CN113136572B - Preparation method of chiral molybdate mesostructured film - Google Patents
Preparation method of chiral molybdate mesostructured film Download PDFInfo
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- CN113136572B CN113136572B CN202010051989.4A CN202010051989A CN113136572B CN 113136572 B CN113136572 B CN 113136572B CN 202010051989 A CN202010051989 A CN 202010051989A CN 113136572 B CN113136572 B CN 113136572B
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- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
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Abstract
The invention aims to solve the problems and provides a preparation method of a chiral molybdate mesostructured film, which can realize fine structure regulation and control and can not leave organic matters such as templates and the like, and the preparation method comprises the following steps: step S1, placing the substrate into a mercaptosilanization reagent, standing for a period of time, taking out and washing; step S2, putting the substrate washed in step S1 into a mixed solution containing a metal source and an inducer; step S3, adding another metal source into the solution of S2, and growing a molybdate mesostructured film on the substrate after a growth reaction is carried out for a preset time; and step S4, removing the residual inducer in the molybdate, wherein the inducer in the step S2 is a chiral inducer.
Description
Technical Field
The invention relates to a preparation method of a chiral molybdate mesostructured film.
Background
Compared with common metal oxides, the molybdate material has a rich electronic structure, electrons and holes of the molybdate material can form excitons through coulomb force, so that the molybdate material has strong interaction with light, electricity and fields, and has the advantage of good biocompatibility, thereby having wide application in the aspects of analysis and detection of catalytic reaction, biomedical treatment and the like.
Currently, various molybdate nanomaterials with different structures, including molybdate nanomaterials with chiral characteristics, have been synthesized by physical or chemical methods. The physical method is to control the morphology of the molybdate material through glancing angle deposition and the like, and the chemical method is to adjust the morphology of the molybdate material through introducing a template.
However, the physical method has a problem that fine structure control is difficult to perform, and the chemical method has a problem that the chiral structure of the material cannot be retained after the template is removed, so that the application of the existing chiral molybdate material is limited.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of a chiral molybdate mesostructured film, which can realize fine structure regulation and control and can not leave organic matters such as templates and the like, and the preparation method comprises the following steps: step S1, placing the substrate into a mercaptosilanization reagent, standing for a period of time, taking out and washing; step S2, placing the washed substrate obtained in step S1 into a mixed solution containing a metal source and an inducer; step S3, adding another metal source and a pH regulator into the mixed solution of S2 to perform a growth reaction for a predetermined time, so as to grow a molybdate mesostructure film on the substrate; and step S4, removing the residual inducer in the molybdate mesostructured film, wherein the inducer in the step S2 is a chiral inducer.
The preparation method of the chiral molybdate mesostructured film provided by the invention can also have the technical characteristics that the mixed solution in the step S3 also contains a pH regulator, wherein the pH regulator is ammonia water, and the content of the pH regulator is 10 mM-70 mM.
The preparation method of the chiral molybdate mesostructured film provided by the invention can also have the technical characteristics that the metal source added in the step S2 is a silver source, a copper source or other plasma resonance metals and a combination thereof, and the metal source added in the step S3 is a molybdenum source.
The preparation method of the chiral molybdate mesostructured film provided by the invention can also have the technical characteristics that the chiral inducer is a chiral compound containing phenyl.
Further, in the above method for preparing a chiral molybdate meso-structured film, the chiral compound containing a phenyl group may be any one of L-phenylglycinol, D-phenylglycinol, L-tyrosine, D-tyrosine, L-tryptophan, D-tryptophan, L-phenylalanine, D-phenylalanine, L-phenylalaninol, D-phenylalaninol, L-phenylglycine, D-phenylglycine, L-phenylpropionic acid, D-phenylpropionic acid, L-2-chloromandelic acid, and D-2-chloromandelic acid.
The preparation method of the chiral molybdate mesostructured film provided by the invention can also have the technical characteristics that the inducer which is removed from the chiral molybdate mesostructured film in the step S4 is extracted by a solvent, and the solvent is ethanol and water.
The preparation method of the chiral molybdate mesostructured film provided by the invention can also have the technical characteristics that in the step S3, the preset time is 2-6 hours.
The preparation method of the chiral molybdate mesostructured film provided by the invention can also have the technical characteristics that the substrate is a molybdenum substrate.
The preparation method of the chiral molybdate mesostructured film provided by the invention can also have the following technical characteristics, wherein the substrate is a substrate which is cleaned in advance, and the manner of cleaning in advance is as follows: putting the substrate into a mixed solution containing concentrated sulfuric acid and hydrogen peroxide, heating, performing ultrasonic treatment, and taking out and washing with deionized water.
Action and Effect of the invention
According to the preparation method of the chiral molybdate mesostructured film provided by the invention, the chiral molybdate mesostructured film is spontaneously assembled to form a chiral structure by the chiral inducer in an inducing mode, so that the chiral structure can be retained after removal, and compared with a material which loses chirality after a template is removed in the prior art, the chiral molybdate mesostructured film prepared by the method can be applied to the fields of chiral catalysis, chiral identification and the like. In general, the preparation method of the molybdate mesostructure film has the advantages of simple synthesis, low cost, wide product application and the like.
Drawings
FIG. 1 is a flow chart of the preparation of a chiral molybdate mesostructured film in accordance with the present invention;
FIG. 2 is a scanning electron micrograph of an R-type silver molybdate mesostructured film according to a first embodiment of the present invention;
FIG. 3 is a high power scanning electron micrograph of a mesostructured R-type silver molybdate film according to a first embodiment of the present invention;
FIG. 4 is a low power transmission electron micrograph of a mesostructured R-type silver molybdate film according to a first embodiment of the present invention;
FIG. 5 is a high power transmission electron micrograph of a mesostructured R-type silver molybdate film according to a first embodiment of the present invention;
fig. 6 is a circular dichroism spectrum of a silver molybdate nanomembrane according to a first embodiment of the present invention;
FIG. 7 is a scanning electron micrograph of a mesostructured R-type silver molybdate film using 33mM ammonia according to example II of the present invention;
FIG. 8 is a high power scanning electron micrograph of a mesostructured R-type silver molybdate film using 33mM ammonia according to example II of the present invention;
FIG. 9 is a scanning electron micrograph of an R-type silver molybdate mesostructured film using 10mM ammonia according to example II of the present invention;
FIG. 10 is a high power scanning electron micrograph of an R-type silver molybdate mesostructured film using 10mM ammonia according to example two of the present invention;
FIG. 11 is a scanning electron micrograph of a mesostructured R-silver molybdate film using 30mM R-phenylglycinol according to example two of the present invention;
FIG. 12 is a high power SEM image of a mesostructured R-type silver molybdate film with 30mM R-phenylglycinol used in example II of the present invention;
FIG. 13 is a SEM image of an R-type copper molybdate mesostructured film according to a third embodiment of the present invention;
FIG. 14 is a high-magnification scanning electron micrograph of an R-type copper molybdate mesostructured film according to example III of the present invention;
FIG. 15 is a scanning electron micrograph of silver molybdate mesostructured films according to a comparative example of the present invention;
FIG. 16 is a high magnification scanning electron micrograph of a silver molybdate mesostructured film according to a comparative example of the present invention.
Detailed Description
The following describes embodiments of the present invention with reference to the drawings.
< example one >
FIG. 1 is a flow chart of the preparation of the chiral silver molybdate mesostructured film of the present invention.
As shown in fig. 1, the preparation method of the chiral silver molybdate mesostructured film specifically comprises the following steps:
step S1, placing the substrate into a mercaptosilanization reagent, standing for a period of time, taking out and washing;
step S2, putting the substrate washed in step S1 into a mixed solution containing a metal source and an inducer;
step S3, adding another metal source and a pH regulator into the solution of S2 to perform growth reaction for a preset time, so as to grow a molybdate mesostructure film on the substrate;
and step S4, removing the residual inducer in the molybdate mesostructured film.
The substrate adopted in step S1 is a molybdenum substrate cleaned in advance, and the method of cleaning in advance is as follows: the silicon substrate is put into a mixed solution containing concentrated sulfuric acid and hydrogen peroxide (the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide is 3:1) and heated for 2 hours at 60 ℃, then is subjected to ultrasonic treatment for half an hour, and then is taken out and washed with deionized water for three times.
The mercaptosilylation reagent adopted in the step S1 is a 5% solution of (3-mercaptopropyl) trimethoxysilane, and the standing time is 2 hours.
The metal source of the step S2 is silver nitrate, and the inducer is chiral inducer D-phenylglycinol.
The metal source of step S3 is sodium molybdate, and the pH adjuster is ammonia water. Specifically, the mixed solution contains 50mM of chiral inducer, 70mM of ammonia water, 66mM of silver nitrate and 33mM of sodium molybdate.
The growth reaction of step S3 was performed by standing at room temperature for a predetermined time of 4 hours.
The residual inducer removed in step S4 is extracted with a solvent, which is ethanol and water, and the solvent is washed three times and then dried.
In the process, the inducer is D-phenylglycinol, and the R-type silver molybdate mesostructured film is prepared. In this example, the mesostructured film of silver molybdate L form was prepared by using L-phenylglycinol as inducer, i.e., the chiral inducer D-phenylglycinol of step S2 in the above process was replaced by L-phenylglycinol, and the rest was unchanged.
Fig. 2 is a low power scanning electron micrograph of the R-type silver molybdate mesostructured film according to the first embodiment of the present invention, fig. 3 is a high power scanning electron micrograph of the R-type silver molybdate mesostructured film according to the first embodiment of the present invention, fig. 4 is a low power transmission electron micrograph of the R-type silver molybdate mesostructured film according to the first embodiment of the present invention, and fig. 5 is a high power transmission electron micrograph of the R-type silver molybdate mesostructured film according to the first embodiment of the present invention.
As can be seen from fig. 2-5, the R-type silver molybdate mesostructured film prepared in this example is composed of a stack of silver molybdate single sheets, each of which has a thickness of about 20 nm. In addition, the appearance of the L-type silver molybdate mesostructured film in the electron micrograph is similar to that of fig. 2 to 5, and is not listed here.
FIG. 6 is a circular dichroism spectrum of a chiral silver molybdate mesostructured film according to a first embodiment of the present invention. In FIG. 6, R-CNAFs are R-type silver molybdate mesostructured films, and L-CNAFs are L-type silver molybdate mesostructured films.
As shown in fig. 6, the R-type silver molybdate mesostructured film and the L-type silver molybdate mesostructured film have distinct circular dichroism, indicating that the two films have opposite chirality, respectively.
< example two >
This example is an experiment of chiral silver molybdate mesostructured films prepared using different experimental conditions.
In this example, three chiral silver molybdate mesostructured films were prepared, and the preparation processes of the three chiral silver molybdate mesostructured films are the same as in the first example, but the conditions are different, and specifically, the following steps are performed:
the first method comprises the following steps: the ammonia dosage in the step S3 is changed to 35 mM;
and the second method comprises the following steps: the dosage of the ammonia water in the step S3 is changed to 10 mM;
and the third is that: the amount of D-phenylglycinol used in step S3 was changed to 30 mM.
FIG. 7 is a scanning electron micrograph of an R-type silver molybdate mesostructured film with an ammonia dosage of 35mM according to example two of the present invention, and FIG. 8 is a scanning electron micrograph of an R-type silver molybdate mesostructured film with an ammonia dosage of 35mM according to example two of the present invention.
As shown in FIGS. 7 and 8, when the amount of ammonia was 35mM, the thickness of each silver molybdate monolith was about 15 nm.
FIG. 9 is a scanning electron micrograph of an R-type silver molybdate mesostructured film with an ammonia dosage of 10mM according to example two of the present invention, and FIG. 10 is a scanning electron micrograph of an R-type silver molybdate mesostructured film with an ammonia dosage of 10mM according to example two of the present invention.
As shown in FIGS. 9 and 10, when the amount of ammonia was 10mM, the thickness of each silver molybdate monolith was about 10 nm.
FIG. 11 is a SEM image of R-type silver molybdate mesostructured film with the amount of D-phenylglycinol changed to 30mM according to a second embodiment of the present invention, and FIG. 12 is a SEM image of R-type silver molybdate mesostructured film with the amount of D-phenylglycinol changed to 30mM according to a second embodiment of the present invention.
As shown in FIGS. 11 and 12, when the amount of D-phenylglycinol was changed to 30mM, the thickness of each silver molybdate single chip was about 18 nm.
The three chiral silver molybdate mesostructured films prepared in this example were also detected to have a pronounced circular dichroism similar to that of the chiral silver molybdate mesostructured film of example one.
< example three >
In order to verify whether the preparation method of the present invention is suitable for other kinds of metal sources, a preparation experiment of the chiral copper molybdate mesostructured film was performed in this example.
In this embodiment, the four steps of the preparation method of the chiral copper molybdate mesostructured film are the same as those of steps S1 to S4 of the embodiment. Except that the silver nitrate in step S2 was changed to 33mM copper acetate.
Fig. 13 is a low-magnification scanning electron micrograph of the R-type copper molybdate mesostructured film of the third example of the present invention, and fig. 14 is a high-magnification scanning electron micrograph of the R-type copper molybdate mesostructured film of the third example of the present invention.
As shown in fig. 13 and 14, the chiral copper molybdate mesostructured film of the present embodiment also exhibits a flower-like morphology that is regularly arranged, which indicates that the preparation method can obtain corresponding flower-like mesostructured film materials for other molybdate materials. In addition, the chiral copper molybdate mesostructured film also has obvious circular dichroism through detection.
< comparative example >
This comparative example is an experiment in which silver molybdate mesostructured films were prepared without the chiral inducing agent of the example. That is, in the preparation process of this comparative example, no chiral inducer was added to the mixed solution of step S2.
FIG. 15 is a scanning electron micrograph of a silver molybdate mesostructured film according to a comparative example of the present invention, and FIG. 16 is a scanning electron micrograph of a silver molybdate mesostructured film according to a comparative example of the present invention.
As shown in fig. 15 and 16, when the chiral inducer is not used, the silver molybdate mesostructured film prepared has a bulk structure, and the thickness of a single bulk structure is about 500 nm. In addition, the silver molybdate mesostructured film is also detected to have circular dichroism.
Examples effects and effects
It can be seen from the above embodiments that the growth process of the molybdate mesostructured film is chirally induced by the chiral inducing agent, so that the molybdate material forms a chiral morphological structure, and the chiral structure can be retained after the chiral inducing agent is removed, so that the molybdate mesostructured film prepared by the method can be applied to the fields of chiral catalysis, chiral identification and the like. In general, the preparation method of the molybdate mesostructure film has the advantages of simple synthesis, low cost, wide product application and the like.
As the ammonia water with the content of 10 mM-70 mM is adopted as the pH regulator in the preparation process, referring to example II, the addition amount of the ammonia water is positively correlated with the thickness of the silver molybdate mesostructured film, and the addition amount of the chiral inducer is also correlated with the thickness of the silver molybdate mesostructured film, so that the morphology of the silver molybdate mesostructured film can be regulated and controlled by regulating the addition amount of the ammonia water.
Because the inducer is L-phenylglycinol or D-phenylglycinol, the molybdate material can form flaky stack, and the chiral morphology is finally obtained. In addition, in the embodiment, the residual organic matter is removed by using a solvent extraction method, so that the appearance of the molybdate material can be maintained, and the interference of the organic matter in the application process can be avoided, for example, the residual organic matter is prevented from influencing the catalytic reaction when the molybdate material is applied as a catalyst.
The above examples are merely illustrative of specific embodiments of the present invention, and the preparation method of the present invention is not limited to the description of the above examples.
For example, in the examples, L-phenylglycinol or D-phenylglycinol is used as the inducer, but in the present invention, other chiral compounds containing a phenyl group, such as any one of L-tyrosine, D-tyrosine, L-tryptophan, D-tryptophan, L-phenylalanine, D-phenylalanine, L-phenylalaninol, D-phenylalaninol, L-phenylglycine, D-phenylglycine, L-phenylpropionic acid, D-phenylpropionic acid, L-2-chloromandelic acid, and D-2-chloromandelic acid, may be used as the inducer. Proved by verification, the chiral compounds containing phenyl can be used as an inducer to be applied to the preparation method of the chiral molybdate mesostructured film.
Claims (6)
1. A preparation method of a chiral molybdate mesostructured film is characterized by comprising the following steps:
step S1, placing the substrate into a mercaptosilanization reagent, standing for a period of time, taking out and washing;
a step S2 of putting the washed substrate obtained in the step S1 into a mixed solution containing a metal source and an inducer;
step S3, adding another metal source and a pH regulator into the mixed solution of S2 to perform a growth reaction for a predetermined time, so as to grow a molybdate mesostructure film on the substrate;
step S4, removing the residual inducer in the molybdate mesostructured film,
wherein the inducer in step S2 is a chiral inducer which is a chiral compound containing phenyl, and the chiral compound containing phenyl is any one of L-phenylglycinol, D-phenylglycinol, L-tyrosine, D-tyrosine, L-tryptophan, D-tryptophan, L-phenylalanine, D-phenylalanine, L-phenylalaninol, D-phenylalaninol, L-phenylglycine, D-phenylglycine, L-phenylpropionic acid, D-phenylpropionic acid, L-2-chloromandelic acid and D-2-chloromandelic acid,
the metal source added in step S2 is a silver source, a copper source, or a combination thereof, and the metal source added in step S3 is a molybdenum source.
2. The method of claim 1, wherein the method comprises:
wherein the pH regulator in the step S3 is ammonia water with the content of 10 mM-70 mM.
3. The method of claim 1, wherein the method comprises:
and S4, removing the residual inducer in the chiral molybdate mesostructured film by adopting a solvent extraction method, wherein the solvent is ethanol and water.
4. The method of claim 1, wherein the method comprises:
in step S3, the predetermined time is 2 hours to 6 hours.
5. The method of claim 1, wherein the method comprises:
wherein the substrate is a molybdenum substrate.
6. The method of claim 1, wherein the method comprises:
the substrate is cleaned in advance, and the manner of cleaning in advance is as follows:
and putting the substrate into a mixed solution containing concentrated sulfuric acid and hydrogen peroxide, heating, performing ultrasonic treatment, and taking out and washing with deionized water.
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