CN118186400A - Method for preparing transition metal-based electrocatalytic water-splitting anode catalytic material and application thereof - Google Patents
Method for preparing transition metal-based electrocatalytic water-splitting anode catalytic material and application thereof Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims description 28
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- 150000003624 transition metals Chemical class 0.000 title claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000003054 catalyst Substances 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000006260 foam Substances 0.000 claims abstract description 45
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 13
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000001509 sodium citrate Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 11
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims abstract description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000011105 stabilization Methods 0.000 claims abstract description 5
- 230000006641 stabilisation Effects 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000010335 hydrothermal treatment Methods 0.000 claims description 17
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 14
- 239000008103 glucose Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 4
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
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- 238000002360 preparation method Methods 0.000 abstract description 33
- 239000011651 chromium Substances 0.000 abstract description 21
- 229910052804 chromium Inorganic materials 0.000 abstract description 5
- 230000007246 mechanism Effects 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000004457 water analysis Methods 0.000 abstract description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 34
- 239000012018 catalyst precursor Substances 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 7
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- 238000005868 electrolysis reaction Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- -1 ni (NO 3)2.6H2O Inorganic materials 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000001994 activation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 5
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention provides a preparation and in-situ stabilization method of an electrocatalytic water analysis oxygen catalyst with high efficiency and long stability and accurate and controllable Ni, fe and Cr ternary components. Relates to the technical field of three-way catalyst preparation and high-efficiency stable electrochemical methods, which comprises the following steps: the preparation method comprises the steps of accurately preparing a ternary metal salt precursor solution, controlling the growth of a high-efficiency catalyst on a conductive substrate, and realizing an ultra-long electrochemical stability mechanism by self-regulating the catalyst in an electrochemical process. The specific electrode preparation process comprises the following steps: 1) Pretreating foam Nickel (NF) to remove surface adsorbate; 2) Dissolving chromium nitrate, nickel nitrate, ferric nitrate, urea and sodium citrate in deionized water to form ternary metal salt precursor solution, and then immersing pretreated foam nickel in the ternary metal salt precursor solution for controllable hydrothermal synthesis; the ternary electrolytic water oxygen evolution catalyst is prepared by adopting non-noble metals with abundant reserves and low price, and can be widely applied to industrial production.
Description
Technical Field
The invention relates to the technical field of efficient and long-stability ternary catalyst preparation and in-situ self-stabilization mechanisms, in particular to a preparation and in-situ stabilization method of an electrocatalytic moisture analysis oxygen catalyst with accurate and controllable Ni, fe and Cr ternary components with high efficiency and long stability and application thereof.
Background
The world is currently facing environmental problems and energy problems, on the one hand, the widespread use of fossil energy causes a series of environmental problems, such as the greenhouse effect caused by the emission of carbon dioxide in large quantities, and on the other hand, fossil energy belongs to non-renewable energy sources, and there is a risk of exhaustion of exploitation, and the world has to consider potential energy crisis. The development of renewable energy sources provides a new idea for synthesizing various green chemicals using renewable electricity, wherein reactants and products of the electrocatalytic decomposition water-to-hydrogen (H2) technology are harmless to the environment, and energy of the renewable energy sources can be stored in the form of H2 chemicals with high heat value, which is a great concern for both environment and economy.
The Oxygen Evolution Reaction (OER) is an important semi-polar reaction of the water electrolysis hydrogen production technology, and because the reaction process involves a step of coupling protons by four electrons, the kinetics process is slower than that of the Hydrogen Evolution Reaction (HER), and the Oxygen Evolution Reaction (OER) is a main part of the energy consumption of the whole water electrolysis hydrogen production technology, researchers hope to develop a catalyst with excellent catalytic activity and stability by researching the kinetics process of the OER reaction so as to reduce the energy consumption of the OER reaction, thereby promoting the large-scale application of the water electrolysis hydrogen production technology. Conventional noble metal catalysts (Ir and Ru and their oxides) have excellent electrocatalytic OER properties, but the high cost, limited reserves and limited stability limit the application of this type of catalysts. Therefore, the electro-catalyst activity is considered, and meanwhile, the catalyst cost is also considered to reduce the water electrolysis hydrogen production cost, so that the requirements of the water electrolysis hydrogen production technology are met.
Meanwhile, the working environment of alkaline electrolyzed water has the characteristics of strong alkalinity and high oxidation potential, and the highly corrosive environment makes it difficult to maintain good catalytic activity of the catalyst after long-term operation, so that the realization of long stability of the alkaline tank faces a great challenge. The introduction of a third element into the anode catalyst to regulate the electronic structure of the catalyst and utilize the self-repairing process in the reaction of the catalyst is a novel and feasible method for realizing the long stability of the anode catalyst in the alkali tank.
In a series of OER catalytic materials with application prospect, layered Double Hydroxides (LDH) of Ni and Fe elements become the main research direction of alkaline OER reaction due to the electronic structure and components convenient to regulate and control, higher catalytic activity and low cost, but the high electrocatalytic activity of the material cannot be sustained for a long time, and the stability cannot be ensured. By doping transition metal elements into NiFe Layered Double Hydroxide (LDH), the structure of the Layered Double Hydroxide (LDH) can be regulated to keep high stability, and the valence states of Ni and Fe elements can be regulated to be converted to high valence states, so that the NiFe Layered Double Hydroxide (LDH) has higher activity.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention provides a preparation and in-situ stabilization method of an electrocatalytic moisture analysis oxygen catalyst with high efficiency and long stability and precise and controllable Ni, fe and Cr ternary components and an application thereof, and effectively solves the problems in the technical background.
In order to achieve the above purpose, the present invention provides the following technical solutions: the invention comprises the following steps:
1) Immersing foam Nickel (NF) in deionized water and HNO 3 (aq) solution in sequence, carrying out ultrasonic pretreatment, and flushing with deionized water for multiple times after the ultrasonic pretreatment is finished to remove nitric acid on the surface;
2) Dissolving chromium nitrate, nickel nitrate, ferric nitrate, urea and sodium citrate in deionized water to form a uniform solution, and then immersing the pretreated foam nickel in the uniform solution for hydrothermal treatment;
3) Taking out the sample, washing the sample with ethanol and deionized water for 3-5 times, preserving the sample in a glucose solution for 3-5 hours, washing the sample with ethanol and deionized water, and drying the washed sample to obtain the catalyst material.
Preferably, the HNO 3 (aq) solution concentration in the step (1) is 0.1mol/L.
Preferably, the molar concentrations of the metal salt, nickel nitrate and iron nitrate in the step (2) are (0.00075M, 0.00105M, 0.00135M, 0.00345M and 0.00495M), 0.003M and 0.012M, respectively.
Preferably, the urea and sodium citrate solutions of step (2) have concentrations of 0.035M and 0.00025M, respectively.
Preferably, the hydrothermal treatment temperature in the step (2) is 140-160 ℃, and the treatment time is 23-25 h.
Preferably, the concentration of the glucose solution in the step (3) is: 0.015M.
Preferably, the sample of step (3) is stored at a temperature of glucose solution of: 50 ℃.
Preferably, the transition metal-based electrocatalytic water splitting anode catalytic material is applied to electrocatalytic water splitting anode catalytic material.
Preferably, the application process is as follows: the catalyst material was put into an alkaline electrolyte, specifically, a KOH electrolyte with ph=14, as a working electrode, a Pt wire electrode as a counter electrode, and a saturated Ag/AgCl electrode as a reference electrode (saturated KCl as a filler liquid), and the overpotential and stability of the oxygen evolution reaction were tested.
The beneficial effects are that: 1. the invention provides a preparation method of a controllable synthesis high-efficiency and long-stability Ni, fe and Cr ternary component electrocatalytic water-analysis oxygen catalyst, which is characterized in that the Cr ion precipitated in the test of the catalytic material is subjected to an in-situ self-repairing electrode mechanism, so that the stability of the catalyst is obviously enhanced, and a feasible method is provided for the synthesis and preparation of a high-efficiency and long-stability commercial catalyst.
2. The Cr-doped NiFe Layered Double Hydroxide (LDH) catalyst (Cr-Ni 2Fe8 LDH-Nickle Foam) does not use noble metal elements, has low cost of raw materials, is easy to purchase, is simple and convenient to operate in the whole preparation process, and has a certain practical significance for the commercial utilization of the catalyst.
3. The overpotential of the catalyst disclosed by the invention is only 190mV at 10mA/cm < 2 >, the catalyst shows excellent OER catalytic activity, and meanwhile, the stability test of the catalyst in a three-electrode system is over 1200h, and the catalytic activity and the stability of the catalyst are superior to those of most reported catalysts.
4. The invention provides an electrocatalyst synthesis idea for alkaline water electrolysis.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a schematic diagram of a preparation flow of a Cr-Ni 2Fe8 LDH-Nickle Foam catalyst prepared by the method;
FIG. 2 is a scanning electron microscope image of the Cr-Ni 2Fe8 LDH-Nickle Foam catalyst prepared by the invention;
FIG. 3 is an X-ray diffraction pattern of a Cr-Ni 2Fe8 LDH catalyst prepared in accordance with the present invention;
FIG. 4 is a CV diagram of an electrochemical in situ activation of a catalyst precursor prepared in accordance with the present invention to a Cr-Ni 2Fe8 LDH-Nickle Foam catalyst;
FIG. 5 is a Linear Sweep Voltammetry (LSV) plot of Cr ion doped Cr-Ni 2Fe8 LDH-Nickle Foam 1-5 at different concentrations of Cr ions obtained in examples 1-5 in KOH at pH=14;
FIG. 6 is a plot of chronopotentials at a current density of 10mA/cm 2 in KOH at pH=14 for example 1 as an oxygen evolution reaction electrocatalyst;
FIG. 7 is a graph of Linear Sweep Voltammetry (LSV) for comparative example after soaking in a 0.1M Cr (NO 3)3) solution for a period of time.
Detailed Description
The following describes embodiments of the present invention in further detail with reference to FIGS. 1-7.
An embodiment, shown in fig. 1-7, provides a method for preparing a transition metal-based electrocatalytic water splitting anode catalytic material and application thereof, comprising the following steps:
1) Immersing foam Nickel (NF) in deionized water and HNO 3 (aq) solution in sequence, carrying out ultrasonic pretreatment, and flushing with deionized water for multiple times after the ultrasonic pretreatment is finished to remove nitric acid on the surface;
2) Dissolving chromium nitrate, nickel nitrate, ferric nitrate, urea and sodium citrate in deionized water to form a uniform solution, and then immersing the pretreated foam nickel in the uniform solution for hydrothermal treatment;
3) Taking out the sample, washing the sample with ethanol and deionized water for 3-5 times, preserving the sample in a glucose solution for 3-5 hours, washing the sample with ethanol and deionized water, and drying the washed sample to obtain the catalyst material.
The HNO 3 (aq) solution concentration of the step (1) is 0.1mol/L.
The molar concentrations of the metal salt, the nickel nitrate and the iron nitrate in the step (2) are respectively (0.00075M, 0.00105M, 0.00135M, 0.00345M and 0.00495M), 0.003M and 0.012M.
The concentration of urea and sodium citrate solution in the step (2) is 0.035M and 0.00025M respectively.
The hydrothermal treatment temperature in the step (2) is 140-160 ℃, and the treatment time is 23-25 h.
The concentration of the glucose solution in the step (3) is as follows: 0.015M.
The application of the transition metal-based electrocatalytic water-splitting anode catalytic material in electrocatalytic water-splitting oxygen reaction.
The application process comprises the following steps: the catalyst material was put into an alkaline electrolyte, specifically, a KOH electrolyte with ph=14, as a working electrode, a Pt wire electrode as a counter electrode, and a saturated Ag/AgCl electrode as a reference electrode (saturated KCl as a filler liquid), and the overpotential and stability of the oxygen evolution reaction were tested.
Preparation of Cr-Ni2Fe8 LDH-Nickle Foam-1
(1) Pretreatment process of foam nickel (Nickle Foam): sequentially immersing foam nickel (Nickle Foam) with the area of 1 x 1cm 2 in deionized water and HNO 3 (aq) solution, carrying out ultrasonic pretreatment, and flushing with deionized water for a plurality of times after the ultrasonic pretreatment is finished to remove nitric acid solution on the surface;
(2) Preparation of a catalyst precursor: placing a mixed solution of Cr (NO 3)3·9H2 O, ni (NO 3)2.6H2O, fe (NO 3)3·9H2 O, urea and sodium citrate) with the concentration of 0.035M and 0.00025M, which are 0.00105M, into a stainless steel autoclave with a polytetrafluoroethylene lining, immersing the pretreated foam nickel into the uniform solution for hydrothermal treatment at 140-160 ℃ for 23-25H, taking out a sample after the hydrothermal treatment is finished, washing the sample with ethanol and deionized water for several times, storing the sample in a glucose solution with the concentration of 0.015M at 50 ℃ for a period of time, washing the sample with ethanol and deionized water, and drying the sample to obtain a precursor of the Cr-Ni 2Fe8 LDH-Nickle Foam-1 catalyst;
(3) Cr-Ni 2Fe8 LDH-Nickle Foam-1 catalyst preparation: and (3) taking the catalyst precursor (1 x 1cm 2) obtained in the step (2) as an anode, taking Pt wires as a counter electrode, taking saturated Ag/AgCl electrodes (taking saturated KCl as a filling liquid) as a reference electrode, performing Cyclic Voltammetry (CV) activation in KOH electrolyte with pH value of 14, wherein the scanning circle number is 50, the scanning speed is 50mV/s, the scanning range is 0-0.85V (vs. Ag/AgCl), and the catalyst material Cr-Ni 2Fe8 LDH-Nickle Foam-1 can be obtained after the Cyclic Voltammetry (CV).
Example 2:
Preparation of Cr-Ni 2Fe8 LDH-Nickle Foam-2
(1) Pretreatment process of foam nickel (Nickle Foam): the experimental procedure was carried out as in example 1 (1);
(2) Preparation of a catalyst precursor: placing a mixed solution of Cr (NO 3)3·9H2 O, ni (NO 3)2·6H2 O) with the concentration of 0.003M and Fe (NO 3)3·9H2 O, urea with the concentration of 0.035M and sodium citrate with the concentration of 0.00025M) with the concentration of 0.00075M into a stainless steel autoclave with a polytetrafluoroethylene lining, immersing the pretreated foam nickel into the uniform solution for hydrothermal treatment at the temperature of 140-160 ℃ for 23-25 h, taking out a sample after the hydrothermal treatment, washing the sample with ethanol and deionized water for several times, storing the sample in a glucose solution with the concentration of 0.015M for a period of time at 50 ℃, washing the sample with ethanol and deionized water, and drying the sample to obtain a precursor of the Cr-Ni 2Fe8 LDH-Nickle Foam-2 catalyst;
(3) Cr-Ni 2Fe8 LDH-Nickle Foam-2 catalyst preparation: the experimental procedure was carried out as in example 1 (3);
example 3:
Preparation of Cr-Ni 2Fe8 LDH-Nickle Foam-3
(1) Pretreatment process of foam nickel (Nickle Foam): the experimental procedure was carried out as in example 1 (1);
(2) Preparation of a catalyst precursor: placing a mixed solution of Cr (NO 3)3·9H2 O, ni (NO 3)2·6H2 O) with the concentration of 0.003M and Fe (NO 3)3·9H2 O, urea with the concentration of 0.035M and sodium citrate with the concentration of 0.00025M) with the concentration of 0.00135M in a stainless steel autoclave with a polytetrafluoroethylene lining, immersing the pretreated foam nickel in the uniform solution for hydrothermal treatment at the temperature of 140-160 ℃ for 23-25 hours, taking out a sample after the hydrothermal treatment, washing the sample with ethanol and deionized water for several times, storing the sample in a glucose solution with the concentration of 0.015M at 50 ℃ for a period of time, washing the sample with ethanol and deionized water, and drying the sample to obtain a precursor of the Cr-Ni 2Fe8 LDH-Nickle Foam-2 catalyst;
(3) Cr-Ni 2Fe8 LDH-Nickle Foam-3 catalyst preparation: the experimental procedure was carried out as in example 1 (3);
Example 4:
Preparation of Cr-Ni 2Fe8 LDH-Nickle Foam-4
(1) Pretreatment process of foam nickel (Nickle Foam): the experimental procedure was carried out as in example 1 (1);
(2) Preparation of a catalyst precursor: placing a mixed solution of 0.00345M Cr (NO 3)3·9H2 O, 0.003M Ni (NO 3)2·6H2 O, 0.012M Fe (NO 3)3·9H2 O, 0.035M urea and 0.00025M sodium citrate) in a stainless steel autoclave with a polytetrafluoroethylene lining, immersing the pretreated foam nickel in the uniform solution for hydrothermal treatment at 140-160 ℃ for 23-25 h, taking out a sample after the hydrothermal treatment, washing the sample with ethanol and deionized water for several times, storing the sample in a glucose solution with 0.015M at 50 ℃ for a period of time, washing the sample with ethanol and deionized water, and drying the sample to obtain a precursor of the Cr-Ni 2Fe8 LDH-Nickle Foam-2 catalyst;
(3) Cr-Ni 2Fe8 LDH-Nickle Foam-4 catalyst preparation: the experimental procedure was carried out as in example 1 (3);
Example 5:
preparation of Cr-Ni 2Fe8 LDH-Nickle Foam-5
(1) Pretreatment process of foam nickel (Nickle Foam): the experimental procedure was carried out as in example 1 (1);
(2) Preparation of a catalyst precursor: placing a mixed solution of 0.00495M Cr (NO 3)3·9H2 O, 0.003M Ni (NO 3)2·6H2 O, 0.012M Fe (NO 3)3·9H2 O, 0.035M urea and 0.00025M sodium citrate) in a stainless steel autoclave with a polytetrafluoroethylene lining, immersing the pretreated foam nickel in the uniform solution for hydrothermal treatment at 140-160 ℃ for 23-25 h, taking out a sample after the hydrothermal treatment, washing the sample with ethanol and deionized water for several times, storing the sample in a glucose solution with 0.015M at 50 ℃ for a period of time, washing the sample with ethanol and deionized water, and drying the sample to obtain a precursor of the Cr-Ni 2Fe8 LDH-Nickle Foam-2 catalyst;
(3) Cr-Ni 2Fe8 LDH-Nickle Foam-5 catalyst preparation: the experimental procedure was carried out as in example 1 (3).
Comparative example:
Preparation of Ni 2Fe8 LDH-Nickle Foam
(1) Pretreatment process of foam nickel (Nickle Foam): the experimental procedure was carried out as in example 1 (1);
(2) Preparation of a catalyst precursor: placing a mixed solution of Ni (NO 3)2·6H2 O, fe (NO 3)3·9H2 O, 0.035M urea and 0.00025M sodium citrate) with the concentration of 0.003M in a stainless steel autoclave with a polytetrafluoroethylene lining, immersing the pretreated foam nickel in the uniform solution for hydrothermal treatment at 140-160 ℃ for 23-25 h, taking out a sample after the hydrothermal treatment, washing the sample with ethanol and deionized water for several times, storing the sample in a glucose solution with the concentration of 0.015M at 50 ℃ for a period of time, washing the sample with ethanol and deionized water, and drying the sample to obtain a precursor of the Ni 2Fe8 LDH-Nickle Foam catalyst;
(3) Preparation of Ni 2Fe8 LDH-Nickle Foam catalyst: the experimental procedure was carried out as in example 1 (3).
FIG. 1 depicts a preparation scheme of a Cr-Ni 2Fe8 LDH-Nickle Foam catalyst, comprising a simple hydrothermal reaction synthesis process and an in situ electrochemical activation process.
As shown in FIG. 2, the catalyst Cr-Ni 2Fe8 LDH-Nickle Foam-1 is a nano-sheet array grown on the surface of foam nickel (Nickle Foam), the transverse length of the nano-sheet is about 300-800 nm, the thickness of the nano-sheet is 10-50 nm, the array exists in the form of nano-sheet, the chemical reaction active area and the catalytic active site of the catalyst are increased, the adsorption of a catalytic reaction intermediate is facilitated, the catalytic reaction dynamics is accelerated, and the catalytic activity is improved.
FIG. 3 shows X-ray diffraction patterns (XRD) of example 1 and comparative example, and the very precise correspondence of the X-ray diffraction peak of comparative example Ni 2Fe8 LDH-Nickle Foam with a standard PDF card, which shows that we indeed synthesized a Layered Double Hydroxide (LDH) structure of NiFe, while doping of Cr element did not change the NiFe Layered Double Hydroxide (LDH) structure, but formed a homogeneous phase.
The electrochemical test systems described below are three-electrode systems, working electrodes (reaction area 1 x 1cm 2) are prepared in examples and comparative examples, pt wire is used as the counter electrode, saturated Ag/AgCl electrode (saturated KCl is used as the filler liquid) is used as the reference electrode, and KOH with ph=14 is used as the electrolyte.
Fig. 4 is a graph of the CV test for in situ electrochemical activation of a catalyst precursor to a catalyst material in example 1, where the catalyst activity after 40 cycles of CV test is no longer significantly improved, indicating that the in situ activation process converts the catalyst precursor to a catalyst material with higher electrochemical activity, and preferably the number of electrochemical in situ activation test cycles is 50.
FIG. 5 shows the comparison of OER linear sweep voltammograms of Cr-Ni 2Fe8 LDH-Nickle Foam 1-5 doped with Cr ions at different concentrations obtained in examples 1-5, as shown in the figure, cr-Ni 2Fe8 LDH-Nickle Foam1 has optimal OER catalytic performance, and Cr (NO 3)3·9H2 O concentration of 0.00105M is used).
FIG. 6 is a chronopotentiometric curve of 10mA/cm 2 for the current density in KOH at pH=14 for example 1 as oxygen evolution electrocatalyst, stability test showing that Cr-Ni 2Fe8 LDH-Nickle Foam1 has a stability of more than 1200 h.
Fig. 7 is a linear sweep voltammogram of comparative example Ni 2Fe8 LDH-Nickle Foam after a period of immersion in 0.1M Cr (NO 3)3 solution), which shows that comparative example Ni 2Fe8 LDH-Nickle Foam after immersion in 0.1M Cr (NO 3)3 solution for a different period of time exhibits different OER catalytic properties and is significantly better than the non-immersed comparative example Ni 2Fe8 LDH-Nickle Foam, which may demonstrate that ions corresponding to Cr element present in the solution can enter into the layered double hydroxide structure of NiFe, thereby affecting the OER electrocatalytic properties of the catalyst.
The beneficial effects are that: 1. the invention provides a preparation method of a controllable synthesis high-efficiency and long-stability Ni, fe and Cr ternary component electrocatalytic water-analysis oxygen catalyst, which is characterized in that the Cr ion precipitated in the test of the catalytic material is subjected to an in-situ self-repairing electrode mechanism, so that the stability of the catalyst is obviously enhanced, and a feasible method is provided for the synthesis and preparation of a high-efficiency and long-stability commercial catalyst.
2. The Cr-doped NiFe Layered Double Hydroxide (LDH) catalyst (Cr-Ni 2Fe8 LDH-Nickle Foam) does not use noble metal elements, has low cost of raw materials, is easy to purchase, is simple and convenient to operate in the whole preparation process, and has a certain practical significance for the commercial utilization of the catalyst.
3. The overpotential of the catalyst at 10mA/cm 2 is only 190mV, the catalyst shows excellent OER catalytic activity, and meanwhile, the stability test of the catalyst in a three-electrode system is over 1200h, and the catalytic activity and the stability of the catalyst are superior to those of most reported catalysts.
4. The invention provides an electrocatalyst synthesis idea for alkaline water electrolysis.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a transition metal-based electrocatalytic water splitting anode catalytic material, comprising the steps of:
1) Immersing foam Nickel (NF) in deionized water and HNO 3 (aq) solution in sequence, carrying out ultrasonic pretreatment, and flushing with deionized water for multiple times after the ultrasonic pretreatment is finished to remove nitric acid on the surface;
2) Dissolving chromium nitrate, nickel nitrate, ferric nitrate, urea and sodium citrate in deionized water to form ternary metal salt precursor solution, and then immersing pretreated foam nickel in the ternary metal salt precursor solution for controllable hydrothermal synthesis;
3) Taking out the sample, washing the sample with ethanol and deionized water for 3-5 times, preserving the sample in a glucose solution for 3-5 hours, washing the sample with ethanol and deionized water, and drying the sample to obtain the catalyst material.
2. A method of preparing a transition metal-based electrocatalytic water splitting anode catalytic material as set forth in claim 1, wherein: the concentration of the HNO 3 (aq) solution in the step (1) is 0.01-0.5 mol/L.
3. A method of preparing a transition metal-based electrocatalytic water splitting anode catalytic material as set forth in claim 1, wherein: the molar concentrations of the chromium nitrate, the nickel nitrate and the ferric nitrate in the step (2) are respectively 0.0001-0.01M, 0.003-0.01M and 0.01-0.1M.
4. A method of preparing a transition metal-based electrocatalytic water splitting anode catalytic material as set forth in claim 1, wherein: the concentration of the urea and the sodium citrate solution in the step (2) is respectively 0.01-0.5M and 0.0001-0.001M.
5. A method of preparing a transition metal-based electrocatalytic water splitting anode catalytic material as set forth in claim 1, wherein: the hydrothermal treatment temperature in the step (2) is 100-180 ℃, and the treatment time is 12-30 h.
6. A method of preparing a transition metal-based electrocatalytic water splitting anode catalytic material as set forth in claim 1, wherein: the concentration of the glucose solution in the step (3) is as follows: 0.01-0.1M.
7. A method of preparing a transition metal-based electrocatalytic water splitting anode catalytic material as set forth in claim 1, wherein: the preservation temperature of the sample in the step (3) in the glucose solution is as follows: 20-70 ℃.
8. The method for in situ stabilization of a catalyst according to claim 1, wherein: cr ions separated out from the catalytic material in the test are subjected to in-situ self-repairing electrode, so that the stability of the catalyst is maintained.
9. The use of the electrocatalytic moisture-resolving oxygen catalyst as set forth in claim 1, wherein: the application of the electrocatalytic moisture analysis oxygen catalyst in electrocatalytic moisture analysis oxygen reaction.
10. The use of the electrocatalytic moisture-resolving oxygen catalyst as set forth in claim 9, wherein: the application process comprises the following steps: the catalyst material was put into an alkaline electrolyte, specifically, a KOH electrolyte with ph=14, as a working electrode, a Pt wire electrode as a counter electrode, and a saturated Ag/AgCl electrode as a reference electrode (saturated KCl as a filler liquid), and the overpotential and stability of the oxygen evolution reaction were tested.
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