CN105236479B - The preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide - Google Patents
The preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of nano titanium oxide with high catalytic activity, it is prepared raw material and includes butyl titanate presoma, the dialdehyde base nanometer crystal cellulose that oxidation processes obtains, and selectively add thickener and surfactant, preparation method prepares butyl titanate and the solution of dialdehyde nanocrystalline cellulose respectively, under high speed shear, obtain both homogeneous mixtures, this mixture is carried out gel and high-temperature calcination processes and i.e. obtains target product.By using the oxidation nanometer crystalline cellulose rich in dialdehyde group as base material, and combine the effect of the auxiliary material such as thickener, surfactant, heating up in the course of reaction calcined in hydro-thermal freeze-drying and follow-up staged, induction presoma tetrabutyl titanate crystallization becomes wheat head shape nano titanium dioxide crystal particle.This crystal grain has good dispersiveness in water, and can be effectively improved its to the treatment effeciency of pigment in waste water, the optimal effectiveness in embodiment can make the degradation rate of methyl orange more than 98.5% in 12min.
Description
Technical field
The present invention relates to the preparation method of a kind of nano titanium oxide, particularly relate to a kind of highly active oxidation and receive
The preparation method of rice crystalline cellulose based titanium dioxide, belongs to the preparing technical field of inorganic nonmetallic nanometer material.
Background technology
In recent years, day by day serious along with World Environment Problems, luminous energy catalysis has become degraded environmental pollution
The important means of thing.Titanium dioxide is inexpensive with it, nontoxic, the advantage of good stability, in photocatalysis field
It is used widely.In early days in research, mostly by titania powder and waste water composition suspension system, but its
Suspension system often also exists solid particle and easily reunites and the shortcoming such as catalyst efficiency difference, and one of its reason is just
The particle being titanium dioxide is relatively big, and dispersiveness is poor, and catalyst is low with the collision probability of target molecule.Cause
How this, prepare and have good dispersion and highly active titanium dioxide optical catalyst, become titanium dioxide
A hot issue in titanium preparation and application.Current numerous research has been working on that particle diameter is less, state
In the middle of the exploitation of the titania of porous or polydispersity, to increase its specific surface area, improve photocatalysis
Activity.
In the last few years, industry engineers and technicians were to improve stability and the photocatalytic activity aspect of titanium dioxide
For the purpose of preparation method done substantial amounts of research-and-development activity, its various modified approach also more to be seen in specially
In profit document and periodical literature.Based on cellulose as natural polymer the abundantest of originating on a kind of earth,
There is renewable and fully biodegradable characteristic, and hydroxyl present on cellulose can promote titanium dioxide
Titanium is carried on the recycling on the surface of cellulose, beneficially titanium dioxide, and cellulose itself has good
Good adsorptivity, it is possible to some organic pollutions in adsorbent solution, and there is the ability strengthening catalytic rate,
The problem alleviating environmental pollution well, therefore causes the very big concern of people.With cellulose or Nanowire
The method that dimension element prepares nano titanium oxide as base material/derivant, is disclosed by following patent document:
1, Chinese invention patent specification publication number CN 103934036 A (publication date July 23 in 2014
Day) " preparation method of a kind of novel titanium dioxide-cellulose composite material " disclose a kind of novel dioxy
Change the preparation method of titanium-fiber element composite, by low temperature preparation titanium tetrachloride and the mixed solution of water, so
Rear addition cellulose is that template carries out hyperthermic treatment, and obtain that titanium dioxide nanocrystalline is carried on cellulose answers
Condensation material, this composite has the strongest catalytic capability under visible light, can be quickly by rhodamine B, methylene
The catalytic organism degradeds such as base is blue.
2, Chinese invention patent specification publication number CN 103203206 A (publication date July 17 in 2013
Day) " Cellulose/titanium dioxide/silica aerogel and preparation method thereof " disclose a kind of cellulose/dioxy
Change titanium/aerosil and preparation method thereof, mainly with nano-cellulose as nucleome, first receive in load
Rice titanium dioxide, the most again coated silica layer, aged, aging, hydrophobization, adhesion-molded and dry
The steps such as dry process, obtain Cellulose/titanium dioxide/silica aerogel, this aeroge have pliability,
High intensity, the characteristic such as antibacterial, can be widely applied to flak jackets, insulation material, compression-resistant material and sapecial coating
In field.
3, Chinese invention patent specification publication number CN 102522211 A (publication date on June 27th, 2012)
" a kind of method of preparing nanometer titanium dioxide slurry through cellulose acidification process " discloses a kind of acidifying cellulosic method
The method preparing nano titania slurry, raw material includes: titanium dioxide powder, acid solution dispersant, surface
Stabilizer, surfactant, first process titanium dioxide powder by acid solution.Then two will processed
Titanium oxide powder has been dissolved in surface stabilizer, surfactant, in point solution that acid solution powder is configured to,
Finally stirring intensification is concentrated to give certain density slurry, and this product has raw material and is easy to get, cheap for manufacturing cost,
Stable performance and output efficiency advantages of higher.
4, Chinese invention patent specification publication number CN 102849964 A (publication date on January 2nd, 2013)
" preparation method of titanium dioxide nanometer microcrystal interface fusion structural material " discloses a kind of nano titania
Crystallite interface preparation method, preparing titanium dioxide P25 powder, the ethanol solution of ethyl cellulose, add respectively
Entering n-butanol, water-bath steams ethanol and makes quasi-colloid；Forerunner is prepared with butyl titanate, ethanol and ethyl acetate
Liquid solution, with 1mol L-1Salpeter solution, deionized water and second alcoholic liquor, be added dropwise to presoma molten
Liquid is also centrifuged, and takes supernatant and puts in quasi-colloid, obtains titanium dioxide slurry, pass through serigraphy after grinding
Titanium dioxide slurry is printed onto on electro-conductive glass by technology.In a kettle., add deionized water and concentrated hydrochloric acid,
Then tilting to put in reaction solution by above-mentioned electro-conductive glass and react, obtain this material, this material can be effective
Improve the efficiency of DSSC.
5, Chinese invention patent specification publication number CN 103172897 A (publication date June 26 in 2013
Day) a kind of Nanowire disclosed in " preparation method of a kind of nano-fibre supported nano titanium oxide mesoporous material "
The preparation method of dimension load nano-titanium dioxide mesoporous material, this invention uses bigger serface, high length-diameter ratio
Biomass cellulose nanofibrils be load, by solgel reaction by hydrogen bond by nanometer titanium dioxide
Titanium scion grafting in nanofiber surface, provided effective response area, and stop gel titania grain
The fast nucleation of son, this technique can regulate mesoporous pore size by the moisture in regulation and control mixed system,
Thus obtain the composite mesoporous aerogel material that mechanical property is strong, load effect good, specific surface area is big.
6, Chinese invention patent specification publication number CN 1907864 A (publication date on February 7th, 2007)
Disclosed in " method of preparing nano titanium dioxide crystallization induced by nano microcrystalline cellulose ", one is with nano microcrystalline
Cellulose prepares square, the method for acicular nanometer titanium dioxide as crystallization derivant, induction.The method is first
Configuration weight percent concentration is the nano micro crystal cellulose aqueous dispersions of 0.01%～5%, adds auxiliary agent, warp
After ultrasonically treated, by dry nano micro crystal cellulose and four titania weight than for 1:1～1:150, to nano microcrystalline
Dripping titanium tetrachloride in cellulose aqueous dispersions, stirring reaction at 20 DEG C～120 DEG C, the reaction time is 2h～15
H, by adjusting above-mentioned process conditions, can respectively obtain square, the nano titanium oxide of needle-like.
In foregoing invention patent 1～4, the cellulose of not mentioned a size of Nano grade is at titanium dioxide compound
Use in preparation, although and patent of invention 5～6 employs nanofiber or nano micro crystal cellulose, but send out
Bright patent 5 is not directed to the preparation of the titanium dioxide nanoparticle of specific form, and patent of invention 6 is not adopted
By the step of high-temperature calcination, and its to prepare product be square or needle-like.Additionally, patent of invention 5～6 does not all carry
To obtained nanometer titanium dioxide titanium products improvement degree in terms of catalysis activity.
Additionally, the preparation result around nano titanium dioxide crystal shows in the prior art, common particle
Shape titanium dioxide dispersiveness in application system is poor, and cannot completely attach to object, to realize filling
Dividing reaction, this also greatly limit the range of application of its finished product.
How to prepare the titanium dioxide optical catalyst with good dispersion and high catalytic activity, become titanium dioxide
The problem that titanium photochemical catalyst industry engineers and technicians extremely pay close attention to, is also titanium dioxide optical catalyst industry work
The problem of journey technical staff urgently R and D.
Summary of the invention
The purpose of the present invention, it is desirable to provide a kind of preparation method with highly active oxidation nanometer titanium dioxide,
Described preparation method is for using homogeneous sol and high-temperature calcination, and the main material of selection is presoma and base material,
Auxiliary material is thickener, surfactant, or without surfactant in mixed liquor, described presoma master
Tetrabutyl titanate to be, described base material is the oxidation nanometer crystalline cellulose rich in dialdehyde base, and described thickener is
Inorganic salts thickener, described surfactant is anion surfactant, or amphoteric surfactant or
Nonionic surfactant, during preparation manipulation, by being controlled by dialdehyde base nanometer crystal cellulose pair
Butyl titanate is degree of gelation in hydro-thermal-freezing dry process, and combines the calcination processing means slowly heated up,
Advantageously a kind of pattern of inductive formation is the high-activity nano sized titanium dioxide crystal grain of wheat head shape, this crystalline substance
Body particle has fine dispersion in water, and can be effectively improved its to the treatment effeciency of pigment in waste water,
Thus overcome the deficiency that prior art exists.
For realizing the purpose of the present invention, be the technical scheme is that
A kind of preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide, it is characterised in that: institute
Stating highly active oxidation nanometer crystalline cellulose based titanium dioxide main material is presoma and nano-grade cellulosic base
Material, auxiliary material is thickener, surfactant, or without surfactant in mixed liquor, described forerunner
Body is mainly tetrabutyl titanate, and described base material is the oxidation nanometer crystalline cellulose rich in dialdehyde base, described thickening
Agent is inorganic salts thickener, and described surfactant is anion surfactant, or amophoteric surface active
Agent or nonionic surfactant, use homogeneous sol and the preparation method of high-temperature calcination, be prepared in wheat
The oxidation nanometer crystalline cellulose based titanium dioxide of fringe pattern, described homogeneous sol and the preparation side of high-temperature calcination
Method, the most rapid including five:
One), under low velocity shear, the organic solvent solution A of preparation presoma tetrabutyl titanate, in the solution
Selectively interpolation thickener, surfactant, or without surfactant in colloidal solution；
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidation reaction；
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is added dropwise over
To colloidal solution B；
Four), water combined with heat treatment freeze-drying, be sufficiently complete gel reaction；
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape；
Above-mentioned five the most rapid operating process are as follows:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, in the solution selectively interpolation thickening
Agent, surfactant, or without surfactant in colloidal solution
Take tetrabutyl titanate presoma and join in appropriate organic solvent solution, presoma and organic solvent
Mass ratio is 1:5～8, by one/multiple thickener, one/kinds of surface activating agent, adds glue after mixing to
In liquid solution, or without surfactant in colloidal solution, adding hydrochloric acid modulation pH is 3～4, and low speed is cut
Machine of cutting processes 25min～35min and prepares to obtain the organic solvent solution A of presoma, cutter low velocity shear
Speeds control is 2000r/min～3000r/min；
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidation reaction
Sodium metaperiodate in mass ratio: nanocrystalline cellulose is that 3:1～6:1 weighs sample, is transferred in there-necked flask,
Flask leads to nitrogen lucifuge, is 40 DEG C～60 DEG C in temperature in the material concentration that mass percent is 5%～8%,
PH is reaction 4h～6h under conditions of 3～4.5, i.e. can get aldehyde group content and is up to 6000 μm ol/g～7500
The bis oxide aldehyde radical nanocrystalline cellulose of μm ol/g (being measured by alkali exhaust method), products obtained therefrom is rhabdolith
Structure, the addition by controlling deionized water obtains the mass percent of oxidation nanometer crystalline cellulose further
Concentration is the colloid emulsion B of 3%～8%；
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is added dropwise over
To colloid emulsion B
Under the relatively slow-speed of revolution of 5000r/min～8000r/min, in the colloid emulsion B of hydrotropism's carrier dropwise
The organic solvent solution A of dropping presoma tetrabutyl titanate, after completion of dropwise addition, improves rotating speed to 20000
R/min～23000r/min down cut 5min～10min, makes two kinds of emulsions be sufficiently mixed, in the process, logical
Cross and add hydrochloric acid and control the pH of system in 3～4；
Four), water combined with heat treatment freeze-drying, be sufficiently complete gel reaction
Above-mentioned mixed emulsion is transferred in water bath with thermostatic control, enters under the rotating speed of 18000r/min～20000r/min
Row hydro-thermal shear treatment 0.5h～1h, it is 45 DEG C～55 DEG C that bath temperature controls, by gained colloidal sol at room temperature bar
After part ageing 48h～50h, carry out freeze-drying, control drying time as 8h～10h；
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape
Lyophilized gel is transferred in high temperature furnace, is first warming up to 200 DEG C with the step rate of 5 DEG C/min,
Then adjusting heating rate is 15 DEG C/min until 415 DEG C～435 DEG C, calcination processing 1h～1.5 at this temperature
The powder titanium dioxide crystal particle of i.e. available white after h, this crystal morphology is special wheat head shape, and
Reactivity is high.
Described dialdehyde base oxidation nanometer crystalline cellulose, for through sodium periodate oxidation process obtain rich in aldehyde radical
Nanocrystalline cellulose, its size index is length 30nm～180nm, diameter 2nm～60nm, described fibre
Dimension element is nanocrystalline for making by oneself or commercially available, and wherein self-control approach can be by hydrolysis, enzymolysis or mechanical treatment sulfuric acid
Salt wood pulp, cotton pulp, cotton linter, the living beings raw material of agricultural waste material, or synthesize bacterium by mushroom
Cellulose, or from tunicate, extraction obtains cellulose substances, a wherein typical preparation process of example
Being described as follows: commercially available sulfate needle cotton starch plate, it is 3%～6% that quality of material percent concentration controls,
Mass fraction be 64.3% sulfuric acid acid solution at 38 DEG C, react 1h～3h, dilute, be centrifuged, wash, dry
Prepare after dry.
Described thickener, for the sodium chloride of inorganic salts thickener, ammonium chloride, potassium chloride, by percent mass
Than calculating, its addition is 2%～8%.
Described surfactant is that anion surfactant is aided with amphoteric surfactant or non-ionic surface is lived
Property agent, wherein anion surfactant is lauryl sodium sulfate, sodium sulfate of polyethenoxy ether of fatty alcohol,
Sodium carboxymethylcellulose, fatty alcohol polyoxyethylene ether sulfate, SAS, wherein amphoteric surface lives
Property agent or nonionic surfactant are coconut oil single ethanol amide, ethylene glycol distearyl fat acid esters.
Described physical shear process uses high-speed shearing machine to carry out, wherein in the process for preparation of precursor solution,
Use slow-revving 2000r/min～3000r/min, use high-revolving 20000 when preparing mixed liquor
R/min～23000r/min, and in hydrothermal treatment process, use high-revolving 18000r/min～20000r/min.
Described calcination processing step, for staged temperature-rise period, first heats up with the step rate of 5 DEG C/min
To 200 DEG C, then adjusting heating rate is 15 DEG C/min until 415 DEG C～435 DEG C, calcines at this temperature
Process 1h～1.5h.
The pattern of described nano titanium dioxide crystal particle is wheat head shape form.
Compared with prior art, the present invention has the advantage that and has the beneficial effect that:
Advantage
It is high that selected substrate material takes from the natural fiber after oxidation processes, security and biodegradability,
The favorable repeatability of product preparation flow.And, the nano titanium oxide in wheat head shape pattern can give it
Higher catalytic reaction activity.
Beneficial effect
1, the present invention use first oxidation nanometer crystalline cellulose containing dialdehyde group as base material, by a high speed
Shear homogeneous and hydro-thermal processes the technological guide presoma tetrabutyl titanate crystallization combined and becomes wheat head shape pattern
The crystal grain of nano titanium oxide；Meanwhile, by process optimization, the process step of high-temperature calcination is changed
Becoming staged heating mode, finally given the nano titanium oxide of a kind of wheat head shape pattern, it has good
Good water dispersible and high reactivity.
2, the raising of titanium dioxide reactivity can suitably reduce its consumption, thus reduce environment unfavorable
Impact, and effectively reduce its application cost.
3, one is provided highly active, in the preparation technology of the titania nanoparticles of wheat head shape pattern,
This both opened a Tiao Xin road for the application of cellulosic material, the most effectively extended the range of application of titanium dioxide.
4, the application of the nano titania of the present invention is extensive, can be as catalysis material, solar energy
Battery material and lithium ion battery negative material etc..
Accompanying drawing explanation
Fig. 1 be the high-activity nano titanium dioxide of wheat head shape pattern atomic force microscope images (wheat head shape,
Magnification ratio is shown in scale).
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme of the present invention is further described.
Embodiment 1
A kind of preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide, use homogeneous sol and
The preparation method of high-temperature calcination, it is prepared raw material and is made up of presoma and base material two large divisions, and is aided with increasing
Thick dose, surfactant, or without surfactant in mixed liquor, presoma therein be metatitanic acid just
Butyl ester, described base material is the oxidation nanometer crystalline cellulose rich in dialdehyde base, and auxiliary material then includes that inorganic salts increases
Thick dose, and anion surfactant be aided with appropriate amphoteric surfactant or nonionic surfactant,
The pattern of the titanium dioxide crystal particle of described preparation is wheat head shape, highly active nano-scale solid particle,
There is in water fine dispersion, and can be effectively improved its to the treatment effeciency of pigment in waste water, it is prepared
Step operation process is:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, in the solution selectively interpolation thickening
Agent, surfactant, or take the addition of tetrabutyl titanate presoma without surfactant in colloidal solution
In appropriate organic solvent solution, the mass ratio of presoma and organic solvent is 1:5～1:8, by one/many
Plant thickener, one/kinds of surface activating agent, add in colloidal solution after mixing, or in colloidal solution
Without surfactant, adding hydrochloric acid modulation pH is 3～4, and the present embodiment pH is 3.5, at low velocity shear machine
Reason 25min～35min, processes 30min, and prepares to obtain the organic solvent solution A of presoma in the present embodiment,
The speeds control of cutter low velocity shear is 2000r/min～3000r/min；
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidation reaction
Sodium metaperiodate in mass ratio: nanocrystalline cellulose is 3:1～6:1, the present embodiment mass ratio is designed as 4:1,
Weighing sample, be transferred in there-necked flask, flask leads to nitrogen lucifuge, in the thing that mass percent is 5%～8%
In material concentration, the present embodiment material concentration is designed as 6%, is 40 DEG C～60 DEG C in temperature, the present embodiment temperature
Design 40 DEG C, under conditions of pH is 3～4.5, the present embodiment pH design 4.5, react 4h～6h, this reality
Execute example reaction time design 4h, i.e. can get aldehyde group content and be up to 6000 μm ol/g～7500 μm ol/g (are passed through
Alkali exhaust method measure) bis oxide aldehyde radical nanocrystalline cellulose, obtained by the present embodiment, aldehyde group content is up to 6800
μm ol/g, product is rhabdolith structure, and the addition by controlling deionized water obtains oxidation nanometer further
The mass percent concentration of crystalline cellulose is the colloid emulsion B of 3%～8%, the oxidation nanometer that the present embodiment obtains
The concentration of crystalline cellulose is 6%；
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is added dropwise over
To colloid emulsion B
Under the relatively slow-speed of revolution of 5000r/min～8000r/min, the relatively low Design of Rotation of the present embodiment is 6000
R/min, dropwise drips the organic solvent solution of presoma tetrabutyl titanate in the colloid emulsion B of hydrotropism's carrier
A, after completion of dropwise addition, raising rotating speed is to 20000r/min～23000r/min down cut 5min～10min, originally
Shear time in embodiment is 10min, makes two kinds of emulsions be sufficiently mixed, in the process, by adding
Hydrochloric acid and control the pH of system in 3～4, it is 3 that the present embodiment controls the pH of system；
Four), water combined with heat treatment freeze-drying, be sufficiently complete gel reaction
Above-mentioned mixed emulsion is transferred in water bath with thermostatic control, enters under the rotating speed of 18000r/min～20000r/min
Row hydro-thermal shear treatment 0.5h～1h, it is 45 DEG C～55 DEG C that bath temperature controls, and in the present embodiment, hydro-thermal is sheared
The time processed and bath temperature are controlled as 1h and 45 DEG C, and at room temperature condition, gained colloidal sol is aged 48
After h～50h, carrying out freeze-drying, control drying time to be 8h～10h, the present embodiment digestion time is with dry
Time is respectively 50h and 9h；
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape
Lyophilized gel is transferred in high temperature furnace, is first warming up to 200 DEG C with the step rate of 5 DEG C/min,
Then adjusting heating rate is 15 DEG C/min until 415 DEG C～435 DEG C, calcination processing 1h～1.5 at this temperature
The powder titanium dioxide crystal particle of i.e. available white after h, its pattern is wheat head shape, as it is shown in figure 1,
And reactivity is high.
Described presoma, for tetrabutyl titanate.
Described organic solvent, for ethanol, the mixture of one or both solvents in isopropanol, the present embodiment
Middle selection ethanol, wherein butyl titanate is 1:5 with the mass ratio of ethanol.
Described dialdehyde base oxidation nanometer crystalline cellulose, for through sodium periodate oxidation process obtain rich in aldehyde radical
Nanocrystalline cellulose, its size index is length 30nm～180nm, diameter 2nm～60nm.Described fibre
Dimension element is nanocrystalline for making by oneself or commercially available, and wherein self-control approach can be by hydrolysis, enzymolysis or mechanical treatment sulfuric acid
Salt wood pulp, cotton pulp, cotton linter, the living beings raw material of agricultural waste material, or synthesize bacterium by mushroom
Cellulose, or from tunicate, extraction obtains cellulose substances, a wherein typical preparation process of example
Being described as follows: commercially available sulfate needle cotton starch plate, it is 3%～6% that inventory percentage matter specific concentration controls,
Mass fraction be 64.3% sulfuric acid acid solution at 38 DEG C, react 1h～3h, dilute, be centrifuged, wash, dry
Prepare after dry.
Described thickener, for the sodium chloride of inorganic salts thickener, ammonium chloride, potassium chloride, in the present embodiment
Selecting sodium chloride, its addition is 0.5g.
Described surfactant is that anion surfactant is aided with amphoteric surfactant or non-ionic surface is lived
Property agent, wherein anion surfactant preferably sodium dodecyl sulfate, sodium sulfate of polyethenoxy ether of fatty alcohol,
Sodium carboxymethylcellulose, fatty alcohol polyoxyethylene ether sulfate, SAS, wherein amphoteric surface lives
Property agent or nonionic surfactant are coconut oil single ethanol amide, ethylene glycol distearyl fat acid esters, this enforcement
Selecting lauryl sodium sulfate and ethylene glycol distearyl fat acid esters in example, its consumption is respectively 0.25g and 0.1g.
Described physical shear process uses high-speed shearing machine to carry out, wherein in the process for preparation of precursor solution,
Use slow-revving 2000r/min～3000r/min, select 3000r/min in the present embodiment, mixed in preparation
Using high-revolving 20000r/min～23000r/min when closing liquid, the present embodiment uses 20000r/min, and
Using high-revolving 18000r/min～20000r/min in hydrothermal treatment process, the present embodiment implements selection 19000
r/min。
Described calcination processing step, for staged temperature-rise period, is first warming up to the step rate of 5 DEG C/min
200 DEG C, then adjusting heating rate is 15 DEG C/min until 415 DEG C～435 DEG C, at this temperature at calcining
Reason 1h～1.5h, the concrete heating step that this enforcement uses is first to be warming up to the step rate of 5 DEG C/min
200 DEG C, then adjusting speed is that 15 DEG C/min is warming up to 415 DEG C, calcination processing 1h at this temperature.
Described nano titanium dioxide crystal particle, its pattern is wheat head shape, as shown in Figure 1.
Evaluate titanium dioxide granule reactivity: use methyl orange to evaluate sample at purple as light degradation object
Photocatalysis performance under outer light, the nano titanium oxide prepared by 0.1g joins 50mL mass concentration 20
In mg/L methyl orange standard liquid, the ultraviolet high-pressure sodium lamp of 250W after stirring, is used to be irradiated (light range
From 10cm), every 3min take sample centrifugal after, by its absorbance of spectrophotometric determination, and calculate first
The degradation rate of base orange understands, and titanium dioxide crystal particle reaction activity prepared by the present invention is high, can be at 12min
Inside make the degradation rate of methyl orange more than 96.5%.
Embodiment 2
A kind of preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide, its step of preparation process
Same as in Example 1, simply unlike: the organic solvent of selection is that the thickener of isopropanol and selection is
Potassium chloride, and without amphoteric surface's agent alive in mixed liquor, its preparation process operating process is:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, in the solution selectively interpolation thickening
Agent, surfactant
Taking 5g tetrabutyl titanate presoma and join in isopropanol, tetrabutyl titanate with the mass ratio of isopropanol is
1:6.5, by 0.2g potassium chloride thickener, 0.35g sodium sulfate of polyethenoxy ether of fatty alcohol anion surface active
Agent, 0.15g coconut oil single ethanol amide nonionic surfactant is added separately in mixed liquor, adds hydrochloric acid and adjusts
PH processed is 3, and low velocity shear machine processes 25min and prepare and to obtain the organic solvent solution A of presoma, cutter
The speeds control of low velocity shear is 2000r/min；
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidation reaction
Sodium metaperiodate in mass ratio: nanocrystalline cellulose is that 3:1 weighs sample, is transferred in there-necked flask, burns
The logical nitrogen lucifuge of bottle, is 47 DEG C in temperature in the material concentration that mass percent is 6.5%, and pH is 3
Under the conditions of react 5h, i.e. can get aldehyde group content and be up to the oxygen of 6800 μm ol/g (being measured by alkali exhaust method)
Changing dialdehyde base nanometer crystal cellulose, products obtained therefrom is rhabdolith structure, further by controlling deionized water
Addition obtain the colloid emulsion B that mass percent concentration is 6% of oxidation nanometer crystalline cellulose；
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is added dropwise over
To colloid emulsion B
Under the relatively slow-speed of revolution of 5000r/min, the colloid emulsion B of hydrotropism's carrier dropwise drips presoma
The organic solvent solution A of tetrabutyl titanate, after completion of dropwise addition, improves rotating speed to 20000r/min down cut 10
Min, makes two kinds of emulsions be sufficiently mixed, and in the process, controls the pH of system by adding hydrochloric acid in 3.5；
Four), water combined with heat treatment freeze-drying, be sufficiently complete gel reaction
Above-mentioned mixed emulsion is transferred in water bath with thermostatic control, under the rotating speed of 20000r/min, carries out hydro-thermal shearing
Processing 0.5h, it is 45 DEG C that bath temperature controls, and by gained colloidal sol after room temperature condition ageing 50h, carries out cold
Lyophilized dry, control drying time as 10h；
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape
Lyophilized gel is transferred in high temperature furnace, is first warming up to 200 DEG C with the step rate of 5 DEG C/min,
Then to adjust heating rate be 15 DEG C/min until 435 DEG C, at this temperature after calcination processing 1h
To the powder titanium dioxide crystal particle of white, its pattern is wheat head shape, as it is shown in figure 1, and react alive
Property is high.
Evaluate titanium dioxide crystal particle reaction activity: use methyl orange to evaluate sample as light degradation object
Photocatalysis performance under ultraviolet light, the nano titanium oxide prepared by 0.1g joins 50mL mass concentration
In 20mg/L methyl orange standard liquid, the ultraviolet high-pressure sodium lamp of 250W after stirring, is used to be irradiated (illumination
Distance 10cm), every 3min take sample centrifugal after, by its absorbance of spectrophotometric determination, and calculate
The degradation rate of methyl orange understands, and titanium dioxide crystal particle reaction activity prepared by the present invention is high, can be 12
Make the degradation rate of methyl orange more than 97.2% in min.
Embodiment 3
A kind of preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide, its step of preparation process
Same as in Example 1, simply unlike: the organic solvent of selection is that the thickener of isopropanol and selection is
Ammonium chloride.Its preparation process operating process is:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, in the solution selectively interpolation thickening
Agent, surfactant
Taking 6g tetrabutyl titanate presoma and join in isopropanol, tetrabutyl titanate with the mass ratio of isopropanol is
1:5.5, by 0.5g ammonium chloride thickener, 0.3g lauryl sodium sulfate anion surfactant, 0.15g
Ethylene glycol distearyl fat acid esters nonionic surfactant is added separately in mixed liquor, adds hydrochloric acid modulation pH and is
3.5, low velocity shear machine processes 28min and prepares and to obtain the organic solvent solution A of presoma, and cutter low speed is cut
The speeds control cut is 2300r/min；
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidation reaction
Sodium metaperiodate in mass ratio: nanocrystalline cellulose is that 4:1 weighs sample, is transferred in there-necked flask, burns
The logical nitrogen lucifuge of bottle, is 45 DEG C in temperature in the material concentration that mass percent is 7%, and pH is 4.5
Under the conditions of react 6h, i.e. can get aldehyde group content and be up to the oxygen of 6200 μm ol/g (being measured by alkali exhaust method)
Changing dialdehyde base nanometer crystal cellulose, products obtained therefrom is rhabdolith structure, further by controlling deionized water
Addition obtain the colloid emulsion B that mass percent concentration is 8% of oxidation nanometer crystalline cellulose；
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is added dropwise over
To colloid emulsion B
Under the relatively slow-speed of revolution of 5000r/min, the colloid emulsion B of hydrotropism's carrier dropwise drips presoma
The organic solvent solution A of tetrabutyl titanate, after completion of dropwise addition, improves rotating speed to 22000r/min down cut 8
Min, makes two kinds of emulsions be sufficiently mixed, and in the process, controls the pH of system by adding hydrochloric acid in 3；
Four), water combined with heat treatment freeze-drying, be sufficiently complete gel reaction
Above-mentioned mixed emulsion is transferred in water bath with thermostatic control, under the rotating speed of 19000r/min, carries out hydro-thermal shearing
Processing 1h, it is 50 DEG C that bath temperature controls, and by gained colloidal sol after room temperature condition ageing 48h, carries out cold
Lyophilized dry, control drying time as 8h；
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target of wheat head shape pattern
Product
Lyophilized gel is transferred in high temperature furnace, is first warming up to 200 DEG C with the step rate of 5 DEG C/min,
Then to adjust heating rate be 15 DEG C/min until 420 DEG C, at this temperature after calcination processing 1h
To the powder titanium dioxide crystal particle of white, its pattern is wheat head shape, as it is shown in figure 1, and react alive
Property is high.
Evaluate titanium dioxide granule reactivity: use methyl orange to evaluate sample at purple as light degradation object
Photocatalysis performance under outer light, the nano titanium oxide prepared by 0.1g joins 50mL mass concentration 20
In mg/L methyl orange standard liquid, the ultraviolet high-pressure sodium lamp of 250W after stirring, is used to be irradiated (light range
From 10cm), every 3min take sample centrifugal after, by its absorbance of spectrophotometric determination, and calculate first
The degradation rate of base orange understands, and titanium dioxide crystal particle reaction activity prepared by the present invention is high, can be at 12min
Inside make the degradation rate of methyl orange more than 96.7%.
Embodiment 4
A kind of preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide, its step of preparation process
Same as in Example 1, simply unlike: the organic solvent of selection is that the thickener of isopropanol and selection is
Potassium chloride, its preparation process operating process is:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, in the solution selectively interpolation thickening
Agent, surfactant
Taking 5g tetrabutyl titanate presoma and join in isopropanol, tetrabutyl titanate with the mass ratio of isopropanol is
1:7, by 0.8g potassium chloride thickener, 0.35g sodium carboxymethylcellulose anion surfactant, 0.15g
Coconut oil single ethanol amide nonionic surfactant is added separately in mixed liquor, adds hydrochloric acid modulation pH and is
3, low velocity shear machine processes 30min and prepares and to obtain the organic solvent solution A of presoma, cutter low velocity shear
Speeds control be 2200r/min；
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidation reaction
Sodium metaperiodate in mass ratio: nanocrystalline cellulose is that 5:1 weighs sample, is transferred in there-necked flask, burns
The logical nitrogen lucifuge of bottle, is 50 DEG C in temperature in the material concentration that mass percent is 6%, and pH is the bar of 3
React 5.5h under part, i.e. can get aldehyde group content and be up to the oxygen of 7300 μm ol/g (being measured by alkali exhaust method)
Changing dialdehyde base nanometer crystal cellulose, products obtained therefrom is rhabdolith structure, further by controlling deionized water
Addition obtain the colloid emulsion B that mass percent concentration is 8% of oxidation nanometer crystalline cellulose；
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is added dropwise over
To colloid emulsion B
Under the relatively slow-speed of revolution of 5500r/min, the colloid emulsion B of hydrotropism's carrier dropwise drips presoma
The organic solvent solution A of tetrabutyl titanate, after completion of dropwise addition, improves rotating speed to 23000r/min down cut 7
Min, makes two kinds of emulsions be sufficiently mixed, and in the process, controls the pH of system by adding hydrochloric acid in 3.5；
Four), water combined with heat treatment freeze-drying, be sufficiently complete gel reaction
Above-mentioned mixed emulsion is transferred in water bath with thermostatic control, under the rotating speed of 20000r/min, carries out hydro-thermal shearing
Processing 1h, it is 50 DEG C that bath temperature controls, and by gained colloidal sol after room temperature condition ageing 50h, carries out cold
Lyophilized dry, control drying time as 9h；
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape
Lyophilized gel is transferred in high temperature furnace, is first warming up to 200 DEG C with the step rate of 5 DEG C/min,
Then to adjust heating rate be 15 DEG C/min until 435 DEG C, at this temperature after calcination processing 1.2h
To the powder titanium dioxide crystal particle of white, its pattern is wheat head shape, as it is shown in figure 1, and react alive
Property is high.
Evaluate titanium dioxide granule reactivity: use methyl orange to evaluate sample at purple as light degradation object
Photocatalysis performance under outer light, the nano titanium oxide prepared by 0.1g joins 50mL mass concentration 20
In mg/L methyl orange standard liquid, the ultraviolet high-pressure sodium lamp of 250W after stirring, is used to be irradiated (light range
From 10cm), every 3min take sample centrifugal after, by its absorbance of spectrophotometric determination, and calculate first
The degradation rate of base orange understands, and titanium dioxide crystal particle reaction activity prepared by the present invention is high, can be at 12min
Inside make the degradation rate of methyl orange more than 98%.
Embodiment 5
A kind of preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide, its step of preparation process
Same as in Example 1, simply unlike: the organic solvent of selection is that the thickener of isopropanol and selection is
Ammonium chloride, its preparation process operating process is:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, in the solution selectively interpolation thickening
Agent, surfactant
Taking 5g tetrabutyl titanate presoma and join in isopropanol, tetrabutyl titanate with the mass ratio of isopropanol is
1:5, by 0.6g ammonium chloride thickener, 0.5g fatty alcohol polyoxyethylene ether sulfate anion surfactant,
0.15g ethylene glycol distearyl fat acid esters nonionic surfactant is added separately in mixed liquor, adds hydrochloric acid modulation
PH is 3.5, and low velocity shear machine processes 28min and prepare and to obtain the organic solvent solution A of presoma, cutter
The speeds control of low velocity shear is 2300r/min；
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidation reaction
Sodium metaperiodate in mass ratio: nanocrystalline cellulose is that 6:1 weighs sample, is transferred in there-necked flask, burns
The logical nitrogen lucifuge of bottle, is 43 DEG C in temperature in the material concentration that mass percent is 8%, and pH is the bar of 4
React 5.5h under part, i.e. can get aldehyde group content and be up to the oxygen of 6500 μm ol/g (being measured by alkali exhaust method)
Changing dialdehyde base nanometer crystal cellulose, products obtained therefrom is rhabdolith structure, further by controlling deionized water
Addition obtain the colloid emulsion B that mass percent concentration is 8% of oxidation nanometer crystalline cellulose；
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is added dropwise over
To colloid emulsion B
Under the relatively slow-speed of revolution of 5000r/min, the colloid emulsion B of hydrotropism's carrier dropwise drips presoma
The organic solvent solution A of tetrabutyl titanate, after completion of dropwise addition, improves rotating speed to 20000r/min down cut 8
Min, makes two kinds of emulsions be sufficiently mixed, and in the process, controls the pH of system by adding hydrochloric acid in 3；
Four), water combined with heat treatment freeze-drying, be sufficiently complete gel reaction
Above-mentioned mixed emulsion is transferred in water bath with thermostatic control, under the rotating speed of 19000r/min, carries out hydro-thermal shearing
Processing 0.55h, it is 48 DEG C that bath temperature controls, and by gained colloidal sol after room temperature condition ageing 48h, carries out
Freeze-drying, controls as 8h drying time；
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target of wheat head shape pattern
Product
Lyophilized gel is transferred in high temperature furnace, is first warming up to 200 DEG C with the step rate of 5 DEG C/min,
Then adjusting heating rate is 15 DEG C/min until 425 DEG C, at this temperature after calcination processing 1.5h
Obtaining the powder titanium dioxide crystal particle of white, its pattern is wheat head shape, as it is shown in figure 1, and reaction
Activity is high.
Evaluate titanium dioxide granule reactivity: use methyl orange to evaluate sample at purple as light degradation object
Photocatalysis performance under outer light, the nano titanium oxide prepared by 0.1g joins 50mL mass concentration 20
In mg/L methyl orange standard liquid, the ultraviolet high-pressure sodium lamp of 250W after stirring, is used to be irradiated (light range
From 10cm), every 3min take sample centrifugal after, by its absorbance of spectrophotometric determination, and calculate first
The degradation rate of base orange understands, and titanium dioxide crystal particle reaction activity prepared by the present invention is high, can be at 12min
Inside make the degradation rate of methyl orange more than 97%.
Embodiment 6
A kind of preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide, its step of preparation process
Same as in Example 1, simply unlike: the organic solvent of selection is that the thickener of isopropanol and selection is
Potassium chloride, its preparation process operating process is:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, in the solution selectively interpolation thickening
Agent, surfactant
Taking 3g tetrabutyl titanate presoma and join in isopropanol, tetrabutyl titanate with the mass ratio of isopropanol is
1:6, by 0.35g potassium chloride thickener, 0.5g SAS anion surfactant, 0.15g second
Glycol distearyl fat acid esters nonionic surfactant is added separately in mixed liquor, adds hydrochloric acid modulation pH and is
3.5, low velocity shear machine processes 28min and prepares and to obtain the organic solvent solution A of presoma, and cutter low speed is cut
The speeds control cut is 2800r/min；
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidation reaction
Sodium metaperiodate in mass ratio: nanocrystalline cellulose is that 5:1 weighs sample, is transferred in there-necked flask, burns
The logical nitrogen lucifuge of bottle, is 55 DEG C in temperature in the material concentration that mass percent is 6.5%, and pH is 3
Under the conditions of react 5.5h, i.e. can get aldehyde group content and be up to 7200 μm ol/g (being measured by alkali exhaust method)
Bis oxide aldehyde radical nanocrystalline cellulose, products obtained therefrom is rhabdolith structure, further by controlling deionization
The addition of water obtains the colloid emulsion B that mass percent concentration is 6.5% of oxidation nanometer crystalline cellulose；
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is dropwise added
Enter to colloid emulsion B
Under the relatively slow-speed of revolution of 8000r/min, the colloid emulsion B of hydrotropism's carrier dropwise drips presoma
The organic solvent solution A of tetrabutyl titanate, after completion of dropwise addition, improves rotating speed to 22000r/min down cut 8
Min, makes two kinds of emulsions be sufficiently mixed, and in the process, controls the pH of system by adding hydrochloric acid in 4；
Four), water combined with heat treatment freeze-drying, be sufficiently complete gel reaction
Above-mentioned mixed emulsion is transferred in water bath with thermostatic control, under the rotating speed of 19500r/min, carries out hydro-thermal shearing
Processing 1h, it is 55 DEG C that bath temperature controls, and by gained colloidal sol after room temperature condition ageing 48h, carries out cold
Lyophilized dry, control drying time as 9h；
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target of wheat head shape pattern
Product
Lyophilized gel is transferred in high temperature furnace, is first warming up to 200 DEG C with the step rate of 5 DEG C/min,
Then to adjust heating rate be 15 DEG C/min until 430 DEG C, at this temperature after calcination processing 1.5h
To the powder titanium dioxide crystal particle of white, its pattern is wheat head shape, as it is shown in figure 1, and react alive
Property is high.
Evaluate titanium dioxide granule reactivity: use methyl orange to evaluate sample at purple as light degradation object
Photocatalysis performance under outer light, the nano titanium oxide prepared by 0.1g joins 50mL mass concentration 20
In mg/L methyl orange standard liquid, the ultraviolet high-pressure sodium lamp of 250W after stirring, is used to be irradiated (light range
From 10cm), every 3min take sample centrifugal after, by its absorbance of spectrophotometric determination, and calculate first
The degradation rate of base orange understands, and titanium dioxide crystal particle reaction activity prepared by the present invention is high, can be at 12min
Inside make the degradation rate of methyl orange more than 97.8%.
Embodiment 7
The preparation method of a kind of highly active nano titanium oxide, its step of preparation process and embodiment 1 phase
Together, unlike simply: the thickener of selection is potassium chloride, and without surfactant, it is prepared
Step operation process is:
One), preparation presoma tetrabutyl titanate organic solvent solution A, add thickener in the solution
Take 5.5g tetrabutyl titanate presoma and join in isopropanol, tetrabutyl titanate and the mass ratio of isopropanol
For 1:7.5, being added to mixed liquor by 0.95g potassium chloride thickener, adding hydrochloric acid modulation pH is 3, and low speed is cut
Machine of cutting processes 30min and prepares to obtain the organic solvent solution A of presoma, the speed control of cutter low velocity shear
It is made as 2500r/min；
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidation reaction
Sodium metaperiodate in mass ratio: nanocrystalline cellulose is that 3.5:1 weighs sample, is transferred in there-necked flask,
Flask leads to nitrogen lucifuge, is 52 DEG C in temperature in the material concentration that mass percent is 7.5%, and pH is 4
Under conditions of react 6h, i.e. can get aldehyde group content and be up to 7000 μm ol/g (being measured by alkali exhaust method)
Bis oxide aldehyde radical nanocrystalline cellulose, products obtained therefrom is rhabdolith structure, further by controlling deionization
The addition of water obtains the colloid emulsion B that mass percent concentration is 6% of oxidation nanometer crystalline cellulose；
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is added dropwise over
To colloid emulsion B
Under the relatively slow-speed of revolution of 6500r/min, the colloid emulsion B of hydrotropism's carrier dropwise drips presoma
The organic solvent solution A of tetrabutyl titanate, after completion of dropwise addition, improves rotating speed to 21000r/min down cut 9
Min, makes two kinds of emulsions be sufficiently mixed, and in the process, controls the pH of system by adding hydrochloric acid in 3.5；
Four), water combined with heat treatment freeze-drying, be sufficiently complete gel reaction
Above-mentioned mixed emulsion is transferred in water bath with thermostatic control, under the rotating speed of 20000r/min, carries out hydro-thermal shearing
Processing 1h, it is 55 DEG C that bath temperature controls, and by gained colloidal sol after room temperature condition ageing 50h, carries out cold
Lyophilized dry, control drying time as 9h；
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target of wheat head shape pattern
Product
Lyophilized gel is transferred in high temperature furnace, is first warming up to 200 DEG C with the step rate of 5 DEG C/min,
Then to adjust heating rate be 15 DEG C/min until 425 DEG C, at this temperature after calcination processing 1.2h
To the powder titanium dioxide crystal particle of white, its pattern is wheat head shape, as it is shown in figure 1, and react alive
Property is high.
Evaluate titanium dioxide granule reactivity: use methyl orange to evaluate sample at purple as light degradation object
Photocatalysis performance under outer light, the nano titanium oxide prepared by 0.1g joins 50mL mass concentration 20
In mg/L methyl orange standard liquid, the ultraviolet high-pressure sodium lamp of 250W after stirring, is used to be irradiated (light range
From 10cm), every 3min take sample centrifugal after, by its absorbance of spectrophotometric determination, and calculate first
The degradation rate of base orange understands, and titanium dioxide crystal particle reaction activity prepared by the present invention is high, can be at 12min
Inside make the degradation rate of methyl orange more than 97.5%.
Embodiment 8
A kind of preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide, its step of preparation process
Same as in Example 1, simply unlike: the thickener of selection is ammonium chloride, and lives without surface
Property agent, its preparation process operating process is:
One), preparation presoma tetrabutyl titanate organic solvent solution A, add thickener in the solution
Taking 7g tetrabutyl titanate presoma and join in isopropanol, tetrabutyl titanate with the mass ratio of isopropanol is
1:8, by 0.95g ammonium chloride thickener, 0.9g sodium sulfate of polyethenoxy ether of fatty alcohol anion surfactant,
0.55g coconut oil single ethanol amide and 0.3g ethylene glycol distearyl fat acid esters nonionic surfactant add extremely
In mixed liquor, adding hydrochloric acid modulation pH is 3.5, and low velocity shear machine processes 30min and prepare and to obtain the having of presoma
Machine solvent solution A, the speeds control of cutter low velocity shear is 2600r/min；
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidation reaction
Sodium metaperiodate in mass ratio: nanocrystalline cellulose is that 4.5:1 weighs sample, is transferred in there-necked flask,
Flask leads to nitrogen lucifuge, is 50 DEG C in temperature in the material concentration that mass percent is 5%, and pH is 3.5
Under conditions of react 6h, i.e. can get aldehyde group content and be up to 7500 μm ol/g (being measured by alkali exhaust method)
Bis oxide aldehyde radical nanocrystalline cellulose, products obtained therefrom is rhabdolith structure, further by controlling deionization
The addition of water obtains the colloid emulsion B that mass percent concentration is 6.5% of oxidation nanometer crystalline cellulose；
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is added dropwise over
To colloid emulsion B
Under the relatively slow-speed of revolution of 6000r/min, the colloid emulsion B of hydrotropism's carrier dropwise drips presoma
The organic solvent solution A of tetrabutyl titanate, after completion of dropwise addition, improves rotating speed to 22500r/min down cut 10
Min, makes two kinds of emulsions be sufficiently mixed, and in the process, controls the pH of system by adding hydrochloric acid in 3；
Four), water combined with heat treatment freeze-drying, be sufficiently complete gel reaction
Above-mentioned mixed emulsion is transferred in water bath with thermostatic control, under the rotating speed of 20000r/min, carries out hydro-thermal shearing
Processing 1h, it is 55 DEG C that bath temperature controls, and by gained colloidal sol after room temperature condition ageing 49h, carries out cold
Lyophilized dry, control drying time as 10h；
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target of wheat head shape pattern
Product
Lyophilized gel is transferred in high temperature furnace, is first warming up to 200 DEG C with the step rate of 5 DEG C/min,
Then adjusting heating rate is 15 DEG C/min until 435 DEG C, at this temperature after calcination processing 1.5h
Obtaining the powder titanium dioxide crystal particle of white, its pattern is wheat head shape, as it is shown in figure 1, and reaction
Activity is high.
Evaluate titanium dioxide granule reactivity: use methyl orange to evaluate sample at purple as light degradation object
Photocatalysis performance under outer light, the nano titanium oxide prepared by 0.1g joins 50mL mass concentration 20
In mg/L methyl orange standard liquid, the ultraviolet high-pressure sodium lamp of 250W after stirring, is used to be irradiated (light range
From 10cm), every 3min take sample centrifugal after, by its absorbance of spectrophotometric determination, and calculate first
The degradation rate of base orange understands, and titanium dioxide crystal particle reaction activity prepared by the present invention is high, can be at 12min
Inside make the degradation rate of methyl orange more than 98.5%.
In the present invention, use the nanocrystalline cellulose prepared by natural fiber degraded through sodium periodate oxidation
After, obtain a kind of oxidation nanometer crystalline cellulose rich in dialdehyde group, using it as supporting substrates, and combine
The effect of the auxiliary material such as thickener, surfactant, heats up in hydro-thermal-freeze-drying and follow-up staged and calcines
Course of reaction in, it is that wheat head shape nano titanium oxide is brilliant that induction presoma tetrabutyl titanate crystallization becomes pattern
Body particle.
In the present invention, described tetrabutyl titanate, thickener and surfactant, it is chemical reagent.
Pattern of the present invention is wheat head shape nano titanium dioxide crystal particle, due to have not yet to see report in China special
Profit document and periodical literature, pattern the most of the present invention is that wheat head shape nano titanium dioxide crystal particle is real belongs to the first
Report.This invention product has good aqueous dispersion, has good value for applications.
The excellent performance of product of the present invention, application technology can contain photocatalysis, ornament materials, insulation material,
Solar cell and multiple fields such as the assembling of lithium ion battery negative material and synthesis.
It is high that the inventive method prepares titanium dioxide crystal particle wheat head pattern particle reaction activity, uses methyl
Orange evaluate sample photocatalysis performance under ultraviolet light as light degradation object, by 0.1g by aldehyde group content
The oxidation nanometer crystalline cellulose of the highest 7500 μm ol/g (being measured by alkali exhaust method) is as prepared by carrier
Titanium dioxide join in 50mL mass concentration 20mg/L methyl orange standard liquid, after stirring use 250
The ultraviolet high-pressure sodium lamp of W is irradiated (luminous range 10cm), every 3min take sample centrifugal after, use
Its absorbance of spectrophotometric determination, and calculate knowable to after the degradation rate of methyl orange, the dioxy of this invention product
Changing titanium crystal beaded catalyst can make the degradation rate of methyl orange more than 98.5% in 12min.
The above is only the preferred embodiment of the present invention, it is noted that for the specialty of the art
For personnel, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these
Improvements and modifications also should be regarded as protection scope of the present invention.
Claims (9)
1. the preparation method of a highly active oxidation nanometer crystalline cellulose based titanium dioxide, it is characterised in that:
Described highly active oxidation nanometer crystalline cellulose based titanium dioxide main material is presoma and nano-grade cellulosic base
Material, auxiliary material is thickener, surfactant, or without surfactant in mixed liquor, described forerunner
Body is mainly tetrabutyl titanate, and described base material is the oxidation nanometer crystalline cellulose rich in dialdehyde base, described thickening
Agent is inorganic salts thickener, and described surfactant is anion surfactant, or amophoteric surface active
Agent or nonionic surfactant, use homogeneous sol and the preparation method of high-temperature calcination, be prepared in wheat
The oxidation nanometer crystalline cellulose based titanium dioxide of spike pattern, described homogeneous sol and the preparation of high-temperature calcination
Method, the most rapid including five:
One), under low velocity shear, the organic solvent solution A of preparation presoma tetrabutyl titanate, in the solution
Selectively interpolation thickener, surfactant, or without surfactant in colloidal solution；
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidation reaction；
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is added dropwise over
To colloidal solution B；
Four), water combined with heat treatment freeze-drying, be sufficiently complete gel reaction；
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape；
Above-mentioned five the most rapid operating process are as follows:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, in the solution selectively interpolation thickening
Agent, surfactant, or without surfactant in colloidal solution
Take tetrabutyl titanate presoma and join in appropriate organic solvent solution, presoma and organic solvent
Mass ratio is 1:5～1:8, by one/multiple thickener, one/kinds of surface activating agent, adds to after mixing
In colloidal solution, or without surfactant in colloidal solution, adding hydrochloric acid modulation pH is 3～4, low speed
Cutter processes 25min～35min and prepares and to obtain the organic solvent solution A of presoma, cutter low velocity shear
Speeds control be 2000r/min～3000r/min；
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidation reaction
Sodium metaperiodate in mass ratio: nanocrystalline cellulose is that 3:1～6:1 weighs sample, is transferred in there-necked flask,
Flask leads to nitrogen lucifuge, is 40 DEG C～60 DEG C in temperature in the material concentration that mass percent is 5%～8%,
PH is reaction 4h～6h under conditions of 3～4.5, i.e. can get aldehyde group content and is up to 6000 μm ol/g～7500
The bis oxide aldehyde radical nanocrystalline cellulose of μm ol/g (being measured by alkali exhaust method), products obtained therefrom is rhabdolith
Structure, the addition by controlling deionized water obtains the mass percent of oxidation nanometer crystalline cellulose further
Concentration is the colloid emulsion B of 3%～8%；
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is added dropwise over
To colloid emulsion B
Under the relatively slow-speed of revolution of 5000r/min～8000r/min, in the colloid emulsion B of hydrotropism's carrier dropwise
The organic solvent solution A of dropping presoma tetrabutyl titanate, after completion of dropwise addition, improves rotating speed to 20000
R/min～23000r/min down cut 5min～10min, makes two kinds of emulsions be sufficiently mixed, in the process, logical
Cross and add hydrochloric acid and control the pH of system in 3～4；
Four), water combined with heat treatment freeze-drying, be sufficiently complete gel reaction
Above-mentioned mixed emulsion is transferred in water bath with thermostatic control, enters under the rotating speed of 18000r/min～20000r/min
Row hydro-thermal shear treatment 0.5h～1h, it is 45 DEG C～55 DEG C that bath temperature controls, by gained colloidal sol at room temperature bar
After part ageing 48h～50h, carry out freeze-drying, control drying time as 8h～10h；
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape
Lyophilized gel is transferred in high temperature furnace, is first warming up to 200 DEG C with the step rate of 5 DEG C/min,
Then adjusting heating rate is 15 DEG C/min until 415 DEG C～435 DEG C, calcination processing 1h～1.5 at this temperature
The powder titanium dioxide crystal particle of i.e. available white after h, this crystal grain pattern is wheat head shape, and instead
Should be active high.
The preparation method of the most highly active oxidation nanometer crystalline cellulose based titanium dioxide,
It is characterized in that: described presoma, for tetrabutyl titanate.
The preparation method of the most highly active oxidation nanometer crystalline cellulose based titanium dioxide,
It is characterized in that: described organic solvent, for ethanol, the mixture of one or both solvents in isopropanol.
The preparation method of the most highly active oxidation nanometer crystalline cellulose based titanium dioxide,
It is characterized in that: described dialdehyde base oxidation nanometer crystalline cellulose, for obtain through sodium periodate oxidation process
Rich in the nanocrystalline cellulose of aldehyde radical, its size index is length 30nm～180nm, diameter 2nm～60nm,
Described Cellulose nanocrystal is self-control or commercially available, and wherein self-control approach can pass through at hydrolysis, enzymolysis or machinery
Reason sulfate wood pulp, cotton pulp, cotton linter, the living beings raw material of agricultural waste material, or closed by mushroom
Becoming bacteria cellulose, or extraction obtains cellulose substances from tunicate, wherein an example is typically made
Standby step is described as follows: commercially available sulfate needle cotton starch plate, and the control of quality of material percent concentration is
3%～6%, the sulfuric acid acid solution that mass fraction is 64.3% is reacted at 38 DEG C 1h～3h, dilute, be centrifuged,
Wash, prepare after drying.
The preparation method of the most highly active oxidation nanometer crystalline cellulose based titanium dioxide,
It is characterized in that: described thickener, for the sodium chloride of inorganic salts thickener, ammonium chloride, potassium chloride, press
Mass percent calculates, and its addition is 2%～8%.
The preparation method of the most highly active oxidation nanometer crystalline cellulose based titanium dioxide,
It is characterized in that: described surfactant be anion surfactant be aided with amphoteric surfactant or non-from
Sub-surface activating agent, wherein anion surfactant preferably sodium dodecyl sulfate, aliphatic alcohol polyethenoxy
Ether sodium sulfate, sodium carboxymethylcellulose, fatty alcohol polyoxyethylene ether sulfate, SAS, wherein
Amphoteric surfactant or nonionic surfactant preferred coconut oil single ethanol amide, ethylene glycol distearyl fat
Acid esters.
The preparation method of the most highly active oxidation nanometer crystalline cellulose based titanium dioxide,
It is characterized in that: described physical shear process uses high-speed shearing machine to carry out, wherein at precursor solution
In process for preparation, use slow-revving 2000r/min～3000r/min, use high rotating speed when preparing mixed liquor
20000r/min～23000r/min, and in hydrothermal treatment process, use high-revolving 18000
R/min～20000r/min.
The preparation method of the most highly active oxidation nanometer crystalline cellulose based titanium dioxide,
It is characterized in that: described calcination processing step, for staged temperature-rise period, first with the step of 5 DEG C/min
Entering ramp to 200 DEG C, then adjusting heating rate is 15 DEG C/min until 415 DEG C～435 DEG C, at this
Temperature lower calcination processes 1h～1.5h.
The preparation method of the most highly active oxidation nanometer crystalline cellulose based titanium dioxide,
It is characterized in that: the pattern of described nano titanium dioxide crystal particle is wheat head shape form.
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| CN108034007B (en) * | 2017-12-06 | 2023-07-14 | 江南大学 | Preparation method of dialdehyde cellulose nanowhisker |
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| CN110551326A (en) * | 2019-08-23 | 2019-12-10 | 北京化工大学 | Cellulose nanocrystal/titanium dioxide chiral nematic structure composite film and preparation method thereof |
| CN111704161B (en) * | 2020-06-15 | 2022-09-13 | 闽江学院 | Hierarchical titanium dioxide microspheres and preparation method and application thereof |
| CN113668252A (en) * | 2021-08-23 | 2021-11-19 | 无锡市鸿庆无纺布有限公司 | Nano non-woven fabric based on nano cellulose antibacterial material and preparation method thereof |
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