CN102836706A - High-temperature thermally stable palladium composite catalyst as well as preparation method and application thereof - Google Patents
High-temperature thermally stable palladium composite catalyst as well as preparation method and application thereof Download PDFInfo
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- CN102836706A CN102836706A CN2012103370016A CN201210337001A CN102836706A CN 102836706 A CN102836706 A CN 102836706A CN 2012103370016 A CN2012103370016 A CN 2012103370016A CN 201210337001 A CN201210337001 A CN 201210337001A CN 102836706 A CN102836706 A CN 102836706A
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Abstract
The invention relates to a high-temperature thermally stable palladium composite catalyst, wherein the catalyst is a core-shell grain in which a SiO2 globule carried with Pd grain is used as the core and mesoporous SiO2 is used as the shell. The invention further relates to a preparation method for the palladium composite catalyst, comprising the following steps: carrying the Pd grain in which hexadecyl trimethyl ammonium bromide is used as ligand on an amino functionalized SiO2 globule, to obtain the SiO2 globule carried with Pd grain; mixing the SiO2 globule carried with Pd grain with tetraethoxysilane, using the hexadecyl trimethyl ammonium bromide ligand of the surface of the Pd grain as a template, sintering, removing the template, directly forming the mesoporous SiO2 shell, thereby obtaining the palladium composite catalyst after preparation. The invention further relates to the application of the palladium composite catalyst in reaction of oxidizing carbon monoxide to be carbon dioxide. The palladium composite catalyst provided by the invention is higher in catalyst activity, higher in thermal stability, and can be recycled repeatedly.
Description
Technical field
The present invention relates to a kind of palladium composite catalyst and preparation method thereof and application of high-temperature thermal stability, belong to the noble metal catalyst technical field in the material science.
Background technology
Can the catalysis multiple useful chemical reaction of palladium composite catalyst and have the characteristics of easy recovery, thereby receive widely and paying close attention to.Pd nano particle shows the pattern catalytic activity relevant with size in many reactions, be the most frequently used catalysis primitive.And Pd nano particle to load on the solid carrier be the effective heterogeneous catalyst of using always.When Pd nano particle no part in surface or stabilizing agent protection, exposed active sites occurs, have the highest catalytic activity.Yet if do not have part and stabilizing agent protection, the high surface energy atom of nanoparticle surface is gathered into body phase material easily, and nano particle is difficult to keep stable status.Therefore, because the influence of surface ligand, metal nanoparticle can not obtain the highest catalytic activity and selectivity.Especially the parcel that does not have strong part, under the Pd nano particle pyroreaction condition, the size change is gathered into the palladium deposition greatly and loses intrinsic catalytic activity easily.Therefore, the Pd nano particle composite catalyst of the heat-staple no part parcel of development high catalytic activity is still important challenge.
In order to make Pd nano particle under the situation of no part parcel, can also have advantages of high catalytic activity and heat endurance; Usually the method that adopts is to make Pd nano particle by inorganic shell (for example: silicon; Carbon and metal oxide etc.) parcel, this shell plays the effect that prevents that Pd nano particle from assembling.This metal core shell structure material is realized through two-step synthetic method, comprises the preparation metal nanoparticle, deposits inorganic shell in surfaces of metal nanoparticles subsequently.At present, the most frequently used means are that Pd nano particle is wrapped in the mesoporous silicon oxide shell.Yet the palladium composite catalyst of these nucleocapsid structures has the problem that many Size Distribution or each nucleocapsid structure only contain a Pd nano particle.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of palladium composite catalyst of high-temperature thermal stability, this catalyst has advantages of high catalytic activity, heat endurance and can repeatedly recycle.
The present invention also aims to provide the preparation method and the application of the palladium composite catalyst of above-mentioned high-temperature thermal stability.
For reaching above-mentioned purpose, the present invention provides a kind of palladium composite catalyst of high-temperature thermal stability, and it is for there being the SiO of Pd particle with load
2Bead is core, with mesoporous SiO
2Core-shell particles for shell.
According to the specific embodiment of the present invention, preferably, in above-mentioned catalyst, said SiO
2The diameter of bead is 200-300nm.
According to the specific embodiment of the present invention, preferably, in above-mentioned catalyst, with said SiO
2The quality of bead is a benchmark, and the content of said Pd particle is 2-5%.
According to the specific embodiment of the present invention, preferably, in above-mentioned catalyst, the particle diameter of said Pd particle is 5-10nm.
According to the specific embodiment of the present invention, preferably, in above-mentioned catalyst, with all SiO in the said catalyst core shell particles
2Quality be benchmark, said SiO
2The content of shell is 15-25%.
According to the specific embodiment of the present invention, preferably, in above-mentioned catalyst, said SiO
2The aperture of shell is 2-5nm.
According to the specific embodiment of the present invention, preferably, in above-mentioned catalyst, the diameter of said core-shell particles is 270-330nm.
According to the specific embodiment of the present invention, preferably, said catalyst prepares through following preparation method:
To be the SiO of the Pd particle load of part with the softex kw to functional amido
2On the bead, obtain the SiO that load has the Pd particle
2Bead;
The SiO that said load is had the Pd particle
2Bead mixes with ethyl orthosilicate, is template with the softex kw part of Pd particle surface, after calcining, removes template, directly forms mesoporous SiO
2Shell forms said catalyst.
More specifically, said catalyst can prepare through following preparation method:
SiO with Pd particle solution and functional amido
2Bead solution joins in the deionized water (consumption of deionized water is as the criterion reacting smoothly), wherein, and the SiO of Pd particle and functional amido
2The mass ratio of bead is 1: 15, and sonicated 3-10 minute, solution kept static 10-30 minute afterwards, utilizes after deionized water washs product, and product is dispersed in the deionized water, obtains the SiO that load has the Pd particle
2The solution of bead;
The SiO that above-mentioned load is had the Pd particle
2The solution of bead is distributed in the deionized water (consumption of deionized water is as the criterion reacting smoothly), and wherein, load has the SiO of Pd particle
2The content of bead is 0.03-0.05mmol, adjusts pH value of solution value to 11, adds the methanol solution of the ethyl orthosilicate of 0.5-3mL volumetric concentration 10% then, 300 ℃-500 ℃ calcinings 2 hours, obtains said palladium composite catalyst.
According to the specific embodiment of the present invention; Preferably; Said Pd particle solution can prepare through following preparation method: the softex kw, citric acid and the tetrachloro palladium sodium that with mass ratio are 7: 39: 1 mix with deionized water (consumption of deionized water is as the criterion reacting smoothly); Refluxed 2 hours at 90 ℃, prepare said Pd particle solution.Wherein, said Pd particle solution is to be the Pd particle solution of part with the softex kw.
According to the specific embodiment of the present invention, preferably, the SiO of said functional amido
2Bead solution can prepare through following preparation method: is ammoniacal liquor, 100mL absolute ethyl alcohol and the mixing of 7mL deionized water of 28wt% with 6.2mL ethyl orthosilicate, 6.5mL concentration; At room temperature stirred 15 hours; Use deionized water and washing with alcohol respectively, prepare SiO
2Bead; With the said SiO of 1-3g
2Bead is distributed in the 100mL isopropyl alcohol, adds 3-triethoxysilyl-1-propylamine of 1-3mL again, and heating is 2 hours under 60-80 ℃ of stirring condition, obtains the SiO of said functional amido
2Bead solution.
The palladium composite catalyst of high-temperature thermal stability provided by the invention, it is with SiO
2Bead is a carrier, and the Pd particle is an active component, at a SiO
2The a plurality of catalytic active center Pd of bead area load nano particle forms the SiO that load has the Pd nano particle
2Bead makes catalyst have high catalytic activity; And make the mesoporous silicon oxide shell be wrapped in the SiO that above-mentioned load has the Pd nano particle
2The outer surface of bead forms the SiO that the Pd particle is arranged with load
2Bead is core, with mesoporous SiO
2Nucleocapsid structure for shell.The introducing of mesoporous silicon oxide shell, prevent that Pd particle size that Yin Gaowen causes from changing or the Pd particle from SiO
2Come off on the bead carrier.Therefore, the mesoporous silicon oxide shell can effectively be protected the Pd nano particle, can improve the heat endurance of catalytic active center Pd nano particle.
The present invention also provides a kind of preparation method of palladium composite catalyst of above-mentioned high-temperature thermal stability, and it may further comprise the steps:
SiO with Pd particle solution and functional amido
2Bead solution joins in the deionized water (consumption of deionized water is as the criterion reacting smoothly), wherein, and the SiO of Pd particle and functional amido
2The mass ratio of bead is 1: 15, and sonicated 3-10 minute, solution kept static 10-30 minute afterwards, utilizes after deionized water washs product, and product is dispersed in the deionized water, obtains the SiO that load has the Pd particle
2The solution of bead;
The SiO that above-mentioned load is had the Pd particle
2The solution of bead is distributed in the deionized water (consumption of deionized water is as the criterion reacting smoothly), and wherein, load has the SiO of Pd particle
2The content of bead is 0.03-0.05mmol, adjusts pH value of solution value to 11, adds the methanol solution of the ethyl orthosilicate of 0.5-3mL volumetric concentration 10% then, 300 ℃-500 ℃ calcinings 2 hours, obtains said palladium composite catalyst.
In above-mentioned preparation method; Preferably; The preparation method of said Pd particle solution may further comprise the steps: the softex kw, citric acid and the tetrachloro palladium sodium that with mass ratio are 7: 39: 1 mix with deionized water (consumption of deionized water is as the criterion reacting smoothly); Refluxed 2 hours at 90 ℃, prepare said Pd particle solution.Wherein, said Pd particle solution is to be the Pd particle solution of part with the softex kw.
In above-mentioned preparation method, preferably, the SiO of said functional amido
2The preparation method of bead solution may further comprise the steps: be ammoniacal liquor, 100mL absolute ethyl alcohol and the mixing of 7mL deionized water of 28wt% with 6.2mL ethyl orthosilicate, 6.5mL concentration; At room temperature stirred 15 hours; Use deionized water and washing with alcohol respectively, prepare SiO
2Bead; With the said SiO of 1-3g
2Bead is distributed in the 100mL isopropyl alcohol, adds 3-triethoxysilyl-1-propylamine of 1-3mL again, and heating is 2 hours under 60-80 ℃ of stirring condition, obtains the SiO of said functional amido
2Bead solution.
In above-mentioned preparation method, load there is the SiO of Pd particle
2After the solution of bead is distributed in the deionized water, can adopt sodium hydroxide solution adjustment pH value of solution value to 11, under the prerequisite that can react smoothly, those skilled in the art can according to circumstances select the concentration of sodium hydroxide solution.
The palladium method for preparing composite catalyst of high-temperature thermal stability provided by the invention adopts the process of multistep self assembly.At SiO
2The bead area load is a plurality of to be the Pd nano particle of part with softex kw (CTAB), forms the SiO that load has the Pd nano particle
2Bead is then at its outer surface parcel SiO
2Shell.300 ℃-500 ℃ the calcining 2 hours, remove template CTAB after, directly form mesoporous SiO in the catalyst pellets sub-surface
2Shell need not extra adding template, promptly prepares the SiO that the Pd particle is arranged with load
2Bead is core, with mesoporous SiO
2Catalyst core shell particles for shell.
The palladium composite catalyst that the present invention also provides above-mentioned high-temperature thermal stability is oxidized to the application in the reaction of carbon dioxide at carbon monoxide.
The palladium composite catalyst of high-temperature thermal stability of the present invention is fit to the reaction that the high temperature carbon monoxide is oxidized to carbon dioxide, and promptly under 200-500 ℃ of reaction condition, catalytic active center Pd nano particle still is fixed on SiO
2In the shell, catalytic activity preferably is provided.After palladium composite catalyst of the present invention used 10 circulations, conversion ratio remained unchanged basically.Therefore, palladium composite catalyst of the present invention is applicable to the pyroreaction of severe reaction conditions, has high high-temp stability.
The defective unstable to the noble metal nano catalyst, that the life-span is short the invention provides a kind of palladium composite catalyst of high-temperature thermal stability, and it is for there being the SiO of Pd particle with load
2Bead is core, with mesoporous SiO
2Core-shell particles for shell.The present invention adopts a plurality of Pd nano particles to be wrapped in the mesoporous silicon oxide shell, has improved activity of such catalysts.Under the pyroreaction condition, the mesoporous silicon oxide shell has been protected Pd nano particle effectively, avoids Pd nano particle change in size that Yin Gaowen causes or comes off and lose catalytic activity from silica bead carrier surface.Therefore, palladium composite catalyst of the present invention has high catalytic activity, high high-temp stability reaches the characteristics that repeatedly recycle.
Description of drawings
Fig. 1 is the temperature variant curve of conversion ratio of palladium composite catalyst catalysis carbon monoxide oxidation reaction of palladium composite catalyst and the Comparative Examples of embodiment.
Fig. 2 is the curve that the conversion ratio of palladium composite catalyst catalysis carbon monoxide oxidation reaction of palladium composite catalyst and the Comparative Examples of embodiment changes with the reaction cycle number of times.
Fig. 3 A is the transmission electron microscope photo of the palladium composite catalyst of Comparative Examples.
Fig. 3 B is the transmission electron microscope photo of the palladium composite catalyst of embodiment.
The specific embodiment
Embodiment
Present embodiment provides a kind of palladium composite catalyst, and it is for there being the SiO of Pd particle with load
2Bead is core, with mesoporous SiO
2Core-shell particles for shell.This Preparation of catalysts method may further comprise the steps:
(1) is ammoniacal liquor, 100mL absolute ethyl alcohol and the mixing of 7mL deionized water of 28wt% with 6.2mL ethyl orthosilicate, 6.5mL concentration, at room temperature stirred 15 hours, respectively wash 2 times with deionized water and ethanol respectively, prepare the SiO that diameter is 200-300nm
2Bead;
(2) 0.05g softex kw (CTAB), 0.275g citric acid, 0.007g tetrachloro palladium sodium, 16mL deionized water are blended in the three-necked bottle of 25mL, reflux 2 hours at 90 ℃, prepare the Pd nano-particle solution.
(3) with the above-mentioned SiO of 1g
2Bead is distributed in the 100mL isopropyl alcohol, adds 3mL 3-triethoxysilyl-1-propylamine again, and 80 ℃ of stirring conditions heated 2 hours down, prepared the SiO of functional amido
2Bead solution;
(4) with the SiO of the above-mentioned functional amido of 1mL
2The above-mentioned Pd nano-particle solution of bead solution and 15mL joins in the 75mL deionized water; Sonicated 3 minutes; Solution kept static 10 minutes afterwards, obtained product after the filtration, utilized deionized water to after the product washing 3 times; Product is dispersed in the 8mL deionized water, obtains the SiO that load has the Pd particle
2The solution of bead;
(5) the above-mentioned load of 5ml there is the SiO of Pd particle
2The aqueous solution of bead is distributed in the 30ml deionized water; Add sodium hydroxide solution and regulate pH value to 11, add the 0.9ml volumetric concentration then and be the methanol solution of 10% ethyl orthosilicate (TEOS), after the filtration; In Muffle furnace, calcined 2 hours for 400 ℃, obtain said palladium composite catalyst.
The transmission electron microscope photo of the palladium composite catalyst that present embodiment provides is shown in Fig. 3 B.
Comparative Examples
This Comparative Examples provides a kind of palladium composite catalyst, and it is SiO
2The load of bead carrier surface is a plurality of to be the catalyst of the Pd particle of part with CTAB.This Preparation of catalysts method is with step (1)-(4) of embodiment.
The transmission electron microscope photo of the palladium composite catalyst that this Comparative Examples provides is shown in Fig. 3 A.
Catalyst performance evaluation
The palladium composite catalyst that embodiment and Comparative Examples are provided is applied to the reaction that the carbon monoxide oxidation forms carbon dioxide.The carbon monoxide oxidation reaction is indoor at ultrahigh vacuum, carries out under the excessive condition of oxygen.With 20mg palladium composite catalyst and 40torr carbon monoxide, 100torr oxygen and balance gas 620torr helium mix are reacted in the 320-500 ℃ of temperature range.Under different reaction temperatures, calculate the conversion ratio of this reaction, experimental result is as shown in Figure 1.The palladium composite catalyst that embodiment and Comparative Examples are provided uses 10 circulations, calculates the conversion ratio of each reaction, and experimental result is as shown in Figure 2.
Fig. 1 has shown the activity of the palladium composite catalyst high-temperature catalytic carbon monoxide oxidation reaction that embodiment and Comparative Examples provide.Along with variation of temperature, embodiment different variation tendencies occurs with the conversion ratio of the reaction of the palladium composite catalyst institute catalysis of Comparative Examples.The palladium composite catalyst of embodiment and Comparative Examples all can make the carbon monoxide oxidation reach 99% conversion ratio.This is illustrated in the palladium composite catalyst of embodiment, and the mesoporous silicon oxide shell makes CO gas fully contact with Pd metal catalytic active component, and its catalytic activity does not reduce because of the introducing of mesoporous silicon oxide shell.But the palladium composite catalyst of embodiment reaches the required temperature of this conversion ratio is about 420 ℃, is about 460 ℃ and the palladium composite catalyst of Comparative Examples is temperature required, and therefore, it is lower that the palladium composite catalyst of embodiment reaches the required temperature of identical conversion ratio.Fig. 2 is the curve that the conversion ratio of the palladium composite catalyst catalysis carbon monoxide oxidation reaction of embodiment and Comparative Examples changes with the reaction cycle number of times.After the palladium composite catalyst of embodiment used 10 circulations, conversion ratio remained unchanged basically, and after 10 circulations of the palladium composite catalyst of Comparative Examples use, conversion ratio significantly reduces.This is illustrated in the palladium composite catalyst of embodiment, and the mesoporous silicon oxide shell has been protected Pd nano particle effectively, makes it under hot environment, keep catalytic activity.Therefore, the palladium composite catalyst of embodiment has high catalytic activity, high high-temp stability, and it can repeatedly be recycled.
Claims (12)
1. the palladium composite catalyst of a high-temperature thermal stability, it is for there being the SiO of Pd particle with load
2Bead is core, with mesoporous SiO
2Core-shell particles for shell.
2. catalyst as claimed in claim 1, wherein, said SiO
2The diameter of bead is 200-300nm.
3. catalyst as claimed in claim 1, wherein, with said SiO
2The quality of bead is a benchmark, and the content of said Pd particle is 2-5%.
4. like claim 1 or 3 described catalyst, wherein, the particle diameter of said Pd particle is 5-10nm.
5. catalyst as claimed in claim 1, wherein, with all SiO in the said catalyst core shell particles
2Quality be benchmark, said SiO
2The content of shell is 15-25%.
6. like claim 1 or 5 described catalyst, wherein, said SiO
2The aperture of shell is 2-5nm.
7. catalyst as claimed in claim 1, wherein, the diameter of said core-shell particles is 270-330nm.
8. like each described catalyst of claim 1-7, it prepares through following preparation method:
To be the SiO of the Pd particle load of part with the softex kw to functional amido
2On the bead, obtain the SiO that load has the Pd particle
2Bead;
The SiO that said load is had the Pd particle
2Bead mixes with ethyl orthosilicate, is template with the softex kw part of Pd particle surface, after calcining, removes template, directly forms mesoporous SiO
2Shell obtains said palladium composite catalyst.
9. the preparation method of the palladium composite catalyst of each described high-temperature thermal stability of claim 1-8, it may further comprise the steps:
SiO with Pd particle solution and functional amido
2Bead solution joins in the deionized water, wherein, and the SiO of Pd particle and functional amido
2The mass ratio of bead is 1: 15, and sonicated 3-10 minute, solution kept static 10-30 minute afterwards, utilizes after deionized water washs product, and product is dispersed in the deionized water, obtains the SiO that load has the Pd particle
2The solution of bead;
The SiO that above-mentioned load is had the Pd particle
2The solution of bead is distributed in the deionized water, and wherein, load has the SiO of Pd particle
2The content of bead is 0.03-0.05mmol, adjusts pH value of solution value to 11, adds the methanol solution of the ethyl orthosilicate of 0.5-3mL volumetric concentration 10% then, 300 ℃-500 ℃ calcinings 2 hours, obtains said palladium composite catalyst.
10. preparation method as claimed in claim 9, wherein, the preparation method of said Pd particle solution may further comprise the steps:
With mass ratio is that 7: 39: 1 softex kw, citric acid and tetrachloro palladium sodium mixes with deionized water, refluxes 2 hours at 90 ℃, prepares said Pd particle solution.
11. preparation method as claimed in claim 9, wherein, the SiO of said functional amido
2The preparation method of bead solution may further comprise the steps:
With 6.2mL ethyl orthosilicate, 6.5mL concentration is ammoniacal liquor, 100mL absolute ethyl alcohol and the mixing of 7mL deionized water of 28wt%, at room temperature stirs 15 hours, uses deionized water and washing with alcohol respectively, prepares SiO
2Bead;
With the said SiO of 1-3g
2Bead is distributed in the 100mL isopropyl alcohol, adds 3-triethoxysilyl-1-propylamine of 1-3mL again, and heating is 2 hours under 60-80 ℃ of stirring condition, obtains the SiO of said functional amido
2Bead solution.
12. each described palladium composite catalyst of claim 1-8 is oxidized to the application in the reaction of carbon dioxide at carbon monoxide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920491A (en) * | 2014-03-05 | 2014-07-16 | 上海师范大学 | Yolk-eggshell structured catalyst and preparation method and application thereof |
| WO2015161701A1 (en) * | 2014-04-22 | 2015-10-29 | 武汉凯迪工程技术研究总院有限公司 | Cobalt-based fischer-tropsch synthesis catalyst coated with mesoporous materials and preparation method therefor |
| CN107774246A (en) * | 2017-09-29 | 2018-03-09 | 兰州大学 | The preparation method and applications of loaded palladium catalyst in a kind of hollow nanometer capsule core |
| CN115181059A (en) * | 2022-07-18 | 2022-10-14 | 苏州诚和医药化学有限公司 | Production process of 3-methyl-4-oxo piperidine-1-carboxylic ester |
-
2012
- 2012-09-12 CN CN201210337001.6A patent/CN102836706B/en active Active
Non-Patent Citations (4)
| Title |
|---|
| 《Journal of Materials Chemistry》 20100806 Yanfei Wang et al. "Silica nanosphere-supported shaped Pd nanoparticles encapsulated with nanoporous silica shell: Efficient and recyclable nanocatalysts" 第7834、7835、7840页 1-12 第20卷, * |
| YANFEI WANG ET AL.: ""Silica nanosphere-supported shaped Pd nanoparticles encapsulated with nanoporous silica shell: Efficient and recyclable nanocatalysts"", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| YANFEI WANG ET AL.: ""Silica nanosphere-supported shaped Pd nanoparticles encapsulated with nanoporous silica shell: Efficient and recyclable nanocatalysts"", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 20, 6 August 2010 (2010-08-06) * |
| 吴天斌等: ""介孔SiO2负载和包覆的纳米金属颗粒的制备与研究"", 《中国材料进展》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103920491A (en) * | 2014-03-05 | 2014-07-16 | 上海师范大学 | Yolk-eggshell structured catalyst and preparation method and application thereof |
| CN103920491B (en) * | 2014-03-05 | 2016-03-30 | 上海师范大学 | A kind of Catalysts and its preparation method and purposes with yolk-eggshell structure |
| WO2015161701A1 (en) * | 2014-04-22 | 2015-10-29 | 武汉凯迪工程技术研究总院有限公司 | Cobalt-based fischer-tropsch synthesis catalyst coated with mesoporous materials and preparation method therefor |
| JP2017521227A (en) * | 2014-04-22 | 2017-08-03 | 武▲漢凱▼迪工程技▲術▼研究▲総▼院有限公司 | Mesoporous material-coated cobalt-based Fischer-Tropsch synthesis catalyst and preparation method thereof |
| RU2642451C1 (en) * | 2014-04-22 | 2018-01-25 | Ухань Кайди Инджиниринг Текнолоджи Рисерч Инститьют Ко., Лтд. | Catalyst of fisher-tropsh synthesis based on cobalt covered with mesoporous materials and method of its production |
| CN107774246A (en) * | 2017-09-29 | 2018-03-09 | 兰州大学 | The preparation method and applications of loaded palladium catalyst in a kind of hollow nanometer capsule core |
| CN107774246B (en) * | 2017-09-29 | 2020-01-14 | 兰州大学 | Preparation method and application of hollow mesoporous silicon nanocapsule core supported palladium catalyst |
| CN115181059A (en) * | 2022-07-18 | 2022-10-14 | 苏州诚和医药化学有限公司 | Production process of 3-methyl-4-oxo piperidine-1-carboxylic ester |
| CN115181059B (en) * | 2022-07-18 | 2023-10-20 | 苏州诚和医药化学有限公司 | Process for producing 3-methyl-4-oxo piperidine-1-carboxylic acid ester |
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