CN1666820A - Noble metal loaded mesoporous silicon oxynitride compound catalyst and its preparation - Google Patents
Noble metal loaded mesoporous silicon oxynitride compound catalyst and its preparation Download PDFInfo
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- CN1666820A CN1666820A CN 200410016919 CN200410016919A CN1666820A CN 1666820 A CN1666820 A CN 1666820A CN 200410016919 CN200410016919 CN 200410016919 CN 200410016919 A CN200410016919 A CN 200410016919A CN 1666820 A CN1666820 A CN 1666820A
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Abstract
The invention provides a noble metal load medium-hole silicon nitride oxide multiple catalysts and its preparation method, which uses the medium-hole silicon oxide as the mother material, the ammonia gas high-temperature nitrification and original acid alkali reaction as the main procedures. The main characteristics are: assemble most of the noble metal nanometer particles into the regular channel of silicon nitride oxide. Because the carrier is silicon nitride oxide, compared with other method, the method has special catalyzing character, so the combination mechanism is essentially different.
Description
Technical field
The invention belongs to field of nanometer material technology, be specifically related to loaded mesoporous silicon oxynitride composite catalyst of a kind of noble metal and preparation method thereof.
Background technology
In recent years, the metal Nano structure material has attracted numerous scientists' research interest owing to have many new special nature.Mainly concentrate on the noble metal at the metal nanoparticle of using in the catalysis, because the polymolecularity of metallic particles is very important in many catalytic action processes, therefore synthetic have high-specific surface area and reproducible noble metal granule with nanostructured of catalytic activity is the important challenge that the material supply section scholars are proposed.Yet, because mesopore silicon oxide has uniform pore-size distribution, high specific area and excellent chemical stability, be considered to prepare nano structural material (as, catalyst, optical material) main, desirable place body material (host).
Yet, because monox mesoporous material itself lacks the activated centre, in the nano-composite catalyst that mesopore silicon oxide supports, mesopore silicon oxide mainly is as supporter (support), and does not show tangible Subjective and Objective catalytic effect (host-guest catalyticeffect).That therefore, explores other has that different chemical is formed and the mesoporous material of sufficient activity position is very important as the place body for preparing nano structural material.Recently, people such as Kapoor has reported CeO
2-ZrO
2The palladium catalyst that the mixed oxide mesoporous material supports shows high selectivity (M.P.Kapoor, A.Raj, Y.Matsumura, Methanoldecomposition over palladium supported mesoporous CeO in the low-temperature decomposition of methyl alcohol
2-ZrO
2Mixed oxides.MicroporousMesoporous Mater.2001,44-45,565).Chen Hangrong etc. have synthesized the Pt nanoparticle of high dispersive by a new ion-exchange process in ordered mesoporous zirconia, this material has shown tangible Subjective and Objective catalytic effect (H.R.Chen as catalyst, J.L.Shi, Y.S.Li, J.N.Yan, Z.L.Hua, H.G.Chen, D.S.Yan, A new method for the synthesis ofhighly dispersive and catalyticlly active platinum nanoparticles confined in mesoporous zirconia, Adv.Mater.2003,15,1078).Therefore, different place bodies may produce different Subjective and Objective effects, and this is a particular importance for catalytic reaction.
In view of the mesoporous silicon oxynitride composite catalyst of noble metal load has very wide application prospect in petrochemical industry and fine chemistry industry are synthetic, the mesoporous silicon oxynitride composite catalyst of synthetic high dispersive noble metal load will have great importance.
Summary of the invention
The object of the present invention is to provide mesoporous silicon oxynitride composite catalyst of a kind of high dispersive noble metal load and preparation method thereof.
For reaching above-mentioned purpose, the present invention is achieved in that
The loaded mesoporous silicon oxynitride composite catalyst of a kind of noble metal, wherein noble metal is highly dispersed state in carrier, and the mass percent of noble metal load capacity is 0.01～10%, and the mass percent of nitrogen is 0.1～28% in the composition of mesoporous silicon oxynitride.
The preparation method of the loaded mesoporous silicon oxynitride composite catalyst of a kind of noble metal, may further comprise the steps: the mesopore silicon oxide presoma that will contain the template agent is put into the material boat, nitrogenize in the pipe furnace of mobile ammonia is arranged, the flow of ammonia is 0.2-10L/min, nitriding temperature is 700-1100 ℃, nitridation time is 0.5-40h, make mesoporous silicon oxynitride carrier material, described mesoporous silicon oxynitride was handled 0.5-10 hour 80-200 ℃ of vacuum outgas, to be dispersed in through the mesoporous silicon oxynitride that obtains after the step 3) in the alcoholic solution of acid noble metal source, then at room temperature, stirring reaction is more than 0.5 hour in the container of sealing, filter afterwards, washing, drying adopts reduction technique with the reduction of gained material, makes product of the present invention at last.
Preferable, can obtain the nitrogen content mass percent by flow, nitriding temperature and the nitridation time of adjusting ammonia is the mesoporous silicon oxynitride carrier material of 0.1-28%.
Preferable, the amount by adjusting the mesoporous silicon oxynitride of carrier and the alcoholic solution concentration of noble metal source are tuned as 0.01～10% with the mass percent of noble metal load capacity.
Preferable, described acid noble metal source is H
2PtCl
6Or H
2AuCl
6
Preferable, described reduction technique is at room temperature adding thermal reduction by the ethanol solution of sodium borohydride reduction or by hydrogen.
The invention has the beneficial effects as follows: the basic character of utilizing nitrogen oxide, make mesoporous silicon oxynitride and acid noble metal generation original position acid-base reaction, noble metal has been incorporated in the duct of mesoporous silicon oxynitride, according to the characteristics of preparation principle, use the composition of the composite catalyst of this method preparation to have very big modulation space.This method with high content of technology, the added value of product height of preparing.Parent stock is cheap and easy to get in addition, and required production equipment is simple, and one-time investment is few, is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 is preparation technology's flow chart of the mesoporous silicon oxynitride composite catalyst of high dispersive noble metal load
Fig. 2 is the little angle XRD figure spectrum of sample: the order mesoporous silicon oxynitride that (a) has the SBA-15 architectural feature; (b) noble metal platinum (Pt) and composite catalyst with order mesoporous silicon oxynitride of SBA-15 architectural feature
Fig. 3 noble metal platinum (Pt) is composed with the wide-angle XRD figure of the composite catalyst of the order mesoporous silicon oxynitride with SBA-15 architectural feature
Fig. 4 is the representational high resolution transmission electron microscopy picture (HRTEM) (electron beam is perpendicular to the duct direction) of the composite catalyst of noble metal platinum (Pt) and the order mesoporous silicon oxynitride with SBA-15 architectural feature
Fig. 5 is a noble metal platinum (Pt) and (electron beam is parallel to the duct direction to the representational high resolution transmission electron microscopy picture (HRTEM) of the composite catalyst of the order mesoporous silicon oxynitride with SBA-15 architectural feature.)
The specific embodiment
Further specify embodiments of the present invention and beneficial effect below in conjunction with accompanying drawing.
The SBA-15 architectural feature mesopore silicon oxide presoma that has that will contain the template agent is put into the alumina material boat, nitrogenize in the pipe furnace of mobile ammonia is arranged.The flow of ammonia is 1.2L/min, and nitriding temperature is 1000 ℃, and nitridation time is 18h, and making the nitrogen content mass percent is 20.1% mesoporous silicon oxynitride carrier material.Then, mesoporous silicon oxynitride after handling 3 hours, is dispersed in the ethanolic solution of chloroplatinic acid in 120 ℃ of vacuum outgas, under the room temperature, stirring reaction is 24 hours in the container of sealing, subsequent filtration, washing, 80 ℃ of vacuum drying make the mesoporous silicon oxynitride composite catalyst of high dispersive Pt load after 12 hours again by the reduction of ethanol solution of sodium borohydride room temperature.Fig. 1 is the mesoporous silicon oxynitride composite catalyst preparation technology flow process of aforementioned high dispersive noble metal load.Fig. 2 (b) is the little angle XRD figure spectrum of the composite catalyst of present embodiment preparation, can clearly be seen that from figure, represent characteristic diffraction peak (100), (110) and (200) of SBA-15 high-visible, this shows through the long nitrogenize of high temperature and has assembled after the Pt that the hexangular ordered meso-hole structure of parent SBA-15 still is held.Yet, to compare with Fig. 2 (a), the intensity of its each diffraction maximum descends to some extent, especially to (110) and (200) diffraction maximum.Fig. 3 is the wide-angle XRD figure spectrum of the composite catalyst of present embodiment preparation, and as can be known, the several main diffraction maximum of Pt shows tangible broadening from the collection of illustrative plates, and this Pt particle size that shows load in mesoporous silicon oxynitride is in nanometer range.Utilization thank rein in formula can be according to the halfwidth of diffraction maximum (111), the average grain particle diameter that rough calculation goes out Pt in the composite catalyst of present embodiment preparation is about 4.0nm.Fig. 4 and Fig. 5 are representational high explanation transmission electron microscope (HRTEM) photo of the composite catalyst of present embodiment preparation.Can be clear that on scheming the load of a large amount of homodisperse Pt metallic particles is in the mesoporous duct.In addition, also can be intuitively, be clear that load through nitrogenize and Pt after, the order mesoporous structure of SBA-15 still is retained, this result with XRD is consistent.Plasmatron spectrographic analysis shows that the Pt content mass percent of this sample is about 8%.
Claims (6)
1. loaded mesoporous silicon oxynitride composite catalyst of noble metal, it is characterized in that: noble metal is highly dispersed state in carrier, the mass percent of noble metal load capacity is 0.01～10%, and the mass percent of nitrogen is 0.1～28% in the composition of mesoporous silicon oxynitride.
2. the preparation method of the loaded mesoporous silicon oxynitride composite catalyst of noble metal is characterized in that may further comprise the steps:
1) the mesopore silicon oxide presoma that will contain the template agent is put into the material boat,
2) nitrogenize in the pipe furnace of mobile ammonia is arranged, the flow of ammonia are 0.2-10L/min, and nitriding temperature is 700-1100 ℃, and nitridation time is 0.5-40h, make mesoporous silicon oxynitride carrier material,
3) described mesoporous silicon oxynitride was handled 0.5-10 hour 80-200 ℃ of vacuum outgas,
4) will be dispersed in through the mesoporous silicon oxynitride that obtains after the step 3) in the alcoholic solution of acid noble metal source, then at room temperature, stirring reaction more than 0.5 hour in the container of sealing filters afterwards, washs, drying,
5) adopt reduction technique with the reduction of gained material, make product of the present invention at last.
3. the preparation method of the loaded mesoporous silicon oxynitride composite catalyst of noble metal according to claim 2, it is characterized in that: in step 2) in, obtaining the nitrogen content mass percent by flow, nitriding temperature and the nitridation time of adjusting ammonia is the mesoporous silicon oxynitride carrier material of 0.1-28%.
4. the preparation method of the loaded mesoporous silicon oxynitride composite catalyst of noble metal according to claim 2 is characterized in that: the amount by adjusting the mesoporous silicon oxynitride of carrier and the alcoholic solution concentration of noble metal source are tuned as 0.01～10% with the mass percent of noble metal load capacity.
5. the preparation method of the loaded mesoporous silicon oxynitride composite catalyst of noble metal according to claim 2 is characterized in that: described acid noble metal source is H
2PtCl
6Or H
2AuCl
6
6. the preparation method of the loaded mesoporous silicon oxynitride composite catalyst of noble metal according to claim 2 is characterized in that: in step 5), described reduction technique is at room temperature adding thermal reduction by the ethanol solution of sodium borohydride reduction or by hydrogen.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012055320A1 (en) * | 2010-10-27 | 2012-05-03 | 中国科学院大连化学物理研究所 | Silicon oxynitride chromatography stationary phase material and preparation therefor and applicable thereof |
| CN102451667A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Silicon oxynitride chromatographic stationary phase material and preparation and application thereof |
| CN102020422B (en) * | 2009-09-14 | 2013-03-20 | 海洋王照明科技股份有限公司 | Method for preparing gold nanoparticles in porous glass |
| CN103007904A (en) * | 2011-09-23 | 2013-04-03 | 中国科学院大连化学物理研究所 | Surface modification bonded silicon oxynitride chromatographic stationary phase material and preparation method thereof |
| CN108934511A (en) * | 2018-07-23 | 2018-12-07 | 柯江波 | Polychrome Bougainvillea spectabilis engrafting method based on Fatsia japonica seed oil-treatment agent |
| CN109041854A (en) * | 2018-07-23 | 2018-12-21 | 柯江波 | The engrafting method of polychrome bougainvillea based on polylysine organization protection liquid |
| CN109197306A (en) * | 2018-07-23 | 2019-01-15 | 柯江波 | A kind of engrafting method of polychrome Bougainvillea spectabilis |
| CN109833869A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of slurry bed hydrogenation catalyst and its preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0832688B1 (en) * | 1996-04-11 | 2007-08-29 | ICT Co., Ltd. | Exhaust gas purifying catalyst and exhaust gas purifying method |
| FR2765492B1 (en) * | 1997-07-03 | 1999-09-17 | Rhodia Chimie Sa | GAS TREATMENT PROCESS FOR THE REDUCTION OF NITROGEN OXIDE EMISSIONS USING A CATALYTIC COMPOSITION WITH A SUPPORT BASED ON SILICA AND TITANIUM OXIDE |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102020422B (en) * | 2009-09-14 | 2013-03-20 | 海洋王照明科技股份有限公司 | Method for preparing gold nanoparticles in porous glass |
| WO2012055320A1 (en) * | 2010-10-27 | 2012-05-03 | 中国科学院大连化学物理研究所 | Silicon oxynitride chromatography stationary phase material and preparation therefor and applicable thereof |
| CN102451667A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Silicon oxynitride chromatographic stationary phase material and preparation and application thereof |
| CN102451667B (en) * | 2010-10-27 | 2014-01-01 | 中国科学院大连化学物理研究所 | Silicon oxynitride chromatographic stationary phase material and preparation and application thereof |
| US9675959B2 (en) | 2010-10-27 | 2017-06-13 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Porous silicon oxynitride materials for chromatographic separation and method of their preparation |
| CN103007904A (en) * | 2011-09-23 | 2013-04-03 | 中国科学院大连化学物理研究所 | Surface modification bonded silicon oxynitride chromatographic stationary phase material and preparation method thereof |
| CN109833869A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of slurry bed hydrogenation catalyst and its preparation method and application |
| CN108934511A (en) * | 2018-07-23 | 2018-12-07 | 柯江波 | Polychrome Bougainvillea spectabilis engrafting method based on Fatsia japonica seed oil-treatment agent |
| CN109041854A (en) * | 2018-07-23 | 2018-12-21 | 柯江波 | The engrafting method of polychrome bougainvillea based on polylysine organization protection liquid |
| CN109197306A (en) * | 2018-07-23 | 2019-01-15 | 柯江波 | A kind of engrafting method of polychrome Bougainvillea spectabilis |
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Granted publication date: 20070912 Termination date: 20130312 |