CN110438528B - Modified foamed nickel loaded noble metal catalyst hydrogen evolution electrode and preparation method thereof - Google Patents
Modified foamed nickel loaded noble metal catalyst hydrogen evolution electrode and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a modified nickel foam supported noble metal catalyst hydrogen evolution electrode and a preparation method thereof, and the modified nickel foam supported noble metal catalyst hydrogen evolution electrode comprises the following steps: (1) pretreating foamed nickel; (2) taking the pretreated foamed nickel as an anode, a platinum sheet as a cathode and an alcohol-water mixed solution of ammonium salt as an electrolyte, and carrying out anodic oxidation retreatment to obtain a modified foamed nickel matrix; (3) placing the modified foam nickel substrate in a precursor homogeneous phase solution containing a noble metal element, heating, and growing the noble metal element on the surface of the modified foam nickel in situ. The foam nickel used in the invention has rich sources, the electrode preparation process is simple and controllable, and the equipment requirement is lower; the prepared noble metal catalyst has small particle size, uniform dispersion and firm combination with a matrix; the loading capacity of the noble metal particles on the modified foam nickel matrix is low, so that the raw material cost is saved; the prepared electrode shows excellent electro-catalytic hydrogen evolution activity and stability for water decomposition, and has important application prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of electrocatalytic hydrogen evolution materials, and particularly relates to a modified nickel foam supported noble metal catalyst hydrogen evolution electrode and a preparation method thereof.
Background
Hydrogen energy has been widely considered as one of alternative clean energy sources to solve the current energy crisis and environmental pollution due to its characteristics of wide source, high energy density, environmental friendliness, and being renewable. Among many hydrogen production technologies, electrocatalytic water decomposition hydrogen can convert electric energy into stable chemical energy, can obtain pure hydrogen without generating other byproducts, and is a very competitive solution for sustainable energy storage. In the electrocatalytic water decomposition process, a high-efficiency catalyst is needed to reduce the overpotential of the hydrogen evolution reaction and improve the catalytic reaction rate, so that the research on the electrode material of the hydrogen evolution catalyst has important significance for promoting the development of the hydrogen energy technology.
The electrocatalytic water-splitting hydrogen-analyzing catalyst mainly comprises two main types of non-noble metals and noble metals, the non-noble metal electrocatalysts are concentrated on semiconductor materials such as transition metal sulfides, selenides, phosphides, carbides and nitrides, and the catalytic activity of the electrocatalysts can not completely meet the industrial requirements temporarily, so that the design of the efficient and stable electrocatalysts based on the noble metals is imperative. The noble metal has more empty d orbitals in the atomic orbitals, has smaller energy level spacing and is easy to coordinate with hydrogen atoms, so the noble metal has higher hydrogen evolution activity in electrocatalytic water decomposition. However, noble metal electrocatalysts are limited in their price and storage capacity, indirectly limiting the large-scale development of industrial hydrogen production. In order to solve the problem, the catalytic activity surface area of the catalyst is usually improved as much as possible, noble metal nano particles are loaded on a plurality of layers of non-noble metal materials or form a noble metal alloy, so that noble metals can be uniformly dispersed in the materials, the interatomic interaction is weakened, and the agglomeration of the noble metals is avoided.
The electrocatalytic performance of noble metal catalysts is related to many factors, including noble metal particle size, dispersibility, substrate material and binding force with the substrate material. The method for preparing the electrocatalytic hydrogen evolution electrode by using the conductive matrix to load the noble metal electrocatalyst in situ is an effective method for preparing the electrocatalytic hydrogen evolution electrode at low cost, has wide sources of commercial Nickel Foam (NF), good conductivity, high porosity and mechanical strength, and can be widely used as an electrode matrix for electrocatalytic water decomposition reaction.
However, the noble metal electrocatalyst is loaded on the foamed nickel substrate by using a coating method, so that the dispersity of the noble metal catalyst on the substrate cannot be effectively controlled, and the active component is easy to fall off from the substrate in the hydrogen release process to weaken the electrocatalytic stability of the electrode. Therefore, the development of a simple method for preparing a hydrogen evolution electrode with a unique structure and a high-activity noble metal catalyst still has a great challenge.
Disclosure of Invention
The invention aims to solve the problems and provide a modified nickel foam supported noble metal catalyst hydrogen evolution electrode and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a modified nickel foam supported noble metal catalyst hydrogen evolution electrode comprises the following steps:
(1) pretreating foamed nickel;
(2) carrying out anodic oxidation retreatment by taking the pretreated foamed nickel as an anode, a platinum sheet as a cathode and an alcohol-water mixed solution of ammonium salt as an electrolyte to obtain a modified foamed nickel matrix and obtain a modified matrix with a nano-porous shape;
(3) and placing the modified foam nickel substrate in a precursor homogeneous phase solution containing a noble metal element, heating, growing the noble metal element on the surface of the modified foam nickel in situ, cooling, washing and drying to obtain the hydrogen evolution electrode with the modified foam nickel loaded with the noble metal particles.
Further, the specific mode of the foam nickel pretreatment in the step (1) is that the foam nickel is respectively treated by ultrasonic in hydrochloric acid solution, ethanol and deionized water to remove surface oxides and grease, then dried in a constant temperature drying box, and then placed in a tubular furnace, and H is carried out2And carrying out temperature programming reduction treatment in the mixed atmosphere of/Ar, and cooling to room temperature to obtain the pretreated foamed nickel.
Further, the foamed nickel is commercial foamed nickel, the thickness of the foamed nickel is 1.0 mm-2.0 mm, and the surface density of the foamed nickel is 200-500 g/m2。
Further, H in the mixed gas2Volume ratio to Ar 1: 5-40 ℃, the reduction treatment temperature of the foamed nickel is 250-500 ℃, the temperature programming rate is 2-10 ℃, and the reduction treatment time is 1-4 h.
Further, the ammonium salt in the electrolyte in the step (2) is one or more of ammonium chloride, ammonium sulfate, ammonium fluoride, ammonium nitrate or ammonium bicarbonate, and the molar concentration of the ammonium salt is 0.0001-0.2 mol/L; the alcohol in the electrolyte is one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol or glycerol, and the mass content of the alcohol in the electrolyte is 5-99%; the volume ratio of alcohol to water in the electrolyte is 1: 0.02 to 2.
Further, in the step (2), the direct current power supply generated by the constant potential rectifier is used for carrying out anodic oxidation retreatment, the voltage of the direct current power supply is 2V-30V, and the time of anodic oxidation treatment is 10-300 min.
Further, the step (3) comprises the following specific steps: adding a precursor homogeneous solution containing noble metal elements into a hydrothermal kettle, placing a modified foam nickel substrate into the solution, sealing, heating to 100-180 ℃, preserving heat for 4-14 h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 40 ℃ to obtain the electrode with the modified foam nickel loaded with noble metal particles.
Further, the precursor containing the noble metal element in the step (3) is one or more of chloroauric acid, chloroplatinic acid, ammonium chlororuthenate, ammonium chlororhodate or ammonium chloropalladate.
Further, the solvent of the precursor solution containing the noble metal element in the step (3) is one or more of water, methanol, ethanol, propanol, isopropanol, ethylene glycol or glycerol, and the concentration of the noble metal element in the precursor solution is 0.0001-0.02 mol/L.
Further, the hydrogen evolution electrode comprises modified foam nickel, a noble metal electrocatalyst growing on the surface of the modified foam nickel in situ and an electrode for water decomposition hydrogen evolution reaction, wherein the noble metal electrocatalyst is one or more of Au, Pt, Ru, Rh and Pd.
Further, the noble metal electrocatalyst is granular, the diameter of the noble metal electrocatalyst is 2-50 nm, and the mass percentage of the noble metal loaded on the substrate is 0.02-1.0%.
Compared with the prior art, the invention has the following beneficial effects:
the foam nickel used in the invention has rich sources, the electrode preparation process is simple and controllable, and the equipment requirement is lower.
The hydrogen evolution electrode of the modified foam nickel supported noble metal electrocatalyst provided by the invention realizes effective dispersion of noble metal particles on the surface of the modified foam nickel base by modifying commercial foam nickel; the low load capacity of the noble metal catalyst on the modified foam nickel matrix is realized by a solvothermal loading method, the mass percentage of the noble metal catalyst is not more than 1%, and the raw material cost is saved; the binding force between the noble metal electrocatalyst material on the electrode and the modified foam nickel matrix is strong, and the problem of falling off of active components in the water decomposition process is effectively solved.
The noble metal electrocatalytic material prepared by the method has a strong synergistic effect with a modified foamed nickel matrix, can remarkably improve the electron transport capacity and the water activation capacity in the water decomposition hydrogen evolution reaction process, shows excellent electrocatalytic hydrogen evolution activity and stability for water decomposition, and has an important application prospect.
The invention adopts a novel method to modify commercial foam nickel, namely, the pretreated foam nickel is subjected to anodic oxidation, porous network nickel oxide can be generated on a foam nickel framework, and the active surface area of a foam nickel matrix is increased; the modified foamed nickel is subjected to heat treatment in a noble metal precursor alcohol aqueous solution, and meanwhile, noble metal nanodots and a nickel hydroxide heterojunction with a porous structure are generated, a high-dispersion noble metal active site is favorable for adsorption and reaction of hydrogen atoms, and the generated nickel hydroxide is favorable for decomposition of water and desorption of hydroxyl on the active site, so that the electro-catalytic hydrogen evolution rate can be effectively improved.
Drawings
Fig. 1 is an X-ray electron spectroscopy (XPS) spectrum of the modified foamed nickel-supported Pt particle electrode prepared in example 1.
Fig. 2 is a photograph of the elemental distribution (EELS) of the modified nickel foam supported Pt particle electrode prepared in example 1.
Fig. 3 is a test result of a modified nickel foam supported Pt particle electrode prepared in example 1 for a water dissociation Hydrogen Evolution Reaction (HER) for 24 hours continuously.
Fig. 4 is a Scanning Electron Microscope (SEM) photograph of the modified nickel foam supported Au particle electrode prepared in example 2.
Fig. 5 is an X-ray diffraction (XRD) spectrum of the modified nickel foam supported Au particle electrode prepared in example 2.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
Commercial nickel foam (thickness 1.6mm, areal density 320 g/m)2) Cut into 2 x 3cm2The size of the powder is placed in 3mol/L hydrochloric acid aqueous solution for ultrasonic treatment for 15min, washed by water, sequentially placed in absolute ethyl alcohol and deionized water for ultrasonic treatment for 20min, and then placed in a constant temperature drying oven for drying at 60 ℃ to constant weight. Placing the dried foamed nickel in a tube furnace and using H2H in an amount of 15% by volume2And (3) carrying out temperature programmed reduction treatment on the/Ar mixed gas, controlling the reduction treatment temperature of the foamed nickel to be 350 ℃, controlling the temperature programmed rate to be 10 ℃/min, controlling the reduction treatment time to be 1h, and cooling to room temperature to obtain the pretreated foamed nickel.
Preparing 0.005mol/L NH4And F, electrolyte, wherein the mixed solvent is ethylene glycol and water, and the volume ratio of the ethylene glycol to the water is 1: 0.1, taking the pretreated foamed nickel as an anode, a commercial platinum sheet as a cathode, and a constant potential rectifier as a direct current power supply, and carrying out anodic oxidation treatment on the foamed nickel, wherein the anodic oxidation voltage is controlled at 20V, and the anodic oxidation treatment time is 120 min. After treatment, a large amount of deionized water is used for washing the foamed nickel, and then the foamed nickel is dried in a constant-temperature drying oven at 60 ℃ to obtain the modified foamed nickel matrix.
Adding 0.003mol/L ethanol water solution of chloroplatinic acid (wherein the volume of ethanol and water is 1:1) into a 50mL hydrothermal kettle, placing the modified foam nickel matrix into the solution, sealing, heating to 120 ℃, preserving heat for 6h, cooling to room temperature, washing with deionized water and absolute ethanol, and drying in a vacuum drying oven at 40 ℃ to obtain the modified foam nickel electrode loaded with Pt particles.
FIG. 1 shows an XPS spectrum of a modified nickel foam supported Pt particle electrode prepared in example 1, and it can be seen that Pt exists in a simple substance form on a modified nickel foam substrate; FIG. 2 shows EELS photographs of modified nickel foam supported Pt particle electrodes prepared in example 1, which show that Pt has better dispersibility on a modified nickel foam substrate.
The performance of the electrode on the water dissociation hydrogen evolution reaction was monitored with the CHI 660E electrochemical workstation at a test ambient temperature of 25 ℃. The procedure was carried out in 1.0M aqueous KOH (pH 13.7) using a standard three-electrode system, the electrode prepared being the working electrode (1cm × 1cm × 1mm), platinum foil (1cm × 1cm) as the counter electrode and Hg/HgO as the reference electrode. The prepared electrode shows excellent electrocatalytic hydrogen evolution activity on water decomposition, and the current density of the electrode is 10mA/cm2The overpotential at this time was only 29mV, with a Tafel slope of 43.5 mV/dec. Fig. 3 shows the test results of the Hydrogen Evolution Reaction (HER) of the modified nickel foam supported Pt particle electrode prepared in example 1 after 24 hours of continuous water decomposition, and it can be seen that the overpotential change is small after 24 hours of continuous reaction in the above system, and the electrode shows good stability.
Example 2
Commercial nickel foam (thickness 1.2mm, areal density 300 g/m)2) Cut into 2 x 3cm2The size of the powder is placed in 3mol/L hydrochloric acid aqueous solution for ultrasonic treatment for 15min, washed by water, sequentially placed in absolute ethyl alcohol and deionized water for ultrasonic treatment for 20min, and then placed in a constant temperature drying oven for drying at 60 ℃ to constant weight. Placing the dried foamed nickel in a tube furnace and using H2H in a volume content of 5%2Carrying out temperature programmed reduction treatment on the/Ar mixed gas, controlling the reduction treatment temperature of the foamed nickel to be 300 ℃, the temperature programmed rate to be 5 ℃/min, controlling the reduction treatment time to be 1h, and cooling to room temperature to obtain the nickel-based alloyObtaining the pretreated foamed nickel.
Preparing 0.005mol/L NH4NO3The electrolyte takes ethanol and water as a mixed solvent, and the volume ratio of the ethanol to the water is 1:1, taking the pretreated foamed nickel as an anode, a commercial platinum sheet as a cathode, and a constant potential rectifier as a direct current power supply to carry out anodic oxidation treatment on the foamed nickel, wherein the anodic oxidation voltage is controlled to be 5V, and the anodic oxidation treatment time is 20 min. After treatment, a large amount of deionized water is used for washing the foamed nickel, and then the foamed nickel is dried in a constant-temperature drying oven at 60 ℃ to obtain the modified foamed nickel matrix.
Adding 0.01mol/L chloroauric acid aqueous solution into a 50mL hydrothermal kettle, placing the modified foam nickel substrate in the solution, sealing, heating to 150 ℃, preserving heat for 4h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 40 ℃ to obtain the modified foam nickel Au particle-loaded electrode.
FIG. 4 shows an SEM photograph of the modified nickel foam loaded Au particle electrode prepared in example 2, which shows that Au has better dispersibility on nickel foam; FIG. 5 shows the XRD spectrum of the modified nickel foam supported Au particle electrode prepared in example 2, and it can be seen that the characteristic diffraction peak of Au is not obvious, which indicates that Au on the synthesized electrode has smaller particle size.
The performance of the electrode on the water dissociation hydrogen evolution reaction was monitored with the CHI 660E electrochemical workstation at a test ambient temperature of 25 ℃. The procedure was carried out in 1.0M aqueous KOH (pH 13.7) using a standard three-electrode system, the electrode prepared being the working electrode (1cm × 1cm × 1mm), platinum foil (1cm × 1cm) as the counter electrode and Hg/HgO as the reference electrode. The prepared electrode shows excellent electrocatalytic hydrogen evolution activity on water decomposition, and the current density of the electrode is 10mA/cm2The overpotential of the electrode is only 43mV, the Tafel slope is 47.6mV/dec, and the overpotential change of the electrode after continuous reaction for 24 hours in the system is small, so that the electrode shows good stability.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. A preparation method of a modified nickel foam supported noble metal catalyst hydrogen evolution electrode is characterized by comprising the following steps:
(1) pretreating foamed nickel;
(2) taking the pretreated foamed nickel as an anode, a platinum sheet as a cathode and an alcohol-water mixed solution of ammonium salt as an electrolyte, and carrying out anodic oxidation retreatment to obtain a modified foamed nickel matrix;
(3) placing the modified foam nickel substrate in a precursor homogeneous phase solution containing a noble metal element, heating, growing the noble metal element on the surface of the modified foam nickel in situ, cooling, washing and drying to obtain the hydrogen evolution electrode with the modified foam nickel loaded with noble metal particles;
the specific mode of the foam nickel pretreatment in the step (1) is that the foam nickel is respectively treated by ultrasonic in hydrochloric acid solution, ethanol and deionized water to remove surface oxides and grease, then dried in a constant temperature drying box, and then placed in a tubular furnace, and H2Carrying out temperature programming reduction treatment in a mixed atmosphere of/Ar, and cooling to room temperature to obtain pretreated foamed nickel;
the precursor containing the noble metal elements in the step (3) is one or more of chloroauric acid, chloroplatinic acid, ammonium chlororuthenate, ammonium chlororhodate or ammonium chloropalladate;
the solvent of the precursor solution containing the noble metal element in the step (3) is one or more of water, methanol, ethanol, propanol, isopropanol, ethylene glycol or glycerol, and the concentration of the noble metal element in the precursor solution is 0.0001-0.02 mol/L.
2. The modified nickel foam supported noble metal catalyst hydrogen evolution of claim 1The preparation method of the electrode is characterized in that the foamed nickel is commercial foamed nickel, the thickness of the foamed nickel is 1.0-2.0 mm, and the surface density of the foamed nickel is 200-500 g/m2。
3. The method for preparing the modified nickel foam supported noble metal catalyst hydrogen evolution electrode as claimed in claim 1, wherein H in the mixed gas2Volume ratio to Ar 1: 5-40 ℃, the reduction treatment temperature of the foamed nickel is 250-500 ℃, the temperature programming rate is 2-10 ℃, and the reduction treatment time is 1-4 h.
4. The preparation method of the modified nickel foam supported noble metal catalyst hydrogen evolution electrode as claimed in claim 1, wherein the ammonium salt in the electrolyte in the step (2) is one or more of ammonium chloride, ammonium sulfate, ammonium fluoride, ammonium nitrate or ammonium bicarbonate, and the molar concentration of the ammonium salt is 0.0001-0.2 mol/L;
the alcohol in the electrolyte is one or more of methanol, ethanol, propanol, isopropanol, ethylene glycol or glycerol, and the mass content of the alcohol in the electrolyte is 5-99%;
the volume ratio of alcohol to water in the electrolyte is 1: 0.02 to 2.
5. The preparation method of the modified nickel foam supported noble metal catalyst hydrogen evolution electrode as claimed in claim 1, wherein the step (2) is performed with anodic oxidation reprocessing by a direct current power supply generated by a potentiostat, the voltage of the direct current power supply is 2V-30V, and the time of the anodic oxidation reprocessing is 10-300 min.
6. A hydrogen evolution electrode prepared by the preparation method according to any one of claims 1 to 5, wherein the hydrogen evolution electrode comprises modified nickel foam, a noble metal electrocatalyst which grows in situ on the surface of the modified nickel foam and an electrode for water decomposition hydrogen evolution reaction, and the noble metal electrocatalyst is one or more of Au, Pt, Ru, Rh and Pd.
7. The hydrogen evolution electrode prepared by the preparation method according to claim 6, wherein the noble metal electrocatalyst is in a granular shape, the diameter of the noble metal electrocatalyst is 2-50 nm, and the mass percentage of the noble metal loaded on the substrate is 0.02-1.0%.
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| IT202000020575A1 (en) | 2020-08-28 | 2022-02-28 | Industrie De Nora Spa | ELECTRODE FOR GAS EVOLUTION IN ELECTROLYTIC PROCESSES |
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