CN116876020A - Preparation method of single-atom iron-doped cobalt-nickel layered double hydroxide catalyst - Google Patents
Preparation method of single-atom iron-doped cobalt-nickel layered double hydroxide catalyst Download PDFInfo
- Publication number
- CN116876020A CN116876020A CN202310683373.2A CN202310683373A CN116876020A CN 116876020 A CN116876020 A CN 116876020A CN 202310683373 A CN202310683373 A CN 202310683373A CN 116876020 A CN116876020 A CN 116876020A
- Authority
- CN
- China
- Prior art keywords
- mixed solution
- layered double
- deionized water
- zif
- doped cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 title claims abstract 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000011259 mixed solution Substances 0.000 claims abstract description 62
- 239000008367 deionised water Substances 0.000 claims abstract description 52
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 31
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 22
- 235000019441 ethanol Nutrition 0.000 claims abstract description 21
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 19
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 102000004190 Enzymes Human genes 0.000 claims 1
- 108090000790 Enzymes Proteins 0.000 claims 1
- 239000011942 biocatalyst Substances 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910020598 Co Fe Inorganic materials 0.000 description 5
- 229910020630 Co Ni Inorganic materials 0.000 description 5
- 229910002519 Co-Fe Inorganic materials 0.000 description 5
- 229910002440 Co–Ni Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000011943 nanocatalyst Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a single-atom iron doped cobalt-nickel layered double-metal hydroxide catalyst, which comprises the following steps of 1, adding a catalyst into C 19 H 42 BrN and Co (NO) 3 ) 2 ·6H 2 Adding deionized water into O, and shaking uniformly to obtain a mixed solution A; step 2, adding deionized water into the 2-methylimidazole, and magnetically stirring to obtain a mixed solution B; step 3, slowly adding the mixed solution A into the mixed solution B, centrifuging after magnetic stirring, cleaning by alcohol, and drying to obtain ZIF-67; step 4, dispersing ZIF-67 in a round bottom flask by using absolute ethyl alcohol; step 5, feSO 4 ·7H 2 O and Ni (NO) 3 ) 2 ·6H 2 Adding O into deionized water, and magnetically stirring to form a mixed solution C; step 6, adding the mixed solution C into the round-bottomed flask in the step 4, uniformly mixing, and then heating in a water bath; step 7, water bath heating knots to be treated in step 6And (3) after bundling, centrifuging, then washing with water, washing with alcohol, and drying to obtain Co-Fe-Ni LDHs.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic material preparation, and particularly relates to a preparation method of a single-atom iron-doped cobalt-nickel layered double hydroxide catalyst.
Background
Driven by the "two carbon" goal, developing a clean, efficient, recyclable hydrogen energy source is one of the effective strategies to achieve this goal. With the rapid development of the industry in China, the demand for hydrogen is also increasing. In 2021, the hydrogen yield of China breaks through 4000 ten thousand tons, and the hydrogen is mainly prepared by adopting a way of thermally converting carbon-based fuel. The traditional approach has high energy consumption and low product purity, raw materials are limited by a supply end, and extremely high carbon dioxide emission is accompanied, which is contrary to the aim of energy conservation and emission reduction in China. Compared with the method, the method for preparing the hydrogen by electrolyzing the water based on green electric drive of wind energy, water energy, solar energy and the like is a more efficient and environment-friendly high-purity hydrogen preparation strategy. However, the current electrolytic water anode Oxygen Evolution (OER) process consumes a large amount of electric energy, and the high cost thereof restricts the commercialization process. Therefore, the development of the anode OER catalyst with high activity reduces the energy consumption cost and has great application prospect.
Noble metal catalysts are still widely regarded as efficient OER catalysts at present, however their high cost and scarcity limit their large scale application. Therefore, the development of the high-efficiency stable low-cost electrocatalyst has important significance for producing hydrogen and oxygen by water electrolysis. In recent years, in the fields of hydrogen production by electrolysis of water and oxygen research, non-noble metal materials such as transition metal compounds, perovskite-type metal compounds, and spinel-type metal compounds have been widely studied as catalysts. The preparation process of the transition metal and oxide catalyst thereof is simple, the resources are rich, the price is relatively low, the activity has a large promotion space, and the catalyst is expected to replace noble metal catalysts. However, the existing transition metal compound electrocatalyst still has the problems of low catalytic activity, poor efficiency and the like in the electrocatalytic process. Therefore, the development of a non-noble metal OER catalyst with better performance than noble metal materials is a key point for improving the water electrolysis efficiency and reducing the cost, and is one of the primary tasks for promoting the large-scale industrial application of the electrolyzed water.
Disclosure of Invention
The invention aims to provide a preparation method of a single-atom iron doped cobalt-nickel layered double-metal hydroxide catalyst, which is used for improving the water electrolysis efficiency and reducing the cost.
In order to solve the technical problems, the invention discloses a preparation method of a single-atom iron-doped cobalt-nickel layered double hydroxide catalyst, which is implemented according to the following steps:
step 1, go to C 19 H 42 BrN and Co (NO) 3 ) 2 ·6H 2 Adding deionized water into O, and shaking uniformly to obtain a mixed solution A;
step 2, adding deionized water into the 2-methylimidazole, and magnetically stirring to obtain a mixed solution B;
step 3, slowly adding the mixed solution A into the mixed solution B, centrifuging after magnetic stirring, cleaning by alcohol, and drying to obtain ZIF-67;
step 4, dispersing ZIF-67 in a round bottom flask by using absolute ethyl alcohol;
step 5, feSO 4 ·7H 2 O and Ni (NO) 3 ) 2 ·6H 2 Adding O into deionized water, and magnetically stirring to form a mixed solution C;
step 6, adding the mixed solution C into the round-bottomed flask in the step 4, uniformly mixing, and then heating in a water bath;
and 7, centrifuging after the water bath heating in the step 6 is finished, washing with water, washing with alcohol, and drying to obtain the Co-Fe-Ni LDHs.
The technical scheme of the invention also has the following characteristics:
as a preferred embodiment of the present invention, in the step 1, every 8 ml deionized water is added with C 19 H 42 BrN is 6-10 mg; co (NO) added 3 ) 2 ·6H 2 O is 240-250 mg
As a preferred embodiment of the invention, in the step 2, every 56 and ml deionized water, the 2-methylimidazole is added in a range of 3632-3640 and 3640 mg
As a preferable mode of the invention, in the step 3, the magnetic stirring time is 20-30 min.
As a preferred embodiment of the present invention, in the step 4, every 120 ml absolute ethyl alcohol, the ZIF-67 is added in a range of 183-190 mg.
In the step 4, the ultrasonic cleaning is adopted for dispersion, and the time is 15-25 min.
As a preferred embodiment of the present invention, in the step 5, feSO is added every 50. 50 ml 4 ·7H 2 O is 114-120 mg, and Ni (NO) 3 ) 2 ·6H 2 O is 954-960 mg; ZIF-67 and FeSO in the mixed solution C 4 ·7H 2 O、Ni(NO 3 ) 2 ·6H 2 The molar ratio of O is about 2:1:8.
As a preferable mode of the invention, in the step 5, the time of the magnetic stirring is 15-25 min.
As a preferable scheme of the invention, in the step 6, the water bath heating temperature is 83-87 ℃ and the time is 120-130 min.
As a preferable mode of the invention, in the step 3 and the step 7, the drying temperature is 60-70 ℃.
Compared with the prior art: the invention relates to a preparation method of a single-atom iron-doped cobalt-nickel layered double hydroxide catalyst, which comprises the following steps of FeSO 4 ·7H 2 O and Ni (NO) 3 ) 2 ·6H 2 Adding the mixed solution of O into an ethanol solution of ZIF-67, doping iron ions and nickel ions by a hydrothermal method, and synthesizing a nano catalyst with special morphology and structure, wherein the nano catalyst presents a nano granular structure; further, it is known from electrochemical performance analysis that: the Co-Fe-Ni LDHs has better catalytic activity to OER when the Co-Fe-Ni ratio is 2:1:8, and the surface current density is 100 mA cm -2 When the corresponding overpotential is the lowest and Tafel slope is the smallest, the Co-Fe-Ni on the surface of Co-Fe-Ni LDHs has electrocatalytic activity to the Co-Fe-NiThe influence is larger.
Drawings
FIG. 1 is a graph showing OER polarization curves of Co-Fe-Ni LDHs prepared in example 1 (2:1:8), ZIF-67 prepared in comparative example 1, co-Fe LDHs prepared in comparative example 2, co-Ni LDHs prepared in comparative example 3, and Co-Fe-Ni LDHs prepared in comparative example 4 in the method of the present invention;
FIG. 2 is a scanning electron microscope image of ZIF-67 prepared in comparative example 1 in the method of the present invention;
FIG. 3 is a scanning electron microscope image of Co-Fe-Ni LDHs (2:1:8) prepared in example 1 in the method of the present invention;
FIG. 4 is a transmission electron microscope image of Co-Fe-Ni LDHs (2:1:8) prepared in example 1 in the method of the present invention;
FIG. 5 is a spherical aberration correcting scanning transmission electron microscope image of Co-Fe-Ni LDHs (2:1:8) prepared in example 1 in the method of the present invention.
Detailed Description
Example 1
The invention relates to a preparation method of a single-atom iron doped cobalt-nickel layered double hydroxide catalyst, which is implemented according to the following steps:
step 1, go to C 19 H 42 BrN and Co (NO) 3 ) 2 ·6H 2 Adding deionized water into O, and shaking uniformly to obtain a mixed solution A; c (C) 19 H 42 BrN is 6 mg, co (NO) 3 ) 2 ·6H 2 240O mg and 8 mL deionized water;
step 2, adding deionized water into the 2-methylimidazole, and magnetically stirring to obtain a mixed solution B; 2-methylimidazole 3632 and mg; deionized water 56 mL;
step 3, slowly adding the mixed solution A into the mixed solution B, centrifuging after magnetic stirring, cleaning for 2 times by alcohol, and drying to obtain ZIF-67; the magnetic stirring time is 20 min; the drying temperature is 60 ℃;
step 4, dispersing ZIF-67 in a round bottom flask by using absolute ethyl alcohol; absolute ethanol 120 mL; ZIF-67 is 183 mg; dispersing by ultrasonic cleaning for 15 min;
step 5, feSO 4 ·7H 2 O and Ni (NO) 3 ) 2 ·6H 2 Adding O into deionized water, and magnetically stirring to form a mixed solution C; feSO 4 ·7H 2 O is 114 mg; ni (NO) 3 ) 2 ·6H 2 O is 954 mg; deionized water 50 mL; ZIF-67, feSO 4 ·7H 2 O、Ni(NO 3 ) 2 ·6H 2 The molar ratio of O is about 2:1:8; magnetically stirring for 15 min to uniformly mix the materials;
step 6, adding the mixed solution C into the round-bottomed flask in the step 4, uniformly mixing, and then heating in a water bath; the heating temperature in the water bath is 83 ℃; the heating time in the water bath is 120 min;
and 7, centrifuging after the water bath heating in the step 6 is finished, washing with water for 2 times, washing with alcohol for 3 times, and drying to obtain Co-Fe-Ni LDHs.
Example 2
The invention relates to a preparation method of a single-atom iron doped cobalt-nickel layered double hydroxide catalyst, which is implemented according to the following steps:
step 1, go to C 19 H 42 BrN and Co (NO) 3 ) 2 ·6H 2 Adding deionized water into O, and shaking uniformly to obtain a mixed solution A; c (C) 19 H 42 BrN is 8 mg, co (NO) 3 ) 2 ·6H 2 240O mg and 8 mL deionized water;
step 2, adding deionized water into the 2-methylimidazole, and magnetically stirring to obtain a mixed solution B; 2-methylimidazole 3636 and mg; deionized water 56 mL;
step 3, slowly adding the mixed solution A into the mixed solution B, centrifuging after magnetic stirring, cleaning for 2 times by alcohol, and drying to obtain ZIF-67; the magnetic stirring time is 25 min; the drying temperature is 65 ℃;
step 4, dispersing ZIF-67 in a round bottom flask by using absolute ethyl alcohol; absolute ethanol 120 mL; ZIF-67 is 187 mg; dispersing by ultrasonic cleaning for 20 min;
step 5, feSO 4 ·7H 2 O and Ni (NO) 3 ) 2 ·6H 2 O is added into deionized water and magnetically stirredStirring to form a mixed solution C; feSO 4 ·7H 2 O is 117 mg; ni (NO) 3 ) 2 ·6H 2 O is 957 mg; deionized water 50 mL; ZIF-67, feSO 4 · 7H 2 O、Ni(NO 3 ) 2 ·6H 2 The molar ratio of O is about 2:1:8; magnetically stirring for 20 min to uniformly mix the materials;
step 6, adding the mixed solution C into the round-bottomed flask in the step 4, uniformly mixing, and then heating in a water bath; the water bath heating temperature is 85 ℃; heating in water bath for 125 min;
and 7, centrifuging after the water bath heating in the step 6 is finished, washing with water for 2 times, washing with alcohol for 3 times, and drying to obtain Co-Fe-Ni LDHs.
Example 3
The invention relates to a preparation method of a single-atom iron doped cobalt-nickel layered double hydroxide catalyst, which is implemented according to the following steps:
step 1, go to C 19 H 42 BrN and Co (NO) 3 ) 2 ·6H 2 Adding deionized water into O, and shaking uniformly to obtain a mixed solution A; c (C) 19 H 42 BrN is 10 mg, co (NO) 3 ) 2 · 6H 2 250 mg for O and 8 mL for deionized water;
step 2, adding deionized water into the 2-methylimidazole, and magnetically stirring to obtain a mixed solution B; 2-methylimidazole 3640 and mg; deionized water 56 mL;
step 3, slowly adding the mixed solution A into the mixed solution B, centrifuging after magnetic stirring, cleaning for 2 times by alcohol, and drying to obtain ZIF-67; the magnetic stirring time is 25 min; the drying temperature is 70 ℃;
step 4, dispersing ZIF-67 in a round bottom flask by using absolute ethyl alcohol; absolute ethanol 120 mL; ZIF-67 is 190 mg; dispersing by ultrasonic cleaning for 25 min;
step 5, feSO 4 ·7H 2 O and Ni (NO) 3 ) 2 ·6H 2 Adding O into deionized water, and magnetically stirring to form a mixed solution C; feSO 4 ·7H 2 O is 120 mg; ni (NO) 3 ) 2 ·6H 2 O is 960 mg; deionized water 50 mL; ZIF-67, feSO 4 ·7H 2 O、Ni(NO3) 2 ·6H 2 The molar ratio of O is about 2:1:8; magnetically stirring for 25 min to uniformly mix the materials;
step 6, adding the mixed solution C into the round-bottomed flask in the step 4, uniformly mixing, and then heating in a water bath; the water bath heating temperature is 87 ℃; the heating time in the water bath is 130 min;
and 7, centrifuging after the water bath heating in the step 6 is finished, washing with water for 2 times, washing with alcohol for 3 times, and drying to obtain Co-Fe-Ni LDHs.
Comparative example 1
Step 1, C 19 H 42 BrN and Co (NO) 3 ) 2 ·6H 2 Adding deionized water into O, and shaking uniformly to obtain a mixed solution A;
C 19 H 42 BrN is 6 mg; co (NO) 3 ) 2 ·6H 2 O is 240 mg; deionized water was 8 mL.
Step 2, adding 2-methylimidazole into deionized water and magnetically stirring to obtain a mixed solution B;
2-methylimidazole 3632 and mg; deionized water 56 mL;
step 3, slowly adding the mixed solution A into the mixed solution B, magnetically stirring, centrifuging, washing with alcohol for 2 times, and drying to obtain ZIF-67;
the magnetic stirring time is 20 min; the drying temperature is 60 ℃;
comparative example 2
Step 1, C 19 H 42 BrN and Co (NO) 3 ) 2 ·6H 2 Adding deionized water into O, and shaking uniformly to obtain a mixed solution A;
C 19 H 42 BrN is 6 mg; co (NO) 3 ) 2 ·6H 2 O is 240 mg; deionized water was 8 mL.
Step 2, adding 2-methylimidazole into deionized water and magnetically stirring to obtain a mixed solution B;
2-methylimidazole 3632 and mg; deionized water 56 mL;
step 3, slowly adding the mixed solution A into the mixed solution B, magnetically stirring, centrifuging, washing with alcohol for 2 times, and drying to obtain ZIF-67;
the magnetic stirring time is 20 min; the drying temperature is 60 ℃;
step 4, absolute ethyl alcohol disperses ZIF-67 in a 250 mL round bottom flask;
absolute ethanol 120 mL; ZIF-67 is 183 mg; dispersing by ultrasonic cleaning for 15 min;
step 5, feSO 4 ·7H 2 Adding deionized water into O to form a mixed solution C;
FeSO 4 ·7H 2 o is 114 mg; deionized water 50 mL; ZIF-67, feSO 4 ·7H 2 The molar ratio of O is about 2:1; magnetically stirring for 15 min to uniformly mix the materials;
step 6, adding the mixed solution C into a round-bottom flask containing ZIF-67, uniformly mixing, and heating in a water bath;
the water bath heating temperature is 85 ℃; the heating time in the water bath is 120 min;
step 7, centrifuging after the water bath is finished, washing with water for 2 times, washing with alcohol for 3 times, and drying to obtain Co-Fe LDHs (2:1);
the drying temperature is 60 ℃;
comparative example 3
Step 1, C 19 H 42 BrN and Co (NO) 3 ) 2 ·6H 2 Adding deionized water into O, and shaking uniformly to obtain a mixed solution A;
C 19 H 42 BrN is 6 mg; co (NO) 3 ) 2 ·6H 2 O is 240 mg; deionized water was 8 mL.
Step 2, adding 2-methylimidazole into deionized water and magnetically stirring to obtain a mixed solution B;
2-methylimidazole 3632 and mg; deionized water 56 mL;
step 3, slowly adding the mixed solution A into the mixed solution B, magnetically stirring, centrifuging, washing with alcohol for 2 times, and drying to obtain ZIF-67;
the magnetic stirring time is 20 min; the drying temperature is 60 ℃;
step 4, absolute ethyl alcohol disperses ZIF-67 in a 250 mL round bottom flask;
absolute ethanol 120 mL; ZIF-67 is 183 mg; dispersing by ultrasonic cleaning for 15 min;
step 5, ni (NO) 3 ) 2 ·6H 2 Adding deionized water into O to form a mixed solution C;
Ni(NO 3 ) 2 ·6H 2 o is 954 mg; deionized water 50 mL; ZIF-67, ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is about 2:8; magnetically stirring for 15 min to uniformly mix the materials;
step 6, adding the mixed solution C into a round-bottom flask containing ZIF-67, uniformly mixing, and heating in a water bath;
the water bath heating temperature is 85 ℃; the heating time in the water bath is 120 min;
step 7, centrifuging after the water bath is finished, washing with water for 2 times, washing with alcohol for 3 times, and drying to obtain Co-Ni LDHs (2:8);
the drying temperature is 60 ℃;
comparative example 4
Step 1, C 19 H 42 BrN and Co (NO) 3 ) 2 ·6H 2 Adding deionized water into O, and shaking uniformly to obtain a mixed solution A;
C 19 H 42 BrN is 6 mg; co (NO) 3 ) 2 ·6H 2 O is 240 mg; deionized water was 8 mL.
Step 2, adding 2-methylimidazole into deionized water and magnetically stirring to obtain a mixed solution B;
2-methylimidazole 3632 and mg; deionized water 56 mL;
step 3, slowly adding the mixed solution A into the mixed solution B, magnetically stirring, centrifuging, washing with alcohol for 2 times, and drying to obtain ZIF-67;
the magnetic stirring time is 20 min; the drying temperature is 60 ℃;
step 4, absolute ethyl alcohol disperses ZIF-67 in a 250 mL round bottom flask;
absolute ethanol 120 mL; ZIF-67 is 183 mg; dispersing by ultrasonic cleaning for 15 min;
step 5, willFeSO 4 ·7H 2 O and Ni (NO) 3 ) 2 ·6H 2 Adding deionized water into O to form a mixed solution C;
FeSO 4 ·7H 2 o is 114 mg; ni (NO) 3 ) 2 ·6H 2 O is 1908 mg; deionized water 50 mL; ZIF-67, feSO 4 ·7H 2 O、Ni(NO 3 ) 2 ·6H 2 The molar ratio of O is about 2:1:16; magnetically stirring for 15 min to mix them uniformly;
step 6, adding the mixed solution C into a round-bottom flask containing ZIF-67, uniformly mixing, and heating in a water bath;
the water bath heating temperature is 85 ℃; the heating time in the water bath is 120 min;
step 7, centrifuging after the water bath is finished, washing with water for 2 times, washing with alcohol for 3 times, and drying to obtain Co-Fe-Ni LDHs (2:1:16);
the drying temperature is 60 ℃;
application example 1
The catalytic electrodes obtained in example 1 and comparative examples 1 to 4 were used for the evaluation of electrochemical oxygen evolution activity under alkaline conditions.
1. Analysis is carried out by adopting a standard three-electrode electrochemical voltammetry scanning method, the electrolyte is 1M KOH solution, and the effective exposure area of the electrode is 1.9625 cm 2 The solution resistance was compensated by 9.5. OMEGA. With a voltammetric sweep rate of 5 mV. S -1 Test temperature: 25 ℃;
2. the electrolytic water oxygen evolution performance of the different catalysts is shown in figure 1: co-Fe-Ni LDHs (2:1:8) (example 1) > Co-Fe-Ni LDHs (2:1:16) (comparative example 4) > Co-Ni LDHs (2:8) (comparative example 3) > Co-Fe LDHs (2:1) (comparative example 2) > ZIF-67 (comparative example 1);
3. the surface current density of the different catalysts is 100 mA cm -2 The corresponding overpotential: co-Fe-Ni LDHs (2:1:8) (examples)<Co-Fe-Ni LDHs (2:1:16) (comparative example 4)<Co-Ni LDHs (2:8) (comparative example 3)<Co-Fe LDHs (2:1) (comparative example 2)<ZIF-67 (comparative example 1);
4. tafel slopes of different catalysts: co-Fe-Ni LDHs (2:1:8) (example 1) < Co-Fe-Ni LDHs (2:1:16) (comparative example 4) < Co-Ni LDHs (2:8) (comparative example 3) < Co-Fe LDHs (2:1) (comparative example 2) < ZIF-67 (comparative example 1);
5. surface resistance of different catalysts: co-Fe-Ni LDHs (2:1:8) (example 1) < Co-Fe-Ni LDHs (2:1:16) (comparative example 4) < Co-Ni LDHs (2:8) (comparative example 3) < Co-Fe LDHs (2:1) (comparative example 2) < ZIF-67 (comparative example 1);
FeSO is carried out 4 ·7H 2 O and Ni (NO) 3 ) 2 ·6H 2 The mixed solution of O is added into the ethanol solution of ZIF-67, and iron ions and nickel ions are doped in through a hydrothermal method, so that the nano catalyst with special morphology and structure is synthesized, and the nano catalyst presents a nano granular structure (figure 3). Further, it is known from electrochemical performance analysis that: the Co-Fe-Ni LDHs has better catalytic activity to OER when the Co-Fe-Ni ratio is 2:1:8, and the surface current density is 100 mA cm -2 The corresponding overpotential is the lowest and the Tafel slope is the smallest. This shows that Co-Fe-Ni with Co-Fe-Ni LDHs surface has a great influence on its electrocatalytic activity. When the Co-Fe-Ni ratio of the Co-Fe-Ni LDHs surface is 2:1:8, the electrocatalytic oxygen evolution activity is optimal.
Claims (10)
1. The preparation method of the monoatomic iron doped cobalt-nickel layered double hydroxide catalyst is characterized by comprising the following steps of:
step 1, go to C 19 H 42 BrN and Co (NO) 3 ) 2 ·6H 2 Adding deionized water into O, and shaking uniformly to obtain a mixed solution A;
step 2, adding deionized water into the 2-methylimidazole, and magnetically stirring to obtain a mixed solution B;
step 3, slowly adding the mixed solution A into the mixed solution B, centrifuging after magnetic stirring, cleaning by alcohol, and drying to obtain ZIF-67;
step 4, dispersing ZIF-67 in a round bottom flask by using absolute ethyl alcohol;
step 5, feSO 4 ·7H 2 O and Ni (NO) 3 ) 2 ·6H 2 O is added toMagnetically stirring the mixture in ionized water to form a mixed solution C;
step 6, adding the mixed solution C into the round-bottomed flask in the step 4, uniformly mixing, and then heating in a water bath;
and 7, centrifuging after the water bath heating in the step 6 is finished, washing with water, washing with alcohol, and drying to obtain the Co-Fe-Ni LDHs.
2. The method for preparing a single-atom iron-doped cobalt-nickel layered double hydroxide catalyst according to claim 1, wherein in the step 1, every 8 ml deionized water, C is added 19 H 42 BrN is 6-10 mg; co (NO) added 3 ) 2 ·6H 2 O is 240-250 mg.
3. The method for preparing a single-atom iron-doped cobalt-nickel layered double hydroxide catalyst according to claim 2, wherein in the step 2, every 56 ml deionized water, 2-methylimidazole is added in a range of 3632-3640-mg.
4. The method for preparing a single-atom iron-doped cobalt-nickel layered double hydroxide catalyst according to claim 3, wherein in the step 3, the magnetic stirring time is 20-30 min.
5. The method for preparing a single-atom iron-doped cobalt-nickel layered double hydroxide catalyst according to claim 4, wherein the ZIF-67 is added in the range of 183-190 mg per 120 ml absolute ethanol in step 4.
6. The method for preparing a single-atom iron-doped cobalt-nickel layered double hydroxide catalyst according to claim 5, wherein in the step 4, the dispersion is performed by ultrasonic cleaning for 15-25 min.
7. The monoatomic iron doped cobalt nickel layered double metal hydroxide according to claim 6A process for preparing a biocatalyst, characterized in that in said step 5, feSO is added every 50. 50 ml 4 ·7H 2 O is 114-120 mg, and Ni (NO) 3 ) 2 ·6H 2 O is 954-960 mg; ZIF-67 and FeSO in the mixed solution C 4 ·7H 2 O、Ni(NO 3 ) 2 ·6H 2 The molar ratio of O is about 2:1:8.
8. The method for preparing a single-atom iron-doped cobalt-nickel layered double hydroxide catalyst according to claim 7, wherein in the step 5, the magnetic stirring time is 15-25 min.
9. The method for preparing a single-atom iron-doped cobalt-nickel layered double hydroxide catalyst according to claim 8, wherein in the step 6, the water bath heating temperature is 83-87 ℃ and the time is 120-130 min.
10. The method for preparing a single-atom iron-doped cobalt-nickel layered double hydroxide catalyst according to claim 9, wherein in the step 3 and the step 7, the drying temperature is 60-70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310683373.2A CN116876020A (en) | 2023-06-09 | 2023-06-09 | Preparation method of single-atom iron-doped cobalt-nickel layered double hydroxide catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310683373.2A CN116876020A (en) | 2023-06-09 | 2023-06-09 | Preparation method of single-atom iron-doped cobalt-nickel layered double hydroxide catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116876020A true CN116876020A (en) | 2023-10-13 |
Family
ID=88265151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310683373.2A Pending CN116876020A (en) | 2023-06-09 | 2023-06-09 | Preparation method of single-atom iron-doped cobalt-nickel layered double hydroxide catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116876020A (en) |
-
2023
- 2023-06-09 CN CN202310683373.2A patent/CN116876020A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110479281B (en) | Electro-catalyst based on FeOOH-NiOOH/NF and preparation method | |
| CN110838588B (en) | Rechargeable zinc-air battery bifunctional catalyst and preparation method and application thereof | |
| CN111672514A (en) | Bifunctional electrocatalytic material and preparation method and application thereof | |
| CN111495394A (en) | Carbon cloth loaded CoS2/MoS2Heterojunction composite material and preparation method and application thereof | |
| CN113637996B (en) | Copper-based nano material for electrocatalytic reduction of carbon dioxide and preparation method thereof | |
| CN112981441A (en) | Preparation method and application of self-supporting type iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode | |
| CN111001414A (en) | Structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material and preparation method thereof | |
| Li et al. | Coupled and decoupled electrochemical water splitting for boosting hydrogen evolution: A review and perspective | |
| CN113443610B (en) | Ruthenium selenide nanosphere electrocatalyst and preparation method and application thereof | |
| CN117230475A (en) | Preparation method of Ni and Mn bimetallic electrocatalyst and small molecule electrooxidation application thereof | |
| CN112090426A (en) | Metal metastable phase electrolyzed water oxygen evolution catalyst and preparation method and application thereof | |
| CN110354870B (en) | Preparation method and application of high-performance silver-doped cobalt sulfide oxygen evolution catalyst | |
| CN117089881A (en) | Preparation method of Pt nanoparticle modified bimetallic LDH catalyst and industrial current density electrolyzed water application thereof | |
| CN116876019A (en) | High-efficiency dual-function electrocatalyst for producing hydrogen by electrolyzing ammonia and preparation method thereof | |
| CN109097788B (en) | Double-carbon coupling transition metal nickel-based quantum dot electrocatalyst and preparation method thereof | |
| CN114164454B (en) | Molybdenum-iron-based phosphide composite material for electrocatalytic organic matter reduction-oxidation pairing coupling and preparation and application thereof | |
| CN116876020A (en) | Preparation method of single-atom iron-doped cobalt-nickel layered double hydroxide catalyst | |
| CN114232027B (en) | Fe (Fe) 5 Ni 4 S8-Ni 3 S 2 Double-function composite NF electrocatalyst and its preparing process and application | |
| CN113981468B (en) | Multi-dimensional nickel-cobalt-based sulfide heterojunction electrocatalytic composite material and preparation method thereof | |
| CN114481209A (en) | Preparation method of Ru-modified iron-based self-supporting hydrogen evolution electrode | |
| CN112501645B (en) | Nickel hydroxide/nickel screen composite hydrogen and oxygen evolution electrode, preparation method and application thereof | |
| CN114561655A (en) | Preparation method and application of rare earth cerium doped nickel sulfide/iron sulfide heterojunction material | |
| CN114921808B (en) | Vanadium-doped iridium dioxide electrocatalyst, and preparation method and application thereof | |
| CN115094475B (en) | Electrode material with high-performance oxygen evolution catalytic activity and preparation method thereof | |
| CN112626553B (en) | Hollow carbon tube composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |