CN111841602A - CuCoMn multi-level structure electrolytic water catalytic material and preparation method thereof - Google Patents
CuCoMn multi-level structure electrolytic water catalytic material and preparation method thereof Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
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- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
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- 239000001301 oxygen Substances 0.000 claims abstract description 30
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- 238000000034 method Methods 0.000 claims abstract description 23
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- 238000006555 catalytic reaction Methods 0.000 claims description 6
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 16
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- 239000010949 copper Substances 0.000 description 14
- 239000011572 manganese Substances 0.000 description 14
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
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- 230000000694 effects Effects 0.000 description 8
- 229940071125 manganese acetate Drugs 0.000 description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
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- 239000010431 corundum Substances 0.000 description 5
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- 229910000510 noble metal Inorganic materials 0.000 description 5
- 229910016507 CuCo Inorganic materials 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 4
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- 229910002521 CoMn Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
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- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
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- 230000004888 barrier function Effects 0.000 description 1
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- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- -1 manganese salt Chemical class 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention discloses a CuCoMn multi-stage structure electrolytic water catalytic material and a preparation method thereof, belonging to the field of composite material preparation. The multi-stage structure of the electrolyzed water catalytic material comprises one-dimensional carbon nanofibers, in-situ grown carbon nanotubes and metal nanoparticles, the mass transfer capacity and the electron mobility of the catalyst in the catalytic process can be greatly improved by utilizing the multi-stage structure, the diffusion of electrolyte and the desorption of gas are facilitated, the electrolyzed water catalytic material has very excellent catalytic hydrogen evolution and oxygen evolution performances under an acidic condition, the hydrogen evolution rate is equivalent to that of commercial Pt/C, the oxygen evolution rate is far superior to that of the commercial Pt/C, and the electrolyzed water catalytic material has a good application prospect.
Description
Technical Field
The invention particularly relates to a CuCoMn multi-stage structure electrolytic water catalytic material and a preparation method thereof, belonging to the field of composite material preparation.
Background
In recent years, as the population continues to increase to cause rapid consumption of energy and the problem of environmental pollution due to the use of fossil fuels is becoming more serious, there is an urgent need to develop more environmentally friendly energy sources. Research has shown that hydrogen combustion per unit mass produces energy up to 2.5 times that of gasoline and water is the only product of hydrogen combustion, and hydrogen has proven to be an ideal energy carrier.
Electrocatalytic hydrolysis technology is of great interest because of its purity of product, high conversion efficiency, simple equipment, etc. The theoretical voltage of water decomposition at room temperature is 1.23V, but the catalytic reaction is easily influenced by temperature, electrolyte, electrode materials and the like, the actually required voltage is often higher than 1.23V, and the existence of overvoltage can cause excessive energy consumption. The high-efficiency catalyst can reduce the reaction energy barrier and accelerate the electrocatalytic hydrolysis process. At present, oxides of Pt, Ir and Ru are the most efficient electrocatalysts for hydrogen evolution reaction and oxygen evolution reaction respectively, however, the noble metal catalysts are high in price and are scarce in content, which greatly limits the commercial application of the noble metal catalysts. In addition, there is a great market need to develop efficient bifunctional catalysts for catalyzing hydrogen and oxygen evolution reactions in the same electrolyte in order to reduce the complexity and cost of the overall electrolytic water system.
Disclosure of Invention
In order to solve the problems, the invention provides a multi-stage structure electrolytic water catalyst based on non-noble metal element CuCoMn and a preparation method thereof. The method has low cost, is simple and easy to obtain, and the obtained CuCoMn/NCNTs electrolyzed water catalytic material has excellent hydrogen evolution activity and oxygen evolution activity under an acidic condition and has good stability.
The chemical composition, morphology and other factors of the catalyst have a crucial influence on the catalytic performance. The catalytic activity of the catalyst can be improved by adjusting the chemical composition of the catalyst and designing a special nano structure. On the one hand, an effective method for adjusting the chemical composition of an electrocatalyst is to dope foreign atoms into the original material, and the synergistic effect between different atoms is beneficial to improving the catalytic activity of the catalyst. On the other hand, optimizing the nanostructure of the electrocatalyst may increase the active specific surface area of the catalyst. The multistage structure can greatly improve the mass transfer capacity and the electron mobility of the catalyst in the catalytic process, thereby improving the catalytic activity of the catalyst.
A first object of the present invention is to provide a method for preparing a multi-stage structured electrolytic water catalytic material based on the non-noble metal element CuCoMn, said method comprising the steps of:
(1) dispersing copper salt, cobalt salt, manganese salt and a nanofiber precursor in an organic solvent to prepare a spinning solution; then preparing a nanofiber membrane through electrostatic spinning;
(2) and (2) calcining and pre-oxidizing the nanofiber membrane obtained in the step (1), and then adding a nitrogen source to calcine and carbonize to obtain the CuCoMn multi-stage structure electrolytic water catalytic material CuCoMn/NCNTs.
In an embodiment of the present invention, the nanofiber precursor in step (1) is one or more of polyacrylonitrile, polyvinylpyrrolidone, and polyvinyl alcohol.
In one embodiment of the invention, the mass fraction of the nanofiber precursor in the spinning solution in the step (1) is 8-20 wt%.
In one embodiment of the present invention, the copper salt in step (1) is one or more of copper chloride and copper acetylacetonate.
In one embodiment of the present invention, the cobalt salt in step (1) is one or more of cobalt chloride, cobalt acetylacetonate and cobalt acetate.
In one embodiment of the present invention, the manganese salt in step (1) is one or more of manganese acetate and manganese acetylacetonate.
In one embodiment of the present invention, the mass ratio of the copper salt, the cobalt salt, and the manganese salt in the spinning solution in step (1) is 1: (0.5-2): (0.5-2). The following specific options are 1:1: 1. 1: 2: 1. 1:1: 2. 1: 0.5: 0.5, preferably in a ratio of 1:1: 1.
In one embodiment of the present invention, the total mass concentration of the metal salts (copper salt, cobalt salt, and manganese salt) in the spinning solution in step (1) is 1.5% to 4.5%.
In one embodiment of the present invention, the parameters of the electrostatic spinning in step (1) are: the spinning voltage is 15-25 kV, the distance from the receiving device to the spinning needle is 10-20 cm, and the solution flow rate is 0.01-0.10 mL/min.
In one embodiment of the present invention, the solvent in step (1) is one or more selected from N, N-dimethylformamide, dimethyl sulfoxide, ethanol, water, and acetone.
In one embodiment of the invention, the calcination pre-oxidation in the step (2) is performed by heating to 180-300 ℃ at a heating rate of 2-20 ℃/min, and performing heat preservation calcination for 2-4 h.
In one embodiment of the invention, the heating rate is preferably one or more of 2 ℃/min, 5 ℃/min, 10 ℃/min and 20 ℃/min.
In one embodiment of the present invention, the temperature of the maintained calcination temperature for the calcination and pre-oxidation in the step (2) is preferably 280 ℃.
In one embodiment of the present invention, the calcination pre-oxidation in step (2) is performed in an air atmosphere.
In an embodiment of the present invention, the calcination and carbonization in step (2) is calcination at 800-1000 ℃ for 2-4 h.
In one embodiment of the present invention, the temperature of the calcination carbonization is preferably 1000 ℃.
In one embodiment of the present invention, the nitrogen source of step (2) comprises: one or more of ammonia gas, melamine, pyridine and pyrrole.
In one embodiment of the present invention, the mass of the nitrogen source in the step (2) is 20 to 50 times the mass of the metal in the nanofiber membrane used in the calcination.
In an embodiment of the present invention, the method specifically includes the following steps:
(1) preparing a nanofiber membrane containing copper, cobalt and manganese: adding copper salt, cobalt salt and manganese salt into N, N-dimethylformamide solution of polyacrylonitrile, uniformly stirring, and spinning the solution by adopting an electrostatic spinning method to obtain a CuCoMn/PAN nanofiber membrane;
(2) preparing the multi-level structure electro-catalysis material consisting of the carbon nano-fiber, the nitrogen-doped carbon nano-tube and the metal nano-particles: calcining the CuCoMn/PAN nanofiber membrane prepared in the step (1), heating to 180-300 ℃ at a heating rate of 2-20 ℃/min, and preserving heat for 2-4 hours in an air atmosphere to perform pre-oxidation; after the heat preservation is finished, heating to 800-1000 ℃ at the speed of 2-20 ℃/min in the inert gas atmosphere, adding a nitrogen source after heating to a specified temperature, and preserving the heat for 2-4 hours; and after the heat preservation is finished, naturally cooling to room temperature in an inert gas atmosphere to obtain the CuCoMn/NCNTs of the CuCoMn multi-stage structure electrolytic water catalytic material.
In one embodiment of the invention, the calcination in step (2) is to place the nano-fiber in a corundum boat and place the corundum boat in the middle of a tube furnace for calcination.
The second purpose of the invention is to provide a multi-stage structure electrolytic water catalytic material CuCoMn/NCNTs based on non-noble metal CuCoMn by utilizing the preparation method.
In one embodiment of the invention, the CuCoMn element is present in the form of Cu, Co and MnO in the electrolytic water catalytic material2The multiphase structure of (1).
In one embodiment of the invention, the multilevel structure in the multilevel structure electrolytic water catalytic material comprises one-dimensional carbon nanofibers, in-situ grown carbon nanotubes and metal nanoparticles.
The third purpose of the invention is to apply the multi-stage structure electrolytic water catalytic material in the field of electrolytic water catalysis.
The fourth purpose of the invention is to provide a method for catalyzing electrolyzed water to carry out hydrogen evolution and oxygen evolution reactions, which utilizes the multi-stage structure electrolyzed water catalytic material as a catalyst.
The invention has the beneficial effects that:
according to the invention, ammonia gas is used as a nitrogen source, and the electrostatic spinning nano-fiber is calcined by a chemical vapor deposition method to obtain the multi-level structure electro-catalysis material consisting of the one-dimensional carbon nano-fiber, the nitrogen-doped carbon nano-tube and the metal nano-particles, so that the experimental method is simple and has repeatability.
The invention utilizes the technology of combining the electrostatic spinning method and the chemical vapor deposition method to prepare the multi-level structure electrocatalyst, wherein the metal nano particles are used as catalytic active sites, and the nitrogen-doped carbon nano tubes generated in situ not only increase the contact area with the electrolyte, but also enhance the electron transmission rate in the catalytic reaction due to the close contact of the nitrogen-doped carbon nano tubes and the carbon nano fibers, thereby being beneficial to improving the catalytic activity.
Drawings
FIG. 1 is a scanning electron microscope image of the CuCoMn/NCNTs electrocatalytic material obtained in example 1.
FIG. 2 is a transmission electron micrograph of the CuCoMn/NCNTs electrocatalytic material obtained in example 1.
FIG. 3 is an X-ray diffraction pattern of the CuCoMn/NCNTs electrocatalytic material obtained in example 1.
FIG. 4 shows the CuCoMn/NCNTs and commercial 20% Pt/C at 0.5M H obtained in example 12SO4And (3) an electrocatalytic performance test chart in medium-acid electrolyte. (a) Polarization curves for hydrogen evolution and oxygen evolution for CuCoMn/NCNTs and commercial 20% Pt/C electrodes; (b) tafel slope plots for hydrogen evolution and oxygen evolution reactions for CuCoMn/NCNTs and commercial 20% Pt/C electrodes; (c) a CuCoMn/NCNTs electrochemical impedance diagram, wherein the test voltage is open-circuit voltage; (d) the overpotential of the test is 10mV according to the time current response curve of CuCoMn/NCNTs.
FIG. 5 shows that the CuCoMn/NCNTs-1 and CuCoMn/NCNTs-3 obtained in example 2 are at 0.5M H2SO4Polarization curves for hydrogen evolution reaction and oxygen evolution reaction in (1).
FIG. 6 is a scanning electron micrograph of CuCoMn/CNFs obtained in comparative example 1.
FIG. 7 is a graph showing CuCo obtained in comparative example 1The Mn/CNFs electrocatalytic material is 0.5M H2SO4Polarization curves of hydrogen evolution and oxygen evolution reactions in (1).
Detailed Description
For a better understanding of the present invention, the following further illustrates the contents of the invention with reference to examples, but the contents of the invention are not limited to the examples given below.
Example 1:
(1) adding 0.15g of copper chloride, 0.15g of cobalt chloride and 0.15g of manganese acetate into 25g of N, N-dimethylformamide solution of polyacrylonitrile with the mass fraction of 12 wt%, uniformly stirring by magnetic force, spinning the solution by adopting an electrostatic spinning method, controlling the spinning voltage to be 18KV, controlling the distance from a roller of a receiving device to the tip of a spinning needle to be 16cm, and controlling the flow rate of the solution to be 0.2mL/min to obtain the CuCoMn/PAN nanofiber membrane.
(2) 0.2g of the prepared CuCoMn/PAN nanofiber membrane is placed in a corundum boat and is placed in the middle of a tube furnace. Firstly, the temperature is raised to 280 ℃ at the heating rate of 5 ℃/min, and the temperature is preserved for 3 hours in the air atmosphere for pre-oxidation. After the heat preservation is finished, heating to 1000 ℃ at the speed of 5 ℃/min in the argon atmosphere, introducing ammonia gas after the temperature reaches 1000 ℃, and preserving the heat for 3 hours in the mixed atmosphere of the ammonia gas and the argon gas at the temperature of 1000 ℃, wherein the gas flow of the ammonia gas is 5 standard milliliters per minute, and the gas flow of the argon gas is 150 standard milliliters per minute. And after the heat preservation is finished, naturally cooling to room temperature in the inert gas atmosphere to obtain the CuCoMn/NCNTs electrolyzed water catalytic material.
A scanning electron microscope is taken for the prepared CuCoMn/NCNTs electrolytic water catalytic material, FIG. 1 is a scanning electron microscope image of CuCoMn/NCNTs, and as can be seen from FIG. 1, a plurality of slender and bent carbon nanotubes grow on carbon nanofibers, the diameter of the carbon nanotubes is about 100nm, and highlight metal nanoparticles are packaged at the tips of the carbon nanotubes to form a unique multilevel structure.
A transmission electron microscope is taken for the prepared CuCoMn/NCNTs electrolytic water catalytic material, FIG. 2 is a transmission electron microscope image of CuCoMn/NCNTs, and as can be seen from FIG. 2, metal nanoparticles are sealed at the tips of carbon nanotubes, the diameter of the metal nanoparticles is about 40nm, and the outer layer of the metal nanoparticles is coated with a graphite carbon layer.
The resulting CuCoMn/NCNTs electrolytic water catalytic material was subjected to X-ray diffraction, FIG. 3 is an X-ray diffraction pattern of CuCoMn/NCNTs, and it can be seen from FIG. 1 that the peaks of CuCoMn/NCNTs at 26 ℃ correspond to the (002) crystal plane of the graphite peak of C, the peaks at 26 ℃ and 50 ℃ are attributed to the (111) crystal plane and the (200) crystal plane of metallic Cu, the peaks at 44 ℃ and 51 ℃ correspond to the (111) crystal plane and the (200) crystal plane of metallic Co, and the peak at 37.7 ℃ is attributed to MnO2The (011) crystal plane of (c). The XRD result shows that the Mn element exists in the form of metal oxide and the Co element and the Cu element exist in the form of metal in the multilevel structure.
The prepared CuCoMn/NCNTs is cut into a regular rectangle (the corresponding mass is 0.2g) of 2x2 cm, and the CuCoMn/NCNTs can be directly used as a working electrode due to self-supporting property, and a standard three-electrode system is used at 0.5M H2SO4The electrocatalytic hydrogen and oxygen evolution activity was tested in the solution of (a).
FIG. 4 shows CuCoMn/NCNTs and commercial 20% Pt/C at 0.5M H 2SO4The electrocatalytic performance test chart in (1). Among them, FIG. 4(a) shows CuCoMn/NCNTs and a commercial 20% Pt/C electrode at 0.5M H2SO4The polarization curves of hydrogen evolution reaction and oxygen evolution reaction in (1) can be seen from FIG. 4(a), and the current density is 10mA cm-2The overpotentials for the hydrogen evolution reactions for commercial Pt/C and CuCoMn/NCNTs were 31mV and 34mV (vs. RHE), respectively. In addition, the current density was 10mA cm-2Under the conditions that the overpotentials of the oxygen evolution reactions of the commercial Pt/C and the CuCoMn/NCNTs are respectively 180mV and 600mV (vs. RHE), the oxygen evolution performance of the CuCoMn/NCNTs electrocatalytic material is far better than that of the commercial Pt/C.
FIG. 4(b) is a Tafel slope plot for CuCoMn/NCNTs and commercial 20% Pt/C, as can be seen from FIG. 4(b), CuCoMn/NCNTs are at 10mA cm-2The Tafel slope of the nearby oxygen evolution reaction is only 133mV dec-1Much lower than the 290mV dec of commercial Pt/C-1. FIGS. 4(a) and 4(b) show that the acidic oxygen evolution performance of CuCoMn/NCNTs electrocatalytic materials is far superior to commercial Pt/C, and the acidic hydrogen evolution performance is comparable to commercial Pt/C.
FIG. 4(c) is an Electrochemical Impedance Spectroscopy (EIS) graph of CuCoMn/NCNTs tested at an open circuit voltage, and it can be seen from FIG. 4(c) that the charge transfer resistance (Rct) value of CuCoMn/NCNTs is only 5.7 Ω, indicating that CuCoMn/NCNTs has a higher electron transfer rate.
FIG. 4(d) is a time current response curve of CuCoMn/NCNTs and commercial 20% Pt/C at an overpotential of 10mV (vs. RHE), and it can be seen from FIG. 4(d) that the CuCoMn/NCNTs catalytic material still maintains 70% of catalytic activity after 20 hours of reaction, indicating that the CuCoMn/NCNTs catalytic material has good stability.
Example 2 investigation of the Effect of Nitrogen Source dosage on catalytic Material
Step (1) is the same as in example 1;
step (2): 0.2g of the prepared CuCoMn/PAN nanofiber membrane is placed in a corundum boat and is placed in the middle of a tube furnace. Firstly, the temperature is raised to 280 ℃ at the heating rate of 5 ℃/min, and the temperature is preserved for 3 hours in the air atmosphere for pre-oxidation. After the heat preservation is finished, heating to 1000 ℃ at the speed of 5 ℃/min in the argon atmosphere, introducing ammonia gas with the gas flow rate of 1 standard milliliter/minute and 3 standard milliliters/minute respectively after the temperature reaches 1000 ℃, and preserving the heat for 3 hours in the mixed atmosphere of the argon gas and the ammonia gas. And after the heat preservation is finished, naturally cooling to room temperature in an inert gas atmosphere to obtain CuCoMn/NCNTs-1 and CuCoMn/NCNTs-3 electrolytic water catalytic materials.
The acidic hydrogen and oxygen evolution performance of CuCoMn/NCNTs-1 and CuCoMn/NCNTs-3 electrolytic water catalytic materials was tested as in example 1.
FIG. 5 shows that CuCoMn/NCNTs-1 and CuCoMn/NCNTs-3 are at 0.5M H2SO4Polarization curves for hydrogen evolution reaction and oxygen evolution reaction in (1). As can be seen from FIG. 5, the current density was 10mA cm-2Next, the overpotentials for the hydrogen evolution reactions of CuCoMn/NCNTs-1 and CuCoMn/NCNTs-3 were 235mV and 108mV (vs. RHE), respectively. The current density is 10mA cm-2Next, the overpotentials for the oxygen evolution reactions of CuCoMn/NCNTs-1 and CuCoMn/NCNTs-3 were 260mV and 410mV (vs. RHE), respectively. FIG. 5 shows that both CuCoMn/NCNTs-1 and CuCoMn/NCNTs-3 electrocatalytic materials have lower hydrogen evolution reactivity than commercial Pt/C, but higher oxygen evolution reactivity than commercial Pt/C.
Example 3 investigation of the Effect of the amount of Metal salt on the catalytic Material
Step (1): referring to example 1, Cu was obtained by replacing the mass ratios of copper chloride, cobalt chloride and manganese acetate with 1:2:1(0.15g of copper chloride, 0.3g of cobalt chloride and 0.15g of manganese acetate), 1:1:2(0.15g of copper chloride, 0.15g of cobalt chloride and 0.3g of manganese acetate), 2:1:1(0.3g of copper chloride, 0.15g of cobalt chloride and 0.15g of manganese acetate), respectively, and keeping the other conditions constant1Co2Mn1PAN nanofiber membrane, Cu1Co1Mn2PAN nanofibrous membrane and Cu2Co1Mn1PAN nanofibrous membranes.
Step (2) As in example 1, Cu was prepared separately1Co2Mn1/NCNTs、Cu1Co1Mn2/NCNTs、Cu2Co1Mn1NCNTs electrolytic water catalytic material.
Cu testing as in example 1 1Co2Mn1/NCNTs、Cu1Co1Mn2/NCNTs、Cu2Co1Mn1The acidic Hydrogen Evolution (HER) and Oxygen Evolution (OER) properties of the/NCNTs electrolytic water catalytic material.
The results are shown in Table 1.
TABLE 1 Performance results for catalyst materials obtained with varying amounts of metal salts
From the results shown in Table 1, it is understood that the content of Mn metal is high, the oxygen evolution performance of the obtained electrolyzed water material is good, the contents of Cu and Co metal are high, and the hydrogen evolution performance of the obtained electrolyzed water material is good.
Example 4 investigation of the effect of the concentration of metal salts in the spin dope on the catalytic material
Step (1): referring to example 1, CuCoMn-0.2/PAN nanofiber membranes, CuCoMn-0.3/PAN nanofiber membranes and CuCoMn-0.4/PAN nanofiber membranes were respectively prepared by electrospinning, with the mass of each metal salt replaced by 0.2g, 0.3g, 0.4g, and the other conditions being unchanged.
The step (2) is the same as the step (1) to prepare CuCoMn-0.2/NCNTs, CuCoMn-0.3/NCNTs and CuCoMn-0.4/NCNTs electrolytic water catalytic materials respectively.
The acidic hydrogen and oxygen evolution properties of CuCoMn-0.2/NCNTs, CuCoMn-0.3/NCNTs, CuCoMn-0.4/NCNTs electrolytic water catalytic materials were tested as in example 1.
The results are shown in Table 2.
TABLE 2 Performance results for catalyst materials obtained at different metal salt concentrations
From the results shown in Table 2, it is understood that as the concentration of the metal salt increases, both the hydrogen evolution and the oxygen evolution properties of the obtained electrolyzed water catalytic material decrease.
Comparative example 1
Step (1) is the same as in example 1;
step (2): 0.2g of the prepared CuCoMn/PAN nanofiber membrane is placed in a corundum boat and is placed in the middle of a tube furnace. Firstly, the temperature is raised to 280 ℃ at the heating rate of 5 ℃/min, and the temperature is preserved for 3 hours in the air atmosphere for pre-oxidation. After the heat preservation is finished, the temperature is raised to 1000 ℃ at the speed of 5 ℃/min under the argon atmosphere, and the heat preservation is carried out for 3 hours under the argon atmosphere. And after the heat preservation is finished, naturally cooling to room temperature in the inert gas atmosphere to obtain the CuCoMn/CNFs electrolytic water catalytic material.
The acidic hydrogen and oxygen evolution performance of CuCoMn/CNFs electrolytic water catalytic materials was tested as in example 1.
A scanning electron microscope is used for shooting the prepared CuCoMn/CNFs electrolytic water catalytic material, and FIG. 6 is a scanning electron microscope image of CuCoMn/CNFs, and it can be observed from FIG. 6 that metal nanoparticles are uniformly loaded on carbon nanofibers after high-temperature carbonization of electrospun PAN fibers is carried out when ammonia gas is not introduced. FIG. 7 shows that CuCoMn/CNFs is 0.5M H2SO4Polarization curves for hydrogen evolution reaction and oxygen evolution reaction in (1). ByAs can be seen in FIG. 7, the current density was 10mA cm-2And overpotentials of hydrogen evolution reaction and oxygen evolution reaction of CuCoMn/CNFs are 270mV and 570mV (vs. RHE), which are far lower than that of CuCoMn/NCNTs electrolyzed water catalytic material obtained after ammonia gas treatment.
Comparative example 2
Step (1): referring to example 1, 0.15g of cobalt chloride and 0.15g of manganese acetate were added to 25g of a 12 wt% polyacrylonitrile solution in N, N-dimethylformamide; adding 0.15g of copper chloride and 0.15g of manganese acetate into 25g of N, N-dimethylformamide solution of polyacrylonitrile with the mass fraction of 12 wt%; adding 0.15g of copper chloride and 0.15g of cobalt chloride into 25g of N, N-dimethylformamide solution of polyacrylonitrile with the mass fraction of 12 wt%, and preparing a CoMn/PAN nano-fiber membrane, a CuMn/PAN nano-fiber membrane and a CuCo/PAN nano-fiber membrane respectively by an electrostatic spinning technology under the same conditions.
The same as the example 1 in the step (2), CoMn/NCNTs, CuMn/NCNTs and CuCo/NCNTs electrolytic water catalytic materials are respectively prepared.
The acidic hydrogen and oxygen evolution properties of the CoMn/NCNTs, CuMn/NCNTs, CuCo/NCNTs two-component metal electrolytic water catalytic materials were tested as in example 1.
The results are shown in Table 3.
TABLE 3 Performance results for two-element metal electrolyzed water catalyst materials
As can be seen from Table 3, the binary metal electrolytic water catalyst does not have both excellent hydrogen evolution activity and oxygen evolution activity compared to the CuCoMn/NCNTs electrolytic water catalyst material prepared in example 1.
Claims (10)
1. A method for preparing a CuCoMn multi-stage structure electrolytic water catalytic material is characterized by comprising the following steps:
(1) dispersing copper salt, cobalt salt, manganese salt and a nanofiber precursor in an organic solvent to prepare a spinning solution; then preparing a nanofiber membrane through electrostatic spinning;
(2) and (2) calcining and pre-oxidizing the nanofiber membrane obtained in the step (1), and then adding a nitrogen source to calcine and carbonize to obtain the multi-level structure electrolytic water catalytic material.
2. The method according to claim 1, wherein the nanofiber precursor in step (1) is one or more of polyacrylonitrile, polyvinylpyrrolidone and polyvinyl alcohol.
3. The method according to claim 1, wherein the mass ratio of the copper salt, the cobalt salt and the manganese salt in the spinning solution of step (1) is 1: (0.5-2): (0.5-2).
4. The method according to claim 1, wherein the total mass concentration of the copper salt, the cobalt salt and the manganese salt in the spinning solution of step (1) is 1.5-4.5%.
5. The method according to claim 1, wherein the mass of the nitrogen source in the step (2) is 20 to 50 times the mass of the metal in the nanofiber membrane used in the calcination.
6. The method as claimed in claim 1, wherein the calcination pre-oxidation in step (2) is performed by heating to 180-300 ℃ at a heating rate of 2-20 ℃/min, and performing heat preservation calcination for 2-4 h.
7. The method according to claim 1, wherein the calcination carbonization in step (2) is calcination at 800-1000 ℃ for 2-4 h.
8. The CuCoMn multilevel-structure electrolytic water catalytic material prepared by the preparation method of any one of claims 1 to 7.
9. The CuCoMn multilevel structure electrolytic water catalytic material of claim 8, which is applied to the field of electrolytic water catalysis.
10. A method for catalyzing electrolyzed water to simultaneously perform hydrogen evolution and oxygen evolution reactions, which is characterized in that the method utilizes the multi-stage structure electrolyzed water catalytic material as claimed in claim 8 as a catalyst.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104153123A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible titanium oxide nanofiber membrane and preparation method thereof |
| CN104404652A (en) * | 2014-11-23 | 2015-03-11 | 吉林大学 | Compound metal oxide water oxidation catalyst and electrostatic spinning preparation method thereof |
| WO2015169786A1 (en) * | 2014-05-06 | 2015-11-12 | Danmarks Tekniske Universitet | Method for producing and controlling the morphology of metal-oxide nanofiber and/or nanotube catalysts |
| CN105478102A (en) * | 2016-02-05 | 2016-04-13 | 扬州大学 | Method for preparing catalyst for electrical catalytic degradation of organic wastewater |
| CN106140162A (en) * | 2016-07-08 | 2016-11-23 | 浙江理工大学 | A kind of preparation method of the copper nano-particle for electrocatalytic hydrogen evolution/carbon nano-fiber hybrid material |
| CN111185188A (en) * | 2019-12-27 | 2020-05-22 | 江南大学 | Iron-cobalt-nickel-copper-based high-entropy alloy electrolytic water catalytic material and preparation method thereof |
-
2020
- 2020-07-03 CN CN202010637053.XA patent/CN111841602B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015169786A1 (en) * | 2014-05-06 | 2015-11-12 | Danmarks Tekniske Universitet | Method for producing and controlling the morphology of metal-oxide nanofiber and/or nanotube catalysts |
| CN104153123A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible titanium oxide nanofiber membrane and preparation method thereof |
| CN104404652A (en) * | 2014-11-23 | 2015-03-11 | 吉林大学 | Compound metal oxide water oxidation catalyst and electrostatic spinning preparation method thereof |
| CN105478102A (en) * | 2016-02-05 | 2016-04-13 | 扬州大学 | Method for preparing catalyst for electrical catalytic degradation of organic wastewater |
| CN106140162A (en) * | 2016-07-08 | 2016-11-23 | 浙江理工大学 | A kind of preparation method of the copper nano-particle for electrocatalytic hydrogen evolution/carbon nano-fiber hybrid material |
| CN111185188A (en) * | 2019-12-27 | 2020-05-22 | 江南大学 | Iron-cobalt-nickel-copper-based high-entropy alloy electrolytic water catalytic material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| MARCUS EINERT,ET AL.: "Electrospun CuO Nanofibers: Stable Nanostructures for Solar Water Spliting", 《CHEMPHOTOCHEM》 * |
| 曹树波: "碳纳米纤维负载铁钴镍材料的制备及其氧还原催化性能", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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