CN111215110A - N-NiMoO4/Ni3N electrode material and preparation method and application thereof - Google Patents
N-NiMoO4/Ni3N electrode material and preparation method and application thereof Download PDFInfo
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- CN111215110A CN111215110A CN202010032065.XA CN202010032065A CN111215110A CN 111215110 A CN111215110 A CN 111215110A CN 202010032065 A CN202010032065 A CN 202010032065A CN 111215110 A CN111215110 A CN 111215110A
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- 229910005809 NiMoO4 Inorganic materials 0.000 title claims abstract description 49
- 239000007772 electrode material Substances 0.000 title claims abstract description 48
- 229910003218 Ni3N Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 170
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 52
- 238000000137 annealing Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000006260 foam Substances 0.000 claims description 15
- 238000000354 decomposition reaction Methods 0.000 claims description 13
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000004070 electrodeposition Methods 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical class C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 239000002073 nanorod Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- 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
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- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
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- 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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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Abstract
The invention provides N-NiMoO4/Ni3The N electrode material is a three-dimensional nano rod-shaped structure taking foamed nickel as a carrier, and nitrogen-doped crystalline NiMoO grows on the carrier4And adhered with crystalline Ni3And N is added. In N-NiMoO4Upper load of Ni3N can greatly improve the conductivity and water adsorption capacity of the material, is favorable for decomposing water to produce hydrogen, and is very goodThe overpotential and energy loss required by hydrogen production are greatly reduced. Meanwhile, the synthetic method is simple, so that the method can be used for large-scale industrial production and has practical application value.
Description
Technical Field
The invention relates to the technical field of hydrogen production and energy by electrocatalysis water decomposition, in particular to N-NiMoO4/Ni3An N electrode material, a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Since the industrial revolution, the human society is rapidly developing, and the use of non-renewable energy resources by human beings is increasing day by day, but the harm caused by the excessive use of non-renewable energy resources is emerging day by day, such as: greenhouse effect, marine pollution, glacier thawing, etc. The potential crisis of energy and the deterioration of ecological environment compel mankind to actively develop new clean energy. Hydrogen energy is taken as a novel energy source with various advantages of safety, reproducibility, high combustion heat value, cleanness, no pollution, no carbon emission and the like, and is considered as the most ideal energy source for replacing non-renewable energy sources, so that the key point for vigorously developing a high-efficiency clean hydrogen production technology is achieved.
The electro-catalytic water splitting hydrogen production is an efficient and pollution-free mode, and when the solution is alkaline, the device and the catalyst are not affected in the electro-catalytic water splitting process. The inventor finds that although transition metal oxides and transition metal hydroxides can promote the electrocatalytic decomposition of water to produce hydrogen, the oxides are poor in conductivity and few in reaction sites, and influence the electrocatalytic decomposition of water under alkaline conditions.
Disclosure of Invention
Therefore, the invention aims to provide N-NiMoO4/Ni3The N electrode material and the preparation method and application thereof adopt a doping strategy and construct a heterojunction to improve the electrical conductivity and the electrocatalytic activity and reduce the voltage required for water decomposition, and have great guiding significance and great industrial value in practical application.
Specifically, the technical scheme of the invention is as follows:
in a first aspect of the invention, the invention provides a N-NiMoO4/Ni3N electrode material, which is a three-dimensional nano rod-shaped structure taking foamed nickel as a carrier, and nitrogen-doped crystalline NiMoO grows on the carrier4And adhered with crystalline Ni3N。
Wherein, N-NiMoO4/Ni3The X-ray diffraction pattern of N is shown in fig. 2 b.
In an embodiment of the invention, the electrode material has N-NiMoO distributed therein4And Ni3Heterojunction interface of N, wherein N is doped into NiMoO4Formation of N-NiMoO4，N-NiMoO4Form NiMoO4Crystal face of (2) with NiMoO4Crystal plane (-112), Ni3The crystal planes (110) and (002) of N are representative of the building heterojunction.
Crystalline N-NiMoO grows in the electrode material4Compared with pure NiMoO4Better solves the problem of conductivity, and in addition, the N-NiMoO4And Ni3N is a lattice stripe to form a heterojunction interface, so that reaction sites on the electrolytic material are obviously increased, and compared with electrode materials such as transition metal oxides, transition metal hydroxides and the like in the prior art, the performance of electrocatalytic decomposition of water to produce hydrogen under an alkaline condition can be effectively improved; in addition, foam nickel is used as a carrier, N-NiMoO4And Ni3N grows on the nano-rod-shaped structure to form a three-dimensional nano-rod-shaped structure, so that more heterojunctions can be exposed, and the activity of the material is further enhanced.
In an embodiment of the present invention, among the electrode materials, NiMoO4And Ni3N is a lattice stripe, and the interplanar spacing thereof is (110)0.237nm, (002)0.214nm and (-112)0.356 nm.
In a second aspect of the invention, the invention provides a N-NiMoO as described in the first aspect above4/Ni3A method of preparing an N-electrode material, comprising:
uniformly mixing a Ni source, a Mo source and deionized water, adding foamed nickel, and performing hydrothermal reaction to obtain the NiMoO-grown alloy4The nickel foam of (4);
the obtained NiMoO grows on4The foam nickel is annealed under the condition of ammonia gas to obtain the NiMoO with nitrogen doping4The nickel foam of (1), wherein the nitrogen is doped with NiMoO4(i.e., N-dot NiMoO)4) Is marked as N-NiMoO4；
To grow N-NiMoO4The foamed nickel is taken as a working electrode, and the nickel salt solution is taken as electrolyte for electrodeposition to obtain N-NiMoO4/Ni(OH)2The nickel foam of (4);
the N-NiMoO obtained by electrodeposition4/Ni(OH)2The foamed nickel is annealed under the condition of ammonia gas to obtain N-NiMoO4/Ni3And (3) N electrode material.
In an embodiment of the invention, the nickel source is selected from nickel salts, preferably nickel nitrate, such as Ni (NO)3)2·6H2O; the molybdenum source is selected from molybdenum salts, preferably ammonium molybdate, such as (NH)4)6Mo7O24·4H2O。
In an embodiment of the invention, the molar ratio of the nickel source to the molybdenum source is between 1:1 and 1.75, preferably 1: 1.75.
In an embodiment of the invention, the concentration of the molybdenum source is 0.2-1 mol/L.
In an embodiment of the present invention, after the Ni source, Mo source and deionized water are mixed uniformly, ammonia is added to make the pH of the solution neutral (pH 7), and then nickel foam is added.
In some embodiments, the nickel foam is preferably used after ultrasonic cleaning in acetone, water, and hydrochloric acid, one after the other.
In some embodiments, the hydrothermal reaction temperature is 130-170 ℃, preferably 150-160 ℃, and the reaction time is 5-7h, further, the hydrothermal reaction temperature is 150 ℃, and the hydrothermal reaction time is 6 h.
In an embodiment of the invention, there is NiMoO grown in said4In the step of annealing the foamed nickel under the ammonia gas condition, the gas flow rate of the ammonia gas is 10 to 40ml/min, and further 20 ml/min.
In some embodiments, the growth has NiMoO4The conditions of the annealing of the foamed nickel in ammonia gas are as follows: heating to 360-400 ℃ under the condition of introducing ammonia gas, preserving heat for 2-4h, wherein the heating rate is 5-15 ℃/min, and then continuing to naturally cool to room temperature in the ammonia gas atmosphere; further, in some embodiments, the annealing conditions are: heating to 380 ℃ under the condition of introducing ammonia gas, preserving heat for 3h, wherein the heating rate is 10 ℃/min, and then continuing to naturally cool to room temperature in the ammonia gas atmosphere.
In the embodiment of the invention, the inventor finds that N-NiMoO has large influence on the performance of the electrode material under the condition that the temperature is heated to 360-400 ℃ at the heating rate of 5-15 ℃/min, then is kept for 2-4 hours, and then is cooled to the room temperature4Better growth on foamed nickel, and N-NiMoO4Has better crystallinity, however, the N-NiMoO is influenced by overhigh or overlow temperature, overlong or insufficient holding time, unstable or excessively fast or excessively slow heating rate and the like4Formation of (D) and crystallinity thereof.
In an embodiment of the present invention, the electrodeposition step is performed to grow N-NiMoO4The foamed nickel is used as a working electrode, the carbon rod is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, and the electrolyte is nickel nitrate solution.
In an embodiment of the present invention, the concentration of the nickel nitrate solution is 0.08 to 0.12mol L-1Preferably 0.1 to 0.12mol L-1Go forward toThe step is 0.1mol L-1。
In an embodiment of the invention, the voltage of the electrodeposition is-0.95 to-1.05V, preferably-1V, the deposition charge is 7-8C, preferably 7C, and the deposition area is 1 x 1cm2。
In an embodiment of the invention, N-NiMoO is added4/Ni(OH)2In the step of annealing the foamed nickel under the ammonia gas condition, the gas flow rate of the ammonia gas is 10 to 40ml/min, and further 20 ml/min.
In an embodiment of the invention, N-NiMoO is added4/Ni(OH)2The conditions of the annealing of the foamed nickel under the ammonia gas condition are as follows: heating to 360-400 ℃ under the condition of introducing ammonia gas, preserving heat for 0.5-1.5h, wherein the heating rate is 5-15 ℃/min, and then continuing to naturally cool to room temperature in the ammonia gas atmosphere; further, in some embodiments, the annealing conditions are: heating to 380 ℃ under the condition of introducing ammonia gas, preserving heat for 1, keeping the heating rate at 10 ℃/min, and then continuing to naturally cool to room temperature in the ammonia gas atmosphere.
Under the condition of the ammonia annealing, the N-NiMoO of the invention is obtained4/Ni3N electrode material, compared with N-NiMoO without ammonia annealing treatment4/Ni(OH)2A large amount of crystalline Ni is formed3N, and with crystalline N-NiMoO4A large number of heterojunction interfaces are formed on the foamed nickel carrier, and the formed heterojunction is more fully exposed, so that the performance and stability of the material are further enhanced, and the material has better conductivity and the performance of electrocatalytic decomposition of water to produce hydrogen under alkaline conditions.
In a third aspect of the invention, the invention provides an electrode comprising the N-NiMoO as defined in the first aspect above4/Ni3And (3) N electrode material.
In a fourth aspect, the present invention also provides the N-NiMoO of the first aspect4/Ni3The N electrode material or the electrode of the third aspect is applied to electrocatalytic decomposition of water to produce hydrogen. N-NiMoO of the invention4/Ni3The N electrode material has a three-dimensional structure consisting of nano rods and has better electrocatalytic decompositionWater activity, in HER, at 10mAcm-2Only 51mV of overpotential is needed under the current of (1), and the Tafel slope is 45.47mV dec-1Reflecting better hydrogen production dynamic performance.
Compared with the prior art, the invention has the beneficial effects that:
1. the synthetic method is simple, and the foam nickel supported N-NiMoO can be obtained by simple hydrothermal, electrodeposition and tubular furnace nitridation methods4/Ni3And (3) N electrode material.
2. The invention is realized by adding N-NiMoO4Upper load of Ni3N can greatly improve the conductivity and water adsorption capacity of the material, is beneficial to the hydrogen production by water decomposition, and greatly reduces the overpotential and energy loss required by the hydrogen production; in particular to the N-NiMoO prepared by the invention4/Ni3The N electrode material has a three-dimensional structure consisting of nano rods, exposes a large number of reaction active sites, and has good electrocatalytic water decomposition activity, conductivity and stability, wherein the molecular weight of the N electrode material in HER is 10mAcm-2Only 51mV of overpotential is needed under the current of (1), and the Tafel slope is 45.47mV dec-1Reflecting better hydrogen production kinetics.
3. The catalyst obtained by the invention has simple preparation process, has great guiding significance for practical application, and has great industrial value.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 shows the NiMoO product of example 1 of the present invention4(a)、N-doped NiMoO4(b)、Ni3N (c) and N-dopedNiMoO4/Ni3SEM picture of N (d-f);
FIG. 2 is an X-ray diffraction pattern of the product of example 1 of the present invention;
FIG. 3 is a diagram of N-NiMoO of the present invention prepared in example 1 of the present invention4/Ni3N electricityTEM images of the pole material;
FIG. 4 is a diagram of N-NiMoO of the present invention prepared in example 1 of the present invention4/Ni3XPS plot of N electrode material;
FIG. 5 shows the inventive N-NiMoO prepared in example 1 of the present invention4/Ni3Lsv (a), tafel (b), exchange current density (c), electrochemically active area (d) and stability (e-f) plots for N electrode materials;
FIG. 6 is a diagram of N-NiMoO of the present invention prepared in example 1 of the present invention4/Ni3Impedance plot of N electrode material.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
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. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
Example 1
Synthesizing N-NiMoO by a method of first hydrothermal, then nitrogen doping, then electrodeposition and finally nitridation4/Ni3N electrode: cutting 2 x 3.5cm2The foamed nickel is then ultrasonically cleaned in acetone, water and 3M hydrochloric acid for 15 minutes respectively for standby. 1.2 mmoleNi (NO)3)2·6H2O and 0.3mmol (NH)4)6Mo7O24·4H2Adding O into 30mL of deionized water, wherein the molar ratio of the Ni source to the Mo source is 12:21, stirring for 30 minutes, adding a certain amount of ammonia water until the pH of the solution is 7.0, stirring for 30 minutes, and addingOne piece of 2 x 3.5cm2The nickel foam of (1). Transferring the mixture into a 40mL autoclave with a polytetrafluoroethylene lining, carrying out hydrothermal treatment for 6h at the temperature of 150 ℃ in an oven, and naturally cooling to room temperature. After cooling, the material was taken out, washed with water and ethanol, and then dried for use. Then NiMoO will grow on4The foamed nickel is placed in a tubular furnace, 20ml/min ammonia gas is introduced, the temperature is raised to 380 ℃ at the speed of 10 ℃/min, the temperature is kept for 3h, and the foamed nickel is naturally cooled to the room temperature in the ammonia gas atmosphere. Will grow with N-NiMoO4The foamed nickel is used as a working electrode, the carbon rod is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, and the electrolyte is 0.1mol L-1Nickel nitrate of (1). In a three-electrode system, an electrochemical workstation is utilized, the deposition is stopped when the deposition electricity quantity is 7C under the voltage of-1V, and the solution is washed and dried for standby. Then N-NiMoO is grown4/Ni(OH)2The foamed nickel is placed in a tubular furnace, 20ml/min ammonia gas is introduced, the temperature is raised to 380 ℃ at the speed of 10 ℃/min, the temperature is kept for 1h, and the foamed nickel is naturally cooled to the room temperature in the ammonia gas atmosphere to obtain N-NiMoO4/Ni3And (3) N electrode material.
It should be noted that, the hydrogen production activity test of electrocatalytic decomposition of water proposed by the present invention is performed by the following method:
the electrocatalytic decomposition water activity test adopts electrochemical Linear Sweep Voltammetry (LSV), and the LSV test is carried out in a three-electrode system in 1M KOH; the performance is compared by comparing the overpotentials under the same current.
Meanwhile, the Tafel slope can be obtained by conversion from data of electrochemical LSV, which reflects the dynamics speed of electrochemical reaction, and the smaller the Tafel slope is, the faster the electro-catalytic hydrogen production dynamics is.
The exchange current density can judge the difficulty of electrode reaction, the electrochemical active area can know the area of electrode material participating in the reaction in the electrode reaction, and long-time CV circulation and I-T test can verify the stability of the material. The resistance test can know the transmission resistance of the current carrier.
FIG. 1 shows the product NiMoO of example 1 of the invention4(a)、N-doped NiMoO4(b)、Ni3N (c) and N-coped NiMoO4/Ni3SEM image of N (d-f), from whichIt is clearly seen that particulate matter was attached to the nanorods.
FIG. 2 shows the X-ray diffraction pattern of the product obtained in this example, and it can be seen that NiMoO4Is crystalline and is corresponding to JCPDS No.33-948, N-NiMoO standard card4Keeps the original shape, Ni3N is crystalline and corresponds to JCPDS No.89-5144, N-NiMoO4/Ni3Not only can find NiMoO in N4The peaks corresponding to the standard cards can also find Ni3N standard card corresponding peak.
FIG. 3 shows the product N-NiMoO obtained in this example4/Ni3TEM image of N electrode material, NiMoO can be seen4And Ni3A lattice fringe of N.
FIG. 4 shows the product N-NiMoO obtained in this example4/Ni3XPS diagram of N electrode material, further proves that N-NiMoO grows4On foamed nickel with Ni3And N is attached.
FIG. 5 shows the product N-NiMoO obtained in this example4/Ni3LSV, Tafel, exchange current density, electrochemical active area and stability diagram of N electrode material, N-NiMoO4/Ni3N has the smallest HER overpotential (at 10 mAcm)-2Only 51mV of overpotential) and Tafel slope (45.47mV dec) were required-1) Exchange current density nearest 0, maximum electrochemically active area (339.42 mFcm)-2) And excellent stability (after 1000 cycles, the performance is not attenuated, and after 3000 cycles, almost no attenuation shows that the stability of the electrode material is good).
FIG. 6 shows the product N-NiMoO obtained in this example4/Ni3Impedance diagram of N electrode material, illustrating N-NiMoO under the same bias4/Ni3The N-impedance is minimal.
Example 2
Synthesizing N-NiMoO by a method of first hydrothermal, then nitrogen doping, then electrodeposition and finally nitridation4/Ni3N electrode: cutting 2 x 3.5cm2The foamed nickel is subjected to ultrasonic cleaning in acetone, water and 3M hydrochloric acid for 15 minutes respectivelyAnd (5) standby. 1.5 mmoleNi (NO)3)2·6H2O and 0.3mmol (NH)4)6Mo7O24·4H2Adding O into 30mL of deionized water, wherein the molar ratio of the Ni source to the Mo source is 5:7, stirring for 30 minutes, adding a certain amount of ammonia water until the pH of the solution is 7.0, stirring for 30 minutes, and adding a piece of 2 x 3.5cm2The nickel foam of (1). Transferring the mixture into a 40mL autoclave with a polytetrafluoroethylene lining, carrying out hydrothermal treatment for 6h at 160 ℃ in an oven, and naturally cooling to room temperature. After cooling, the material was taken out, washed with water and ethanol, and then dried for use. Then NiMoO will grow on4The foamed nickel is placed in a tubular furnace, 20ml/min ammonia gas is introduced, the temperature is raised to 380 ℃ at the speed of 10 ℃/min, the temperature is kept for 3h, and the foamed nickel is naturally cooled to the room temperature in the ammonia gas atmosphere. Will grow with N-NiMoO4The foamed nickel is used as a working electrode, the carbon rod is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, and the electrolyte is 0.12mol L-1Nickel nitrate of (1). In a three-electrode system, an electrochemical workstation is utilized, the deposition is stopped when the deposition electricity quantity is 7C under the voltage of-1V, and the solution is washed and dried for standby. Then N-NiMoO is grown4/Ni(OH)2The foamed nickel is placed in a tubular furnace, 10ml/min ammonia gas is introduced, the temperature is raised to 380 ℃ at the speed of 10 ℃/min, the temperature is kept for 1h, and the foamed nickel is naturally cooled to the room temperature in the ammonia gas atmosphere to obtain N-NiMoO4/Ni3And (3) N electrode material. Compared with the electrode material in the embodiment 1, the electrode material has the advantages of no difference in appearance and equivalent performance except that the rod-shaped structure is slightly thickened.
Example 3
Synthesizing N-NiMoO by a method of first hydrothermal, then nitrogen doping, then electrodeposition and finally nitridation4/Ni3N electrode: cutting 2 x 3.5cm2The foamed nickel is then ultrasonically cleaned in acetone, water and 3M hydrochloric acid for 15 minutes respectively for standby. 2.1 mmoleNi (NO)3)2·6H2O and 0.3mmol (NH)4)6Mo7O24·4H2Adding O into 30mL of deionized water, wherein the molar ratio of the Ni source to the Mo source is 1:1, stirring for 30 minutes, adding a certain amount of ammonia water until the pH of the solution is 7.0, stirring for 30 minutes, and adding a piece of 2 x 3.5cm2Foam ofNickel. Transferring the mixture into a 40mL autoclave with a polytetrafluoroethylene lining, carrying out hydrothermal treatment for 6h at the temperature of 150 ℃ in an oven, and naturally cooling to room temperature. After cooling, the material was taken out, washed with water and ethanol, and then dried for use. Then NiMoO will grow on4The foamed nickel is placed in a tubular furnace, 20ml/min ammonia gas is introduced, the temperature is raised to 380 ℃ at the speed of 10 ℃/min, the temperature is kept for 3h, and the foamed nickel is naturally cooled to the room temperature in the ammonia gas atmosphere. Will grow with N-NiMoO4The foamed nickel is used as a working electrode, the carbon rod is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, and the electrolyte is 0.1mol L-1Nickel nitrate of (1). In a three-electrode system, an electrochemical workstation is utilized, the deposition is stopped when the deposition electricity quantity is 7C under the voltage of-1V, and the solution is washed and dried for standby. Then N-NiMoO is grown4/Ni(OH)2The foamed nickel is placed in a tubular furnace, 20ml/min ammonia gas is introduced, the temperature is raised to 380 ℃ at the speed of 10 ℃/min, the temperature is kept for 1h, and the foamed nickel is naturally cooled to the room temperature in the ammonia gas atmosphere to obtain N-NiMoO4/Ni3And (3) N electrode material. Compared with the electrode material in the embodiment 1, the electrode material has no difference in morphology and has comparable performance.
Example 4
The difference from example 1 is only that no nitrogen doping process, NiMoO is prepared4/Ni3And (3) N electrode material. It has a lattice-striped structure, but compared to example 1, NiMoO4/Ni3The surface of the N nano rod is relatively smooth. In addition, the hydrogen production activity of the electrocatalytic decomposition water is tested according to the method of the example 1, and the result shows that the conductivity is inferior to that of the example 1, the overpotential and the Tafel slope are both larger than those of the example 1, but are better than that of the electrode material Ni3N, the electrochemical active area is much smaller than that of example 1 but better than that of electrode material Ni3N。
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. 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. N-NiMoO4/Ni3N electrode material, which is a three-dimensional nano rod-shaped structure taking foamed nickel as a carrier, and nitrogen-doped crystalline NiMoO grows on the carrier4And adhered with crystalline Ni3N。
2. N-NiMoO according to claim 14/Ni3The N electrode material is characterized in that N-NiMoO is distributed in the electrode material4And Ni3Heterojunction interface of N, wherein N-NiMoO4Crystal face and NiMoO4Crystal plane (-112), Ni3The crystal planes (110) and (002) of N constitute a heterojunction.
3. N-NiMoO according to claim 1 or 24/Ni3N electrode material, characterized in that, in the electrode material, NiMoO4And Ni3N is a lattice stripe, and the interplanar spacing thereof is (110)0.237nm, (002)0.214nm and (-112)0.356 nm.
4. N-NiMoO according to any one of claims 1 to 34/Ni3A method of preparing an N-electrode material, comprising: uniformly mixing a Ni source, a Mo source and deionized water, adding foamed nickel, and performing hydrothermal reaction to obtain the NiMoO-grown alloy4The nickel foam of (4); the obtained NiMoO grows on4The foam nickel is annealed under the condition of ammonia gas to obtain the NiMoO with nitrogen doping4The nickel foam of (1), wherein the nitrogen is doped with NiMoO4Is marked as N-NiMoO4(ii) a To grow N-NiMoO4The foamed nickel is taken as a working electrode, and the nickel salt solution is taken as electrolyte for electrodeposition to obtain N-NiMoO4/Ni(OH)2The nickel foam of (4); the N-NiMoO obtained by electrodeposition4/Ni(OH)2The foamed nickel is annealed under the condition of ammonia gas to obtain N-NiMoO4/Ni3And (3) N electrode material.
5. The method according to claim 4, wherein the nickel source is selected from nickel salts, preferably nickel nitrate; the molybdenum source is selected from molybdenum salts, preferably ammonium molybdate;
preferably, the molar ratio of the nickel source to the molybdenum source is 1:1-1.75, preferably 1: 1.75;
preferably, the concentration of the molybdenum source is 0.2-1 mol/L;
preferably, after the Ni source, the Mo source and the deionized water are uniformly mixed, adding ammonia water to adjust the pH value of the solution to be neutral;
preferably, the hydrothermal reaction temperature is 130-170 ℃, preferably 150-160 ℃, and the reaction time is 5-7 h;
preferably, the temperature of the hydrothermal reaction is 150 ℃ and the time of the hydrothermal reaction is 6 h.
6. The method according to claim 4, wherein NiMoO is grown on the surface of the substrate4In the step of annealing the foamed nickel under the condition of ammonia gas, the gas flow rate of the ammonia gas is 10-40ml/min, and preferably 20 ml/min;
preferably, there is NiMoO in said growth4In the step of annealing the foamed nickel under the ammonia gas condition, the annealing condition is as follows: heating to 360-400 ℃ under the condition of introducing ammonia gas, preserving heat for 2-4h, wherein the heating rate is 5-15 ℃/min, and then continuing to naturally cool to room temperature in the ammonia gas atmosphere;
preferably, there is NiMoO in said growth4In the step of annealing the foamed nickel under the ammonia gas condition, the annealing condition is as follows: heating to 380 ℃ under the condition of introducing ammonia gas, preserving heat for 3h, wherein the heating rate is 10 ℃/min, and then continuing to naturally cool to room temperature in the ammonia gas atmosphere.
7. The method according to claim 4, wherein in the electrodeposition step, N-NiMoO is grown4The foamed nickel is a working electrode, the carbon rod is a counter electrode, the Ag/AgCl electrode is a reference electrode, and the electrolyte is a nickel nitrate solution;
preferably, the concentration of the nickel nitrate solution is 0.08-0.12mol L-1Preferably 0.1 to 0.12mol L-1；
Preferably, the voltage of the electrodeposition is-0.95 to-1.05V, preferably-1V, the deposition electric quantity is 7-8C, preferably 7C, and the deposition area is 1 x 1cm2。
8. The method according to claim 4, wherein N-NiMoO is added4/Ni(OH)2In the step of annealing the foamed nickel under the condition of ammonia gas, the gas flow rate of the ammonia gas is 10-40ml/min, and preferably 20 ml/min;
preferably, the N-NiMoO is added4/Ni(OH)2In the step of annealing the foamed nickel under the ammonia gas condition, the annealing condition is as follows: heating to 360-400 ℃ under the condition of introducing ammonia gas, preserving heat for 0.5-1.5h, wherein the heating rate is 5-15 ℃/min, and then continuing to naturally cool to room temperature in the ammonia gas atmosphere;
preferably, the N-NiMoO is added4/Ni(OH)2In the step of annealing the foamed nickel under the ammonia gas condition, the annealing condition is as follows: heating to 380 ℃ under the condition of introducing ammonia gas, preserving heat for 1, keeping the heating rate at 10 ℃/min, and then continuing to naturally cool to room temperature in the ammonia gas atmosphere.
9. An electrode comprising the N-NiMoO of any one of claims 1 to 34/Ni3And (3) N electrode material.
10. N-NiMoO according to any one of claims 1 to 34/Ni3Use of an N-electrode material or an electrode according to claim 9 for the electrocatalytic decomposition of water to produce hydrogen.
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