CN115110108B - Porous nickel-molybdenum alloy electrocatalytic material and preparation method and application thereof - Google Patents

Porous nickel-molybdenum alloy electrocatalytic material and preparation method and application thereof Download PDF

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CN115110108B
CN115110108B CN202210698630.5A CN202210698630A CN115110108B CN 115110108 B CN115110108 B CN 115110108B CN 202210698630 A CN202210698630 A CN 202210698630A CN 115110108 B CN115110108 B CN 115110108B
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molybdenum alloy
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molybdenum
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袁斌
陈志鹏
彭伟良
李少波
胡仁宗
朱敏
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South China University of Technology SCUT
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Abstract

The invention belongs to the technical field of electrocatalytic materials, and discloses a porous nickel-molybdenum alloy electrocatalytic material, and a preparation method and application thereof. The method comprises the following steps: 1) Plastically deforming the nickel-molybdenum alloy to obtain a deformed nickel-molybdenum alloy; 2) Pretreating the deformed nickel-molybdenum alloy to remove impurities on the surface, thereby obtaining clean deformed nickel-molybdenum alloy; 3) HNO of 3 And copper salt are dissolved in water to obtain an etching solution; 4) And (3) placing the deformed nickel-molybdenum alloy into an etching solution for dealloying reaction, and carrying out subsequent treatment to obtain the porous nickel-molybdenum alloy electrocatalytic material. The method of the invention is simple and convenient, the economic cost is low, and the obtained electrocatalytic material not only can greatly reduce the overpotential of hydrogen evolution reaction, but also still has good stability under high current density. The electrocatalytic material is used for electrocatalytic hydrolysis hydrogen production, and can realize large-scale production.

Description

Porous nickel-molybdenum alloy electrocatalytic material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrocatalytic materials, and particularly relates to a porous nickel-molybdenum alloy electrocatalytic material, and a preparation method and application thereof. The electrocatalytic material is used in the field of electrocatalytic water decomposition.
Background
In the current society, petroleum, natural gas and other non-renewable fossil energy sources still occupy a huge proportion in the total energy consumption plate, so that the problem of energy shortage is becoming serious. In addition, burning fossil fuels will produce and emit harmful greenhouse gases (such as CO 2 ) Toxic gases (e.g. SO 2 ) Thereby causing a series of related environmental problems such as greenhouse effect, ozone layer destruction, etc. Therefore, there is an urgent need to develop a technology for efficient clean, continuous energy supply and storage thereof.
Hydrogen (H) 2 ) Has a high heat value (281 kJ mol) -1 ) And zero carbon emissions, are considered to be one of the cleanest energy sources, and are the first choice to replace fossil fuels and to solve the global energy and environmental pollution problems. The electrolytic water hydrogen production (or electrocatalytic water decomposition) has the advantages of high efficiency, no carbon, no regional limitation, high hydrogen production purity and the like, and is considered as one of the hydrogen production methods with the most development potential at present. The hydrogen production by water electrolysis can store the electric power generated by renewable energy sources with volatility for a long time for high-efficiency use, and is an important ring for building a green hydrogen energy network in the future.
At present, the electrocatalytic water decomposition still has the outstanding problems of high energy consumption, low conversion efficiency, high cost and the like. The method has very important significance by developing a cheap and efficient electrocatalytic electrode material for water electrolysis reaction, thereby meeting the application of hydrogen production technology in industrial production. The hydrogen evolution reaction (hydrogen evolution reaction, HER) is one of the important reactions of electrocatalytic water decomposition, with the noble metal Pt being the most efficient and stable HER electrocatalytic material. The high cost and scarcity of Pt, however, limits its commercial large-scale application. Therefore, developing a non-noble metal electrode material with excellent electrocatalytic performance and low cost is a key problem to be solved in the large-scale application process of the technology for preparing hydrogen by advancing electrolysis of water. In the non-noble metal electrocatalytic electrode material, nickel and molybdenum enable the hydrogen adsorption free energy of the alloy to be close to 0eV through the synergistic effect, and the electrode material has excellent HER electricityThe catalytic performance is the best non-noble metal base bimetallic electrocatalytic material accepted in hydrogen evolution reaction. However, currently, nickel-molybdenum electrocatalytic electrode materials mainly load nickel-molybdenum-based nanoparticles on a conductive substrate (porous glassy carbon or foam nickel) in a hydrothermal method or an electrodeposition mode, and the nanoparticle catalytic materials have excellent electrocatalytic HER performance. However, the loading method for preparing the nano material is complicated, has high energy consumption, is not suitable for industrialized mass production, the obtained nano particles are easy to agglomerate, the nano structure is easy to be degraded, the binding force between the nano particles and the matrix is weak, if the nano catalyst is connected with the matrix by adopting an adhesive, the outstanding problems of large interface contact resistance, more lost catalytic active sites and the like are caused, the long-term stability is poor, and the service life is one of the key problems to be solved in the present urgency under the condition of high current density. For example: patent application CN202110487183.4 discloses a preparation method of a branch-leaf type heterostructure full water-splitting catalyst, wherein a NiMo-P@CoFe-LDH catalyst is prepared on foam nickel by sequentially adopting a hydrothermal method, a gas-phase phosphating method and an electrodeposition method, has a unique branch-leaf type morphology, can be used as a difunctional electrolytic water catalyst, and has higher catalytic activity. However, the weak bonding force between the nano catalyst and the matrix makes the nano catalyst only 50mA/cm 2 Is stable for 24 hours under the current density of (2) which is far less than 300-2000 mA/cm required by industrial application 2 Is required for the current density of the battery. In addition, the complex preparation process of the catalyst also limits the industrial mass production thereof. Therefore, development of electrocatalytic materials which are simple in preparation process and can stably operate for a long time under high current density is necessary.
The direct use of bulk nickel-molybdenum alloy as electrocatalytic material can operate stably at high current density, but its overpotential is large and catalytic efficiency is low, mainly due to its fewer active catalytic sites and specific surface area. Therefore, it is a feasible way to produce porous surfaces with high specific surface area on bulk nickel-molybdenum alloys, but nickel-molybdenum alloys have good corrosion resistance and it is difficult to form porous surfaces.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a porous nickel-molybdenum alloy electrocatalytic material. The invention utilizes stress corrosion and preferential corrosion principles to obtain residual strain through large plastic deformation, and then prepares the porous nickel-molybdenum alloy electrocatalytic material through a one-step dealloying method, wherein the microcosmic appearance of the electrocatalytic material consists of a plurality of micron particles, and each micron particle is provided with a double-scale micro-nano pore. The electrocatalytic material provided by the invention has excellent HER electrocatalytic activity and stability under high current density, and the preparation method is simple, so that the electrocatalytic material has a good application prospect.
Another object of the present invention is to provide a porous nickel-molybdenum alloy electrocatalytic material obtained by the above preparation method.
It is a further object of the present invention to provide the use of the porous nickel-molybdenum electrocatalytic material as described above. The porous nickel-molybdenum alloy electrocatalytic material is used for electrocatalytic hydrolysis hydrogen production.
The aim of the invention is achieved by the following technical scheme:
the preparation method of the porous nickel-molybdenum alloy electrocatalytic material comprises the following steps:
(1) Plastic deformation: plastically deforming the nickel-molybdenum alloy at room temperature to obtain a deformed nickel-molybdenum alloy;
(2) Pretreatment: pretreating the deformed nickel-molybdenum alloy to remove impurities on the surface, thereby obtaining clean deformed nickel-molybdenum alloy;
(3) Preparing an etching solution: HNO of 3 And copper salt are dissolved in water to obtain an etching solution;
(4) Dealloying: and (3) placing the deformed nickel-molybdenum alloy obtained in the step (2) into the corrosive solution obtained in the step (3) for dealloying reaction, and carrying out subsequent treatment to obtain the porous nickel-molybdenum alloy electrocatalytic material.
The nickel-molybdenum alloy in the step (1) is a Hastelloy B series alloy, and specifically comprises one of Hastelloy B, hastelloy B-2, hastelloy B-3 and Hastelloy B-4. The nickel-molybdenum alloy mainly comprises Ni, mo, fe and other elements, wherein the mass fraction of the Ni element is 58-70%, the mass fraction of the Mo element is 26-33%, and the mass fraction of the Fe element is 1-6%.
The nickel-molybdenum alloy in the step (1) is a bulk alloy.
The deformation amount of the plastic deformation in the step (1) is 40-90%; the plastic deformation may be by rolling, extrusion, drawing or the like.
The pretreatment in the step (2) specifically means that the oxide skin on the surface of the deformed nickel-molybdenum alloy is removed by sanding, and then the sanded alloy is respectively ultrasonically cleaned by hydrochloric acid, water and ethanol, and then dried.
In the pretreatment of the step (2), 180-360 mesh SiC sand paper is used for polishing, and the polishing time is 5-15 min.
In the pretreatment of the step (2), the concentration of hydrochloric acid is 2-3M; sequentially washing with hydrochloric acid, water and ethanol for 20-30 min respectively; the drying temperature is 60-80 ℃, the drying time is 4-6 h, the drying is vacuum drying, and the vacuum degree of the drying is 1000-4000 Pa.
The copper salt in the step (3) is more than one of copper nitrate or copper acetate; the copper nitrate is Cu (NO) 3 ) 2 And its hydrate, copper acetate is Cu (CO) 2 CH 3 ) 2 And hydrates thereof.
HNO as described in the step (3) 3 The mass ratio of the copper salt to the water is (3-6): (2-14): 60.
the etching solution is placed in the step (3) by stirring at a rotation speed of 50 to 150rpm.
The dealloying reaction temperature in the step (4) is 60-80 ℃, and the dealloying reaction time is 5-10 h. The reaction is carried out under stirring; the stirring speed is 50-150 rpm.
The subsequent treatment is to wash the dealloyed nickel-molybdenum alloy with water and ethanol respectively after the reaction is finished, and then dry the nickel-molybdenum alloy in a vacuum drying oven.
In the subsequent treatment of the step (4), the washing times of the water and the ethanol are 2-3 times, and the washing time is 5-10 min each time.
In the subsequent treatment of the step (4), the temperature of the vacuum drying is 60-80 ℃, the drying time is 4-6 h, and the vacuum degree of the drying is 1000-4000 Pa.
The porous nickel-molybdenum alloy electrocatalytic material is prepared by the preparation method, wherein the porous morphology consists of micron particles, the size of each micron particle is 20-100 mu m, and each micron particle consists of 500 nm-2 mu m double-scale micro-nano holes.
The porous nickel-molybdenum alloy electrocatalytic material is applied as a HER electrode in the field of electrocatalytic water splitting.
The invention selects commercial Hastelloy B series alloy as initial master alloy, which specifically comprises one of Hastelloy B, hastelloy B-2, hastelloy B-3, hastelloy B-4 and the like. The alloy has low price and easy acquisition, mainly comprises Ni, mo, fe and other elements, wherein the mass fraction of the Ni element is 58-70%, the mass fraction of the Mo element is 26-33%, and the mass fraction of the Fe element is 1-6%. Residual stress is caused to the initial master alloy by 40-90% plastic deformation, and nickel-molybdenum alloys are more prone to corrosion due to the presence of stress. Further, using the potential difference between different elements as HNO 3 And a copper salt selected from Cu (NO) containing or not containing crystal water as a dealloying solution 3 ) 2 Crystallization water or Cu (CO) free of crystallization water 2 CH 3 ) 2 At least one of them. Due to NO under acidic conditions 3 - Has strong oxidizing property, and Cu 2+ Can promote the corrosion process of the Hastelloy B alloy, so that Ni element with lower potential in the nickel-molybdenum alloy is dissolved out, thereby realizing the rapid and low-cost preparation of the porous nickel-molybdenum alloy electrocatalytic material. The porous nickel-molybdenum alloy electrocatalytic material with high specific surface area can improve thermodynamic and kinetic conditions in the electrocatalytic water splitting process, improve water splitting efficiency, and reduce consumption of electrode materials and electric energy on the premise of ensuring high gas production, thereby reducing cost.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The porous nickel-molybdenum alloy electrocatalytic material is prepared by adopting a simple large plastic deformation and dealloying method, the preparation process is simple, the time consumption is short, the energy consumption is low, meanwhile, the Hastelloy B series which is used in a mature commercialized mode is selected as the nickel-molybdenum alloy initial alloy, the cost is low, the acquisition mode is convenient, and the economic benefit of electrode material preparation is increased.
(2) The surface of the porous electrode prepared by the invention is composed of a plurality of micron particles, and the micron particles are provided with three-dimensional communicated pore canals, which are beneficial to mass transfer process and gas diffusion in the electrolysis process, and meanwhile, the holes of the micro-nano structure greatly increase the specific surface area of the electrode, expose more active sites and improve thermodynamic and kinetic conditions in the electrolysis process.
(3) The porous nickel-molybdenum alloy is used as an electrocatalytic material, so that the activity of the porous nickel-molybdenum alloy can be kept for a long time under high current density, and the porous nickel-molybdenum alloy is more suitable for actual industrial production and application.
Drawings
FIG. 1 is an electron microscope image of example 1 at 300 Xmagnification of the original nickel-molybdenum alloy;
FIG. 2 is a sample of the sample obtained by HNO in example 1 3 +Cu(NO 3 ) 2 Scanning electron microscope pictures of porous nickel-molybdenum alloy prepared by solution dealloying, wherein (a) is an electron microscope picture which is magnified 300 times, and (b) is an electron microscope picture which is magnified 3000 times;
FIG. 3 is a polarization curve of the porous nickel-molybdenum alloy and the original nickel-molybdenum alloy of example 1;
FIG. 4 is a Tafel slope plot of the porous nickel-molybdenum alloy and the original nickel-molybdenum alloy of example 1;
FIG. 5 is a graph of porous nickel-molybdenum alloy at 1A/cm for example 1 2 Performing stability test for 12 hours under the current density;
FIG. 6 is a sample of HNO in example 2 3 +Cu(CO 2 CH 3 ) 2 Scanning electron microscope pictures of porous nickel-molybdenum alloy prepared by solution dealloying, wherein (a) is an electron microscope picture which is magnified 300 times, and (b) is an electron microscope picture which is magnified 3000 times;
FIG. 7 is a sample of the sample obtained by HNO in example 3 3 +Cu(NO 3 ) 2 ·3H 2 Scanning electron microscope image of porous nickel-molybdenum alloy prepared by O solution dealloying, wherein (a) in the image is 300 times of electric magnificationA mirror image, wherein (b) is an electron mirror image magnified 3000 times;
FIG. 8 shows the reaction of HNO in example 4 3 +Cu(CO 2 CH 3 ) 2 ·H 2 A scanning electron microscope image of the porous nickel-molybdenum alloy prepared by dealloying the O solution, wherein (a) is an electron microscope image with 500 times magnification, and (b) is an electron microscope image with 3000 times magnification;
FIG. 9 is a sample of comparative example 1 by HNO 3 Scanning electron microscope pictures of nickel-molybdenum alloy prepared by dealloying the solution, wherein (a) in the pictures is an electron microscope picture with 500 times magnification, and (b) in the pictures is an electron microscope picture with 3000 times magnification;
FIG. 10 shows the composition of comparative example 2 by Cu (NO 3 ) 2 Scanning electron microscope pictures of nickel-molybdenum alloy prepared by dealloying the solution, wherein (a) in the pictures is an electron microscope picture with 500 times magnification, and (b) in the pictures is an electron microscope picture with 3000 times magnification;
FIG. 11 shows comparative example 3, which was not subjected to plastic deformation, by HNO 3 +Cu(CO 2 CH 3 ) 2 And (b) a scanning electron microscope image of the nickel-molybdenum alloy prepared by dealloying the solution, wherein (a) is an electron microscope image with a magnification of 500 times, and (b) is an electron microscope image with a magnification of 3000 times.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto.
Example 1
(1) Plastic deformation: the commercial nickel-molybdenum alloy plate Hastelloy B is selected as an initial master alloy, the brand is NS3201, the nickel-molybdenum alloy plate is mainly composed of Ni, mo, fe and other elements, the mass fraction of the Ni element is 65%, the mass fraction of the Mo element is 28%, the mass fraction of the Fe element is 5%, and the initial thickness of the alloy plate is 3mm; carrying out rolling deformation treatment on the alloy plate at room temperature, wherein the deformation is 60%, and the thickness of the rolled deformed alloy plate is 1.2mm;
(2) Pretreatment: grinding the surface of the deformed nickel-molybdenum alloy plate by using 180-mesh SiC sand paper for 5min, respectively ultrasonically cleaning the ground alloy plate by using 2M hydrochloric acid, deionized water and ethanol for 20min, and then drying the alloy plate in a vacuum drying oven with the vacuum degree of 1000Pa at the temperature of 60 ℃ for 5h;
(3) Preparing an etching solution: 3 parts by weight of analytically pure HNO 3 And 14 parts of Cu (NO) 3 ) 2 Dissolving in 60 parts of deionized water, and magnetically stirring for 5 minutes at 150 revolutions per minute to obtain an etching solution;
(4) Dealloying: putting the dried deformed nickel-molybdenum alloy plate obtained in the step (2) into the corrosion solution obtained in the step (3), fully stirring, and then performing dealloying reaction in a water bath kettle, wherein the temperature of the water bath kettle is set to be 60 ℃, and the reaction time is 7 hours; and after the reaction is finished, respectively washing the dealloyed nickel-molybdenum alloy with deionized water and ethanol for 3 times, wherein the time is 5min each time, and then drying the nickel-molybdenum alloy in a vacuum drying oven with the vacuum degree of 4000Pa at 60 ℃ for 6h to obtain the porous nickel-molybdenum alloy electrocatalytic material.
A300 times magnification electron microscope image of a commercial nickel-molybdenum alloy Hastelloy B (brand NS 3201) is shown in FIG. 1, and the whole surface presents a flat microscopic morphology without a pore structure. After plastic deformation and dealloying of commercial nickel-molybdenum alloy Hastelloy B, the surface morphology is shown in figure 2, the alloy surface becomes rough and is separated into particles with a micron-sized particle size of 20-100 microns under the magnification factor of 300 times in figure 2 (a), double-scale micro-nano holes with the size of 500 nm-2 microns can be observed on the particles with the size of 3000 times in figure 2 (B) to generate, and the holes penetrate through the particles and are communicated with each other, so that the contact area of electrode materials and electrolyte is greatly increased, more catalytic active sites are exposed, the mass transfer process of the electrolyte and the dissipation of generated gas in the electrolytic process are accelerated, and thermodynamic and kinetic conditions in the electrocatalytic water decomposition reaction process are improved.
Adopting a three-electrode system, respectively taking the porous nickel-molybdenum alloy prepared in the embodiment and the original commercial nickel-molybdenum alloy as working electrodes, taking a graphite rod as a counter electrode and mercury oxide mercury as a reference electrode, and carrying out electrochemical test on a Gamry electrochemical workstation to characterize the electrocatalytic water decomposition HER performance of the porous nickel-molybdenum alloy; the specific test parameters are as follows: linear sweep voltammetry (Linear sweep voltammetry) was selected for overpotential measurementsThe scanning voltage interval is between-0.85V and-1.35V (vs. Hg/HgO), the scanning speed is 5mV/s, the voltage is converted into electrode potential relative to the reversible hydrogen electrode after the test is finished, and the conversion formula is as follows: erhe= EHg/hgo+0.059×ph+0.098. Stability test was performed by selecting Chronopotentiometry (Chronopotentiometry), the current density was set at 1A/cm 2 The time was 12h.
FIG. 3 is a polarization curve of the porous nickel-molybdenum alloy and the original nickel-molybdenum alloy of example 1; FIG. 4 is a Tafel slope plot of the porous nickel-molybdenum alloy and the original nickel-molybdenum alloy of example 1; FIG. 5 is a graph of porous nickel-molybdenum alloy at 1A/cm for example 1 2 Stability testing was performed at current density for 12h.
As can be seen from FIGS. 3 and 4, the invention adopts commercial bulk nickel-molybdenum alloy as the working electrode, has better electrochemical performance, and has 10mA cm after dealloying the commercial bulk nickel-molybdenum alloy to generate a porous structure -2 The overpotential of (a) is reduced from 132mV to 99mV, the Tafel slope is reduced from 272mV/dec to 147mV/dec, the thermodynamic and kinetic conditions in the process of the electrocatalytic water decomposition reaction are improved, and the electrochemical performance is further improved. Applying 1A/cm to porous nickel-molybdenum alloy electrode material 2 Constant current density, stability test was performed for up to 12 hours, and as shown in fig. 5, the potential change of the porous nickel-molybdenum electrode was almost negligible, showing good stability. Therefore, the porous nickel-molybdenum alloy is used as an electrode material for electrocatalytic water analysis hydrogen reaction, so that the electrolysis efficiency is greatly improved, and the consumption of the electrode material and the electric energy is reduced under the same gas yield.
Example 2
(1) Plastic deformation: the commercial nickel-molybdenum alloy plate Hastelloy B-2 is selected as an initial master alloy, the brand is NS3202, the nickel-molybdenum alloy plate is mainly composed of Ni, mo, fe and other elements, the mass fraction of the Ni element is 65%, the mass fraction of the Mo element is 29%, the mass fraction of the Fe element is 2%, and the initial thickness of the alloy plate is 5mm; carrying out rolling deformation treatment on the alloy plate at room temperature, wherein the deformation is 90%, and the thickness of the rolled deformed alloy plate is 0.5mm;
(2) Pretreatment: grinding the surface of the deformed nickel-molybdenum alloy plate by using 360-mesh SiC sand paper for 10min, respectively ultrasonically cleaning the ground alloy plate by using 2M hydrochloric acid, deionized water and ethanol for 30min, and then drying the alloy plate in a vacuum drying oven with the vacuum degree of 4000Pa at 80 ℃ for 4h;
(3) Preparing an etching solution: 3 parts by weight of analytically pure HNO 3 And 7 parts of Cu (CO) 2 CH 3 ) 2 Dissolving in 60 parts of deionized water, and magnetically stirring for 5 minutes at 150 revolutions per minute to obtain an etching solution;
(4) Dealloying: putting the dried deformed nickel-molybdenum alloy plate obtained in the step (2) into the corrosion solution obtained in the step (3), fully stirring, and then performing dealloying reaction in a water bath kettle, wherein the temperature of the water bath kettle is set to be 70 ℃, and the reaction time is set to be 5 hours; and after the reaction is finished, washing the dealloyed nickel-molybdenum alloy with deionized water and ethanol for 3 times, wherein the time is 5min each time, and then drying the nickel-molybdenum alloy in a vacuum drying oven with the vacuum degree of 2000Pa at 80 ℃ for 4h to obtain the porous nickel-molybdenum alloy electrocatalytic material.
After plastic deformation and dealloying of commercial nickel-molybdenum alloy Hastelloy B-2, the surface morphology is shown in fig. 6, the alloy surface is roughened under the magnification factor of 300 times in fig. 6 (a), the alloy surface is separated into particles with a micron-sized particle size of 20-100 μm, the double-scale micro-nano holes with the size of 500 nm-2 μm can be observed on the particles with the magnification factor of 3000 times in fig. 6 (B), the contact area of electrode materials and electrolyte is greatly increased, more catalytic active sites are exposed, the mass transfer process of the electrolyte and the dissipation of generated gas are accelerated by the three-dimensional hole structure, the thermodynamic and kinetic conditions in the process of electrocatalytic water decomposition reaction are improved, the overpotential and Tafel slope of oxygen evolution reaction can be reduced, and the corresponding test result is similar to that of example 1.
Example 3
(1) Plastic deformation: commercial nickel-molybdenum alloy rod Hastelloy B-3 is selected as an initial master alloy, the brand is NS3203, the nickel-molybdenum alloy rod mainly comprises elements such as Ni, mo, fe, cr and the like, the mass fraction of the Ni element is 63%, the mass fraction of the Mo element is 28%, the mass fraction of the Fe element is 2%, the mass fraction of the Cr element is 2%, and the initial diameter of the alloy rod is 10mm. Carrying out drawing deformation treatment on the alloy plate at room temperature, wherein the deformation is 43.75%, and the diameter of a deformed alloy rod after drawing is 7.5mm;
(2) Pretreatment: grinding the surface of the deformed nickel-molybdenum alloy by using 180-mesh SiC sand paper for 10min, respectively ultrasonically cleaning the ground alloy by using 3M hydrochloric acid, deionized water and ethanol for 20min, and then drying for 5h at 70 ℃ in a vacuum drying oven with the vacuum degree of 2000 Pa;
(3) Preparing an etching solution: 3 parts by weight of analytically pure HNO 3 And 2 parts of Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 60 parts of deionized water and magnetically stirred for 5 minutes at 150 revolutions per minute to obtain an etching solution;
(4) Dealloying: putting the dried deformed nickel-molybdenum alloy obtained in the step (2) into the corrosion solution obtained in the step (3), fully stirring, and then performing dealloying reaction in a water bath kettle, wherein the temperature of the water bath kettle is set to be 60 ℃, and the reaction time is 5 hours; and after the reaction is finished, washing the dealloyed nickel-molybdenum alloy with deionized water and ethanol for 3 times, wherein the time is 5min each time, and then drying the nickel-molybdenum alloy in a vacuum drying oven with the vacuum degree of 2000Pa at the temperature of 70 ℃ for 5h to obtain the porous nickel-molybdenum alloy electrocatalytic material.
After plastic deformation and dealloying of commercial nickel-molybdenum alloy Hastelloy B-3, the surface morphology is shown in fig. 7, the alloy surface is roughened under the magnification factor of 300 times in fig. 7 (a), the alloy surface is separated into particles with a micron-sized particle size of 20-100 μm, the double-scale micro-nano holes with the size of 500 nm-2 μm can be observed on the particles with the magnification factor of 3000 times in fig. 7 (B), the contact area of electrode materials and electrolyte is greatly increased, more catalytic active sites are exposed, the mass transfer process of the electrolyte and the dissipation of generated gas are accelerated by the three-dimensional hole structure, the thermodynamic and kinetic conditions in the process of electrocatalytic water decomposition reaction are improved, the overpotential and Tafel slope of oxygen evolution reaction can be reduced, and the corresponding test result is similar to that of example 1.
Example 4
(1) Plastic deformation: commercial nickel-molybdenum alloy rod Hastelloy B-4 is selected as an initial master alloy, the brand is NS3204, the nickel-molybdenum alloy rod mainly comprises elements such as Ni, mo, fe, cr and the like, the mass fraction of the Ni element is 60%, the mass fraction of the Mo element is 28%, the mass fraction of the Fe element is 4%, the mass fraction of the Cr element is 1%, and the initial diameter of the alloy rod is 10mm. Performing extrusion deformation treatment on the alloy rod at room temperature, wherein the deformation amount is 44%, and the diameter of the extruded deformed alloy rod is 12mm;
(2) Pretreatment: grinding the surface of the deformed nickel-molybdenum alloy by using 360-mesh SiC sand paper for 15min, respectively ultrasonically cleaning the ground alloy by using 2M hydrochloric acid, deionized water and ethanol for 30min, and then drying the alloy in a vacuum drying oven with the vacuum degree of 1000Pa at the temperature of 60 ℃ for 6h;
(3) Preparing an etching solution: 3 parts by weight of analytically pure HNO 3 And 1 part of Cu (CO) 2 CH 3 ) 2 ·H 2 O is dissolved in 30 parts of deionized water and magnetically stirred for 5 minutes at 150 revolutions per minute to obtain an etching solution;
(4) Dealloying: putting the dried deformed nickel-molybdenum alloy obtained in the step (2) into the corrosion solution obtained in the step (3), fully stirring, and then performing dealloying reaction in a water bath kettle, wherein the temperature of the water bath kettle is set to be 60 ℃, and the reaction time is set to be 10 hours; and after the reaction is finished, washing the dealloyed nickel-molybdenum alloy with deionized water and ethanol for 3 times, wherein the time is 5min each time, and then drying the nickel-molybdenum alloy in a vacuum drying oven with the vacuum degree of 1000Pa at the temperature of 60 ℃ for 6h to obtain the porous nickel-molybdenum alloy electrocatalytic material.
After plastic deformation and dealloying of commercial nickel-molybdenum alloy Hastelloy B-4, the surface morphology is shown in fig. 8, the alloy surface is roughened under the magnification factor of 500 times in fig. 8 (a), the alloy surface is separated into particles with a micron-sized particle size of 20-100 μm, the double-scale micro-nano holes with the size of 500 nm-2 μm can be observed on the particles with the magnification factor of 3000 times in fig. 8 (B), the holes penetrate through the particles and are communicated with each other, the contact area of electrode materials and electrolyte is greatly increased, more catalytic active sites are exposed, the mass transfer process of the electrolyte and the dissipation of generated gas in the electrolytic process are accelerated by the three-dimensional hole structure, the thermodynamic and kinetic conditions in the electrocatalytic water splitting reaction process are improved, the overpotential and Tafel slope of the oxygen splitting reaction can be reduced, and the corresponding test result is similar to that of example 1.
Comparative example 1
(1) The commercial nickel-molybdenum alloy plate Hastelloy B is selected as an initial master alloy, the brand is NS3201, the nickel-molybdenum alloy plate is mainly composed of Ni, mo, fe and other elements, the mass fraction of the Ni element is 65%, the mass fraction of the Mo element is 28%, the mass fraction of the Fe element is 5%, and the initial thickness of the alloy plate is 3mm; carrying out rolling deformation treatment on the alloy plate at room temperature, wherein the deformation is 60%, and the thickness of the rolled deformed alloy plate is 1.2mm;
(2) Grinding the surface of the deformed nickel-molybdenum alloy by using 180-mesh SiC sand paper for 5min, respectively ultrasonically cleaning the ground alloy by using 2M hydrochloric acid, deionized water and ethanol for 20min, and then drying for 5h at 60 ℃ in a vacuum drying oven with the vacuum degree of 1000 Pa;
(3) 1 part of analytically pure HNO by weight fraction 3 Dissolving in 20 parts of deionized water, and magnetically stirring for 5 minutes at 150 revolutions per minute to obtain an etching solution;
(4) Putting the dried deformed nickel-molybdenum alloy obtained in the step (2) into the corrosion solution obtained in the step (3), fully stirring, and then reacting in a water bath, wherein the temperature of the water bath is set to be 60 ℃ and the reaction time is 7 hours; and after the reaction is finished, washing the dealloyed nickel-molybdenum alloy with deionized water and ethanol for 3 times, wherein the time is 5min each time, and then drying the nickel-molybdenum alloy in a vacuum drying oven with the vacuum degree of 4000Pa at 60 ℃ for 6h to obtain the nickel-molybdenum alloy material.
Commercial nickel-molybdenum alloy Hastelloy B is plastically deformed and is only in HNO 3 After the reaction in the etching solution, the surface morphology is as shown in fig. 9, the alloy surface is seen to be flat at a magnification of 500 times in fig. 9 (a), and a plurality of pitting-like pits with a size of 0.5 to 2 μm are observed on the alloy surface at a magnification of 3000 times in fig. 9 (b), and the entire alloy does not form a porous structure. While example 1 uses HNO 3 +Cu(NO 3 ) 2 The three-dimensional porous structure is obtained after the dealloying reaction of the corrosive solution, the contact area of the electrode material and the electrolyte is increased, more catalytic active sites are exposed, the mass transfer process of the electrolyte in the electrolysis process and the dissipation of generated gas are accelerated by the three-dimensional porous structure, and the thermodynamic and kinetic conditions in the electrocatalytic water splitting reaction process are improved.
Comparative example 2
(1) Plastic deformation: the commercial nickel-molybdenum alloy plate Hastelloy B is selected as an initial master alloy, the brand is NS3201, the nickel-molybdenum alloy plate is mainly composed of Ni, mo, fe and other elements, the mass fraction of the Ni element is 65%, the mass fraction of the Mo element is 28%, the mass fraction of the Fe element is 5%, and the initial thickness of the alloy plate is 3mm; carrying out rolling deformation treatment on the alloy plate at room temperature, wherein the deformation is 60%, and the thickness of the rolled deformed alloy plate is 1.2mm;
(2) Pretreatment: grinding the surface of the deformed nickel-molybdenum alloy by using 180-mesh SiC sand paper for 5min, respectively ultrasonically cleaning the ground alloy by using 2M hydrochloric acid, deionized water and ethanol for 20min, and then drying for 5h at 60 ℃ in a vacuum drying oven with the vacuum degree of 1000 Pa;
(3) Preparing an etching solution: in weight fractions, 7 parts of analytically pure Cu (NO 3 ) 2 Dissolving in 30 parts of deionized water, and magnetically stirring for 5 minutes at 150 revolutions per minute to obtain an etching solution;
(4) Dealloying: putting the dried deformed nickel-molybdenum alloy obtained in the step (2) into the corrosion solution obtained in the step (3), fully stirring, and then performing dealloying reaction in a water bath kettle, wherein the temperature of the water bath kettle is set to be 60 ℃, and the reaction time is set to be 10 hours; and after the reaction is finished, washing the dealloyed nickel-molybdenum alloy with deionized water and ethanol for 3 times, wherein the time is 5min each time, and then drying the dealloyed nickel-molybdenum alloy in a vacuum drying oven with the vacuum degree of 4000Pa at 60 ℃ for 6h to obtain the dealloyed nickel-molybdenum alloy electrocatalytic material.
Commercial nickel-molybdenum alloy Hastelloy B is plastically deformed and is only coated with Cu (NO 3 ) 2 After dealloying in the etching solution, the surface morphology is as shown in FIG. 10, and the surface of the alloy is seen to have a single convex shape at a magnification of 500 times in FIG. 10 (a)The alloy substrate was observed to be in the form of wrinkles with cracks occurring and the entire alloy did not form a porous structure at a magnification of 3000 times in fig. 10 (b) with a size of between 5 and 20 μm. While example 1 uses HNO 3 +Cu(NO 3 ) 2 The three-dimensional porous structure is obtained after the dealloying reaction of the corrosive solution, the contact area of the electrode material and the electrolyte is increased, more catalytic active sites are exposed, the mass transfer process of the electrolyte in the electrolysis process and the dissipation of generated gas are accelerated by the three-dimensional porous structure, and the thermodynamic and kinetic conditions in the electrocatalytic water splitting reaction process are improved.
Comparative example 3
(1) Alloy selection: the commercial nickel-molybdenum alloy plate Hastelloy B-2 is selected as an initial alloy, the brand is NS3202, the nickel-molybdenum alloy plate mainly comprises elements such as Ni, mo, fe and the like, the mass fraction of the Ni element is 65%, the mass fraction of the Mo element is 29%, the mass fraction of the Fe element is 2%, and the thickness of the alloy plate is 1mm;
(2) Pretreatment: grinding the surface of the nickel-molybdenum alloy plate by using 360-mesh SiC sand paper for 10min, respectively ultrasonically cleaning the ground alloy plate by using 2M hydrochloric acid, deionized water and ethanol for 30min, and then drying the alloy plate in a vacuum drying oven with the vacuum degree of 4000Pa at 80 ℃ for 4h;
(3) Preparing an etching solution: 3 parts by weight of analytically pure HNO 3 And 7 parts of Cu (CO) 2 CH 3 ) 2 Dissolving in 60 parts of deionized water, and magnetically stirring for 5 minutes at 150 revolutions per minute to obtain an etching solution;
(4) Dealloying: putting the dried nickel-molybdenum alloy plate obtained in the step (2) into the corrosion solution obtained in the step (3), fully stirring, and then performing dealloying reaction in a water bath kettle, wherein the temperature of the water bath kettle is set to be 70 ℃, and the reaction time is set to be 5 hours; and after the reaction is finished, washing the dealloyed nickel-molybdenum alloy with deionized water and ethanol for 3 times, wherein the time is 5min each time, and then drying the dealloyed nickel-molybdenum alloy in a vacuum drying oven with the vacuum degree of 2000Pa at 80 ℃ for 4h to obtain the dealloyed nickel-molybdenum alloy electrocatalytic material.
Commercial nickel-molybdenum alloy Hastelloy B-2 is not plastically deformed, onlyHNO 3 +Cu(CO 2 CH 3 ) 2 After dealloying in the etching solution, the surface morphology is as shown in fig. 11, and at a magnification of 500 times in fig. 11 (a), it can be seen that the alloy surface is no longer flat and undulation occurs, and at a magnification of 3000 times in fig. 11 (b), it can be seen that the entire alloy does not form a porous structure. While example 2 was subjected to plastic deformation and HNO was used 3 +Cu(CO 2 CH 3 ) 2 The three-dimensional porous structure is obtained after the dealloying reaction of the corrosive solution, the contact area of the electrode material and the electrolyte is increased, more catalytic active sites are exposed, the mass transfer process of the electrolyte in the electrolysis process and the dissipation of generated gas are accelerated by the three-dimensional porous structure, and the thermodynamic and kinetic conditions in the electrocatalytic water splitting reaction process are improved.
Comparative example 4
This comparative example differs from example 1 in that: hydrochloric acid and copper nitrate are selected to replace nitric acid and copper nitrate in the embodiment 1; or nitric acid and copper chloride are selected to replace nitric acid and copper nitrate in the embodiment 1, and other preparation conditions are the same as the embodiment 1.
After hydrochloric acid and copper nitrate are selected, the alloy is still silvery white after corrosion, and no porous is formed.
After nitric acid and copper chloride are selected, the alloy is still silvery white after corrosion, and no porous is formed.

Claims (8)

1. A preparation method of a porous nickel-molybdenum alloy electrocatalytic material is characterized by comprising the following steps: the method comprises the following steps:
(1) Plastic deformation: plastically deforming the nickel-molybdenum alloy to obtain a deformed nickel-molybdenum alloy;
(2) Pretreatment: pretreating the deformed nickel-molybdenum alloy to remove impurities on the surface, thereby obtaining clean deformed nickel-molybdenum alloy;
(3) Preparing an etching solution: HNO of 3 And copper salt are dissolved in water to obtain an etching solution;
(4) Dealloying: placing the deformed nickel-molybdenum alloy obtained in the step (2) into the corrosive solution obtained in the step (3) for dealloying reaction, and carrying out subsequent treatment to obtain the porous nickel-molybdenum alloy electrocatalytic material;
the deformation amount of the plastic deformation in the step (1) is 40-90%; plastic deformation is performed at room temperature;
the copper salt in the step (3) is more than one of copper nitrate containing crystal water or not containing crystal water and copper acetate containing crystal water or not containing crystal water;
the HNO in step (3) 3 The mass ratio of copper salt to water is (3-6): (2-14): 60;
the temperature of the dealloying reaction in the step (4) is 60-80 ℃, and the dealloying reaction time is 5-10 h;
the nickel-molybdenum alloy in the step (1) is Hastelloy B series alloy.
2. The method for preparing the porous nickel-molybdenum alloy electrocatalytic material according to claim 1, wherein the method comprises the following steps: the nickel-molybdenum alloy in the step (1) specifically comprises one of Hastelloy B, hastelloy B-2, hastelloy B-3 and Hastelloy B-4.
3. The method for preparing the porous nickel-molybdenum alloy electrocatalytic material according to claim 1, wherein the method comprises the following steps: the pretreatment in the step (2) specifically means that the oxide skin on the surface of the deformed nickel-molybdenum alloy is removed by sanding, and then the sanded alloy is respectively ultrasonically cleaned by hydrochloric acid, water and ethanol, and then dried.
4. A method for preparing the porous nickel-molybdenum alloy electrocatalytic material according to claim 3, wherein: in the pretreatment of the step (2), 180-360 mesh SiC sand paper is used for polishing, and the polishing time is 5-15 min;
in the pretreatment of the step (2), the concentration of hydrochloric acid is 2-3M; respectively cleaning with hydrochloric acid, water and ethanol for 20-30 min; the drying temperature is 60-80 ℃, the drying time is 4-6 h, the drying is vacuum drying, and the vacuum degree of the drying is 1000-4000 Pa.
5. The method for preparing the porous nickel-molybdenum alloy electrocatalytic material according to claim 1, wherein the method comprises the following steps:
the reaction in step (4) is carried out under stirring; the stirring speed is 50-150 rpm;
the subsequent treatment means that after the reaction is finished, the dealloyed nickel-molybdenum alloy is washed by water and ethanol respectively and dried.
6. A porous nickel-molybdenum alloy electrocatalytic material obtained by the method of any one of claims 1-5.
7. The porous nickel-molybdenum electrocatalytic material of claim 6, wherein: the porous morphology in the material is composed of micron particles, the size of each micron particle is 20-100 mu m, and each micron particle is composed of 500 nm-2 mu m double-scale micro-nano holes.
8. Use of the porous nickel-molybdenum electrocatalytic material according to claim 6 or 7, characterized in that: the porous nickel-molybdenum alloy electrocatalytic material is used for HER electrodes in electrocatalytic water splitting hydrogen production.
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