CN118109865A - Ternary NiFeX self-supporting electrode and preparation method and application thereof - Google Patents
Ternary NiFeX self-supporting electrode and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000004767 nitrides Chemical class 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 238000005121 nitriding Methods 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 105
- 229910052759 nickel Inorganic materials 0.000 claims description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 16
- 239000006260 foam Substances 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000002073 nanorod Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000003624 transition metals Chemical group 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000013077 target material Substances 0.000 claims 1
- 238000007740 vapor deposition Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 64
- 239000003054 catalyst Substances 0.000 abstract description 59
- 238000005868 electrolysis reaction Methods 0.000 abstract description 25
- 238000012546 transfer Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 abstract description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract description 2
- 239000004202 carbamide Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 31
- 229910021641 deionized water Inorganic materials 0.000 description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 22
- 238000001035 drying Methods 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 11
- 238000001132 ultrasonic dispersion Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000000840 electrochemical analysis Methods 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 235000015393 sodium molybdate Nutrition 0.000 description 5
- 239000011684 sodium molybdate Substances 0.000 description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- -1 transition metal nitrides Chemical class 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention relates to the field of full-water electrolysis, in particular to a ternary NiFeX self-supporting electrode, a preparation method and application thereof. According to the preparation method of the ternary NiFeX self-supporting electrode, provided by the invention, defects and N are introduced and nitride is formed simultaneously through nitriding treatment, the adsorption capacity of an intermediate is optimized, the density of active sites is improved, the charge transfer capacity and the bubble diffusion capacity are promoted, the promotion of the full-water electrolysis performance is promoted, excellent performance is also shown on a battery, namely, the high current density is realized under low cell voltage, and the commercial application prospect of an alkaline AEM electrolytic cell is greatly improved. The hydrothermal synthesis method without urea and ammonium fluoride is adopted, so that on one hand, the experimental safety is greatly improved, on the other hand, the method is simple in process, safe to operate, simple and easily available in raw materials, low in cost and easy for mass production, and can provide the high-efficiency and stable full-water electrolysis hydrogen production bifunctional catalyst.
Description
Technical Field
The invention relates to the field of full-water electrolysis, in particular to a ternary NiFeX self-supporting electrode, a preparation method and application thereof.
Background
Due to the high energy density (142 MJ kg -1) and nuisance free use, hydrogen (H 2) plays an increasingly important role as an ideal energy source (Nature energy.3 (2018) 773-782). The electrolyzed water may utilize electrical energy generated from waste heat or coupled with renewable but intermittent energy to achieve the production of high purity hydrogen. The non-noble metal-based catalyst can greatly reduce the cost of water electrolysis, thereby further reducing the hydrogen production cost.
NiFe-based catalysts have great research prospects in alkaline all-water electrolysis, few achieve performance approaching or even superior to commercial noble metals in three-electrode systems, but their performance expression on alkaline AEM cells is limited, i.e. they still have problems in terms of practical and industrial applications. On the one hand, the intrinsic activity is to be further improved, and on the other hand, the mass transfer and bubble diffusion rates in the electrolytic cell are to be optimized.
Ternary NiFe-based catalysts are widely used in the electrolytic water hydrogen-evolution reaction HER (hydrogen evolution reaction) and oxygen-evolution reaction OER (oxygen evolution reaction), but it is generally difficult to achieve both excellent HER and OER catalytic activities, resulting in poor performance in all-water electrolysis, or require the use of a commercial noble metal catalyst as the other polar reaction catalyst to achieve slightly better performance in all-water electrolysis, i.e., their intrinsic activity limits the application in all-water electrolysis. And the effective active site density, mass transfer and bubble diffusion capabilities, etc. of the ternary NiFe-based catalyst also affect the activity of its all-water electrolysis. In addition, in the AEM electrolytic cell device, the performance of the ternary NiFe-based catalyst is more easily limited in consideration of the problems of gas diffusion, AEM membrane mass transfer and the like in a limited space.
Many transition metal nitrides have a metal characteristic of zero band gap, and the filling state changes due to the shrinkage of the d-band of the metal narrowing by the nitriding process. This unique energy band structure can lead to the adjustment and optimization of the bond energy of metal-hydrogen, accelerate charge transfer, and achieve the goal of improving conductivity and catalytic activity (Advanced science.6 (2019) 1801829). The in-situ growth of the catalytic material on the self-supporting electrode can greatly improve the conductivity of the material, and meanwhile, the catalytic material has a large specific surface area, can effectively increase the density of active sites and promote mass transfer, and is beneficial to the rapid diffusion of bubbles. In addition, the introduction of defects is also an effective strategy for improving the intrinsic activity of the catalyst, and the reactants are easier to adsorb and activate by reducing the coordination number of atoms and modifying the electronic structure. By further improving the capacity of charge mass transfer, active site density and bubble diffusion of the ternary NiFe-based catalyst, the performance expression of the ternary NiFe-based catalyst in an AEM electrolytic cell can be effectively improved.
The technical development at the present stage is mainly focused on the full water electrolysis of the NiFe-based self-supporting electrode, the synthesis of the ternary NiFe-based full water electrolysis catalyst is basically realized on the 3D self-supporting electrode, the intrinsic activity of the ternary NiFe-based full water electrolysis catalyst is further improved by introducing defects through pyrolysis in a reducing atmosphere, but the defect introducing mode can only realize the improvement of the activity of a single reaction, and commercial noble metal is still required as another electrode catalyst in the full water electrolysis and an AEM electrolytic cell, so that the hydrogen production cost is still improved. There are few ways to optimize catalytic activity by modulating the metal-hydrogen bond energy through nitrogen doping, and more complex synthetic methods may be required to achieve nitrogen doping on this basis.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a ternary NiFeX self-supporting electrode, and a preparation method and application thereof.
The invention provides a ternary NiFeX self-supporting electrode, which comprises the following components:
A conductive substrate and a Fe-doped NiX nitride nanorod composited on the conductive substrate; the X is selected from transition metals; the atomic mole ratio of Ni, fe and X in the Fe-doped NiX nitride nano rod is (4-9): (0.5-1.4): (3-10).
In particular, the electrically conductive substrate according to the invention is preferably selected from nickel felt, iron felt, titanium felt or foamed nickel. X according to the invention is preferably selected from Co, cr, mn, W, V or Mo. The atomic mole ratio of Ni, fe and X in the Fe-doped NiX nitride nano rod is preferably (4-9): (0.5-1): (3-10).
The invention also provides a preparation method of the ternary NiFeX self-supporting electrode, which comprises the following steps:
S1) carrying out hydrothermal reaction on a conductive substrate in a solution of a Ni source, a Fe source and an X source; the X is selected from transition metals;
s2) nitriding the product obtained in the step S1) to obtain the ternary NiFeX self-supporting electrode.
The inventor creatively discovers that by nitriding the ternary NiFeX precursor on the conductive substrate, defects and N can be simultaneously introduced to form nitride, and by nitriding the ternary NiFeX precursor with relatively low Fe content, an Fe-doped NiX nitride nano rod array can be formed on the conductive substrate, so that excellent full-water electrolysis performance is realized. The proportion of Ni in the Ni source, fe in the Fe source, X in the X source and solvent in the solution is (4-9) mmol: (0.5-1.4) mmol: (3-10) mmol: (15-80) mL. Preferably, the ratio of Ni in the Ni source, fe in the Fe source, X in the X source and solvent in the solution is (4-9) mmol: (0.5-1) mmol: (3-10) mmol: (15-80) mL.
The invention firstly carries out hydrothermal reaction on a conductive substrate in a solution of a Ni source, a Fe source and an X source. Specifically, the method comprises the steps of dissolving a Ni source, a Fe source and an X source in water to obtain a solution of the Ni source, the Fe source and the X source; and placing the conductive substrate in the solution of the Ni source, the Fe source and the X source for hydrothermal reaction. More specifically, the invention dissolves Ni source, fe source and X source in water at room temperature, and obtains solution of Ni source, fe source and X source by ultrasonic dispersion; and completely placing the conductive substrate in the solution of the Ni source, the Fe source and the X source for hydrothermal reaction. The temperature of the hydrothermal reaction is 120-180 ℃; the hydrothermal reaction time is 6-10 h. The conductive substrate disclosed by the invention also comprises ultrasonic washing in acetone, 1-6 mol/L HCl and deionized water respectively before hydrothermal reaction. After the hydrothermal reaction, the method further comprises the steps of cleaning and drying the product obtained after the hydrothermal reaction.
The X source is specifically selected from a Co source, a Cr source, a Mn source, a W source, a V source or a Mo source, and is more specifically selected from X chloride, X sulfate, X nitrate, X acetate, X acid salt or metaX acid salt; in certain embodiments of the invention, the X source is selected from sodium molybdate, ammonium molybdate, sodium tungstate, chromium chloride, manganese sulfate, or sodium metavanadate. The Ni source is preferably at least one selected from Ni nitrate, ni chloride, ni acetylacetonate, ni sulfate or Ni acetate; in certain embodiments of the present invention, the Ni source is selected from at least one of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, or nickel acetylacetonate. The Fe source is at least one selected from Fe nitrate, fe chloride, fe acetylacetonate, fe sulfate or Fe acetate; in certain embodiments of the present invention, the Fe source is selected from at least one of iron nitrate, iron chloride, iron sulfate, iron acetate, or iron acetylacetonate. The conductive substrate is selected from nickel felt, iron felt, titanium felt or foam nickel.
After the hydrothermal reaction is carried out, the product obtained after the hydrothermal reaction is nitrided, and the ternary NiFeX self-supporting electrode is obtained. The nitriding process can simultaneously introduce defects and N to form nitride, wherein Ni in a Ni source and X in an X source are nitrided into NiX nitride, and Fe in an Fe source is not nitrided due to the too small content and is doped into the NiX nitride in an atomic mode to replace Ni or X atoms.
The invention carries out the nitridation of the product obtained after the hydrothermal reaction into: calcining a product obtained after the hydrothermal reaction in an ammonia atmosphere; or calcining the product obtained after the hydrothermal reaction in the atmosphere of the mixed gas of ammonia and hydrogen; or mixing and calcining the product obtained after the hydrothermal reaction with the graphite phase C 3N4. Specifically, the product obtained after the hydrothermal reaction is calcined under the atmosphere of ammonia gas or the mixed gas of ammonia gas and hydrogen gas to obtain the ternary NiFeX self-supporting electrode; the volume ratio of the ammonia to the hydrogen in the mixed gas of the ammonia and the hydrogen is (90-95): (5-10). The invention can also mix and calcine the product obtained after the hydrothermal reaction and the graphite phase C 3N4, the graphite phase C 3N4 can decompose nitrogen-rich atomic groups with high activity to nitride metal into nitride, and the ternary NiFeX self-supporting electrode can be obtained. The temperature and time of calcination are the temperature and time of nitriding, and the nitriding temperature is 400-550 ℃; the nitriding time is 1-3.5 h. In certain embodiments of the invention, the calcination is at a rate of 2 to 10 ℃/min.
The invention provides application of the ternary NiFeX self-supporting electrode in hydrogen production by alkaline full-water electrolysis. The invention also provides an electrolytic cell comprising a cathode, an anode and a diaphragm arranged between the cathode and the anode; the cathode and the anode are the ternary NiFeX self-supporting electrode obtained by the technical scheme or the preparation method. In certain embodiments of the invention, the electrolytic cell is an AEM electrolytic cell; the membrane is an AEM mass transfer membrane.
The invention provides a ternary NiFeX self-supporting electrode, and a preparation method and application thereof. According to the preparation method of the ternary NiFeX self-supporting electrode, provided by the invention, defects and N are introduced and nitride is formed simultaneously through nitriding treatment, the adsorption capacity of an intermediate is optimized, the density of active sites is improved, the charge transfer capacity and the bubble diffusion capacity are promoted, the promotion of the full-water electrolysis performance is promoted, excellent performance is also shown on a battery, namely, the high current density is realized under low cell voltage, and the commercial application prospect of an alkaline AEM electrolytic cell is greatly improved. The hydrothermal synthesis method without urea and ammonium fluoride is adopted, so that the experimental safety is greatly improved, the ammonium fluoride has strong corrosiveness and toxicity, corrosive hydrogen fluoride gas is decomposed and released when meeting acid, and ammonia with irritation is released when meeting alkali, toxic corrosive smoke is generated when the ammonia is decomposed by high heat, and waste liquid after hydrothermal treatment is also required to be treated independently, so that the risk of the experimental process is greatly increased. On the other hand, the invention has simple process, safe operation, simple and easily obtained raw materials, low cost and easy mass production, and can provide the high-efficiency and stable full-water electrolysis hydrogen production bifunctional catalyst.
Drawings
FIG. 1 is a scanning electron microscope image of the NiFeMo-N catalyst prepared in example 1;
FIG. 2 is a transmission electron microscopic view of the NiFeMo-N catalyst prepared in example 1;
FIG. 3 is an XRD pattern of the NiFeMo-N catalyst prepared in example 1;
FIG. 4 is a graph of HER versus LSV for an undoped NiFeMo catalyst and a NiFeMo-N catalyst prepared in example 1;
FIG. 5 is a graph of a comparison of two electrode tests of an undoped NiFeMo catalyst and a NiFeMo-N catalyst prepared in example 1;
FIG. 6 is an AEM full water electrolytic polarization curve test of the NiFeMo-N catalyst prepared in example 1;
FIG. 7 is a LSV test chart of HER of the NiFeW-N catalyst prepared in example 2;
FIG. 8 is a LSV test chart of HER of the NiFeCr-N catalyst prepared in example 3;
FIG. 9 is a LSV test chart of HER of NiFeV-N catalyst prepared in example 6;
fig. 10 is a graph of LSV test of HER of NiFeMo-N catalyst obtained in comparative example 1.
Detailed Description
The invention discloses a ternary NiFeX self-supporting electrode, a preparation method and application thereof. Those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
The invention is further illustrated by the following examples:
Example 1
0.6Mmol of nickel nitrate, 0.375mmol of sodium molybdate and 0.075mmol of ferric nitrate nonahydrate are dissolved in 30mL of deionized water, and after ultrasonic dispersion to form a clear solution, transferred to a 50mL hydrothermal kettle. Cutting nickel felt into 1 x 3cm 2, respectively placing in acetone, 2mol/L HCl and deionized water, performing ultrasonic treatment for 10min, and drying at 60deg.C in an oven. And then placing the treated nickel felt in a hydrothermal kettle, reacting for 6 hours at 120 ℃, washing the nickel felt with deionized water, and placing the nickel felt in an oven for drying for 3 hours at 60 ℃. The obtained sample is placed in a tube furnace for NH 3 at 400 ℃ for 1h, the heating rate is 2 ℃/min, and the NiFeMo-N catalyst is obtained after cooling.
SEM characterization, TEM characterization and XRD detection are carried out on the NiFeMo-N catalyst prepared in the example 1, the SEM characterization results are shown in figure 1, and figure 1 is a scanning electron microscope diagram of the NiFeMo-N catalyst prepared in the example 1; the TEM characterization result is shown in FIG. 2, and FIG. 2 is a transmission electron microscope image of the NiFeMo-N catalyst prepared in example 1; the XRD detection results are shown in FIG. 3, and FIG. 3 is an XRD pattern of the NiFeMo-N catalyst prepared in example 1. As can be seen from fig. 1 to 3, the NiFeMo-N catalyst prepared in example 1 is a nanorod structure, which has a heterogeneous interface of a metal phase and a metal nitride, wherein lattice spacing results of the metal phase and the nitride phase show that there is a certain deviation from the values of standard Ni (111) and Ni 3Mo3 N (310), because the doping of Fe replaces Ni or Mo atoms therein, resulting in a certain change of lattice spacing.
Three-electrode and two-electrode electrochemical tests were performed on the NiFeMo-N catalyst after nitrogen doping, which had excellent HER and OER activities and low voltage in the two-electrode system, as shown in FIG. 4 and FIG. 5, FIG. 4 is a HER versus LSV test chart of the NiFeMo catalyst without N doping and the NiFeMo-N catalyst prepared in example 1, and FIG. 5 is a two-electrode test versus chart of the NiFeMo catalyst without N doping and the NiFeMo-N catalyst prepared in example 1. Alkaline AEM full-water electrolytic polarization curve test was performed on the prepared NiFeMo-N, which had a high current density at a low cell pressure, as shown in FIG. 6, and FIG. 6 is an AEM full-water electrolytic polarization curve test of the NiFeMo-N catalyst prepared in example 1.
Example 2
0.375Mmol nickel nitrate, 0.375mmol sodium tungstate and 0.075mmol ferric nitrate nonahydrate are dissolved in 30mL deionized water, and after ultrasonic dispersion to form a clear solution, transferred to a 50mL hydrothermal kettle. Cutting nickel felt into 1 x 3cm 2, respectively placing in acetone, 2mol/L HCl and deionized water, performing ultrasonic treatment for 10min, and drying at 60deg.C in an oven. And then placing the treated nickel felt in a hydrothermal kettle, reacting at 140 ℃ for 8 hours, washing the nickel felt with deionized water, and placing the nickel felt in an oven to dry at 60 ℃ for 3 hours. And (3) placing the obtained sample in a tubular furnace, treating with NH 3 at 450 ℃ for 2 hours, heating at a rate of 2.5 ℃/min, and cooling to obtain the NiFeW-N catalyst.
SEM characterization, three-electrode electrochemical test and alkaline AEM full-water electrolysis test were performed on the NiFeW-N catalyst obtained in example 2, the results are shown in FIG. 7, and FIG. 7 is a LSV test chart of HER of the NiFeW-N catalyst prepared in example 2.
Example 3
1.2Mmol of nickel chloride, 0.9mmol of chromium chloride and 0.15mmol of anhydrous ferric chloride are dissolved in 60mL of deionized water, and after ultrasonic dispersion to form a transparent solution, the transparent solution is transferred into a 100mL hydrothermal kettle. The iron felt is cut into 1 x 6cm 2, then is respectively placed in acetone, 3mol/L HCl and deionized water for ultrasonic treatment for 10min, and then is placed in an oven for drying at 60 ℃. And then placing the treated iron felt in a hydrothermal kettle, reacting for 10 hours at 140 ℃, washing the iron felt with deionized water, and placing the iron felt in an oven for drying for 3 hours at 60 ℃. The obtained sample is placed in a tubular furnace for NH 3 at 500 ℃ for 3 hours, the heating rate is 5 ℃/min, and the NiFeCr-N catalyst is obtained after cooling.
SEM characterization, three-electrode electrochemical test and alkaline AEM full-water electrolysis test were performed on the NiFeCr-N catalyst obtained in example 3, the results are shown in FIG. 8, and FIG. 8 is a LSV test chart of HER of the NiFeCr-N catalyst prepared in example 3.
Example 4
0.675Mmol nickel sulfate, 0.3mmol manganese sulfate and 0.075mmol iron sulfate were dissolved in 30mL deionized water, and after ultrasonic dispersion to form a clear solution, transferred to a 50mL hydrothermal kettle. Cutting the titanium felt into 1 x 3cm 2, respectively placing in acetone, 3mol/L HCl and deionized water, performing ultrasonic treatment for 10min, and placing in an oven for drying at 60 ℃. And then placing the treated titanium felt in a hydrothermal kettle, reacting for 6 hours at 160 ℃, washing the titanium felt with deionized water, and placing the titanium felt in an oven for drying for 3 hours at 60 ℃. The obtained sample is placed in a tubular furnace for NH 3 at 500 ℃ for 3.5 hours, the heating rate is 5 ℃/min, and the NiFeMn-N catalyst is obtained after cooling.
SEM characterization, three-electrode electrochemical test and alkaline AEM full water electrolysis test were performed on NiFeMn-N catalyst obtained in example 4, and the results were similar to example 1.
Example 5
0.675Mmol nickel acetate, 0.375mmol sodium molybdate and 0.075mmol iron acetate were dissolved in 30mL deionized water, and after ultrasonic dispersion to form a clear solution, transferred to a 50mL hydrothermal kettle. The foam nickel is cut into 1 x 3cm 2 and then is respectively placed in acetone, 2mol/L HCl and deionized water for ultrasonic treatment for 10min, and then is placed in an oven for drying at 60 ℃. Then placing the treated foam nickel in a hydrothermal kettle, reacting for 6 hours at 120 ℃, washing the foam nickel with deionized water, and placing in an oven for drying for 3 hours at 60 ℃. The obtained sample is placed in a tube furnace for NH 3 at 400 ℃ for 1h, the heating rate is 2 ℃/min, and the NiFeMo-N catalyst is obtained after cooling.
SEM characterization, three-electrode electrochemical test and alkaline AEM full-water electrolysis test were performed on the NiFeMo-N catalyst obtained in example 5, and the results were similar to example 1.
Example 6
0.6Mmol of nickel acetylacetonate, 0.375mmol of sodium metavanadate and 0.075mmol of ferric acetylacetonate are dissolved in 30mL of deionized water, and after ultrasonic dispersion to form a clear solution, transferred to a50 mL hydrothermal kettle. The foam nickel is cut into 1 x 3cm 2 and then is respectively placed in acetone, 2mol/L HCl and deionized water for ultrasonic treatment for 10min, and then is placed in an oven for drying at 60 ℃. Then placing the treated foam nickel in a hydrothermal kettle, reacting for 8 hours at 140 ℃, washing the foam nickel with deionized water, and placing the foam nickel in an oven for drying for 3 hours at 60 ℃. The obtained sample is placed in a tube furnace for NH 3 at 450 ℃ for 1h, the heating rate is 2.5 ℃/min, and the NiFeV-N catalyst is obtained after cooling.
SEM characterization, three-electrode electrochemical test and alkaline AEM full water electrolysis test were performed on NiFeV-N catalyst obtained in example 6, and the results are shown in FIG. 9, and FIG. 9 is a LSV test chart of HER of NiFeV-N catalyst prepared in example 6.
Example 7
0.675Mmol of nickel chloride, 0.6mmol of sodium metavanadate and 0.15mmol of ferric chloride were dissolved in 30mL of deionized water, and after ultrasonic dispersion to form a clear solution, transferred to a 50mL hydrothermal kettle. Cutting nickel felt into 1 x 3cm 2, respectively placing in acetone, 2mol/L HCl and deionized water, performing ultrasonic treatment for 10min, and drying at 60deg.C in an oven. And then placing the treated nickel felt in a hydrothermal kettle, reacting for 6 hours at 160 ℃, washing the nickel felt with deionized water, and placing the nickel felt in an oven for drying for 3 hours at 60 ℃. The obtained sample is placed in a tubular furnace for NH 3 at 500 ℃ for 2 hours, the heating rate is 5 ℃/min, and the NiFeV-N catalyst is obtained after cooling.
SEM characterization, three-electrode electrochemical test and alkaline AEM total water electrolysis test were performed on NiFeV-N obtained in example 7, and the results were similar to those of example 1.
Example 8
0.525Mmol of nickel sulfate, 0.375mmol of sodium molybdate and 0.0375mmol of ferric sulfate were dissolved in 30mL of deionized water, and after ultrasonic dispersion to form a clear solution, transferred to a 50mL hydrothermal kettle. Cutting nickel felt into 1 x 3cm 2, respectively placing in acetone, 2mol/L HCl and deionized water, performing ultrasonic treatment for 10min, and drying at 60deg.C in an oven. And then placing the treated nickel felt in a hydrothermal kettle, reacting for 10 hours at 180 ℃, washing the nickel felt with deionized water, and placing the nickel felt in an oven for drying for 3 hours at 60 ℃. And (3) placing the obtained sample in a tubular furnace, treating with NH 3 at 550 ℃ for 3 hours, heating at a speed of 5 ℃/min, and cooling to obtain the NiFeMo catalyst.
SEM characterization, three-electrode electrochemical test and alkaline AEM full-water electrolysis test were performed on the NiFeMo catalyst obtained in example 8, and the results were similar to example 1.
Example 9
0.6Mmol of nickel chloride, 0.107mmol of ammonium molybdate and 0.075mmol of ferric chloride are dissolved in 30mL of deionized water, and after ultrasonic dispersion to form a transparent solution, the transparent solution is transferred to a 50mL hydrothermal kettle. The foam nickel is cut into 1 x 3cm 2 and then is respectively placed in acetone, 2mol/L HCl and deionized water for ultrasonic treatment for 10min, and then is placed in an oven for drying at 60 ℃. Then placing the treated foam nickel in a hydrothermal kettle, reacting for 6 hours at 180 ℃, washing the foam nickel with deionized water, and placing in an oven for drying for 3 hours at 60 ℃. The obtained sample is placed in a tube furnace for NH 3/H2 (volume ratio is 5%H 2+95％NH3) treatment for 1h at 450 ℃, the heating rate is 2 ℃/min, and the target catalyst is obtained after cooling.
Comparative example 1
0.6Mmol of nickel nitrate, 0.375mmol of sodium molybdate and 0.225mmol of ferric nitrate nonahydrate were dissolved in 30mL of deionized water, and after ultrasonic dispersion to form a clear solution, transferred to a 50mL hydrothermal kettle. Cutting nickel felt into 1 x 3cm 2, respectively placing in acetone, 2mol/L HCl and deionized water, performing ultrasonic treatment for 10min, and drying at 60deg.C in an oven. Then placing the treated foam nickel in a hydrothermal kettle, reacting for 6 hours at 120 ℃, washing the foam nickel with deionized water, and placing in an oven for drying for 3 hours at 60 ℃. The obtained sample is placed in a tube furnace for NH 3 at 400 ℃ for 1h, the heating rate is 2 ℃/min, and the NiFeMo-N catalyst is obtained after cooling.
The results of the LSV test of HER were shown in FIG. 10 for the NiFeMo-N catalyst obtained in comparative example 1, and FIG. 10 is a graph showing the LSV test of HER for the NiFeMo-N catalyst obtained in comparative example 1. As can be seen from fig. 10, adding more Fe during the feeding in the hydrothermal stage tends to cause uneven surface growth of the hydrothermal precursor, thereby causing a decrease in the performance of the electrolyzed water, and there is substantially no improvement in the performance as compared with the NiFeMo catalyst not subjected to NH 3 treatment.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. A ternary NiFeX self-supporting electrode, comprising:
A conductive substrate;
an Fe-doped NiX nitride nanorod composited on the conductive substrate; the X is selected from transition metals;
The atomic mole ratio of Ni, fe and X in the Fe-doped NiX nitride nano rod is (4-9): (0.5-1.4): (3-10).
2. The ternary NiFeX self-supporting electrode according to claim 1, wherein the atomic molar ratio of Ni, fe and X in said Fe-doped nifx nitride nanorods is (4-9): (0.5-1): (3-10).
3. The ternary NiFeX self-supporting electrode according to claim 1, wherein said conductive substrate is selected from nickel felt, iron felt, titanium felt or nickel foam;
the X is Co, cr, mn, W, V or Mo.
4. The preparation method of the ternary NiFeX self-supporting electrode is characterized by comprising the following steps of:
S1) carrying out hydrothermal reaction on a conductive substrate in a solution of a Ni source, a Fe source and an X source; the X source is selected from transition metal sources; the ratio of Ni in the Ni source, fe in the Fe source, X in the X source and solvent in the solution is (4-9) mmol: (0.5-1.4) mmol: (3-10) mmol: (15-80) mL;
s2) nitriding the product obtained in the step S1) to obtain the ternary NiFeX self-supporting electrode.
5. The method according to claim 4, wherein in step S1), the ratio of Ni in the Ni source, fe in the Fe source, X in the X source and the solvent in the solution is (4 to 9) mmol: (0.5-1) mmol: (3-10) mmol: (15-80) mL.
6. The method of claim 4, wherein in step S1), the conductive substrate is selected from nickel felt, iron felt, titanium felt, or foam nickel;
the X source is selected from a Co source, a Cr source, a Mn source, a W source, a V source or a Mo source.
7. The method according to claim 4, wherein in step S1), the temperature of the hydrothermal reaction is 120 to 180 ℃; the hydrothermal reaction time is 6-10 h.
8. The method according to claim 4, wherein in step S2), nitriding the product obtained in step S1) is specifically: calcining the product obtained in the step S1) in an ammonia atmosphere;
or calcining the product obtained in the step S1) in the atmosphere of the mixed gas of ammonia and hydrogen;
or taking graphite phase C 3N4 as a target material to carry out vapor deposition on the product obtained in the step S1).
9. The method according to claim 4, wherein in step S2), the nitriding temperature is 400 to 550 ℃; the nitriding time is 1-3.5 h.
10. An electrolytic cell comprising a cathode, an anode, and a separator disposed between the cathode and the anode;
The cathode and the anode are the ternary NiFeX self-supporting electrode obtained by the preparation method of any one of claims 1 to 3 or the ternary NiFeX self-supporting electrode obtained by the preparation method of any one of claims 4 to 8.
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