CN103861592A - Method for preparing Au@ CeO2 hollow core-shell nanometer material - Google Patents
Method for preparing Au@ CeO2 hollow core-shell nanometer material Download PDFInfo
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- CN103861592A CN103861592A CN201410128914.6A CN201410128914A CN103861592A CN 103861592 A CN103861592 A CN 103861592A CN 201410128914 A CN201410128914 A CN 201410128914A CN 103861592 A CN103861592 A CN 103861592A
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Abstract
The invention provides a method for preparing a Au@ CeO2 hollow core-shell nanometer material. The method takes glucose as a carbon source, and comprises the steps of respectively covering carbon layers on the surfaces of gold nanoparticles by a hydrothermal method to form a Au@ C core-shell structure; enabling a Au@ C nanometer material to fully react with a cerous nitrate solution to enable Ce<3+> to be attached on the surfaces of carbon spheres; and enabling Ce<3+> to have reaction with oxygen under high-temperature calcination to generate CeO2, decomposing the carbon layers, and forming a cavity between Au and CeO2 to form the Au@ CeO2 hollow core-shell nanometer nanoparticles. The hollow core-shell nanometer material is good in CO catalytic oxidation performance; and catalytic oxidation can be completely carried out on CO at the temperature of about 100DEG C; the Au@ CeO2 hollow core-shell nanometer material can be repeatedly used for four times for a total of 50h, and still maintains good catalytic activity, so that the cerium dioxide shell has a good protection function for the gold nanoparticles. The preparation method has the advantages of being mild in conditions, environment-friendly, etc.
Description
Technical field
The present invention relates to one and prepare Au@CeO
2the method of hollow core shell nanometer material, is specifically related to the CeO by Au@
2hollow core shell nanometer material is for CO catalytic oxidation technology.
Background technology
Ceria (CeO
2) there is superior storage and discharge the function of oxygen, be active very high catalyst in rare earth oxide.Gold nano also has high catalytic activity.Gold nano and these two kinds of materials with catalytic performance of ceria being organically combined, improve the catalytic performance of composite nano materials by the synergy of storeroom, is one of focus of catalyst research.At present, research is mainly the CeO for preparing support type
2nanocatalyst, wherein, modal is that golden nanometer particle is loaded to CeO
2surface, forms Au/CeO
2support type composite nano materials.Although this composite shows good catalytic activity in the time processing carbon monoxide in vehicle exhaust and nitrogen oxide, due to the golden nanometer particle inactivation of easily reuniting, cause the waste of catalyst.Therefore, how to protect golden nanometer particle, making it in catalytic reaction process, keep good chemical stability is the major issue that will consider in catalyst research process, and the nano material of hollow core shell structure can well address this problem.
The nano material of hollow nucleocapsid (yolk-shell) structure, due to the protective effect of shell, makes core core nano particle under the critical conditions such as high temperature, effectively avoid reuniting, thereby keeps good chemical dispersion and stability.Due to the synergy between core, shell material, the reactivity of material is also played to facilitation, the nano material of the structure of this uniqueness and superior performance, carries at catalysis, medicine, the field such as electrode attracts wide attention.
The conventional method of preparing hollow core shell nanometer material has hard template method, soft template method etc.Soft template method is prepared the organic reagents that use in the process of hollow core shell nanometer material more, and environmental pollution is larger, and subsequent processes is loaded down with trivial details; Hard template method can effectively avoid using organic reagent.Preparation method using silica as hard template material, because the hydrolysis rate of silane reagent is fast, wayward, be HF or NaOH at the follow-up reagent using while removing silica template, the amount of these severe corrosive reagent is more difficult control also.In recent years, the advantages such as carbon ball template is cheap with it, preparation condition is gentle, de-carbon process is simple cause researcher's extensive concern, wherein, prepare carbon template using glucose as carbon source and become the comparatively ideal selection of preparing carbon ball with the advantage of environmental protection.
Document Arnal P M, Comotti M, Schuth F.
chem. Int. Ed., 2006,45 (48): in 8224-8227, use SiO
2prepare Au@SiO as template
2@ZrO
2many shells nucleocapsid structure, SiO in the middle of corroding by NaOH
2layer, prepares Au@ZrO
2hollow core shell structure, and this material is applied to CO catalytic oxidation, this Au@ZrO in the time of approximately 240 DEG C
2hollow core shell nanometer material can be by CO complete catalysts oxidation.
Document Galeano C, G ü ttel R, Paul M, Arnal P, Lu A H, Schuth F.
chem. Eur. J., 2011,17 (30): in 8434-8439, use SiO
2do template and prepare Au@SiO
2@ZrO
2the nano material of structure, selects the middle SiO of HF corrosion
2layer, obtains Au@ZrO
2hollow core shell structure, still, is removing SiO
2zrO in process
2shell damages to some extent.This material, for CO catalytic oxidation, is shown to this material is about 240 DEG C by temperature required CO complete catalysts oxidation.
Summary of the invention
The object of this invention is to provide one and prepare Au@CeO
2the method of hollow core shell nanometer material, this Au@CeO
2hollow core shell nanometer material is a kind of catalyst of efficient stable of CO catalytic oxidation.
Taking glucose as carbon source, adopt hydro-thermal method at gold nano coated with carbon bed, form Au@C core-shell nano, this Au@C core-shell nano material and cerous nitrate are fully acted on, make Ce
3+be adsorbed in carbon ball surface, under high-temperature calcination, Ce
3+react with oxygen and generate CeO
2, meanwhile, middle carbon-coating decomposes, Au and CeO
2between there is cavity, form Au@CeO
2hollow core core/shell nanoparticles.
Concrete preparation process is as follows:
A. gold chloride is dissolved in deionized water, be mixed with the solution that concentration is 0.5 g/L, be heated to 60-100 DEG C in water-bath after, add fast appropriate natrium citricum, after stirring 30 min, stop reaction, naturally cool to room temperature, adding 0.25 mL concentration is the polyvinylpyrrolidone of 0.015 g/mL, stirs 24 h under room temperature, after centrifugal, add the ultrasonic dispersion of appropriate amount of deionized water, obtain aurosol.
B. get appropriate aurosol and mix with the glucose solution of 0.3-0.5 mol/L, at 160-180 DEG C, react 4-12 h, centrifugal after cool to room temperature, obtain the nano material of Au@C nucleocapsid structure.
C. Au@C core-shell material is mixed with cerous nitrate solution, at 160 DEG C, react certain hour, make Ce
3+fully be adsorbed in carbon ball surface, by centrifugal product, wash and be dried.
D. dried sample is warming up to 500 DEG C with the speed of 1 DEG C/min, and at this temperature, keeps 3 h, obtain Au@CeO
2hollow core shell material.
Adopt the method to prepare hollow core shell nanometer material and there is the advantage such as mild condition, environmental protection.This nano material, for catalysis CO oxidation, is found to it has good catalytic performance, can be by CO complete catalysts oxidation 100 DEG C of left and right; Reuse 4 times, be respectively 12 h, 13 h, 12 h, 13 h 50 h altogether, Au@CeO
2hollow core shell nanometer material still keeps good catalytic activity, illustrates that ceria shell has good protective effect to gold nano.
The invention has the beneficial effects as follows: select carbon ball to do template, by Au and CeO
2these two kinds of catalysis materials combine, and have prepared Au@CeO
2hollow core-shell structured nanomaterials.This material CO catalytic oxidation, demonstrates good catalytic performance, just can be by CO complete catalysts oxidation under lower temperature (approximately 100 DEG C).CeO
2shell has effectively been protected Au nano particle, has avoided Au nanometer to reunite and in course of reaction, has kept good dispersiveness and stability.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture (TEM) of the Au@C core-shell nano material that obtains of embodiment 1.
Fig. 2 is the transmission electron microscope picture (TEM) of the Au@C core-shell nano material that obtains of embodiment 2.
Fig. 3 is the transmission electron microscope picture (TEM) of the Au@C core-shell nano material that obtains of embodiment 3.
Fig. 4 is the Au@CeO that embodiment 3 obtains
2the transmission electron microscope picture (TEM) of hollow core shell nanometer material.
Fig. 5 is the Au@CeO that embodiment 3 obtains
2the x-ray diffraction pattern (XRD) of hollow core shell nanometer material.
Fig. 6 is the Au@CeO that embodiment 3 obtains
2the catalytically active assessment figure of hollow core shell nanometer material.
Fig. 7 is the Au@CeO that embodiment 3 obtains
2the catalytic stability figure of hollow core shell nanometer material.
Fig. 8 is the transmission electron microscope picture (TEM) of the Au@C core-shell nano material that obtains of embodiment 4.
Fig. 9 is the transmission electron microscope picture (TEM) of the Au@C core-shell nano material that obtains of embodiment 5.
Detailed description of the invention
Embodiment 1:
A. the chlorauric acid solution of getting 34.5 mL concentration and be 0.5 g/L is heated to 100 DEG C in oil bath, adding fast 1 mL mass fraction is the sodium citrate solution of 3 %, after reacting 30 min, stop heating, naturally cool to room temperature, adding 0.25 mL concentration is the polyvinylpyrrolidone of 0.015 g/mL, stirs 24 h under room temperature, the centrifugal supernatant of removing, add the ultrasonic dispersion of 15 mL deionized water, obtain aurosol.
B. get 5 mL aurosols and fully mix with 70 mL deionized waters, 4.45 g glucose, mixed liquor is placed in to 100 mL reactors, at 160 DEG C of reaction 8 h, naturally cool to room temperature, through the centrifugal Au@C core-shell nano material that obtains.Product pattern as shown in Figure 1.From TEM figure, intuitively find out Au@C core-shell nano globulate, particle diameter approximately 95 nm.
C. getting appropriate Au@C core-shell nano material and 62 mL concentration after centrifugal is the Ce (NO of 0.01 mol/L
3)
3solution mixes, and mixed liquor is placed in to 100 mL reactors, at 160 DEG C of reaction 12 h, naturally cool to centrifugal after room temperature, wash and be dried.
D. dry sample is placed in to tube furnace, rises to 500 DEG C with the heating rate of 1 DEG C/min, keep 3 h at 500 DEG C, carbon-coating is removed completely, forms Au@CeO
2hollow core shell structure.
Embodiment 2:
A. with example 1.
B. get 5 mL aurosols and fully mix with 70 mL deionized waters, 4.45 g glucose, be placed in 100 mL reactors, at 160 DEG C of reaction 10 h, naturally cool to room temperature, through the centrifugal Au@C core-shell nano material that obtains.Product pattern as shown in Figure 2.From TEM figure, intuitively find out Au@C core-shell nano globulate, particle diameter approximately 135 nm.
C. with example 1.
D. with example 1.
Embodiment 3:
A. with example 1.
B. get 5 mL aurosols and fully mix with 70 mL deionized waters, 4.45 g glucose, be placed in 100 mL reactors, at 160 DEG C of reaction 12 h, naturally cool to room temperature, through the centrifugal Au@C core-shell nano material that obtains.Product pattern as shown in Figure 3.From TEM figure, intuitively find out, Au C core-shell nano becomes the spherical of rule, particle diameter approximately 263 nm, and pattern, the particle diameter of product are very even.
C. with example 1.
D. with example 1, product pattern is shown in Fig. 4.Product is made up of core and shell two parts as can be seen from Figure 4, has certain cavity between core and shell, is therefore referred to as hollow core shell nanometer material.This Au@CeO
2hollow core core/shell nanoparticles globulate, average grain diameter approximately 110 nm, because carbon decomposes dimensional contraction approximately 58 % that cause material.Because making Au nano particle, the existence of cavity is positioned at CeO
2one side of shell, this also illustrates that Au nano particle can move freely in shell, thereby provides more avtive spot for catalytic reaction.Product is carried out to XRD analysis (Fig. 5).Find out from Fig. 5, except Au and CeO
2diffraction maximum do not detect outward and the peak of other material illustrate that this product is purer.Au and CeO
2diffraction peak shape fine, the degree of crystallinity of illustrative material is fine.Can judge in conjunction with Fig. 4 and Fig. 5, this product is Au and CeO
2two kinds of Au@CeO that material forms
2the nano material of hollow core shell structure.
E.Au@CeO
2hollow core shell nanometer material CO catalytic oxidation performance.Get 50 mg Au@CeO
2hollow core shell nanometer material, mix with 0.4 g quartz sand, be filled into quartz ampoule (internal diameter 6 mm, long 40 cm) in, adopt electric furnace temperature programming heating, the conversion ratio of determining CO by the content of gas before and after the reaction of gas chromatograph on-line monitoring, between the conversion ratio of CO and catalytic oxidation temperature, relation is shown in Fig. 6.Fig. 6 demonstration, this material can be by CO complete catalysts oxidation in the time of 100 DEG C, illustrates that this material has good catalytic activity.And document Arnal P M, Comotti M, Schuth F.
chem. Int. Ed., 2006,45 (48): 8224-8227 and document Galeano C, G ü ttel R, Paul M, Arnal P, Lu A H, Schuth F.
chem. Eur. J., 2011,17 (30): the Au@ZrO in 8434-8439
2hollow core shell nanometer material could be by CO complete catalysts oxidation at 240 DEG C.
F.Au@CeO
2the catalytic stability of hollow core shell nanometer material.Get 50 mg Au@CeO
2hollow core shell nanometer material, mixes with 0.4 g quartz sand, is filled in quartz ampoule, tests the conversion ratio (Fig. 7) of CO at 80 DEG C, retest 4 times, and each testing time is respectively 12 h, 13 h, 12 h, 13 h, amounts to 50 h.Find out from Fig. 7, reuse rear Au@CeO
2the catalytic activity of hollow core shell nanometer material, without significant change, does not have deactivation phenomenom, and Au@CeO is described
2hollow core shell nanometer material has good catalytic stability, and this has benefited from CeO
2the protection of shell to Au nanometer.
Embodiment 4:
A. getting 34.5 mL concentration is the chlorauric acid solution of 0.5 g/L, add 111 mL deionized waters, be heated to 60 DEG C under vigorous stirring in water-bath, adding fast 4.0 mL mass fractions is the sodium citrate solution of 1 %, after reaction 30min, stop heating, naturally cool to room temperature.
B. get 75 mL aurosols and fully mix with 4.45 g glucose, mixed liquor is placed in to 100 mL reactors, at 180 DEG C of reaction 6 h, naturally cool to room temperature, through the centrifugal Au@C core-shell nano material that obtains.The TEM of product as shown in Figure 8, the particle diameter of this material approximately 236 nm, be rule spherical, and pattern and particle diameter even.
C. with example 1.
D. with example 1.
Embodiment 5:
A. with example 4.
B. get 75 mL aurosols and fully mix with 7.50 g glucose, mixed liquor is placed in to 100 mL reactors, at 180 DEG C of reaction 6 h, naturally cool to room temperature, through the centrifugal Au@C core-shell nano material that obtains.As shown in Figure 9, Au@C core-shell nano is the spherical of rule to the TEM of product, and pattern and particle diameter more even, compared with Fig. 8, it is large that its particle diameter becomes, approximately 293 nm illustrates the particle size that can change product by the concentration of adjustment glucose.
C. with example 1.
D. with example 1.
Claims (3)
1. prepare Au CeO for one kind
2the method of hollow core shell nanometer material, concrete preparation process is as follows:
A. getting appropriate concentration is 0.5 g/L chlorauric acid solution, in water-bath, be heated to 60-100 DEG C, add appropriate natrium citricum, after stirring 30 min, stop reaction, naturally cool to room temperature, adding 0.25 mL concentration is the polyvinylpyrrolidone (PVP) of 0.015 g/mL, stirs 24 h under room temperature, after centrifugal, add the ultrasonic dispersion of appropriate amount of deionized water, obtain aurosol;
B. get appropriate aurosol and mix with 0.3-0.5 mol/L glucose solution, at 160-180 DEG C, react 4-12 h, centrifugal after cool to room temperature, obtain the nano material of Au@C nucleocapsid structure;
C. Au@C core-shell material is mixed with cerous nitrate solution, at 160 DEG C, react certain hour, make Ce
3+fully be adsorbed in carbon ball surface, by centrifugal product, wash and be dried;
D. by dried product with 1 DEG C of min
-1speed be warming up to 500 DEG C, at this temperature, keep 3 h, obtain Au@CeO
2hollow core shell structure.
2. preparation Au@CeO according to claim 1
2the method of hollow core shell nanometer material, it is characterized in that, taking carbon ball as template, gold and two kinds of catalysis materials of ceria are combined, improve the catalytic performance of composite nano materials by the synergy of storeroom, this material has the ability of good CO catalytic oxidation, just can make CO complete oxidation at 100 DEG C.
3. preparation Au@CeO according to claim 1
2the method of hollow core shell nanometer material, is characterized in that, because gold nano is wrapped in ceria shell inside, the agglomeration that can effectively avoid high temperature action to cause, makes Au@CeO
2hollow core shell nanometer material keeps good chemical stability.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105727988A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | Platinum composite catalyst, preparation method therefor and application of platinum composite catalyst |
| JP2017012999A (en) * | 2015-07-01 | 2017-01-19 | 国立大学法人大阪大学 | Gold-cerium oxide complex catalyst and selective hydrogenation method using the catalyst |
| CN107576649A (en) * | 2017-09-19 | 2018-01-12 | 辽宁大学 | A kind of new carbon-based core-shell material for Raman spectrum detection and its preparation method and application |
| JP2020507452A (en) * | 2017-02-02 | 2020-03-12 | 本田技研工業株式会社 | Core shell |
| CN111036198A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Double-shell core-shell structure metal catalyst and preparation method thereof |
| CN111280176A (en) * | 2019-08-28 | 2020-06-16 | 大连民族大学 | Au/CeO2Bactericide and preparation method and application thereof |
| CN111841631A (en) * | 2020-08-05 | 2020-10-30 | 济南大学 | Polypyrrole-cerium dioxide-gold composite nano material |
| CN116273022A (en) * | 2023-03-21 | 2023-06-23 | 昆明理工大学 | Catalytic material with hollow core-shell structure and preparation method and application thereof |
-
2014
- 2014-04-02 CN CN201410128914.6A patent/CN103861592A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| JIAN QI等: "Facile synthesis of core-shell Au@CeO2 nanocomposites with remarkably enhanced catalytic activity for CO oxidation", 《ENERGY ＆ ENVIRONMENTAL SCIENCE》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105727988A (en) * | 2014-12-10 | 2016-07-06 | 中国石油天然气股份有限公司 | Platinum composite catalyst, preparation method therefor and application of platinum composite catalyst |
| CN105727988B (en) * | 2014-12-10 | 2019-03-12 | 中国石油天然气股份有限公司 | Platinum composite catalyst, preparation method and application |
| JP2017012999A (en) * | 2015-07-01 | 2017-01-19 | 国立大学法人大阪大学 | Gold-cerium oxide complex catalyst and selective hydrogenation method using the catalyst |
| JP2020507452A (en) * | 2017-02-02 | 2020-03-12 | 本田技研工業株式会社 | Core shell |
| CN107576649A (en) * | 2017-09-19 | 2018-01-12 | 辽宁大学 | A kind of new carbon-based core-shell material for Raman spectrum detection and its preparation method and application |
| CN111036198A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Double-shell core-shell structure metal catalyst and preparation method thereof |
| CN111036198B (en) * | 2018-10-12 | 2023-04-28 | 中国石油化工股份有限公司 | Double-shell core-shell structure metal catalyst and preparation method thereof |
| CN111280176A (en) * | 2019-08-28 | 2020-06-16 | 大连民族大学 | Au/CeO2Bactericide and preparation method and application thereof |
| CN111841631A (en) * | 2020-08-05 | 2020-10-30 | 济南大学 | Polypyrrole-cerium dioxide-gold composite nano material |
| CN111841631B (en) * | 2020-08-05 | 2021-11-02 | 济南大学 | Polypyrrole-cerium dioxide-gold composite nano material |
| CN116273022A (en) * | 2023-03-21 | 2023-06-23 | 昆明理工大学 | Catalytic material with hollow core-shell structure and preparation method and application thereof |
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Application publication date: 20140618 |