CN101920210B - Efficient nanocatalyst Au-VSB-5 for CO catalytic oxidation - Google Patents
Efficient nanocatalyst Au-VSB-5 for CO catalytic oxidation Download PDFInfo
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- CN101920210B CN101920210B CN2009100529870A CN200910052987A CN101920210B CN 101920210 B CN101920210 B CN 101920210B CN 2009100529870 A CN2009100529870 A CN 2009100529870A CN 200910052987 A CN200910052987 A CN 200910052987A CN 101920210 B CN101920210 B CN 101920210B
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Abstract
The invention relates to an efficient nanocatalyst Au-VSB-5 for CO catalytic oxidation. In the method, inorganic chloride salt and phosphoric acid are taken as raw materials, organic amine is taken as a template agent, and water is taken as a solvent, the inorganic chloride salt, the phosphoric acid, the organic amine and the water are synthesized into a nano-pore nickel phosphate nanocrystal. The water solution of golden inorganic salts with different concentrations is prepared and the synthesized nano-pore nickel phosphate nanocrystal powder is placed into the prepared golden inorganic salt solution. Under the condition of steady stir in an intermediate speed mode, golden particles are introduced into a pore canal, deionized water is used for removing gold ions which do not enter the pore canal and drying is conducted at room temperature. The dried powder sample is reduced by the mixed gas of the hydrogen and the nitrogen to obtain the composite material with even size and obvious quantum effect, wherein the nano-Au is carried in a nano-pore canal. The nano-pore nickel phosphate powder carrying the nano-Au is placed in a quartz tube and CO catalytic oxidation is performed by taking O2 as an oxidizing agent and He as a carrier gas, and carrying out temperature programming, thus complete conversion of the CO can be realized at the lower temperature.
Description
Affiliated field:
The invention relates to the preparation method of the effective catalyst of CO low-temperature catalytic oxidation, belong to the nano-catalytic field.
Technical background:
The CO oxidation reaction is that one of important reaction of vehicle exhaust is especially controlled in the control air pollution.Simultaneously, the CO oxidation is in the processing of industrial waste gas, fuel cell, CO
2The purification for gas of laser instrument, the elimination of trace amounts of CO and the aspects such as control of vehicle exhaust have important practical value in CO gas sensor, breath for gas purifier, the closed system.Simultaneously, in petrochemical industry, also there is the imperfect combustion of charcoal in the catalyst surface burning process.Optionally eliminate a spot of CO in the hydrogen-rich gas and concerning the popularization of fuel cell and environmental protection, profound significance (J.H.Jiang, Q.M.Gao, Z.Chen are arranged; Journal ofMolecular Catalysis A:Chemical; 2008,280,233-239; J.Zhu, Q.Gao, Z.Chen, Appl.Catal.B:Environ., 2008,81,236-243).Though the molecular sieve carried nm of gold of tradition shows certain catalytic activity to the catalytic oxidation of CO, the complete conversion temperature that transforms perhaps CO fully that often is difficult to realize CO is up to 400-500 ℃, and the preparation process is more complicated also, is unfavorable for commercial production.Therefore, research and development CO oxidation catalyst efficient, low-cost, that have good stability is significant.
VSB-5 is a kind of novel inorganic micropore nickel phosphate molecular sieve analog functional material; Have character such as ion-exchange, absorption, catalysis and Chu Qing (A.K.Cheetham, G.Ferey, Qiuming Gao etc., Angew.Chem.Int.Ed.Engl., 2001; 40,2831).The pore passage structure of the big specific area of VSB-5 and the 1.1nm of one dimension is fit to the efficient nano catalyst of payload size homogeneous very much.VSB-5 shows alkalescence, himself is a kind of oxidation reduction catalyst efficiently, in addition; VSB-5 can be through hydro-thermal or synthetic fast (2h) (A.K.Cheetham, the G.F é rey et al. of microwave; Chem.Mater., 16:1394 (2004)), synthetic yield is high.Therefore, through the method for self assembly, catalyst is incorporated into the nano catalytic material that is expected to obtain excellent performance among the duct of VSB-5.
The efficient nano Preparation of catalysts method that the purpose of this invention is to provide a kind of CO of preparation low-temperature catalytic oxidation, the nano-pore nickel phosphate crystal diameter of this method preparation is lower than 100nm, and nm of gold size homogeneous is urged O
2Be oxidant, be fit to suitability for industrialized production.
Inorganic nickel of the present invention (comprising nickel chloride, nickel acetate etc.), orthophosphoric acid, triethylamine are raw material, and water is solvent, and hydro-thermal is synthesized the VSB-5 nanocrystal.The VSB-5 of nm of gold assembling is to be raw material with the gold chloride, and gold ion is incorporated among the duct, through hydrogen reducing, obtains homodisperse nm of gold again.Catalytic reaction be to be raw material with CO, O
2Be oxidant, He is carrier gas, carries out the catalytic oxidation of CO, and its reaction condition is:
The concentration of gold chloride is: 0.001 ~ 0.008M, and the amount of VSB-5 nanocrystal is 0.4 ~ 0.6g;
Reaction temperature is a room temperature, and the reaction time is 2d;
The hydrogen reducing temperature of gold ion is 160 ~ 200 ℃, and the recovery time is 80 ~ 120min;
The consumption of catalyst A u-VSB-5 is 0.1 ~ 0.15g in the catalytic performance test;
It is 1% that catalytic reaction adopts mist: CO, O
2Be 4%, 95% to be He, (volume ratio);
The mist flow velocity is 40-80mL/min, preferably, and 50mL/min;
Mixture pressure is a normal pressure.
Concrete technical process step is:
A. nickel chloride, orthophosphoric acid, triethylamine are raw material, and water is solvent, and 170 ℃ of hydro-thermals obtained the crystallization powder in 2 days, and the separation of crystallization powder, washing, drying are obtained the former powder of VSB-5 nanocrystal.
B. gold chloride is configured to solution in different concentration, under stirring condition, adds a certain amount of synthetic VSB-5 nanocrystalline powder, gold ion is incorporated among the nano pore.
The VSB-5 powder that c. will contain gold ion is with distilled water washing 3 ~ 4 times, drying at room temperature.Washing process of the present invention can be removed the gold ion of duct outer surface, and remaining gold ion is limited among the duct.
(1.1nm) nm of gold that the VSB-5 powder that d. will contain gold ion obtains the size homogeneous with 5% hydrogen (remainder is a nitrogen) reduction is scattered in the Au-VSB-5 powder among the duct.Ultra-violet absorption spectrum has shown tangible quantum size effect.
Above-mentioned synthetic good Au-VSB-5 powder is packed in the quartz ampoule of 12mm, is oxidant with oxygen, and He is carrier gas, carries out the oxidation catalysis reaction of CO.Be reflected under the gentle condition of normal pressure and carry out, adopt temperature programming, reaction time 12h.The result shows the catalyst with respect to the molecular sieve carried nm of gold of tradition, and CO can be converted into CO by the direct catalytic oxidation of Au-VSB-5 fully at 240 ℃
2
Description of drawings:
Fig. 1 assembles the XRD figure of the VSB-5 nanocrystal before and after the Au
Fig. 2 assembles the UV-vis collection of illustrative plates of the powder before and after the Au
Fig. 3 CO is with the conversion rate curve of temperature programming process
The specific embodiment
Through embodiment the present invention is detailed below, but the present invention only is confined to embodiment by no means.
1.19g nickel chloride, 0.34mL orthophosphoric acid, the 2.10mL triethylamine, 14mL water, mixing mixes, and obtains initial collosol and gel mixture, initial collosol and gel mixed material is moved in the stainless steel synthesis reactor seal, and 170 ℃ of crystallization, crystallization time is 2 days.Solid crystallized product is separated with mother liquor, spend deionised water 3 times, after drying under 60～100 ℃ of air conditionses, obtain the former powder of VSB-5 molecular sieve analog nanocrystal of the present invention.XRD analysis shows similar with the VSB-5 pure sample of bibliographical information, explains that the structure of this material and VSB-5 is consistent.Like Fig. 1.
Take by weighing the dry good former powder of VSB-5 nanocrystal of 0.5g, join to mix in the 2mM chlorauric acid solution that 20mL configures and stirred 2 days, solid powder is separated with mother liquor, the gold ion that does not get among the duct is removed in deionized water washing 4 times, and 40 ~ 80 ℃, drying.With dried sample 200 ℃ down with 5% hydrogen (remaining nitrogen) reductase 12 hour, obtain the Au-VSB-5 sample of the 1.1nmAu dispersion of size homogeneous.It is similar with the VSB-5 pure sample that XRD analysis shows, explain load to nanometer Au among the duct after, VSB-5 fertile material structure is not damaged, UV-vis analysis demonstration Au plasma resonance absworption peak narrows down, and with respect to body the blue shift of 150nm is arranged mutually.Like Fig. 2
Embodiment 3
Take by weighing the 0.1gAu-VSB-5 powder sample, be placed in the quartz ampoule, feed CO, O
2With the He reaction mixture gas, mist flow velocity 50mL/min, temperature programming adopts gas-chromatography to carry out on-line analysis, discovers that CO can be by complete catalytic oxidation in the time of 260 ℃.Like Fig. 3.
Embodiment 4
With embodiment 3, with embodiment 3, after finishing a catalytic cycle; After treating sample cooling cool to room temperature, feed gas, under identical flow velocity, carry out the catalysis test again with component; Adopt gas-chromatography to carry out on-line analysis, discover that CO can realize transforming fully at 198 ℃.Like Fig. 3.
In contrast to embodiment 3, take by weighing the 0.15gAu-VSB-1 powder and replace the Au-VSB-5 powder, carry out the catalytic oxidation of CO under the same conditions, catalyst does not demonstrate catalytic activity.
The foregoing description can find out that the present invention introduces through gold ion among the nano-pore VSB-5 nanocrystal duct, the nm of gold that can synthesize size homogeneous 1.1nm.This building-up process is easy, and easily-controlled reaction conditions is suitable for industrialization and adopts.In addition, the Au-VSB-5 that the present invention synthesized has shown excellent catalytic performance, can realize the conversion fully of CO at lower temperature.Catalyst with respect to the molecular sieve carried nm of gold of tradition; The conversion fully or the complete conversion temperature that can realize CO are lower, and the load capacity of nm of gold is few, and the preparation process is simple; Reduced cost, the suitability for industrialized production synthetic for this material provides more advantageous conditions.
Claims (1)
1. efficient nano Preparation of catalysts technology is characterized in that:
Take by weighing the dry good former powder of VSB-5 nanocrystal of 0.5g, join to mix in the 2mM chlorauric acid solution that 20mL configures and stirred 2 days, solid powder is separated with mother liquor, the gold ion that does not get among the duct is removed in deionized water washing 4 times, and 40～80 ℃, drying; With dried sample 200 ℃ down with 5% hydrogen, remaining nitrogen, reductase 12 hour obtains the Au-VSB-5 sample of the 1.1nmAu dispersion of size homogeneous.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326811A (en) * | 2000-08-29 | 2001-12-19 | 烟台大学 | Practical low-temperature CO oxidizing catalyst |
| CN1583564A (en) * | 2004-06-09 | 2005-02-23 | 中国科学院上海硅酸盐研究所 | Inorganic microporous nickle and cobalt phosphate molecular sieves materials and their synthesis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326811A (en) * | 2000-08-29 | 2001-12-19 | 烟台大学 | Practical low-temperature CO oxidizing catalyst |
| CN1583564A (en) * | 2004-06-09 | 2005-02-23 | 中国科学院上海硅酸盐研究所 | Inorganic microporous nickle and cobalt phosphate molecular sieves materials and their synthesis |
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