CN110104672B - Preparation method of silicon-containing carbonate type hydrotalcite-like ultrathin sheet - Google Patents

Preparation method of silicon-containing carbonate type hydrotalcite-like ultrathin sheet Download PDF

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CN110104672B
CN110104672B CN201910405433.8A CN201910405433A CN110104672B CN 110104672 B CN110104672 B CN 110104672B CN 201910405433 A CN201910405433 A CN 201910405433A CN 110104672 B CN110104672 B CN 110104672B
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侯万国
于淼
杜娜
李海平
宋淑娥
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Abstract

The invention discloses a preparation method of a silicon-containing carbonate hydrotalcite-like ultrathin sheet. Will contain Si4+And mixed salt solution of divalent and trivalent metal ions and Na2CO3And adding the mixed alkali solution of NaOH and the mixed alkali solution into the reactor while stirring, and controlling the pH of the reaction system to be 9-11 by adjusting the relative addition rate of the mixed alkali solution and the NaOH. Wherein the divalent metal ion is Mg2+、Co2+、Ni2+、Cu2+Or Zn2+The trivalent metal ion is Al3+、Cr3+Or Fe3+. Prepared Si-CO3The HTlc ultrathin sheet is less than 3 nanometers in thickness and consists of 2-4 hydrotalcite-like crystal layers; si4+The molar ratio of the metal ions to the metal ions is 0.16 to 0.27. The preparation method has the advantages of simple process, mild condition, low cost, environmental friendliness, easiness in industrialization and the like. Prepared Si-CO3the-HTlc ultrathin sheet has important application prospect in the fields of catalysis, energy storage, flame retardants, composite materials and the like.

Description

Preparation method of silicon-containing carbonate type hydrotalcite-like ultrathin sheet
Technical Field
The invention discloses a preparation method of a silicon-containing carbonate hydrotalcite-like ultrathin sheet, belonging to the technical field of inorganic layered materials.
Background
Hydrotalcite-like compound (HTlc) is an inorganic layered material, the structure positive charge of the layer sheet is carried out, the interlayer belt can exchange anions to balance the structure positive charge of the layer sheet, and the hydrotalcite-like compound (HTlc) has wide application prospect in the fields of catalysts, electromagnetic materials, energy storage materials, medical carriers, ion exchange and adsorbents, organic-inorganic hybrid materials, flame retardants, hydrogel and the like. HTlc generally consists of divalent and trivalent metal cations, with the recent appearance of tetravalent cations such as Zr4+、Se4+、Ti4+、V4+And Sn4+HTlc of (1). However, the prepared HTlc containing the tetravalent metal cation is thick plate particles consisting of 20 crystal layers or more, and even macroscopic irregular (micron-scale stone-shaped) particles. Research shows that when HTlc exists in a single-layer sheet or ultrathin sheet (containing 2-5 crystal layers), the HTlc has more excellent performance than thick sheets and macroscopic particles, and simultaneously, the single-layer sheet or the ultrathin sheet can also be used as an assembly element to construct a composite functional material becauseBut is of great interest.
HTlc may be named according to its interlayer anion type, e.g., CO3 2-、NO3 -Or Cl-When called carbonate form (abbreviated as CO)3HTlc), nitrate type (NO)3-HTlc) or chloride ion type (Cl-HTlc). The preparation technique of HTlc has been widely studied. For example, chinese patent document CN107555491A discloses a method for preparing nitrate radical intercalated cobalt aluminum hydrotalcite in one step by coprecipitation, which uses acetic acid-sodium acetate buffer solution to stably control the pH value of the preparation system to 4.00-5.00, uses cobalt nitrate hexahydrate and aluminum nitrate nonahydrate as raw materials, sodium hydroxide as precipitant, uses deionized water as solvent and detergent, and prepares the intercalated cobalt aluminum hydrotalcite as thick flake NO-containing hydrotalcite by solution preparation, coprecipitation, hydrothermal treatment, washing, suction filtration and drying3-HTlc particles. For another example, chinese patent document CN107651712A discloses a method for preparing nitrate radical intercalation nickel aluminum hydrotalcite in one step by coprecipitation, which uses acetic acid-sodium acetate buffer solution to stably control the pH value of the preparation system at 4.00-5.00, uses nickel nitrate hexahydrate and aluminum nitrate nonahydrate as raw materials, sodium hydroxide as precipitant, and deionized water as solvent and detergent, and prepares nitrate radical intercalation nickel aluminum hydrotalcite, which is also thick-sheet NO intercalation nickel aluminum hydrotalcite3-HTlc particles. Meanwhile, the prior data disclose the preparation method of HTlc ultrathin slice containing divalent and trivalent metal ions, which is realized by using an organic solvent such as formamide, dimethyl sulfoxide, chloroform or toluene and the like as a medium under the assistance of a surfactant (or a surface active substance) and by adopting a top-down stripping method or a bottom-up chemical synthesis method. However, the surfactant is difficult to remove from the product, and the organic solvent used is toxic, which limits its practical application. In addition, these processes can only produce NO containing divalent and trivalent metal ions3-HTlc and Cl-HTlc ultrathin flakes, unable to produce CO3-HTlc ultra-flakes, preparation of CO containing a tetravalent cation3HTlc ultra-thin sheets with even more protrusionsAnd (4) war property.
Disclosure of Invention
Aiming at the defects of the prior preparation technology, the invention provides a silicon-containing carbonate HTlc (abbreviated as Si-CO)3-HTlc) stable state coprecipitation preparation of ultrathin flakes. The method does not need the assistance of surface active substances or organic solvents, has simple synthesis process, mild conditions, low cost, high and stable yield, is environment-friendly and is easy to industrialize.
A preparation method of a silicon-containing carbonate hydrotalcite-like ultrathin sheet comprises the following preparation steps:
A. dissolving soluble divalent metal salt and trivalent metal salt in water to prepare mixed salt solution;
B. mixing SiCl4Adding the mixture into the mixed salt solution obtained in the step A, and uniformly stirring to obtain a cation mixed solution;
C. NaOH and Na are prepared2CO3The mixed aqueous alkali solution of (1) for standby;
D. c, dropwise adding and mixing the cation mixed solution obtained in the step B and the mixed alkali water solution obtained in the step C under stirring, and controlling the pH of the reaction system to be 9-10 by adjusting the relative dropwise adding rate of the cation mixed solution and the mixed alkali water solution; stirring for reaction for 5-15 minutes, filtering, washing with water to be neutral, and filtering to obtain a gel product;
E. d, dispersing the gel product obtained in the step D in water, and performing ultrasonic dispersion to obtain Si-CO3-HTlc ultra-thin flake dispersion; or, freezing and drying the gel product obtained in the step D to obtain Si-CO3-HTlc ultrathin flakes.
According to the present invention, it is preferable that, of the soluble divalent metal salt and trivalent metal salt described in step a: the divalent metal ion being Mg2+、Co2+、Ni2+、Cu2+And Zn2+One of (1); the trivalent metal ion being Al3+、Cr3+And Fe3+One of (1);
preferably, the soluble divalent metal salt and trivalent metal salt are chlorides or nitrates;
preferably, the ratio of the divalent metal salt to the trivalent metal salt is: the molar ratio of the divalent metal ions to the trivalent metal ions is 2/1-4/l, preferably 3/1;
preferably, in the mixed salt solution, the total concentration of the divalent metal salt and the trivalent metal salt is 0.35-0.48 mol/L, and preferably 0.44 mol/L.
According to the present invention, preferably, SiCl is used in the step B4Adding amount: added SiCl4The ratio of the number of moles of (a) to the number of moles of the trivalent metal salt is 0.25 to 1.0:1, preferably 0.5: 1.
According to the invention, it is preferred that NaOH and Na are mixed in the aqueous alkaline solution in step C2CO3In a molar ratio of 1: (0.4 to 0.8), and more preferably 1: 0.5. Wherein NaOH is used as a precipitant to provide OH-，Na2CO3Providing interlayer anion CO3 2-. If the proportion of NaOH is too large, MgOH and Al (OH) are easily obtained3Mixtures (without HTlc structure); if Na2CO3The ratio of (A) is too large, and a carbonate mixture is easily obtained.
According to the present invention, it is preferable that the ratio of the dropping rates of the mixed cation solution and the mixed alkali aqueous solution in the step D is 1 (0.7 to 0.9). If the dropping speed of the mixed alkaline aqueous solution is too slow, namely the pH value of the reaction system is too low, uneven precipitation is caused, HTlc and Al (OH) are formed3A mixture of (a); if the dropping speed of the mixed aqueous alkali is too fast, namely the pH value of the reaction system is too high, carbonate impurities (namely non-pure phase HTlc products) are easy to generate.
Preferably, after the mixed alkali is added dropwise in the step D, the mixture is stirred for reaction for 10 minutes and then filtered. The reaction time is too long, and thick particles are easy to form.
The thickness of the silicon-containing carbonate group type hydrotalcite-like ultrathin sheet prepared by the method is less than 3 nanometers, and the silicon-containing carbonate group type hydrotalcite-like ultrathin sheet is composed of 2-4 hydrotalcite-like crystal layers; prepared Si-CO3In HTlc, Si4+The molar ratio of the metal ions to the metal ions is 0.16-0.27: 1.
The principle of the invention is as follows:
the method disclosed by the invention is characterized in that under the optimal condition, a pure-phase HTlc ultrathin sheet is formed by controlling the nucleation rate and the growth time through a coprecipitation process, the sheet-sheet accumulation is not generated due to the electrostatic repulsion effect, and the ultrathin sheet hydrogel is formed after washing. The ultra-thin flake dispersion can be maintained in an ultra-thin flake state by directly dispersing the ultra-thin flake dispersion in water without hydrothermal treatment (the hydrothermal treatment causes flake-flake accumulation to form thick flake particles); or directly freeze-drying to obtain ultrathin powder. Particularly, the storage period of the ultrathin hydrogel is not longer than two days, and the ultrathin hydrogel is stored below 30 ℃, otherwise thick particles are easily formed.
Si-CO prepared by the method of the invention3-HTlc ultrathin flake characterization includes: x-ray diffraction (XRD), Transmission Electron Microscope (TEM), Atomic Force Microscope (AFM), Scanning Electron Microscope (SEM), and BET specific surface area measurement.
The invention has the outstanding advantages that:
(1) the invention adopts a steady-state coprecipitation method to synthesize Si-CO3The HTlc ultrathin sheet overcomes the defect that the carbonate hydrotalcite ultrathin sheet cannot be successfully prepared by the traditional method, increases the types of the HTlc ultrathin sheet and can expand the application range of the HTlc ultrathin sheet;
(2) Si-CO prepared by the invention3The thickness of the-HTlc ultrathin sheet is less than 3 nanometers, the specific surface area is large and can reach 266m2More than g;
(3) the preparation method adopted by the invention has simple process, can successfully prepare the carbonate ultra-thin sheet without using an organic solvent, is environment-friendly, has mild reaction conditions and low cost, and is easy for industrialization;
(4) Si-CO prepared by the invention3The HTlc ultrathin sheet has important application prospect in the fields of catalysis, energy storage, flame retardants, composite materials and the like.
Drawings
FIG. 1 shows Si-CO prepared in example 13XRD pattern of HTlc ultrathin flakes.
FIG. 2 shows Si-CO prepared in example 13TEM images of HTlc ultrathin sections.
FIG. 3 shows Si-CO prepared in example 13AFM images of HTlc ultrathin flakes.
FIG. 4 shows Si-CO prepared in example 13SEM image of HTlc ultrathin flakes.
FIG. 5 shows Si-CO prepared in example 13-map of specific surface area of HTlc ultrathin flakes.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example l
A. 12.72g (0.090mol) of ZnCl2And 7.52g (0.030mol) AlCl3·6H2Dissolving O in 270mL of water, and uniformly stirring to obtain a mixed salt solution;
B. 1.80mL (0.015mol) of SiCl4Dropwise adding the liquid into the mixed salt solution obtained in the step A while stirring to obtain a cation mixed solution;
C. 3.60g (0.090mol) of solid NaOH and 6.36g (0.060mol) of solid Na are mixed2CO3Dissolving in 300mL of water, and uniformly stirring to prepare a mixed alkali solution;
D. simultaneously dripping the cation mixed solution obtained in the step B and the mixed alkali solution obtained in the step C into a beaker, stirring and controlling the pH value of the reaction system to be about 10 by adjusting the relative dripping rate of the cation mixed solution and the mixed alkali solution; after the dropwise addition is finished, stirring for 10 minutes at room temperature, filtering, washing to be neutral by water, and filtering again to obtain a gel product;
E. dispersing the gel product in water, and ultrasonically dispersing for 10 minutes to obtain Si-CO3-HTlc ultra-thin flake dispersion; freeze drying the gel product to obtain Si-CO3-HTlc ultrathin flakes.
Elemental analysis of the product of this example showed the chemical composition [ Zn ]0.59Al0.25Si0.16(OH)2](CO3)0.285(ii) a The product was analyzed by XRD (see FIG. 1), TEM (see FIG. 2), AFM (see FIG. 3) and SEM (see FIG. 4) to prove to be ultrathin; the specific surface area is 266m measured by a BET method2G (see FIG. 5), significantly larger than the specific surface area of conventional HTlc particles (10 m)2/g)。
Example 2
A. 22.05g (0.086mol) of Mg (NO)3)2·6H2O and 5.55g (0.023mol) AlCl3·6H2Dissolving O in 270mL of water, and uniformly stirring to obtain a mixed salt solution;
B. 1.67mL (0.015mol) of SiCl4Dropwise adding the liquid into the mixed salt solution obtained in the step A while stirring to obtain a mixed cation solution;
C. 3.60g (0.090mol) of solid NaOH and 6.36g (0.060mol) of solid Na are mixed2CO3Dissolving in 300mL of water, and uniformly stirring to prepare a mixed alkali solution;
D. dropping the mixed cation solution obtained in the step B and the mixed alkali solution obtained in the step C into a beaker at the same time, stirring and controlling the pH value of the reaction system to be about 10 by adjusting the relative dropping rate of the mixed cation solution and the mixed alkali solution; after the dropwise addition is finished, stirring for 15 minutes at room temperature, filtering, washing to be neutral by water, and filtering again to obtain a gel product;
E. freeze-drying the gel product to obtain Mg-Al-Si-CO3-HTlc ultrathin flakes.
Example 3
A. 19.75g (0.083mol) of CoCl2·6H2O and 16.97g (0.042mol) Fe (NO)3)3·9H2Dissolving O in 270mL of water, and uniformly stirring to obtain a mixed salt solution;
B. 2.30mL (0.020mol) SiCl4Dropwise adding the liquid into the mixed salt solution obtained in the step A while stirring to obtain a mixed cation solution;
C. 3.60g (0.090mol) of solid NaOH and 6.36g (0.060mol) of solid Na are mixed2CO3Dissolving in 300mL of water, and uniformly stirring to prepare a mixed alkali solution;
D. dropping the mixed cation solution obtained in the step B and the mixed alkali solution obtained in the step C into a beaker at the same time, stirring and controlling the pH value of the reaction system to be about 10 by adjusting the relative dropping rate of the mixed cation solution and the mixed alkali solution; after the dropwise addition is finished, stirring for 5 minutes at room temperature, filtering, and washing with water to be neutral to obtain a gel product;
E. freeze-drying the gel product to obtain Co-Fe-Si-CO3-HTlc ultrathin flakes.
Example 4
A. 19.25g (0.081mol) of NiCl are introduced2·6H2O and 10.80g (0.027mol) Cr (NO)3)3·9H2Dissolving O in 270mL of water, and uniformly stirring to obtain a mixed salt solution;
B. 3.11mL (0.027mol) of SiCl4Liquid, method for producing the same and use thereofDropwise adding the mixed solution into the mixed salt solution obtained in the step A while stirring to obtain a mixed cation solution;
C. 3.60g (0.090mol) of solid NaOH and 6.36g (0.060mol) of solid Na are mixed2CO3Dissolving in 300mL of water, and uniformly stirring to prepare a mixed alkali solution;
D. dropping the mixed cation solution obtained in the step B and the mixed alkali solution obtained in the step C into a beaker at the same time, stirring and controlling the pH value of the reaction system to be about 10 by adjusting the relative dropping rate of the mixed cation solution and the mixed alkali solution; after the dropwise addition is finished, stirring for 10 minutes at room temperature, filtering, and washing with water to be neutral to obtain a gel product;
E. freeze-drying the gel product to obtain Ni-Cr-Si-CO3-HTlc ultrathin flakes.
Example 5
A. 15.35g (0.090mol) of CuCl2·2H2O and 6.03g (0.025mol) AlCl3·6H2Dissolving O in 270mL of water, and uniformly stirring to obtain a mixed salt solution;
B. 2.65mL (0.023mol) of SiCl4Dropwise adding the liquid into the mixed salt solution obtained in the step A while stirring to obtain a mixed cation solution;
C. 3.60g (0.090mol) of solid NaOH and 6.36g (0.060mol) of solid Na are mixed2CO3Dissolving in 300mL of water, and uniformly stirring to prepare a mixed alkali solution;
D. dropping the mixed cation solution obtained in the step B and the mixed alkali solution obtained in the step C into a beaker at the same time, stirring and controlling the pH value of the reaction system to be about 10 by adjusting the relative dropping rate of the mixed cation solution and the mixed alkali solution; after the dropwise addition is finished, stirring for 10 minutes at room temperature, filtering, and washing with water to be neutral to obtain a gel product;
E. freeze-drying the gel product to obtain Cu-Al-Si-CO3-HTlc ultrathin flakes.
Comparative example 1
A. 12.72g (0.090mol) of ZnCl2And 7.52g (0.030mol) AlCl3·6H2Dissolving O in 270mL of water, and uniformly stirring to obtain a mixed salt solution;
B. 1.80mL (0.015mol) of SiCl4Dropwise adding the liquid into the mixed salt solution obtained in the step A under stirring to obtain cation mixtureA solution;
C. 3.60g (0.090mol) of solid NaOH and 6.36g (0.060mol) of solid Na are mixed2CO3Dissolving in 300mL of water, and uniformly stirring to prepare a mixed alkali solution;
D. simultaneously dripping the cation mixed solution obtained in the step B and the mixed alkali solution obtained in the step C into a beaker, stirring and controlling the pH value of the reaction system to be about 10 by adjusting the relative dripping rate of the cation mixed solution and the mixed alkali solution; after the dropwise addition is finished, stirring for 24 hours at room temperature, filtering, washing to be neutral by water, and filtering again to obtain a filter cake;
E. adding the filter cake into water, and the ultra-thin dispersion cannot be obtained because the filter cake cannot be uniformly dispersed by ultrasonic.
Since stirring was carried out at room temperature for another 24 hours in step D, the reaction time (crystal nucleus growth time) was too long, and macroscopic particles were formed.
Comparative example 2
A. 10.50g (0.077mol) of ZnCl are introduced2And 6.27g (0.026mol) AlCl3·6H2Dissolving O in 270mL of water, and uniformly stirring to obtain a mixed salt solution;
B. 3.80mL (0.032mol) of SiCl4Dropwise adding the liquid into the mixed salt solution obtained in the step A while stirring to obtain a cation mixed solution;
C. 3.60g (0.090mol) of solid NaOH and 6.36g (0.060mol) of solid Na are mixed2CO3Dissolving in 300mL of water, and uniformly stirring to prepare a mixed alkali solution;
D. simultaneously dripping the cation mixed solution obtained in the step B and the mixed alkali solution obtained in the step C into a beaker, stirring and controlling the pH value of the reaction system to be about 10 by adjusting the relative dripping rate of the cation mixed solution and the mixed alkali solution; after the dropwise addition is finished, stirring for 10 minutes at room temperature, filtering, washing to be neutral by water, and filtering again to obtain a gel product;
E. after freeze-drying the gel-like product, the product is not hydrotalcite-like.
Because of SiCl4Too large an amount of addition forms SiO2And (3) impurity phase.
Comparative example 3
A. 12.72g (0.090mol) of ZnCl2And 7.52g (0.030mol) AlCl3·6H2O dissolved in 270mL of waterStirring uniformly to obtain a mixed salt solution;
B. 1.80mL (0.015mol) of SiCl4Dropwise adding the liquid into the mixed salt solution obtained in the step A while stirring to obtain a cation mixed solution;
C. 3.60g (0.090mol) of solid NaOH and 6.36g (0.060mol) of solid Na are mixed2CO3Dissolving in 300mL of water, and uniformly stirring to prepare a mixed alkali solution;
D. simultaneously dripping the cation mixed solution obtained in the step B and the mixed alkali solution obtained in the step C into a beaker, stirring, controlling the pH value of the reaction system to be about 4 by adjusting the relative dripping rate of the cation mixed solution and the mixed alkali solution, stirring for 10 minutes at room temperature after dripping is finished, filtering, washing with water to be neutral, and filtering again to obtain a gel product;
E. after freeze-drying the gel-like product, the product is not hydrotalcite-like.
Due to the low pH, an inhomogeneous precipitation occurs, Al (OH) being formed3And (3) impurity phase.

Claims (8)

1. The preparation method of the silicon-containing carbonate group type hydrotalcite-like ultrathin sheet comprises the following steps of (1) preparing a silicon-containing carbonate group type hydrotalcite-like ultrathin sheet with the thickness of less than 3 nanometers, wherein the silicon-containing carbonate group type hydrotalcite-like ultrathin sheet consists of 2-4 hydrotalcite-like crystal layers; in the prepared silicon-containing carbonate hydrotalcite-like ultrathin sheet, Si4+The molar ratio of the metal ions to the metal ions is 0.16-0.27: 1;
the preparation method comprises the following steps:
A. dissolving soluble divalent metal salt and trivalent metal salt in water to prepare mixed salt solution;
B. mixing SiCl4Adding the mixture into the mixed salt solution obtained in the step A, and uniformly stirring to obtain a cation mixed solution; the SiCl4Adding amount: added SiCl4The ratio of the number of moles of the trivalent metal salt to the number of moles of the trivalent metal salt is 0.25 to 1.0: 1;
C. NaOH and Na are prepared2CO3The mixed aqueous alkali solution of (1) for standby;
D. c, dropwise adding and mixing the cation mixed solution obtained in the step B and the mixed alkali water solution obtained in the step C under stirring, and controlling the pH of the reaction system to be 9-10 by adjusting the relative dropwise adding rate of the cation mixed solution and the mixed alkali water solution; stirring for reaction for 5-15 minutes, filtering, washing with water to be neutral, and filtering to obtain a gel product;
E. d, dispersing the gel product obtained in the step D in water, and performing ultrasonic dispersion to obtain a silicon-containing carbonate hydrotalcite-like ultrathin sheet dispersion; or, freezing and drying the gel product obtained in the step D to obtain the silicon-containing carbonate group type hydrotalcite-like ultrathin flake powder.
2. The method for preparing the ultrathin hydrotalcite-like sheet containing silicon carbonate according to claim 1, wherein in the soluble divalent metal salt and trivalent metal salt in step a: the divalent metal ion being Mg2+、Co2+、Ni2+、Cu2+And Zn2+One of (1); the trivalent metal ion being Al3+、Cr3+And Fe3+One kind of (1).
3. The method for preparing the ultrathin hydrotalcite-like sheet containing silicon carbonate according to claim 2, wherein the soluble divalent metal salt and trivalent metal salt are chlorides or nitrates.
4. The method for preparing the silicon-containing carbonate hydrotalcite ultrathin sheet according to claim 2, wherein the ratio of the divalent metal salt to the trivalent metal salt is as follows: the molar ratio of the divalent to trivalent metal ions is 2/1-4/l.
5. The method for preparing the ultrathin hydrotalcite-like sheet containing silicon carbonate according to claim 1, wherein the total concentration of the divalent metal salt and the trivalent metal salt in the mixed salt solution is 0.48 to 0.35 mol/L.
6. The method for preparing the silicon-containing carbonate hydrotalcite-like ultrathin sheet according to claim 1, wherein NaOH and Na are mixed in the aqueous alkali solution in the step C2CO3In a molar ratio of 1: (0.4-0.8).
7. The method for preparing the silicon-containing carbonate hydrotalcite ultrathin sheet according to claim 1, wherein the ratio of the dropping rates of the cation mixed solution and the mixed alkaline aqueous solution in step D is 1 (0.7-0.9).
8. The method for preparing the silicon-containing carbonate hydrotalcite ultrathin sheet according to claim 1, wherein the step D is carried out by adding the mixed alkali dropwise, stirring for reaction for 10 minutes, and filtering.
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