CN110156059B - Preparation method of light-driven calcium carbonate with layered structure - Google Patents
Preparation method of light-driven calcium carbonate with layered structure Download PDFInfo
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Abstract
The invention relates to a preparation method of calcium carbonate with a layered structure, which is characterized by comprising the following steps: 1) dissolving anhydrous calcium chloride in deionized water, and stirring to obtain a clear and transparent solution A; 2) dissolving rhodamine B in deionized water, and stirring to obtain a clear transparent solution B; 3) adding the solution B into the solution A, adding methanol, continuously keeping the temperature of the solution at 20-35 ℃, and stirring for 10-15min to obtain a clear and transparent solution C; 4) taking a proper amount of solution C as crystallization mother liquor; and (3) placing the crystallization mother liquor in a closed container, and standing and crystallizing the crystallization mother liquor in the carbon dioxide atmosphere and under the illumination of a xenon lamp to obtain the layered calcium carbonate. The calcium carbonate prepared by the method is of a regular hexagonal structure, and the layered stacking structure of the calcium carbonate is very close to a natural shell structure. The reaction system has mild reaction, easily controlled reaction conditions, strong operability, high repeatability and good calcium carbonate purity, and provides a simple and mild method for artificially synthesizing layered calcium carbonate.
Description
Technical Field
The invention relates to a preparation method of calcium carbonate with a layered structure, belongs to the field of material preparation, and particularly relates to a preparation method of calcium carbonate with a layered structure under the drive of light.
Background
It is well known that the composition and structure of a material determine the properties of the material, which affect the use of the material. New materials and new appearances are always hot spots of research in the scientific community, can provide solutions for many problems, and are also one of the main directions of the development of the science and technology in the 21 st century. The research on the structure and the shape of the material is a deeper marching towards the understanding and the application of the human body to the material properties. The study of experience from nature and the application thereof to artificial systems are research hotspots in nearly two decades, various phenomena in the nature also provide infinite inspiration for the design and preparation of advanced materials, the structure forming process of natural substances is the result of billion year evolution and natural selection, and generally, the natural substances can complete the structure forming process at room temperature to grow delicate microstructures to obtain unique functions. However, the modern industrial method for preparing materials with similar performance often needs high temperature and other conditions. The formation process, composition and structure mechanism of the natural biological material are important inspiration for the design and preparation of modern materials.
Photosynthesis is considered as the most important chemical reaction on the earth, and is the basis of survival of the biological world, the photosynthesis is a biosynthesis process finished at room temperature, the core of the photosynthesis is light capture and excitation, electron transmission and redox reaction on active sites of two photosystems (photosystem I and photosystem II), the current artificial photosynthesis mainly focuses on hydrogen production by photolysis, carbon dioxide reduction, nitrogen fixation, organic matter synthesis and the like, and the research of combination of the photosynthesis and inorganic minerals is still few. The transmission of photoelectrons and holes will increase the energy transmission path of the original mineralization system, and further lead to the change of the mineralization kinetic process, therefore, the auxiliary driving force of the light energy can be utilized to change the path and the morphology of the mineral formation, so as to improve the performance of the material.
Calcium carbonate is an important biomineralization material and is a biomineralization material which is researched more at present, and has higher research value and application potential in the scientific and industrial fields due to the special optical properties, mechanical properties and the like. In recent years, the regulation of the size and morphology of calcium carbonate has become a key to its widespread use. The shape of the existing biomimetic synthesized calcium carbonate has various shapes such as square, spherical, needle-shaped, sheet and the like, and calcium carbonate products with different crystal forms and shapes have different application fields and functions. The calcium carbonate with the ordered layered structure is synthesized by people inspired by the ordered layered structure and the excellent mechanical property of shells, and is mainly regulated and controlled by utilizing polymeric macromolecules or natural proteins in the existing research of preparing the calcium carbonate with the ordered layered structure. For example, Shushuhong et al utilizes double hydrophilic block copolymer to regulate calcium carbonate (Langmuir,2006,22(14): 6125-. However, these do not give a particularly regular lamellar structure and the preparation times are long and the process is cumbersome.
According to the experiment of the invention, the preparation of the lamellar calcium carbonate under the drive of light has the advantages of simplicity, convenience and high efficiency, and the reaction is mild and environment-friendly.
Disclosure of Invention
The invention aims to provide a preparation method of calcium carbonate with a layered structure under the drive of light, which is simple and mild, and the obtained calcium carbonate has a layered structure.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of light-driven lamellar calcium carbonate is characterized by comprising the following steps:
1) anhydrous calcium chloride (CaCl)2) Dissolving in deionized water, placing in an environment of 20-35 ℃, and stirring for 10-15min to obtain a clear transparent solution A;
2) dissolving rhodamine B in deionized water, placing the mixture in an environment with the temperature of 20-35 ℃, and stirring for 10-15min to obtain a clear transparent solution B;
3) adding a proper amount of the solution B into the solution A, adding a certain amount of methanol, continuously keeping the temperature of the solution at 20-35 ℃, and stirring for 10-15min to obtain a clear and transparent solution C;
4) taking a proper amount of the solution C as crystallization mother liquor, placing the crystallization mother liquor in a closed container, and standing and crystallizing the crystallization mother liquor in the whole process under the carbon dioxide atmosphere and the xenon lamp illumination to obtain the layered calcium carbonate.
In the scheme, rhodamine b (dye) is excited by illumination, electrons on the outermost layer of molecules are transited from a ground state to an excited state, and electrons and holes can be provided.
In the scheme, the methanol (hole trapping agent) is used for trapping holes, so that the electron utilization rate is improved, and the illumination efficiency is enhanced.
In the above scheme, the concentration of rhodamine b (dye) in the crystallization mother liquor can be 10-7-10-4mol/L, preferably 5X 10-7-10-6mol/L。
In the above scheme, the volume fraction of methanol in the crystallization mother liquor can be 0.1-10%, preferably 5% -8%.
In the above scheme, the concentration of calcium chloride in the crystallization mother liquor can be 10mmol/L-50 mmol/L.
In the scheme, the xenon lamp light intensity can be 350W, and the distance between the xenon lamp light and the crystallization mother liquor can be 25-35 cm.
In the scheme, the calcium carbonate grows in a sealing device in a standing mode under a xenon lamp light source.
In the above scheme, in the step 4), the calcium carbonate growth temperature may be 0-15 ℃, and the growth time may be 2-10 hours, preferably 6-8 hours.
In the above scheme, the carbon dioxide source may be carbon dioxide released by decomposition of ammonium carbonate or ammonium bicarbonate.
In the scheme, in the step 4), a phi 150 glass dish is used as a sealing system for calcium carbonate growth, and firstly, a phi 50 glass dish filled with 5g of ammonium carbonate is placed on one side of the glass dish; then, placing a phi 60 glass dish on the other side, pouring 20ml of uniformly mixed crystallization mother liquor, placing the glass dish into a cover glass, sealing and pricking 9 holes by using a preservative film, finally, sealing the phi 150 glass dish by using the preservative film to form a sealing system, placing the sealing system into an ice water bath, and irradiating the crystallization mother liquor in a carbon dioxide atmosphere and a xenon lamp in the whole process; and after 2-10 hours, taking out the cover glass, and covering the cover glass to obtain the calcium carbonate with the layered structure.
The invention prepares the layered calcium carbonate under the common regulation and control of a xenon lamp light source, a dye and methanol. Under the co-regulation and control of the dye and the methanol, a large amount of even pure-phase layered hexagonal calcium carbonate can be obtained, and the concentration of the methanol and the dye only influences the amount of the layered hexagonal calcium carbonate.
The invention has the advantages that: (1) the invention successfully constructs the synthetic preparation combining photosynthesis and biomineralization, successfully utilizes energy transmission between photoproduction electrons and holes to realize the regulation and control of the biomineralization process of calcium carbonate, provides support for subsequently disclosing the influence rule of the coupling effect of photosynthesis and biomineralization on the forming process of the material structure in different synthetic systems, and opens up a new channel for realizing the efficient room-temperature preparation of high-performance inorganic materials; (2) the calcium carbonate prepared by the method has larger shape difference with the common calcium carbonate, the obtained calcium carbonate with a layered structure has uniform crystal form, the calcium carbonate prepared by the method has a regular hexagonal structure, the layered stacking structure of the calcium carbonate is very close to a natural shell structure, and the calcium carbonate has great promotion effect on understanding the mineralization mechanism more deeply; (3) the method has the advantages of simple preparation process, low cost, easy control and mild conditions.
Drawings
FIG. 1 is a FESEM picture of the product obtained in example 1 of the present invention.
FIG. 2 is an XRD pattern of the product obtained in example 1 of the present invention.
FIG. 3 is a FESEM picture of the product obtained in example 2 of the present invention.
FIG. 4 is an XRD pattern of the product obtained in example 2 of the present invention.
FIG. 5 is a TEM image of the product obtained in example 2 of the present invention.
FIG. 6 is a SAED picture of the product obtained in example 2 of the present invention.
FIG. 7 is a FESEM picture of the product obtained in example 3 of the present invention.
FIG. 8 is an XRD pattern of the product obtained in example 3 of the present invention.
FIG. 9 is a TEM image of the product obtained in example 3 of the present invention.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
Firstly, distilled water is used as a solvent, and calcium chloride with the concentration of 40mmol/L, methanol with the volume fraction of 8 percent and rhodamine b with the concentration of 5 multiplied by 10 are prepared in a beaker-7And (3) magnetically stirring the mol/L crystallization mother liquor (which is prepared under stirring in an environment of 20-35 ℃) at the room temperature at the speed of 800rad/min for 15min (a beaker is wrapped by an aluminum foil and protected from light; the preparation of a calcium chloride solution and a rhodamine b solution is omitted, and only the stirring time after final mixing is written, and the same is carried out below). A phi 150 glass dish is used as a sealing system for calcium carbonate growth, firstly, a phi 50 glass dish filled with 5g of ammonium carbonate (the ammonium carbonate is a supply source of carbon dioxide) is placed on one side of the glass dish; then, placing a phi 60 glass dish on the other side, pouring 20ml of uniformly mixed mother liquor, placing the glass dish into a cover glass, sealing the glass dish by using a preservative film to form 9 holes, finally, sealing the phi 150 glass dish by using the preservative film to form a sealing system, placing the sealing system into an ice water bath, and irradiating the crystallized mother liquor in a carbon dioxide atmosphere and a xenon lamp in the whole process; and after 4 hours, taking out the cover glass, washing with alcohol, drying, observing, and obtaining the calcium carbonate with the layered structure on the cover glass.
The FESEM picture of the obtained product is shown in figure 1, and the FESEM result in figure 1 shows that the calcium carbonate crystal is composed of a large number of layered hexagonal structures, and the obtained layered hexagons are formed by primary assembly of nanoparticle basic units into hexagons and further layer-by-layer assembly; thus obtaining a fresh reported pure-phase hexagonal layered calcium carbonate by utilizing photogenerated electrons and hole regulation. The XRD pattern of the obtained product is shown in figure 2, the XRD diffraction peak in figure 2 corresponds to that of calcite PDF card, and the layered hexagonal calcium carbonate sample is pure-phase calcite.
Example 2
Firstly, distilled water is used as a solvent, and calcium chloride with the concentration of 40mmol/L, methanol with the volume fraction of 8 percent and rhodamine b with the concentration of 5 multiplied by 10 are prepared in a beaker-7And (3) magnetically stirring the mol/L crystallization mother liquor (prepared under stirring at the environment of 20-35 ℃) at the speed of 800rad/min for 15min at room temperature (the beaker is wrapped by aluminum foil and protected from light). Taking a phi 150 glass dish as a sealing system for calcium carbonate growth, firstly, placing a phi 50 glass dish filled with 5g of ammonium carbonate on one side of an opening; then, a glass dish of phi 60 is placed on the other side, 20ml of uniformly mixed mother liquor is poured, a cover glass is placed, then a preservative film is used for sealing and pricking 9 holes, finally, the glass dish of phi 150 is sealed by the preservative film to form a sealing system, and the sealing system is placed in an ice water bath, and the crystallized mother liquor is irradiated in the carbon dioxide atmosphere and a xenon lamp in the whole process. And after 6 hours, taking out the cover glass, washing with alcohol, drying, observing, and obtaining the calcium carbonate with the layered structure on the cover glass.
The FESEM picture of the obtained product is shown in fig. 3, and in fig. 3, the calcium carbonate obtained under this condition is regular calcium carbonate crystals assembled from hexagonal layers. The XRD pattern of the obtained product is shown in figure 4, and in figure 4, the phase of the obtained hexagonal calcium carbonate assembled layer by layer is calcite calcium carbonate. The TEM picture of the obtained product is shown in fig. 5, and fig. 5 further proves that the obtained calcium carbonate crystal is composed of a regular hexagonal structure and is a hexagonal aggregate formed by stacking nano-particles layer by layer. The SAED picture of the obtained product is shown in fig. 6, the diffraction pattern of the region is a clear diffraction spot, and has single crystal electron diffraction characteristics, and it can be judged that the hexagonal layered structure substance crystal has a preferred orientation, and is a typical mesoscopic crystal. By measuring the interplanar spacing thereof, the interplanar spacing is equal to that of CaCO3Calcite (101), (012) were matched.
Example 3
Firstly, distilled water is used as a solvent, and calcium chloride with the concentration of 40mmol/L, methanol with the volume fraction of 8 percent and rhodamine b with the concentration of 1 multiplied by 10 are prepared in a beaker-6And (3) magnetically stirring the mol/L crystallization mother liquor (prepared under stirring at the environment of 20-35 ℃) at the speed of 800rad/min for 15min at room temperature (the beaker is wrapped by aluminum foil and protected from light). Taking a phi 150 glass dish as a sealing system for calcium carbonate growth, firstly, placing a phi 50 glass dish filled with 5g of ammonium carbonate on one side of an opening; then, a glass dish of phi 60 is placed on the other side, 20ml of uniformly mixed mother liquor is poured, a cover glass is placed, then a preservative film is used for sealing and pricking 9 holes, finally, the glass dish of phi 150 is sealed by the preservative film to form a sealing system, and the sealing system is placed in an ice water bath, and the crystallized mother liquor is irradiated in the carbon dioxide atmosphere and a xenon lamp in the whole process. And after 6 hours, taking out the cover glass, washing with alcohol, drying, observing, and obtaining the calcium carbonate with the layered structure on the cover glass.
The FESEM picture of the obtained product is shown in figure 7, and the FESEM result in figure 7 shows that the calcium carbonate crystals obtained under the condition are all layer-by-layer assembled hexagonal calcium carbonate, and the hexagonal calcium carbonate with larger size is formed by further growing the calcium carbonate crystals with smaller size. The XRD pattern of the obtained product is shown in figure 8, the XRD diffraction peak in figure 8 corresponds to that of calcite PDF card, and the layered hexagonal calcium carbonate sample is pure-phase calcite. The TEM image of the obtained product is shown in FIG. 9, and under high resolution, the layer-by-layer assembled hexagonal structure can be clearly seen, and the hexagonal structure is a hexagonal aggregate formed by stacking nano-particles layer by layer.
Example 4
Firstly, distilled water is used as a solvent, and calcium chloride with the concentration of 10mmol/L, methanol with the volume fraction of 5 percent and rhodamine b with the concentration of 1 multiplied by 10 are prepared in a beaker-6The crystallization mother liquor in mol/L is magnetically stirred at room temperature for 30min at a speed of 800rad/min (the beaker is wrapped with aluminum foil and protected from light). Taking a phi 150 glass dish as a sealing system for calcium carbonate growth, firstly, placing a phi 50 glass dish filled with 5g of ammonium carbonate on one side of an opening; then, a glass vessel of phi 60 is placed on the other side, 20ml of the uniformly mixed mother liquor is poured into the glass vessel, a cover glass is placed into the glass vessel, then, a preservative film is used for sealing and pricking 9 holes, and finally, a preservative film is used for sealing phi 150 glass dish forms a sealed system, is placed in an ice-water bath and is irradiated with the crystallization mother liquor in a carbon dioxide atmosphere and a xenon lamp all the way. And after 2 hours, taking out the cover glass, washing with alcohol, drying, observing, and obtaining the calcium carbonate with the layered structure on the cover glass.
Example 5
Firstly, distilled water is used as a solvent, and calcium chloride with the concentration of 50mmol/L, methanol with the volume fraction of 10 percent and rhodamine b with the concentration of 5 multiplied by 10 are prepared in a beaker-7The crystallization mother liquor in mol/L was magnetically stirred at room temperature at a rate of 800rad/min for 45min (the beaker was wrapped with aluminum foil and protected from light). Taking a phi 150 glass dish as a sealing system for calcium carbonate growth, firstly, placing a phi 50 glass dish filled with 5g of ammonium carbonate on one side of an opening; then, a glass dish of phi 60 is placed on the other side, 20ml of uniformly mixed mother liquor is poured, a cover glass is placed, then a preservative film is used for sealing and pricking 9 holes, finally, the glass dish of phi 150 is sealed by the preservative film to form a sealing system, and the sealing system is placed in an ice water bath, and the crystallized mother liquor is irradiated in the carbon dioxide atmosphere and a xenon lamp in the whole process. After 10 hours, the cover glass is taken out, washed by alcohol, dried and observed, and the calcium carbonate with the layered structure is obtained on the cover glass.
The above description is only a preferred embodiment of the present invention and is not intended to limit the embodiment. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (6)
1. A preparation method of light-driven lamellar calcium carbonate is characterized by comprising the following steps:
1) dissolving anhydrous calcium chloride in deionized water, placing the solution in an environment with the temperature of 20-35 ℃, and stirring to obtain a clear transparent solution A;
2) dissolving rhodamine B in deionized water, placing the mixture in an environment with the temperature of 20-35 ℃, and stirring to obtain a clear transparent solution B;
3) adding the solution B into the solution A, adding methanol, continuously keeping the temperature of the solution at 20-35 ℃, and stirring to obtain a clear and transparent solution C;
4) getTaking a proper amount of solution C as crystallization mother liquor; in the crystallization mother liquor, the concentration of rhodamine b is 10-7-10-4mol/L; in the crystallization mother liquor, the volume fraction of methanol is 0.1-10%; in the crystallization mother liquor, the concentration of calcium chloride is 10mmol/L-50 mmol/L;
placing the crystallization mother liquor in a closed container, and standing and crystallizing the crystallization mother liquor in the carbon dioxide atmosphere and under the illumination of a xenon lamp to obtain layered calcium carbonate;
the carbon dioxide source is carbon dioxide released by decomposing ammonium carbonate or ammonium bicarbonate;
the light intensity of a xenon lamp is 350W, and the distance between the illumination of the xenon lamp and the crystallization mother liquor is 25-35 cm;
the growth temperature of the calcium carbonate is 0-15 ℃, and the growth time is 2-10 hours.
2. The method for preparing calcium carbonate with a layered structure under light drive as claimed in claim 1, wherein the concentration of rhodamine b in the mother solution for crystallization is 5 x 10-7-10-6mol/L。
3. The method for preparing calcium carbonate with a lamellar structure under optical drive according to claim 1, characterized in that the volume fraction of methanol in the mother liquor of crystallization is 5% -8%.
4. The method of claim 1, wherein the growth time is 6-8 hours.
5. The method for preparing the calcium carbonate with the layered structure under the drive of the light according to claim 1, wherein the stirring time in the step 1) is 10-15 min; the stirring time in the step 2) is 10-15 min; the stirring time in the step 3) is 10-15 min.
6. The method for preparing lamellar structure calcium carbonate under optical drive according to claim 1, wherein in step 4), a glass vessel of phi 150 is used as the sealing system for calcium carbonate growth, and first, a phi 50 glass vessel containing 5g of ammonium carbonate is placed on one side of the glass vessel with an opening; then, placing a phi 60 glass dish on the other side, pouring 20mL of uniformly mixed crystallization mother liquor, placing the glass dish into a cover glass, sealing and pricking 9 holes with a preservative film, finally, sealing the phi 150 glass dish with the preservative film to form a sealing system, placing the sealing system in an ice water bath, and irradiating the crystallization mother liquor in a carbon dioxide atmosphere and a xenon lamp in the whole process; and after 2-10 hours, taking out the cover glass, and covering the cover glass to obtain the calcium carbonate with the layered structure.
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