CN113668007B - Hydrogen evolution catalyst and preparation method and application thereof - Google Patents
Hydrogen evolution catalyst and preparation method and application thereof Download PDFInfo
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- CN113668007B CN113668007B CN202110836878.9A CN202110836878A CN113668007B CN 113668007 B CN113668007 B CN 113668007B CN 202110836878 A CN202110836878 A CN 202110836878A CN 113668007 B CN113668007 B CN 113668007B
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Abstract
The invention relates to a hydrogen evolution catalyst, a preparation method and application thereof. The hydrogen evolution catalyst comprises rare earth metal element doped nickel disulfide. The hydrogen evolution catalyst is a non-noble metal high-activity hydrogen evolution catalyst, has good conductivity and large surface area, and simultaneously has a large number of active sites, so that the catalyst has good hydrogen evolution catalytic performance. In addition, the catalyst of the invention has good stability, and can be stable for at least 50000 seconds.
Description
Technical Field
The invention belongs to the field of electrochemical catalysis, and particularly relates to a hydrogen evolution catalyst, and a preparation method and application thereof.
Technical Field
With the rapid consumption of fossil fuels and the resulting environmental problems, researchers are striving to find sustainable alternative energy sources and methods for storing and converting energy sources. Hydrogen is the best fossil fuel alternative as a clean energy carrier with the highest specific energy density. The hydrogen production by water electrolysis has the advantages of high purity, simple process, no pollution, rich resources and the like. Most renewable energy sources provide power for the end use, and excess power is used to electrolyze water to produce storable hydrogen and oxygen. Hydrogen is then transported to areas where energy is scarce and serves industrial, traffic, civilian, etc. fields. However, the scarcity and high cost of platinum-based and iridium-based materials have hindered the large-scale use of electrocatalytic water decomposition.
Disclosure of Invention
The invention aims at providing a hydrogen evolution catalyst, a preparation method of the hydrogen evolution catalyst and an application of the hydrogen evolution catalyst.
In a first aspect, the present invention provides a hydrogen evolution catalyst comprising a rare earth element doped nickel disulfide. According to the invention, through doping of rare earth elements, the energy band of nickel disulfide is regulated and controlled by utilizing a special 4f 5d structure of rare earth metals, the electrocatalytic activity of nickel sulfide can be obviously improved, and the cyclic stability of the nickel sulfide can be improved, so that the hydrogen evolution catalyst has excellent electrocatalytic moisture analysis hydrogen performance.
According to some embodiments of the present invention, the rare earth element in the hydrogen evolution catalyst of the present invention is doped in an atomic substitution into the crystal lattice of nickel disulfide, thereby replacing the nickel sites and forming bonds with sulfur.
According to some embodiments of the invention, the rare earth element doped nickel disulfide has a molar content of rare earth elements of 2% -30%, for example 3%, 4%, 6%, 7%, 9%, 11%, 12%, 14%, 16%, 18%, 21%, 23%, 25%, 27%, 29% or any value therebetween. The molar content of the rare earth metal element is too high, so that rare earth oxide is easy to generate, and the electrocatalytic moisture analysis hydrogen performance of the catalyst is not facilitated.
In some embodiments, the molar content of rare earth metal elements is 5% -20%. In some embodiments, the molar content of rare earth metal elements is 8% -15%. In some embodiments, the molar content of rare earth metal elements is 8% -10%.
According to some embodiments of the invention, the rare earth metal element is selected from one or more of scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).
According to some embodiments of the invention, the rare earth element doped nickel disulfide is structured as a nanoplatelet. The nano sheet structure can effectively improve the specific surface area of the catalyst.
According to some embodiments of the invention, the catalyst further comprises a substrate on which the rare earth element doped nickel disulfide is supported. In some embodiments, the substrate is a conductive substrate. According to some embodiments, the substrate is selected from one or more of carbon cloth, nickel foam, and conductive glass. In some embodiments, the substrate is carbon cloth, also known as carbon paper or carbon fiber cloth, which is a braid composed of carbon fibers interlaced. In some embodiments, the substrate is nickel foam. In some embodiments, the substrate is a conductive glass.
According to some embodiments of the invention, the rare earth element doped nickel disulfide is present on the substrate at a loading of 2mg/cm 2 -10mg/cm 2 For example 2.5mg/cm 2 、3.0mg/cm 2 、3.5mg/cm 2 、4.0mg/cm 2 、4.5mg/cm 2 、5.0mg/cm 2 、6.0mg/cm 2 、7.0mg/cm 2 、8.0mg/cm 2 、9.0mg/cm 2 Or any value therebetween. In some embodiments of the invention, the rare earth doped nickel disulfide is present at a loading of 2mg/cm on the substrate 2 -8.5mg/cm 2 . In some embodiments, the rare earth doped nickel disulfide is present at a loading of 2.5mg/cm on the substrate 2 -5.0mg/cm 2 。
In a second aspect, the present invention provides a method of preparing a hydrogen evolution catalyst comprising sulfiding a precursor comprising a rare earth hydroxide and nickel hydroxide.
According to some embodiments of the invention, the vulcanization is achieved using chemical vapor deposition. According to some embodiments of the invention, the sulfiding comprises heating the precursor in an inert atmosphere in the presence of a sulfur source to 200 ℃ to 500 ℃, preferably 300 ℃ to 400 ℃, for 1h to 12h, preferably 2 to 6h. According to some embodiments of the invention, the sulfur source is selected from one of sublimated sulfur powder or thiourea, preferably sublimated sulfur. According to some embodiments of the invention, the inert gas may be selected from nitrogen and argon, preferably argon.
According to some embodiments of the invention, the preparation of the precursor comprises: the substrate is immersed in a solution containing a rare earth metal source and a nickel source for electrochemical deposition. In some embodiments, electrochemical deposition is performed by a three electrode system.
According to some embodiments of the invention, electrochemical deposition includes deposition at a potential of-0.8V to-1.5V, preferably-0.9V to-1.2V, more preferably-1.0V to-1.1V. According to some embodiments of the invention, the deposition time is 600s-7200s, e.g. 800s, 1000s, 1500s, 2000s, 2500s, 3000s, 3500s, 4000s, 4500s, 5000s, 5500s, 6000s, 6500s, 7000s or any value in between. In some embodiments, the deposition time is 900s-3600s.
According to some embodiments of the invention, the catalyst is prepared by first forming rare earth metal hydroxides and nickel hydroxide on a substrate using electrochemical deposition, and then performing sulfidation using chemical vapor deposition.
According to some embodiments of the invention, the substrate surface may be washed with an acid solution, such as ultrasonic washing, followed by washing with an organic solvent and water and drying, prior to immersing the substrate in the solution containing the rare earth metal source and the nickel source. In some embodiments, the acid solution may be an organic acid solution or an inorganic acid solution, preferably at least one of formic acid, acetic acid, sulfuric acid, hydrochloric acid, and nitric acid. In some embodiments, the organic solvent may be an alcohol or ketone, such as methanol, ethanol, isopropanol, acetone, and the like, preferably ethanol or acetone. In some embodiments, the acid concentration is from 0.2M (mol/L) to 1.5M, preferably from 0.8M to 1.2M.
According to some embodiments of the invention, the molar ratio of the rare earth metal source and the nickel source is 1:2-1:49, e.g., 1:3, 1:6, 1:8, 1:10, 1:11, 1:13, 1:14, 1:15, 1:17, 1:20, 1:22, 1:25, 1:27, 1:29, 1:30, 1:33, 1:35, 1:37, 1:39, 1:40, 1:43, 1:45, or any value therebetween. In some embodiments, the molar ratio of the rare earth metal source to the nickel source is from 1:2 to 1:29. In some embodiments, the molar ratio of the rare earth metal source to the nickel source is from 1:4 to 1:19. In some embodiments, the molar ratio of the rare earth metal source to the nickel source is from 1:5 to 1:12.
According to some embodiments of the invention, the sulfur source has a mass of 100mg-1000mg, such as 200mg, 400mg, 600mg or 800mg, etc. In some embodiments, the sulfur source is 300mg to 500mg by mass.
According to some embodiments of the invention, the rare earth metal source is selected from one or more of a nitrate of a rare earth metal or a chloride salt of a rare earth metal. In some embodiments, the rare earth metal source is selected from soluble salts of rare earth metals. In some embodiments of the present invention, the rare earth metal is selected from one or more of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
According to some embodiments of the invention, the nickel source is selected from nickel nitrate and/or nickel chloride. In some embodiments, the nickel source is selected from soluble salts of nickel.
According to some embodiments of the invention, the substrate is selected from one or more of carbon cloth, nickel foam, and conductive glass. In some embodiments, the substrate is a conductive substrate. According to some embodiments, the substrate is selected from one or more of carbon cloth, nickel foam, and conductive glass. In some embodiments, the substrate is carbon cloth, also known as carbon paper or carbon fiber cloth, which is a braid composed of carbon fibers interlaced. In some embodiments, the substrate is nickel foam. In some embodiments, the substrate is a conductive glass.
According to some embodiments of the invention, the preparation method of the hydrogen evolution catalyst comprises the following specific steps:
step S2, placing a substrate in a solution containing rare earth metal salt and nickel salt, and performing electrochemical deposition through a three-electrode system to obtain a hydrogen evolution catalyst precursor;
step S3, washing the hydrogen evolution catalyst precursor, and then putting the washed hydrogen evolution catalyst precursor into a vacuum oven to be dried for 1 to 4 hours at the temperature of 40 to 70 ℃, preferably for 2 to 3 hours at the temperature of 50 to 60 ℃;
and S4, placing the hydrogen evolution catalyst precursor processed in the step S3 in a tube furnace, adding sublimed sulfur, and reacting with high-temperature inert gas to obtain the hydrogen evolution catalyst.
Preferably, the substrate is selected from at least one of carbon cloth, conductive glass, foam nickel, more preferably carbon cloth.
In a specific embodiment of the above method, in step S2, the nickel salt is selected from soluble nickel salts, preferably nickel nitrate or nickel chloride, more preferably nickel nitrate.
In a specific embodiment of the above method, in step S2, the rare earth metal salt is preferably a soluble rare earth metal salt, preferably a nitrate or chloride salt, more preferably a nitrate salt.
In the specific embodiment of the above method, in step S2, the ratio of the rare earth metal salt to the nickel salt is preferably 2:58-20:40, and more preferably 5:55-10:50.
In a specific embodiment of the above method, in step S2, the deposition potential is preferably from-0.8V to-1.5V, more preferably from-0.9V to-1.2V, and even more preferably from-1.0V to-1.1V. The deposition time is preferably 600s-7200s, and more preferably 900s-3600s.
In a specific embodiment of the above method, in step S3, the amount of sublimed sulfur is preferably 100mg to 1000mg, more preferably 300mg to 500mg, and the reaction condition is preferably 200 ℃ to 500 ℃,1h to 12h, more preferably 300 ℃ to 400 ℃,2h to 6h. The inert gas may be selected from nitrogen and argon, preferably argon.
The hydrogen evolution catalyst is prepared by an electrochemical codeposition method and a solid phase reaction method, and is simple and quick to operate. The preparation method provided by the invention comprises the steps of firstly growing nano flaky rare earth-nickel metal and hydroxide on a substrate, and then vulcanizing the material. The high catalytic activity and high catalytic stability of the hydrogen evolution catalyst are realized by utilizing the high specific surface area of the nano-sheet and the energy band regulation and control of the rare earth element on the nickel disulfide.
In a third aspect, the invention provides the use of the hydrogen evolution catalyst described above for the preparation of hydrogen and/or oxygen by water splitting.
In a fourth aspect, the present invention provides a water splitting process comprising electrolyzing water in the presence of a hydrogen evolution catalyst according to the present invention.
The hydrogen evolution catalyst provided by the invention comprises a substrate and rare earth doped nickel disulfide grown on the substrate. The hydrogen evolution catalyst is a non-noble metal high-activity hydrogen evolution catalyst, has good conductivity and large surface area, and simultaneously has a large number of active sites, so that the catalyst has good hydrogen evolution catalytic performance. In addition, the hydrogen evolution catalyst has good stability, and can be stable for at least 50000 seconds.
Drawings
FIG. 1 is an X-ray diffraction pattern of the products prepared by doping different rare earth elements in example 1 and comparative example 1.
FIG. 2 is a transmission electron micrograph of the product prepared in example 1.
FIG. 3 is an in situ electrocatalytic Raman spectrum of the product prepared in example 1.
FIG. 4 is a linear sweep voltammetry curve of the product prepared in example 1-example 4 as a catalyst to promote hydrogen evolution reaction.
FIG. 5 is a linear sweep voltammetry curve of the product prepared in example 1 as a catalyst to promote hydrogen evolution reaction.
FIG. 6 is a graph showing the stability of the product prepared in example 1 as a catalyst for promoting hydrogen evolution reaction.
Detailed Description
The present invention will be further illustrated by the following specific examples, but the scope of the present invention is not limited thereto.
Ultrapure water with the conductivity of 18.25MΩ is used in the experimental process, and all reagents used in the experiment are analytically pure.
The main instruments and reagents used:
the CHI760E electrochemical workstation (Shanghai Chen Hua instruments Co.) is used for linear sweep voltammetry test;
the ultra-pure water device of Utility laboratory (Chengdu ultra-pure technology Co., ltd.) is used for preparing ultra-pure water;
an electronic balance (Shanghai platinum mechanical equipments Co., ltd.) for weighing the medicine;
table X-ray diffractometer (MiniFlex 600, co., ltd.) for X-ray diffraction characterization;
JSM-6701F cold field emission scanning electron microscope (Japanese electronics Co., ltd.) for appearance characterization of hydrogen evolution catalysis;
a laser confocal raman spectrometer (HORIBA FRANCE SAS, lab RAM HR Evolution) for characterization of hydrogen evolution catalysts;
vacuum drying oven (Shanghai-constant scientific instruments Co., ltd.);
KQ5200 ultrasonic cleaner (Kunshan ultrasonic instruments Co., ltd.);
working electrode: a three-electrode system, ag/AgCl (CHI instruments Co., USA) as a reference electrode and platinum as a counter electrode;
bench type drying oven (Chongqing test equipment factory);
nickel nitrate (chengdou koilong chemical institute);
praseodymium nitrate, samarium nitrate, europium nitrate, dysprosium nitrate, holmium nitrate and ytterbium nitrate (beijing enoki technology limited);
carbon cloth (Shanghai Hesen electric Co., ltd.), conductive glass (Zhuhai Kai electronic components Co., ltd., model FTO-P002), foam nickel (Guangshengjia New Material Co., ltd.).
Examples 1 to 4 are examples of preparation of the water-splitting catalyst according to the invention
Example 1
One piece was 2X 3cm 2 Putting the carbon cloth into 1M nitric acid solution for ultrasonic treatment for a plurality of minutes, taking out, washing the carbon cloth with ethanol and water for a plurality of times, and putting the carbon cloth into a vacuum drying oven for drying at 50 ℃.
5mL of 0.1M (mol/L) rare earth nitrate aqueous solution (ytterbium nitrate, holmium nitrate, dysprosium nitrate, samarium nitrate, praseodymium nitrate) and 55mL of 0.1M Ni (NO) 3 ) 2 ·6H 2 Placing the O aqueous solution in a 100mL beaker, and placing the pretreated carbon cloth materialThe material is immersed in the mixed solution and connected with a working electrode, the material is taken out after reacting for 3600s under the voltage of-1.0V, is washed by deionized water, and is dried for 2 hours in a vacuum oven at 50 ℃ to obtain the nano sheet-shaped precursor.
The vulcanization process is carried out in a vacuum tube furnace of a vapor deposition system. The precursor and 300mg of sulfur powder are added into a vacuum tube furnace, and argon is introduced to an atmospheric pressure steady state after the tube furnace is vacuumized. Heating to 300 ℃ at a heating rate of 10 ℃/min, reacting for 2 hours, and cooling to room temperature at a cooling rate of 100 ℃/h to obtain the rare earth doped nickel disulfide with the nano-sheet structure, namely Yb-NiS 2 -C、Ho-NiS 2 -C、Dy-NiS 2 -C、Sm-NiS 2 -C、Pr-NiS 2 -C。
Wherein Yb-NiS 2 in-C, yb-NiS 2 The mol content of Yb is 10.6 percent, and Yb-NiS is calculated 2 The load capacity on the carbon cloth is 2.70mg/cm 2 ；
Ho-NiS 2 in-C, ho-NiS 2 The molar content of Ho is 13.2 percent, ho-NiS 2 The load capacity on the carbon cloth is 3.19mg/cm 2 ；
Dy-NiS 2 in-C, dy-NiS 2 Calculated, the molar content of Dy is 8.2 percent, dy-NiS 2 The load capacity on the carbon cloth is 2.85mg/cm 2 ；
Sm-NiS 2 in-C, sm-NiS 2 The molar content of Sm is 7.4 percent, and Sm-NiS 2 The load capacity on the carbon cloth is 2.76mg/cm 2 ；
Pr-NiS 2 in-C, pr-NiS 2 The mol content of Pr is 9.9%, pr-NiS 2 The load on the carbon cloth is 2.88mg/cm 2 。
The final product obtained in this example has an X-ray diffraction pattern as shown in FIG. 1. Wherein Ho-NiS 2 The electron micrograph of C is shown in FIG. 2 and the in situ Raman spectrum is shown in FIG. 3. The doping of the rare earth element is beneficial to regulating and controlling the energy level structure of nickel disulfide and promoting the reaction to adsorb hydrogen through the in-situ Raman spectrum change, so that the electrocatalytic activity and stability of the nickel disulfide are promoted.
Example 2
One piece was 2X 3cm 2 The foam nickel is put into 1M nitric acid solution for ultrasonic treatment for a plurality of minutes, taken out, washed by ethanol and water for a plurality of times, and put into a vacuum drying oven for drying at 50 ℃.
20mL of a 0.1M aqueous solution of rare earth holmium nitrate and 40mL of 0.1M Ni (NO 3 ) 2 ·6H 2 The O aqueous solution is placed in a 100mL beaker, the pretreated foam nickel is immersed in the mixed solution and connected with a working electrode, the foam nickel is taken out after reaction for 1800 seconds under the voltage of-1.2V, is washed by deionized water, and is dried in a vacuum oven at 50 ℃ for 2 hours, so that the nano flaky precursor is obtained.
The vulcanization process is carried out in a vacuum tube furnace of a vapor deposition system. The precursor and 500mg of sulfur powder are added into a vacuum tube furnace, and argon is introduced to an atmospheric pressure steady state after the tube furnace is vacuumized. Heating to 400 ℃ at a heating rate of 10 ℃/min, reacting for 4 hours, and cooling to room temperature at a cooling rate of 100 ℃/h to obtain the rare earth doped nickel disulfide with the nano-sheet structure, namely Ho-NiS 2 -nickel foam. Ho-NiS 2 In foam nickel, ho-NiS 2 The molar content of Ho is 46.5 percent, ho-NiS 2 The loading on the foam nickel was 5.08mg/cm 2 。
Example 3
One piece was 2X 3cm 2 Putting the conductive glass into 1M nitric acid solution for ultrasonic treatment for a plurality of minutes, taking out, washing the conductive glass with ethanol and water for a plurality of times, and putting the conductive glass into a vacuum drying oven for drying at 50 ℃.
2mL of 0.1M rare earth holmium nitrate aqueous solution and 58mL of 0.1M Ni (NO 3 ) 2 ·6H 2 The O aqueous solution is placed in a 100mL beaker, the pretreated conductive glass is immersed in the mixed solution and connected with a working electrode, the reaction is carried out for 7200s under the voltage of-0.8V, the reaction is taken out, deionized water is used for cleaning, and then the reaction is dried in a vacuum oven at 50 ℃ for 2 hours, so that the nano sheet-shaped precursor is obtained.
The vulcanization process is carried out in a vacuum tube furnace of a vapor deposition system. Adding the precursor and 100mg of sulfur powder into a vacuum tube furnace, vacuumizing the tube furnace, and introducing argon into the atmospherePressing to a stable state. Heating to 400 ℃ at a heating rate of 10 ℃/min, reacting for 6 hours, and cooling to room temperature at a cooling rate of 100 ℃/h to obtain the rare earth doped nickel disulfide with the nano-sheet structure, namely Ho-NiS 2 -an electrically conductive glass. Ho-NiS 2 In the conductive glass, ho-NiS 2 The molar content of Ho is 6.1 percent, ho-NiS 2 The loading on the conductive glass was 8.01mg/cm 2 。
Example 4
One piece was 2X 3cm 2 Putting the carbon cloth into 1M nitric acid solution for ultrasonic treatment for a plurality of minutes, taking out, washing the carbon cloth with ethanol and water for a plurality of times, and putting the carbon cloth into a vacuum drying oven for drying at 50 ℃.
10mL of a 0.1M aqueous solution of rare earth holmium nitrate and 50mL of 0.1M Ni (NO 3 ) 2 ·6H 2 Placing the O aqueous solution in a 100mL beaker, immersing the pretreated carbon cloth material in the mixed solution, connecting with a working electrode, taking out after reaction for 900s under the voltage of-1.5V, washing with deionized water, and then drying in a vacuum oven at 50 ℃ for 2h to obtain the nano sheet-shaped precursor.
The vulcanization process is carried out in a vacuum tube furnace of a vapor deposition system. The precursor and 1000mg of sulfur powder are added into a vacuum tube furnace, and argon is introduced to the atmosphere pressure to be stable after the tube furnace is vacuumized. Heating to 300 ℃ at a heating rate of 10 ℃/min, reacting for 12 hours, and cooling to room temperature at a cooling rate of 100 ℃/h to obtain the rare earth doped nickel disulfide with the nano-sheet structure, namely Ho-NiS 2 -C2。Ho-NiS 2 In C2, ho-NiS 2 The molar content of Ho is 21.6 percent, ho-NiS 2 The load capacity on the carbon cloth is 2.11mg/cm 2 。
Comparative example 1
One piece was 2X 3cm 2 Putting the carbon cloth into 1M nitric acid solution for ultrasonic treatment for a plurality of minutes, taking out, washing the carbon cloth with ethanol and water for a plurality of times, and putting the carbon cloth into a vacuum drying oven for drying at 50 ℃.
60mL of 0.1M Ni (NO 3 ) 2 ·6H 2 Placing O aqueous solution in 100mL beaker, immersing pretreated carbon cloth material in the solution, and charging with working electricityThe poles are connected, the mixture is taken out after being reacted for 3600s under the voltage of-1.0V, and is washed by deionized water, and then the mixture is dried for 2 hours in a vacuum oven at 50 ℃ to obtain the nano flaky precursor.
The vulcanization process is carried out in a vacuum tube furnace of a vapor deposition system. The precursor and 300mg of sulfur powder are added into a vacuum tube furnace, and argon is introduced to an atmospheric pressure steady state after the tube furnace is vacuumized. Heating to 300 ℃ at a heating rate of 10 ℃/min, reacting for 2 hours, and cooling to room temperature at a cooling rate of 100 ℃/h to obtain nickel disulfide with a nano-sheet structure, namely NiS 2 -C, wherein, niS 2 The load capacity on the carbon cloth is 2.13mg/cm 2 。
Test example 1
Example 1 (Ho-NiS 2 C), example 2, example 3, example 4, and comparative example 1 were cut into a three-electrode system of 0.5cm X1 cm sandwiched between electrode clamps as a working electrode, platinum as a counter electrode, hg/HgO as a reference electrode, and the three-electrode system was inserted into a 1M potassium hydroxide solution having a molar concentration to conduct a hydrogen evolution reaction, and the three-electrode system was scanned in a range of potential window-1V to-2V at a scanning speed of 2mV/s, to obtain a hydrogen evolution curve, as shown in FIG. 4.
The same test was performed on different rare earth doped nickel disulphides in example 1, resulting in different rare earth doped hydrogen evolution curves, as shown in fig. 5.
Test example 2
The product obtained in example 1 (Ho-NiS 2 C) cutting the mixture into a three-electrode system with 0.5cm multiplied by 1cm clamped on an electrode clamp as a working electrode, platinum as a counter electrode and Hg/HgO as a reference electrode, inserting the three-electrode system into 1M potassium hydroxide solution with molar concentration for carrying out a constant voltage method stability test curve, and carrying out a potential test at 1.2V for 50000 seconds in a potential window to obtain a constant voltage method stability test curve, as shown in FIG. 6.
As can be seen from the above examples and the accompanying drawings, the hydrogen evolution catalyst of the present invention has excellent electrocatalytic activity. The hydrogen evolution catalyst has large surface area and a large number of active sites, and the factors lead the hydrogen evolution catalyst to have good hydrogen evolution catalytic performance. In addition, the hydrogen evolution catalyst has good stability, and can be stable for at least 50000 seconds.
It should be noted that the above-described embodiments are only for explaining the present invention and do not limit the present invention in any way. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (16)
1. The hydrogen evolution catalyst comprises a substrate and rare earth metal element doped nickel disulfide supported on the substrate, wherein the rare earth metal element doped nickel disulfide has a nano-sheet structure, the substrate is a conductive substrate, and the molar content of rare earth metal elements in the rare earth metal element doped nickel disulfide is 2% -30%.
2. The catalyst according to claim 1, wherein the rare earth metal element doped nickel disulfide has a molar content of rare earth metal elements of 5% to 20%.
3. The catalyst according to claim 1, wherein the molar content of rare earth metal element is 8% -15%.
4. The catalyst of claim 1 or 2, wherein the rare earth metal element is selected from one or more of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
5. A catalyst according to any one of claims 1 to 3, wherein the substrate is selected from one or more of carbon cloth, nickel foam and conductive glass.
6. The catalyst of claim 5, wherein the rare earth doped nickel disulfide is present on the substrate at a loading of 2mg/cm 2 -10mg/cm 2 。
7. A preparation method of a hydrogen evolution catalyst comprises the steps of vulcanizing a precursor, wherein the precursor comprises rare earth metal hydroxide and nickel hydroxide;
the preparation of the precursor comprises the following steps: immersing the substrate in a solution containing a rare earth metal source and a nickel source, performing electrochemical deposition,
wherein the molar ratio of the rare earth metal source to the nickel source is 1:2-1:49, and the substrate is a conductive substrate.
8. The method of claim 7, wherein the sulfiding comprises heating the precursor to 200 ℃ to 500 ℃ in the presence of a sulfur source in an inert atmosphere for 1h to 12h;
and/or electrochemical deposition includes: depositing at the potential of-0.8V to-1.5V for 600s-7200s.
9. The method of claim 8, wherein the sulfiding comprises heating the precursor to 300 ℃ to 400 ℃ in the presence of a sulfur source in an inert atmosphere for 2h to 6h;
and/or electrochemical deposition includes: depositing at the potential of-0.9V to-1.2V for 900s-3600s.
10. The method of preparing according to claim 8, wherein the electrochemical deposition comprises: deposited at a potential of-1.0V to-1.1V.
11. The method of any one of claims 8-10, wherein the molar ratio of the rare earth metal source to the nickel source is 1:2-1:29;
and/or the sulfur source has a mass of 100mg to 1000mg.
12. The method of claim 11, wherein the molar ratio of the rare earth metal source to the nickel source is 1:4 to 1:19;
and/or the sulfur source has a mass of 300mg to 500mg.
13. The method of claim 11, wherein the molar ratio of the rare earth metal source to the nickel source is 1:5 to 1:12.
14. The method of any one of claims 7 to 10, wherein the rare earth metal source is selected from one or more of a nitrate of a rare earth metal or a chloride salt of a rare earth metal;
and/or the nickel source is selected from nickel nitrate and/or nickel chloride;
and/or the substrate is selected from one or more of carbon cloth, foam nickel and conductive glass.
15. The method of claim 14, wherein the rare earth metal is selected from one or more of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
16. Use of a catalyst according to any one of claims 1 to 6 or a catalyst prepared according to the preparation method of any one of claims 7 to 15 for the preparation of hydrogen and/or oxygen by water splitting.
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