CN103007932A - Method for preparing titanium dioxide nanobelt load thermometal integral catalyst - Google Patents
Method for preparing titanium dioxide nanobelt load thermometal integral catalyst Download PDFInfo
- Publication number
- CN103007932A CN103007932A CN2012105329730A CN201210532973A CN103007932A CN 103007932 A CN103007932 A CN 103007932A CN 2012105329730 A CN2012105329730 A CN 2012105329730A CN 201210532973 A CN201210532973 A CN 201210532973A CN 103007932 A CN103007932 A CN 103007932A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- belts
- dioxide nano
- load
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing a titanium dioxide nanobelt load thermometal integral catalyst. The method comprises the following steps of: depositing a large number of silver nanoparticles on the surface of a titanium dioxide nanobelt by a photodeposition method, carrying out in situ substitution reaction in chloroauric acid solution to obtain a thermometal load type catalyst, and finally carrying out suction filtration and film pressing on the catalyst to prepare the titanium dioxide nanobelt load thermometal integral catalyst. Particles on the surface of the titanium dioxide nanobelt load thermometal integral catalyst prepared by the invention are uniform in distribution and relatively small in particle size. The titanium dioxide nanobelt load thermometal integral catalyst is quantized and controllable in composition, has high catalytic activity, high selectivity and high stability, and is easy to recover and recycle. In addition, the method is suitable for large-scale industrial applications.
Description
Technical field
The present invention relates to a kind of preparation method of titanium dioxide nano-belts load bimetallic integral catalyzer, relate in particular to the adjustable titanium dioxide nano-belts supported bimetal catalyst of a kind of composition that can be used for the processes such as alcohols selective oxidation, CO oxidation and methyl alcohol, formic acid catalytic oxidation and the preparation method of integral catalyzer thereof, belong to the chemical catalyst technical field.
Background technology
Light deposition is a kind of common carrying method, and namely under certain condition, metal salt solution is reduced to the process of metal simple-substance under the condition that semiconductor substance existence and illumination are arranged.At present, select the object of the method deposition materials mostly to be semi-conductive monometallic load, in the metal salt solution that the hole complexing agent is arranged, add semi-conducting material, preparation support type material under illumination condition.
The original position displacement is a kind of common chemical reaction, and namely under certain condition, the salting liquid of metal is after adding another kind of active metal simple-substance, and the metal ion in the solution can be out replaced, generates the process of simple substance.At present, select the material of the method preparation mostly to be active metal and alloy thereof.
In recent years, the researcher begins to adopt Photodeposition to prepare catalyst and the photochemical catalyst of support type, as: 2000, the people such as Denis Mas adopted Photodeposition to prepare Ag/TiO
2Photochemical catalyst comes catalytic degradation N
2O(Journal of Catalysis 2000 194:71-79); 2004, Mark A.Barteau etc. prepared finely dispersed Ag/TiO by the method for light deposition
2And Au/TiO
2Catalyst (Nano Letters 20055:2058-2062).Therefore, Photodeposition has become one of effective ways of preparation catalysis material, this method simple possible, easy and simple to handle, be easy to repetition, and can obtain simple substance attitude metal, be applicable to fairly large preparation support materials for catalysts, and can also control size and the degree of scatter of plated metal particle by control light deposition time and intensity of illumination.
In recent years, the researcher begins to adopt the standby alloy material of original position conversion legal system, as: 2006, Younan Xia etc. changed legal system for gold and silver nanometer sylphon (J.AM.CHEM.SOC.2007129:1733-1742) with original position.Therefore the original position displacement method also is one of effective ways of preparation alloy material, these method simple possible, easy and simple to handle, good reproducibility, be applicable to the preparation of extensive alloy material, and control displacement degree and composition proportion of composing by control sedimentation time and solution concentration.
But above-mentioned these researchs all are to be conceived to single load type metal catalyst and the alloy material of non-loading type, and the alloying pellet of load can not reach nano-scale and evenly distribution.Adopt infusion process about the method that prepare the alloy loaded catalyst in the existing report, this procedure is complicated more, and product is not easy separation, and load capacity is little etc.Catalyst catalytic efficiency in the process of catalytic reaction of preparation is lower, selectively bad in the existing report in addition, and easily sintering the most important thing is poor stability, is difficult to reach long catalysis requirement.
Adopt light deposition-standby loaded catalyst of original position displacement legal system, particularly supported bimetal catalyst and integral catalyzer thereof still appear in the newspapers at the end on titanium dioxide nano-belts.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of preparation method of titanium dioxide nano-belts load bimetallic integral catalyzer has been proposed, catalyst with the present invention's preparation, even particle distribution, the particle diameter on surface be less, become to be grouped into and quantize controlled and have high catalytic activity, high selectivity and high stability, be easy to reclaim and recycling, and the method is applicable to large-scale commercial application.
Main technical schemes of the present invention is passed through first the light deposition method at a large amount of silver nano-grains of titanium dioxide nano-belts surface deposition, then pass through the original position displacement reaction in chlorauric acid solution, obtain the catalyst of bimetallic support type, with catalyst suction filtration compacting film forming, realize the preparation of integer catalyzer at last.
A kind of preparation method of titanium dioxide nano-belts load bimetallic integral catalyzer comprises the steps:
(1) titanium dioxide is dispersed in the sodium hydroxide solution of molar concentration 8～12M, the mass volume ratio of titanium dioxide and sodium hydroxide solution is (1～10): 400, the g/ml of unit, 180～220 ℃ of alkali thermal responses are 24～72 hours in thermostatic drying chamber, obtain the sodium titanate nanobelt; Then in the hydrochloric acid solution of molar concentration 0.05～0.2M, carry out ion-exchange, obtain the metatitanic acid nanobelt, again with the metatitanic acid nanobelt in Muffle furnace 500～700 ℃ the calcining 1～3 hour, obtain titanium dioxide nano-belts;
(2) get titanium dioxide nano-belts that step (1) makes according to mass volume ratio 1:(100～400) ultrasonic being dispersed in the absolute ethyl alcohol of ratio, the g/ml of unit makes the titanium dioxide alcohol suspending liquid;
With silver nitrate according to mass volume ratio (1～10): the ratio of (0.5～2) is dissolved in the absolute ethyl alcohol, the g/L of unit; Make the ethanolic solution of silver nitrate;
With the ethanolic solution of titanium dioxide ethanolic solution and silver nitrate according to volume ratio 1:(1～2) mix, 20～1000W xenon lamp irradiation deposit, 1～10min, washing makes titanium dioxide nano-belts load silver sample;
(3) the titanium dioxide nano-belts load silver sample that step (2) is made is by mass volume ratio 1:(0.2～15) be scattered in the deionized water, the mg/ml of unit, under 120～160 ℃ of oil bath conditions, stir 2～30min, the mass volume ratio 1:(1 of the titanium dioxide nano-belts load silver sample that then makes by step (2)～10) adding mass concentration is in 0.1～10g/L chlorauric acid solution, the g/ml of unit, continue to stir 1～30min, through centrifugal, washing, make the titanium dioxide nano-belts supported bimetal catalyst;
(4) with the titanium dioxide nano-belts supported bimetal catalyst process suction filtration press mold that obtains in the step (3), making diameter is the titanium dioxide nano-belts load bimetallic integral catalyzer of 5～10mm.
Preferred according to the present invention, the mass volume ratio of titanium dioxide and NaOH suspension is 1:200 in the described step (1).
Preferred according to the present invention, the alkali thermal response time is 48～72 hours in the described step (1).
Preferred according to the present invention, xenon lamp shines for to shine 1～5min under 20～500W xenon lamp in the described step (2).
Preferred according to the present invention, washing is for to wash 1～3 time with absolute ethyl alcohol, then with anaerobic deionization washing 1～5 time in the described step (2).
Preferred according to the present invention, the mass volume ratio of silver nitrate and absolute ethyl alcohol is (1～5) in the described step (2): (0.5～2).
Preferred according to the present invention, centrifugal condition is in the described step (3): 10000～15000 rev/mins, and centrifugal 2～5 minutes.
Preferred according to the present invention, washing and then is washed 1～3 time with deionized water for being that 1～10% weak aqua ammonia is washed 1～3 time with mass concentration in the described step (3); Or wash 1～3 time with saturated nacl aqueous solution, wash 1～3 time with deionized water again; Or soak 10～30min with the iron nitrate solution of 0.05～0.5M, wash 1～3 time with deionized water again.
Preferred according to the present invention, oil bath temperature is 120～140 ℃ in the described step (3), and mixing time is 10～20min.
Preferred according to the present invention, the concentration of chlorauric acid solution is 5～10g/L in the described step (3), and the continuation mixing time is 20～30min.
The present invention has the following advantages:
1, the present invention by light deposition-original position displacement legal system get that surperficial noble metal granule is evenly distributed, the titanium dioxide nano-belts load bimetallic integral catalyzer of high catalytic activity, high selectivity, high stability;
2, the titanium dioxide nano-belts load bimetallic integral catalyzer that makes of the present invention, its surperficial noble metal granule size, that load capacity is adjustable is controlled, can improve by changing bimetallic proportion of composing the catalytic activity of catalyst;
3, preparation method of the present invention is by first light deposition, and the method for rear original position displacement can make the load of titanium dioxide nano-belts monometallic become the bimetallic load, the bimetallic heterojunction structure of simple realization titanium dioxide nano-belts, and metal group is proportional regulates and control;
4, the catalyst that makes of the present invention is titanium dioxide nano-belts supported bimetal catalyst and integral catalyzer thereof, and technique is simple, and is easy to operate, good reproducibility, and have high catalytic activity, high selectivity and high stability;
5, the titanium dioxide nano-belts supported bimetal catalyst of preparation of the present invention can pass through the suction filtration press mold, makes integral catalyzer, can macroscopic view independently exist, and is easy to recycle and reuse.
Description of drawings
Fig. 1, titanium dioxide nano-belts supported bimetal catalyst that embodiment 2 makes and high resolution transmission electron microscopy (HRTEM) photo of integral catalyzer thereof.
SEM (SEM) photo of the titanium dioxide nano-belts load bimetallic integral catalyzer that Fig. 2, embodiment 2 make.
X-ray photoelectron power spectrum (XPS) analysis result of the titanium dioxide nano-belts load bimetallic integral catalyzer that Fig. 3, embodiment 1 make.
The optical photograph of the titanium dioxide nano-belts load bimetallic integral catalyzer that Fig. 4, embodiment 1 make.
The optical photograph of titanium dioxide nano-belts load bimetallic integral catalyzer in the vertical quartz tube reactor that Fig. 5, embodiment 1 make.
The different catalysts catalytic performance contrast block diagram that Fig. 6, distinct methods make.
Fig. 7, the catalytic performance curve map of titanium dioxide nano-belts load bimetallic integral catalyzer in the phenmethylol gas phase catalytic oxidation reaction.
The specific embodiment
Below in conjunction with embodiment and Figure of description technical scheme of the present invention is described further, but institute of the present invention protection domain is not limited to this.
Titanium dioxide described in the embodiment is available from German Degussa company;
A kind of preparation method of titanium dioxide nano-belts load bimetallic integral catalyzer comprises the steps:
(1) 0.1g titanium dioxide being dispersed in 20ml concentration is in the 10M sodium hydroxide solution, and 200 ℃ of alkali thermal responses are 48 hours in thermostatic drying chamber, obtain the sodium titanate nanobelt; Then be to carry out ion-exchange in the 0.1M hydrochloric acid with the 1000ml molar concentration, obtain the metatitanic acid nanobelt, again with the metatitanic acid nanobelt in Muffle furnace 600 ℃ the calcining 2 hours, obtain titanium dioxide nano-belts;
(2) get the 0.1g titanium dioxide nano-belts that step (1) makes, evenly spread in the 10mL absolute ethyl alcohol, ultrasonic being uniformly dispersed makes the titanium dioxide alcohol suspending liquid; Get the 0.05g silver nitrate and be dissolved in the 10mL absolute ethyl alcohol, make the ethanolic solution of silver nitrate; After the ethanolic solution of titanium dioxide alcohol suspending liquid and silver nitrate mixed, under the 500W xenon lamp, shine 2min, obtain the bottle green suspension; With the centrifugal 3min of suspension 1000r/min that obtains, absolute ethyl alcohol is washed 2 times, and deionization washing 3 times obtains titanium dioxide nano-belts depositing silver sample;
(3) sample with the titanium dioxide nano-belts depositing silver sample that makes in the step (2) places the 100mL there-necked flask, adds the 50mL deionized water and is uniformly dispersed, and there-necked flask is placed 140 ℃ of oil bath pans, magnetic agitation 10min; Get the chlorauric acid solution of 1mL 10g/L, be diluted to 5mL with deionized water, slowly dropwise be added drop-wise in the there-necked flask under the magnetic agitation, continue to boil 20min, with gained sample centrifuge washing, be that 1% weak aqua ammonia is washed 2 times with mass concentration first, wash 3 times with deionized water again, make the titanium dioxide nano-belts supported bimetal catalyst.
(4) with the titanium dioxide nano-belts supported bimetal catalyst process suction filtration press mold that makes in (3), making diameter is the titanium dioxide nano-belts load bimetallic integral catalyzer of 5～10mm.
The titanium dioxide nano-belts load bimetallic integral catalyzer of said method system, it is take titanium dioxide nano-belts as carrier, and gold and silver alloy particles uniform load form at titanium dioxide nano-belts; Wherein, nanobelt is of a size of long 5～10 μ m, wide 50～200nm, thick 10～50nm, gold loading are 20～30at.%(atomic percent), silver-colored load capacity is 10～20at.%; The bimetallic particle diameter is 1～2nm, and grain spacing is 5～10nm, and described uniform particles is distributed on each face and each rib of titanium dioxide nano-belts, and it is evenly distributed, blank and a large amount of agglomerations without large tracts of land.Titanium dioxide nano-belts load bimetallic integral catalyzer is diameter 5～10mm, and thick is the membranaceous of 0.5～2mm.
The TEM figure of above-mentioned titanium dioxide nano-belts load bimetallic integral catalyzer sees accompanying drawing 1, and x-ray photoelectron power spectrum (XPS) analysis result is seen Fig. 3, and the result shows, contains gold and silver element in this titanium dioxide nano-belts bimetallic catalyst.The optical photograph of this catalyst is seen Fig. 4.
A kind of preparation method of titanium dioxide nano-belts load bimetallic integral catalyzer comprises the steps:
(1) 0.1g titanium dioxide being dispersed in 40ml concentration is in the 12M sodium hydroxide solution, 220 ℃ of alkali thermal responses are 72 hours in thermostatic drying chamber, obtain the sodium titanate nanobelt, then be to carry out ion-exchange in the 0.2M hydrochloric acid with 1000ml concentration, obtain the metatitanic acid nanobelt, again with the metatitanic acid nanobelt in Muffle furnace 700 ℃ the calcining 3 hours, obtain titanium dioxide nano-belts;
(2) get the 0.1g titanium dioxide nano-belts that step (1) makes, evenly spread in the 20mL absolute ethyl alcohol, ultrasonic being uniformly dispersed makes the titanium dioxide ethanolic solution; Get the 0.05g silver nitrate and be dissolved in the 20mL absolute ethyl alcohol, make the ethanolic solution of silver nitrate; After the ethanolic solution of titanium dioxide ethanolic solution and silver nitrate mixed, under the 1000W xenon lamp, shine 10min, obtain the bottle green suspension, with the centrifugal 3min of suspension 1000r/min that obtains, absolute ethyl alcohol is washed 2 times, and deionization washing 3 times obtains titanium dioxide nano-belts depositing silver sample.
(3) sample with the titanium dioxide deposition silver that makes in the step (2) places the 150mL there-necked flask, adds the 100mL deionized water and is uniformly dispersed, and there-necked flask is placed 160 ℃ of oil bath pans, boils 10min under the magnetic agitation.Get the chlorauric acid solution of 1mL 10g/L, be diluted to 5mL, slowly dropwise be added drop-wise in the there-necked flask under the magnetic agitation.Continue to boil 20min.With gained sample centrifuge washing, wash 2 times with saturated nacl aqueous solution first, wash 3 times with deionized water again.Get final product to get the titanium dioxide nano-belts supported bimetal catalyst.
(4) with the titanium dioxide nano-belts supported bimetal catalyst process suction filtration press mold that obtains in (3), making diameter is the titanium dioxide nano-belts load bimetallic integral catalyzer of 5～10mm.
The titanium dioxide nano-belts load bimetallic integral catalyzer of said method system, it is take titanium dioxide nano-belts as carrier, and gold and silver bimetal granule load on the titanium dioxide nano-belts and form; Wherein, nanobelt is of a size of long 5～10 μ m, wide 50～200nm, thick 10～50nm, gold loading are 20～30at.%(atomic percent), silver-colored load capacity is 10～20at.%; The bimetallic particle diameter is 1～3nm, and grain spacing is 5～10nm, and described uniform particles is distributed on each face and each rib of titanium dioxide nano-belts, and it is evenly distributed, blank and a large amount of agglomerations without large tracts of land.
A kind of preparation method of titanium dioxide nano-belts load bimetallic integral catalyzer, step is as follows:
(1) 0.1g titanium dioxide being dispersed in 10ml concentration is in the 8M sodium hydroxide solution, and 180 ℃ of alkali thermal responses are 24 hours in thermostatic drying chamber.Obtain the sodium titanate nanobelt, then in 1000mL 0.05M hydrochloric acid, carry out ion-exchange, obtain the metatitanic acid nanobelt, again with the metatitanic acid nanobelt in Muffle furnace 500 ℃ the calcining 1 hour, obtain titanium dioxide nano-belts.
(2) get the 0.1g titanium dioxide nano-belts, evenly spread in the 5mL absolute ethyl alcohol ultrasonic being uniformly dispersed.Get the 0.05g silver nitrate, in the 5mL absolute ethyl alcohol, dissolve.After above-mentioned two liquid are mixed, under the 200W xenon lamp, shine 1min, obtain the bottle green suspension.With the centrifugal 3min of suspension 1000r/min that obtains, absolute ethyl alcohol is washed 2 times, and deionization washing 3 times obtains titanium dioxide nano-belts depositing silver sample.
(3) sample with the titanium dioxide deposition silver that makes in the step (2) places the 50mL there-necked flask, adds the 20mL deionized water and is uniformly dispersed.There-necked flask is placed 120 ℃ of oil bath pans, boil 10min under the magnetic agitation.Get the chlorauric acid solution of 1mL 10g/L, be diluted to 5mL, slowly dropwise be added drop-wise in the there-necked flask under the magnetic agitation.Continue to boil 20min.With gained sample centrifuge washing, be the iron nitrate solution immersion 20min of 0.2M with molar concentration then, wash 3 times with deionized water again, get final product to get the titanium dichloride load bimetallic catalyst.
(4) with the titanium dioxide nano-belts bimetallic supported catalyst process suction filtration press mold that obtains in (3), making diameter is the titanium dioxide nano-belts load bimetallic integral catalyzer of 5～10mm.
Said method has made a kind of, and it is take titanium dioxide nano-belts as carrier, and gold and silver alloy particles load on the titanium dioxide nano-belts and form; Wherein, nanobelt is of a size of long 5～10 μ m, wide 50～200nm, thick 10～50nm, gold loading are 20～30at.%(atomic percent), silver-colored load capacity is 1～10at.%; The metal particle diameter is 1～2nm, and grain spacing is 5～10nm, and described uniform particles is distributed on each face and each rib of titanium dioxide nano-belts, and it is evenly distributed, blank and a large amount of agglomerations without large tracts of land.
The catalytic performance test
The experiment test method:
Gas phase catalytic reaction carries out in fixed reactor (small-sized catalytic reaction evaluating apparatus).Under normal pressure, 240 ℃ of reaction conditions, liquid phenenyl methyl alcohol is with 0.36mmol min
-1Speed enter preheating furnace by the syringe pump supply, O
2With 9.2cm
3Min
-1, N
2With 34.8cm
3Min
-1(AIR Proportional) enters preheating furnace.After fully vaporization, mixing, three kinds of gas enters the fixed reactor that 20mg catalyst powder and quartz sand mixture or prepared integer catalyzer are housed.Product and unreacted phenmethylol are used gas chromatographic detection after reclaiming by the cold-trap condensation.
Titanium dioxide nano-belts supported bimetal catalyst and quartz sand mixture, the titanium dioxide nano-belts load bimetallic integral catalyzer of embodiment 1 preparation are placed fixed bed reactors, be used for testing the catalytic performance of prepared catalyst.
Catalytic result as shown in Figure 6.Accompanying drawing 6 compares for the catalytic performance of the different catalysts of distinct methods preparation, be respectively titanium dioxide nano-belts blank, titanium dioxide nano-belts carried silver catalyst, titanium dioxide nano-belts load gold catalyst and nanobelt supported bimetal catalyst at 240 ℃, under the normal pressure, react the selective and benzaldehyde productive rate of the phenmethylol conversion ratio, benzaldehyde of 5 hours gained.
Can be found out by data among Fig. 6: compare with other catalyst, the conversion ratio of titanium dioxide nano-belts supported bimetal catalyst and selectively all higher all reaches more than 90%.Having shown good catalytic performance, is a kind of new catalyst that has application prospect.
The conversion ratio that the result shows phenmethylol among Fig. 7 is more than 75%, benzaldehyde selectively more than 90%, through 6 hours reaction kept stable.Titanium dioxide nano-belts load bimetallic integral catalyzer has the more superior gas phase catalysis characteristics such as high conversion, high selectivity and high stability as can be known, is a kind of new catalyst that has application prospect.
Claims (10)
1. the preparation method of a titanium dioxide nano-belts load bimetallic integral catalyzer is characterized in that, comprises the steps:
(1) titanium dioxide is dispersed in the sodium hydroxide solution of molar concentration 8～12M, the mass volume ratio of titanium dioxide and sodium hydroxide solution is (1～10): 400, the g/ml of unit, 180～220 ℃ of alkali thermal responses are 24～72 hours in thermostatic drying chamber, obtain the sodium titanate nanobelt; Then in the hydrochloric acid solution of molar concentration 0.05～0.2M, carry out ion-exchange, obtain the metatitanic acid nanobelt, again with the metatitanic acid nanobelt in Muffle furnace 500～700 ℃ the calcining 1～3 hour, obtain titanium dioxide nano-belts;
(2) get titanium dioxide nano-belts that step (1) makes according to mass volume ratio 1:(100～400) ultrasonic being dispersed in the absolute ethyl alcohol of ratio, the g/ml of unit makes the titanium dioxide alcohol suspending liquid;
With silver nitrate according to mass volume ratio (1～10): the ratio of (0.5～2) is dissolved in the absolute ethyl alcohol, the g/L of unit; Make the ethanolic solution of silver nitrate;
With the ethanolic solution of titanium dioxide ethanolic solution and silver nitrate according to volume ratio 1:(1～2) mix, 20～1000W xenon lamp irradiation deposit, 1～10min, washing makes titanium dioxide nano-belts load silver sample;
(3) the titanium dioxide nano-belts load silver sample that step (2) is made is by mass volume ratio 1:(0.2～15) be scattered in the deionized water, the mg/ml of unit, under 120～160 ℃ of oil bath conditions, stir 2～30min, the mass volume ratio 1:(1 of the titanium dioxide nano-belts load silver sample that then makes by step (2)～10) adding mass concentration is in 0.1～10g/L chlorauric acid solution, the g/ml of unit, continue to stir 1～30min, through centrifugal, washing, make the titanium dioxide nano-belts supported bimetal catalyst;
(4) with the titanium dioxide nano-belts supported bimetal catalyst process suction filtration press mold that obtains in the step (3), making diameter is the titanium dioxide nano-belts load bimetallic integral catalyzer of 5～10mm.
2. preparation method as claimed in claim 1 is characterized in that, the mass volume ratio of titanium dioxide and NaOH suspension is 1:200 in the described step (1).
3. preparation method as claimed in claim 1 is characterized in that, the alkali thermal response time is 48～72 hours in the described step (1).
4. preparation method as claimed in claim 1 is characterized in that, xenon lamp shines for to shine 1～5min under 20～500W xenon lamp in the described step (2).
5. preparation method as claimed in claim 1 is characterized in that, washing is for to wash 1～3 time with absolute ethyl alcohol, then with anaerobic deionization washing 1～5 time in the described step (2).
6. preparation method as claimed in claim 1 is characterized in that, the mass volume ratio of silver nitrate and absolute ethyl alcohol is (1～5) in the described step (2): (0.5～2).
7. preparation method as claimed in claim 1 is characterized in that, centrifugal condition is in the described step (3): 10000～15000 rev/mins, and centrifugal 2～5 minutes.
8. preparation method as claimed in claim 1 is characterized in that, washing and then is washed 1～3 time with deionized water for being that 1～10% weak aqua ammonia is washed 1～3 time with mass concentration in the described step (3); Or wash 1～3 time with saturated nacl aqueous solution, wash 1～3 time with deionized water again; Or soak 10～30min with the iron nitrate solution of 0.05～0.5M, wash 1～3 time with deionized water again.
9. preparation method as claimed in claim 1 is characterized in that, oil bath temperature is 120～140 ℃ in the described step (3), and mixing time is 10～20min.
10. preparation method as claimed in claim 1 is characterized in that, the concentration of chlorauric acid solution is 5～10g/L in the described step (3), and the continuation mixing time is 20～30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210532973.0A CN103007932B (en) | 2012-12-11 | 2012-12-11 | Method for preparing titanium dioxide nanobelt load thermometal integral catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210532973.0A CN103007932B (en) | 2012-12-11 | 2012-12-11 | Method for preparing titanium dioxide nanobelt load thermometal integral catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103007932A true CN103007932A (en) | 2013-04-03 |
| CN103007932B CN103007932B (en) | 2014-09-03 |
Family
ID=47957364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210532973.0A Expired - Fee Related CN103007932B (en) | 2012-12-11 | 2012-12-11 | Method for preparing titanium dioxide nanobelt load thermometal integral catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103007932B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103433058A (en) * | 2013-09-02 | 2013-12-11 | 山东大学 | Au-Cu/TiO2-NBs bimetal nanometer structure integral type catalyst as well as preparation method and application thereof |
| CN104549368A (en) * | 2015-01-28 | 2015-04-29 | 山东大学 | Preparation method of load bimetal type Cu-Pt/TiO2-NBs catalyst and application |
| CN104805503A (en) * | 2015-03-20 | 2015-07-29 | 浙江大学 | Perovskite type lead titanate/silver nanocomposite and preparation method thereof |
| CN105347387A (en) * | 2015-12-01 | 2016-02-24 | 安徽大学 | Preparation method for Au-Ag co-modified N-doped ZnO nanorods and application of ZnO nanorods to hydrogen production through photo-electrochemical hydrolysis |
| CN106824180A (en) * | 2017-01-23 | 2017-06-13 | 安徽大学 | Sodium titanate supported palladium catalyst and preparation method thereof |
| CN108187692A (en) * | 2018-01-08 | 2018-06-22 | 山东大学 | A kind of nano titania porous ceramic catalyst of supported bi-metallic and its preparation method and application |
| CN108714422A (en) * | 2018-04-18 | 2018-10-30 | 山东大学 | A kind of mixed with titanium silicate nanometer bringing onto load metal palladium nano-particles integral catalyzer and the preparation method and application thereof |
| CN109052378A (en) * | 2018-10-30 | 2018-12-21 | 济南大学 | A kind of preparation method of cobalt modification nitrogen-doped graphene nanobelt |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157043A (en) * | 2007-09-26 | 2008-04-09 | 山东大学 | A nucleocapsid type nanometer stephanoporate metal catalyst as well as its preparing method |
| CN101219377A (en) * | 2008-01-11 | 2008-07-16 | 山东大学 | Precious metal/one-dimensional titanium dioxide nanostructure composite material and method for producing the same |
| CN101961651A (en) * | 2010-11-01 | 2011-02-02 | 浙江大学 | Method for preparing noble metal modified one-dimensional titanium dioxide Hg-removing catalyst |
| CN102240546A (en) * | 2011-04-22 | 2011-11-16 | 山东大学 | Method for preparing titanium dioxide-supported noble metal visible light material |
| CN102430405A (en) * | 2011-09-15 | 2012-05-02 | 复旦大学 | Loaded bimetallic nano-catalyst used for benzoic acid and sodium salt preparation as well as its preparation method |
| CN102489295A (en) * | 2011-12-07 | 2012-06-13 | 中国科学院福建物质结构研究所 | Metal-loaded titanium-based catalyst and preparation method thereof |
-
2012
- 2012-12-11 CN CN201210532973.0A patent/CN103007932B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157043A (en) * | 2007-09-26 | 2008-04-09 | 山东大学 | A nucleocapsid type nanometer stephanoporate metal catalyst as well as its preparing method |
| CN101219377A (en) * | 2008-01-11 | 2008-07-16 | 山东大学 | Precious metal/one-dimensional titanium dioxide nanostructure composite material and method for producing the same |
| CN101961651A (en) * | 2010-11-01 | 2011-02-02 | 浙江大学 | Method for preparing noble metal modified one-dimensional titanium dioxide Hg-removing catalyst |
| CN102240546A (en) * | 2011-04-22 | 2011-11-16 | 山东大学 | Method for preparing titanium dioxide-supported noble metal visible light material |
| CN102430405A (en) * | 2011-09-15 | 2012-05-02 | 复旦大学 | Loaded bimetallic nano-catalyst used for benzoic acid and sodium salt preparation as well as its preparation method |
| CN102489295A (en) * | 2011-12-07 | 2012-06-13 | 中国科学院福建物质结构研究所 | Metal-loaded titanium-based catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| QIAO AN ET AL: "Fe3O4@Carbon Microsphere Supported Ag−Au Bimetallic Nanocrystals with the Enhanced Catalytic Activity and Selectivity for the Reduction of Nitroaromatic Compounds", 《THE JOURNAL OF PHYSICAL CHEMISTRY》 * |
| QIAO AN ET AL: "Fe3O4@Carbon Microsphere Supported Ag−Au Bimetallic Nanocrystals with the Enhanced Catalytic Activity and Selectivity for the Reduction of Nitroaromatic Compounds", 《THE JOURNAL OF PHYSICAL CHEMISTRY》, vol. 116, 1 October 2012 (2012-10-01), pages 22432 - 22440 * |
| YUGANG SUN ET AL: "Mechanistic Study on the Replacement Reaction between Silver Nanostructures and Chloroauric Acid in Aqueous Medium", 《JOURNAL OF AMERICAN CHEMICAL SOCIETY》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103433058A (en) * | 2013-09-02 | 2013-12-11 | 山东大学 | Au-Cu/TiO2-NBs bimetal nanometer structure integral type catalyst as well as preparation method and application thereof |
| CN103433058B (en) * | 2013-09-02 | 2015-08-26 | 山东大学 | Au-Cu/TiO 2-NBs bimetal nanostructure integral catalyzer, preparation method and application thereof |
| CN104549368A (en) * | 2015-01-28 | 2015-04-29 | 山东大学 | Preparation method of load bimetal type Cu-Pt/TiO2-NBs catalyst and application |
| CN104805503A (en) * | 2015-03-20 | 2015-07-29 | 浙江大学 | Perovskite type lead titanate/silver nanocomposite and preparation method thereof |
| CN104805503B (en) * | 2015-03-20 | 2017-05-31 | 浙江大学 | Ca-Ti ore type lead titanates/argentum nano composite material and preparation method thereof |
| CN105347387A (en) * | 2015-12-01 | 2016-02-24 | 安徽大学 | Preparation method for Au-Ag co-modified N-doped ZnO nanorods and application of ZnO nanorods to hydrogen production through photo-electrochemical hydrolysis |
| CN106824180A (en) * | 2017-01-23 | 2017-06-13 | 安徽大学 | Sodium titanate supported palladium catalyst and preparation method thereof |
| CN108187692A (en) * | 2018-01-08 | 2018-06-22 | 山东大学 | A kind of nano titania porous ceramic catalyst of supported bi-metallic and its preparation method and application |
| CN108714422A (en) * | 2018-04-18 | 2018-10-30 | 山东大学 | A kind of mixed with titanium silicate nanometer bringing onto load metal palladium nano-particles integral catalyzer and the preparation method and application thereof |
| CN108714422B (en) * | 2018-04-18 | 2021-04-13 | 山东大学 | Mixed titanate nanoribbon supported metal palladium nanoparticle monolithic catalyst and preparation method and application thereof |
| CN109052378A (en) * | 2018-10-30 | 2018-12-21 | 济南大学 | A kind of preparation method of cobalt modification nitrogen-doped graphene nanobelt |
| CN109052378B (en) * | 2018-10-30 | 2021-11-23 | 济南大学 | Preparation method of cobalt-modified nitrogen-doped graphene nanoribbon |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103007932B (en) | 2014-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103007932B (en) | Method for preparing titanium dioxide nanobelt load thermometal integral catalyst | |
| Duan et al. | Bimetallic nanoparticles/metal-organic frameworks: Synthesis, applications and challenges | |
| Wen et al. | Plasmonic Au@ Pd nanoparticles supported on a basic metal–organic framework: Synergic boosting of H2 production from formic acid | |
| Wang et al. | Modulating catalytic performance of metal–organic framework composites by localized surface plasmon resonance | |
| Bönnemann et al. | Nanoscopic metal particles− synthetic methods and potential applications | |
| Ge et al. | Highly efficient Pt decorated CoCu bimetallic nanoparticles protected in silica for hydrogen production from ammonia–borane | |
| Wei et al. | Bimetallic nanoparticles meet polymeric carbon nitride: Fabrications, catalytic applications and perspectives | |
| Pan et al. | Defect-mediated growth of noble-metal (Ag, Pt, and Pd) nanoparticles on TiO2 with oxygen vacancies for photocatalytic redox reactions under visible light | |
| Jin et al. | Synthesis of Pd nanocrystals enclosed by {100} facets and with sizes< 10 nm for application in CO oxidation | |
| Cheng et al. | Green synthesis of plasmonic Ag nanoparticles anchored TiO2 nanorod arrays using cold plasma for visible-light-driven photocatalytic reduction of CO2 | |
| Su et al. | Fabrication of high-activity hybrid Pt@ ZnO catalyst on carbon cloth by atomic layer deposition for photoassisted electro-oxidation of methanol | |
| Verma et al. | Enhancement of Ag‐based plasmonic photocatalysis in hydrogen production from ammonia borane by the assistance of single‐site Ti‐oxide moieties within a silica framework | |
| CN103721708B (en) | A kind of Silver/titanium dioxide composite heterostructure and preparation method thereof | |
| Feng et al. | Sea-urchin-like hollow CuMoO4–CoMoO4 hybrid microspheres, a noble-metal-like robust catalyst for the fast hydrogen production from ammonia borane | |
| Wang et al. | Zero-dimensional/two-dimensional Au25 (Cys) 18 nanoclusters/g-C3N4 nanosheets composites for enhanced photocatalytic hydrogen production under visible light | |
| Fang et al. | Synthesis of novel ultrasmall Au-loaded magnetic SiO2/carbon yolk-shell ellipsoids as highly reactive and recoverable nanocatalysts | |
| Xiao et al. | MOF-5 derived C-doped ZnO decorated with Cu cocatalyst for enhancing visible-light driven photocatalytic hydrogen evolution | |
| CN103433058A (en) | Au-Cu/TiO2-NBs bimetal nanometer structure integral type catalyst as well as preparation method and application thereof | |
| Chen et al. | Shape-controlled synthesis of ruthenium nanocrystals and their catalytic applications | |
| Xiao et al. | The new identity of cellulose pulp: a green silver nanoparticles support for highly efficient catalytic hydrogenation of 4-nitrophenol | |
| CN104549263B (en) | A kind of Pd/ niobic acid nanometer sheet catalyst and its preparation method and application | |
| Tai et al. | Fabrication of CdS/Pt/MIL-125 with effective spatial separation for improved visible-light catalytic H2 evolution using γ-ray irradiation | |
| CN104815651A (en) | Preparation method of precious metal/titanium dioxide nano composite | |
| CN110694690A (en) | Method for preparing metal monatomic catalyst | |
| Tan et al. | Amorphous nickel coating on carbon nanotubes supported Pt nanoparticles as a highly durable and active electrocatalyst for methanol oxidation reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140903 Termination date: 20161211 |