CN111686743A - La/NF hydrogen evolution material and preparation method and application thereof - Google Patents
La/NF hydrogen evolution material and preparation method and application thereof Download PDFInfo
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- CN111686743A CN111686743A CN202010432670.6A CN202010432670A CN111686743A CN 111686743 A CN111686743 A CN 111686743A CN 202010432670 A CN202010432670 A CN 202010432670A CN 111686743 A CN111686743 A CN 111686743A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 131
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 131
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000000463 material Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000000243 solution Substances 0.000 claims abstract description 58
- 238000004070 electrodeposition Methods 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 35
- 150000002603 lanthanum Chemical class 0.000 claims abstract description 29
- 239000006260 foam Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 44
- FDFPDGIMPRFRJP-UHFFFAOYSA-K trichlorolanthanum;heptahydrate Chemical group O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] FDFPDGIMPRFRJP-UHFFFAOYSA-K 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 6
- 229920000557 Nafion® Polymers 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 13
- 229910021607 Silver chloride Inorganic materials 0.000 description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 238000002604 ultrasonography Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/83—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 rare earths or actinides
-
- B01J35/33—
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a La/NF hydrogen evolution material and a preparation method and application thereof, wherein the preparation method of the hydrogen evolution material comprises the following steps: 1) dissolving lanthanum salt in water, and uniformly dispersing to obtain a lanthanum salt solution; 2) preparing La/NF by using a lanthanum salt solution as an electrodeposition solution and foam nickel as a carrier by adopting a one-step electrodeposition method; 3) washing and drying the La/NF to obtain the La/NF hydrogen evolution material; in the hydrogen evolution material, the loading amount of La in the nickel foam is 10-20 wt%; the La/NF hydrogen evolution material is applied to electrocatalytic hydrogen evolution reaction. Compared with the prior art, the lanthanum metal is introduced to be combined with the foam nickel, so that the active sites of the foam nickel material can be increased, the hydrogen evolution performance of the material is improved, the cost is low, and the industrial development is expected to be oriented.
Description
Technical Field
The invention belongs to the technical field of hydrogen energy sources, and relates to a La/NF hydrogen evolution material, and a preparation method and application thereof.
Background
Hydrogen energy is an ideal energy source, a byproduct after the energy is released is water, the environment is not polluted, and the energy problem in human sustainable development is effectively solved. Hydrogen elements exist in water in the form of compounds, and earth has abundant water resources, so that hydrogen can be obtained by decomposing water. Since the electric energy can be directly produced by fossil fuel, solar energy, hydroenergy, wind energy, geothermal energy, nuclear energy, tidal energy and the like, the hydrogen production by electrolyzing water by using the electric energy is a feasible and effective hydrogen production technology. In order to reduce energy consumption during water electrolysis and improve hydrogen evolution efficiency, a cathode hydrogen evolution material is required.
The foamed nickel is a three-dimensional porous metal functional material, has the characteristics of more pores, large specific surface area and the like, and is widely applied to the fields of nickel-hydrogen battery electrode materials, fuel cells and the like. However, although these materials have a good electrochemical active area, the electrochemical performance of the foamed nickel material is limited, which limits its further applications.
Disclosure of Invention
The invention aims to provide a La/NF hydrogen evolution material and a preparation method and application thereof, which achieve the effect of enhancing the performance by taking foam nickel as a carrier to load metal ions, and further overcome the problem of limited electrochemical performance of the foam nickel material.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of La/NF hydrogen evolution material comprises the following steps:
1) dissolving lanthanum salt in water, and uniformly dispersing to obtain a lanthanum salt solution;
2) preparing La/NF by using a lanthanum salt solution as an electrodeposition solution and foam Nickel (NF) as a carrier by adopting a one-step electrodeposition method;
3) and washing and drying the La/NF to obtain the La/NF hydrogen evolution material.
Further, in the step 1), the lanthanum salt is lanthanum chloride heptahydrate; in the lanthanum salt solution, the addition ratio of the lanthanum chloride heptahydrate to water is 1mmol (0.5-5) mL.
Further, in the step 1), the dispersion is ultrasonic dispersion, and the ultrasonic dispersion time is 5-10 min. Clear solution was obtained after ultrasonic dispersion.
Further, in the step 2), the electrodeposition process is carried out at room temperature (the lanthanum salt solution in the electrodeposition process is also at room temperature), the scanning rate for electrodeposition is 9.5-10.5mV/s, and the electrodeposition time is 30-90 s. And performing one-step electrodeposition reaction by using a glassy carbon electrode as a working electrode, a silver chloride electrode as a reference electrode and a platinum wire electrode as an auxiliary electrode.
Further, in step 3), the washing process is as follows: washing La/NF with water and anhydrous ethanol for 2-3 times.
Further, in the step 3), the temperature is 80-90 ℃ and the time is 4-12h in the drying process.
The La/NF hydrogen evolution material is prepared by the method.
Further, in the hydrogen evolution material, the loading amount of La in the nickel foam is 10-20 wt%.
An application of La/NF hydrogen evolution material in electrocatalytic hydrogen evolution reaction.
Further, when in application, the La/NF hydrogen evolution material and the Nafion solution are uniformly mixed, and then are dripped on a glassy carbon electrode, and the glassy carbon electrode for hydrogen evolution is obtained after drying and is used as a working electrode in the electrocatalytic hydrogen evolution reaction.
The application method specifically comprises the following steps:
(1) weighing 1mg of La/NF hydrogen evolution material, dissolving the La/NF hydrogen evolution material in 100 mu L of prepared 0.5 wt% of a Nation solution, absorbing 12-18 mu L of the solution on a glassy carbon electrode after uniform dispersion under ultrasound, and naturally airing to obtain the hydrogen evolution glassy carbon electrode;
(2) preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive out air, cleaning with 1.0M potassium hydroxide solution to obtain the surface of the hydrogen evolution glassy carbon electrode, connecting the obtained hydrogen evolution glassy carbon electrode, Ag/AgCl electrode and platinum electrode to an electrochemical workstation, and carrying out electrocatalytic hydrogen evolution reaction in the electrolyte.
The La/NF hydrogen evolution material prepared by the invention is used as an alloy catalyst, and has lower synthesis cost than most catalysts. Lanthanum metal is a rare earth metal, and is present in the largest amount among rare earth elements. In addition, lanthanum is more active, has strong adsorption effect on hydrogen atoms, provides active sites for the foam nickel material after being combined with the foam nickel, improves the electrochemical performance of the synthetic material, and has simple synthetic method.
In the present invention, the purpose of electrodeposition is: the current direction is controlled by the applied voltage, the ions are promoted to be loaded on the foamed nickel material, the obtained product has uniform plating layer, and the components and the thickness of the plating layer are easy to control. The purpose of the washing is: the metal ions are reduced by electrons on the surface of the cathode to form a metal or alloy coating which carries some unreacted ions and is removed by cleaning.
Compared with the prior art, the invention has the following characteristics:
1) in the invention, the foam nickel is a metal material with three-dimensional porosity, the porosity is about 95 percent, the foam nickel is beneficial to water and gas to pass through, and the foam nickel has the advantages of good stability, multiple pores, heat resistance, small bulk density, large specific surface area and the like; lanthanum is used as rare earth metal, is relatively active, has strong adsorption effect on hydrogen atoms, and can greatly improve the hydrogen evolution performance of the nickel foam after being loaded on the nickel foam. Therefore, by introducing lanthanum metal and combining with the foamed nickel, the active sites of the foamed nickel material can be increased, thereby improving the hydrogen evolution performance of the material;
2) the La/NF hydrogen evolution material prepared by the method has low raw material cost and simple preparation method, and the Tafel slope and the overpotential of the hydrogen evolution material are low, so the hydrogen evolution material has good hydrogen evolution effect, and the material has good stability due to the introduction of non-noble metal elements.
3) The La/NF hydrogen evolution material prepared by the invention electrolyzes water in an alkaline medium, has good hydrogen evolution effect and lower cost, and is expected to be oriented to industrial development.
Drawings
FIG. 1 is an SEM image of the La/NF hydrogen evolution material produced in example 1;
FIG. 2 is a Tafel slope plot of the La/NF hydrogen evolution material produced in example 1;
FIG. 3 is a polarization plot of the La/NF hydrogen evolution material produced in example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The raw materials used in the examples of the present invention are commercially available unless otherwise specified.
Example 1:
10mmol of lanthanum chloride heptahydrate
50mL of deionized water
The La/NF hydrogen evolution material is prepared by the preparation method comprising the following steps:
dissolving 10mmol of lanthanum chloride heptahydrate in 50mL of deionized water, and carrying out ultrasonic treatment in an ultrasonic oscillator for 5min until the solution is dissolved by stirring. After no solid particles exist in the solution, the solution is placed in an electrodeposition device, a working electrode is connected with 16mm multiplied by 6mm multiplied by 1mm of foamed nickel, and the electrodeposition solution is maintained at room temperature at the scanning speed of 10 mV/s. And (3) taking out the La/NF after the electro-deposition is finished, treating the La/NF, putting the La/NF into an oven, and drying the La/NF at the temperature of 80 ℃ to finally obtain the La/NF hydrogen evolution material. FIG. 1 is an SEM image of the prepared La/NF hydrogen evolution material, and it can be seen from FIG. 1 that La is successfully loaded on the surface of the foamed nickel by the electrodeposition method.
Application example 1:
the La/NF hydrogen evolution material prepared in the example 1 is grinded, the surface of the glassy carbon electrode is grinded by 0.05 μm alumina, the residual sample is removed, and the glassy carbon electrode is washed by ethanol and deionized water and dried.
(1) 0.5 wt% of Nation solution was prepared with anhydrous methanol. Weighing 1mg of La/NF hydrogen evolution material, dissolving in 100 mu L of prepared Nation solution, and uniformly dispersing for 2h under ultrasound. Then, 12. mu.L of the solution was pipetted onto a glassy carbon electrode and air-dried naturally.
(2) Preparing 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introducing nitrogen to drive away air, cleaning the electrode surface of the hydrogen evolution glassy carbon electrode by using the 1.0M potassium hydroxide solution, connecting the hydrogen evolution glassy carbon electrode, the Ag/AgCl electrode and the platinum electrode to an electrochemical workstation, and measuring the electrocatalytic hydrogen evolution performance of the electrode material in the electrolyte. As shown in FIG. 2 and FIG. 3, the Tafel slope of the material is 157mV dec-1At a current density of 10mA cm-2The overpotential of (2) is 240 mV. After 1000 CV tests, the deviation between the LSV curve and the LSV curve before the test is not large, which indicates that the material has good stability.
Example 2:
lanthanum chloride heptahydrate 25mmol
50mL of deionized water
The La/NF hydrogen evolution material is prepared by the preparation method comprising the following steps:
dissolving 25mmol of lanthanum chloride heptahydrate in 50mL of deionized water, and carrying out ultrasonic treatment in an ultrasonic oscillator for 5min until the solution is dissolved by stirring. After no solid particles exist in the solution, the solution is placed in an electrodeposition device, a working electrode is connected with 16mm multiplied by 6mm multiplied by 1mm of foamed nickel, and the electrodeposition solution is maintained at room temperature at the scanning speed of 10 mV/s. And (3) taking out the La/NF after the electro-deposition is finished, treating the La/NF, putting the La/NF into an oven, and drying the La/NF at the temperature of 80 ℃ to finally obtain the La/NF hydrogen evolution material.
Application example 2:
the La/NF hydrogen evolution material prepared in the example 2 is grinded, the surface of the glassy carbon electrode is grinded by 0.05 μm alumina, the residual sample is removed, and the glassy carbon electrode is washed by ethanol and deionized water and dried.
(1) 0.5 wt% of Nation solution was prepared with anhydrous methanol. Weighing 1mg of La/NF hydrogen evolution material, dissolving in 100 mu L of prepared Nation solution, and uniformly dispersing for 2h under ultrasound. Then, 12. mu.L of the solution was pipetted onto a glassy carbon electrode and air-dried naturally.
(2) Preparing 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introducing nitrogen to drive away air, cleaning the electrode surface of the hydrogen evolution glassy carbon electrode by using the 1.0M potassium hydroxide solution, connecting the hydrogen evolution glassy carbon electrode, the Ag/AgCl electrode and the platinum electrode to an electrochemical workstation, and measuring the electrocatalytic hydrogen evolution performance of the electrode material in the electrolyte. The Tafel slope of the material is 211mV dec after testing-1At a current density of 10mA cm-2The overpotential of (2) is 118 mV. After 1000 CV tests, the deviation between the LSV curve and the LSV curve before the test is not large, which indicates that the material has good stability.
Example 3:
50mmol of lanthanum chloride heptahydrate
50mL of deionized water
The La/NF hydrogen evolution material is prepared by the preparation method comprising the following steps:
dissolving 50mmol of lanthanum chloride heptahydrate in 50mL of deionized water, and carrying out ultrasonic treatment in an ultrasonic oscillator for 5min until the solution is dissolved by stirring. After no solid particles exist in the solution, the solution is placed in an electrodeposition device, a working electrode is connected with 16mm multiplied by 6mm multiplied by 1mm of foamed nickel, and the electrodeposition solution is maintained at room temperature at the scanning speed of 10 mV/s. And (3) taking out the La/NF after the electro-deposition is finished, treating the La/NF, putting the La/NF into an oven, and drying the La/NF at the temperature of 80 ℃ to finally obtain the La/NF hydrogen evolution material.
Application example 3:
the La/NF hydrogen evolution material prepared in the example 3 is grinded, the surface of the glassy carbon electrode is grinded by 0.05 μm alumina, the residual sample is removed, and the glassy carbon electrode is washed by ethanol and deionized water and dried.
(1) 0.5 wt% of Nation solution was prepared with anhydrous methanol. Weighing 1mg of La/NF hydrogen evolution material, dissolving in 100 mu L of prepared Nation solution, and uniformly dispersing for 2h under ultrasound. Then, 12. mu.L of the solution was pipetted onto a glassy carbon electrode and air-dried naturally.
(2) Preparing 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introducing nitrogen to drive away air, cleaning the electrode surface of the hydrogen evolution glassy carbon electrode by using the 1.0M potassium hydroxide solution, connecting the hydrogen evolution glassy carbon electrode, the Ag/AgCl electrode and the platinum electrode to an electrochemical workstation, and measuring the electrocatalytic hydrogen evolution performance of the electrode material in the electrolyte. The Tafel slope of the material is 176mV dec after testing-1At a current density of 10mA cm-2The overpotential of (2) is 101 mV. After 1000 CV tests, the deviation between the LSV curve and the LSV curve before the test is not large, which indicates that the material has good stability.
Example 4:
100mmol of lanthanum chloride heptahydrate
50mL of deionized water
The La/NF hydrogen evolution material is prepared by the preparation method comprising the following steps:
dissolving 100mmol of lanthanum chloride heptahydrate in 50mL of deionized water, and carrying out ultrasonic treatment in an ultrasonic oscillator for 5min until the solution is dissolved by stirring. After no solid particles exist in the solution, the solution is placed in an electrodeposition device, a working electrode is connected with 16mm multiplied by 6mm multiplied by 1mm of foamed nickel, and the electrodeposition solution is maintained at room temperature at the scanning speed of 10 mV/s. And (3) taking out the La/NF after the electro-deposition is finished, treating the La/NF, putting the La/NF into an oven, and drying the La/NF at the temperature of 80 ℃ to finally obtain the La/NF hydrogen evolution material.
Application example 4:
the La/NF hydrogen evolution material prepared in the example 4 is grinded, the surface of the glassy carbon electrode is grinded by 0.05 μm alumina, the residual sample is removed, and the glassy carbon electrode is washed by ethanol and deionized water and dried.
(1) 0.5 wt% of Nation solution was prepared with anhydrous methanol. Weighing 1mg of La/NF hydrogen evolution material, dissolving in 100 mu L of prepared Nation solution, and uniformly dispersing for 2h under ultrasound. Then, 12. mu.L of the solution was pipetted onto a glassy carbon electrode and air-dried naturally.
(2) Preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive off air, and using 1.0M oxyhydrogenThe electrode surface of the hydrogen evolution glassy carbon electrode is cleaned by potassium solution, then the hydrogen evolution glassy carbon electrode, the Ag/AgCl electrode and the platinum electrode are connected with an electrochemical workstation, and the electrocatalytic hydrogen evolution performance of the electrode material is measured in electrolyte. The Tafel slope of the material is 189mV dec after testing-1At a current density of 10mA cm-2The overpotential of (2) is 113 mV. After 1000 CV tests, the deviation between the LSV curve and the LSV curve before the test is not large, which indicates that the material has poor stability.
Comparative example 1:
varying the scanning rate of electro-deposition to 25mV/s
50mmol of lanthanum chloride heptahydrate
50mL of deionized water
The La/NF hydrogen evolution material is prepared by the preparation method comprising the following steps:
dissolving 50mmol of lanthanum chloride heptahydrate in 50mL of deionized water, and carrying out ultrasonic treatment in an ultrasonic oscillator for 5min until the solution is dissolved by stirring. After no solid particles exist in the solution, the solution is placed in an electrodeposition device, a working electrode is connected with 16mm multiplied by 6mm multiplied by 1mm of foamed nickel, and the electrodeposition solution is maintained at room temperature at the scanning speed of 25 mV/s. And (3) taking out the La/NF after the electro-deposition is finished, treating the La/NF, putting the La/NF into an oven, and drying the La/NF at the temperature of 80 ℃ to finally obtain the La/NF hydrogen evolution material.
Application comparative example 1:
and (3) grinding the La/NF hydrogen evolution material prepared in the comparative example 1, grinding the surface of the glassy carbon electrode by using 0.05 mu m of alumina, removing a residual sample, washing by using ethanol and deionized water, and airing.
(1) 0.5 wt% of Nation solution was prepared with anhydrous methanol. Weighing 1mg of La/NF hydrogen evolution material, dissolving in 100 mu L of prepared Nation solution, and uniformly dispersing for 2h under ultrasound. Then, 12. mu.L of the solution was pipetted onto a glassy carbon electrode and air-dried naturally.
(2) Preparing 1.0M potassium hydroxide solution as electrocatalytic electrolyte, introducing nitrogen to drive out air, cleaning the electrode surface of the hydrogen evolution glassy carbon electrode by using 1.0M potassium hydroxide solution, connecting the hydrogen evolution glassy carbon electrode, the Ag/AgCl electrode and the platinum electrode to an electrochemical workstation, and measuring the electric potential of the electrode material in the electrolytePerformance in catalyzing hydrogen evolution. The Tafel slope of the material is 191mV dec-1At a current density of 10mA cm-2The overpotential of (3) is 271 mV.
Comparative example 2:
varying the scanning rate of electro-deposition to 50mV/s
50mmol of lanthanum chloride heptahydrate
50mL of deionized water
The La/NF hydrogen evolution material is prepared by the preparation method comprising the following steps:
dissolving 50mmol of lanthanum chloride heptahydrate in 50mL of deionized water, and carrying out ultrasonic treatment in an ultrasonic oscillator for 5min until the solution is dissolved by stirring. After no solid particles exist in the solution, the solution is placed in an electrodeposition device, a working electrode is connected with 16mm multiplied by 6mm multiplied by 1mm of foamed nickel, and the electrodeposition solution is maintained at room temperature at a scanning speed of 50 mV/s. And (3) taking out the La/NF after the electro-deposition is finished, treating the La/NF, putting the La/NF into an oven, and drying the La/NF at the temperature of 80 ℃ to finally obtain the La/NF hydrogen evolution material.
Application comparative example 2:
and (3) grinding the La/NF hydrogen evolution material prepared in the comparative example 2, grinding the surface of the glassy carbon electrode by using 0.05 mu m of alumina, removing a residual sample, washing by using ethanol and deionized water, and airing.
(1) 0.5 wt% of Nation solution was prepared with anhydrous methanol. Weighing 1mg of La/NF hydrogen evolution material, dissolving in 100 mu L of prepared Nation solution, and uniformly dispersing for 2h under ultrasound. Then, 12. mu.L of the solution was pipetted onto a glassy carbon electrode and air-dried naturally.
(2) Preparing 1.0M potassium hydroxide solution as an electrocatalytic electrolyte, introducing nitrogen to drive away air, cleaning the electrode surface of the hydrogen evolution glassy carbon electrode by using the 1.0M potassium hydroxide solution, connecting the hydrogen evolution glassy carbon electrode, the Ag/AgCl electrode and the platinum electrode to an electrochemical workstation, and measuring the electrocatalytic hydrogen evolution performance of the electrode material in the electrolyte. The Tafel slope of the material is 203mV dec-1At a current density of 10mA cm-2The overpotential of (2) is 294 mV.
As can be seen from examples 1-4 and comparative examples 1-2, the electrochemical performance of the La/NF hydrogen evolution material is best when the molar concentration of lanthanum chloride heptahydrate is 1mmol/mL and the scanning rate of electrodeposition is 10 mV/s.
Example 5:
a preparation method of the La/NF hydrogen evolution material comprises the following steps:
1) dissolving lanthanum salt in water, and uniformly dispersing to obtain a lanthanum salt solution;
2) preparing La/NF by using a lanthanum salt solution as an electrodeposition solution and foam nickel as a carrier by adopting a one-step electrodeposition method;
3) and washing and drying the La/NF to obtain the La/NF hydrogen evolution material.
In the step 1), the lanthanum salt is lanthanum chloride heptahydrate; in the lanthanum salt solution, the addition ratio of the lanthanum chloride heptahydrate to the water is 1mmol:0.5 mL. The dispersion is ultrasonic dispersion, and the ultrasonic dispersion time is 10 min.
In step 2), the electrodeposition process was carried out at room temperature with a scan rate of 9.5 mV/s.
In the step 3), the washing process is as follows: La/NF was washed 3 times with water and absolute ethanol. In the drying process, the temperature is 80 ℃ and the time is 12 h.
In the hydrogen evolution material, the loading of La in the nickel foam was 10 wt%.
The La/NF hydrogen evolution material is applied to electrocatalytic hydrogen evolution reaction, and when in application, the La/NF hydrogen evolution material and Nafion solution are uniformly mixed, dripped on a glassy carbon electrode, and dried to obtain the hydrogen evolution glassy carbon electrode which is used as a working electrode in the electrocatalytic hydrogen evolution reaction.
Example 6:
a preparation method of the La/NF hydrogen evolution material comprises the following steps:
1) dissolving lanthanum salt in water, and uniformly dispersing to obtain a lanthanum salt solution;
2) preparing La/NF by using a lanthanum salt solution as an electrodeposition solution and foam nickel as a carrier by adopting a one-step electrodeposition method;
3) and washing and drying the La/NF to obtain the La/NF hydrogen evolution material.
In the step 1), the lanthanum salt is lanthanum chloride heptahydrate; in the lanthanum salt solution, the addition ratio of the lanthanum chloride heptahydrate to the water is 1mmol:5 mL. The dispersion is ultrasonic dispersion, and the ultrasonic dispersion time is 5 min.
In step 2), the electrodeposition process was carried out at room temperature with a scan rate of 10.5 mV/s.
In the step 3), the washing process is as follows: La/NF was washed 2 times with water and absolute ethanol. In the drying process, the temperature is 90 ℃ and the time is 4 h.
In the hydrogen evolution material, the loading of La in the nickel foam was 20 wt%.
The La/NF hydrogen evolution material is applied to electrocatalytic hydrogen evolution reaction, and when in application, the La/NF hydrogen evolution material and Nafion solution are uniformly mixed, dripped on a glassy carbon electrode, and dried to obtain the hydrogen evolution glassy carbon electrode which is used as a working electrode in the electrocatalytic hydrogen evolution reaction.
Example 7:
a preparation method of the La/NF hydrogen evolution material comprises the following steps:
1) dissolving lanthanum salt in water, and uniformly dispersing to obtain a lanthanum salt solution;
2) preparing La/NF by using a lanthanum salt solution as an electrodeposition solution and foam nickel as a carrier by adopting a one-step electrodeposition method;
3) and washing and drying the La/NF to obtain the La/NF hydrogen evolution material.
In the step 1), the lanthanum salt is lanthanum chloride heptahydrate; in the lanthanum salt solution, the addition ratio of the lanthanum chloride heptahydrate to the water is 1mmol:1 mL. The dispersion is ultrasonic dispersion, and the time of ultrasonic dispersion is 7 min.
In step 2), the electrodeposition process is carried out at room temperature, and the scanning rate for electrodeposition is 10 mV/s.
In the step 3), the washing process is as follows: La/NF was washed 2 times with water and absolute ethanol. In the drying process, the temperature is 85 ℃ and the time is 8 h.
In the hydrogen evolution material, the loading of La in the nickel foam was 15 wt%.
The La/NF hydrogen evolution material is applied to electrocatalytic hydrogen evolution reaction, and when in application, the La/NF hydrogen evolution material and Nafion solution are uniformly mixed, dripped on a glassy carbon electrode, and dried to obtain the hydrogen evolution glassy carbon electrode which is used as a working electrode in the electrocatalytic hydrogen evolution reaction.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of La/NF hydrogen evolution material is characterized by comprising the following steps:
1) dissolving lanthanum salt in water, and uniformly dispersing to obtain a lanthanum salt solution;
2) preparing La/NF by using a lanthanum salt solution as an electrodeposition solution and foam nickel as a carrier by adopting a one-step electrodeposition method;
3) and washing and drying the La/NF to obtain the La/NF hydrogen evolution material.
2. The method for preparing a La/NF hydrogen evolution material as claimed in claim 1, wherein in the step 1), the lanthanum salt is lanthanum chloride heptahydrate; in the lanthanum salt solution, the addition ratio of the lanthanum chloride heptahydrate to water is 1mmol (0.5-5) mL.
3. The method for preparing the La/NF hydrogen evolution material according to claim 1, wherein in the step 1), the dispersion is ultrasonic dispersion, and the time of the ultrasonic dispersion is 5-10 min.
4. The method for preparing La/NF hydrogen evolution material according to claim 1, wherein in the step 2), the electrodeposition process is carried out at room temperature, and the scanning rate for electrodeposition is 9.5-10.5 mV/s.
5. The method for preparing La/NF hydrogen evolution material according to claim 1, wherein in the step 3), the washing process is as follows: washing La/NF with water and anhydrous ethanol for 2-3 times.
6. The method for preparing the La/NF hydrogen evolution material according to claim 1, wherein in the step 3), the temperature is 80-90 ℃ and the time is 4-12h in the drying process.
7. A La/NF hydrogen evolution material, characterized in that it is prepared with a method according to any of claims 1 to 6.
8. A La/NF hydrogen evolution material according to claim 7, wherein the loading of La in the nickel foam is 10 wt% to 20 wt%.
9. Use of a La/NF hydrogen evolution material according to claim 7 in electrocatalytic hydrogen evolution reactions.
10. The application of the La/NF hydrogen evolution material in the electrocatalytic hydrogen evolution reaction as claimed in claim 8, wherein in the application, the La/NF hydrogen evolution material is uniformly mixed with Nafion solution, and then is dripped on a glassy carbon electrode, and the glassy carbon electrode is dried to obtain the hydrogen evolution glassy carbon electrode which is used as a working electrode in the electrocatalytic hydrogen evolution reaction.
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| CN113130216A (en) * | 2021-03-31 | 2021-07-16 | 上海应用技术大学 | Molybdenum disulfide @ ZIF-67@ CoO-NF composite material and synthesis and application thereof |
| CN113279004A (en) * | 2021-04-07 | 2021-08-20 | 上海应用技术大学 | La-Mo-S/NF-C hydrogen evolution material and preparation method and application thereof |
| CN113774420A (en) * | 2020-11-23 | 2021-12-10 | 天津师范大学 | Self-supporting nickel-ytterbium oxide composite electrode and preparation method and application thereof |
| US11549188B2 (en) | 2021-04-28 | 2023-01-10 | Industrial Technology Research Institute | Membrane electrode assembly and method for hydrogen evolution by electrolysis |
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