CN109399595A - Mesoporous phosphonic acids molybdenum material and its preparation method and application - Google Patents
Mesoporous phosphonic acids molybdenum material and its preparation method and application Download PDFInfo
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Abstract
The present invention is suitable for technical field of mesoporous materials, disclose mesoporous phosphonic acids molybdenum material and its preparation method and application, wherein, the preparation method of mesoporous phosphonic acids molybdenum material includes: that cetyl trimethylammonium bromide is dissolved in deionized water, and ethylenediamine tetramethylene phosphonic acid and sodium hydroxide is added and heating water bath obtains the first solution；Ammonium molybdate is dissolved in deionized water, the first solution is added and heating water bath obtains the second solution；Second solution is aged, is rinsed, is dried to obtain the first powder；First powder is mixed with hydrochloric acid, dehydrated alcohol and carries out water-bath and obtains third solution, is dried to obtain the second powder；Second powder is added in the first alcohol mixeding liquid containing chloroplatinic acid or chloroplatinate, the second alcohol mixeding liquid for being dissolved with sodium borohydride is added, is dried to obtain third powder；Third powder is calcined to the mesoporous phosphonic acids molybdenum material that load is made and has platinum.Mesoporous phosphonic acids molybdenum material surface produced by the present invention is in electronegativity and Supported Pt Nanoparticles, has excellent anti-interference ability.
Description
Technical field
The present invention relates to technical field of mesoporous materials more particularly to mesoporous phosphonic acids molybdenum material and its preparation method and application.
Background technique
Mesoporous material refers to nano-porous materials of the channel diameter between 2 nanometers to 50 nanometers, due to having very
High pore capacities and specific surface area, higher thermal stability and hydrothermal stability, be easy to modulation regular nano-pore (such as aperture,
Dimension etc.), abundant and easily designed surface group and regulatable macro morphology (such as film, fiber, ball), so big
Molecule separation, biosensor, catalysis, absorption, microelectronics, optics and prepare the fields such as novel nano-material have it is preferable
Application prospect.Phosphonate is class I organic-inorganic hybrid material, it has backbone element type more, duct or cagelike structure etc.
Feature is widely used in the fields such as catalysis, absorption, biosensor and ion exchange.
Currently, the preparation method about mesoporous material, based on use hard template method, hard template method is containing with fixation
The porous material of rigid backbone is template, fills object presoma in the duct of hard mould agent, obtains by converted in-situ anti-
Phase replicated architecture, a kind of method of nano materials.Presoma is in the limiting substrate of hard template in the synthesis process
Assembling and growth, due to the restriction effect in rigid duct, presoma can grow crystallization at a relatively high temperature.It is existing
In technology, the common hard template method preparation method of mesoporous material are as follows: with mesopore silicon oxide, polyoxyethylene polyoxypropylene copolymer
F127, SBA-15 etc. are hard mould agent, etc. hard mould agent is fallen by relevant reagent erosion removal after material solidifications, to obtain
Material with meso-hole structure.However, this method is in concrete application, there are still following defects: when removing hard mould agent
Often since removal is not thorough, has residual to bring certain negative effect to the performance of material, hard mould agent removal
It is not thorough while can also cause certain pollution and injury to the mesoporous material of formation.
Summary of the invention
The first purpose of this invention is to provide a kind of preparation method of mesoporous phosphonic acids molybdenum material, aim to solve the problem that existing
In technology preparation have when the material of meso-hole structure due to more than removal hard mould agent residual quantity and the technology that influences material property is asked
Topic.
In order to achieve the above objectives, scheme provided by the invention is: the preparation method of mesoporous phosphonic acids molybdenum material, including walks as follows
It is rapid:
First solution preparation step, cetyl trimethylammonium bromide is dissolved in deionized water, and ethylenediamine is then added
Simultaneously heating water bath obtains the first solution for tetramethylene phosphonic acid and sodium hydroxide；
Ammonium molybdate is added in deionized water simultaneously stirring and dissolving, it is molten to be then added described first by the second solution preparation step
Simultaneously heating water bath obtains the second solution to liquid；
Second solution is aged, and is rinsed with deionized water by the first powder preparation step, then toasts
It is dried to obtain the first powder；
Second powder preparation step, first powder is mixed with hydrochloric acid, dehydrated alcohol and carries out heating water bath obtains
Then the pH value adjustment of the third solution to neutrality is dried drying by third solution, obtain the second powder；
Second powder is added and mixes containing the first ethyl alcohol of chloroplatinic acid or chloroplatinate by third powder preparation step
In liquid and immersion obtains third solution, then the third solution will be added dissolved with the second alcohol mixeding liquid of sodium borohydride
In, then baking is dried to obtain third powder for stirring；
Calcining step calcines the third powder under the protection of inert gas, so that load, which is made, the mesoporous of platinum
Phosphonic acids molybdenum material.
Optionally, in the calcining step, the inert gas is nitrogen or argon gas；And/or
In the calcining step, the calcining duration is 0.1 hour~200 hours；And/or
In the calcining step, the temperature of the calcining is 100 DEG C~1200 DEG C.
Optionally, the embodiment of the calcining step are as follows: the third powder is placed in the reaction tube of tube furnace, to
It is passed through nitrogen or argon gas in the reaction tube, and calcines the third powder in tube furnace 5 ± 1 hour hour, and calcines
Temperature is 400 DEG C ± 100 DEG C, so that the mesoporous phosphonic acids molybdenum material that load has platinum be made.
Optionally, the embodiment of first solution preparation step are as follows: by the hexadecane of 0.005mol ± 0.003mol
Base trimethylammonium bromide is dissolved in the deionized water of 20mL ± 10mL, and the ethylenediamine of 0.001mol ± 0.0005mol is then added
The sodium hydroxide of tetramethylene phosphonic acid and 0.008mol ± 0.004mol, and heating water bath 30 divides in 45 DEG C ± 10 DEG C of temperature
± 20 points, so that first solution be made.
Optionally, the embodiment of second solution preparation step are as follows: by the ammonium molybdate of 0.048mol ± 0.012mol
It is put into the deionized water of 5mL ± 1.5mL simultaneously stirring and dissolving, first solution is then added and in 45 DEG C ± 10 DEG C of temperature
Middle heating water bath ± 1 hour 2 hours, so that second solution be made.
Optionally, the embodiment of first powder preparation step are as follows: by the internally placed pressure of the second solution
In autoclave pressure greater than an atmospheric pressure, it is aged in 120 DEG C ± 40 DEG C of temperature ± 10 hours 24 hours, is floated with deionized water
It washes 1~5 time, is then placed in oven, drying ± 5 hours 12 hours is toasted in 60 DEG C ± 20 DEG C of temperature, so that institute be made
State the first powder.
Optionally, the embodiment of second powder preparation step are as follows: by the salt of first powder and 15mL ± 5mL
Sour, 15mL ± 5mL dehydrated alcohol mixes and obtains third in heating water bath ± 2 hours 6 hours in 60 DEG C ± 20 DEG C of temperature
Solution, the interior sodium hydroxide solution that is added of Xiang Suoshu third solution is to neutrality, then to exist the pH value adjustment of the third solution
Drying ± 5 hours 12 hours is toasted in 60 DEG C ± 20 DEG C of temperature, so that second powder be made；And/or
The embodiment of the third powder preparation step are as follows: by second powder of 3g ± 1g be added 3mL ± 1mL and
It is impregnated in interior the first alcohol mixeding liquid containing 0.019mol ± 0.005mol chloroplatinic acid or chloroplatinate ± 10 hours 24 hours
The third solution is obtained, then will be added described the dissolved with the second alcohol mixeding liquid of 0.5mol ± 0.1mol sodium borohydride
In three solution, stirs ± 1 hour 2 hours, drying ± 5 hours 12 hours is then toasted in 60 DEG C ± 20 DEG C of temperature, thus
The third powder is made.
Second object of the present invention is to provide a kind of mesoporous phosphonic acids molybdenum material, uses above-mentioned mesoporous phosphonic acids molybdenum materials
The preparation method of material is made.
Third object of the present invention is to provide a kind of application of above-mentioned mesoporous phosphonic acids molybdenum material, specifically, described
Mesoporous phosphonic acids molybdenum material is used to prepare the carrier of bioactive substance.
Optionally, the mesoporous phosphonic acids molybdenum material is used to prepare in biosensor target determinand and offer for identification
The bio-sensing layer of reacting environment.
Mesoporous phosphonic acids molybdenum material provided by the invention and its preparation method and application uses hard template legal system compared to existing
Standby mesoporous material, has the following beneficial effects:
1) work as soft template using surfactant as cetyl trimethylammonium bromide, in this way, removing removing template
It is relatively mild when agent, it is not easy to have an impact the pore structure of material, template agent removing can be removed to the full extent.Second
Remove template agent removing with hydrochloric acid and dehydrated alcohol in powder preparation step, and subsequent calcination process also correspond to one it is secondary
The link for removing template agent removing further reduces the residual quantity of template, this is not available for existing hard template method.
2) ethylenediamine tetramethylene phosphonic acid used in preparation process also provides carbon source and nitrogen while providing phosphorus source
Source is equivalent to and introduces two kinds of nonmetalloids of C and N in the skeleton of phosphonic acids molybdenum, forms organic and inorganic heterozygosis porous material
Skeleton structure, effectively improve the electric conductivity and stability for ultimately forming hole phosphonic acids molybdenum material.Thus manufactured meso-hole structure
Not only contribute to mass transfer, moreover it is possible to a high specific surface area be provided, active site is increased.And the nitrogen of electronegativity difference
Atom is easy to form synergistic effect with carbon atom, is conducive to the quick progress of redox reaction, while the heterogeneous original in material
Covalent bonding together between son also improves the stability of material to a certain degree.The skeleton structure of organic and inorganic heterozygosis porous material
It is to be bonded together to form by organic group and inorganic matter, organo-functional group is dispersed in skeleton, this allows it in certain journey
Artificial adjustment is carried out on degree.At the same time, inorganic, organic component heterogeneity is combined, so that heterozygosis porous material is being urged
Change etc. shows huge potentiality.
3) the mesoporous phosphonic acids molybdenum material being prepared into is surface in electronegativity and the mesoporous phosphonic acids molybdenum of Supported Pt Nanoparticles, is had excellent
Anti-interference ability does not have to add anti-interference layer by the property of itself, the speed of response can be improved in anti-interference test.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without creative efforts belongs to the model that the present invention protects
It encloses.
It should be noted that the description for being related to " first ", " second " etc. in the present invention is used for description purposes only, and cannot
It is interpreted as its relative importance of indication or suggestion or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include at least one of the features.In addition, the skill between each embodiment
Art scheme can be combined with each other, but must be based on can be realized by those of ordinary skill in the art, when technical solution
Will be understood that the combination of this technical solution is not present in conjunction with there is conflicting or cannot achieve when, also not the present invention claims
Protection scope within.
The preparation method of mesoporous phosphonic acids molybdenum material provided in an embodiment of the present invention, includes the following steps:
First solution preparation step, by cetyl trimethylammonium bromide (referred to as CTAB, chemical formula C19H42BrN)
It is dissolved in deionized water, ethylenediamine tetramethylene phosphonic acid (referred to as EDTMPA, chemical formula C is then added6H20N2O12P4) and
Simultaneously heating water bath obtains the first solution to sodium hydroxide (chemical formula NaOH)；Water-bath is a kind of heating with water as a heat transfer medium
Method heats the vessel of heated material into the water, the substance in vessel can be made to obtain uniformly；
Second solution preparation step, by ammonium molybdate (chemical formula H8MoN2O4) simultaneously stirring and dissolving is added in deionized water, so
After first solution is added and heating water bath obtains the second solution；
Second solution is aged, and is rinsed with deionized water by the first powder preparation step, then toasts
It is dried to obtain the first powder；Ageing refers to after solution precipitating is complete, when the precipitating just generated being allowed to place one section together with mother liquor
Between process；
Second powder preparation step, first powder is mixed with hydrochloric acid, dehydrated alcohol and carries out heating water bath obtains
Then the pH value adjustment of the third solution to neutrality is dried drying by third solution, obtain the second powder；Hydrochloric acid is chlorination
The aqueous solution of hydrogen；
Second powder is added and mixes containing the first ethyl alcohol of chloroplatinic acid or chloroplatinate by third powder preparation step
In liquid and immersion obtains third solution, then will be dissolved with sodium borohydride (chemical formula NaBH4) the second alcohol mixeding liquid add
Enter in the third solution, then baking is dried to obtain third powder for stirring；First alcohol mixeding liquid is specially chloroplatinic acid or chlorine
The mixed liquor of platinate and ethyl alcohol；Second alcohol mixeding liquid is specially the mixed liquor of six hydration sodium borohydrides and ethyl alcohol；
Calcining step calcines the third powder under the protection of inert gas, so that load, which is made, the mesoporous of platinum
Phosphonic acids molybdenum material.Calcining is the process being heat-treated in air or inert gas at a certain temperature.
Specifically, in the first solution preparation step, ethylenediamine tetramethylene phosphonic acid and sodium hydroxide can occur in soda acid
And reaction, reaction equation are as follows: C6H12N2O4P4(OH)8+ 8NaOH=C6H12N2O4P4(ONa)8+8H2O.It prepares and walks in the second solution
In rapid, ammonium molybdate is chemically reacted with the first solution, preliminarily forms unformed phosphonic acids molybdenum.In the first powder preparation step
In, ageing mainly forms pore structure using the property of surfactant, and rinsing mainly tentatively washes away the table for having neither part nor lot in pore-forming
Face activating agent, inorganic ion such as Na+Equal impurity.In the second powder preparation step, the mixed liquor master of hydrochloric acid and dehydrated alcohol
If forming meso-hole structure for extracting to fall to participate in the surfactant of pore-forming to get mesoporous phosphonic acids molybdenum is arrived, the second powder is
Mesoporous phosphonic acids molybdenum, but mesoporous phosphonic acids molybdenum at this time does not have Supported Pt Nanoparticles.In third powder preparation step, hydroboration will be dissolved with
Second alcohol mixeding liquid of sodium is added in the third solution and can chemically react, and the platinum in chloroplatinic acid is reduced out, shape
At Pt nanoparticle.In calcining step, inert gas can protection materials be not oxidized in high temperature, calcination process can also remove
Template.
Wherein, mesoporous phosphonic acids molybdenum material overall surface in electronegativity be because are as follows: in the first solution preparation step, ethylenediamine
Tetramethylene phosphonic acid comes with organo-functional group, formation-P-O after ethylenediamine tetramethylene phosphonic acid and sodium hydroxide reaction-Key, band
There is negative electrical charge；In third powder preparation step, the Pt nanoparticle that chloroplatinic acid reduction reaction obtains is negatively charged, final platinum nanometer
Particulate load is on mesoporous phosphonic acids molybdenum, so that surface electronegativity is integrally presented in the mesoporous phosphonic acids molybdenum material being finally made.
In the preparation method of mesoporous phosphonic acids molybdenum material provided in an embodiment of the present invention, cetyl trimethylammonium bromide is used
Such surfactant works as soft template so that relatively mild when removing template agent removing, is not easy the pore structure to material
It has an impact, template can be completely removed to the full extent.Hydrochloric acid and dehydrated alcohol are used in the second powder preparation step
Template agent removing is removed, and also corresponds to the secondary link for removing template agent removing in subsequent calcination process, is dramatically dropped
Low influence of the template to the hole phosphonic acids molybdenum material performance being finally made.
In addition, the ethylenediamine tetramethylene phosphonic acid used in preparation process, also provides carbon source while providing phosphorus source
And nitrogen source, it is equivalent to and introduces two kinds of nonmetalloids of C and N in the skeleton of phosphonic acids molybdenum, it is porous to form organic and inorganic heterozygosis
The skeleton structure of material effectively improves the electric conductivity and stability for ultimately forming hole phosphonic acids molybdenum material.Thus manufactured mesoporous
Structure not only contributes to mass transfer, moreover it is possible to provide a high specific surface area, increase active site.And electronegativity difference
Nitrogen-atoms be easy to carbon atom formed synergistic effect, be conducive to the quick progress of redox reaction, while different in material
The interatomic Covalent bonding together of matter, also improves the stability of material to a certain degree.The skeleton of organic and inorganic heterozygosis porous material
Structure is bonded together to form by organic group and inorganic matter, organo-functional group is dispersed in skeleton, this allows it one
Determine to carry out artificial adjustment in degree.At the same time, inorganic, organic component heterogeneity is combined, so that heterozygosis porous material
In terms of show huge potentiality.
Preferably, in the first solution preparation step, the amount of cetyl trimethylammonium bromide be 0.005mol ±
0.003mol, the amount of the deionized water for dissolving cetyl trimethylammonium bromide are 20mL ± 10mL.
It is further preferable that in the first solution preparation step, the amount of cetyl trimethylammonium bromide be 0.005mol ±
0.001mol, the amount of the deionized water for dissolving cetyl trimethylammonium bromide are 20mL ± 2mL.
Preferably, in the first solution preparation step, the amount of ethylenediamine tetramethylene phosphonic acid is 0.001mol ± 0.0005mol
, the amount of sodium hydroxide is 0.008mol ± 0.004mol.
It is further preferable that in the first solution preparation step, the amount of ethylenediamine tetramethylene phosphonic acid be 0.001mol ±
0.0002mol's, the amount of sodium hydroxide is 0.008mol ± 0.001mol.
Preferably, in the first solution preparation step, the temperature of heating water bath is 45 DEG C ± 10 DEG C, and the time of heating water bath is
30 points ± 20 points.
It is further preferable that in the first solution preparation step, the temperature of heating water bath is 45 DEG C ± 5 DEG C, heating water bath when
Between be 30 points ± 5 points.
As a preferred embodiment of the present embodiment, the embodiment of first solution preparation step are as follows: will
The cetyl trimethylammonium bromide of 0.005mol ± 0.001mol is dissolved in the deionized water of 20mL ± 2mL, is then added
The ethylenediamine tetramethylene phosphonic acid of 0.001mol ± 0.0002mol and the sodium hydroxide of 0.008mol ± 0.001mol, and 45
Heating water bath 30 divides ± 5 points in DEG C ± 5 DEG C of temperature, so that first solution be made.
Preferably, in second solution preparation step, the amount of ammonium molybdate is 0.048mol ± 0.012mol, for dissolving
The amount of the deionized water of ammonium molybdate is 5mL ± 1.5mL.
It is further preferable that the amount of ammonium molybdate is 0.048mol ± 0.002mol in second solution preparation step, it is used for
The amount for dissolving the deionized water of ammonium molybdate is 5mL ± 0.5mL.
Preferably, in the second solution preparation step, the temperature of heating water bath is 45 DEG C ± 10 DEG C, and the time of heating water bath is
± 1 hour 2 hours.
It is further preferable that in the second solution preparation step, the temperature of heating water bath is 45 DEG C ± 5 DEG C, heating water bath when
Between be ± 0.1 hour 2 hours.
As a preferred embodiment of the present embodiment, the embodiment of second solution preparation step are as follows: will
The ammonium molybdate of 0.048mol ± 0.002mol is put into the deionized water of 5mL ± 0.5mL and stirring and dissolving, is then added described the
One solution and heating water bath ± 0.1 hour 2 hours in 45 DEG C ± 5 DEG C of temperature, so that second solution be made.
Preferably, in first powder preparation step, the temperature of ageing is 120 DEG C ± 40 DEG C, and the time of ageing is 24
± 10 hours hours.
It is further preferable that the temperature of ageing is 120 DEG C ± 10 DEG C in first powder preparation step, the time of ageing
It is ± 0.5 hour 24 hours.
Preferably, in first powder preparation step, time rinsed to rinse 1~5 time using deionized water is rinsed
Number can be 1 time or 2 times or 3 times or 4 times or 5 times.
It is further preferable that rinsing in first powder preparation step to be rinsed 2~4 times using deionized water.
Preferably, in first powder preparation step, toasting dry temperature is 60 DEG C ± 20 DEG C, when toasting dry
Between be ± 5 hours 12 hours.
It is further preferable that toasting dry temperature is 60 DEG C ± 5 DEG C in first powder preparation step, drying is toasted
Time be ± 0.5 hour 12 hours.
As a preferred embodiment of the present embodiment, the embodiment of first powder preparation step are as follows: will be described
The internally placed pressure of second solution is greater than in the autoclave pressure of an atmospheric pressure, and it is small that 24 are aged in 120 DEG C ± 10 DEG C of temperature
When ± 0.5 hour, rinsed 3 times, be then placed in oven with deionized water, it is small that dry 12 are toasted in 60 DEG C ± 5 DEG C of temperature
When ± 0.5 hour, so that first powder be made.Pressure in autoclave pressure is between 0.101MPa~100MPa.Herein, it presses
Power kettle is mainly used for providing the reaction environment for being greater than an atmospheric pressure, is tied with forming hole using the property of surfactant
Structure.
Preferably, in second powder preparation step, the amount of hydrochloric acid is 15mL ± 5mL, and the amount of dehydrated alcohol is 15mL
±5mL。
It is further preferable that the amount of hydrochloric acid is 15mL ± 1mL, and the amount of dehydrated alcohol is in second powder preparation step
15mL±1mL。
Preferably, in second powder preparation step, the temperature of heating water bath is 60 DEG C ± 20 DEG C, heating water bath when
Between be ± 2 hours 6 hours.
It is further preferable that the temperature of heating water bath is 60 DEG C ± 5 DEG C, heating water bath in second powder preparation step
Time be ± 0.2 hour 6 hours.
Preferably, in second powder preparation step, by the pH value adjustment of third solution to neutral mode are as follows: to the
Sodium hydroxide solution is added in three solution.As a preferable embodiment, the present embodiment is molten using the sodium hydroxide of 0.01mol
Drop neutralizes surely, and the PH of third solution is adjusted to neutrality.
Preferably, in second powder preparation step, toasting dry temperature is 60 DEG C ± 20 DEG C, when toasting dry
Between be ± 5 hours 12 hours.
Preferably, in second powder preparation step, toasting dry temperature is 60 DEG C ± 5 DEG C, when toasting dry
Between be ± 0.5 hour 12 hours.
As a preferred embodiment of the present embodiment, the embodiment of second powder preparation step are as follows: will be described
First powder is mixed with the dehydrated alcohol of the hydrochloric acid of 15mL ± 1mL, 15mL ± 1mL and water-bath adds in 60 DEG C ± 5 DEG C of temperature
Heat obtains third solution in ± 0.2 hour 6 hours, sodium hydroxide solution is added into third solution with by the PH of the third solution
Value is adjusted to neutrality, and drying ± 0.5 hour 12 hours is then toasted in 60 DEG C ± 5 DEG C of temperature, to be made described second
Powder.
Preferably, in the third powder preparation step, the amount using the second powder is 3g ± 1g, the first ethyl alcohol used
The amount of mixed liquor is 3mL ± 1mL, and contains the chloroplatinic acid or chloroplatinic acid of 0.019mol ± 0.005mol in the first alcohol mixeding liquid
Salt, soaking time are ± 10 hours 24 hours.
It is further preferable that in the third powder preparation step, the amount using the second powder is 3g ± 0.2g, the used
The amount of one alcohol mixeding liquid is 3mL ± 0.2mL, and contains the chloroplatinic acid of 0.019mol ± 0.001mol in the first alcohol mixeding liquid
Or chloroplatinate, soaking time are ± 1 hour 24 hours.
Preferably, in the third powder preparation step, the first alcohol mixeding liquid is specially six hydration chloroplatinic acid (chemical formulas
It is H2PtCl6·6H2O) with the mixed liquor of ethyl alcohol；It of courses, in concrete application, the first alcohol mixeding liquid can also be platinic sodium chloride
Or the mixed liquor of the chloroplatinates such as potassium chloroplatinate and ethyl alcohol.Preferably, in the third powder preparation step, the second ethyl alcohol is mixed
The sodium borohydride for containing 0.5mol ± 0.1mol in liquid is closed, mixing time is ± 1 hour 2 hours.
It is further preferable that containing 0.5mol ± 0.05mol in the second alcohol mixeding liquid in the third powder preparation step
Sodium borohydride, mixing time be ± 0.2 hour 2 hours.
Preferably, in the third powder preparation step, toasting dry temperature is 60 DEG C ± 20 DEG C, when toasting dry
Between be ± 5 hours 12 hours.
It is further preferable that toasting dry temperature is 60 DEG C ± 5 DEG C in the third powder preparation step, drying is toasted
Time be ± 0.5 hour 12 hours.
As a preferred embodiment of the present embodiment, the embodiment of the third powder preparation step are as follows: by 3g ±
3mL ± 0.2mL and interior first containing the hydration chloroplatinic acid of 0.019mol ± 0.001mol six is added in second powder of 0.2g
It is impregnated in alcohol mixeding liquid ± 1 hour 24 hours and obtains the third solution, then will be dissolved with 0.5mol ± 0.05mol boron hydrogen
The second alcohol mixeding liquid for changing sodium is added in the third solution, stirs ± 0.2 hour 2 hours, then in 60 DEG C ± 5 DEG C of temperature
Drying ± 0.5 hour 12 hours is toasted in degree, so that the third powder be made.
Preferably, in the calcining step, the inert gas is nitrogen or argon gas.
Preferably, in the calcining step, the calcining duration is 0.1 hour~200 hours.
It is further preferable that the calcining duration is ± 1 hour 5 hours in the calcining step.
Preferably, in the calcining step, the temperature of the calcining is 100 DEG C~1200 DEG C.
It is further preferable that the temperature of the calcining is 400 DEG C ± 100 DEG C in the calcining step.
As a preferred embodiment of the present embodiment, the embodiment of the calcining step are as follows: be filled with porcelain boat described
Third powder is placed in the reaction tube of tube furnace, is passed through nitrogen or argon gas in Xiang Suoshu reaction tube, and the flow velocity of nitrogen or argon gas is
60ml/min ± 5ml/min, and so that the third powder is calcined 5 hours in tube furnace ± 0.1 hour, and calcination temperature is
400 DEG C ± 10 DEG C, so that the mesoporous phosphonic acids molybdenum material that load has platinum be made.In calcining step, need to not stop logical nitrogen or
Argon gas is completed to calcination process.Be passed through into reaction tube nitrogen or argon gas effect be in order to exclude the air in reaction tube, and
The atmosphere of one inert gas is provided, the material in reaction tube is not protected not to be oxidized by oxygen in high temperature.
As a preferred embodiment of the present embodiment, the embodiment of the preparation method of mesoporous phosphonic acids salt material are as follows: will
2g cetyl trimethylammonium bromide is dissolved in 20mL deionized water, then be added 0.436g ethylenediamine tetramethylene phosphonic acid and
0.32g sodium hydroxide simultaneously heats 30 minutes in 45 DEG C of water-baths, and the first solution is made.Weigh 5mL deionized water and 9.408g molybdenum
Sour ammonium and stirring and dissolving, are then added in the first solution and heat 2 hours in 45 DEG C of water-baths, and the second solution is made.By second
Solution is transferred in autoclave, is aged 24 hours at 120 DEG C, is rinsed 3 times with deionized water, is then done at 60 DEG C in an oven
Dry 12 hours, the first powder is made.The first obtained powder is mixed with 15mL hydrochloric acid and 15mL dehydrated alcohol, then at 60 DEG C
It heats 6 hours in water-bath, is then adjusted to neutrality pH, it is 12 hours dry at 60 DEG C, the second powder is made, i.e., does not load
The mesoporous phosphonic acids molybdenum powder of platinum.The second powder of 3g is added in the ethanol solution of the hydration chloroplatinic acid of 3mL six and is impregnated 24 hours
To third solution, then the 0.5mol sodium borohydride dissolved with ethanol solution is added in third solution, is stirred 120 minutes, with
Obtain third powder within dry 12 hours at 60 DEG C afterwards.Third powder is loaded with porcelain boat to be placed in the reaction tube in tube furnace, to
Nitrogen is passed through in reaction tube, the flow velocity of nitrogen is 60ml/min, is calcined 5 hours in tube furnace, and calcination temperature is 400 DEG C, from
And surface is made in electronegativity and the mesoporous phosphonic acids molybdenum of Supported Pt Nanoparticles.
The preparation method of mesoporous phosphonic acids salt material provided in an embodiment of the present invention, it is intended to prepare a kind of surface electronegativity and negative
Transition metal and nonmetalloid are introduced skeleton, are synthesized and had by hydrothermal synthesis method by the mesoporous phosphonic acids salt material for carrying platinum
There is the surface electronegativity organic and inorganic heterozygosis phosphonic acids molybdenum of meso-hole structure, using ethylenediamine tetramethylene phosphonic acid as phosphorus source, ammonium molybdate is
Molybdenum source, cetyl trimethylammonium bromide are template, using the characteristic of surfactant, are provided by hydrothermal synthesis method preparation
There is the phosphonic acids molybdenum of pore structure, then remove template with a certain proportion of ethyl alcohol and hydrochloric acid, then by drying, calcining, is had
There is the surface electronegativity organic and inorganic heterozygosis phosphonic acids molybdenum of meso-hole structure.
The preparation method of mesoporous phosphonic acids salt material provided in an embodiment of the present invention works as template using ionic surfactant
Agent, and have the operating procedure (the second powder preparation step and calcining step) for removing template agent removing twice, it is ensured that template removal
Completely, and not the service performance of material is influenced；Two kinds of nonmetalloids of C and N are introduced in skeleton, further improve material
Performance, and be dispersed with organo-functional group in organic and inorganic heterozygosis porous material skeleton, this allow it to a certain extent
Artificial adjustment is carried out, also in relation with inorganic, organic component heterogeneity.
In the embodiment of the present invention, the preparation of mesoporous phosphonic acids molybdenum material using the hydrothermal synthesis in soft template method side
Method.Specifically, soft template method is using molecule flexible as template, such as surfactant.By soft template and constitute
Stronger interaction force (electrostatic force, hydrogen bond etc.), template between inorganic (or organic) the predecessor species of mesoporous framework
Synergistically compound skeleton is constructed in self assembly with skeleton species.Soft template method mainly has two synthesis paths: hydrothermal synthesis and solvent
Evaporation induced self-assembly.Wherein, hydrothermal synthesis: in synthesis process, structure directing agent (surfactant etc.) and presoma compared with
After reacting at a temperature of low, then handling under higher temperature and pressure keeps pore structure more rigid and stable, which is typical
" sol-gel " process, can be carried out under alkalinity, acid and neutrallty condition.
Further, the embodiment of the invention also provides a kind of mesoporous phosphonic acids molybdenum material, above-mentioned mesoporous phosphonic acids is used
The preparation method of molybdenum material is made.The mesoporous phosphonic acids molybdenum material being prepared into using the preparation method of above-mentioned mesoporous phosphonic acids molybdenum material
It is surface in electronegativity and the mesoporous phosphonic acids molybdenum of Supported Pt Nanoparticles, there is excellent anti-interference ability, do not have to by the property of itself
Anti-interference layer is added, the speed of response can be improved in anti-interference test.
Further, the embodiment of the invention also provides a kind of applications of above-mentioned mesoporous phosphonic acids molybdenum material, specifically, institute
Give an account of the carrier that hole phosphonic acids molybdenum material is used to prepare bioactive substance.
Preferably, the mesoporous phosphonic acids molybdenum material is used to prepare in biosensor target determinand and offer for identification
The bio-sensing layer of reacting environment.Since the surface of above-mentioned mesoporous phosphonic acids salt material is in electronegativity, therefore, it is used for being prepared into
Sarcosine biosensor have excellent interference free performance.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all at this
Under the inventive concept of invention, using equivalent structure transformation made by present specification, or directly/it is used in other indirectly
Relevant technical field is included in scope of patent protection of the invention.
Claims (10)
1. the preparation method of mesoporous phosphonic acids molybdenum material, which comprises the steps of:
First solution preparation step, cetyl trimethylammonium bromide is dissolved in deionized water, and it is sub- that ethylenediamine tetraacetic is then added
Simultaneously heating water bath obtains the first solution for methylphosphonic acid and sodium hydroxide；
Ammonium molybdate is added in deionized water simultaneously stirring and dissolving, first solution is then added simultaneously by the second solution preparation step
Heating water bath obtains the second solution；
Second solution is aged, and is rinsed with deionized water by the first powder preparation step, then toasts drying
Obtain the first powder；
Second powder preparation step, first powder is mixed with hydrochloric acid, dehydrated alcohol and carries out heating water bath obtains third
Then the pH value adjustment of the third solution to neutrality is dried drying by solution, obtain the second powder；
Second powder is added in the first alcohol mixeding liquid containing chloroplatinic acid or chloroplatinate third powder preparation step
And impregnate and obtain third solution, then the second alcohol mixeding liquid dissolved with sodium borohydride is added in the third solution, is stirred
It mixes then baking and is dried to obtain third powder；
Calcining step calcines the third powder under the protection of inert gas, so that the mesoporous phosphonic acids that load has platinum be made
Molybdenum material.
2. the preparation method of mesoporous phosphonic acids molybdenum material as described in claim 1, which is characterized in that in the calcining step, institute
Stating inert gas is nitrogen or argon gas；And/or
In the calcining step, the calcining duration is 0.1 hour~200 hours；And/or
In the calcining step, the temperature of the calcining is 100 DEG C~1200 DEG C.
3. the preparation method of mesoporous phosphonic acids molybdenum material as claimed in claim 2, which is characterized in that the implementation of the calcining step
Mode are as follows: the third powder is placed in the reaction tube of tube furnace, nitrogen or argon gas are passed through in Xiang Suoshu reaction tube, and makes institute
It states third powder and calcines 5 hours in tube furnace ± 1 hour, and calcination temperature is 400 DEG C ± 100 DEG C, so that load, which is made, to be had
The mesoporous phosphonic acids molybdenum material of platinum.
4. the preparation method of mesoporous phosphonic acids molybdenum material as described in claim 1, which is characterized in that the first solution preparation step
Rapid embodiment are as follows: by the cetyl trimethylammonium bromide of 0.005mol ± 0.003mol be dissolved in 20mL ± 10mL go from
In sub- water, the ethylenediamine tetramethylene phosphonic acid and 0.008mol ± 0.004mol of 0.001mol ± 0.0005mol is then added
Sodium hydroxide, and heating water bath 30 divides ± 20 points in 45 DEG C ± 10 DEG C of temperature, so that first solution be made.
5. such as the preparation method of the described in any item mesoporous phosphonic acids molybdenum materials of Claims 1-4, which is characterized in that described second
The embodiment of solution preparation step are as follows: the ammonium molybdate of 0.048mol ± 0.012mol is put into the deionized water of 5mL ± 1.5mL
In and stirring and dissolving, first solution and heating water bath ± 1 hour 2 hours in 45 DEG C ± 10 DEG C of temperature is then added,
To which second solution be made.
6. such as the preparation method of the described in any item mesoporous phosphonic acids molybdenum materials of Claims 1-4, which is characterized in that described first
The embodiment of powder preparation step are as follows: the internally placed pressure of the second solution is greater than to the autoclave pressure of an atmospheric pressure
In, it is aged in 120 DEG C ± 40 DEG C of temperature ± 10 hours 24 hours, is rinsed 1~5 time with deionized water, be then placed in oven
In, drying ± 5 hours 12 hours is toasted in 60 DEG C ± 20 DEG C of temperature, so that first powder be made.
7. such as the preparation method of the described in any item mesoporous phosphonic acids molybdenum materials of Claims 1-4, which is characterized in that described second
The embodiment of powder preparation step are as follows: by the hydrochloric acid of first powder and 15mL ± 5mL, the dehydrated alcohol of 15mL ± 5mL
Third solution is mixed and obtained for heating water bath ± 2 hours 6 hours in 60 DEG C ± 20 DEG C of temperature, is added in Xiang Suoshu third solution
Enter sodium hydroxide solution then to toast the pH value adjustment of the third solution to neutrality in 60 DEG C ± 20 DEG C of temperature dry
± 5 hours dry 12 hours, so that second powder be made；And/or
The embodiment of the third powder preparation step are as follows: 3mL ± 1mL is added in second powder of 3g ± 1g and is included
Have to impregnate in the first alcohol mixeding liquid of 0.019mol ± 0.005mol chloroplatinic acid or chloroplatinate ± 10 hours 24 hours and obtain
Then it will be molten the third will to be added dissolved with the second alcohol mixeding liquid of 0.5mol ± 0.1mol sodium borohydride in the third solution
It in liquid, stirs ± 1 hour 2 hours, drying ± 5 hours 12 hours is then toasted in 60 DEG C ± 20 DEG C of temperature, to be made
The third powder.
8. mesoporous phosphonic acids molybdenum material, which is characterized in that it uses mesoporous phosphonic acids molybdenum materials as described in any one of claim 1 to 7
The preparation method of material is made.
9. the application of mesoporous phosphonic acids molybdenum material as claimed in claim 8, which is characterized in that the mesoporous phosphonic acids molybdenum material is used for
Prepare the carrier of bioactive substance.
10. the application of mesoporous phosphonic acids molybdenum material as claimed in claim 9, which is characterized in that the mesoporous phosphonic acids molybdenum material is used
In preparing in biosensor target determinand for identification and provide the bio-sensing layer of reacting environment.
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| CN111672527A (en) * | 2020-06-22 | 2020-09-18 | 齐鲁工业大学 | Molybdenum phosphide catalyst and preparation method thereof |
| CN112742473A (en) * | 2020-12-29 | 2021-05-04 | 深圳大学 | Anti-interference electrocatalytic material, preparation method thereof and electrochemical biosensor |
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| CN101036873A (en) * | 2007-01-23 | 2007-09-19 | 南开大学 | Organic phosphonium transition metal salt graded hole material preparing method and the application |
| CN101558093A (en) * | 2006-12-14 | 2009-10-14 | 巴斯夫欧洲公司 | Fine-particulate polymer dispersions comprising starch |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101558093A (en) * | 2006-12-14 | 2009-10-14 | 巴斯夫欧洲公司 | Fine-particulate polymer dispersions comprising starch |
| CN101036873A (en) * | 2007-01-23 | 2007-09-19 | 南开大学 | Organic phosphonium transition metal salt graded hole material preparing method and the application |
Cited By (2)
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|---|---|---|---|---|
| CN111672527A (en) * | 2020-06-22 | 2020-09-18 | 齐鲁工业大学 | Molybdenum phosphide catalyst and preparation method thereof |
| CN112742473A (en) * | 2020-12-29 | 2021-05-04 | 深圳大学 | Anti-interference electrocatalytic material, preparation method thereof and electrochemical biosensor |
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