CN109746022A - A kind of preparation method and its application method of the high dispersing copper zinc catalyst for carbon dioxide reduction - Google Patents
A kind of preparation method and its application method of the high dispersing copper zinc catalyst for carbon dioxide reduction Download PDFInfo
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Abstract
The present invention proposes the preparation method and its application method of a kind of high dispersing copper zinc catalyst for carbon dioxide reduction.This method first synthesizes the copper oxide nano particle presoma with uniform grading, then the copper oxide composite nano materials of ZIF-8 MOFs cladding are prepared by liquid phase synthesis, the high dispersing copper zinc catalyst of nitrogen-doped carbon skeleton cladding is obtained after temperature-programmed calcination.It is characteristic of the invention that copper oxide nano particle is added during preparing MOFs material ZIF-8 in this method, so that copper oxide nanometer particle is uniformly carried in MOFs in situ, while obtaining the high dispersive zinc of carbon skeleton cladding after high-temperature calcination, also achieve the reduction and redisperse of copper, and there is also a large amount of pyridine nitrogens in carbon skeleton, develop a kind of novel preparation technology of the high dispersing copper zinc catalyst of pyridine nitrogen-doped carbon skeletal support, and the catalyst is applied to hydrogenation of carbon dioxide reduction and is prepared in reaction of carbon monoxide, with excellent catalytic activity, the copper zinc active site of high dispersive and the presence of a large amount of pyridine nitrogens all have very big facilitation to the promotion of catalytic activity.
Description
Technical field
The present invention proposes preparation method and its user of a kind of high dispersing copper zinc catalyst for carbon dioxide reduction
Method belongs to field of material synthesis technology.The catalyst is then in situ by liquid phase synthesis using copper oxide and zinc ion as presoma
The copper oxide composite nano materials of ZIF-8 MOFs cladding are prepared in load, and nitrogen-doped carbon bone is obtained after temperature-programmed calcination
The high dispersing copper zinc catalyst of frame cladding.It is used for the catalyst to be catalyzed carbon dioxide reduction reaction, there is preferable catalysis to live
Property.
Background technique
The burning of fossil fuel results in a large amount of discharges of carbon dioxide, causes greenhouse effects, to accelerate the whole world
Warm.Therefore, the trapping of carbon dioxide, seal up for safekeeping and especially urgent using seeming.Wherein, the chemical conversion of carbon dioxide is realized
Due to the popularity of raw material sources and the importance of product, one of most promising Land use systems are become.Wherein, it utilizes
Carbon dioxide reduction is concerned for carbon monoxide because of its technical feasibility by inverse water gas shift reation (RWGS).
Catalyst currently used for RWGS reaction is mostly loaded noble metal catalyst, and the transition of relative low price is golden
The research of metal catalyst is always research hotspot in recent years, and copper-based catalysts are exactly wherein popular one of catalyst.Generally recognize
For metal nanoparticle content is higher, particle is smaller higher more dispersing then catalytic activity, for RWGS reaction, according to
Formula (1) is then more conducive to the progress of the reaction it is found that temperature is higher, but high temperature can cause the sintering of copper nano particles, from
And the reduction of catalytic activity is caused even to inactivate, the poor thermal stability of catalyst seriously limits its application.Therefore, one is developed
Kind of the high dispersive and high copper-based catalysts of thermal stability have great application prospect.
H2 + CO2 ⇌ H2O+ CO ΔHR (1073 K) = 37 kJ/mol (1)
It is generally believed that the hydrogenating reduction of carbon dioxide occurs in the interface of metal and metal oxide, in copper zinc catalyst system
In, other than metallic copper, zinc oxide also plays vital effect in the reaction.This patent leads to as starting point
Metallic copper phase and zinc oxide phase high degree of dispersion are opened, promote its catalytic activity, have simultaneously by the restriction effect for crossing MOFs carbon skeleton
Effect prevents the reunion of the metal active centres in high-temperature reaction process, improves its catalytic stability.In addition, containing in carbon skeleton
There is a large amount of nitrogen active site, promote absorption and activation to carbon dioxide, to further improve to carbon dioxide also
The catalytic activity of original reaction.
Summary of the invention
It is an object of the invention to propose a kind of high score of nitrogen-doped carbon skeletal support for carbon dioxide reduction reaction
The preparation method and its application method of copper zinc catalyst are dissipated, this method can be while generating the copper and zinc of high dispersive, will
MOFs skeleton carbon turns to the stable carbon skeleton containing a large amount of nitrogen sites, while playing the role of supporting dispersed metal, also promotes
The promotion of catalytic activity and catalytic stability.By the composite catalyst be applied to catalysis carbon dioxide reduction reaction, have compared with
High catalytic activity and selectivity of product.
The specific technical solution of the present invention is as described below:
Scheme 1, a kind of preparation method of the high dispersing copper zinc catalyst for carbon dioxide reduction, it is characterised in that comprising following
Step:
(1) the organic alcoholic solution for preparing the copper nitrate of mass fraction 10%, is then added a certain amount of water and organic acid, room temperature
Lower stirring at least 1 hour, obtains mixed solution A, wherein the mass ratio of the organic alcoholic solution and water and organic acid of copper nitrate is
20‒50:1:1；
(2) mixed solution A is transferred in hydrothermal reaction kettle, 150 180 °C lower isothermal reaction 3 12 hours, then take out
Reaction kettle is cooled to room temperature, and obtains sample B；
(3) the zinc salt methanol solution that mass fraction is 5% is prepared, is mixed with a certain amount of sample B, stirs at least 30 points at room temperature
Clock obtains sample C, and wherein sample B accounts for 20% the 60% of zinc salt methanol solution mass fraction；
(4) it prepares mass fraction and is 5% 2-methylimidazole methanol solution, and it is mixed with sample C, stir 6 24 at room temperature
Hour, it is then centrifuged for and is sufficiently washed with methanol, obtain sample D after drying；Wherein mole of 2-methylimidazole and zinc ion
Than for 2 10:1；
(5) under the inert gas atmosphere of flowing, sample D is warming up in tube furnace with the heating rate of 15 °C/min
300 400 °C and maintenance at least 2 hours, 500 800 °C then are warming up to the heating rate of 5 10 °C/min and is maintained extremely
It is 2 hours few, it is down to room temperature then to get required high dispersing copper zinc catalyst is arrived, wherein the volume space velocity of inert gas is
600‒1200 h-1。
Scheme 2, preparation method according to scheme 1, which is characterized in that the Organic Alcohol is ethyl alcohol, ethylene glycol, gathers
One or more of ethylene glycol, 1,2- propylene glycol, glycerine.
Scheme 3, preparation method according to scheme 1, which is characterized in that the organic acid is formic acid, acetic acid, third
One or more of acid, butyric acid.
Scheme 4, preparation method according to scheme 1, which is characterized in that the zinc salt is zinc nitrate, zinc acetate, chlorine
Change one or more of zinc.
Scheme 5, a kind of preparation method of the high dispersing copper zinc catalyst for carbon dioxide reduction, it is characterised in that include
Following steps:
1) the organic alcoholic solution for preparing the copper nitrate of mass fraction 10%, is then added a certain amount of water and organic acid, at room temperature
Stirring at least 1 hour, obtains mixed solution A, and wherein the mass ratio of organic alcoholic solution of copper nitrate and water and organic acid is 20
50:1:1；
2) mixed solution A is transferred in hydrothermal reaction kettle, 150 180 °C lower isothermal reaction 3 12 hours, then take out anti-
Kettle is answered, is cooled to room temperature, sample B is obtained；
3) the zinc salt methanol solution that mass fraction is 5% and the 2-methylimidazole methanol solution that mass fraction is 5% are prepared, by two
Person quickly mixes, while a certain amount of sample B is added, and stirs 6 24 hours at room temperature, is then centrifuged for and is sufficiently washed with methanol
It washs, obtains sample C after drying；Wherein the molar ratio of 2-methylimidazole and zinc ion is 2 10:1, and it is molten that sample B accounts for zinc salt methanol
20% the 60% of liquid mass fraction；
4) under the inert gas atmosphere of flowing, sample C is warming up in tube furnace with the heating rate of 15 °C/min
300 400 °C and maintenance at least 2 hours, gas is then switched to ammonia, is warming up to the heating rate of 5 10 °C/min
500 800 °C and maintenance at least 2 hours, it is then switched to inert gas again, is down to room temperature under inert gas atmosphere, i.e.,
Required high dispersing copper zinc catalyst is obtained, wherein the volume space velocity of inert gas is 600 1200 h-1, the volume space velocity of ammonia
For 300 600 h-1。
Scheme 6, the preparation method according to scheme 5, which is characterized in that the Organic Alcohol is ethyl alcohol, ethylene glycol, gathers
One or more of ethylene glycol, 1,2- propylene glycol, glycerine.
Scheme 7, the preparation method according to scheme 5, which is characterized in that the organic acid is formic acid, acetic acid, third
One or more of acid, butyric acid.
Scheme 8, the preparation method according to scheme 5, which is characterized in that the zinc salt is zinc nitrate, zinc acetate, chlorine
Change one or more of zinc.
Scheme 9, a kind of preparation method of the high dispersing copper zinc catalyst for carbon dioxide reduction, which is characterized in that make
It is made with the described in any item preparation methods of scheme 18.
Application method described in scheme 10, a kind of scheme 9 for the high dispersing copper zinc catalyst of carbon dioxide reduction,
It is characterized in that comprising the steps of:
1) 0.4 g is taken to be placed in the constant temperature section of fixed bed reactors after grinding the high dispersing copper zinc catalyst of preparation,
It is warming up to 400 500 °C under the hydrogen atmosphere of flowing and maintains at least 2 hours, hydrogen volume air speed is 3,000 9000 h-1,
2) it is then cooled to 300 500 °C of reaction temperature, is passed through carbon dioxide gas later, wherein carbon dioxide volume is empty
Speed is 3000 h-1, the volume ratio of carbon dioxide and hydrogen is 1:1 5.
Compared with existing copper zinc catalyst for carbon dioxide reduction reaction and preparation method thereof, the present invention has such as
Lower innovation:
(1) by way of loading in situ, copper nano-particle is limited in carbon skeleton, improves the stability of catalyst.Benefit
With the coordination of 2-methylimidazole and zinc ion, copper oxide nano particle is coated in MOFs by liquid phase synthesis, is passed through
After high-temperature roasting, while generating stable carbon skeleton, copper oxide is reduced to copper, and the presence of this stable carbon skeleton can
Effectively to prevent the sintering of the metallic copper in high-temperature reaction process, to promote the stability of catalyst.
(2) in high-temperature calcination process, due to the restriction effect of ligand, it is therefore prevented that MOFs decomposes generated zinc oxide
Aggregation, has achieved high dispersive, meanwhile, copper oxide particle by carbon during being restored due to organic ligand and formation
The restriction effect of carbon skeleton, promotes the redisperse of copper, so that the high dispersive of copper is realized, the copper zinc active sites of this high dispersive
Point is conducive to the promotion of catalytic performance.
(3) nitrogen can be introduced, to improve catalyst as organic ligand in carbon skeleton using 2-methylimidazole
Activity.The presence of nitrogen especially pyridine nitrogen can promote the absorption to carbon dioxide and active intermediate kind, in turn
Promote carbon dioxide reduction reaction activity.The use of 2-methylimidazole is conducive to introduce a large amount of nitrogenous sites in carbon skeleton especially
It is pyridine nitrogen site, to promote the catalytic performance of carbon dioxide reduction.
(4) as described in specific technical solution 5, carrying out roasting using ammonia can be improved the quantity of nitrogenous active site.?
During carrying out high temperature cabonization, is roasted using ammonia atmosphere, the nitrogen element content in carbon skeleton can be further increased,
The nitrogen active site for obtaining more polymolecularities, to promote catalytic performance.
(5) the high dispersing copper zinc catalyst of obtained nitrogen-doped carbon skeletal support shows in carbon dioxide reduction reaction
High activity out, due to the polymolecularity of metal active centres, the facilitation of nitrogenous active site in addition, carbon dioxide reduction
It can be significantly improved.
Detailed description of the invention
Fig. 1: the stereoscan photograph of Cat-1 prepared by embodiment 1；
Fig. 2: the transmission electron microscope photo of Cat-1 prepared by embodiment 1.
Specific embodiment
In order to make industry personnels more fully understand technical solution of the present invention, following embodiment is now listed.But this
It is that in order to facilitate the understanding of the present invention, these embodiments can not be used to limit the scope of the invention, all according to this hair
The variation of non-intrinsically safe made by bright application protection scope and improvement etc., still should be regarded as scope of patent protection of the invention.This hair
Bright specific application protection scope proposes in the dependent claims.
Embodiment 1
(1) ethylene glycol solution for preparing the copper nitrate that mass fraction is 10%, weighs the 100 g solution, 2 g water is added, at room temperature
Stirring 1 hour, is then added 2 g acetic acid, continues stirring 1 hour at room temperature, obtains mixed solution A；
(2) mixed solution A is transferred in hydrothermal reaction kettle, 180 °C lower isothermal reaction 6 hours, then take out reaction kettle, it is cold
But to room temperature, sample B is obtained；
(3) the zinc nitrate methanol solution that mass fraction is 5% is prepared, weighs the 200 g solution, and it is added in 50 g sample B
In, it stirs 30 minutes at room temperature, obtains sample C；
(4) it prepares mass fraction and is 5% 2-methylimidazole methanol solution, and 600 g is taken to mix with sample C, stir 6 at room temperature
Hour, it is 4 hours dry at a temperature of 80 DEG C after being centrifuged, being washed, it is then 4 hours dry at a temperature of 120 DEG C, obtain sample
Product D；
(5) under the nitrogen gas atmosphere of flowing, sample D is placed in the constant temperature section of tube furnace, with the heating speed of 5 °C/min
Rate is warming up to 300 °C and maintains 2 hours, is then warming up to 700 °C and maintenance 2 hours with the heating rate of 5 °C/min, so
It is down to room temperature afterwards to get to required high dispersing copper zinc catalyst, number Cat-1, wherein nitrogen volume space velocity is 600
h-1。
Embodiment 2
(1) glycerite for preparing the copper nitrate that mass fraction is 10%, weighs the 150 g solution, and 4 g water are added, stir at room temperature
It mixes 1 hour, 4 g acetic acid is then added, continue stirring 1 hour at room temperature, obtain mixed solution A；
(2) mixed solution A is transferred in hydrothermal reaction kettle, 160 °C lower isothermal reaction 12 hours, then take out reaction kettle, it is cold
But to room temperature, sample B is obtained；
(3) the zinc chloride methanol solution that mass fraction is 5% is prepared, weighs the 200 g solution, and it is added in 80 g sample B
In, it stirs 30 minutes at room temperature, obtains sample C；
(4) it prepares mass fraction and is 5% 2-methylimidazole methanol solution, and 800 g is taken to mix with sample C, stir 12 at room temperature
Hour, it is 4 hours dry at a temperature of 80 DEG C after being centrifuged, being washed, it is then 4 hours dry at a temperature of 120 DEG C, obtain sample
Product D；
(5) under the nitrogen gas atmosphere of flowing, sample D is placed in the constant temperature section of tube furnace, with the heating speed of 5 °C/min
Rate is warming up to 300 °C and maintains 2 hours, is then warming up to 700 °C and maintenance 2 hours with the heating rate of 5 °C/min, so
It is down to room temperature afterwards to get to required high dispersing copper zinc catalyst, number Cat-2, wherein nitrogen volume space velocity is 600
h-1。
Embodiment 3
(1) aqueous isopropanol for preparing the copper nitrate that mass fraction is 10%, weighs the 100 g solution, 2 g water is added, at room temperature
Stirring 1 hour, is then added 2 g acetic acid, continues stirring 1 hour at room temperature, obtains mixed solution A；
(2) mixed solution A is transferred in hydrothermal reaction kettle, 180 °C lower isothermal reaction 12 hours, then take out reaction kettle, it is cold
But to room temperature, sample B is obtained；
(3) the zinc acetate methanol solution that mass fraction is 5% is prepared, weighs the 200 g solution, and it is added in 50 g sample B
In, it stirs 30 minutes at room temperature, obtains sample C；
(4) it prepares mass fraction and is 5% 2-methylimidazole methanol solution, and 400 g is taken to mix with sample C, stir 6 at room temperature
Hour, it is 4 hours dry at a temperature of 80 DEG C after being centrifuged, being washed, it is then 4 hours dry at a temperature of 120 DEG C, obtain sample
Product D；
(5) under the nitrogen gas atmosphere of flowing, sample D is placed in the constant temperature section of tube furnace, with the heating speed of 5 °C/min
Rate is warming up to 300 °C and maintains 2 hours, is then warming up to 600 °C and maintenance 2 hours with the heating rate of 5 °C/min, so
It is down to room temperature afterwards to get to required high dispersing copper zinc catalyst, number Cat-3, wherein nitrogen volume space velocity is 600
h-1。
Embodiment 4
(1) ethylene glycol solution for preparing the copper nitrate of mass fraction 10%, weighs the 100 g solution, and 2 g water are added, stir at room temperature
It mixes 1 hour, 2 g acetic acid is then added, continue stirring 1 hour at room temperature, obtain mixed solution A；
(2) mixed solution A is transferred in hydrothermal reaction kettle, 180 °C lower isothermal reaction 6 hours, then take out reaction kettle,
It is cooled to room temperature, obtains sample B；
(3) the zinc nitrate methanol solution that mass fraction is 5% and the 2-methylimidazole methanol solution that mass fraction is 5% are prepared,
200 g and 600 g are taken respectively, the two is quickly mixed, while 50 g sample B are added, and are stirred 6 hours at room temperature, are centrifuged, are washed
It is 4 hours dry at a temperature of 80 DEG C after washing, it is then 4 hours dry at a temperature of 120 DEG C, obtain sample C；
(4) under the nitrogen gas atmosphere of flowing, sample C is warming up to 300 in tube furnace with the heating rate of 5 °C/min
°C and maintain 2 hours, gas is then switched to ammonia, 700 °C is warming up to the heating rate of 5 °C/min and maintains 2 small
When, it is then switched to nitrogen again, is down to room temperature in a nitrogen atmosphere to get to required high dispersing copper zinc catalyst, numbers
For Cat-4, wherein nitrogen volume space velocity is 1200 h-1, ammonia volume space velocity is 600 h-1。
Embodiment 5
(1) glycerite for preparing the copper nitrate of mass fraction 10%, weighs the 150 g solution, and 4 g water are added, stir at room temperature
1 hour, 4 g acetic acid are then added, continues stirring 1 hour at room temperature, obtains mixed solution A；
(2) mixed solution A is transferred in hydrothermal reaction kettle, 160 °C lower isothermal reaction 12 hours, then take out reaction kettle,
It is cooled to room temperature, obtains sample B；
(3) the zinc chloride methanol solution that mass fraction is 5% and the 2-methylimidazole methanol solution that mass fraction is 5% are prepared,
200 g and 800 g are taken respectively, the two is quickly mixed, while 80 g sample B are added, and are stirred 12 hours at room temperature, be centrifuged,
It is 4 hours dry at a temperature of 80 DEG C after washing, it is then 4 hours dry at a temperature of 120 DEG C, obtain sample C；
(4) under the nitrogen gas atmosphere of flowing, sample C is warming up to 300 in tube furnace with the heating rate of 5 °C/min
°C and maintain 2 hours, gas is then switched to ammonia, 600 °C is warming up to the heating rate of 5 °C/min and maintains 2 small
When, it is then switched to nitrogen again, is down to room temperature in a nitrogen atmosphere to get to required high dispersing copper zinc catalyst, numbers
For Cat-5, wherein nitrogen volume space velocity is 1200 h-1, ammonia volume space velocity is 600 h-1。
Embodiment 6
(1) aqueous isopropanol for preparing the copper nitrate of mass fraction 10%, weighs the 100 g solution, and 2 g water are added, stir at room temperature
It mixes 1 hour, 2 g acetic acid is then added, continue stirring 1 hour at room temperature, obtain mixed solution A；
(2) mixed solution A is transferred in hydrothermal reaction kettle, 180 °C lower isothermal reaction 12 hours, then take out reaction kettle,
It is cooled to room temperature, obtains sample B；
(3) the zinc acetate methanol solution that mass fraction is 5% and the 2-methylimidazole methanol solution that mass fraction is 5% are prepared,
200 g and 400 g are taken respectively, the two is quickly mixed, while 50 g sample B are added, and are stirred 6 hours at room temperature, are centrifuged, are washed
It is 4 hours dry at a temperature of 80 DEG C after washing, it is then 4 hours dry at a temperature of 120 DEG C, obtain sample C；
(4) under the nitrogen gas atmosphere of flowing, sample C is warming up to 300 in tube furnace with the heating rate of 5 °C/min
°C and maintain 2 hours, gas is then switched to ammonia, 800 °C is warming up to the heating rate of 5 °C/min and maintains 2 small
When, it is then switched to nitrogen again, is down to room temperature in a nitrogen atmosphere to get to required high dispersing copper zinc catalyst, numbers
For Cat-6, wherein nitrogen volume space velocity is 1200 h-1, ammonia volume space velocity is 600 h-1。
Comparative example 1
Prepare the nitrogenous carbon material without metal, it is therefore intended that make comparisons with embodiment 1, understand metallic site to the shadow of catalytic activity
It rings.
The step of preparation process is with embodiment 1 is identical, but after obtaining the copper zinc catalyst Cat-1 of high dispersive, by 1.0
G catalyst is mixed with excessive 5% dilute nitric acid solution, is stirred 12 hours at room temperature, after filtered, washed to neutrality, then will filter
Cake dries 6 hours in 120 °C to get the nitrogenous carbon material without metal, number Cat-7 is arrived.
The evaluation procedure and condition of catalyst are as follows: by the high dispersing copper zinc catalyst of preparation after grinding, 0.4 g is taken to set
In the constant temperature section of fixed bed reactors, it is warming up to 400 °C under the hydrogen atmosphere of flowing and maintains 2 hours, hydrogen volume is empty
Speed is 3000 h-1, 500 °C of reaction temperature is then raised temperature to, is passed through carbon dioxide gas later, wherein carbon dioxide volume
Air speed is 3000 h-1, the volume ratio of carbon dioxide and hydrogen is 1:3.It is formed with gas chromatographic analysis product, was adopted every 30 minutes
Sample is primary, carries out sampling analysis, the carbon dioxide conversion and an oxygen of different high dispersing copper zinc catalysts with the point reacted 2 hours
Changing carbon selectivity correlation data, it is as shown in the table:
| Catalyst number | Carbon dioxide conversion (%) | Carbon monoxide selective (%) |
| Cat-1 | 35.3 | >99 |
| Cat-2 | 34.9 | >99 |
| Cat-3 | 34.5 | >99 |
| Cat-4 | 39.2 | >99 |
| Cat-5 | 37.9 | >99 |
| Cat-6 | 37.4 | >99 |
| Cat-7 | 2.1 | >99 |
Claims (10)
1. a kind of preparation method of the high dispersing copper zinc catalyst for carbon dioxide reduction, it is characterised in that include following step
It is rapid:
1) the organic alcoholic solution for preparing the copper nitrate of mass fraction 10%, is then added a certain amount of water and organic acid, at room temperature
Stirring at least 1 hour, obtains mixed solution A, and wherein the mass ratio of organic alcoholic solution of copper nitrate and water and organic acid is 20
50:1:1；
2) mixed solution A is transferred in hydrothermal reaction kettle, 150 180 °C lower isothermal reaction 3 12 hours, then take out anti-
Kettle is answered, is cooled to room temperature, sample B is obtained；
3) the zinc salt methanol solution that mass fraction is 5% is prepared, is mixed with a certain amount of sample B, stirs at least 30 points at room temperature
Clock obtains sample C, and wherein sample B accounts for 20% the 60% of zinc salt methanol solution mass fraction；
4) it prepares mass fraction and is 5% 2-methylimidazole methanol solution, and it is mixed with sample C, it is small to stir 6 24 at room temperature
When, it is then centrifuged for and is sufficiently washed with methanol, obtain sample D after drying；The wherein molar ratio of 2-methylimidazole and zinc ion
For 2 10:1；
5) under the inert gas atmosphere of flowing, sample D is warming up in tube furnace with the heating rate of 15 °C/min
300 400 °C and maintenance at least 2 hours, 500 800 °C then are warming up to the heating rate of 5 10 °C/min and is maintained extremely
It is 2 hours few, it is down to room temperature then to get required high dispersing copper zinc catalyst is arrived, wherein the volume space velocity of inert gas is
600‒1200 h-1。
2. preparation method according to claim 1, which is characterized in that the Organic Alcohol is ethyl alcohol, ethylene glycol, poly- second two
One or more of alcohol, 1,2- propylene glycol, glycerine.
3. preparation method according to claim 1, which is characterized in that the organic acid is formic acid, acetic acid, propionic acid, fourth
One or more of acid.
4. preparation method according to claim 1, which is characterized in that the zinc salt is zinc nitrate, zinc acetate, zinc chloride
One or more of.
5. a kind of preparation method of the high dispersing copper zinc catalyst for carbon dioxide reduction, it is characterised in that include following step
It is rapid:
1) the organic alcoholic solution for preparing the copper nitrate of mass fraction 10%, is then added a certain amount of water and organic acid, at room temperature
Stirring at least 1 hour, obtains mixed solution A, and wherein the mass ratio of organic alcoholic solution of copper nitrate and water and organic acid is 20
50:1:1；
2) mixed solution A is transferred in hydrothermal reaction kettle, 150 180 °C lower isothermal reaction 3 12 hours, then take out anti-
Kettle is answered, is cooled to room temperature, sample B is obtained；
3) the zinc salt methanol solution that mass fraction is 5% and the 2-methylimidazole methanol solution that mass fraction is 5% are prepared, by two
Person quickly mixes, while a certain amount of sample B is added, and stirs 6 24 hours at room temperature, is then centrifuged for and is sufficiently washed with methanol
It washs, obtains sample C after drying；Wherein the molar ratio of 2-methylimidazole and zinc ion is 2 10:1, and it is molten that sample B accounts for zinc salt methanol
20% the 60% of liquid mass fraction；
4) under the inert gas atmosphere of flowing, sample C is warming up in tube furnace with the heating rate of 15 °C/min
300 400 °C and maintenance at least 2 hours, gas is then switched to ammonia, is warming up to the heating rate of 5 10 °C/min
500 800 °C and maintenance at least 2 hours, it is then switched to inert gas again, is down to room temperature under inert gas atmosphere, i.e.,
Required high dispersing copper zinc catalyst is obtained, wherein the volume space velocity of inert gas is 600 1200 h-1, the volume space velocity of ammonia
For 300 600 h-1。
6. preparation method according to claim 5, which is characterized in that the Organic Alcohol is ethyl alcohol, ethylene glycol, poly- second two
One or more of alcohol, 1,2- propylene glycol, glycerine.
7. preparation method according to claim 5, which is characterized in that the organic acid is formic acid, acetic acid, propionic acid, fourth
One or more of acid.
8. preparation method according to claim 5, which is characterized in that the zinc salt is zinc nitrate, zinc acetate, zinc chloride
One or more of.
9. a kind of preparation method of the high dispersing copper zinc catalyst for carbon dioxide reduction, which is characterized in that wanted using right
18 described in any item preparation methods are asked to be made.
10. a kind of application method of the high dispersing copper zinc catalyst as claimed in claim 9 for carbon dioxide reduction, feature
It is to comprise the steps of:
1) 0.4 g is taken to be placed in the constant temperature section of fixed bed reactors after grinding the high dispersing copper zinc catalyst of preparation,
It is warming up to 400 500 °C under the hydrogen atmosphere of flowing and maintains at least 2 hours, hydrogen volume air speed is 3,000 9000 h-1；
2) reaction temperature for then changing temperature to 300 500 °C, is passed through carbon dioxide gas, wherein carbon dioxide body later
Product air speed is 3000 h-1, the volume ratio of carbon dioxide and hydrogen is 1:1 5.
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| CN113073343B (en) * | 2021-03-15 | 2023-02-28 | 南开大学 | Synthetic efficient electrocatalysis CO 2 Method for reducing copper-zinc bimetallic catalyst |
| CN113684495A (en) * | 2021-07-19 | 2021-11-23 | 华南理工大学 | Nitrogen-doped carbon-zinc oxide composite material and preparation method and application thereof |
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| CN115010944A (en) * | 2022-06-16 | 2022-09-06 | 重庆大学 | Method for preparing metal-organic framework structure material by using copper alkaline carbonate |
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