CN115613069A - Transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis and preparation method thereof - Google Patents
Transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 239000001257 hydrogen Substances 0.000 title claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- -1 Transition metal nitride Chemical class 0.000 title claims abstract description 40
- 239000013535 sea water Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 24
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000004744 fabric Substances 0.000 claims abstract description 34
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 32
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
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- 239000012298 atmosphere Substances 0.000 claims abstract description 13
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 7
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- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 claims description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910003294 NiMo Inorganic materials 0.000 description 9
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
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- 150000004985 diamines Chemical class 0.000 description 1
- NUVDSAKVXWKOAW-UHFFFAOYSA-L dichloronickel;ethanol Chemical compound CCO.Cl[Ni]Cl NUVDSAKVXWKOAW-UHFFFAOYSA-L 0.000 description 1
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Images
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/056—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of textile or non-woven fabric
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
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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
The invention discloses a transition metal nitride Ni-Mo-N catalyst for seawater electrolysis hydrogen production and a preparation method thereof, wherein the preparation method comprises the following steps: cleaning the carbon cloth, and soaking the carbon cloth in dilute sulfuric acid at 70-100 ℃ to obtain pretreated carbon cloth; dropwise adding a nickel chloride solution into the nitrogen heterocyclic compound solution to ensure that the molar ratio of the nitrogen heterocyclic compound to the nickel chloride is 1.25-0.5, and after the dropwise adding is finished, continuously stirring for reaction to obtain a nitrogen-containing Ni complex; adding the pretreated carbon cloth into a mixed aqueous solution containing a nitrogen Ni complex and ammonium molybdate, carrying out hydrothermal reaction, and drying a product to obtain a NiMoN @ NC precursor; respectively placing the NiMoN @ NC precursor and the dinitrile amine in two containers, wherein the dinitrile amine is positioned at the upstream, heating to 400-450 ℃ in a mixed atmosphere of hydrogen and argon, keeping the temperature for a set time, subsequently heating to 600-800 ℃, and keeping the temperature for the set time to prepare the NiMoN @ NC catalyst.
Description
Technical Field
The invention relates to the field of catalytic materials, in particular to a transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis and a preparation method thereof.
Background
Cl present in seawater - The interfering ions can cause catalyst poisoning, reduced stability and increased hydrogen evolution overpotential. Therefore, the electrolysis of seawater for Hydrogen Evolution Reaction (HER) puts higher demands on the activity and stability of the catalyst. In recent years, transition metal Ni-based catalysts are widely applied to the field of hydrogen production by alkaline electrolyte, and are artificially and hopefully substituted for noble metal Hydrogen Evolution Reaction (HER) catalysts. Some researches show that when Mo with a semi-filled d orbit is introduced into a Ni-based catalyst, the electronic structure of the catalyst is changed due to the electronic interaction between Ni and Mo, the HER energy barrier is reduced, and the hydrogen evolution activity of the catalyst is greatly improved. In addition, a non-metal N element is introduced into the transition metal catalyst to form the Ni-Mo-N catalyst, so that the stability of the catalyst in different electrolyte environments can be further improved.
The conditions for preparing transition metal nitrides are severe, mainly because nitrogen atoms are inserted into crystal lattices of transition metals, and are thermodynamically unfavorable, the nitrogen atoms are easy to diffuse out of the metal crystal lattices, and the nitridation of metals is relatively difficult. At present, the method for preparing Ni-Mo-N mainly comprises the steps of firstly preparing transition metal oxide Ni-Mo-O and then carrying out high-temperature nitridation in an ammonia atmosphere. This method has a problem that nitriding is incomplete and the catalyst contains an oxide or an elemental metal which is not nitrided.
The other method is that nickel chloride is used as nickel source, ammonium molybdate tetrahydrate is used as molybdenum source, the prepared precursor is stored in ice bath, finally precursor containing Ni and Mo is put in NH 3 Carrying out pyrolysis treatment in an atmosphere to obtain the Ni-Mo-N catalyst. The methodDue to catalyst precursors in NH 3 Nitriding in gas atmosphere, uncontrollable nitriding degree, and certain amount of non-nitrided NiMoO contained in catalyst 4 The activity of the catalyst is reduced. In the preparation process of the transition metal nitride HER catalyst, the control of the nitridation degree is difficult, and other phases with low activity or poor stability can appear due to poor control of the nitridation degree.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a transition metal nitride Ni-Mo-N catalyst for seawater electrolysis hydrogen production and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of a transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis, which comprises the following steps:
cleaning the carbon cloth, and soaking the carbon cloth in dilute sulfuric acid at 70-100 ℃ to obtain pretreated carbon cloth;
dropwise adding a nickel chloride solution into the nitrogen heterocyclic compound solution to ensure that the molar ratio of the nitrogen heterocyclic compound to the nickel chloride is 1.25-0.5, and after the dropwise adding is finished, continuously stirring for reaction to obtain a nitrogen-containing Ni complex;
adding the pretreated carbon cloth into a mixed aqueous solution containing a nitrogen Ni complex and ammonium molybdate, carrying out hydrothermal reaction, and drying a product to obtain a NiMoN @ NC precursor;
putting the NiMoN @ NC precursor and the dinitrile amine into two containers respectively, wherein the dinitrile amine is positioned at the upstream, heating to 400-450 ℃ in a mixed atmosphere of hydrogen and argon, keeping the temperature for a set time, then heating to 600-800 ℃ and keeping the temperature for a set time to prepare the NiMoN @ NC catalyst.
In a second aspect, the invention provides a transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis, which is prepared by the preparation method.
The beneficial effects achieved by one or more of the embodiments of the invention are as follows:
(1) The preparation method of the invention adopts cheap non-noble metal Ni and Mo active components, has simple operation steps, mild preparation conditions, no use of expensive reagents and strong corrosion resistance of metal nitrides, so that the catalyst has the characteristics of low cost, high activity, good stability and the like.
(2) When preparing the nitrogen-containing Ni complex, a heterocyclic compound which contains active hydrogen and amino and has high nitrogen content with the N/C being more than or equal to 2.5 is selected as a ligand. Such as 5-amino-1H-tetrazole (CH) 3 N 5 ) The molecular formula of the Ni-based catalyst contains active hydrogen, and the N/C molar ratio is as high as 5.0 because the nitrogen content is very high, therefore, heterocyclic compounds are combined with metals through the N on the active hydrogen to form a complex, so that the obtained Ni complex with firm combination and high nitrogen content can provide sufficient nitrogen sources for the catalyst, ensure that an N source is firmly combined with a catalyst precursor, form metal nitride through pyrolysis, and improve the stability and the activity of the catalyst. In addition, the amino group in the molecular formula can not only provide nitrogen during pyrolysis, but also regulate and control the pore structure of the catalyst in the high-temperature nitridation process, so that the catalyst forms a hierarchical pore structure, and the charge/mass transfer is promoted, thereby improving the activity of the catalyst.
(3) Dinitrile diamine is used as a secondary nitrogen source, and when nitriding is carried out in an argon atmosphere, a certain amount of hydrogen is added and a segmented temperature programmed nitriding method is adopted, so that sufficient nitriding and reduction of metal in the catalyst are further promoted, the catalyst is ensured not to contain other phases with low activity or poor stability, and the HER stability and activity of the catalyst are further improved.
(4) The cheap and widely-sourced rice husks are used as a seawater pretreatment agent, and microorganisms and solid impurities in seawater are removed, so that the service life of the catalyst is prolonged, the operation is simple, and the cost is low.
(5) The Ni-Mo-N catalyst prepared by the invention and the application method thereof in seawater electrolysis have higher HER activity and higher stability, can be suitable for the actual seawater electrolysis hydrogen production process, and lay a foundation for the industrialization of seawater hydrogen production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a synthesis route diagram of the NiMoN @ NC catalyst in example 2 of the present invention;
FIG. 2 is an SEM image of a NiMoN @ NC catalyst prepared in example 2 of the present invention;
FIG. 3 is an SEM picture of a NiMoN @ NC-No-Ar catalyst prepared in example 2 of the present invention;
FIG. 4 is an XRD pattern of a NiMoN @ NC catalyst prepared in example 2 of the present invention;
FIG. 5 is EIS curves of NiMoN @ NC and NiMoN @ NC-No-Ar catalysts in alkali liquor in example 3 of the present invention;
FIG. 6 is the LSV curves of the NiMoN @ NC, niMoN @ NC-No and NiMoN @ NC-No-Ar catalysts in alkali liquor in example 3 of the present invention;
FIG. 7 is Tafel curves of NiMoN @ NC, niMoN @ NC-No and NiMoN @ NC-No-Ar catalysts in alkali liquor in example 5 of the present invention;
FIG. 8 is the LSV curves of NiMoN @ NC and NiMoN @ NC-No-Ar catalysts in treated seawater of example 5 of the present invention;
FIG. 9 is the Tafel plot of NiMoN @ NC and NiMoN @ NC-No-Ar catalysts in treated seawater of example 5 of the present invention;
FIG. 10 is a comparison of the stability of NiMoN @ NC and NiMoN @ NC-No-Ar catalysts in seawater after treatment.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In a first aspect, the invention provides a preparation method of a transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis, which comprises the following steps:
cleaning the carbon cloth, and soaking the carbon cloth in dilute sulfuric acid at 70-100 ℃ to obtain pretreated carbon cloth;
dropwise adding a nickel chloride solution into the nitrogen heterocyclic compound solution to ensure that the molar ratio of the nitrogen heterocyclic compound to the nickel chloride is 1.25-0.5, and after the dropwise adding is finished, continuously stirring for reaction to obtain a nitrogen-containing Ni complex;
adding the pretreated carbon cloth into a mixed aqueous solution containing a nitrogen Ni complex and ammonium molybdate, carrying out hydrothermal reaction, and drying a product to obtain a NiMoN @ NC precursor;
respectively placing the NiMoN @ NC precursor and the dinitrile amine in two containers, wherein the dinitrile amine is positioned at the upstream, heating to 400-450 ℃ in a mixed atmosphere of hydrogen and argon, keeping the temperature for a set time, subsequently heating to 600-800 ℃, keeping the temperature for a set time, and heating at a rate of 2-5 ℃ for min -1 To obtain the NiMoN @ NC catalyst.
In some embodiments, the carbon cloth is cleaned by soaking in ethanol, then soaking in 0.5-2M hydrochloric acid solution, performing ultrasonic treatment for 0.5-2h, and drying.
In some embodiments, the dilute sulfuric acid has a concentration of 0.3 to 1M, the dilute sulfuric acid is refluxed and the carbon cloth is treated in the refluxed dilute sulfuric acid solution for 2 to 4 hours.
In some embodiments, the nitrogen heterocyclic compound is 5-amino-1H-tetrazole or 3,5-diamino-1,2,4-triazole. The two compounds contain amino and active hydrogen, and have high nitrogen content, and N/C is more than or equal to 2.5.
In some embodiments, the solvent in the nitrogen heterocyclic compound solution and the nickel chloride solution is absolute ethanol. Compared with water as a solvent, the catalyst prepared by using absolute ethyl alcohol as the solvent has better performance and faster reaction speed.
Preferably, after the dropwise addition of the nickel chloride solution is finished, stirring is continued for 10-20min.
In some embodiments, the molar ratio of nickel chloride to ammonium molybdate is 1.
In some embodiments, the temperature of the hydrothermal reaction is 150 to 180 ℃ and the time of the hydrothermal reaction is 3 to 6 hours.
In some embodiments, the hydrogen volume fraction in the mixed atmosphere of hydrogen and argon is 6% to 15%.
In a second aspect, the invention provides a transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis, which is prepared by the preparation method.
Example 1
Synthesis of this nitrogen-containing Ni complex:
1) The nitrogen-containing Ni complex is prepared as follows:
to 20mL of a 0.025mol/L ethanol solution of 5-amino-1H-tetrazole, 20mL of an ethanol solution of nickel chloride was slowly added dropwise with stirring, wherein the molar ratio of the nitrogen heterocyclic compound to the nickel chloride was 1.50. And after the dropwise addition, continuously stirring for 20min to obtain green precipitate, centrifuging, washing and vacuum-drying to obtain the nitrogen-containing Ni complex.
For comparison, (a) the above experiment was carried out with water instead of the solvent absolute ethanol, with the other conditions unchanged; (b) The solvent absolute ethanol was replaced by water with the other conditions being unchanged, while the stirring time was extended to 6h for carrying out the experiment.
2) The experimental results obtained in this example:
in the case of absolute ethanol solvent, when the ethanol solution of nickel chloride is slowly dripped into the ethanol solution of 5-amino-1H-tetrazole, green precipitates are immediately separated out, 0.134g of nitrogen-containing Ni complex is obtained after the reaction is finished, and the yield is 89.4%. Therefore, the reaction time can be shortened by using the absolute ethyl alcohol as a solvent, and the nitrogen-containing Ni complex can be quickly synthesized under the condition of not adding other catalysts.
When water is used as a solvent, slowly dropwise adding the ethanol solution of nickel chloride into the ethanol solution of 5-amino-1H-tetrazole, wherein the color of the solution turns green after dropwise adding the nickel chloride solution, the color gradually deepens along with the increase of the adding amount, stirring is continued for 20 minutes after dropwise adding, no precipitate is generated, and the stirring time is prolonged to 6 hours, and no precipitate is generated. Shows that the metallic nickel in the solution is always Ni within 6h by using water as a solvent +2 In the form which does not react with 5-amino-1H-tetrazole to form a nitrogen-containing Ni complex.
Example 2
This Ni-Mo-N catalyst was prepared by the following method:
1) Preparation of NiMoN @ NC catalyst:
the synthetic route of the NiMoN @ NC catalyst is shown in FIG. 1, and specifically comprises the following steps:
soaking the carbon cloth in ethanol and 1M hydrochloric acid solution in sequence, performing ultrasonic pretreatment for 1h, and drying to remove pollutants on the surface.
Then the carbon cloth is treated by 0.5M sulfuric acid solution at 80 ℃ for 3 hours for standby. To a solution of 20mL of 0.025mol/L3,5-diamino-1,2,4-triazole in ethanol was slowly added dropwise, while stirring, 20mL of an ethanol solution of nickel chloride, wherein the molar ratio of the nitrogen heterocyclic compound to the nickel chloride was 1.25. And (4) after the dropwise addition, continuously stirring for 20min to obtain green precipitate, centrifuging, washing and drying in vacuum to obtain the nitrogen-containing Ni complex.
Adding a nitrogen-containing Ni complex into 80mL of distilled water, then adding ammonium molybdate, mixing, wherein the theoretical molar ratio of nickel chloride to ammonium molybdate is 1.25, transferring the mixed solution into a polytetrafluoroethylene lining reaction kettle, then adding treated carbon cloth, carrying out hydrothermal reaction at 150 ℃ for 6h, cooling to room temperature, taking out the carbon cloth loaded with a catalyst precursor, and drying at 70 ℃ overnight to obtain a NiMoN @ NC precursor for later use;
respectively placing the prepared NiMoN @ NC precursor and 2g of dicyandiamide in two quartz boats, heating the dicyandiamide at the upstream to 450 ℃ in the atmosphere of hydrogen/argon (the hydrogen content is 10%) for 1h, then heating to 700 ℃ for 2h, and heating at the rate of 3 ℃ for min -1 To obtain the NiMoN @ NC catalyst.
For comparison, other conditions are unchanged, and nickel chloride is used for replacing the nitrogen-containing Ni complex when the precursor is prepared; the catalyst prepared by nitriding in an argon atmosphere at the time of nitriding is designated as NiMoN @ NC-No-Ar catalyst.
2) The nimon @ nc catalyst SEM, XRD, TG characterization of the precursor, and impedance EIS characterization obtained in this example:
SEM characterization results for the NiMoN @ NC catalyst obtained in 1) are shown in FIG. 2. The results show that, as can be seen from fig. 2, the catalyst forms a regular strip-shaped morphology on the surface of the carbon cloth, and the particles are uniformly distributed without obvious aggregation phenomenon. In addition, comparative catalyst NiMoN @ NC-N 0 SEM image of-Ar is shown in FIG. 3, the surface NiMoN particles are fewer, and agglomeration phenomenon occurs. It is shown that the process of the invention not only promotes the formation of the active phase, but also helps to obtain a highly dispersed active phase.
For the catalyst obtained in 1) under NiMoN @ NCXRD characterization of the reagent is shown in FIG. 4. As can be seen from fig. 4, the characteristic peak appearing between 20 ° and 30 ° is derived from the graphite carbon peak of the carbon cloth. Peaks at 32.8, 37.2 °, 43.2 ° and 50.4 ° correspond to PDF #29-0931 standard card, typical of Ni 0.2 Mo 0.8 N characteristic peak. Further, the peak appearing at 43.7 ° is Ni 3 Characteristic peak of N (PDF # 10-0280). No observation of NiMoO 4 And characteristic peaks of other phases such as simple substance metal, etc., which show that the catalyst is fully nitrided and reduced, and the main phases are NiMoN and Ni 3 And (4) an N structure.
The TG characterization result of the NiMoN @ NC catalyst precursor shows that the catalyst has two rapid weight loss areas, the first weight loss is the removal of water, and the second weight loss is the decomposition of a ligand, and is near 350-430 ℃. If the temperature of the region is raised too fast, too much N is lost, which results in that the degree of nitridation of the metal cannot be guaranteed. Therefore, the use of the two-stage temperature programming method helps to promote the nitridation of the metal.
Respectively taking NiMoN @ NC and NiMo 3 N@NC-N 0 Ar is a working electrode, a calomel electrode is a reference electrode, a carbon rod electrode is a counter electrode, a three-electrode system is established, and the Nyquist impedance EIS of the NiMoN @ NC catalyst is tested in a 1M KOH solution, and the result is shown in figure 5. As can be seen from FIG. 5, it is similar to NiMo 3 N@NC-N 0 -Ar(R ct =1.1 Ω) has a lower R than that of nimon @ nc ct The value of (0.5 Ω) indicates that the catalyst of the present invention has good electrical conductivity. The amino contained in the nitrogen-containing Ni complex is mainly used for providing nitrogen during pyrolysis to ensure that the catalyst is fully nitrided, and the pore structure of the catalyst can be regulated and controlled in the high-temperature nitriding process to improve the conductivity of the catalyst, so that charge/mass transfer is promoted.
Example 3
The preparation method of the NiMoN @ NC catalyst comprises the following steps:
soaking the carbon cloth in ethanol and 1M hydrochloric acid solution in sequence, performing ultrasonic pretreatment for 1h, and drying to remove pollutants on the surface.
Then the carbon cloth is treated by refluxing with 0.5M sulfuric acid solution at 80 ℃ for 3h for later use. While stirring, slowly dropwise adding 20mL of nickel chloride ethanol solution into 20mL of 0.025mol/L3,5-diamino-1,2,4-triazole (N/C is more than or equal to 2.5), wherein the molar ratio of the nitrogen heterocyclic compound to the nickel chloride is 1.25. And after the dropwise addition, continuously stirring for 15min to obtain green precipitate, centrifuging, washing and vacuum-drying to obtain the nitrogen-containing Ni complex.
Adding a nitrogen-containing Ni complex into 80mL of distilled water, then adding ammonium molybdate, mixing, wherein the theoretical molar ratio of nickel chloride to ammonium molybdate is 1.75, transferring the mixed solution into a polytetrafluoroethylene lining reaction kettle, then adding treated carbon cloth, carrying out hydrothermal reaction at 180 ℃ for 3h, cooling to room temperature, taking out the carbon cloth loaded with a catalyst precursor, and drying at 70 ℃ overnight to obtain a NiMoN @ NC precursor for later use;
respectively placing the prepared NiMoxN @ NC precursor and 2g of dicyandiamide in two quartz boats, heating the dicyandiamide at the upstream to 400 ℃ in the atmosphere of hydrogen/argon (the content of hydrogen is 15 percent), keeping the temperature for 1h, then heating to 700 ℃ and keeping the temperature for 2h, and the heating rate is 3 ℃ for min -1 To obtain the NiMoN @ NC catalyst.
For comparison, the other conditions are not changed, (a) when preparing the precursor, the catalyst prepared by using nickel chloride to replace the nitrogen-containing Ni complex is recorded as NiMoN @ NC-No catalyst; (b) When preparing the precursor, nickel chloride is used for replacing the nitrogen-containing Ni complex; the catalyst prepared by nitriding in an argon atmosphere at the time of nitriding is designated as NiMoN @ NC-No-Ar catalyst.
The HER performance of the NiMoN @ NC catalyst obtained in the embodiment in alkaline solution is as follows:
respectively taking NiMoN @ NC, niMoN @ NC-No and NiMo 3 N@NC-N 0 Ar is used as a working electrode, a calomel electrode is used as a reference electrode, a carbon rod electrode is used as a counter electrode, a three-electrode system is established, and the HER catalytic activity of the NiMoN @ NC catalyst is tested in a 1M KOH solution, and the result is shown in figure 5. As can be seen from FIG. 5, the NiMoN @ NC catalyst is 10mA/cm 2 Overpotential η below 10 70mV with NiMo 3 N@NC-N 0 (η 10 =110 mV) and NiMo 3 N@NC-N 0 -Ar(η 10 =129 mV), the overpotential is reduced by 40mV and 59mV respectively, which shows that the method provided by the invention can obviously improve the HER activity of the catalyst. In other words, under otherwise identical conditions, chlorination is replaced by a nitrogen-containing Ni complexFor nickel, the overpotential decreased by 40mV, and for nitridation with hydrogen/argon instead of argon, the overpotential decreased by 19mV. The Tafel (Tafel) curve is shown in FIG. 6, the Tafel slope of NiMoN @ NC catalyst is only 85mV/dec, which is lower than that of NiMo 3 N@NC-N 0 (97 mV/dec) and NiMo 3 N@NC-N 0 Ar (103 mV/dec), indicating that the prepared catalyst has good catalytic activity.
Example 4
Preparation of NiMoN @ NC catalyst:
soaking the carbon cloth in ethanol and 1M hydrochloric acid solution in sequence, performing ultrasonic pretreatment for 1h, and drying to remove pollutants on the surface.
Then the carbon cloth is treated by 0.5M sulfuric acid solution at 80 ℃ for 3 hours for standby. To 20mL of a 0.025mol/L solution of 3,5-diamino-1,2,4-triazole in ethanol (N/C.gtoreq.2.5) was slowly added dropwise, with stirring, 20mL of a nickel chloride solution in ethanol, wherein the molar ratio of the nitrogen heterocyclic compound to the nickel chloride was 1.25. And (4) after the dropwise addition, continuously stirring for 20min to obtain green precipitate, centrifuging, washing and drying in vacuum to obtain the nitrogen-containing Ni complex.
Adding a nitrogen-containing Ni complex into 80mL of distilled water, then adding ammonium molybdate, mixing, wherein the theoretical molar ratio of nickel chloride to ammonium molybdate is 1.75, transferring the mixed solution into a polytetrafluoroethylene lining reaction kettle, then adding treated carbon cloth, carrying out hydrothermal reaction at 180 ℃ for 3h, cooling to room temperature, taking out the carbon cloth loaded with a catalyst precursor, and drying at 70 ℃ overnight to obtain a NiMoN @ NC precursor for later use;
respectively placing the prepared NiMoxN @ NC precursor and 2g of dicyandiamide in two quartz boats, heating the dicyandiamide at the upstream to 450 ℃ in the atmosphere of hydrogen/argon (the hydrogen content is 10 percent), keeping the temperature for 1h, then heating to 700 ℃ and keeping the temperature for 2h, and the heating rate is 3 ℃ for min -1 To obtain the NiMoN @ NC catalyst.
For comparison, the precursor was prepared using nickel chloride instead of the nitrogen-containing Ni complex, and the resulting precursor was nitrided under an argon atmosphere to prepare a NiMoN @ NC-No-Ar catalyst, with the other conditions being unchanged.
The HER activity and stability of the nimon @ nc catalyst obtained in this example in seawater:
pretreatment of seawater. Using rice husk as raw material, at 750 deg.C N 2 The active carbon is prepared by carbonizing for 2h in the atmosphere, the pretreatment of the seawater contains three layers, the uppermost layer is rice hull active carbon, the middle layer is a Cellulose hydrophilic membrane, and the lowermost layer is a PTFE membrane. The method comprises the steps of taking seawater from the yellow sea, enabling the taken seawater to slowly flow from top to bottom, enabling the seawater to pass through a seawater pretreatment layer, enabling a pretreatment adsorbent to be excited by irradiation of a simulated solar light source, enabling electrons to jump from a valence band to a conduction band, and further carrying out pretreatment on the seawater.
Respectively mixing prepared Ni-Mo-N @ NC and NiMo 3 N@NC-N 0 And inserting an Ar electrode system into the seawater obtained by pretreatment to serve as a working electrode, taking a calomel electrode as a reference electrode, taking a carbon rod electrode as a counter electrode, establishing a three-electrode system, and inspecting the HER activity and stability of the catalyst. The HER catalytic activity of the NiMoN @ NC catalyst is shown in FIG. 7. As can be seen from FIG. 7, the NiMoN @ NC catalyst was 10mA/cm 2 Overpotential η below 10 124mV with NiMo 3 N@NC-N 0 -Ar(η 10 =181 mV), indicating that the method proposed by the present invention can significantly increase HER activity of the catalyst in electrolyzed seawater. The Tafel (Tafel) curve is shown in FIG. 8, the Tafel slope of NiMoN @ NC catalyst is only 155mV/dec, which is much lower than that of NiMoN @ NC-N 0 Ar (250 mV/dec) shows that the catalyst obtained by the method provided by the invention has good catalytic activity.
The stability curve of the catalyst is shown in FIG. 9. As can be seen from the figure, during the test 12h, the NiMoN @ NC catalyst was at a load current of 10mA/cm 2 The corresponding voltage drops only slightly; and NiMoN @ NC-N 0 Ar catalyst, the voltage drop trend is obvious during the test for 12 h. It can be seen that the catalyst obtained by the method provided by the invention has good stability.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis is characterized by comprising the following steps: the method comprises the following steps:
cleaning the carbon cloth, and soaking the carbon cloth in dilute sulfuric acid at 70-100 ℃ to obtain pretreated carbon cloth;
dropwise adding a nickel chloride solution into the nitrogen heterocyclic compound solution to ensure that the molar ratio of the nitrogen heterocyclic compound to the nickel chloride is 1.25-0.5, and after the dropwise adding is finished, continuously stirring for reaction to obtain a nitrogen-containing Ni complex;
adding the pretreated carbon cloth into a mixed aqueous solution containing a nitrogen Ni complex and ammonium molybdate, carrying out hydrothermal reaction, and drying a product to obtain a NiMoN @ NC precursor;
respectively placing the precursor of NiMoN @ NC and dicyandiamide in two containers, heating to 400-450 deg.C in the mixed atmosphere of hydrogen and argon, and maintaining for a set time at a heating rate of 2-5 deg.C for min -1 Then raising the temperature to 600-800 ℃ and keeping the temperature for a set time to prepare the NiMoN @ NC catalyst.
2. The preparation method of the transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis according to claim 1, characterized in that: the carbon cloth cleaning method comprises the steps of soaking in ethanol, then soaking in 0.5-2M hydrochloric acid solution, carrying out ultrasonic treatment for 0.5-2h, and drying.
3. The preparation method of the transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis according to claim 1, characterized in that: the concentration of the dilute sulfuric acid is 0.3-1M, the dilute sulfuric acid is set to be refluxed, and the treatment time of the carbon cloth in the refluxed dilute sulfuric acid solution is 2-4h.
4. The preparation method of the transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis according to claim 1, characterized in that: the nitrogen heterocyclic compound is 5-amino-1H-tetrazole or 3,5-diamino-1,2,4-triazole.
5. The preparation method of the transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis according to claim 1, characterized in that: the solvent in the nitrogen heterocyclic compound solution and the nickel chloride solution is absolute ethyl alcohol.
6. The preparation method of the transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis according to claim 1, characterized in that: and after the dropwise addition of the nickel chloride solution is finished, continuously stirring for 10-20min.
7. The preparation method of the transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis according to claim 1, characterized in that: the molar ratio of nickel chloride to ammonium molybdate is 1.25-0.75.
8. The method for preparing the transition metal nitride Ni-Mo-N catalyst for the hydrogen production by seawater electrolysis according to claim 1, wherein the method comprises the following steps: the temperature of the hydrothermal reaction is 150-180 ℃, and the time of the hydrothermal reaction is 3-6h.
9. The method for preparing the transition metal nitride Ni-Mo-N catalyst for the hydrogen production by seawater electrolysis according to claim 1, wherein the method comprises the following steps: in the mixed atmosphere of hydrogen and argon, the volume fraction of hydrogen is 6-15%.
10. A transition metal nitride Ni-Mo-N catalyst for hydrogen production by seawater electrolysis is characterized in that: prepared by the preparation method of any one of claims 1 to 9.
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