO solution of M in L with 5mL of 3.32X 10-3Uniformly mixing the M solution of zinc acetate dihydrate in DMSO, and standing for 1 day to obtain inverted gel; of gelsThe concentration is 0.073 wt%;
(2) preparation of xerogels
And (2) shaking the wet gel in the step (1), dripping the wet gel into liquid nitrogen drop by drop, quickly freezing, and quickly transferring to a precooled freeze dryer for freeze drying to obtain dry gel.
Example 2
Preparation of Metal organogel (Zn-L) (example gelling concentration 1.13 wt.)
(1) Preparation of Wet gels
Uniformly mixing 5mL of 0.025M L DMSO solution and 5mL of 0.05M zinc acetate dihydrate DMSO solution, and standing for 2 minutes to obtain an inverted gel; the concentration of the gel was 1.13 wt%;
(2) preparation of xerogels
And (2) shaking the wet gel in the step (1), dripping the wet gel into liquid nitrogen drop by drop, quickly freezing, and quickly transferring to a precooled freeze dryer for freeze drying to obtain dry gel.
Example 3
Preparation of Metal organogel (Zn-L) (example gelling concentration 0.28 wt.)
(1) Preparation of Wet gels
5mL of 6.25X 10-3Uniformly mixing the DMSO solution of the L of the M with 5mL of DMSO solution of 0.0125M zinc acetate dihydrate, and standing for 5 minutes to obtain an inverted gel; the concentration of the gel was 0.28 wt%;
(2) preparation of xerogels
And (2) shaking the wet gel in the step (1), dripping the wet gel into liquid nitrogen drop by drop, quickly freezing, and quickly transferring to a precooled freeze dryer for freeze drying to obtain dry gel.
Product characterization
(1) Ultraviolet-visible absorption spectrum characterization of metal organogel Zn-L
The characterization instrument of the ultraviolet visible absorption spectrum of the metal organic gel Zn-L is a Perkin-Elemer Lambda 900 spectrometer. The testing range is 250 nm-650 nm, and the step length is 1 nm; concentration of gel as H6Calculation of the concentration of L, H6The concentration of L was 4.16×10-5M, metal organogel Zn-L concentration is diluted to 4.16X 10-5And M. As can be seen from FIG. 3, the new absorption peak appears in the product in the range of 400-650 nm, which can be attributed to H6L is a charge transfer transition generated after coordination with zinc ions.
(2) Infrared spectrum characterization of metal organogel Zn-L
The characterization instrument of the infrared Spectrum of the metal organogel Zn-L is a Perkin-Elmer Spectrum-2000 FTIR spectrometer. The test range is 4000 cm-1-400 cm-1ATR mode test is adopted. H6The L is dried powder, and the metal organogel Zn-L is dried gel processed by freeze drying. As can be seen from FIG. 4, the product is 3400 cm-1-3100 cm-1The number of vibration absorption peaks in the range was decreased and the intensity was weakened, indicating that H6Part of active O-H and N-H protons in L are removed due to the coordination of O, N atoms and zinc ions; at 1652 cm-1-1606 cm-1The peak of vibration belonging to carbonyl group is red-shifted to 1598 cm-1Here, the coordination of the carbonyl group to the zinc ion is illustrated.
(3) Rheological characterization of Metal organogels Zn-L
Rheological characterization the instrument used was a HAAKE Rheostress 6000 rheometer. The experimental temperature was 25.00 ℃. The test mode is a dynamic mode. Fig. 5 a is a dynamic strain amplitude modulus diagram, and fig. 5 b is a dynamic frequency sweep modulus diagram. As can be seen from a in FIG. 5, the linear viscoelastic region is 0.001% -11%; the storage modulus G 'is greater than the loss modulus G' when the strain is less than 11%, and the storage modulus G 'is less than the loss modulus G' when the strain is more than 11%, i.e. the stress at the transformation point is 11%. B in FIG. 5 shows that the storage modulus G 'is greater than the loss modulus G' when the frequency is less than 14 Hz; when the frequency is greater than 14HZ, G' and G ″ both begin to increase and tend to coincide.
(4) Morphology characterization of metal organogel Zn-L
The appearance characterization instrument of the metal organogel Zn-L is a Nova NanoSEM 230 field emission scanning electron microscope. The test product employed a Zn-L xerogel. Preparing a sample: taking a small piece of xerogel by using forceps, and lightly rubbing the xerogel on the surface of the conductive adhesive; then, the mixture was blown 3 times with an ear washing ball, and then sprayed with gold for 1 minute. As can be seen from fig. 6, the xerogel has a fibrous structure, the diameter of the fiber is between tens of nanometers and hundreds of nanometers, and the length can reach tens of micrometers.
(5) Thermal stability characterization of Metal organogels Zn-L
The characterization instrument for the thermal stability of the metal organogel Zn-L is a TGA/DSC 3+ synchronous thermal analyzer. The test range is 30-800 ℃, and the heating rate is 10 ℃/min. The test product employed a freeze-dried treated xerogel. As can be seen from FIG. 7, at temperatures below 400 deg.C, the xerogel loses weight primarily as solvent molecules are removed; above 400 ℃, the xerogel structure begins to break down.
(6) Characterization of specific surface area of Metal organogel Zn-L
The appearance characterization instrument of the metal organogel Zn-L is an asap2460 specific surface area and porosity analyzer. The test product was a freeze-dried treated xerogel. The dosage is 49.0 mg, and the activation condition is vacuum treatment at 350 ℃ for 12 hours. The Zn-L xerogel has a specific surface area of 3412 m2g-1。
And (3) functional characterization of a product:
(1) characterization of dye adsorption Properties of Metal organogels Zn-L
The dye adsorption performance characterization instrument of the metal organogel Zn-L is the same as that in the step (1). The product used was a freeze-dried Zn-L xerogel. The test range is 250 nm-800 nm, and the step size is 1 nm. The dosage of the xerogel is between 5.0 mg and 8.0 mg; the dyes used were rhodamine b, methylene blue, methyl violet, methyl orange and alizarin R, respectively. The concentration of the dye is 0.001M, the solvent is deionized water, and the dosage is 1.0-2.0 mL. Before testing, the dry gel is dispersed in corresponding dye solution, after standing for 2 days, the supernatant fluid is centrifuged and taken out, and the ultraviolet visible absorption spectrum is tested under the same dilution times as the dye solution without adsorption treatment. As shown in fig. 9, first, xerogel has better adsorption properties for positively charged dyes; secondly, the xerogel has a stronger adsorption capacity to methylene blue with a smaller molecular volume. Indicating that the gel is selective not only for dye charge, but also for dye molecular size.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (4)
1. A preparation method of a low-concentration metal organic gel with high specific surface area is characterized by comprising the following steps: the compound is prepared by taking (E) -4,4'- (azobenzene) diacyl (N, N' - (salicyloyl hydrazine)) and zinc acetate dihydrate as raw materials and dimethyl sulfoxide as a solvent; the (E) -4,4'- (azobenzene) diacyl (N, N' - (salicyloyl hydrazide)) has a structural formula as follows:
2. The method for preparing a low concentration high specific surface area metal organogel according to claim 1, wherein: the preparation method of the (E) -4,4'- (azobenzene) diacyl (N, N' - (salicyloyl hydrazide)) comprises the following steps:
1) carrying out reflux reaction on methyl salicylate and hydrazine hydrate in an absolute ethyl alcohol solvent, and cooling at room temperature to separate out salicyloyl hydrazine;
2) reacting p-nitrobenzoic acid in an alkaline solution containing glucose for 2 days, adding acetic acid until no gas is generated, and filtering and washing to obtain earthy yellow powder, namely 4,4' -azobenzene dicarboxylic acid;
3) 4,4 '-azobenzene dicarboxylic acid and thionyl chloride are subjected to acyl chlorination by taking DMF as a catalyst to obtain 4,4' -azobenzene diacid chloride;
4) using the salicyloyl hydrazine prepared in the step 1) and the 4,4' -azobenzene diacid chloride prepared in the step 3) as reactants, using triethylamine as a catalyst, using DMF as a solvent, carrying out heating reflux reaction, removing the solvent, washing the precipitate with absolute ethyl alcohol, and obtaining orange-red powder, namely (E) -4,4' - (azobenzene) diacyl (N, N ' - (salicyloyl hydrazide)).
3. The process for the preparation of a metal organogel according to claim 1, characterized in that: the method specifically comprises the following steps:
(1) respectively dissolving (E) -4,4'- (azobenzene) diacyl (N, N' - (salicyloyl hydrazine)) and zinc acetate dihydrate into dimethyl sulfoxide, uniformly mixing the two obtained solutions to obtain an orange-red mixed solution, and sealing and standing at room temperature for 2 min-24 h to obtain wet gel; the molar ratio of the (E) -4,4'- (azobenzene) diacyl (N, N' - (salicyloyl hydrazide)) to the zinc acetate dihydrate is 1: 2;
(2) and (2) freeze-drying the wet gel obtained in the step (1) to obtain the metal organic gel.
4. The process for the preparation of a metal organogel according to claim 3, characterized in that: the wet gel obtained in the step (1) has a gel mass fraction of 0.073-1.13 wt%.
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