CN104495916B - Amination nano titanium oxide, preparation method and applications - Google Patents

Amination nano titanium oxide, preparation method and applications Download PDF

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CN104495916B
CN104495916B CN201410479585.XA CN201410479585A CN104495916B CN 104495916 B CN104495916 B CN 104495916B CN 201410479585 A CN201410479585 A CN 201410479585A CN 104495916 B CN104495916 B CN 104495916B
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titanium oxide
nano titanium
amination
preparation
ethylenediamine
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CN104495916A (en
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陶玉贵
方毅
沈亚东
胡梦君
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Anhui Polytechnic University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

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Abstract

The invention discloses a kind of amination nano titanium oxide, preparation method and applications, described preparation method includes: a, mixed mutually with ethylenediamine solution with the operation of prepared Freamine Ⅲ by amino acid；B, butyl titanate is mixed with described Freamine Ⅲ and haptoreaction is with the operation of prepared amination nano titanium oxide.The surface of this nano titanium oxide can stably immobilized enzyme so that this this amination nano titanium oxide can extensively be applied in fixed enzyme vector；The step simultaneously preparing this amination nano titanium oxide is simple, and raw material is easy to get.

Description

Amination nano titanium oxide, preparation method and applications
Technical field
The present invention relates to nano titanium oxide, in particular it relates to a kind of amination nano titanium oxide and Preparation method, and this amination nano titanium oxide application in fixed enzyme vector.
Background technology
Big for function molecule is grafted on inorganic particulate surface, is to prepare the important of functional composite particles at present Approach.At inorganic (micron order and nanoscale) the big molecule of microparticle surfaces grafting functional, make the big molecule of function The functional excellent mechanical properties with inorganic particles, heat combines with chemical stability, can give particle Many new characteristics, as amphipathic, light sensitivity, biologically active, chemism, dispersibility, absorption Performance and the chelating ability etc. to metal ion, can be widely applied to chromatographic stationary phases, heterogeneous catalysis, Enzyme immobilizatio, the separation of large biological molecule, the crowd such as activeness and quietness of Novel adsorption separation material and plastics Many scientific researches and practical application area.
Nano-TiO2It is that one studies nano material earlier, owing to its specific surface area is big, surface-active Higher, weatherability and the feature such as corrosion resistance is good, uvioresistant ability is strong and be widely used in coating, change Cosmetic, catalyst, photosensitive material, packaging for foodstuff, environment-friendly engineering, medicine and other fields.In recent years, with The development of nanometer technology, genetic engineering, proteomics, it has been found that nano-TiO2Table The basis being to increase its application is modified in face.At present, basis and application to nano-TiO2Do Numerous studies, have found that titanium dioxide surface contains substantial amounts of oh group so that its be easy to There is association reaction in other functional groups, thus prepares surface and contain the functional nano TiO of several functions group2 Particle, so can be carried out nano-TiO2Functionalization, fixing, and carry out the table of other complexity Face reaction etc. so that it is have more being widely applied property.
Cellular glass, porous silicon ball, aluminum oxide and diatomite are current widely used inorganic carriers, But they need the activation through strong acid or highly basic when for immobilised enzymes, then return for a long time in toluene Stream carries out silanization, and the preparation process of carrier is loaded down with trivial details.Nano titanium oxide is due to its good biofacies simultaneously The advantages such as capacitive, bigger specific surface area are widely used in multiple enzyme immobilizatio.But the biggest In most cases, enzyme is after being fixed to nano-carrier, and its catalysis activity all has reduction in various degree.
Summary of the invention
It is an object of the invention to provide a kind of amination nano titanium oxide and this amination nano-silica Change preparation method and this amination nano titanium oxide application in fixed enzyme vector of titanium.This nanometer The surface of titanium dioxide has abundant amino, so that this amination nano titanium oxide is fixing Change in zymophore and can extensively apply；The step simultaneously preparing this amination nano titanium oxide is simple, former Material is easy to get.
By research, the present inventor finds that the amino on inorganic carrier surface can not only play fixing site Effect, simultaneously works as protecting the function of the enzyme of absorption on inorganic carrier so that enzyme is it can be avoided that base catalysis The holding of the activity of the destruction to enzyme molecule native conformation such as agent, high-speed stirred and high temperature, beneficially enzyme. The surface amino groups density of many empty glass, many empty silicon balls and pure nano titanium oxide is the most relatively low, therefore the present invention People carries out amido modified preparation amination nano titanium oxide on the surface of nano titanium oxide, so that ammonia Just there is abundant amino on base nano titanium oxide surface to serve as fixing site, simultaneously in order to keep enzyme Activity so that this amination nano titanium oxide can make as efficient fixed enzyme vector With.
To achieve these goals, the present invention provides the preparation method of a kind of amination nano titanium oxide, Described preparation method includes:
A, lysine is mixed with ethylenediamine solution mutually with the operation of prepared lysine solution；
B, butyl titanate is mixed with described lysine solution and haptoreaction with prepared amination nanometer The operation of titanium dioxide.
Present invention provides a kind of amination nano titanium oxide, described amination nano titanium oxide leads to Cross above-mentioned preparation method to be prepared from.
Present invention also offers the application in fixed enzyme vector of the above-mentioned amination nano titanium oxide.
By technique scheme, the present invention passes through water heat transfer nano titanium oxide, and is directly receiving The surface of rice titanium dioxide carries out amination modification and obtains amination nano titanium oxide.This amination nanometer The amino density on the surface of titanium dioxide may be up to 3mmol g-1, so that this amination nano-silica Change titanium to use as fixed enzyme vector completely.The preparation method of this nano titanium oxide is one simultaneously One-step hydrothermal, step is simple, and only needs solvent washing simply just can purify.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of specification, with Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.? In accompanying drawing:
Fig. 1 is the result statistical chart of the amino content on each nano titanium oxide surface in detection example 1；
Fig. 2 is amination nano titanium oxide A1 and the FT-IR of nano titanium oxide B1 in detection example 2 Collection of illustrative plates；
Fig. 3 is nano titanium oxide B1 SEM figure under amplifying 30,000 times in detection example 3；
Fig. 4 is nano titanium oxide B1 SEM figure under amplifying 100,000 times in detection example 3；
Fig. 5 is amination nano titanium oxide A1 SEM figure under amplifying 30,000 times in detection example 3；
Fig. 6 is amination nano titanium oxide A1 SEM figure under amplifying 100,000 times in detection example 3；
Fig. 7 is the Tg figure of amination nano titanium oxide A1 and nano titanium oxide B1 in detection example 3.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides the preparation method of a kind of amination nano titanium oxide, described preparation method bag Include:
A, lysine is mixed with ethylenediamine solution mutually with the operation of prepared lysine solution；
B, butyl titanate is mixed with described lysine solution and haptoreaction with prepared amination nanometer The operation of titanium dioxide.
Said method is in ethylenediamine solution, directly by one pot of hydro-thermal method by lysine, ethylenediamine and titanium Acid four butyl esters carry out haptoreaction, and prepared surface is formed with the nano titanium oxide of a large amount of amino.This amino The amino changing nano titanium oxide surface can be as the fixing site of immobilized enzyme, so that this amination It is complete that nano titanium oxide can stably play effect of immobilized enzyme, i.e. this amination nano titanium oxide Can use as efficient fixed enzyme vector.
In the present invention, the consumption of each reactant can change in wide scope, i.e. butyl titanate, The consumption of the ethylenediamine in lysine and ethylenediamine solution can select in wide scope.So that institute The density on the surface stating nano titanium oxide is bigger, it is preferable that relative to metatitanic acid four fourth of 100 weight portions Ester, the consumption of described lysine is 2-20 weight portion, the consumption of the ethylenediamine in described ethylenediamine solution For 20-300 weight portion.It is highly preferred that relative to the butyl titanate of 100 weight portions, described bad ammonia The consumption of acid is 5-15 weight portion, and the consumption of the ethylenediamine in described ethylenediamine solution is 80-210 weight Part.
In step a, ethylenediamine solution used can be now with the current, it is also possible to is commercially available ethylenediamine Solution.Can volatilize with steam in view of ethylenediamine and easily absorbing carbon dioxide generates non-volatile from air Carbonate, it is preferable that ethylenediamine solution used is now with the current, i.e. before step a, described Preparation method also includes ethylenediamine and solvent are mixed the operation with prepared ethylenediamine solution.
In the embodiment that ethylenediamine solution used is now with the current, molten in described ethylenediamine solution Agent is water, and relative to the butyl titanate of 100 weight portions, the consumption of described solvent is 700-1000 Weight portion.
It addition, for the productivity improving amination nano titanium oxide, it is preferable that described catalytic Reaction temperature is 100-120 DEG C, and the described catalytic reaction time is 10-12h.
Meanwhile, present invention provides a kind of amination nano titanium oxide, described amination nano-silica Change titanium to be prepared from by above-mentioned preparation method.
Additionally, present invention also offers above-mentioned amination nano titanium oxide in fixed enzyme vector Application.From the foregoing, the amino density on surface can be up to 3mmol g-1Nano titanium oxide complete Entirely can serve as fixed enzyme vector to use.
Hereinafter will be described the present invention by embodiment.In following example, amino density is joined The detection method of number is: take W0G nano-TiO2At V1mLN1The standard HCl solution of mol/L soaks More than 3h, then rinses the nano-TiO after bubble with water2And collect washing lotion, and use N2Mol/L standard NaOH Solution carries out back titration, spends standard NaOH solution V2ML, calculates amino content with following formula (A, mmol/g): A=(N1V1-N2V2)/W0；FFIR parameter (FT-IR) is passed through The IRPrestige-21 FTIR technique instrument of Japan's Shimadzu records；ESEM (SEM) spectrogram is recorded by the S-4800 SEM instrument of FDAC；DTG is joined Number (Tg figure) is recorded by the DSC6200 Thermal Synthetic Analysis instrument of NSK Electronics Co., Ltd..
Lysine be the Hui Xing biochemical reagents Co., Ltd trade mark be the commercially available product of 62016734, metatitanic acid four fourth Ester be Chemical Reagent Co., Ltd., Sinopharm Group's trade mark be the commercially available product of 80122828, ethylenediamine is Shanghai The Ling Feng chemical reagent Co., Ltd trade mark is the commercially available product of 10009518.
Embodiment 1
Anhydrous ethylenediamine is dissolved in after distilled water mixes and is made into 30mL ethylenediamine solution (Wherein ethylenediamine 5g, water 25g), then the lysine of 0.4g is added extremely In above-mentioned ethylenediamine solution and mix formation lysine solution, then by 3mL (3g) metatitanic acid positive four Butyl ester also stirs 30min formation reaction solution, and reaction solution is placed in polytetrafluoroethyllining lining inner bag In stainless steel cauldron, at 100 DEG C, carry out hydro-thermal reaction be precipitated；Finally receive centrifugal for sediment Collection, and clean with distilled water, absolute ethyl alcohol and distilled water successively, and in 60 DEG C of dry 10h, obtain amino Change nano titanium oxide A1.
The amino content of this amination nano titanium oxide is 3mmol g-1。
Embodiment 2
Carry out according to the method for embodiment 1, except that lysine is 0.3g, prepare amination nanometer Titanium dioxide A2.
The amino content of this amination nano titanium oxide is 2.7mmol g-1。
Embodiment 3
Carry out according to the method for embodiment 1, except that lysine is 0.5g, prepare amination nanometer Titanium dioxide A3.
The amino content of this amination nano titanium oxide is 2.8mmol g-1。
Embodiment 4
Carry out according to the method for embodiment 1, except that lysine is 0.2g, prepare amination nanometer Titanium dioxide A4.
The amino content of this amination nano titanium oxide is 2.5mmol g-1。
Embodiment 5
Carry out according to the method for embodiment 1, except that lysine is 0.7g, prepare amination nanometer Titanium dioxide A5.
The amino content of this amination nano titanium oxide is 2.3mmol g-1。
Embodiment 6
Carry out according to the method for embodiment 1, except that ethylenediamine and water in 30mL ethylenediamine solution Volume ratio be 0.5:5.5, prepare amination nano titanium oxide A6.
The amino content of this amination nano titanium oxide is 2.0mmol g-1。
Embodiment 7
Carry out according to the method for embodiment 1, except that ethylenediamine and water in 30mL ethylenediamine solution Volume ratio be 0.75:5.25, prepare amination nano titanium oxide A7.
The amino content of this amination nano titanium oxide is 2.4mmol g-1。
Embodiment 8
Carry out according to the method for embodiment 1, except that ethylenediamine and water in 30mL ethylenediamine solution Volume ratio be 1.25:4.75, prepare amination nano titanium oxide A8.
The amino content of this amination nano titanium oxide is 2.6mmol g-1。
Embodiment 9
Carry out according to the method for embodiment 1, except that catalytic temperature is 120 DEG C, prepare Amination nano titanium oxide A9.
The amino content of this amination nano titanium oxide is 2.5mmol g-1。
Comparative example 1
Carry out according to the method for embodiment 1, except that without lysine, prepare nanometer titanium dioxide Titanium B1.
The amino content of this amination nano titanium oxide is 1mmol g-1.Illustrate reaction system does not adds Adding lysine, the amino content on nano titanium oxide surface is extremely low, and this nano titanium oxide is difficult to as height The fixed enzyme vector of effect uses.
Comparative example 2
Carry out according to the method for embodiment 1, except that without anhydrous ethylenediamine, prepare nanometer two Titanium oxide B2.
The amino content of this amination nano titanium oxide is 1.7mmol g-1.Illustrate in reaction system not Adding anhydrous ethylenediamine, the amino content on nano titanium oxide surface is extremely low, and this nano titanium oxide is difficult to Use as efficient fixed enzyme vector.
Detection example 1
Amination nano titanium oxide A1-A5 and nano titanium oxide B1 is carried out the inspection of amino content Surveying, testing result is shown in Fig. 1.As shown in Figure 1, lysine containing the amino on nano titanium oxide surface Amount has vital impact, if without lysine in reaction system, this nano titanium oxide cannot Use as efficient fixed enzyme vector.Meanwhile, the consumption of lysine at 0.3-0.5g, especially 0.4g Time, the content of the amino on nano titanium oxide surface is maximum.This is due to when the consumption of lysine is too much, Owing to the existence of lysine is unfavorable for the synergy of anhydrous ethylenediamine and titanate, have impact on nano-silica Change the forming process of titanium, thus cause the content of the amino on nano titanium oxide surface the highest；Work as lysine Consumption very few time, system lacks the NH of positively charged4 +Group is carried out with electronegative nano titanium oxide Dress, thus cause the content of the amino on nano titanium oxide surface the highest.
Detection example 2
Amination nano titanium oxide A1 and nano titanium oxide B1 is carried out FT-IR detection, result Seeing Fig. 2, wherein: a curve is the infrared spectrum of nano titanium oxide A1, b curve is nanometer titanium dioxide The infrared spectrum of titanium B1.As shown in Figure 2, it is 1400cm in wave number-1, amination nano titanium oxide A1 has strong absorption to infrared light, thus illustrates amino functional to roll into a ball successfully and be connected on nano titanium oxide surface.
Detection example 3
Amination nano titanium oxide A1 and nano titanium oxide B1 is being amplified 30,000 times and 10 respectively Carrying out SEM detection under ten thousand times, result is shown in Fig. 3-Fig. 6.Fig. 3 and Fig. 4 is nano titanium oxide respectively B1 SEM figure under amplifying 30,000 times and 100,000 times, from the two figure, nano titanium oxide The arrangement in the form of sheets of B1, but this arrangement mode is the most chaotic, and these nanometer sheet thickness are 40-70nm.Fig. 5 and Fig. 6 is that amination nano titanium oxide A1 is amplifying 30,000 times and 100,000 respectively SEM figure under Bei, from the two figure, amination nano titanium oxide A1 is regular Palta type Dense arrangement, the thickness of these nanometer sheet is at about 10nm, and wherein thinnest part reaches 7nm.
Nanometer sheet known to those skilled in the art is the thinnest more can carry more enzyme, the thus thickness of nanometer sheet Analyze visible nano titanium oxide B1 on degree and be not suitable as fixed enzyme vector, and amination nanometer two Titanium oxide A1 has the prospect as fixed enzyme vector.Above understanding from another point of view, lysine is to nanometer The growth of titanium dioxide and the formation of pattern have the most important impact.
Detection example 4
Amination nano titanium oxide A1 and nano titanium oxide B1 is carried out Tg detection, result respectively Seeing Fig. 7, wherein, a is the Tg curve of nano titanium oxide B1, and b is amination nano titanium oxide The Tg curve of A1.
It can be seen that a curve linearly declined before 400 DEG C, mass loss is serious, 400 After DEG C, along with the rising of temperature, nano titanium oxide B1 is held nearly constant.B curve is 400 Linearly declining before DEG C, mass loss is serious, and mass loss is 35.90%；Between 400-500 DEG C, There is a constant weight phase；Between 500-600 DEG C, mass loss is serious；After 600 DEG C, along with temperature Rising, nano titanium oxide B1 keep constant.Wherein, the mass loss between 500-600 DEG C 1.50% is the amino on amination nano titanium oxide A1 surface and the thermal decomposition of hydroxyl causes, thus Indirectly illustrate that amination nano titanium oxide A1 rich surface is containing amino and hydroxyl.
From embodiment and comparative example, pass through under the synergy of lysine, ethylenediamine and titanate The nano titanium oxide rich surface that hydro-thermal method is made contains amino, it is possible to make as efficient fixed enzyme vector With.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not The repetition wanted, various possible combinations are illustrated by the present invention the most separately.
Additionally, can also be combined between the various different embodiment of the present invention, as long as its Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (6)

1. the preparation method of an amination nano titanium oxide, it is characterised in that described preparation method Including:
A, lysine is mixed with ethylenediamine solution mutually with the operation of prepared lysine solution；
B, butyl titanate is mixed with described lysine solution and haptoreaction with prepared amination nanometer The operation of titanium dioxide；
Wherein, relative to the butyl titanate of 100 weight portions, the consumption of described lysine is 2-20 weight Amount part, the consumption of the ethylenediamine in described ethylenediamine solution is 20-300 weight portion；Described contact is anti- The reaction temperature answered is 100-120 DEG C, and the described catalytic reaction time is 10-12h..
The preparation method of amination nano titanium oxide the most according to claim 1, wherein, phase For the butyl titanate of 100 weight portions, the consumption of described lysine is that 5-15 measures part, described second two The consumption of the ethylenediamine in amine aqueous solution is 80-210 weight portion.
The preparation method of amination nano titanium oxide the most according to claim 1 and 2, wherein, Before step a, described preparation method also includes mixing with prepared ethylenediamine solution ethylenediamine and water Operation.
The preparation method of amination nano titanium oxide the most according to claim 3, wherein, phase For the butyl titanate of 100 weight portions, the consumption of described water is 700-1000 weight portion.
5. an amination nano titanium oxide, it is characterised in that described amination nano titanium oxide It is prepared from by the preparation method described in any one in claim 1-4.
Amination nano titanium oxide the most according to claim 5 answering in fixed enzyme vector With.
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CN109943557A (en) * 2019-03-20 2019-06-28 江西师范大学 A kind of preparation method of immobilization chitosan enzyme and its carrier
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