CN105413749B - A kind of material load CoB of ZIF 8 method for preparing catalyst - Google Patents
A kind of material load CoB of ZIF 8 method for preparing catalyst Download PDFInfo
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- CN105413749B CN105413749B CN201510891468.9A CN201510891468A CN105413749B CN 105413749 B CN105413749 B CN 105413749B CN 201510891468 A CN201510891468 A CN 201510891468A CN 105413749 B CN105413749 B CN 105413749B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention belongs to catalyzing manufacturing of hydrogen field, the more particularly to a kind of material load CoB of ZIF 8 method for preparing catalyst, including（1）With cobalt salt, zinc salt, 2 methylimidazoles etc. for raw material, the hybrid materials of ZIF 8/ZIF 67 are prepared；（2）The solution containing reducing agent is prepared, obtains solution A；（3）Excessive solution A is slowly injected into the hybrid materials of ZIF 8/ZIF 67, stirs, obtains suspension B；（4）Solution B is stood into a period of time, it is further reduced, obtains suspension C；（5）Suspension C is filtered, washing, be dried in vacuo the catalyst for producing the material load CoB of ZIF 8；（6）The load C oB catalyst of ZIF 8 is used to be catalyzed sodium borohydride hydrolysis.Low in investment cost of the present invention, catalyst service life length, has large surface area, can dramatically speed up preparing hydrogen by sodium borohydride hydrolysis speed, effectively reduce reaction activity.
Description
Technical field
The invention belongs to catalyzing manufacturing of hydrogen field, more particularly to a kind of ZIF-8 material loads CoB method for preparing catalyst.
Background technology
The limited reserves of fossil fuel make the mankind be faced with unprecedented energy crisis, while its combustion product is arranged
It is put into air and accelerates greenhouse effects.These problems are faced, there is an urgent need to find a kind of new energy that can be substituted by the present mankind
Source.Hydrogen Energy receives much attention as a kind of reproducible green energy resource, and the efficient utilization of Hydrogen Energy becomes people and ground
The focus studied carefully, wherein having obvious advantage using hydrogen as fuel.But seek hydrogen storage conveniently, safely, practical
Technology is still a challenge.
NaBH4Hydrogen-storage density is high, and hydrogen content is up to 10.6%, about the 5 of common metal cyanide times, and NaBH4Hydrolysis
Not discharge of noxious gases in hydrogen production process, hydrogen purity is high, without the pernicious gas for making fuel cell be poisoned, simultaneously because not
External energy is needed, the utilization ratio of energy is high, makes NaBH4Hydrolysis as a kind of new hydrogen production technology conveniently, safely by
Paid close attention to by scientific research personnel.
In order to realize quick controllable production hydrogen, it is necessary to which selecting a kind of efficient catalyst as hydrogen atom is compound turns into hydrogen molecule
Place be catalyzed its hydrolysis.Conventional catalyst has two classes, and one kind is noble metal, such as Pt, Ru and its alloy, another
Class is the base metals such as NiB, CoB.Because the with high costs and reserves of noble metal are limited, it is difficult to meet large-scale application, and
Base metal can also have fabulous performance, so in terms of current research is concentrated mainly on non-precious metal catalyst.
The content of the invention
Reduced it is contemplated that providing a kind of equipment in place of overcome the deficiencies in the prior art, low in investment cost, and
Catalyst service life is grown, and has large surface area, can dramatically speed up reaction rate, effectively reduces the use of reaction activity
The method of ZIF-8 load C oB catalyst sodium borohydride hydrogen manufacturing.
A kind of ZIF-8 material loads CoB method for preparing catalyst, can be carried out as follows.
（1）By cobalt salt and zinc salt dissolving in a solvent, the solution containing cobalt and zinc is prepared.
（2）By 2-methylimidazole dissolving in a solvent, the ligand solution containing 2-methylimidazole is prepared.
（3）By step（1）Resulting solution pours into step（2）In resulting solution, at room temperature stirring a period of time, it is transferred to
In 100mL reactors, pyroreaction for a period of time, cools down, and filters, is drying to obtain ZIF-8/ZIF-67 and mixes sill.
（4）The solution containing reducing agent is prepared, obtains solution A.
（5）Excessive reductant solution A is slowly injected into step（3）The ZIF-8/ZIF-67 hybrid materials of gained, stirring,
Reduce the cobalt ions wherein contained and obtain suspension B, stand a period of time.
（6）By step（5）Suspension B after middle standing, filter, washing, be dried in vacuo and produce ZIF-8 load Cs oB catalysis
Agent.
（7）Take sodium borohydride to be added in the thermostatic container equipped with alkaline solution, add step（6）In obtained ZIF-
8 load C oB catalyst.
（8）With the process of Weight Lab software records catalytic reactions.
As a kind of preferred scheme, step of the present invention（1）In cobalt salt be cobalt nitrate or cobalt chloride, zinc salt is nitric acid
Zinc or zinc chloride.
Further, step of the present invention（1）In zinc salt be zinc nitrate or zinc chloride.
Further, step of the present invention（1）And step（2）Solvent for use is DMF.
Further, step of the present invention（3）In, cobalt ions and mole sum of zinc ion and rubbing for 2-methylimidazole
You are than being 1:1~30.
Further, in hybrid materials of the present invention, the mol ratio of cobalt ions and zinc ion is 5~60：100.
Further, step of the present invention（3）In high temperature be 120~140 DEG C, the time is 24~72h.
Further, step of the present invention（4）All reducing agents are NaBH4；Prepare reducing agent solvent for go from
Sub- water or ethanol.
Further, CoB quality is the 5%~60% of ZIF-8 mass in ZIF-8 load Cs oB catalyst of the present invention.
Further, step of the present invention（7）In alkaline solution be sodium hydroxide the aqueous solution；The matter of sodium hydroxide
It is 5% to measure concentration；The quality of ZIF-8 load C oB catalyst and the mass ratio of sodium borohydride are：2~10: 100.
Research finds that cobalt-base catalyst has extensive prospects for commercial application, and CoB is in preparation process, due to its magnetic
Surface, which is easily reunited, causes catalyst granules larger, and decentralization is not high, so load type Co B catalyst has more application prospect.
ZIFs materials are a kind of higher metal-organic framework materials of stability, have higher specific surface area and can modulation duct knot
Structure, and ZIFs materials can also be stable in the presence of in alkaline solution.
In ZIF-8 load C oB catalyst prepared by the present invention, ZIF-8 has higher specific surface area, controllable duct
Structure, and prepared hybrid materials are the ZIFs materials of binary metal, overcome adsorption intensity and adsorptive selectivity
The defects of not high, active component CoB degree of scatter and immobilized intensity are improved, the ZIF-8 load C oB catalyst of preparation is existed
Dosage is few in catalytic reaction process, and has good activity and stability, has dramatically speeded up preparing hydrogen by sodium borohydride hydrolysis speed,
Reaction activity is effectively reduced, it is significant that hydrogen is released to liquid phase hydrogen storage.
Brief description of the drawings
With reference to specific embodiment, the invention will be further described.Material involved in the present invention, which includes, not to be limited to
With the statement in following examples.
Fig. 1 is the obtained ZIF-8 material supports SEM figures of the present invention.
Fig. 2 is the XRD of the obtained ZIF-8 load C oB catalyst of the present invention.
Fig. 3 is the Arrhenius curve map of the obtained ZIF-8 load C oB catalysts sodium borohydride hydrolysis of the present invention.
Embodiment
In embodiment, the X-ray diffraction measure of finished product is with German Brooker D8 Advance type X-ray diffractions
Instrument, experimental condition are：X ray CuK α target emanations, graphite monochromator, tube voltage 35KV, tube current 40mA, filter plate Co, sweep
It is 8 °/min to retouch speed, and step width is 0.02 °.
Embodiment 1.
0.5471g cobalt nitrate hexahydrates [Co (NO are weighed first3)2·6H2O] and 0.5593g zinc nitrate hexahydrates [Zn (NO3)2·
6H2O] fully dissolved is in 30mLN, N-2 NMFs（DMF）In；3.087g2- methylimidazoles are weighed to be dissolved in 30mL DMF；
Both of which is ultrasonic 5 minutes, then former solution is poured into the latter solution, by mixed solution, room temperature is stirred on magnetic stirring apparatus
Mix 30 minutes.Then mixed solution is transferred in 100mL reactors, is put into 140 DEG C of insulation 72h in air dry oven, cools down,
Filter, washing, drying can be obtained by ZIF-8/ZIF-67 hybrid materials.Then 0.6232g sodium borohydrides are weighed to be dissolved in
In 15mL absolute ethyl alcohols and the mixed solution of 15mL deionized waters, obtained mixed solution is added dropwise to 1g by syringe pump
ZIF sills in, after being added dropwise to complete, stand 30 minutes, then filter and be washed with deionized three times, gained sediment is put
Enter in vacuum drying oven, open vavuum pump, after vacuum arrival -0.1MPa, begin to warm up to after 40 DEG C of dry 4h, treat that vacuum is done
Dry box temperature degree takes out dried object after dropping to room temperature, obtains ZIF-8 load C oB catalyst.Sodium borohydride is taken to be added to equipped with quality
Concentration is in the thermostatic container of 5% alkaline solution of sodium hydroxide, adds ZIF-8 load C oB catalyst（ZIF-8 load Cs oB is urged
The quality of agent and the mass ratio of sodium borohydride are：2~10: 100）, 25 DEG C of reaction temperature, with Weight Lab software records
The process of catalytic reaction, catalyst hydrogen production rate in sodium borohydride hydrogen manufacturing is 996mLmin-1.g-1。
Embodiment 2.
0.0274g cobalt nitrate hexahydrates [Co (NO are weighed first3)2·6H2O] and 0.5593g zinc nitrate hexahydrates [Zn (NO3)2·
6H2O] fully dissolved is in 30mLN, N-2 NMFs（DMF）In；Weigh 1.6207g2- methylimidazoles and be dissolved in 30mL DMF
In；Both of which is ultrasonic 5 minutes, then former solution is poured into the latter solution, by mixed solution in magnetic stirring apparatus upper chamber
Temperature stirring 30 minutes.Then mixed solution is transferred in 100mL reactors, is put into 140 DEG C of insulation 72h in air dry oven,
Cooling, filter, washing, drying can be obtained by ZIF-8/ZIF-67 hybrid materials.Then the dissolving of 0.6232g sodium borohydrides is weighed
In 15mL absolute ethyl alcohols and the mixed solution of 15mL deionized waters, obtained mixed solution is added dropwise to by syringe pump
In 1g ZIF sills, after being added dropwise to complete, 30 minutes are stood, then filters and is washed with deionized three times, gained sediment
It is put into vacuum drying oven, opens vavuum pump, after vacuum arrival -0.1MPa, begin to warm up to after 40 DEG C of dry 4h, treat vacuum
Drying box temperature takes out dried object after dropping to room temperature, obtains ZIF-8 load C oB catalyst.Sodium borohydride is taken to be added to equipped with matter
Concentration is measured in the thermostatic container of 5% alkaline solution of sodium hydroxide, to add ZIF-8 load C oB catalyst（ZIF-8 load Cs oB
The quality of catalyst and the mass ratio of sodium borohydride are：2~10: 100）, 25 DEG C of reaction temperature, remembered with Weight Lab softwares
The process of catalytic reaction is recorded, catalyst hydrogen production rate in sodium borohydride hydrogen manufacturing is 496 mLmin-1·g-1。
Embodiment 3.
0.0547g cobalt nitrate hexahydrates [Co (NO are weighed first3)2·6H2O] and 0.5593g zinc nitrate hexahydrates [Zn (NO3)2·
6H2O] fully dissolved is in 30mLN, N-2 NMFs（DMF）In；Weigh 1.6979g2- methylimidazoles and be dissolved in 30mL DMF
In；Both of which is ultrasonic 5 minutes, then former solution is poured into the latter solution, by mixed solution in magnetic stirring apparatus upper chamber
Temperature stirring 30 minutes.Then mixed solution is transferred in 100mL reactors, is put into 140 DEG C of insulation 72h in air dry oven,
Cooling, filter, washing, drying can be obtained by ZIF-8/ZIF-67 hybrid materials.Then the dissolving of 0.6232g sodium borohydrides is weighed
In 15mL absolute ethyl alcohols and the mixed solution of 15mL deionized waters, obtained mixed solution is added dropwise to by syringe pump
In 1g ZIF sills, after being added dropwise to complete, 30 minutes are stood, then filters and is washed with deionized three times, gained sediment
It is put into vacuum drying oven, opens vavuum pump, after vacuum arrival -0.1MPa, begin to warm up to after 40 DEG C of dry 4h, treat vacuum
Drying box temperature takes out dried object after dropping to room temperature, obtains ZIF-8 load C oB catalyst.Sodium borohydride is taken to be added to equipped with matter
Concentration is measured in the thermostatic container of 5% alkaline solution of sodium hydroxide, to add ZIF-8 load C oB catalyst（ZIF-8 load Cs oB
The quality of catalyst and the mass ratio of sodium borohydride are：2~10: 100）, 25 DEG C of reaction temperature, remembered with Weight Lab softwares
The process of catalytic reaction is recorded, catalyst hydrogen production rate in sodium borohydride hydrogen manufacturing is 812 mLmin-1·g-1。
Embodiment 4.
0.1094g cobalt nitrate hexahydrates [Co (NO are weighed first3)2·6H2O] and 0.5593g zinc nitrate hexahydrates [Zn (NO3)2·
6H2O] fully dissolved is in 30mLN, N-2 NMFs（DMF）In；Weigh 1.8522g2- methylimidazoles and be dissolved in 30mL DMF
In；Both of which is ultrasonic 5 minutes, then former solution is poured into the latter solution, by mixed solution in magnetic stirring apparatus upper chamber
Temperature stirring 30 minutes.Then mixed solution is transferred in 100mL reactors, is put into 140 DEG C of insulation 72h in air dry oven,
Cooling, filter, washing, drying can be obtained by ZIF-8/ZIF-67 hybrid materials.Then the dissolving of 0.6232g sodium borohydrides is weighed
In 15mL absolute ethyl alcohols and the mixed solution of 15mL deionized waters, obtained mixed solution is added dropwise to by syringe pump
In 1g ZIF sills, after being added dropwise to complete, 30 minutes are stood, then filters and is washed with deionized three times, gained sediment
It is put into vacuum drying oven, opens vavuum pump, after vacuum arrival -0.1MPa, begin to warm up to after 40 DEG C of dry 4h, treat vacuum
Drying box temperature takes out dried object after dropping to room temperature, obtains ZIF-8 load C oB catalyst.Sodium borohydride is taken to be added to equipped with matter
Concentration is measured in the thermostatic container of 5% alkaline solution of sodium hydroxide, to add ZIF-8 load C oB catalyst（ZIF-8 load Cs oB
The quality of catalyst and the mass ratio of sodium borohydride are：2~10: 100）, 25 DEG C of reaction temperature, remembered with Weight Lab softwares
The process of catalytic reaction is recorded, catalyst hydrogen production rate in sodium borohydride hydrogen manufacturing is 934 mLmin-1·g-1。
Embodiment 5.
0.5471g cobalt nitrate hexahydrates [Co (NO are weighed first3)2·6H2O] and 0.5593g zinc nitrate hexahydrates [Zn (NO3)2·
6H2O] fully dissolved is in 30mLN, N-2 NMFs（DMF）In；Weigh 0.6174g2- methylimidazoles and be dissolved in 30mL DMF
In；Both of which is ultrasonic 5 minutes, then former solution is poured into the latter solution, by mixed solution in magnetic stirring apparatus upper chamber
Temperature stirring 30 minutes.Then mixed solution is transferred in 100mL reactors, is put into 140 DEG C of insulation 72h in air dry oven,
Cooling, filter, washing, drying can be obtained by ZIF-8/ZIF-67 hybrid materials.Then the dissolving of 0.6232g sodium borohydrides is weighed
In 15mL absolute ethyl alcohols and the mixed solution of 15mL deionized waters, obtained mixed solution is added dropwise to by syringe pump
In 1g ZIF sills, after being added dropwise to complete, 30 minutes are stood, then filters and is washed with deionized three times, gained sediment
It is put into vacuum drying oven, opens vavuum pump, after vacuum arrival -0.1MPa, begin to warm up to after 40 DEG C of dry 4h, treat vacuum
Drying box temperature takes out dried object after dropping to room temperature, obtains ZIF-8 load C oB catalyst.Sodium borohydride is taken to be added to equipped with matter
Concentration is measured in the thermostatic container of 5% alkaline solution of sodium hydroxide, to add ZIF-8 load C oB catalyst（ZIF-8 load Cs oB
The quality of catalyst and the mass ratio of sodium borohydride are：2~10: 100）, 25 DEG C of reaction temperature, remembered with Weight Lab softwares
The process of catalytic reaction is recorded, catalyst hydrogen production rate in sodium borohydride hydrogen manufacturing is 1083 mLmin-1·g-1。
Embodiment 6.
0.5471g cobalt nitrate hexahydrates [Co (NO are weighed first3)2·6H2O] and 0.5593g zinc nitrate hexahydrates [Zn (NO3)2·
6H2O] fully dissolved is in 30mLN, N-2 NMFs（DMF）In；Weigh 0.3087g2- methylimidazoles and be dissolved in 30mL DMF
In；Both of which is ultrasonic 5 minutes, then former solution is poured into the latter solution, by mixed solution in magnetic stirring apparatus upper chamber
Temperature stirring 30 minutes.Then mixed solution is transferred in 100mL reactors, is put into 140 DEG C of insulation 72h in air dry oven,
Cooling, filter, washing, drying can be obtained by ZIF-8/ZIF-67 hybrid materials.Then the dissolving of 0.6232g sodium borohydrides is weighed
In 15mL absolute ethyl alcohols and the mixed solution of 15mL deionized waters, obtained mixed solution is added dropwise to by syringe pump
In 1g ZIF sills, after being added dropwise to complete, 30 minutes are stood, then filters and is washed with deionized three times, gained sediment
It is put into vacuum drying oven, opens vavuum pump, after vacuum arrival -0.1MPa, begin to warm up to after 40 DEG C of dry 4h, treat vacuum
Drying box temperature takes out dried object after dropping to room temperature, obtains ZIF-8 load C oB catalyst.Sodium borohydride is taken to be added to equipped with matter
Concentration is measured in the thermostatic container of 5% alkaline solution of sodium hydroxide, to add ZIF-8 load C oB catalyst（ZIF-8 load Cs oB
The quality of catalyst and the mass ratio of sodium borohydride are：2~10: 100）, 25 DEG C of reaction temperature, remembered with Weight Lab softwares
The process of catalytic reaction is recorded, catalyst hydrogen production rate in sodium borohydride hydrogen manufacturing is 1200 mLmin-1·g-1。
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (9)
1. a kind of ZIF-8 material loads CoB method for preparing catalyst, it is characterised in that carry out as follows：
（1）By cobalt salt and zinc salt dissolving in a solvent, the solution containing cobalt and zinc is prepared；
（2）By 2-methylimidazole dissolving in a solvent, the ligand solution containing 2-methylimidazole is prepared；
（3）By step（1）Resulting solution pours into step（2）In resulting solution, at room temperature stirring a period of time, 100mL is transferred to
In reactor, pyroreaction for a period of time, cools down, and filters, is drying to obtain ZIF-8/ZIF-67 hybrid materials；
（4）The solution containing reducing agent is prepared, obtains solution A；The reducing agent is NaBH4 ；The solvent for preparing reducing agent is to go
Ionized water or ethanol；
（5）Excessive reductant solution A is slowly injected into step（3）In the ZIF-8/ZIF-67 hybrid materials of gained, stir, also
Cobalt ions in former ZIF-67 therein obtains suspension B, stands a period of time；
（6）By step（5）Suspension B after middle standing, filter, washing, be dried in vacuo and produce ZIF-8 load C oB catalyst；
（7）Take sodium borohydride to be added in the thermostatic container equipped with alkaline solution, add step（6）In obtained ZIF-8 bear
Carry CoB catalyst；
（8）With the process of Weight Lab software records catalytic reactions.
A kind of 2. ZIF-8 material loads CoB according to claim 1 method for preparing catalyst, it is characterised in that：It is described
Step（1）In cobalt salt be cobalt nitrate or cobalt chloride.
A kind of 3. ZIF-8 material loads CoB according to claim 2 method for preparing catalyst, it is characterised in that：It is described
Step（1）In zinc salt be zinc nitrate or zinc chloride.
A kind of 4. ZIF-8 material loads CoB according to claim 3 method for preparing catalyst, it is characterised in that：It is described
Step（1）And step（2）Solvent for use is DMF.
A kind of 5. ZIF-8 material loads CoB according to claim 4 method for preparing catalyst, it is characterised in that：It is described
Step（3）In, the mol ratio of mole sum and 2-methylimidazole of cobalt ions and zinc ion is 1:1~30.
A kind of 6. ZIF-8 material loads CoB according to claim 5 method for preparing catalyst, it is characterised in that：It is described
Hybrid materials in the mol ratio of cobalt ions and zinc ion be 5~60：100.
A kind of 7. ZIF-8 material loads CoB according to claim 6 method for preparing catalyst, it is characterised in that：It is described
Step（3）In high temperature be 120~140 DEG C, the reaction time is 24~72h.
A kind of 8. ZIF-8 material loads CoB according to claim 7 method for preparing catalyst, it is characterised in that：It is described
CoB quality is the 5%~60% of ZIF-8 mass in ZIF-8 load C oB catalyst.
A kind of 9. ZIF-8 material loads CoB according to claim 8 method for preparing catalyst, it is characterised in that：It is described
Step（7）In alkaline solution be sodium hydroxide the aqueous solution；The mass concentration of sodium hydroxide is 5%；ZIF-8 load Cs oB is catalyzed
The quality of agent and the mass ratio of sodium borohydride are：2~10: 100.
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| CN109126849A (en) * | 2017-06-28 | 2019-01-04 | 中国科学院大连化学物理研究所 | A method of preparing the monatomic catalyst of Ni-N-C |
| CN108187745A (en) * | 2017-12-12 | 2018-06-22 | 宁波市河清源技术转移服务有限公司 | A kind of preparation method of methanation catalyst prepared by synthetic gas |
| CN109939682A (en) * | 2019-03-29 | 2019-06-28 | 洛阳师范学院 | M-B/γ-Al2O3The preparation method and application of catalyst |
| CN110523424B (en) * | 2019-08-15 | 2021-09-07 | 广西师范大学 | Catalyst for hydrogen production based on Ru/NPC-CoxO and preparation method thereof |
| CN116586623B (en) * | 2023-03-24 | 2024-04-30 | 闽都创新实验室 | In-situ co-reduction preparation method of copper-based medium-entropy alloy nano material |
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