CN110841687A - Nickel hydroxide thin layer coated tungsten nitride nanowire composite material and preparation method and application thereof - Google Patents
Nickel hydroxide thin layer coated tungsten nitride nanowire composite material and preparation method and application thereof Download PDFInfo
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- -1 tungsten nitride Chemical class 0.000 title claims abstract description 103
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 102
- 239000010937 tungsten Substances 0.000 title claims abstract description 102
- 239000002070 nanowire Substances 0.000 title claims abstract description 89
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 69
- 239000004917 carbon fiber Substances 0.000 claims description 69
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000009713 electroplating Methods 0.000 claims description 26
- 238000004070 electrodeposition Methods 0.000 claims description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 14
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 14
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000005121 nitriding Methods 0.000 claims 2
- 238000011161 development Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 90
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 238000001816 cooling Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 12
- 235000011130 ammonium sulphate Nutrition 0.000 description 12
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 11
- 238000007865 diluting Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000010411 electrocatalyst Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- 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
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- 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
- C25B11/091—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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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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Abstract
The invention provides a nickel hydroxide thin layer coated tungsten nitride nanowire composite material and a preparation method and application thereof. The preparation process has the advantages of simple flow, easy operation and low cost, and the obtained composite material has improved electrocatalytic performance and has the potential of large-scale application to the development of industrial alkaline electrolyzed water catalysts.
Description
Technical Field
The invention relates to a composite material, in particular to a nickel hydroxide thin layer coated tungsten nitride nanowire composite material and a preparation method and application thereof.
Background
The current society is facing to the serious problems of energy crisis, environmental pollution and the like, and the preparation of hydrogen by electrocatalysis water decomposition is an effective method for solving the current crisis. However, in the actual hydrogen production process by electrocatalytic decomposition of water, the improvement of the water decomposition efficiency is severely restricted by the kinetic obstruction of the hydrogen evolution reaction, so that the search for a high-efficiency hydrogen evolution electrocatalyst becomes the key for improving the efficiency. At present, the platinum group noble metals are recognized as the most efficient hydrogen evolution electrocatalysts, but the wide application of the noble metal materials is greatly limited due to the small amount of the noble metal materials on the earth and high preparation cost. Therefore, there is a need to develop a hydrogen evolution electrocatalyst which is highly efficient, stable, environmentally friendly and inexpensive.
Tungsten nitride, a member of the transition metal nitrides, has metal-like properties, and can ensure rapid transfer of electrons. Meanwhile, nitrogen in the tungsten nitride can adjust the electron concentration around the metal atoms, so that the adsorption and desorption of the metal atoms on reaction intermediates are optimized, and the tungsten nitride has good electrocatalytic hydrogen evolution activity. However, under alkaline conditions, tungsten nitride is limited by low water adsorption and dissociation capacity, resulting in a slow Volmer reaction, the first step reaction of water electrolysis, which in turn affects the overall hydrogen evolution process of alkaline electrolyzed water.
Disclosure of Invention
The invention aims to provide a tungsten nitride nanowire composite material coated by a nickel hydroxide thin layer so as to solve the problems of low water adsorption and dissociation capability and slow Volmer reaction of the existing alkaline electrolyzed water catalyst.
The second purpose of the invention is to provide a preparation method of the tungsten nitride nanowire composite material coated by the nickel hydroxide thin layer.
The invention also aims to provide the application of the nickel hydroxide thin layer coated tungsten nitride nanowire composite material in the aspect of an alkaline hydrogen evolution electrocatalyst.
One of the objects of the invention is achieved by:
a tungsten nitride nanowire composite material coated by a nickel hydroxide thin layer uniformly grows tungsten nitride nanowires on the surface of a substrate to form a self-supporting electrode structure, the nickel hydroxide thin layer is uniformly coated on the surface of the tungsten nitride nanowires, and the thickness of the nickel hydroxide thin layer is 3-7 nm, preferably 4-6 nm, and more preferably 5 nm.
The nickel hydroxide thin layer coated tungsten nitride nanowire composite material is prepared by adopting the following method: firstly, loading a hydrated tungsten oxide nanowire precursor on a substrate; then, carrying out high-temperature nitridation on the hydrated tungsten oxide nanowire precursor in the presence of ammonia gas to obtain a tungsten nitride porous nanowire; and finally, electroplating a nickel hydroxide thin layer on the surface of the tungsten nitride porous nanowire by an electrochemical deposition method to obtain the tungsten nitride nanowire composite material coated by the nickel hydroxide thin layer.
When the nickel hydroxide thin layer coated tungsten nitride nanowire composite material is used as an industrial alkaline electrolytic water catalyst, the current density is 20 mA/cm2The overpotential is 170 to 268 mV, preferably 170 mV.
The second purpose of the invention is realized by the following steps:
a preparation method of a tungsten nitride nanowire composite material coated by a nickel hydroxide thin layer comprises the following steps:
(a) loading a hydrated tungsten oxide nanowire precursor on a substrate;
(b) carrying out high-temperature nitridation on the substrate-loaded hydrated tungsten oxide nanowire precursor obtained in the step (a) in a roasting furnace in an ammonia atmosphere to obtain a substrate-loaded tungsten nitride nanowire;
(c) electroplating a nickel hydroxide thin layer on the surface of the substrate-supported tungsten nitride nanowire obtained in the step (b) by using an electrochemical deposition method to obtain the tungsten nitride nanowire composite material coated by the nickel hydroxide thin layer.
In step (a), the substrate may be selected from substrate materials commonly used in the art, such as carbon fiber paper, nickel foam, copper foam, titanium sheet, and the like, and preferably, carbon fiber paper with a size of 2 × 5 cm is selected2。
In the step (a), a hydrothermal method is adopted, specifically, a hydrothermal synthesis method is adopted to load a hydrated tungsten oxide nanowire precursor on a substrate, the hydrothermal synthesis method can adopt reaction temperature and reaction time known by those skilled in the art, preferably, the reaction temperature is 150-200 ℃, and the reaction time is 6-24 h; more preferably, the reaction temperature is 180 ℃ and the reaction time is 16 h.
The hydrated tungsten oxide nanowire precursor can be synthesized by adopting known raw materials and solvents, preferably, an acidic solution containing tungsten ions is mixed with oxalic acid to obtain a transparent solution, and then ammonium sulfate is dissolved in the solution to obtain a final reaction solution.
Optionally, the acidic solution containing tungsten ions is a solution obtained by dissolving inorganic tungstate in deionized water and then adjusting the pH of the solution to 1.2, wherein the inorganic tungstate is sodium tungstate or ammonium tungstate.
Specifically, sodium tungstate dihydrate is used as a raw material, deionized water is used as a solvent, and the ratio of sodium tungstate dihydrate to deionized water is 12.5 mmol: 100 mL of the solution is prepared, hydrochloric acid is added dropwise to adjust the pH value of the solution to 1.2, then 35 mmol of oxalic acid dihydrate is dissolved in the solution, the solution is diluted to 250 mL, and finally 12.5 g of ammonium sulfate is added to obtain a colorless transparent solution.
When the hydrated tungsten oxide nanowire precursor is loaded on the substrate, the obtained reaction liquid is transferred into a reaction container, the substrate is placed obliquely close to the wall, and a hydrothermal synthesis reaction is carried out at a set temperature.
In the step (b), the reaction temperature of the high-temperature nitridation is preferably 500-800 ℃, and more preferably 600-700 ℃.
The time of the high-temperature nitridation is preferably 30-180 min, and more preferably 60-120 min.
In the step (c), a three-electrode system is adopted for electrochemical deposition, specifically, a tungsten nitride nanowire composite material coated by a nickel hydroxide thin layer loaded on a substrate is used as a working electrode, platinum is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, 0.1 moL/L of nickel nitrate solution is used as electroplating solution, the constant potential is-1V, and the electroplating time is preferably 200-600 s.
The third purpose of the invention is realized by the following steps:
the nickel hydroxide thin layer coated tungsten nitride nanowire composite material is applied to industrial electrolytic water catalysts, particularly the field of alkaline hydrogen evolution electrocatalysis.
When the nickel hydroxide thin layer coated tungsten nitride nanowire composite material is used as an industrial alkaline electrolytic water catalyst, the current density is 20 mA/cm2The overpotential is 170 to 268 mV, preferably 170 mV.
According to the invention, a hydrated tungsten oxide nanowire precursor is loaded on a substrate through a solvothermal reaction, the hydrated tungsten oxide nanowire precursor is subjected to high-temperature nitridation in ammonia gas, and then a nickel hydroxide thin layer-coated tungsten nitride nanowire composite material is obtained through electrochemical deposition, wherein tungsten nitride nanowires in the obtained composite material grow on the surface of the substrate, and the surface of the tungsten nitride nanowires is uniformly coated by the nickel hydroxide thin layer. The composite material is beneficial to enhancing the water adsorption and dissociation capability of the surface of the tungsten nitride, accelerating the Volmer reaction process, effectively accelerating the electron transfer rate of the internal tungsten nitride, improving the hydrogen evolution activity of the catalyst and improving the electrocatalytic performance.
The preparation process of the composite material is simple, easy to operate, low in cost and easy to carry out large-scale production, and has the potential of large-scale application for the development of industrial alkaline electrolyzed water catalysts.
Drawings
FIG. 1 is an XRD spectrum of the sample prepared in example 1 and carbon fiber paper and tungsten nitride standard samples.
Fig. 2 is an XPS chart of a sample prepared in example 1.
Fig. 3 is an SEM image of the sample prepared in example 1.
Fig. 4 is a TEM image of the sample prepared in example 1.
FIG. 5 is an XRD spectrum of the sample prepared in comparative example 1 and carbon fiber paper and tungsten nitride standard samples.
Fig. 6 is an XPS chart of the sample prepared in comparative example 1.
Fig. 7 is an SEM image of the sample prepared in comparative example 1.
Fig. 8 is a TEM image of the sample prepared in comparative example 1.
FIG. 9 is a polarization curve of samples prepared in examples 1-9 and comparative example 1.
FIG. 10 is the Tafel slope for the samples prepared in example 1, comparative example 1.
Detailed Description
The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.
Procedures and methods not described in detail in the following examples are conventional methods well known in the art, and the reagents used in the examples are either analytically or chemically pure and are either commercially available or prepared by methods well known to those of ordinary skill in the art. The following examples all achieve the objects of the present invention.
Example 1
Dissolving 2.5mmol of sodium tungstate dihydrate in 20 mL of deionized water to obtain a colorless transparent solution, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1.2 to obtain a light yellow solution, then adding 7 mmol of oxalic acid dihydrate into the solution, diluting the solution to 50 mL, and adding 2.5 g of ammonium sulfate to obtain a colorless transparent solution. Transferring the mixed solution into a reaction kettle, and simultaneously transferring carbon fiber paper (2 multiplied by 5 cm)2) Placing the carbon fiber paper obliquely against the wall, heating to 180 ℃, reacting for 16 h, then naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and drying in vacuum at 60 ℃ for 12 h. And (3) placing the sample in a tube furnace, heating to 700 ℃ at a speed of 5 ℃/min under ammonia gas (with a flow rate of 60 sccm), keeping the temperature for 120 min, and naturally cooling to room temperature to obtain the carbon fiber paper loaded tungsten nitride nanowire.
Electrochemical deposition: a three-electrode system is adopted, the carbon fiber paper loaded tungsten nitride nanowire is used as a working electrode, platinum is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, 0.1 moL/L nickel nitrate solution is used as electroplating solution, the electrodeposition potential is-1V, and the electroplating time is 400 s, so that the nickel hydroxide thin layer coated tungsten nitride nanowire composite material is obtained.
The prepared material is characterized, and the obtained results are shown in figures 1-4. As can be seen from FIG. 1, the tungsten nitride phase in the prepared nickel hydroxide thin-layer-coated tungsten nitride nanowire composite material is identical to WN 65-2898 of JCPDS cards, and no nickel hydroxide peak exists in the sample, which indicates that nickel hydroxide exists in an amorphous state; as can be seen from FIG. 2, the nickel element in the composite material is Ni (OH)2The form exists. As can be seen from FIGS. 3 to 4, the obtained composite material is uniformly loaded on the carbon fiber paper, the composite material is in a nanowire structure, the surface of the tungsten nitride nanowire is uniformly wrapped with a nickel hydroxide thin layer, and the thickness of the nickel hydroxide thin layer is about 5 nm.
Comparative example 1
Dissolving 2.5mmol of sodium tungstate dihydrate in 20 mL of deionized water to obtain a colorless transparent solution, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1.2 to obtain a light yellow solution, then adding 7 mmol of oxalic acid dihydrate into the solution, diluting the solution to 50 mL, and adding 2.5 g of ammonium sulfate to obtain a colorless transparent solution. Transferring the mixed solution into a reaction kettle, and simultaneously transferring carbon fiber paper (2 multiplied by 5 cm)2) Placing the carbon fiber paper obliquely against the wall, heating to 180 ℃, reacting for 16 h, then naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and drying in vacuum at 60 ℃ for 12 h. And (3) placing the sample in a tube furnace, heating to 700 ℃ at a speed of 5 ℃/min under ammonia gas (with a flow rate of 60 sccm), keeping the temperature for 120 min, and naturally cooling to room temperature to obtain the carbon fiber paper loaded tungsten nitride nanowire.
The prepared material is characterized, and the obtained result is shown in figures 5-8. As can be seen from FIG. 5, the tungsten nitride phase in the prepared carbon fiber paper-loaded tungsten nitride nanowire is identical to WN 65-2898 of JCPDS cards. As can be seen from fig. 6, the obtained material is a nanowire-like structure and is uniformly loaded on the carbon fiber paper. As can be seen from fig. 7, the tungsten nitride nanowire is a porous structure. As can be seen from fig. 8, no Ni element is present in the composite material.
Example 2
Dissolving 2.5mmol of sodium tungstate dihydrate in 20 mL of deionized water to obtain a colorless transparent solution, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1.2 to obtain a light yellow solution, then adding 7 mmol of oxalic acid dihydrate into the solution, diluting the solution to 50 mL, and adding 2.5 g of ammonium sulfate to obtain a colorless transparent solution. Transferring the mixed solution into a reaction kettle, and simultaneously transferring carbon fiber paper (2 multiplied by 5 cm)2) Placing the carbon fiber paper obliquely against the wall, heating to 180 ℃, reacting for 16 h, then naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and drying in vacuum at 60 ℃ for 12 h. And (3) placing the sample in a tube furnace, heating to 500 ℃ at the speed of 5 ℃/min under ammonia gas (the flow rate is 60 sccm), keeping the temperature for 120 min, and naturally cooling to room temperature to obtain the carbon fiber paper loaded tungsten nitride nanowire.
Electrochemical deposition: a three-electrode system is adopted, the carbon fiber paper loaded tungsten nitride nanowire is used as a working electrode, platinum is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, 0.1 moL/L nickel nitrate solution is used as electroplating solution, the electrodeposition potential is-1V, and the electroplating time is 400 s, so that the nickel hydroxide thin layer coated tungsten nitride nanowire composite material is obtained.
Example 3
Dissolving 2.5mmol of sodium tungstate dihydrate in 20 mL of deionized water to obtain a colorless transparent solution, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1.2 to obtain a light yellow solution, then adding 7 mmol of oxalic acid dihydrate into the solution, diluting the solution to 50 mL, and adding 2.5 g of ammonium sulfate to obtain a colorless transparent solution. Transferring the mixed solution into a reaction kettle, and simultaneously transferring carbon fiber paper (2 multiplied by 5 cm)2) Placing the carbon fiber paper obliquely against the wall, heating to 180 ℃, reacting for 16 h, then naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and drying in vacuum at 60 ℃ for 12 h. And (3) placing the sample in a tube furnace, heating to 600 ℃ at the speed of 5 ℃/min under ammonia gas (the flow rate is 60 sccm), keeping the temperature for 120 min, and naturally cooling to room temperature to obtain the carbon fiber paper loaded tungsten nitride nanowire.
Electrochemical deposition: a three-electrode system is adopted, the carbon fiber paper loaded tungsten nitride nanowire is used as a working electrode, platinum is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, 0.1 moL/L nickel nitrate solution is used as electroplating solution, the electrodeposition potential is-1V, and the electroplating time is 400 s, so that the nickel hydroxide thin layer coated tungsten nitride nanowire composite material is obtained.
Example 4
Dissolving 2.5mmol of sodium tungstate dihydrate in 20 mL of deionized water to obtain a colorless transparent solution, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1.2 to obtain a light yellow solution, then adding 7 mmol of oxalic acid dihydrate into the solution, diluting the solution to 50 mL, and adding 2.5 g of ammonium sulfate to obtain a colorless transparent solution. Transferring the mixed solution into a reaction kettle, and simultaneously transferring carbon fiber paper (2 multiplied by 5 cm)2) Placing the carbon fiber paper obliquely against the wall, heating to 180 ℃, reacting for 16 h, then naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and drying in vacuum at 60 ℃ for 12 h. Placing the sample in a tube furnace, heating to 800 deg.C at 5 deg.C/min under ammonia gas (flow rate of 60 sccm), maintaining for 120 min, and naturally standingAnd cooling to room temperature to obtain the carbon fiber paper loaded tungsten nitride nanowire.
Electrochemical deposition: a three-electrode system is adopted, the carbon fiber paper loaded tungsten nitride nanowire is used as a working electrode, platinum is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, 0.1 moL/L nickel nitrate solution is used as electroplating solution, the electrodeposition potential is-1V, and the electroplating time is 400 s, so that the nickel hydroxide thin layer coated tungsten nitride nanowire composite material is obtained.
Example 5
Dissolving 2.5mmol of sodium tungstate dihydrate in 20 mL of deionized water to obtain a colorless transparent solution, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1.2 to obtain a light yellow solution, then adding 7 mmol of oxalic acid dihydrate into the solution, diluting the solution to 50 mL, and adding 2.5 g of ammonium sulfate to obtain a colorless transparent solution. Transferring the mixed solution into a reaction kettle, and simultaneously transferring carbon fiber paper (2 multiplied by 5 cm)2) Placing the carbon fiber paper obliquely against the wall, heating to 180 ℃, reacting for 16 h, then naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and drying in vacuum at 60 ℃ for 12 h. And (3) placing the sample in a tube furnace, heating to 700 ℃ at a speed of 5 ℃/min under ammonia gas (with a flow rate of 60 sccm), keeping the temperature for 30 min, and naturally cooling to room temperature to obtain the carbon fiber paper loaded tungsten nitride nanowire.
Electrochemical deposition: a three-electrode system is adopted, the carbon fiber paper loaded tungsten nitride nanowire is used as a working electrode, platinum is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, 0.1 moL/L nickel nitrate solution is used as electroplating solution, the electrodeposition potential is-1V, and the electroplating time is 400 s, so that the nickel hydroxide thin layer coated tungsten nitride nanowire composite material is obtained.
Example 6
Dissolving 2.5mmol of sodium tungstate dihydrate in 20 mL of deionized water to obtain a colorless transparent solution, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1.2 to obtain a light yellow solution, then adding 7 mmol of oxalic acid dihydrate into the solution, diluting the solution to 50 mL, and adding 2.5 g of ammonium sulfate to obtain a colorless transparent solution. Transferring the mixed solution into a reaction kettle, and simultaneously transferring carbon fiber paper (2 multiplied by 5 cm)2) Placing the carbon fiber paper obliquely against the wall, heating to 180 ℃, reacting for 16 h, naturally cooling, taking out the carbon fiber paper and using deionized waterWashing with water, and vacuum drying at 60 deg.C for 12 hr. And (3) placing the sample in a tube furnace, heating to 700 ℃ at a speed of 5 ℃/min under ammonia gas (with a flow rate of 60 sccm), keeping the temperature for 60 min, and naturally cooling to room temperature to obtain the carbon fiber paper loaded tungsten nitride nanowire.
Electrochemical deposition: a three-electrode system is adopted, the carbon fiber paper loaded tungsten nitride nanowire is used as a working electrode, platinum is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, 0.1 moL/L nickel nitrate solution is used as electroplating solution, the electrodeposition potential is-1V, and the electroplating time is 400 s, so that the nickel hydroxide thin layer coated tungsten nitride nanowire composite material is obtained.
Example 7
Dissolving 2.5mmol of sodium tungstate dihydrate in 20 mL of deionized water to obtain a colorless transparent solution, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1.2 to obtain a light yellow solution, then adding 7 mmol of oxalic acid dihydrate into the solution, diluting the solution to 50 mL, and adding 2.5 g of ammonium sulfate to obtain a colorless transparent solution. Transferring the mixed solution into a reaction kettle, and simultaneously transferring carbon fiber paper (2 multiplied by 5 cm)2) Placing the carbon fiber paper obliquely against the wall, heating to 180 ℃, reacting for 16 h, then naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and drying in vacuum at 60 ℃ for 12 h. And (3) placing the sample in a tube furnace, heating to 700 ℃ at a speed of 5 ℃/min under ammonia gas (with a flow rate of 60 sccm), keeping the temperature for 180 min, and naturally cooling to room temperature to obtain the carbon fiber paper loaded tungsten nitride nanowire.
Electrochemical deposition: a three-electrode system is adopted, the carbon fiber paper loaded tungsten nitride nanowire is used as a working electrode, platinum is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, 0.1 moL/L nickel nitrate solution is used as electroplating solution, the electrodeposition potential is-1V, and the electroplating time is 400 s, so that the nickel hydroxide thin layer coated tungsten nitride nanowire composite material is obtained.
Example 8
Dissolving 2.5mmol of sodium tungstate dihydrate in 20 mL of deionized water to obtain a colorless transparent solution, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1.2 to obtain a light yellow solution, then adding 7 mmol of oxalic acid dihydrate into the solution, diluting the solution to 50 mL, and adding 2.5 g of ammonium sulfate to obtain a colorless transparent solution. Mixing the mixed solutionTransferring the mixture into a reaction kettle, and simultaneously transferring carbon fiber paper (2 multiplied by 5 cm)2) Placing the carbon fiber paper obliquely against the wall, heating to 180 ℃, reacting for 16 h, then naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and drying in vacuum at 60 ℃ for 12 h. And (3) placing the sample in a tube furnace, heating to 700 ℃ at a speed of 5 ℃/min under ammonia gas (with a flow rate of 60 sccm), keeping the temperature for 120 min, and naturally cooling to room temperature to obtain the carbon fiber paper loaded tungsten nitride nanowire.
Electrochemical deposition: a three-electrode system is adopted, the carbon fiber paper loaded tungsten nitride nanowire is used as a working electrode, platinum is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, 0.1 moL/L nickel nitrate solution is used as electroplating solution, the electrodeposition potential is-1V, and the electroplating time is 200 s, so that the nickel hydroxide thin layer coated tungsten nitride nanowire composite material is obtained.
Example 9
Dissolving 2.5mmol of sodium tungstate dihydrate in 20 mL of deionized water to obtain a colorless transparent solution, dropwise adding hydrochloric acid to adjust the pH value of the solution to 1.2 to obtain a light yellow solution, then adding 7 mmol of oxalic acid dihydrate into the solution, diluting the solution to 50 mL, and adding 2.5 g of ammonium sulfate to obtain a colorless transparent solution. Transferring the mixed solution into a reaction kettle, and simultaneously transferring carbon fiber paper (2 multiplied by 5 cm)2) Placing the carbon fiber paper obliquely against the wall, heating to 180 ℃, reacting for 16 h, then naturally cooling, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water, and drying in vacuum at 60 ℃ for 12 h. And (3) placing the sample in a tube furnace, heating to 700 ℃ at a speed of 5 ℃/min under ammonia gas (with a flow rate of 60 sccm), keeping the temperature for 120 min, and naturally cooling to room temperature to obtain the carbon fiber paper loaded tungsten nitride nanowire.
Electrochemical deposition: a three-electrode system is adopted, the carbon fiber paper loaded tungsten nitride nanowire is used as a working electrode, platinum is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, 0.1 moL/L nickel nitrate solution is used as electroplating solution, the electrodeposition potential is-1V, and the electroplating time is 600 s, so that the nickel hydroxide thin layer coated tungsten nitride nanowire composite material is obtained.
Example 10
The nickel hydroxide thin layer prepared in the examples 1-9 is coated with the tungsten nitride nanowire composite material and the carbon fiber paper negative prepared in the comparative example 1The tungsten nitride nanowire-loaded material is used for alkaline catalytic hydrogen evolution. The samples were electrochemically characterized using an electrochemical workstation and measured using a three-electrode system. The mercury/mercury oxide electrode is used as a reference electrode, the carbon fiber paper loaded tungsten nitride nanowire material or the carbon fiber paper loaded nickel hydroxide thin layer coated tungsten nitride nanowire composite material is used as a working electrode, and 1M KOH is used as electrolyte. The electrochemical performance of the materials prepared in examples 1-9 and comparative example 1 is characterized by scanning the polarization curve, the scanning speed is 5 mV/s, and the test potential is converted into the standard hydrogen electrode potential. The results of the obtained polarization curves are shown in FIG. 9, when the current density is 20 mA/cm2The results of overpotential values for the respective samples are shown in table 1.
TABLE 1 Current Density of 20 mA/cm2Over potential value of each sample
As can be seen from FIG. 9 and Table 1, the nickel hydroxide thin layer coated tungsten nitride nanowire composite material prepared in example 1 has excellent electrocatalytic hydrogen production performance, and when the current density is 20 mA/cm2In the process, the overpotential value is the lowest and is 170 mV, and the composite material obtained in examples 1-9 has excellent performance compared with the pure tungsten nitride nanowire prepared in comparative example 1, which indicates that the nickel hydroxide thin layer uniformly wrapped on the surface of the tungsten nitride is beneficial to greatly improving the electrocatalysis performance.
The Tafel slopes of the samples of example 1 and comparative example 1 obtained from the polarization curve of FIG. 9 are shown in FIG. 10, and it can be seen from the graphs that the Tafel slope of the nickel hydroxide thin layer coated tungsten nitride nanowire composite material prepared in example 1 is 96mV/dec, and the Tafel slope of the tungsten nitride nanowire material prepared in comparative example 1 is 118 mV/dec, both values lie between the Volmer reaction (120 mV/dec) and the Heyrovsky reaction (40 mV/dec), indicating that both follow the Volmer-Heyrovsky reaction mechanism. Meanwhile, the Tafel slope of the tungsten nitride nanowire material prepared in the comparative example 1 is closer to 120mV/dec, which shows that the sample is more limited by Volmer reaction, while the nickel hydroxide thin layer coated tungsten nitride nanowire composite material prepared in the example 1 has a faster Volmer reaction rate, so that the Volmer reaction process of the obtained nickel hydroxide thin layer coated tungsten nitride nanowire composite material is accelerated, and the nickel hydroxide/tungsten nitride composite material with excellent alkaline electrocatalytic performance can be directly prepared by adopting the method provided by the invention.
Claims (10)
1. The tungsten nitride nanowire composite material coated by the nickel hydroxide thin layer is characterized in that tungsten nitride nanowires uniformly grow on a substrate, the nickel hydroxide thin layer is uniformly coated on the surfaces of the tungsten nitride nanowires, and the thickness of the nickel hydroxide thin layer is 3-7 nm.
2. The nickel hydroxide thin layer coated tungsten nitride nanowire composite material as claimed in claim 1, wherein the nickel hydroxide thin layer coated tungsten nitride nanowire composite material is prepared by the following method: firstly, loading a hydrated tungsten oxide nanowire precursor on a substrate; then, performing high-temperature nitridation on the hydrated tungsten oxide nanowire precursor in an ammonia atmosphere to obtain a tungsten nitride nanowire; and finally, electroplating a nickel hydroxide thin layer on the surface of the tungsten nitride nanowire by an electrochemical deposition method to obtain the tungsten nitride nanowire composite material coated by the nickel hydroxide thin layer.
3. The preparation method of the nickel hydroxide thin layer coated tungsten nitride nanowire composite material as claimed in claim 1, characterized by comprising the following steps:
(a) loading a hydrated tungsten oxide nanowire precursor on a substrate;
(b) performing high-temperature nitridation on the substrate-loaded hydrated tungsten oxide nanowire precursor obtained in the step (a) in an ammonia atmosphere to obtain a substrate-loaded tungsten nitride nanowire;
(c) electroplating a nickel hydroxide thin layer on the surface of the substrate-supported tungsten nitride nanowire obtained in the step (b) by using an electrochemical deposition method to obtain the tungsten nitride nanowire composite material coated by the nickel hydroxide thin layer.
4. The method for preparing the nickel hydroxide thin layer coated tungsten nitride nanowire composite material according to claim 3, wherein in the step (a), the substrate is carbon fiber paper, foamed nickel, foamed copper or titanium sheet.
5. The method for preparing the nickel hydroxide thin-layer-coated tungsten nitride nanowire composite material according to claim 3, wherein in the step (a), a hydrated tungsten oxide nanowire precursor is loaded on the substrate by a solvothermal method.
6. The method for preparing the nickel hydroxide thin layer coated tungsten nitride nanowire composite material according to claim 5, wherein a solvent in the solvothermal method is water, the reaction temperature is 150-200 ℃, and the reaction time is 6-24 hours.
7. The method for preparing the nickel hydroxide thin layer coated tungsten nitride nanowire composite material according to claim 3, wherein in the step (b), the nitriding temperature is 500-800 ℃, and the nitriding time is 30-180 min.
8. The method for preparing the nickel hydroxide thin layer coated tungsten nitride nanowire composite material according to claim 3, wherein in the step (c), the electrochemical deposition adopts a three-electrode system, the nickel hydroxide thin layer coated tungsten nitride nanowire composite material is used as a working electrode, a platinum sheet is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, a nickel nitrate solution is used as an electroplating solution, and the electroplating time is 200-600 s.
9. The use of the nickel hydroxide thin layer coated tungsten nitride nanowire composite material of claim 1 in the field of industrial alkaline electrolytic water catalysts.
10. The application of the nickel hydroxide thin-layer-coated tungsten nitride nanowire composite material in the field of industrial alkaline electrolytic water catalysts according to claim 8, characterized in that when the current density is 20 mA/cm2The overpotential is 170-268 mV.
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