CN116065164A - Synthesis of metal MOF catalytic material and application of metal MOF catalytic material in rechargeable zinc-air battery and full-decomposition water hydrogen production - Google Patents
Synthesis of metal MOF catalytic material and application of metal MOF catalytic material in rechargeable zinc-air battery and full-decomposition water hydrogen production Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 63
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 14
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- 238000006243 chemical reaction Methods 0.000 claims description 9
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
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- C25B11/095—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 at least one of the compounds being organic
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Abstract
The invention belongs to the technical field of functional catalyst materials, and particularly relates to synthesis of a metal MOF catalytic material and application of the metal MOF catalytic material in a rechargeable zinc-air battery and full-decomposition water hydrogen production. The invention adopts inexpensive non-noble metal as raw material, the preparation process is simple, the synthesized CoFe-P catalytic material has excellent hydrogen precipitation and oxygen precipitation catalytic performance in the aspect of full water decomposition hydrogen production, and the catalyst is used for rechargeable zinc-air batteries, has good long-cycle stability, and is a high-efficiency and durable multifunctional electrocatalyst. The catalyst material is applied to rechargeable zinc-air batteries and full-decomposition water hydrogen production devices, not only can simplify equipment and reduce cost, but also can improve efficiency, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of functional catalyst materials, and particularly relates to synthesis of a metal MOF catalytic material and application of the metal MOF catalytic material in a rechargeable zinc-air battery and full-decomposition water hydrogen production.
Background
Metal-organic framework (MOF) compounds are a class of porous coordination polymers formed by self-assembling and interconnecting Metal ions and organic molecules through coordination reaction, and have highly ordered pore structures, extremely high porosity and extremely high specific surface area. The MOF forming process comprises nucleation and growth processes which occur through self-assembly of organic ligands and metal nodes, the morphology, the composition and the structure of the MOF are extremely diverse, and the excellent physicochemical characteristics of the MOF material enable the MOF material to have important application in the fields of energy storage, catalysis, analysis and the like. Currently, most MOF-derived materials are single metal compounds, and synthesis of bimetallic compounds derived from MOFs remains difficult: the high complexity of the MOF formation process will result in the nucleation and growth of coordination polymers being separated when the second metal ion is added. Therefore, development of bimetallic MOF derived materials has a certain significance for development of MOF material diversity.
Rechargeable zinc-air cells are important electrochemical energy conversion devices whose key to efficiency is the oxygen reduction/oxygen evolution electrochemical process. The kinetics of both reactions are slow and efficient catalysts are required to reduce the activation energy of the reaction. At present, a rechargeable zinc-air battery generally adopts a mixed material as a catalyst, namely noble metal (such as Pt, pd, au, ir and the like) is used as an oxygen reduction reaction catalyst, and noble metal oxide (such as RuO 2 、IrO 2 Etc.) are oxygen evolution reaction catalysts. However, the method is thatHowever, precious metal-based materials are difficult to perform as bi-functional catalysts, and the use of mixed catalysts also increases the cost and structural complexity of rechargeable zinc-air batteries. Meanwhile, the noble metal-based material has the problems of high cost, poor stability, slow reaction kinetics and the like. Therefore, development of non-noble metal catalytic materials with excellent catalytic performance and good stability is beneficial to development of rechargeable zinc-air batteries.
Hydrogen will play a vital role in the development of low carbon future. The hydrogen production by electrolysis of water is one of the best means for storing the electricity generated by renewable energy sources in the hydrogen, is also one of the most important hydrogen production industries at present, and is different from the hydrogen production by fossil fuel, the hydrogen production method does not generate harmful byproducts, does not aggravate the greenhouse effect, and alleviates the environmental problem to a certain extent. Electrocatalysts play an essential and important role in the production of hydrogen by electrolysis of water, and current commercial catalysts are mainly noble metal-based compounds, ir and Ru and their oxides are used in anodic oxygen evolution reactions, pt being a well-known cathodic hydrogen evolution catalyst. However, the large-scale application of the noble metal-based catalyst is limited by factors such as cost, reserves and the like, so that the research and development of the high-activity non-noble metal-based catalyst have great significance for the development of hydrogen production by water electrolysis.
In summary, the development of non-noble metal dual-function catalytic materials which can be used for rechargeable zinc-air batteries and fully-decomposed water to produce hydrogen has great application prospects.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention synthesizes a metal MOF catalytic material CoFe-P, which belongs to a non-noble metal dual-function catalytic material and can be simultaneously used for a rechargeable zinc-air battery and full-decomposition water hydrogen production.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
the first aspect of the invention provides a method for synthesizing a metallic MOF catalytic material CoFe-P, comprising the following steps:
s1, dissolving fumaric acid in an organic solvent, adding cobalt acetate and ferric nitrate under a stirring state, heating to 80-120 ℃ for 12 hours after stirring and dissolving, cooling to room temperature, washing and drying to obtain a precursor;
s2, annealing the precursor in an inert gas atmosphere to obtain CoFe 2 O 4 A material;
s3, for CoFe under inert gas atmosphere 2 O 4 And (3) carrying out a phosphating reaction on the material to obtain the CoFe-P catalytic material.
The CoFe-P catalytic material is synthesized by adopting a template method and a reduction method, and the catalyst is not only suitable for rechargeable zinc-air batteries, and has excellent catalytic performance and long-cycle stability, but also can be used for full-water-splitting hydrogen production, and has better full-electrolytic water-splitting hydrogen catalytic performance.
Preferably, the molar ratio of fumaric acid, ferric nitrate and cobalt acetate is 32 (1-3): 1.
Preferably, the temperature rising rate of the step S1 is 8-12 ℃/min; the organic solvent of step S1 includes, but is not limited to DMF.
Preferably, in step S1, the concentration of fumaric acid in the organic solvent is 10-20mmol/20mL.
Preferably, in the step S2, the annealing treatment is that the temperature is firstly increased to 400-500 ℃ at the speed of 1-3 ℃/min, the temperature is kept for 1-3h, then the temperature is reduced to 350-450 ℃ at the speed of 2-4 ℃/min, and finally the temperature is naturally reduced to a greenhouse.
Preferably, in step S3, the phosphating is performed by treating CoFe 2 O 4 The material and sodium hypophosphite are put into two ends of the same porcelain boat, and then heated to 350-450 ℃ at a speed of 2-4 ℃/min under the inert gas atmosphere, and kept for 1-3h.
Preferably CoFe 2 O 4 The mass ratio of the material to the sodium hypophosphite is 1:15 respectively.
The second aspect of the invention provides a metal MOF catalytic material CoFe-P prepared by the synthesis method of the first aspect.
In a third aspect the invention provides the use of a metallic MOF catalytic material CoFe-P as described in the first aspect in a rechargeable zinc-air battery.
In a third aspect, the invention provides an application of the metal MOF catalytic material CoFe-P in full-decomposition of water to produce hydrogen.
The research shows that the CoFe-P catalytic material synthesized by the invention has excellent oxygen precipitation catalytic performance in the aspect of full water decomposition hydrogen production, is used for a rechargeable zinc-air battery, has good long-cycle stability, is an efficient and durable electrocatalyst, can be applied to the rechargeable zinc-air battery and full water decomposition hydrogen production, can simplify equipment and reduce cost, can improve efficiency, and has good application prospect.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a preparation method of a metal MOF catalytic material CoFe-P, which uses cobalt acetate as a cobalt source, adopts a template method to prepare a precursor, and carries out annealing treatment on the precursor to obtain the CoFe 2 O 4 Then to CoFe 2 O 4 And (3) carrying out phosphating treatment, and synthesizing the CoFe-P catalytic material by using a reduction method. The catalytic material has excellent oxygen precipitation catalytic performance, the oxygen precipitation potential is only 150mV vs RHE, the hydrogen production performance of full electrolysis water is better, meanwhile, the catalytic material is assembled into a chargeable zinc-air battery, and when the discharge/charge reaches 350 cycles, the voltage gap is not obviously increased, and the long-cycle stability is good. The invention adopts inexpensive non-noble metal as raw material, the preparation process is simple, and the synthesized CoFe-P catalytic material has excellent oxygen precipitation catalytic performance, is an efficient and durable electrocatalyst, can be applied to rechargeable zinc-air batteries and full-decomposition water hydrogen production, not only can simplify equipment and reduce cost, but also can improve efficiency, and has good application prospect.
Drawings
FIG. 1 is a graph showing the catalytic performance of the CoFe-P catalyst material prepared in example 1 in a 1M KOH electrolyte;
fig. 2 is a graph showing charge-discharge cycle performance of a rechargeable zinc-air cell assembled from the CoFe-P catalytic material prepared in example 1.
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples, unless otherwise specified, are conventional, and the experimental materials used in the following examples, unless otherwise specified, are commercially available.
EXAMPLE 1 Synthesis of metallic MOF catalytic Material CoFe-P
(1) 16mmol of fumaric acid is weighed and dissolved in 20mL of DMF solution, stirred for 4h to be fully dissolved, then 0.5mmol of cobalt acetate and 1mmol of ferric nitrate are added in the continuous stirring process, stirring is carried out for 4h to be fully dissolved, then the solution is transferred into a 50mL polytetrafluoroethylene hydrothermal kettle, and the temperature is raised to 100 ℃ at the speed of 10 ℃/min and maintained for 12h. And after the temperature is reduced to room temperature, sequentially performing centrifugal washing for a plurality of times by using absolute ethyl alcohol and DMF, and drying at 60 ℃ to obtain a precursor.
(2) The precursor is put into a tube furnace for annealing treatment under the nitrogen atmosphere, firstly, the temperature is raised to 450 ℃ at the speed of 2 ℃/min, the temperature is kept for 2 hours, then the temperature is lowered to 400 ℃ at the speed of 3 ℃/min, and finally, the temperature is naturally lowered to a greenhouse, and the CoFe is obtained 2 O 4 A material.
(3) To synthesize CoFe 2 O 4 Performing phosphating reaction to obtain CoFe 2 O 4 The material and sodium hypophosphite are placed at two ends of the same porcelain boat, the mass ratio of the material to the sodium hypophosphite is 1:15 respectively, then the material and the sodium hypophosphite are placed in a tube furnace, heated to 400 ℃ at a speed of 3 ℃/min under the nitrogen atmosphere, kept for 2 hours, and finally cooled to room temperature, so as to obtain the CoFe-P catalytic material.
EXAMPLE 2 Synthesis of metallic MOF catalytic Material CoFe-P
The preparation method was the same as in example 1, except that the amount of ferric nitrate used in step (1) was 0.5mmol.
EXAMPLE 3 Synthesis of metallic MOF catalytic Material CoFe-P
The preparation process was the same as in example 1, except that the amount of ferric nitrate used in step (1) was 1.5mmol.
Experimental example 1 full-electrolytic aquatic Hydrogen Performance test of metallic MOF catalytic Material CoFe-P
And testing the linear sweep voltammetry curve of the CoFe-P catalytic material in a 1M KOH solution in a two-electrode, taking the CoFe-P catalytic material as an active substance, loading the CoFe-P catalytic material on cabot carbon black to form a sample to be tested (CoFe-P and cabot carbon black are added into a water/isopropanol mixed solution (1:4, v: v) according to the mass ratio of 1:4), uniformly dispersing by ultrasonic waves, and then drying, then measuring 4mg of the sample to be tested and 80 mu L of 5wt% Nafion binder, dispersing in 1mL of a mixed solution (1:4, v: v) of water and isopropanol, and carrying out ultrasonic waves for 1h until the solution is black. Then 5 mu L of dispersion liquid is measured and dripped on a glassy carbon electrode with the diameter of 5mm, and then CoFe-P II CoFe-P two electrodes are used for testing the hydrogen catalytic performance of the full electrolysis water to obtain a catalytic performance curve, as shown in figure 1, and meanwhile Pt/C L I RuO is used 2 the/C two electrodes served as controls.
As can be seen from FIG. 1, the CoFe-P synthesized in example 1 has good hydrogen catalytic performance of full-electrolysis water, the precipitation potential in 1MKOH electrolyte is 1.50V vs RHE, and the current density is 10mA/cm 2 The potential was 1.55V vs RHE. Meanwhile, the full electrolysis water of CoFe-P has hydrogen production performance equivalent to that of the traditional Pt/C catalytic material, and even more advantages.
Furthermore, the CoFe-P catalytic materials of examples 2 and 3 have similar full electrolysis water hydrogen production properties.
Experimental example 2 rechargeable zinc-air cell Performance and charge-discharge stability test of metallic MOF catalytic Material CoFe-P
At 6 mol.L -1 And 0.2 mol.L -1 Zn (Ac) 2 As an electrolyte, 2.0mg cm of the electrolyte was coated -2 A rechargeable zinc-air battery was constructed using a composite material of the CoFe-P catalytic material of example 1, which was prepared by compacting a nickel mesh (current collector) with a waterproof carbon film (diffusion layer) as a cathode and a zinc foil as an anode, and then subjected to charge and discharge tests using an Arbin battery test system in the united states, and tested for capacity and cycle stability of the zinc-air battery.
As can be seen from fig. 2, the voltage gap is not significantly increased when the zinc-air battery assembled from the CoFe-P catalytic material is discharged/charged for 350 cycles, and the stability of the long cycle is very good, which indicates that the CoFe-P catalyst is suitable for use in the zinc-air battery.
In addition, the CoFe-P catalytic materials of examples 2 and 3 were used in rechargeable zinc-air batteries, and the voltage gap was not significantly increased when discharged/charged for 350 cycles, and also exhibited good long-cycle stability.
In conclusion, the CoFe-P catalytic material synthesized by the method has excellent oxygen precipitation catalytic performance, is an efficient and durable electrocatalyst, can be applied to rechargeable zinc-air batteries and full-decomposition water hydrogen production, and has a huge application prospect.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (10)
1. The synthesis method of the metal MOF catalytic material CoFe-P is characterized by comprising the following steps of:
s1, dissolving fumaric acid in an organic solvent, adding cobalt acetate and ferric nitrate under a stirring state, heating to 80-120 ℃ for 12 hours after stirring and dissolving, cooling to room temperature, washing and drying to obtain a precursor;
s2, annealing the precursor in an inert gas atmosphere to obtain CoFe 2 O 4 A material;
s3, for CoFe under inert gas atmosphere 2 O 4 And (3) carrying out a phosphating reaction on the material to obtain the CoFe-P catalytic material.
2. The method for synthesizing metallic MOF catalytic material CoFe-P as claimed in claim 1, wherein the molar ratio of fumaric acid, ferric nitrate and cobalt acetate is 32 (1-3): 1.
3. The method for synthesizing metallic MOF catalytic material CoFe-P as set forth in claim 1, wherein the temperature rising rate of step S1 is 8-12 ℃/min.
4. The method for synthesizing metallic MOF catalytic material CoFe-P as claimed in claim 1, wherein in step S1, the concentration of fumaric acid in the organic solvent is 10-20mmol/20mL.
5. The method according to claim 1, wherein in step S2, the annealing process is performed by heating to 400-500 ℃ at a rate of 1-3 ℃/min, maintaining for 1-3 hours, cooling to 350-450 ℃ at a rate of 2-4 ℃/min, and naturally cooling to a greenhouse.
6. The method for synthesizing metallic MOF catalytic material CoFe-P as set forth in claim 1, wherein in step S3, said phosphating is performed by subjecting CoFe 2 O 4 The material and sodium hypophosphite are put into two ends of the same porcelain boat, and then heated to 350-450 ℃ at a speed of 2-4 ℃/min under the inert gas atmosphere, and kept for 1-3h.
7. The method for synthesizing metallic MOF catalytic material CoFe-P as set forth in claim 5, wherein CoFe 2 O 4 The mass ratio of the material to the sodium hypophosphite is 1:15 respectively.
8. A metallic MOF catalytic material CoFe-P prepared by the synthesis method of any one of claims 1 to 7.
9. Use of a metallic MOF catalytic material CoFe-P according to claim 8 in a rechargeable zinc-air battery.
10. Use of the metallic MOF catalytic material CoFe-P of claim 8 for the full decomposition of water to produce hydrogen.
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