CN112337479B - Method for preparing high-activity ternary metal boride hydrogen evolution catalyst by using waste aluminum foil - Google Patents
Method for preparing high-activity ternary metal boride hydrogen evolution catalyst by using waste aluminum foil Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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Abstract
The invention discloses a method for preparing a high-activity ternary metal boride hydrogen evolution catalyst by using waste aluminum foil, which comprises the following steps: (1) washing the cut waste aluminum foil by hydrochloric acid, performing ultrasonic treatment by using ethylene glycol and acetone respectively, and soaking the treated waste aluminum foil in a manganese chloride solution for later use, wherein A is marked; (2) adding a sodium sulfate solution into the solution A until the pH value of the solution is 4 to obtain a solution B; (3) adding ferric trichloride solution into B to obtain C; (4) taking an aluminum foil as a working electrode, a platinum net as an auxiliary electrode and C as electrolyte, electrifying and efficiently electrodepositing, and simultaneously dropwise adding a sodium borohydride solution into the solution C; (5) and washing and drying the self-supporting electrode by absolute ethyl alcohol and deionized water in sequence to obtain the high-activity ternary Al-Fe-Mn boride hydrogen evolution catalyst. The preparation method has the advantages of short preparation period, capability of quickly preparing the hydrogen evolution catalyst, stable performance of the catalyst, high catalytic activity and regular nano block shape.
Description
Technical Field
The invention belongs to the field of waste resource utilization and catalytic chemistry, relates to a preparation method of a hydrogen evolution catalyst applied to electrolyzed water, and particularly relates to a method for preparing a high-activity ternary metal hydrogen evolution catalyst by using waste aluminum foil.
Background
The traditional fossil energy supply mode of energy shortage has become a bottleneck restricting sustainable development of human society, and the search for novel energy with high energy, no pollution and reproducibility is one of the current global research hotspots. The hydrogen energy has the characteristics of abundant resources, high heat value and the like, is not limited by factors such as seasons, regions and the like compared with renewable energy sources such as wind energy, solar energy and the like, and is considered as the most potential alternative energy source for development in the future. The hydrogen production technology with the most application prospect is realized due to the advantages of zero environmental pollution emission, high utilization of surplus energy of intermittent renewable energy sources and the like. The alkaline water electrolysis hydrogen production process is widely applied to the water electrolysis industry due to the advantages of mature technology, safety, reliability, simple operation and the like. It is well known that the electrolysis of water consists of two half-reactions, cathodic Hydrogen Evolution (HER) and anodic Oxygen Evolution (OER), for HER it is necessary to use a highly efficient HER catalyst to reduce the overpotential and accelerate the reaction kinetics. At present, platinum group metal is the HER catalyst with the best performance, but the price is high, and the reserves are scarce, so that the large-scale popularization and application of the water electrolysis hydrogen production technology are prevented. Based on this background, the development and design of non-noble metal HER electrocatalysts with low cost and superior performance is the key to realizing energy efficient conversion, and has also become a hot spot for research by scientists.
In recent years, Metal Borides (MBs) have become HER catalysts with great application prospects due to low price, simple preparation and high stability. However, the conventional metal boride preparation methods such as a solid-phase sintering method, a molten salt electrolysis method and the like have the disadvantages of large size, uneven dispersion, complex synthesis process and high energy consumption, and are not suitable for large-scale popularization and production. The electrochemical deposition method is a novel surface treatment technology which utilizes a reducing agent to reduce metal ions in a plating solution and deposits the metal ions on the surface of a substrate to form a functional metal film, and compared with other IMBs preparation methods, the electrochemical deposition method has the advantages of simple process, low cost, high deposition efficiency, uniform particle size and the like. Therefore, the electrochemical deposition method is adopted to prepare the multi-element metal boride with excellent catalytic activity, and a new idea is provided for further improving the catalytic activity of the catalyst.
The aluminum foil is a necessary material used in lithium ion batteries, however, with the popularization of new energy electric vehicles and the use of power batteries, the service life of the lithium ion batteries is continuously declined, and the waste disposal problem of the retired lithium ion batteries has to be faced after the service life of the lithium ion batteries is reached. At present, no report is found on the preparation of an anode hydrogen evolution electrocatalyst with high activity and stability by recycling waste aluminum foil.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for preparing a high-activity ternary metal hydrogen evolution catalyst by using waste aluminum foils, which adopts the waste aluminum foils as raw materials, prepares the high-efficiency ternary metal boride catalyst in a short time by an electrochemical deposition method at room temperature, and accelerates the reaction rate by adding ferric trichloride in the synthesis process to ensure that ferric iron and the aluminum foils perform oxidation-reduction reaction in the electrodeposition process.
The technical scheme provided by the invention is as follows:
a method for preparing a high-activity ternary metal boride hydrogen evolution catalyst by using waste aluminum foils sequentially comprises the following steps:
(1) washing the cut waste aluminum foil with hydrochloric acid in sequence, performing ultrasonic treatment for 30min with ethylene glycol and acetone respectively, and soaking the treated waste aluminum foil in a manganese chloride solution for later use, and marking as A;
the purpose of ultrasonic treatment with ethylene glycol and acetone in this step, respectively, is; firstly, performing ultrasonic treatment by using ethylene glycol to clean impurities such as graphite, organic binder PVDF and the like remained on the aluminum foil, and then performing ultrasonic treatment by using acetone to clean the ethylene glycol remained in the washing process, so as to prepare for next oxidation-reduction reaction and electrochemical deposition;
(2) adding sodium sulfate solution into A until the pH value of the solution is 4 to obtain B;
in this step, the pH of the solution B needs to be controlled at 4, mainly because the acidity of the solution is crucial in the subsequent electrodeposition process, mainly reflecting that the electrodeposition plating solution needs weak acidity to achieve the conversion of aluminum foil into aluminum ions; when the pH is less than 4, excessive aluminum foil can be converted into aluminum ions, so that the form of the aluminum foil is seriously damaged and the subsequent electrodeposition effect is influenced, and when the pH is between 4 and 7, the efficiency of converting the aluminum foil into the aluminum ions is low, the concentration of the aluminum ions in the subsequent electrodeposition process cannot be reached, and the aluminum cannot participate in the reaction;
(3) adding 5-10mL of ferric trichloride solution into B to obtain C;
in the step, ferric trichloride is added, so that the overall reaction rate is accelerated through the redox reaction of ferric iron and the aluminum foil in the subsequent electrodeposition process, the specific expression is that the ferric iron can show extremely strong oxidizability in the current electroplating solution environment, the treated aluminum foil has extremely strong reducibility, the ferric iron and the aluminum foil can carry out the redox reaction rapidly, and then the nano-particles with regular shapes can be prepared rapidly and efficiently;
(4) an aluminum foil is used as a working electrode, a platinum net is used as an auxiliary electrode, C is used as an electrolyte to form an electrochemical double-electrode system, the electrochemical double-electrode system is electrified to carry out electrochemical deposition reaction, rapid and efficient electrodeposition is carried out on the aluminum foil, 2-5mL of sodium borohydride solution is dropwise added into the electrolyte C during electrodeposition, the dropwise adding rate of the sodium borohydride solution is uniform dropwise adding in the electrodeposition process, so that boron elements can be uniformly introduced in situ, the reaction process is uniform and stable, the active sites of the material are uniform, and the whole catalytic activity is good;
in the step, the electrochemical system is a double-electrode system, and compared with a three-electrode electrochemical system for carrying out an electrodeposition reaction, the method has the advantages of simple operation, low cost, no need of a relatively unstable reference electrode such as a mercury/mercury oxide electrode and the like in the electrodeposition process; in addition, boron element can be introduced in situ by adding sodium borohydride in the electrodeposition process, which is crucial to the final shape, size and catalytic performance of the material, and uniform and stable multi-element metal boride is formed after reaction;
(5) and (3) washing the self-supporting electrode for 3-6 times by using absolute ethyl alcohol and deionized water in sequence, and drying in vacuum to obtain the self-supporting high-activity ternary Al-Fe-Mn boride hydrogen evolution catalyst.
As a limitation of the present invention:
in the step (1), the molar concentration of the hydrochloric acid is 3M;
in the step (II), the manganese chloride solution is 30-50 mmol.
In the third step (3), the concentration of the ferric trichloride solution is 0.5mM-0.8 mM.
And (IV) in the step (4), the concentration of the sodium borohydride solution is 5 mM.
In the step (4), the current density of the electrochemical deposition reaction is 2A/cm2Reaction 100-150 s;
in this step, the current density and the deposition time in the electrochemical deposition process have important influence on the morphology and the particle size of the final product when the current density is less than 2A/cm2In the process, the adhesion between the electrodeposited nano particles and the self-supporting electrode is poor, so that the electrocatalyst is easy to fall off in the electrocatalysis process, and the catalysis effect is influenced; when the current density is more than 2A/cm2In the process of electrodeposition, more nanoparticles can be rapidly generated, the transmission of electrolyte ions and electrons among the nanoparticles is weakened due to particle stacking, and the electrocatalysis performance is reduced;
when the electrodeposition time is less than 100s, the density of the nanoparticles generated by electrodeposition is low, so that the electrocatalytic performance of the nanoparticles is reduced; when the electrodeposition time is longer than 150s, more nano particles are generated in electrodeposition, so that the transmission of electrolyte ions and electrons among the nano particles is weakened, and the electrocatalysis performance is reduced;
sixthly, in the step (5), the drying temperature is 60-100 ℃, and the drying time is 6-12 h;
the high-activity Al-Fe-Mn ternary boride hydrogen evolution catalyst has more active sites by introducing boron in situ in the electrochemical reaction process, and the catalytic activity of the high-activity Al-Fe-Mn ternary boride hydrogen evolution catalyst is greatly improved.
In the electrochemical deposition process of the invention, the specific reaction process is as follows: firstly, ferric iron and aluminum foil are subjected to rapid oxidation-reduction reaction in an electroplating solution system, and meanwhile, a sodium borohydride reducing agent is added in situ in the reaction process, so that boron is introduced in situ in the reaction process, and a large amount of ternary metal boride with active sites is rapidly formed, so that a nano catalyst with excellent hydrogen evolution catalytic activity is finally formed, and the in-situ introduction of boron in the process is crucial to the improvement of the catalytic activity of the catalyst.
The invention also has a limitation that the high-activity ternary Al-Fe-Mn boride hydrogen evolution catalyst is a blocky structure with the diameter of 20-40 nm; as is well known, the structure of the material directly influences the catalytic performance of the material, and the material prepared by the method is in the range of 20-40nm, so that the material has excellent catalytic activity.
The above-described preparation process as a whole for preparing the catalyst of the invention is associated with the fact that the individual steps are not readily cleavable.
Compared with the prior art, the invention has the following advantages:
1. the method adopts the waste aluminum foil as the raw material, prepares the self-supporting high-activity ternary metal boride hydrogen evolution catalyst by combining an electrochemical method at room temperature and an oxidation-reduction reaction, has simple production process, easy control of the process, short period and low cost, and is suitable for large-scale industrial production.
2. Ferric trichloride is added in the synthesis process, so that ferric iron and aluminum foil are subjected to redox reaction in the electrodeposition process to accelerate the reaction rate, the preparation period is greatly shortened, and the method has obvious economic benefit in industrial batch production.
3. The boron element is introduced in situ in the electrodeposition process, so that the prepared ternary metal boride has more active sites, and meanwhile, the hydrogen evolution catalytic performance of the catalyst is greatly improved under the synergistic catalytic action between the ternary metal and the boron in the catalytic process, the catalytic stability is good, and the catalytic performance is basically kept unchanged after 1000 cycles.
4. Realizes the recycling of waste, can realize large-scale production and realizes industrialization.
The method is suitable for preparing the high-activity ternary metal boride hydrogen evolution catalyst by utilizing the waste aluminum foil.
The embodiments of the present invention will be described in further detail with reference to the accompanying drawings.
Drawings
FIG. 1 is a TEM image of a sample prepared in example 1 of the present invention;
FIG. 2 is a transmission electron microscope image at high magnification of a sample prepared in example 2 of the present invention;
FIG. 3 is a LSV graph of a sample prepared in example 3 of the present invention;
FIG. 4 is a diagram of elemental analysis of a sample prepared in example 4 of the present invention;
FIG. 5 is a graph of electrocatalytic cycle stability for samples made in example 5 of the present invention;
FIG. 6 is a comparison of the LSV curves of the samples prepared in example 5, example 6 and example 7 of the present invention;
FIG. 7 is a TEM image of a sample prepared in example 7 of the present invention.
Detailed Description
The reagents used in the following examples were commercially available unless otherwise specified, and the preparation methods and detection methods used were those according to the prior art unless otherwise specified.
Example 1
The embodiment is a method for preparing a high-activity ternary metal boride hydrogen evolution catalyst by using waste aluminum foils, which is sequentially carried out according to the following steps:
(11) pretreatment of waste aluminum foil: washing the cut waste aluminum foils (the waste aluminum foils are materials stripped from the waste lithium ion battery electrodes containing aluminum elements) by 3M hydrochloric acid in sequence, then performing ultrasonic treatment for 30min by using ethylene glycol and acetone respectively, and soaking the treated waste aluminum foils in 30mmol of manganese chloride solution for later use, wherein the solution is marked as A1;
(12) adding a certain amount of sodium sulfate solution into the A1 until the pH value of the solution is 4 to obtain B1;
(13) adding 10mL of 0.5mM ferric trichloride solution into B1 to obtain C1;
(14) an electrochemical double-electrode system is formed by using an aluminum foil as a working electrode, a platinum mesh as an auxiliary electrode and an electrolyte containing manganese salt and iron salt consisting of C1, and the current density is 2A/cm2Performing a reaction for 100s, performing rapid and efficient electrodeposition on the aluminum foil, and simultaneously uniformly and slowly dropwise adding 2mL of 5mM sodium borohydride solution into the C1 solution in the electrodeposition process;
(15) and washing the self-supporting electrode for 6 times by absolute ethyl alcohol and deionized water in sequence, and drying for 6 hours in vacuum at 100 ℃ to obtain the high-activity ternary Al-Fe-Mn boride hydrogen evolution catalyst.
FIG. 1 is a TEM image of a sample prepared in example 1 of the present invention, wherein the material has a regular bulk structure and is interlaced with each other, and the structure is favorable for the transmission of ions and electrons.
Example 2
The embodiment is a method for preparing a high-activity ternary metal boride hydrogen evolution catalyst by using waste aluminum foils, which is sequentially carried out according to the following steps:
(21) pretreatment of waste aluminum foil: washing the cut waste aluminum foils (the waste aluminum foils are materials stripped from the waste lithium ion battery electrodes containing aluminum elements) by 3M hydrochloric acid in sequence, then performing ultrasonic treatment for 30min by using ethylene glycol and acetone respectively, and soaking the treated waste aluminum foils in 50mmol of manganese chloride solution for later use, wherein the A1 is marked;
(22) adding a certain amount of sodium sulfate solution into the A1 until the pH value of the solution is 4 to obtain B1;
(23) adding 5mL of 0.8mM ferric trichloride solution into B1 to obtain C1;
(24) the aluminum foil is used as a working electrode,platinum net is used as auxiliary electrode, electrolyte containing manganese salt and iron salt and consisting of C1 is adopted to form an electrochemical double-electrode system, and the current density is 2A/cm2Performing a next reaction for 150s, performing rapid and efficient electrodeposition on the aluminum foil, and simultaneously uniformly and slowly dropwise adding 5mL of 5mM sodium borohydride solution into the C1 solution in the electrodeposition process;
(25) and (3) washing the self-supporting electrode for 3 times by using absolute ethyl alcohol and deionized water in sequence, and drying the self-supporting electrode for 10 hours in vacuum at the temperature of 80 ℃ to obtain the high-activity ternary Al-Fe-Mn boride hydrogen evolution catalyst.
FIG. 2 is a transmission electron microscope image of the sample prepared in example 2 of the present invention under high magnification, from which it can be seen that the sample is a regular structure assembled by many small particles of different sizes, and the diameter of the sample nano-block is 20-40 nm.
Example 3
The embodiment is a method for preparing a high-activity ternary metal boride hydrogen evolution catalyst by using waste aluminum foils, which is sequentially carried out according to the following steps:
(31) pretreatment of waste aluminum foil: washing the cut waste aluminum foils (the waste aluminum foils are materials stripped from the waste lithium ion battery electrodes containing aluminum elements) by 3M hydrochloric acid in sequence, then performing ultrasonic treatment for 30min by using ethylene glycol and acetone respectively, and soaking the treated waste aluminum foils in 40mmol of manganese chloride solution for later use, wherein the solution is marked as A1;
(32) adding a certain amount of sodium sulfate solution into the A1 until the pH value of the solution is 4 to obtain B1;
(33) 8mL of 0.6mM ferric chloride solution is added into the B1 to obtain C1;
(34) an electrochemical double-electrode system is formed by using an aluminum foil as a working electrode, a platinum mesh as an auxiliary electrode and an electrolyte containing manganese salt and iron salt consisting of C1, and the current density is 2A/cm2Performing a next reaction for 120s, performing rapid and efficient electrodeposition on the aluminum foil, and meanwhile, slowly and uniformly dropwise adding 3mL of 5mM sodium borohydride solution into the C1 solution in the electrodeposition process;
(35) and (3) washing the self-supporting electrode for 5 times by using absolute ethyl alcohol and deionized water in sequence, and drying the washed self-supporting electrode for 12 hours in vacuum at the temperature of 60 ℃ to obtain the high-activity ternary Al-Fe-Mn boride hydrogen evolution catalyst.
FIG. 3 is a graph of the electrocatalytic LSV of a sample prepared in example 3 of the present invention, from which it can be seen that the current density is 50mA-2The overpotential for hydrogen evolution was 274mV, which indicates that the trimetallic boride catalyst of this example has excellent catalytic activity for hydrogen evolution.
In the embodiment, the prepared high-activity ternary Al-Fe-Mn boride hydrogen evolution catalyst is subjected to a high-magnification transmission electron microscope test and a cycle stability test (not shown in the embodiment), and the result shows that a sample has a nano-block structure and the diameter of 20-40nm, and the catalytic performance of the material is basically kept unchanged after 1000 cycles of catalytic cycle, so that the material has good cycle stability.
Example 4
The embodiment is a method for preparing a high-activity ternary metal boride hydrogen evolution catalyst by using waste aluminum foils, which is sequentially carried out according to the following steps:
(41) pretreatment of waste aluminum foil: washing the cut waste aluminum foils (the waste aluminum foils are materials stripped from the waste lithium ion battery electrodes containing aluminum elements) by 3M hydrochloric acid in sequence, then performing ultrasonic treatment for 30min by using ethylene glycol and acetone respectively, and soaking the treated waste aluminum foils in 40mmol of manganese chloride solution for later use, wherein the solution is marked as A1;
(42) adding a certain amount of sodium sulfate solution into the A1 until the pH value of the solution is 4 to obtain B1;
(43) 6mL of 0.5mM ferric trichloride solution is added into the B1 to obtain C1;
(44) an electrochemical double-electrode system is formed by using an aluminum foil as a working electrode, a platinum mesh as an auxiliary electrode and an electrolyte containing manganese salt and iron salt consisting of C1, and the current density is 2A/cm2Performing a next reaction for 140s, performing rapid and efficient electrodeposition on the aluminum foil, and meanwhile, slowly and uniformly dropwise adding 3mL of 5mM sodium borohydride solution into the C1 solution in the electrodeposition process;
(45) and washing the self-supporting electrode for 6 times by absolute ethyl alcohol and deionized water in sequence, and drying for 6 hours in vacuum at 100 ℃ to obtain the high-activity ternary Al-Fe-Mn boride hydrogen evolution catalyst.
FIG. 4 is an elemental analysis chart of a sample obtained in example 4 of the present invention, from which it can be seen that the material is a ternary metal boride compound of Al-Fe-Mn, and it is confirmed that aluminum ions, manganese ions and iron ions smoothly react with boron, and the content of aluminum accounts for 16.74%.
In the embodiment, the prepared high-activity ternary Al-Fe-Mn boride hydrogen evolution catalyst is subjected to a high-magnification transmission electron microscope test and a cycle stability test (not shown in the embodiment), and the result shows that a sample has a nano-block structure and the diameter of 20-40nm, and the catalytic performance of the material is basically kept unchanged after 1000 cycles of catalytic cycle, so that the material has good cycle stability.
Example 5
The embodiment is a method for preparing a high-activity ternary metal boride hydrogen evolution catalyst by using waste aluminum foils, which is sequentially carried out according to the following steps:
(51) pretreatment of waste aluminum foil: washing the cut waste aluminum foils (the waste aluminum foils are materials stripped from the waste lithium ion battery electrodes containing aluminum elements) by 3M hydrochloric acid in sequence, then performing ultrasonic treatment for 30min by using ethylene glycol and acetone respectively, and soaking the treated waste aluminum foils in 35mmol of manganese chloride solution for later use, wherein the solution is marked as A1;
(52) adding a certain amount of sodium sulfate solution into the A1 until the pH value of the solution is 4 to obtain B1;
(53) adding 10mL of 0.6mM ferric trichloride solution into the B1 to obtain C1;
(54) an electrochemical double-electrode system is formed by using an aluminum foil as a working electrode, a platinum mesh as an auxiliary electrode and an electrolyte containing manganese salt and iron salt consisting of C1, and the current density is 2A/cm2Performing a next reaction for 150s, performing rapid and efficient electrodeposition on the aluminum foil, and simultaneously slowly and uniformly dropwise adding 5mL of 5mM sodium borohydride solution into the C1 solution in the electrodeposition process;
(55) and (3) washing the self-supporting electrode for 5 times by using absolute ethyl alcohol and deionized water in sequence, and drying the washed self-supporting electrode for 6 hours in vacuum at the temperature of 100 ℃ to obtain the high-activity ternary Al-Fe-Mn boride hydrogen evolution catalyst.
FIG. 5 is a cycle stability test of the sample prepared in example 5 of the present invention, and the results show that the catalyst has good cycle stability with the catalytic performance substantially unchanged after 1000 cycles of catalytic cycle.
The high-power transmission electron microscope test (not shown in the embodiment) is also carried out on the prepared high-activity ternary Al-Fe-Mn boride hydrogen evolution catalyst, and the result shows that the sample has a nano-block structure and the diameter is 20-40 nm.
Example 6 comparative example 1
In the process of preparing the ternary metal hydrogen evolution catalyst, boron element can be introduced in situ by dropwise adding sodium borohydride during electrochemical deposition reaction, which has a crucial influence on the improvement of the overall catalytic performance of the invention, and this embodiment researches the boron element. The following is a method for preparing a ternary metal hydrogen evolution catalyst (aluminum-iron-manganese ternary metal hydrogen evolution catalyst) by using waste aluminum foil, which is similar to the preparation steps of the example 5, and is different only in that: during the preparation process, no sodium borohydride solution is added.
The method comprises the following specific steps:
(61) pretreatment of waste aluminum foil: washing the cut waste aluminum foils (the waste aluminum foils are materials stripped from the waste lithium ion battery electrodes containing aluminum elements) by 3M hydrochloric acid in sequence, then performing ultrasonic treatment for 30min by using ethylene glycol and acetone respectively, and soaking the treated waste aluminum foils in 35mmol of manganese chloride solution for later use, wherein the solution is marked as A1;
(62) adding a certain amount of sodium sulfate solution into the A1 until the pH value of the solution is 4 to obtain B1;
(63) adding 10mL of 0.6mM ferric trichloride solution into the B1 to obtain C1;
(64) an electrochemical double-electrode system is formed by using an aluminum foil as a working electrode, a platinum net as an auxiliary electrode and an electrolyte containing manganese salt and iron salt consisting of C1, and the current density is 2A/cm2Performing a lower reaction for 150s, and performing rapid and efficient electrodeposition on the aluminum foil;
(65) and washing the self-supporting electrode with absolute ethyl alcohol and deionized water for 5 times in sequence, and drying the electrode in vacuum for 6 hours at 100 ℃ to obtain the ternary Al-Fe-Mn hydrogen evolution catalyst.
FIG. 6 is a comparison of LSV curves for samples prepared according to the invention from example 5, example 6 and example 7 (examples described below); as can be seen from the figure, after ferric trichloride and sodium borohydride are added into a reaction solution, the performance of the catalyst prepared in example 5 is obviously superior to that of the catalyst prepared in example 6 (no sodium borohydride solution is added) and the catalyst prepared in example 7 (no ferric trichloride solution is added), which shows that the addition of ferric trichloride and sodium borohydride has an important effect on the preparation of a high-activity Al-Fe-Mn ternary metal electro-catalytic material. In the preparation process, ferric iron can perform a rapid oxidation reduction reaction with aluminum foil in the electroplating solution system, three ions of Al, Fe and Mn can rapidly react with sodium borohydride in the electrodeposition process by adding sodium borohydride, boron active sites are introduced and uniformly distributed, so that a ternary metal boride can be formed, the regular nanometer morphology is formed, and meanwhile, in the catalytic hydrogen evolution process, the three metals of Al, Fe and Mn and boron are subjected to concerted catalysis, so that a composite active center beneficial to the electrocatalytic reaction is formed, the concerted catalysis effect is achieved, and the catalytic performance of the catalyst is greatly improved.
Example 7 comparative example 2
This example is a method for preparing a high-activity bimetallic boride hydrogen evolution catalyst (an aluminum-manganese bimetallic hydrogen evolution catalyst) from waste aluminum foil, which is similar to the preparation steps of example 5, and is different therefrom only in that: in the preparation process, no ferric trichloride solution is added.
The preparation method comprises the following specific steps:
(71) pretreatment of waste aluminum foil: washing the cut waste aluminum foils (the waste aluminum foils are materials stripped from the waste lithium ion battery electrodes containing aluminum elements) by 3M hydrochloric acid in sequence, then performing ultrasonic treatment for 30min by using ethylene glycol and acetone respectively, and soaking the treated waste aluminum foils in 35mmol of manganese chloride solution for later use, wherein the solution is marked as A1;
(72) adding a certain amount of sodium sulfate solution into the A1 until the pH value of the solution is 4 to obtain B1;
(73) aluminum foil is used as a working electrode, a platinum net is used as an auxiliary electrode, electrolyte containing manganese salt and consisting of B1 is adopted,forming an electrochemical double-electrode system with a current density of 2A/cm2Performing electrodeposition for 150s on the aluminum foil, and slowly and uniformly dropwise adding 5mL of 5mM sodium borohydride solution into the C1 solution in the electrodeposition process;
(74) and washing the self-supporting electrode with absolute ethyl alcohol and deionized water for 5 times in sequence, and drying the electrode in vacuum at 100 ℃ for 6 hours to obtain the bimetallic boride hydrogen evolution catalyst.
FIG. 7 is a transmission electron microscope image at high magnification of a sample prepared in example 7 of the present invention, from which it can be seen that the material has an irregular bulk structure, with a diameter of about 3-6 microns. As can be seen from the figure, compared with comparative example 5, in the experiment, the ferric trichloride solution is not added, and in the electrodeposition process, a material with regular morphology is not formed, and the diameter of the material is larger, so that the catalytic effect of two metals in the catalytic process is poorer; in addition, because no ferric ion reacts with the aluminum foil, the number of the catalytic active sites of the generated metal boride catalyst is reduced, and the catalytic activity of the metal boride catalyst is poor.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for preparing a high-activity ternary metal boride hydrogen evolution catalyst by using waste aluminum foils is characterized by sequentially carrying out the following steps:
(1) washing the cut waste aluminum foil with hydrochloric acid in sequence, performing ultrasonic treatment for 30min with ethylene glycol and acetone respectively, and soaking the treated waste aluminum foil in a manganese chloride solution for later use, and marking as A;
(2) adding a sodium sulfate solution into the solution A until the pH value of the solution is 4 to obtain a solution B;
(3) adding 5-10mL of ferric trichloride solution into the B to obtain C;
(4) forming an electrochemical double-electrode system by taking an aluminum foil as a working electrode, a platinum net as an auxiliary electrode and C as electrolyte, electrifying to perform electrochemical deposition reaction, quickly and efficiently electrodepositing on the aluminum foil, and dripping 2-5mL of sodium borohydride solution into the solution C while electrodepositing;
(5) and washing the self-supporting electrode for 3-6 times by absolute ethyl alcohol and deionized water in sequence, and drying in vacuum to obtain the high-activity ternary Al-Fe-Mn boride hydrogen evolution catalyst.
2. The method for preparing a high-activity ternary metal boride hydrogen evolution catalyst using waste aluminum foil according to claim 1, wherein the hydrochloric acid has a molar concentration of 3M in the step (1).
3. The method for preparing a high-activity ternary metal boride hydrogen evolution catalyst using waste aluminum foil according to claim 1, wherein in the step (1), the manganese chloride solution is 30 to 50 mmol.
4. The method for preparing a high-activity ternary metal boride hydrogen evolution catalyst using waste aluminum foil according to claim 1, wherein the concentration of the ferric trichloride solution in the step (3) is 0.5 to 0.8 mM.
5. The method for preparing a high-activity ternary metal boride hydrogen evolution catalyst using waste aluminum foil as claimed in claim 1, wherein the current density of the electrochemical deposition reaction in the step (4) is 2A/cm2Reaction 100-150 s.
6. The method for preparing a high-activity ternary metal boride hydrogen evolution catalyst using waste aluminum foil according to claim 1, wherein the concentration of the sodium borohydride solution is 5mM in the step (4).
7. The method for preparing a highly active ternary metal boride hydrogen evolution catalyst using waste aluminum foil according to claim 1, wherein the drying temperature is 60 to 100 ℃ and the drying time is 6 to 12 hours in step (5).
8. The method for preparing the high-activity ternary metal boride hydrogen evolution catalyst using waste aluminum foil according to any one of claims 1 to 7, wherein the high-activity ternary Al-Fe-Mn boride hydrogen evolution catalyst is a block structure with a diameter of 20 to 40 nm.
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|---|---|---|---|---|
| US3926844A (en) * | 1973-02-17 | 1975-12-16 | Deutsche Automobilgesellsch | Catalysts for the cathodic hydrogen development |
| CN109518217A (en) * | 2018-11-23 | 2019-03-26 | 济南大学 | A kind of preparation method of the Ni-based oxygen-separating catalyst of boronation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3926844A (en) * | 1973-02-17 | 1975-12-16 | Deutsche Automobilgesellsch | Catalysts for the cathodic hydrogen development |
| CN109518217A (en) * | 2018-11-23 | 2019-03-26 | 济南大学 | A kind of preparation method of the Ni-based oxygen-separating catalyst of boronation |
Non-Patent Citations (1)
| Title |
|---|
| Zhaomei Sun et. al..Efficient alkaline hydrogen evolution electrocatalysis enabled by an amorphous Co–Mo–B film.《Dalton Trans》.2018,第47卷第7640页. * |
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