CN105413749A - Preparation method of catalyst with ZIF-8 material loading CoB - Google Patents
Preparation method of catalyst with ZIF-8 material loading CoB Download PDFInfo
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- CN105413749A CN105413749A CN201510891468.9A CN201510891468A CN105413749A CN 105413749 A CN105413749 A CN 105413749A CN 201510891468 A CN201510891468 A CN 201510891468A CN 105413749 A CN105413749 A CN 105413749A
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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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- 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 the field of catalytic hydrogen preparation, and particularly relates to a preparation method of a catalyst with a ZIF-8 material loading CoB. The preparation method comprises the following steps: (1) preparing a ZIF-8/ZIF-67 hybrid material from cobalt salt, zinc salt, 2-methylimidazole and the like; (2) preparing a solution with a reducing agent, thus obtaining a solution A; (3) slowly injecting an excessive amount of solution A into the ZIF-8/ZIF-67 hybrid material, and stirring, thus obtaining a suspension B; (4) stewing the solution B for a period of time to further reduce the suspension B, and obtaining a suspension C; (5) performing suction filtration and washing on the suspension C, and drying the suspension C in vacuum, thus obtaining the catalyst with the ZIF-8 material carrying CoB; and (6) applying the catalyst with the ZIF-8 material loading CoB in catalyzing hydrolysis reaction of sodium borohydride. The preparation method disclosed by the invention is low in investment cost; the catalyst is long in service life and larger in surface area; the rate of generating hydrogen by hydrolysis of sodium borohydride can be obviously accelerated, and the reaction activation energy can be effectively reduced.
Description
Technical field
The invention belongs to catalyzing manufacturing of hydrogen field, particularly the method for preparing catalyst of a kind of ZIF-8 material load CoB.
Background technology
The fossil fuel limited reserves mankind are faced with unprecedented energy crisis, its combustion product is discharged in air and accelerates greenhouse effects simultaneously.Face these problems, the present mankind are in the urgent need to finding a kind of new forms of energy that can substitute.Hydrogen Energy receives much attention as the reproducible green energy resource of one, and the efficiency utilization of Hydrogen Energy becomes the focus of people's research, wherein uses hydrogen to have obvious advantage as fuel.But seek safety, convenient, practical hydrogen storage technology remains a challenge.
NaBH
4hydrogen-storage density is high, and hydrogen content reaches 10.6%, is about 5 times of common metal cyanide, and NaBH
4hydrolytic hydrogen production process in not discharge of noxious gases, hydrogen purity is high, and not containing the pernicious gas making fuel cell poisoning, simultaneously owing to not needing external energy, the utilization ratio of energy is high, makes NaBH
4be hydrolyzed as a kind of safe, easily new hydrogen production technology receive the concern of scientific research personnel.
In order to realize quick controlled product hydrogen, its hydrolysis of catalysis is carried out in the place that a kind of efficient catalyst must be selected to become hydrogen molecule as hydrogen atom compound.Conventional catalyst has two classes, and a class is noble metal, and as Pt, Ru and alloy etc. thereof, another kind of is the base metals such as NiB, CoB.Due to the with high costs of noble metal and reserves limited, be difficult to meet large-scale application, and base metal also can have fabulous performance, so current research mainly concentrates on non-precious metal catalyst aspect.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art part and provide a kind of equipment to reduce, low in investment cost, and catalyst long service life, there is large surface area, significantly can accelerate reaction rate, effectively reduce the method for the employing ZIF-8 load C oB catalyst sodium borohydride hydrogen manufacturing of reaction activity.
A method for preparing catalyst of ZIF-8 material load CoB, can carry out as follows.
(1) cobalt salt and zinc salt are dissolved in a solvent, preparation contains the solution of cobalt and zinc.
(2) glyoxal ethyline is dissolved in a solvent, the ligand solution of preparation containing glyoxal ethyline.
(3) pour in step (2) gained solution by step (1) gained solution, stirred at ambient temperature a period of time, be transferred in 100mL reactor, pyroreaction a period of time, cooling, suction filtration, is drying to obtain ZIF-8/ZIF-67 and mixes sill.
(4) solution of preparation containing reducing agent, obtains solution A.
(5) excessive reductant solution A is slowly injected into the ZIF-8/ZIF-67 hybrid materials of step (3) gained, stirs, the cobalt ions wherein contained that reduces obtains suspension B, leaves standstill a period of time.
(6) by step (5) leave standstill after suspension B, suction filtration, washing, namely vacuum drying obtains ZIF-8 load C oB catalyst.
(7) get sodium borohydride to join and be equipped with in the thermostatic container of alkaline solution, then add the ZIF-8 load C oB catalyst obtained in step (6).
(8) by the process of WeightLab software records catalytic reaction.
As a kind of preferred version, the cobalt salt in step of the present invention (1) is cobalt nitrate or cobalt chloride, and zinc salt is zinc nitrate or zinc chloride.
Further, the zinc salt in step of the present invention (1) is zinc nitrate or zinc chloride.
Further, step of the present invention (1) and step (2) solvent for use are DMF.
Further, in step of the present invention (3), mole sum of cobalt ions and zinc ion and the mol ratio of glyoxal ethyline are 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, the high temperature in step of the present invention (3) is 120 ~ 140 DEG C, and the time is 24 ~ 72h.
Further, the reducing agent that step of the present invention (4) is all is NaBH
4; The solvent of preparation reducing agent is deionized water or ethanol.
Further, in ZIF-8 load C oB catalyst of the present invention, the quality of CoB is 5% ~ 60% of ZIF-8 quality.
Further, the alkaline solution in step of the present invention (7) is the aqueous solution of NaOH; The mass concentration of NaOH is 5%; The quality of ZIF-8 load C oB catalyst and the mass ratio of sodium borohydride are: 2 ~ 10:100.
Research finds, cobalt-base catalyst has prospects for commercial application widely, and CoB is in preparation process, and easily reunite due to its magnetic surface and cause catalyst granules comparatively large, decentralization is not high, so load type Co B catalyst has more application prospect.ZIFs material is the metal-organic framework material that a kind of stability is higher, has higher specific area and can the pore passage structure of modulation, and ZIFs material can also stable existence in alkaline solution.
In ZIF-8 load C oB catalyst prepared by the present invention, ZIF-8 has higher specific area, controlled pore passage structure, and prepared hybrid materials are ZIFs materials of binary metal, overcome adsorption intensity and the not high defect of adsorptive selectivity, improve the degree of scatter of active component CoB and immobilized intensity, make ZIF-8 load C oB catalyst consumption in catalytic reaction process of preparation few, and there is good activity and stability, significantly accelerate preparing hydrogen by sodium borohydride hydrolysis speed, effective reduction reaction activity, significant to liquid phase storage hydrogen release hydrogen.
Accompanying drawing explanation
Below in conjunction with specific embodiment, the invention will be further described.Material involved in the present invention comprises the statement do not limited to following examples.
Fig. 1 is that the present invention obtains ZIF-8 material support SEM and schemes.
Fig. 2 is the XRD figure that the present invention obtains ZIF-8 load C oB catalyst.
Fig. 3 is the Arrhenius curve map that the present invention obtains the hydrolysis of ZIF-8 load C oB catalyst sodium borohydride.
Detailed description of the invention
In embodiment, it is that experimental condition is: X-ray CuK α target emanation with German Brooker D8Advance type X-ray diffractometer that the X-ray diffraction of obtained finished product measures, graphite monochromator, tube voltage 35KV, tube current 40mA, filter plate is Co, and sweep speed is 8 °/min, and walking wide is 0.02 °.
Embodiment 1.
First 0.5471g cobalt nitrate hexahydrate [Co (NO is taken
3)
26H
2o] and 0.5593g zinc nitrate hexahydrate [Zn (NO
3)
26H
2o] CL is in 30mLN, N-2 NMF (DMF); Taking 3.087g2-methylimidazole is dissolved in 30mLDMF; Will both all ultrasonic 5 minutes, then former solution is poured in the latter solution, by mixed solution stirring at room temperature 30 minutes on magnetic stirring apparatus.Then mixed solution is transferred in 100mL reactor, put into air dry oven 140 DEG C insulation 72h, cooling, suction filtration, washing, drying just can obtain ZIF-8/ZIF-67 hybrid materials.Then taking 0.6232g sodium borohydride is dissolved in the mixed solution of 15mL absolute ethyl alcohol and 15mL deionized water, the mixed solution obtained dropwise is joined in the ZIF sill of 1g by syringe pump, after being added dropwise to complete, leave standstill 30 minutes, then suction filtration spend deionized water three times, gained sediment puts into vacuum drying oven, open vavuum pump, when after vacuum arrival-0.1MPa, after starting to be heated to 40 DEG C of dry 4h, drop to after room temperature until vacuum drying chamber temperature and take out dry thing, obtain ZIF-8 load C oB catalyst.Get sodium borohydride and join that mass concentration is housed is in the thermostatic container of 5% alkaline solution of sodium hydroxide, (quality of ZIF-8 load C oB catalyst and the mass ratio of sodium borohydride are: 2 ~ 10:100) to add ZIF-8 load C oB catalyst again, reaction temperature 25 DEG C, by the process of WeightLab software records catalytic reaction, this catalyst hydrogen production rate in sodium borohydride hydrogen manufacturing is 996mLmin
-1.g
-1.
Embodiment 2.
First 0.0274g cobalt nitrate hexahydrate [Co (NO is taken
3)
26H
2o] and 0.5593g zinc nitrate hexahydrate [Zn (NO
3)
26H
2o] CL is in 30mLN, N-2 NMF (DMF); Taking 1.6207g2-methylimidazole is dissolved in 30mLDMF; Will both all ultrasonic 5 minutes, then former solution is poured in the latter solution, by mixed solution stirring at room temperature 30 minutes on magnetic stirring apparatus.Then mixed solution is transferred in 100mL reactor, put into air dry oven 140 DEG C insulation 72h, cooling, suction filtration, washing, drying just can obtain ZIF-8/ZIF-67 hybrid materials.Then taking 0.6232g sodium borohydride is dissolved in the mixed solution of 15mL absolute ethyl alcohol and 15mL deionized water, the mixed solution obtained dropwise is joined in the ZIF sill of 1g by syringe pump, after being added dropwise to complete, leave standstill 30 minutes, then suction filtration spend deionized water three times, gained sediment puts into vacuum drying oven, open vavuum pump, when after vacuum arrival-0.1MPa, after starting to be heated to 40 DEG C of dry 4h, drop to after room temperature until vacuum drying chamber temperature and take out dry thing, obtain ZIF-8 load C oB catalyst.Get sodium borohydride and join that mass concentration is housed is in the thermostatic container of 5% alkaline solution of sodium hydroxide, (quality of ZIF-8 load C oB catalyst and the mass ratio of sodium borohydride are: 2 ~ 10:100) to add ZIF-8 load C oB catalyst again, reaction temperature 25 DEG C, by the process of WeightLab software records catalytic reaction, this catalyst hydrogen production rate in sodium borohydride hydrogen manufacturing is 496mLmin
-1g
-1.
Embodiment 3.
First 0.0547g cobalt nitrate hexahydrate [Co (NO is taken
3)
26H
2o] and 0.5593g zinc nitrate hexahydrate [Zn (NO
3)
26H
2o] CL is in 30mLN, N-2 NMF (DMF); Taking 1.6979g2-methylimidazole is dissolved in 30mLDMF; Will both all ultrasonic 5 minutes, then former solution is poured in the latter solution, by mixed solution stirring at room temperature 30 minutes on magnetic stirring apparatus.Then mixed solution is transferred in 100mL reactor, put into air dry oven 140 DEG C insulation 72h, cooling, suction filtration, washing, drying just can obtain ZIF-8/ZIF-67 hybrid materials.Then taking 0.6232g sodium borohydride is dissolved in the mixed solution of 15mL absolute ethyl alcohol and 15mL deionized water, the mixed solution obtained dropwise is joined in the ZIF sill of 1g by syringe pump, after being added dropwise to complete, leave standstill 30 minutes, then suction filtration spend deionized water three times, gained sediment puts into vacuum drying oven, open vavuum pump, when after vacuum arrival-0.1MPa, after starting to be heated to 40 DEG C of dry 4h, drop to after room temperature until vacuum drying chamber temperature and take out dry thing, obtain ZIF-8 load C oB catalyst.Get sodium borohydride and join that mass concentration is housed is in the thermostatic container of 5% alkaline solution of sodium hydroxide, (quality of ZIF-8 load C oB catalyst and the mass ratio of sodium borohydride are: 2 ~ 10:100) to add ZIF-8 load C oB catalyst again, reaction temperature 25 DEG C, by the process of WeightLab software records catalytic reaction, this catalyst hydrogen production rate in sodium borohydride hydrogen manufacturing is 812mLmin
-1g
-1.
Embodiment 4.
First 0.1094g cobalt nitrate hexahydrate [Co (NO is taken
3)
26H
2o] and 0.5593g zinc nitrate hexahydrate [Zn (NO
3)
26H
2o] CL is in 30mLN, N-2 NMF (DMF); Taking 1.8522g2-methylimidazole is dissolved in 30mLDMF; Will both all ultrasonic 5 minutes, then former solution is poured in the latter solution, by mixed solution stirring at room temperature 30 minutes on magnetic stirring apparatus.Then mixed solution is transferred in 100mL reactor, put into air dry oven 140 DEG C insulation 72h, cooling, suction filtration, washing, drying just can obtain ZIF-8/ZIF-67 hybrid materials.Then taking 0.6232g sodium borohydride is dissolved in the mixed solution of 15mL absolute ethyl alcohol and 15mL deionized water, the mixed solution obtained dropwise is joined in the ZIF sill of 1g by syringe pump, after being added dropwise to complete, leave standstill 30 minutes, then suction filtration spend deionized water three times, gained sediment puts into vacuum drying oven, open vavuum pump, when after vacuum arrival-0.1MPa, after starting to be heated to 40 DEG C of dry 4h, drop to after room temperature until vacuum drying chamber temperature and take out dry thing, obtain ZIF-8 load C oB catalyst.Get sodium borohydride and join that mass concentration is housed is in the thermostatic container of 5% alkaline solution of sodium hydroxide, (quality of ZIF-8 load C oB catalyst and the mass ratio of sodium borohydride are: 2 ~ 10:100) to add ZIF-8 load C oB catalyst again, reaction temperature 25 DEG C, by the process of WeightLab software records catalytic reaction, this catalyst hydrogen production rate in sodium borohydride hydrogen manufacturing is 934mLmin
-1g
-1.
Embodiment 5.
First 0.5471g cobalt nitrate hexahydrate [Co (NO is taken
3)
26H
2o] and 0.5593g zinc nitrate hexahydrate [Zn (NO
3)
26H
2o] CL is in 30mLN, N-2 NMF (DMF); Taking 0.6174g2-methylimidazole is dissolved in 30mLDMF; Will both all ultrasonic 5 minutes, then former solution is poured in the latter solution, by mixed solution stirring at room temperature 30 minutes on magnetic stirring apparatus.Then mixed solution is transferred in 100mL reactor, put into air dry oven 140 DEG C insulation 72h, cooling, suction filtration, washing, drying just can obtain ZIF-8/ZIF-67 hybrid materials.Then taking 0.6232g sodium borohydride is dissolved in the mixed solution of 15mL absolute ethyl alcohol and 15mL deionized water, the mixed solution obtained dropwise is joined in the ZIF sill of 1g by syringe pump, after being added dropwise to complete, leave standstill 30 minutes, then suction filtration spend deionized water three times, gained sediment puts into vacuum drying oven, open vavuum pump, when after vacuum arrival-0.1MPa, after starting to be heated to 40 DEG C of dry 4h, drop to after room temperature until vacuum drying chamber temperature and take out dry thing, obtain ZIF-8 load C oB catalyst.Get sodium borohydride and join that mass concentration is housed is in the thermostatic container of 5% alkaline solution of sodium hydroxide, (quality of ZIF-8 load C oB catalyst and the mass ratio of sodium borohydride are: 2 ~ 10:100) to add ZIF-8 load C oB catalyst again, reaction temperature 25 DEG C, by the process of WeightLab software records catalytic reaction, this catalyst hydrogen production rate in sodium borohydride hydrogen manufacturing is 1083mLmin
-1g
-1.
Embodiment 6.
First 0.5471g cobalt nitrate hexahydrate [Co (NO is taken
3)
26H
2o] and 0.5593g zinc nitrate hexahydrate [Zn (NO
3)
26H
2o] CL is in 30mLN, N-2 NMF (DMF); Taking 0.3087g2-methylimidazole is dissolved in 30mLDMF; Will both all ultrasonic 5 minutes, then former solution is poured in the latter solution, by mixed solution stirring at room temperature 30 minutes on magnetic stirring apparatus.Then mixed solution is transferred in 100mL reactor, put into air dry oven 140 DEG C insulation 72h, cooling, suction filtration, washing, drying just can obtain ZIF-8/ZIF-67 hybrid materials.Then taking 0.6232g sodium borohydride is dissolved in the mixed solution of 15mL absolute ethyl alcohol and 15mL deionized water, the mixed solution obtained dropwise is joined in the ZIF sill of 1g by syringe pump, after being added dropwise to complete, leave standstill 30 minutes, then suction filtration spend deionized water three times, gained sediment puts into vacuum drying oven, open vavuum pump, when after vacuum arrival-0.1MPa, after starting to be heated to 40 DEG C of dry 4h, drop to after room temperature until vacuum drying chamber temperature and take out dry thing, obtain ZIF-8 load C oB catalyst.Get sodium borohydride and join that mass concentration is housed is in the thermostatic container of 5% alkaline solution of sodium hydroxide, (quality of ZIF-8 load C oB catalyst and the mass ratio of sodium borohydride are: 2 ~ 10:100) to add ZIF-8 load C oB catalyst again, reaction temperature 25 DEG C, by the process of WeightLab software records catalytic reaction, this catalyst hydrogen production rate in sodium borohydride hydrogen manufacturing is 1200mLmin
-1g
-1.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a method for preparing catalyst of ZIF-8 material load CoB, is characterized in that, carries out as follows:
(1) cobalt salt and zinc salt are dissolved in a solvent, preparation contains the solution of cobalt and zinc;
(2) glyoxal ethyline is dissolved in a solvent, the ligand solution of preparation containing glyoxal ethyline;
(3) pour in step (2) gained solution by step (1) gained solution, stirred at ambient temperature a period of time, be transferred in 100mL reactor, pyroreaction a period of time, cooling, suction filtration, is drying to obtain ZIF-8/ZIF-67 hybrid materials;
(4) solution of preparation containing reducing agent, obtains solution A;
(5) excessive reductant solution A be slowly injected in the ZIF-8/ZIF-67 hybrid materials of step (3) gained, stir, the cobalt ions in reduction ZIF-67 wherein obtains suspension B, leaves standstill a period of time;
(6) by step (5) leave standstill after suspension B, suction filtration, washing, namely vacuum drying obtains ZIF-8 load C oB catalyst;
(7) get sodium borohydride to join and be equipped with in the thermostatic container of alkaline solution, then add the ZIF-8 load C oB catalyst obtained in step (6);
(8) by the process of WeightLab software records catalytic reaction.
2. the method for preparing catalyst of a kind of ZIF-8 material load CoB according to claims 1, is characterized in that: the cobalt salt in described step (1) is cobalt nitrate or cobalt chloride.
3. the method for preparing catalyst of a kind of ZIF-8 material load CoB according to claims 2, is characterized in that: the zinc salt in described step (1) is zinc nitrate or zinc chloride.
4. the method for preparing catalyst of a kind of ZIF-8 material load CoB according to claims 3, is characterized in that: described step (1) and step (2) solvent for use are DMF.
5. the method for preparing catalyst of a kind of ZIF-8 material load CoB according to claims 4, is characterized in that: in described step (3), mole sum of cobalt ions and zinc ion and the mol ratio of glyoxal ethyline are 1:1 ~ 30.
6. the method for preparing catalyst of a kind of ZIF-8 material load CoB according to claims 5, is characterized in that: in described hybrid materials, the mol ratio of cobalt ions and zinc ion is 5 ~ 60:100.
7. the method for preparing catalyst of a kind of ZIF-8 material load CoB according to claims 6, it is characterized in that: the high temperature in described step (3) is 120 ~ 140 DEG C, the reaction time is 24 ~ 72h.
8. the method for preparing catalyst of a kind of ZIF-8 material load CoB according to claims 7, is characterized in that: described step (4) reducing agent used is NaBH
4; The solvent of preparation reducing agent is deionized water or ethanol.
9. the method for preparing catalyst of a kind of ZIF-8 material load CoB according to claims 8, is characterized in that: in described ZIF-8 load C oB catalyst, the quality of CoB is 5% ~ 60% of ZIF-8 quality.
10. the method for preparing catalyst of a kind of ZIF-8 material load CoB according to claims 9, is characterized in that: the alkaline solution in described step (7) is the aqueous solution of NaOH; The mass concentration of NaOH is 5%; The quality of ZIF-8 load C oB catalyst and the mass ratio of sodium borohydride are: 2 ~ 10:100.
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| 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 |
| 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 |
| CN109939682A (en) * | 2019-03-29 | 2019-06-28 | 洛阳师范学院 | M-B/γ-Al2O3The preparation method and application of catalyst |
| CN110523424A (en) * | 2019-08-15 | 2019-12-03 | 广西师范大学 | One kind being based on Ru/NPC-CoxO catalyst for preparing hydrogen and preparation method |
| CN116586623A (en) * | 2023-03-24 | 2023-08-15 | 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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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106861637A (en) * | 2017-03-30 | 2017-06-20 | 丽水学院 | A kind of method that use Zn-ef ficiency doping improves the water stabilities of ZIF 67 |
| 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 |
| CN110523424A (en) * | 2019-08-15 | 2019-12-03 | 广西师范大学 | One kind being based on Ru/NPC-CoxO catalyst for preparing hydrogen and preparation method |
| 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 |
| CN116586623A (en) * | 2023-03-24 | 2023-08-15 | 闽都创新实验室 | In-situ co-reduction preparation method of copper-based medium-entropy alloy nano material |
| 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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