CN116116423A - Active porous nickel-based catalyst, preparation method and application thereof - Google Patents

Active porous nickel-based catalyst, preparation method and application thereof Download PDF

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CN116116423A
CN116116423A CN202211618018.9A CN202211618018A CN116116423A CN 116116423 A CN116116423 A CN 116116423A CN 202211618018 A CN202211618018 A CN 202211618018A CN 116116423 A CN116116423 A CN 116116423A
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metal
nickel
catalyst
mesh
conductive substrate
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张琪
鞠贵冬
刘桂林
郑钦臻
张羽
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Jiangsu Shuangliang Hydrogen Energy Technology Co ltd
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Shuangliang New Energy Equipment Co ltd
Shuangliang Eco Energy Systems Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The invention provides an active porous nickel-based catalyst, which comprises a porous conductive substrate and a hydrogen evolution catalyst layer compounded on the surface of the porous conductive substrate; the hydrogen evolution catalyst layer is prepared by pore-forming a catalyst coating through alkali liquor, and the catalyst coating comprises a first metal, a second metal and silicon dioxide; the first metal is one or more of nickel, cobalt and ironSeed; the second metal is one or more of platinum, ruthenium and molybdenum; the hydrogen evolution catalyst comprises 30-90 atomic percent of first metal, 5-30 atomic percent of second metal and 5-60 atomic percent of Si. The invention uses plasma spraying technology to spray molybdenum, nickel and SiO 2 Proper proportioning is carried out, the thickness of the coating is controlled, and the utilization rate of the active site of the catalyst is improved. Using SiO 2 As a pore-forming agent, the pore-forming process does not produce hydrogen. The invention also provides a preparation method and application of the active porous nickel catalyst.

Description

Active porous nickel-based catalyst, preparation method and application thereof
Technical Field
The invention belongs to the technical field of hydrogen production by water electrolysis, and particularly relates to an active porous nickel-based catalyst, a preparation method and application thereof.
Background
The use of fossil fuels leads to the increase of global energy demand and climate change, and the advantages of the hydrogen, such as the highest energy density, good combustion performance, cleanness, no pollution and the like, are widely focused, so that people are promoted to research various catalytic systems so as to realize the conversion and storage of renewable energy and carbon neutral energy. In order to solve the problems of insufficient energy sources, environmental management and the like in the future, the aim of carbon neutralization and carbon peak is proposed, renewable energy sources are utilized for generating electricity, and then electrocatalytic water decomposition is carried out to produce hydrogen (H) 2 ) Providing a promising strategy for this goal. In recent years, with the continuous development of novel power generation technologies (such as solar power generation, wind power generation, nuclear power generation, hydroelectric power generation, geothermal power generation and the like) and the continuous optimization and upgrading of a power grid system, the advantages of the water electrolysis hydrogen production technology are continuously amplified.
To date, the most effective electrolyzed water catalysts are Pt group based noble metal material catalysts, which are difficult to use on a large scale in practical applications due to scarcity and high cost limitations. The most central problem faced by the current electrolytic water hydrogen production is the development of an efficient, stable and low-cost hydrogen production electrocatalyst. Among non-noble metals, ni has a lower free energy of hydrogen adsorption (ΔG H* ) Higher catalytic activity, and the catalytic activity in non-noble metal is expressed as Ni > Mo > Co > W > Te > Cu in turn. But in comparison with noble metals, is presentNi-based catalysts have low catalytic activity, poor electrical conductivity, slow hydrogen evolution process, poor durability, and these problems need to be ameliorated by suitable means.
At present, the mature preparation method of the alkaline electrocatalyst electrode mainly adopts methods of thermal spraying, electroplating and the like. Among them, the thermal spraying method is more common. The organic solvent is also unavoidable to pollute the environment in the preparation process of the catalyst electrode. For example, CN 113694928A reports the use of organic ligands and metal-to-metal organic complexes sprayed onto conductive substrates. Therefore, there is a need for a nickel-based electrocatalyst formulation that does not use organic compounds, is environmentally friendly, has high catalyst utilization, and is safer to prepare and use.
Disclosure of Invention
The invention aims to provide an active porous nickel-based catalyst, a preparation method and application thereof, and the active porous nickel-based catalyst has high electrocatalytic utilization rate, and the preparation process is environment-friendly and safe.
The invention provides an active porous nickel-based catalyst, which comprises a porous conductive substrate and a hydrogen evolution catalyst layer compounded on the surface of the porous conductive substrate;
the hydrogen evolution catalyst layer is prepared by pore-forming a catalyst coating through alkali liquor, and the catalyst coating comprises a first metal, a second metal and silicon dioxide;
the first metal is one or more of nickel, cobalt and iron; the second metal is one or more of platinum, ruthenium and molybdenum;
in the catalyst coating, the atomic percentage of the first metal is 30-90%, the atomic percentage of the second metal is 5-30%, and the atomic percentage of Si is 5-60%.
Preferably, the porous conductive substrate is nickel screen, and the mesh number of the nickel screen is 40-100 mesh.
Preferably, the thickness of the hydrogen evolution catalyst layer is 10 to 100 μm.
Preferably, the average pore diameter of the hydrogen evolution catalyst layer is 0.3-0.8 μm, and the porosity is 1-5%.
The present invention provides a process for the preparation of an active porous nickel-based catalyst as described above comprising the steps of:
a) Mixing the first metal powder, the second metal powder and the silicon dioxide powder to obtain a mixture;
b) Spraying the mixture on the surface of the porous conductive substrate by using a plasma spraying method;
c) Immersing the sprayed porous conductive substrate into alkali liquor for pore-forming, and then performing electrochemical activation to obtain the active porous nickel-based catalyst.
Preferably, the mesh number of the first metal powder is 100-600 mesh, the mesh number of the second metal powder is 100-600 mesh, and the mesh number of the silicon dioxide powder is 100-600 mesh.
Preferably, in the plasma spraying, the distance between the nozzle and the porous conductive substrate is 10-500 mm, the speed of the spray gun is 50-1000 mm/s, and in the plasma spraying, the temperature of the mixture is 300-1200 ℃.
Preferably, the lye comprises potassium hydroxide and/or sodium hydroxide; the concentration of the alkali liquor is 1-10 mol/L.
Preferably, the temperature of pore-forming is 30-50 ℃, and the time of pore-forming is 12-36 h.
The present invention provides the use of an active porous nickel-based catalyst as described above in the production of hydrogen by electrolysis of water.
The invention provides an active porous nickel-based catalyst, which comprises a porous conductive substrate and a hydrogen evolution catalyst layer compounded on the surface of the porous conductive substrate; the hydrogen evolution catalyst layer is prepared by pore-forming a catalyst coating through alkali liquor, and the catalyst coating comprises a first metal, a second metal and silicon dioxide; the first metal is one or more of nickel, cobalt and iron; the second metal is one or more of platinum, ruthenium and molybdenum; the hydrogen evolution catalyst comprises 30-90 atomic percent of first metal, 5-30 atomic percent of second metal and 5-60 atomic percent of Si. The invention uses plasma spraying technology to spray molybdenum, nickel and SiO 2 Proper proportion is carried out, the thickness of the coating is controlled to be less than 100 mu m, and the coating is sprayed on the conductive substrate to improve the active site of the catalystThe utilization rate of the points reduces the waste of catalyst materials. And SiO is used 2 The method replaces Al and Zn as pore formers, has lower price, does not generate hydrogen in the pore-forming process, and is suitable for industrialized mass production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the HER (hydrogen evolution) polarization of the electrocatalyst electrode obtained in the comparative example;
FIG. 2 is a graph showing the HER (hydrogen evolution) polarization of the electrocatalyst electrode obtained in example 1;
FIG. 3 is a graph showing the HER (hydrogen evolution) polarization of the electrocatalyst electrode obtained in example 2;
FIG. 4 is a graph showing the HER (hydrogen evolution) polarization of the electrocatalyst electrode obtained in example 3;
fig. 5 is a HER (hydrogen evolution) polarization curve of the electrocatalyst electrode obtained in example 4;
FIG. 6 is a graph showing the HER (hydrogen evolution) polarization of the electrocatalyst electrode obtained in example 5;
FIG. 7 is a photograph of a high purity nickel mesh conductive substrate used in examples 1-5 and comparative examples;
FIG. 8 is a photograph of the electrocatalyst electrode obtained in example 1;
FIG. 9 is a photograph of the electrocatalyst electrode obtained in example 2;
FIG. 10 is a photograph of the electrocatalyst electrode obtained in example 3;
FIG. 11 is a photograph of the electrocatalyst electrode obtained in example 4;
FIG. 12 is a photograph of the electrocatalyst electrode obtained in example 5;
FIG. 13 is a scanning electron micrograph of the electrocatalyst electrode obtained in example 1.
Detailed Description
The invention provides an active porous nickel-based catalyst, which comprises a porous conductive substrate and a hydrogen evolution catalyst layer compounded on the surface of the porous conductive substrate;
the hydrogen evolution catalyst layer is prepared by pore-forming a catalyst coating through alkali liquor, and the catalyst coating comprises a first metal, a second metal and silicon dioxide;
the first metal is one or more of nickel, cobalt and iron; the second metal is one or more of platinum, ruthenium and molybdenum;
the hydrogen evolution catalyst comprises 30-90 atomic percent of first metal, 5-30 atomic percent of second metal and 5-60 atomic percent of Si.
In the present invention, the porous conductive substrate is preferably a nickel mesh, and the mesh number of the nickel mesh is preferably 40 to 100 mesh, more preferably 50 to 80 mesh.
In the present invention, the atomic percentage of the first metal is preferably 30 to 90%, more preferably 40 to 80%, such as 30%,35%,40%,45%,50%,55%,60%,65%,70%,75%,80%,85%,90%, preferably a range value in which any of the above values is an upper limit or a lower limit; the atomic percentage of the second metal is preferably 5 to 30%, more preferably 10 to 25%, such as 5%,10%,15%,20%,25%,30%, preferably a range value having any of the above values as an upper limit or a lower limit; the atomic percentage of Si is preferably 5 to 60%, more preferably 10 to 55%, such as 5%,10%,15%,20%,25%,30%,35%,40%,45%,50%,55%,60%, preferably a range having any of the above values as an upper limit or a lower limit.
In the present invention, the thickness of the hydrogen evolution catalyst layer is preferably 10 to 100 μm, more preferably 20 to 80 μm, most preferably 30 to 60 μm, and the hydrogen evolution catalyst layer has a pore structure, and the pore diameter is preferably 0.3 to 0.8 μm, more preferably 0.5 to 0.8 μm; the porosity is preferably 1 to 5%, more preferably 2 to 4%.
The invention also provides a preparation method of the active porous nickel-based catalyst, which comprises the following steps:
a) Mixing the first metal powder, the second metal powder and the silicon dioxide powder to obtain a mixture;
b) Spraying the mixture on the surface of the porous conductive substrate by using a plasma spraying method;
c) Immersing the sprayed porous conductive substrate into alkali liquor for pore-forming, and then performing electrochemical activation to obtain the active porous nickel-based catalyst.
In the present invention, the types and amounts of the first metal powder, the second metal powder and the silica powder are the same as those of the first metal, the second metal and the silica described above, and the present invention is not repeated here.
The first metal powder, the second metal powder and the silicon dioxide powder are preferably mixed to obtain a mixture, and the mixing is preferably mechanical mixing, such as ball milling, which is a mixing method well known to those skilled in the art, and the invention is not repeated herein.
In the present invention, the mesh number of the first metal powder is preferably 100 to 600 mesh, more preferably 200 to 500 mesh; the mesh number of the second metal powder is 100 to 600 mesh, more preferably 200 to 500 mesh; the mesh number of the silica powder is 100 to 600 mesh, more preferably 200 to 500 mesh.
After the mixture is obtained, the invention uses a plasma spraying method to spray the mixture on the surface of the porous conductive substrate to obtain the catalyst coating.
The porous conductive substrate such as nickel screen is preferably pretreated firstly, and the specific steps are as follows:
firstly, alkali liquor is used for cleaning the surface of the conductive substrate to remove stains, and then acid liquor is used for removing oxides on the surface of the conductive substrate.
In the present invention, the lye preferably comprises potassium hydroxide and/or sodium hydroxide; the concentration of the alkali liquor is preferably 1 to 10mol/L, more preferably 2 to 8mol/L, such as 1mol/L,2mol/L,3mol/L,4mol/L,5mol/L,6mol/L,7mol/L,8mol/L,9mol/L,10mol/L, preferably a range value having any of the above values as an upper limit or a lower limit; the acid liquor is preferably one or more of hydrochloric acid, sulfuric acid and nitric acid; the concentration of the acid solution is preferably 0.1 to 3mol/L, more preferably 0.5 to 3mol/L, such as 0.1mol/L,0.5mol/L,1mol/L,1.5mol/L,2mol/L,2.5mol/L,3mol/L, preferably a range value having any of the above values as an upper limit or a lower limit.
In the invention, the gas used for plasma spraying is preferably one or more of nitrogen, argon, helium, hydrogen and air; in the plasma spraying, the distance between the nozzle and the porous conductive substrate is preferably 10 to 500mm, more preferably 50 to 400mm, such as 10mm,50mm,100mm,150mm,200mm,250mm,300mm,350mm,400mm,450mm,500mm, preferably a range having any of the above values as an upper limit or a lower limit; the speed of the spray gun is preferably 50 to 1000mm/s, more preferably 100 to 800mm/s, such as 50mm/s,100mm/s,200mm/s,300mm/s,400mm/s,500mm/s,600mm/s,700mm/s,800mm/s,900mm/s,1000mm/s, preferably a range value having any of the above values as an upper limit or a lower limit; in the plasma spraying, the temperature of the mixture is preferably 300 to 1200 ℃, more preferably 500 to 1000 ℃, such as 300 ℃,400 ℃,500 ℃,600 ℃,700 ℃,800 ℃,900 ℃,1000 ℃,1100 ℃,1200 ℃, and preferably ranges from any of the above values as the upper limit or the lower limit.
In the present invention, the thickness of the catalyst coating layer is preferably 10 to 100. Mu.m, more preferably 20 to 80. Mu.m, and most preferably 30 to 60. Mu.m.
After the catalyst coating is obtained, the catalyst coating is immersed in alkali liquor for pore forming, and a porous catalyst layer is obtained.
In the present invention, the lye preferably comprises potassium hydroxide and/or sodium hydroxide; the concentration of the alkali liquid is preferably 1 to 10mol/L, more preferably 2 to 8mol/L, such as 1mol/L,2mol/L,3mol/L,4mol/L,5mol/L,6mol/L,7mol/L,8mol/L,9mol/L,10mol/L, preferably a range value having any of the above values as an upper limit or a lower limit.
In the present invention, the pore-forming temperature is preferably 30 to 50 ℃, more preferably 40 ℃; the pore-forming time is preferably 12 to 36 hours, more preferably 24 hours.
After pore-forming is completed, the porous catalyst layer is subjected to electrochemical activation, so that the active porous nickel-based catalyst is obtained.
In the invention, the electrochemical activation can be performed by cyclic voltammetry or constant voltage electrochemical method. Preferably, cyclic voltammetry is used, and in the present invention, the cyclic voltammetry preferably has an initial voltage of-0.99 to-0.98V, more preferably-0.986V, a final voltage of-1.5 to-1.7V, more preferably-1.6V, and a scanning rate of preferably 90 to 110mV/s, more preferably 100mV/s, and is cycled 300 to 350 times.
The invention provides an active porous nickel-based catalyst, which comprises a porous conductive substrate and a hydrogen evolution catalyst layer compounded on the surface of the porous conductive substrate; the hydrogen evolution catalyst layer is prepared by pore-forming a catalyst coating through alkali liquor, and the catalyst coating comprises a first metal, a second metal and silicon dioxide; the first metal is one or more of nickel, cobalt and iron; the second metal is one or more of platinum, ruthenium and molybdenum; the hydrogen evolution catalyst comprises 30-90 atomic percent of first metal, 5-30 atomic percent of second metal and 5-60 atomic percent of Si.
Compared with the prior majority of Ni-based catalysts, the invention creatively uses Mo and SiO 2 The elements such as Mo and Ni are doped into the Ni-based catalyst to form an alloy, so that the active sites of the catalyst are increased. SiO (SiO) 2 Is dissolved by alkali liquor to generate a large number of cavities, increases the specific surface area of the catalyst, does not generate hydrogen in the process, and ensures the safety of industrialized large-scale preparation and use. Under the combined action, the electric conductivity of the electrocatalyst is improved, the transfer rate of electrons on the surface of the catalyst is accelerated, and the catalytic activity of the Ni-based catalyst is improved.
Compared with the existing preparation process of most Ni-based catalysts, the preparation method has the advantages that powder is directly and uniformly mixed and then sprayed on the conductive base material through a plasma spraying technology, a solvent is not used, high-temperature roasting is not needed, the operation is simpler, and the time required in the preparation process is greatly shortened. Meanwhile, the use of solvents is avoided in the process, so that harmful waste liquid and waste gas are not generated, and the method is more environment-friendly.
In order to further illustrate the present invention, the following examples are provided to illustrate an active porous nickel-based catalyst, its preparation method and application, but should not be construed as limiting the scope of the invention.
In the following examples, the purity of the nickel powder used was > 99%, the purity of the silica was > 97%, and the purity of the molybdenum powder was > 99%.
The nickel screen with 60 meshes is adopted as a conductive substrate, the purity of the nickel screen is more than 99 percent, and the specification is 100 multiplied by 100mm 2 . Soaking in 6mol/L KOH solution to clean stains on the surface of the nickel screen, washing with deionized water, cleaning oxide components on the surface of the nickel screen with 3mol/L HCl, continuing washing with deionized water, and airing for later use.
The detection method comprises the following steps:
300g of KOH solids (purity > 99%) were dissolved in 700g of deionized water to prepare a 30wt% KOH solution, and the nickel mesh was immersed in the KOH solution for 24 hours to serve as the electrocatalyst cathode. Hg/HgO is used as reference electrode, 100X 100mm 2 The graphite sheet was used as an anode and 30wt% KOH solution was used as an electrolyte for electrochemical testing.
The hydrogen evolution performance of the electrocatalyst cathode was tested using a CS150M electrochemical workstation from keite and a CS2020B current expander, converted to a RHE (reversible hydrogen electrode) relative value according to the equation E (vs RHE) =e (vs Hg/HgO) +0.098+0.059×ph, calculated according to the equation E (vs RHE) =e (vs Hg/HgO) +0.986, based on the actual pH of a 30wt% KOH solution.
Comparative example
Nickel powder (mesh number is 200) and aluminum powder (mesh number is 200) are adopted, and the nickel powder is: the molar ratio of the aluminum powder is 8.5:1.5. after the mixture is uniformly mixed by using a ball mill, the mixture is uniformly sprayed on a nickel screen with the mesh number of 60 by using a plasma spraying technology, and the average spraying thickness is 50 mu m. Selecting 100X 100mm 2 The sprayed nickel mesh was soaked in 30wt% KOH solution for 24 hours. Using an electrochemical workstation, cyclic voltammetry was used, setting an initial voltage of-0.986V, a termination voltage of-1.6V, a scan rate of 100mV/s, and cycling 300 times.
Using the aboveIs tested by an electrochemical workstation with a current density of 10mA/cm 2 When the voltage was-1.269V, the overpotential was 283mV by conversion.
Example 1
The invention adopts nickel powder (with the mesh number of 200), molybdenum powder (with the mesh number of 200) and silicon dioxide powder (with the mesh number of 400), and the nickel powder: molybdenum powder: the molar ratio of the silicon dioxide powder is 8.5:1:0.5. after the mixture is uniformly mixed by using a ball mill, the mixture is uniformly sprayed on a nickel screen with the mesh number of 60 by using a plasma spraying technology, and the average spraying thickness is 50 mu m. Selecting 100X 100mm 2 The sprayed nickel mesh was soaked in 30wt% KOH solution for 24 hours. Using an electrochemical workstation, cyclic voltammetry was used, setting an initial voltage of-0.986V, a termination voltage of-1.6V, a scan rate of 100mV/s, and cycling 300 times.
The test was carried out using the electrochemical workstation in the comparative example, with a current density of 10mA/cm 2 When the voltage was-1.158V, the overpotential was 172mV by conversion. The overpotential was reduced by 110mV compared to the comparative example.
Example 2
The invention adopts nickel powder (with the mesh number of 200), molybdenum powder (with the mesh number of 200) and silicon dioxide powder (with the mesh number of 400), and the nickel powder: molybdenum powder: the mole ratio of the silicon dioxide powder is 8:1:1. after the mixture is uniformly mixed by using a ball mill, the mixture is uniformly sprayed on a nickel screen with the mesh number of 60 by using a plasma spraying technology, and the average spraying thickness is 50 mu m. Selecting 100X 100mm 2 The sprayed nickel mesh was soaked in 30wt% KOH solution for 24 hours. Using an electrochemical workstation, cyclic voltammetry was used, setting an initial voltage of-0.986V, a termination voltage of-1.6V, a scan rate of 100mV/s, and cycling 300 times.
The test was carried out using the electrochemical workstation in the comparative example, with a current density of 10mA/cm 2 The voltage was-1.236V, and the overpotential was 250mV by conversion. The overpotential was reduced by 33mV compared to the comparative example.
Example 3
The invention adopts nickel powder (with the mesh number of 200), molybdenum powder (with the mesh number of 200) and silicon dioxide powder (with the mesh number of 400), and the nickel powder: molybdenum powder: the molar ratio of the silicon dioxide powder is 7.5:1:1.5. mixing evenly by using ball millAnd then uniformly spraying the mixed material on a nickel screen with the mesh number of 60 by a plasma spraying technology, wherein the average spraying thickness is 50 mu m. Selecting 100X 100mm 2 The sprayed nickel mesh was soaked in 30wt% KOH solution for 24 hours. Using an electrochemical workstation, cyclic voltammetry was used, setting an initial voltage of-0.986V, a termination voltage of-1.6V, a scan rate of 100mV/s, and cycling 300 times.
The test was carried out using the electrochemical workstation in the comparative example, with a current density of 10mA/cm 2 When the voltage was-1.245V, the overpotential was 259mV by conversion. The overpotential was reduced by 24mV compared to the comparative example.
Example 4
The invention adopts nickel powder (with the mesh number of 200), molybdenum powder (with the mesh number of 200) and silicon dioxide powder (with the mesh number of 400), and the nickel powder: molybdenum powder: the molar ratio of the silicon dioxide powder is 7.5:2:0.5. after the mixture is uniformly mixed by using a ball mill, the mixture is uniformly sprayed on a nickel screen with the mesh number of 60 by using a plasma spraying technology, and the average spraying thickness is 50 mu m. Selecting 100X 100mm 2 The sprayed nickel mesh was soaked in 30wt% KOH solution for 24 hours. Using an electrochemical workstation, cyclic voltammetry was used, setting an initial voltage of-0.986V, a termination voltage of-1.6V, a scan rate of 100mV/s, and cycling 300 times.
The test was carried out using the electrochemical workstation in the comparative example, with a current density of 10mA/cm 2 When the voltage was-1.253V, the overpotential was 267mV by conversion. The overpotential was reduced by 16mV compared to the comparative example.
Example 5
The invention adopts nickel powder (with the mesh number of 200), molybdenum powder (with the mesh number of 200) and silicon dioxide powder (with the mesh number of 400), and the nickel powder: molybdenum powder: the mole ratio of the silicon dioxide powder is 7:2:1. after the mixture is uniformly mixed by using a ball mill, the mixture is uniformly sprayed on a nickel screen with the mesh number of 60 by using a plasma spraying technology, and the average spraying thickness is 50 mu m. Selecting 100X 100mm 2 The sprayed nickel mesh was soaked in 30wt% KOH solution for 24 hours. Using an electrochemical workstation, cyclic voltammetry was used, setting an initial voltage of-0.986V, a termination voltage of-1.6V, a scan rate of 100mV/s, and cycling 300 times.
Electrochemical operation using the comparative exampleThe station was tested with a current density of 10mA/cm 2 At this time, the voltage was-1.275V, and the overpotential was 289mV by conversion. The overpotential was increased by 6mV compared to the comparative example.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. An active porous nickel-based catalyst comprises a porous conductive substrate and a hydrogen evolution catalyst layer compounded on the surface of the porous conductive substrate;
the hydrogen evolution catalyst layer is prepared by pore-forming a catalyst coating through alkali liquor, and the catalyst coating comprises a first metal, a second metal and silicon dioxide;
the first metal is one or more of nickel, cobalt and iron; the second metal is one or more of platinum, ruthenium and molybdenum;
in the catalyst coating, the atomic percentage of the first metal is 30-90%, the atomic percentage of the second metal is 5-30%, and the atomic percentage of Si is 5-60%.
2. The active porous nickel-based catalyst according to claim 1, wherein the porous conductive substrate is a nickel mesh having a mesh number of 40 to 100 mesh.
3. The active porous nickel-based catalyst according to claim 1, wherein the hydrogen evolution catalyst layer has a thickness of 10 to 100 μm.
4. The active porous nickel-based catalyst according to claim 1, wherein the hydrogen evolution catalyst layer has an average pore diameter of 0.3 to 0.8 μm and a porosity of 1 to 5%.
5. The method for preparing an active porous nickel-based catalyst according to claim 1, comprising the steps of:
a) Mixing the first metal powder, the second metal powder and the silicon dioxide powder to obtain a mixture;
b) Spraying the mixture on the surface of the porous conductive substrate by using a plasma spraying method;
c) Immersing the sprayed porous conductive substrate into alkali liquor for pore-forming, and then performing electrochemical activation to obtain the active porous nickel-based catalyst.
6. The method according to claim 5, wherein the first metal powder has a mesh size of 100 to 600 mesh, the second metal powder has a mesh size of 100 to 600 mesh, and the silica powder has a mesh size of 100 to 600 mesh.
7. The method according to claim 5, wherein the distance between the nozzle and the porous conductive substrate is 10 to 500mm, the speed of the spray gun is 50 to 1000mm/s, and the temperature of the mixture is 300 to 1200 ℃.
8. The method according to claim 5, wherein the lye comprises potassium hydroxide and/or sodium hydroxide; the concentration of the alkali liquor is 1-10 mol/L.
9. The method according to claim 5, wherein the pore-forming temperature is 30-50 ℃, and the pore-forming time is 12-36 hours.
10. Use of an active porous nickel-based catalyst according to any of claims 1-4 for the production of hydrogen by electrolysis of water.
CN202211618018.9A 2022-12-15 2022-12-15 Active porous nickel-based catalyst, preparation method and application thereof Pending CN116116423A (en)

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