CN117070990A - Ru/CoP/CC composite nanowire array electrocatalyst and preparation method and application thereof - Google Patents
Ru/CoP/CC composite nanowire array electrocatalyst and preparation method and application thereof Download PDFInfo
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- 239000002070 nanowire Substances 0.000 title claims abstract description 73
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 239000004744 fabric Substances 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 12
- 239000012498 ultrapure water Substances 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004202 carbamide Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 229910017855 NH 4 F Inorganic materials 0.000 claims abstract description 5
- 238000011010 flushing procedure Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims description 7
- 238000003491 array Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention belongs to the technical field of electrocatalysts, and particularly discloses a Ru/CoP/CC composite nanowire array electrocatalyst, and a preparation method and application thereof, wherein the preparation method comprises the following steps: ultrasonic washing carbon cloth in nitric acid, ultrasonic washing in ultrapure water and ethanol, and baking for later use; co (NO) 3 ) 2 ·6H 2 O、NH 4 F. Mixing urea in ultrapure water to obtain a transparent solution, and carrying out hydrothermal reaction on the carbon cloth subjected to ultrasonic treatment and the transparent solution at 120-180 ℃ for 6-10 hours; taking out and cooling, repeatedly flushing with deionized water and ethanol, and preserving heat at 50-70 ℃ for 0.5-1.5h to obtain a nanowire array precursor; cl is added 3 H 2 Uniformly dripping ORu on a nanowire array precursor, and vacuum-maintaining at 60-80 ℃ to obtain a Ru/CoOH/CC composite nanowire array; respectively placing a phosphorus source and a Ru/CoOH/CC composite nanowire array at the upwind direction and downwind direction positions of a tube furnace; at H 2 Heating reaction in Ar and then in Ar 2 And (3) cooling to obtain the Ru/CoP/CC composite nanowire array electrocatalyst.
Description
Technical Field
The invention belongs to the technical field of electrocatalysts, and particularly relates to a Ru/CoP/CC composite nanowire array electrocatalyst, and a preparation method and application thereof.
Background
In recent years, there is an urgent need to explore renewable and sustainable clean energy sources such as solar energy, hydrogen energy, wind energy, etc., and hydrogen energy is considered to be an ideal substitute for conventional fossil fuels due to its high combustion enthalpy and energy density, and environmental friendliness, and has attracted widespread attention in new energy conversion devices in the future.
The Hydrogen Evolution Reaction (HER) of electrolyzed water has rich raw water resources and high purity of generated hydrogen, which is considered as a promising hydrogen production method, but the method needs an electrocatalyst for catalysis, so the weight of the Hydrogen Evolution Reaction (HER) is that the electrocatalyst with low cost, high efficiency and good stability is sought.
However, at present, electrocatalysts are mostly composed of noble metal-based materials, such as Pt/C for HER and RuO for OER 2 The method comprises the steps of carrying out a first treatment on the surface of the The high cost, low storage capacity and scarcity limit the large-scale application of the catalysts, and the technical process is not easy to prepare in batches and the electrocatalytic performance is also to be improved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the Ru/CoP/CC composite nanowire array electrocatalyst which has low cost and easy batch preparation in the process and can increase the electrocatalyst performance, and the preparation method and the application thereof.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the preparation method of the Ru/CoP/CC composite nanowire array electrocatalyst comprises the following steps:
step 1: soaking carbon cloth in 1-3mol/L nitric acid solution, ultrasonically washing for 2-3h, respectively ultrasonically washing in ultrapure water and ethanol for 1-1.5h, and then baking the carbon cloth at 70-90 ℃ for 1-1.5h for later use;
mixing 2-4mmol of Co (NO 3) 2.6H2O, 10-15mmol of NH4F and 10-15mmol of urea in 20-40mL of ultrapure water to obtain a transparent solution, and carrying out hydrothermal reaction on the carbon cloth subjected to ultrasonic cleaning and the transparent solution at 120-180 ℃ for 6-10 hours; taking out and cooling to room temperature, repeatedly flushing the carbon cloth subjected to the hydrothermal treatment by deionized water and ethanol, and preserving the temperature of the flushed carbon cloth at 50-70 ℃ for 0.5-1.5h to obtain a nanowire array precursor;
step 2: uniformly dripping 160-640 mu L of 4-8mmol/L Cl3H2ORu solution on a nanowire array precursor, and vacuum-maintaining at 60-80 ℃ for 6-8H to obtain a Ru/CoOH/CC composite nanowire array;
step 3: the method comprises the steps that 0.5-2g of phosphorus source and Ru/CoOH/CC composite nanowire arrays (1 cm multiplied by 1 cm) - (2 cm multiplied by 2 cm) are respectively positioned at the upwind position and the downwind position of a tube furnace; at H 2 Heating Ar to 300-500 ℃ and then reacting for 2-5h, then heating Ar 2 And naturally cooling to room temperature to obtain the Ru/CoP/CC composite nanowire array electrocatalyst.
Further, the phosphorus source is NaH 2 PO 2 Red phosphorus, white phosphorus and phosphorus trichloride.
Further, the carbon cloth in the step 1 has a size of (1 cm×1 cm) - (2 cm×2 cm).
Further, the times of washing the carbon cloth subjected to the hydrothermal treatment in the step 1 by deionized water and ethanol are 3-5 times.
Further, in the step 3, the heating rate of the tube furnace is 0.5-2 ℃/min.
The Ru/CoP/CC composite nanowire array electrocatalyst prepared by the preparation method is in a regular nanowire array form.
The application of the Ru/CoP/CC composite nanowire array electrocatalyst as an HER electrocatalyst in water electrolysis hydrogen production is provided.
Compared with the prior art, the invention has the following technical effects:
transition Metal Phosphides (TMPs) in the raw materials of the invention are widely focused by scientific researchers due to controllable structure and components, excellent conductivity and good conductivity; phosphorus can not only bind to protons, but also mitigate interactions with catalytic intermediates; therefore, the electrocatalyst of the invention synthesizes Transition Metal Phosphide (TMPs) and phosphorus serving as main raw materials into TMPs with hydrogenase-like catalytic mechanism as HER electrocatalyst, which can greatly increase the electrocatalyst performance.
The Ru/CoP/CC composite nanowire array electrocatalyst loaded on the surface of the carbon cloth, which is prepared by the preparation method, can effectively catalyze the HER process in acidic and alkaline solutions; the Ru/CoP/CC composite nanowire array electrocatalyst can effectively expose active sites and is beneficial to ensuring directional transmission of electrons. Meanwhile, the doping of Ru can optimize the electronic structure of CoP and accelerate charge transfer among Ru, co and P. The electrocatalyst has low cost, is easy to prepare in batches in the process, and has good application prospect in the electrolysis of water to produce hydrogen.
Specifically, the electrocatalyst prepared by the preparation method is in a regular nanowire array form, and the regular nanowire array form has a highly ordered nanowire structure, so that the effective active surface area of the catalyst is greatly increased. This will increase the contact area between the catalyst and the reactants, increase the reaction rate, and enhance the adsorption capacity of the catalyst to the reactants. The electrocatalyst with regular nanowire array form in the invention has the lowest overpotential and Tafel slope under the acidic and alkaline conditions, and is prepared in 1MKOH solution and 0.5MH 2 SO 4 In solution, the electrocatalyst showed good catalytic performance in HER: at a current density of 10mA/cm 2 The HER overpotential was 66mV and 48mV, respectively; in addition, the electrocatalyst also has excellent durability and good electrochemical stability.
In conclusion, the Ru/CoP/CC composite nanowire array electrocatalyst prepared by the preparation method has the advantages of low cost, easiness in batch preparation in the technical process and capability of increasing the electrocatalyst performance.
Drawings
FIG. 1 is an SEM image of an intermediate nanowire array precursor of example 1 of the present invention;
FIG. 2 is an SEM image of the final Ru/CoP/CC composite nanowire array of example 1 of the present invention;
FIG. 3 is an enlarged view of SEM image of the final Ru/CoP/CC composite nanowire array of example 1 of the present invention;
FIG. 4 shows XRD patterns of Ru/CoP/CC composite nanowire array electrocatalysts according to examples 1, 2, and 3 of the invention;
FIG. 5 is a LSV graph of Ru/CoP/CC composite nanowire array electrocatalyst and Pt/C vs. HER in 0.5M sulfuric acid solution for examples 1, 2, 3 of the invention;
FIG. 6 is a Tafel slope plot of Ru/CoP/CC composite nanowire array electrocatalyst and Pt/C versus HER in 0.5M sulfuric acid solution for examples 1, 2, 3 of the invention;
FIG. 7 is a bar graph of the overpotential of the Ru/CoP/CC composite nanowire array electrocatalyst and Pt/C versus HER in a 0.5M sulfuric acid solution for examples 1, 2, and 3 of the invention;
FIG. 8 is a LSV graph of the Ru/CoP/CC composite nanowire array electrocatalyst and Pt/C vs. HER in 1MKOH solution for examples 1, 2, and 3 of the invention;
FIG. 9 is a Tafel electrode pattern of the Ru/CoP/CC composite nanowire array electrocatalyst and Pt/C vs. HER in 1MKOH solution for examples 1, 2, 3 of the invention;
FIG. 10 is a histogram of the overpotential of the Ru/CoP/CC composite nanowire array electrocatalyst and Pt/C versus HER in 1MKOH solution for examples 1, 2, and 3 of the present invention.
Detailed Description
The following examples illustrate the invention in further detail.
Examples
Example 1
The preparation method of the Ru/CoP/CC composite nanowire array electrocatalyst comprises the following steps:
immersing 2cm×2cm carbon cloth in nitric acid solution, ultrasonic washing at 60deg.C for 2.5 hr, ultrasonic washing in ultrapure water and ethanol for 1 hr, and baking at 80deg.C1h, and the concentration of the nitric acid solution is 1mol/L. At the same time, 2mmol of Co (NO 3 ) 2 ·6H 2 O, 10mmol NH 4 F. 10mmol of urea was mixed in 30mL of ultra pure water to obtain a transparent solution. The carbon cloth after ultrasonic cleaning and the obtained transparent solution are sequentially put into a stainless steel Teflon high-pressure reactor with the volume of 50mL, and are stored in an oven with the temperature of 130 ℃ for 8 hours. Then, the reaction system was naturally cooled to room temperature. Washing the carbon cloth subjected to the hydrothermal treatment with deionized water and ethanol for 3 times, removing ions remained on the surface, and keeping the washed carbon cloth in an oven at 60 ℃ for 1h to obtain a nanowire array precursor;
tiling nanowire array precursor generated by hydrothermal reaction on a culture dish, and applying 160 mu L of Cl with the concentration of 5mmol/L 3 H 2 And (3) uniformly dripping ORu on carbon cloth, and keeping the carbon cloth at 60 ℃ for 6 hours in a vacuum drying oven to obtain the Ru/CoOH/CC composite nanowire array.
1g of phosphorus source (NaH) 2 PO 2 ) And the Ru/CoOH/CC composite nanowire arrays with the size of 2 multiplied by 2 are respectively positioned at the upwind position and the downwind position of the tube furnace. At H 2 Raising the temperature of the tubular furnace to 350 ℃ at a speed of 2 ℃/min in Ar, reacting for 2h, wherein the reaction system is in Ar 2 And naturally cooling to room temperature to obtain the final Ru/CoP/CC composite nanowire array electrocatalyst.
Example 2
The preparation method of the Ru/CoP/CC composite nanowire array electrocatalyst comprises the following steps:
immersing 2cm×2cm carbon cloth in nitric acid solution at 60deg.C for ultrasonic washing for 2 hr, respectively ultrasonic washing in ultrapure water and ethanol for 1 hr, and baking the carbon cloth in oven at 70deg.C for 1.5 hr with nitric acid solution concentration of 2mol/L. At the same time, 3mmol of Co (NO 3 ) 2 ·6H 2 O, 12mmol NH 4 F. 12mmol of urea was mixed in 20mL of ultrapure water to obtain a transparent solution. The carbon cloth after ultrasonic cleaning and the obtained transparent solution are sequentially put into a stainless steel Teflon high-pressure reactor with the volume of 50mL, and are preserved for 10 hours in an oven with the temperature of 120 ℃. Then, the reaction system was naturally cooled to room temperature. Washing the carbon cloth after the hydrothermal treatment with deionized water and ethanol for 4 times to remove the residual ions on the surface,maintaining the washed carbon cloth in an oven at 50 ℃ for 1.5 hours to obtain a nanowire array precursor;
tiling nanowire array precursor generated by hydrothermal reaction on a culture dish, and adding 320 mu L of 8mmol/L Cl 3 H 2 And (3) uniformly dripping ORu on carbon cloth, and keeping the carbon cloth at 70 ℃ for 7 hours in a vacuum drying oven to obtain the Ru/CoOH/CC composite nanowire array.
2g of phosphorus source (NaH) 2 PO 2 ) And the Ru/CoOH/CC composite nanowire arrays with the length of 2cm multiplied by 2cm are respectively positioned at the upwind position and the downwind position of the tube furnace. At H 2 Raising the temperature of the tubular furnace to 500 ℃ at a speed of 1 ℃/min in Ar, reacting for 3 hours, wherein the reaction system is in Ar 2 And naturally cooling to room temperature to obtain the final Ru/CoP/CC composite nanowire array electrocatalyst.
Example 3
The preparation method of the Ru/CoP/CC composite nanowire array electrocatalyst comprises the following steps:
1cm by 1cm carbon cloth was immersed in a nitric acid solution at 60℃for ultrasonic washing for 3 hours, then each of the ultrasonic washing was performed in ultrapure water and ethanol for 1.5 hours, and finally the carbon cloth was baked in a 90℃oven for 1 hour, with the nitric acid solution having a concentration of 3mol/L. At the same time, 4mmol of Co (NO 3 ) 2 ·6H 2 O, 15mmol NH 4 F. 15mmol of urea was mixed in 40mL of ultrapure water to obtain a transparent solution. The carbon cloth after ultrasonic cleaning and the obtained transparent solution are sequentially put into a stainless steel Teflon high-pressure reactor with the volume of 50mL, and are preserved for 6 hours in an oven with the temperature of 180 ℃. Then, the reaction system was naturally cooled to room temperature. Washing the carbon cloth subjected to the hydrothermal treatment with deionized water and ethanol for 5 times, removing ions remained on the surface, and keeping the washed carbon cloth in an oven at 70 ℃ for 0.5h to obtain a nanowire array precursor;
tiling nanowire array precursor generated by hydrothermal reaction on a culture dish, and adding 640 mu L of 4mmol/L Cl 3 H 2 And (3) uniformly dripping ORu on carbon cloth, and keeping the carbon cloth at 80 ℃ for 8 hours in a vacuum drying oven to obtain the Ru/CoOH/CC composite nanowire array.
0.5g of phosphorus source (NaH) 2 PO 2 ) And Ru/CoOH/CC composite nanowire arrays of 1cm multiplied by 1cm are respectively positionedIn upwind and downwind positions of the tube furnace. At H 2 Raising the temperature of the tube furnace to 300 ℃ at a speed of 0.5 ℃/min in Ar, reacting for 5h, wherein the reaction system is in Ar 2 And naturally cooling to room temperature to obtain the final Ru/CoP/CC composite nanowire array electrocatalyst.
As can be seen with reference to fig. 1, coP/CC is a regular nanowire array morphology; after Ru is added, the nanowire array is widened by combining with figures 2 and 3, and Ru cluster load is arranged on the surface of the nanowire array; FIG. 4 shows XRD patterns of Ru/CoP/CC composite nanowire array electrocatalysts in examples 1, 2 and 3, and different Ru content modified CoP/CC have obvious peaks at 31.6 degrees, 36.3 degrees and 48.1 degrees, which are consistent with (011) and (111) (211) crystal planes of CoP nanocrystals (JCPDS No. 97-062-4588), indicating that CoP crystals were successfully prepared after phosphating. There is no characteristic peak of Ru in the spectrum, probably due to the low Ru content, whereas XRD is not detected.
In connection with fig. 5, 6, 7, it can be seen that: the Ru/CoP/CC composite nanowire array electrocatalyst prepared by the method of the invention has the advantages of 10mA/cm under an acidic environment 2 The overpotential at this point was about 48mV, close to commercial Pt/C electrodes, with smaller Tafel; the dynamics are faster; the stability is good; in connection with fig. 8, 9, 10, it can be seen that: the Ru/CoP/CC composite nanowire array electrocatalyst prepared by the method of the invention has the concentration of 10mA/cm in alkaline environment 2 The overpotential at this point was about 66mV, close to commercial Pt/C electrodes, with smaller Tafel; the dynamics are faster; the stability is good.
Claims (7)
1. The preparation method of the Ru/CoP/CC composite nanowire array electrocatalyst is characterized by comprising the following steps of:
step 1: soaking carbon cloth in 1-3mol/L nitric acid solution, ultrasonically washing for 2-3h, respectively ultrasonically washing in ultrapure water and ethanol for 1-1.5h, and then baking the carbon cloth at 70-90 ℃ for 1-1.5h for later use;
2-4mmol of Co (NO) 3 ) 2 ·6H 2 O, 10-15mmol NH 4 F. 10-15mmol of urea is mixed in 20-40mL of ultrapure water to obtain transparent solution, and the carbon cloth after ultrasonic cleaning and the transparent solution are subjected to hydrothermal reaction for 6-10h at 120-180 ℃; taking outCooling to room temperature, repeatedly flushing the carbon cloth subjected to the hydrothermal treatment by deionized water and ethanol, and preserving the heat of the flushed carbon cloth at 50-70 ℃ for 0.5-1.5h to obtain a nanowire array precursor;
step 2: 160-640 mu L of Cl with the concentration of 4-8mmol/L 3 H 2 Uniformly dripping ORu solution on the nanowire array precursor, and maintaining the vacuum at 60-80 ℃ for 6-8 hours to obtain the Ru/CoOH/CC composite nanowire array;
step 3: the method comprises the steps that 0.5-2g of phosphorus source and Ru/CoOH/CC composite nanowire arrays (1 cm multiplied by 1 cm) - (2 cm multiplied by 2 cm) are respectively positioned at the upwind position and the downwind position of a tube furnace; at H 2 Heating Ar to 300-500 ℃ and then reacting for 2-5h, then heating Ar 2 And naturally cooling to room temperature to obtain the Ru/CoP/CC composite nanowire array electrocatalyst.
2. The method for preparing Ru/CoP/CC composite nanowire array electrocatalyst according to claim 1, wherein the phosphorus source is NaH 2 PO 2 Red phosphorus, white phosphorus and phosphorus trichloride.
3. The method for preparing a Ru/CoP/CC composite nanowire array electrocatalyst according to claim 1, wherein the carbon cloth size in step 1 is (1 cm x 1 cm) - (2 cm x 2 cm).
4. The method for preparing the Ru/CoP/CC composite nanowire array electrocatalyst according to claim 1, wherein the number of times that the carbon cloth subjected to the hydrothermal treatment in the step 1 is rinsed with deionized water and ethanol is 3-5.
5. The method for preparing the Ru/CoP/CC composite nanowire array electrocatalyst according to claim 1, wherein in the step 3, the heating rate of the tube furnace is 0.5-2 ℃/min.
6. A Ru/CoP/CC composite nanowire array electrocatalyst produced by the method of any one of claims 1-5, wherein: the electrocatalyst is in the form of a regular nanowire array.
7. Use of a Ru/CoP/CC composite nanowire array electrocatalyst as defined in claim 6 as a HER electrocatalyst in the electrolysis of water to produce hydrogen.
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