CN113666427B - Transition metal layered double hydroxide modified by phytic acid and preparation method and application thereof - Google Patents
Transition metal layered double hydroxide modified by phytic acid and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses transition metal layered double hydroxide modified by phytic acid and a preparation method and application thereof, belonging to the technical field of preparation of electrolytic water anode electrode materials. The preparation method comprises the following steps: sequentially dissolving transition metal salt and alkaline substances in a solvent, uniformly mixing, adding the pretreated conductive substrate, and growing transition metal layered double hydroxide on the surface of the conductive substrate in situ by adopting a hydrothermal method or a solvothermal method; and then immersing the conductive substrate with the transition metal layered double hydroxide growing on the surface into a phytic acid solution, and preparing the transition metal layered double hydroxide modified by the phytic acid by a solvothermal method. The preparation method is simple and feasible, and the reaction conditions are mild. The prepared transition metal layered double hydroxide modified by phytic acid is used as an electrocatalyst of water oxidation reaction, and shows excellent catalytic activity and durability in alkaline electrolyte.
Description
Technical Field
The invention belongs to the technical field of electrolytic water anode electrode material preparation, and particularly relates to transition metal layered double hydroxide modified by phytic acid, a preparation method and application thereof, in particular to application of the transition metal layered double hydroxide as a water oxidation electrocatalyst in electrocatalytic decomposition of water.
Background
In the face of increasingly severe environmental pollution and energy crisis, it is crucial to develop efficient energy storage and conversion systems, such as electrolytic water devices and metal-air batteries. The water oxidation reaction (OER) at the anode is an important reaction in water electrolysis devices and metal-air batteries, since the reaction involves a four electron transfer process, resulting in slow kinetics of the water oxidation reaction. Iridium dioxide and ruthenium dioxide exhibit excellent catalytic activity for the water oxidation reaction, but iridium and ruthenium have low reserves, are expensive, and cannot be kept stable for a long time in the catalytic process. Therefore, the development of non-noble metal electrocatalysts with high water oxidation activity and durability has been the focus of research.
Among various transition metal-based water oxidation electrocatalysts, transition metal Layered Double Hydroxides (LDHs) have received much attention due to their abundant reserves, unique two-dimensional layered structures, and densely distributed active sites. However, the poor conductivity and the inability to maintain the activity and stability at high current density have restricted the large-scale industrial production and commercialization thereof.
For the above reasons, the present application has been made.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior transition metal layered double hydroxide in activity and stability, and provides a transition metal layered double hydroxide modified by phytic acid and a preparation method and application thereof. The preparation method is simple and controllable, economic and environment-friendly, and the transition metal layered double hydroxide modified by the phytic acid prepared by the invention is used as a water oxidation electrocatalyst for electrocatalytic decomposition of water, and can keep excellent activity and stability under high current density.
In order to achieve one of the above objects of the present invention, the present invention adopts the following technical solutions:
a preparation method of transition metal layered double hydroxide modified by phytic acid specifically comprises the following steps:
sequentially dissolving transition metal salt and alkaline substances in a solvent, uniformly mixing, adding the pretreated conductive substrate, and growing transition metal layered double hydroxide on the surface of the conductive substrate in situ by adopting a hydrothermal method or a solvothermal method; and then immersing the conductive substrate with the transition metal layered double hydroxide growing on the surface into a phytic acid solution, and preparing the transition metal layered double hydroxide modified by the phytic acid by a solvothermal method.
Further, according to the above technical solution, the conductive substrate may be one or more of Nickel Foam (NF), copper foam, iron foam, or aluminum foam, and preferably, nickel foam.
Further, in the above technical solution, the transition metal in the transition metal salt includes one or more of Co, Ni, Fe, Mn, and Cr.
Further, in the above technical solution, the transition metal salt includes one or more of transition metal nitrate, halide salt, acetate, sulfate and phosphate.
Further, in the above technical scheme, the alkaline substance includes one or more of urea, sodium hydroxide, potassium hydroxide, hexamethylenetetramine, and cetyltrimethylammonium bromide.
Further, in the above technical scheme, the solvent comprises one or more of water, methanol and ethanol.
Further, in the above technical solution, the molar ratio of the transition metal salt to the basic substance is 1: 0.5-10.
Further, in the above technical scheme, the dosage of the transition metal salt and the solvent may not be particularly limited as long as the uniform dispersion of the raw materials can be achieved; more preferably, the amount ratio of the transition metal salt to the solvent is (0.5-3) mmol: (10-80) mL.
Further, according to the above technical solution, the transition metal layered double hydroxide may be any one of CoFe-LDH, CoMn-LDH, NiCo-LDH, NiCr-LDH, NiFe-LDH, NiMn-LDH, FeCr-LDH, NiCoMn-LDH, and the like.
Further, according to the technical scheme, the pretreatment process of the conductive substrate comprises the following steps: and sequentially placing the conductive substrate in a dilute hydrochloric acid solution, acetone and deionized water for ultrasonic treatment for a period of time, taking out, and placing in a vacuum drying oven for drying.
Preferably, in the technical scheme, the concentration of the dilute hydrochloric acid is 1-5 mol/L.
Preferably, in the above technical solution, the ultrasonic treatment time is preferably 5-15min, and more preferably 10 min.
Further, in the above technical scheme, the specific preparation method of the transition metal layered double hydroxide is as follows:
dissolving metal salt and alkaline substance in solvent in sequence, and mixing; then sequentially transferring the obtained mixed solution and the pretreated conductive substrate to a high-pressure reaction kettle for constant-temperature reaction for 6-24h at the temperature of 100-200 ℃; and after the reaction is finished, naturally cooling to room temperature, taking out the conductive substrate with the surface uniformly covered, washing and drying to obtain the conductive substrate with the transition metal layered double hydroxide growing on the surface.
Preferably, in the above technical solution, the washing process specifically includes: the washing is performed by alternately washing with deionized water and absolute ethyl alcohol for 2-5 times, preferably 3 times.
Preferably, in the above technical solution, the drying process specifically includes: and drying the washed product in an oven at the temperature of 60-80 ℃ for 4-12 h.
Specifically, the Phytic Acid (PA) in the technical scheme is also named as Phytic acid and inositol hexaphosphoric acid, and the molecular formula is C6H18O24P6Is an organic phosphorus compound extracted from plant seeds.
Further, in the technical scheme, the concentration of the phytic acid solution is 0.01-0.2 mol/L; wherein: the solvent adopted in the phytic acid solution can be one or more of water, methanol and ethanol.
Further, in the above technical scheme, the specific preparation method of the phytic acid modified transition metal layered double hydroxide is as follows:
soaking the conductive substrate with the transition metal layered double hydroxide growing on the surface in phytic acid solution, and then transferring the conductive substrate into a high-pressure reaction kettle to react for 3 to 12 hours at a constant temperature of between 40 and 120 ℃; and after the reaction is finished, naturally cooling to room temperature, taking out the conductive substrate, washing and drying to obtain the transition metal layered double hydroxide modified by the phytic acid.
Preferably, in the above technical solution, the washing process specifically includes: the washing is performed by alternately washing with deionized water and absolute ethyl alcohol for 2-5 times, preferably 3 times.
Preferably, in the above technical solution, the drying process specifically includes: and drying the washed product in an oven at 60-80 ℃ for 4-12 h.
The second object of the present invention is to provide the phytic acid modified transition metal layered double hydroxide prepared by the above-mentioned method.
The third purpose of the invention is to provide the application of the phytic acid modified transition metal layered double hydroxide prepared by the method as a water oxidation electrocatalyst in electrocatalytic decomposition of water.
The water oxidation electrocatalyst comprises the phytic acid modified transition metal layered double hydroxide prepared by the method.
The invention has the remarkable advantages and beneficial effects that:
1. the preparation process of the invention is simple and easy, the price is low, the reaction condition is mild, and the preparation period is short.
2. According to the invention, foam Nickel (NF) is used as a preferable conductive substrate, and the prepared phytic acid modified layered double hydroxide water oxidation electrocatalyst has a 3D multi-stage structure, so that the exposure of active sites is facilitated, and the diffusion of electrolyte and precipitated gas is promoted.
3. The phosphoric acid group in the phytic acid adopted by the invention has strong chelating capacity, can react with Metal ions in the transition Metal layered double hydroxide to form Metal-O-P bonds, and simultaneously forms a phytic acid layer on the surface of the transition Metal layered double hydroxide, thereby playing a role in protection and being beneficial to improving the durability of the catalyst.
4. The introduction of the phytic acid further enhances the conductivity of the transition metal layered double hydroxide, promotes electron transmission, and regulates and controls the electron spin state of the transition metal, so that the transition metal has proper adsorption energy with an oxygen-containing intermediate generated in the oxygen precipitation process, thereby greatly improving the activity of the water oxidation reaction.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern of NiCo-LDH/NF and PA-NiCo-LDH/NF prepared in example 1 of the present invention;
FIG. 2 is a Scanning Electron Micrograph (SEM) of PA-NiCo-LDH/NF prepared in example 1 of the present invention at different magnifications;
FIG. 3 is a Fourier transform infrared spectrum of PA-NiCo-LDH/NF prepared in example 1 of the present invention;
FIG. 4 shows NiCo-LDH/NF and PA-NiCo-LDH/NF prepared in example 1 of the present invention, as well as nickel foam (Bare NF) and IrO in the prior art2The NF catalyst is respectively used in a linear sweep voltammetry curve comparison graph obtained by a water oxidation performance test in 1M KOH electrolyte;
FIG. 5 is a comparison of the Nyquist plots for NiCo-LDH/NF and PA-NiCo-LDH/NF and Nickel Foam (NF) in 1M KOH electrolyte prepared in example 1 of the present invention;
FIG. 6 is a graph of current density versus time in 1M KOH electrolyte for PA-NiCo-LDH/NF prepared in example 1 of the present invention;
FIG. 7 is a comparison of linear sweep voltammograms obtained from NiCoMn-LDH/NF and PA-NiCoMn-LDH/NF prepared in example 2 of the present invention in a 1M KOH electrolyte for water oxidation performance testing;
FIG. 8 is a comparison of linear sweep voltammograms obtained from the oxidation performance test of CoMn-LDH/NF and PA-CoMn-LDH/NF prepared in example 3 of the present invention in 1M KOH electrolyte;
FIG. 9 is a comparison of linear sweep voltammograms obtained from the water oxidation performance tests of NiCr-LDH/NF and PA-NiCr-LDH/NF prepared in example 4 of the present invention in 1M KOH electrolyte.
Detailed Description
Aiming at the problems or defects in the prior art, the invention provides a simple, feasible, economic and environment-friendly preparation method of phytic acid modified transition metal layered double hydroxide, and the phytic acid modified transition metal layered double hydroxide is used as a water oxidation electrocatalyst with high activity and durability.
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The test methods used in the following examples are all conventional methods unless otherwise specified; the raw materials and reagents used are, unless otherwise specified, those commercially available from ordinary commercial sources.
Example 1
In this example, nickel nitrate hexahydrate and cobalt nitrate hexahydrate are used together as a transition metal salt, and cetyltrimethylammonium bromide is used as an alkaline substance, so as to further illustrate the preparation method of the phytic acid modified transition metal layered double hydroxide.
The preparation method of the transition metal layered double hydroxide (PA-NiCo-LDH/NF) modified by phytic acid of the embodiment specifically comprises the following steps:
(a) preparation of Nickel Foam (NF)And (3) treatment: cutting into pieces of 3 × 7cm-2The foam Nickel (NF) is sequentially placed in 1mol/L dilute hydrochloric acid solution, acetone and deionized water for ultrasonic treatment for 10min, and after the ultrasonic treatment is finished, the foam Nickel (NF) is taken out and is placed in a vacuum drying oven at 60 ℃ for drying for 2h to obtain pretreated foam nickel;
(b) carrying out solvothermal reaction: 0.6543g (2.25mmol) of nickel nitrate hexahydrate, 0.2183g (0.75mmol) of cobalt nitrate hexahydrate and 1g (2.74mmol) of hexadecyl trimethyl ammonium bromide are sequentially dissolved in a mixed solvent consisting of 60mL of methanol and 12mL of deionized water and uniformly mixed; sequentially transferring the obtained mixed solution and the foam Nickel (NF) pretreated in the step (a) into a 100mL polytetrafluoroethylene high-pressure reaction kettle, sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle into a drying oven, and reacting for 24 hours at a constant temperature of 180 ℃; after the reaction is finished, naturally cooling the high-pressure reaction kettle to room temperature, taking out the foam Nickel (NF) uniformly covered by the light green substances, respectively and alternately flushing the foam Nickel (NF) with deionized water and absolute ethyl alcohol for 3 times, and then placing the foam Nickel (NF) in an oven at 80 ℃ for drying for 4 hours to obtain NiCo-LDH/NF;
(c) solvent thermal reaction: cutting NiCo-LDH/NF prepared in the step (b) into a size of 1 multiplied by 3cm-2Placing the small pieces into a phytic acid solution consisting of 1mL of 50% phytic acid aqueous solution and 10mL of absolute ethyl alcohol, transferring the phytic acid solution into a 25mL polytetrafluoroethylene high-pressure reaction kettle, sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle into an oven to perform constant-temperature reaction for 6 hours at the temperature of 100 ℃; after the reaction is finished, naturally cooling the high-pressure reaction kettle to room temperature, taking out the foam Nickel (NF) uniformly covered by the dark green substances, alternately washing the foam Nickel (NF) with deionized water and absolute ethyl alcohol for 3 times respectively, and then placing the foam Nickel (NF) in an oven at 60 ℃ for drying for 4 hours to obtain the PA-NiCo-LDH/NF.
FIG. 1 is an X-ray diffraction pattern of NiCo-LDH/NF and PA-NiCo-LDH/NF prepared in example 1, showing that the crystallinity of PA-NiCo-LDH/NF is reduced.
FIG. 2 is a Scanning Electron Micrograph (SEM) of PA-NiCo-LDH/NF prepared in example 1 at different magnifications. From the low-magnification SEM picture of FIG. 2a, it can be seen that the prepared PA-NiCo-LDH/NF has a 3D multi-stage structure. From the high power SEM picture of fig. 2b, it can be seen that the nanosheet array is vertically densely distributed on the surface of the foamed nickel. The 3D multilevel structure is beneficial to the exposure of active sites, promotes the diffusion of electrolytes and precipitated gases, and is beneficial to the water oxidation reaction under large current.
FIG. 3 is a Fourier transform infrared spectrum of PA-NiCo-LDH/NF prepared in example 1 of the present invention. Successful modification of phytic acid can be seen.
Example 2
This example further illustrates the preparation method of the phytic acid modified transition metal layered double hydroxide according to the present application, using nickel nitrate hexahydrate, cobalt nitrate hexahydrate, and manganese nitrate tetrahydrate as the transition metal salts together, and cetyltrimethylammonium bromide as the alkaline substance.
The preparation method of the transition metal layered double hydroxide (PA-NiCoMn-LDH/NF) modified by phytic acid of the embodiment specifically comprises the following steps:
(a) pretreatment of foamed Nickel (NF): cutting into pieces of 3 × 7cm-2The foam Nickel (NF) is sequentially placed in 3mol/L dilute hydrochloric acid solution, acetone and deionized water for ultrasonic treatment for 10min, and after the ultrasonic treatment is finished, the foam Nickel (NF) is taken out and placed in a vacuum drying oven at 60 ℃ for drying for 2h to obtain pretreated foam nickel;
(b) solvent thermal reaction: 0.2908g (1mmol) of nickel nitrate hexahydrate, 0.2910g (1mmol) of cobalt nitrate hexahydrate, 0.2510g (1mmol) of manganese nitrate tetrahydrate and 1g (2.74mmol) of hexadecyl trimethyl ammonium bromide are sequentially dissolved in a mixed solvent consisting of 60mL of methanol and 12mL of deionized water and uniformly mixed; sequentially transferring the obtained mixed solution and the foam Nickel (NF) pretreated in the step (a) into a 100mL polytetrafluoroethylene high-pressure reaction kettle, sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle into a drying oven, and reacting for 24 hours at a constant temperature of 180 ℃; after the reaction is finished, naturally cooling the high-pressure reaction kettle to room temperature, taking out the foam Nickel (NF) uniformly covered by the brown substance, alternately washing the foam Nickel (NF) with deionized water and absolute ethyl alcohol for 3 times respectively, and then placing the foam Nickel (NF) in an oven at 80 ℃ for drying for 4 hours to obtain NiCoMn-LDH/NF;
(c) solvent thermal reaction: cutting NiCoMn-LDH/NF prepared in the step (b) into a size of 1 x 3cm-2Is smallThe preparation method comprises the following steps of (1) placing the tablets in a phytic acid solution consisting of 50% phytic acid aqueous solution and 10mL of absolute ethyl alcohol by mass fraction, then transferring the phytic acid solution into a 25mL polytetrafluoroethylene high-pressure reaction kettle, sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in an oven to perform constant-temperature reaction for 12 hours at 80 ℃; after the reaction is finished, naturally cooling the high-pressure reaction kettle to room temperature, taking out the foamed Nickel (NF), alternately washing the foamed Nickel (NF) with deionized water and absolute ethyl alcohol for 3 times respectively, and then drying the foamed Nickel (NF) in an oven at the temperature of 60 ℃ for 4 hours to obtain the PA-NiCoMn-LDH/NF.
Example 3
In this example, cobalt nitrate hexahydrate and manganese nitrate tetrahydrate are used together as a transition metal salt, and cetyltrimethylammonium bromide is used as an alkaline substance, so as to further illustrate the preparation method of the phytic acid modified transition metal layered double hydroxide.
The preparation method of the transition metal layered double hydroxide (PA-CoMn-LDH/NF) modified by phytic acid of the embodiment specifically comprises the following steps:
(a) pretreatment of foam Nickel (NF): cutting into pieces of 3 × 7cm-2The foam Nickel (NF) is sequentially placed in 2mol/L dilute hydrochloric acid solution, acetone and deionized water for ultrasonic treatment for 10min, and after the ultrasonic treatment is finished, the foam Nickel (NF) is taken out and placed in a vacuum drying oven at 60 ℃ for drying for 2h to obtain pretreated foam nickel;
(b) solvent thermal reaction: 0.6548g (2.25mmol) of cobalt nitrate hexahydrate, 0.1883g (0.75mmol) of manganese nitrate tetrahydrate and 1g (2.74mmol) of hexadecyl trimethyl ammonium bromide are dissolved in a mixed solvent consisting of 60mL of anhydrous methanol and 12mL of deionized water and uniformly mixed; sequentially transferring the obtained mixed solution and the foam Nickel (NF) pretreated in the step (a) into a 100mL polytetrafluoroethylene high-pressure reaction kettle, sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle into a drying oven, and reacting for 24 hours at a constant temperature of 180 ℃; after the reaction is finished, naturally cooling the high-pressure reaction kettle to room temperature, taking out the foam Nickel (NF) uniformly covered by the brown substance, alternately washing the foam Nickel (NF) with deionized water and absolute ethyl alcohol for 3 times respectively, and then placing the foam Nickel (NF) in an oven at 60 ℃ for drying for 6 hours to obtain CoMn-LDH/NF;
(c) solvent thermal reaction: the CoMn-L prepared in the step (b) is addedCutting DH/NF into pieces with the size of 1 × 3cm-2Placing the small pieces into phytic acid solution consisting of 0.5mL of phytic acid aqueous solution with the volume fraction of 50% and 10mL of absolute ethyl alcohol, transferring the small pieces into a 25mL polytetrafluoroethylene high-pressure reaction kettle, sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle into an oven to perform constant-temperature reaction for 3 hours at 80 ℃; after the reaction is finished, naturally cooling the high-pressure reaction kettle to room temperature, taking out the foam Nickel (NF) uniformly covered by the dark green substances, respectively and alternately washing the foam Nickel (NF) with deionized water and absolute ethyl alcohol for 3 times, and then placing the foam Nickel (NF) in an oven at 60 ℃ for drying for 12 hours to obtain the PA-CoMn-LDH/NF.
Example 4
In this example, nickel nitrate hexahydrate and chromium nitrate nonahydrate are used together as a transition metal salt, and urea is used as an alkaline substance, so as to further illustrate the preparation method of the phytic acid modified transition metal layered double hydroxide.
The preparation method of the transition metal layered double hydroxide (PA-NiCr-LDH/NF) modified by phytic acid of the embodiment specifically comprises the following steps:
(a) pretreatment of foam Nickel (NF): cutting into a sheet with a size of 1 × 2cm-2The foam Nickel (NF) is sequentially placed in a dilute hydrochloric acid solution of 5mol/L, acetone and deionized water for ultrasonic treatment for 10min, and after the ultrasonic treatment is finished, the foam Nickel (NF) is taken out and is placed in a vacuum drying oven at 60 ℃ for drying for 2h to obtain pretreated foam nickel;
(b) hydrothermal reaction: sequentially dissolving 0.1745g (0.6mmol) of nickel chloride hexahydrate, 0.08g (0.2mmol) of chromium nitrate nonahydrate and 0.12g (2mmol) of urea in 15mL of deionized water, and uniformly mixing; sequentially transferring the obtained mixed solution and the foam Nickel (NF) pretreated in the step (a) into a 25mL polytetrafluoroethylene high-pressure reaction kettle, sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle into a drying oven, and reacting for 12 hours at a constant temperature of 120 ℃; and after the reaction is finished, naturally cooling the high-pressure reaction kettle to room temperature, taking out the foam Nickel (NF) uniformly covered by the light green substances, washing the foam Nickel (NF) with deionized water and absolute ethyl alcohol for 3 times respectively, and then placing the foam Nickel (NF) in an oven at 80 ℃ for drying for 4 hours to obtain the NiCr-LDH/NF.
(c) Solvent thermal reaction: putting the NiCr-LDH/NF prepared in the step (b) into a phytic acid solution consisting of 1mL of a phytic acid aqueous solution with the volume fraction of 50% and 10mL of absolute ethyl alcohol, then transferring the phytic acid solution into a 25mL polytetrafluoroethylene high-pressure reaction kettle, sealing the high-pressure reaction kettle, and putting the high-pressure reaction kettle into an oven to react for 6 hours at the temperature of 60 ℃; after the reaction is finished, naturally cooling the high-pressure reaction kettle to room temperature, taking out the foamed Nickel (NF), washing the foamed Nickel (NF) with deionized water and absolute ethyl alcohol for 3 times respectively, and then drying the foamed Nickel (NF) in an oven at 60 ℃ for 4 hours to obtain the PA-NiCr-LDH/NF.
And (3) electrochemical performance testing: the products prepared in the above examples, as well as nickel foam (Bare NF) and IrO of the prior art were tested using a Gamry electrochemical workstation2Water oxidation activity of NF catalyst.
The electrochemical performance test of the products prepared in the above embodiments all uses Hg/HgO electrode as reference electrode, carbon rod as counter electrode, foamed nickel (for example, PA-NiCo-LDH/NF prepared in embodiment 1 of the present invention) loaded with catalyst as working electrode, the electrolyte is 1M KOH, oxygen is introduced for 30min before the water oxidation performance test, so that the electrolyte is saturated with oxygen, oxygen is introduced in the whole course of the test to ensure that the equilibrium potential of the water oxidation reaction is not changed, and the sweep rate of the linear sweep voltammetry test is 5 mV/s.
FIG. 4 shows NiCo-LDH/NF and PA-NiCo-LDH/NF prepared in example 1 of the present invention, as well as nickel foam (Bare NF) and IrO in the prior art2Comparison of linear sweep voltammograms obtained from the performance test of NF catalysts in 1M KOH electrolyte for water oxidation. It can be seen that the current density is 100mA cm-2The overpotential of PA-NiCo-LDH/NF is 260mV, which is far lower than 373mV of NiCo-LDH/NF, indicating excellent water oxidation activity.
FIG. 5 is a comparison of the Nyquist plots for NiCo-LDH/NF and PA-NiCo-LDH/NF and Nickel Foam (NF) in 1M KOH electrolyte prepared in example 1 of the present invention. It can be seen that the electron transfer impedance of PA-NiCo-LDH/NF is far less than that of NiCo-LDH/NF, and the phytic acid modification is proved to obviously improve the conductivity of the transition metal layered double hydroxide.
FIG. 6 is a graph of current density versus time in 1M KOH electrolyte for PA-NiCo-LDH/NF prepared in example 1 of the present invention. Can seeThe output PA-NiCo-LDH/NF can be kept at 500mA cm-2The high current density of the high-voltage transformer reaches 500h, almost no attenuation exists, and the excellent stability of the high-voltage transformer under the high current density is shown.
FIG. 7 is a comparison of linear sweep voltammograms obtained from NiCoMn-LDH/NF and PA-NiCoMn-LDH/NF prepared in example 2 of the present invention in a 1M KOH electrolyte for water oxidation performance testing. It can be seen that the current density is 100mA cm-2The overpotential of the PA-NiCoMn-LDH/NF is 280mV, which is far lower than 390mV of the NiCoMn-LDH/NF, indicating the excellent water oxidation activity.
FIG. 8 is a comparison graph of linear sweep voltammograms of CoMn-LDH/NF and PA-CoMn-LDH/NF prepared in example 3 of the present invention in a 1M KOH electrolyte for testing water oxidation performance. It can be seen that the current density is 100mA cm-2The overpotential of PA-CoMn-LDH/NF is 270mV, which is far lower than 370mV of CoMn-LDH/NF, indicating excellent water oxidation activity.
FIG. 9 is a comparison of linear sweep voltammograms obtained from the water oxidation performance tests of NiCr-LDH/NF and PA-NiCr-LDH/NF prepared in example 4 of the present invention in 1M KOH electrolyte. It can be seen that the current density is 100mA cm-2The overpotential of PA-NiCr-LDH/NF is 271mV lower than 318mV of NiCr-LDH/NF, which shows excellent water oxidation activity.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A preparation method of transition metal layered double hydroxide modified by phytic acid is characterized by comprising the following steps: the method specifically comprises the following steps:
sequentially dissolving transition metal salt and alkaline substances in a solvent, uniformly mixing, adding the pretreated conductive substrate, and growing transition metal layered double hydroxide on the surface of the conductive substrate in situ by adopting a hydrothermal method or a solvothermal method; then immersing the conductive substrate with the transition metal layered double hydroxide growing on the surface into a phytic acid solution, and preparing the transition metal layered double hydroxide modified by the phytic acid by a solvothermal method; wherein: the transition metal in the transition metal salt comprises at least two of Co, Ni, Fe, Mn and Cr.
2. The method for preparing the phytic acid modified transition metal layered double hydroxide according to claim 1, wherein: the alkaline substance comprises one or more of urea, sodium hydroxide, potassium hydroxide, hexamethylenetetramine and hexadecyl trimethyl ammonium bromide.
3. The method for preparing the phytic acid modified transition metal layered double hydroxide according to claim 1, wherein: the molar ratio of the transition metal salt to the alkaline substance is 1: 0.5-10.
4. The method for preparing the phytic acid modified transition metal layered double hydroxide according to claim 1, wherein: the transition metal layered double hydroxide is any one of CoFe-LDH, CoMn-LDH, NiCo-LDH, NiCr-LDH, NiFe-LDH, NiMn-LDH, FeCr-LDH and NiCoMn-LDH.
5. The method for preparing the phytic acid modified transition metal layered double hydroxide according to claim 1, wherein: the specific preparation method of the transition metal layered double hydroxide comprises the following steps:
dissolving transition metal salt and alkaline substance in solvent in sequence, and mixing; then sequentially transferring the obtained mixed solution and the pretreated conductive substrate to a high-pressure reaction kettle for constant-temperature reaction for 6-24h at the temperature of 100-200 ℃; and after the reaction is finished, naturally cooling to room temperature, taking out the conductive substrate with the surface uniformly covered, washing and drying to obtain the conductive substrate with the transition metal layered double hydroxide growing on the surface.
6. The method for preparing the phytic acid modified transition metal layered double hydroxide according to claim 1, wherein: the specific preparation method of the phytic acid modified transition metal layered double hydroxide comprises the following steps:
soaking the conductive substrate with the transition metal layered double hydroxide growing on the surface in phytic acid solution, and then transferring the conductive substrate into a high-pressure reaction kettle to react for 3 to 12 hours at a constant temperature of between 40 and 120 ℃; and after the reaction is finished, naturally cooling to room temperature, taking out the conductive substrate, washing and drying to obtain the transition metal layered double hydroxide modified by the phytic acid.
7. The phytic acid-modified transition metal layered double hydroxide prepared by the method for preparing phytic acid-modified transition metal layered double hydroxide according to any one of claims 1 to 6.
8. Use of the phytic acid modified transition metal layered double hydroxide prepared by the method of any one of claims 1 to 6 as a water oxidation electrocatalyst for electrocatalytic decomposition of water.
9. A water oxidation electrocatalyst comprising the phytic acid modified transition metal layered double hydroxide prepared according to the method of any one of claims 1 to 6.
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| CN113862709B (en) * | 2021-11-23 | 2024-01-16 | 西北工业大学 | Method for catalyzing and oxidizing benzyl alcohol based on phytic acid modified foam nickel electrode |
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