CN103924263A - Preparation method of high-performance nickel-based ruthenium-containing compound oxide hydrogen evolution electrode - Google Patents
Preparation method of high-performance nickel-based ruthenium-containing compound oxide hydrogen evolution electrode Download PDFInfo
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Abstract
The invention provides a preparation method of a high-performance nickel-based ruthenium-containing compound oxide hydrogen evolution electrode, and belongs to the field of electric catalytic hydrogen evolution in chlorine alkali industry. The method comprises the following steps: firstly, putting a foam nickel substrate into an acetone solution and carrying out ultrasonic concussion for 15 minutes so as to perform chemical degreasing; then, soaking the foam nickel substrate in a 3mol/L hydrochloric acid aqueous solution for 0.5 hour so as to remove oxides from the surface of the foam nickel substrate; finally, carrying out in-situ growth of nickel ruthenium oxide nanorods on the surface of the pretreated foam nickel substrate by virtue of a solvent thermal synthesis method, thereby obtaining the hydrogen evolution electrode with good catalytic performance and high stability. The method is simple and novel and is convenient and feasible to operate. The prepared nickel-based ruthenium-containing compound oxide hydrogen evolution electrode has a unique nanorod structure; the coating surface of the electrode is flat and flawless without a fracturing phenomenon. Thus, the electrode provided by the invention can be widely taken as a hydrogen evolution electrode material for alkaline electrolysis water.
Description
Technical field
The invention belongs to electrocatalytic hydrogen evolution field, particularly the Ni-based preparation method containing ruthenium composite oxides hydrogen-precipitating electrode of a kind of high-performance.
Background technology
Hydrogen energy source is due to aboundresources, safely cleaning, and superior performance, at very likely substitute fossil fuels and be subject to people's great attention in future.Hydrogen can be prepared by number of ways, wherein water electrolysis hydrogen production technology maturation, and technique is simple, pollution-free, and the hydrogen purity of preparation is high, is the best approach of preparing hydrogen.In actual brine electrolysis hydrogen production process, because overpotential of hydrogen evolution is larger, make brine electrolysis industrial consumption energy large, so preparation has the catalytic hydrogen evolution electrode of high activity and stability, reduce the electrode overpotential in electrolytic process, it is very necessary reducing energy consumption.Ni-based electrode due to low cost, preparation is simple, catalytic hydrogen evolution superior performance, develops into gradually hydrogen evolution electrode material ideal in alkaline medium.Although wherein foam nickel electrode has greater activity, degeneration-resistant CURRENT OXIDATION ability is low, and bad mechanical strength easily causes vesicular structure to cave in, and activity is difficult to maintain.RuO
2under cathode hydrogen evolution current potential, energy stable existence, is difficult for being reduced and poisoning, and has higher specific surface area and superior catalytic activity, so it is also widely used industrial simultaneously.Chinese invention patent CN102864464A discloses " preparation method of a kind of high catalytic activity and high stability hydrogen-precipitating electrode ", this method is pulse plating Ni coating in Ni substrate first, then on Ni coating, apply the coating liquid that contains ruthenium, form Ni-based Ni/RuO through roasting
2combined electrode.Although prepared electrode hydrogen evolution activity is better, coating and substrate caking power are poor, and electrode surface presents tiny crackle, the problem that existence and stability is not high.Chinese invention patent CN103422116A discloses " preparation method of the compound hydrogen-precipitating electrode of a kind of porous Ni-base ru oxide ", first the method forms nickel porous in nickel substrate by cathodic electrodeposition, then at porous Ni-base substrates ru oxide, annealed processing, forms porous Ni-base ru oxide combined electrode.The electrode of preparation demonstrates higher catalytic activity and stability, but adopts two-step approach to form respectively nickel porous and ru oxide, can not effectively utilize the synergistic effect between nickel ruthenium, makes it reach more excellent catalytic effect.
Summary of the invention
The nickel ru oxide coating that the present invention is directed to tradition preparation is easily washed away and is corroded and the problems such as causing shortening electrode life that easily comes off by bubble, provides a kind of high-performance the Ni-based preparation method containing ruthenium composite oxides hydrogen-precipitating electrode.This preparation method's main advantage is to adopt solvent process for thermosynthesizing, growth in situ nickel ru oxide nanometer rod in nickel foam substrate, and the electrode specific surface area of acquisition is large, is combined firmly with substrate, has good Hydrogen Evolution Performance and higher stability.
The invention provides the Ni-based preparation method containing ruthenium composite oxides hydrogen-precipitating electrode of a kind of high-performance, its concrete grammar step comprises the pre-treatment of (1), nickel foam substrate
Nickel foam substrate is put into the ultrasonic concussion of acetone soln and within 15 minutes, carry out electrochemical deoiling, then the aqueous hydrochloric acid of putting into volumetric molar concentration and be 3mol/L soaks 0.5 hour, the oxide compound on the nickel substrate that defoams surface, finally rinses well with deionized water, stand-by after natural air drying;
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 1～100mmol/L, and the volumetric molar concentration of ruthenium trichloride is 0.1～50mmol/L, and the volumetric molar concentration of urea is 0-200mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 60～300 DEG C, react 1～72 hour; After question response finishes, rinse well with deionized water, in retort furnace, 200～600 DEG C of anneal 0.5～20 hour, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.The present invention adopts after technique scheme, mainly contains following advantage:
(1) specific surface area is large, can fully expose avtive spot, improves catalytic activity.The nickel ru oxide nanometer rod of growth in situ can effectively increase the specific surface area of electrode, and the space between nanometer rod can provide passage for electrolytical transmission, makes the effective desorption of hydrogen of generation, thereby improves catalytic activity.
(2) nanometer rod of growth in situ is combined with substrate firmly, electrode coating surfacing leakless, and " be full of cracks " phenomenon does not produce, and has improved the stability of electrode.
The inventive method is simply novel, and easy to operate feasible, the nickel ru oxide hydrogen-precipitating electrode of preparation has unique nanorod structure, demonstrates higher catalytic activity for hydrogen evolution and stability, can be extensively as the hydrogen evolution electrode material of electrolyzed alkaline water.
Brief description of the drawings
Fig. 1 is the prepared Ni-based liberation of hydrogen linear time base sweep curve containing ruthenium composite oxides electrode of embodiment 1～3.
In figure: curve 1 be taking embodiment 1 prepared Ni-based containing ruthenium composite oxides electrode as working electrode, mercury/mercuric oxide electrode is reference electrode, platinized platinum is to electrode, 6mol/L aqueous sodium hydroxide solution is electrolytic solution, temperature is 25 DEG C, and scanning speed is the liberation of hydrogen linear time base sweep curve under 5mV/s condition.
Curve 2 be taking embodiment 2 prepared Ni-based containing ruthenium composite oxides electrode as working electrode, mercury/mercuric oxide electrode is reference electrode, and platinized platinum is to electrode, and 6mol/L aqueous sodium hydroxide solution is electrolytic solution, temperature is 25 DEG C, and scanning speed is the liberation of hydrogen linear time base sweep curve under 5mV/s condition.
Curve 3 be taking embodiment 3 prepared Ni-based containing ruthenium composite oxides electrode as working electrode, mercury/mercuric oxide electrode is reference electrode, and platinized platinum is to electrode, and 6mol/L aqueous sodium hydroxide solution is electrolytic solution, temperature is 25 DEG C, and scanning speed is the liberation of hydrogen linear time base sweep curve under 5mV/s condition.
Fig. 2 is nickel foam and the prepared Ni-based liberation of hydrogen linear time base sweep curve containing ruthenium composite oxides electrode of embodiment 6～8 in contrast experiment.
In figure: curve 1 is taking nickel foam in contrast experiment as working electrode, mercury/mercuric oxide electrode is reference electrode, and platinized platinum is to electrode, and 6mol/L aqueous sodium hydroxide solution is electrolytic solution, temperature is 25 DEG C, and scanning speed is the liberation of hydrogen linear time base sweep curve under 5mV/s condition.
Curve 2 be taking embodiment 6 prepared Ni-based containing ruthenium composite oxides electrode as working electrode, mercury/mercuric oxide electrode is reference electrode, and platinized platinum is to electrode, and 6mol/L aqueous sodium hydroxide solution is electrolytic solution, temperature is 25 DEG C, and scanning speed is the liberation of hydrogen linear time base sweep curve under 5mV/s condition.
Curve 3 be taking embodiment 7 prepared Ni-based containing ruthenium composite oxides electrode as working electrode, mercury/mercuric oxide electrode is reference electrode, and platinized platinum is to electrode, and 6mol/L aqueous sodium hydroxide solution is electrolytic solution, temperature is 25 DEG C, and scanning speed is the liberation of hydrogen linear time base sweep curve under 5mV/s condition.
Curve 4 be taking embodiment 8 prepared Ni-based containing ruthenium composite oxides electrode as working electrode, mercury/mercuric oxide electrode is reference electrode, and platinized platinum is to electrode, and 6mol/L aqueous sodium hydroxide solution is electrolytic solution, temperature is 25 DEG C, and scanning speed is the liberation of hydrogen linear time base sweep curve under 5mV/s condition.
Fig. 3 is the prepared Ni-based time-measuring electric potential graphic representation of ruthenium composite oxides electrode under 500mA electric current that contain of embodiment 8.
Fig. 3 is the time-measuring electric potential curve that the prepared electrode of embodiment 8 is tested on CHI660D electrochemical workstation (Shanghai Chen Hua instrument company).Test condition: three-electrode system, the aqueous sodium hydroxide solution of 6mol/L is electrolyte solution, embodiment 8 prepared Ni-based containing ruthenium composite oxides electrode be working electrode, mercury/mercuric oxide electrode is reference electrode, platinized platinum is to electrode, and cathode current density is 500mAcm
-2, lasting electrolysis time is 60 hours.
Fig. 4 is the Ni-based stereoscan photograph containing ruthenium composite oxides full surface prepared by embodiment 8.
Fig. 5 is the Ni-based stereoscan photograph containing the strip off of ruthenium composite oxides part prepared by embodiment 8.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment 1
(1), the pre-treatment of nickel foam substrate
Nickel foam substrate is put into the ultrasonic concussion of acetone soln and within 15 minutes, carry out electrochemical deoiling, then the aqueous hydrochloric acid of putting into volumetric molar concentration and be 3mol/L soaks 0.5 hour, remove the oxide compound of Ni foam substrate surface, finally rinse well with deionized water, stand-by after natural air drying;
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 8mmol/L, and the volumetric molar concentration of ruthenium trichloride is 2mmol/L, and the volumetric molar concentration of urea is 20mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 160 DEG C, react 12 hours; After question response finishes, rinse well with deionized water, in retort furnace, 400 DEG C of anneal 1 hour, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
(3), Ni-based containing the test of ruthenium composite oxides electrode Hydrogen Evolution Performance
Adopt three-electrode system, taking the aqueous sodium hydroxide solution of 6mol/L as electrolyte solution, it is Ni-based that prepared by step (2) is working electrode containing ruthenium composite oxides electrode, mercury/mercuric oxide electrode is reference electrode, and platinized platinum is to electrode, (CHI660d on electrochemical workstation, Shanghai Chen Hua instrument company) test its linear sweep voltammetry curve, probe temperature is 25 DEG C, and scanning speed is 5mV/s, and sweep limit is curve 1 in-0.8～-1.4V test result corresponding diagram 1.
Embodiment 2
Step (1) is with step (1) in embodiment 1.
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 8mmol/L, and the volumetric molar concentration of ruthenium trichloride is 2mmol/L, and the volumetric molar concentration of urea is 20mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 120 DEG C, react 12 hours; After question response finishes, rinse well with deionized water, in retort furnace, 400 DEG C of anneal 1 hour, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
(3), Ni-based containing the test of ruthenium composite oxides electrode Hydrogen Evolution Performance
Adopt three-electrode system, taking the aqueous sodium hydroxide solution of 6mol/L as electrolyte solution, it is Ni-based that prepared by step (2) is working electrode containing ruthenium composite oxides electrode, mercury/mercuric oxide electrode is reference electrode, and platinized platinum is to electrode, (CHI660d on electrochemical workstation, Shanghai Chen Hua instrument company) test its linear sweep voltammetry curve, probe temperature is 25 DEG C, and scanning speed is 5mV/s, and sweep limit is curve 2 in-0.8～-1.4V test result corresponding diagram 1.
Embodiment 3
Step (1) is with step (1) in embodiment 1.
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 8mmol/L, and the volumetric molar concentration of ruthenium trichloride is 2mmol/L, and the volumetric molar concentration of urea is 20mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 90 DEG C, react 12 hours; After question response finishes, rinse well with deionized water, in retort furnace, 400 DEG C of anneal 1 hour, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
(3), Ni-based containing the test of ruthenium composite oxides electrode Hydrogen Evolution Performance
Adopt three-electrode system, taking the aqueous sodium hydroxide solution of 6mol/L as electrolyte solution, it is Ni-based that prepared by step (2) is working electrode containing ruthenium composite oxides electrode, mercury/mercuric oxide electrode is reference electrode, and platinized platinum is to electrode, (CHI660d on electrochemical workstation, Shanghai Chen Hua instrument company) test its linear sweep voltammetry curve, probe temperature is 25 DEG C, and scanning speed is 5mV/s, and sweep limit is curve 3 in-0.8～-1.4V test result corresponding diagram 1.
Embodiment 4
Step (1) is with step (1) in embodiment 1.
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 100mmol/L, and the volumetric molar concentration of ruthenium trichloride is 50mmol/L, and the volumetric molar concentration of urea is 200mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 300 DEG C, react 1 hour; After question response finishes, rinse well with deionized water, in retort furnace, 600 DEG C of anneal 0.5 hour, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
Embodiment 5
Step (1) is with step (1) in embodiment 1.
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 1mmol/L, the volumetric molar concentration of ruthenium trichloride is 0.1mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 60 DEG C, react 72 hours; After question response finishes, rinse well with deionized water, in retort furnace, 200 DEG C of anneal 20 hours, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
Embodiment 6
Step (1) is with step (1) in embodiment 1.
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 8mmol/L, and the volumetric molar concentration of ruthenium trichloride is 2mmol/L, and the volumetric molar concentration of urea is 60mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 90 DEG C, react 12 hours; After question response finishes, rinse well with deionized water, in retort furnace, 300 DEG C of anneal 10 hours, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
(3), Ni-based containing the test of ruthenium composite oxides electrode Hydrogen Evolution Performance
Adopt three-electrode system, taking the aqueous sodium hydroxide solution of 6mol/L as electrolyte solution, it is Ni-based that prepared by step (2) is working electrode containing ruthenium composite oxides electrode, mercury/mercuric oxide electrode is reference electrode, and platinized platinum is to electrode, (CHI660d on electrochemical workstation, Shanghai Chen Hua instrument company) test its linear sweep voltammetry curve, probe temperature is 25 DEG C, and scanning speed is 5mV/s, and sweep limit is curve 2 in-0.8～-1.4V test result corresponding diagram 2.
Embodiment 7
Step (1) is with step (1) in embodiment 1.
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 8mmol/L, and the volumetric molar concentration of ruthenium trichloride is 2mmol/L, and the volumetric molar concentration of urea is 40mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 90 DEG C, react 12 hours; After question response finishes, rinse well with deionized water, in retort furnace, 300 DEG C of anneal 10 hours, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
(3), Ni-based containing the test of ruthenium composite oxides electrode Hydrogen Evolution Performance
Adopt three-electrode system, taking the aqueous sodium hydroxide solution of 6mol/L as electrolyte solution, prepared by step (2) is Ni-based containing very working electrode of ruthenium composite oxides, mercury/mercuric oxide electrode is reference electrode, and platinized platinum is to electrode, (CHI660d on electrochemical workstation, Shanghai Chen Hua instrument company) test its linear sweep voltammetry curve, probe temperature is 25 DEG C, and scanning speed is 5mV/s, and sweep limit is curve 3 in-0.8～-1.4V test result corresponding diagram 2.
Embodiment 8
Step (1) is with step (1) in embodiment 1.
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 8mmol/L, and the volumetric molar concentration of ruthenium trichloride is 2mmol/L, and the volumetric molar concentration of urea is 20mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 90 DEG C, react 12 hours; After question response finishes, rinse well with deionized water, in retort furnace, 300 DEG C of anneal 10 hours, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
(3), Ni-based containing the test of ruthenium composite oxides electrode Hydrogen Evolution Performance
Adopt three-electrode system, taking the aqueous sodium hydroxide solution of 6mol/L as electrolyte solution, it is Ni-based that prepared by step (2) is working electrode containing ruthenium composite oxides electrode, mercury/mercuric oxide electrode is reference electrode, and platinized platinum is to electrode, (CHI660d on electrochemical workstation, Shanghai Chen Hua instrument company) test its linear sweep voltammetry curve, probe temperature is 25 DEG C, and scanning speed is 5mV/s, and sweep limit is curve 4 in-0.8～-1.4V test result corresponding diagram 2.
(4), the Ni-based ruthenium composite oxides electrode stability that contains can be tested
Adopt three-electrode system, taking the aqueous sodium hydroxide solution of 6mol/L as electrolyte solution, it is Ni-based that prepared by step (2) is working electrode containing ruthenium composite oxides electrode, mercury/mercuric oxide electrode is reference electrode, platinized platinum is to electrode, and on electrochemical workstation, (CHI660d, Shanghai Chen Hua instrument company) tests its time-measuring electric potential curve under 500mA electric current, thereby measure its stability, test result corresponding diagram 3.
(5), Ni-based containing the apparent pattern of ruthenium composite oxides electrode
The FEI Nova400 type scanning electronic microscope (SEM) of utilizing Dutch FEI Co. to produce is observed the prepared Ni-based ruthenium composite oxides electrode surface pattern that contains, and SEM photo is as Fig. 4 and Fig. 5.
Contrast experiment
The preprocessing process of nickel foam is with embodiment 1 step (1)
Adopt three-electrode system, taking the aqueous sodium hydroxide solution of 6mol/L as electrolyte solution, the pretreated nickel foam of step (1) is working electrode, mercury/mercuric oxide electrode is reference electrode, and platinized platinum is to electrode, (CHI660d on electrochemical workstation, Shanghai Chen Hua instrument company) test its linear sweep voltammetry curve, probe temperature is 25 DEG C, and scanning speed is 5mV/s, and sweep limit is curve 1 in-0.8～-1.4V test result corresponding diagram 2.
Test-results of the present invention
(1), can be found out by Fig. 1 and Fig. 2 linear time base sweep curve, the content of temperature and urea has obvious impact to the activity of the prepared electrode of the present invention.Prepared Ni-based containing the ruthenium composite oxides hydrogen-precipitating electrode pure foam nickel electrode of comparing of the present invention, has better Hydrogen Evolution Performance, when voltage is-1.35V(vs.Hg/HgO) time, foam nickel electrode liberation of hydrogen current density is 123mAcm
-2, and the prepared Ni-based liberation of hydrogen current density containing ruthenium composite oxides electrode is up to 353mAcm
-2, be 2.87 times of nickel foam, illustrate that prepared electrode materials Hydrogen Evolution Performance is superior.
(2), can find out from Fig. 3 curve result, adopting prepared Ni-based of the present invention is 500mAcm containing ruthenium composite oxides electrode in current density
-2lower continuous current continues electrolysis 60 hours, and overpotential of hydrogen evolution is initially 0.402V, and test becomes 0.450V after finishing, and overpotential has only increased by 11.9%.Can find out that prepared electrode has satisfactory stability.
(3) can be found out by stereoscan photograph, the Ni-based smooth leakless of ruthenium composite oxides electrode surface that contains that the present invention is prepared, nanometer rod vertical-growth, in nickel foam substrate, is evenly distributed closely, illustrates that this method successfully synthesizes nickel ru oxide nanometer rod in nickel foam substrate.Obviously increase the specific surface area of electrode than nickel foam, improved the catalytic activity for hydrogen evolution of electrode.
Claims (9)
1. the Ni-based preparation method containing ruthenium composite oxides hydrogen-precipitating electrode of high-performance, its concrete grammar step comprises
(1), the pre-treatment of nickel foam substrate
Nickel foam substrate is put into the ultrasonic concussion of acetone soln and within 15 minutes, carry out electrochemical deoiling, then the aqueous hydrochloric acid of putting into volumetric molar concentration and be 3mol/L soaks 0.5 hour, the oxide compound on the nickel substrate that defoams surface, finally rinses well with deionized water, stand-by after natural air drying;
It is characterized in that:
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 1～100mmol/L, and the volumetric molar concentration of ruthenium trichloride is 0.1～50mmol/L, and the volumetric molar concentration of urea is 0-200mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 60～300 DEG C, react 1～72 hour; After question response finishes, rinse well with deionized water, in retort furnace, 200～600 DEG C of anneal 0.5～20 hour, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
2. according to the Ni-based preparation method containing ruthenium composite oxides hydrogen-precipitating electrode of a kind of high-performance claimed in claim 1, it is characterized in that concrete preparation method's step (2):
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 8mmol/L, and the volumetric molar concentration of ruthenium trichloride is 2mmol/L, and the volumetric molar concentration of urea is 20mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 160 DEG C, react 12 hours; After question response finishes, rinse well with deionized water, in retort furnace, 400 DEG C of anneal 1 hour, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
3. according to the Ni-based preparation method containing ruthenium composite oxides hydrogen-precipitating electrode of a kind of high-performance claimed in claim 1, it is characterized in that concrete preparation method's step (2):
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 8mmol/L, and the volumetric molar concentration of ruthenium trichloride is 2mmol/L, and the volumetric molar concentration of urea is 20mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 120 DEG C, react 12 hours; After question response finishes, rinse well with deionized water, in retort furnace, 400 DEG C of anneal 1 hour, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
4. according to the Ni-based preparation method containing ruthenium composite oxides hydrogen-precipitating electrode of a kind of high-performance claimed in claim 1, it is characterized in that concrete preparation method's step (2):
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 8mmol/L, and the volumetric molar concentration of ruthenium trichloride is 2mmol/L, and the volumetric molar concentration of urea is 20mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 90 DEG C, react 12 hours; After question response finishes, rinse well with deionized water, in retort furnace, 400 DEG C of anneal 1 hour, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
5. according to the Ni-based preparation method containing ruthenium composite oxides hydrogen-precipitating electrode of a kind of high-performance claimed in claim 1, it is characterized in that concrete preparation method's step (2):
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 100mmol/L, and the volumetric molar concentration of ruthenium trichloride is 50mmol/L, and the volumetric molar concentration of urea is 200mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 300 DEG C, react 1 hour; After question response finishes, rinse well with deionized water, in retort furnace, 600 DEG C of anneal 0.5 hour, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
6. according to the Ni-based preparation method containing ruthenium composite oxides hydrogen-precipitating electrode of a kind of high-performance claimed in claim 1, it is characterized in that concrete preparation method's step (2):
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 1mmol/L, the volumetric molar concentration of ruthenium trichloride is 0.1mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 60 DEG C, react 72 hours; After question response finishes, rinse well with deionized water, in retort furnace, 200 DEG C of anneal 20 hours, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
7. according to the Ni-based preparation method containing ruthenium composite oxides hydrogen-precipitating electrode of a kind of high-performance claimed in claim 1, it is characterized in that concrete preparation method's step (2):
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 8mmol/L, and the volumetric molar concentration of ruthenium trichloride is 2mmol/L, and the volumetric molar concentration of urea is 60mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 90 DEG C, react 12 hours; After question response finishes, rinse well with deionized water, in retort furnace, 300 DEG C of anneal 10 hours, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
8. according to the Ni-based preparation method containing ruthenium composite oxides hydrogen-precipitating electrode of a kind of high-performance claimed in claim 1, it is characterized in that concrete preparation method's step (2):
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 8mmol/L, and the volumetric molar concentration of ruthenium trichloride is 2mmol/L, and the volumetric molar concentration of urea is 40mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 90 DEG C, react 12 hours; After question response finishes, rinse well with deionized water, in retort furnace, 300 DEG C of anneal 10 hours, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
9. according to the Ni-based preparation method containing ruthenium composite oxides hydrogen-precipitating electrode of a kind of high-performance claimed in claim 1, it is characterized in that concrete preparation method's step (2):
(2), prepare the Ni-based ruthenium composite oxides hydrogen-precipitating electrode that contains taking nickel foam as substrate
Taking ethylene glycol as solvent, the nickel ruthenium precursor solution that configuration contains nickelous chloride, ruthenium trichloride and urea, wherein the volumetric molar concentration of nickelous chloride is 8mmol/L, and the volumetric molar concentration of ruthenium trichloride is 2mmol/L, and the volumetric molar concentration of urea is 20mmol/L; Pretreated step (1) nickel foam substrate is put into the reactor that contains nickel ruthenium precursor solution, under the condition of 90 DEG C, react 12 hours; After question response finishes, rinse well with deionized water, in retort furnace, 300 DEG C of anneal 10 hours, are cooled to room temperature, make Ni-based containing ruthenium composite oxides hydrogen-precipitating electrode.
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| CN112354544B (en) * | 2019-07-24 | 2023-04-28 | 南京理工大学 | Nickel hydroxide layer coated simple substance ruthenium structure hydrogen evolution catalyst and preparation method thereof |
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| CN114717601A (en) * | 2022-05-17 | 2022-07-08 | 临沂大学 | Three-phase interface composite integrated alkaline water electrolysis hydrogen production electrode and preparation method thereof |
| CN114717601B (en) * | 2022-05-17 | 2024-01-30 | 临沂大学 | Three-phase interface composite integrated alkaline water electrolysis hydrogen production electrode and preparation method thereof |
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