CN116926957B - Preparation method and application of dysprosium-doped nickel-metal organic frame composite material - Google Patents

Preparation method and application of dysprosium-doped nickel-metal organic frame composite material Download PDF

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CN116926957B
CN116926957B CN202310873967.XA CN202310873967A CN116926957B CN 116926957 B CN116926957 B CN 116926957B CN 202310873967 A CN202310873967 A CN 202310873967A CN 116926957 B CN116926957 B CN 116926957B
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dysprosium
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nickel
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杨秀林
廖淼
黄志洋
刘正琪
王丽霞
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Guangxi Normal University
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Abstract

The invention discloses a preparation method and application of a dysprosium-doped nickel-metal organic framework composite material, and belongs to the technical field of electrocatalytic oxygen evolution reaction. The method specifically comprises the following steps: and growing a dysprosium-doped nickel-metal organic frame in the structure in situ on the carrier by a one-step hydrothermal method to obtain the dysprosium-doped nickel-metal organic frame composite material. The dysprosium doped nickel-metal organic framework composite material has excellent electrocatalytic oxygen evolution performance, good full water decomposition performance, excellent conductivity and good stability under alkaline conditions, can be used as an excellent catalyst for electrocatalytic oxygen evolution reaction, and has certain practical application potential. The preparation method is very simple, has short preparation flow and is convenient for commercial popularization.

Description

Preparation method and application of dysprosium-doped nickel-metal organic frame composite material
Technical Field
The invention relates to the technical field of electrocatalytic oxygen evolution reaction, in particular to a preparation method and application of dysprosium doped nickel-metal organic frame composite material.
Background
In order to cope with the problems of energy exhaustion, environmental pollution, etc., it is becoming a great trend to develop renewable new energy sources that replace fossil energy sources. The hydrogen energy is sustainable and environment-friendly green ideal energy, and has higher energy density. Hydrogen is stored in water on earth mainly in the form of compounds. Electrochemical water splitting is a potential approach to achieving sustainable production of hydrogen and is currently the most promising green commercial hydrogen production process.
Among these, the electrocatalytic oxygen evolution reaction is a key step in water decomposition. However, oxygen Evolution (OER) is a four electron transfer process, severely limiting the overall efficiency of water splitting due to slow kinetics and high reaction overpotential. While RuO 2 and IrO 2 are considered the most effective OER electrocatalysts, their poor stability, scarcity and high price severely hamper their large-scale commercial application. Therefore, there is an urgent need to develop efficient, inexpensive and stable non-noble metal OER catalysts.
Transition metal-organic frameworks (MOFs) are one of the candidates for constructing novel high-efficiency OER electrocatalysts due to their high specific surface area, highly porous structure and rich active metal centers. However, MOFs are generally poor in conductivity and stability and can only utilize a portion of the metal active sites, which greatly limits their electrocatalytic properties. Therefore, it is necessary to modify MOFs and develop MOFs with better conductivity and OER catalytic activity.
Disclosure of Invention
The invention aims to provide a preparation method and application of dysprosium-doped nickel-metal organic framework composite material, so as to solve the problems in the prior art.
In order to achieve the above object, the present invention provides the following solutions:
one of the technical schemes of the invention is as follows: the dysprosium-doped nickel-metal organic frame composite material (Dy@Ni-MOF for short) is obtained by growing a nickel-metal organic frame doped with dysprosium on a carrier in situ on the carrier by a one-step hydrothermal method.
Further, the method for in-situ growing the dysprosium doped nickel-metal organic framework inside the structure on the carrier by a one-step hydrothermal method comprises the following steps: dissolving dysprosium source, nickel source, organic ligand source and regulator in mixed water solution to obtain reaction solution; and adding the carrier into the reaction solution, and heating to perform hydrothermal reaction to obtain the dysprosium-doped nickel-metal organic framework composite material.
Further, the dysprosium source is dysprosium nitrate; the nickel source is nickel nitrate; the organic ligand source is 2, 5-dihydroxyterephthalic acid (DHTA); the regulator is salicylic acid; the carrier is carbon cloth.
The carbon cloth has good extensibility and flexibility, is high-temperature resistant, and has a framework which is not damaged under extreme conditions, thus being suitable for being used as a carrier of the dysprosium doped nickel-metal organic framework composite material.
The regulator salicylic acid plays the following roles in the reaction process: (1) The hydroxyl in the salicylic acid structure and the metal ion form a coordination bond, so that the structure of the Ni-MOF is stabilized; (2) Salicylic acid is used as a reaction regulator in the synthesis process, the pH value of the reaction is regulated, the formation of Ni-MOF is controlled, and the purity of the Ni-MOF is improved; (3) Forming connection with metal Ni ions in the synthesis process, participating in constructing a porous structure of Ni-MOF as a bridging ligand, and adjusting the size and shape of a pore canal; (4) When the metal and ligand bonds are very strong, metal-ligand complexes are formed rather than crystalline long range order structures, in which case salicylic acid may prevent the ligand from forming complexes with the metal too rapidly by coordination with the metal.
In addition, salicylic acid is selected as a regulator instead of other acids in the present invention because salicylic acid has the following advantages: (1) mildness: salicylic acid is a milder organic acid and is less acidic than strong acids (e.g., sulfuric acid, hydrochloric acid). Strong acids dissolve crystals formed by MOFs, resulting in slow crystal growth. Therefore, salicylic acid is more suitable to be used in the synthesis process of Ni-MOF under mild conditions. (2) versatility: salicylic acid can be used as an organic ligand to participate in metal coordination chemical reaction to form Metal Organic Framework (MOF) and the like. In addition, salicylic acid can be used as an acidic catalyst. (3) availability: salicylic acid is a relatively common organic acid, easy to prepare and obtain, and is more common and economical than some rare or expensive acidic catalysts.
Further, dysprosium source by mole ratio: nickel source: organic ligand source: regulator = 0.05-0.2:0.7:0.216:0.216; the dosage ratio of the nickel source to the mixed aqueous solution is 0.7 mmol/18 mL.
Further preferably, the dysprosium source is in terms of molar ratio: nickel source: organic ligand source: regulator=0.1:0.7:0.216:0.216.
Further, the ratio of the nickel source to the carrier is 0.7mmol:4.5cm 2 (support surface area).
Further, the mixed aqueous solution is formed by mixing N, N-dimethylformamide, ethanol and water.
Further, N-dimethylformamide: ethanol: water=1:1:1.
Further, the temperature of the hydrothermal reaction was 150 ℃ for 12 hours.
Further, the specific operation of dissolving the dysprosium source, the nickel source, the organic ligand source and the regulator in the mixed aqueous solution is as follows: dysprosium source, nickel source, organic ligand source and regulator were added to water and sonicated for 30 minutes.
Further, the method also comprises a pretreatment operation on the carrier, in particular: the support was cut to the desired dimensions and then washed in sulfuric acid solution, deionized water and ethanol, respectively.
Further, the specific operation of the washing is as follows: respectively ultrasonically washing in 0.5mol/L sulfuric acid solution, deionized water and ethanol for 15 minutes, circularly washing for three times, and naturally airing.
Further, after the hydrothermal reaction is finished, the method further comprises washing and drying operations, specifically: the dysprosium-doped nickel-metal organic framework-loaded carbon cloth was thermally reacted with water rinse water three times and then dried at 50 ℃ for 12 hours.
The dysprosium-doped nickel-metal organic framework composite material is prepared by a one-step hydrothermal method, and the preparation method has the following advantages: (1) increasing the product yield: the one-step hydrothermal method can avoid loss caused by falling of the material grown on the carbon cloth in situ, and is more beneficial to the in-situ growth of the material; (2) improving product purity: the probability of generating impurities and side reactions can be reduced; (3) simplified synthesis steps: the process for synthesizing the composite material by the one-step hydrothermal method is simple to operate, and complex steps are avoided.
The second technical scheme of the invention is as follows: the dysprosium-doped nickel-metal organic frame composite material prepared by the preparation method of the dysprosium-doped nickel-metal organic frame composite material.
The third technical scheme of the invention: the application of the dysprosium doped nickel-metal organic framework composite material in the electrocatalytic oxygen evolution reaction.
Further, the dysprosium-doped nickel-metal organic framework composite material is used as a catalyst for electrocatalytic oxygen evolution reaction.
Further, the dysprosium-doped nickel-metal organic framework composite material is used as an electrode (anode) of an electrocatalytic oxygen evolution reaction system.
The invention discloses the following technical effects:
(1) According to the invention, the dysprosium-doped nickel-metal organic framework is grown in situ on the carrier by a simple one-step hydrothermal method, so that the dysprosium-doped nickel-metal organic framework composite material (Dy@Ni-MOF composite material) is obtained, and the electronic structure of the Ni-MOF is effectively regulated and controlled by successful doping of rare earth element Dy, so that the conductivity and OER catalytic performance of the composite material are improved. The Dy@Ni-MOF composite material has excellent OER performance and good conductivity under alkaline conditions, and has long-term stability. In the process of full water decomposition, the Dy@Ni-MOF prepared by the method also shows excellent full water decomposition performance and good stability, which shows that the Dy@Ni-MOF prepared by the method can be used as an excellent catalyst for the electrocatalytic oxygen evolution reaction and has a certain practical application potential.
(2) The preparation method is simple, has short preparation flow, greatly shortens the preparation time cost and is convenient for commercial popularization; in addition, the Dy@Ni-MOF composite material prepared by the method can be directly used as an anode for an electrocatalytic oxygen evolution reaction, and is very convenient to apply.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments 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 other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray powder diffraction pattern of Dy@Ni-MOF composite materials prepared in examples 1-3 and Ni-MOF prepared in comparative example 1.
FIG. 2 is a Raman spectrum of the Dy@Ni-MOF composite material prepared in example 2 and the Ni-MOF prepared in comparative example 1.
FIG. 3 is a Fourier transform infrared spectrum of Dy@Ni-MOF composite material prepared in example 2, ni-MOF prepared in comparative example 1, and DHTA.
FIG. 4 is a scanning electron microscope image of the Dy@Ni-MOF composite material prepared in examples 1-3 and the Ni-MOF prepared in comparative example 1; wherein a is the Ni-MOF of comparative example 1; b is 0.05Dy@Ni-MOF of example 1; c is 0.1Dy@Ni-MOF of example 2; d is 0.2Dy@Ni-MOF of example 3.
FIG. 5 is a scanning electron micrograph of the Ni-MOF prepared in comparative example 1 and various electron micrographs of Dy@Ni-MOF composite material prepared in example 2; wherein a-b are scanning electron microscope pictures of Ni-MOF and Dy@Ni-MOF respectively; c-k are respectively a transmission electron microscope image, a high-resolution transmission electron microscope image, an atomic force microscope image, a corresponding high-level section image of an atomic force microscope, a high-angle annular dark field transmission electron microscope image and distribution diagrams of all elements of the Dy@Ni-MOF.
FIG. 6 is an X-ray photoelectron spectrum and an ultraviolet electron spectrum of the Ni-MOF composite material prepared in comparative example 1 and Dy@Ni-MOF composite material prepared in example 2; wherein a is an X-ray photoelectron spectrum; b-e is ultraviolet electron energy spectrum.
FIG. 7 is a graph showing the results of ohmic testing of a Ni-MOF composite material prepared in comparative example 1 and Dy@Ni-MOF composite material prepared in example 2 using a multimeter; wherein a is Ni-MOF, and b is Dy@Ni-MOF.
FIG. 8 is the results of electrochemical performance tests of Dy@Ni-MOF composite materials prepared in examples 1-3 in 1.0M KOH; wherein a is an electrocatalytic oxygen evolution linear scanning curve; b is a tafel slope diagram; c is an electrochemical impedance spectrogram; d is a linear scan curve normalized by the electrochemically active surface area.
FIG. 9 is a graph showing various performance comparisons of Dy@Ni-MOF composite material prepared in example 2 with Ni-MOF prepared in comparative example 1, ruO 2 electrode material prepared in comparative example 3, and other existing catalysts; wherein a-b are an electrocatalytic oxygen evolution linear scanning curve and a Tafil slope chart of Dy@Ni-MOF, ni-MOF and RuO 2 electrode materials; c is a Tafil slope plot of Dy@Ni-MOF versus the catalyst reported in the prior art; d is an electrochemical impedance spectrum of Dy@Ni-MOF, ni-MOF and RuO 2; e is a relation diagram of turnover frequency and overpotential of Ni-MOF and Dy@Ni-MOF; f is the linear sweep voltammetric polarization curve after initial and 1000 cyclic voltammetry cycles of Dy@Ni-MOF.
FIG. 10 is a cyclic voltammetry curve and an electric double layer capacitance plot of the Dy@Ni-MOF composite material prepared in example 2 and the Ni-MOF prepared in comparative example 1 in a non-Faraday potential interval; wherein a-b are cyclic voltammetry curves of Dy@Ni-MOF and Ni-MOF respectively; c is an electric double layer capacitance diagram of Dy@Ni-MOF and Ni-MOF; d is a linear sweep voltammetry plot of the normalized electrochemically active surface areas of Ni-MOF and Dy@Ni-MOF.
FIG. 11 is a graph showing the whole water splitting process and results; wherein a is a full water splitting schematic diagram; b is the polarization curve in 1.0M KOH of a two-electrode system consisting of the Dy@Ni-MOF composite material prepared in example 2 and the Pt/C electrode material prepared in comparative example 2, and a two-electrode system consisting of the Pt/C electrode material prepared in comparative example 2 and the RuO 2 electrode material prepared in comparative example 3; c is a comparison of the two electrode system consisting of Dy@Ni-MOF and Pt/C electrode materials with the full water splitting cell voltages reported in the prior art; d is the stability test result of the two-electrode system consisting of Dy@Ni-MOF and Pt/C electrode materials.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
Dy@Ni-MOF composite material is prepared by a one-step hydrothermal method and comprises the following steps of:
(1) Pretreating carbon cloth: cutting carbon cloth into pieces of 1.5X3 cm 2, respectively ultrasonic washing in 0.5mol/L sulfuric acid solution, deionized water and ethanol for 15min, circularly washing for three times, and naturally air drying for use.
(2) Preparing a reaction solution: respectively weighing 0.05mmol of dysprosium nitrate hexahydrate, 0.7mmol of nickel nitrate hexahydrate, 0.216mmol of 2, 5-dihydroxyterephthalic acid and 0.216mmol of salicylic acid, adding into 18mL of mixed aqueous solution (prepared by mixing water, ethanol and N, N-dimethylformamide according to the volume ratio of 1:1:1), and carrying out ultrasonic treatment for 30 minutes.
One-step hydrothermal reaction: placing the carbon treated in the step (1) in the reaction solution prepared in the step (2), carrying out heat preservation reaction in an oven at 150 ℃ for 12 hours, naturally cooling after the reaction is finished, flushing the carbon cloth loaded with the dysprosium-doped nickel-metal organic framework with water for three times, and then placing the carbon cloth in the oven and drying the carbon cloth at 50 ℃ for 12 hours to obtain the 0.05Dy@Ni-MOF composite material (0.05 represents Dy element content of 0.05 mmol).
Example 2
Dy@Ni-MOF composite material is prepared by a one-step hydrothermal method and comprises the following steps of:
(1) Pretreating carbon cloth: cutting carbon cloth into pieces of 1.5X3 cm 2, respectively ultrasonic washing in 0.5mol/L sulfuric acid solution, deionized water and ethanol for 15min, circularly washing for three times, and naturally air drying for use.
(2) Preparing a reaction solution: respectively weighing 0.1mmol of dysprosium nitrate hexahydrate, 0.7mmol of nickel nitrate hexahydrate, 0.216mmol of 2, 5-dihydroxyterephthalic acid and 0.216mmol of salicylic acid, adding into 18mL of mixed aqueous solution (prepared by mixing water, ethanol and N, N-dimethylformamide according to the volume ratio of 1:1:1), and carrying out ultrasonic treatment for 30 minutes.
One-step hydrothermal reaction: placing the carbon treated in the step (1) in the reaction solution prepared in the step (2), carrying out heat preservation reaction in an oven at 150 ℃ for 12 hours, naturally cooling after the reaction is finished, flushing the carbon cloth loaded with the dysprosium-doped nickel-metal organic framework with water for three times, and then placing the carbon cloth in the oven and drying the carbon cloth at 50 ℃ for 12 hours to obtain the 0.1Dy@Ni-MOF composite material (0.1 represents the Dy element content of 0.1 mmol).
Example 3
Dy@Ni-MOF composite material is prepared by a one-step hydrothermal method and comprises the following steps of:
(1) Pretreating carbon cloth: cutting carbon cloth into pieces of 1.5X3 cm 2, respectively ultrasonic washing in 0.5mol/L sulfuric acid solution, deionized water and ethanol for 15min, circularly washing for three times, and naturally air drying for use.
(2) Preparing a reaction solution: respectively weighing 0.2mmol of dysprosium nitrate hexahydrate, 0.7mmol of nickel nitrate hexahydrate, 0.216mmol of 2, 5-dihydroxyterephthalic acid and 0.216mmol of salicylic acid, adding into 18mL of mixed aqueous solution (prepared by mixing water, ethanol and N, N-dimethylformamide according to the volume ratio of 1:1:1), and carrying out ultrasonic treatment for 30 minutes.
One-step hydrothermal reaction: placing the carbon treated in the step (1) in the reaction solution prepared in the step (2), carrying out heat preservation reaction in an oven at 150 ℃ for 12 hours, naturally cooling after the reaction is finished, flushing the carbon cloth loaded with the dysprosium-doped nickel-metal organic framework with water for three times, and then placing the carbon cloth in the oven and drying the carbon cloth at 50 ℃ for 12 hours to obtain the 0.2Dy@Ni-MOF composite material (0.2 represents the Dy element content of 0.2 mmol).
Comparative example 1
The one-step hydrothermal method for preparing the Ni-MOF composite material comprises the following steps:
(1) Pretreating carbon cloth: cutting carbon cloth into pieces of 1.5X3 cm 2, respectively ultrasonic washing in 0.5mol/L sulfuric acid solution, deionized water and ethanol for 15min, circularly washing for three times, and naturally air drying for use.
(2) Preparing a reaction solution: respectively weighing 0.7mmol of nickel nitrate hexahydrate, 0.216mmol of 2, 5-dihydroxyterephthalic acid and 0.216mmol of salicylic acid, adding into 18mL of mixed solution (prepared by mixing water, ethanol and N, N-dimethylformamide according to the volume ratio of 1:1:1), and carrying out ultrasonic treatment for 30 minutes.
One-step hydrothermal reaction: arranging the carbon treated in the step (1) in the reaction solution prepared in the step (2), carrying out heat preservation reaction in an oven at 150 ℃ for 12 hours, naturally cooling after the reaction is finished, flushing the carbon cloth loaded with the nickel-metal organic framework with water for three times, and then drying in the oven at 50 ℃ for 12 hours to obtain the Ni-MOF composite material.
Comparative example 2
Preparation of Pt/C electrode material
2Mg of Pt/C (commercially available) was weighed and added to a mixed solution of 200. Mu.L of deionized water, 200. Mu.L of absolute ethyl alcohol and 50. Mu.L of Nafion solution, and subjected to ultrasonic dissolution for 30 minutes, and then the Pt/C slurry after ultrasonic homogenization was dropped on 1cm 2 of carbon cloth and dried at room temperature for standby.
Comparative example 3
Preparation of RuO 2 electrode material
2Mg of RuO 2 (commercially available) was weighed and added to a mixed solution of 200. Mu.L of deionized water, 200. Mu.L of absolute ethyl alcohol and 50. Mu.L of Nafion solution, and the solution was sonicated for 30 minutes, and then the sonicated uniform slurry of RuO 2 was dropped onto 1cm 2 carbon cloth and dried at room temperature for use.
Effect verification
1. Characterization of structure, composition, morphology and conductivity
(1) FIG. 1 is an X-ray powder diffraction pattern of Dy@Ni-MOF composite materials prepared in examples 1-3 of the present invention and Ni-MOF prepared in comparative example 1. As can be seen from fig. 1, the dy@ni-MOF composite materials prepared in examples 1-3 have characteristic peaks of typical X-ray powder diffraction of Ni-MOF, and in the Dy doping process, dy@ni-MOF exhibits a similar crystal structure as Ni-MOF, indicating a lower Dy doping loading. The main diffraction peak of Dy@Ni-MOF has a slight negative shift compared to Ni-MOF, and the diffraction peak intensity is reduced. This is because the incorporation of Dy affects the coordination between the original Ni center and the organic ligands, indicating that Dy is doped into the Ni-MOF lattice. FIG. 2 is a Raman spectrum of Dy@Ni-MOF composite material prepared in example 2 of the present invention and Ni-MOF prepared in comparative example 1. As can be seen from fig. 2, the peaks at 1619cm -1、1556cm-1 and 580cm -1 are caused by stretching and bending vibrations of the benzene ring, the small peaks at 829cm -1 and 420cm -1 are caused by C-H bending vibrations and metal-oxygen bond (Ni-O) vibrations in the benzene ring, respectively, v (COO -) vibrations occur at 1493cm -1 and 1419cm -1, and the peak at 1282cm -1 corresponds to v (C-O) vibrations, which are caused by deprotonation of the hydroxyl group. The above results further confirm the synthesis of Ni-MOF.
(2) FIG. 3 is a Fourier transform infrared spectrum of Dy@Ni-MOF composite material prepared in example 2 of the present invention, ni-MOF prepared in comparative example 1, and 2, 5-dihydroxyterephthalic acid (DHTA). As can be seen from FIG. 3, dy@Ni-MOF and Ni-MOF have similar Fourier transform infrared spectra, indicating that their molecular structures are similar. Furthermore, the presence of carboxylate vibration signals (1540 cm -1 and 1388cm -1) confirms the presence of metal-organic coordination bonds for Dy@Ni-MOF and indicates that some carboxylate groups are exposed on the Dy@Ni-MOF surface, which favors water adsorption during OER. In addition, the carboxyl peak (1654 cm -1) disappeared with pure DHTA ligand, indicating that there was no free ligand in Dy@Ni-MOF.
(3) FIG. 4 is a scanning electron microscope image of Dy@Ni-MOF composite materials prepared in examples 1-3 of the present invention and Ni-MOF prepared in comparative example 1. Where a is the Ni-MOF of comparative example 1, b is the 0.05Dy@Ni-MOF of example 1, c is the 0.1Dy@Ni-MOF of example 2, and d is the 0.2Dy@Ni-MOF of example 3. As can be seen from fig. 4, the Ni-MOF exhibited a cotton shape and had a serious agglomeration phenomenon; dy@Ni-MOF is in a shape of a nanometer needle tip; these results indicate that dysprosium doping greatly alters the morphology of the Ni-MOF and prevents aggregation of the material. When the Dy doping amount is 0.1mmol (example 2), the nanoneedle grows uniformly on the carbon cloth, which is advantageous in accelerating dispersion of the electrolyte and release of bubbles.
(4) FIG. 5 is a scanning electron micrograph of the Ni-MOF prepared in comparative example 1 and various electron micrographs of Dy@Ni-MOF composite material prepared in example 2 of the present invention. Wherein a-b are scanning electron microscope pictures of Ni-MOF and Dy@Ni-MOF respectively, and the a-b can show that the Ni-MOF is cotton-shaped and has agglomeration phenomenon; dy@Ni-MOF is in a nano needle tip shape and uniformly grows on the carbon cloth. c is a transmission electron microscope image of Dy@Ni-MOF, and the nano needle-shaped morphology of Dy@Ni-MOF is further confirmed. d is a high resolution transmission electron micrograph of Dy@Ni-MOF (inset: corresponding selected area electron diffraction pattern), and it is known from d that Dy@Ni-MOF has no obvious lattice fringes and no obvious diffraction rings because the MOF structure is very sensitive to electron beams. e is an atomic force microscope image of Dy@Ni-MOF, f is a corresponding high profile view of an atomic force microscope of Dy@Ni-MOF, and the thickness of Dy@Ni-MOF is about 137nm as known from e-f. g-k is a high-angle annular dark field transmission electron microscope image of Dy@Ni-MOF and a distribution diagram of each element, and the fact that each element is uniformly distributed in the material is known from g-k, so that successful doping of Dy in the Ni-MOF is fully demonstrated.
(5) FIG. 6 is an X-ray photoelectron spectrum and an ultraviolet electron spectrum of the Ni-MOF composite material prepared in comparative example 1 and Dy@Ni-MOF composite material prepared in example 2 of the present invention. Wherein a is an X-ray photoelectron spectrum, and compared with Ni-MOF, in Dy doped Dy@Ni-MOF, ni 2p moves to higher binding energy, which indicates that Dy regulates the electron state of the Ni center, so that stronger electron interaction exists between Dy and Ni. b-e is ultraviolet electron energy spectrum, and it is known from b-e that Dy@Ni-MOF has a work function of 3.01eV and is far lower than that of Ni-MOF by 4.42eV, which indicates that electrons can be easily transferred from the inside of the catalyst to the surface after Dy doping, and electron exchange is carried out with reactants, so that rapid dynamics is realized. In addition, the valence band maximum of Ni-MOF is about 5.18eV, while the valence band maximum of Dy@Ni-MOF is about 4.96eV, which indicates an increase in the electrical conductivity of the catalyst after Dy doping, with a shift in the valence band toward the Fermi level. Therefore, the ultraviolet electron energy spectrum can effectively prove that the doping of the rare earth element Dy greatly improves the conductivity of the catalyst.
FIG. 7 is a graph showing the results of measuring resistance using a multimeter ohm-shift for the Ni-MOF prepared in comparative example 1 and Dy@Ni-MOF composite material prepared in example 2 of the present invention. Wherein a is Ni-MOF, and b is Dy@Ni-MOF. As can be seen from fig. 7, the dy@ni-MOF composite material prepared in example 2 has a resistance of 37.90 Ω, which is much smaller than the Ni-MOF (169.09 Ω) prepared in comparative example 1, demonstrating that Dy doping does greatly improve the conductivity of the Ni-MOF.
In addition, the resistivity and conductivity of the Ni-MOF prepared in example 1 and dy@ni-MOF composite material prepared in example 2 of the present invention were measured using four probes, and the results are shown in table 1:
TABLE 1
As can be seen from table 1, the dy@ni-MOF prepared in example 2 of the present invention has a smaller resistivity and a larger conductivity than the Ni-MOF prepared in comparative example 1, which further demonstrates that Dy doping greatly improves the conductivity of the Ni-MOF.
2. Electrochemical testing
The testing method comprises the following steps: electrocatalytic oxygen evolution tests were performed on an electrochemical workstation (Bio-Logic VMP3, france) using a three electrode system. Dy@Ni-MOF prepared in examples 1-3 was used as a working electrode, a graphite plate was used as a counter electrode, a saturated calomel electrode was used as a reference electrode, a 1.0M KOH solution was used as an electrolyte, the test temperature was 25 ℃, the scanning speed was 0.5mV s -1, and the scanning range was 0-1.0V (vs SCE). The electrode potential is obtained by saturating the calomel electrode and performing reversible hydrogen electrode (Reversible hydrogen electrode, RHE) and impedance compensation correction. All potentials in the present invention are obtained according to the following Nernst equation:
ERHE＝ESCE+0.241+0.059pH-iR
Where i is the current tested and R is the solution impedance. Electrolyzed water testing was performed on an electrochemical workstation (Bio-Logic VMP3, france) using a two electrode system.
The test results were as follows:
(1) FIG. 8 shows the results of electrochemical performance tests of Dy@Ni-MOF composite materials prepared in examples 1-3 of the present invention in 1.0M KOH. Wherein a is an electrocatalytic oxygen evolution linear scanning curve; b is a tafel slope diagram; c is an electrochemical impedance spectrogram; d is a linear scan curve normalized by the electrochemically active surface area, and the inset in d is the electrochemically active surface area (ECSA). From a-c, it is evident that Dy@Ni-MOF catalysts obtained when the dysprosium content was 0.1mmol have more excellent electrochemical oxygen evolution properties among Dy@Ni-MOFs having different dysprosium contents prepared in examples 1 to 3. From d, it is clear that among Dy@Ni-MOFs with different dysprosium contents prepared in examples 1-3, although the electrochemically active surface area (ECSA) of 0.1Dy@Ni-MOF was the smallest, the intrinsic activity evaluated by normalizing the current density to the electrochemical specific surface area was the largest, which suggests that its enhanced OER performance is independent of ECSA.
(2) FIG. 9 shows various performance comparison results of Dy@Ni-MOF composite material prepared in example 2 of the present invention and Ni-MOF prepared in comparative example 1, ruO 2 electrode material prepared in comparative example 3, and other existing catalysts. Wherein a-b is an electrocatalytic oxygen evolution linear scanning curve and a Tafel slope chart of Dy@Ni-MOF, ni-MOF and RuO 2 electrode materials, and c is a Tafel slope chart of Dy@Ni-MOF (This work) and a catalyst 【5％NiCo-MOF(International Journal ofHydrogen Energy,2021,46,416-424)、CO2P/CoP@NPGCs(Journal ofIndustrial and Engineering Chemistry,2022,106,492-502)、CoMo-MI-600(International Journal ofHydrogen Energy,2021,46,22268-22276)、Co-BTC(Chemical Engineering Journal,2022,446,137045)、Sc-CoBDC-3(Journal ofSolid State Chemistry,2022,312,123202)、F-Co-MOFs(International Journal ofHydrogen Energy,2022,47,30484-30493)、Zn2(bim)4@CoS(Inorganic Chemistry Frontiers,2022,9,6102-6107)、Co-MOF-5fibers(Inorganic Chemistry,2021,60,9899–9911)、C SMCRI-10(Chemical Engineering Journal,2022,429,132301)、V0.09-Ni0.91MOF/NF(Chemistry-A European Journal,2022,28,e202201784)、Ni-MOF-FA(ElectrochimicaActa,2020,354,136682)、Ni(Pz)-E-PVP(ACS Applied Materials&Interfaces,2022,14,47775–47787)、ZnCoNi/(Ppy/CNTs)4(Chinese Journal of Catalysis,2022,43,1316-1323)】 reported in the prior art; from a-c, it is seen that Dy@Ni-MOF has an overpotential of 246mV at a current density of 10mA cm -2, comparable to commercial RuO 2 (comparative example 3), and superior to Ni-MOF and other catalysts reported in the prior art. d is the electrochemical impedance spectra of Dy@Ni-MOF, ni-MOF and RuO 2, and d shows that Dy@Ni-MOF exhibits the lowest charge transfer impedance (Rct). e is a graph of turnover frequency and overpotential of Ni-MOF and Dy@Ni-MOF, and e shows that the turnover frequency value of Dy@Ni-MOF is highest, which indicates that the catalyst has excellent electrocatalytic oxygen evolution conversion efficiency and strong intrinsic catalytic activity. f is a linear sweep voltammetric polarization curve (inset: chronopotentiometric curve) of Dy@Ni-MOF after initial and 1000 cyclic voltammetry cycles, f shows that the electrocatalytic oxygen evolution performance of Dy@Ni-MOF hardly declines after 1000 CV scans. In addition, the operation was continued for 80 hours under 10mA cm -2, and the overpotential was hardly increased, further demonstrating the superior stability.
(3) FIG. 10 is a cyclic voltammetry curve and an electric double layer capacitance plot of Dy@Ni-MOF composite material prepared in example 2 and Ni-MOF prepared in comparative example 1 in a non-Faraday potential zone. Where a-b are cyclic voltammetry curves of Dy@Ni-MOF and Ni-MOF at different scan rates (20, 30, 40, 50, 60 and 70mV s -1) in the non-Faraday potential interval, respectively, from which the electric double layer capacitances (C dl) of Dy@Ni-MOF and Ni-MOF were calculated. c is an electric double layer capacitance map of Dy@Ni-MOF and Ni-MOF, and it is understood from c that the Dy@Ni-MOF catalyst prepared in example 2 has a double layer capacitance value of 2.23mF cm -2. d is a linear sweep voltammetry plot of normalized electrochemically active surface areas of Dy@Ni-MOF and Ni-MOF (inset: dy@Ni-MOF versus Ni-MOF), and it is clear from d that while the electrochemically active surface area of the Dy@Ni-MOF catalyst prepared in example 2 is smaller than that of the Ni-MOF catalyst prepared in comparative example 1, the specific activity Dy@Ni-MOF estimated by normalizing the current density to the surface area of the electrocatalyst is greater, indicating that its enhanced OER performance is independent of ECSA.
(4) FIG. 11 shows the whole water splitting process and results. Wherein a is a full water splitting schematic diagram. b is a polarization curve in 1.0M KOH of a two-electrode system consisting of the Dy@Ni-MOF composite material prepared in example 2 of the present invention and the Pt/C electrode material prepared in comparative example 2, and a two-electrode system consisting of the Pt/C electrode material prepared in comparative example 2 and the RuO 2 electrode material prepared in comparative example 3, it is known that when the current density reaches 10 and 100mA cm -2, the battery voltages of the two-electrode device assembled with the Dy@Ni-MOF as the anode are 1.51 and 1.67V, respectively, and as the current density increases, the battery voltages of the two electrodes at the same current density are larger, which indicates that the Dy@Ni-MOF composite material prepared in the present invention has excellent full hydrolysis performance and is superior to the two electrodes consisting of Pt/C and RuO 2. C is a comparison of the voltage of the full water-splitting battery 【KC-MLH/NF-12(Advanced Functional Materials,2023,33,2211260)、CCS-NiFeP-20(Advanced Functional Material,2022,32,2200733)、Fe2P-NiCoP(Materials Today Physics,2022,24,100684)、FeCu-BTC/WO3-WC(Applied Catalysis B:Environmental,2023,331,122711)、NiCoFeP-C(Journal ofEnergy Chemistry,2022,74,149-158)、Ru@CoFe/D-MOFs(Inorganic Chemistry Frontiers,2022,9,6158-6166)、Ni-250-2@NF(Journal of Materials ChemistryA,2023,11,5222-5232)、Fe2V-MOF(ACS AppliedMaterials&Interfaces,2022,14,37804–37813)、Fe-Co-NiMOF(Journal of the American Chemical Society,2022,144,3411–3428)、Co/Mn-ZIF@Fe-Co-Mn PBA(Nano Research,2023,16,3695–3702)、CdFe-BDC(ACS Applied Materials&Interfaces,2022,14,46374–46385)、Co-BTC(Chemical Engineering Journal,2022,446,137045)】 reported in the prior art with the two-electrode system composed of Dy@Ni-MOF (This work) prepared in example 2 of the present invention and the Pt/C electrode material prepared in comparative example 2, and as can be seen from C, the full water-splitting performance of the Dy@Ni-MOF composite material prepared in the present invention is superior to that of most OER catalysts reported in the prior art. d is the stability test result of the two-electrode system consisting of Dy@Ni-MOF prepared in example 2 of the invention and Pt/C electrode material prepared in comparative example 2, and the two-electrode system can stably run for 100 hours at 10mA cm -2, which also shows that the Dy@Ni-MOF composite material prepared in the invention has better stability and durability.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.

Claims (7)

1. The preparation method of the dysprosium doped nickel-metal organic framework composite material is characterized by comprising the following steps of: dissolving dysprosium source, nickel source, organic ligand source and regulator in mixed water solution to obtain reaction solution; adding a carrier into the reaction solution, heating to perform hydrothermal reaction to obtain the dysprosium-doped nickel-metal organic frame composite material;
the dysprosium source is dysprosium nitrate; the nickel source is nickel nitrate; the organic ligand source is 2, 5-dihydroxyterephthalic acid; the regulator is salicylic acid; the carrier is carbon cloth;
Dysprosium source in terms of molar usage ratio: nickel source: organic ligand source: regulator = 0.05-0.2:0.7:0.216:0.216; the dosage ratio of the nickel source to the mixed aqueous solution is 0.7 mmol/18 mL.
2. The method of preparing a dysprosium doped nickel-metal organic framework composite material of claim 1, wherein the mixed aqueous solution is formed by mixing N, N-dimethylformamide, ethanol and water.
3. The method for preparing the dysprosium doped nickel-metal organic framework composite material according to claim 2, wherein the N, N-dimethylformamide is as follows: ethanol: water=1:1:1.
4. The method of preparing a dysprosium doped nickel-metal organic framework composite material of claim 1, wherein the hydrothermal reaction is performed at a temperature of 150 ℃ for a period of 12 hours.
5. The method of preparing the dysprosium doped nickel-metal organic framework composite material of claim 1, further comprising a pretreatment operation on a carrier, specifically: the support was cut to the desired dimensions and then washed in sulfuric acid solution, deionized water and ethanol, respectively.
6. A dysprosium doped nickel-metal organic framework composite material prepared by the method of preparing a dysprosium doped nickel-metal organic framework composite material according to any one of claims 1-5.
7. Use of the dysprosium doped nickel-metal organic framework composite material of claim 6 in an electrocatalytic oxygen evolution reaction.
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