CN116065265A - Cobalt-molybdenum co-doped porous nanowire and preparation method and application thereof - Google Patents
Cobalt-molybdenum co-doped porous nanowire and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of transition metal catalysts, and provides a cobalt-molybdenum co-doped porous nanowire, a preparation method and application thereof. The method comprises the following steps: mixing polystyrene, molybdenum acetylacetonate, zinc chloride and N, N-dimethylamide, and carrying out electrostatic spinning to obtain a zinc and molybdenum co-doped fiber film; acidifying the zinc and molybdenum co-doped fiber film to obtain a sulfonated fiber film; mixing the sulfonated fiber film, an ethanol solution of pyrrole, a cobalt nitrate solution and ammonium thiosulfate, and carrying out polymerization reaction to obtain a polypyrrole-coated polystyrene nanowire co-doped with zinc, cobalt and molybdenum; and finally carbonizing the mixture to obtain the cobalt-molybdenum co-doped porous nanowire. The invention has reasonable design of each working procedure and lower cost of raw materials, and is suitable for mass production. The cobalt-molybdenum co-doped porous nanowire prepared by the preparation method has excellent hydrogen evolution performance, and the hydrogen evolution overpotential reaches 85mV in a 1.0mol/L potassium hydroxide solution.
Description
Technical Field
The invention relates to the technical field of transition metal catalysts, in particular to a cobalt-molybdenum co-doped porous nanowire, a preparation method and application thereof.
Background
With the development of economy and society, people have an increasing demand for energy, however, nonrenewable fossil fuels are increasingly exhausted, and environmental pollution caused by fossil fuels is also increasingly serious. Renewable, clean and environment-friendly novel hydrogen energy with high energy utilization rate gradually goes into the production and life of people. Among them, the hydrogen production by water electrolysis is a new trend of next generation energy production due to low energy consumption, high hydrogen purity and easy large-scale application. At present, the hydrogen production electrode material for water electrolysis with optimal performance is platinum or platinum-based nano material, but the reserves are limited, the price is high, and the industrial production of the technology is greatly limited. In addition, the transition metal catalyst developed at the present stage has the defects of poor stability, low hydrogen evolution performance, low catalyst active area, high catalyst load and the like. Therefore, the development of a transition metal catalyst with low price, high activity, excellent stability and low loading has very important significance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a cobalt-molybdenum co-doped porous nanowire, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of cobalt-molybdenum co-doped porous nanowire, which comprises the following steps:
(1) Mixing polystyrene, molybdenum acetylacetonate, zinc chloride and N, N-dimethylamide, and carrying out electrostatic spinning to obtain a zinc and molybdenum co-doped fiber film;
(2) Acidifying the zinc and molybdenum co-doped fiber film to obtain a sulfonated fiber film;
(3) Mixing the sulfonated fiber film, an ethanol solution of pyrrole, a cobalt nitrate solution and ammonium thiosulfate, and carrying out polymerization reaction to obtain a polypyrrole-coated polystyrene nanowire co-doped with zinc, cobalt and molybdenum;
(4) Carbonizing the polypyrrole coated polystyrene nanowire co-doped with zinc, cobalt and molybdenum to obtain the cobalt-molybdenum co-doped porous nanowire.
Preferably, the mass-volume ratio of the polystyrene, the molybdenum acetylacetonate, the zinc chloride and the N, N-dimethylamide in the step (1) is 1.0-1.2 g:0.05 to 0.25g:0.1 to 0.3g: 8-12 mL.
Preferably, the voltage of the electrostatic spinning in the step (1) is 12-20 kV, the spinning distance is 10-20 cm, and the rotating speed of the roller is 350-450 r/min.
Preferably, the mass fraction of the acidified sulfuric acid solution in the step (2) is 97-99%, and the mass volume ratio of the zinc and molybdenum co-doped fiber film to the sulfuric acid solution is 1g: 95-105 mL;
the acidification temperature is 20-30 ℃, and the acidification time is 2.5-3.5 h.
Preferably, the mass concentration of the ethanol solution of the pyrrole in the step (3) is 0.4-0.6 g/L, and the concentration of the cobalt nitrate solution is 0.1-0.3 mmol/L.
Preferably, the volume mass ratio of the ethanol solution of pyrrole, the cobalt nitrate solution of the step (3) and the polystyrene of the step (1) is 180-220 mL: 40-60 mL:1.0 to 1.2g, wherein the molar ratio of the ammonium thiosulfate to the pyrrole is 0.8 to 1.2:0.8 to 1.2.
Preferably, the polymerization reaction in the step (3) is carried out at a temperature of 3 to 7 ℃ for 22 to 26 hours.
Preferably, the heating rate of the carbonization in the step (4) is 2-4 ℃/min, the target temperature is 850-950 ℃, and the heat preservation time after reaching the target temperature is 1.5-2.5 h.
The invention also provides the cobalt-molybdenum co-doped porous nanowire obtained by the preparation method.
The invention also provides application of the cobalt-molybdenum co-doped porous nanowire in hydrogen production by water electrolysis.
The beneficial effects of the invention are as follows:
the invention provides a preparation method of cobalt-molybdenum co-doped porous nanowire, which comprises the following steps: mixing polystyrene, molybdenum acetylacetonate, zinc chloride and N, N-dimethylamide, and carrying out electrostatic spinning to obtain a zinc and molybdenum co-doped fiber film; acidifying the zinc and molybdenum co-doped fiber film to obtain a sulfonated fiber film; mixing the sulfonated fiber film, an ethanol solution of pyrrole, a cobalt nitrate solution and ammonium thiosulfate, and carrying out polymerization reaction to obtain a polypyrrole-coated polystyrene nanowire co-doped with zinc, cobalt and molybdenum; carbonizing the polypyrrole coated polystyrene nanowire co-doped with zinc, cobalt and molybdenum to obtain the cobalt-molybdenum co-doped porous nanowire. The invention has reasonable design of each working procedure, lower cost of raw materials and easy regulation and control of the appearance of the finished product, and is suitable for large-scale production. The cobalt-molybdenum co-doped porous nanowire prepared by the preparation method has excellent hydrogen evolution performance, and the hydrogen evolution overpotential reaches 85mV in a 1.0mol/L potassium hydroxide solution.
Detailed Description
The invention provides a preparation method of cobalt-molybdenum co-doped porous nanowire, which comprises the following steps:
(1) Mixing polystyrene, molybdenum acetylacetonate, zinc chloride and N, N-dimethylamide, and carrying out electrostatic spinning to obtain a zinc and molybdenum co-doped fiber film;
(2) Acidifying the zinc and molybdenum co-doped fiber film to obtain a sulfonated fiber film;
(3) Mixing the sulfonated fiber film, an ethanol solution of pyrrole, a cobalt nitrate solution and ammonium thiosulfate, and carrying out polymerization reaction to obtain a polypyrrole-coated polystyrene nanowire co-doped with zinc, cobalt and molybdenum;
(4) Carbonizing the polypyrrole coated polystyrene nanowire co-doped with zinc, cobalt and molybdenum to obtain the cobalt-molybdenum co-doped porous nanowire.
In the invention, the mass-volume ratio of the polystyrene, the molybdenum acetylacetonate, the zinc chloride and the N, N-dimethylamide in the step (1) is preferably 1.0-1.2 g:0.05 to 0.25g:0.1 to 0.3g:8 to 12mL, more preferably 1.05 to 1.15g:0.10 to 0.20g:0.15 to 0.25g:9 to 11mL, more preferably 1.07 to 1.13g:0.12 to 0.18g: 0.17-0.23 g: 9.5-10.5 mL.
In the present invention, the temperature of the mixing in the step (1) is preferably 20 to 30 ℃, more preferably 22 to 28 ℃, still more preferably 24 to 26 ℃; the rotation speed is preferably 200 to 400r/min, more preferably 250 to 350r/min, and still more preferably 270 to 330r/min; the time is preferably 4 to 6 hours, more preferably 4.5 to 5.5 hours, and still more preferably 4.7 to 5.3 hours.
In the present invention, the voltage of the electrospinning in the step (1) is preferably 12 to 20kV, more preferably 14 to 18kV, and even more preferably 15 to 17kV; the spinning distance is preferably 10 to 20cm, more preferably 12 to 18cm, still more preferably 14 to 16cm; the rotation speed of the roller is preferably 350 to 450r/min, more preferably 370 to 430r/min, and still more preferably 390 to 410r/min.
In the invention, the acidification in the step (2) is to fully immerse the zinc and molybdenum co-doped fiber film in sulfuric acid solution, and the sulfonated fiber film is obtained after a certain time.
In the present invention, the mass fraction of the acidified sulfuric acid solution in step (2) is preferably 97 to 99%, more preferably 97.5 to 98.5%, still more preferably 97.7 to 98.3%; the mass volume ratio of the zinc and molybdenum co-doped fiber film to the sulfuric acid solution is preferably 1g:95 to 105mL, more preferably 1g: 97-103 mL, more preferably 1g: 99-101 mL; the acidification temperature is preferably 20-30 ℃, more preferably 22-28 ℃, and even more preferably 24-26 ℃; the acidification time is preferably 2.5 to 3.5 hours, more preferably 2.6 to 3.4 hours, and even more preferably 2.7 to 3.3 hours.
In the invention, after the acidification of the step (2) is finished, the obtained sulfonated fiber film is preferably washed, and then the subsequent process is carried out; the washing is alternately performed with deionized water and absolute ethyl alcohol, and the number of the alternations is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more.
In the present invention, the mass concentration of the ethanol solution of pyrrole in the step (3) is preferably 0.4 to 0.6g/L, more preferably 0.45 to 0.55g/L, still more preferably 0.47 to 0.53g/L; the concentration of the cobalt nitrate solution is preferably 0.1 to 0.3mmol/L, more preferably 0.15 to 0.25mmol/L, and still more preferably 0.17 to 0.23mmol/L.
In the invention, the volume mass ratio of the ethanol solution of pyrrole in the step (3), the cobalt nitrate solution and the polystyrene in the step (1) is preferably 180-220 mL: 40-60 mL:1.0 to 1.2g, more preferably 190 to 210mL: 45-55 mL:1.05 to 1.15g, more preferably 195 to 205mL: 47-53 mL:1.07 to 1.13g; the molar ratio of the ammonium thiosulfate to the pyrrole is preferably 0.8-1.2: 0.8 to 1.2, more preferably 0.85 to 1.15:0.85 to 1.15, more preferably 0.9 to 1.1:0.9 to 1.1.
In the present invention, the mixing of step (3) specifically comprises the steps of:
(a) Soaking the sulfonated fiber film in an pyrrole ethanol solution to obtain a first mixed solution;
(b) Adding the cobalt nitrate solution into the first mixed solution, and standing to obtain a second mixed solution;
(c) Ammonium thiosulfate is added to the second mixed solution to carry out subsequent polymerization.
In the present invention, the soaking temperature in the step (a) is preferably 3 to 7 ℃, more preferably 4 to 6 ℃, and even more preferably 4.5 to 5.5 ℃; the time is preferably 22 to 26 hours, more preferably 23 to 25 hours, and still more preferably 23.5 to 24.5 hours.
In the present invention, the temperature of the standing in the step (b) is preferably 3 to 7 ℃, more preferably 4 to 6 ℃, still more preferably 4.5 to 5.5 ℃; the time is preferably 22 to 26 hours, more preferably 23 to 25 hours, and still more preferably 23.5 to 24.5 hours.
In the present invention, the temperature of the polymerization reaction in the step (3) is preferably 3 to 7 ℃, more preferably 4 to 6 ℃, still more preferably 4.5 to 5.5 ℃; the time is preferably 22 to 26 hours, more preferably 23 to 25 hours, and still more preferably 23.5 to 24.5 hours.
In the invention, after the polymerization reaction in the step (3) is finished, the obtained polypyrrole coated polystyrene nanowire co-doped with zinc, cobalt and molybdenum is subjected to suction filtration by using ethanol, and is soaked by using N, N-dimethyl amide (DMF) after the completion of the suction filtration, and then is carbonized.
In the invention, a new DMF solution needs to be replaced in the soaking process, and the interval time of replacement is preferably 7-9 h, more preferably 7.5-8.5 h, and even more preferably 7.7-8.3 h; the mass ratio of the volume of DMF solution used in a single time to the polystyrene of step (1) is preferably 130-170 mL:1.0 to 1.2g, more preferably 140 to 160mL:1.05 to 1.15g, more preferably 145 to 155mL:1.07 to 1.13g; the total time of the soaking is preferably 22 to 26 hours, more preferably 23 to 25 hours, and still more preferably 23.5 to 24.5 hours.
In the invention, the DMF is used for soaking to dissolve part of polystyrene, so that the polystyrene can be decomposed to generate multiple holes at high temperature, and zinc ions are melted and volatilized at high temperature to obtain a micropore structure.
In the present invention, the heating rate of the carbonization in the step (4) is preferably 2 to 4 ℃/min, more preferably 2.5 to 3.5 ℃/min, and even more preferably 2.7 to 3.3 ℃/min; the target temperature is preferably 850 to 950 ℃, more preferably 860 to 940 ℃, still more preferably 870 to 930 ℃; the holding time after reaching the target temperature is preferably 1.5 to 2.5 hours, more preferably 1.7 to 2.3 hours, and still more preferably 1.9 to 2.1 hours.
The invention also provides the cobalt-molybdenum co-doped porous nanowire obtained by the preparation method.
The invention also provides application of the cobalt-molybdenum co-doped porous nanowire in hydrogen production by water electrolysis.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 1.12g of polystyrene, 0.15g of molybdenum acetylacetonate and 0.2g of zinc chloride into 10mLN, N-dimethylamide, stirring at 25 ℃ for 5 hours at a rotating speed of 300r/min, and then carrying out electrostatic spinning on the obtained mixed solution, wherein the set voltage is 15kV, the spinning distance is 15cm, and the rotating speed of a roller is 400r/min, so as to prepare a zinc-molybdenum co-doped fiber film; immersing the zinc-molybdenum co-doped fiber film into a sulfuric acid solution with the mass fraction of 98% (the mass volume ratio of the zinc-molybdenum co-doped fiber film to the sulfuric acid solution is 1g:100 mL), and acidifying for 3 hours at 25 ℃ to obtain a sulfonated fiber film; then washing the obtained sulfonated fiber film alternately by using deionized water and absolute ethyl alcohol (the alternating times are 3 times); immersing the fiber film into 200mL of pyrrole ethanol solution with the mass concentration of 0.5g/L after washing is finished, immersing for 24 hours at the temperature of 5 ℃, then adding 50mL of cobalt nitrate solution with the mass concentration of 0.2mmol/L, standing for 24 hours at the temperature of 5 ℃, finally adding ammonium thiosulfate (the molar ratio of the ammonium thiosulfate to pyrrole is 1:1) into the mixed solution, and carrying out polymerization reaction for 24 hours at the temperature of 5 ℃ to obtain the zinc, cobalt and molybdenum co-doped polypyrrole coated polystyrene nanowire; carrying out suction filtration on the obtained nanowire by using ethanol, and then soaking the nanowire by using DMF (in the soaking process, a new DMF solution needs to be replaced, the replacement interval time is 8 hours, the volume of single DMF is 150mL, the total soaking time is 24 hours), so as to obtain a small amount of polystyrene nanowire coated by polypyrrole co-doped with zinc, cobalt and molybdenum; finally, heating the porous nano-wire to 900 ℃ at a heating rate of 3 ℃/min for carbonization, and preserving heat for 2 hours at 900 ℃ to obtain the cobalt-molybdenum co-doped porous nano-wire.
The cobalt-molybdenum co-doped porous nanowire prepared in the embodiment is subjected to hydrogen evolution performance test, so that the hydrogen evolution overpotential of the cobalt-molybdenum co-doped porous nanowire in a 1.0mol/L potassium hydroxide solution is 85mV, and the cobalt-molybdenum co-doped porous nanowire has excellent hydrogen evolution performance.
Example 2
Adding 1.16g of polystyrene, 0.17g of molybdenum acetylacetonate and 0.22g of zinc chloride into 11mLN, N-dimethylamide, stirring at a speed of 350r/min for 5.3 hours at 26 ℃, and then carrying out electrostatic spinning on the obtained mixed solution, wherein the set voltage is 17kV, the spinning distance is 16cm, and the rotating speed of a roller is 420r/min, so as to prepare a zinc-molybdenum co-doped fiber film; immersing the zinc-molybdenum co-doped fiber film into a sulfuric acid solution with the mass fraction of 98.5% (the mass volume ratio of the zinc-molybdenum co-doped fiber film to the sulfuric acid solution is 1g:102 mL), and acidifying for 2.6h at 26 ℃ to obtain a sulfonated fiber film; then washing the obtained sulfonated fiber film alternately by using deionized water and absolute ethyl alcohol (the alternating times are 4 times); immersing the fiber film into 205mL of pyrrole ethanol solution with the mass concentration of 0.55g/L after the washing is finished, immersing for 23h at the temperature of 4 ℃, then adding 52mL of cobalt nitrate solution with the mass concentration of 0.22mmol/L, standing for 23h at the temperature of 4 ℃, finally adding ammonium thiosulfate (the molar ratio of the ammonium thiosulfate to pyrrole is 0.95:1) into the mixed solution, and carrying out polymerization reaction for 23h at the temperature of 4 ℃ to obtain the polypyrrole-coated polystyrene nanowire co-doped with zinc, cobalt and molybdenum; carrying out suction filtration on the obtained nanowire by using ethanol, and then soaking the nanowire by using DMF (in the soaking process, a new DMF solution needs to be replaced, the replacement interval time is 8.5h, the volume of single DMF is 155mL, the total soaking time is 25.5 h), so as to obtain a small amount of polystyrene nanowire coated by polypyrrole co-doped with zinc, cobalt and molybdenum; finally, the cobalt-molybdenum co-doped porous nanowire is carbonized by heating to 920 ℃ at a heating rate of 4 ℃/min, and preserving heat for 2.1h at 920 ℃ to obtain the cobalt-molybdenum co-doped porous nanowire.
The cobalt-molybdenum co-doped porous nanowire prepared in the embodiment is subjected to hydrogen evolution performance test, and the hydrogen evolution overpotential of the cobalt-molybdenum co-doped porous nanowire in a 1.0mol/L potassium hydroxide solution is 81mV.
Example 3
Adding 1.06g of polystyrene, 0.08g of molybdenum acetylacetonate and 0.17g of zinc chloride into 9mLN, N-dimethylamide, stirring at a speed of 250r/min for 4.5 hours at 23 ℃, and then carrying out electrostatic spinning on the obtained mixed solution, wherein the set voltage is 14kV, the spinning distance is 12cm, and the rotating speed of a roller is 350r/min to prepare a zinc-molybdenum co-doped fiber film; immersing the zinc-molybdenum co-doped fiber film into a sulfuric acid solution with the mass fraction of 97% (the mass volume ratio of the zinc-molybdenum co-doped fiber film to the sulfuric acid solution is 1g:97 mL), and acidifying for 3.3h at 23 ℃ to obtain a sulfonated fiber film; then washing the obtained sulfonated fiber film alternately by using deionized water and absolute ethyl alcohol (the alternating times are 3 times); immersing the fiber film into 195mL of pyrrole ethanol solution with the mass concentration of 0.46g/L after the washing is finished, immersing for 25 hours at the temperature of 6 ℃, then adding 45mL of cobalt nitrate solution with the concentration of 0.18mmol/L, standing for 23 hours at the temperature of 6 ℃, finally adding ammonium thiosulfate (the molar ratio of the ammonium thiosulfate to pyrrole is 1.1:1) into the mixed solution, and carrying out polymerization reaction for 24 hours at the temperature of 6 ℃ to obtain the polypyrrole-coated polystyrene nanowire co-doped with zinc, cobalt and molybdenum; carrying out suction filtration on the obtained nanowire by using ethanol, and then soaking the nanowire by using DMF (the replacement of a new DMF solution is needed in the soaking process, the replacement interval time is 7.5h, the volume of single DMF is 150mL, the total soaking time is 22.5 h), so as to obtain a small amount of polystyrene nanowire coated by polypyrrole co-doped with zinc, cobalt and molybdenum; and finally, heating the porous nano-wire to 880 ℃ at a heating rate of 2.5 ℃/min for carbonization, and preserving heat for 1.8 hours at 880 ℃ to obtain the cobalt-molybdenum co-doped porous nano-wire.
The cobalt-molybdenum co-doped porous nanowire prepared in the embodiment is subjected to hydrogen evolution performance test, and the hydrogen evolution overpotential of the cobalt-molybdenum co-doped porous nanowire in a 1.0mol/L potassium hydroxide solution is 83mV.
The embodiment shows that the preparation method provided by the invention has reasonable design of each process and lower cost of raw materials, and is suitable for large-scale production. The cobalt-molybdenum co-doped porous nanowire prepared by the preparation method has excellent hydrogen evolution performance, and the hydrogen evolution overpotential reaches 85mV in a 1.0mol/L potassium hydroxide solution.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the cobalt-molybdenum co-doped porous nanowire is characterized by comprising the following steps of:
(1) Mixing polystyrene, molybdenum acetylacetonate, zinc chloride and N, N-dimethylamide, and carrying out electrostatic spinning to obtain a zinc and molybdenum co-doped fiber film;
(2) Acidifying the zinc and molybdenum co-doped fiber film to obtain a sulfonated fiber film;
(3) Mixing the sulfonated fiber film, an ethanol solution of pyrrole, a cobalt nitrate solution and ammonium thiosulfate, and carrying out polymerization reaction to obtain a polypyrrole-coated polystyrene nanowire co-doped with zinc, cobalt and molybdenum;
(4) Carbonizing the polypyrrole coated polystyrene nanowire co-doped with zinc, cobalt and molybdenum to obtain the cobalt-molybdenum co-doped porous nanowire.
2. The preparation method according to claim 1, wherein the mass-to-volume ratio of the polystyrene, the molybdenum acetylacetonate, the zinc chloride and the N, N-dimethylamide in the step (1) is 1.0-1.2 g:0.05 to 0.25g:0.1 to 0.3g: 8-12 mL.
3. The method according to claim 2, wherein the voltage of the electrostatic spinning in the step (1) is 12-20 kV, the spinning distance is 10-20 cm, and the rotating speed of the roller is 350-450 r/min.
4. A method according to any one of claims 1 to 3, wherein the mass fraction of the acidified sulfuric acid solution in step (2) is 97 to 99%, and the mass-to-volume ratio of the zinc-molybdenum co-doped fiber film to the sulfuric acid solution is 1g: 95-105 mL;
the acidification temperature is 20-30 ℃, and the acidification time is 2.5-3.5 h.
5. The process according to claim 4, wherein the alcoholic solution of pyrrole in step (3) has a mass concentration of 0.4 to 0.6g/L and the cobalt nitrate solution has a concentration of 0.1 to 0.3mmol/L.
6. The preparation method of claim 5, wherein the volume mass ratio of the ethanol solution of pyrrole, the cobalt nitrate solution of step (3) to the polystyrene of step (1) is 180-220 mL: 40-60 mL:1.0 to 1.2g, wherein the molar ratio of the ammonium thiosulfate to the pyrrole is 0.8 to 1.2:0.8 to 1.2.
7. The process according to claim 5 or 6, wherein the polymerization reaction in step (3) is carried out at a temperature of 3 to 7℃for a period of 22 to 26 hours.
8. The method according to claim 7, wherein the carbonization in step (4) has a heating rate of 2 to 4 ℃/min, a target temperature of 850 to 950 ℃, and a holding time of 1.5 to 2.5 hours after reaching the target temperature.
9. Cobalt-molybdenum co-doped porous nanowire obtained by the preparation method according to any one of claims 1 to 8.
10. Use of the cobalt-molybdenum co-doped porous nanowire of claim 9 in hydrogen production by water electrolysis.
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