CN107442160A - A kind of preparation method of anti-sintering loading type Pd base catalysis material - Google Patents
A kind of preparation method of anti-sintering loading type Pd base catalysis material Download PDFInfo
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- CN107442160A CN107442160A CN201710517120.2A CN201710517120A CN107442160A CN 107442160 A CN107442160 A CN 107442160A CN 201710517120 A CN201710517120 A CN 201710517120A CN 107442160 A CN107442160 A CN 107442160A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/22—Noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The present invention relates to catalysis material technology of preparing, it is desirable to provide a kind of preparation method of anti-sintering loading type Pd base catalysis material.Including step：Palladium presoma is dissolved in polar solvent, is then added as the mesoporous zeolite molecular sieve of carrier, the back flow reaction 6~100 hours under the conditions of stirring with 0~150 DEG C, the Pd nano-particles for making to be formed after redox are selectively supported in the duct of mesoporous zeolite；Then filter, after washing solid using the polar solvent, ethanol and deionized water successively, then be dried, obtain anti-sintering loading type Pd base catalysis material.The loading type Pd base catalysis material of the inventive method synthesis has the characteristics that：The most of selectivity of Pd nano-particles is supported in the duct of mesoporous zeolite；Under the conditions of high-temperature process and pyroreaction, Pd nano-particles are not reunited, and have high stability.
Description
Technical field
The invention belongs to catalysis material technology of preparing, more particularly to a kind of preparation of anti-sintering loading type Pd base catalysis material
Method.
Background technology
Supported, heterogeneous catalysis material is very important part in heterogeneous catalysis.Because particle diameter is got under the same terms
The exposure ratio of small then metallic atom is higher, and corresponding catalytic effect is better, so people have developed many strategies and gone to reduce
The particle diameter of nano particle.But smaller nano grain surface can be higher, more easy aggregation easier during the course of the reaction
Sintering forms big nano particle.Noble metal base nano-catalyst is especially particularly, and then causes the activity drop of catalysis material
It is low.If by handling redisperse, certain expense can be produced, is often lost more than gain.Therefore, how high activity loading type is improved
The stability of multinomial catalyst, it is the important topic of heterogeneous catalysis field all the time.
In recent years, scientific research personnel has carried out substantial amounts of work and proposed to be correspondingly improved heterogeneous catalysis stability of material
Strategy.Summary is got up, and their strategy mainly covers nano particle with metal oxide, and it is former to reduce nano grain surface
The sub chance by thermophoresis, and then prevent the sintering of nano particle.It is but such to handle the portion that sacrifice catalyst unavoidably
Divide activity.If nano particle can be placed in mesopore orbit, because the restriction effect in duct makes it be obtained pole by thermophoresis
Big suppression, it is possible to without sacrificing its activity, and simultaneously this rock-steady structure can be kept not to be destroyed.Mesopore molecular sieve is
A kind of aluminosilicate crystal or aluminum phosphate crystals with very high heat endurance and big specific surface area, its it is existing it is mesoporous can
To meet the demand.If can be by the mesopore orbit of the loaded mesoporous zeolite of nano particle, can realization keeping urging
Higher active this purpose is also kept while changing material high stability.Regrettably, this imagination is never preferable
Realization rate.
The content of the invention
The technical problem to be solved in the present invention is to overcome deficiency of the prior art, there is provided a kind of anti-sintering loading type Pd
The preparation method of base catalysis material.
To solve technical problem, solution of the invention is：
A kind of preparation method of anti-sintering loading type Pd base catalysis material is provided, comprised the following steps：
Palladium presoma is dissolved in polar solvent, is then added as the mesopore molecular sieve of carrier, stirring and 0~
Back flow reaction 6~100 hours under the conditions of 150 DEG C, the Pd nano-particles for making to be formed after redox are selectively supported on mesoporous
In the duct of zeolite；Then filter, after washing solid using the polar solvent, ethanol and deionized water successively, then done
It is dry, obtain anti-sintering loading type Pd base catalysis material；
The polar solvent is any one in dichloromethane, chloroform or 1,2- dichloroethanes；
In the mixed solution of palladium presoma and polar solvent, Pd concentration range is 0.01~10mmol/L；Per 50ml
0.1~10g mesopore molecular sieves are added in mixed solution.
In the present invention, the palladium presoma is the organic ligand Pd sources for having reproducibility, is palladium or palladium acetylacetonate
In one kind.
In the present invention, the mesoporous zeolite is the Si-Al molecular sieve containing equivalance pore structure, is mesoporous Y molecular sieve, mesoporous
Any one in Beta molecular sieves, mesoporous ZSM-5 molecular sieve or mesoporous MOR molecular sieves.
In the present invention, its aperture (diameter) of catalysis material prepared is in 6nm or so.
Inventive principle describes：
Pd presoma is dissolved in polar solvent by the present invention, adds mesoporous zeolite stirring, and the oxygen of body is derived from by palladium
Change reduction and the mesoporous enrichment to Pd presomas of mesoporous zeolite, finally give oriented load and be situated between in mesoporous zeolite
In hole, there is the loading type Pd@mesoporous zeolite catalysis materials of high temperature anti-sintering property.
In the preparation process of conventional load type metal catalytic material, its distribution of activated centre metal on carrier is random
, after high-temperature process or experience pyroreaction, the metal nanoparticle in activated centre will inevitably occur
Migration and reunion, and then greatly influence its reactivity.And the present invention dexterously utilizes the mesoporous offer one of mesoporous zeolite
The environment of polarity assembles the Pd presomas in solution, is allowed to optionally be distributed on carrier zeolite, then by presoma have
The machine anion reduction of itself, the metal nanoparticle of oriented load is formed at the mesoporous position of mesoporous zeolite, there is Jie
When the iris action in hole, high-temperature process and pyroreaction, the metal nanoparticle in activated centre will confinement in mesoporous inside,
Do not reunite, so as to have higher stability.
Compared with prior art, the beneficial effects of the present invention are：
The loading type Pd base catalysis material of the inventive method synthesis has the characteristics that：
(1) the most of selectivity of Pd nano-particles is supported in the duct of mesoporous zeolite；
(2) under the conditions of high-temperature process and pyroreaction, Pd nano-particles are not reunited, and have high stability.
Brief description of the drawings
Fig. 1 is the high power transmission electron microscope picture (HRTEM) of sample；
Fig. 2 is X-ray diffraction (XRD) phenogram of sample；
Fig. 3 is the transmission electron microscope picture (TEM) of (b) after high-temperature sample before processing (a) and processing；
Fig. 4 is sample N2Adsorption isotherm；
Fig. 5 is the transmission electron microscope picture (TEM) of sample；
Fig. 6 is X-ray diffraction (XRD) phenogram of sample；
Fig. 7 is the nano particle diameter distribution map of sample.
Fig. 8 is the transmission electron microscope picture (TEM) of the reacted Pd/Y catalyst of CO.
Fig. 9 is the reacted Pd@Y catalyst transmission electron microscope pictures (TEM) of CO.
Figure 10 is the catalytic activity changing trend diagram of Pd/Y and Pd@Y catalyst after CO reactions.
Embodiment
Relevant content is stated in detail below by way of specific embodiment.
Embodiment 1
The mesoporous Y molecular sieves of 5g are added in the dichloromethane solution of 50mL (1mmol/L) palladium, and are stirred at 50 DEG C
Mix backflow 48h.Then filter, successively wash obtained solid with substantial amounts of dichloromethane, ethanol and deionized water, further do
Pd@Y catalysis materials are obtained after dry processing.Material passes through transmission electron microscope observing pattern (Fig. 1).
Embodiment 2
The mesoporous Y molecular sieves of 0.1g are added in 1, the 2- dichloroethane solutions of 50ml (0.5mmol/L) palladium acetylacetonate,
And it is stirred at reflux 6h at 80 DEG C.Then filter, successively wash to obtain with substantial amounts of 1,2- dichloroethanes, ethanol and deionized water
Solid, be further dried processing after obtain Pd@Y catalysis materials.The XRD of material, which is characterized, sees Fig. 2.
Embodiment 3
The mesoporous Y molecular sieves of 0.5g are added in the dichloromethane solution of 50ml (2mmol/L) palladium, and at 25 DEG C
It is stirred at reflux 48h.Then filter, successively wash obtained solid with substantial amounts of dichloromethane, ethanol and deionized water, further
Pd@Y catalysis materials are obtained after drying process.Its transmission electron microscope picture before and after 600 DEG C of high-temperature calcinations see Fig. 3 (a calcining before, b
After calcining), it can be seen that its Pd Nanoparticle Size is basically unchanged.
Embodiment 4
The mesoporous Y molecular sieves of 2g are added in the dichloromethane solution of 50ml (5mmol/L) palladium, and at 150 DEG C
It is stirred at reflux 16h.Then filter, successively wash obtained solid with substantial amounts of dichloromethane, ethanol and deionized water, further
Pd@Y catalysis materials are obtained after drying process.
Embodiment 5
The mesoporous Y molecular sieves of 2g are added in the chloroform soln of 50ml (5mmol/L) palladium, and are stirred at 50 DEG C
Mix backflow 24h.Then filter, successively wash obtained solid with substantial amounts of chloroform, ethanol and deionized water, further do
Pd@Y catalysis materials are obtained after dry processing.Its N2 adsorption isotherm is shown in Fig. 4
Embodiment 6
The mesoporous Beta molecular sieves of 0.1g are added in the chloroform soln of 50ml (0.5mmol/L) palladium, and 0
24h is stirred at reflux at DEG C.Then filter, successively wash obtained solid with substantial amounts of chloroform, ethanol and deionized water, enter
Pd@Beta catalysis materials are obtained after one step drying process.Material is characterized by transmission electron microscope observing pattern (Fig. 5), the XRD of material
See Fig. 6.
Embodiment 7
The mesoporous ZSM-5 molecular sieves of 1g are added in the chloroform soln of 50ml (5mmol/L) palladium, and 100
100h is stirred at reflux at DEG C.Then filter, successively wash obtained solid with substantial amounts of chloroform, ethanol and deionized water,
Pd@ZSM-5 catalysis materials are obtained after processing is further dried.The XRD of material, which is characterized, sees Fig. 6.
Embodiment 8
The mesoporous MOR molecular sieves of 10g are added in the dichloromethane solution of 50ml (10mmol/L) palladium, and at 50 DEG C
Under be stirred at reflux 80h.Then filter, successively wash obtained solid with substantial amounts of dichloromethane, ethanol and deionized water, enter one
Pd@MOR catalysis materials are obtained after step drying process.
Embodiment 9
The mesoporous Y molecular sieves of 0.5g are added in the dichloromethane solution of 50ml (1mmol/L) palladium, and at 30 DEG C
24h is stirred at reflux, is then filtered.Obtained solid successively is washed with substantial amounts of dichloromethane, ethanol and deionized water, further
Pd@Y catalysis materials are obtained after drying process.The grain size distribution of its Pd nano-particle is shown in Fig. 7.
Embodiment 10
The mesoporous Y molecular sieves of 0.5g are added in the dichloromethane solution of 50ml (0.01mmol/L) palladium, and 30
6h is stirred at reflux at DEG C, is then filtered.Obtained solid successively is washed with substantial amounts of dichloromethane, ethanol and deionized water, is entered
Pd@Y catalysis materials are obtained after one step drying process.
Embodiment 11
Conventional impregnation method prepares Pd/Y type catalyst：Pd precursor palladium nitrates are dissolved in 2mL water, add 1g Y molecules
Sieve, ultrasonic immersing 1h, 80 degree drying, Conventional catalytic material Pd/Y then is arrived by roasting and hydrogen reducing, then by Pd/Y
Handled together with Pd@Y catalysis materials obtained by embodiment 10 by 600 DEG C of high-temperature calcinations, obtained material is subjected to grain
Footpath counts, and obtained data see the table below 1.
Table 1
| Catalysis material | Initial size/nm | After high-temperature process/nm |
| Pd/Y | 3.6 | 17.4 |
| Pd@Y | 3.7 | 4.1 |
Embodiment 12
Pd/Y and Pd@Y in embodiment 11 are used for CO oxidation reactions, after 450 DEG C of pyroreactions 30 hours, taken
Go out catalyst, carry out TEM transmission signs and observe its particle size, as a result as shown in Figure 8 and Figure 9.And two kinds of materials are at 190 DEG C
Catalytic activity variation tendency is shown in Figure 10.
Claims (3)
1. a kind of preparation method of anti-sintering loading type Pd base catalysis material, it is characterised in that comprise the following steps：
Palladium presoma is dissolved in polar solvent, is then added as the mesoporous zeolite molecular sieve of carrier, stirring and 0~
Back flow reaction 6~100 hours under the conditions of 150 DEG C, the Pd nano-particles for making to be formed after redox are selectively supported on mesoporous
In the duct of zeolite；Then filter, after washing solid using the polar solvent, ethanol and deionized water successively, then done
It is dry, obtain anti-sintering loading type Pd base catalysis material；
The polar solvent is any one in dichloromethane, chloroform or 1,2- dichloroethanes；
In the mixed solution of palladium presoma and polar solvent, Pd concentration range is 0.01~10mmol/L；Mixed per 50ml
0.1~10g mesopore molecular sieves are added in solution.
2. according to the method for claim 1, it is characterised in that the palladium presoma is the organic ligand Pd for having reproducibility
Source, it is one kind in palladium or palladium acetylacetonate.
3. according to the method for claim 1, it is characterised in that the mesoporous zeolite is the sial boiling containing equivalance pore structure
Stone molecular sieve, it is any in mesoporous Y molecular sieve, mesoporous Beta molecular sieves, mesoporous ZSM-5 molecular sieve or mesoporous MOR molecular sieves
It is a kind of.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111215122A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Palladium-based methane catalytic combustion catalyst, preparation and application |
| CN112023977A (en) * | 2020-08-17 | 2020-12-04 | 西安交通大学 | Y-type molecular sieve packaged platinum group noble metal nanoparticle catalyst and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211037A (en) * | 2011-04-13 | 2011-10-12 | 浙江大学 | New method for preparing supported gold catalyst with anti-sintering property |
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- 2017-06-29 CN CN201710517120.2A patent/CN107442160B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211037A (en) * | 2011-04-13 | 2011-10-12 | 浙江大学 | New method for preparing supported gold catalyst with anti-sintering property |
Non-Patent Citations (1)
| Title |
|---|
| HAI-BO WANG 等: "Palladium immobilized in the nanocages of SBA-16: An efficient and recyclable catalyst for Suzuki coupling reaction", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111215122A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Palladium-based methane catalytic combustion catalyst, preparation and application |
| CN111215122B (en) * | 2018-11-26 | 2023-02-03 | 中国科学院大连化学物理研究所 | Palladium-based methane catalytic combustion catalyst, preparation and application |
| CN112023977A (en) * | 2020-08-17 | 2020-12-04 | 西安交通大学 | Y-type molecular sieve packaged platinum group noble metal nanoparticle catalyst and preparation method thereof |
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