CN109896545A - A kind of hollow shell-type titanium dioxide nano material, hollow shell-type titanium dioxide nano material of silver load and preparation method thereof - Google Patents
A kind of hollow shell-type titanium dioxide nano material, hollow shell-type titanium dioxide nano material of silver load and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of hollow shell-type titanium dioxide nano materials, the hollow shell-type titanium dioxide nano material of silver load and preparation method thereof.Hollow shell-type titanium dioxide nano material the preparation method comprises the following steps: RF dispersion liquid and ammonium hydroxide are uniformly mixed with dehydrated alcohol, then plus butyl titanate is reacted, successively by centrifuge separation, washing, dry and two one-step baking the step of, hollow shell-type titanium dioxide nano material is made, wherein, the volume ratio of dehydrated alcohol, RF dispersion liquid, ammonium hydroxide and butyl titanate is (40~50): (4~6): (0.1~0.4): (0.75~1.5).The present invention is by ultraviolet radiation sedimentation by deposition of silver in hollow shell-type titanium dioxide nano material surface, the hollow shell-type titanium dioxide nano material of obtained silver load.Hollow shell-type titanium dioxide nano material prepared by the present invention and the hollow shell-type titanium dioxide nano material of silver load are all anatase crystal, and the degradation efficiency of Pyrogentisinic Acid is high.
Description
Technical field
The invention belongs to inorganic nano photocatalyst material and its preparation field more particularly to a kind of hollow shell-type titanium dioxides
Titanium nano material, hollow shell-type titanium dioxide nano material of silver load and preparation method thereof.
Background technique
The discharge of the industry phenol wastewater such as petrochemical industry, medicine, pesticide, papermaking causes serious prestige to environment
The side of body, and the phenol wastewater of high concentration can corrode skin and mucous membrane, destroy biological central nervous system.The place of traditional phenol wastewater
Reason method is mainly: extraction, absorption method, chemical precipitation method, chemical oxidization method etc., but these methods all can be to a certain degree
On cause secondary pollution, and energy consumption is high, and degradation is not thorough.In the environment of advocating Green Chemistry, photocatalysis oxidation technique goes out
Now bring great convenience to solve phenol wastewater.
Titanium dioxide (TiO2) photochemical catalyst has absorption and degradation capability well to organic pollutant, and with no selection
Property, it is without secondary pollution, at a low price, it is efficient the advantages that, caused extensive concern.But TiO2As the main face of photochemical catalyst
Face two large problems: (1) TiO2Semiconductor forbidden bandwidth determines that it is only capable of the light source that absorbing wavelength is less than 387nm, to visible light
Absorptivity is very poor, low to the utilization rate of solar energy；(2) photo-generated carrier low separation efficiency, light induced electron utilization rate are low.New construction
TiO2Design, the exploitation of photochemical catalyst, can further enhance its photocatalytic activity, and expand TiO2The application range of photochemical catalyst.
Chinese patent application CN201710683148.3 discloses a kind of titanium dioxide hollow nucleocapsid of molybdenum disulfide cladding
The preparation method and applications of structure composite photochemical catalyst, although the composite photo-catalyst of patent application preparation can be high rapidly
4- nitrophenol is reduced to 4-aminophenol by effect ground, but this is only converted the nitro above phenol for amino, and not right
Phenol main body is degraded, it is well known that nitro reduction is to be relatively easy to, and the degradation of phenol is difficult, and therefore, this is specially
Benefit applies for that composite photo-catalyst obtained is not appropriate for Phenol-Containing Wastewater Treatment；In addition, molybdenum disulfide is flaky substance, and carrier sheet
Shape substance (such as molybdenum disulfide, graphene oxide etc.) is likely to cause the serious agglomeration of loaded article and titanium dioxide, seriously
The specific surface area for losing catalyst, to influence the degradation effect of composite photo-catalyst.Chinese patent application
CN201310259237.7 discloses a kind of nano titanium dioxide photocatalyst and preparation method thereof of silver load, but the patent
The nano titanium dioxide photocatalyst of the silver load of application preparation is poor to the degradation efficiency of methylene blue (MB), 200min's
In period, MB degradation amount also can only achieve 70% or so；And it is well known that in phenol, methylene blue (MB), rhodamine B
(RhB) and in methyl orange (MO) these common Recalcitrant chemicals, phenol is most difficult to degradation, and MB is most degradable；Cause
This, the nano titanium dioxide photocatalyst of the silver load of patent application preparation is also not suitable for as photocatalyst treatment containing phenol
Waste water.
To sum up, it is therefore desirable to provide the novel titanium dioxide nano material of one kind to improve the degradation of titanium dioxide Pyrogentisinic Acid
Efficiency.
Summary of the invention
Of the existing technology in order to solve the problems, such as, the object of the present invention is to provide a kind of hollow shell-type nano titanias
Material, hollow shell-type titanium dioxide nano material of silver load and preparation method thereof.Hollow shell-type titanium dioxide prepared by the present invention
Titanium nano material and the hollow shell-type titanium dioxide nano material of silver load have hollow structure, large specific surface area, hollow structure
Inside and outside to all have chain carrier position, the degradation efficiency of high catalytic efficiency, Pyrogentisinic Acid is high, can quickly and efficiently remove phenol；
Preparation method of the invention has many advantages, such as that process is simple, high-efficient, low energy consumption and pollution-free.
To achieve the goals above, the present invention provides a kind of hollow shell-type titanium dioxide nano material in first aspect
Preparation method, described method includes following steps:
(1) resorcinol formaldehyde resin dispersion liquid and ammonium hydroxide are uniformly mixed with dehydrated alcohol, obtain mixed liquor, then will
Butyl titanate, which is added dropwise in the mixed liquor, to be reacted, and reaction product solution is obtained；The dehydrated alcohol, the isophthalic two
The volume ratio of fluosite dispersion liquid, the ammonium hydroxide and the butyl titanate is (40~50): (4~6): (0.1~
0.4): (0.75~1.5)；
(2) reaction product solution that step (1) obtains successively is passed through into step with centrifugal separation, washing step and dry step
Suddenly, the titanic oxide material with core-shell structure is obtained；With
(3) titanic oxide material with core-shell structure for obtaining step (2) first roasts 2~4h in nitrogen atmosphere,
Then 2~4h is roasted in air atmosphere, and hollow shell-type titanium dioxide nano material is made.
Preferably, the method also includes the system of the resorcinol formaldehyde resin dispersion liquid is carried out before step (1)
Standby step, which includes following sub-step:
(a) ammonium hydroxide is uniformly mixed with water and dehydrated alcohol, obtains the first mixed solution, it is then molten toward first mixing
Resorcinol is added in liquid and is uniformly mixed, obtains the second mixed solution；
(b) formalin is added in the second mixed solution that step (a) is obtained and is reacted, obtain resorcinol formaldehyde
Then the resorcinol formaldehyde resin solution is successively passed through step with centrifugal separation and washing step, between obtaining by resin solution
Resorcinol formaldehyde resin；With
(c) resorcinol formaldehyde resin obtained with dehydrated alcohol dispersion steps (b) obtains the resorcinol formaldehyde tree
Rouge dispersion liquid.
Preferably, in step (a), the volume ratio of the water, the dehydrated alcohol and the ammonium hydroxide is (30~60):
(10~20): (0.2~0.4)；The molar ratio of the formaldehyde contained in the resorcinol and the formalin is 1:(1~2)；
And/or in step (b), the temperature of the reaction is 30~35 DEG C, and the time of the reaction is 18~30h.
Preferably, in step (1), the temperature of the reaction is 70~100 DEG C, and the time of the reaction is 2~4h.
Preferably, the temperature roasted in nitrogen atmosphere and/or the temperature roasted in air atmosphere are 400~500 DEG C.
The present invention provides hollow shell-type two made from preparation method of the present invention described in first aspect in second aspect
Titanium dioxide nano material.
The present invention provides a kind of preparation method of the hollow shell-type titanium dioxide nano material of silver load in the third aspect,
Described method includes following steps:
S1, with silver nitrate aqueous solution by hollow shell-type titanium dioxide made from preparation method of the present invention described in first aspect
Titanium nano material is uniformly dispersed, and obtains hollow shell-type titanium oxide dispersion；With
S2, the hollow shell-type titanium oxide dispersion is handled so that silver is supported on the hollow shell with ultraviolet light
The hollow shell-type titanium dioxide nano material of silver load is made in the surface of formula titanium dioxide nano material.
Preferably, the silver nitrate contained in the hollow shell-type titanium dioxide nano material and the silver nitrate aqueous solution
Mass ratio is 0.1:(0.001~0.015), preferably 0.1:(0.0015~0.009).
Preferably, the concentration of the silver nitrate aqueous solution is 0.03~0.19g/L.
The present invention provides in silver load made from preparation method of the present invention described in the third aspect in fourth aspect
Ghost formula titanium dioxide nano material.
The present invention at least has the following beneficial effects: compared with prior art
1, the present invention uses resorcinol formaldehyde resin (RF) to prepare the titanium dioxide with core-shell structure for template
Material (RF@TiO2), then by two one-step bakings obtain with new structural hollow shell-type titanium dioxide nano material (in
Hollow structure TiO2), the TiO with this hollow structure2Nanostructure large specific surface area, inside and outside active center, catalytic efficiency
It is high；In addition, silver-colored (Ag) is deposited on hollow structure TiO by ultraviolet radiation sedimentation by the present invention2Surface, using Ag load into
One step improves the separative efficiency of photo-generated carrier spatially, and then hollow shell-type nano titania has been significantly increased
The light-catalyzed reaction activity of material and the degradation efficiency of Pyrogentisinic Acid.
2, the present invention passes through the dehydrated alcohol, the resorcinol formaldehyde resin dispersion liquid, the ammonium hydroxide and the titanium
The reasonable volume of rational proportion especially ammonium hydroxide between sour four butyl esters, it is in few that titanium dioxide granule in the present invention, which has been effectively ensured,
Reunite or monodispersed state so that shell thickness can regulate and control between 20~90nm effectively prevents existing titanium dioxide
Grain combine with silver insufficient causes catalytic efficiency low there are the too small easy reunion of particle, activated centre are exposed as photochemical catalyst
Problem.
3, preparation method of the invention has many advantages, such as that process is simple, high-efficient, low energy consumption and pollution-free；Present invention preparation
Hollow shell-type titanium dioxide nano material and silver load hollow shell-type titanium dioxide nano material be all anatase crystal, it is right
The degradation efficiency of phenol is high, can quickly and efficiently remove phenol, the degradation rate of hollow shell-type titanium dioxide nano material Pyrogentisinic Acid
It can reach 90% or so in the period of 150~210min, the hollow shell-type titanium dioxide nano material Pyrogentisinic Acid of silver load
Degradation rate can reach 90% or so in the period of 90~120min.
Detailed description of the invention
Fig. 1 is hollow TiO prepared by embodiment 12Scanning electron microscope diagram (SEM figure).(a) in figure, (b), (c) and
(d) the SEM figure of sample HT-0.10, HT-0.20, HT-0.30 and HT-0.35 are respectively corresponded.
Fig. 2 is hollow TiO prepared by embodiment 12Transmission electron microscope figure (TEM figure).(a) in figure, (b), (c) and
(d) the TEM figure of sample HT-0.10, HT-0.20, HT-0.30 and HT-0.35 are respectively corresponded.
Fig. 3 is hollow TiO prepared by embodiment 12The X-ray diffraction spectrogram (XRD spectra) of sample.(a) in figure, (b),
(c) XRD spectra of sample HT-0.35, HT-0.30, HT-0.20 and HT-0.10 are respectively corresponded with (d).
Fig. 4 is HT@Ag and hollow TiO prepared by embodiment 12The X-ray diffraction spectrogram (XRD spectra) of sample.In figure
(a), (b), (c) and (d) respectively correspond sample HT-9, HT-6, HT-3 and HT-0.30 (hollow TiO2) XRD spectra.
Fig. 5 is hollow TiO prepared by embodiment 12With high resolution transmission electron microscopy (the high power TEM of HT@Ag sample
Figure).(a) corresponding hollow TiO in figure2(HT-0.30) high power TEM schemes, the high power TEM of (b) corresponding HT@Ag (HT-6) in figure
Figure.
Fig. 6 is four kinds of hollow TiO in embodiment 22UV-visible absorption spectrum.In figure (a), (b), (c) and (d)
Respectively correspond sample HT-0.10, HT-0.20, HT-0.30 and HT-0.35 illumination different time (0min, 15min, 30min,
60min, 120min, 150min, 210min, 240min) after UV-visible absorption spectrum.
Fig. 7 is in embodiment 2 with four kinds of hollow TiO2When being degraded for catalyst phenol concentration with degradation time change
Change curve.
Fig. 8 is the UV-visible absorption spectrum of four kinds of HT@Ag in embodiment 3.(a), (b), (c) and (d) difference in figure
Counter sample HT-1.5, HT-3, HT-6 and HT-9 illumination different time (0min, 10min, 20min, 30min, 45min,
60min, 75min, 90min, 105min, 120min) after UV-visible absorption spectrum；Wherein, HT-3 does not survey illumination
UV-visible absorption spectrum after 120min, HT-6 do not survey the uv-visible absorption spectra after illumination 105min and 120min
Figure.
Fig. 9 is that phenol concentration is bent with the variation of degradation time when being degraded using four kinds of HT@Ag as catalyst in embodiment 3
Line.
Figure 10 is scanning electron microscopy of the present invention using the resorcinol formaldehyde resin (RF) of different ammonia volumes preparation
Mirror figure (SEM figure).In figure (a), (b), (c), (d) and (e) corresponding ammonia volume for preparing RF be 0.2mL, 0.25mL,
0.30mL, 0.35mL and 0.4mL.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation method of hollow shell-type titanium dioxide nano material, the method in first aspect
Include the following steps:
(1) resorcinol formaldehyde resin dispersion liquid and ammonium hydroxide are uniformly mixed with dehydrated alcohol, obtain mixed liquor, then will
Butyl titanate (butyl titanate), which is added dropwise in the mixed liquor, to be reacted, and reaction product solution is obtained；The dehydrated alcohol,
The volume ratio of the resorcinol formaldehyde resin dispersion liquid (RF dispersion liquid), the ammonium hydroxide and the butyl titanate be (40~
50): (4~6): (0.1~0.4): (0.75~1.5) (such as 40:4:0.1:0.75,40:4:0.2:0.75,40:4:0.3:
0.75、40:4:0.4:0.75、45:5:0.1:1、45:5:0.2:1、45:5:0.3:1、45:5:0.4:1、50:6:0.1:1.5、
50:6:0.2:1.5,50:6:0.3:1.5 or 50:6:0.4:1.5)；In the present invention, the ammonium hydroxide is the aqueous solution of ammonia, such as
It can be the aqueous solution of 25~28wt% containing ammonia；In the present invention, butyl titanate is added dropwise in the mixed liquor and is carried out instead
The temperature answered for example can be 70~100 DEG C, and the time of the reaction for example can be 2~4h.
(2) reaction product solution that step (1) obtains successively is passed through into step with centrifugal separation, washing step and dry step
Suddenly, the titanic oxide material with core-shell structure is obtained；In the present invention, it such as can be washed with dehydrated alcohol by centrifugation point
It is multiple from the sample that step obtains, then by the sample after washing at 60 DEG C the dried overnight dioxy for obtaining that there is core-shell structure
Change titanium material；In the present invention, the titanic oxide material with core-shell structure is also denoted as RF@TiO2。
(3) titanic oxide material with core-shell structure for obtaining step (2) is first in nitrogen atmosphere (N2Atmosphere) in roasting
Burn 2~4h (such as 2,2.5,3,3.5 or 4h), then in the air atmosphere (air atmosphere) 2~4h of roasting (such as 2,2.5,3,
3.5 or 4h), hollow shell-type titanium dioxide nano material is made；In the present invention, the temperature that is roasted in nitrogen atmosphere and/or
The temperature roasted in air atmosphere for example can be 400~500 DEG C；In the present invention, by hollow shell-type nano titania
Material is also denoted as hollow structure TiO2Or hollow TiO2Or HT.In the present invention, first roasting is to make RF carbon in nitrogen atmosphere
Change, after in air roasting be in order to remove carbonization after RF obtain hollow TiO2(spherical TiO2), it avoids directly in air
Roasting, RF are directly contacted with air, it may occur that violent volume expansion leads to hollow TiO2It is broken for half chou of size unevenness
The TiO of structure2(broken TiO2)；And broken titanium dioxide does not have the surface same sex of spherical tio2, carries out load bead in next step
If particle, it will cause loaded article and be unevenly distributed, a large amount of loaded article is caused to be distributed in the concave surface internal layer of broken titanium dioxide, it can
The load capacity that can be will cause on the inside of concave surface is too high, and the load capacity on the outside of concave surface is too low, causes outside physico-chemical property in fragment
It is inhomogenous, seriously affect photocatalytic activity.
The present invention uses resorcinol formaldehyde resin (RF) to prepare the titanium dioxide titanium with core-shell structure for template
Expect (RF@TiO2), it is then obtained by two one-step bakings (hollow with new structural hollow shell-type titanium dioxide nano material
Structure Ti O2), the TiO with this hollow structure2Nanostructure large specific surface area, inside and outside active center, catalytic efficiency
It is high；The present invention passes through the dehydrated alcohol, the resorcinol formaldehyde resin dispersion liquid, the ammonium hydroxide and the butyl titanate
Between rational proportion especially step (1) in ammonium hydroxide reasonable volume, titanium dioxide granule in the present invention, which has been effectively ensured, is in
It is few to reunite or monodispersed state so that shell thickness regulate and control between 20~90nm effectively prevents existing titanium dioxide
Particle combine with silver as photochemical catalyst there are particle too it is small it is easy reunite, activated centre is exposed insufficient causes catalytic efficiency low
The problem of.In step (1) of the invention, the dosage of ammonium hydroxide can not be excessive, otherwise has a large amount of TiO2It is uncoated in RF table
Face, but adhesion to each other, RF@TiO2Occur it is serious agglomerate into big block structure, to eventually lead in obtained
The degradation effect of ghost formula titanium dioxide nano material Pyrogentisinic Acid is poor；In step (1) of the invention, resorcinol formaldehyde tree
The number of rouge dispersion liquid dosage, determines TiO2The thickness of shell；RF inside, TiO2Outside, ball packet spherical structure is formed, when
TiO2The timing of presoma (butyl titanate) dosage one, different RF dosages determine different thickness, it is produced by the present invention in
The shell thickness of ghost formula titanium dioxide nano material can regulate and control between 20~90nm.
According to some specific embodiments, RF@TiO2Preparation process are as follows: take the RF dispersion liquid of 5mL be placed in 45mL without
In the ammonia spirit of water-ethanol and 0.10~0.30mL, it is ultrasonically treated 0.5h, is placed in three-necked flask, three-necked flask is put into collection
In hot type constant temperature blender with magnetic force, 1h is stirred at room temperature, so that dehydrated alcohol is by resorcinol formaldehyde resin dispersion liquid and ammonia
Water is uniformly mixed；Then 0.75~1.5mL butyl titanate is added dropwise dropwise and reacts 2.5h at 85 DEG C, centrifugation (centrifuge separation) is simultaneously
The sample being centrifugally separating to obtain is washed three times with dehydrated alcohol, it is finally dried overnight at 60 DEG C, the RF@is made
TiO2。
According to some specific embodiments, hollow TiO2Preparation process are as follows: by RF@TiO resulting after drying2Sample
In N23h is roasted in atmosphere at 500 DEG C, then roasts 3h at 500 DEG C in air atmosphere, the hollow TiO is made2(HT)。
In the present invention, the maturing temperature is risen in nitrogen atmosphere and/or the liter of the maturing temperature is risen in air atmosphere
Warm rate for example can be 1.5~3 DEG C/min (such as 1.5,2,2.5 or 3 DEG C/min).In the present invention, before roasting
TiO2For amorphous titania, do not have catalytic activity；Heating rate is too fast to will affect TiO2The generation of anatase, and be easy
Cause TiO2Reunion in crystallization process；Anatase has preferable adsorption capacity and its photo-generate electron-hole pair to organic matter
Compound ability it is lower, therefore photocatalytic activity is higher.
According to some preferred embodiments, the method also includes the resorcinol first is carried out before step (1)
The preparation step of urea formaldehyde dispersion liquid, the preparation step include following sub-step:
(a) ammonium hydroxide is uniformly mixed with water (such as distilled water or deionized water) and dehydrated alcohol, it is molten obtains the first mixing
Then liquid is added resorcinol and is uniformly mixed into first mixed solution, obtains the second mixed solution；
(b) formalin is added in the second mixed solution that step (a) is obtained and is reacted, obtain resorcinol formaldehyde
Then the resorcinol formaldehyde resin solution is successively passed through step with centrifugal separation and washing step, between obtaining by resin solution
Resorcinol formaldehyde resin；With
(c) resorcinol formaldehyde resin obtained with dehydrated alcohol dispersion steps (b) obtains the resorcinol formaldehyde tree
Rouge dispersion liquid.
According to some preferred embodiments, in step (a), the body of the water, the dehydrated alcohol and the ammonium hydroxide
Product is than being (30~60): (10~20): (0.2~0.4) (such as 30:10:0.2,30:10:0.25,30:10:0.3,30:10:
0.35、30:10:0.4、40:16:0.2、40:16:0.25、40:16:0.3、40:16:0.35、40:16:0.4、50:20:0.2、
50:20:0.25、50:20:0.3、50:20:0.35、50:20:0.4、60:20:0.2、60:20:0.25、60:20:0.3、60:
20:0.35 or 60:20:0.4)；In step (a) of the present invention, the different patterns to resorcinol formaldehyde resin of ammonia volume
With significant impact, when other raw material dosages such as water, dehydrated alcohol are identical, using the isophthalic two of different ammonia volumes preparation
The scanning electron microscope diagram (SEM figure) of fluosite (RF) as shown in Figure 10, (a) in Figure 10, (b), (c), (d) and (e)
Scale be 500nm: from Figure 10 (a), (b) it can be seen that when ammonia volume be 0.2mL, 0.25mL when, RF particle has
Apparent reunion, particle disperse non-uniform phenomenon, and have some irregular shapes, this is because less ammonia volume,
Enough hydrogen bonds and methylol cannot be provided in emulsion, are unfavorable for quickly carrying out and be unfavorable for being formed small for condensation reaction
The RF nanometer bead of spherolite diameter；From figure (c), (d), (e) as can be seen that prepared RF nanometer bead is monodisperse status；From
(c) is schemed as can be seen that resulting dispersed nano bead partial size is unevenly distributed, this is perhaps when ammonia volume is 0.30mL
It is influenced by RF bead surface tension；From figure (e) as can be seen that when ammonia volume is 0.4mL, prepared uniform particle diameter
RF nanometer bead have slight agglomeration, this is because the excessive of ammonium hydroxide is added so that resorcinol and polymerizeing for formaldehyde are anti-
Answer excessive velocities, the ammonium ion (NH on emulsion droplet surface4 +) provide positive charge rate be not enough to effectively prevent RF reunion；From figure
(d) as can be seen that having obtained RF nanometers of beads of monodisperse of uniform particle diameter when ammonia volume is 0.35mL；In the present invention,
Rate of polymerization, surface tension, hydrogen bond of RF etc. play an important role to the preparation of the RF nanometers of beads of monodisperse of uniform particle diameter.
According to some preferred embodiments, the molar ratio of the formaldehyde contained in the resorcinol and the formalin
For 1:(1~2) (such as 1:1,1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9 or 1:
It 2) is preferably 1:1.5；And/or in step (b), the temperature of the reaction is 30~35 DEG C, the time of the reaction is 18~
30h (such as 18,20,22,24,26,28 or 30h).
According to some specific embodiments, the preparation process of RF dispersion liquid are as follows: 0.35mL ammonium hydroxide is added to 40mL and is steamed
It in the solution of distilled water and 16mL dehydrated alcohol, is placed in three-necked flask, three-necked flask is put into heat collecting type constant temperature blender with magnetic force
In, 1h is stirred at room temperature so that the aqueous solution of ammonium hydroxide and dehydrated alcohol is sufficiently mixed, obtains the first mixed solution, is conducive to next
The progress of reaction is walked, 0.4g resorcinol is then added into first mixed solution, continues stirring 0.5h and is uniformly mixed, obtain
To the second mixed solution；Second mixed solution is warming up to 30 DEG C, the reaction of 0.56mL formalin is added for 24 hours, between obtaining
Then the resorcinol formaldehyde resin solution is centrifuged and is used the mixed of dehydrated alcohol and distilled water by resorcinol formaldehyde resin solution
It closes solution and washs three times samples obtained by centrifugation, obtain resorcinol formaldehyde resin；The resorcinol formaldehyde tree that will be obtained
Rouge is scattered in 40mL dehydrated alcohol, and it is spare to obtain the resorcinol formaldehyde resin dispersion liquid.
According to some preferred embodiments, in step (1), the temperature of the reaction is 70~100 DEG C (such as 70
DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C or 100 DEG C), time of the reaction be 2~4h (such as 2,2.5,3,3.5 or
4h)。
According to some preferred embodiments, the temperature that is roasted in nitrogen atmosphere and/or roasted in air atmosphere
Temperature is 400~500 DEG C (such as 400 DEG C, 450 DEG C or 500 DEG C).
The present invention provides hollow shell-type two made from preparation method of the present invention described in first aspect in second aspect
Titanium dioxide nano material.The degradation efficiency of hollow shell-type titanium dioxide nano material Pyrogentisinic Acid produced by the present invention is high, can be quick
Phenol is efficiently removed, the degradation rate of Pyrogentisinic Acid can reach 90% or so in the period of 150~210min.
The present invention provides a kind of preparation method of the hollow shell-type titanium dioxide nano material of silver load in the third aspect,
Described method includes following steps:
S1, with silver nitrate aqueous solution by hollow shell-type titanium dioxide made from preparation method of the present invention described in first aspect
Titanium nano material is uniformly dispersed, and obtains hollow shell-type titanium oxide dispersion；With
S2, the hollow shell-type titanium oxide dispersion is handled so that silver is supported on the hollow shell with ultraviolet light
The hollow shell-type titanium dioxide nano material of silver load is made in the surface of formula titanium dioxide nano material；In the present invention, such as
The light source of high-pressure sodium lamp or black light lamp as ultraviolet light can be used；In the present invention, by the hollow shell-type two of silver-colored (Ag) load
Titanium dioxide nano material is also denoted as HT@Ag.
The present invention is by ultraviolet radiation sedimentation by deposition of silver in hollow structure TiO2Surface is loaded further using Ag
The separative efficiency of photo-generated carrier spatially is improved, and then hollow shell-type titanium dioxide nano material has been significantly increased
Light-catalyzed reaction activity and Pyrogentisinic Acid degradation efficiency.Hollow shell-type titanium dioxide nano material and silver prepared by the present invention
The hollow shell-type titanium dioxide nano material of load is all anatase crystal, after load silver, anatase there is no being destroyed and
It is converted into Rutile Type or brookite, anatase has preferable adsorption capacity and its photo-generate electron-hole pair to organic matter
Compound ability it is lower, therefore photocatalytic activity is higher；The hollow shell-type nano titania material of silver load produced by the present invention
Expect that the degradation efficiency of Pyrogentisinic Acid is high, can quickly and efficiently remove phenol, the period of the degradation rate of Pyrogentisinic Acid in 90~120min
It can reach 90% or so.
According to some preferred embodiments, the hollow shell-type titanium dioxide that the method also includes loading silver obtained
Step, washing step and drying steps are successively centrifuged in nano material.
According to some preferred embodiments, the hollow shell-type titanium dioxide nano material and the silver nitrate aqueous solution
In the mass ratio of silver nitrate that contains be 0.1:(0.001~0.015) (such as 0.1:0.001,0.1:0.0015,0.1:
0.002、0.1:0.0025、0.1:0.003、0.1:0.004、0.1:0.005、0.1:0.006、0.1:0.007、0.1:0.008、
0.1:0.009,0.1:0.01,0.1:0.012 or 1:0.015), preferably 0.1:(0.0015~0.009) (such as 0.1:
0.0015、0.1:0.002、0.1:0.0025、0.1:0.003、0.1:0.004、0.1:0.005、0.1:0.006、0.1:
0.007,0.1:0.008 or 0.1:0.009).In the present invention, it is preferred to for the hollow shell-type titanium dioxide nano material and institute
The mass ratio for stating the silver nitrate contained in silver nitrate aqueous solution is 0.1:(0.0015~0.009) it is more preferably 0.1:0.006, it can
So that the photocatalytic degradation effect of HT@Ag Pyrogentisinic Acid's solution obtained is best, phenol can be more quickly removed.
According to some preferred embodiments, the concentration of the silver nitrate aqueous solution be 0.03~0.19g/L (such as
0.03,0.04,0.05,0.06,0.09,0.1,0.11,0.12,0.13,0.14,0.15,0.16,0.17,0.18 or 0.19g/
L).In the present invention, silver nitrate aqueous solution refers to the aqueous solution containing silver nitrate, and the concentration of silver nitrate aqueous solution refers to unit
The quality of the silver nitrate contained in the silver nitrate aqueous solution of volume.
According to some specific embodiments, the preparation process of HT@Ag are as follows: take hollow TiO2Particle (HT particle) 0.1g points
It dissipates in the 80mL distilled water containing different quality silver nitrate (such as 0.0015g, 0.003g, 0.006g and 0.009g), ultrasound
5min obtains hollow shell-type titanium oxide dispersion；By the hollow shell-type titanium oxide dispersion transposition in 200mL quartz ampoule
In, and 1h is irradiated under 350W high-pressure sodium lamp under conditions of magnetic stirring, wherein quartz ampoule distance high-voltage mercury lamp 15cm, is centrifuged simultaneously
Three times are washed with the mixed solution of dehydrated alcohol and distilled water and obtains a series of HT@Ag samples, are placed in dried overnight at 60 DEG C.
The present invention provides in silver load made from preparation method of the present invention described in the third aspect in fourth aspect
Ghost formula titanium dioxide nano material.
Hereafter will the present invention is further described by way of example, but protection scope of the present invention is not limited to these
Embodiment.
Embodiment 1: hollow TiO2Preparation with HT@Ag is tested.
1. the preparation of RF dispersion liquid: 0.35mL ammonium hydroxide is added in the solution of 40mL distilled water and 16mL dehydrated alcohol,
It is placed in three-necked flask, three-necked flask is put into heat collecting type constant temperature blender with magnetic force, 1h is stirred at room temperature, 0.4g isophthalic two is added
Phenol continues to stir 0.5h, is warming up to 30 DEG C, is added 0.56mL formalin, reaction be centrifuged afterwards for 24 hours and with dehydrated alcohol with distill
The mixed solution of water washes three times and obtains sample, and being redispersed in 40mL dehydrated alcohol, to obtain RF dispersion liquid spare.
②RF@TiO2Preparation: take four parts of 5mLRF dispersion liquids be respectively placed in 45mL dehydrated alcohol and 0.10mL, 0.20mL,
In the ammonia spirit of 0.30mL, 0.35mL, it is ultrasonically treated 0.5h, is placed in three-necked flask, three-necked flask is put into heat collecting type perseverance
In warm magnetic stirring apparatus, 1h is stirred at room temperature, obtains four portions of mixed liquors, 1mL metatitanic acid four is added dropwise dropwise into mixed liquor described in every part
Butyl ester reacts 2.5h at 85 DEG C, obtains four parts of reaction product solutions, and every part of reaction product solution is centrifuged and is used anhydrous
Ethyl alcohol washes three times and obtains four parts of samples (RF@TiO2Sample), four parts of samples are dried overnight at 60 DEG C.
3. hollow TiO2(HT) preparation: by four parts of samples resulting after drying first in N2It is roasted at 500 DEG C in atmosphere
3h then roasts 3h at 500 DEG C in air atmosphere, and hollow TiO is made2(HT)；In N2The maturing temperature is risen in atmosphere
It is 2 DEG C/min with the heating rate for rising to the maturing temperature in air atmosphere；By the hollow TiO of gained2(HT) sample is according to 2.
The difference of middle ammonia volume is denoted as HT-0.10, HT-0.20, HT-0.30 and HT-0.35 respectively.
4. the preparation of ultraviolet diffraction catalysis HT Ag: take sample HT-0.30 particle 0.1g be scattered in respectively containing 0.0015g,
In four parts of 80mL distilled water of 0.003g, 0.006g and 0.009g silver nitrate, ultrasonic 5min obtains four parts of hollow shell-type titanium dioxides
Titanium dispersion liquid；By four parts of hollow shell-type titanium oxide dispersion transposition in 200mL quartz ampoule, and in the condition of magnetic stirring
Under 1h is irradiated under 350W high-pressure sodium lamp, wherein quartz ampoule distance high-voltage mercury lamp 15cm is centrifuged and with dehydrated alcohol and distilled water
Mixed solution wash three times and obtain a series of HT@Ag samples, be placed in dried overnight at 60 DEG C；By gained HT@Ag sample according to nitre
The difference of sour silver dosage is denoted as HT-1.5, HT-3, HT-6 and HT-9 respectively, the silver nitrate dosage being corresponding in turn to be 0.0015g,
0.003g, 0.006g and 0.009g, also show respectively the theoretical silver content (weight percent content) of HT@Ag be respectively 1.5%,
3%, 6% and 9%.
Four parts of hollow TiO made from the present embodiment2Scanning electron microscope (SEM) figure of sample is as shown in Figure 1.From Fig. 1
It is found that can significantly find out when ammonia volume is 0.1mL and 0.2mL, particle is in monodisperse status, and particle size is equal
Even, butyl titanate (TBOT) is ideally hydrolyzed by heterogeneous nucleation-homogeneous nucleation on the surface RF；When ammonia volume is 0.3mL
When, have between particle it is slight stick to each other, this may be the increase due to ammonia vol, so that hydroxide ion OH in solution-Contain
Measure higher, the hydrolytic condensation rate of TBOT is too fast, and most titanium oligomer are coated on the surface RF, but adjacent R F@TiO2Hydrolysis
Homogeneous nucleation occurs between obtained shell titanium oligomer, causes RF@TiO2Residual adhesion；When ammonia volume is 0.35mL,
A large amount of TiO2It is uncoated on the surface RF, but adhesion to each other, RF@TiO2Occur it is serious agglomerate into big block structure,
This may be because of hydroxide ion OH-Content continues growing, so that the hydrolytic condensation rate of TBOT is greater than titanium oligomer and exists
RF@TiO2The homogeneous nucleation rate on surface, small part titanium oligomer is coated on the surface RF, but most of titanium oligomer does not exist
RF@TiO2Surface homogeneous nucleation, but the homogeneous nucleation between titanium oligomer is coated on RF@TiO2Surface forms big packet
Cover body.
Four parts of hollow TiO made from the present embodiment2Transmission electron microscope figure (TEM) figure of sample is as shown in Figure 2.From figure
2 it is found that the present invention has obtained hollow structure TiO by two one-step bakings2Nano particle, and there is different thickness, with ammonium hydroxide
The increase of dosage, hollow structure TiO2Shell thickness also gradually increases, hollow when ammonia volume increases to 0.2mL from 0.1mL
Structure Ti O2Shell thickness has a great increase, increases to about 73nm from about 20nm；When ammonia volume increases to 0.3mL
When with 0.35mL, hollow structure TiO2Shell thickness about 85nm and 90nm respectively.The inventors discovered that ammonia volume is continued growing,
Hollow structure TiO2Shell thickness there will not be too many increase.
Four parts of hollow TiO made from the present embodiment2The X-ray diffraction spectrogram (XRD spectra) of sample is as shown in figure 3, in figure
What 2 θ of abscissa was indicated is twice (the 2 θ angle of diffraction) of the angle of diffraction, and unit is degree (degree), ordinate Intensities in figure
What is indicated is intensity；It is to occur spy at 25.34 °, 37.78 °, 48.02 °, 53.92 ° and 55.08 ° in the 2 θ angles of diffraction in Fig. 3
Peak is levied, TiO is respectively corresponded2(101), (004), (200), (105) and (211) crystal face (JCPDS21-1272) of anatase；
In Fig. 3, characteristic peak is had no in other positions and is occurred, illustrates hollow TiO made from two one-step baking of the present embodiment2Sample is all sharp
Titanium ore crystal form.
The results are shown in Table 1 for the X-ray energy spectrum analysis (EDS elemental analysis) of four parts of HT@Ag samples made from the present embodiment,
As can be known from the results of Table 1, Ag is successfully supported on hollow TiO2Surface, although actual negative carrying capacity has with theoretical negative carrying capacity
Deviation, this may be that part silver nitrate crystal is not reduced, be lost after centrifugation.
During tri- parts of HT@Ag samples of HT-3, HT-6 and HT-9 made from the present embodiment and ammonia volume are obtained when being 0.3mL
Empty TiO2The X-ray diffraction spectrogram (XRD spectra) of sample (HT-0.30) is as shown in figure 4, what 2 θ of abscissa indicated in figure is diffraction
Twice (the 2 θ angle of diffraction) at angle, unit are degree (degree), and what ordinate Intensities was indicated in figure is intensity；In Fig. 4
In, from the XRD spectra comparison of (a)-(c) and (d) it is found that the characteristic peak of anatase titania has, after illustrating loaded Ag,
Anatase is not destroyed and is converted into Rutile Type or brookite, and is to occur one at 44 ° in the 2 θ angles of diffraction
New characteristic peak, for the characteristic peak of silver, this shows that Ag has been supported on hollow TiO by the present invention2Surface.
Hollow TiO made from the present embodiment2With the high resolution transmission electron microscopy (high power TEM figure) of HT@Ag sample
As shown in figure 5, from Fig. 5 lattice fringe can be clearly observed, it is clean well to illustrate that sample made from the present embodiment possesses
Cleanliness, wherein spacing of lattice is 101 crystal faces that 0.35nm is titanium dioxide, and spacing of lattice is 111 crystal faces that 0.24nm is silver.
Embodiment 2: hollow TiO2(HT) experiment of degradation of phenol.
Four kinds of HT nano particles in the embodiment 1 of 20mg are weighed respectively, are dispersed in four parts of 40mL respectively, concentration is 400 μ
In the phenol aaerosol solution of mol/L, four parts of phenol aaerosol solutions containing HT nano particle are stirred 30 points in a dark environment
Clock is balanced with reaching adsorption-desorption of the phenol on composite nanometer particle surface, high-pressure sodium lamp is opened, after illumination different time
(taking a sample at interval of 15min or 30min) takes out 2mL suspension and is centrifugated out catalyst, analyzes supernatant
The UV-visible absorption spectrum of (ultraviolet-uisible spectrophotometer UV1900/UV1901PCS), phenol and its intermediate product is such as
Shown in Fig. 6, in figure, the corresponding ultraviolet absorption peak of phenol abscissa Wavelength in 270nm, figure indicates wavelength, and unit is
Nm, ordinate Absorbance indicates absorbance in figure.
As can be seen from Figure 6, when phenol degradation efficiency (degradation rate) reaches 90% or so, HT-0.10 time-consuming 210min, HT-
0.20 time-consuming 180min, HT-0.30 time-consuming 150min, HT-0.35 time-consuming 240min；With HT-0.10, HT-0.20, HT-0.30
When with HT-0.35 as photocatalyst for degrading phenol, the degradation curve of phenol at any time is as shown in fig. 7, the phenol specifically obtained
Concentration and corresponding phenol degradation efficiency are as shown in table 2.In Fig. 7, abscissa Irradiation time indicates degradation time,
Unit is min, and ordinate C indicates that concentration, unit are μM (μm ol/L)；As can be seen from Figure 7, when ammonia volume is 0.30mL,
Ultraviolet optical diffraction 180min, phenol is degradable, and wherein the photocatalysis performance of ultraviolet lighting 30-60min is the most obvious.From table 2
Result it is found that HT-0.30 has apparent advantage relative to other three samples, especially relative to HT-0.10 and HT-
0.35, wherein when ultraviolet diffraction 150min, HT-0.30 degradation efficiency reaches 95.74%, is much higher than nanometer reported in the literature
Titanium dioxide hollow ball catalyst amount is 1.0g/L, when ultraviolet diffraction 180min the degradation efficiency of Pyrogentisinic Acid be 81% (referring to:
Dian-Ping W,Qian Z,Shou-Xin L.Synthesis of nanosize TiO_2hollow sphere via
acid catalytic hydrolysis-hydrothermal method[J].Journal of Functional
Materials,2012,43(23):3222-3227+3231.)。
The experiment of embodiment 3:HT@Ag degradation of phenol.
Four kinds of HT@Ag nano particles in the embodiment 1 of 20mg are weighed respectively, and being dispersed in four parts of 40mL, concentration respectively is
In the phenol aaerosol solution of 400 μm of ol/L, four parts of phenol aaerosol solutions containing HT@Ag nano particle are stirred in a dark environment
It mixes 30 minutes and is balanced with reaching adsorption-desorption of the phenol on composite nanometer particle surface, high-pressure sodium lamp is opened, in illumination difference
Between after (taking a sample at interval of 10min or 15min) take out 2mL suspension and be centrifugated out catalyst, supernatant is carried out
It analyzes (ultraviolet-uisible spectrophotometer UV1900/UV1901PCS), the uv-visible absorption spectra of phenol and its intermediate product
For figure as shown in figure 8, in figure, the corresponding ultraviolet absorption peak of phenol abscissa Wavelength in 270nm, figure indicates wavelength, single
Position is nm, and ordinate Absorbance indicates absorbance in figure.
As it can be observed in the picture that sample HT-6 is in ultraviolet optical diffraction 90min, benzene compared to sample HT-1.5, HT-3 and HT-9
The absorbance of phenol and its intermediate product is almost 0, it is seen that phenol and its intermediate product are almost degraded completely；Although HT-1.5, HT-
3.0 and HT-9 photocatalysis performance is poor, but compared to simple HT-0.30, photocatalysis performance has apparent advantage；With
When HT-1.5, HT-3, HT-6 and HT-9 are as photocatalyst for degrading phenol, the degradation curve of phenol at any time is as shown in figure 9, tool
The phenol concentration and corresponding phenol degradation efficiency that body obtains are as shown in table 3.In Fig. 9, abscissa Irradiation time
Indicate that degradation time, unit min, ordinate C indicate that concentration, unit are μM (μm ol/L)；From fig. 9, it can be seen that when turning on light
When Pyrogentisinic Acid's solution carries out light-catalyzed reaction, phenol concentration has the tendency that one first increases and degrades afterwards, the wherein degradation of HT-6
Rate is most fast, in 90min by phenol is degradable and degradation curve more straight line, illustrates that its degradation rate is quite stable.From
For the result of table 3 it is found that the photocatalysis performance of HT-3 and HT-6 is more excellent, the degradation rate in 90min is respectively 88.753% He
98.978%, relative to the hollow type titanium dioxide nano material of unsupported silver, the hollow shell-type nano titania of silver load
The photocatalysis efficiency of material is significantly improved.
Comparative example 1:RF@TiO2Preparation with HT@Ag is tested.
Comparative example 1 prepares RF@TiO using with method (step is 1., 2. and 4. identical) essentially identical in embodiment 12With
HT@Ag, the difference is that: in 3., by four parts of samples resulting after drying in N26h is roasted at 500 DEG C in atmosphere, in N2
The heating rate that the maturing temperature is risen in atmosphere is 2 DEG C/min.
Using identical test method in embodiment 2 to four kinds of RF@TiO made from this comparative example2Nano particle Pyrogentisinic Acid
Degradation efficiency tested, after illumination 240min, 2. in ammonia volume be respectively 0.1mL, 0.20mL, 0.30mL and
RF@TiO made from 0.35mL2The degradation efficiency of nano particle Pyrogentisinic Acid is respectively 58%, 65%, 76% and 49%.
Using identical test method in embodiment 3 to four kinds of HT@Ag nano particle Pyrogentisinic Acids' made from this comparative example
Degradation efficiency is tested, and after illumination 120min, silver nitrate dosage is respectively 0.0015g, 0.003g, 0.006g and 0.009g
The degradation efficiency of HT@Ag nano particle Pyrogentisinic Acid obtained is respectively 59%, 67%, 78% and 50%.
Comparative example 2: broken TiO2With broken TiO2The preparation of@Ag is tested.
Comparative example 2 prepares broken TiO using with method (step is 1., 2. and 4. identical) essentially identical in embodiment 12With
Broken TiO2@Ag, the difference is that: in 3., four parts of samples resulting after drying are roasted at 500 DEG C in air atmosphere
6h is burnt, the heating rate that the maturing temperature is risen in air atmosphere is 2 DEG C/min.
Using identical test method in embodiment 2 to four kinds of broken TiO made from this comparative example2Nano particle Pyrogentisinic Acid
Degradation efficiency tested, as a result are as follows: when phenol degradation efficiency (degradation rate) reaches 90% or so, 2. in ammonia volume be
TiO is crushed made from 0.10mL2Time-consuming 190min, 2. middle ammonia volume is that TiO is crushed made from 0.20mL2Time-consuming 170min, 2.
Middle ammonia volume is that TiO is crushed made from 0.30mL2Time-consuming 135min, 2. middle ammonia volume is that TiO is crushed made from 0.35mL2
Time-consuming 210min.
Using identical test method in embodiment 3 to four kinds of broken TiO made from this comparative example2@Ag nano particle pair
The degradation efficiency of phenol is tested, after illumination 90min, silver nitrate dosage be respectively 0.0015g, 0.003g, 0.006g and
TiO is crushed made from 0.009g2The degradation efficiency of@Ag nano particle Pyrogentisinic Acid is respectively 41%, 62%, 71% and 46%.
From the result of this comparative example it is recognized that while being crushed drop of the titanium dioxide than spherical tio2 made from this comparative example
It is quite a lot of to solve effect, this is because more specific surface areas, more active sites can be exposed after broken；But made from this comparative example
Broken titanium dioxide degradation efficiency of Pyrogentisinic Acid after load silver is far below hollow TiO2It is right after (spherical tio2) load silver
The degradation efficiency of phenol, this may be to carry out in next step since broken titanium dioxide does not have the surface same sex of spherical tio2
If loading small spherical particles, it will cause loaded article and be unevenly distributed, a large amount of loaded article is caused to be distributed in the recessed of broken titanium dioxide
Face internal layer, the load capacity being likely to result on the inside of concave surface is too high, and the load capacity on the outside of concave surface is too low, causes outside object in fragment
Change the inhomogenous of property, seriously affects photocatalytic activity.
Comparative example 3
A kind of preparation method of the titanium dioxide hollow core-shell structure composite photo-catalyst of molybdenum disulfide cladding, is specifically pressed
What following steps carried out:
One, by SiO2Powder is dispersed in mixed solution, obtains reaction system, by four fourth of metatitanic acid after ultrasonic disperse 15min
Ester is added in reaction system, obtains suspension, and suspension is stirred 12h, centrifugation point in the case where temperature is 45 DEG C of water bath condition
From washing is dried to obtain white solid, and white solid is calcined 1h under conditions of temperature is 550 DEG C, obtains SiO2@TiO2；Institute
Stating mixed solution is dehydrated alcohol and NH3·H2The mixed liquor of O, wherein NH3·H2The weight percent of O is 25%~28%；Institute
State SiO2The quality of powder and the volume ratio of mixed solution are 0.15g:200mL；The SiO2The quality and butyl titanate of powder
Volume ratio be 1g:1mL.
Two, by 0.15g (NH4)6Mo7O24·4H2O and 0.32g urea is dissolved in 30mL deionized water, then is added thereto
Enter the SiO that 0.1g step 1 obtains2@TiO2It is transferred in reaction kettle after ultrasonic disperse 20min, under conditions of temperature is 180 DEG C
10h is reacted, black precipitate is obtained, black precipitate is first used to adopt again for ethanol washing 3~5 times is washed with deionized 3~5 times,
Obtain clean sample；Clean sample is dried into 10~14h under conditions of temperature is 50 DEG C, obtains black powder, it will be black
Color powder is added to the NH that concentration is 0.1mol/L4HF230min is stirred in solution, is washed drying, is obtained hollow core-shell structure
TiO2@MoS2Composite photo-catalyst.
Using identical test method in embodiment 3 to hollow core-shell structure TiO made from this comparative example2@MoS2Complex light
The degradation efficiency of catalyst Pyrogentisinic Acid is tested, after illumination 120min, TiO2@MoS2The drop of composite photo-catalyst Pyrogentisinic Acid
Solution efficiency only reaches 36%.
The constituent content comparison of HT@Ag sample after table 1:Ag load.
Table 2: different hollow TiO2Nano particle is in different light application time phenol residual concentrations and its degradation rate.
Table 3: different HT@Ag nano particles are in different light application time phenol residual concentrations and its degradation rate.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of preparation method of hollow shell-type titanium dioxide nano material, which is characterized in that described method includes following steps:
(1) resorcinol formaldehyde resin dispersion liquid and ammonium hydroxide are uniformly mixed with dehydrated alcohol, obtain mixed liquor, then by metatitanic acid
Four butyl esters, which are added dropwise in the mixed liquor, to be reacted, and reaction product solution is obtained；The dehydrated alcohol, the resorcinol first
The volume ratio of urea formaldehyde dispersion liquid, the ammonium hydroxide and the butyl titanate is (40~50): (4~6): (0.1~0.4):
(0.75~1.5)；
(2) reaction product solution that step (1) obtains successively is passed through into step with centrifugal separation, washing step and drying steps, obtained
To the titanic oxide material with core-shell structure；With
(3) titanic oxide material with core-shell structure for obtaining step (2) first roasts 2~4h in nitrogen atmosphere, then
2~4h is roasted in air atmosphere, and hollow shell-type titanium dioxide nano material is made.
2. preparation method according to claim 1, which is characterized in that the method also includes carrying out before step (1)
The preparation step of the resorcinol formaldehyde resin dispersion liquid, the preparation step include following sub-step:
(a) ammonium hydroxide is uniformly mixed with water and dehydrated alcohol, obtains the first mixed solution, then into first mixed solution
Resorcinol is added and is uniformly mixed, obtains the second mixed solution；
(b) formalin is added in the second mixed solution that step (a) is obtained and is reacted, obtain resorcinol formaldehyde resin
Then the resorcinol formaldehyde resin solution is successively passed through step with centrifugal separation and washing step, obtains isophthalic two by solution
Fluosite；With
(c) resorcinol formaldehyde resin obtained with dehydrated alcohol dispersion steps (b) obtains the resorcinol formaldehyde resin point
Dispersion liquid.
3. preparation method according to claim 2, it is characterised in that:
In step (a), the volume ratio of the water, the dehydrated alcohol and the ammonium hydroxide is (30~60): (10~20): (0.2
~0.4)；
The molar ratio of the formaldehyde contained in the resorcinol and the formalin is 1:(1~2)；And/or
In step (b), the temperature of the reaction is 30~35 DEG C, and the time of the reaction is 18~30h.
4. preparation method according to any one of claims 1 to 3, it is characterised in that:
In step (1), the temperature of the reaction is 70~100 DEG C, and the time of the reaction is 2~4h.
5. preparation method according to any one of claims 1 to 3, it is characterised in that:
The temperature roasted in nitrogen atmosphere and/or the temperature roasted in air atmosphere are 400~500 DEG C.
6. hollow shell-type titanium dioxide nano material made from preparation method according to any one of claims 1 to 5.
7. a kind of preparation method of the hollow shell-type titanium dioxide nano material of silver load, which is characterized in that the method includes
Following steps:
S1, with silver nitrate aqueous solution by hollow shell-type titanium dioxide made from preparation method described in any one of claim 1 to 5
Nano material is uniformly dispersed, and obtains hollow shell-type titanium oxide dispersion；With
S2, the hollow shell-type titanium oxide dispersion is handled so that silver is supported on the hollow shell-type two with ultraviolet light
The hollow shell-type titanium dioxide nano material of silver load is made in the surface of titanium dioxide nano material.
8. preparation method according to claim 7, it is characterised in that:
The mass ratio of the silver nitrate contained in the hollow shell-type titanium dioxide nano material and the silver nitrate aqueous solution is
0.1:(0.001~0.015), preferably 0.1:(0.0015~0.009).
9. preparation method according to claim 7 or 8, it is characterised in that:
The concentration of the silver nitrate aqueous solution is 0.03~0.19g/L.
10. the hollow shell-type nano titania of the load of silver made from preparation method according to any one of claims 7 to 9
Material.
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