CN110257859B - Co2P/Ni2P/Al2O3/NF multi-stage structure composite electrode and preparation method thereof - Google Patents

Co2P/Ni2P/Al2O3/NF multi-stage structure composite electrode and preparation method thereof Download PDF

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CN110257859B
CN110257859B CN201910571319.2A CN201910571319A CN110257859B CN 110257859 B CN110257859 B CN 110257859B CN 201910571319 A CN201910571319 A CN 201910571319A CN 110257859 B CN110257859 B CN 110257859B
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宋彩霞
王德宝
邢苗苗
孙媛媛
赵健
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Dongying Ruigang Pipeline Engineering Co ltd
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Qingdao University of Science and Technology
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Abstract

The invention discloses a Co2P/Ni2P/Al2O3a/NF multi-stage structure composite electrode and a preparation method thereof. Characterized in that said Co2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode is Co grown on foamed nickel as substrate2P、Ni2P、Al2O3A high-efficiency electrocatalysis electrode composed of ternary composite nano-sheet multi-level structure; the preparation method is that the foam nickel is used as an electrode substrate material, a hydrothermal method and a pyrolysis method are combined, and Co directly grows on the surface of the foam nickel2P、Ni2P、Al2O3Ternary composite high-efficiency electrode material to obtain Co2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode. The preparation method has simple process, and adopts the combination of a hydrothermal method with mild reaction conditions and a pyrolysis method to prepare Co2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode has higher electrolysis efficiency and electrocatalysis stability when being used for hydrogen production and oxygen production by double-function water electrolysis.

Description

Co2P/Ni2P/Al2O3/NF multi-stage structure composite electrode and preparation method thereof
Technical Field
The invention belongs to the field of electrode materials, and relates to Co2P/Ni2P/Al2O3a/NF multi-stage structure composite electrode and a preparation method thereof, in particular to a Co for hydrogen and oxygen production by double-function water electrolysis2P/Ni2P/Al2O3A preparation method of a composite electrode with a NF multistage structure.
Background
The search for low-cost and high-performance electrolytic water electrode materials is always the direction and pursuit of scientific researchers. Although the noble metal electrode has excellent performance, the noble metal electrode has high cost and deficient resources, and the wide application and development of the noble metal electrode are limited. To reduce the costThe electrochemical performance is improved, the use of noble metals is reduced, and the transition metal catalyst is widely concerned by people. The transition metal catalyst has excellent electrochemical performance, low cost and simple preparation method, so that the transition metal catalyst is rapidly developed to replace a noble metal electrode material. In recent years, transition metal phosphides, in addition to noble metals and transition metal hydroxides, have received much attention from researchers because of their excellent electrochemical properties due to their unique structures and properties. Through experiments, researchers find that the transition metal phosphide has very low surface energy, and is beneficial to the adsorption of hydrogen ions and the desorption of hydrogen, so that the activation energy of the water electrolysis reaction is reduced, the reaction is accelerated, and the high-efficiency catalysis effect is achieved. Among the elements on the earth, Co is one of the elements which are abundant on the earth, has low price and good electrocatalytic performance, and is the electrode material for electrolyzing water which is most researched at present. Therefore, the phosphide has wide application prospect. The electrolytic water experiment shows that the excellent electrolytic water performance and stability can be matched with Pt and IrO2The water electrolysis system of the formed all-noble metal electrode is comparable to that of the water electrolysis system.
The invention adopts a simple hydrothermal method, takes foam Nickel (NF) as an electrode substrate material, grows a hydrotalcite-like CoAl-LDH film on the NF substrate by one-step reaction to obtain a CoAl-LDH/NF composite electrode, the obtained CoAl-LDH film material is a multilevel structure self-assembled by mutually staggered nano sheets, then takes the CoAl-LDH/NF composite material as a precursor, and adopts a method of thermal decomposition of sodium hypophosphite to phosphorize the composite electrode material to obtain Co2P/Ni2P/Al2O3The obtained electrode material has larger specific surface area, thereby exposing more active sites, and simultaneously Al2O3The structure is more stable due to the existence of the metal oxide, so that the electrolytic water catalysis performance and the stability of the electrode material are improved.
Disclosure of Invention
Aiming at the current situations of small specific surface area, low activity and poor stability of a composite electrode in the prior art, the invention provides Co2P/Ni2P/Al2O3The invention overcomes the defects of complex preparation process, high cost, and particularly difficult preparation of Co with high specific surface area, high activity and high stability of the conventional electrode2P/Ni2P/Al2O3a/NF composite electrode and the like, provides a Co for hydrogen and oxygen production by double-function water electrolysis2P/Ni2P/Al2O3A preparation method of a composite electrode with a NF multistage structure. The method is characterized in that a simple hydrothermal method and a pyrolysis method are combined, NF is used as an electrode substrate material, a hydrotalcite-like CoAl-LDH film is grown on the NF substrate to obtain a CoAl-LDH/NF composite electrode, the obtained CoAl-LDH film is a multilevel structure formed by self-assembling of mutually staggered nanosheets and has a large specific surface area, so that more active sites can be exposed, and meanwhile, Al can be used as a material for preparing the composite electrode2O3The structure is more stable due to the existence of the metal oxide, so that the electrolytic performance and the stability of the electrode are improved.
The preparation method comprises the following steps:
(1) cutting NF into square electrode pieces with the size of 1cm multiplied by 1cm, then putting the cut NF pieces into a beaker, adding acetone, carrying out ultrasonic treatment for 5-10min, taking out the electrode pieces, putting the electrode pieces into deionized water, carrying out ultrasonic water washing for 5-10min, taking out the electrode pieces, putting the electrode pieces into 1-5mol/L HCl for soaking for 10-15min, then taking out the electrode pieces, carrying out washing by using the deionized water, and putting the electrode pieces into a vacuum drying box for drying;
(2) weighing 0.05-1.0mmol of cobalt nitrate and 0.05-1.0mmol of aluminum nitrate in a beaker, and adding deionized water to dissolve to prepare a solution A;
(3) weighing 0.5-10.0mmol of urea in a beaker, adding deionized water for dissolving to prepare a solution B;
(4) mixing the solution A obtained in the step (2) with the solution B obtained in the step (3), adding 1-10mL of ethylene glycol to prepare a 20mL mixed solution, carrying out ultrasonic treatment on the mixed solution for 30min, and then transferring the mixed solution to a reaction kettle;
(5) quickly putting the NF sheet pretreated in the step (1) into the mixed solution obtained in the step (4), reacting for 3-24h at the temperature of 100-180 ℃, taking out the electrode sheet after cooling, respectively washing with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum drying oven to obtain the CoAl-LDH/NF multi-stage structure composite electrode;
(6) weighing 0.1-5g of sodium hypophosphite as a phosphorus source, putting the prepared CoAl-LDH/NF sample and the sodium hypophosphite into a tube furnace for phosphating, using nitrogen as protective gas, raising the temperature to 200-500 ℃ at the temperature rise speed of 1-10 ℃/min, preserving the temperature for 30-300min, respectively washing with deionized water and absolute ethyl alcohol for three times after cooling to room temperature, and finally placing in a vacuum drying box for drying.
The invention has the advantages that: the Ag/CoAl-LDH/NF electrode prepared by the method is a multi-stage structure self-assembled by nano sheets which are staggered with each other, the specific surface area and active sites are increased, the adsorption of hydrogen ions and the desorption of hydrogen are promoted, the electrolyte can enter the electrode, the electrocatalytic efficiency can be improved, the Ag/CoAl-LDH/NF electrode has good electrolytic activity for hydrogen production and oxygen production by dual-function electrolysis of water, and the stability of the electrode is greatly improved.
Drawings
FIG. 1 shows the Co prepared in the first example2P/Ni2P/Al2O3XRD spectrogram of/NF multi-stage structure composite electrode.
FIG. 2 shows the Co prepared in the first example2P/Ni2P/Al2O3SEM pictures of different magnifications of the/NF multi-stage structure composite electrode.
FIG. 3 is an EDS elemental map of the Ag/CoAl-LDH/NF multi-stage structure composite electrode prepared in example one.
FIG. 4 shows Co prepared in the first embodiment and the first comparative embodiment2P/Ni2P/Al2O3Linear sweep voltammetry of/NF multi-stage structured composite electrodes.
FIG. 5 is Tafel curves of Ag/CoAl-LDH/NF multi-level structure composite electrode prepared in example one and CoAl-LDH/NF electrode prepared in comparison example one for producing hydrogen by electrolyzing water.
FIG. 6 shows an embodimentExample 1 Co2P/Ni2P/Al2O3The timing current curve of the/NF multi-stage structure composite electrode for electrolyzing water to prepare hydrogen under 200mV overpotential.
FIG. 7 shows the Co prepared in the first example2P/Ni2P/Al2O3Composite electrode with/NF multi-stage structure, CoAl-LDH/NF electrode prepared by the method of the comparative example I and IrO2The electrodes and NF electrodes were used for linear sweep voltammograms obtained from OER performance testing.
FIG. 8 shows the Co prepared in the first example2P/Ni2P/Al2O3The CoAl-LDH/NF electrode prepared by the method of the first comparative example and the/NF multi-level structure composite electrode is used for a Tafel curve corresponding to the oxygen production by electrolyzing water.
FIG. 9 shows the Co prepared in the first embodiment2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode electrolyzes water to produce oxygen at 300mV overpotential to time the current curve.
Detailed Description
The invention is illustrated in more detail below by way of examples:
the first embodiment is as follows:
(1) cutting NF into square electrode pieces with the size of 1cm multiplied by 1cm, then putting the cut NF pieces into a beaker, adding an acetone solution, carrying out ultrasonic treatment for 10min, taking out the electrode pieces, putting the electrode pieces into deionized water, carrying out ultrasonic water washing for 5min, taking out the electrode pieces, putting the electrode pieces into 2mol/L HCl, soaking for 10min, then taking out the electrode pieces, washing with the deionized water, and putting the electrode pieces into a vacuum drying oven for drying;
(2) weighing 0.2mmol of cobalt nitrate and 0.1mmol of aluminum nitrate in a beaker, and adding deionized water to dissolve to prepare a solution A;
(3) weighing 1.8mmol of urea in a beaker, adding deionized water for dissolving to prepare a solution B;
(4) mixing the solution A in the step (2) with the solution B in the step (3), adding 2mL of glycol to prepare a mixed solution of 20mL, carrying out ultrasonic treatment on the mixed solution for 30min, and then transferring the mixed solution to a reaction kettle;
(5) quickly putting the NF sheet pretreated in the step (1) into the mixed solution obtained in the step (4), reacting for 9h at 100 ℃, cooling, taking out the electrode slice, respectively washing with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum drying oven to obtain CoAl-LDH/NF;
(6) weighing 3g of sodium hypophosphite as a phosphorus source, putting the prepared CoAl-LDH/NF sample and the sodium hypophosphite into a tube furnace for phosphating, using nitrogen as protective gas, heating to 300 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 150min, cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times, and finally drying in a vacuum drying oven to obtain Co2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode.
Example two:
(1) cutting NF into square electrode pieces with the size of 1cm multiplied by 1cm, then putting the cut NF pieces into a beaker, adding acetone, carrying out ultrasonic treatment for 10min, taking out the electrode pieces, putting the electrode pieces into deionized water, carrying out ultrasonic water washing for 5min, taking out the electrode pieces, putting the electrode pieces into 2mol/L HCl, soaking for 10min, then taking out the electrode pieces, washing with the deionized water, and putting the electrode pieces into a vacuum drying oven for drying;
(2) weighing 0.2mmol of cobalt nitrate and 0.1mmol of aluminum nitrate in a beaker, and adding deionized water to dissolve to prepare a solution A;
(3) weighing 1.8mmol of urea in a beaker, adding deionized water for dissolving to prepare a solution B;
(4) mixing the solution A obtained in the step (2) with the solution B obtained in the step (3), adding 6mL of ethylene glycol to prepare a mixed solution of 20mL, carrying out ultrasonic treatment on the mixed solution for 30min, and then transferring the mixed solution to a reaction kettle;
(5) quickly putting the NF sheet pretreated in the step (1) into the mixed solution obtained in the step (4), reacting for 9h at 100 ℃, cooling, taking out the electrode slice, respectively washing with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum drying oven to obtain CoAl-LDH/NF;
(6) weighing 1g of sodium hypophosphite as a phosphorus source, putting the prepared CoAl-LDH/NF sample and the sodium hypophosphite into a tube furnace for phosphating, using nitrogen as a protective gas, and raising the temperature at a speed of 10 ℃/minHeating to 300 ℃, keeping the temperature for 150min, respectively washing with deionized water and absolute ethyl alcohol for three times after cooling to room temperature, and finally drying in a vacuum drying oven to obtain Co2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode.
Example three:
(1) cutting NF into square electrode pieces with the size of 1cm multiplied by 1cm, then putting the cut NF pieces into a beaker, adding acetone, carrying out ultrasonic treatment for 10min, taking out the electrode pieces, putting the electrode pieces into deionized water, carrying out ultrasonic water washing for 5min, taking out the electrode pieces, putting the electrode pieces into 2mol/L HCl, soaking for 10min, then taking out the electrode pieces, washing with the deionized water, and putting the electrode pieces into a vacuum drying oven for drying;
(2) weighing 0.2mmol of cobalt nitrate and 0.1mmol of aluminum nitrate in a beaker, and adding deionized water to dissolve to prepare a solution A;
(3) weighing 3.6mmol of urea in a beaker, adding deionized water for dissolving to prepare a solution B;
(4) mixing the solution A in the step (2) with the solution B in the step (3), adding 2mL of glycol to prepare a mixed solution of 20mL, carrying out ultrasonic treatment on the mixed solution for 30min, and then transferring the mixed solution to a reaction kettle;
(5) quickly putting the NF sheet pretreated in the step (1) into the mixed solution obtained in the step (4), reacting for 9h at 100 ℃, cooling, taking out the electrode slice, respectively washing with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum drying oven to obtain CoAl-LDH/NF;
(6) weighing 0.5g of sodium hypophosphite as a phosphorus source, putting the prepared CoAl-LDH/NF sample and the sodium hypophosphite into a tube furnace for phosphating, using nitrogen as protective gas, heating to 400 ℃ at the heating rate of 5 ℃/min, preserving heat for 300min, respectively washing with deionized water and absolute ethyl alcohol for three times after cooling to room temperature, and finally drying in a vacuum drying box to obtain Co2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode.
Example four:
(1) cutting NF into square electrode pieces with the size of 1cm multiplied by 1cm, then putting the cut NF pieces into a beaker, adding acetone, carrying out ultrasonic treatment for 10min, taking out the electrode pieces, putting the electrode pieces into deionized water, carrying out ultrasonic water washing for 5min, taking out the electrode pieces, putting the electrode pieces into 2mol/L HCl, soaking for 10min, then taking out the electrode pieces, washing with the deionized water, and putting the electrode pieces into a vacuum drying oven for drying;
(2) weighing 0.4mmol of cobalt nitrate and 0.2mmol of aluminum nitrate in a beaker, and adding deionized water to dissolve to prepare a solution A;
(3) weighing 3.6mmol of urea in a beaker, adding deionized water for dissolving to prepare a solution B;
(4) mixing the solution A obtained in the step (2) with the solution B obtained in the step (3), adding 4mL of ethylene glycol to prepare a 20mL mixed solution, carrying out ultrasonic treatment on the mixed solution for 30min, and then transferring the mixed solution to a reaction kettle;
(5) quickly putting the NF sheet pretreated in the step (1) into the mixed solution obtained in the step (4), reacting for 12 h at 150 ℃, cooling, taking out the electrode slice, respectively washing with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum drying oven to obtain CoAl-LDH/NF;
(6) weighing 3g of sodium hypophosphite as a phosphorus source, putting the prepared CoAl-LDH/NF sample and the sodium hypophosphite into a tube furnace for phosphating, using nitrogen as protective gas, heating to 300 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 150min, cooling to room temperature, washing with deionized water and absolute ethyl alcohol for three times, and finally drying in a vacuum drying oven to obtain Co2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode.
Example five:
(1) cutting NF into square electrode pieces with the size of 1cm multiplied by 1cm, then putting the cut NF pieces into a beaker, adding acetone, carrying out ultrasonic treatment for 5min, taking out the electrode pieces, putting the electrode pieces into deionized water, carrying out ultrasonic water washing for 10min, taking out the electrode pieces, putting the electrode pieces into 2mol/L HCl, soaking for 15min, then taking out the electrode pieces, washing with the deionized water, and putting the electrode pieces into a vacuum drying oven for drying;
(2) weighing 1mmol of cobalt nitrate and 0.5mmol of aluminum nitrate in a beaker, and adding deionized water to dissolve to prepare a solution A;
(3) weighing 9mmol of urea in a beaker, adding deionized water for dissolving to prepare a solution B;
(4) mixing the solution A in the step (2) with the solution B in the step (3), adding 10mL of glycol to prepare a mixed solution of 20mL, carrying out ultrasonic treatment on the mixed solution for 30min, and then transferring the mixed solution to a reaction kettle;
(5) quickly putting the NF sheet pretreated in the step (1) into the mixed solution obtained in the step (4), reacting for 6h at 100 ℃, cooling, taking out the electrode slice, respectively washing with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum drying oven to obtain CoAl-LDH/NF;
(6) weighing 1g of sodium hypophosphite as a phosphorus source, putting the prepared CoAl-LDH/NF sample and the sodium hypophosphite into a tube furnace for phosphating, using nitrogen as protective gas, heating to 300 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 90min, respectively washing with deionized water and absolute ethyl alcohol for three times after cooling to room temperature, and finally drying in a vacuum drying oven to obtain Co2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode.
Example six:
(1) cutting NF into square electrode pieces with the size of 1cm multiplied by 1cm, then putting the cut NF pieces into a beaker, adding acetone, carrying out ultrasonic treatment for 10min, taking out the electrode pieces, putting the electrode pieces into deionized water, carrying out ultrasonic water washing for 10min, taking out the electrode pieces, putting the electrode pieces into 2mol/L HCl, soaking for 15min, then taking out the electrode pieces, washing with the deionized water, and putting the electrode pieces into a vacuum drying oven for drying;
(2) weighing 0.6mmol of cobalt nitrate and 0.3mmol of aluminum nitrate in a beaker, and adding deionized water to dissolve to prepare a solution A;
(3) weighing 3.6mmol of urea in a beaker, adding deionized water for dissolving to prepare a solution B;
(4) mixing the solution A in the step (2) with the solution B in the step (3), adding 10mL of glycol to prepare a mixed solution of 20mL, carrying out ultrasonic treatment on the mixed solution for 30min, and then transferring the mixed solution to a reaction kettle;
(5) quickly putting the NF sheet pretreated in the step (1) into the mixed solution obtained in the step (4), reacting for 6h at 180 ℃, cooling, taking out the electrode slice, respectively washing with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum drying oven to obtain CoAl-LDH/NF;
(6) weighing 2g of sodium hypophosphite as a phosphorus source, putting the prepared CoAl-LDH/NF sample and the sodium hypophosphite into a tube furnace for phosphating, using nitrogen as protective gas, heating to 300 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 120min, respectively washing with deionized water and absolute ethyl alcohol for three times after cooling to room temperature, and finally drying in a vacuum drying oven to obtain Co2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode.
Example seven:
(1) cutting NF into square electrode pieces with the size of 1cm multiplied by 1cm, then putting the cut NF pieces into a beaker, adding acetone, carrying out ultrasonic treatment for 10min, taking out the electrode pieces, putting the electrode pieces into deionized water, carrying out ultrasonic water washing for 10min, taking out the electrode pieces, putting the electrode pieces into 2mol/L HCl, soaking for 15min, then taking out the electrode pieces, washing with the deionized water, and putting the electrode pieces into a vacuum drying oven for drying;
(2) weighing 0.6mmol of cobalt nitrate and 0.3mmol of aluminum nitrate in a beaker, and adding deionized water to dissolve to prepare a solution A;
(3) weighing 7.2mmol of urea in a beaker, adding deionized water for dissolving to prepare a solution B;
(4) mixing the solution A in the step (2) with the solution B in the step (3), adding 10mL of glycol to prepare a mixed solution of 20mL, carrying out ultrasonic treatment on the mixed solution for 30min, and then transferring the mixed solution to a reaction kettle;
(5) quickly putting the NF sheet pretreated in the step (1) into the mixed solution obtained in the step (4), reacting for 24 hours at 100 ℃, cooling, taking out the electrode sheet, respectively washing with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum drying oven to obtain CoAl-LDH/NF;
(6) weighing 1g of sodium hypophosphite as a phosphorus source, putting the prepared CoAl-LDH/NF sample and the sodium hypophosphite into a tube furnace for phosphating, using nitrogen as protective gas, raising the temperature to 300 ℃ at the temperature rise speed of 5 ℃/min, preserving the temperature for 240min, and waiting for the sodium hypophosphite to be treatedCooling to room temperature, washing with deionized water and anhydrous ethanol for three times, and drying in a vacuum drying oven to obtain Co2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode.
The first comparative example is as follows:
(1) cutting NF into square electrode pieces with the size of 1cm multiplied by 1cm, then putting the cut NF pieces into a beaker, adding acetone, carrying out ultrasonic treatment for 10min, taking out the electrode pieces, putting the electrode pieces into deionized water, carrying out ultrasonic water washing for 5min, taking out the electrode pieces, putting the electrode pieces into 2mol/L HCl, soaking for 10min, then taking out the electrode pieces, washing with the deionized water, and putting the electrode pieces into a vacuum drying oven for drying;
(2) weighing 0.2mmol of cobalt nitrate and 0.1mmol of aluminum nitrate in a beaker, and adding deionized water to dissolve to prepare a solution A;
(3) weighing 1.8mmol of urea in a beaker, adding deionized water for dissolving to prepare a solution B;
(4) mixing the solution A in the step (2) with the solution B in the step (3), adding 2mL of glycol to prepare a mixed solution of 20mL, carrying out ultrasonic treatment on the mixed solution for 30min, and then transferring the mixed solution to a reaction kettle;
(5) and (3) quickly putting the NF sheet pretreated in the step (1) into the mixed solution obtained in the step (4), reacting for 9h at 100 ℃, cooling, taking out the electrode sheet, respectively washing with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum drying oven to obtain the CoAl-LDH/NF multi-stage structure composite electrode.
FIG. 1 shows Co prepared by the method of the first embodiment of the present invention2P/Ni2P/Al2O3XRD spectrogram of/NF multi-stage structure composite electrode. In the figure, strong diffraction peaks at 2 θ of 44.5 ° and 51.8 ° correspond to the (111) and (200) crystal planes of Ni standard card (PDF 04-0850). The weak diffraction peak can be based on Co2Diffraction peaks for P signature (PDF 65-2381) and Ni2Characteristic diffraction peaks of P (PDF 65-1989), respectively indexed to Co2P and Ni2P, Al appeared at diffraction angles 2 θ of 35.7 °,42.2 °, and 46.9 °2O3Characteristic (114), (205), (207) diffraction peaks (PDF #10-0414), indicating that the material preparedIs Co2P/Ni2P/Al2O3a/NF composite material.
FIG. 2 shows Co prepared by the method of the first embodiment of the present invention2P/Ni2P/Al2O3SEM pictures of different magnifications of the/NF multi-stage structure composite electrode. From the low power SEM picture of fig. 2a, it can be seen that the basic framework structure of NF, the framework surface is quite rough. The NF framework surface is locally enlarged to obtain a figure 2b, and as can be seen from the figure 2b, the NF surface is of a multi-stage structure self-assembled by nano sheets which are mutually staggered, the structure not only increases the specific surface area and active sites, promotes the adsorption of hydrogen ions and the desorption of hydrogen, but also is beneficial to the electrolyte to enter the inside of the electrode, and meanwhile, the Al framework surface is locally enlarged to obtain the figure 2b2O3The introduction of (2) improves the structural stability, is beneficial to improving the electrolysis efficiency, and greatly improves the stability of the electrode.
FIG. 3 shows Co prepared by the method of the first embodiment of the present invention2P/Ni2P/Al2O3EDS element distribution map of the/NF multi-stage structure composite electrode. As can be seen from the figure, Co, Al, O and P are uniformly distributed on NF.
FIG. 4 shows Co prepared by the method of the first embodiment of the present invention2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode, the CoAl-LDH/NF electrode prepared by the method of the comparison example, the Pt/C electrode and the NF electrode are used for the linear sweep voltammetry curve of hydrogen production by electrolyzing water. As can be seen from the figure, when the current density was-10 mA/cm-2Of Co prepared2P/Ni2P/Al2O3The overpotential of the/NF multi-stage structure composite electrode is 70mV, which is close to that of a Pt/C electrode, while the overpotential of the CoAl-LDH/NF electrode prepared in the first comparative example is 206mV, and the overpotential of a single NF electrode is 390 mV. Illustrating Co prepared by the method of the present invention2P/Ni2P/Al2O3the/NF has high activity equivalent to that of the Pt/C electrode.
FIG. 5 shows Co prepared by the method of the first embodiment of the present invention2P/Ni2P/Al2O3Composite electrode with/NF (nitrogen-nitrogen) multi-stage structure and Co prepared by method in comparative example IThe Al-LDH/NF electrode is used for the Tafel curve corresponding to the hydrogen production by electrolyzing water, and Co can be seen from the graph2P/Ni2P/Al2O3The gradient of the Tafel curve of the/NF electrode was 44.8mV/dec, which was lower than that of the CoAl-LDH/NF electrode (71 mV/dec). Compared with the gradient of a Tafel curve, the overpotential shows that the kinetic efficiency of hydrogen production by water electrolysis of the Ag/CoAl-LDH/NF electrode is far higher than that of hydrogen production by CoAl-LDH/NF electrode, and is equivalent to that of a Pt/C electrode.
FIG. 6 shows the Co prepared in the first example2P/Ni2P/Al2O3The timing current curve of the/NF multi-stage structure composite electrode under 200mV overpotential is used for representing the stability of the prepared electrode. The electrodes were reacted at an overpotential of 200mV for 24h, and it can be seen from the figure that the current density remained essentially unchanged until 24h, indicating that Co2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode has good stability of hydrogen production by electrolyzing water.
FIG. 7 shows Co prepared by the method of the first embodiment of the present invention2P/Ni2P/Al2O3Composite electrode with/NF multi-stage structure, CoAl-LDH/NF electrode prepared by the method of the comparative example I and IrO2The electrode and the NF electrode are used for linear sweep voltammetry curves obtained by the performance test of the oxygen production by electrolyzing water. As can be seen from the graph, when the current density was 10mA/cm-2Of Co prepared2P/Ni2P/ Al2O3The overpotential of the/NF multi-stage structure composite electrode is 300mV, and the commercial IrO2The overpotential of the electrode made of the catalyst is equivalent to 294 mV, which is less than 359mV of CoAl-LDH/NF and 451 mV of foamed Ni prepared in the comparative example I, and the Co prepared by the method of the invention is proved2P/Ni2P/Al2O3the/NF has high oxygen production activity by electrolyzing water.
FIG. 8 shows Co prepared by the method of the first embodiment of the present invention2P/Ni2P/Al2O3The CoAl-LDH/NF electrode prepared by the method of the comparative example is used for the Tafel curve corresponding to the oxygen production by electrolyzing water, and Co can be seen from the graph2P/Ni2P/Al2O3The gradient of Tafel curve of the/NF electrode is 50.8mV/dec, which are both lower than that of IrO2The electrode Tafel curve slope of 65mV/dec, the CoAl-LDH/NF electrode Tafel curve slope (89mV/dec) and the foam Ni Tafel curve slope of 103 mV/dec. Co is illustrated by comparison of the overpotential and the Tafel curve slope2P/Ni2P/Al2O3The efficiency of oxygen production by water electrolysis of NF electrode is far higher than the oxygen production effect of CoAl-LDH/NF and IrO2The electrodes are equivalent.
FIG. 9 shows the Co prepared in the first example2P/Ni2P/Al2O3The timing current curve of the/NF multistage structure composite electrode under 300mV overpotential is used for representing the stability of the prepared electrode. The electrodes were reacted at 300mV overpotential for 24h, and it can be seen from the figure that the current density remained essentially unchanged until 24h, indicating that Co2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode has good stability of oxygen generation by electrolyzing water.
It can be found by way of example that Co prepared by the present invention2P/Ni2P/Al2O3the/NF multi-level structure composite electrode has high-activity hydrogen production performance by water electrolysis and high-activity oxygen production performance by water electrolysis. The improvement of the electrolytic performance of the '1 + 1' is far more than 2, and is derived from Co2P、Ni2P、Al2O3The synergistic interaction of the nano sheets, good electron transmission and high specific surface area of the porous structure, and the high electrocatalytic activity has important significance for the development of hydrogen production and oxygen production by double-function water electrolysis.
Co prepared by the invention2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode has good electrocatalytic degradation performance on electrocatalytic degradation of various organic dyes in aqueous solution, and can be used for treating organic wastewater.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, substitutions, simplifications, etc. without departing from the principle and process of the present invention are all equivalent substitutions and shall be included in the protection scope of the present invention.

Claims (1)

1. Co2P/Ni2P/Al2O3The preparation method of the/NF multi-stage structure composite electrode is characterized in that the composite electrode is formed by mutually staggered Co grown on a foamed Nickel (NF) substrate2P/Ni2P/Al2O3Co staggered with each other and formed by nano-sheet assembled multi-level structure composite material2P/Ni2P/Al2O3The nano-sheet composite material is obtained by pyrolyzing and phosphating a NF substrate and cobalt-aluminum hydrotalcite nano-sheets growing on the NF substrate, and specifically comprises the following steps:
(1) cutting NF into square electrode pieces with the size of 1cm multiplied by 1cm, then putting the cut NF pieces into a beaker, adding acetone, carrying out ultrasonic treatment for 5-10min, taking out the electrode pieces, putting the electrode pieces into deionized water, carrying out ultrasonic water washing for 5-10min, taking out the electrode pieces, putting the electrode pieces into 1-5mol/L HCl for soaking for 10-15min, then taking out the electrode pieces, carrying out washing by using the deionized water, and putting the electrode pieces into a vacuum drying box for drying;
(2) weighing 0.05-1.0mmol of cobalt nitrate and 0.05-1.0mmol of aluminum nitrate in a beaker, and adding deionized water to dissolve to prepare a solution A;
(3) weighing 0.5-10.0mmol of urea in a beaker, adding deionized water for dissolving to prepare a solution B;
(4) mixing the solution A obtained in the step (2) with the solution B obtained in the step (3), adding 1-10mL of ethylene glycol to prepare a 20mL mixed solution, carrying out ultrasonic treatment on the mixed solution for 30min, and then transferring the mixed solution to a reaction kettle;
(5) quickly putting the NF sheet pretreated in the step (1) into the mixed solution obtained in the step (4), reacting for 3-24h at the temperature of 100 ℃ and 180 ℃, taking out the electrode sheet after cooling, respectively washing with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum drying oven to obtain CoAl-LDH/NF;
(6) weighing 0.1-5g of sodium hypophosphite as a phosphorus source, putting the prepared CoAl-LDH/NF sample and the sodium hypophosphite into a tube furnace for phosphating, using nitrogen as a protective gas, and heating at a speed of 1-10 ℃/minHeating to 200 ℃ and 500 ℃, keeping the temperature for 30-300min, respectively washing with deionized water and absolute ethyl alcohol for three times after cooling to room temperature, and finally drying in a vacuum drying oven to obtain Co2P/Ni2P/Al2O3the/NF multi-stage structure composite electrode.
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