CN109046426B - Nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst and preparation method thereof - Google Patents
Nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst and preparation method thereof Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 52
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 42
- 239000011593 sulfur Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 43
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 238000005245 sintering Methods 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 19
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- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 16
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003556 thioamides Chemical class 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 5
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- 238000000034 method Methods 0.000 claims description 39
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- 239000000243 solution Substances 0.000 claims description 29
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- 241000755266 Kathetostoma giganteum Species 0.000 claims description 25
- 239000010935 stainless steel Substances 0.000 claims description 25
- 229910001220 stainless steel Inorganic materials 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 238000009987 spinning Methods 0.000 claims description 20
- 239000002121 nanofiber Substances 0.000 claims description 18
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000012856 weighed raw material Substances 0.000 claims description 5
- BNLLHLUAOXAUNQ-UHFFFAOYSA-N n-methylethanethioamide Chemical compound CNC(C)=S BNLLHLUAOXAUNQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 claims description 3
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- LKNQXZAHNDFIQY-UHFFFAOYSA-N n,n-dimethylethanethioamide Chemical compound CN(C)C(C)=S LKNQXZAHNDFIQY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
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- 238000006555 catalytic reaction Methods 0.000 abstract description 9
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/33—
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- B01J35/40—
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- B01J35/58—
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst and a preparation method thereof, and relates to a nickel-cobalt-based carbon fiber electrolytic water catalyst and a preparation method thereof. The invention aims to solve the problems of low electrolysis efficiency and poor stability of the adopted catalyst in the existing hydrogen preparation. The catalyst is composed of a carbon fiber substrate and nano particles; the nano particles are loaded in the carbon fiber matrix and on the surface of the carbon fiber matrix. The preparation method comprises the following steps: according to the formula NixCoyNzAnd NiaCobScWeighing nickel nitrate, cobalt nitrate and thioamide compounds according to the molar ratio of the elements, and adding polyvinylpyrrolidone to obtain a precursor solution; carrying out electrostatic spinning; and finally, high-temperature sintering is carried out. The nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst material has good catalyst activity and stability. And the double-function catalysis of hydrogen evolution and oxygen evolution is realized, and the electrolytic efficiency is up to 95 percent. The invention is suitable for preparing the electrolytic water catalyst.
Description
Technical Field
The invention relates to a nickel-cobalt-based carbon fiber water electrolysis catalyst and a preparation method thereof.
Background
With the increasing energy crisis and environmental pollution, the development of various new energy sources and renewable energy sources has been highly valued by countries all over the world, and green renewable energy sources such as wind energy, solar energy and water power bring hopes for people to solve the energy crisis. Researchers in various countries around the world have invested a great deal of effort in studying these technologies for the utilization of green energy and have been with great success. Wherein the technologies of wind power generation, photovoltaic power generation, hydroelectric power generation and the like are applied in large scale. Most of green renewable energy sources have the characteristic of uneven space-time distribution, which requires that the energy sources can be effectively captured, stored, transported and converted so as to meet the requirements of different places and time periods. And the hydrogen is taken as a secondary energy source, so that the hydrogen has the advantages of cleanness, no pollution, high efficiency, storage and transportation and the like, and is considered as an ideal energy carrier. The hydrogen is obtained by using water with abundant reserves and low price as a raw material, and the electric energy can be stored in chemical bonds of the hydrogen through hydrogen production by electrolysis. When energy is needed, the energy can be released through combustion and can be converted into electric energy again through a hydrogen fuel cell. Whichever way energy is released, the final product is water with zero carbon emissions. When the electric energy used by electrolysis comes from renewable energy sources such as wind energy, solar energy and the like, the green cycle and sustainable utilization of the energy sources are really realized by human beings.
Currently, a low-carbon steel cathode and a nickel-plated cathode are widely used in hydrogen preparation in industry, but the electrolytic efficiency of the carbon steel cathode and the nickel-plated cathode is very low, and is only 50% (the electrolytic efficiency is faradaic efficiency, which describes the transfer efficiency of charges in an electrochemical reaction system, and the specific calculation method is the ratio of the charges utilized by the products obtained by reaction to the total charge of an external circuit; meanwhile, hydrogen evolution overpotentials of the low-carbon steel cathode and the nickel-plated cathode respectively reach 380mV and 480 mV. The influence of over-high hydrogen evolution potential is high energy consumption, which is not beneficial to the hydrogen preparation; the noble metals such as Pt, Rh and Pd have excellent electrocatalytic activity as catalyst materials, but the cost is too high to be popularized. After the noble metal catalyst reacts for a period of time, the noble metal catalyst is easy to agglomerate and has poor dispersibility, so that the structure of the catalyst is changed, and the catalytic performance of the catalyst is influenced; therefore, the development of a novel non-noble metal catalyst material with high electrolysis efficiency and low overpotential of electrolyzed water has become a popular subject for research by researchers in various countries.
At present, the main catalysts are carbon-based catalysts. Although the pure carbon material has good conductivity, the catalytic activity and stability are poor, and the requirement of people on an ideal catalyst is difficult to meet. However, as non-metallic elements such as nitrogen and sulfur are doped into the carbon matrix, the carbon matrix generates a large amount of disordered structure and a large specific surface area. Among the numerous catalysts, non-metal/transition metal co-doped carbon materials are considered to be the most ideal substitute for noble metal-based catalysts, mainly due to their lower price and higher catalytic activity. The structure and morphology of the carbon matrix in the catalyst material also influence the electrocatalytic performance of the catalyst material, which is mainly related to the defect structure and the specific surface area of the carbon matrix. The carbon-based material mainly comprises: graphene materials, carbon nanotube materials, porous carbon materials, and the like. However, the preparation process of the carbon material is complicated, and large-scale commercial production is not easy to realize. The existing nitrogen and sulfur doped carbon material has poor stability, and because the doping is realized by adopting an external nitriding and vulcanizing treatment method, the change of the electronic structure and the crystal structure of the carbon material is concentrated on the surface layer of a carbon carrier, so the carbon material is easy to corrode in the catalytic reaction process; the existing doping method of the nitrogen and sulfur doped carbon material adopts external doping, the uniformity and the thoroughness of doping are difficult to realize, in addition, the catalyst adopted in the existing stage hydrogen preparation only has the single catalytic function of hydrogen precipitation or oxygen precipitation, and can not realize dual-function catalysis, so that two catalysts are required to be selected in the existing hydrogen preparation, and the hydrogen preparation cost is increased.
Disclosure of Invention
The invention provides a nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst and a preparation method thereof, aiming at solving the problems of low electrolysis efficiency and poor stability of the adopted catalyst in the existing hydrogen preparation.
The nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst consists of a carbon fiber matrix and nano particles; the nano particles are loaded in the carbon fiber matrix and on the surface of the carbon fiber matrix; the nano particles are nickel cobalt nitride and nickel cobalt sulfide, and the molecular formula of the nickel cobalt nitride is NixCoyNzIn the molecular formula, x is 1-2, y is 1-2, and z is 1-2; the molecular formula of the nickel cobalt sulfide is NiaCobScIn the molecular formula, a is 1-2, b is 1-2, and c is 1-2; the particle size of the nanoparticles is 3-7 nm.
The preparation method of the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst comprises the following steps:
firstly, preparing an electrostatic spinning precursor solution:
according to the formula NixCoyNzAnd NiaCobScWeighing nickel nitrate, cobalt nitrate and thioamide compounds as raw materials according to the molar ratio of the elements, adding the weighed raw materials into N, N-dimethylformamide to obtain a mixed solution a, magnetically stirring the mixed solution a at a constant speed at room temperature until the raw materials are completely dissolved, adding polyvinylpyrrolidone to obtain a mixed solution b, and magnetically stirring the mixed solution b at a constant speed for 4-6 hours to obtain a completely dissolved transparent electrostatic spinning precursor solution; molecular formula NixCoyNzWherein x is 1-2, y is 1-2, and z is 1-2; molecular formula NiaCobScWherein a is 1-2, b is 1-2, and c is 1-2;
the thioamide compound is thioacetamide or a thioacetamide derivative;
the total mass concentration of the nickel nitrate, the cobalt nitrate and the thioamide compound in the mixed solution a is 5-30 wt%;
step one, the mass concentration of polyvinylpyrrolidone in the mixed solution b is 5-20 wt%;
the thioacetamide derivative is one or a mixture of N-methyl thioacetamide, N-methyl thiourea and N, N-dimethyl thioacetamide according to any proportion.
Secondly, carrying out electrostatic spinning to obtain nano fibers;
the ambient temperature of the electrostatic spinning is 20-35 ℃, and the relative humidity is 10-30%;
the electrostatic spinning process comprises the following steps: adding the electrostatic spinning precursor solution obtained in the first step into an injector, adopting a stainless steel flat-head needle as a spinning nozzle, adopting a nickel net as a spinning receiving net, connecting the positive pole of a direct-current power supply with the stainless steel flat-head needle, connecting the negative pole of the direct-current power supply with the nickel net, and adjusting the included angle between the injector and the horizontal direction to be 30-60 degrees;
the capacity of the injector is 5mL, the inner diameter of the stainless steel flat-head needle is 0.5-0.9 mm, the direct-current voltage between the end part of the stainless steel flat-head needle and the nickel net is 15-30 kV, and the distance between the end part of the stainless steel flat-head needle and the nickel net is 10-20 cm;
thirdly, high temperature sintering
Putting the nanofiber obtained in the step two into a tubular furnace for high-temperature sintering to complete;
the high-temperature sintering process comprises the following steps: heating from room temperature to 600-1000 ℃ at a heating rate of 3-12 ℃/min, and keeping the temperature for 2-3 h; the sintering atmosphere during the high-temperature sintering is air atmosphere, nitrogen atmosphere or hydrogen atmosphere;
the reaction principle of the invention is as follows:
the forming mechanism of the carbon fiber of the present invention is: in the electrostatic spinning process, metal salt and polyvinylpyrrolidone (PVP) are dissolved in N, N-Dimethylformamide (DMF) to form a high polymer solution, nanofibers are formed in a high-voltage electrostatic field, the obtained nanofibers are placed in a tube furnace and are carbonized at high temperature under the protection of inert gas, and H, O element in the high polymer is H2Removing the form of O, and forming the carbon nano-fiber by the remaining carbon element; in the high-temperature carbonization process, nitrate ions of metal nitrate are decomposed at high temperature to generate gas, thioacetamide and derivatives thereof are decomposed at high temperature to form ammonia gas and gaseous sulfides, the ammonia gas reacts with nickel and cobalt to generate nickel and cobalt nitrides, and the gaseous sulfides react with nickel and cobalt to generate nickel and cobalt sulfides.
The invention has the following beneficial effects:
1. the invention adopts the electrostatic spinning technology to prepare the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst material, and is a simple and effective preparation method, different elements are simultaneously doped into a carbon fiber framework, in the preparation process of the spinning solution, metal salt, a nitrogen source and a sulfur source are all dissolved in the spinning solution, the metal salt, the nitrogen source and the sulfur source are uniformly dispersed in the nano fibers in the process of forming the nano fibers by electrostatic spinning, and a catalytic active site fixed in a carbon matrix structure is formed after the treatment of a later-stage high-temperature sintering process, so that the catalytic active site is fixed in the carbon matrix structure, and the activity and the stability of the catalyst are further improved.
2. According to the invention, thioacetamide or thioacetamide derivatives with chelation, vulcanization and nitridation are added into the spinning solution, so that not only is nitridation and vulcanization of the active center of the transition metal realized, but also the chelation of the metal salt and the thioacetamide or thioacetamide derivatives in the spinning solution during dissolution realizes uniform dispersion of metal particles on the nanofibers in the later electrostatic spinning process, and the chelation of the added chelating agent enables the metal particles to avoid the agglomeration of the active center in the high-temperature carbonization process, so that the nanocrystallization of the active center is realized, nanoparticles with the average particle size of 5nm are obtained, and the active area is increased.
3. In the nitrogen and sulfur in-situ Co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst material, Ni and Co have unfilled valence layer d orbitals, so that the catalyst material has a catalytic effect on hydrogen precipitation and oxygen precipitation reactions, and further saves the cost in the actual production process, reduces the process complexity, simplifies the requirements of equipment and processes, and better realizes large-scale application;
4. the existing nitrogen and sulfur doped catalyst only adopts single nonmetal doping, and the invention adopts two nonmetal codoping and utilizes the synergistic action between nitrogen and sulfur and the synergistic action between nitrogen, sulfur and carbon to jointly improve the performance of the catalyst.
5. The nitrogen source and the sulfur source are dissolved by the solution in the early stage of electrostatic spinning and are uniformly dispersed in the fiber along with the spinning process, so that the doping from inside to outside can be realized in the high-temperature sintering process. In the catalytic reaction process in the using process, the carbon fibers can protect nickel-cobalt nitride nanoparticles and nickel-cobalt sulfide nanoparticles in the carbon fibers, and the stability is improved. Meanwhile, the in-situ nitridation and vulcanization from inside to outside generate structural defects in the crystal structures of the interior and the surface of the carbon material; electronic defects are generated in electronic structures inside and on the surface of the carbon material, so that the catalytic activity is improved;
6. the catalyst obtained by the invention realizes the dual-function catalysis of hydrogen precipitation and oxygen precipitation, and the electrolytic efficiency is as high as 95%; has the potential of practical application.
Description of the drawings:
FIG. 1 is an SEM image of a catalyst obtained in example one;
FIG. 2 is a TEM image of the catalyst obtained in example one;
FIG. 3 is a graph of oxygen evolution performance of the catalyst under alkaline conditions in example two;
FIG. 4 is a graph of the hydrogen evolution performance of the catalyst under basic conditions in example two.
The specific implementation mode is as follows:
the technical scheme of the invention is not limited to the specific embodiments listed below, and any reasonable combination of the specific embodiments is included.
The first embodiment is as follows: the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst in the embodiment is composed of a carbon fiber matrix and nanoparticles; the nano particles are loaded in the carbon fiber matrix and on the surface of the carbon fiber matrix; the nano particles are nickel cobalt nitride and nickel cobalt sulfide, and the molecular formula of the nickel cobalt nitride is NixCoyNzIn the molecular formula, x is 1-2, y is 1-2, and z is 1-2; the molecular formula of the nickel cobalt sulfide is NiaCobScIn the molecular formula, a is 1-2, b is 1-2, and c is 1-2.
The embodiment has the following beneficial effects:
1. in the nitrogen and sulfur in-situ Co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst material, Ni and Co have unfilled valence layer d orbitals, so that the catalyst material has a catalytic effect on hydrogen precipitation and oxygen precipitation reactions, and further saves the cost in the actual production process, reduces the process complexity, simplifies the requirements of equipment and processes, and better realizes large-scale application;
2. the existing nitrogen and sulfur doped catalyst only adopts single non-metal doping, and the catalyst performance is jointly improved by adopting two non-metal co-doping and utilizing the synergistic action between nitrogen and sulfur and the synergistic action between nitrogen, sulfur and carbon.
3. The catalyst obtained by the embodiment realizes the dual-function catalysis of hydrogen precipitation and oxygen precipitation, and the electrolytic efficiency is as high as 95%; has the potential of practical application.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the particle size of the nanoparticles is 3-7 nm. Other steps and parameters are the same as in the first embodiment.
The third concrete implementation mode: the preparation method of the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst in the embodiment is carried out according to the following steps:
firstly, preparing an electrostatic spinning precursor solution:
according to the formula NixCoyNzAnd NiaCobScWeighing nickel nitrate, cobalt nitrate and thioamide compounds as raw materials according to the molar ratio of the elements, adding the weighed raw materials into N, N-dimethylformamide to obtain a mixed solution a, magnetically stirring the mixed solution a at a constant speed at room temperature until the raw materials are completely dissolved, adding polyvinylpyrrolidone to obtain a mixed solution b, and magnetically stirring the mixed solution b at a constant speed for 4-6 hours to obtain a completely dissolved transparent electrostatic spinning precursor solution; molecular formula NixCoyNzWherein x is 1-2, y is 1-2, and z is 1-2; molecular formula NiaCobScWherein a is 1-2, b is 1-2, and c is 1-2;
the thioamide compound is thioacetamide or a thioacetamide derivative;
the total mass concentration of the nickel nitrate, the cobalt nitrate and the thioamide compound in the mixed solution a is 5-30 wt%;
secondly, carrying out electrostatic spinning to obtain nano fibers;
the ambient temperature of the electrostatic spinning is 20-35 ℃, and the relative humidity is 10-30%;
thirdly, high temperature sintering
And D, placing the nanofiber obtained in the step two into a tubular furnace for high-temperature sintering, and thus completing the process.
The beneficial effects of the embodiment are as follows:
1. the embodiment adopts the electrostatic spinning technology to prepare the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst material, and is a simple and effective preparation method, different elements are simultaneously doped into a carbon fiber framework, in the preparation process of the spinning solution, the metal salt, the nitrogen source and the sulfur source are all dissolved in the spinning solution, the metal salt, the nitrogen source and the sulfur source are uniformly dispersed in the nanofibers in the process of forming the nanofibers through electrostatic spinning, and the catalytic active sites fixed in a carbon matrix structure are formed after the subsequent high-temperature sintering process treatment, so that the catalytic active sites are fixed in the carbon matrix structure, and the activity and the stability of the catalyst are further improved.
2. According to the embodiment, thioacetamide or thioacetamide derivatives with chelation, vulcanization and nitridation functions are added into the spinning solution, so that nitridation and vulcanization of an active center of transition metal are realized, meanwhile, the chelation effect of metal salt and thioacetamide or thioacetamide derivatives in the spinning solution during dissolution realizes uniform dispersion of metal particles on nanofibers in the later electrostatic spinning process, the chelation effect of the added chelating agent enables the metal particles to avoid agglomeration of the active center in the high-temperature carbonization process, the nanocrystallization of the active center is also realized, nanoparticles with the average particle size of 5nm are obtained, and the active area is increased.
3. In the nitrogen and sulfur in-situ Co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst material, Ni and Co have unfilled valence layer d orbitals, so that the catalyst material has a catalytic effect on hydrogen precipitation and oxygen precipitation reactions, and further saves the cost in the actual production process, reduces the process complexity, simplifies the requirements of equipment and processes, and better realizes large-scale application;
4. the existing nitrogen and sulfur doped catalyst only adopts single non-metal doping, and the catalyst performance is jointly improved by adopting two non-metal co-doping and utilizing the synergistic action between nitrogen and sulfur and the synergistic action between nitrogen, sulfur and carbon.
5. The nitrogen source and the sulfur source of the embodiment are dissolved by the solution in the early stage of the electrostatic spinning and are uniformly dispersed in the fiber along with the spinning process, so that the doping from inside to outside can be realized in the high-temperature sintering process. In the catalytic reaction process in the using process, the carbon fibers can protect nickel-cobalt nitride nanoparticles and nickel-cobalt sulfide nanoparticles in the carbon fibers, and the stability is improved. Meanwhile, the in-situ nitridation and vulcanization from inside to outside generate structural defects in the crystal structures of the interior and the surface of the carbon material; electronic defects are generated in electronic structures inside and on the surface of the carbon material, so that the catalytic activity is improved;
6. the catalyst obtained by the embodiment realizes the dual-function catalysis of hydrogen precipitation and oxygen precipitation, and the electrolytic efficiency is as high as 95%; has the potential of practical application.
The fourth concrete implementation mode: the third difference between the present embodiment and the specific embodiment is that: in the step one, the mass concentration of polyvinylpyrrolidone in the mixed solution b is 5-20 wt%. Other steps and parameters are the same as those in the third embodiment.
In the embodiment, the mass concentration of polyvinylpyrrolidone (PVP) in N, N-dimethylformamide is 5 to 20wt%, and at this concentration, polymer molecular chains form entanglement in the solution and have a certain viscosity, which is a necessary condition for preparing polymer fibers by an electrostatic spinning technology. After the polymer solution jet flow is formed on the surface of the Taylor cone, the jet flow is stretched by the electric field force in a high-voltage electrostatic field, and the sufficiently entangled molecular chains are oriented along the axial direction of the jet flow, so that the stretching of the electric field force can be balanced, the continuity of the jet flow is maintained, fibers are formed, and otherwise, the jet flow can be broken to form bead fibers and the like.
The fifth concrete implementation mode: this embodiment is different from the third or fourth embodiment in that: the thioacetamide derivative is one or a mixture of N-methyl thioacetamide, N-methyl thiourea and N, N-dimethyl thioacetamide according to any proportion. The other steps and parameters are the same as those of the third or fourth embodiment.
This implementationIn the mode, thioacetamide or thioacetamide derivatives have chelation, nitridation and vulcanization functions, and the reaction principle is as follows: metal ion M2+(M ═ Ni, Co) and thioacetamide or thioacetamide derivatives form a molecular chelate with N, S-coordination, the prior chelation before complexing with PVP ensures the dispersibility of metal ions on PVP high polymer, the metal ions are nitrided and sulfurized in the high-temperature sintering process to obtain nickel-cobalt nitride nanoparticles and nickel-cobalt sulfide nanoparticles, the PVP high polymer is converted into carbon fibers, and the obtained nickel-cobalt nitride nanoparticles and nickel-cobalt sulfide nanoparticles are uniformly dispersed in the carbon fibers and on the surfaces of the carbon fibers; the nickel cobalt nitride nanoparticles and the nickel cobalt sulfide nanoparticles are used as catalytic active sites for the reaction of hydrogen precipitation and oxygen precipitation, so that the catalytic active sites are uniformly dispersed in the carbon fibers and on the surfaces of the carbon fibers;
the principle of good catalytic active site dispersibility is as follows: (1) the electrostatic spinning process provides a precondition for uniform dispersion of the catalytic active sites, and compared with solid-phase mixing, the liquid-phase mixing in the preparation process of the electrostatic spinning solution can better realize uniform dispersion of the catalyst; (2) chelation by the added chelating agent enhances the dispersibility of the metal ions.
Metal ion M2+The reaction equation of (M ═ Ni, Co) with thioacetamide or thioacetamide derivatives is shown below:
the nickel-cobalt nitride nano particles and the nickel-cobalt sulfide nano particles are in the nanometer level, are superfine materials in a transition region where atomic clusters and macroscopic objects are located, are typical mesoscopic systems, and have special properties such as surface effects, small-size effects, quantum size effects and macroscopic quantum tunneling effects. Therefore, compared with the traditional catalyst, the nickel-cobalt nitride nanoparticles and the nickel-cobalt sulfide nanoparticles have higher catalytic efficiency and selectivity, the surface atomic number is increased along with the reduction of the particle size of the nanoparticles, and meanwhile, the reduction of the particle size can increase the active specific surface area of the catalyst and improve the catalytic performance of the catalyst.
The sixth specific implementation mode: the difference between this embodiment and one of the third to fifth embodiments is: the electrostatic spinning process in the step two comprises the following steps: and (2) adding the electrostatic spinning precursor solution obtained in the step one into an injector, adopting a stainless steel flat-head needle as a spinning nozzle, adopting a nickel net as a spinning receiving net, connecting the positive pole of a direct current power supply with the stainless steel flat-head needle, connecting the negative pole of the direct current power supply with the nickel net, and adjusting the included angle between the injector and the horizontal direction to be 30-60 degrees. Other steps and parameters are the same as in one of the third to fifth embodiments.
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that: the capacity of the injector is 5mL, the inner diameter of the stainless steel flat-head needle is 0.5-0.9 mm, the direct-current voltage between the end part of the stainless steel flat-head needle and the nickel net is 15-30 kV, and the distance between the end part of the stainless steel flat-head needle and the nickel net is 10-20 cm. The other steps and parameters are the same as in embodiment six.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the high-temperature sintering process comprises the following steps: heating from room temperature to 600-1000 ℃ at a heating rate of 3-12 ℃/min, and keeping the temperature for 2-3 h. Other steps and parameters are the same as in one of the first to seventh embodiments.
The specific implementation method nine: the eighth embodiment is different from the eighth embodiment in that: and step three, the sintering atmosphere during high-temperature sintering is air atmosphere, nitrogen atmosphere or hydrogen atmosphere. The other steps and parameters are the same as in embodiment eight.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: the preparation method of the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst comprises the following steps:
firstly, preparing an electrostatic spinning precursor solution:
according to the formula NixCoyNzAnd NiaCobScEach element inWeighing nickel nitrate, cobalt nitrate and thioamide compounds as raw materials, adding the weighed raw materials into N, N-dimethylformamide to obtain a mixed solution a, magnetically stirring the mixed solution a at a constant speed at room temperature until the raw materials are completely dissolved, adding polyvinylpyrrolidone to obtain a mixed solution b, and magnetically stirring the mixed solution b at a constant speed for 4-6 hours to obtain a completely dissolved transparent electrostatic spinning precursor solution; molecular formula NixCoyNzWherein x is 1, y is 2, and z is 2; molecular formula NiaCobScWherein a is 1, b is 2, and c is 2;
the thioamide compound is thioacetamide; the total mass concentration of the nickel nitrate, the cobalt nitrate and the thioamide compound in the mixed solution a is 5 wt%; the mass concentration of polyvinylpyrrolidone (PVP) in the mixed solution b is 5 wt%;
secondly, carrying out electrostatic spinning to obtain nano fibers;
the ambient temperature of the electrostatic spinning is 30 ℃, and the relative humidity is 20%; the electrostatic spinning process comprises the following steps: adding the electrostatic spinning precursor solution obtained in the step one into an injector, adopting a stainless steel flat-head needle as a spinning nozzle, adopting a nickel net as a spinning receiving net, connecting the positive pole of a direct current power supply with the stainless steel flat-head needle, connecting the negative pole of the direct current power supply with the nickel net, and adjusting the included angle between the injector and the horizontal direction to be 45 degrees; the capacity of the injector is 5mL, the inner diameter of the stainless steel flat-head needle is 0.6mm, the direct-current voltage between the end part of the stainless steel flat-head needle and the nickel net is 20kV, and the distance between the end part of the stainless steel flat-head needle and the nickel net is 15 cm;
thirdly, high temperature sintering
Putting the nanofiber obtained in the step two into a tubular furnace for high-temperature sintering to complete; the high-temperature sintering process comprises the following steps: heating from room temperature to 1000 ℃ at the heating rate of 7 ℃/min and preserving heat for 3 h; the sintering atmosphere during the high-temperature sintering is a nitrogen atmosphere.
FIG. 1 is an SEM image of a catalyst obtained in example one; as can be seen from fig. 1, the catalyst has a structure in which nickel-cobalt nitride nanoparticles and nickel-cobalt sulfide nanoparticles are loaded inside and on the surface of carbon fibers, the diameter of the carbon fibers is uniform, and no bond exists between the fibers; FIG. 2 is a TEM image of the catalyst obtained in the first example, and it can be seen from FIG. 2 that the average particle size of the catalyst particles is about 5nm, which actually realizes the nanocrystallization of the catalyst, thereby effectively improving the electrochemical performance;
example 2: the preparation method of the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst comprises the following steps:
firstly, preparing an electrostatic spinning precursor solution:
according to the formula NixCoyNzAnd NiaCobScWeighing nickel nitrate, cobalt nitrate and thioamide compounds as raw materials according to the molar ratio of the elements, adding the weighed raw materials into N, N-dimethylformamide to obtain a mixed solution a, magnetically stirring the mixed solution a at a constant speed at room temperature until the raw materials are completely dissolved, adding polyvinylpyrrolidone to obtain a mixed solution b, and magnetically stirring the mixed solution b at a constant speed for 4-6 hours to obtain a completely dissolved transparent electrostatic spinning precursor solution; molecular formula NixCoyNzWherein x is 1, y is 2, and z is 1; molecular formula NiaCobScWherein a is 1, b is 2, and c is 1;
the total mass concentration of the nickel nitrate, the cobalt nitrate and the thioamide compound in the mixed solution a is 30 wt%; the mass concentration of polyvinylpyrrolidone in the mixed solution b is 20 wt%; the thioamide compound is a thioacetamide derivative; the thioacetamide derivative is N-methyl thioacetamide;
secondly, carrying out electrostatic spinning to obtain nano fibers;
the ambient temperature of the electrostatic spinning is 20 ℃, and the relative humidity is 10%; the electrostatic spinning process comprises the following steps: adding the electrostatic spinning precursor solution obtained in the step one into an injector, adopting a stainless steel flat-head needle as a spinning nozzle, adopting a nickel net as a spinning receiving net, connecting the positive pole of a direct current power supply with the stainless steel flat-head needle, connecting the negative pole of the direct current power supply with the nickel net, and adjusting the included angle of the injector and the horizontal direction to be 30 degrees;
the capacity of the injector is 5mL, the inner diameter of the stainless steel flat-head needle is 0.5mm, the direct-current voltage between the end part of the stainless steel flat-head needle and the nickel net is 15kV, and the distance between the end part of the stainless steel flat-head needle and the nickel net is 10 cm;
thirdly, high temperature sintering
Putting the nanofiber obtained in the step two into a tubular furnace for high-temperature sintering to complete;
the high-temperature sintering process comprises the following steps: heating from room temperature to 600 ℃ at the heating rate of 3 ℃/min and preserving heat for 3 hours; the sintering atmosphere during the high-temperature sintering is a hydrogen atmosphere;
FIG. 3 is a graph of oxygen evolution performance of the catalyst under alkaline conditions in example two; as can be seen from FIG. 3, the initial overpotential for the oxygen evolution reaction was only 199mV, and the current density was 10mA cm-2The overpotential of the time is only 263 mV; thus, the catalyst prepared in example two is shown to have significantly better performance than the catalyst used in actual production. FIG. 4 is a graph of the hydrogen evolution performance of the catalyst under basic conditions in example two; from FIG. 4, it can be seen that the initial overpotential is 136mV, when the current density is 10mA cm-2The overpotential of time is only 244 mV; in the second embodiment, the catalyst has high catalytic reaction rate, low energy consumption and high catalytic efficiency.
Claims (8)
1. The preparation method of the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst is characterized by comprising the following steps of: the preparation method comprises the following steps:
firstly, preparing an electrostatic spinning precursor solution:
according to the formula NixCoyNzAnd NiaCobScWeighing nickel nitrate, cobalt nitrate and thioamide compounds as raw materials according to the molar ratio of the elements, adding the weighed raw materials into N, N-dimethylformamide to obtain a mixed solution a, magnetically stirring the mixed solution a at a constant speed at room temperature until the raw materials are completely dissolved, adding polyvinylpyrrolidone to obtain a mixed solution b, and magnetically stirring the mixed solution b at a constant speed for 4-6 hours to obtain a completely dissolved transparent electrostatic spinning precursor solution; molecular formula NixCoyNzWherein x is 1-2, y is 1-2, and z is 1-2; molecular formula NiaCobScWherein a is 1-2, b is 1-2, and c is 1-2;
the thioamide compound is thioacetamide or a thioacetamide derivative;
the total mass concentration of the nickel nitrate, the cobalt nitrate and the thioamide compound in the mixed solution a is 5-30 wt%;
secondly, carrying out electrostatic spinning to obtain nano fibers;
the environment temperature of the electrostatic spinning is 20-35 ℃, and the relative humidity is 10-30%;
thirdly, high temperature sintering
Putting the nanofiber obtained in the step two into a tubular furnace for high-temperature sintering to complete;
the obtained catalyst consists of a carbon fiber substrate and nano particles; the nano particles are loaded in the carbon fiber matrix and on the surface of the carbon fiber matrix;
the nano particles are nickel cobalt nitride and nickel cobalt sulfide, and the molecular formula of the nickel cobalt nitride is NixCoyNzIn the molecular formula, x is 1-2, y is 1-2, and z is 1-2; the molecular formula of the nickel cobalt sulfide is NiaCobScIn the molecular formula, a is 1-2, b is 1-2, and c is 1-2.
2. The preparation method of the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst according to claim 1, characterized in that: in the step one, the mass concentration of polyvinylpyrrolidone in the mixed solution b is 5-20 wt%.
3. The preparation method of the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst according to claim 1, characterized in that: the thioacetamide derivative is one or a mixture of N-methyl thioacetamide, N-methyl thiourea and N, N-dimethyl thioacetamide according to any proportion.
4. The preparation method of the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst according to claim 1, characterized in that: the electrostatic spinning process in the step two comprises the following steps: and (2) adding the electrostatic spinning precursor solution obtained in the step one into an injector, adopting a stainless steel flat-head needle as a spinning nozzle, adopting a nickel net as a spinning receiving net, connecting the positive pole of a direct current power supply with the stainless steel flat-head needle, connecting the negative pole of the direct current power supply with the nickel net, and adjusting the included angle between the injector and the horizontal direction to be 30-60 degrees.
5. The preparation method of the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst according to claim 4, characterized in that: the capacity of the injector is 5mL, the inner diameter of the stainless steel flat-head needle is 0.5-0.9 mm, the direct-current voltage between the end part of the stainless steel flat-head needle and the nickel net is 15-30 kV, and the distance between the end part of the stainless steel flat-head needle and the nickel net is 10-20 cm.
6. The preparation method of the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst according to claim 1, characterized in that: the high-temperature sintering process comprises the following steps: raising the temperature from room temperature to 600-1000 ℃ at a temperature raising rate of 3-12 ℃/min and preserving the temperature for 2-3 h.
7. The preparation method of the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst according to claim 1, characterized in that: and step three, the sintering atmosphere during high-temperature sintering is air atmosphere, nitrogen atmosphere or hydrogen atmosphere.
8. The preparation method of the nitrogen and sulfur in-situ co-doped nickel-cobalt-based carbon fiber electrolytic water catalyst according to claim 1, characterized in that: the particle size of the nanoparticles is 3-7 nm.
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