CN113941331B - Stabilizing Ni on surface of catalyst 3+ Method for active site and application - Google Patents
Stabilizing Ni on surface of catalyst 3+ Method for active site and application Download PDFInfo
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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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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Abstract
The invention relates to a method for stabilizing Ni on the surface of a catalyst 3+ Method for preparing metal-defective Co by using active site and application of active site 3‑x O 4 Co is to 3‑x O 4 Co is prepared by compounding with NiO as an electron acceptor carrier 3‑ x O 4 NiO catalyst by Co 3‑x O 4 The strong electron interaction between NiO and NiO accelerates electron transport and promotes Ni on the surface of the catalyst 2+ To Ni 3+ Thereby stabilizing the catalyst surface Ni 3+ An active site. The invention can effectively stabilize the Ni on the surface of the catalyst 3+ Active site, construction Co 3‑x O 4 The NiO powder catalyst has simple preparation process, low cost and easy industrial application. Contains rich Ni 3+ Co of (C) 3‑ x O 4 The NiO can effectively regulate the adsorption configuration of oxygen-containing intermediates (OH, O and OOH), has proper binding energy, reduces the change of free energy of Gibbs, improves conductivity, accelerates OER reaction kinetics, and has great application prospect in electrocatalytic moisture analysis oxygen reaction.
Description
Technical Field
The invention belongs to the technical field of nano material synthesis and electrocatalysis, and in particular relates to a method for stabilizing Ni on the surface of a catalyst 3+ Methods and uses of active sites.
Background
Currently, the large consumption of traditional fossil fuels makes energy crisis and environmental problems two major issues facing human society. The development and utilization of novel renewable and clean energy sources is an important approach to solve energy and environmental problems. Among them, hydrogen energy is an effective substitute for traditional fossil fuels due to the characteristics of clean and pollution-free properties, high energy density, etc. Electrocatalytic water decomposition is an effective method for achieving large-scale hydrogen production. However, oxygen Evolution Reactions (OER) occurring at the anode of electrocatalytic water splitting devices involve complex 4-electron transfer processes and exhibit slow reaction kinetics. At present, noble metal catalysts (such as Ir and Ru-based catalysts) can accelerate the water decomposition kinetics and reduce the reaction overpotential so as to have high electrocatalytic efficiency, but the problems of high cost, scarcity, lower durability and the like of noble metal materials limit the wide application of the noble metal materials. Therefore, the design and synthesis of the non-noble metal-based OER (oxygen evolution reaction) catalyst with excellent performance is of great significance for realizing large-scale electrocatalytic water electrolysis hydrogen production reaction.
Recently, cobalt-based and nickel-based transition metal oxides have been widely used to electrocatalytic OER. However, single types of metal oxide catalysts have insufficient catalytically active sites, poor conductivity and electron transfer capability, and too strong/weak binding energy of oxygen-containing intermediates to meet commercial applications. The construction of heterogeneous nanostructures using interface engineering strategies is considered an effective strategy to improve OER performance. Many studies have demonstrated that, due to the appropriate electronic structure (3 d 7 ,t 2g 6 e g 1 )，Ni 3+ Plays a key role in improving OER performance. However, ni having high formation energy in NiO 3+ The surface sites are not stable. Furthermore, differences in the lattice strain of elements in heterogeneous nanostructures lead to differences in their redox potential and structural order. Therefore, how to increase the surface Ni 3+ The structural stability of the sites, further enhancing OER performance, is very important and highly desirable.
The strength of the interaction between the two components in the heterogeneous nanostructure has a significant impact on the activity and stability of the catalyst. Using metal-deficient Co 3-x O 4 As electron acceptor carriers, not only Co can be used 3-x O 4 The strong electron interaction of NiO accelerates electron transport, promoting surface Ni 2+ To Ni 3+ And can stabilize the catalyst surface Ni 3+ Active sites, thereby improving catalyst activity and stability.
Disclosure of Invention
One of the purposes of the present invention is to propose a stable catalyst surface Ni 3+ Active site method using metal-deficient Co 3-x O 4 Strategy of compounding NiO nanoclusters by Co 3-x O 4 The strong electron interaction between NiO and NiO accelerates electron transport, and promotes the surface Ni 2+ To Ni 3+ Is used for solving the transformation of Ni on the surface of the catalyst 3+ The method has the advantages of simplicity, low cost and industrial application prospect.
Another object of the present invention is to provide Co obtained by the aforementioned method 3-x O 4 Use of a NiO powder catalyst in a highly efficient electrocatalytic moisture desorption oxygen reaction.
The invention is realized by the following technical proposal, and the invention provides a method for stabilizing Ni on the surface of a catalyst 3+ The active site method specifically comprises the following steps: preparation of Metal deficient Co 3-x O 4 In the metal-deficient Co 3-x O 4 In which the molar ratio of Co to O is less than 0.75, co is added to the catalyst 3-x O 4 Co is prepared by compounding with NiO as an electron acceptor carrier 3-x O 4 NiO catalyst by Co 3-x O 4 The strong electron interaction between NiO and NiO accelerates electron transport and promotes Ni on the surface of the catalyst 2+ To Ni 3+ Thereby stabilizing the catalyst surface Ni 3+ An active site.
The surface Ni of the stable catalyst 3+ The active site method specifically comprises the following steps:
(1) Preparation of Metal deficient Co 3-x O 4 Nanoparticles
Fully mixing cobalt acetate and glycerin in a polytetrafluoroethylene-lined hydrothermal kettle, magnetically stirring for 1h, placing the hydrothermal kettle in a 180 ℃ oven for constant-temperature hydrothermal treatment for 2h, naturally cooling, centrifuging the obtained solution, collecting the obtained solid, washing with absolute ethyl alcohol, drying, roasting the dried sample in a tubular furnace at 300 ℃ for 2h in the air atmosphere,obtaining the metal defective Co 3-x O 4 A nanoparticle;
(2) Preparation of Co 3-x O 4 NiO powder catalyst
Nickel acetate and Co 3-x O 4 Uniformly mixing the nano particles in absolute ethyl alcohol, and carrying out ultrasonic treatment for 2 hours; transferring the obtained solution into a polytetrafluoroethylene-lined hydrothermal kettle, and placing the hydrothermal kettle in a 180 ℃ oven to keep the constant temperature for 2 hours; washing the obtained sample with absolute ethyl alcohol, centrifuging, drying, calcining for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, and finally obtaining Co 3-x O 4 NiO powder catalyst.
Further, in the step (1), the amount of cobalt acetate is 1g, the amount of glycerin is 1-80g, and the obtained metal-deficient Co 3-x O 4 The molar ratio of Co to O in the nanoparticle was 0.56 or 0.65.
Further, nickel acetate and Co in step (2) 3-x O 4 The molar ratio of (3) is 20:1 or 15:1 or 10:1 or 8:1 or 4:1 or 2:1 or 1:1 or 1:2 or 1:4 or 1:8 or 1:10 or 1:15 or 1:20).
Further, the heating rates of the tube furnace and the oven are 5 ℃/min.
Further, the obtained Co 3-x O 4 NiO is a spherical nanoparticle with a diameter of 20nm.
The surface Ni of the stable catalyst 3+ Active site method, co prepared 3-x O 4 The application of the NiO powder catalyst in the electrocatalytic water analysis oxygen reaction specifically comprises the following steps:
(1) Preparation of working electrode
5mg of prepared Co 3-x O 4 NiO catalyst and 1mg of conductive carbon (VXC-72 RC) were dispersed in 1mL of an isopropanol/water (3:1 by volume) solution containing 10. Mu.L of 5wt% Nafion, and a homogeneous catalyst mixture was formed after sonication. Then 25. Mu.L of the obtained catalyst mixture was uniformly coated on the glassy carbon electrode and naturally dried at room temperature. Air-drying overnight to obtain Co 3-x O 4 A NiO working electrode.
(2) Electrocatalytic moisture analysis oxygen Performance test
OER performance tests were performed on the CHI 760E electrochemical workstation using a three electrode system, 1M KOH as electrolyte. The glassy carbon electrode (diameter is 5 nm) loaded with the catalyst is used as a working electrode, the reference electrode is an Hg/HgO electrode, and the counter electrode is a graphite rod electrode.
Using a scan rate of 10mVs -1 Linear sweep voltammetry of (c) gives an iR uncorrected polarization curve. By using the Nernst equation (E RHE ＝E M +0.059×ph+0.109), the measured potential can be converted to a Reversible Hydrogen Electrode (RHE) potential.
Electrochemical Impedance Spectroscopy (EIS) measurement is in the range of 0.01-10 5 Measured at 0.68V (vs Hg/HgO) applied in the frequency range of Hz.
Chronopotentiometric test at 10mAcm -1 At a current density of foamed nickel (1X 1 cm) 2 25. Mu.L of the catalyst mixture was added dropwise, and naturally dried) for 24 hours.
Prior to electrochemical testing, the solution was saturated with oxygen continuously to 1M KOH solution and stirring was continued to promote gas diffusion.
Electrochemical performance testing found: co (Co) 3-x O 4 NiO at 10mAcm -2 And 50mAcm -2 The lower has low overpotential of 252mV and 341mV, and the decrease of activity after long-term (greater than 24 h) stability test is negligible. Co (Co) 3-x O 4 NiO has a low Taphill slope (76 mVdec -1 ) And high TOF value (0.025 s -1 380mV overpotential). Co (Co) 3-x O 4 NiO has a high electrochemical active area (ECSA, 1033.3 cm) 2 )。
The beneficial technical effects of the invention are as follows:
(1) The invention adopts metal defective Co 3-x O 4 As an electron acceptor carrier, ni on the surface of the catalyst can be effectively stabilized 3+ Active site, thus constructing Co 3-x O 4 NiO powder catalyst and is used for electrocatalytic water analysis oxygen reaction. Co (Co) 3-x O 4 The preparation process of the NiO powder catalyst is simple, the cost is low, and the NiO powder catalyst is easy to control and apply industrially.
(2) In the electric fieldIn chemistry, contains rich Ni 3+ Co of (C) 3-x O 4 NiO can effectively regulate the adsorption configuration of oxygen-containing intermediates (OH, O and OOH) and has proper binding energy, so that the change of gibbs free energy is reduced, the conductivity is improved, and the OER reaction kinetics is accelerated. NiO and Co 3-x O 4 The strong electron interaction between the two leads to good stability of the catalyst.
Drawings
FIG. 1 is a Co of the present invention 3-x O 4 Schematic of NiO powder catalyst synthesis.
FIG. 2 is Co in example 1 3-x O 4 NiO powder type catalyst electron microscope and element distribution diagram.
FIG. 3 is Co in example 1 3-x O 4 XRD pattern of NiO powder catalyst.
FIG. 4 is Co in example 1 3-x O 4 XPS diagram of NiO powder catalyst.
FIG. 5 is Co in example 1 3-x O 4 Electrocatalytic oxygen evolution polarization curve of NiO powder catalyst.
FIG. 6 is Co in example 1 3-x O 4 Stability performance diagram of NiO powder catalyst.
FIG. 7 is Co in example 1 3-x O 4 Electric double layer capacitance of NiO powder catalyst.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following specific examples and drawings. The following examples are based on the technology of the present invention and give detailed embodiments and operation steps, but the scope of the present invention is not limited to the following examples.
Example 1
1g of cobalt acetate and 37.5g of glycerin are weighed and uniformly mixed in a 100mL hydrothermal kettle, after magnetic stirring for 1h, the hydrothermal kettle is put in a 180 ℃ oven for constant temperature hydrothermal treatment for 2h. After natural cooling, the resulting solution was centrifuged and the resulting violet solid was collected and washed 3-5 times with absolute ethanol followed by drying in an oven at 60 ℃ for 12h. Roasting the dried sample at 300 ℃ in the air atmosphere in a tube furnace for 2h, the heating rate of the tube furnace is 5 ℃/min, and finally the cobalt-defect type Co rich in metal defects is obtained 3-x O 4 Elemental analysis and XPS characterization to obtain cobalt-defect Co 3-x O 4 The molar ratio of Co to O was about 0.56. Subsequently, nickel acetate and Co in a molar ratio of 1:4 were reacted 3-x O 4 Uniformly mixing in absolute ethyl alcohol, carrying out ultrasonic treatment for 2 hours, transferring the obtained solution into a polytetrafluoroethylene-lined hydrothermal kettle, and placing the hydrothermal kettle in a 180 ℃ oven for constant temperature maintenance for 2 hours, wherein the heating rate of the oven is 5 ℃/min. Washing the obtained solid sample with absolute ethyl alcohol, centrifugally drying, calcining for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, and finally obtaining Co 3-x O 4 NiO powder catalyst.
FIG. 1 is Co 3-x O 4 Schematic of the process of synthesizing NiO powder catalyst.
Fig. 2 is a transmission electron microscope image and an element distribution diagram of the catalyst obtained in this example. As can be seen from the figure, co 3-x O 4 NiO is in the form of spherical nanoparticles with the diameter of 20nm and has obvious polycrystalline characteristics. Lattice fringes of 0.209nm correspond to the (200) crystal plane of NiO, and lattice fringes of 0.470nm and 0.291nm correspond to Co 3-x O 4 The (111) and (220) planes. NiO and Co 3-x O 4 There is a distinct phase interface between them. EDS results showed uniform distribution of Ni, co and O elements and determined that the atomic proportions of Co and Ni were 31.60% and 1.21%, respectively.
FIG. 3 is Co 3-x O 4 /NiO、Co 3-x O 4 、Co 3 O 4 Is shown to correspond to cubic phase Co with peaks of 2θ=19°, 31.3 °, 36.8 °, 38.5 °, 44.8 °, 55.7 °, 59.4 ° and 65.2 ° 3 O 4 (111), (220), (311), (222), (400), (220), (511) and (440). For Co 3-x O 4 NiO and Co 3 O 4 The NiO powder catalyst has low loading and small size, and no diffraction peak of NiO is found. Furthermore, due to the similar ionic radius (Co 3+ ，0.61nm；Ni 2+ 0.69 nm) and a small amount of NiO, no peak shift occurred. But due to heterostructure formation, peak intensityAnd (3) lowering.
FIG. 4 (a) is Co 3-x O 4 XPS plot of Ni in NiO sample, FIG. 4 (b) is Co 3-x O 4 /NiO、Co 3-x O 4 、Co 3 O 4 XPS for Co in sample, FIG. 4 (c) is Co 3-x O 4 /NiO、Co 3-x O 4 、Co 3 O 4 XPS plot of O in samples. For Co 3-x O 4 /NiO，Ni 3+ Located at 855.7eV and 873.2eV, ni 2+ Located at 854.2eV and 871.6eV. Co (Co) 3-x O 4 NiO surface Ni 3+ The content was 84.62% calculated as the integrated area. With Co 3 O 4 In comparison with Co 3-x O 4 NiO and Co 3-x O 4 The Co 2p peak of (c) shifts to lower binding energy. Wherein the surface Co 3+ And Co 2+ In Co 3-x O 4 The element content of NiO is 51.44% and 48.56%, respectively, in Co 3-x O 4 The element content in the alloy is 50.78% and 49.22%, respectively, in Co 3 O 4 The element content in the steel is 43.20% and 56.80%, respectively. Clearly, the presence of cobalt defects contributes to surface Co 3+ Increased content of Co 3-x O 4 NiO and Co 3-x O 4 With similar surface Co 3+ The content is as follows. The O1s spectrum of the sample shows that the peak at 529.8eV corresponds to the lattice oxygen generated by Co-O and Ni-O bonds. The 532eV peak corresponds to defective O 2- /O - Species, indicating Co 3 O 4 Oxygen vacancies exist in the reactor. The peaks of 531-531.3eV are due to hydroxyl groups and physically adsorbed moisture.
Co prepared in this example 3-x O 4 The NiO catalyst was fabricated into electrochemical electrodes and its application in electrocatalytic moisture-resolved oxygen reactions was studied:
(1) Preparation of working electrode
5mg of prepared Co 3-x O 4 NiO catalyst and 1mg of conductive carbon (VXC-72 RC) were dispersed in 1mL of an isopropyl alcohol/water (3:1) solution containing 10. Mu.L of 5wt% Nafion, and a homogeneous catalyst mixture was formed after sonication. Then 20. Mu.L of the obtained catalyst mixture was uniformly coated on a glassy carbon electrode and at room temperatureNaturally drying, and air-drying overnight to obtain Co 3-x O 4 A NiO working electrode.
(2) Electrocatalytic moisture analysis oxygen Performance test
OER performance tests were performed on the CHI 760E electrochemical workstation using a three electrode system, 1M KOH as electrolyte. Loaded with Co 3-x O 4 The glassy carbon electrode (diameter 5 nm) of the NiO catalyst is used as a working electrode, the reference electrode is an Hg/HgO electrode filled with 1M KOH solution, and the counter electrode is a graphite rod electrode.
Using a scan rate of 10mVs -1 Linear sweep voltammetry of (c) gives an iR uncorrected polarization curve. By using the Nernst equation (E RHE ＝E M +0.059×ph+0.109), the measured potential can be converted to a Reversible Hydrogen Electrode (RHE) potential. Electrochemical Impedance Spectroscopy (EIS) measurement is in the range of 0.01-10 5 Measured at 0.68V (vs Hg/HgO) applied in the frequency range of Hz. Chronopotentiometric test at 10mAcm -1 At a current density of foamed nickel (1X 1 cm) 2 25. Mu.L of the catalyst mixture was added dropwise, and naturally dried) for 24 hours. Prior to electrochemical testing, the solution was saturated with oxygen continuously to 1M KOH solution and stirring was continued to promote gas diffusion.
FIG. 5 is Co obtained in this example 3-x O 4 The electrocatalytic oxygen evolution polarization curve graph of the NiO powder catalyst shows that Co 3-x O 4 NiO at 0.1mAcm -2 At the initial potential (E onset ) And at 10mAcm -2 The overpotential at this point is much lower than Co 3 O 4 /NiO、Co 3-x O 4 And Co 3 O 4 。Co 3-x O 4 NiO at 10mAcm -2 And 50mAcm -2 Lower have low overpotential of 252mV and 341mV and have higher OER activity than other samples.
FIG. 6 is Co obtained in this example 3-x O 4 Stability performance graph of NiO powder catalyst, after 24 hours stability test, the activity of the catalyst is hardly attenuated.
FIG. 7 is Co obtained in this example 3-x O 4 Electric double layer capacitor of NiO powder catalyst, its electric double layer capacitorValues up to 62.0mF/cm 2 Further calculate Co 3-x O 4 The electrochemical active area of the NiO powder catalyst is up to 1033.3cm 2 (ECSA＝C dl /C s Wherein C s Is 0.06mF/cm 2 )。
Example 2
1g of cobalt acetate and 9.5g of glycerol are weighed and uniformly mixed in a 100mL hydrothermal kettle, after magnetic stirring for 1h, the hydrothermal kettle is placed in a 180 ℃ oven for constant temperature hydrothermal treatment for 2h. After natural cooling, the resulting solution was centrifuged and the resulting violet solid was collected and washed 3-5 times with absolute ethanol followed by drying in an oven at 60 ℃ for 12h. Roasting the dried sample for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, wherein the heating rate of the tube furnace is 5 ℃/min, and finally obtaining the cobalt-defective Co rich in metal defects 3-x O 4 Elemental analysis and XPS characterization to obtain cobalt-defect Co 3-x O 4 The molar ratio of Co to O was about 0.65. Subsequently, nickel acetate and Co in a molar ratio of 1:4 were reacted 3-x O 4 Uniformly mixing in absolute ethyl alcohol, carrying out ultrasonic treatment for 2 hours, transferring the obtained solution into a hydrothermal kettle lined with polytetrafluoroethylene, placing the hydrothermal kettle in a 180 ℃ oven, keeping the constant temperature for 2 hours, and keeping the temperature rise rate of the oven at 5 ℃/min. Washing the obtained solid sample with absolute ethyl alcohol, centrifuging, drying, calcining for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, and finally obtaining Co 3-x O 4 NiO powder catalyst.
Example 3
1g of cobalt acetate and 75.8g of glycerin are weighed and uniformly mixed in a 100mL hydrothermal kettle, after magnetic stirring for 1h, the hydrothermal kettle is placed in a 180 ℃ oven for constant temperature hydrothermal treatment for 2h. After natural cooling, the resulting solution was centrifuged and the resulting violet solid was collected and washed 3-5 times with absolute ethanol followed by drying in an oven at 60 ℃ for 12h. Roasting the dried sample for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, wherein the heating rate of the tube furnace is 5 ℃/min, and finally obtaining the cobalt-defective Co rich in metal defects 3-x O 4 Elemental analysis and XPS characterization to obtain cobalt-defect Co 3-x O 4 The molar ratio of Co to O was about 0.56. Subsequently, nickel acetate and Co in a molar ratio of 1:4 were reacted 3-x O 4 In the absence of water BMixing the materials in alcohol uniformly, carrying out ultrasonic treatment for 2 hours, transferring the obtained solution into a hydrothermal kettle lined with polytetrafluoroethylene, and keeping the hydrothermal kettle at a constant temperature in a 180 ℃ oven for 2 hours, wherein the temperature rising rate of the oven is 5 ℃/min. Washing the obtained solid sample with absolute ethyl alcohol, centrifuging, drying, calcining for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, and finally obtaining Co 3-x O 4 NiO powder catalyst.
Example 4
1g of cobalt acetate and 37.5g of glycerin are weighed and uniformly mixed in a 100mL hydrothermal kettle, after magnetic stirring for 1h, the hydrothermal kettle is placed in a 180 ℃ oven for constant temperature hydrothermal treatment for 2h. After natural cooling, the resulting solution was centrifuged and the resulting violet solid was collected and washed 3-5 times with absolute ethanol followed by drying in an oven at 60 ℃ for 12h. Roasting the dried sample for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, wherein the heating rate of the tube furnace is 5 ℃/min, and finally obtaining the cobalt-defective Co rich in metal defects 3-x O 4 Elemental analysis and XPS characterization to obtain cobalt-defect Co 3-x O 4 The molar ratio of Co to O was about 0.56. Subsequently, nickel acetate and Co in a molar ratio of 1:8 were reacted 3-x O 4 Uniformly mixing in absolute ethyl alcohol, carrying out ultrasonic treatment for 2 hours, transferring the obtained solution into a hydrothermal kettle lined with polytetrafluoroethylene, placing the hydrothermal kettle in a 180 ℃ oven, keeping the constant temperature for 2 hours, and keeping the temperature rise rate of the oven at 5 ℃/min. Washing the obtained solid sample with absolute ethyl alcohol, centrifuging, drying, calcining for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, and finally obtaining Co 3-x O 4 NiO powder catalyst.
Example 5
1g of cobalt acetate and 37.5g of glycerin are weighed and uniformly mixed in a 100mL hydrothermal kettle, after magnetic stirring for 1h, the hydrothermal kettle is placed in a 180 ℃ oven for constant temperature hydrothermal treatment for 2h. After natural cooling, the resulting solution was centrifuged and the resulting violet solid was collected and washed 3-5 times with absolute ethanol followed by drying in an oven at 60 ℃ for 12h. Roasting the dried sample for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, wherein the heating rate of the tube furnace is 5 ℃/min, and finally obtaining the cobalt-defective Co rich in metal defects 3-x O 4 Elemental analysis and XPS characterization to obtain cobalt-defect Co 3-x O 4 The molar ratio of Co to O was about 0.56. Subsequently, nickel acetate and Co in a molar ratio of 1:1 were reacted 3-x O 4 Uniformly mixing in absolute ethyl alcohol, carrying out ultrasonic treatment for 2 hours, transferring the obtained solution into a hydrothermal kettle lined with polytetrafluoroethylene, placing the hydrothermal kettle in a 180 ℃ oven, keeping the constant temperature for 2 hours, and keeping the temperature rise rate of the oven at 5 ℃/min. Washing the obtained solid sample with absolute ethyl alcohol, centrifuging, drying, calcining for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, and finally obtaining Co 3-x O 4 NiO powder catalyst.
Example 6
1g of cobalt acetate and 37.5g of glycerin are weighed and uniformly mixed in a 100mL hydrothermal kettle, after magnetic stirring for 1h, the hydrothermal kettle is placed in a 180 ℃ oven for constant temperature hydrothermal treatment for 2h. After natural cooling, the resulting solution was centrifuged and the resulting violet solid was collected and washed 3-5 times with absolute ethanol followed by drying in an oven at 60 ℃ for 12h. Roasting the dried sample for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, wherein the heating rate of the tube furnace is 5 ℃/min, and finally obtaining the cobalt-defective Co rich in metal defects 3-x O 4 Elemental analysis and XPS characterization to obtain cobalt-defect Co 3-x O 4 The molar ratio of Co to O was about 0.56. Subsequently, nickel acetate and Co in a molar ratio of 1:15 were reacted 3-x O 4 Uniformly mixing in absolute ethyl alcohol, carrying out ultrasonic treatment for 2 hours, transferring the obtained solution into a hydrothermal kettle lined with polytetrafluoroethylene, placing the hydrothermal kettle in a 180 ℃ oven, keeping the constant temperature for 2 hours, and keeping the temperature rise rate of the oven at 5 ℃/min. Washing the obtained solid sample with absolute ethyl alcohol, centrifuging, drying, calcining for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, and finally obtaining Co 3-x O 4 NiO powder catalyst.
Example 7
1g of cobalt acetate and 37.5g of glycerin are weighed and uniformly mixed in a 100mL hydrothermal kettle, after magnetic stirring for 1h, the hydrothermal kettle is placed in a 180 ℃ oven for constant temperature hydrothermal treatment for 2h. After natural cooling, the resulting solution was centrifuged and the resulting violet solid was collected and washed 3-5 times with absolute ethanol followed by drying in an oven at 60 ℃ for 12h. Roasting the dried sample for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, wherein the heating rate of the tube furnace is 5 ℃/min, and finally obtaining the gold-enriched sampleCobalt deficient Co that is defective 3-x O 4 Elemental analysis and XPS characterization to obtain cobalt-defect Co 3-x O 4 The molar ratio of Co to O was about 0.56. Subsequently, nickel acetate and Co in a molar ratio of 1:20 were reacted 3-x O 4 Uniformly mixing in absolute ethyl alcohol, carrying out ultrasonic treatment for 2 hours, transferring the obtained solution into a hydrothermal kettle lined with polytetrafluoroethylene, placing the hydrothermal kettle in a 180 ℃ oven, keeping the constant temperature for 2 hours, and keeping the temperature rise rate of the oven at 5 ℃/min. Washing the obtained solid sample with absolute ethyl alcohol, centrifuging, drying, calcining for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, and finally obtaining Co 3-x O 4 NiO powder catalyst.
Example 8
1g of cobalt acetate and 37.5g of glycerin are weighed and uniformly mixed in a 100mL hydrothermal kettle, after magnetic stirring for 1h, the hydrothermal kettle is placed in a 180 ℃ oven for constant temperature hydrothermal treatment for 2h. After natural cooling, the resulting solution was centrifuged and the resulting violet solid was collected and washed 3-5 times with absolute ethanol followed by drying in an oven at 60 ℃ for 12h. Roasting the dried sample for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, wherein the heating rate of the tube furnace is 5 ℃/min, and finally obtaining the cobalt-defective Co rich in metal defects 3-x O 4 Elemental analysis and XPS characterization to obtain cobalt-defect Co 3-x O 4 The molar ratio of Co to O was about 0.56. Subsequently, nickel acetate and Co in a molar ratio of 4:1 were reacted 3-x O 4 Uniformly mixing in absolute ethyl alcohol, carrying out ultrasonic treatment for 2 hours, transferring the obtained solution into a hydrothermal kettle lined with polytetrafluoroethylene, placing the hydrothermal kettle in a 180 ℃ oven, keeping the constant temperature for 2 hours, and keeping the temperature rise rate of the oven at 5 ℃/min. Washing the obtained solid sample with absolute ethyl alcohol, centrifuging, drying, calcining for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, and finally obtaining Co 3-x O 4 NiO powder catalyst.
Example 9
1g of cobalt acetate and 37.5g of glycerin are weighed and uniformly mixed in a 100mL hydrothermal kettle, after magnetic stirring for 1h, the hydrothermal kettle is placed in a 180 ℃ oven for constant temperature hydrothermal treatment for 2h. After natural cooling, the resulting solution was centrifuged and the resulting violet solid was collected and washed 3-5 times with absolute ethanol followed by drying in an oven at 60 ℃ for 12h. DryingRoasting the sample in a tubular furnace at 300 ℃ for 2 hours in the air atmosphere, wherein the heating rate of the tubular furnace is 5 ℃/min, and finally obtaining the cobalt-defective Co rich in metal defects 3-x O 4 Elemental analysis and XPS characterization to obtain cobalt-defect Co 3-x O 4 The molar ratio of Co to O was about 0.56. Subsequently, nickel acetate and Co in a molar ratio of 8:1 were reacted 3-x O 4 Uniformly mixing in absolute ethyl alcohol, carrying out ultrasonic treatment for 2 hours, transferring the obtained solution into a hydrothermal kettle lined with polytetrafluoroethylene, placing the hydrothermal kettle in a 180 ℃ oven, keeping the constant temperature for 2 hours, and keeping the temperature rise rate of the oven at 5 ℃/min. Washing the obtained solid sample with absolute ethyl alcohol, centrifuging, drying, calcining for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, and finally obtaining Co 3-x O 4 NiO powder catalyst.
Example 10
1g of cobalt acetate and 37.5g of glycerin are weighed and uniformly mixed in a 100mL hydrothermal kettle, after magnetic stirring for 1h, the hydrothermal kettle is placed in a 180 ℃ oven for constant temperature hydrothermal treatment for 2h. After natural cooling, the resulting solution was centrifuged and the resulting violet solid was collected and washed 3-5 times with absolute ethanol followed by drying in an oven at 60 ℃ for 12h. Roasting the dried sample for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, wherein the heating rate of the tube furnace is 5 ℃/min, and finally obtaining the cobalt-defective Co rich in metal defects 3-x O 4 Elemental analysis and XPS characterization to obtain cobalt-defect Co 3-x O 4 The molar ratio of Co to O was about 0.56. Subsequently, nickel acetate and Co in a molar ratio of 20:1 were combined 3-x O 4 Uniformly mixing in absolute ethyl alcohol, carrying out ultrasonic treatment for 2 hours, transferring the obtained solution into a hydrothermal kettle lined with polytetrafluoroethylene, placing the hydrothermal kettle in a 180 ℃ oven, keeping the constant temperature for 2 hours, and keeping the temperature rise rate of the oven at 5 ℃/min. Washing the obtained solid sample with absolute ethyl alcohol, centrifuging, drying, calcining for 2 hours at 300 ℃ in the air atmosphere in a tube furnace, and finally obtaining Co 3-x O 4 NiO powder catalyst.
The foregoing is merely an embodiment of the present invention, and the present invention is not limited in any way, and may have other embodiments according to the above structures and functions, which are not listed. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention without departing from the scope of the technical solution of the present invention will still fall within the scope of the technical solution of the present invention.
Claims (3)
1. Stabilizing Ni on surface of catalyst 3+ A method for preparing an active site, characterized by preparing a metal-deficient Co x3- O 4 In the metal-deficient Co x3- O 4 In which the molar ratio of Co to O is less than 0.75, co is added to the catalyst x3- O 4 Co is prepared by compounding with NiO as an electron acceptor carrier x3- O 4 NiO catalyst by Co x3- O 4 The strong electron interaction between NiO and NiO accelerates electron transport and promotes Ni on the surface of the catalyst 2+ To Ni 3+ Thereby stabilizing the catalyst surface Ni 3+ The active site comprises the following specific steps:
(1) Preparation of Metal deficient Co x3- O 4 Nanoparticles
Fully mixing cobalt acetate and glycerin in a polytetrafluoroethylene-lined hydrothermal kettle, magnetically stirring 1-h, placing the hydrothermal kettle in a 180 ℃ oven for constant-temperature hydrothermal 2-h, naturally cooling, centrifuging the obtained solution, collecting the obtained solid, washing with absolute ethyl alcohol, drying, roasting the dried sample in a tubular furnace at 300 ℃ for 2-h in the air atmosphere, and obtaining the metal-defective Co x3- O 4 A nanoparticle;
(2) Preparation of Co x3- O 4 NiO powder catalyst
Nickel acetate and Co x3- O 4 The nanoparticles are uniformly mixed in absolute ethanol according to the molar ratio of 20:1 or 15:1 or 10:1 or 8:1 or 4:1 or 2:1 or 1:1 or 1:2 or 1:4 or 1:8 or 1:10 or 1:15 or 1:20, and subjected to ultrasonic treatment of 2h; transferring the obtained solution into a polytetrafluoroethylene-lined hydrothermal kettle, and placing the hydrothermal kettle in a 180 ℃ oven to keep the constant temperature for 2h; washing the obtained sample with absolute ethyl alcohol, centrifuging, drying, and calcining at 300 ℃ in the air atmosphere in a tube furnace for 2h, finally obtaining Co x3- O 4 NiO powder catalyst, co x3- O 4 NiO powder catalyst is spherical nanometer particle with diameter of 20nm, and is used as catalyst for electrocatalytic water analysis oxygen reaction, co x3- O 4 When NiO is used as a working electrode for electrocatalytic water analysis of oxygen, the NiO is prepared at 10mAcm -2 With an overpotential of 252mV and an electric double layer capacitance of up to 62.0mF/cm 2 The electrochemical active area is as high as 1033.3cm 2 。
2. The stable catalyst surface Ni of claim 1 3+ The active site method is characterized in that the heating rate of the tube furnace and the baking oven is 5 ℃/min.
3. The stable catalyst surface Ni of claim 1 3+ A method for preparing an active site, characterized in that in the step (1), cobalt acetate is used in an amount of 1 to g and glycerin is used in an amount of 1 to 80 to g, and the obtained metal-deficient Co x3- O 4 The molar ratio of Co to O in the nanoparticle was 0.56 or 0.65.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101227004A (en) * | 2008-01-30 | 2008-07-23 | 哈尔滨工程大学 | Fuel cell cathode material of composite oxides containing cobalt |
| CN104525203A (en) * | 2014-12-17 | 2015-04-22 | 华东师范大学 | Preparation method and application of Co3O4/NiO composite mesoporous nanoparticles |
| CN106807378A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of hexagon nickel cobalt oxide oxygen-separating catalyst and its preparation method and application |
| CN109012673A (en) * | 2018-07-12 | 2018-12-18 | 青岛大学 | A kind of preparation method and application of oxygen-separating catalyst |
| WO2020096022A1 (en) * | 2018-11-08 | 2020-05-14 | 国立大学法人北海道大学 | Material for oxygen evolution (oer) electrode catalyst, and use thereof |
| CN113186560A (en) * | 2021-03-30 | 2021-07-30 | 广州费舍尔人工智能技术有限公司 | Ni-rich alloy3+Nickel cobaltate modified carbon ball electrode catalyst |
-
2021
- 2021-10-29 CN CN202111272360.3A patent/CN113941331B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101227004A (en) * | 2008-01-30 | 2008-07-23 | 哈尔滨工程大学 | Fuel cell cathode material of composite oxides containing cobalt |
| CN104525203A (en) * | 2014-12-17 | 2015-04-22 | 华东师范大学 | Preparation method and application of Co3O4/NiO composite mesoporous nanoparticles |
| CN106807378A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of hexagon nickel cobalt oxide oxygen-separating catalyst and its preparation method and application |
| CN109012673A (en) * | 2018-07-12 | 2018-12-18 | 青岛大学 | A kind of preparation method and application of oxygen-separating catalyst |
| WO2020096022A1 (en) * | 2018-11-08 | 2020-05-14 | 国立大学法人北海道大学 | Material for oxygen evolution (oer) electrode catalyst, and use thereof |
| CN113186560A (en) * | 2021-03-30 | 2021-07-30 | 广州费舍尔人工智能技术有限公司 | Ni-rich alloy3+Nickel cobaltate modified carbon ball electrode catalyst |
Non-Patent Citations (3)
| Title |
|---|
| Abdul QayoomMugheri et al..Co3O4/NiO bifunctional electrocatalyst for water splitting.《Electrochimica Acta》.2019,第306卷第10,12页. * |
| Meiyan Cui et al..Ni3+-Induced Hole States Enhance the Oxygen Evolution Reaction Activity of NixCo3−xO4 Electrocatalysts.《Chem. Mater.》.2019,第31卷第7618−7625页. * |
| Rongrong Zhang et al..Engineering Cobalt Defects in Cobalt Oxide for Highly Efficient Electrocatalytic Oxygen Evolution.《ACS Catal.》.2018,第8卷第3804-3806页. * |
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