CN102784654A - Supported hollow nanometer alloy ball catalyst, its preparation method and its use - Google Patents
Supported hollow nanometer alloy ball catalyst, its preparation method and its use Download PDFInfo
- Publication number
- CN102784654A CN102784654A CN2012102519080A CN201210251908A CN102784654A CN 102784654 A CN102784654 A CN 102784654A CN 2012102519080 A CN2012102519080 A CN 2012102519080A CN 201210251908 A CN201210251908 A CN 201210251908A CN 102784654 A CN102784654 A CN 102784654A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nanoalloy
- preparation
- washing
- support type
- 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.)
- Pending
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a supported hollow nanometer alloy ball catalyst, its preparation method and its use. The hollow nanometer alloy ball diameter of the catalyst is 3.0-10.0nm, the wall thickness of the catalyst is 1.0-4.0nm, the load capacity of the catalyst is 0.1-5.0wt%, the specific surface area of the catalyst is 100-900m<2>/g, the pore volume of the catalyst is 0.3-1.5cm<3>/g, and the pore diameter of the catalyst is 3.0-20.0nm. In the invention, the preparation of "ship-in-bottle" structure hollow nanometer alloy balls is realized through a three-step method. The supported hollow nanometer alloy balls can be used for the preparation of a halogenated aniline through the hydrogenation of liquid halogenated nitrobenzene as a catalyst, the catalytic performance of the supported hollow nanometer alloy ball catalyst is better than that of corresponding supported nanometer particle single metals and alloy catalysts, the supported hollow nanometer alloy ball catalyst can be repeatedly used, and has a further longer life than hollow nanometer alloy ball catalysts loaded on the outer surface of silica.
Description
Technical field
The present invention relates to catalyst field, specifically, relate to the purposes of a kind of support type hollow Nanoalloy sphere catalyst and preparation method thereof and catalysis liquid phase halogenated nitrobenzene hydrogenation system halo aniline.
Background technology
In recent years, hollow material is owing to its multiple different applicability, and for example light crystallization, medicine transmission, filling and catalysis have attracted more and more people's attention.In various hollow material, the hollow metal ball becomes a kind of novel effective catalyst just gradually owing to have high surface, low-density, easy recovery, self-supporting, low cost and good advantages such as Surface Permeability.Discover that the metal surface with negative cruvature can change the absorption mode of multiple reaction substrate, thereby change the selectivity of catalytic reaction.But when the size of hollow Metal Ball was big, its surface is tending towards smooth, and was just less to the impact effect of distribution of reaction products.Therefore, in order to obtain significant skin effect, need the synthetic undersized hollow metal material of design.On the other hand, the modulation metal is formed, and especially forms alloy material and can improve catalytic activity and selectivity greatly.So hollow Nanoalloy ball is expected to become one type of high activity, high selectivity metallic catalyst.
Diameter is that nano level hollow metal material has colloidal nature because density is hanged down very much, and this causes it to separate very difficulty, is difficult to practical application.In addition, metallic catalyst is used for hydrogenation and oxidation reaction more, and the reaction of these types is generally exothermic reaction, or under hot conditions, carries out.The structural stability that how to keep the hollow nano metal material is to realize the key point of its commercial Application.Hollow Nanoalloy ball is introduced in the duct of porous oxide carrier, removed stabilizing agent after dwindling the duct window, can make the hollow Nanoalloy sphere catalyst of " ship in the bottle " structure.This catalyst not only is easy to reclaim, and has high thermal stability, can solve the problem that exists in the above-mentioned hollow Nanoalloy ball catalytic applications.
Summary of the invention
The object of the present invention is to provide a kind of support type hollow Nanoalloy sphere catalyst and preparation method thereof, for existing metallic catalyst field increases one type of new varieties.
Another object of the present invention is in order the purposes of above-mentioned this catalyst to be provided, to use it for liquid phase halogenated nitrobenzene hydrogenation system halo aniline.
The object of the invention can be realized through following technical scheme.
A kind of support type hollow Nanoalloy sphere catalyst, it is characterized in that: hollow Nanoalloy bulb diameter is 3.0-10.0nm, and wall thickness is 1.0-4.0nm, and load capacity is 0.1-5.0wt%, and specific surface area of catalyst is 100-900m
2/ g, pore volume are 0.3-1.5cm
3/ g, the aperture is 3.0-20.0nm.
The preparation method of above-mentioned this support type hollow Nanoalloy sphere catalyst comprises the steps:
(1) under the protection of inert gas atmosphere, in the aqueous solution of metalline A and stabilizing agent, add the reducing agent aqueous solution and the rapid aqueous solution that adds slaine B, stir 5-60min, inorganic salts or organic salt that said slaine A is nickel, cobalt or iron; Said stabilizing agent is a polyvinylpyrrolidone; Inorganic salts or organic salt that said slaine B is platinum, gold or ruthenium; Said reducing agent is KBH
4, NaBH
4Or the mixture of its any ratio; The mol ratio of slaine A and slaine B is 1:1; Reducing agent is 1:1-10:1 with the ratio of the total mole number of slaine A and B, preferred 10:3;
(2) under 10-50 ℃,, in the hydrochloric acid of 5-trimethylbenzene and KCl, add the positive tetraethyl orthosilicate of hydrochloric acid volume 2-10% to containing triblock copolymer F127,1,3; Stir 0.5-5h, add the 3-aminopropyl triethoxysilane of positive tetraethyl orthosilicate volume 10-15% then, stir 2-48h, leave standstill 2-48h, suction filtration under 50-160 ℃; Washing, drying adds products obtained therefrom in the hydrochloric acid and under 50-160 ℃, to leave standstill 12-96h, suction filtration, washing; Drying adds products obtained therefrom in the toluene, adds the trim,ethylchlorosilane of volume of toluene 4-6% again, stirs 2-48h; Suction filtration, washing, drying, products obtained therefrom adds in the ethanolic solution of HCl; 50-120 ℃ of backflow 2-48h, suction filtration, washing, drying;
(3) step (2) products obtained therefrom is added in step (1) the gained solution ultrasonic dispersion, suction filtration; 50-150 ℃ of vacuum drying 1-10h, products obtained therefrom adds in the toluene, adds the MTES of volume of toluene 5-10% then; 50-100 ℃ of backflow 2-24h; Washing, drying gets support type hollow Nanoalloy sphere catalyst.
Triblock copolymer F127,1,3 in the step (2), the mass ratio of 5-trimethylbenzene and KCl is 1:1-1.1:2-2.2, preferred 1:1:2, the mass concentration in hydrochloric acid is 3-8%.
The mass concentration of the ethanolic solution of hydrochloric acid and HCl is 2-15% in the step (2).
Product with the present invention's preparation carries out structural characterization through following means: transmission electron microscope photo obtains under 200kV at Japanese JEOL JEM2010 type high-resolution-ration transmission electric-lens.
Support type hollow Nanoalloy sphere catalyst of the present invention can be used for liquid phase halogenated nitrobenzene hydrogenation system halo aniline; Not only catalytic performance is superior to corresponding loaded nano particle monometallic and alloy catalyst; And can be repeatedly used, the life-span is far above the hollow Nanoalloy sphere catalyst that loads on the silica outer surface.
Description of drawings
Fig. 1 is the TEM photo of the sample of the embodiment of the invention 1 preparation.
Fig. 2 is the catalytic performance figure of the embodiment of the invention 1 and the sample of embodiment 3 preparations.
The specific embodiment
Is further detailed, clear, the intactly explanation of doing how to realize below in conjunction with specific embodiment to the present invention, and listed embodiment only further explains the present invention, does not therefore limit the present invention.
Agents useful for same is chemical pure in the embodiment of the invention.
Embodiment 1
(1) with 8.0mg NiCl
26H
2O and 25mg polyvinylpyrrolidone add in the 50mL water, and ultrasonic 15min feeds high-purity argon gas 15min.20 ℃ of NaBH that add 20mL 0.013mol/L down
4The aqueous solution, and add the K of 20mL 0.0017mol/L rapidly
2PtCl
6The aqueous solution stirs 30min.
Under (2) 30 ℃, with 2.0g triblock copolymer F127,2.0g1,3,5-trimethylbenzene and 5.0g KCl add in the HCl aqueous solution of 120mL 2.0mol/L, stirring and dissolving.Add the positive tetraethyl orthosilicate of 9.0mL, stir 2h.30 ℃ add the 0.4mL3-aminopropyl triethoxysilane down, stir 20h.100 ℃ leave standstill 24h, suction filtration, washing, dry products.Sample after the drying is added in the HCl aqueous solution of 150mL 2.0mol/L, 140 ℃ leave standstill 48h.Suction filtration, washing, dry products.The said goods is added in the 50mL toluene, and 70 ℃ add the 3mL trim,ethylchlorosilane down, stir 24h.Suction filtration, washing, dry products add in the HCl ethanolic solution of 500mL2.0mol/L 80 ℃ of backflow 24h.Suction filtration, washing, dry products.
(3) 0.5g step (2) product is added in step 1 solution ultrasonic 30min of 60W.Suction filtration, 90 ℃ of vacuum drying 4h.Add 30mL toluene and 0.1mL MTES, 70 ℃ of backflow 10h.The second alcohol and water respectively washs three times, promptly obtains support type hollow Nanoalloy sphere catalyst, uses Pt-Ni-H/NH
2&CH
3-mSiO
2Expression.
Fig. 1 is the TEM photo of the prepared sample of present embodiment, is 7.5nm from the visible gained hollow Nanoalloy bulb diameter of photo, and parietal layer is 2.0nm, and is dispersed in the mesopore orbit of silica.Specific surface area of catalyst is 408m
2/ g, pore volume are 0.84cm
3/ g, the aperture is 10.8nm.
Embodiment 2
(1) with 8.0mg NiCl
26H
2O and 25mg polyvinylpyrrolidone add in the 50mL water, and ultrasonic 15min feeds high-purity argon gas 15min.20 ℃ of NaBH that add 20mL 0.013mol/L down
4The aqueous solution, and add the K of 20mL 0.0017mol/L rapidly
2PtCl
6The aqueous solution stirs 30min.
Under (2) 30 ℃, with 2.0g triblock copolymer F127,2.0g1,3,5-trimethylbenzene and 5.0g KCl add in the HCl aqueous solution of 120mL 2.0mol/L, stirring and dissolving.Add the positive tetraethyl orthosilicate of 9.0mL, stir 22h.100 ℃ leave standstill 24h, suction filtration, washing, dry products.Sample after the drying is added in the HCl aqueous solution of 150mL 2.0mol/L, 140 ℃ leave standstill 48h.Suction filtration, washing, dry products.The said goods is added in the 50mL toluene, and 70 ℃ add the 3mL trim,ethylchlorosilane down, stir 24h.Suction filtration, washing, dry products add in the HCl ethanolic solution of 500mL 2.0mol/L 80 ℃ of backflow 24h.Suction filtration, washing, dry products.
(3) 0.5g step 2 product is added in step 1 solution ultrasonic 30min of 60W.Suction filtration, 90 ℃ of vacuum drying 4h.Add 30mL toluene and 0.1mL MTES, 70 ℃ of backflow 10h.The second alcohol and water respectively washs three times, promptly obtains support type hollow Nanoalloy sphere catalyst, uses Pt-Ni-H/CH
3-mSiO
2Expression.Hollow Nanoalloy bulb diameter is 7.5nm, and parietal layer is 2.0nm.Specific surface area of catalyst is 450m
2/ g, pore volume are 0.95cm
3/ g, the aperture is 13.2nm.
Embodiment 3
(1) with 8.0mg NiCl
26H
2O and 25mg polyvinylpyrrolidone add in the 50mL water, and ultrasonic 15min feeds high-purity argon gas 15min.20 ℃ of NaBH that add 20mL 0.013mol/L down
4The aqueous solution, and add the K of 20mL 0.0017mol/L rapidly
2PtCl
6The aqueous solution stirs 30min.
(2) the positive tetraethyl orthosilicate of 9.0mL is added in the HCl aqueous solution of 120mL2.0mol/L, stir 2h.30 ℃ add 0.4mL 3-aminopropyl triethoxysilane down, stir 20h.Suction filtration, washing, dry products.
(3) 0.5g step 2 product is added in step 1 solution, stir 30min.The second alcohol and water respectively washs three times, promptly obtains support type hollow Nanoalloy sphere catalyst, uses Pt-Ni-H/NH
2-SiO
2Expression.Hollow Nanoalloy bulb diameter is 7.5nm, and parietal layer is 2.0nm.Specific surface area of catalyst is 100m
2/ g, pore volume are 0.3cm
3/ g, the aperture is 3.0nm.
Embodiment 4
Under (1) 30 ℃, with 2.0g triblock copolymer F127,2.0g1,3,5-trimethylbenzene and 5.0g KCl add in the HCl aqueous solution of 120mL2.0mol/L, stirring and dissolving.Add the positive tetraethyl orthosilicate of 9.0mL, stir 22h.100 ℃ leave standstill 24h, suction filtration, washing, dry products.Sample after the drying is added in the HCl aqueous solution of 150mL 2.0mol/L, 140 ℃ leave standstill 48h.Suction filtration, washing, dry products.The said goods is added in the 50mL toluene, and 70 ℃ add the 3mL trim,ethylchlorosilane down, stir 24h.Suction filtration, washing, dry products add in the HCl ethanolic solution of 500mL 2.0mol/L 80 ℃ of backflow 24h.Suction filtration, washing, dry products.
(2) 0.5g step 1 product is added the K of 20mL 0.0017mol/L
2PtCl
6In the aqueous solution, leave standstill 12h.90 ℃ of vacuum drying 4h, 120 ℃ of roasting 2h in the air.20 ℃ of NaBH that add 10mL 0.013mol/L down
4The aqueous solution stirs 30min, and the second alcohol and water respectively washs three times, promptly obtains loaded nano particle single-metal reforming catalyst, uses Pt-NP/NH
2&CH
3-mSiO
2Expression.The metallic particles diameter is 2.0nm.Specific surface area of catalyst is 310m
2/ g, pore volume are 0.87cm
3/ g, the aperture is 11.5nm.
Embodiment 5
Under (1) 30 ℃, with 2.0g triblock copolymer F127,2.0g1,3,5-trimethylbenzene and 5.0g KCl add in the HCl aqueous solution of 120mL 2.0mol/L, stirring and dissolving.Add the positive tetraethyl orthosilicate of 9.0mL, stir 22h.100 ℃ leave standstill 24h, suction filtration, washing, dry products.Sample after the drying is added in the HCl aqueous solution of 150mL 2.0mol/L, 140 ℃ leave standstill 48h.Suction filtration, washing, dry products.The said goods is added in the 50mL toluene, and 70 ℃ add the 3mL trim,ethylchlorosilane down, stir 24h.Suction filtration, washing, dry products add in the HCl ethanolic solution of 500mL 2.0mol/L 80 ℃ of backflow 24h.Suction filtration, washing, dry products.
(2) 0.5g step 1 product is added 20mL 0.0017mol/L NiCl
26H
2O and 0.0017mol/L K
2PtCl
6Mixed aqueous solution in, leave standstill 12h.90 ℃ of vacuum drying 4h, 120 ℃ of roasting 2h in the air.20 ℃ of NaBH that add 20mL 0.013mol/L down
4The aqueous solution stirs 30min, and the second alcohol and water respectively washs three times, promptly obtains loaded nano particle alloy catalyst, uses Pt-Ni-NP/NH
2&CH
3-mSiO
2Expression.The metallic particles diameter is 2.2nm.Specific surface area of catalyst is 284m
2/ g, pore volume are 0.84cm
3/ g, the aperture is 10.6nm.
Embodiment 6
Embodiment 1-5 gained catalyst is used for the reaction of liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum; That is: in the 250mL three-necked bottle, add 0.5g catalyst, 20mmol parachloronitrobenzene and 50mL ethanol successively; Feed hydrogen, constant temperature is at 30 ℃, and the control mixing speed is 800rpm.Product is with the gas chromatographic detection of being furnished with DE-5 chromatographic column and hydrogen flame detector, and all activity datas are all through repeated experiments more than three times, and error range is in 5%, and the catalytic performance data are seen shown in the table 1.
Embodiment 7
Pt-Ni-H/NH with the reaction system that is used for liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum among the embodiment 6
2&CH
3-mSiO
2And Pt-Ni-H/NH
2-SiO
2Catalyst centrifugalizes, with being applied in the reaction of the liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum described in the embodiment 6 for the second time after the washing with alcohol.
Present embodiment has been verified Pt-Ni-H/NH
2&CH
3-mSiO
2And Pt-Ni-H/NH
2-SiO
2Catalyst carries out the catalytic performance that secondary uses, and concrete catalytic performance data are seen shown in Figure 2.
Embodiment 8
Pt-Ni-H/NH with the reaction system that is used for liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum among the embodiment 7
2&CH
3-mSiO
2And Pt-Ni-H/NH
2-SiO
2Catalyst centrifugalizes, in the reaction that is applied to the liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum described in the embodiment 6 after the washing with alcohol for the third time.
Present embodiment has been verified Pt-Ni-H/NH
2&CH
3-mSiO
2And Pt-Ni-H/NH
2-SiO
2Catalyst carries out the catalytic performance that uses three times, and concrete catalytic performance data are seen shown in Figure 2.
Embodiment 9
Pt-Ni-H/NH with the reaction system that is used for liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum among the embodiment 8
2&CH
3-mSiO
2And Pt-Ni-H/NH
2-SiO
2Catalyst centrifugalizes, in the reaction that is applied to the liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum described in the embodiment 6 after the washing with alcohol for the 4th time.
Present embodiment has been verified Pt-Ni-H/NH
2&CH
3-mSiO
2And Pt-Ni-H/NH
2-SiO
2Catalyst carries out the catalytic performance that uses four times, and concrete catalytic performance data are seen shown in Figure 2.
Embodiment 10
Pt-Ni-H/NH with the reaction system that is used for liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum among the embodiment 9
2&CH
3-mSiO
2And Pt-Ni-H/NH
2-SiO
2Catalyst centrifugalizes, in the reaction that is applied to the liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum described in the embodiment 6 after the washing with alcohol for the 5th time.
Present embodiment has been verified Pt-Ni-H/NH
2&CH
3-mSiO
2And Pt-Ni-H/NH
2-SiO
2Catalyst carries out the catalytic performance that uses five times, and concrete catalytic performance data are seen shown in Figure 2.
Embodiment 11
Pt-Ni-H/NH with the reaction system that is used for liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum among the embodiment 10
2&CH
3-mSiO
2And Pt-Ni-H/NH
2-SiO
2Catalyst centrifugalizes, in the reaction that is applied to the liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum described in the embodiment 6 after the washing with alcohol for the 6th time.
Present embodiment has been verified Pt-Ni-H/NH
2&CH
3-mSiO
2And Pt-Ni-H/NH
2-SiO
2Catalyst carries out the catalytic performance that uses six times, and concrete catalytic performance data are seen shown in Figure 2.
Embodiment 12
Pt-Ni-H/NH with the reaction system that is used for liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum among the embodiment 11
2&CH
3-mSiO
2And Pt-Ni-H/NH
2-SiO
2Catalyst centrifugalizes, in the reaction that is applied to the liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum described in the embodiment 6 after the washing with alcohol for the 7th time.
Present embodiment has been verified Pt-Ni-H/NH
2&CH
3-mSiO
2And Pt-Ni-H/NH
2-SiO
2Catalyst carries out the catalytic performance that uses seven times, and concrete catalytic performance data are seen shown in Figure 2.
Embodiment 13
Pt-Ni-H/NH with the reaction system that is used for liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum among the embodiment 12
2&CH
3-mSiO
2And Pt-Ni-H/NH
2-SiO
2Catalyst centrifugalizes, in the reaction that is applied to the liquid phase parachloronitrobenzene hydrogenation preparing parachloroanilinum described in the embodiment 6 after the washing with alcohol for the 8th time.
Present embodiment has been verified Pt-Ni-H/NH
2&CH
3-mSiO
2And Pt-Ni-H/NH
2-SiO
2Catalyst carries out the catalytic performance that uses eight times, and concrete catalytic performance data are seen shown in Figure 2.
The catalytic performance data of catalyst among table 1 embodiment
Can find out from experimental result; " ship in the bottle " structure hollow Nanoalloy sphere catalyst of the present invention's preparation can be applicable to liquid phase halogenated nitrobenzene hydrogenation system halo aniline; Not only catalytic performance is superior to corresponding solid nano particle monometallic and alloy catalyst; And can be repeatedly used, the life-span is far above the hollow Nanoalloy sphere catalyst that loads on the silica outer surface.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have change and change.All within spirit of the present invention and principle, any modification of being done, improvement etc. all should be included within protection scope of the present invention.
Claims (7)
1. support type hollow Nanoalloy sphere catalyst, it is characterized in that: hollow Nanoalloy bulb diameter is 3.0-10.0nm, and wall thickness is 1.0-4.0nm, and load capacity is 0.1-5.0wt%, and specific surface area of catalyst is 100-900m
2/ g, pore volume are 0.3-1.5cm
3/ g, the aperture is 3.0-20.0nm.
2. the preparation method of the said support type hollow of claim 1 Nanoalloy sphere catalyst is characterized in that: comprise the steps:
(1) under the protection of inert gas atmosphere, in the aqueous solution of metalline A and stabilizing agent, add the reducing agent aqueous solution and the rapid aqueous solution that adds slaine B, stir 5-60min, inorganic salts or organic salt that said slaine A is nickel, cobalt or iron; Said stabilizing agent is a polyvinylpyrrolidone; Inorganic salts or organic salt that said slaine B is platinum, gold or ruthenium; Said reducing agent is KBH
4, NaBH
4Or the mixture of its any ratio; The mol ratio of slaine A and slaine B is 1:1; Reducing agent is 1:1-10:1 with the ratio of the total mole number of slaine A and B;
(2) under 10-50 ℃,, in the hydrochloric acid of 5-trimethylbenzene and KCl, add the positive tetraethyl orthosilicate of hydrochloric acid volume 2-10% to containing triblock copolymer F127,1,3; Stir 0.5-5h, add the 3-aminopropyl triethoxysilane of positive tetraethyl orthosilicate volume 10-15% then, stir 2-48h, leave standstill 2-48h, suction filtration under 50-160 ℃; Washing, drying adds products obtained therefrom in the hydrochloric acid and under 50-160 ℃, to leave standstill 12-96h, suction filtration, washing; Drying adds products obtained therefrom in the toluene, adds the trim,ethylchlorosilane of volume of toluene 4-6% again, stirs 2-48h; Suction filtration, washing, drying, products obtained therefrom adds in the ethanolic solution of HCl; 50-120 ℃ of backflow 2-48h, suction filtration, washing, drying;
(3) step (2) products obtained therefrom is added in step (1) the gained solution ultrasonic dispersion, suction filtration; 50-150 ℃ of vacuum drying 1-10h, products obtained therefrom adds in the toluene, adds the MTES of volume of toluene 5-10% then; 50-100 ℃ of backflow 2-24h; Washing, drying gets support type hollow Nanoalloy sphere catalyst.
3. the preparation method of the said support type hollow of claim 1 Nanoalloy sphere catalyst is characterized in that: reducing agent is 10:3 with the ratio of the total mole number of slaine A and B in the step (1).
4. the preparation method of the said support type hollow of claim 1 Nanoalloy sphere catalyst; It is characterized in that: triblock copolymer F127,1,3 in the step (2), the mass ratio of 5-trimethylbenzene and KCl is 1:1-1.1:2-2.2; Preferred 1:1:2, the mass concentration in hydrochloric acid is 3-8%.
5. the preparation method of the said support type hollow of claim 4 Nanoalloy sphere catalyst is characterized in that: triblock copolymer F127,1,3 in the step (2), the mass ratio of 5-trimethylbenzene and KCl is preferred 1:1:2.
6. the preparation method of the said support type hollow of claim 1 Nanoalloy sphere catalyst is characterized in that: the mass concentration of the ethanolic solution of hydrochloric acid and HCl is 2-15% in the step (2).
7. the described support type hollow of claim 1 Nanoalloy sphere catalyst is used for liquid phase halogenated nitrobenzene hydrogenation system halo aniline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102519080A CN102784654A (en) | 2012-07-19 | 2012-07-19 | Supported hollow nanometer alloy ball catalyst, its preparation method and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102519080A CN102784654A (en) | 2012-07-19 | 2012-07-19 | Supported hollow nanometer alloy ball catalyst, its preparation method and its use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102784654A true CN102784654A (en) | 2012-11-21 |
Family
ID=47150352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102519080A Pending CN102784654A (en) | 2012-07-19 | 2012-07-19 | Supported hollow nanometer alloy ball catalyst, its preparation method and its use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102784654A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105680054A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Preparation method for supported hollow-structured alloy catalyst for low-temperature fuel cell |
| CN106457403A (en) * | 2014-06-13 | 2017-02-22 | 株式会社Lg化学 | Method for fabricating hollow metal nano particles and hollow metal nano particles fabricated by the method |
| CN106824183A (en) * | 2016-12-28 | 2017-06-13 | 苏州大学 | Hollow mesoporous Nano carbon balls composite of load gold nano particle and preparation method thereof and the application in lasting treatment CO |
| CN109174099A (en) * | 2018-08-30 | 2019-01-11 | 南京理工大学 | A kind of SiO2The preparation method of metal composite hollow ball catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157034A (en) * | 2007-11-13 | 2008-04-09 | 上海师范大学 | A non-crystal alloy catalyst as well as its preparing method and purpose |
| CN101380577A (en) * | 2008-10-17 | 2009-03-11 | 上海师范大学 | Hollow amorphous alloy nano-sphere catalyst, preparation method and use thereof |
-
2012
- 2012-07-19 CN CN2012102519080A patent/CN102784654A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157034A (en) * | 2007-11-13 | 2008-04-09 | 上海师范大学 | A non-crystal alloy catalyst as well as its preparing method and purpose |
| CN101380577A (en) * | 2008-10-17 | 2009-03-11 | 上海师范大学 | Hollow amorphous alloy nano-sphere catalyst, preparation method and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| HUI LI ET AL: "Hollow Pt-Ni alloy nanospheres with tunable chamber structure and enhanced activity", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106457403A (en) * | 2014-06-13 | 2017-02-22 | 株式会社Lg化学 | Method for fabricating hollow metal nano particles and hollow metal nano particles fabricated by the method |
| CN105680054A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Preparation method for supported hollow-structured alloy catalyst for low-temperature fuel cell |
| CN106824183A (en) * | 2016-12-28 | 2017-06-13 | 苏州大学 | Hollow mesoporous Nano carbon balls composite of load gold nano particle and preparation method thereof and the application in lasting treatment CO |
| CN106824183B (en) * | 2016-12-28 | 2019-10-25 | 苏州大学 | The hollow mesoporous Nano carbon balls composite material and preparation method of load gold nano particle and the application in lasting processing CO |
| CN110639515A (en) * | 2016-12-28 | 2020-01-03 | 苏州大学 | Hollow mesoporous carbon nanosphere composite material loaded with gold nanoparticles and application of composite material in continuous CO treatment |
| CN110639515B (en) * | 2016-12-28 | 2022-04-15 | 苏州大学 | Hollow mesoporous carbon nanosphere composite material loaded with gold nanoparticles and application of composite material in continuous CO treatment |
| CN109174099A (en) * | 2018-08-30 | 2019-01-11 | 南京理工大学 | A kind of SiO2The preparation method of metal composite hollow ball catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Architecture and preparation of hollow catalytic devices | |
| CN102642843B (en) | Method for simultaneously preparing multilevel-structure mesoporous silicon dioxide and carbon nano material | |
| JP5415425B2 (en) | Sintering resistant catalyst used in hydrogenation and dehydrogenation reactions and process for producing the same | |
| CN109305915A (en) | The synthetic method of parachloroanilinum | |
| CN106984303B (en) | A kind of foramen magnum-mesoporous γ-Al in grade hole supporting noble metal2O3Catalyst and preparation method thereof | |
| US20130164536A1 (en) | Porous Metal Oxide Particles and Their Methods of Synthesis | |
| CN102909005A (en) | Graphene-based composite material with surface coated by mesoporous silica and loaded with noble metal nanoparticles, as well as preparation method and application of graphene-based composite material | |
| CN103949254B (en) | Cu@mSiO2 core-shell nano catalyst for preparing hydrogen from ammonia borane and hydrazine borane by hydrolysis and preparation method of catalyst | |
| WO2017128946A1 (en) | Highly-dispersed particulate catalyst for use in hydrogen peroxide synthesis, preparation method therefor and application thereof | |
| CN102784654A (en) | Supported hollow nanometer alloy ball catalyst, its preparation method and its use | |
| CN105517699B (en) | Yolk-shell particles, catalyst and preparation method thereof | |
| JP2016503376A (en) | Encapsulated nanoparticles | |
| CN104998649A (en) | Preparation method for core-shell-structured nickel base methane dry reforming catalyst | |
| Geng et al. | Rational design of CuO/SiO2 nanocatalyst with anchor structure and hydrophilic surface for efficient hydrogenation of nitrophenol | |
| CN104607201B (en) | Ordered mesoporous LaCoO3 and LaMnO3 supported nano Ag catalyst and preparation and application thereof | |
| Gao et al. | Palladium-encapsulated hollow porous carbon nanospheres as nanoreactors for highly efficient and size-selective catalysis | |
| Sun et al. | Controllable integration of ultrasmall noble metal nanoparticles into mesoporous silica matrixes by a self-assembly method | |
| Sun et al. | Yolk-shell structured Pt-CeO2@ Ni-SiO2 as an efficient catalyst for enhanced hydrogen production from ethanol steam reforming | |
| CN109718787B (en) | Cerium/yttrium stabilized zirconia support and catalyst | |
| US10584030B2 (en) | Nanocrystalline composite catalyst for storing/supplying hydrogen, nanocrystalline composite catalyst mixture for storing/supplying hydrogen, and method for supplying hydrogen | |
| JP4296908B2 (en) | Catalyst body and method for producing the same | |
| Zhang et al. | Porous and hollow metal-layer@ SiO 2 nanocomposites as stable nanoreactors for hydrocarbon selective oxidation | |
| Wang et al. | Synthesis of morphology-controllable mesoporous Co3O4 and CeO2 | |
| CN106607018A (en) | Low carbon alkane dehydrogenation catalyst, and preparation method and applications thereof | |
| CN104841453A (en) | Three-dimensional ordered macroporous Au-Pd-CoO/MOx catalyst, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121121 |