CN109399595B - Mesoporous molybdenum phosphonate material and preparation method and application thereof - Google Patents
Mesoporous molybdenum phosphonate material and preparation method and application thereof Download PDFInfo
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Abstract
The invention is suitable for the technical field of mesoporous materials, and discloses a mesoporous molybdenum phosphonate material, a preparation method and application thereof, wherein the preparation method of the mesoporous molybdenum phosphonate material comprises the following steps: dissolving hexadecyl trimethyl ammonium bromide in deionized water, adding ethylenediamine tetramethylene phosphonic acid and sodium hydroxide, and heating in a water bath to obtain a first solution; dissolving ammonium molybdate in deionized water, adding the first solution, and heating in a water bath to obtain a second solution; aging, rinsing and drying the second solution to obtain first powder; mixing the first powder with hydrochloric acid and absolute ethyl alcohol, carrying out water bath to obtain a third solution, and drying to obtain a second powder; adding the second powder into a first ethanol mixed solution containing chloroplatinic acid or chloroplatinic acid salt, adding a second ethanol mixed solution dissolved with sodium borohydride, and drying to obtain third powder; and calcining the third powder to obtain the mesoporous molybdenum phosphonate material loaded with platinum. The mesoporous molybdenum phosphonate material prepared by the method disclosed by the invention is electronegative in surface, is loaded with platinum, and has excellent anti-interference capability.
Description
Technical Field
The invention relates to the technical field of mesoporous materials, in particular to a mesoporous molybdenum phosphonate material and a preparation method and application thereof.
Background
The mesoporous material is a nano porous material with the pore diameter of between 2 and 50 nanometers, and has a good application prospect in the fields of macromolecule separation, biosensors, catalysis, adsorption, microelectronics, optics, preparation of novel nano materials and the like due to the fact that the mesoporous material has very high pore volume and specific surface area, high thermal stability and hydrothermal stability, regular nano pores (such as pore diameter, dimension and the like) which are easy to modulate, abundant and easy-to-design surface groups and controllable macro morphology (such as membranes, fibers, spheres and the like). The phosphonate is an organic-inorganic hybrid material, has the characteristics of various skeleton elements, pore channel or cage-shaped structure and the like, and is widely applied to the fields of catalysis, adsorption, biosensors, ion exchange and the like.
At present, the preparation method of mesoporous materials is mainly a hard template method, and the hard template method is a method for synthesizing nano materials by using a porous material containing a fixed rigid framework as a template, filling an object precursor in a pore channel of a hard template agent, and obtaining an inverse replica structure through in-situ conversion. The precursor is assembled and grown in the limited space of the hard template in the synthesis process, and the precursor can grow and crystallize at relatively high temperature due to the limiting effect of the rigid pore passage. In the prior art, a common hard template method for preparing mesoporous materials comprises the following steps: mesoporous silicon oxide, polyoxypropylene polyoxyethylene copolymer F127, SBA-15 and the like are used as hard template agents, and the hard template agents are corroded and removed through related reagents after the materials are solidified, so that the materials with the mesoporous structure are obtained. However, this method still has the following drawbacks in specific applications: when the hard template agent is removed, the removal is incomplete and residues exist, so that certain negative effects are brought to the performance of the material, and the incomplete removal of the hard template agent causes certain pollution and damage to the formed mesoporous material.
Disclosure of Invention
The invention aims to provide a preparation method of a mesoporous molybdenum phosphonate material, which aims to solve the technical problem that the performance of the material is influenced by the removal of a large amount of residual hard template agent when the material with a mesoporous structure is prepared in the prior art.
In order to achieve the purpose, the invention provides the following scheme: the preparation method of the mesoporous molybdenum phosphonate material comprises the following steps:
a first solution preparation step, namely dissolving hexadecyl trimethyl ammonium bromide in deionized water, then adding ethylene diamine tetramethylene phosphonic acid and sodium hydroxide, and heating in a water bath to obtain a first solution;
a second solution preparation step, adding ammonium molybdate into deionized water, stirring and dissolving, then adding the first solution, and heating in a water bath to obtain a second solution;
a first powder preparation step, namely aging the second solution, rinsing the second solution by using deionized water, and then baking and drying the second solution to obtain first powder;
a second powder preparation step, mixing the first powder with hydrochloric acid and absolute ethyl alcohol, heating in a water bath to obtain a third solution, adjusting the p H value of the third solution to be neutral, and drying to obtain second powder;
a third powder preparation step of adding the second powder into a first ethanol mixed solution containing chloroplatinic acid or chloroplatinic acid salt and soaking to obtain a third solution, then adding a second ethanol mixed solution in which sodium borohydride is dissolved into the third solution, stirring, and then baking and drying to obtain third powder;
and a calcining step, calcining the third powder under the protection of inert gas, thereby preparing the mesoporous molybdenum phosphonate material loaded with platinum.
Optionally, in the calcining step, the inert gas is nitrogen or argon; and/or the presence of a gas in the atmosphere,
in the calcining step, the calcining duration is 0.1-200 hours; and/or the presence of a gas in the atmosphere,
in the calcining step, the calcining temperature is 100-1200 ℃.
Alternatively, embodiments of the calcining step are: and placing the third powder in a reaction tube of a tube furnace, introducing nitrogen or argon into the reaction tube, and calcining the third powder in the tube furnace for 5 +/-1 hours at the calcining temperature of 400 +/-100 ℃, so as to prepare the mesoporous molybdenum phosphonate material loaded with platinum.
Alternatively, embodiments of the first solution preparation step are: 0.005mol +/-0.003 mol of hexadecyl trimethyl ammonium bromide is dissolved in 20mL +/-10 mL of deionized water, then 0.001mol +/-0.0005 mol of ethylenediamine tetramethylene phosphonic acid and 0.008mol +/-0.004 mol of sodium hydroxide are added, and the mixture is heated in a water bath at the temperature of 45 +/-10 ℃ for 30 minutes +/-20 minutes, so that the first solution is prepared.
Optionally, embodiments of the second solution preparation step are: 0.048mol ± 0.012mol of ammonium molybdate was put into 5mL ± 1.5mL of deionized water and dissolved with stirring, and then the first solution was added and heated in a water bath at a temperature of 45 ℃ ± 10 ℃ for 2 hours ± 1 hour to prepare the second solution.
Optionally, embodiments of the first powder preparation step are: and placing the second solution in a pressure kettle with the internal pressure more than one atmosphere, aging at the temperature of 120 +/-40 ℃ for 24 hours +/-10 hours, rinsing with deionized water for 1-5 times, then placing in an oven, and baking and drying at the temperature of 60 +/-20 ℃ for 12 hours +/-5 hours to obtain the first powder.
Optionally, embodiments of the second powder preparation step are: mixing the first powder with 15mL +/-5 mL of hydrochloric acid and 15mL +/-5 mL of absolute ethyl alcohol, heating in a water bath at the temperature of 60 +/-20 ℃ for 6 hours +/-2 hours to obtain a third solution, adding a sodium hydroxide solution into the third solution to adjust the p H value of the third solution to be neutral, and then baking and drying at the temperature of 60 +/-20 ℃ for 12 hours +/-5 hours to obtain a second powder; and/or the presence of a gas in the atmosphere,
an embodiment of the third powder preparation step is: adding 3g +/-1 g of the second powder into 3mL +/-1 mL of first ethanol mixed solution containing 0.019mol +/-0.005 mol of chloroplatinic acid or chloroplatinic acid salt, soaking for 24 hours +/-10 hours to obtain a third solution, then adding second ethanol mixed solution dissolved with 0.5mol +/-0.1 mol of sodium borohydride into the third solution, stirring for 2 hours +/-1 hour, and then baking and drying at 60 +/-20 ℃ for 12 hours +/-5 hours to obtain the third powder.
The second objective of the present invention is to provide a mesoporous molybdenum phosphonate material, which is prepared by the preparation method of the mesoporous molybdenum phosphonate material.
The third purpose of the present invention is to provide an application of the mesoporous molybdenum phosphonate material, and specifically, the mesoporous molybdenum phosphonate material is used for preparing a carrier of a bioactive substance.
Optionally, the mesoporous molybdenum phosphonate material is used for preparing a biological sensitive layer used for identifying a target analyte and providing a reaction site in a biosensor.
Compared with the prior art that the mesoporous material is prepared by adopting a hard template method, the mesoporous molybdenum phosphonate material and the preparation method and the application thereof provided by the invention have the following beneficial effects that:
1) the surfactant such as cetyl trimethyl ammonium bromide is used as a soft template agent, so that the template agent is relatively mild when being removed, the pore structure of the material is not easily influenced, and the template agent can be removed to the maximum extent. Hydrochloric acid and absolute ethyl alcohol are used for removing the template agent in the second powder preparation step, and the subsequent calcining process is also equivalent to a link of removing the template agent for the second time, so that the residual quantity of the template agent is further reduced, which is not possessed by the existing hard template method.
2) The ethylene diamine tetramethylene phosphonic acid adopted in the preparation process provides a phosphorus source and also provides a carbon source and a nitrogen source, namely two non-metal elements of C and N are introduced into the framework of molybdenum phosphonate, so that the framework structure of the organic-inorganic hybrid porous material is formed, and the conductivity and the stability of the finally formed porous molybdenum phosphonate material are effectively improved. The prepared mesoporous structure is beneficial to material transmission, and can provide a high specific surface area and increase catalytic active sites. And nitrogen atoms with different electronegativities are easy to form a synergistic effect with carbon atoms, so that the rapid oxidation-reduction reaction is facilitated, and meanwhile, the stability of the material is improved to a certain extent due to the covalent bond combination among heterogeneous atoms in the material. The skeleton structure of the organic-inorganic hybrid porous material is formed by bonding organic groups and inorganic substances, and organic functional groups are distributed in the skeleton, so that the organic-inorganic hybrid porous material can be manually regulated to a certain extent. Meanwhile, different properties of inorganic and organic components are combined, so that the hybrid porous material has great potential in the aspects of catalysis and the like.
3) The prepared mesoporous molybdenum phosphonate material is mesoporous molybdenum phosphonate with electronegativity on the surface and platinum loading, has excellent anti-interference capability, does not need to add an anti-interference layer depending on the property of the mesoporous molybdenum phosphonate material, and can improve the response rate in an anti-interference test.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the description relating to "first", "second", etc. in the present invention is for descriptive purposes only and is not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The preparation method of the mesoporous molybdenum phosphonate material provided by the embodiment of the invention comprises the following steps:
a first solution preparation step of adding cetyltrimethylammonium bromide (CTAB for short, chemical formula C)19H42BrN) is dissolved in deionized water, and then ethylenediamine tetramethylene phosphonic acid (abbreviated as EDTMPA, chemical formula C) is added6H20N2O12P4) And sodium hydroxide (chemical formula is NaOH) and heating in water bath to obtain a first solution; the water bath is a heating method using water as a heat transfer medium, namely, a vessel of a heated substance is put into water for heating, so that the substances in the vessel can be uniform;
a second solution preparation step of adding ammonium molybdate (chemical formula H)8MoN2O4) Adding the mixture into deionized water, stirring and dissolving, then adding the first solution, and heating in a water bath to obtain a second solution;
a first powder preparation step, namely aging the second solution, rinsing the second solution by using deionized water, and then baking and drying the second solution to obtain first powder; aging refers to a process of allowing the initially generated precipitate to stand with the mother liquor for a period of time after the solution is completely precipitated;
a second powder preparation step, mixing the first powder with hydrochloric acid and absolute ethyl alcohol, heating in a water bath to obtain a third solution, adjusting the p H value of the third solution to be neutral, and drying to obtain second powder; hydrochloric acid is an aqueous solution of hydrogen chloride;
a third powder preparation step of adding the second powder to a first ethanol mixed solution containing chloroplatinic acid or chloroplatinic acid salt and soaking to obtain a third solutionThen dissolving sodium borohydride (chemical formula is NaBH)4) Adding the second ethanol mixed solution into the third solution, stirring, and then baking and drying to obtain third powder; the first ethanol mixed solution is specifically a mixed solution of chloroplatinic acid or chloroplatinic acid salt and ethanol; the second ethanol mixed solution is specifically a mixed solution of sodium borohydride hexahydrate and ethanol;
and a calcining step, calcining the third powder under the protection of inert gas, thereby preparing the mesoporous molybdenum phosphonate material loaded with platinum. Calcination is a process in which heat treatment is carried out at a certain temperature in air or an inert gas flow.
Specifically, in the first solution preparation step, acid-base neutralization reaction of ethylenediamine tetramethylene phosphonic acid and sodium hydroxide occurs, and the reaction formula is as follows: c6H12N2O4P4(OH)8+8NaOH＝C6H12N2O4P4(ONa) 8+8H2And O. In the second solution preparation step, ammonium molybdate chemically reacts with the first solution to initially form amorphous molybdenum phosphonate. In the first powder preparation step, aging is mainly to form pore structure by using the property of surfactant, rinsing is mainly to primarily wash away surfactant not participating in pore formation, inorganic salt ion such as Na+And the like. In the second powder preparation step, the mixed solution of hydrochloric acid and absolute ethyl alcohol is mainly used for extracting the surfactant participating in pore forming to form a mesoporous structure, and the mesoporous molybdenum phosphonate is obtained, and the second powder is the mesoporous molybdenum phosphonate, but the mesoporous molybdenum phosphonate is not loaded with platinum at the moment. In the third powder preparation step, a second ethanol mixed solution in which sodium borohydride is dissolved is added into the third solution to generate a chemical reaction, and platinum in chloroplatinic acid is reduced to form platinum nanoparticles. During the calcination step, the inert gas protects the material from oxidation at high temperatures, and the calcination process also removes the templating agent.
The reason why the overall surface of the mesoporous molybdenum phosphonate material is electronegative is as follows: in the first solution preparation step, the ethylenediamine tetramethylene phosphonic acid has organic functional groups, and the ethylenediamine tetramethylene phosphonic acid reacts with sodium hydroxide to form-P-O-A bond, bearing a negative charge; in the third powder preparation step, platinum nanoparticles obtained by chloroplatinic acid reduction reaction are negatively charged, and finally the platinum nanoparticles are loaded on mesoporous molybdenum phosphonate, so that the finally prepared mesoporous molybdenum phosphonate material integrally presents surface electronegativity.
In the preparation method of the mesoporous molybdenum phosphonate material provided by the embodiment of the invention, the surfactant such as cetyl trimethyl ammonium bromide is used as a soft template agent, so that the template agent is relatively mild when being removed, the pore structure of the material is not easily affected, and the template agent can be completely removed to the greatest extent. Hydrochloric acid and absolute ethyl alcohol are used for removing the template agent in the second powder preparation step, and the subsequent calcining process is also equivalent to a link of removing the template agent for the second time, so that the influence of the template agent on the performance of the finally prepared molybdenum phosphononate material is greatly reduced.
In addition, the ethylene diamine tetramethylene phosphonic acid adopted in the preparation process provides a phosphorus source and also provides a carbon source and a nitrogen source, namely two non-metallic elements of C and N are introduced into the framework of the molybdenum phosphonate, so that the framework structure of the organic-inorganic hybrid porous material is formed, and the conductivity and the stability of the finally formed porous molybdenum phosphonate material are effectively improved. The prepared mesoporous structure is beneficial to material transmission, and can provide a high specific surface area and increase catalytic active sites. And nitrogen atoms with different electronegativities are easy to form a synergistic effect with carbon atoms, so that the rapid oxidation-reduction reaction is facilitated, and meanwhile, the stability of the material is improved to a certain extent due to the covalent bond combination among heterogeneous atoms in the material. The skeleton structure of the organic-inorganic hybrid porous material is formed by bonding organic groups and inorganic substances, and organic functional groups are distributed in the skeleton, so that the organic-inorganic hybrid porous material can be manually regulated to a certain extent. Meanwhile, different properties of inorganic and organic components are combined, so that the hybrid porous material has great potential in the aspects of catalysis and the like.
Preferably, in the first solution preparing step, the amount of cetyltrimethylammonium bromide is 0.005mol ± 0.003mol, and the amount of deionized water used to dissolve cetyltrimethylammonium bromide is 20mL ± 10 mL.
More preferably, in the first solution preparing step, the amount of cetyltrimethylammonium bromide is 0.005mol ± 0.001mol, and the amount of deionized water used to dissolve cetyltrimethylammonium bromide is 20mL ± 2 mL.
Preferably, in the first solution preparation step, the amount of ethylenediaminetetramethylenephosphonic acid is 0.001mol ± 0.0005mol and the amount of sodium hydroxide is 0.008mol ± 0.004 mol.
More preferably, in the first solution preparation step, the amount of ethylenediaminetetramethylenephosphonic acid is 0.001 mol. + -. 0.0002mol and the amount of sodium hydroxide is 0.008 mol. + -. 0.001 mol.
Preferably, in the first solution preparation step, the temperature of the water bath heating is 45 ℃ +/-10 ℃, and the time of the water bath heating is 30 minutes +/-20 minutes.
More preferably, in the first solution preparation step, the temperature of the water bath heating is 45 ℃. + -. 5 ℃ and the time of the water bath heating is 30 minutes. + -. 5 minutes.
As a preferred embodiment of this embodiment, the first solution preparation step is implemented by: 0.005mol +/-0.001 mol of hexadecyl trimethyl ammonium bromide is dissolved in 20mL +/-2 mL of deionized water, then 0.001mol +/-0.0002 mol of ethylene diamine tetramethylene phosphonic acid and 0.008mol +/-0.001 mol of sodium hydroxide are added, and the mixture is heated in a water bath at the temperature of 45 +/-5 ℃ for 30 minutes +/-5 minutes, so that the first solution is prepared.
Preferably, in the second solution preparing step, the amount of ammonium molybdate is 0.048mol ± 0.012mol, and the amount of deionized water used for dissolving ammonium molybdate is 5mL ± 1.5 mL.
More preferably, in the second solution preparing step, the amount of ammonium molybdate is 0.048mol ± 0.002mol, and the amount of deionized water used for dissolving ammonium molybdate is 5mL ± 0.5 mL.
Preferably, in the second solution preparation step, the temperature of the water bath heating is 45 ℃. + -. 10 ℃ and the time of the water bath heating is 2 hours. + -. 1 hour.
More preferably, in the second solution preparation step, the temperature of the water bath heating is 45 ℃. + -. 5 ℃ and the time of the water bath heating is 2 hours. + -. 0.1 hour.
As a preferred embodiment of this embodiment, the second solution preparation step is implemented by: 0.048mol ± 0.002mol of ammonium molybdate was put into 5mL ± 0.5mL of deionized water and dissolved with stirring, and then the first solution was added and heated in a water bath at a temperature of 45 ℃ ± 5 ℃ for 2 hours ± 0.1 hour to prepare the second solution.
Preferably, in the first powder preparation step, the temperature for aging is 120 ℃. + -. 40 ℃ and the time for aging is 24 hours. + -. 10 hours.
More preferably, in the first powder preparation step, the temperature of aging is 120 ℃. + -. 10 ℃ and the time of aging is 24 hours. + -. 0.5 hours.
Preferably, in the first powder preparation step, the rinsing is performed 1 to 5 times by using deionized water, that is, the number of times of rinsing may be 1 time, 2 times, 3 times, 4 times or 5 times.
More preferably, in the first powder preparation step, the rinsing is performed 2 to 4 times by using deionized water.
Preferably, in the first powder preparation step, the temperature of the baking and drying is 60 ℃ ± 20 ℃, and the time of the baking and drying is 12 hours ± 5 hours.
More preferably, in the first powder preparation step, the temperature of the bake-drying is 60 ℃ ± 5 ℃, and the time of the bake-drying is 12 hours ± 0.5 hours.
As a preferred embodiment of this embodiment, the first powder preparation step is implemented by: placing the second solution in a pressure kettle with an internal pressure greater than one atmosphere, aging at 120 ℃ + -10 ℃ for 24 hours + -0.5 hours, rinsing with deionized water 3 times, then placing in an oven, and baking and drying at 60 ℃ + -5 ℃ for 12 hours + -0.5 hours, thereby preparing the first powder. The pressure in the pressure kettle is between 0.101MPa and 100 MPa. Here, the autoclave is mainly used to provide a reaction environment of more than one atmosphere to form a pore structure using the property of the surfactant.
Preferably, in the second powder preparation step, the amount of hydrochloric acid is 15 mL. + -.5 mL, and the amount of absolute ethanol is 15 mL. + -.5 mL.
More preferably, in the second powder preparation step, the amount of hydrochloric acid is 15 mL. + -.1 mL, and the amount of anhydrous ethanol is 15 mL. + -.1 mL.
Preferably, in the second powder preparation step, the temperature of the water bath heating is 60 ℃ +/-20 ℃, and the time of the water bath heating is 6 hours +/-2 hours.
More preferably, in the second powder preparation step, the temperature of water bath heating is 60 ℃ ± 5 ℃, and the time of water bath heating is 6 hours ± 0.2 hours.
Preferably, in the second powder preparation step, the p H value of the third solution is adjusted to be neutral in such a manner that: adding sodium hydroxide solution into the third solution. As a preferred embodiment, the third solution is titrated to neutralize with 0.01mol of NaOH solution to adjust the pH of the third solution to neutral.
Preferably, in the second powder preparation step, the temperature of the baking and drying is 60 ℃ ± 20 ℃, and the time of the baking and drying is 12 hours ± 5 hours.
Preferably, in the second powder preparation step, the temperature of the baking and drying is 60 ℃ ± 5 ℃, and the time of the baking and drying is 12 hours ± 0.5 hour.
As a preferred embodiment of this embodiment, the second powder preparation step is implemented by: mixing the first powder with 15mL +/-1 mL of hydrochloric acid and 15mL +/-1 mL of absolute ethyl alcohol, heating in a water bath at the temperature of 60 +/-5 ℃ for 6 hours +/-0.2 hours to obtain a third solution, adding a sodium hydroxide solution into the third solution to adjust the p H value of the third solution to be neutral, and then baking and drying at the temperature of 60 +/-5 ℃ for 12 hours +/-0.5 hours to obtain the second powder.
Preferably, in the third powder preparation step, the amount of the second powder is 3g ± 1g, the amount of the first ethanol mixed solution is 3mL ± 1mL, and the first ethanol mixed solution contains 0.019mol ± 0.005mol of chloroplatinic acid or chloroplatinic acid salt, and the soaking time is 24 hours ± 10 hours.
More preferably, in the third powder preparation step, the amount of the second powder used is 3g ± 0.2g, the amount of the first ethanol mixture used is 3mL ± 0.2mL, and the first ethanol mixture contains 0.019mol ± 0.001mol of chloroplatinic acid or chloroplatinic acid salt, and the soaking time is 24 hours ± 1 hour.
Preferably, in the third powder preparation step, the first ethanol mixed solution is specifically chloroplatinic acid hexahydrate (chemical formula is H)2PtCl6·6H2O) mixed solution with ethanol; of course, in a specific application, the first ethanol mixed solution may also be a mixed solution of alcohol and a chloroplatinate such as sodium chloroplatinate or potassium chloroplatinate. Preferably, in the third powder preparation step, the second ethanol mixture contains 0.5mol ± 0.1mol of sodium borohydride, and the stirring time is 2 hours ± 1 hour.
More preferably, in the third powder preparation step, the second ethanol mixture contains 0.5mol ± 0.05mol of sodium borohydride, and the stirring time is 2 hours ± 0.2 hours.
Preferably, in the third powder preparation step, the temperature of the baking and drying is 60 ℃ ± 20 ℃, and the time of the baking and drying is 12 hours ± 5 hours.
More preferably, in the third powder preparation step, the temperature of the bake-drying is 60 ℃ ± 5 ℃, and the time of the bake-drying is 12 hours ± 0.5 hours.
As a preferred embodiment of this embodiment, the third powder preparation step is implemented by: adding 3g + -0.2 g of the second powder into 3mL + -0.2 mL of a first ethanol mixed solution containing 0.019mol + -0.001 mol of chloroplatinic acid hexahydrate for soaking for 24 hours + -1 hour to obtain the third solution, adding a second ethanol mixed solution in which 0.5mol + -0.05 mol of sodium borohydride is dissolved into the third solution, stirring for 2 hours + -0.2 hour, and then baking and drying at 60 deg.C + -5 deg.C for 12 hours + -0.5 hour to obtain the third powder.
Preferably, in the calcining step, the inert gas is nitrogen or argon.
Preferably, in the calcining step, the calcining is continued for 0.1 to 200 hours.
More preferably, in the calcining step, the calcining is continued for a time of 5 hours ± 1 hour.
Preferably, in the calcining step, the calcining temperature is 100 ℃ to 1200 ℃.
More preferably, in the calcining step, the temperature of the calcining is 400 ℃ ± 100 ℃.
As a preferred embodiment of this embodiment, the calcination step is performed by: and loading the third powder in a porcelain boat, placing the third powder in a reaction tube of a tube furnace, introducing nitrogen or argon into the reaction tube, wherein the flow rate of the nitrogen or argon is 60ml/min +/-5 ml/min, calcining the third powder in the tube furnace for 5 hours +/-0.1 hour at the calcining temperature of 400 ℃ +/-10 ℃, and thus obtaining the platinum-loaded mesoporous molybdenum phosphonate material. In the calcination step, nitrogen or argon is not required to be continuously introduced to the calcination process. The function of introducing nitrogen or argon into the reaction tube is to remove air from the reaction tube and provide an inert gas atmosphere without protecting the materials in the reaction tube from being oxidized by oxygen at high temperature.
As a preferred embodiment of this embodiment, the preparation method of the mesoporous phosphonate material includes: 2g of cetyltrimethylammonium bromide was dissolved in 20mL of deionized water, and then 0.436g of ethylenediaminetetramethylenephosphonic acid and 0.32g of sodium hydroxide were added and heated in a water bath at 45 ℃ for 30 minutes to prepare a first solution. 5mL of deionized water and 9.408g of ammonium molybdate were weighed and dissolved with stirring, then added to the first solution and heated in a water bath at 45 ℃ for 2 hours to make a second solution. The second solution was transferred to an autoclave, aged at 120 ℃ for 24 hours, rinsed 3 times with deionized water, and then dried in an oven at 60 ℃ for 12 hours to produce a first powder. The obtained first powder was mixed with 15mL of hydrochloric acid and 15mL of anhydrous ethanol, and then heated in a water bath at 60 ℃ for 6 hours, followed by adjusting the pH to neutral, and dried at 60 ℃ for 12 hours to obtain a second powder, i.e., a mesoporous molybdenum phosphonate powder not supporting platinum. 3g of the second powder was added to 3mL of an ethanol solution of chloroplatinic acid hexahydrate and soaked for 24 hours to obtain a third solution, and then 0.5mol of sodium borohydride dissolved in the ethanol solution was added to the third solution, stirred for 120 minutes, and then dried at 60 ℃ for 12 hours to obtain a third powder. Loading the third powder into a ceramic boat, placing the ceramic boat in a reaction tube in a tube furnace, introducing nitrogen into the reaction tube, calcining the ceramic boat in the tube furnace for 5 hours at the calcining temperature of 400 ℃ at the flow rate of 60ml/min to prepare the mesoporous molybdenum phosphonate with electronegativity on the surface and platinum loading.
The preparation method of the mesoporous phosphonate material provided by the embodiment of the invention aims to prepare the mesoporous phosphonate material with surface electronegativity and platinum loading, transition metal and non-metal elements are introduced into a framework, the surface electronegativity organic-inorganic hybrid molybdenum phosphonate with a mesoporous structure is synthesized by a hydrothermal synthesis method, ethylenediamine tetramethylene phosphonic acid is used as a phosphorus source, ammonium molybdate is used as a molybdenum source, hexadecyl trimethyl ammonium bromide is used as a template agent, the characteristics of a surfactant are utilized, the hydrothermal synthesis method is used for preparing the molybdenum phosphonate with a porous structure, the template agent is removed by ethanol and hydrochloric acid in a certain proportion, and then the surface electronegativity organic-inorganic hybrid molybdenum phosphonate with the mesoporous structure is obtained by drying and calcining.
According to the preparation method of the mesoporous phosphonate material, the ionic surfactant is used as the template, and the operation steps (the second powder preparation step and the calcination step) of removing the template are carried out twice, so that the template is completely removed, and the use performance of the material is not influenced; the framework is introduced with two non-metal elements of C and N, which further improves the performance of the material, and the organic-inorganic hybrid porous material framework is distributed with organic functional groups, which makes it possible to be manually controlled to a certain extent and combines different properties of inorganic and organic components.
In the embodiment of the invention, the mesoporous molybdenum phosphonate material is prepared by a hydrothermal synthesis method in a soft template method. Specifically, the soft template method employs a flexible molecule as a template agent, such as a surfactant or the like. The template agent and the framework species are self-assembled synergistically to construct a composite framework by a strong interaction force (electrostatic force, hydrogen bond, etc.) between the soft template agent and the inorganic (or organic) precursor species constituting the mesoporous framework. The soft template method has two main synthesis paths: hydrothermal synthesis and solvent volatilization induced self-assembly. Wherein, the hydrothermal synthesis: in the synthesis process, after the structure directing agent (surfactant and the like) and the precursor react at a lower temperature, the pore structure is treated at a higher temperature and pressure to make the pore structure more rigid and stable, and the process is a typical 'sol-gel' process and can be carried out under alkaline, acidic and neutral conditions.
Further, the embodiment of the invention also provides a mesoporous molybdenum phosphonate material, which is prepared by adopting the preparation method of the mesoporous molybdenum phosphonate material. The mesoporous molybdenum phosphonate material prepared by the preparation method of the mesoporous molybdenum phosphonate material is mesoporous molybdenum phosphonate with electronegative surface and platinum loading, has excellent anti-interference capability, does not need to add an anti-interference layer depending on the property of the mesoporous molybdenum phosphonate material, and can improve the response rate in an anti-interference test.
Further, the embodiment of the invention also provides an application of the mesoporous molybdenum phosphonate material, and specifically, the mesoporous molybdenum phosphonate material is used for preparing a carrier of a bioactive substance.
Preferably, the mesoporous molybdenum phosphonate material is used for preparing a biological sensitive layer used for identifying a target analyte and providing a reaction site in a biosensor. The surface of the mesoporous phosphonate material is electronegative, so that the sarcosine biosensor prepared by the mesoporous phosphonate material has excellent anti-interference performance.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (6)
1. The preparation method of the mesoporous molybdenum phosphonate material is characterized by comprising the following steps:
a first solution preparation step, namely dissolving hexadecyl trimethyl ammonium bromide in deionized water, then adding ethylene diamine tetramethylene phosphonic acid and sodium hydroxide, and heating in a water bath to obtain a first solution;
a second solution preparation step, adding ammonium molybdate into deionized water, stirring and dissolving, then adding the first solution, and heating in a water bath to obtain a second solution;
a first powder preparation step, namely aging the second solution, rinsing the second solution by using deionized water, and then baking and drying the second solution to obtain first powder;
a second powder preparation step, mixing the first powder with hydrochloric acid and absolute ethyl alcohol, heating in a water bath to obtain a third solution, adjusting the p H value of the third solution to be neutral, and drying to obtain second powder;
a third powder preparation step of adding the second powder into a first ethanol mixed solution containing chloroplatinic acid or chloroplatinic acid salt and soaking to obtain a third solution, then adding a second ethanol mixed solution in which sodium borohydride is dissolved into the third solution, stirring, and then baking and drying to obtain third powder;
calcining the third powder under the protection of inert gas to obtain a platinum-loaded mesoporous molybdenum phosphonate material;
the first solution preparation step is carried out as follows: dissolving 0.005mol +/-0.003 mol of hexadecyl trimethyl ammonium bromide in 20mL +/-10 mL of deionized water, then adding 0.001mol +/-0.0005 mol of ethylenediamine tetramethylene phosphonic acid and 0.008mol +/-0.004 mol of sodium hydroxide, and heating in a water bath at the temperature of 45 +/-10 ℃ for 30 minutes +/-20 minutes to prepare a first solution;
the second solution preparation step is carried out as follows: 0.048mol +/-0.012 mol of ammonium molybdate is put into 5mL +/-1.5 mL of deionized water and stirred for dissolving, then the first solution is added and heated in a water bath at the temperature of 45 +/-10 ℃ for 2 hours +/-1 hour, thus preparing the second solution;
an embodiment of the first powder preparation step is: placing the second solution in a pressure kettle with the internal pressure greater than one atmosphere, aging at 120 +/-40 ℃ for 24 +/-10 hours, rinsing with deionized water for 1-5 times, then placing in an oven, and baking and drying at 60 +/-20 ℃ for 12 +/-5 hours to obtain the first powder;
an embodiment of the second powder preparation step is: mixing the first powder with 15mL +/-5 mL of hydrochloric acid and 15mL +/-5 mL of absolute ethyl alcohol, heating in a water bath at the temperature of 60 +/-20 ℃ for 6 hours +/-2 hours to obtain a third solution, adding a sodium hydroxide solution into the third solution to adjust the p H value of the third solution to be neutral, and then baking and drying at the temperature of 60 +/-20 ℃ for 12 hours +/-5 hours to obtain a second powder; and/or the presence of a gas in the atmosphere,
an embodiment of the third powder preparation step is: adding 3g +/-1 g of the second powder into 3mL +/-1 mL of first ethanol mixed solution containing 0.019mol +/-0.005 mol of chloroplatinic acid or chloroplatinic acid salt, soaking for 24 hours +/-10 hours to obtain a third solution, then adding second ethanol mixed solution dissolved with 0.5mol +/-0.1 mol of sodium borohydride into the third solution, stirring for 2 hours +/-1 hour, and then baking and drying at 60 +/-20 ℃ for 12 hours +/-5 hours to obtain the third powder.
2. The method for preparing the molybdenum mesoporous phosphonate material according to claim 1, wherein in the calcining step, the inert gas is nitrogen or argon; and/or the presence of a gas in the atmosphere,
in the calcining step, the calcining duration is 0.1-200 hours; and/or the presence of a gas in the atmosphere,
in the calcining step, the calcining temperature is 100-1200 ℃.
3. The method for preparing the mesoporous molybdenum phosphonate material of claim 2, wherein the calcining step is performed by: and placing the third powder in a reaction tube of a tube furnace, introducing nitrogen or argon into the reaction tube, and calcining the third powder in the tube furnace for 5 hours +/-1 hour at the calcining temperature of 400 +/-100 ℃, so as to prepare the mesoporous molybdenum phosphonate material loaded with platinum.
4. The mesoporous molybdenum phosphonate material is characterized by being prepared by the preparation method of the mesoporous molybdenum phosphonate material as set forth in any one of claims 1 to 3.
5. The use of the mesoporous molybdenum phosphonate material of claim 4, wherein the mesoporous molybdenum phosphonate material is used to prepare a support for a biologically active substance.
6. The use of the mesoporous molybdenum phosphonate material of claim 5, wherein the mesoporous molybdenum phosphonate material is used to prepare a bio-sensitive layer for identifying a target analyte and providing a reaction site in a biosensor.
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