CN103924260A - Composite hydrogen evolution electrode with copper and cobalt loaded on three-dimensional foamed nickel and preparation method thereof - Google Patents
Composite hydrogen evolution electrode with copper and cobalt loaded on three-dimensional foamed nickel and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a hydrogen evolution electrode with copper and cobalt loaded on three-dimensional foamed nickel, which can be used for an electro-catalysis hydrogen evolution reaction in alkaline solution and is capable of simultaneously loading base metals and a preparation method thereof, and belongs to the technical fields of material science and hydrogen production by electro-catalysis. The technical problem to be solved is to provide the composite hydrogen evolution electrode with copper and cobalt loaded on three-dimensional foamed nickel and a preparation method thereof. A method of plating a composite coating on an electro-mechanical surface is adopted, and copper and cobalt are electro-plated on the three-dimensional foamed nickel in sequence, so that the composite hydrogen evolution electrode is prepared. The prepared electrode has high catalytic activity, is non-toxic, and can keep stable structure and chemical activity under an alkaline condition. In addition, the preparation process of the composite hydrogen evolution electrode is simple, and is suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of electrocatalytic hydrogen evolution reaction in basic solution that can be used for, the three-dimensional foam Ni copper of the base metal of load simultaneously hydrogen-precipitating electrode and hydrogen-precipitating electrode of cobalt and preparation method thereof, belong to materials science field and electrocatalysis hydrogen preparation field.
Background technology
What the mankind mainly utilized at present is the non-renewable fossil energies such as oil, coal, and due to the mankind's overexploitation, these fossil energies face exhausted danger already; And the use of fossil oil causes serious environmental pollution to the mankind, such as Greenhouse effect, acid rain and haze etc., the mankind's healthy and existence in serious threat.Hydrogen, because of advantages such as its source is abundant, cleanliness without any pollution, burning highly effectives, is considered to optimal energy carrier.Water electrolysis hydrogen production is one of important method likely realizing scale operation hydrogen.In water electrolysis hydrogen production, the selection of electrode, the design of structure and preparation technology's optimization is the key of water electrolysis hydrogen production always, very important effect is played in its minimizing to the raising of the reduction of electrode cost, catalyst utilization and electrolysis energy consumption, and can affect again electrolysis process large-scale industrial production simultaneously.The precious metal such as Pd and Pt is the metal electrode material with good electric catalytic hydrogen evolution activity, but because these precious metals are expensive, therefore be difficult to widely apply in industrial production, research and develop the novel cathode base metal material hydrogen-precipitating electrode that cheap, high reactivity and overpotential of hydrogen evolution are low extremely important.
Summary of the invention
The present invention overcomes the deficiency that prior art exists, and technical problem to be solved has been to provide compound hydrogen-precipitating electrode of a kind of three-dimensional foam Ni copper and cobalt and preparation method thereof.It mainly adopts electrochemical surface composite deposite method, at three-dimensional foam nickel surface successively electro-coppering and cobalt, it is high, nontoxic that the electrode making has catalytic activity, can under alkaline condition, keep structure and chemically reactive stable, and its preparation technology is simple, is applicable to scale operation.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: the compound hydrogen-precipitating electrode of a kind of three-dimensional foam Ni copper and cobalt, comprise: electrode, described electrode is to be carrier by three-dimensional foam nickel, copper and cobalt are loaded metal, and by electrochemical method, be deposited on successively the surface of three-dimensional foam nickel, and wherein metallic copper coating is interior, and cobalt metal coating is outside.
Preferably, the purity of described carrier is 99.99% three-dimensional porous nickel foam, and porosity is 95%.
A preparation method for the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt, carries out according to following steps,
A, by three-dimensional foam nickel degreasing degreasing 1-2 minute in acetone, with ultrapure water, clean, be then placed on acidifying activation in the hydrochloric acid soln of 18wt.%, be finally placed on ultrasonic 4-7 minute in ultrapure water;
B, the three-dimensional foam nickel after processing in step a is put in copper plating solution, take copper sheet as anode, three-dimensional foam nickel is negative electrode, in current density, is 0.01-0.05A/cm
2electric current under use multifunctional pulse electroplating power supply galvanic deposit 500-700s;
C, by electrochemical deposition in step b the three-dimensional foam nickel of copper with ultrapure water, clean, and then in ultrapure water ultrasonic 4-7 minute;
D, the three-dimensional foam nickel after ultrasonic in step c is put in cobalt plating solution, take cobalt rod as anode, the three-dimensional foam nickel after copper facing is ultrasonic is negative electrode, in current density, is 0.01-0.05 A/cm
2electric current under use multifunctional pulse electroplating power supply galvanic deposit 500-700s;
E, the three-dimensional foam nickel that electrochemical deposition in steps d is crossed to copper and cobalt clean with ultrapure water, then are placed in after the ultrasonic 4-7 of ultrapure water minute;
Envrionment temperature in f, above-mentioned steps a, b, c, d, e is 10-30 ℃, can obtain the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt.
Preferably, the copper plating solution in described step b or be pyrophosphate copper plating solution, or be alkaline cyanide-free copper plating solution, or be acid copper plating solution.
Preferably, the cobalt plating solution in described steps d or be vitriol cobalt plating solution, or be chloride system cobalt plating solution.
Preferably, described pyrophosphate copper plating solution or be copper pyrophosphate solution, or be one or both mixed solution in copper pyrophosphate solution and potassium pyrophosphate solution, ammonium citrate solution; Described alkaline cyanide-free copper plating solution or be cupric sulfate pentahydrate solution, or be one or more mixed solution in cupric sulfate pentahydrate solution and biuret solution, sodium hydroxide solution, glycerine; Described acid copper plating solution or be the mixed solution of cupric sulfate pentahydrate and boric acid.
Preferably, described vitriol cobalt plating solution or be heptahydrate solution, or be one or both mixed solution in heptahydrate solution and triethanolamine solution, ZCA additive; Described chloride system cobalt plating solution or be CoCL2 6H2O solution, or be the mixed solution of CoCL2 6H2O and boric acid.
The present invention compared with prior art has following beneficial effect.
1, the three-dimensional foam Ni copper that prepared by the present invention and the hydrogen-precipitating electrode of cobalt, by using three-dimensional porous nickel foam to do carrier, effectively increased contact reacts area.
2, the three-dimensional foam Ni copper that prepared by the present invention and the hydrogen-precipitating electrode of cobalt, by electrochemically depositing copper and cobalt on nickel foam, utilize its synergistic effect, greatly reduce the overpotential of hydrogen evolution of nickel foam, improved the performance of electrocatalytic hydrogen evolution and the stability of electrode.
3, in the present invention, base metal copper and cobalt and nickel foam are effectively combined, comparing other loads has precious metal element hydrogen-precipitating electrode, and starting material source is abundant, and low price, has reduced production cost greatly.
4, the present invention is by electrochemical method successively deposited copper thin layer and cobalt thin layer, and control, affected by environment little is stablized, is easy to this technical maturity.
5, the inventive method technique is simple, easy and simple to handle, is applicable to preparing on a large scale the compound hydrogen-precipitating electrode of high reactivity of three-dimensional foam Ni copper and cobalt.
Accompanying drawing explanation
Fig. 1 is the macrostate figure of the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt in the present invention.
Fig. 2 is that in the present invention, the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt amplifies the scanning electron microscope (SEM) photograph of 500 times.
Fig. 3 is that in the present invention, the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt amplifies the scanning electron microscope (SEM) photograph of 5000 times.
Fig. 4 is that the surface chemistry composition EDX of the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt in the present invention can spectrogram.
Fig. 5 is three-dimensional foam Ni copper and the compound hydrogen-precipitating electrode of cobalt and the XRD figure of pure foam nickel electrode spectrum comparison diagram in the present invention.
Fig. 6 is three-dimensional foam Ni copper and the compound hydrogen-precipitating electrode of cobalt and the evolving hydrogen reaction cyclic voltammetric comparison diagram of pure foam nickel electrode in the present invention.
Embodiment
Below in conjunction with accompanying drawing, specific embodiments of the invention are described further.
The compound hydrogen-precipitating electrode of a kind of three-dimensional foam Ni copper and cobalt, comprise: electrode, it is characterized in that: described electrode is to be carrier by three-dimensional foam nickel, metallic copper and cobalt are loaded metal, and by being electrochemically-deposited in the surface of three-dimensional foam nickel, described carrier is that purity is 99.99% three-dimensional porous nickel foam, and porosity is 95%.
As shown in Figure 1, the macrostate figure of the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt.Fig. 2 is low power scanning electron microscope (SEM) photograph, can see obvious three-dimensional framework structure.Fig. 3 is high power stereoscan photograph, can see that the compound hydrogen-precipitating electrode of three-dimensional foam nickel surface is owing to having deposited successively coarse that copper layer and cobalt layer become.Fig. 4 is the surface chemistry composition EDX energy spectrogram of the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt, and by finding out by spectrogram, the cobalt atom on electrode top layer approaches 99%, also has a small amount of copper atom to be detected.
Embodiment 1
A preparation method for the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt, carries out according to following steps,
A, by three-dimensional foam nickel degreasing degreasing 1 minute in acetone, with ultrapure water, clean, be then placed on acidifying activation in the hydrochloric acid soln of 18wt.%, be finally placed in ultrapure water ultrasonic 4 minutes;
B, the three-dimensional foam nickel after processing in step a is put into copper pyrophosphate solution, or in copper pyrophosphate solution and potassium pyrophosphate solution, ammonium citrate solution in one or both mixed solution, take copper sheet as anode, and three-dimensional foam nickel is negative electrode, in current density, is 0.01A/cm
2electric current under use multifunctional pulse electroplating power supply galvanic deposit 500s;
C, by electrochemical deposition in step b the three-dimensional foam nickel of copper with ultrapure water, clean, and then in ultrapure water ultrasonic 4 minutes;
D, the three-dimensional foam nickel after ultrasonic in step c is put into heptahydrate solution, or in heptahydrate solution and triethanolamine solution, ZCA additive in one or both mixed solution, take cobalt rod as anode, three-dimensional foam nickel after copper facing is ultrasonic is negative electrode, in current density, is 0.05A/cm
2electric current under use multifunctional pulse electroplating power supply galvanic deposit 500s;
E, the three-dimensional foam nickel that electrochemical deposition in steps d is crossed to copper and cobalt clean with ultrapure water, then are placed in ultrapure water after ultrasonic 4 minutes;
Envrionment temperature in f, above-mentioned steps a, b, c, d, e is 10 ℃, can obtain the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt.
Embodiment 2
A preparation method for the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt, carries out according to following steps,
A, by three-dimensional foam nickel degreasing degreasing 1 minute in acetone, with ultrapure water, clean, be then placed on acidifying activation in the hydrochloric acid soln of 18wt.%, be finally placed in ultrapure water ultrasonic 5 minutes;
B, the three-dimensional foam nickel after processing in step a is put into cupric sulfate pentahydrate solution, or in cupric sulfate pentahydrate solution and biuret solution, sodium hydroxide solution, glycerine in one or more mixed solution, take copper sheet as anode, and three-dimensional foam nickel is negative electrode, in current density, is 0.03A/cm
2electric current under use multifunctional pulse electroplating power supply galvanic deposit 600s;
C, by electrochemical deposition in step b the three-dimensional foam nickel of copper with ultrapure water, clean, and then in ultrapure water ultrasonic 5 minutes;
D, the three-dimensional foam nickel after ultrasonic in step c is put in the solution of heptahydrate and trolamine, take cobalt rod as anode, the three-dimensional foam nickel after copper facing is ultrasonic is negative electrode, in current density, is 0.03A/cm
2electric current under use multifunctional pulse electroplating power supply galvanic deposit 600s;
E, the three-dimensional foam nickel that electrochemical deposition in steps d is crossed to copper and cobalt clean with ultrapure water, then are placed in ultrapure water after ultrasonic 5 minutes;
Envrionment temperature in f, above-mentioned steps a, b, c, d, e is 20 ℃, can obtain the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt.
Embodiment 3
A preparation method for the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt, carries out according to following steps,
A, by three-dimensional foam nickel degreasing degreasing 1 minute in acetone, with ultrapure water, clean, be then placed on acidifying activation in the hydrochloric acid soln of 18wt.%, be finally placed in ultrapure water ultrasonic 7 minutes;
B, the three-dimensional foam nickel after processing in step a is put in the mixed solution of cupric sulfate pentahydrate and boric acid, take copper sheet as anode, three-dimensional foam nickel is negative electrode, in current density, is 0.05A/cm
2electric current under use multifunctional pulse electroplating power supply galvanic deposit 700s;
C, by electrochemical deposition in step b the three-dimensional foam nickel of copper with ultrapure water, clean, and then in ultrapure water ultrasonic 7 minutes;
D, the three-dimensional foam nickel after ultrasonic in step c is put in CoCL2 6H2O and boric acid mixing solutions, take cobalt rod as anode, the three-dimensional foam nickel after copper facing is ultrasonic is negative electrode, in current density, is 0.01A/cm
2electric current under use multifunctional pulse electroplating power supply galvanic deposit 700s;
E, the three-dimensional foam nickel that electrochemical deposition in steps d is crossed to copper and cobalt clean with ultrapure water, then are placed in ultrapure water after ultrasonic 7 minutes;
Envrionment temperature in f, above-mentioned steps a, b, c, d, e is 30 ℃, can obtain the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt.
As shown in Figure 5, the XRD crystalline structure figure contrast of the compound hydrogen-precipitating electrode of pure foam nickel and three-dimensional foam Ni copper and cobalt, can see that surperficial cobalt is face-centred cubic structure, its diffraction peak almost overlaps with the diffraction peak of matrix nickel, can detect faint copper diffraction peak simultaneously.The cyclic voltammetric liberation of hydrogen curve of the compound hydrogen-precipitating electrode that Fig. 6 has provided respectively pure foam nickel and three-dimensional foam Ni copper and cobalt in 1.0M potassium hydroxide solution, scanning speed is 50 mVs
-1, it is active that the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt shows obviously high electrocatalytic hydrogen evolution.
In sum, three-dimensional foam Ni copper prepared by the present invention and the hydrogen-precipitating electrode of cobalt, by using three-dimensional porous nickel foam to do carrier, effectively increased contact reacts area; By electrochemically depositing copper layer and cobalt layer successively on nickel foam, utilize its synergistic effect, greatly reduce the overpotential of hydrogen evolution of nickel foam, improved the stability of its electrocatalytic hydrogen evolution performance and electrode, by base metal copper and cobalt and nickel foam are effectively combined, compare the hydrogen-precipitating electrode that other loads have precious metal element, starting material source is abundant simultaneously, low price, greatly reduces production cost.
By reference to the accompanying drawings embodiments of the invention are described in detail above; but the present invention is not limited to above-described embodiment; in the ken possessing those of ordinary skills; various variations can also be under the prerequisite that does not depart from aim of the present invention, made obtaining, also protection scope of the present invention should be considered as.
Claims (7)
1. the compound hydrogen-precipitating electrode of a three-dimensional foam Ni copper and cobalt, comprise: electrode, it is characterized in that: described electrode is to be carrier by three-dimensional foam nickel, copper and cobalt are loaded metal, and by electrochemical method, be deposited on successively the surface of three-dimensional foam nickel, wherein metallic copper coating is interior, and cobalt metal coating outside.
2. the compound hydrogen-precipitating electrode of a kind of three-dimensional foam Ni copper as claimed in claim 1 and cobalt, is characterized in that: the purity of described carrier is 99.99% three-dimensional porous nickel foam, and porosity is 95%.
3. the preparation method of the compound hydrogen-precipitating electrode of a kind of three-dimensional foam Ni copper as claimed in claim 1 and cobalt, is characterized in that: according to following steps, carries out,
A, by three-dimensional foam nickel degreasing degreasing 1-2 minute in acetone, with ultrapure water, clean, be then placed on acidifying activation in the hydrochloric acid soln of 18wt.%, be finally placed on ultrasonic 4-7 minute in ultrapure water;
B, the three-dimensional foam nickel after processing in step a is put in copper plating solution, take copper sheet as anode, three-dimensional foam nickel is negative electrode, in current density, is 0.01-0.05A/cm
2electric current under use multifunctional pulse electroplating power supply galvanic deposit 500-700s;
C, by electrochemical deposition in step b the three-dimensional foam nickel of copper with ultrapure water, clean, and then in ultrapure water ultrasonic 4-7 minute;
D, the three-dimensional foam nickel after ultrasonic in step c is put in cobalt plating solution, take cobalt rod as anode, the three-dimensional foam nickel after copper facing is ultrasonic is negative electrode, in current density, is 0.01-0.05 A/cm
2electric current under use multifunctional pulse electroplating power supply galvanic deposit 500-700s;
E, the three-dimensional foam nickel that electrochemical deposition in steps d is crossed to copper and cobalt clean with ultrapure water, then are placed in after the ultrasonic 4-7 of ultrapure water minute;
Envrionment temperature in f, above-mentioned steps a, b, c, d, e is 10-30 ℃, can obtain the compound hydrogen-precipitating electrode of three-dimensional foam Ni copper and cobalt.
4. the preparation method of the compound hydrogen-precipitating electrode of a kind of three-dimensional foam Ni copper as claimed in claim 3 and cobalt, it is characterized in that: the copper plating solution in described step b or for pyrophosphate copper plating solution, or be alkaline cyanide-free copper plating solution, or be acid copper plating solution.
5. the preparation method of the compound hydrogen-precipitating electrode of a kind of three-dimensional foam Ni copper as claimed in claim 3 and cobalt, is characterized in that: the cobalt plating solution in described steps d or be vitriol cobalt plating solution, or be chloride system cobalt plating solution.
6. the preparation method of the compound hydrogen-precipitating electrode of a kind of three-dimensional foam Ni copper as claimed in claim 4 and cobalt, it is characterized in that: described pyrophosphate copper plating solution or for copper pyrophosphate solution, or be one or both mixed solution in copper pyrophosphate solution and potassium pyrophosphate solution, ammonium citrate solution; Described alkaline cyanide-free copper plating solution or be cupric sulfate pentahydrate solution, or be one or more mixed solution in cupric sulfate pentahydrate solution and biuret solution, sodium hydroxide solution, glycerine; Described acid copper plating solution or be the mixed solution of cupric sulfate pentahydrate and boric acid.
7. the preparation method of the compound hydrogen-precipitating electrode of a kind of three-dimensional foam Ni copper as claimed in claim 5 and cobalt, it is characterized in that: described vitriol cobalt plating solution or for heptahydrate solution, or be one or both mixed solution in heptahydrate solution and triethanolamine solution, ZCA additive; Described chloride system cobalt plating solution or be CoCL2 6H2O solution, or be the mixed solution of CoCL2 6H2O and boric acid.
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