CN104056657A - Hierarchical pore SnO2/ZSM-5 alcohol fuel battery anode catalyst and preparation method thereof - Google Patents
Hierarchical pore SnO2/ZSM-5 alcohol fuel battery anode catalyst and preparation method thereof Download PDFInfo
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- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a hierarchical pore SnO2/ZSM-5 alcohol fuel battery anode catalyst and a preparation method thereof. A SnO2/mesoporous zeolite material is provided with crystallized porous walls, and the surface of the SnO2/mesoporous zeolite material is uniformly loaded with SnO2 crystallized nano particles.
Description
Technical field
The present invention relates to a kind of methanol fuel cell anode catalyzer and preparation method thereof, be specifically related to a kind of multi-stage porous (mesoporous) zeolite that can serve as methanol fuel cell anode catalyzer and preparation method thereof.
Background technology
In polymer film low-temperature fuel cell, DMFC (DMFCs) taking methyl alcohol as fuel is the most promising TRT, have advantages of that methyl alcohol source is abundant, low price, be easy to carry about with one and store, be particularly suitable for the removable electrical source of power as various uses.Therefore, DMFCs causes worldwide extensive concern.The at present study hotspot of DMFC, be also its apply middle need the major technique difficulty that solves it-, seek exactly efficient methanol electrooxidation catalyst, improve the speed of methanol oxidation, reduce the polarization of anode.
Domestic and international reported DMFCs anode catalyst material at present, is to be substantially all main noble metal catalyst with platinum metal (as Pt, Au, Ph, Pd, Ru etc.), and such noble metal catalyst has high catalytic activity to the electrochemical oxidation of methyl alcohol.But noble metal catalyst, particularly Pt very easily adsorb intermediate product CO in the progressively dehydrogenation oxidation process of methyl alcohol
-ads, this CO
-adsa large amount of absorption of species can cover the active site of Pt catalyst, and CO " poisoning " phenomenon of Pt catalyst occurs, thereby cause the inactivation of Pt catalyst.For fear of CO " poisoning " phenomenon of Pt catalyst, PtRu binary, PtRuW or PtRuMo ternary alloy catalyst are developed out again, and wherein PtRu bianry alloy catalyst is the most effective anti-CO anode catalyst.But PtRu is noble metal, expensive, greatly hinder the large-scale commercial application of DMFCs.Develop the anti-CO anode catalyst of high performance novel non-noble metal, in keeping high catalytic efficiency, there is good anti-CO poisoning performance, it is one of focus in DMFCs application always, how preparing methanol fuel cell catalyst cheap, excellent performance, is one of primary study direction of art technology.
Summary of the invention
The present invention is intended to overcome the defect that existing methanol fuel cell catalyst is expensive, be not suitable for large-scale commercial application, the invention provides a kind of multi-stage porous (mesoporous) zeolite that can serve as methanol fuel cell catalyst and preparation method thereof.
The invention provides a kind of SnO
2/ multi-stage porous (mesoporous) zeolitic material, described SnO
2/ multi-stage porous (mesoporous) zeolitic material has crystallization hole wall, and its surface uniform ground load has SnO
2crystalline nanometer particle.
Preferably, the specific area of described multi-stage porous (mesoporous) zeolite is 300～501m
2/ g, aperture is 2～50nm, SnO
2crystalline nanometer particle is that particle diameter is 3～8nm.
Preferably, described SnO
2in/multi-stage porous (mesoporous) zeolitic material, SnO
2the weight percentage of crystalline nanometer particle is 2.25～9wt%.
The present invention also provides one to prepare above-mentioned SnO
2the method of/multi-stage porous (mesoporous) zeolite, described method comprises:
1) adopt the modifying surface of silane coupler to zeolite precursor body, make the surface band negative electrical charge of zeolite precursor body;
2) splash into containing Sn
4+the aqueous solution, stir, described zeolite precursor body utilize its surface with negative electrical charge absorption Sn
4+;
3) splash into alkali lye, stir the Sn that makes described zeolite precursor surface
4+be converted into Sn (OH)
4;
4) by step 3) in preparation surface there is Sn (OH)
4zeolite precursor body, in 400～700 DEG C of heat treatments so that the crystallization of pore wall of described zeolite precursor body make its surperficial Sn (OH)
4thermal decomposition is SnO
2crystalline nanometer particle.
Preferably, described zeolite precursor body is ZSM-5 zeolite molecular sieve.
Preferably, step 1) described step 1) comprise zeolite precursor body is dispersed in the mixed solution of water and ethanol, splash into the ethanolic solution of silane coupler, stir 5～7 hours so that the surface of described zeolite precursor body is arrived in the hydrolysate grafting of silane coupler in 10～15 DEG C.
Preferably, step 1) in, the mass ratio of described zeolite precursor body and silane coupler is (0.5～1): (0.2～0.4).
Preferably, step 2) in, containing Sn
4+the aqueous solution be the butter of tin aqueous solution, step 3) in, described alkali lye is ammoniacal liquor or NaOH solution.
Preferably, step 4) in, heat treatment time is 5～7 hours.
The present invention also provides above-mentioned SnO
2the application of/Mesoporous Zeolite Materials, described SnO
2/ Mesoporous Zeolite Materials is for the preparation of methanol fuel cell anode catalyzer.
Beneficial effect of the present invention:
1, adopt surfactant first to prepare the presoma of multi-stage porous (mesoporous) zeolite ZSM-5, then form crystallization hole wall through Overheating Treatment, simultaneously Sn (OH)
4also thermal decomposition forms nano SnO
2;
2, adopting silane coupler is negative electricity by the surface modification of multi-stage porous (mesoporous) zeolite ZSM-5, makes the Sn of positively charged
4+evenly be electrostatically drawn to its surface, thereby form the SnO of high dispersive
2nanocrystal;
3, SnO of the present invention
2/ multi-stage porous (mesoporous) zeolite ZSM-5 composite does not use noble metal, multi-stage porous (mesoporous) zeolite ZSM-5 and nanocrystal SnO
2between concerted catalysis, make this composite show the active and anti-CO poisoning performance of high methanol electro-oxidizing-catalyzing.
Brief description of the drawings
Fig. 1 shows the 4.5wt%SnO preparing in an embodiment of the invention
2the XRD collection of illustrative plates of/multi-stage porous (mesoporous) zeolite ZSM-5 composite;
Fig. 2 shows the 4.5wt%SnO preparing in three embodiments of the present invention
2the SEM photo of/multi-stage porous (mesoporous) zeolite ZSM-5 composite;
Fig. 3 shows the 4.5wt%SnO preparing in two embodiments of the present invention
2transmission electron microscope (TEM) photo of/multi-stage porous (mesoporous) zeolite ZSM-5 composite;
Fig. 4 A shows the 4.5wt%SnO preparing in an embodiment of the invention
2the electrochemistry CV curve of/multi-stage porous (mesoporous) zeolite ZSM-5 composite in 0.5M NaOH solution, sweep speed is 50mV s
-1, the oxidation stripping CV curve to CO under room temperature condition;
Fig. 4 B shows the 4.5wt%SnO preparing in an embodiment of the invention
2the electrochemistry CV curve of/multi-stage porous (mesoporous) zeolite ZSM-5 composite in 0.5M NaOH solution, sweep speed is 50mV s
-1, the electrochemical catalytic oxidation curve to variable concentrations methanol solution under room temperature condition;
Fig. 4 C shows the 4.5wt%SnO preparing in an embodiment of the invention
2the electrochemistry CV curve of/multi-stage porous (mesoporous) zeolite ZSM-5 composite in 0.5M NaOH solution, sweep speed is 50mV s
-1, under room temperature condition circulation 1000 processes in methanol oxidation peak current density.
Detailed description of the invention
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for the present invention is described, and unrestricted the present invention.
The invention provides a kind of novel SnO that can serve as methanol fuel cell (DMFC) anode catalyst
2/ multi-stage porous (mesoporous) zeolite ZSM-5 and preparation method thereof.The specific area of this catalyst is 300～501m
2/ g, aperture size is 2～50nm, SnO
2nano particle (diameter is 3～8nm) is evenly distributed on the outer surface of multi-stage porous (mesoporous) zeolite ZSM-5, and multi-stage porous (mesoporous) ZSM-5 is not only as catalyst carrier, simultaneously and SnO
2nano particle forms concerted catalysis effect, shows high methanol electro-oxidizing-catalyzing performance and anti-CO poisoning performance, and SnO
2nano particle good dispersion, consumption low (4.5wt%).In its preparation process, first prepare multi-stage porous (mesoporous) ZSM-5 presoma, then utilizing silane coupler (TPHAC) is electronegative by its surface modification, makes positive charge Sn
4+uniform ion is adsorbed in its outer surface, passes through NH
3.H
2the titration of O or NaOH alkalies forms Sn (OH)
4, and obtain SnO by heat treatment (400～700 DEG C)
2/ multi-stage porous (mesoporous) ZSM-5 anode catalyst material.SnO of the present invention
2/ multi-stage porous (mesoporous) ZSM-5 anode catalyst does not use noble metal (Pt, Pd, Ru, Au, Ag etc.), and this catalyst is by the modifying surface of multi-stage porous (mesoporous) ZSM-5 is realized to SnO
2the uniform load of nano particle, not only reduces the cost of battery greatly, has also avoided the intoxicating phenomenon of positive C O, its preparation condition gentleness simultaneously, easy operating.
The invention provides a kind of multi-stage porous (mesoporous) zeolite that can serve as methanol fuel cell anode catalyzer, described SnO
2/ multi-stage porous (mesoporous) zeolite ZSM-5 is multi-stage porous (mesoporous) composite materials with crystallization hole wall.
Described SnO
2the specific area of/multi-stage porous (mesoporous) zeolite ZSM-5 catalyst is 300～501m
2/ g.
Described SnO
2the aperture of/multi-stage porous (mesoporous) zeolite ZSM-5 catalyst is 2～50nm.
Described SnO
2base metal SnO in/multi-stage porous (mesoporous) zeolite ZSM-5 catalyst
2that particle diameter is the crystallization nano particle of 3～8nm.
The present invention also provides a kind of described SnO that can serve as methanol fuel cell anode catalyzer
2the preparation method of/multi-stage porous (mesoporous) zeolite ZSM-5, described method comprises:
A) first Hydrothermal Synthesis multi-stage porous (mesoporous) zeolite molecular sieve is as presoma;
B) adopt the method for surface modification (as adopted silane coupler) to make multi-stage porous (mesoporous) ZSM-5 surface band negative electrical charge, utilize electrostatic interaction by Sn
4+evenly grafting is to the surface of multi-stage porous (mesoporous) ZSM-5;
C) by titration alkali lye (NH
3.H
2o or NaOH) formation Sn (OH)
4;
D) when within 5～7 hours, making multi-stage porous (mesoporous) ZSM-5 crystallization of pore wall by 400～700 DEG C of heat treatments, Sn (OH)
4thermal decomposition forms SnO
2.
Zeolitic material is the study hotspot of domestic and international researcher always; such heterogeneous catalysis occupies consequence in the field such as petrochemical industry and catalyst preparation, is the conventional solid acid catalysts of reaction such as alkylation, acyl group, isomerization, aromatisation and aldol condensation.In order to solve the restriction of its micropore (≤1.2nm) to diffusion in reaction, scientific research personnel adopts surfactant to prepare to have the zeolite ZSM-5 material of meso-hole structure, and the ZSM-5 of this meso-hole structure has facilitation to the dehydrogenation of methyl alcohol.Tin oxide (SnO
2) be a kind of semiconductor, be widely used in solar cell, lithium battery, Proton Exchange Membrane Fuel Cells and DMFCs, wherein the application in DMFCs is all and the compound electro-oxidizing-catalyzings that are applied to methyl alcohol on carbon carrier that support such as precious metals pt, Pd, Ru.If utilize method that the charges of different polarity attract mutually by SnO
2nano particle uniform load, to the surface of multi-stage porous (mesoporous) zeolite ZSM-5, is prepared SnO
2/ multi-stage porous (mesoporous) ZSM-5 catalyst, by multi-stage porous (mesoporous) ZSM-5 and SnO
2synergy, reach the dehydrogenation oxidation to methanol molecules.At present in this respect, particularly, by the eelctro-catalyst aspect of multi-stage porous (mesoporous) zeolite molecular sieve application alcohols battery, yet there are no this type of report both at home and abroad.
Described multi-stage porous (mesoporous) zeolite preferably has the composite mesoporous thing material of crystallization hole wall, as ZSM-5.
A SnO of the present invention
2the specific solution of/multi-stage porous (mesoporous) zeolite ZSM-5 is:
(1) preparation of zeolite molecular sieve carrier: 0.3066～0.5g aluminium isopropoxide and 15.624～25.4795g silester mix and add 45～73g water at room temperature to stir, drip subsequently 10.98～17.71g TPAOH (TPAOH, 25wt%), the mixed solution of 0.27～0.44g NaOH and 25-45g water, stir 3-6h under 40 DEG C of conditions after, transfer in 100 DEG C of oil baths and continue to stir 2d, above reaction is carried out in the 250ml of favorable sealing property Duran bottle;
(2) by the suspension of above-mentioned gained, carry out centrifugal or suction filtration, gained powder, after 100 DEG C of baking oven inner dryings, obtains multi-stage porous (mesoporous) ZSM-5 zeolite as presoma;
(3) will after above-mentioned 0.5～1g zeolite molecular sieve powder porphyrize, add ultrasonic being uniformly dispersed in 100～200ml water and 60～120g alcohol mixeding liquid, then slowly splash into 30ml and be dissolved with 0.2～0.4g silane coupler (TPHAC, 60% methanol solution) ethanolic solution, under 10 DEG C of conditions, stir 5～7h, guarantee that silane coupler is slowly hydrolyzed grafting to molecular sieve surface;
(4) splash into subsequently the SnCl that 10～20mL concentration is 0.03mol/L
45H
2the O aqueous solution, continues to stir 2h;
(5) last, the ammoniacal liquor that is 1.2mol/L by 10～20mL concentration or NaOH solution slowly splash into above-mentioned mixed system, under room temperature, stir 12h;
(6), by centrifugal above-mentioned suspension or suction filtration, gained powder is dry in 100 DEG C of baking ovens calcined 5～7h under 400～700 DEG C of conditions after 3～8 hours in Muffle furnace, finally obtained high-dispersion nano SnO
2support multi-stage porous (mesoporous) zeolite ZSM-5 particle surface, i.e. SnO
2/ ZSM-5;
The 4.5wt%SnO preparing according to above technological process
2the particle of/multi-stage porous (mesoporous) ZSM-5 composite is elliposoidal, and size is 200～400nm, crystallization of pore wall, and specific area is 300-500m
2/ g, aperture is 2～50nm, SnO
2the particle diameter of nanocrystal is 3～8nm.
Advantage of the present invention is as follows:
(1) adopt surfactant first to prepare the presoma of multi-stage porous (mesoporous) zeolite ZSM-5, then form crystallization hole wall through Overheating Treatment, simultaneously Sn (OH)
4also thermal decomposition forms nano SnO
2;
(2) adopting silane coupler is negative electricity by the surface modification of multi-stage porous (mesoporous) ZSM-5, makes the Sn of positively charged
4+evenly be electrostatically drawn to its surface, thereby form the SnO of high dispersive
2nanocrystal;
(3) SnO of the present invention
2/ multi-stage porous (mesoporous) ZSM-5 composite does not use noble metal, multi-stage porous (mesoporous) ZSM-5 and nanocrystal SnO
2between concerted catalysis, make this composite show the active and anti-CO poisoning performance of high methanol electro-oxidizing-catalyzing.
Fig. 1 shows the 4.5wt%SnO preparing in an embodiment of the invention
2the XRD collection of illustrative plates of/multi-stage porous (mesoporous) zeolite ZSM-5 composite;
Fig. 2 shows the 4.5wt%SnO preparing in three embodiments of the present invention
2the SEM photo of/multi-stage porous (mesoporous) zeolite ZSM-5 composite;
Fig. 3 shows the 4.5wt%SnO preparing in two embodiments of the present invention
2transmission electron microscope (TEM) photo of/multi-stage porous (mesoporous) zeolite ZSM-5 composite;
Fig. 4 A shows the 4.5wt%SnO preparing in an embodiment of the invention
2the electrochemistry CV curve of/multi-stage porous (mesoporous) zeolite ZSM-5 composite in 0.5M NaOH solution, sweep speed is 50mV s
-1, the oxidation stripping CV curve to CO under room temperature condition;
Fig. 4 B shows the 4.5wt%SnO preparing in an embodiment of the invention
2the electrochemistry CV curve of/multi-stage porous (mesoporous) zeolite ZSM-5 composite in 0.5M NaOH solution, sweep speed is 50mV s
-1, the electrochemical catalytic oxidation curve to variable concentrations methanol solution under room temperature condition;
Fig. 4 C shows the 4.5wt%SnO preparing in an embodiment of the invention
2the electrochemistry CV curve of/multi-stage porous (mesoporous) zeolite ZSM-5 composite in 0.5M NaOH solution, sweep speed is 50mV s
-1, under room temperature condition circulation 1000 processes in methanol oxidation peak current density.
Below further list some exemplary embodiments so that the present invention to be described better.Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in and limit the scope of the invention for the present invention is described, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjust and all belong to protection scope of the present invention.In addition, concrete proportioning in following technological parameter, time, temperature etc. are only also exemplary, and those skilled in the art can select suitable value in the scope of above-mentioned restriction.
Embodiment 1
According to technique scheme of the present invention and technological process, first prepare multi-stage porous (mesoporous) ZSM-5 zeolite persursor material.Taking 0.3066g aluminium isopropoxide and 15.624g silester mixes and adds 45g water at room temperature to stir, drip subsequently 10.98g TPAOH (TPAOH, 25wt%), the mixed solution of 0.27g NaOH and 45g water, stir 3h under 40 DEG C of conditions after, transfer in 100 DEG C of oil baths and continue to stir 2d, above reaction is carried out in the 250mlDuran of favorable sealing property bottle.Above-mentioned suspension is through suction filtration, and gained powder, after 100 DEG C of baking oven inner dryings, obtains multi-stage porous (mesoporous) ZSM-5 zeolite;
Get after the above-mentioned zeolite molecular sieve powder of 0.5g porphyrize, add ultrasonic being uniformly dispersed in 100ml water and 60g alcohol mixeding liquid, then slowly splash into the ethanolic solution that 30ml is dissolved with 0.2g silane coupler (TPHAC, 60% methanol solution), under 10 DEG C of conditions, stir 5h; Splash into subsequently the SnCl that 10mL concentration is 0.03mol/L
4.5H
2the O aqueous solution, continues to stir 2h.The ammoniacal liquor that is 1.2mol/L by 10mL concentration afterwards slowly splashes into above-mentioned mixed system, under room temperature, stirs 12h.After this suspension is centrifugal, gained powder is dry in 100 DEG C of baking ovens calcined 7h under 400 DEG C of conditions after 3 hours in Muffle furnace, obtained multi-stage porous (mesoporous) 4.5wt%SnO
2/ ZSM-5 composite;
Wherein, SnO
2content measurement mode be inductively coupled plasma atomic emission spectrometry instrument (ICP-OES);
Gained SnO
2the specific area of/multi-stage porous (mesoporous) ZSM-5 composite is 501m
2/ g (table 1), is irregular spheroidal, is of a size of～200nm, as shown in (A) SEM photo in Fig. 2.
Embodiment 2
According to (with embodiment 1) described in technological process, take 0.3066g aluminium isopropoxide and 15.624g silester and mix and add 25g water to prepare multi-stage porous (mesoporous) ZSM-5 zeolite, other operate with embodiment 1, and electrostatic attraction Sn
4+the powder of rear gained is calcined 7h under 550 DEG C of conditions in Muffle furnace, obtains SnO
2/ multi-stage porous (mesoporous) ZSM-5 composite; The specific area of this composite is 371m
2/ g (table 1), is shaped as irregular elliposoidal, is of a size of～300nm, and aperture size is 10～50nm, as shown in the SEM photo of B in Fig. 2 and D; And this material shows high catalytic activity to the electrochemical catalytic oxidation of CO, as shown in Figure 4 A, there is good anti-CO poisoning performance.
Embodiment 3
According to (with embodiment 1) described in technological process, take 0.3066g aluminium isopropoxide and 15.624g silester and mix and add 25g water to prepare multi-stage porous (mesoporous) ZSM-5 zeolite, other operate with embodiment 1, and electrostatic attraction Sn
4+the powder of rear gained is calcined 5h under 700 DEG C of conditions in Muffle furnace, obtains SnO
2/ multi-stage porous (mesoporous) ZSM-5 composite.This composite shows good crystallinity, as shown in the XRD collection of illustrative plates in Fig. 1; Specific area is 300m
2/ g (as table 1); Be shaped as irregular elliposoidal, be of a size of～400nm, as shown in the SEM photo of (C) in Fig. 2.
The prepared multi-stage porous of table 1. (mesoporous) SnO
2the pore structure parameter of/ZSM-5 composite
| Sample | BET specific area/m 2.g -1 |
| SnO 2/ ZSM-5 (embodiment 1) | 501 |
| SnO 2/ ZSM-5 (embodiment 2) | 371 |
| SnO 2/ ZSM-5 (embodiment 3) | 300 |
Embodiment 4
Described in technological process, taking 0.5g aluminium isopropoxide and 25.4795g silester mixes and adds 73g water at room temperature to stir, drip subsequently 17.71g TPAOH (TPAOH, 25wt%), the mixed solution of 0.44g NaOH and 45g water, stir 6h under 40 DEG C of conditions after, transfer in 100 DEG C of oil baths and continue to stir 2d, above reaction is carried out in the 250ml of favorable sealing property Duran bottle.By the suspension of above-mentioned gained, carry out centrifugal multi-stage porous (mesoporous) the ZSM-5 zeolite presoma that obtains;
Get the above-mentioned zeolite molecular sieve powder of 1g and add ultrasonic dispersion 3h in 200ml water and 120g alcohol mixeding liquid, then slowly splash into 30ml and be dissolved with 0.4g silane coupler (TPHAC, 60% methanol solution) ethanolic solution, under 10 DEG C of conditions, stir 7h, make silane coupler slowly be hydrolyzed also grafting to molecular sieve surface.Splash into subsequently the SnCl that 20mL concentration is 0.03mol/L
4.5H
2the O aqueous solution, stirs after 2h, and the NaOH solution 20mL that is 1.2mol/L by concentration slowly splashes into, and continues stirring at room temperature 12h.This suspension, after in centrifugal, 100 DEG C of baking ovens dry 8 hours, is calcined 5h under 550 DEG C of conditions in Muffle furnace, obtains 4.5wt%SnO
2/ ZSM-5 composite;
The transmission electron microscope photo of this composite as shown in the illustration of A in Fig. 3, wherein SnO
2the diameter of nano particle is 3nm, and as shown in A in Fig. 3, and this multi-stage porous (mesoporous) material do not using under the condition of any noble metal, shows high methanol electro-oxidizing-catalyzing performance, as shown in Figure 4 B; Even after 1000 circulations, the electrocatalytic oxidation galvanic current of methyl alcohol is not significantly declined, as shown in Figure 4 C, show stable electrochemical catalysis activity.
Embodiment 5
According to (with embodiment 4) described in technological process, change the calcination time of compound, in Muffle furnace, under 550 DEG C of conditions, calcine 7h, other operate with embodiment 4.Obtain SnO
2the transmission electron microscope photo of/ZSM-5 composite as shown in the illustration of B in Fig. 3, wherein SnO
2the diameter of nano particle is～8nm, as shown in the high power transmission electron microscope of B in Fig. 3.
Claims (10)
1. a SnO
2/ Mesoporous Zeolite Materials, is characterized in that, described SnO
2/ Mesoporous Zeolite Materials has crystallization hole wall, and its surface uniform ground load has SnO
2crystalline nanometer particle.
2. mesoporous zeolite according to claim 1, is characterized in that, described SnO
2the specific area of/Mesoporous Zeolite Materials is 300-501 m
2/ g, aperture is 2-50nm, SnO
2the particle diameter of crystalline nanometer particle is 3-8nm.
3. mesoporous zeolite according to claim 1, is characterized in that, described SnO
2in/Mesoporous Zeolite Materials, SnO
2the weight percentage of crystalline nanometer particle is 2.25-9wt%.
4. prepare arbitrary described SnO in claim 1-3 for one kind
2the method of/mesoporous zeolite, is characterized in that, described method comprises:
1) adopt the modifying surface of silane coupler to zeolite precursor body, make the surface band negative electrical charge of zeolite precursor body;
2) splash into containing Sn
4+the aqueous solution, stir, described zeolite precursor body utilize its surface with negative electrical charge absorption Sn
4+;
3) splash into alkali lye, stir the Sn that makes described zeolite precursor surface
4+be converted into Sn (OH)
4;
4) surface of preparing in step 3) is there is to Sn (OH)
4zeolite precursor body, in 400～700 DEG C of heat treatments so that the crystallization of pore wall of described zeolite precursor body make its surperficial Sn (OH)
4thermal decomposition is SnO
2crystalline nanometer particle.
5. method according to claim 4, is characterized in that, described zeolite precursor body is ZSM-5 zeolite molecular sieve.
6. according to the method described in claim 4 or 5, it is characterized in that, described step 1) comprises zeolite precursor body is dispersed in the mixed solution of water and ethanol, splash into the ethanolic solution of silane coupler, stir 5～7 hours so that the surface of described zeolite precursor body is arrived in the hydrolysate grafting of silane coupler in 10～15 DEG C.
7. method according to claim 6, is characterized in that, the mass ratio of described zeolite precursor body and silane coupler is (0.5～1): (0.2～0.4).
8. according to arbitrary described method in claim 4-7, it is characterized in that step 2) in, containing Sn
4+the aqueous solution be the butter of tin aqueous solution, in step 3), described alkali lye is ammoniacal liquor or NaOH solution.
9. according to arbitrary described method in claim 4-8, it is characterized in that, in step 4), heat treatment time is 5～7 hours.
10. according to SnO described in any one in claim 1-3
2the application of/Mesoporous Zeolite Materials, described SnO
2/ Mesoporous Zeolite Materials is for the preparation of methanol fuel cell anode catalyzer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879900A (en) * | 2016-04-29 | 2016-08-24 | 中国科学院上海硅酸盐研究所 | MnO2 nanosheet modified mesoporous ZSM-5 ORR (oxygen reduction reaction) catalyst and preparation method thereof |
| CN108341425A (en) * | 2018-02-05 | 2018-07-31 | 大连理工大学 | The preparation method and application of tin oxide/nano-ZSM-5 composite material |
| CN108767278A (en) * | 2018-06-11 | 2018-11-06 | 佛山腾鲤新能源科技有限公司 | A kind of fuel-cell catalyst |
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| CN1470458A (en) * | 2003-06-11 | 2004-01-28 | 复旦大学 | Zeolite-based nano metal oxide composite material and its preparing method |
| CN1490618A (en) * | 2003-07-29 | 2004-04-21 | 复旦大学 | Zeolite based tin peroxide gas sensitive material and preparation |
| JP2009117287A (en) * | 2007-11-09 | 2009-05-28 | Osaka Prefecture Univ | Catalyst for direct type alcohol fuel cell electrode, and manufacturing method of catalyst for that electrode |
| CN103157504A (en) * | 2011-12-12 | 2013-06-19 | 江南大学 | Novel mesoporous Fe2O3-SnO2-ZSM-5 solid acid prepared by impregnation method, and application study for catalyzing degradation of organic pollutants |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1470458A (en) * | 2003-06-11 | 2004-01-28 | 复旦大学 | Zeolite-based nano metal oxide composite material and its preparing method |
| CN1490618A (en) * | 2003-07-29 | 2004-04-21 | 复旦大学 | Zeolite based tin peroxide gas sensitive material and preparation |
| JP2009117287A (en) * | 2007-11-09 | 2009-05-28 | Osaka Prefecture Univ | Catalyst for direct type alcohol fuel cell electrode, and manufacturing method of catalyst for that electrode |
| CN103157504A (en) * | 2011-12-12 | 2013-06-19 | 江南大学 | Novel mesoporous Fe2O3-SnO2-ZSM-5 solid acid prepared by impregnation method, and application study for catalyzing degradation of organic pollutants |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879900A (en) * | 2016-04-29 | 2016-08-24 | 中国科学院上海硅酸盐研究所 | MnO2 nanosheet modified mesoporous ZSM-5 ORR (oxygen reduction reaction) catalyst and preparation method thereof |
| CN108341425A (en) * | 2018-02-05 | 2018-07-31 | 大连理工大学 | The preparation method and application of tin oxide/nano-ZSM-5 composite material |
| CN108767278A (en) * | 2018-06-11 | 2018-11-06 | 佛山腾鲤新能源科技有限公司 | A kind of fuel-cell catalyst |
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