CN109603832A - A kind of method of a large amount of flower-shaped cobalt-based double-metal hydroxide of quick preparation - Google Patents
A kind of method of a large amount of flower-shaped cobalt-based double-metal hydroxide of quick preparation Download PDFInfo
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- CN109603832A CN109603832A CN201811618358.5A CN201811618358A CN109603832A CN 109603832 A CN109603832 A CN 109603832A CN 201811618358 A CN201811618358 A CN 201811618358A CN 109603832 A CN109603832 A CN 109603832A
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- flower
- methylimidazole
- nitrate hexahydrate
- metal hydroxide
- based double
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 16
- 239000010941 cobalt Substances 0.000 title claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 42
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims abstract description 26
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000002604 ultrasonography Methods 0.000 claims abstract description 10
- UQPKFUZWTGSHJD-UHFFFAOYSA-N CO.O.O.O.O.O.O.[N+](=O)(O)[O-] Chemical compound CO.O.O.O.O.O.O.[N+](=O)(O)[O-] UQPKFUZWTGSHJD-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001507 sample dispersion Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241001104043 Syringa Species 0.000 description 1
- 235000004338 Syringa vulgaris Nutrition 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The method that the present invention has opened a kind of a large amount of flower-shaped cobalt-based double-metal hydroxide of quick preparation, the methanol dispersion liquid of cabaltous nitrate hexahydrate is uniformly mixed by this method with the methanol dispersion liquid of 2-methylimidazole, making 75~105mmol/L of concentration of cabaltous nitrate hexahydrate, the concentration of 2-methylimidazole in gained mixed liquor is 30~125mmol/L, and the molar ratio of cabaltous nitrate hexahydrate and 2-methylimidazole is 1:0.3~1.2, ultrasound 20~40 minutes, prepare regular appearance, monodispersed flower-shaped cobalt-based double-metal hydroxide (Co-LDH) at 0~50 DEG C.The Co-LDH of the method for the present invention synthesis has very excellent OER performance, η10=309mV has very excellent advantage in terms of replacing precious metal catalyst electrolysis water.
Description
Technical field
The invention belongs to electro-catalysis technical fields, and in particular to a kind of quickly to prepare a large amount of flower-shaped cobalt-based bimetal hydroxides
The method of object (Co-LDH).
Background technique
Hydrogen Energy is a kind of ideal clean energy resource, has the unrivaled huge advantage of other new energy and bright prospects.
It is all mainly with water (H although tellurian hydrogen resource very abundant2O mode) exists, individually with hydrogen molecule (H2)
Existing amount is considerably less.Therefore, production hydrogen is the primary link of large-scale use hydrogen energy source.Currently, in alkaline electrolysis pond
Hydrogen producing technology it is the most mature, have begun and be industrially used to prepare High Purity Hydrogen.And exist in alkaline industries
The higher problem of energy consumption, developing efficiently stable cheap alkaline liberation of hydrogen (HER) analysis oxygen (OER) elctro-catalyst is current weight
In it is weight.
Electrolysis water is a kind of effective means for converting electrical energy into chemical energy.In anode water oxidation reaction occurs for electrolysis water
(OER) oxygen is generated, reduction reaction occurs in cathode and generates hydrogen (HER).Wherein the process of OER reaction needs to shift 4e-, is
The very slow process of one dynamics needs to apply the generation of very high overvoltage (overpotential) ability drive response.
In OER reaction, catalyst introducing helps to reduce overpotential, to improve the transformation efficiency of the energy.It is durable, efficient, low at
Originally, environment-friendly type oxygen evolution reaction elctro-catalyst is one of important prerequisite of renewable energy technologies commercial applications.Co sill quilt
Think substitution noble metal-based catalysts in have good prospect, have at present prepare cobalt-based OER catalyst method it is more numerous
It is trivial, or need to react for a long time at high temperature under high pressure using reaction kettle.
Summary of the invention
Technical problem to be solved by the present invention lies in provide a kind of a large amount of flower-shaped cobalt-based bimetal hydroxides of quickly preparation
The method of object.
Solving technical solution used by above-mentioned technical problem is: by the methanol dispersion liquid of cabaltous nitrate hexahydrate and 2- methyl
The methanol dispersion liquid of imidazoles is uniformly mixed, and the concentration of cabaltous nitrate hexahydrate is 75~105mmol/L, 2- methyl in gained mixed liquor
The concentration of imidazoles is 30~125mmol/L, and the molar ratio of cabaltous nitrate hexahydrate and 2-methylimidazole is 1:0.3~1.2,0
Ultrasound 20~40 minutes, obtain flower-shaped cobalt-based double-metal hydroxide at~50 DEG C.
In above-mentioned preparation method, preferably the concentration of cabaltous nitrate hexahydrate is 85~95mmol/L, 2- first in gained mixed liquor
The concentration of base imidazoles is 60~80mmol/L, and the molar ratio of cabaltous nitrate hexahydrate and 2-methylimidazole is 1:0.6~1.0.
In above-mentioned preparation method, ultrasound 30 minutes further preferably at room temperature~40 DEG C.
In above-mentioned preparation method, the power of the preferably described ultrasound is 600~1000W, frequency is 30~50KHz.
Beneficial effects of the present invention are as follows:
The present invention does not need to add any other substance, only need to be by the methanol solution of cabaltous nitrate hexahydrate and 2-methylimidazole
It mixes, by adjusting the concentration of cabaltous nitrate hexahydrate and 2-methylimidazole, molar ratio, is using mild ultrasound condition
Flower-shaped cobalt-based double-metal hydroxide (Co-LDH) can quickly be prepared.Operation of the present invention is simple, mild condition, preparation time
Short, product Co-LDH regular appearance, good dispersion, yield is high, applied widely, and product compare commercialized Ir-C or
RuO2All there is very excellent OER effect.
Detailed description of the invention
Fig. 1 is the FESEM figure of flower-shaped Co-LDH obtained in embodiment 1.
Fig. 2 is the FETEM figure of flower-shaped Co-LDH obtained in embodiment 1.
Fig. 3 is the AFM figure of flower-shaped Co-LDH obtained in embodiment 1.
Fig. 4 is the energy spectrum diagram of flower-shaped Co-LDH obtained in embodiment 1.
Fig. 5 is the XRD diagram of flower-shaped Co-LDH obtained in embodiment 1.
Fig. 6 is the Raman spectrogram of flower-shaped Co-LDH obtained in embodiment 1.
Fig. 7 is the XPS swarming of flower-shaped Co-LDH obtained in embodiment 1.
Fig. 8 is the OER test chart of flower-shaped Co-LDH obtained in embodiment 1.
Fig. 9 is the FESEM figure of flower-shaped Co-LDH obtained in embodiment 2.
Figure 10 is the FESEM figure of flower-shaped Co-LDH obtained in embodiment 3.
Figure 11 is the FESEM figure of flower-shaped Co-LDH obtained in embodiment 4.
Figure 12 is the Co (OH) prepared in comparative example 12FESEM figure.
Figure 13 is the Co (OH) prepared in comparative example 12XRD diagram.
Figure 14 is the FESEM figure of the ZIF-67 prepared in comparative example 3.
Figure 15 is the XRD diagram of the ZIF-67 prepared in comparative example 3.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention not only limits
In these embodiments.
Embodiment 1
By the methanol dispersion liquid of 25mL 125mmol/L cabaltous nitrate hexahydrate and 10mL 250mmol/L 2-methylimidazole
Methanol dispersion liquid be uniformly mixed, in gained mixed liquor the concentration of cabaltous nitrate hexahydrate be 89.29mmol/L, 2-methylimidazole it is dense
Degree is 71.42mmol/L, and the molar ratio of cabaltous nitrate hexahydrate and 2-methylimidazole is 1:0.8, is existed using ultrasonic cleaner
Room temperature ultrasound 30 minutes, prepare flower-shaped Co-LDH under the conditions of power is 800W, frequency is 40KHz.
Above-mentioned gained sample is characterized using XRD, scanning electron microscope, transmission electron microscope, electron spectrum, the result is shown in Figure 1~
6.As seen from Figure 1, the flower-shaped bead of monodisperse that sample is 2~3 μm, by the transmission electron microscope photo of Fig. 2 sample individual particle as it can be seen that sample
Product are made of very thin single sheet, and Fig. 3 is the AFM figure of homogenizer treated sample, may further prove sample
Product are made of very thin single sheet, and the energy spectrum analysis of Fig. 4 illustrates that sample mainly contains Co and O element (due to sample dispersion
The test done on silicon wafer, so siliceous), the XRD spectrum of Fig. 5 and the Raman map warp and document of Fig. 6
(J.mater.Chem.A.2018.6.5999) comparison proves Co-LDH, and Fig. 7 carries out swarming to Co element XPS in sample, really
It is recognized mainly by Co2+With Co3+Composition.In summary characterization result, it was demonstrated that the present embodiment is prepared is flower-shaped Co-LDH.
It is tested using the OER performance of CHI760E Shanghai Chen Hua electrochemical workstation Co-LDH flower-shaped to gained, simultaneously
Equivalent is taken to be commercialized RuO under the same conditions2As a comparison, method particularly includes: take 5mg sample dispersion in 1mL solution
(0.1mL how phenol+0.9mL deionized water), using Gamry RDE710 as working electrode, using calomel electrode as reference electrode, with carbon
Stick is auxiliary electrode, and 4 μ L active materials is taken to be laid in working electrode surface, is electricity with 1mol/LKOH aqueous solution (pH=13.8)
Liquid is solved, 25 DEG C of the ring disk speed of constant temperature are 1600r/min, as a result see Fig. 8.As seen from the figure, gained Co-LDH has very excellent
OER performance, η10=309mV, compared with the commercialization RuO of equivalent as a comparison2Low 109.2mV.
Embodiment 2
In the present embodiment, ultrasound 30 minutes at 0 DEG C, other steps are same as Example 1, and it is relatively small to prepare particle
Flower-shaped Co-LDH (see Fig. 9).
Embodiment 3
In the present embodiment, by the methanol dispersion liquid of 25mL 125mmol/L cabaltous nitrate hexahydrate and 5mL 250mmol/L 2-
The methanol dispersion liquid of methylimidazole is uniformly mixed, and the concentration of cabaltous nitrate hexahydrate is 104.17mmol/L, 2- in gained mixed liquor
The concentration of methylimidazole is 41.67mmol/L, and the molar ratio of cabaltous nitrate hexahydrate and 2-methylimidazole is 1:0.4, other steps
It is rapid same as Example 1, prepare flower-shaped Co-LDH (see Figure 10).
Embodiment 4
In the present embodiment, by the methanol dispersion liquid and 15mL 250mmol/L of 25mL 125mmol/L cabaltous nitrate hexahydrate
The methanol dispersion liquid of 2-methylimidazole is uniformly mixed, and the concentration of cabaltous nitrate hexahydrate is 78.13mmol/L, 2- in gained mixed liquor
The concentration of methylimidazole is 93.75mmol/L, and the molar ratio of cabaltous nitrate hexahydrate and 2-methylimidazole is 1:1.2, other steps
It is rapid same as Example 1, prepare flower-shaped Co-LDH (see Figure 11).
Comparative example 1
25mL 125mmol/L cabaltous nitrate hexahydrate aqueous solution and 10mL 250mmol/L 2-methylimidazole aqueous solution are mixed
It closes, 50 DEG C of water bath sonicators are handled 30 minutes, obtain Co (OH)2(see Figure 12 and Figure 13).
Comparative example 2
By the methanol of the methanol dispersion liquid of 5mL 10mmol/L cabaltous nitrate hexahydrate and 5mL 20mmol/L 2-methylimidazole
Dispersion liquid mixing, 60 DEG C of water bath sonicators are handled 1 hour, and no product, solution is still lilac red；Continuation is ultrasonic to 24 hours,
Still generated without product.
Comparative example 3
By the first of the methanol dispersion liquid of 5mL 100mmol/L cabaltous nitrate hexahydrate and 5mL 200mmol/L 2-methylimidazole
The mixing of alcohol dispersion liquid, 60 DEG C of water bath sonicators are handled 1 hour, are generated purple and are not dissolved product, are ZIF- through the structural characterization product
67 particles (see Figure 14 and Figure 15).
Claims (6)
1. a kind of method for quickly preparing a large amount of flower-shaped cobalt-based double-metal hydroxides, it is characterised in that: by cabaltous nitrate hexahydrate
Methanol dispersion liquid be uniformly mixed with the methanol dispersion liquid of 2-methylimidazole, the concentration of cabaltous nitrate hexahydrate is in gained mixed liquor
75~105mmol/L, 2-methylimidazole concentration be 30~125mmol/L, and cabaltous nitrate hexahydrate and 2-methylimidazole rub
You are than being 1:0.3~1.2, and ultrasound 20~40 minutes, obtain flower-shaped cobalt-based double-metal hydroxide at 0~50 DEG C.
2. the method for a large amount of flower-shaped cobalt-based double-metal hydroxide of quick preparation according to claim 1, it is characterised in that:
The concentration of cabaltous nitrate hexahydrate is 85~95mmol/L in gained mixed liquor.
3. the method for a large amount of flower-shaped cobalt-based double-metal hydroxide of quick preparation according to claim 2, it is characterised in that:
The concentration of 2-methylimidazole is 60~80mmol/L in gained mixed liquor.
4. the method for a large amount of flower-shaped cobalt-based double-metal hydroxide of quick preparation according to claim 3, it is characterised in that:
The molar ratio of cabaltous nitrate hexahydrate and 2-methylimidazole is 1:0.6~1.0 in gained mixed liquor.
5. the method for a large amount of flower-shaped cobalt-based double-metal hydroxide of quick preparation according to claim 1, it is characterised in that:
Ultrasound 30 minutes at room temperature~40 DEG C.
6. the method for a large amount of flower-shaped cobalt-based double-metal hydroxide of quick preparation according to claim 1, it is characterised in that:
The power of the ultrasound is 600~1000W, frequency is 30~50KHz.
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| CN111792678A (en) * | 2020-07-24 | 2020-10-20 | 福州大学 | Pure cobalt hydrotalcite-like compound and preparation method thereof |
| CN112375229A (en) * | 2020-11-24 | 2021-02-19 | 长春理工大学 | ZIF-67 material with hierarchical structure and preparation method and application thereof |
| CN114653374A (en) * | 2022-04-02 | 2022-06-24 | 北京师范大学 | Double-metal hydroxide and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110106518A (en) * | 2019-06-19 | 2019-08-09 | 西京学院 | A kind of composite material and preparation method for alkaline electrocatalytic hydrogen evolution |
| CN111792678A (en) * | 2020-07-24 | 2020-10-20 | 福州大学 | Pure cobalt hydrotalcite-like compound and preparation method thereof |
| CN112375229A (en) * | 2020-11-24 | 2021-02-19 | 长春理工大学 | ZIF-67 material with hierarchical structure and preparation method and application thereof |
| CN114653374A (en) * | 2022-04-02 | 2022-06-24 | 北京师范大学 | Double-metal hydroxide and preparation method and application thereof |
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