CN110975937A - Preparation method and application of metal organic framework compound electrocatalyst - Google Patents
Preparation method and application of metal organic framework compound electrocatalyst Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 75
- 150000001875 compounds Chemical class 0.000 title claims abstract description 40
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 38
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 19
- 239000011975 tartaric acid Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 33
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- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- IFZHNZIVFDUDRB-UHFFFAOYSA-J C(=O)([O-])C(O)C(O)C(=O)[O-].[Fe+2].[Ni+2].C(=O)([O-])C(O)C(O)C(=O)[O-] Chemical compound C(=O)([O-])C(O)C(O)C(=O)[O-].[Fe+2].[Ni+2].C(=O)([O-])C(O)C(O)C(=O)[O-] IFZHNZIVFDUDRB-UHFFFAOYSA-J 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000013384 organic framework Substances 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000002057 nanoflower Substances 0.000 description 5
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- 229910000510 noble metal Inorganic materials 0.000 description 4
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- 238000003917 TEM image Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- -1 transition metal nitrides Chemical class 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- 238000001069 Raman spectroscopy Methods 0.000 description 2
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- 229910021607 Silver chloride Inorganic materials 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 239000013082 iron-based metal-organic framework Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
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- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B01J35/33—
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- B01J35/50—
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- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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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
- 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
- B01J2531/842—Iron
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method and application of a metal organic framework compound electrocatalyst. The preparation method comprises the following steps: mixing tartaric acid and FeCl3·6H2O and Ni (NO)3)2·6H2Dissolving O in methanol respectively; mixing the two, and transferring into a reaction kettle; vertically putting the foamed nickel into a reaction kettle, heating the reaction kettle for reaction, and naturally cooling; taking out the foamed nickel, washing with ethanol, and finally vacuum drying. In a three-electrode system, the metal organic framework compound electrocatalyst is directly used as a working electrodeIn the electrolyte, electrocatalytic water decomposition oxygen evolution reaction is carried out. The invention utilizes the strong coordination capability of tartaric acid, and forms the three-dimensional nanometer flower iron-nickel tartrate bimetallic organic framework compound formed by two-dimensional nanometer sheets by one-step wet chemical method self-assembly with foamed nickel as a substrate, and the compound has excellent electrocatalytic oxygen evolution activity and excellent cycling stability under high current density.
Description
Technical Field
The invention relates to a preparation method and application of a high-efficiency oxygen precipitation reaction electrocatalyst prepared by a wet chemical method, in particular to a preparation method and application of a metal organic framework compound electrocatalyst (marked as FeNi-MOF/NF), belonging to the technical field of three-dimensional self-supporting metal organic framework compound materials.
Background
Increasing fossil fuel consumption and deteriorating ecological problems are driving the constant search for renewable and clean energy sources, such as metal air batteries, fuel cells and water electrolysis plants. Electrocatalytic water splitting is considered a promising approach to sustainable, safe and environmentally friendly hydrogen fuel energy with hopes of addressing the current energy crisis. The water splitting reaction can be divided into two half-reactions occurring at the electrodes, namely an Oxygen Evolution Reaction (OER) and a Hydrogen Evolution Reaction (HER), and the efficiency of the two half-reactions is a key factor determining the overall water splitting performance. However, OER involves multiple proton coupled electron transfer, with concomitant cleavage of O-H and formation of O-O, so OER kinetics are very slow and have large overpotentials. Thus hindering large-scale application of the electrolyzed water. Therefore, it is necessary to explore an electrocatalyst with high activity and high stability to lower the energy barrier of elementary reactions in each step and promote the electrochemical processes. So far, the catalysts that OER has commercialized are still noble metal-based materials, such as Ir and Ru oxides, but the high cost, poor stability and global scarcity of these noble metals have greatly hampered their practical application. There is therefore an urgent need to develop non-noble metal catalysts which are both cost-effective and catalytically active and stable.
In recent years, researchers have invested much effort in various OER electrocatalyst materials, such as metal-organic framework combinationsCompounds, transition metal phosphides, transition metal nitrides, transition metal oxides, transition metal sulfides, transition metal carbides, layered double and triple metal double hydroxides, and self-supporting materials, among others. Self-supporting materials in particular have gained much attention because of the relative simplicity of the synthesis method, which avoids the use of binders. Although great progress has been made in the catalytic activity of OER, good cycle stability of the catalyst is also required in large-scale practical applications, and most of the catalysts are currently used at a low current density (10 mA/cm)2) The lower circulation is carried out for tens of hours or tens of hours, and few catalysts are used at high current density (100 mA/cm)2) The lower cycle is more than 100 hours, and the stability of the catalyst at a large current density is more important in view of economic efficiency when electrolyzing water. We grown the bimetallic organic complex in situ on foamed nickel and used the OER catalyst which could be stably cycled for 120h at a current density of 100mA/cm 2.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to prepare the three-dimensional nanometer flower iron nickel tartrate bimetallic organic framework compound under the condition of no template and surfactant.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a metal organic framework compound electrocatalyst is characterized by comprising the following steps:
step 1): proportionally mixing FeCl3·6H2O and Ni (NO)3)2·6H2Dissolving O in methanol to obtain solution A; dissolving tartaric acid in methanol to obtain a solution B;
step 2): adding the solution B into the solution A, then adjusting the pH value of the mixed solution by using a methanol solution of NaOH, stirring uniformly, and transferring the mixed solution into a reaction kettle;
step 3): vertically putting the foamed nickel into a reaction kettle, heating the reaction kettle for reaction, and naturally cooling;
step 4): taking out the foamed nickel, washing with ethanol, and finally vacuum drying.
Preferably, FeCl in the step 1)3·6H2O、Ni(NO3)2·6H2The molar ratio of O to methanol is 4:4: 1; the molar ratio of tartaric acid to methanol was 4: 1.
Preferably, the volume ratio of the solution A to the solution B in the step 2) is 1: 1.
Preferably, the nickel foam in the step 3) is washed by 1M HCl, ethanol and deionized water in sequence in advance.
Preferably, the heating temperature of the reaction kettle in the step 3) is 90-130 ℃, and the reaction time is 7-15 h.
Preferably, the temperature of vacuum drying in the step 4) is 60 DEG C
The invention also provides application of the metal organic framework compound electrocatalyst prepared by the preparation method of the metal organic framework compound electrocatalyst, which is characterized in that in a three-electrode system, the metal organic framework compound electrocatalyst is directly used as a working electrode to be placed in electrolyte to carry out electrocatalytic water decomposition oxygen separation reaction.
Preferably, the electrolyte is a 1M KOH solution.
According to the invention, under the condition of no template and surfactant, the strong coordination capacity of tartaric acid is utilized, the three-dimensional nanoflower iron-nickel tartrate bimetallic organic framework compound formed by two-dimensional nanosheets is formed by self-assembly of foamed nickel serving as a substrate through a one-step wet chemical method, and the prepared three-dimensional self-supporting material has excellent electrocatalytic oxygen evolution activity and excellent cycling stability under high current density.
Compared with the prior art, the invention has the beneficial effects that:
1. the selected substrate is foamed nickel with better conductivity, and the metal organic framework compound grows on the conductive substrate in situ, so that poor inter-particle electron migration between the electroactive center and the current collector is avoided, and the kinetics of the water decomposition reaction is accelerated.
2. Layered nanoflowers with the catalyst diameter of about 1 mu m are closely arranged on a substrate, ultrathin and mutually-crosslinked nanosheets provide enough channels for rapid electron transfer, and the nanosheets are provided with abundant open gaps, so that more active sites are exposed.
3. The material is of an amorphous structure, and the amorphous material has more surface unsaturated sites, so that reactants have better adsorption performance, and have more excellent catalytic activity. In addition, since the local structure of the adsorption site is easily distorted by the intermediate, the amorphous structure has high structural flexibility
4. The prepared material can generate large pi bonds in the OER reaction process, so that the catalyst has excellent catalytic performance and ultra-long cycle life.
In conclusion, the method for preparing the material with the high-hydrophilicity hierarchical nanoflower structure by the wet chemical method is simple and easy to operate, does not need subsequent high-temperature carbonization treatment, and is easy for large-scale production; the prepared material has great advantages in the aspects of catalytic oxygen evolution and energy conversion, and in the catalytic oxygen evolution reaction, the prepared composite material has small overpotential under the action of a high current density and still has excellent stability under the action of a high current density, so that the preparation method is very favorable for realizing large-scale application.
Drawings
FIG. 1a is a scanning electron micrograph of a metal-organic framework compound FeNi-MOF prepared in example 1 at 500 nm;
FIG. 1b is a scanning electron micrograph of a metal-organic framework compound FeNi-MOF prepared in example 1 at 200 nm;
FIG. 1c is a transmission electron micrograph of a metal organic framework compound FeNi-MOF prepared in example 1 at 200 nm;
FIG. 1d is a transmission electron micrograph at 100nm of a metal-organic framework compound FeNi-MOF prepared in example 1 and the corresponding EDS energy spectrum;
FIG. 1e is the EDS spectrum of the metal-organic framework compound FeNi-MOF prepared in example 1;
FIG. 2a is an XRD pattern of a metal organic framework compound FeNi-MOF/NF prepared in example 1;
FIG. 2b is a comparison of XPS spectra before and after reaction of the metal organic framework compound FeNi-MOF/NF prepared in example 1;
FIG. 2c is a graph comparing in situ Raman during the process of the metal organic framework compound FeNi-MOF/NF prepared in example 1;
FIG. 2d is an infrared spectrum of a metal organic framework compound FeNi-MOF/NF obtained in example 1 before and after reaction and tartaric acid;
FIG. 2e is a thermogravimetric plot of tartaric acid before and after the reaction of the metal-organic framework compound FeNi-MOF/NF prepared in example 1;
FIG. 2f is the ultraviolet diffuse reflection spectrum of tartaric acid before and after the reaction of the metal-organic framework compound FeNi-MOF/NF prepared in example 1;
FIG. 3 shows the DFT calculation results of FeNi-MOF/NF OER reaction of the metal-organic framework compound prepared in example 1;
FIG. 4a is the LSV curve of the metal-organic framework compound FeNi-MOF/NF and its control prepared in example 1;
FIG. 4b is the Tafel slope of the metal organic framework compound FeNi-MOF/NF and its control made in example 1;
FIG. 4c is an i-t test of the metal organic framework compound FeNi-MOF/NF prepared in example 1;
FIG. 4d is an impedance spectrum of the metal organic framework compound FeNi-MOF/NF and its control prepared in example 1.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1: preparation of three-dimensional self-supporting metal organic framework compound FeNi-MOF/NF
(1) According to 0.1802g FeCl3·6H2O and 0.0969g Ni (NO)3)2·6H2Dissolving O in 7mL of methanol to obtain solution A, and dissolving 0.1501g of tartaric acid in 7mL of methanol to obtain solution B;
(2) adding the solution B into the solution A, adjusting the pH of the solution to 3 by using 1M NaOH methanol solution, stirring uniformly, and transferring the solution into a 20mL reaction kettle;
(3) will already use 1M HCl, B1X2cm washed with alcohol and deionized water2Vertically placing the foamed nickel into a reaction kettle, placing the reaction kettle into a 130 ℃ oven for reaction for 7 hours, and naturally cooling;
(4) washing the reacted foam nickel with ethanol, and vacuum drying at 60 ℃;
(5) electrochemical testing: and (3) measuring a linear scanning voltammetry curve of the FeNi-MOF/NF in a three-electrode system (the electrode of the metal organic framework compound FeNi-MOF/NF prepared in the step (4) is used as a working electrode, a silver/silver chloride electrode is used as a reference electrode, and a graphite electrode is used as an auxiliary electrode). The electrolyte solution used for the test was a 1M KOH solution.
Example 2: preparation of three-dimensional self-supporting metal organic framework compounds Fe-MOF/NF and Ni-MOF/NF
(1) According to 0.1802g FeCl3·6H2O(0.0969g Ni(NO3)2·6H2O) is dissolved in 7mL of methanol to obtain solution A, and 0.1501g of tartaric acid is dissolved in 7mL of methanol to obtain solution B;
(2) adding the solution B into the solution A, adjusting the pH of the solution to 3 by using a NaOH methanol solution, uniformly stirring, and transferring the solution into a 20mL reaction kettle;
(3) washing 1x2cm with 1MHCl, ethanol and deionized water2Vertically placing the foamed nickel into a reaction kettle, placing the reaction kettle into a 130 ℃ oven for reaction for 7 hours, and naturally cooling;
(4) the reacted nickel foam was washed with ethanol and dried under vacuum at 60 ℃.
Comparative example
(1)5mg RuO2Dispersing in 1mL of mixed solution, wherein the solution consists of 180 mu L of deionized water, 800 mu L of isopropanol and 20 mu L of Nafion, and ultrasonically dispersing for 40 min;
(2) loading 50 of the dispersion liquid on cleaned foamed nickel, wherein the loading area is 1 cm;
(3) electrochemical testing: in a three-electrode system (coated with RuO prepared in step (2))2A glassy carbon electrode as a working electrode, a silver/silver chloride electrode as a reference electrode, and a platinum sheet electrode as an auxiliary electrode), RuO is measured2Linear sweep voltammogram of/NF. The electrolyte solution used for the test was a 1M KOH solution.
FeNi-MOF/NF, Fe-MOF/NF, Ni-MOF/NF, RuO obtained in examples 1-2 and comparative examples2All electrochemical performances of/NF, NF were tested by means of an electrochemical workstation, which was a chenhua electrochemical workstation, model No. CHI 660E.
FeNi-MOF is scanned under 500nm by using a field emission scanning electron microscope (model number is FESEM, JEOL, FEG-XL30S, manufacturer is Japanese JEOL electron company), an obtained scanning electron microscope image is shown in figure 1a, as can be seen from the scanning electron microscope, layered nanoflowers with the diameter of about 1 mu m are closely arranged on a substrate, ultrathin and mutually crosslinked nanosheets provide enough channels for rapid electron transfer, and abundant open gaps are formed among the nanosheets.
The FeNi-MOF was scanned at 500nm using a transmission electron microscope (model JEOL JEM-2100F, manufactured by JEOL electronics of Japan) and the transmission electron micrograph obtained is shown in FIG. 1c, from which it can be seen that the FeNi-MOF consists of two parts, and the layered nanoflowers with a diameter of about 1 μm were closely arranged on the substrate.
The XRD pattern obtained by testing with an X-ray diffractometer (model: Burker-AXS D8, manufacturer: Burker, Germany) with FeNi-MOF/NF is shown in FIG. 2, in FIG. 2a, the abscissa is 2 theta angle and the ordinate is diffraction intensity.
The in-situ Raman spectrum obtained by the test is shown in FIG. 2c, and the in-situ Raman spectrum is shown in FIG. 2 c; the abscissa is the wavenumber and the ordinate is the reflectivity. The spectrum is in-situ Raman of the FeNi-MOF/NF catalyst in a 0.1M KOH electrolyte in the CV cycle process along with the increase of voltage.
Performing infrared test on FeNi-MOF/NF before and after reaction and tartaric acid by a spectrum two-way infrared spectrometer; the obtained infrared spectrum is shown in FIG. 2d, in which FIG. 2d, the abscissa represents the wave number and the ordinate represents the transmittance. Before represents the infrared spectrum of the FeNi-MOF/NF, after the FeNi-MOF/NF participates in the OER reaction, after is the infrared spectrum of the FeNi-MOF/NF, tartaric acid represents the infrared spectrum of the tartaric acid.
The thermogravimetric graph obtained by the NETZSCH STA 409 PC in the thermogravimetric test is shown in fig. 2e, wherein the abscissa is temperature and the ordinate is weight loss rate. Beforee represents the thermogravimetry of FeNi-MOF/NF, after FeNi-MOF/NF participates in OER reaction, tartaric acid represents the thermogravimetry of tartaric acid.
The ultraviolet spectrum obtained by the UV-2401PC test for ultraviolet-visible diffuse reflection is shown in FIG. 2f, in which the abscissa is the wave number and the ordinate is the reflectance. Before represents the ultraviolet diffuse reflection spectrum of the FeNi-MOF/NF, after is the ultraviolet diffuse reflection spectrum of the FeNi-MOF/NF after the FeNi-MOF/NF participates in the OER reaction, and tartaric acid represents the ultraviolet diffuse reflection spectrum of tartaric acid.
The three-dimensional self-supporting metal organic framework compound material prepared by the method has the advantages of simple and feasible synthesis method, no non-noble metal material in the used metal, greatly reduced cost, excellent catalytic activity and cycle stability under the current density, and very necessary realization of commercial application.
Claims (8)
1. A preparation method of a metal organic framework compound electrocatalyst is characterized by comprising the following steps:
step 1): proportionally mixing FeCl3·6H2O and Ni (NO)3)2·6H2Dissolving O in methanol to obtain solution A; dissolving tartaric acid in methanol to obtain a solution B;
step 2): adding the solution B into the solution A, then adjusting the pH value of the mixed solution by using a methanol solution of NaOH, stirring uniformly, and transferring the mixed solution into a reaction kettle;
step 3): vertically putting the foamed nickel into a reaction kettle, heating the reaction kettle for reaction, and naturally cooling;
step 4): taking out the foamed nickel, washing with ethanol, and finally vacuum drying.
2. The method of preparing the metal-organic framework compound electrocatalyst according to claim 1, wherein the FeCl in step 1) is FeCl3·6H2O、Ni(NO3)2·6H2The molar ratio of O to methanol is 4:4: 1; the molar ratio of tartaric acid to methanol was 4: 1.
3. The method for preparing a metal-organic framework compound electrocatalyst according to claim 1, wherein the volume ratio of the solution a to the solution B in step 2) is 1: 1.
4. The method of preparing a metal organic framework electrocatalyst according to claim 1, wherein the nickel foam in step 3) is washed with 1M HCl, ethanol, and deionized water in sequence.
5. The method for preparing the metal-organic framework compound electrocatalyst according to claim 1, wherein the heating temperature of the reaction vessel in step 3) is 90-130 ℃ and the reaction time is 7-15 h.
6. The method for preparing a metal-organic framework compound electrocatalyst according to claim 1, wherein the temperature of vacuum drying in step 4) is 60 ℃.
7. Use of the metal-organic framework electrocatalyst prepared by the process of any one of claims 1 to 6, wherein the metal-organic framework electrocatalyst is used as a working electrode in a three-electrode system and is directly placed in an electrolyte to perform electrocatalytic water-splitting oxygen evolution reaction.
8. The use according to claim 7, wherein the electrolyte is a 1M KOH solution.
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