CN114686915B - Cobalt-iron bimetallic phosphide nanosphere derived from metal organic framework, and preparation method and application thereof - Google Patents
Cobalt-iron bimetallic phosphide nanosphere derived from metal organic framework, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a cobalt-iron bimetallic phosphide nanosphere derived from a metal organic framework, and a preparation method and application thereof, and belongs to the field of catalytic electrode materials. Synthesizing a metal organic framework precursor by using cobalt and iron as substrates and using 1,3, 5-benzene tricarboxylic acid as an organic ligand through a hydrothermal method, and performing low-temperature phosphating on the precursor in a tube furnace to obtain the cobalt-iron bimetallic phosphide nanospheres. It can be used as a catalytic electrode material for catalyzing hydrogen and oxygen evolution reaction in the process of hydrogen production by water electrolysis, and can be used for preparing hydrogen and oxygen at a concentration of 10mA cm ‑2 The hydrogen evolution catalytic performance in the acid solution and the alkaline solution can reach over-potential of 138 mV and 193mV respectively, the oxygen evolution performance in the alkaline solution can reach over-potential of 293mV, and the current density in the 1M KOH solution is 10mA cm ‑2 The voltage of full water decomposition can reach 1.62V, and the method has good circulation stability, simple preparation process and convenient industrialized application.
Description
Technical Field
The invention belongs to the field of catalytic electrode materials, and particularly relates to a cobalt-iron bimetallic phosphide nanosphere derived from a metal organic framework, and a preparation method and application thereof.
Background
In recent years, hydrogen (H) 2 ) Particular attention has been paid as a sustainable energy source. Among the processes for large-scale production of hydrogen, the most efficient clean process is the electrolysis of water to produce hydrogen. However, the overall kinetics of the electrolyzed water reaction are slow due to the lack of reaction kinetics of the two decisive half reactions, hydrogen Evolution (HER) and Oxygen Evolution (OER). It is therefore necessary to find a catalyst which is highly clean to increase the reactivity.
According to previous reports, noble metal materials such as Pt/C and RuO 2 Can obviously improve the reactivity of HER and OER respectively. However, noble metal materials are costly, poorly stable and of limited availability, impeding their large-scale use. Therefore, it is urgent to find a catalyst with low cost and high activity. Among these materials, transition Metal Phosphides (TMPs) are attracting attention for their excellent properties and environmental friendliness. However, TMPS composed of a single metal does not exert optimal performance. In addition, metal-organic frameworks (MOFs) have received great attention due to their unique properties. However, MOF is not very conductive and therefore cannot be used directly as a catalyst for water electrolysis. Meanwhile, the active centers of many catalysts are easy to lose efficacy in the catalytic process, and the stability of materials is poor.
Disclosure of Invention
In order to overcome the defects in the prior art, the main purpose of the invention is to provide a preparation method of cobalt-iron bimetallic phosphide nanospheres derived from a metal-organic framework, which is to synthesize a metal-organic framework precursor taking cobalt and iron as substrates and 1,3, 5-benzene tricarboxylic acid as an organic ligand by a hydrothermal method, and then to carry out phosphorization on the precursor in a tube furnace by a low-temperature phosphorization method.
The invention also aims to provide the cobalt-iron bimetallic phosphide nanospheres derived from the metal-organic framework, which are obtained by the preparation method and have high catalytic activity and good cycle stability.
The invention also aims to provide the application of the cobalt-iron bimetallic phosphide nanospheres derived from the metal-organic framework in catalyzing hydrogen and oxygen evolution reaction in the process of producing hydrogen by electrolyzing water.
The above object of the present invention is achieved by the following technical solutions:
the preparation method of the cobalt-iron bimetallic phosphide nanospheres derived from the metal organic framework comprises the following steps:
(1) Dissolving polyvinylpyrrolidone (PVP) in a mixed solution of N, N-Dimethylformamide (DMF) and Ethylene Glycol (EG), mixing uniformly, and adding 1,3, 5-benzenetricarboxylic acid (H) 3 BTC) cobalt acetylacetonate(Co(acac) 2 ) And ferric acetylacetonate (Fe (acac) 3 ) Transferring the obtained mixed solution into a high-pressure reaction kettle for hydrothermal reaction, after the reaction is finished, cooling the temperature in the kettle to room temperature, centrifuging a reaction product, washing the reaction product with deionized water and ethanol respectively, collecting the product, and drying to obtain the cobalt-iron bimetallic-based organic framework nanospheres;
(2) The cobalt-iron bimetallic-based organic framework nanospheres obtained in the step (1) and sodium hypophosphite (NaH) 2 PO 2 ) Respectively put into a porcelain boat, put downstream and upstream of a quartz tube in a tube furnace, and put into N 2 Heating under atmosphere, heating to the phosphating reaction temperature, and then preserving heat for low-temperature phosphating to obtain the cobalt-iron bimetallic phosphide nanospheres.
Further, in the step (1), the concentration of cobalt acetylacetonate in the mixed solution is 1.82×10 -3 –5.47×10 -3 mol L -1 Iron acetylacetonate concentration was 1.99X10 -3 –5.42×10 -3 mol L -1 The concentration of polyvinylpyrrolidone was 3.56X10 -2 mol L -1 The concentration of 1,3, 5-benzenetricarboxylic acid is 4.46×10 -3 mol L -1 ；
The mass fraction of the ethylene glycol is 99.7%, and the addition amount of the solvent is 28.8mL;
the mass fraction of the N, N-dimethylformamide is 99.5%, and the solvent addition amount is 48mL;
the hydrothermal reaction temperature is 160-200 ℃ and the hydrothermal time is 3h;
the drying temperature is 50-60 ℃ and the drying time is 4-6h.
Further, in the step (2), the sodium hypophosphite is sodium hypophosphite monohydrate with the purity of 99%; the purity of the nitrogen is 99%; the phosphating reaction temperature is 350 ℃, and the temperature rising rate is 3 ℃ for min -1 The heat preservation time is 2h.
The invention also provides a cobalt-iron bimetallic phosphide nanosphere derived from the metal-organic framework, and the cobalt-iron bimetallic phosphide nanosphere is prepared by the preparation method of the cobalt-iron bimetallic phosphide nanosphere derived from the metal-organic framework.
The invention also provides a catalytic electrode material which comprises the cobalt-iron bimetallic phosphide nanospheres derived from the metal-organic framework.
The invention also provides application of the cobalt-iron bimetallic phosphide nanospheres derived from the metal-organic framework or the catalytic electrode material in catalytic hydrogen and oxygen evolution reaction in the process of producing hydrogen by electrolyzing water.
Compared with the prior art, the invention has the beneficial effects that: the cobalt-iron bimetallic phosphide nanospheres obtained by the method have good catalytic performance as a catalytic electrode material and good cycling stability, and can be used for catalyzing hydrogen and oxygen evolution reactions in the process of producing hydrogen by electrolyzing water.
Drawings
FIG. 1 is a flow chart of the preparation of metal-organic framework-derived cobalt-iron bimetallic phosphide nanospheres in an embodiment;
FIG. 2 is a SEM image of different multiples of a metal-organic framework-derived cobalt-iron bimetallic phosphide nanosphere according to one embodiment;
FIG. 3 is a low-magnification TEM photograph of a metal-organic framework-derived cobalt-iron bimetallic phosphide nanosphere according to one embodiment;
FIG. 4 is a high-magnification TEM photograph of a metal-organic framework-derived cobalt-iron bimetallic phosphide nanosphere according to one embodiment;
FIG. 5 is a graph (a) showing the full water splitting performance and a graph (b) showing the cycling stability of the metal organic framework-derived cobalt-iron bimetallic phosphide nanospheres according to an example.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention.
Example 1
In this example, a metal-organic framework-derived cobalt-iron bimetallic phosphide nanosphere was prepared according to the method shown in fig. 1, and the steps were as follows:
step 1, preparing a cobalt-iron bimetallic organic framework precursor: 300mg of polyvinylpyrrolidone are dissolved in 48mL of N, N-dimethylformamide and 28.8mL of ethylene glycol. After magnetic stirring for 30min, PVP was completely dispersed in the mixed solution. 72mg of 1,3, 5-benzenetricarboxylic acid, 108mg of cobalt acetylacetonate and 54mg of iron acetylacetonate were then added thereto and stirred for 20 minutes to form a uniform dispersion. The solution was transferred to a teflon-lined stainless steel autoclave, reacted at 200 ℃ for 3 hours, after the reaction was completed, the autoclave temperature was lowered to room temperature, centrifuged at 8000rpm in a centrifuge for 10 minutes, and washed with deionized water and ethanol, respectively, several times. Collecting the product, and drying at 60 ℃ overnight to obtain the cobalt-iron bimetallic-based organic framework nanospheres;
step 2, preparing cobalt-iron bimetallic phosphide nanospheres: and respectively placing the obtained cobalt-iron bimetallic organic framework precursor and sodium hypophosphite into a porcelain boat, and placing the porcelain boat at the downstream and upstream of a quartz tube in a tube furnace. Then, at N 2 At 3 ℃ for min under atmosphere -1 And (3) heating the tubular furnace from room temperature to 350 ℃ and preserving heat for 2 hours to obtain the cobalt-iron bimetallic phosphide nanospheres.
Example 2
In this example, a metal-organic framework-derived cobalt-iron bimetallic phosphide nanosphere was prepared according to the method shown in fig. 1, and the steps were as follows:
step 1, preparing a cobalt-iron bimetallic organic framework precursor: 300mg of polyvinylpyrrolidone are dissolved in 48mL of N, N-dimethylformamide and 28.8mL of ethylene glycol. After magnetic stirring for 30min, PVP was completely dispersed in the mixed solution. 72mg of 1,3, 5-benzenetricarboxylic acid, 108mg of cobalt acetylacetonate and 54mg of iron acetylacetonate were then added thereto and stirred for 20 minutes to form a uniform dispersion. The solution was transferred to a teflon-lined stainless steel autoclave, reacted at 180 ℃ for 3 hours, after the reaction was completed, the autoclave temperature was lowered to room temperature, centrifuged at 8000rpm in a centrifuge for 10 minutes, and washed with deionized water and ethanol, respectively, several times. Collecting the product, and drying at 60 ℃ overnight to obtain the cobalt-iron bimetallic-based organic framework nanospheres;
step 2, preparingPreparing cobalt-iron bimetallic phosphide nanospheres: and respectively placing the obtained cobalt-iron bimetallic organic framework precursor and sodium hypophosphite into a porcelain boat, and placing the porcelain boat at the downstream and upstream of a quartz tube in a tube furnace. Then, at N 2 At 3 ℃ for min under atmosphere -1 And (3) heating the tubular furnace from room temperature to 350 ℃ and preserving heat for 2 hours to obtain the cobalt-iron bimetallic phosphide nanospheres.
Example 3
In this example, a metal-organic framework-derived cobalt-iron bimetallic phosphide nanosphere was prepared according to the method shown in fig. 1, and the steps were as follows:
step 1, preparing a cobalt-iron bimetallic organic framework precursor: 300mg of polyvinylpyrrolidone are dissolved in 48mL of N, N-dimethylformamide and 28.8mL of ethylene glycol. After magnetic stirring for 30min, PVP was completely dispersed in the mixed solution. 72mg of 1,3, 5-benzenetricarboxylic acid, 108mg of cobalt acetylacetonate and 54mg of iron acetylacetonate were then added thereto and stirred for 20 minutes to form a uniform dispersion. The solution was transferred to a teflon-lined stainless steel autoclave, reacted at 160 ℃ for 3 hours, after the reaction was completed, the autoclave temperature was lowered to room temperature, centrifuged at 8000rpm in a centrifuge for 10 minutes, and washed with deionized water and ethanol, respectively, several times. Collecting the product, and drying at 60 ℃ overnight to obtain the cobalt-iron bimetallic-based organic framework nanospheres;
step 2, preparing cobalt-iron bimetallic phosphide nanospheres: and respectively placing the obtained cobalt-iron bimetallic organic framework precursor and sodium hypophosphite into a porcelain boat, and placing the porcelain boat at the downstream and upstream of a quartz tube in a tube furnace. Then, at N 2 At 3 ℃ for min under atmosphere -1 And (3) heating the tubular furnace from room temperature to 350 ℃ and preserving heat for 2 hours to obtain the cobalt-iron bimetallic phosphide nanospheres.
Example 4
In this example, a metal-organic framework-derived cobalt-iron bimetallic phosphide nanosphere was prepared according to the method shown in fig. 1, and the steps were as follows:
step 1, preparing a cobalt-iron bimetallic organic framework precursor: 300mg of polyvinylpyrrolidone are dissolved in 48mL of N, N-dimethylformamide and 28.8mL of ethylene glycol. After magnetic stirring for 30min, PVP was completely dispersed in the mixed solution. 72mg of 1,3, 5-benzenetricarboxylic acid, 73mg of cobalt acetylacetonate and 101mg of iron acetylacetonate were then added, and stirred for 20 minutes to form a uniform dispersion. The solution was transferred to a teflon-lined stainless steel autoclave, reacted at 200 ℃ for 3 hours, after the reaction was completed, the autoclave temperature was lowered to room temperature, centrifuged at 8000rpm in a centrifuge for 10 minutes, and washed with deionized water and ethanol, respectively, several times. Collecting the product, and drying at 60 ℃ overnight to obtain the cobalt-iron bimetallic-based organic framework nanospheres;
step 2, preparing cobalt-iron bimetallic phosphide nanospheres: and respectively placing the obtained cobalt-iron bimetallic organic framework precursor and sodium hypophosphite into a porcelain boat, and placing the porcelain boat at the downstream and upstream of a quartz tube in a tube furnace. Then, at N 2 At 3 ℃ for min under atmosphere -1 And (3) heating the tubular furnace from room temperature to 350 ℃ and preserving heat for 2 hours to obtain the cobalt-iron bimetallic phosphide nanospheres.
Example 5
In this example, a metal-organic framework-derived cobalt-iron bimetallic phosphide nanosphere was prepared according to the method shown in fig. 1, and the steps were as follows:
step 1, preparing a cobalt-iron bimetallic organic framework precursor: 300mg of polyvinylpyrrolidone are dissolved in 48mL of N, N-dimethylformamide and 28.8mL of ethylene glycol. After magnetic stirring for 30min, PVP was completely dispersed in the mixed solution. 72mg of 1,3, 5-benzenetricarboxylic acid, 36mg of cobalt acetylacetonate and 147mg of iron acetylacetonate were then added, and stirred for 20 minutes to form a uniform dispersion. The solution was transferred to a teflon-lined stainless steel autoclave, reacted at 200 ℃ for 3 hours, after the reaction was completed, the autoclave temperature was lowered to room temperature, centrifuged at 8000rpm in a centrifuge for 10 minutes, and washed with deionized water and ethanol, respectively, several times. Collecting the product, and drying at 60 ℃ overnight to obtain the cobalt-iron bimetallic-based organic framework nanospheres;
step 2, preparing cobalt-iron bimetallic phosphide nanospheres: and respectively placing the obtained cobalt-iron bimetallic organic framework precursor and sodium hypophosphite into a porcelain boat, and placing the porcelain boat at the downstream and upstream of a quartz tube in a tube furnace. Then, at N 2 At 3 ℃ for min under atmosphere -1 Is heated from room temperature to 350 ℃ andand (5) preserving heat for 2 hours to obtain the cobalt-iron bimetallic phosphide nanospheres.
The microstructure of the cobalt-iron bimetallic phosphide nanospheres prepared in the embodiment is shown in figures 2-4, and the cobalt-iron bimetallic phosphide nanospheres are used as working electrodes, silver/silver chloride (alkaline solution) or saturated calomel (acidic solution) are used as reference electrodes, carbon rods are used as auxiliary electrodes, and 1mol L of cobalt-iron bimetallic phosphide nanospheres are used as reference electrodes -1 Potassium hydroxide solution of (C) and 0.5mol L -1 As electrolyte, to form a three-electrode system. Constant current charge and discharge tests were performed at the CHI660E electrochemical workstation in alkaline and acidic solutions at potential ranges of-1.5-1V (vs. silver/silver chloride) and-1-0.8V, respectively, with the following results: at 10mA cm -2 The performance of hydrogen evolution catalysis can reach over-potential of 138 mV and 193mV in acid solution and alkaline solution respectively, the performance of oxygen evolution can reach over-potential of 293mV in alkaline solution, and the current density is 10mA cm in 1M KOH solution -2 The voltage of the fully hydrolyzed water can reach 1.62V (fig. 5 a) and has good cycling stability (fig. 5 b).
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (5)
1. The preparation method of the cobalt-iron bimetallic phosphide nanospheres derived from the metal organic framework is characterized by comprising the following steps of:
(1) Dissolving polyvinylpyrrolidone in a mixed solution of N, N-dimethylformamide and ethylene glycol, uniformly mixing, adding 1,3, 5-benzene tricarboxylic acid, cobalt acetylacetonate and ferric acetylacetonate, transferring the obtained mixed solution into a high-pressure reaction kettle for hydrothermal reaction, cooling the temperature in the kettle to room temperature after the reaction is finished, centrifuging a reaction product, washing the reaction product with deionized water and ethanol respectively, collecting the product, and drying to obtain the cobalt-iron bimetallic-based organic frame nanospheres;
in the mixed solution, the concentration of the cobalt acetylacetonate is 1.82 multiplied by 10 -3 –5.47×10 -3 mol L -1 Iron acetylacetonate concentration was 1.99X10 -3 –5.42×10 -3 mol L -1 The concentration of polyvinylpyrrolidone was 3.56X10 -2 mol L -1 The concentration of 1,3, 5-benzenetricarboxylic acid is 4.46×10 -3 mol L -1 ；
The hydrothermal reaction temperature is 160-200 ℃ and the hydrothermal time is 3h; the drying temperature is 50-60 ℃ and the drying time is 4-6h;
(2) The cobalt-iron bimetallic-based organic framework nanospheres and sodium hypophosphite obtained in the step (1) are respectively put into a porcelain boat, are put at the downstream and upstream of a quartz tube in a tube furnace, and are put at N 2 Heating under atmosphere, heating to the phosphating reaction temperature, and then preserving heat for low-temperature phosphating to obtain cobalt-iron bimetallic phosphide nanospheres;
the sodium hypophosphite is sodium hypophosphite monohydrate with the purity of 99%; the purity of the nitrogen is 99%;
the phosphating reaction temperature is 350 ℃, and the temperature rising rate is 3 ℃ for min -1 The heat preservation time is 2h.
2. The method for preparing the cobalt-iron bimetallic phosphide nanospheres derived from the metal-organic framework according to claim 1, wherein in the step (1), the mass fraction of ethylene glycol is 99.7%, and the solvent addition amount is 28.8mL; the mass fraction of N, N-dimethylformamide was 99.5%, and the solvent addition amount was 48mL.
3. A metal-organic framework-derived cobalt-iron bimetallic phosphide nanosphere prepared by the method for preparing a metal-organic framework-derived cobalt-iron bimetallic phosphide nanosphere according to claim 1 or 2.
4. A catalytic electrode material comprising the metal-organic framework-derived cobalt-iron bimetallic phosphide nanospheres of claim 3.
5. Use of the metal-organic framework-derived cobalt-iron bimetallic phosphide nanospheres of claim 3 or the catalytic electrode material of claim 4 in catalytic hydrogen evolution and oxygen evolution reactions in the process of producing hydrogen by electrolysis of water.
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