CN112044442B - Preparation method and application of beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects - Google Patents
Preparation method and application of beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects Download PDFInfo
- Publication number
- CN112044442B CN112044442B CN202010920261.0A CN202010920261A CN112044442B CN 112044442 B CN112044442 B CN 112044442B CN 202010920261 A CN202010920261 A CN 202010920261A CN 112044442 B CN112044442 B CN 112044442B
- Authority
- CN
- China
- Prior art keywords
- iron hydroxide
- carbon nanotube
- nickel iron
- beta
- phase nickel
- 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.)
- Active
Links
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 45
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 45
- QJSRJXPVIMXHBW-UHFFFAOYSA-J iron(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Fe+2].[Ni+2] QJSRJXPVIMXHBW-UHFFFAOYSA-J 0.000 title claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 230000007547 defect Effects 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 carbon nanotube compound Chemical class 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 10
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 9
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 8
- 239000002071 nanotube Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229920000557 Nafion® Polymers 0.000 claims description 2
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000001132 ultrasonic dispersion Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910000863 Ferronickel Inorganic materials 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/33—
-
- B01J35/61—
-
- 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
- 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
-
- 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 discloses a preparation method and application of a beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects, which comprises the following steps: (1) Uniformly dispersing the carbon oxide nanotubes in deionized water (filled with nitrogen) by adopting an ultrasonic dispersion technology; (2) Adding nickel chloride hexahydrate, ferrous chloride tetrahydrate, hexamethylenetetramine and ammonium fluoride into the solution, transferring the solution to a reaction kettle, and reacting at 120 ℃ for 6 hours to obtain a nickel iron hydroxide/carbon nanotube compound; (3) And dispersing the obtained material in a mixed solution of hydrogen peroxide and water at room temperature, and oxidizing the nickel iron hydroxide/carbon nanotube composite to different defect degrees for different time. The method has the advantages of cheap and easily-obtained raw materials, convenient synthesis, simple equipment, no pollution in the production process, rapid realization of large-scale production, more defect sites and active centers of the material and better electrolyzed water oxygen evolution performance.
Description
Technical Field
The invention relates to a preparation technology suitable for transition metal hydroxides, in particular to a preparation method and application of a controllable beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects.
Background
The use of traditional fossil fuels (coal, oil, natural gas, etc.) causes energy depletion, causes severe environmental problems such as greenhouse effect, acid rain, ozone layer destruction, etc., and seriously affects the survival and development of human beings, so that a clean and sustainable new energy source has to be found to replace the traditional fossil fuels to meet the needs of human beings (Journal of the American Chemical Society 137.10 (2015): 3638-3648). Hydrogen has the advantages of high energy density, high combustion calorific value, zero pollution and the like, and is therefore considered to be one of the best candidates for replacing conventional fossil fuels (Nano Research 8.1 (2014): 23-39). The electrolysis of water to produce hydrogen and oxygen is one of the known effective ways to obtain hydrogen gas of high purity. The hydrogen production by water electrolysis consists of two half reactions, namely Hydrogen Evolution Reaction (HER) at a cathode and Oxygen Evolution Reaction (OER) at an anode (Energy)&Environmental science 6.10 (2013): 2921-2924). OER involves a complex four electron transfer process, a kinetically slow process, compared to HER, which is a simple two electron transfer process, so that a higher overpotential is required to meet the reaction requirements, which seriously affects the water splitting efficiency (Journal of the American Chemical Society 136.18 (2014): 6744-53). Therefore, a suitable catalyst is needed to reduce the overpotential required in OER processes and increase the efficiency of water electrolysis. In recent years, noble metals and their derivatives (e.g., irO) have been widely recognized 2 And RuO 2 ) Are the best OER catalysts, but they have low reserves, are expensive, have poor stability and are therefore not amenable to large scale practical use (angelwald Chemie International Edition (2014)). 3d transition metal is cheapAbundant reserves, has become the focus of research in recent years, wherein the ferronickel double metal hydroxide has been widely researched due to the unique layered structure thereof. Since the hydroxide has poor conductivity, and the layered material spontaneously aggregates together to reduce the surface free energy thereof, the specific surface area of the material is reduced, and the number of active sites is reduced, so that the efficiency of electrolyzing water is reduced, and the energy consumption is increased. The carbon nano tube and the ferronickel bimetal hydroxide are compounded and the defects are introduced, so that the conductivity of the material can be effectively improved, and the number of active sites of the material is increased, so that the catalytic activity is improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a beta-phase nickel iron hydroxide/carbon nano tube compound with atomic defects, the synthesis process has higher safety and simple operation, and the product has the characteristics of magnetic property, low density, large specific surface area and the like; the method has the advantages of cheap and easily obtained raw materials, convenient synthesis, simple equipment, no pollution in the production process, rapid realization of large-scale production, more defect sites and active centers of the material, and better electrolyzed water oxygen evolution performance.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects comprises the following steps:
(1) Ultrasonically dispersing a certain amount of carbon oxide nano tubes in deionized water which is filled with nitrogen to obtain carbon oxide nano tube dispersion liquid;
(2) Dissolving nickel chloride hexahydrate, ferrous chloride tetrahydrate, hexamethylenetetramine and ammonium fluoride in the carbon oxide nanotube dispersion liquid prepared in the step (1) to obtain a mixed liquid;
(3) Transferring the mixed liquid obtained in the step (2) to a reaction kettle, and reacting the solution in the closed reaction kettle at 120-160 ℃ for 6-24 hours to obtain a beta-phase nickel iron hydroxide/carbon nanotube compound;
(4) And (4) placing the beta-phase nickel iron hydroxide/carbon nano tube compound synthesized in the step (3) in a mixed solution of hydrogen peroxide and water at room temperature, and mechanically stirring for a certain time to carry out oxidation reaction to obtain the beta-phase nickel iron hydroxide/carbon nano tube compound with atomic defects.
Further, the concentration of the oxidized carbon nanotube dispersion liquid in the step (1) is 0.125 mg/mL-0.25 mg/mL.
Further, in the step (2), the molar concentration of nickel nitrate hexahydrate is 0.0375-0.05625 mol/L, the molar concentration of ferrous chloride tetrahydrate is 0.0375-0.01875 mol/L, the molar concentration of hexamethylenetetramine is 0.05-0.03 mol/L, and the molar concentration of ammonium fluoride is 0.035-0.015 mol/L.
Further, the volume ratio of the hydrogen peroxide to the water in the mixed solution of the hydrogen peroxide and the water in the step (4) is 1.
Further, the time for mechanical stirring in the step (4) is 3 to 36 hours.
The application of the beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects prepared by the preparation method in the electrolytic water comprises the following steps: 2.5 mg of a beta-phase nickel iron hydroxide/carbon nanotube composite having atomic defects was weighed, transferred to a 5 ml centrifuge tube, and 800. Mu.l of isopropyl alcohol, 800. Mu.l of deionized water and 14. Mu.l of Nafion solution were added to obtain a mixed solution, and after 30 minutes of ultrasonication, 9.6. Mu.l of the mixed solution was spotted on a glassy carbon electrode and dried at 95 ℃ for 12 hours, followed by conducting an electrolytic water test.
The beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects prepared by the invention can be ultrasonically dispersed in ethanol, and then the structure and the appearance of a nano wire are observed by means of a scanning electron microscope or a transmission electron microscope and the like.
Compared with the prior art, the invention has the following advantages: 1. the invention can prepare the beta-phase ferronickel hydroxide/carbon nanotube with atomic defects, and the defect sites can adjust the electron charge distribution of the catalyst and influence the coordination environment of reaction sites, thereby being beneficial to the rapid transfer of electrons and optimizing the adsorption free energy of intermediate species (OH, O and OOH), thereby improving the efficiency of OER, improving the performance of OER and reducing the consumption of electric energy. 2. The invention adopts a hydrothermal synthesis technology, has relatively simple experimental technology, is easy to operate, has simple equipment requirement, and can greatly reduce the production cost. 3. The invention adopts the hexamethylenetetramine as the alkali source, has small harm to human body and reduces the pollution to the environment. 4. The beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects prepared by the method has uniform size distribution and easy synthesis, and can be widely applied to the fields of magnetism, biological pharmacy, machinery, electronics, optics and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a β -phase nickel iron hydroxide/carbon nanotube composite with atomic defects prepared according to the present invention;
FIG. 2 is a transmission electron microscope image of a beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects prepared in accordance with the present invention;
FIG. 3 is a scanning electron microscope image of a beta-phase nickel iron hydroxide/carbon nanotube composite prepared according to the present invention;
fig. 4 shows the electrolytic water oxygen evolution performance of the beta-phase nickel iron hydroxide/carbon nanotube composite (ii) and the beta-phase nickel iron hydroxide/carbon nanotube composite (i) with atomic defects prepared by the present invention (fig. a is an oxygen evolution polarization curve, fig. b is a tafel slope, fig. c is an electrochemical active area, and fig. d is impedance).
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1 preparation of atomic deficient beta-phase nickel iron hydroxide/carbon nanotube composites
Weigh 10mg of carbon oxide nanotubes into 40ml of deionized water (already open)N 2 ) Performing medium-temperature ultrasonic dispersion for 30min, then adding 0.0357g (0.0375 mol/L) of nickel chloride hexahydrate, 0.0299g (0.0375 mol/L) of ferrous chloride tetrahydrate, 0.2804g (0.05 mol/L) of hexamethylenetetramine and 0.0222g (0.015 mol/L) of ammonium fluoride, dissolving, transferring the mixture into a polytetrafluoroethylene high-temperature autoclave, reacting for 120 ℃/6 h, cooling, and performing suction filtration and washing by using deionized water to obtain black powder. The powder was then dispersed in 50ml of a mixed solution of hydrogen peroxide and water (volume ratio 1).
Example 2 preparation of beta-phase Nickel iron hydroxide/carbon nanotube composite
Weigh 10mg of carbon nanotubes into 40ml of deionized water (N passed through) 2 ) And (3) performing medium-temperature ultrasonic treatment for 30min for dispersion, then adding 0.0357g (0.0375 mol/L) of nickel chloride hexahydrate, 0.0299g (0.0375 mol/L) of ferrous chloride tetrahydrate, 0.2804g (0.05 mol/L) of hexamethylenetetramine and 0.0222g (0.015 mol/L) of ammonium fluoride, dissolving, transferring the solution into a polytetrafluoroethylene high-temperature autoclave, reacting for 120 ℃/6 h, cooling, and performing suction filtration and washing by using deionized water to obtain black powder.
The synthesized atomic defect beta-phase nickel iron hydroxide/carbon nanotube composite is shown in fig. 1-2, which indicates the successful growth of the nanosheets on the carbon nanotubes, and the beta-phase nickel iron hydroxide/carbon nanotube composite is shown in fig. 3.
The oxygen evolution performance of the electrolyzed water is shown in figure 4, the oxygen evolution overpotential of the beta-phase nickel iron hydroxide/carbon nano tube composite with atomic defects is 244 mV, and the tafel slope is 41 mV/dec; the oxygen evolution overpotential of the beta-phase nickel iron hydroxide/carbon nano tube compound is 281 mV; the tafel slope was 61 mV/dec.
Example 3 preparation of atomic deficient beta-phase nickel iron hydroxide/carbon nanotube composites
Weigh 5mg of oxidized carbon nanotubes into 40ml of deionized water (already N) 2 ) Dispersing for 30min by medium ultrasonic wave, adding nickel chloride hexahydrate 0.05625mol/L, ferrous chloride tetrahydrate 0.01875mol/L, hexamethylenetetramine 0.03mol/L and ammonium fluoride 0.035mol/L for dissolving, transferring into polytetrafluoroethylene high-temperature autoclaveAnd after reacting for 24 hours at 120 ℃, cooling, and performing suction filtration and washing by using deionized water to obtain black powder. And then dispersing the powder in a mixed solution of 50mL of hydrogen peroxide and water (the volume ratio is 1).
Example 4 preparation of atomic deficient beta-phase nickel iron hydroxide/carbon nanotube composites
Weigh 8mg of oxidized carbon nanotubes into 40ml of deionized water (N passed) 2 ) Performing medium-temperature ultrasonic dispersion for 30min, then adding 0.045mol/L nickel chloride hexahydrate, 0.025mol/L ferrous chloride tetrahydrate, 0.01mol/L hexamethylenetetramine and 0.02mol/L ammonium fluoride, dissolving, transferring the solution into a polytetrafluoroethylene high-temperature autoclave, reacting for 3 h at 160 ℃, cooling, and performing suction filtration and washing by using deionized water to obtain black powder. And then dispersing the powder in a mixed solution of 50mL of hydrogen peroxide and water (the volume ratio is 1).
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. A preparation method of beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects is characterized by comprising the following steps:
(1) Ultrasonically dispersing a certain amount of carbon oxide nano tubes in deionized water which is filled with nitrogen to obtain carbon oxide nano tube dispersion liquid;
(2) Dissolving nickel chloride hexahydrate, ferrous chloride tetrahydrate, hexamethylenetetramine and ammonium fluoride in the carbon oxide nanotube dispersion liquid prepared in the step (1) to obtain a mixed liquid;
(3) Transferring the mixed liquid obtained in the step (2) to a reaction kettle, and reacting the solution in the closed reaction kettle at the temperature of 120-160 ℃ for 3-24 hours to obtain a beta-phase nickel iron hydroxide/carbon nanotube compound;
(4) Placing the beta-phase nickel iron hydroxide/carbon nano tube compound synthesized in the step (3) in a mixed solution of hydrogen peroxide and water at room temperature, and mechanically stirring for a certain time to carry out oxidation reaction to obtain the beta-phase nickel iron hydroxide/carbon nano tube compound with atomic defects;
the molar concentration of nickel nitrate hexahydrate in the mixed liquid in the step (2) is 0.0375-0.05625 mol/L, the molar concentration of ferrous chloride tetrahydrate is 0.01875 mol/L-0.0375 mol/L, the molar concentration of hexamethylenetetramine is 0.03-0.05 mol/L, and the molar concentration of ammonium fluoride is 0.015-0.035 mol/L.
2. The method of preparing β -phase nickel iron hydroxide/carbon nanotube composite with atomic defects of claim 1, characterized in that: the concentration of the oxidized carbon nanotube dispersion liquid in the step (1) is 0.125 mg/mL-0.25 mg/mL.
3. The method of preparing β -phase nickel iron hydroxide/carbon nanotube composite with atomic defects of claim 1, characterized in that: the volume ratio of the hydrogen peroxide to the water in the mixed solution of the hydrogen peroxide and the water in the step (4) is 1.
4. The method of preparing β -phase nickel iron hydroxide/carbon nanotube composite with atomic defects of claim 1, characterized in that: the time for mechanical stirring in the step (4) is 3 to 36 hours.
5. Use of the atomic defect beta-phase nickel iron hydroxide/carbon nanotube composite produced by the production method according to any one of claims 1 to 4 in electrolytic water.
6. Use according to claim 5, characterized by the following steps: 2.5 mg of a beta-phase nickel iron hydroxide/carbon nanotube composite having atomic defects was weighed, transferred to a 5 ml centrifuge tube, and 800. Mu.l of isopropyl alcohol, 800. Mu.l of deionized water and 14. Mu.l of Nafion solution were added to obtain a mixed solution, and after 30 minutes of ultrasonication, 9.6. Mu.l of the mixed solution was spotted on a glassy carbon electrode and dried at 95 ℃ for 12 hours, followed by conducting an electrolytic water test.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010920261.0A CN112044442B (en) | 2020-09-04 | 2020-09-04 | Preparation method and application of beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010920261.0A CN112044442B (en) | 2020-09-04 | 2020-09-04 | Preparation method and application of beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112044442A CN112044442A (en) | 2020-12-08 |
| CN112044442B true CN112044442B (en) | 2022-12-13 |
Family
ID=73608000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010920261.0A Active CN112044442B (en) | 2020-09-04 | 2020-09-04 | Preparation method and application of beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112044442B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881961B (en) * | 2021-11-11 | 2023-04-25 | 郑州大学 | Platinum single-atom catalyst and preparation method and application thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101635353A (en) * | 2009-08-19 | 2010-01-27 | 桂林理工大学 | Method for preparing compound electrode active material of nickel hydroxide/carbon nano tube |
| CN103943372A (en) * | 2014-05-08 | 2014-07-23 | 扬州大学 | Nickel hydroxide/multi-walled carbon nanotube composite material and preparation method thereof |
| CN105514450A (en) * | 2015-12-20 | 2016-04-20 | 青岛科技大学 | Nitrogen-doped graphene-ferronickel hydrotalcite difunctional oxygen catalyst and preparation method and application thereof |
| CN106241896A (en) * | 2016-08-04 | 2016-12-21 | 合肥中科富华新材料有限公司 | A kind of preparation method of β nickel hydroxide nano sheet |
| CN106917106A (en) * | 2017-01-18 | 2017-07-04 | 北京化工大学 | A kind of preparation method by hydrotalcite topology Synthesis super thin metal alloy nano chip arrays material |
| CN107871875A (en) * | 2016-09-26 | 2018-04-03 | 中国科学院大连化学物理研究所 | A kind of oxygen evolution reaction elctro-catalyst, its preparation method and application |
| CN110656348A (en) * | 2019-10-25 | 2020-01-07 | 上海电力大学 | Electrocatalytic oxygen evolution electrode and preparation and application thereof |
| CN110773173A (en) * | 2019-11-28 | 2020-02-11 | 郑州大学 | Bifunctional catalyst β -Ni (OH) 2/NF, preparation method and application thereof |
| CN111054343A (en) * | 2019-12-11 | 2020-04-24 | 清华-伯克利深圳学院筹备办公室 | Electrocatalytic oxygen evolution material and preparation method thereof |
| CN111229232A (en) * | 2020-03-20 | 2020-06-05 | 苏州大学 | Foam nickel-based porous NiFe hydrotalcite nanosheet and preparation and application thereof |
| CN111313041A (en) * | 2019-06-17 | 2020-06-19 | 北京纳米能源与***研究所 | Nickel-iron hydroxide electrocatalyst, preparation method and application thereof, self-energy supply system and application thereof |
| WO2020168390A1 (en) * | 2019-02-21 | 2020-08-27 | Newsouth Innovations Pty Limited | Nanoparticle and its use as a water-splitting catalyst |
-
2020
- 2020-09-04 CN CN202010920261.0A patent/CN112044442B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101635353A (en) * | 2009-08-19 | 2010-01-27 | 桂林理工大学 | Method for preparing compound electrode active material of nickel hydroxide/carbon nano tube |
| CN103943372A (en) * | 2014-05-08 | 2014-07-23 | 扬州大学 | Nickel hydroxide/multi-walled carbon nanotube composite material and preparation method thereof |
| CN105514450A (en) * | 2015-12-20 | 2016-04-20 | 青岛科技大学 | Nitrogen-doped graphene-ferronickel hydrotalcite difunctional oxygen catalyst and preparation method and application thereof |
| CN106241896A (en) * | 2016-08-04 | 2016-12-21 | 合肥中科富华新材料有限公司 | A kind of preparation method of β nickel hydroxide nano sheet |
| CN107871875A (en) * | 2016-09-26 | 2018-04-03 | 中国科学院大连化学物理研究所 | A kind of oxygen evolution reaction elctro-catalyst, its preparation method and application |
| CN106917106A (en) * | 2017-01-18 | 2017-07-04 | 北京化工大学 | A kind of preparation method by hydrotalcite topology Synthesis super thin metal alloy nano chip arrays material |
| WO2020168390A1 (en) * | 2019-02-21 | 2020-08-27 | Newsouth Innovations Pty Limited | Nanoparticle and its use as a water-splitting catalyst |
| CN111313041A (en) * | 2019-06-17 | 2020-06-19 | 北京纳米能源与***研究所 | Nickel-iron hydroxide electrocatalyst, preparation method and application thereof, self-energy supply system and application thereof |
| CN110656348A (en) * | 2019-10-25 | 2020-01-07 | 上海电力大学 | Electrocatalytic oxygen evolution electrode and preparation and application thereof |
| CN110773173A (en) * | 2019-11-28 | 2020-02-11 | 郑州大学 | Bifunctional catalyst β -Ni (OH) 2/NF, preparation method and application thereof |
| CN111054343A (en) * | 2019-12-11 | 2020-04-24 | 清华-伯克利深圳学院筹备办公室 | Electrocatalytic oxygen evolution material and preparation method thereof |
| CN111229232A (en) * | 2020-03-20 | 2020-06-05 | 苏州大学 | Foam nickel-based porous NiFe hydrotalcite nanosheet and preparation and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| An Advanced Ni-Fe Layered Double Hydroxide Electrocatalyst for Water Oxidation;Ming Dong et.al;《Journal of the American Chemical Society》;20130523;第135卷;摘要、第8452页右栏、第8453页左栏 * |
| Bifunctional Ni1-xFex layered double hydroxides/Ni foam electrodes for high-efficient overall water splitting: A study on compositional tuning and valence state evolution;Qingyun Liu et.al;《International Journal of Hydrogen Energy》;20160623;第42卷;第5560-5568页 * |
| Nanostructured hybrid NiFeOOH/CNT electrocatalysts for oxygen evolution reaction with low overpotential;Feng Rong et.al;《RSC Advances》;20160726;第74536-74544页 * |
| NiFe-based nanostructures on nickel foam as highly efficiently electrocatalysts for oxygen and hydrogen evolution reactions;Wei Zhang等;《Journal of Energy Chemistry》;20191215(第12期);第15页 * |
| 以泡沫镍为基底的镍铁类水滑石的制备及表征;韩银凤等;《化学工程师》;20181231;第276卷(第9期);第67-69页 * |
| 层状双金属氢氧化物用于催化水氧化的研究进展;王瑞瑞等;《化工学报》;20160131(第01期);第55-72页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112044442A (en) | 2020-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yao et al. | A chemical etching strategy to improve and stabilize RuO2-based nanoassemblies for acidic oxygen evolution | |
| CN108554413B (en) | Three-dimensional multi-stage structure high-dispersion nickel-based electro-catalytic material and preparation method thereof | |
| CN111111707B (en) | Selenium-doped nickel hercynite/nickel oxyhydroxide composite electrocatalyst material and preparation method and application thereof | |
| CN110711590B (en) | One-dimensional cobalt-sulfur compound/cuprous sulfide compound nano-array @ foamy copper material and preparation method and application thereof | |
| CN113019398B (en) | High-activity self-supporting OER electrocatalyst material and preparation method and application thereof | |
| CN111282588A (en) | Catalyst for hydrogen evolution by electrolyzing water and preparation method and application thereof | |
| CN112044442B (en) | Preparation method and application of beta-phase nickel iron hydroxide/carbon nanotube composite with atomic defects | |
| CN112962109B (en) | Preparation method and application of antimony-doped copper/cuprous oxide electro-catalytic material | |
| CN114214664A (en) | Cobalt-doped molybdenum disulfide electrocatalytic material and preparation method and application thereof | |
| Han et al. | Design yolk-shelled FeCo layered double hydroxide via a “one-stone-two-birds” strategy for oxygen evolution reaction | |
| CN110721700B (en) | Copper-cobalt-sulfur nanosheet array/molybdenum foil composite material, and preparation method and application thereof | |
| CN109097788B (en) | Double-carbon coupling transition metal nickel-based quantum dot electrocatalyst and preparation method thereof | |
| CN114774983B (en) | Ultra-small Ru nanocluster supported on MoO 3-x Double-function composite material of nano belt and preparation method and application thereof | |
| CN113355687B (en) | Tin-based bimetallic carbide @ carbon nanochain core-shell structure and preparation method and application thereof | |
| Yang et al. | Ce doped Co (PO3) 2@ NF bifunctional electrocatalyst for water decomposition | |
| CN114457373B (en) | Preparation method and application of monatomic material with Ni-N2+2 stereo configuration active sites | |
| CN112962117B (en) | Preparation method of graphene-molybdenum sulfide/molybdenum oxide nano composite and method for enhancing hydrogen evolution under near infrared | |
| CN115710726A (en) | Self-supporting transition metal hydroxide or oxide composite material, preparation method and application of self-supporting transition metal hydroxide or oxide composite material in electrocatalytic oxygen evolution | |
| CN115125578B (en) | Preparation method of B-S co-doped nickel-cobalt-based electrolytic water oxygen evolution catalyst | |
| CN114214636B (en) | Method for preparing cobalt-based nanosheet self-supporting electrode by selenium-containing ligand and application of cobalt-based nanosheet self-supporting electrode | |
| CN114574890B (en) | Self-forming phosphorus-doped redox graphene aerogel catalyst and preparation method and application thereof | |
| Gao et al. | Fabrication of CoTe2/Te composites for highly hydrogen evolution reaction in alkaline solution | |
| CN112960653B (en) | Sulfur-doped iron selenide nanorod material as well as preparation method and application thereof | |
| CN110064409B (en) | Pt/VS2Catalytic material, preparation method and application thereof | |
| Lu et al. | Phosphorus-rich CoP4@ NC Nanoarrays for Efficient Nitrate-to-Ammonia Electroreduction |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |