CN110102348B - Electrocatalyst with hollow structure and preparation method thereof - Google Patents
Electrocatalyst with hollow structure and preparation method thereof Download PDFInfo
- Publication number
- CN110102348B CN110102348B CN201910432582.3A CN201910432582A CN110102348B CN 110102348 B CN110102348 B CN 110102348B CN 201910432582 A CN201910432582 A CN 201910432582A CN 110102348 B CN110102348 B CN 110102348B
- Authority
- CN
- China
- Prior art keywords
- framework material
- hollow structure
- zif
- cobalt
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 72
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 34
- 239000010941 cobalt Substances 0.000 claims abstract description 34
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 30
- 239000010457 zeolite Substances 0.000 claims abstract description 30
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 24
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 17
- 239000010452 phosphate Substances 0.000 claims abstract description 15
- -1 zeolite imidazole ester Chemical class 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 17
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 14
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 13
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 4
- 229910017709 Ni Co Inorganic materials 0.000 claims description 3
- 229910003267 Ni-Co Inorganic materials 0.000 claims description 3
- 229910003262 Ni‐Co Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 235000021317 phosphate Nutrition 0.000 description 10
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- NGKWYRANVWGTGG-UHFFFAOYSA-N [Ni++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Ni++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O NGKWYRANVWGTGG-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
Classifications
-
- 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
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Abstract
The invention relates to an electrocatalyst with a hollow structure and a preparation method thereof, wherein the preparation method of the electrocatalyst with the hollow structure comprises the following steps: adding a metal organic framework material and soluble phosphate into a solvent, carrying out hydrothermal reaction for 5-15 hours at 120-150 ℃, and then centrifuging, washing and drying to obtain the electrocatalyst with the hollow structure; the metal organic framework material is at least one of a cobalt-based zeolite imidazole ester framework material ZIF-67 and a nickel-doped cobalt-based zeolite imidazole ester framework material Ni-ZIF-67.
Description
Technical Field
The invention relates to an electrocatalyst with a hollow structure and a preparation method thereof, in particular to a metal phosphate electrocatalyst with a hollow structure and a preparation method thereof, belonging to the field of electrocatalysis.
Background
The excessive consumption of fossil energy such as petroleum, coal, natural gas and the like causes increasingly serious energy crisis and environmental pollution, so renewable and sustainable clean energy such as solar energy, wind energy, ocean energy, nuclear energy and the like are actively developed to replace fossil fuel in the world nowadays. With the increase of the proportion of renewable energy sources in energy supply, the energy structure of the future society will change correspondingly. The hydrogen is used as clean and efficient secondary energy, has the advantages of high heat value, zero emission (no emission of any greenhouse gas), high reaction speed, convenience for storage and the like, is an ideal energy carrier, is expected to replace gasoline and natural gasEtc. will play an important role in future energy structures. The technology for producing hydrogen by commercial electrolysis of water is the most mature, is an important way for obtaining hydrogen energy, and is considered to replace the next generation method for producing hydrogen fuel by steam reforming to eliminate the dependence on natural gas, reduce the cost and increase the purity of the hydrogen fuel. The water electrolysis reaction (water splitting) is an important reaction in the field of energy and environmental catalysis, and involves two half reactions, one is the anodic Oxygen Evolution Reaction (OER) and the other is the cathodic Hydrogen Evolution Reaction (HER), and the two half reactions are restricted with each other. Especially, the over potential of the cathode OER reaction is high, the use of an electrocatalyst is seriously depended on, the quality of the catalyst directly determines the total voltage required by water electrolysis and the conversion efficiency of electric energy and hydrogen energy, and the catalyst plays a key role in hydrogen production by water electrolysis. Due to the traditional noble metal iridium dioxide (IrO)2) With ruthenium dioxide (RuO)2) The problems of resource scarcity, high price and the like exist, and the large regular application of the organic electroluminescent material on devices is greatly limited. Therefore, finding suitable non-noble metal catalysts has become a significant international challenge in the energy and environmental field.
Transition metal phosphates are one common transition metal compound. The metal ions are active centers, and the phosphate groups can be used as proton acceptors to promote proton coupling electron transfer kinetics and stabilize the active centers, so that the organic electroluminescent material has excellent OER catalytic performance and particularly has higher activity and stability under a neutral condition. However, the conventional transition metal phosphate has low specific surface area, low active potential and poor conductivity, thereby limiting the catalytic activity.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide an electrocatalyst having a hollow structure and a method of preparing the same.
On one hand, the invention provides a preparation method of an electrocatalyst with a hollow structure, which comprises the steps of adding a metal organic framework material and soluble phosphate into a solvent, carrying out hydrothermal reaction for 5-15 hours at 120-150 ℃, and then carrying out centrifugation, washing and drying to obtain the electrocatalyst with the hollow structure;
the metal organic framework material is at least one of a cobalt-based zeolite imidazole ester framework material ZIF-67 and a nickel-doped cobalt-based zeolite imidazole ester framework material Ni-ZIF-67; preferably, the nickel-doped cobalt-based zeolite imidazolate framework material is at least one of Ni-50-ZIF-67, Ni-100-ZIF-67 and Ni-250-ZIF-67.
In the invention, metal organic framework Materials (MOFs) are selected for preparing the transition metal phosphate for the first time, and the porous multidimensional periodic reticular framework material formed by self-assembly of covalent bond coordination between transition metal atom clusters and organic ligands containing multiple teeth has the characteristics of large specific surface area, developed pore channels, good dispersion on metals and the like. Taking cobalt-based zeolite imidazole ester framework material ZIF-67 as an example, mixing the material ZIF-67 as a precursor for preparing transition metal phosphate with soluble phosphate, carrying out hydrothermal reaction for 5-15 hours at 120-150 ℃, wherein the soluble phosphate reacts with metal ions in the ZIF-67 on the surface of the ZIF-67 to obtain the transition metal phosphate, and the metal ions are more easily migrated to the transition metal phosphate reacted with the phosphate ions in the ZIF-67, namely the Couendall effect, because the metal ions are faster than the phosphate ions in the ZIF-67, the interior of the transition metal phosphate presents a hollow structure due to the migration of the metal ions to the outside. And centrifuging, washing and drying to finally obtain the electrocatalyst with a hollow structure. Taking a cobalt-based zeolite imidazolate framework material ZIF-67 doped with nickel as an example, mixing the material ZIF-67 as a precursor for preparing a transition metal phosphate with a soluble phosphate, carrying out a hydrothermal reaction for 5-15 hours at 120-150 ℃, wherein the transition metal phosphate obtained by the reaction is also in a hollow structure due to the similar Cogen effect of the cobalt-based zeolite imidazolate framework material ZIF-67 in the process, and then centrifuging, washing and drying the product to finally obtain the electrocatalyst with the hollow structure (wherein Ni doping has no influence on the formation of the hollow structure).
Preferably, the cobalt-based zeolite imidazolate framework material ZIF-67 is added into a solution containing a nickel source and stirred and mixed to obtain a nickel-doped cobalt-based zeolite imidazolate framework material Ni-ZIF-67, wherein the mass ratio of the nickel source to the cobalt-based zeolite imidazolate framework material ZIF-67 is (0.5-2.5): 1, preferably (1.0 to 1.5): 1.
further, preferably, the nickel source is at least one of nickel nitrate, nickel chloride, nickel acetate, and nickel sulfate.
Further, the temperature of the stirring and mixing is preferably room temperature (10 to 30 ℃) for 3 to 10 hours.
Preferably, the soluble phosphate is sodium monohydrogen phosphate.
Preferably, the mass ratio of the metal organic framework material to the soluble phosphate is 1: (2-5).
Preferably, the aqueous solution containing the soluble phosphate is added into the ethanol solution containing the metal organic framework material, and then the hydrothermal reaction is carried out. It should be noted that the mixing sequence is intended to be simple to operate and has no particular requirement.
Preferably, the preparation method of the cobalt-based zeolite imidazolate framework material ZIF-67 comprises the following steps:
(1) dispersing cobalt nitrate and dimethyl imidazole in a solvent to obtain a mixed solution;
(2) and standing the obtained mixed solution for 5-40 hours, and then performing centrifugal separation, washing and drying to obtain the cobalt-based zeolite imidazole ester framework material ZIF-67.
In another aspect, the present invention provides an electrocatalyst with a hollow structure prepared according to the above preparation method, wherein the electrocatalyst with a hollow structure is a metal phosphate with a hollow structure, for example, Co with a hollow structure3(PO4)2Or Ni-Co having a hollow structure3(PO4)2。
Has the advantages that:
the preparation method has the advantages of simple and convenient reaction, easy control, low cost of used raw materials, easy obtainment of target products and better catalytic activity of the obtained electrocatalyst.
Drawings
FIG. 1 is a TEM photograph of a metal phosphate material having a hollow structure prepared in example 1;
FIG. 2 is an XRD pattern of a metal phosphate material having a hollow structure prepared in example 1;
FIG. 3 shows the metal phosphate material with hollow structure, the metal phosphate materials with different Ni doping amounts and the noble metal RuO prepared in example 12LSV performance graph of (a).
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, the electrocatalyst having a hollow structure is a metal phosphate having a hollow structure, preferably Co having a hollow structure3(PO4)2Or Ni-Co having a hollow structure3(PO4)2。
In one embodiment of the present invention, metal organic framework Materials (MOFs) are first selected to prepare metal phosphate electrocatalysts. The following exemplarily illustrates a preparation method of the electrocatalyst having a hollow structure.
The metal organic framework material and soluble phosphate are reacted by a hydrothermal method to obtain the electrocatalyst with a hollow structure, namely the metal phosphate material with the hollow structure. Specifically, the metal organic framework material and soluble phosphate are added into a solvent, hydrothermal reaction is carried out for 5-15 hours at 120-150 ℃, and then centrifugation, washing and drying are carried out to obtain the electrocatalyst with the hollow structure. In an alternative embodiment, the soluble phosphate salt is sodium monohydrogen phosphate. The mass ratio of the metal organic framework material to the soluble phosphate may be 1: (2-5). The metal organic framework material can be cobalt-based zeolite imidazolate framework material ZIF-67, nickel-doped cobalt-based zeolite imidazolate framework material Ni-ZIF-67 and the like. Wherein, the Ni-ZIF-67 of the cobalt-based zeolite imidazole ester framework material doped with nickel is preferably Ni-50-ZIF-67, Ni-100-ZIF-67, Ni-250-ZIF-67 and the like.
As an example of a preparation method of the electrocatalyst having a hollow structure, an amount of Ni-ZIF-67 was weighed into ethanol, and then dispersed by ultrasound. Then, a certain amount of sodium monohydrogen phosphate is weighed and dissolved in deionized water, and the solution is stirred until the solution is clear. Then, the aqueous solution of sodium monohydrogen phosphate was added to the dispersed Ni-ZIF-67 ethanol solution, and stirred at room temperature for 1 hour. Transferring the obtained uniform mixed solution into a reaction kettle, and reacting for 5-15 hours at 120-150 ℃. And after cooling at room temperature, centrifugally separating, washing and drying the obtained product to obtain the electrocatalyst with a hollow structure.
In an embodiment of the present invention, when the metal organic framework material is a cobalt-based zeolitic imidazolate framework material ZIF-67, the cobalt-based zeolitic imidazolate framework material (ZIF-67, which is one of MOF materials) may be synthesized by a normal temperature precipitation method. Specifically, a certain amount of cobalt nitrate and dimethyl imidazole are dissolved in a solvent (such as methanol, deionized water, etc.) respectively, and the solution is stirred until the solution is clear. Then, the solution of cobalt nitrate is poured into the solution of dimethylimidazole, and stirred for a certain period of time (for example, 5 minutes), to obtain a mixed solution. The resulting homogeneously mixed solution is allowed to stand for a certain period of time (for example, 24 hours). And then, centrifugally separating, washing and drying the product to obtain the cobalt-based zeolite imidazole ester framework material (ZIF-67).
In an embodiment of the invention, when the metal organic framework material is a nickel-doped cobalt-based zeolite imidazolate framework material Ni-ZIF-67, Ni ions can be doped into the cobalt-based zeolite imidazolate framework material ZIF-67 to synthesize the nickel-doped cobalt-based zeolite imidazolate framework material (Ni-ZIF-67). Specifically, the cobalt-based zeolite imidazolate framework material ZIF-67 is added into a solution containing a nickel source (a solvent can be methanol, ethanol and the like) and stirred and mixed to prepare the nickel-doped cobalt-based zeolite imidazolate framework material Ni-ZIF-67. Wherein the temperature for stirring and mixing can be room temperature (10-30 ℃) and the time can be 3-10 hours. The mass ratio of the nickel source to the cobalt-based zeolite imidazole ester framework material ZIF-67 can be (0.5-2.5): 1, preferably (1.0 to 1.5): 1. as an example, a certain amount of nickel nitrate hexahydrate is weighed and dissolved in methanol, and stirred until the solution is clear. Adding the obtained ZIF-67 into a methanol solution of nickel nitrate with a certain concentration, carrying out ultrasonic dispersion for 5 minutes, and stirring for 3 hours at normal temperature. And then centrifugally separating, washing and drying the product to obtain the nickel-doped cobalt-based zeolite imidazole ester framework material (Ni-ZIF-67). The nickel nitrate methanol solution is not more than 25 mg/mL.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
3.492g of cobalt nitrate hexahydrate and 3.941g of dimethylimidazole were weighed out and dissolved in 120mL and 40mL of methanol, respectively, and the solution was stirred until clear. The methanolic cobalt nitrate solution was then poured into the methanolic dimethylimidazole solution and stirred for 5 minutes. The resulting homogeneous mixed solution was allowed to stand for 24 h. And then, centrifugally separating, washing and drying the product to obtain the cobalt-based zeolite imidazole ester framework material (ZIF-67).
20mg of ZIF-67 was weighed into 32ml of ethanol, followed by dispersion by sonication. 60mg of sodium monohydrogen phosphate are then dissolved in 16ml of deionized water and the solution is stirred until clear. Then, an aqueous solution of sodium monohydrogen phosphate was added to the well dispersed ZIF-67 ethanol solution, and stirred at room temperature for 1 hour. The obtained uniform mixed solution is transferred into a reaction kettle of 80ml and reacted for 12 hours at the temperature of 120-150 ℃. After the mixture is cooled at room temperature, the obtained product is centrifugally separated, washed and dried to obtain the metal phosphate material (Co) with a hollow structure3(PO4)2)。
Example 2
3.492g of cobalt nitrate hexahydrate and 3.941g of dimethylimidazole were weighed out and dissolved in 120mL and 40mL of methanol, respectively, and the solution was stirred until clear. The methanolic cobalt nitrate solution was then poured into the methanolic dimethylimidazole solution and stirred for 5 minutes. The resulting homogeneous mixed solution was allowed to stand for 24 h. And then, centrifugally separating, washing and drying the product to obtain ZIF-67.
50mg of nickel nitrate hexahydrate are weighed out and dissolved in 10mL of methanol, and the solution is stirred until the solution is clear. Weighing 100mg of ZIF-67, adding the ZIF-67 into a methanol solution of nickel nitrate, carrying out ultrasonic dispersion for 5 minutes, then carrying out stirring reaction for 3 hours, and then carrying out centrifugal separation, washing and drying on the product to obtain the Ni-50-ZIF-67.
20mg of Ni-ZIF-67-50 was weighed into 32ml of ethanol, followed by dispersion by sonication. 60mg of sodium monohydrogen phosphate are then dissolved in 16ml of deionized water and the solution is stirred until clear. Then, the aqueous solution of sodium monohydrogen phosphate was added to the dispersed Ni-ZIF-67-50 ethanol solution, and stirred at room temperature for 1 hour. The obtained uniform mixed solution is transferred into a reaction kettle of 80ml and reacted for 12 hours at the temperature of 120-150 ℃. After the mixture is cooled at room temperature, the obtained product is centrifugally separated, washed and dried to obtain the metal phosphate material (Ni-50-Co) with a hollow structure3(PO4)2)。
Example 3
3.492g of cobalt nitrate hexahydrate and 3.941g of dimethylimidazole were weighed out and dissolved in 120mL and 40mL of methanol, respectively, and the solution was stirred until clear. The methanolic cobalt nitrate solution was then poured into the methanolic dimethylimidazole solution and stirred for 5 minutes. The resulting homogeneous mixed solution was allowed to stand for 24 h. And then, centrifugally separating, washing and drying the product to obtain ZIF-67.
100mg of nickel nitrate hexahydrate is weighed and dissolved in 10mL of methanol, and the solution is stirred until the solution is clear. Weighing 100mg of ZIF-67, adding the ZIF-67 into a methanol solution of nickel nitrate, carrying out ultrasonic dispersion for 5 minutes, then carrying out stirring reaction for 3 hours, and then carrying out centrifugal separation, washing and drying on the product to obtain the Ni-100-ZIF-67.
20mg of Ni-ZIF-67-100 was weighed into 32ml of ethanol, followed by dispersion by sonication. 60mg of sodium monohydrogen phosphate are then dissolved in 16ml of deionized water and the solution is stirred until clear. Then adding the aqueous solution of sodium monohydrogen phosphate into the dispersed Ni-ZIF-67-100 ethanol solution, and stirring for 1 hour at room temperature. Mixing the obtained mixtureThe solution is transferred into a 80ml reaction kettle and reacted for 12 hours at the temperature of 120-150 ℃. After the mixture is cooled at room temperature, the obtained product is centrifugally separated, washed and dried to obtain the metal phosphate material (Ni-100-Co) with a hollow structure3(PO4)2)。
Example 4
3.492g of cobalt nitrate hexahydrate and 3.941g of dimethylimidazole were weighed out and dissolved in 120mL and 40mL of methanol, respectively, and the solution was stirred until clear. The methanolic cobalt nitrate solution was then poured into the methanolic dimethylimidazole solution and stirred for 5 minutes. The resulting homogeneous mixed solution was allowed to stand for 24 h. And then, centrifugally separating, washing and drying the product to obtain ZIF-67.
250mg of nickel nitrate hexahydrate is weighed and dissolved in 10mL of methanol, and the solution is stirred until clear. Weighing 100mg of ZIF-67, adding the ZIF-67 into a methanol solution of nickel nitrate, carrying out ultrasonic dispersion for 5 minutes, then carrying out stirring reaction for 3 hours, and then carrying out centrifugal separation, washing and drying on the product to obtain Ni-250-ZIF-67.
20mg of Ni-ZIF-67-250 was weighed into 32ml of ethanol, followed by dispersion by sonication. 60mg of sodium monohydrogen phosphate are then dissolved in 16ml of deionized water and the solution is stirred until clear. Then adding the aqueous solution of sodium monohydrogen phosphate into the dispersed Ni-ZIF-67-250 ethanol solution, and stirring for 1 hour at room temperature. The obtained uniform mixed solution is transferred into a reaction kettle of 80ml and reacted for 12 hours at the temperature of 120-150 ℃. After the mixture is cooled at room temperature, the obtained product is centrifugally separated, washed and dried to obtain the metal phosphate material (Ni-250-Co) with a hollow structure3(PO4)2)。
Fig. 1 is a TEM representation of the metal phosphate obtained in example 1. It can be seen that Co3(PO4)2The particle size is around 700nm and exhibits a hollow structure. The hollow structure material is beneficial to exposing more active sites and improving the catalytic performance of the material.
Fig. 2 is an XRD characterization pattern of the metal phosphate obtained in example 1. Compared with the standard PDF card, the material presents Co3(PO4)2Phase, crystallinity is poor.
FIG. 3 shows the metal phosphate material with hollow structure, the metal phosphate materials with different Ni doping amounts and the noble metal RuO prepared in example 12LSV performance graph of (a). The graph is used for representing the catalytic activity of the catalyst in the process of electrolyzing water to generate oxygen, the smaller the required voltage under the same current density is, the better the catalytic effect is, the graph can show that the catalytic performance of the metal phosphate is firstly improved and then reduced along with the doping amount of Ni, and the main reason is that the intrinsic catalytic activity of the transition metal phosphate catalytic sites is firstly improved and then reduced along with the doping amount of Ni.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (8)
1. A preparation method of an electrocatalyst with a hollow structure is characterized in that the electrocatalyst with the hollow structure is metal phosphate with a hollow structure; adding a metal organic framework material and soluble phosphate into a solvent, carrying out hydrothermal reaction for 5-15 hours at 120-150 ℃, and then centrifuging, washing and drying to obtain the electrocatalyst with the hollow structure; the soluble phosphate is sodium monohydrogen phosphate;
the metal organic framework material is a nickel-doped cobalt-based zeolite imidazolate framework material Ni-ZIF-67; adding the cobalt-based zeolite imidazolate framework material ZIF-67 into a methanol solution containing a nickel source, and stirring and mixing to obtain a nickel-doped cobalt-based zeolite imidazolate framework material Ni-ZIF-67; the mass ratio of the nickel source to the cobalt-based zeolite imidazole ester framework material ZIF-67 is (0.5-2.5): 1.
2. the preparation method according to claim 1, wherein the mass ratio of the nickel source to the cobalt-based zeolitic imidazolate framework material ZIF-67 is (1-1.5): 1.
3. the production method according to claim 1, wherein the nickel source is at least one of nickel nitrate, nickel chloride, nickel acetate, and nickel sulfate.
4. The method according to claim 1, wherein the stirring and mixing are carried out at room temperature for 3 to 10 hours.
5. The method according to claim 1, wherein the mass ratio of the metal-organic framework material to the soluble phosphate is 1: (2-5).
6. The method according to claim 1, wherein the aqueous solution containing the soluble phosphate is added to the ethanol solution containing the metal-organic framework material, and the hydrothermal reaction is performed.
7. The preparation method according to any one of claims 1 to 6, wherein the preparation method of the cobalt-based zeolitic imidazolate framework material ZIF-67 comprises:
(1) dispersing cobalt nitrate and dimethyl imidazole in a solvent to obtain a mixed solution;
(2) and standing the obtained mixed solution for 5-40 hours, and then performing centrifugal separation, washing and drying to obtain the cobalt-based zeolite imidazole ester framework material ZIF-67.
8. An electrocatalyst having a hollow structure prepared by the preparation method according to any one of claims 1 to 7, wherein the electrocatalyst having a hollow structure is a metal phosphate having a hollow structure, and the metal phosphate having a hollow structure is Ni-Co having a hollow structure3(PO4)2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910432582.3A CN110102348B (en) | 2019-05-23 | 2019-05-23 | Electrocatalyst with hollow structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910432582.3A CN110102348B (en) | 2019-05-23 | 2019-05-23 | Electrocatalyst with hollow structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110102348A CN110102348A (en) | 2019-08-09 |
| CN110102348B true CN110102348B (en) | 2022-03-08 |
Family
ID=67491729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910432582.3A Active CN110102348B (en) | 2019-05-23 | 2019-05-23 | Electrocatalyst with hollow structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110102348B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110436430B (en) * | 2019-08-21 | 2022-07-19 | 河南师范大学 | Preparation method and application of bifunctional electrocatalyst |
| CN110818911A (en) * | 2019-11-27 | 2020-02-21 | 江苏师范大学 | Synthesis method of ZIF-67-Co nano material with cuboctahedral hollow structure |
| CN112591728A (en) * | 2020-12-15 | 2021-04-02 | 四川大学 | Waste paper aerogel, aerogel derivative and preparation method thereof |
| CN113145145A (en) * | 2021-04-06 | 2021-07-23 | 北京化工大学 | Cobalt phosphate catalyst capable of efficiently activating PMS (permanent magnet synchronous motor), and preparation method and application thereof |
| CN115050972B (en) * | 2022-04-15 | 2024-01-30 | 黑龙江大学 | Polyhedral carbon-shell-supported transition metal-based hydrogen oxidation catalyst carrier and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108722452A (en) * | 2018-05-30 | 2018-11-02 | 中国科学技术大学 | A kind of difunctional metal phosphide catalyst, preparation method and its application |
| CN108816258A (en) * | 2018-06-13 | 2018-11-16 | 吉林大学 | A kind of hollow carbon material, preparation method and its application in catalytic electrolysis aquatic products hydrogen in situ for adulterating hollow phosphatization cobalt nanoparticle |
| CN109652815A (en) * | 2019-01-11 | 2019-04-19 | 河南师范大学 | A kind of preparation method of the layered double-hydroxide elctro-catalyst as derived from MOF with hollow structure |
-
2019
- 2019-05-23 CN CN201910432582.3A patent/CN110102348B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108722452A (en) * | 2018-05-30 | 2018-11-02 | 中国科学技术大学 | A kind of difunctional metal phosphide catalyst, preparation method and its application |
| CN108816258A (en) * | 2018-06-13 | 2018-11-16 | 吉林大学 | A kind of hollow carbon material, preparation method and its application in catalytic electrolysis aquatic products hydrogen in situ for adulterating hollow phosphatization cobalt nanoparticle |
| CN109652815A (en) * | 2019-01-11 | 2019-04-19 | 河南师范大学 | A kind of preparation method of the layered double-hydroxide elctro-catalyst as derived from MOF with hollow structure |
Non-Patent Citations (2)
| Title |
|---|
| Construction of Hollow Cobalt−Nickel Phosphate Nanocages through a Controllable Etching Strategy for High Supercapacitor Performances;Zhenyu Xiao,et.al.;《ACS Appl. Energy Mater.》;20190108;第2卷;第1087页Experimental Section * |
| Rapid synthesis of mesoporous NixCo3−x(PO4)2 hollow shells showing enhanced electrocatalytic and supercapacitor performance;Jingchao Zhang,et.al.;《J. Mater. Chem. A》;20141007;第2卷;摘要，第20182页Introduction * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110102348A (en) | 2019-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110102348B (en) | Electrocatalyst with hollow structure and preparation method thereof | |
| Chen et al. | Hierarchical porous NiFe-P@ NC as an efficient electrocatalyst for alkaline hydrogen production and seawater electrolysis at high current density | |
| CN109731586B (en) | Preparation method and application of copper-containing metal organic framework-derived hierarchical porous copper phosphide/carbohydrate electrolysis electrocatalyst | |
| WO2021232751A1 (en) | Porous coo/cop nanotubes, preparation method therefor and use thereof | |
| CN113249739B (en) | Metal phosphide-loaded monatomic catalyst, preparation method thereof and application of metal phosphide-loaded monatomic catalyst as hydrogen evolution reaction electrocatalyst | |
| CN113105645B (en) | Preparation method, product and application of nickel-based metal organic framework compound | |
| CN110534762A (en) | A kind of preparation method of cobalt and the 3-D ordered multiporous C catalyst of N doping | |
| CN108299656B (en) | Trinuclear copper cluster-based coordination polymer, preparation method and application thereof | |
| CN109055975A (en) | One kind preparing porous Ni based on two-dimensional metallic organic backbone template2The method of P/C electrode | |
| CN109174188A (en) | A kind of preparation of Heteroatom doping carbon material/Ni-MOF composite electrocatalyst | |
| CN109289858B (en) | Cobalt oxide and cerium dioxide composite oxide, and preparation method and application thereof | |
| CN112663085A (en) | Preparation method and application of high-performance cobalt-based oxygen evolution electrocatalytic nanomaterial | |
| CN108102108B (en) | Preparation method of copper-based metal organic framework material and application of copper-based metal organic framework material in electro-catalysis hydrogen production | |
| CN111996543B (en) | Vanadium-doped nickel selenide heterojunction self-supporting electrode and preparation method and application thereof | |
| Li et al. | Ni2Se3− CuSex Heterostructure as a Highly Efficient Bifunctional Electrocatalyst for Urea‐Assisted Hydrogen Generation | |
| CN110560094B (en) | Preparation method of 3D porous cobalt-tin-molybdenum trimetal catalyst | |
| CN109970988B (en) | Cobalt-based coordination polymer and application thereof as electrocatalytic hydrogen production catalyst | |
| CN114606511B (en) | Preparation method and electrocatalytic application of MOF@LDH composite material | |
| CN108842165B (en) | Solvothermal preparation of sulfur doped NiFe (CN)5NO electrolysis water oxygen evolution catalyst and application thereof | |
| CN115125547B (en) | Preparation and application of Mo/Nb double-doped Co hollow mesoporous carbon nano-box catalyst | |
| CN112921342B (en) | CeO loaded2Hollow MnCo of nanoparticles2O4Preparation method of catalyst, obtained material and application | |
| CN113026033A (en) | Cobalt-doped ruthenium-based catalyst, preparation method thereof and application of cobalt-doped ruthenium-based catalyst as acidic oxygen precipitation reaction electrocatalyst | |
| CN115651209B (en) | Preparation method and application of MIL-53 (Al-Cu) nanosheets | |
| CN116779890B (en) | Defect-state Pd nano-sheet electrocatalyst and preparation method thereof | |
| CN114736388B (en) | Fe-doped novel two-dimensional Co-MOFs composite material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |