CN112736259A - Method for preparing metal monoatomic electrocatalytic oxygen reduction catalyst through confined space - Google Patents
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Abstract
The invention discloses a method for preparing a metal monatomic electrocatalytic oxygen reduction catalyst through a confined space. The monatomic catalyst prepared by the limited space can maintain the original macroscopic two-dimensional leaf-shaped appearance, and realize larger specific surface area, so that the contact area with reactants in the reaction process is increased; meanwhile, the movement of metal atoms can be limited, the agglomeration of the metal atoms is prevented, the dispersity of the metal atoms is enhanced, and the metal atoms exist in a single atom form finally. The catalyst not only improves the stability of the catalyst, but also improves the utilization rate of metal atoms, forms more active sites and has potential application prospect in the field of electrocatalytic oxygen reduction. The preparation method is simple, the used raw materials are cheap and easy to obtain, and the method is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic oxygen reduction catalysts, and particularly relates to a method for preparing a monatomic catalyst through a confined space.
Background
With the development of industry, the requirement on energy is more and more, the environmental problem is more and more serious, the search for efficient and clean secondary energy is important, the technology of clean energy is continuously developed and improved at present, and the technologies of solar energy, wind energy, electric energy and the like are widely applied. The technologies meet a large demand on energy sources, reduce the emission of pollutants, and the production of wind energy and solar energy is intermittent and cannot be regulated and controlled according to the demand. The electric energy can be stored by the battery and supplied at any time according to the production and living needs of people, so that the major problem can be solved. Current common pollution-free, sustainable energy conversion and storage technologies include fuel cells, metal-air cells, and the like. The oxygen reduction reaction plays a crucial role as the cathode reaction of a fuel cell and a metal air cell, and the search for a high-efficiency and stable catalyst is a scientific problem to be solved urgently.
The oxygen reduction reaction is a multi-electron involved and slow kinetic process, and the rare precious metals such as Pt, Ir, etc. show good catalytic performance at present, but due to the scarcity, the price is high, and the practical application of the precious metals is greatly hindered. In recent years, inexpensive transition metals and their nitrogen and oxide compounds having low cost, high catalytic activity and high stability have been used in electrocatalytic research. Metal-organic frameworks (MOFs) are highly crystalline materials formed by coordination of Metal ions, Metal clusters and organic ligands, such as Zeolite imidazole framework materials (ZIFs) as a branch of MOFs, which not only have the advantages of large specific surface area, controllable pore structure and the like, but also can provide rich C, N microenvironment for metals after high-temperature carbonization due to the fact that the ZIFs contain rich C, N elements, and catalytic efficiency of the MOFs is improved.
Disclosure of Invention
The invention aims to provide a preparation method of a confined space metal monatomic catalyst for electrocatalytic oxygen reduction, which is prepared by using SiO2AsThe confined space shell not only improves the contact area with reactants in the reaction process, but also prevents the agglomeration of metal atoms, thereby showing excellent activity and stability to meet the requirements of application and development of related fields.
Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:
1. ZIF-L (Zn) -supported metal source
Dissolving 2-methylimidazole in deionized water to form a solution A; dissolving zinc nitrate hexahydrate and a metal source in deionized water to form a solution B; adding the solution A into the solution B, stirring at room temperature for 2-10 hours, centrifuging, washing, and drying a precipitate to obtain a metal source @ ZIF-L (Zn); wherein the metal source is ferric triacetylacetonate (Fe (acac)3) Any one of ferric nitrate, ferric chloride, ferric acetate, cobalt acetylacetonate, cobalt nitrate, cobalt acetate, cobalt chloride, nickel nitrate, copper nitrate, chloroplatinic acid, ruthenium chloride and silver nitrate.
2. Coated SiO2
Dispersing the metal source @ ZIF-L (Zn) in the step 1 in deionized water, then respectively adding cetyl trimethyl ammonium bromide, NaOH and tetraethyl silicate methanol solution, stirring at room temperature for 0.5-4 hours, then centrifugally washing and drying the mixed solution to obtain the metal source @ ZIF-L (Zn) @ SiO2。
3. Preparation of M-N-C @ SiO2
The metal source of the step 2 @ ZIF-L (Zn) @ SiO2Placing the mixture in a tube furnace, heating the mixture to 800-1100 ℃ in nitrogen flow, and keeping the temperature for 2-8 hours to obtain M-N-C @ SiO2Wherein M represents any one of Fe, Co, Ni, Cu, Pt, Ru and Ag.
4. SiO removal2
Mixing the M-N-C @ SiO of the step 32Adding the mixture into 2-4 mol/L NaOH aqueous solution, refluxing for 2-8 hours at 50-100 ℃, centrifugally washing with deionized water until the pH of the supernatant is 6-8, and adding 0.5-2 mol/L H2SO4Pouring the aqueous solution into the precipitate, refluxing for 12-24 hours at 50-100 ℃, centrifugally washing with deionized water until the pH of the supernatant is 6-8, drying, placing in a tube furnace, and performing filtration on the filtrate in the tube furnaceAnd heating to 800-1100 ℃ in nitrogen flow, and keeping for 1-4 hours to obtain the monatomic M-N-C catalyst.
In the step 1, the molar ratio of the 2-methylimidazole to the zinc nitrate and the metal source is preferably 8:1:0.005 to 0.02.
In the step 2, the mass ratio of the metal source @ ZIF-L (Zn), the hexadecyl trimethyl ammonium bromide, the NaOH and the tetraethyl silicate is preferably 1: 0.2-0.3: 0.09-0.12: 1.8-2.0.
In the above step 3, the metal source of step 2 @ ZIF-L (Zn) @ SiO2And (3) placing the mixture in a tubular furnace, heating the mixture to 900-1000 ℃ in nitrogen flow, and keeping the temperature for 2-4 hours. Further preferably, the heating rate is 2-5 ℃/min.
In the above step 4, M-N-C @ SiO of step 3 is preferably used2Adding the mixture into a 3mol/L NaOH aqueous solution, and refluxing for 3-5 hours at 70-80 ℃.
In the above step 4, it is preferable to add 1mol/L H2SO4Pouring the aqueous solution into the precipitate, and refluxing for 18-20 hours at 70-80 ℃.
In the step 4, the heating is preferably carried out at 900 to 1000 ℃ in a nitrogen flow and the temperature is kept for 2 to 3 hours. Further preferably, the heating rate is 2-5 ℃/min.
The invention has the following beneficial effects:
1. the invention takes cheap and easily available leafy ZIF-L (Zn) as a carrier, and provides an abundant C, N microenvironment for metal active sites; taking various types of metal salts as metal sources; with mesoporous SiO2As the shell of the limited space, the method can maintain the original macroscopic two-dimensional leaf-shaped appearance and improve the contact area with reactants in the reaction process; meanwhile, the movement of metal atoms can be limited, the agglomeration of the metal atoms is prevented, the dispersibility of the metal atoms is enhanced, a single-atom catalytic site is formed, a C, N-based catalyst can be induced to generate mesopores, the material transfer process in the oxygen reduction process is improved, the utilization rate of the metal atoms is effectively improved, and the electrochemical performance is improved.
2. Compared with commercial Pt/C catalysts, the metal monatomic catalyst prepared by the confined space method disclosed by the invention has excellent oxygen reduction activity and stability, and can be applied to cathode catalysts of fuel cells, metal cells and the like.
3. The preparation method is simple, rapid, green and environment-friendly, and is suitable for industrial large-scale production.
Drawings
FIG. 1 is Fe (acac) prepared in example 13High power SEM spectrum of @ ZIF-L (Zn).
FIG. 2 is Fe (acac) prepared in example 13@ZIF-L(Zn)@SiO2High power SEM spectra of (a).
FIG. 3 is Fe-N-C @ SiO prepared in example 12High power SEM spectra of (a).
FIG. 4 is a high power SEM image of Fe SAs/N-C prepared in example 1.
FIG. 5 is a spherical aberration corrected STEM spectrum of Fe SAs/N-C prepared in example 1.
Fig. 6 is a linear sweep voltammogram of Fe SAs/N-C prepared in example 1 and commercial Pt/C, respectively, as a catalyst in aqueous KOH at pH 13.
Fig. 7 is a chronoamperometric curve (relative to RHE) for Fe SAs/N-C prepared in example 1 and commercial Pt/C, respectively, as catalysts at 0.664V constant potential in aqueous KOH at pH 13.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
1. ZIF-L (Zn) Fe (acac) load3
1.97g (24mmol) of 2-methylimidazole were dissolved in 60mL of deionized water to form solution A. 0.89g (3mmol) of Zn (NO)3)2·6H2O and 10mg (0.028mmol) Fe (acac)3Dissolved in 60mL of deionized water to form solution B. Adding the solution A into the solution B, stirring for 4 hours at room temperature, centrifugally washing by deionized water, and drying an orange precipitate at 70 ℃ to obtain Fe (acac)3@ ZIF-L (Zn). As can be seen from FIG. 1, Fe (acac) was obtained3@ ZIF-L (Zn) exhibits a leafy morphology.
2. Bag (bag)Coated with SiO2
Mixing 300mg Fe (acac)3@ ZIF-L (Zn) was dispersed in 120mL of deionized water, then 3mL of a 25mg/mL aqueous cetyltrimethylammonium bromide solution, 4.8mL of a 6mg/mL aqueous NaOH solution, and 3.6mL of a tetraethyl silicate (TEOS) methanol solution (0.6mL of TEOS in 3mL of methanol) were added, and after stirring at room temperature for 1 hour, the mixed solution was centrifugally washed with deionized water and dried at 70 ℃ to obtain Fe (acac)3@ZIF-L(Zn)@SiO2. As can be seen from FIG. 2, the SiO coating2The appearance of the postleaf is not obviously changed.
3. Preparation of Fe-N-C @ SiO2
Mixing the Fe (acac) of step 23@ZIF-L(Zn)@SiO2Placing in a tube furnace, heating to 900 deg.C at a speed of 5 deg.C/min in nitrogen flow, and maintaining for 2 hr to obtain black powder Fe-N-C @ SiO2. As can be seen from FIG. 3, the ZIF-L (Zn) leafy morphology remains after carbonization and no metal particles are agglomerated together.
4. SiO removal2
100mg of Fe-N-C @ SiO2Adding into 50mL of 3mol/L NaOH aqueous solution, refluxing for 4 hours at 70 ℃, centrifugally washing by deionized water until the pH of the supernatant is 7, and adding 50mL of 1mol/L H2SO4Pouring the aqueous solution into the precipitate, refluxing at 70 deg.C for 20 hr, centrifuging with deionized water to wash to obtain supernatant with pH of 7, and washing to remove mesoporous SiO2Drying at 70 ℃, then placing in a tube furnace, heating to 900 ℃ at the speed of 5 ℃/min in nitrogen flow, and keeping for 2 hours to obtain black powder, namely the monatomic Fe-N-C catalyst (marked as Fe SAs/N-C). As can be seen from FIG. 4, SiO was washed away2Then, the leaf-shaped appearance can be maintained, and a large number of mesopores are formed on the surface of the leaf. It is apparent from FIG. 5 that Fe exists in a monoatomic form as indicated by the arrows in the drawing.
Example 2
1. ZIF-L (Zn) -loaded Co (NO)3)2
1.97g (24mmol) of 2-methylimidazole were dissolved in 60mL of deionized water to form solution A. 0.89g (3mmol) of Zn (NO)3)2·6H2O and 8mg (0.027mmol) Co (NO)3)2·6H2O was dissolved in 60mL of deionized water to form solution B. Adding the solution A into the solution B, stirring for 4 hours at room temperature, centrifugally washing with deionized water, and drying an orange precipitate at 70 ℃ to obtain Co (NO)3)2@ZIF-L(Zn)。
2. Coated SiO2
300mg of Co (NO)3)2@ ZIF-L (Zn) was dispersed in 120mL of deionized water, then 3mL of a 25mg/mL aqueous solution of cetyltrimethylammonium bromide, 4.8mL of a 6mg/mL aqueous solution of NaOH, and 3.6mL of a solution of tetraethyl silicate (TEOS) in methanol (0.6mL of TEOS in 3mL of methanol) were added, and after stirring at room temperature for 1 hour, the mixed solution was centrifugally washed with deionized water and dried at 70 ℃ to obtain Co (NO) (NO: TEOS)3)2@ZIF-L(Zn)@SiO2。
3. Preparation of Co-N-C @ SiO2
Mixing step 2 Co (NO)3)2@ZIF-L(Zn)@SiO2Placing in a tube furnace, heating to 800 deg.C at 3 deg.C/min in nitrogen flow, and maintaining for 3 hr to obtain black powder Co-N-C @ SiO2。
4. SiO removal2
100mg of Co-N-C @ SiO2Adding into 50mL of 3mol/L NaOH aqueous solution, refluxing for 4 hours at 70 ℃, centrifugally washing by deionized water until the pH of the supernatant is 7, and adding 50mL of 1mol/L H2SO4Pouring the aqueous solution into the precipitate, refluxing at 70 deg.C for 20 hr, centrifuging with deionized water to wash to obtain supernatant with pH of 7, and washing to remove mesoporous SiO2Drying at 70 ℃, placing in a tube furnace, heating to 800 ℃ at the speed of 3 ℃/min in nitrogen flow, and keeping for 3 hours to obtain black powder, namely the monatomic Co-N-C catalyst.
Example 3
1. ZIF-L (Zn) loaded with H2PtCl6
1.97g (24mmol) of 2-methylimidazole were dissolved in 60mL of deionized water to form solution A. 0.89g (3mmol) of Zn (NO)3)2·6H2O and 4.8. mu.L (0.028mmol) of H2PtCl6Dissolved in 60mL of deionized water to form solution B. Adding the solution AAdding the mixture into the solution B, stirring for 4 hours at room temperature, centrifugally washing by using deionized water, and drying an orange precipitate at 70 ℃ to obtain H2PtCl6@ZIF-L(Zn)。
2. Coated SiO2
Mixing 300mg of H2PtCl6@ ZIF-L (Zn) was dispersed in 120mL of deionized water, then 3mL of a 25mg/mL aqueous solution of cetyltrimethylammonium bromide, 4.8mL of a 6mg/mL aqueous solution of NaOH, and 3.6mL of a solution of tetraethyl silicate (TEOS) in methanol (0.6mL of TEOS in 3mL of methanol) were added, and after stirring at room temperature for 1 hour, the mixed solution was centrifugally washed with deionized water and dried at 70 ℃ to give H2PtCl6@ZIF-L(Zn)@SiO2。
3. Preparation of Pt-N-C @ SiO2
H of step 22PtCl6@ZIF-L(Zn)@SiO2Placing in a tube furnace, heating to 900 deg.C at 2 deg.C/min in nitrogen flow, and maintaining for 3 hr to obtain black powder Pt-N-C @ SiO2。
4. SiO removal2
100mg of Pt-N-C @ SiO2Adding into 50mL of 3mol/L NaOH aqueous solution, refluxing at 70 ℃ for 5 hours, centrifugally washing with deionized water until the pH of the supernatant is 7, and adding 50mL of 1mol/L H2SO4Pouring the aqueous solution into the precipitate, refluxing at 70 deg.C for 24 hr, centrifuging with deionized water to wash to obtain supernatant with pH of 7, and washing to remove mesoporous SiO2Drying at 70 ℃, placing in a tube furnace, heating to 900 ℃ at the speed of 2 ℃/min in nitrogen flow, and keeping for 2 hours to obtain black powder, namely the monatomic Pt-N-C.
To demonstrate the beneficial effects of the present invention, Fe SAs/N-C prepared in example 1 was drop-coated as a catalyst on a working electrode (area 0.196 cm)-2Rotating disk electrode) with a reference electrode Ag/AgCl and a counter electrode graphite rod, and the oxygen reduction performance was tested by linear sweep voltammetry (5mV/s) in KOH aqueous solution with pH 13, the results of which are shown in fig. 6. As can be seen from FIG. 6, the half-wave potential of oxygen reduction can reach E1/2The limiting current density can reach 5.5mA/cm when the voltage is 0.907V2Higher than commercialHalf-wave potential E of Pt/C catalyst1/20.874V, has potential great commercial value. In addition, a potentiostatic (0.664V) chronoamperometric curve was also tested by the above three-electrode system, and the results are shown in fig. 7. As shown in FIG. 7, the current density was maintained at 80% or higher after 14 hours of electrolysis, which was more stable than the commercial Pt/C catalyst.
Claims (9)
1. A method for preparing a metal monoatomic electrocatalytic oxygen reduction catalyst through a confined space, characterized in that the method consists of the following steps:
(1) ZIF-L (Zn) -supported metal source
Dissolving 2-methylimidazole in deionized water to form a solution A; dissolving zinc nitrate hexahydrate and a metal source in deionized water to form a solution B; adding the solution A into the solution B, stirring at room temperature for 2-10 hours, centrifuging, washing, and drying a precipitate to obtain a metal source @ ZIF-L (Zn); wherein the metal source is any one of ferric triacetylacetonate, ferric nitrate, ferric chloride, ferric acetate, cobalt acetylacetonate, cobalt nitrate, cobalt acetate, cobalt chloride, nickel nitrate, copper nitrate, chloroplatinic acid, ruthenium chloride and silver nitrate;
(2) coated SiO2
Dispersing the metal source @ ZIF-L (Zn) in the step (1) in deionized water, then respectively adding cetyl trimethyl ammonium bromide, NaOH and tetraethyl silicate methanol solution, stirring at room temperature for 0.5-4 hours, then centrifugally washing and drying the mixed solution to obtain the metal source @ ZIF-L (Zn) @ SiO2；
(3) Preparation of M-N-C @ SiO2
The metal source @ ZIF-L (Zn) @ SiO in the step (2)2Placing the mixture in a tube furnace, heating the mixture to 800-1100 ℃ in nitrogen flow, and keeping the temperature for 2-8 hours to obtain M-N-C @ SiO2Wherein M represents any one of Fe, Co, Ni, Cu, Pt, Ru and Ag;
(4) SiO removal2
Mixing the M-N-C @ SiO of the step (3)2Adding the mixture into 2-4 mol/L NaOH aqueous solution, refluxing for 2-8 hours at 50-100 ℃, centrifugally washing with deionized water until the pH of the supernatant is 6-8, and adding 0.5～2mol/L H2SO4And pouring the aqueous solution into the precipitate, refluxing for 12-24 hours at 50-100 ℃, centrifugally washing with deionized water until the pH of the supernatant is 6-8, drying, placing in a tubular furnace, heating to 800-1100 ℃ in nitrogen flow, and keeping for 1-4 hours to obtain the monatomic M-N-C catalyst.
2. The method of preparing a metal monatomic electrocatalytic oxygen reduction catalyst through a confined space according to claim 1, wherein: in the step (1), the molar ratio of the 2-methylimidazole to the zinc nitrate to the metal source is 8:1: 0.005-0.02.
3. The method of preparing a metal monatomic electrocatalytic oxygen reduction catalyst through a confined space according to claim 1, wherein: in the step (2), the mass ratio of the metal source @ ZIF-L (Zn), the hexadecyl trimethyl ammonium bromide, the NaOH and the tetraethyl silicate is 1: 0.2-0.3: 0.09-0.12: 1.8-2.0.
4. The method of preparing a metal monatomic electrocatalytic oxygen reduction catalyst through a confined space according to claim 1, wherein: in the step (3), the metal source @ ZIF-L (Zn) @ SiO in the step (2)2And (3) placing the mixture in a tubular furnace, heating the mixture to 900-1000 ℃ in nitrogen flow, and keeping the temperature for 2-4 hours.
5. The method for preparing a metal monoatomic electrocatalytic oxygen reduction catalyst through a confined space according to claim 1 or 4, wherein: in the step (3), the heating rate is 2-5 ℃/min.
6. The method of preparing a metal monatomic electrocatalytic oxygen reduction catalyst through a confined space according to claim 1, wherein: in the step (4), the M-N-C @ SiO in the step (3) is added2Adding the mixture into a 3mol/L NaOH aqueous solution, and refluxing for 3-5 hours at 70-80 ℃.
7. The method of claim 1The method for preparing the metal monoatomic electrocatalytic oxygen reduction catalyst through the confined space is characterized by comprising the following steps of: in the step (4), 1mol/L H is added2SO4Pouring the aqueous solution into the precipitate, and refluxing for 18-20 hours at 70-80 ℃.
8. The method of preparing a metal monatomic electrocatalytic oxygen reduction catalyst through a confined space according to claim 1, wherein: in the step (4), heating to 900-1000 ℃ in nitrogen flow, and keeping for 2-3 hours.
9. A method for preparing a metal monoatomic electrocatalytic oxygen reduction catalyst through a confined space according to claim 1 or 8, wherein: in the step (4), the heating rate is 2-5 ℃/min.
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