CN112928271A - In-situ delamination method of hydrotalcite nanosheet array for electrocatalytic small molecule oxidation coupling hydrogen production - Google Patents
In-situ delamination method of hydrotalcite nanosheet array for electrocatalytic small molecule oxidation coupling hydrogen production Download PDFInfo
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Abstract
The invention discloses an in-situ delamination method of a hydrotalcite nanosheet array for electrocatalytic small molecule oxidation coupled hydrogen production, which comprises the following steps: hydrothermal growth of a hydrotalcite nanosheet array; and (II) carrying out electrochemical in-situ delamination on the talc nanosheet array and the like. The invention provides a simple and rapid electrochemical in-situ delamination method for a hydrotalcite nanosheet array, and the ultrathin hydrotalcite nanosheet array prepared by the method can be used in the fields of storage and conversion of various clean energy sources such as electrocatalysis micromolecule oxidation coupling hydrogen production and the like; the synthesis steps are rapid and mild, the stripping method is mild in condition and simple and convenient to operate, and the stripped ultrathin LDHs nanosheets are high in activity and good in stability.
Description
Technical Field
The invention belongs to the field of inorganic nano material synthesis, and particularly relates to an in-situ delamination method of a hydrotalcite nanosheet array for hydrogen production through electrocatalysis small-molecule oxidation coupling.
Background
The consumption of fossil fuel and the pollution problem caused by the fossil fuel are serious problems facing all people, and the search for renewable green clean energy is one of the important directions of current scientific research. Hydrogen as a clean energy has the advantages of high heat value, no greenhouse gas emission during combustion and the like, and the hydrogen production method with great potential is realized by electrically catalyzing and decomposing water. How to design a low-cost high-activity electrocatalyst is the key. In addition, the overpotential required for the oxygen evolution reaction (one of the half reactions for electrocatalytic decomposition of water) is large, the generated oxygen is not very valuable, and there is a risk of explosion when mixed with the generated hydrogen. Therefore, the development of thermodynamically more powerful small molecule oxidation reaction to replace the oxygen evolution reaction for coupled hydrogen production has received more and more attention. The small-molecule oxidation reaction can accelerate the hydrogen production efficiency and prepare chemicals with high added values. However, the products of small molecule oxidation are more and the competition of oxygen evolution reaction leads to a decrease in its efficiency. Therefore, the small-molecule electrocatalyst with low development cost, good selectivity and high efficiency is a hot spot of current scientific research.
Layered double hydroxides (LDHs, also known as hydrotalcite) are a typical host-guest layered material, and are widely researched in the field of electrocatalysts due to the characteristics of adjustable structure and performance. However, its large thickness and size become one of the factors limiting its activity. Therefore, how to prepare the LDHs with the ultrathin structure is the key for improving the catalytic performance of the LDHs. The traditional method for preparing the ultrathin LDHs is mainly a layer stripping method, namely, a large block of synthesized LDHs is stripped, so that an ultrathin structure is obtained. The liquid phase stripping method needs to add an organic solvent, and LDHs stripped are easy to re-stack; the gas phase stripping method has high requirements on equipment, and simultaneously, the stripping efficiency is low. Therefore, how to realize the high-efficiency delamination of the LDHs and obtain the ultrathin LDHs electrocatalyst with high activity and good stability still remains a problem.
Disclosure of Invention
The invention is provided for overcoming the defects in the prior art, and aims to provide an in-situ delamination method of a hydrotalcite nanosheet array for electrocatalysis small-molecule oxidation coupling hydrogen production.
The invention is realized by the following technical scheme:
an in-situ delamination method of a hydrotalcite nanosheet array for electrocatalytic small-molecule oxidation coupled hydrogen production comprises the following steps:
hydrothermal growth of hydrotalcite nanosheet arrays
Preparing a mixed solution of metal salt and urea with a certain concentration and ultrasonically dispersing;
(ii) putting the cleaned conductive substrate into a hydrothermal kettle containing the mixed solution in the step (i) for hydrothermal growth, and after the growth is finished, washing and drying the obtained nanosheet array;
(II) electrochemical in-situ delamination of hydrotalcite nanosheet array
Using the nanosheet array obtained in the step (I) as a battery anode, and using a metal lithium sheet as a battery cathode to assemble a battery;
(ii) subjecting the assembled battery to deposition of metallic lithium in a battery test system;
(iii) after the deposition process is finished, disassembling the battery, taking out the deposited positive electrode nanosheet array, placing the positive electrode nanosheet array into a solvent for standing and stripping, and cleaning and drying the nanosheet array after stripping to obtain the stripped ultrathin hydrotalcite nanosheet array.
In the technical scheme, the metal salt is metal nitrate or metal chloride; the mixed solution of the metal salt and the urea adopts deionized water as a solvent.
In the above technical scheme, the metal salt is Fe (NO)3)3、FeCl2、FeCl3、FeSO4、Fe2(SO4)3、Co(NO3)2、CoCl2、CoSO4、Ni(NO3)2、NiCl2、NiSO4、Cu(NO3)2、CuCl2、CuSO4、Zn(NO3)2、V(NO3)4、TiCl4、VCl4、MoCl5、H8MoN2O4Any one or more of them.
In the technical scheme, the concentration of the metal salt is 0.1 mM-5 mM; the concentration of the urea is 0.5 mM-25 mM.
In the above technical scheme, the conductive substrate is any one of carbon fiber cloth, carbon fiber paper, copper foam, copper mesh, nickel foam, nickel sheet, titanium sheet or FTO.
In the above technical solution, the method for cleaning the conductive substrate specifically comprises: and sequentially performing ultrasonic treatment on the conductive substrate for 15min by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water respectively.
In the technical scheme, the temperature of the hydrothermal growth is 90-120 ℃, and the growth time is determined according to the type of the metal salt; the temperature of the drying was 60 ℃.
In the technical scheme, the electrolyte of the battery is LiNO-containing electrolyte3An ether electrolyte added; the diameter of the nanosheet array serving as the battery anode is 10-16 mm.
In the technical scheme, the discharge current is 0.1 mA-1 mA during the deposition of the metal lithium, the discharge time is 2 h-24 h, and the deposition time is determined according to the anode material.
In the technical scheme, the standing time for standing and stripping is 2-12 h; the solvent for standing and stripping is any one or more of water, methanol or ethanol.
The invention has the beneficial effects that:
according to the invention, in-situ delamination of the LDHs nanosheets is realized by using a simple and rapid electrochemical method, no organic delamination solvent is required to be added in the delamination process, the delamination efficiency is high, and the delaminated ultrathin structure can be kept stable on a substrate; the invention not only creates a brand-new LDHs stripping method, but also the nanosheet prepared by the method has excellent performance and application prospect, and is expected to be applied to various fields such as electro-catalytic Oxygen Evolution Reaction (OER), electro-catalytic Hydrogen Evolution Reaction (HER), electro-catalytic biomass oxidation, lithium battery anode materials, fuel cells and the like.
Drawings
FIG. 1 is a scanning electron micrograph of an ultrathin cobalt aluminum hydrotalcite nanosheet array prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope photograph of an ultra-thin nickel aluminum hydrotalcite nanosheet array prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope photograph of a nickel iron ultrathin hydrotalcite nanosheet array prepared in example 3 of the present invention;
FIG. 4 is a characterization of 5-hydroxymethylfurfural oxidation performance of cobalt-aluminum ultrathin hydrotalcite nanosheet arrays prepared in example 1 of the present invention;
FIG. 5 is a characteristic of benzyl alcohol oxidation performance of nickel aluminum ultrathin hydrotalcite nanosheet array prepared in example 2 of the present invention;
fig. 6 is an aniline oxidation performance characterization of the nickel iron ultrathin hydrotalcite nanosheet array prepared in example 3 of the present invention.
Detailed Description
In order to make the technical scheme of the present invention better understood by those skilled in the art, the technical scheme of the in-situ delamination method of a hydrotalcite nanosheet array for hydrogen production through electrocatalytic small molecule oxidation coupling according to the present invention is further described below by referring to the drawings of the specification and through specific embodiments.
An in-situ delamination method of a hydrotalcite nanosheet array for electrocatalytic small-molecule oxidation coupled hydrogen production comprises the following steps:
hydrothermal growth of hydrotalcite nanosheet arrays
Dissolving metal salt and urea by deionized water and ultrasonically dispersing to obtain a mixed solution of the metal salt and the urea;
the metal salt is metal nitrate or metal chloride, and is Fe (NO)3)3、FeCl2、FeCl3、FeSO4、Fe2(SO4)3、Co(NO3)2、CoCl2、CoSO4、Ni(NO3)2、NiCl2、NiSO4、Cu(NO3)2、CuCl2、CuSO4、Zn(NO3)2、V(NO3)4、TiCl4、VCl4、MoCl5Or H8MoN2O4Any one or more of;
the concentration of the metal salt is 0.1 mM-5 mM; the concentration of the urea is 0.5 mM-25 mM; the volume of the deionized water is 25 mL-100 mL;
(ii) putting the cleaned conductive substrate into a hydrothermal kettle containing the mixed solution in the step (i) for hydrothermal growth, and after the growth is finished, washing and drying the obtained nanosheet array;
cleaning a conductive substrate, then placing the conductive substrate into a polytetrafluoroethylene hydrothermal kettle, adding the dispersed mixed solution obtained in the step (i), and carrying out reaction growth at the temperature of 90-120 ℃, wherein the growth time and temperature are properly adjusted according to the type of the selected salt; after the growth is finished, washing the obtained nanosheet array, and drying the nanosheet array in a 60 ℃ drying oven;
the conductive substrate is any one of carbon fiber cloth, carbon fiber paper, copper foam, copper mesh, nickel foam, nickel sheet, titanium sheet or FTO;
the cleaning method of the conductive substrate specifically comprises the following steps: sequentially performing ultrasonic treatment on the conductive substrate for about 15min by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water respectively to remove impurities on the surface;
(II) electrochemical in-situ delamination of hydrotalcite nanosheet array
Cutting the hydrotalcite nanosheet array obtained in the step (I) into a proper size (the diameter is 10-16mm), using the hydrotalcite nanosheet array as a battery anode, and using a metal lithium sheet as a cathode to assemble the battery, wherein the electrolyte contains LiNO3And an ether electrolyte is added.
(ii) subjecting the assembled cell to deposition of metallic lithium in a battery test system: the discharge current is: 0.1-1mA, the discharge time is 2-24 h, and the specific deposition time is properly adjusted according to different anode materials;
(iii) after the deposition process is finished, disassembling the battery, taking out the deposited positive electrode nanosheet array, and then putting the positive electrode nanosheet array into a solvent for standing and stripping, wherein the standing time is 2-12 h. And (3) after stripping, cleaning the nanosheet array and drying the nanosheet array in an oven to obtain the ultrathin LDHs nanosheet array after stripping.
The stripping solvent is any one of deionized water, methanol or ethanol.
Example 1
The method for synthesizing the cobalt-aluminum ultrathin hydrotalcite nanosheet array comprises the following specific steps of:
growing a cobalt-aluminum hydrotalcite nanosheet array on the surface of a foamed nickel substrate by using a hydrothermal method;
mixing Co (NO)3)2、Al(NO3)3Dissolving urea with deionized water, and performing ultrasonic dispersion to obtain a mixed solution of the urea and the deionized water;
sequentially performing ultrasonic treatment on the foamed nickel substrate for about 15min by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water respectively to remove impurities on the surface;
cleaning a foamed nickel substrate, putting the cleaned foamed nickel substrate into a polytetrafluoroethylene hydrothermal kettle, adding the dispersed mixed solution, and carrying out reaction growth for 6 hours at 90 ℃; after the growth is finished, washing the obtained nanosheet array, and drying the nanosheet array in a 60 ℃ drying oven;
(ii) taking the cobalt-aluminum hydrotalcite nanosheet array obtained in the previous step as a positive electrode to carry out lithium battery assembly and discharge for 12 hours;
and (iii) after the discharging is finished, disassembling the battery, removing the positive electrode, placing the positive electrode into an absolute ethyl alcohol solution, standing for 6 hours, and drying to obtain the cobalt-aluminum ultrathin hydrotalcite nanosheet array.
Fig. 1 is a scanning electron microscope photograph of the cobalt-aluminum ultrathin hydrotalcite nanosheet array obtained by preparation.
Fig. 4 shows that the prepared cobalt-aluminum ultrathin hydrotalcite nanosheet has a linear voltammetry scanning curve for electrocatalysis of 5-hydroxymethylfurfural oxidation in an alkaline solution (1 mol/l of potassium hydroxide solution), and shows a larger current in an electrolyte containing 10 mmol/l of 5-hydroxymethylfurfural, which indicates that the prepared cobalt-aluminum ultrathin hydrotalcite nanosheet has good electrocatalytic oxidation performance of 5-hydroxymethylfurfural.
Example 2
The method for synthesizing the nickel-aluminum ultrathin hydrotalcite nanosheet array comprises the following specific steps of:
growing a nickel-aluminum hydrotalcite nanosheet array on the surface of the carbon fiber cloth substrate by using a hydrothermal method;
mixing Ni (NO)3)2、Al(NO3)3Dissolving urea with deionized water, and performing ultrasonic dispersion to obtain a mixed solution of the urea and the deionized water;
sequentially performing ultrasonic treatment on the carbon fiber cloth substrate for about 15min by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water respectively to remove impurities on the surface;
cleaning a carbon fiber cloth substrate, putting the cleaned carbon fiber cloth substrate into a polytetrafluoroethylene hydrothermal kettle, adding the dispersed mixed solution, and carrying out reaction growth for 8 hours at 110 ℃; after the growth is finished, washing the obtained nanosheet array, and drying the nanosheet array in a 60 ℃ drying oven;
(ii) taking the nickel-aluminum hydrotalcite nanosheet array obtained in the previous step as a positive electrode to carry out lithium battery assembly and discharge for 18 hours;
and (iii) after the discharging is finished, disassembling the battery, removing the positive electrode, placing the battery into an absolute ethyl alcohol solution, standing for 10 hours, and drying to obtain the nickel-aluminum ultrathin hydrotalcite nanosheet array.
Fig. 2 is a scanning electron microscope photograph of the prepared nickel-aluminum ultrathin hydrotalcite nanosheet array.
Fig. 5 shows a linear voltammetry scanning curve of the prepared nickel-aluminum ultrathin hydrotalcite nanosheet in an alkaline solution (1 mol/l of potassium hydroxide solution) for electrocatalytic oxidation of benzaldehyde, and the nickel-aluminum ultrathin hydrotalcite nanosheet shows a larger current in an electrolyte containing 10 mmol/l of benzaldehyde, which indicates that the prepared nickel-aluminum ultrathin hydrotalcite nanosheet has good electrocatalytic oxidation performance of benzaldehyde.
Example 3
The method for synthesizing the nickel iron ultrathin hydrotalcite nanosheet array comprises the following specific steps:
growing a nickel iron hydrotalcite nanosheet array on the surface of the carbon fiber cloth substrate by using a hydrothermal method;
mixing Ni (NO)3)2、Fe(NO3)3Dissolving urea with deionized water, and performing ultrasonic dispersion to obtain a mixed solution of the urea and the deionized water;
sequentially performing ultrasonic treatment on the carbon fiber cloth substrate for about 15min by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water respectively to remove impurities on the surface;
cleaning a carbon fiber cloth substrate, putting the cleaned carbon fiber cloth substrate into a polytetrafluoroethylene hydrothermal kettle, adding the dispersed mixed solution, and carrying out reaction growth for 12 hours at 120 ℃; after the growth is finished, washing the obtained nanosheet array, and drying the nanosheet array in a 60 ℃ drying oven;
(ii) taking the nickel-iron hydrotalcite nanosheet array obtained in the last step as a positive electrode to carry out lithium battery assembly and discharge for 12 hours;
and (iii) after the discharging is finished, disassembling the battery, removing the positive electrode, placing the battery into an anhydrous methanol solution, standing for 12 hours, and drying to obtain the nickel iron ultrathin hydrotalcite nanosheet array.
Fig. 2 is a scanning electron microscope photograph of the prepared nickel iron ultrathin hydrotalcite nanosheet array.
Fig. 5 shows a linear voltammetry scan curve of the prepared nickel-iron ultrathin hydrotalcite nanosheet in an alkaline solution (1 mol/l potassium hydroxide solution) for electrocatalytic aniline oxidation, and the nickel-iron ultrathin hydrotalcite nanosheet shows a larger current in an electrolyte containing 10 mmol/l aniline, which indicates that the prepared nickel-iron ultrathin hydrotalcite nanosheet has good aniline electrocatalytic oxidation performance.
The invention provides a preparation method of an ultrathin hydrotalcite nanosheet array for small-molecule oxidation coupled hydrogen production, which is realized by an in-situ stripping strategy, and the ultrathin hydrotalcite nanosheet array with the thickness of below 5nm is obtained by in-situ stripping of the hydrotalcite nanosheets on a conductive substrate.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. An in-situ delamination method of a hydrotalcite nanosheet array for electrocatalytic small-molecule oxidation coupled hydrogen production is characterized by comprising the following steps of: the method comprises the following steps:
hydrothermal growth of hydrotalcite nanosheet arrays
Preparing a mixed solution of metal salt and urea with a certain concentration and ultrasonically dispersing;
(ii) putting the cleaned conductive substrate into a hydrothermal kettle containing the mixed solution in the step (i) for hydrothermal growth, and after the growth is finished, washing and drying the obtained nanosheet array;
(II) electrochemical in-situ delamination of hydrotalcite nanosheet array
Using the nanosheet array obtained in the step (I) as a battery anode, and using a metal lithium sheet as a battery cathode to assemble a battery;
(ii) subjecting the assembled battery to deposition of metallic lithium in a battery test system;
(iii) after the deposition process is finished, disassembling the battery, taking out the deposited positive electrode nanosheet array, placing the positive electrode nanosheet array into a solvent for standing and stripping, and cleaning and drying the nanosheet array after stripping to obtain the stripped ultrathin hydrotalcite nanosheet array.
2. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the metal salt is metal nitrate or metal chloride; the mixed solution of the metal salt and the urea adopts deionized water as a solvent.
3. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 2, wherein: the metal salt is Fe (NO)3)3、FeCl2、FeCl3、FeSO4、Fe2(SO4)3、Co(NO3)2、CoCl2、CoSO4、Ni(NO3)2、NiCl2、NiSO4、Cu(NO3)2、CuCl2、CuSO4、Zn(NO3)2、V(NO3)4、TiCl4、VCl4、MoCl5、H8MoN2O4Any one or more of them.
4. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the concentration of the metal salt is 0.1 mM-5 mM; the concentration of the urea is 0.5 mM-25 mM.
5. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the conductive substrate is any one of carbon fiber cloth, carbon fiber paper, copper foam, copper mesh, nickel foam, nickel sheet, titanium sheet or FTO.
6. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the cleaning method of the conductive substrate specifically comprises the following steps: and sequentially performing ultrasonic treatment on the conductive substrate for 15min by using dilute hydrochloric acid, acetone, absolute ethyl alcohol and deionized water respectively.
7. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the temperature of the hydrothermal growth is 90-120 ℃, and the growth time is determined according to the type of the metal salt; the temperature of the drying was 60 ℃.
8. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the electrolyte of the battery is LiNO-containing electrolyte3An ether electrolyte added; the diameter of the nanosheet array serving as the battery anode is 10-16 mm.
9. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the discharge current is 0.1 mA-1 mA during the deposition of the metal lithium, the discharge time is 2 h-24 h, and the deposition time is determined according to the anode material.
10. The in-situ delamination method of the hydrotalcite nanosheet array for electrocatalytic small molecule oxidation-coupled hydrogen production according to claim 1, wherein: the standing time for the standing stripping is 2-12 h; the solvent for standing and stripping is any one or more of water, methanol or ethanol.
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孟格等: "水滑石纳米阵列电极在能量储存和转化中的应用", 《中国科学:化学》, no. 04, 20 April 2017 (2017-04-20), pages 32 - 43 * |
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CN114959771A (en) * | 2022-04-19 | 2022-08-30 | 南京信息工程大学 | Nickel-based electrocatalyst and electrolytic cell for degrading formaldehyde wastewater by hydrogen production |
CN114959771B (en) * | 2022-04-19 | 2023-10-20 | 南京信息工程大学 | Nickel-based electrocatalyst and hydrogen production synergistic formaldehyde wastewater degradation electrolytic cell |
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