CN106076396B - A kind of preparation method and applications of the Cu support type mesoporous catalysts of Au doping - Google Patents
A kind of preparation method and applications of the Cu support type mesoporous catalysts of Au doping Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method and applications of the Cu support type mesoporous catalysts of Au doping, belong to nanocomposite technical field.By modified mesopore molecular sieve NH215 powder of SBA is 30.7 by liquid-solid ratio：1~92.1：1ml/g is added to a concentration of 0.0025mol/LHAuCl4It is stirred in solution, then under the conditions of ultrasonic agitation, adds in reducing agent NaBH4Reduction reaction is carried out, is filtered, washed, obtains solid product；Solid product is placed in the copper nitrate solution of a concentration of 0.2mol/L and stirs, be then filtered, washed, roast after Au Cu support type mesoporous catalysts are prepared.The present invention is directed to be doped in high-content Cu support type mesoporous catalysts using a small amount of noble metal Au, while ensureing catalytic activity, reduce catalyst particle size, the dispersibility for increasing particle, improve the anti-sintering of catalyst and H2Dissociative ability, being finally reached improves CO2The purpose of the catalytic performance of preparing methanol by hydrogenation.
Description
Technical field
The present invention relates to a kind of preparation method and applications of the Cu support type mesoporous catalysts of Au doping, belong to nanometer and answer
Condensation material technical field.
Background technology
With the rapid development of modern industry, CO2Discharge capacity it is increasing.It is well known that CO2Direct emission in wave
Also in the greenhouse effects of the aggravation earth while taking carbon resource, therefore CO2Utilization be particularly important.CH3OH is as one
The important Organic Chemicals of kind and the clean fuel with development prospect so that CO2Hydrogenation is for CH3OH is CO2It recycles
One of effective way, be of great significance in environmental protection and energy field.
It is to realize CO to obtain effective catalyst2Hydrogenation CH3The key of OH process industrializations.Study at present it is more be with
The copper-based catalysts Cu/ZnO/Al that coprecipitation is prepared2O3Or Cu/ZnO/ZrO2Catalyst.Wherein Cu/ZnO/ZrO2It urges
Agent can be under the conditions of low-temp low-pressure by CO2Methanol is converted to, is a kind of very promising hydrogenation catalyst.But it is co-precipitated legal system
Catalyst there are the defects of specific surface area is small, dispersion degree is poor, active ingredient copper easy-sintering, therefore, some high-ratio surfaces
Mesoporous material starts to be concerned.Wherein mesoporous molecular sieve SBA-15 with the pore passage structure of its high-sequential, high-specific surface area, can
The advantages that aperture of tune, big wall thickness, good hydrothermal stability, is widely used in various catalysis reactions.
Some researches show that the H on copper-based catalysts2Absorption dissociation amount it is inadequate so that CO2Conversion ratio it is relatively low.Cause
How this, improve H2Volume of activation be improve CO2One of key technology of conversion ratio.In recent years, Au nano particles are superior with its
Catalytic performance and receive extensive concern.Au can be limited in its duct to obtain in mesoporous molecular sieve SBA-15 by high-ratio surface
Secure satisfactory grades scattered, small size Au nano particles.At the same time, some researches show that activation H can be dissociated in Au active sites2And Au and Cu
IB races are respectively positioned on, there is similar lattice structure it to be made easily to form alloy to improve whole anti-caking power and reduce integral particle
Size improves catalytic activity.
Invention content
For the above-mentioned prior art there are the problem of and deficiency, the Cu support types that the present invention provides a kind of Au doping mesoporous urges
The preparation method and applications of agent.The present invention is directed to be doped in the mesoporous catalysis of high-content Cu support types using a small amount of noble metal Au
Agent, ensure catalytic activity while, reduce catalyst particle size, increase particle dispersibility, improve catalyst it is anti-sintering and
H2Dissociative ability, being finally reached improves CO2The purpose of the catalytic performance of preparing methanol by hydrogenation, the present invention pass through following technical side
Case is realized.
A kind of preparation method of the Cu support type mesoporous catalysts of Au doping, by modified mesopore molecular sieve NH2-SBA-15
Powder is 30.7 by liquid-solid ratio：1~92.1：1ml/g is added to a concentration of 0.0025mol/LHAuCl4It is stirred in solution, then
Under the conditions of ultrasonic agitation, reducing agent NaBH is added in4Reduction reaction is carried out, is filtered, washed, obtains solid product；Solid product
Be placed in the copper nitrate solution of a concentration of 0.2mol/L and stir, be then filtered, washed, roast after Au-Cu support types are prepared
Mesoporous catalyst.
It is as follows：
（1）First by modified mesopore molecular sieve NH2- SBA-15 powder is 30.7 by liquid-solid ratio：1~92.1：1ml/g adds
Enter to a concentration of 0.0025mol/LHAuCl4In solution, the magnetic agitation 3h at 25 DEG C；Then under the conditions of ultrasonic agitation, add
Enter the reducing agent NaBH of a concentration of 0.1mol/L4Reduction reaction 30min is carried out, is filtered, washed（It is filtered using absolute ethyl alcohol
4~6 times, washing 2~3 times）, obtain solid product；
（2）By step（1）Obtained solid product is placed in the copper nitrate solution of a concentration of 0.2mol/L, is 50 in temperature
DEG C stirring 3h obtains mixed solution, and mixed solution obtains solid product, solid product drying after being filtered, washed（At 80~110 DEG C
16~18h of lower drying）5h is roasted at being afterwards 300~500 DEG C in temperature, that is, Au-Cu support type mesoporous catalysts are prepared.
Above-mentioned mass fraction=(m that Au in Au-Cu support type mesoporous catalysts is preparedAu/m(CuO+NH2-SBA-15))×
100%；The mass fraction of CuO=(mCuO/m(CuO +NH2-SBA-15))×100%。
The mesopore molecular sieve NH of the modification2The preparation of-SBA-15 powder is as follows：
1. under 40 DEG C of stirring conditions, by P123It is dissolved in aqueous hydrochloric acid solution, then adds in TEOS, agitated, crystallization,
Filtering, dry, calcination steps, are made SBA-15；Above-mentioned P123, aqueous hydrochloric acid solution, TEOS molar ratio be 1：340：60；
2. 1. SBA-15,300ml absolute ethyl alcohol that 12mlAPTES, 4g step obtain is mixed in three-necked flask, ultrasound
30min is stirred, 120 DEG C are refluxed 16h and obtain solution；
3. 2. step is obtained solution spend absolute ethyl alcohol be filtered 5 times, washing obtain solid 3 times；
4. 3. step to be obtained to solid dry 16h at 60 DEG C, modified mesopore molecular sieve NH is obtained2- SBA-15 powder
End.
A kind of above-mentioned Au-Cu support types mesoporous catalyst that is prepared can be applied in CO2Hydrogenation reaction prepares methanol process
In, specific steps：
1.5gAu-Cu support type mesoporous catalysts are positioned over CO2In the fixed bed reactors of preparing methanol by hydrogenation.First in
5%H28h is restored at 250 DEG C of/95%Ar atmosphere, then in 75%CO2/25%H2The lower 280 DEG C of reactions 7h of atmosphere, finally by
6890 gas-chromatographies of Agilent Technologies (GC) are detected analysis to tail gas and liquid product, pass through external standard method
Calculate XCO2（CO2Conversion ratio）And YCH3OH（The yield of methanol）.
The beneficial effects of the invention are as follows：
（1）Catalyst has high specific surface area, good dispersibility；
（2）Au-Cu synergistic effects reduce integral particle size to improve the anti-caking power of Au, Cu；
（3）The addition of Au promotes the generation of Hydrogen spillover phenomenon, is conducive to H2Dissociative；
（4）For CO2Hydrogenation CH3OH reacts, and compared to the Cu support type mesoporous catalysts relatively prepared with condition, Au-Cu is born
Load type mesoporous catalyst catalytic effect significantly improves.
Description of the drawings
Fig. 1 is the Au-Cu support type mesoporous catalysts HRTEM figures that the embodiment of the present invention 3 is prepared；
Fig. 2 is the Cu support type mesoporous catalysts HRTEM figures that contrast test of the present invention is prepared；
Fig. 3 is the Au-Cu support type mesoporous catalysts of different Au contents that contrast test, embodiment 1 to 4 are prepared
CO2Conversion ratio comparison diagram；
Fig. 4 is the Au-Cu support type mesoporous catalysts of different Au contents that contrast test, embodiment 1 to 4 are prepared
CH3OH selectivity comparison diagrams.
Specific embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
The preparation method of the Cu support type mesoporous catalysts of Au doping, is as follows：
（1）The mesopore molecular sieve NH that 1.5g is modified first2- SBA-15 powder is 30.7 by liquid-solid ratio：1ml/g is added to
A concentration of 0.0025mol/LHAuCl4In solution, the magnetic agitation 3h at 25 DEG C；Then under the conditions of ultrasonic agitation, 5ml is added in
The reducing agent NaBH of a concentration of 0.1mol/L4Reduction reaction 30min is carried out, is filtered, washed（4 are filtered using absolute ethyl alcohol
~6 times, washing 2~3 times）, obtain solid product；
（2）By step（1）Obtained 1.523g solid products are placed in the copper nitrate solution of 50ml, a concentration of 0.2mol/L
In, mixed solution is obtained for 50 DEG C of stirring 3h in temperature, mixed solution obtains solid product after being filtered, washed, solid product is done
It is dry（The dry 16h at 110 DEG C）5h is roasted at being afterwards 350 DEG C in temperature, that is, Au-Cu support type mesoporous catalysts are prepared
（It is denoted as 1%Au-35%Cu/SBA-15）.
The mesopore molecular sieve NH of above-mentioned modification2The preparation of-SBA-15 powder is as follows：
1. under 40 DEG C of stirring conditions, by P123It is dissolved in a concentration of 2mol/L aqueous hydrochloric acid solutions, then adds in TEOS,
Agitated, crystallization, filtering, drying, roasting（5h is roasted under the conditions of being 550 DEG C in temperature）SBA-15 is made in step；Above-mentioned P123、
Aqueous hydrochloric acid solution, TEOS molar ratio be 1：340：60；
2. 1. SBA-15,300ml absolute ethyl alcohol that 12mlAPTES, 4g step obtain is mixed in three-necked flask, ultrasound
30min is stirred, 120 DEG C are refluxed 16h and obtain solution；
3. 2. step is obtained solution spend absolute ethyl alcohol be filtered 5 times, washing obtain solid 3 times；
4. 3. step to be obtained to solid dry 16h at 60 DEG C, modified mesopore molecular sieve NH is obtained2- SBA-15 powder
End.
Embodiment 2
The preparation method of the Cu support type mesoporous catalysts of Au doping, is as follows：
（1）The mesopore molecular sieve NH that 1.5g is modified first2- SBA-15 powder is 46.05 by liquid-solid ratio：1ml/g is added in
To a concentration of 0.0025mol/LHAuCl4In solution, the magnetic agitation 3h at 25 DEG C；Then it under the conditions of ultrasonic agitation, adds in
The reducing agent NaBH of a concentration of 0.1mol/L of 5ml4Reduction reaction 30min is carried out, is filtered, washed（It was carried out using absolute ethyl alcohol
It filters 4~6 times, wash 2~3 times）, obtain solid product；
（2）By step（1）Obtained 1.535g solid products are placed in the copper nitrate solution of 50ml, a concentration of 0.2mol/L
In, mixed solution is obtained for 50 DEG C of stirring 3h in temperature, mixed solution obtains solid product after being filtered, washed, solid product is done
It is dry（The dry 16h at 110 DEG C）5h is roasted at being afterwards 350 DEG C in temperature, that is, Au-Cu support type mesoporous catalysts are prepared
（It is denoted as 1.5%Au-35%Cu/SBA-15）.
The mesopore molecular sieve NH of above-mentioned modification2The preparation of-SBA-15 powder is as follows：
1. under 40 DEG C of stirring conditions, by P123It is dissolved in a concentration of 2mol/L aqueous hydrochloric acid solutions, then adds in TEOS,
Agitated, crystallization, filtering, drying, roasting（5h is roasted under the conditions of being 550 DEG C in temperature）SBA-15 is made in step；Above-mentioned P123、
Aqueous hydrochloric acid solution, TEOS molar ratio be 1：340：60；
2. 1. SBA-15,300ml absolute ethyl alcohol that 12mlAPTES, 4g step obtain is mixed in three-necked flask, ultrasound
30min is stirred, 120 DEG C are refluxed 16h and obtain solution；
3. 2. step is obtained solution spend absolute ethyl alcohol be filtered 5 times, washing obtain solid 3 times；
4. 3. step to be obtained to solid dry 16h at 60 DEG C, modified mesopore molecular sieve NH is obtained2- SBA-15 powder
End.
Embodiment 3
The preparation method of the Cu support type mesoporous catalysts of Au doping, is as follows：
（1）The mesopore molecular sieve NH that 1.5g is modified first2- SBA-15 powder is 61.4 by liquid-solid ratio：1ml/g is added to
A concentration of 0.0025mol/LHAuCl4In solution, the magnetic agitation 3h at 25 DEG C；Then it under the conditions of ultrasonic agitation, adds in
The reducing agent NaBH of a concentration of 0.1mol/L of 10ml4Reduction reaction 30min is carried out, is filtered, washed（It was carried out using absolute ethyl alcohol
It filters 4~6 times, wash 2~3 times）, obtain solid product；
（2）By step（1）Obtained 1.546g solid products are placed in the copper nitrate solution of 50ml, a concentration of 0.2mol/L
In, mixed solution is obtained for 50 DEG C of stirring 3h in temperature, mixed solution obtains solid product after being filtered, washed, solid product is done
It is dry（The dry 16h at 110 DEG C）5h is roasted at being afterwards 350 DEG C in temperature, that is, Au-Cu support type mesoporous catalysts are prepared
（It is denoted as 2%Au-35%Cu/SBA-15）, the Au-Cu support type mesoporous catalysts HRTEM figures being prepared are as shown in Figure 1.
The mesopore molecular sieve NH of above-mentioned modification2The preparation of-SBA-15 powder is as follows：
1. under 40 DEG C of stirring conditions, by P123It is dissolved in a concentration of 2mol/L aqueous hydrochloric acid solutions, then adds in TEOS,
Agitated, crystallization, filtering, drying, roasting（5h is roasted under the conditions of being 550 DEG C in temperature）SBA-15 is made in step；Above-mentioned P123、
Aqueous hydrochloric acid solution, TEOS molar ratio be 1：340：60；
2. 1. SBA-15,300ml absolute ethyl alcohol that 12mlAPTES, 4g step obtain is mixed in three-necked flask, ultrasound
30min is stirred, 120 DEG C are refluxed 16h and obtain solution；
3. 2. step is obtained solution spend absolute ethyl alcohol be filtered 5 times, washing obtain solid 3 times；
4. 3. step to be obtained to solid dry 16h at 60 DEG C, modified mesopore molecular sieve NH is obtained2- SBA-15 powder
End.
Embodiment 4
The preparation method of the Cu support type mesoporous catalysts of Au doping, is as follows：
（1）The mesopore molecular sieve NH that 1.5g is modified first2- SBA-15 powder is 92.1 by liquid-solid ratio：1ml/g is added to
A concentration of 0.0025mol/LHAuCl4In solution, the magnetic agitation 3h at 25 DEG C；Then it under the conditions of ultrasonic agitation, adds in
The reducing agent NaBH of a concentration of 0.1mol/L of 15ml4Reduction reaction 30min is carried out, is filtered, washed（It was carried out using absolute ethyl alcohol
It filters 4~6 times, wash 2~3 times）, obtain solid product；
（2）By step（1）1.569 obtained g solid products are placed in the copper nitrate solution of 50 ml, a concentration of 0.2mol/L
In, mixed solution is obtained for 50 DEG C of stirring 3h in temperature, mixed solution obtains solid product after being filtered, washed, solid product is done
It is dry（The dry 16h at 110 DEG C）5h is roasted at being afterwards 350 DEG C in temperature, that is, Au-Cu support type mesoporous catalysts are prepared
（It is denoted as 3%Au-35%Cu/SBA-15）.
The mesopore molecular sieve NH of above-mentioned modification2The preparation of-SBA-15 powder is as follows：
1. under 40 DEG C of stirring conditions, by P123It is dissolved in a concentration of 2mol/L aqueous hydrochloric acid solutions, then adds in TEOS,
Agitated, crystallization, filtering, drying, roasting（5h is roasted under the conditions of being 550 DEG C in temperature）SBA-15 is made in step；Above-mentioned P123、
Aqueous hydrochloric acid solution, TEOS molar ratio be 1：340：60；
2. 1. SBA-15,300ml absolute ethyl alcohol that 12mlAPTES, 4g step obtain is mixed in three-necked flask, ultrasound
30min is stirred, 120 DEG C are refluxed 16h and obtain solution；
3. 2. step is obtained solution spend absolute ethyl alcohol be filtered 5 times, washing obtain solid 3 times；
4. 3. step to be obtained to solid dry 16h at 60 DEG C, modified mesopore molecular sieve NH is obtained2- SBA-15 powder
End.
Contrast test
The process for preparing Cu support type mesoporous catalysts is：
The mesopore molecular sieve NH that 1.5g is modified first2- SBA-15 powder（Mesopore molecular sieve NH2It is prepared by-SBA-15 powder
Process is as shown in embodiment 1 to 4）It is placed in the copper nitrate solution of 50ml, a concentration of 0.2mol/L, is 50 DEG C of stirring 3h in temperature
Mixed solution is obtained, mixed solution obtains solid product, solid product drying after being filtered, washed（The dry 16h at 110 DEG C）Afterwards
5h is roasted at being 350 DEG C in temperature, that is, Cu support type mesoporous catalysts are prepared（It is denoted as 35%Cu/SBA-15）, prepare Cu and bear
Load type mesoporous catalyst HRTEM figures are as shown in Figure 2.
The Au-Cu support type mesoporous catalysts of difference Au contents in embodiment 1 to 4 and contrast test are applied in CO2
Hydrogenation reaction is prepared in methanol process, specific steps：
1.5gAu-Cu support type mesoporous catalysts are positioned over CO2In the fixed bed reactors of preparing methanol by hydrogenation.First in
5%H28h is restored at 250 DEG C of/95%Ar atmosphere, then in 75%CO2/25%H2The lower 280 DEG C of reactions 7h of atmosphere, finally by
6890 gas-chromatographies of Agilent Technologies (GC) are detected analysis to tail gas and liquid product, pass through external standard method
Calculate XCO2And SCH3OH。
The Au-Cu support type mesoporous catalysts CO of different Au contents2Conversion ratio comparison diagram is as shown in figure 3, can be with from Fig. 3
Find out the increase X with Au contentsCO2First increase reduce afterwards and Au load capacity be 2wt.% when up to 24.9%, in institute's sample
Highest XCO2；The Au-Cu support type mesoporous catalysts CH of different Au contents3OH selectivity comparison diagram is as shown in figure 4, from Fig. 4
It can be seen that with the increase CH of Au contents3OH selectivity first increases and then decreases, when Au contents are 2wt.%, CH3OH selectivity
Reach optimum level.
Embodiment 5
The preparation method of the Cu support type mesoporous catalysts of Au doping, is as follows：
（1）The mesopore molecular sieve NH that 1.5g is modified first2- SBA-15 powder is 92.1 by liquid-solid ratio：1ml/g is added to
A concentration of 0.0025mol/LHAuCl4In solution, the magnetic agitation 3h at 25 DEG C；Then it under the conditions of ultrasonic agitation, adds in
The reducing agent NaBH of a concentration of 0.1mol/L of 20ml4Reduction reaction 30min is carried out, is filtered, washed（It was carried out using absolute ethyl alcohol
It filters 4~6 times, wash 2~3 times）, obtain solid product；
（2）By step（1）Obtained 1.569g solid products are placed in the copper nitrate solution of 50ml, a concentration of 0.2mol/L
In, mixed solution is obtained for 50 DEG C of stirring 3h in temperature, mixed solution obtains solid product after being filtered, washed, solid product is done
It is dry（The dry 18h at 80 DEG C）5h is roasted at being afterwards 300 DEG C in temperature, that is, Au-Cu support type mesoporous catalysts are prepared（Note
For 3%Au-35%Cu/SBA-15）.
The mesopore molecular sieve NH of above-mentioned modification2The preparation of-SBA-15 powder is as follows：
1. under 40 DEG C of stirring conditions, by P123It is dissolved in a concentration of 2mol/L aqueous hydrochloric acid solutions, then adds in TEOS,
Agitated, crystallization, filtering, drying, roasting（5h is roasted under the conditions of being 550 DEG C in temperature）SBA-15 is made in step；Above-mentioned P123、
Aqueous hydrochloric acid solution, TEOS molar ratio be 1：340：60；
2. 1. SBA-15,300ml absolute ethyl alcohol that 12mlAPTES, 4g step obtain is mixed in three-necked flask, ultrasound
30min is stirred, 120 DEG C are refluxed 16h and obtain solution；
3. 2. step is obtained solution spend absolute ethyl alcohol be filtered 5 times, washing obtain solid 3 times；
4. 3. step to be obtained to solid dry 16h at 60 DEG C, modified mesopore molecular sieve NH is obtained2- SBA-15 powder
End.
Embodiment 6
The preparation method of the Cu support type mesoporous catalysts of Au doping, is as follows：
（1）The mesopore molecular sieve NH that 1.5g is modified first2- SBA-15 powder is 92.1 by liquid-solid ratio：1ml/g is added to
A concentration of 0.0025mol/LHAuCl4In solution, the magnetic agitation 3h at 25 DEG C；Then it under the conditions of ultrasonic agitation, adds in
The reducing agent NaBH of a concentration of 0.1mol/L of 20ml4Reduction reaction 30min is carried out, is filtered, washed（It was carried out using absolute ethyl alcohol
It filters 4~6 times, wash 2~3 times）, obtain solid product；
（2）By step（1）Obtained 1.569g solid products are placed in the copper nitrate solution of 50ml, a concentration of 0.2mol/L
In, mixed solution is obtained for 50 DEG C of stirring 3h in temperature, mixed solution obtains solid product after being filtered, washed, solid product is done
It is dry（The dry 18h at 80 DEG C）5h is roasted at being afterwards 500 DEG C in temperature, that is, Au-Cu support type mesoporous catalysts are prepared（Note
For 3%Au-35%Cu/SBA-15）.
The mesopore molecular sieve NH of above-mentioned modification2The preparation of-SBA-15 powder is as follows：
1. under 40 DEG C of stirring conditions, by P123It is dissolved in a concentration of 2mol/L aqueous hydrochloric acid solutions, then adds in TEOS,
Agitated, crystallization, filtering, drying, roasting（5h is roasted under the conditions of being 550 DEG C in temperature）SBA-15 is made in step；Above-mentioned P123、
Aqueous hydrochloric acid solution, TEOS molar ratio be 1：340：60；
2. 1. SBA-15,300ml absolute ethyl alcohol that 12mlAPTES, 4g step obtain is mixed in three-necked flask, ultrasound
30min is stirred, 120 DEG C are refluxed 16h and obtain solution；
3. 2. step is obtained solution spend absolute ethyl alcohol be filtered 5 times, washing obtain solid 3 times；
4. 3. step to be obtained to solid dry 16h at 60 DEG C, modified mesopore molecular sieve NH is obtained2- SBA-15 powder
End.
The specific embodiment of the present invention is explained in detail above in association with attached drawing, but the present invention is not limited to above-mentioned
Embodiment, within the knowledge of a person skilled in the art, can also be before present inventive concept not be departed from
Put that various changes can be made.
Claims (4)
1. a kind of preparation method of the Cu support type mesoporous catalysts of Au doping, it is characterised in that：By modified mesopore molecular sieve
NH2- SBA-15 powder is 30.7 by liquid-solid ratio：1~92.1：1ml/g is added to a concentration of 0.0025mol/LHAuCl4In solution
Stirring then under the conditions of ultrasonic agitation, adds in reducing agent NaBH4Reduction reaction is carried out, is filtered, washed, obtains solid product；
Solid product is placed in the copper nitrate solution of a concentration of 0.2mol/L and stirs, be then filtered, washed, roast after Au- is prepared
Cu support type mesoporous catalysts.
2. the preparation method of the Cu support type mesoporous catalysts of Au doping according to claim 1, it is characterised in that specific
Step is as follows：
（1）First by modified mesopore molecular sieve NH2- SBA-15 powder is 30.7 by liquid-solid ratio：1~92.1：1ml/g is added to
A concentration of 0.0025mol/LHAuCl4In solution, the magnetic agitation 3h at 25 DEG C；Then it under the conditions of ultrasonic agitation, adds in dense
Spend the reducing agent NaBH for 0.1mol/L4Reduction reaction 30min is carried out, is filtered, washed, obtains solid product；
（2）By step（1）Obtained solid product is placed in the copper nitrate solution of a concentration of 0.2mol/L, is stirred in temperature for 50 DEG C
Mix 3h and obtain mixed solution, mixed solution obtains solid product after being filtered, washed, after solid product drying temperature for 300~
5h is roasted at 500 DEG C, that is, Au-Cu support type mesoporous catalysts are prepared.
3. the preparation method of the Cu support type mesoporous catalysts of Au doping according to claim 1 or 2, it is characterised in that：
The mesopore molecular sieve NH of the modification2The preparation of-SBA-15 powder is as follows：
1. under 40 DEG C of stirring conditions, by P123Be dissolved in aqueous hydrochloric acid solution, then add in TEOS, agitated, crystallization, filtering,
SBA-15 is made in dry, calcination steps；
2. 1. SBA-15 that APTES, step are obtained, absolute ethyl alcohol are mixed in three-necked flask, be stirred by ultrasonic 30min, 120 DEG C
It is refluxed 16h and obtains solution；
3. 2. step is obtained solution with absolute ethyl alcohol be filtered 5 times, washing obtain solid 3 times；
4. 3. step to be obtained to solid dry 16h at 60 DEG C, modified mesopore molecular sieve NH is obtained2- SBA-15 powder.
4. a kind of Au-Cu support types mesoporous catalyst is in CO2Hydrogenation reaction prepares the application in methanol process, it is characterised in that：Institute
Pore catalyst is given an account of to be made for any preparation method of claims 1 or 2.
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| JP2013163675A (en) * | 2007-10-30 | 2013-08-22 | Toyama Univ | Hydrogen reduction method of carbon dioxide |
| CN103933978A (en) * | 2014-04-10 | 2014-07-23 | 中国科学院福建物质结构研究所 | Supported nanocatalyst for catalytic conversion of carbon dioxide as well as preparation method and application thereof |
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2016
- 2016-06-06 CN CN201610391440.3A patent/CN106076396B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013163675A (en) * | 2007-10-30 | 2013-08-22 | Toyama Univ | Hydrogen reduction method of carbon dioxide |
| CN103933978A (en) * | 2014-04-10 | 2014-07-23 | 中国科学院福建物质结构研究所 | Supported nanocatalyst for catalytic conversion of carbon dioxide as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Au–Cu Alloy nanoparticles confined in SBA-15 as a highly efficient catalyst for CO oxidation;Xiaoyan Liu，et al;《ChemComm》;20080502;全文 * |
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