CN111558379B - Preparation method of hollow spherical black lead copper ore phase metal oxide electrocatalyst, electrocatalyst and application thereof - Google Patents
Preparation method of hollow spherical black lead copper ore phase metal oxide electrocatalyst, electrocatalyst and application thereof Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 49
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 22
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 12
- 239000010949 copper Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 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 abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 15
- 229910000906 Bronze Inorganic materials 0.000 claims description 11
- 239000010974 bronze Substances 0.000 claims description 11
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 5
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- 238000012360 testing method Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 3
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- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
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- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/33—
-
- B01J35/51—
-
- B01J35/60—
-
- 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
- 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
-
- 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 provides a preparation method of a hollow spherical black lead copper ore phase metal oxide electrocatalyst, which comprises the following steps: (1) uniformly mixing N, N-dimethylformamide and acetone to form a mixed solvent, respectively adding nickel nitrate hexahydrate, manganese nitrate tetrahydrate and isophthalic acid into the mixed solvent, and stirring to obtain a uniform mixed solution; (2) transferring the mixed solution into a high-pressure reaction kettle, heating and maintaining, cooling to room temperature, centrifuging, and washing to obtain a suspension; (3) putting the suspension into a glass culture dish, drying in an oven, transferring into a crucible, and performing heat treatment to obtain Ni6MnO8Hollow spheres, namely NMO-HS. The invention can prepare the electrocatalyst with a unique structure, has larger specific surface area, is beneficial to exposing more active sites and faster electron transfer capability, further shows smaller overpotential and Tafel slope in OER, has excellent stability and improves the catalytic performance of the catalyst.
Description
Technical Field
The invention relates to a preparation method of a hollow spherical black lead copper ore phase metal oxide electrocatalyst, the electrocatalyst and application thereof.
Background
With the shortage of energy and environmental pollution, people pay more attention to the problems. The hydrogen with the advantages of water, environmental friendliness and the like as a reaction product is considered to be one of ideal green energy ways in the future, wherein the electrochemical water dissociation provides a simple, efficient and clean energy storage and conversion technology for preparing the hydrogen. Electrochemical water dissociation consists of two important reactions: hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER). However, the multi-step proton-coupled electron transfer and slow kinetics of OER greatly limit electrochemical water splitting. To date, Ru and Ir-based compounds remain the best catalysts for OER, but their scarcity and high cost have prevented their widespread use. Therefore, it is important and urgent to search for low-cost and high-efficiency OER electrocatalysts.
In recent years, transition metal oxides, particularly the first row of 3d metals (e.g., Ni, Co, Fe, and Mn), have attracted considerable attention from researchers due to their abundant and inexpensive reserves. In addition to this, in order to improve the catalytic activity of the catalyst, enhancing the activity of the catalyst itself and increasing the density of active sites are considered as two important effective methods. The number of active sites can be effectively increased by designing the morphology structure of the catalyst, so that the catalytic activity of the catalyst is enhanced. Meanwhile, according to literature reports, the bimetallic or trimetallic oxide can improve the inherent activity of the electrocatalyst by the synergistic effect of metals, adjusting the electronic structure, and the like.
In view of the above problems, there is a need to develop a new method for preparing an OER electrocatalyst with low cost and high efficiency.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a hollow spherical black lead copper ore phase metal oxide electrocatalyst, the electrocatalyst and application thereof, and the prepared electrocatalyst has the characteristics of high stability and excellent catalytic performance.
The first purpose of the invention is to provide a preparation method of a hollow sphere black lead copper ore phase metal oxide electrocatalyst, which comprises the following steps:
(1) uniformly mixing N, N-dimethylformamide and acetone to form a mixed solvent, respectively adding nickel nitrate hexahydrate, manganese nitrate tetrahydrate and isophthalic acid into the mixed solvent, and stirring to obtain a uniform mixed solution;
(2) transferring the mixed solution into a high-pressure reaction kettle, heating and maintaining, cooling to room temperature, centrifuging, and washing to obtain a suspension;
(3) putting the suspension into a glass culture dish, drying the suspension in an oven, transferring the suspension into a crucible, and carrying out heat treatment to obtain Ni6MnO8Hollow spheres, namely NMO-HS.
Specifically, in the step (1), the feeding molar ratio of the nickel nitrate hexahydrate, the manganese nitrate tetrahydrate and the isophthalic acid is 1-2:1-2: 3.
Specifically, in the step (1), the feeding volume ratio of the N, N-dimethylformamide to the acetone is 1: 0.8-1.2.
Specifically, in the step (2), the mixed solution is transferred to a high-pressure reaction kettle and is kept at 150-170 ℃ for 3-5h, and the suspension is obtained by using absolute ethyl alcohol and deionized water for centrifugation and washing.
Specifically, in the step (3), the temperature for drying in the oven is 50-70 ℃.
Specifically, in the step (3), the heat treatment is calcination in air at 480-520 ℃ for 25-35min and at 3 ℃ for 3 min-1The heating rate of (3) to effect calcination.
The second purpose of the invention is to provide an electrocatalyst, which is prepared by the preparation method of the hollow sphere black lead copper ore phase metal oxide electrocatalyst.
A third object of the present invention is to provide a use of the above electrocatalyst for oxygen evolution.
The preparation method of the hollow spherical black lead copper ore phase metal oxide electrocatalyst can prepare the electrocatalyst with a unique structure, has a larger specific surface area, is beneficial to exposing more active sites and faster electron transfer capacity, further shows smaller overpotential and Tafel slope in OER, has excellent stability, and improves the catalytic performance of the catalyst. The invention provides a new way for preparing the OER-oriented binary transition metal oxide in an efficient and controllable manner.
Drawings
FIGS. 1a) and b) SEM images of NMO-HS of example 1 of the present invention at different magnifications; c) TEM image of NMO-HS of inventive example 1; d) HRTEM image of NMO-HS of example 1 of the present invention;
FIG. 2a) is an X-ray diffraction diagram of NMO-HS according to example 1 of the present invention; b) n of NMO-HS according to example 1 of the invention2Adsorption and desorption isotherms, and the inset is the corresponding pore size distribution of the sample;
FIG. 3 OER electrochemical Performance of NMO-HS of example 1 of the invention: a) an LSV curve; b) tafel plot from a); c) double electric layer capacitor C of NMO-HS of the inventiondl(ii) a d) Electrochemical impedance spectroscopy of the NMO-HS material of the present invention.
Detailed Description
The invention provides a preparation method of a hollow sphere black lead copper ore phase metal oxide electrocatalyst, the electrocatalyst and application thereof.
The hollow sphere black lead copper ore phase metal oxide electrocatalyst is Ni6MnO8Hollow spheres (NMO-HS).
Firstly, the method comprises the following steps: ni6MnO8The preparation process of the hollow sphere (NMO-HS) comprises the following steps:
(1) uniformly mixing N, N-dimethylformamide and acetone to form a mixed solvent, respectively adding nickel nitrate hexahydrate, manganese nitrate tetrahydrate and isophthalic acid into the mixed solvent, and stirring to obtain a uniform mixed solution; the feeding molar ratio of the nickel nitrate hexahydrate, the manganese nitrate tetrahydrate and the isophthalic acid is 1-2:1-2: 3. The feeding volume ratio of the N, N-dimethylformamide to the acetone is 1: 9-11.
(2) Transferring the mixed solution into a high-pressure reaction kettle, keeping the temperature of the high-pressure reaction kettle at 150-170 ℃ for 3-5h, cooling the high-pressure reaction kettle to room temperature, centrifuging the high-pressure reaction kettle by using absolute ethyl alcohol and deionized water, and washing the high-pressure reaction kettle to obtain suspension.
(3) Placing the suspension in a glass culture dish, drying in an oven (50-70 deg.C), transferring to a crucible, and performing heat treatment (calcining at 500 deg.C in air for 30min, and calcining at 3 deg.C for 3 min)-1Heating rate of (3) to obtain Ni)6MnO8Hollow spheres, namely NMO-HS.
The application of the prepared electrocatalyst in oxygen evolution specifically comprises the following steps:
(1) the prepared electrocatalyst sample (5mg) and acetylene black (5mg) were dissolved in Nafion solution (0.095mL) and ethanol (0.35mL), and they were sonicated for 30 minutes to form a uniform catalyst ink. Thereafter, a catalyst ink (7. mu.L) was dropped onto a glassy carbon electrode (GC, diameter 5mm, surface area 0.196 cm)2) And dried in air at room temperature. Finally, a uniform and smooth catalyst film covering the glassy carbon electrode (mass loading: 0.4mg cm) can be obtained-2)。
(2) For removing impurities from the surface of the catalyst, in N2Saturated 0.1MKOH solution at 50 mV s-1The cyclic voltammetry test was performed at a scan rate of 0 to 0.965V (relative to the reversible hydrogen electrode).
(3) And (3) testing the Oxygen Evolution Reaction (OER) performance of the catalyst by adopting a linear sweep voltammetry method. The test conditions were: at a speed of 1600rpm and 10mV s-1At a scanning speed of N2The test was performed in a saturated 0.1m koh electrolyte and the test voltage range was: 0.965V-1.865V (relative to reversible hydrogen electrode).
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry.
Example 1 this example provides a method for preparing a hollow sphere black lead bronze phase metal oxide electrocatalyst, an electrocatalyst and its use, comprising the steps of:
(1) uniformly mixing 30mL of LN, N-dimethylformamide and 30mL of acetone to form a mixed solvent, respectively adding 0.117g of nickel nitrate hexahydrate, 0.0497g of manganese nitrate tetrahydrate and 0.0997g of isophthalic acid into the mixed solvent, and stirring for 90min to obtain a uniform mixed solution;
(2) and transferring the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, keeping the mixed solution at 160 ℃ for 4 hours, cooling the mixed solution to room temperature, and centrifuging and washing the cooled mixed solution by using absolute ethyl alcohol and deionized water to obtain a suspension.
(3) Placing the suspension in a glass culture dish, drying in a 60 deg.C oven, transferring to a crucible, and performing heat treatment (calcining at 500 deg.C in air for 30min, and at 3 deg.C for 3 min)-1Heating rate of (3) to obtain Ni)6MnO8Hollow spheres, namely NMO-HS. .
The electrocatalyst synthesized above was applied to oxygen evolution.
Example 2 this example provides a method of preparing a hollow sphere black lead bronze phase metal oxide electrocatalyst, an electrocatalyst and its use, which is substantially identical to that of example 1 except that: in the step (1), the feeding molar ratio of nickel nitrate hexahydrate, manganese nitrate tetrahydrate and isophthalic acid is 1: 2: 3.
example 3 this example provides a method of preparing a hollow sphere black lead bronze phase metal oxide electrocatalyst, an electrocatalyst and its use, which is substantially identical to that of example 1 except that: in the step (1), the feeding molar ratio of nickel nitrate hexahydrate, manganese nitrate tetrahydrate and isophthalic acid is 1: 1: 3.
example 4 this example provides a method of preparing a hollow sphere black lead bronze phase metal oxide electrocatalyst, an electrocatalyst and its use, which is substantially identical to that of example 1 except that: in step (2), the temperature is maintained at 150 ℃ for 3 h.
Example 5 this example provides a method of preparing a hollow sphere black lead bronze phase metal oxide electrocatalyst, an electrocatalyst and its use, which is substantially identical to that of example 1 except that: in step (2), the temperature is kept at 170 ℃ for 5 h.
Comparative example 1 this comparative example provides a method of preparing a hollow sphere black lead bronze phase metal oxide electrocatalyst, an electrocatalyst and its use, which is essentially the same as in example 1 except that: in the step (1), the feeding molar ratio of nickel nitrate hexahydrate, manganese nitrate tetrahydrate and isophthalic acid is 2: 1: 5.
comparative example 2 this comparative example provides a method of preparing a hollow sphere black lead bronze phase metal oxide electrocatalyst, an electrocatalyst and its use, which is essentially the same as in example 1 except that: in the step (1), the feeding molar ratio of nickel nitrate hexahydrate, manganese nitrate tetrahydrate and isophthalic acid is 2: 1: 1.
comparative example 3 this comparative example provides a method of preparing a hollow sphere black lead bronze phase metal oxide electrocatalyst, an electrocatalyst and its use, which is essentially the same as in example 1 except that: in step (2), the temperature is kept at 140 ℃ for 5 h.
The following table is a table of performance test data for the electrocatalysts prepared in examples 1-7 and comparative examples 1-3:
| initial potential | Overpotential @10mA cm-2 | Current density @1.65V | |
| Example 1 | 1.596 V | 451 mV | 5.54mA cm-2 |
| Example 2 | 1.632V | 463mV | 5.09mA cm-2 |
| Examples3 | 1.623V | 462mV | 5.10mA cm-2 |
| Example 4 | 1.618V | 456mV | 5.24mA cm-2 |
| Example 5 | 1.624V | 462mV | 5.14mA cm-2 |
| Comparative example 1 | 1.643V | 472mV | 4.61mA cm-2 |
| Comparative example 2 | 1.656V | 484mV | 4.12mA cm-2 |
| Comparative example 3 | 1.651V | 475mV | 4.65mA cm-2 |
It can be seen from examples 1-3 and comparative examples 1-2 that by varying the molar ratio of the different precursors, the catalysts prepared exhibit different properties. The feeding molar ratio of nickel nitrate hexahydrate, manganese nitrate tetrahydrate and isophthalic acid in the precursor is 2: 1: 3, the best electrocatalytic performance is shown.
As can be seen from examples 1, 4 to 5 and comparative example 3, there was little change in the performance of the prepared catalyst by setting different hydrothermal reaction temperatures and times, and the performance was degraded as the hydrothermal reaction temperature and time were increased.
FIGS. 1a and b show Ni synthesized as hollow sphere structure in example 16MnO8SEM image of the material (NMO-HS), TEM image of FIG. 1c shows that the hollow sphere structure is prepared, and as shown in FIG. 1d, the interplanar spacing of NMO-HS is determined to be 0.251nm and 0.48nm, corresponding to Ni in the BlueCorte phase, respectively6MnO8The (113) and (111) crystal planes of (c).
FIG. 2a shows the X-ray diffraction (XRD) pattern of the NMO-HS sample of example 1, together with Ni in the black lead bronze phase6MnO8Is consistent with (JCPDS No. 49-1295). Wherein NMO-HS shows strong diffraction peaks at 2 θ ═ 18.49 °, 30.36 °, 35.76 °, 37.38 °, 43.45 °, 57.56 ° and 63.11 °, corresponding to Ni of the black-plumbite phase, respectively6MnO8The (111), (022), (113), (222), (004), (333) and (044) crystal planes of (c). FIG. 2b shows N as NMO-HS sample2The adsorption and desorption curves are shown as type IV isotherms. The corresponding pore size distribution of the NMO-HS catalyst is shown in the inset of fig. 2b, indicating that the samples all have a mesoporous structure, which facilitates the permeation and transport of electrolyte and oxygen.
FIGS. 3a and b show NMO-HS of example 1 at 10mA cm-2The overpotential under the current density is 451 mV, and the Tafel slope is 109mVdec-1. As shown in fig. 3c and d, the double layer capacitance test and the electrochemical impedance spectroscopy test of NMO-HS demonstrated that NMO-HS possessed a large electrochemically active area and excellent conductivity properties.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (5)
1. A preparation method of a hollow sphere black lead copper ore phase metal oxide electrocatalyst is characterized by comprising the following steps:
(1) uniformly mixing N, N-dimethylformamide and acetone to form a mixed solvent, respectively adding nickel nitrate hexahydrate, manganese nitrate tetrahydrate and isophthalic acid into the mixed solvent, and stirring to obtain a uniform mixed solution; the feeding molar ratio of the nickel nitrate hexahydrate, the manganese nitrate tetrahydrate and the isophthalic acid is 1-2:1-2: 3;
(2) transferring the mixed solution into a high-pressure reaction kettle, heating and maintaining, cooling to room temperature, centrifuging, and washing to obtain a suspension; transferring the mixed solution into a high-pressure reaction kettle, keeping the temperature of the high-pressure reaction kettle at 150-170 ℃ for 3-5 hours, and centrifuging and washing the high-pressure reaction kettle by using absolute ethyl alcohol and deionized water to obtain a suspension;
(3) putting the suspension into a glass culture dish, drying the suspension in an oven, transferring the suspension into a crucible, and carrying out heat treatment to obtain Ni6MnO8Hollow spheres, namely NMO-HS; the heat treatment is calcining in air at 480-520 deg.C for 25-35min, and at 3 deg.C for 3 min-1The heating rate of (3) to effect calcination.
2. The method of preparing a hollow sphere black lead bronze phase metal oxide electrocatalyst according to claim 1, wherein: in the step (1), the feeding volume ratio of the N, N-dimethylformamide to the acetone is 1: 0.8-1.2.
3. The method of preparing a hollow sphere black lead bronze phase metal oxide electrocatalyst according to claim 1, wherein: in the step (3), the drying temperature in the oven is 50-70 ℃.
4. An electrocatalyst prepared by a method of preparing a hollow sphere black lead copper ore phase metal oxide electrocatalyst according to any one of claims 1 to 3.
5. Use of an electrocatalyst according to claim 4 for oxygen evolution.
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| CN202010433700 | 2020-05-21 | ||
| CN2020104337005 | 2020-05-21 |
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| CN111558379B true CN111558379B (en) | 2021-02-09 |
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