CN102836706B - 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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- CN102836706B CN102836706B CN201210337001.6A CN201210337001A CN102836706B CN 102836706 B CN102836706 B CN 102836706B CN 201210337001 A CN201210337001 A CN 201210337001A CN 102836706 B CN102836706 B CN 102836706B
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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
Palladium composite catalyst that the present invention relates to a kind of high-temperature thermal stability and preparation method thereof and application, belong to the noble metal catalyst technical field in material science.
Background technology
The multiple useful chemical reaction of palladium composite catalyst energy catalysis and have the advantages that easily reclaim, is thus paid close attention to widely.Pd nano particle shows the pattern catalytic activity relevant with size in many reactions, is the most frequently used catalysis primitive.And Pd nano particle load is conventional effective heterogeneous catalyst on a solid support.When Pd nano particle surface is without part or stabilizing agent protection, there is exposed active sites, there is the highest catalytic activity.But if without part and stabilizing agent protection, the high surface energy atom of nanoparticle surface is easily gathered into body phase material, and nano particle is difficult to keep stable state.Therefore, due to the impact of surface ligand, metal nanoparticle can not obtain the highest catalytic activity and selective.Especially, without the parcel of strong part, under Pd nano particle pyroreaction condition, easy size change is gathered into greatly palladium precipitation and loses intrinsic catalytic activity.Therefore, the heat-staple Pd nano particle composite catalyst without part parcel developing high catalytic activity is still important challenge.
Higher catalytic activity and heat endurance can also be had when wrapping up without part to make Pd nano particle, the method of usual employing makes Pd nano particle by inorganic shell (such as: silicon, carbon and metal oxide etc.) parcel, this shell plays the effect preventing Pd nano particle from assembling.This metal Core-shell structure material is realized by two-step synthetic method, comprises and prepares metal nanoparticle, deposits inorganic shell subsequently in surfaces of metal nanoparticles.At present, the most frequently used means are that Pd nano particle is wrapped in mesoporous silicon oxide shell.But the palladium composite catalyst of these nucleocapsid structures has many Size Distribution or the problem of each nucleocapsid structure only containing 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 higher catalytic activity, heat endurance and can repeatedly recycling.
The present invention also aims to preparation method and the application of the palladium composite catalyst that above-mentioned high-temperature thermal stability is provided.
For reaching above-mentioned purpose, the invention provides a kind of palladium composite catalyst of high-temperature thermal stability, it is the SiO having Pd particle with load
2bead is core, with mesoporous SiO
2for the core-shell particles of shell.
According to the specific embodiment of the present invention, preferably, in above-mentioned catalyst, described SiO
2the diameter of bead is 200-300nm.
According to the specific embodiment of the present invention, preferably, in above-mentioned catalyst, with described SiO
2the quality of bead is benchmark, and the content of described Pd particle is 2-5%.
According to the specific embodiment of the present invention, preferably, in above-mentioned catalyst, the particle diameter of described Pd particle is 5-10nm.
According to the specific embodiment of the present invention, preferably, in above-mentioned catalyst, with all SiO in described catalyst core shell particles
2quality be benchmark, described SiO
2the content of shell is 15-25%.
According to the specific embodiment of the present invention, preferably, in above-mentioned catalyst, described 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 described core-shell particles is 270-330nm.
According to the specific embodiment of the present invention, preferably, described catalyst is prepared by following preparation method:
To take softex kw as the SiO of Pd particle load to functional amido of part
2on bead, obtain the SiO that load has Pd particle
2bead;
Described load there is the SiO of Pd particle
2bead mixes with ethyl orthosilicate, and with the softex kw part of Pd particle surface for template, after calcining, removing template, directly forms mesoporous SiO
2shell, forms described catalyst.
More specifically, described catalyst can be prepared by following preparation method:
By the SiO of Pd particle solution and functional amido
2bead solution joins in deionized water (consumption of deionized water is as the criterion can carry out reaction smoothly), wherein, and the SiO of Pd particle and functional amido
2the mass ratio of bead is 1: 15, ultrasonic process 3-10 minute, and solution keeps static 10-30 minute afterwards, utilizes after deionized water washs product, by product dispersion in deionized water, obtains the SiO that load has Pd particle
2the solution of bead;
Above-mentioned load there is the SiO of Pd particle
2the Solution Dispersion of bead is in deionized water (consumption of deionized water is as the criterion can carry out reaction smoothly), and wherein, load has the SiO of Pd particle
2the content of bead is 0.03-0.05mmol, and adjustment solution ph to 11, then adds the methanol solution of the ethyl orthosilicate of 0.5-3mL volumetric concentration 10%, 300 DEG C-500 DEG C calcinings 2 hours, obtains described palladium composite catalyst.
According to the specific embodiment of the present invention, preferably, described Pd particle solution can be prepared by following preparation method: be that the softex kw of 7: 39: 1, citric acid and tetrachloro palladium sodium mix with deionized water (consumption of deionized water is as the criterion can carry out reaction smoothly) by mass ratio, 90 DEG C of backflows 2 hours, prepare described Pd particle solution.Wherein, described Pd particle solution take softex kw as the Pd particle solution of part.
According to the specific embodiment of the present invention, preferably, the SiO of described functional amido
2bead solution can be prepared by following preparation method: be the ammoniacal liquor of 28wt%, 100mL absolute ethyl alcohol and the mixing of 7mL deionized water by 6.2mL ethyl orthosilicate, 6.5mL concentration, at room temperature stir 15 hours, respectively with deionized water and ethanol washing, prepare SiO
2bead; By SiO described in 1-3g
2bead is distributed in 100mL isopropyl alcohol, then adds the 3-triethoxysilyl-1-propylamine of 1-3mL, heats 2 hours, obtain the SiO of described functional amido under 60-80 DEG C of stirring condition
2bead solution.
The palladium composite catalyst of high-temperature thermal stability provided by the invention, it is with SiO
2bead is carrier, and Pd particle is active component, at a SiO
2bead surface load multiple catalytic active center Pd nano particle, forms the SiO that load has Pd nano particle
2bead, makes catalyst have high catalytic activity; And mesoporous silicon oxide shell is wrapped in SiO that above-mentioned load has Pd nano particle
2the outer surface of bead, forms the SiO having Pd particle with load
2bead is core, with mesoporous SiO
2for the nucleocapsid structure of shell.The introducing of mesoporous silicon oxide shell, the Pd particle size preventing Yin Gaowen from causing change or Pd particle are from SiO
2bead carrier comes off.Therefore, mesoporous silicon oxide shell can effectively protect 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 comprises the following steps:
By the SiO of Pd particle solution and functional amido
2bead solution joins in deionized water (consumption of deionized water is as the criterion can carry out reaction smoothly), wherein, and the SiO of Pd particle and functional amido
2the mass ratio of bead is 1: 15, ultrasonic process 3-10 minute, and solution keeps static 10-30 minute afterwards, utilizes after deionized water washs product, by product dispersion in deionized water, obtains the SiO that load has Pd particle
2the solution of bead;
Above-mentioned load there is the SiO of Pd particle
2the Solution Dispersion of bead is in deionized water (consumption of deionized water is as the criterion can carry out reaction smoothly), and wherein, load has the SiO of Pd particle
2the content of bead is 0.03-0.05mmol, and adjustment solution ph to 11, then adds the methanol solution of the ethyl orthosilicate of 0.5-3mL volumetric concentration 10%, 300 DEG C-500 DEG C calcinings 2 hours, obtains described palladium composite catalyst.
In above-mentioned preparation method, preferably, the preparation method of described Pd particle solution comprises the following steps: be that the softex kw of 7: 39: 1, citric acid and tetrachloro palladium sodium mix with deionized water (consumption of deionized water is as the criterion can carry out reaction smoothly) by mass ratio, 90 DEG C of backflows 2 hours, prepare described Pd particle solution.Wherein, described Pd particle solution take softex kw as the Pd particle solution of part.
In above-mentioned preparation method, preferably, the SiO of described functional amido
2the preparation method of bead solution comprises the following steps: be the ammoniacal liquor of 28wt%, 100mL absolute ethyl alcohol and the mixing of 7mL deionized water by 6.2mL ethyl orthosilicate, 6.5mL concentration, at room temperature stir 15 hours, respectively with deionized water and ethanol washing, prepare SiO
2bead; By SiO described in 1-3g
2bead is distributed in 100mL isopropyl alcohol, then adds the 3-triethoxysilyl-1-propylamine of 1-3mL, heats 2 hours, obtain the SiO of described functional amido under 60-80 DEG C of stirring condition
2bead solution.
In above-mentioned preparation method, load there is the SiO of Pd particle
2the Solution Dispersion of bead in deionized water after, sodium hydroxide solution can be adopted to adjust solution ph to 11, and under can carrying out the prerequisite of reacting 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 Pd nano particle that bead surface load is multiple is part with softex kw (CTAB), forms the SiO that load has Pd nano particle
2bead, then at its outer surface parcel SiO
2shell.300 DEG C-500 DEG C calcinings 2 hours, after removing template CTAB, directly form mesoporous SiO in catalyst pellets sub-surface
2shell, without the need to additionally adding template, namely prepares the SiO having Pd particle with load
2bead is core, with mesoporous SiO
2for the catalyst core shell particles of shell.
The present invention also provides the palladium composite catalyst of above-mentioned high-temperature thermal stability to become application in the reaction of carbon dioxide at Oxidation of Carbon Monoxide.
The palladium composite catalyst of high-temperature thermal stability of the present invention is applicable to the reaction that high temperature Oxidation of Carbon Monoxide becomes carbon dioxide, and namely under 200-500 DEG C of reaction condition, catalytic active center Pd nano particle is still fixed on SiO
2in shell, provide good catalytic activity.After palladium composite catalyst of the present invention uses 10 to circulate, conversion ratio remains unchanged substantially.Therefore, palladium composite catalyst of the present invention is applicable to the pyroreaction of severe reaction conditions, has high high-temp stability.
Unstable for noble metal nano catalyst, the defect that the life-span is short, the invention provides a kind of palladium composite catalyst of high-temperature thermal stability, and it is the SiO having Pd particle with load
2bead is core, with mesoporous SiO
2for the core-shell particles of shell.The present invention adopts multiple Pd nano particle to be wrapped in mesoporous silicon oxide shell, improves the activity of catalyst.Under pyroreaction condition, mesoporous silicon oxide shell protects Pd nano particle effectively, the Pd nano particle change in size avoiding Yin Gaowen to cause or come off from silicon oxide pellets carrier surface and lose catalytic activity.Therefore, the palladium composite catalyst of the present invention feature that there is high catalytic activity, high high-temp stability and repeatedly recycle.
Accompanying drawing explanation
Fig. 1 is the temperature variant curve of conversion ratio of the palladium composite catalyst of embodiment and the palladium composite catalyst catalytic CO oxidation reaction of comparative example.
Fig. 2 is the curve that the conversion ratio of the palladium composite catalyst of embodiment and the palladium composite catalyst catalytic CO oxidation reaction of comparative example changes with reaction cycle number of times.
Fig. 3 A is the transmission electron microscope photo of the palladium composite catalyst of comparative example.
Fig. 3 B is the transmission electron microscope photo of the palladium composite catalyst of embodiment.
Detailed description of the invention
Embodiment
The present embodiment provides a kind of palladium composite catalyst, and it is the SiO having Pd particle with load
2bead is core, with mesoporous SiO
2for the core-shell particles of shell.The preparation method of this catalyst comprises the following steps:
(1) be the ammoniacal liquor of 28wt%, 100mL absolute ethyl alcohol and the mixing of 7mL deionized water by 6.2mL ethyl orthosilicate, 6.5mL concentration, at room temperature stir 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, 90 DEG C of backflows 2 hours, prepare Pd nano-particle solution.
(3) by above-mentioned for 1g SiO
2bead is distributed in 100mL isopropyl alcohol, then adds 3mL 3-triethoxysilyl-1-propylamine, heats 2 hours, prepare the SiO of functional amido under 80 DEG C of stirring conditions
2bead solution;
(4) by the SiO of above-mentioned for 1mL functional amido
2bead solution and the above-mentioned Pd nano-particle solution of 15mL join in 75mL deionized water, ultrasonic process 3 minutes, solution keeps static 10 minutes afterwards, product is obtained after filtration, deionized water is utilized to wash after 3 times to product, product is dispersed in 8mL deionized water, obtains the SiO that load has Pd particle
2the solution of bead;
(5) above-mentioned for 5ml load there is the SiO of Pd particle
2the aqueous dispersion of bead is in 30ml deionized water, add sodium hydroxide solution adjust ph to 11, then the methanol solution that 0.9ml volumetric concentration is the ethyl orthosilicate (TEOS) of 10% is added, after filtration, calcine 2 hours for 400 DEG C in Muffle furnace, obtain described palladium composite catalyst.
The transmission electron microscope photo of the palladium composite catalyst that the present embodiment provides as shown in Figure 3 B.
Comparative example
This comparative example provides a kind of palladium composite catalyst, and it is SiO
2the load of bead carrier surface is multiple take CTAB as the catalyst of the Pd particle of part.The preparation method of this catalyst is with step (1)-(4) of embodiment.
The transmission electron microscope photo of the palladium composite catalyst that this comparative example provides as shown in Figure 3A.
Catalyst performance evaluation
Palladium composite catalyst embodiment and comparative example provided is applied to the reaction that Oxidation of Carbon Monoxide forms carbon dioxide.Oxidation of Carbon Monoxide reaction is indoor at ultrahigh vacuum, carries out under oxygen excess conditions.By 20mg palladium composite catalyst and 40torr carbon monoxide, 100torr oxygen and Balance Air 620torr helium mix, react in 320-500 DEG C of temperature range.Under different reaction temperatures, calculate the conversion ratio of this reaction, experimental result as shown in Figure 1.Palladium composite catalyst embodiment and comparative example provided uses 10 to circulate, and calculates the conversion ratio of every secondary response, and experimental result as shown in Figure 2.
The activity that the palladium composite catalyst high-temperature catalytic Oxidation of Carbon Monoxide that Fig. 1 indicates embodiment and comparative example to be provided reacts.Along with the change of temperature, there is different variation tendencies from the conversion ratio of the reaction of the palladium composite catalyst institute catalysis of comparative example in embodiment.The palladium composite catalyst of embodiment and comparative example all can make Oxidation of Carbon Monoxide reach the conversion ratio of 99%.This shows in the palladium composite catalyst of embodiment, and mesoporous silicon oxide shell makes CO gas fully contact with Pd metal catalytic activity component, and its catalytic activity does not reduce because of the introducing of mesoporous silicon oxide shell.But the palladium composite catalyst temperature reached needed for this conversion ratio of embodiment is about 420 DEG C, and the palladium composite catalyst of comparative example is temperature required is about 460 DEG C, and therefore, it is lower that the palladium composite catalyst of embodiment reaches the identical temperature needed for conversion ratio.Fig. 2 is the curve that the conversion ratio of the palladium composite catalyst catalytic CO oxidation reaction of embodiment and comparative example changes with reaction cycle number of times.After the palladium composite catalyst of embodiment uses 10 to circulate, conversion ratio remains unchanged substantially, and after the palladium composite catalyst of comparative example uses 10 to circulate, conversion ratio significantly reduces.This shows that mesoporous silicon oxide shell protects Pd nano particle effectively in the palladium composite catalyst of embodiment, makes it keep catalytic activity in high temperature environments.Therefore, the palladium composite catalyst of embodiment has high catalytic activity, high high-temp stability, makes it repeatedly recycle.
Claims (8)
1. a preparation method for the palladium composite catalyst of high-temperature thermal stability, the palladium composite catalyst of described high-temperature thermal stability is the SiO having Pd particle with load
2bead is core, with mesoporous SiO
2for the core-shell particles of shell, this preparation method comprises the following steps:
By the SiO of Pd particle solution and functional amido
2bead solution joins in deionized water, wherein, and the SiO of Pd particle and functional amido
2the mass ratio of bead is 1:15, ultrasonic process 3-10 minute, and solution keeps static 10-30 minute afterwards, utilizes after deionized water washs product, by product dispersion in deionized water, obtains the SiO that load has Pd particle
2the solution of bead;
Above-mentioned load there is the SiO of Pd particle
2the Solution Dispersion of bead is in deionized water, and wherein, load has the SiO of Pd particle
2the content of bead is 0.03-0.05mmol, and adjustment solution ph to 11, then adds the methanol solution of the ethyl orthosilicate of 0.5-3mL volumetric concentration 10%, 300 DEG C-500 DEG C calcinings 2 hours, obtains described palladium composite catalyst;
Wherein, described Pd particle solution prepares by the following method: be that the softex kw of 7:39:1, citric acid and tetrachloro palladium sodium mix with deionized water by mass ratio, 90 DEG C of backflows 2 hours, prepares described Pd particle solution.
2. preparation method as claimed in claim 1, wherein, the SiO of described functional amido
2the preparation method of bead solution comprises the following steps:
Be the ammoniacal liquor of 28wt%, 100mL absolute ethyl alcohol and the mixing of 7mL deionized water by 6.2mL ethyl orthosilicate, 6.5mL concentration, at room temperature stir 15 hours, respectively with deionized water and ethanol washing, prepare SiO
2bead;
By SiO described in 1-3g
2bead is distributed in 100mL isopropyl alcohol, then adds the 3-triethoxysilyl-1-propylamine of 1-3mL, heats 2 hours, obtain the SiO of described functional amido under 60-80 DEG C of stirring condition
2bead solution.
3. preparation method as claimed in claim 1, wherein, described SiO
2the diameter of bead is 200-300nm.
4. preparation method as claimed in claim 1, wherein, with described SiO
2the quality of bead is benchmark, and the content of described Pd particle is 2-5%.
5. the preparation method as described in claim 1 or 4, wherein, the particle diameter of described Pd particle is 5-10nm.
6. preparation method as claimed in claim 1, wherein, with all SiO in described catalyst core shell particles
2quality be benchmark, described SiO
2the content of shell is 15-25%.
7. the preparation method as described in claim 1 or 6, wherein, described SiO
2the aperture of shell is 2-5nm.
8. preparation method as claimed in claim 1, wherein, the diameter of described core-shell particles is 270-330nm.
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| CN103920496B (en) * | 2014-04-22 | 2015-11-18 | 武汉凯迪工程技术研究总院有限公司 | Mesoporous material clad type Co based Fischer-Tropsch synthesis catalyst and preparation method thereof |
| 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 |
| 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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| "Silica nanosphere-supported shaped Pd nanoparticles encapsulated with nanoporous silica shell: Efficient and recyclable nanocatalysts";Yanfei Wang et al.;《Journal of Materials Chemistry》;20100806;第20卷;第7834、7835、7840页 * |
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