CN105013516A - Supported multistage structure silver-silver halide-titanium dioxide composite light visible catalytic material and preparation method therefor - Google Patents
Supported multistage structure silver-silver halide-titanium dioxide composite light visible catalytic material and preparation method therefor Download PDFInfo
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Abstract
The invention discloses a supported multistage structure silver-silver halide-titanium dioxide composite light visible catalytic material and a preparation method therefor. According to the method provided by the invention, by carrying out four steps of supporter pretreatment, direct hydrolysis,generation of silver sulfide and photoreduction, nanometer silver/silver halide grains, and sub-microscale titanium dioxide grains are fixedly supported on different vectors, thereby preparing and obtaining the supported multistage structure silver-silver halide-titanium dioxide composite light visible catalytic material. The whole preparation process is easy to operate and controllable, and has good reproducibility; product yield is greater than 80%; and the prepared photocatalytic materials have efficient visible light catalytic performance, and can be repeatedly used, and have a very high practical value.
Description
Technical field
The present invention relates to a kind of titanium dioxide optical catalyst, be specifically related to a kind of support type multilevel hierarchy silver-silver halide-titanium dioxide composite visible light catalytic material and preparation method thereof.
Background technology
Photocatalitic Technique of Semiconductor is a kind of green, the efficient method removing Organic Pollutants In Water, and the semiconductor catalysis material that exploitation has excellent photocatalysis performance is the focus that photocatalysis is studied always.In numerous semi-conducting material, titanium dioxide has that specific area is large, low cost, stability advantages of higher, is the extensive concern of researcher always.
But photoresponse scope narrower be one of key issue of restriction optically catalytic TiO 2 performance, by noble-metal-supported, ion doping or add the means such as light-sensitive coloring agent, the catalytic performance of titanium dioxide and the response to visible ray can be improved.
Such as application number is the preparation method that the Chinese patent of 201510053214.X discloses a kind of nano-silver loaded titanium dioxide optical catalyst, this preparation method comprises: in a kettle., drop into 20 grams of hydrogen peroxide, 2.5 grams of NaOH, slowly add 20 grams of titanium tetrachlorides after dissolving, heated sealed pressurization, insulation, that cooling for reflux obtains the titanium dioxide nanocrystalline hydrosol is for subsequent use; Joined in 10 milliliters of absolute ethyl alcohols by 0.017 gram of silver nitrate, join in 20 milliliters of ethanol of 0.10 gram of polyvinylpyrrolidone, the obtained spherical nano-silver of reaction is for subsequent use; 10 grams of titanium dioxide nanocrystalline hydrosols of the spherical nano-silver 0.01 gram and aforementioned preparation of getting aforementioned preparation react, and continue ultrasonic disperse 30 minutes, obtained photochemical catalyst.
But, although the plasma resonance effect on noble silver simple substance surface effectively can strengthen the absorption of titanium dioxide to visible ray, silver/titanium dioxide composite catalyst easily oxidized, catalytic performance is stable not.Recent silver/halogenation silver/titanium dioxide multistage composite material receives the concern of scientific research personnel because having visible light catalytic performance and good stability.
But there is the shortcomings such as repeatable poor, uncontrollable and complicated process of preparation in the appearance structure of current this kind of silver/silver halide/titanium dioxide composite catalyst, size, preparation technology aspect, catalytic performance also has much room for improvement, and does not also prepare the effective ways of stable homogeneous multilevel hierarchy silver/halogenation silver/titanium dioxide compound catalyze material at present (see document: Materials Chemistry and Physics 143 (2013) 393-399; Journal of Hazardous Materials 263 (2013) 541 – 549; Journal ofAlloys and Compounds 639 (2015) 153 – 161; Ultrasonics Sonochemistry 26 (2015) 370 – 377.).In addition, large, the high in cost of production problem of the recovery difficult of this kind of compound catalyze material also has to be solved.
Summary of the invention
The invention provides the preparation method of a kind of support type multilevel hierarchy silver-silver halide-titanium dioxide composite visible light catalytic material, this preparation method is easy and simple to handle.
A preparation method for support type multilevel hierarchy silver-silver halide-titanium dioxide composite visible light catalytic material, comprises the following steps:
(1) carrier material is immersed in strong acid solution and strong base solution successively makes reflow treatment, obtain pretreated carrier material;
(2) ammonium salt or sodium salt, titanium tetrachloride being joined concentration is successively in the strong acid solution of 0.1% ~ 1%, obtains solution A, is joined in solution A by described pretreated carrier material and make reflow treatment, obtain load type titanium dioxide photocatalytic material;
(3) by polyelectrolyte stabilizing agent, silver ion salt, organic solvent with (0.3 ~ 0.4) gram: (0.08 ~ 0.09) gram: 100 milliliters ratio mixing, obtain solution B, by described load type titanium dioxide photocatalytic material with (0.4 ~ 0.6) gram: the ratio of 40 milliliters joins in solution B, obtain suspension;
By halide salt, organic solvent with (0.08 ~ 0.09) gram: the ratio mixing of 100 milliliters, obtains solution C;
By suspension, solution C with volume ratio 5:1 ~ 1:1 mixing, be heated to 60 DEG C of isothermal reactions 1 ~ 2 hour, obtain support type silver halide-photocatalysis material of titanium dioxide;
(4) photo-reduction process is done to described support type silver halide-photocatalysis material of titanium dioxide, obtain described support type multilevel hierarchy silver-silver halide-titanium dioxide composite visible light catalytic material.
The present invention prepares support type multilevel hierarchy silver-silver halide-titanium dioxide composite visible light catalytic material by Vehicle element-direct hydrolysis-generation silver halide precipitation-photo-reduction four steps, whole preparation process is easy and simple to handle, process control, has good repeatability; And efficiency of pcr product is more than 80%.
Particularly, described preparation method comprises:
(1) carrier material is immersed in strong acid solution and strong base solution successively makes reflow treatment, obtain pretreated carrier material;
Described carrier material can select carbon fiber, three-dimensional grapheme aeroge, molecular sieve, CNT or carbon black.
As preferably, carrier material is immersed in successively pH be 1.0 strong acid solution and pH be in the strong base solution of 13, reflux 2.5 ~ 3.5 hours at 90 DEG C.
After strong acid treatment, carrier material original smooth, shape of threads crack structtire can be transformed into without the surface of scratch; With after through highly basic reason, further increase the rough degree of surfaces of carrier materials, there is many vermiform ducts in surfaces of carrier materials, the size in hole is about 10 ran.After strong acid, highly basic process, the specific area of carrier material significantly increases, and is convenient to the attachment of catalyst, improves the binding ability of carrier material and catalyst.
(2) ammonium salt or sodium salt, titanium tetrachloride being joined concentration is successively in the strong acid solution of 0.01 mol/L, obtains solution A, is added in solution A by described pretreated carrier material and make reflow treatment, obtain load type titanium dioxide photocatalytic material;
Described reflow treatment is preferably and refluxes 1 ~ 5 hour at 90 DEG C.
In strong acid solution, add hot reflux, be conducive to the speed reducing titanium tetrachloride hydrolysis nucleation, titanium dioxide is slowly formed, the formation just nuclear particle and the titanium dioxide aggregation generated is grown up, first nuclear particle constantly precipitates to assemble and forms Titanium dioxide spherical particle.
As preferably, titanium tetrachloride is dropwise joined in strong acid solution with the ratio of 1 ~ 1.5 milliliter: 100 milliliters.Titanium tetrachloride adds more, and the productive rate of titanium dioxide granule is higher, but particle size also can strain greatly mutually simultaneously.
Ammonium salt in backflow system or sodium salt are used for providing alkali ion (ammonium ion and sodium ion), in titanium dioxide forming process, these alkali ions can insert titanium dioxide interlayer, change the surface topography of simple titanium dioxide granule, increase specific area, thus obtain the titanium dioxide granule of two-dimensional layered structure.
As preferably, in step (2), the ratio that adds of ammonium salt or sodium salt and titanium tetrachloride is 0.01 ~ 0.04 gram: 1 milliliter.The mixed proportion of ammonium salt or sodium salt and titanium tetrachloride is controlled in certain scope, is conducive to ensureing that titanium dioxide surface forms good layered porous structure; When titanium tetrachloride is too much, the pore structure of titanium dioxide surface can become not obvious; And when ammonium salt or sodium salt too much time, then can not form complete poriferous titanium dioxide particle, cannot be carried on carrier.
(3) by polyelectrolyte stabilizing agent, silver ion salt, organic solvent with (0.3 ~ 0.4) gram: (0.08 ~ 0.09) gram: 100 milliliters ratio mixing, obtain solution B, by described load type titanium dioxide photocatalytic material with (0.4 ~ 0.6) gram: the ratio of 40 milliliters joins in solution B, obtain suspension;
By halide salt, organic solvent with (0.08 ~ 0.09) gram: the ratio mixing of 100 milliliters, obtains solution C;
By suspension, solution C with volume ratio 5:1 ~ 1:1 mixing, be heated to 60 DEG C of isothermal reactions 1 ~ 2 hour, obtain support type silver halide-photocatalysis material of titanium dioxide;
Described polyelectrolyte stabilizing agent can select poly-methyl pyrrole alkane ketone, PEO or diallyl dimethyl amine hydrochlorate.
Described silver ion salt can select silver nitrate, silver ammino solution etc.
Described halide salt can select alkali metal halide salt (as KBr), ammonium halide, and halogenated transition metal salt etc.
(4) photo-reduction process is done to described support type silver halide-photocatalysis material of titanium dioxide, obtain described support type multilevel hierarchy silver-silver halide-titanium dioxide composite visible light catalytic material.
As preferably, described photo-reduction was treated to: by described support type silver halide-photocatalysis material of titanium dioxide dispersion in deionized water, with hernia light irradiation 25 ~ 35 minutes.
Present invention also offers the support type multilevel hierarchy silver-silver halide-titanium dioxide composite visible light catalytic material utilizing described preparation method to obtain.
For decomposition of methyl orange solution, when visible ray (wavelength>=420nm) irradiates 110 minutes, pure titinium dioxide can degrade 9% methyl orange, the titanium dioxide of traditional silver-doped can degrade 50% methyl orange, and support type multilevel hierarchy of the present invention silver-silver halide-titanium dioxide composite visible light catalytic material can degrade 100% methyl orange; Further, the degradation rate constant of catalysis material of the present invention reaches 0.024 minute
-1, higher than the titanium dioxide (0.0037-0.018 minute of precious metal doping
-1) and commercialization P25 (0.0028-0.015 minute
-1, under ultraviolet light conditions); After use 5 times, still more than 85% is remained on to the percent of decolourization of methyl orange.
Compared with prior art, beneficial effect of the present invention is:
The present invention is by Vehicle element-direct hydrolysis-generation silver halide precipitation-photo-reduction four steps, nanometer-level silver/silver halide particle, submicron order titanium dioxide granule are firmly carried on dissimilar carrier, prepare support type multilevel hierarchy silver-silver halide-titanium dioxide composite visible light catalytic material, whole preparation process is easy and simple to handle, process control, has good repeatability; And efficiency of pcr product is more than 80%; Obtained catalysis material has efficient visible light catalytic performance, is easy to reclaim, and repeated multiple timesly can use, has very strong practical value.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic observation figure of silver-silver bromide-titanium dioxide-glass fibre compound catalyze material of the present invention;
Fig. 2 is the scanning electron microscopic observation figure of silver-silver bromide-titanium dioxide compound catalyze material prepared by comparative example 1;
Fig. 3 A is with catalysis time change curve in different catalysts effect Methyl Orange concentration;
Wherein, C/C
0represent the change compared to initial conditions methyl orange concentration; Lower same;
Fig. 3 B is at different catalysts effect Methyl Orange concentration parameter ln (C/C
0) with the graph of a relation of light application time t;
Wherein, In (C
0/ C) represent the logarithm numerical value that change in concentration numerical value is corresponding; Fig. 4 is that silver-silver bromide-titanium dioxide-glass fibre compound catalyze material of the present invention is degraded the cyclical stability testing result of methyl orange solution under visible light;
Wherein, " 1
strun " represent first time circulation, " 2
ndrun " represent second time circulation, " 3
rdrun " represent third time circulation, " 4
thrun " represent the 4th circulation, " 5
thrun " represent the 5th circulation.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment 1
A preparation method for support type multilevel hierarchy silver-silver halide-titanium dioxide composite visible light catalytic material, comprises the following steps:
(1) glass fibre is immersed in successively in the concentrated sulfuric acid solution of pH=1.0 and the potassium hydroxide solution of pH=13.0, reflux 3 hours at 90 DEG C respectively, after cooling, suction filtration isolates glass fibre, and by washed with de-ionized water to neutral, dry at 50 DEG C, obtain pretreated glass fibre, for subsequent use.
(2) 1.5 grams of ammonium sulfate are slowly joined in 100 milliliters of sulfuric acid solutions (0.01 mol/L), stir 5 minutes in ice-water bath, obtain the sulfuric acid solution being dissolved with ammonium sulfate;
Dropwise being joined by 1 milliliter of titanium tetrachloride is dissolved with in the sulfuric acid solution of ammonium sulfate, drips while stir until solution went clear, obtains solution A;
Getting 0.5 gram of pretreated glass fibre immerses in solution A, reflux 3 hours at 90 DEG C subsequently, after cooling, suction filtration isolates glass fibre, alternately cleans for several times with deionized water and ethanol, at 60 DEG C after vacuum drying, obtained ball-type titanium dioxide-glass fiber compound material.
(3) 0.12 gram of poly-methyl pyrrole alkane ketone and 0.035 gram of liquor argenti nitratis ophthalmicus are added in 40 milliliters of ethylene glycol, after mixing, obtain solution B;
0.55 gram of ball-type titanium dioxide/glass fiber compound material is joined in solution B, obtains suspension;
0.024 gram of KBr is joined in 20 milliliters of ethylene glycol, after mixing, obtains solution C;
By suspension, solution C mixing, be heated to 60 DEG C of isothermal reactions 1.5 hours, the alternately washing of products therefrom deionized water and ethanol, obtained silver bromide-titanium dioxide-glass fiber photocatalysis material.
(4) silver halide-titanium dioxide/glass fiber photocatalysis material is dispersed in 50 ml deionized water, with hernia light irradiation 30 minutes, products therefrom is spent deionized water, and vacuum drying more than 3 hours at 60 DEG C, obtained silver-silver bromide-titanium dioxide-glass fibre compound catalyze material.
The scanning electron microscopic observation figure of this silver-silver bromide-titanium dioxide-glass fibre compound catalyze material is shown in Fig. 1.
Embodiment 2 ~ 4
Adopt the method identical with embodiment 1, but in step (2), the addition of titanium tetrachloride changes into: 0.5 milliliter, 1.5 milliliters, 2 milliliters, prepare silver-silver bromide-titanium dioxide-glass fibre compound catalyze material.
Comparative example 1
Adopt the method identical with embodiment 1, but do not add pretreated glass fibre in step (2), prepare silver-silver bromide-titanium dioxide compound catalyze material.
The scanning electron microscopic observation figure of this silver-silver bromide-titanium dioxide compound catalyze material is shown in Fig. 2.
Test example 1
Under radiation of visible light (wavelength >=420nm), with the titanium dioxide (J.Phys.Chem.C of pure titinium dioxide, silver-doped, 2012,116,17721.), the titanium dioxide (J.Mater.Chem. of doping platinum, 2011,21,7596.), commercialization P25 as a comparison, silver-silver bromide-titanium dioxide-glass fibre compound catalyze material prepared by detection embodiment 1 ~ 4, the silver-silver bromide-titanium dioxide compound catalyze material of comparative example 1 preparation are to the degradation rate (catalyst amount 20 milligrams of methyl orange, catalysis time 110 minutes), testing result is in table 1.
After degradation experiment terminates, adopt filter method to reclaim the obtained silver-silver bromide-titanium dioxide composite catalyzing catalyst of embodiment 1 ~ 5, and detect the rate of recovery of each catalyst, testing result is in table 1.
Table 1
| Catalyst type | Methyl orange degradation rate (%) | The rate of recovery (%) |
| Embodiment 1 | 100 | 90 |
| Embodiment 2 | 95 | 90 |
| Embodiment 3 | 92 | 90 |
| Embodiment 4 | 93 | 90 |
| Comparative example 1 | 90 | 60 |
| Pure titinium dioxide | 9 | 40 |
| The titanium dioxide of silver-doped | 85 | 42 |
| The titanium dioxide of doping platinum | 80 | 45 |
| Commercialization P25 | 88 | 60 |
From table 1, in the titanium dioxide granule of two-dimentional lamellar structure, silver-doped/silver halide can significantly improve the catalytic performance of catalyst; And after being carried on the carriers such as glass fibre, catalytic performance improves further, be obviously better than the titanium deoxide catalyst of the noble metals such as current business-like catalyst (P25) and simple silver-doped, platinum; The recovery of supported silver/silver halide/titanium dioxide composite catalyst is also higher, reaches more than 90%.
Embodiment 5 ~ 8
Adopt the method identical with embodiment 1, but in step (2), the addition of ammonium sulfate changes into: 0.005 gram, 0.01 gram, 0.02 gram, 0.05 gram, prepare silver-silver bromide-titanium dioxide-glass fibre compound catalyze material.
Test example 2
Adopt the method identical with embodiment 1, detect the silver-silver bromide-titanium dioxide-glass fibre compound catalyze material of embodiment 5 ~ 8 preparation to the degradation rate of methyl orange, testing result is in table 2.
Table 2
| Catalyst type | Methyl orange degradation rate (%) | The rate of recovery (%) |
| Embodiment 5 | 85 | 90 |
| Embodiment 6 | 90 | 90 |
| Embodiment 7 | 99 | 90 |
| Embodiment 8 | 90 | 90 |
From table 2, along with increasing of ammonium sulfate addition, titanium dioxide granule surface intercalation hole increases, and the specific area of titanium dioxide granule increases, and the catalytic performance of catalysis material is improved gradually.In addition, ammonium sulfate addition is too much, and cause the particle forming complete poriferous titanium dioxide to reduce, the catalyst of supported on carriers reduces, and causes catalytic performance to decline to some extent.Owing to being carried on fiberglass surfacing, the rate of recovery of catalyst remains unchanged substantially.
Embodiment 9 ~ 11
Adopt the method identical with embodiment 1, but the addition of silver nitrate and KBr changes in step (3): 0.035 gram and 0.048 gram, 0.035 gram and 0.012 gram, 0.035 gram and 0.006 gram, prepare silver-silver bromide-titanium dioxide-glass fibre compound catalyze material.
Test example 3
Adopt the method identical with embodiment 1, detect the silver-silver bromide-titanium dioxide-glass fibre compound catalyze material of embodiment 9 ~ 11 preparation to the degradation rate of methyl orange, testing result is in table 3.
Table 3
| Catalyst type | Methyl orange degradation rate (%) | The rate of recovery (%) |
| Embodiment 9 | 100 | 90 |
| Embodiment 10 | 92 | 90 |
| Embodiment 11 | 78 | 90 |
From table 3, within the specific limits, KBr addition fewer, the silver bromide precipitation of generation is fewer, and then causes reducing the minimizing of the silver generated, and catalyst performance reduces gradually.
Embodiment 12 ~ 15
Adopt the method identical with embodiment 1, but change step (4) the middle hernia light irradiation time into: 20 minutes, 25 minutes, 35 minutes, 40 minutes, prepare silver-silver bromide-titanium dioxide-glass fibre compound catalyze material.
Test example 2
Adopt the method identical with embodiment 1, detect the silver-silver bromide-titanium dioxide-glass fibre compound catalyze material of embodiment 12 ~ 15 preparation to the degradation rate of methyl orange, testing result is in table 4.
Table 4
| Catalyst type | Methyl orange degradation rate (%) | The rate of recovery (%) |
| Embodiment 12 | 80 | 90 |
| Embodiment 13 | 95 | 90 |
| Embodiment 14 | 100 | 90 |
| Embodiment 15 | 95 | 90 |
From table 4, the hernia light irradiation time is longer, and the silver that reduction generates is more, and the catalytic performance of catalyst improves gradually.But irradiation time is long, cause all silver bromides to become elemental silver, the facilitation of silver/silver bromide to catalyst weakens, and catalytic performance starts again to decline.
Test example 4
Silver-silver bromide-titanium dioxide-glass fibre the compound catalyze material of Example 1, adopt the method identical with test example 1 to detect its degradation rate to methyl orange, degrade after terminating and reclaim again, degrade, circulation degraded like this 5 times, detect the stability of this catalyst, testing result is in table 5.
Table 5
| Circulation degraded number of times | Methyl orange degradation rate (%) | The rate of recovery (%) |
| 1st time | 100 | 90 |
| 2nd time | 100 | 90 |
| 3rd time | 100 | 90 |
| The 4th | 95 | 88 |
| The 5th | 95 | 85 |
From table 5, by silver, silver bromide, titanium dichloride load in carrier surfaces such as glass fibres, not only can improve catalytic performance further, also significantly improve the recovery of catalyst.
Claims (6)
1. a preparation method for support type multilevel hierarchy silver-silver halide-titanium dioxide composite visible light catalytic material, is characterized in that, comprise the following steps:
(1) carrier material is immersed in strong acid solution and strong base solution successively makes reflow treatment, obtain pretreated carrier material;
(2) ammonium salt or sodium salt, titanium tetrachloride being joined concentration is successively in the strong acid solution of 0.1% ~ 1%, obtains solution A, is joined in solution A by described pretreated carrier material and make reflow treatment, obtain load type titanium dioxide photocatalytic material;
(3) by polyelectrolyte stabilizing agent, silver ion salt, organic solvent with (0.3 ~ 0.4) gram: (0.08 ~ 0.09) gram: 100 milliliters ratio mixing, obtain solution B, by described load type titanium dioxide photocatalytic material with (0.4 ~ 0.6) gram: the ratio of 40 milliliters joins in solution B, obtain suspension;
By halide salt, organic solvent with (0.08 ~ 0.09) gram: the ratio mixing of 100 milliliters, obtains solution C;
By suspension, solution C with volume ratio 5:1 ~ 1:1 mixing, be heated to 60 DEG C of isothermal reactions 1 ~ 2 hour, obtain support type silver halide-photocatalysis material of titanium dioxide;
(4) photo-reduction process is done to described support type silver halide-photocatalysis material of titanium dioxide, obtain described support type multilevel hierarchy silver-silver halide-titanium dioxide composite visible light catalytic material.
2. preparation method as claimed in claim 1, is characterized in that, in step (1), carrier material is immersed in successively pH be 1.0 strong acid solution and pH be in the strong base solution of 13, reflux 2.5 ~ 3.5 hours at 90 DEG C.
3. preparation method as claimed in claim 1, is characterized in that, in step (2), dropwise joined in strong acid solution by titanium tetrachloride with the ratio of 1 ~ 1.5 milliliter: 100 milliliters.
4. preparation method as claimed in claim 3, it is characterized in that, in step (2), the ratio that adds of ammonium salt or sodium salt and titanium tetrachloride is 0.01 ~ 0.04 gram: 1 milliliter.
5. preparation method as claimed in claim 1, it is characterized in that, in step (4), described photo-reduction was treated to: by described support type silver halide-photocatalysis material of titanium dioxide dispersion in deionized water, with hernia light irradiation 25 ~ 35 minutes.
6. support type multilevel hierarchy silver-silver halide-titanium dioxide composite visible light catalytic material of obtaining of the arbitrary described preparation method of Claims 1 to 5.
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| CN105771977A (en) * | 2016-03-22 | 2016-07-20 | 济南大学 | Method for preparing graphene oxide coated carbon fiber-silver loaded TiO2 nano-wire array composite materials and application thereof |
| CN106732690A (en) * | 2016-11-15 | 2017-05-31 | 武汉理工大学 | Ag@AgCl/TiO2The preparation method of graphene oxide composite material |
| CN107537522A (en) * | 2017-09-25 | 2018-01-05 | 中国科学院广州地球化学研究所 | Composite of silver-colored silver halide load iron nano-mineral and preparation method thereof |
| CN111111708A (en) * | 2019-11-12 | 2020-05-08 | 常州良福朗清生物科技有限公司 | Preparation method and application of silver/silver halide loaded mesoporous titanium dioxide microspheres |
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