Foam nickel-molybdenum alloy doped with carbon quantum dots and preparation method thereof
阅读说明：本技术 一种掺杂碳量子点的泡沫镍钼合金及制备方法 (Foam nickel-molybdenum alloy doped with carbon quantum dots and preparation method thereof ) 是由 朱日龙 李国希 柳栋宝 童春义 王朝阳 潘亮 于 2020-12-31 设计创作，主要内容包括：本发明公开一种掺杂碳量子点的泡沫镍钼合金及制备方法,该方法包括以下步骤：(1)按照已知配方制备一份电沉积泡沫镍钼合金的电镀液；(2)采用葡萄糖水热法制备葡萄糖碳量子点溶液；(3)将葡萄糖碳量子点冷冻干燥成碳量子点固体,并将其研磨成碳量子点粉末后加入步骤(1)所得的溶液中以得到电沉积溶液；(4)以镍、钼为阳极,泡沫镍为阴极,放置于所述电沉积溶液中,采用单阴极、二阳极的方式进行电沉积；(5)将上述溶液加热到35～55℃,以表观阴极电流密度110～130mA/cm～2进行电沉积。利用该方法制备的掺杂碳量子点的泡沫镍钼合金具有镀层质量好、析氢效果好、稳定性强且含钼量高的有益效果。(The invention discloses a foamed nickel-molybdenum alloy doped with carbon quantum dots and a preparation method thereof, wherein the method comprises the following steps: (1) preparing a bath of electrodeposited foamed nickel molybdenum alloy according to known formulations; (2) preparing a glucose carbon quantum dot solution by adopting a glucose hydrothermal method; (3) freeze-drying glucose carbon quantum dots into carbon quantum dot solids, grinding the carbon quantum dot solids into carbon quantum dot powder, and adding the carbon quantum dot powder into the solution obtained in the step (1) to obtain an electrodeposition solution; (4) putting nickel and molybdenum as anodes and foamed nickel as cathodes in the electrodeposition solution, and performing electrodeposition in a single-cathode and two-anode mode; (5) heating the solution to 35-55 ℃ at an apparent cathode current density of 110-130 mA/cm 2 To carry outAnd (4) electrodeposition. The foam nickel-molybdenum alloy doped with the carbon quantum dots prepared by the method has the beneficial effects of good coating quality, good hydrogen evolution effect, strong stability and high molybdenum content.)
1. A preparation method of a foam nickel-molybdenum alloy doped with carbon quantum dots is characterized by comprising the following steps:
(1) providing carbon quantum dot powder and electroplating solution of the electrodeposition foam nickel-molybdenum alloy, and adding the carbon quantum dot powder into the electroplating solution of the electrodeposition foam nickel-molybdenum alloy to prepare electrodeposition solution;
(2) providing foamed nickel, placing the foamed nickel in the electrodeposition solution, and performing electrodeposition by using nickel and molybdenum as anodes and foamed nickel as cathodes in a single-cathode and two-anode mode;
(3) heating the solution to 35-55 ℃ at an apparent cathode current density of 110-130 mA/cm2And performing electrodeposition.
2. The preparation method according to claim 1, wherein the concentration of the carbon quantum dot powder in the electrodeposition solution in the step (1) is 50 to 150 mg/L.
3. The preparation method according to claim 2, wherein the concentration of the carbon quantum dot powder in the electrodeposition solution in the step (1) is 80-120 mg/L.
4. The method according to claim 1, wherein the method for preparing the carbon quantum dot powder in step (1) comprises: preparing a glucose carbon quantum dot solution by adopting a glucose hydrothermal method; and (3) freeze-drying the glucose carbon quantum dot solution to prepare a carbon quantum dot solid, and grinding the carbon quantum dot solid into carbon quantum dot powder.
5. The method as claimed in claim 1, wherein the plating solution in step (1) comprises a nickel salt and a molybdenum salt, and the molecular ratio of the nickel salt to the molybdenum salt is in the range of 6: 1-10: 1.
6. the method according to claim 5, wherein the nickel salt and the molybdenum salt in step (1) are nickel sulfate and ammonium molybdate, and the electroplating solution further comprises deionized water, nickel sulfate, ammonium molybdate, trisodium citrate, sodium chloride, 25% ammonia, 1, 4-butynediol and saccharin.
7. The method according to claim 1, wherein the cathode is degreased, derusted and activated before the electrodeposition in step (2); the anode was activated with nitric acid.
8. A foamed nickel molybdenum alloy doped with carbon quantum dots, which is prepared by the preparation method of any one of the claims 1 to 7.
9. The foamed nickel molybdenum alloy according to claim 8, wherein the material is used as a cathode to realize high-efficiency hydrogen evolution.
Technical Field
The invention relates to the technical field of preparation of hydrogen evolution materials, in particular to a preparation method of a foam nickel-molybdenum alloy doped with carbon quantum dots.
Background
The continuous consumption of fossil energy leads to a gradual decline in reserves, which will eventually lead to their exhaustion, which has prompted the search for other types of new energy. Hydrogen is an ideal new energy source and can replace part of fossil fuels. The electrolysis of water to produce hydrogen is one of the important methods to capture hydrogen energy, but it requires a high performance electrocatalyst. Platinum and platinum-based metals have high electrocatalytic activity, but their application is limited by high cost. Therefore, there is an urgent need to develop a durable and inexpensive catalytic material having high hydrogen evolution reactivity. Recently, many efforts have been made to develop transition metal (e.g., nickel, cobalt, iron, molybdenum) alloys and carbides, nitrides, sulfides and phosphides thereof. Particularly, foamed nickel having a unique structure has received much attention due to its high catalytic activity. Furthermore, the properties of the nickel foam may be further improved by adding other metals, such as molybdenum to the nickel foam to form a nickel-molybdenum alloy, since a synergistic effect may be created between the different metals. Thus, bimetallic catalysts are generally more active.
Among common binary alloy materials, the hydrogen evolution activity of nickel-molybdenum alloy is better than that of nickel-cobalt alloy, nickel-tungsten alloy and nickel-iron alloy. The content of molybdenum in the nickel-molybdenum alloy is the key for determining the hydrogen evolution performance of the alloy, but the conventional method is difficult to realize deposition with higher concentration, so that the application and the hydrogen evolution effect of the nickel-molybdenum alloy are limited. Therefore, the content and the dispersion degree of molybdenum in the nickel-molybdenum alloy are improved, and the hydrogen evolution performance of the nickel-molybdenum alloy is expected to be improved.
The foregoing description is provided for general background information and is not admitted to be prior art.
Disclosure of Invention
The invention aims to provide a foam nickel-molybdenum alloy with good plating quality, good hydrogen evolution effect, strong stability and high molybdenum content and a preparation method thereof.
The invention provides a preparation method of a foam nickel-molybdenum alloy doped with carbon quantum dots, which comprises the following steps:
(1) providing carbon quantum dot powder and electroplating solution of the electrodeposition foam nickel-molybdenum alloy, and adding the carbon quantum dot powder into the electroplating solution of the electrodeposition foam nickel-molybdenum alloy to prepare electrodeposition solution;
(2) providing foamed nickel, placing the foamed nickel in the electrodeposition solution, and performing electrodeposition by using nickel and molybdenum as anodes and foamed nickel as cathodes in a single-cathode and two-anode mode;
(3) heating the solution to 35-55 ℃ at an apparent cathode current density of 110-130 mA/cm2And performing electrodeposition.
Further, the concentration of the carbon quantum dot powder in the electrodeposition solution in the step (1) is 50-150 mg/L.
Further, the concentration of the carbon quantum dot powder in the electrodeposition solution in the step (1) is 80-120 mg/L.
Further, the preparation method of the carbon quantum dot powder in the step (1) comprises the following steps: preparing a glucose carbon quantum dot solution by adopting a glucose hydrothermal method; and (3) freeze-drying the glucose carbon quantum dot solution to prepare a carbon quantum dot solid, and grinding the carbon quantum dot solid into carbon quantum dot powder.
Further, the electroplating solution in the step (1) comprises nickel salt and molybdenum salt, and the molecular ratio of the nickel salt to the molybdenum salt is in the range of 6: 1-10: 1.
further, the nickel salt and the molybdenum salt in the step (1) are nickel sulfate and ammonium molybdate, and the electroplating solution further comprises deionized water, nickel sulfate, ammonium molybdate, trisodium citrate, sodium chloride, 25% ammonia water, 1, 4-butynediol and saccharin.
Further, before the electrodeposition in the step (2), performing oil removal, rust removal and activation on the cathode; the anode was activated with nitric acid.
A foam nickel-molybdenum alloy doped with carbon quantum dots is prepared by the preparation method.
Further, the material is used as a cathode to realize high-efficiency hydrogen evolution.
The preparation method of the carbon quantum dot doped foam nickel-molybdenum alloy provided by the invention has the beneficial effects of good coating quality, good hydrogen evolution effect, strong stability and high molybdenum content.
(1) The electrodeposition is carried out by adopting a single cathode and two anodes. Because the anodic dissolution current efficiency of nickel and molybdenum is far higher than the cathodic deposition current efficiency of nickel and molybdenum, the current density is controlled by adjusting the voltage of the nickel and molybdenum anodes, thereby maintaining the stability of the concentration of nickel ions and molybdenum ions in the electrodeposition solution and electrodepositing the foam nickel-molybdenum alloy with stable quality.
(2) The preparation method adds the glucose carbon quantum dots into the formula. The addition of carbon quantum dots increases the surface area of the foamed nickel substrate, provides space for the deposition of more molybdenum particles, and provides more space for the adsorption and desorption of hydrogen. Meanwhile, the carbon quantum dots are also substances with low hydrogen evolution overpotentials, and can help to reduce the hydrogen evolution overpotentials of the foam nickel-molybdenum alloy.
(3) The temperature in the electrodeposition process of the preparation method is controlled to be 35-55 ℃, and the apparent cathode current density is 110-130 mA/cm2Deviations from this temperature range or current density range lead to a considerable reduction in the hydrogen evolution activity of the electrodeposited carbon quantum dot doped nickel molybdenum foam alloy.
(4) The foam nickel-molybdenum alloy doped with the carbon quantum dots prepared by the preparation method has good hydrogen evolution effect and low energy consumption. At 25 ℃ 5M H2SO4In solution, the cathodic current density measured according to the polarization curve is 200A/m2The voltage (vs SHE) can reach-0.085V.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
In this embodiment, the preparation method of the carbon quantum dot doped foam nickel-molybdenum alloy is to electrodeposit the nickel-molybdenum alloy on a foam nickel substrate and dope the carbon quantum dot, and the formula of the electrodeposition solution used in the method includes nickel sulfate, ammonium molybdate, trisodium citrate, sodium chloride, 25% by mass of ammonia water, 1, 4-butynediol, saccharin, and glucose carbon quantum dots. The method comprises the following steps:
(1) preparing a part of electroplating solution of the electrodeposited foamed nickel-molybdenum alloy according to a known formula, wherein the main components of the electroplating solution comprise deionized water, nickel sulfate, ammonium molybdate, trisodium citrate, sodium chloride, 25% ammonia water (mass fraction), 1, 4-butynediol and saccharin;
(2) preparing a glucose carbon quantum dot solution by adopting a glucose hydrothermal method;
(3) freezing and drying the glucose carbon quantum dot solution to prepare a carbon quantum dot solid, grinding the carbon quantum dot solid into carbon quantum dot powder, and adding the carbon quantum dot powder into the solution obtained in the step (1) to obtain an electrodeposition solution;
(4) taking nickel and molybdenum (which can be blocks, rods or particles and are held by a basket) as anodes and foamed nickel as cathodes, and performing electrodeposition by adopting a single-cathode mode and a double-anode mode;
(5) heating the solution to 35-55 ℃ at an apparent cathode current density of 110-130 mA/cm2And performing electrodeposition.
In the step (1), the nickel sulfate, the ammonium molybdate, the trisodium citrate, the sodium chloride, 25% ammonia water (mass fraction), the 1, 4-butynediol and the saccharin are respectively 80g, 10g, 160g, 10g, 30ml, 0.1g and 0.5g in each liter of electrodeposition solution.
The carbon quantum dot powder in the step (3) is 100mg in each liter of the electrodeposition solution.
Degreasing, derusting and activating the cathode before the electrodeposition in the step (4); the anode was activated with nitric acid.
The solution temperature in the step (5) is 45 ℃, and the apparent cathode current density is 115mA/cm2。
The electrodeposition layer obtained by the method has good quality, the electrodeposition solution system is stable, the operation is convenient, the air pollution is small, and the cathode current density measured according to the polarization curve is 200A/m2The standard potential can reach-0.085V, and the industrial production requirement can be met.
Example 2
In contrast to example 1, the solution temperature in step (5) of the process was 35 ℃ and the apparent cathodic currentThe density was 110mA/cm2。
The electrodeposition layer obtained by the method has good quality, the electrodeposition solution system is stable, the operation is convenient, the air pollution is small, and the cathode current density measured according to the polarization curve is 200A/m2The standard potential can reach-0.1V, and the industrial production requirement can be met.
Example 3
In contrast to example 1, in step (5) of the process, the solution temperature was 55 ℃ and the apparent cathodic current density was 130mA/cm2。
The electrodeposition layer obtained by the method has good quality, the electrodeposition solution system is stable, the operation is convenient, the air pollution is small, and the cathode current density measured according to the polarization curve is 200A/m2The standard potential can reach-0.1V, and the industrial production requirement can be met.
Example 4
Unlike example 1, this method uses a formulation with 50mg of carbon quantum dots per liter of electrodeposition solution.
The solution temperature in the step (5) is 45 ℃, and the apparent cathode current density is 115m A/cm2。
The electrodeposition layer obtained by the method has good quality, the electrodeposition solution system is stable, the operation is convenient, the air pollution is small, and the cathode current density measured according to the polarization curve is 200A/m2The standard potential can reach-0.11V, and the industrial production requirement can be met.
Example 5
Unlike example 1, this method uses a formulation with 50mg of carbon quantum dots per liter of electrodeposition solution.
The solution temperature in the step (5) is 35 ℃, and the apparent cathode current density is 110m A/cm2。
The electrodeposition layer obtained by the method has good quality, the electrodeposition solution system is stable, the operation is convenient, the air pollution is small, and the cathode current density measured according to the polarization curve is 200A/m2The standard potential can reach-0.13V, and the industrial production requirement can be met.
Example 6
Unlike example 1, this method uses a formulation with 50mg of carbon quantum dots per liter of electrodeposition solution.
The solution temperature in the step (5) is 55 ℃, and the apparent cathode current density is 130m A/cm2。
The electrodeposition layer obtained by the method has good quality, the electrodeposition solution system is stable, the operation is convenient, the air pollution is small, and the cathode current density measured according to the polarization curve is 200A/m2The standard potential can reach-0.13V, and the industrial production requirement can be met.
Example 7
Unlike example 1, the method used a formulation with 150mg of carbon quantum dots per liter of electrodeposition solution.
The solution temperature in the step (5) is 45 ℃, and the apparent cathode current density is 115m A/cm2。
The electrodeposition layer obtained by the method has good quality, the electrodeposition solution system is stable, the operation is convenient, the air pollution is small, and the cathode current density measured according to the polarization curve is 200A/m2The standard potential can reach-0.09V, and the industrial production requirement can be met.
Example 8
Unlike example 1, the method used a formulation with 150mg of carbon quantum dots per liter of electrodeposition solution.
The solution temperature in the step (5) is 35 ℃, and the apparent cathode current density is 110m A/cm2。
The electrodeposition layer obtained by the method has good quality, the electrodeposition solution system is stable, the operation is convenient, the air pollution is small, and the cathode current density measured according to the polarization curve is 200A/m2The standard potential can reach-0.11V, and the industrial production requirement can be met.
Example 9
Unlike example 1, the method used a formulation with 150mg of carbon quantum dots per liter of electrodeposition solution.
The solution temperature in the step (5) is 55 ℃, and the apparent cathode current density is 130m A/cm2。
The obtained electrodeposition layer has good quality, and the electrodeposition solution is liquidStable system, convenient operation, small air pollution, and cathode current density of 200A/m measured according to polarization curve2The standard potential can reach-0.11V, and the industrial production requirement can be met.
As used herein, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, including not only those elements listed, but also other elements not expressly listed.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.