CN118127550A - Preparation method and application of plasma-treated metal organic framework electrocatalyst - Google Patents
Preparation method and application of plasma-treated metal organic framework electrocatalyst Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 34
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 35
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000006260 foam Substances 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 230000005291 magnetic effect Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000005711 Benzoic acid Substances 0.000 claims description 8
- 235000010233 benzoic acid Nutrition 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000012918 MOF catalyst Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000009832 plasma treatment Methods 0.000 abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
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- 238000013112 stability test Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000005684 electric field Effects 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/085—Organic compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of a Metal Organic Frameworks (MOFs) electrocatalyst subjected to plasma treatment, and belongs to the technical field of catalysis. The surface of the treated MOF material shows better interface characteristics, has more exposed active sites, modulated coordination environment and optimized electronic structure, is more suitable for electrocatalytic reactions such as anodic oxygen evolution reaction and the like, and has important practical significance for promoting the development of clean energy conversion devices such as water electrolytic cells, metal-air batteries, fuel cells and the like.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method and application of a plasma-treated metal organic framework electrocatalyst.
Background
Electrochemical water splitting can produce high-purity hydrogen with high energy density and zero carbon emission, and is favored as a sustainable strategic technology for solving global energy demands and slowing down environmental degradation problems. Among other things, the Oxygen Evolution Reaction (OER) of the anode faces challenges arising from the slow kinetics of the multi-step proton-coupled electron transfer process, severely hampering the successful implementation of efficient reversible chemical/electrical energy conversion at the solid-liquid-gas phase catalytic interface. Therefore, there is an urgent need to design advanced OER electrocatalysts, which can improve energy conversion efficiency. Noble metal ruthenium (Ru) and iridium (Ir) based catalysts, which have heretofore been considered commercial standards for OER, have limited their use in commercial applications due to high cost, limited resources and insufficient durability.
The transition metal has the characteristics of rich earth resources, economy, excellent catalytic activity and strong stability, and has made remarkable progress in OER electrocatalyst research. Among them, metal Organic Frameworks (MOFs) materials having independent active sites, porous structures, flexible tunability, and extremely large specific surface area exhibit excellent OER activity and stability, making them promising candidates for replacing noble metal-based catalysts. However, most MOFs suffer from the disadvantages of low conductivity, insufficient intrinsic activity, and blocked mass transfer, which constitutes a bottleneck for the utilization of MOFs in electrochemical water splitting. The existing performance regulation and control methods of MOFs-based anode OER electrocatalyst are limited to complicated morphology regulation and control, expensive ligand replacement and the like, and the development of the MOFs-based electrocatalyst is hindered due to high-energy consumption pyrolysis reaction and complicated mechanism exploration process in the use process of the methods, so that a simple and efficient treatment technology is needed to realize the preparation of the MOFs-based electrocatalyst with high performance, high activity and high OER selectivity.
Disclosure of Invention
Based on the prior research and the existing problems, the invention provides a preparation method of the metal organic framework electrocatalyst treated by argon plasma after further research and analysis, and the chemical modification of the surface of the metal organic framework material can be realized by the treatment of the argon plasma, so that the conductivity is improved, the catalytic activity is enhanced, and the surface of the treated metal organic framework shows better interface characteristics, so that the metal organic framework electrocatalyst is more suitable for electrocatalytic reactions such as anodic oxygen evolution reactions.
In order to achieve the above purpose, the present invention provides the following technical solutions: the method comprises the following steps:
step 1, foam nickel pretreatment: removing oxides and organic matters on the surface of the foam nickel, and drying for later use;
step 2, preparing Ni-MOF-BA/NF on the treated foam nickel, which comprises the following steps:
Step 2.1: adding Ni (NO 3)2·6H2 O into a mixed solution containing N, N-dimethylformamide, ethanol and deionized water, and fully dissolving;
step 2.2: adding terephthalic acid and benzoic acid into the solution obtained in the step 2.1, and uniformly mixing;
Step 2.3: transferring the solution obtained in the step 2.2 into a reaction kettle, immersing the pretreated foam nickel into the solution for reaction, washing the product after the reaction is finished by ethanol and deionized water, and drying to obtain Ni-MOF-BA/NF;
And 3, placing the Ni-MOF-BA/NF obtained in the step two in a plasma generator, vacuumizing, introducing argon, starting the ion generator to ionize the argon into plasma, and modifying the Ni-MOF-BA/NF by using high-energy particles to obtain the Ni-MOF-BA-P/NF.
Preferably, in the step 1, HCl, absolute ethyl alcohol and deionized water are sequentially used for ultrasonic cleaning for 15-20 min respectively, and the materials are dried for standby.
Preferably, ni (molar ratio of NO 3)2·6H2 O, terephthalic acid and benzoic acid is 1-1.1:0.6-0.7:0.4-0.5).
Preferably, the volume ratio of the N, N-dimethylformamide to the ethanol to the deionized water is 16-20:1:1.
Preferably, the solutions in step 2.1 and step 2.2 are stirred by a magnetic stirrer for 10-15 min under the condition of 700-800 r/min.
Preferably, in step 2.3, the solution is sealed in an autoclave at 120℃for 12 hours.
Preferably, in the step 3, after vacuumizing for 5min and introducing argon for 5min, the plasma generator is started, the power is kept at 80W, and the irradiation is performed for 5min.
In another aspect, the invention also provides a metal organic framework electrocatalyst prepared by the above-mentioned preparation method.
Furthermore, the invention also provides an application of the metal organic framework electrocatalyst, wherein the prepared MOF catalyst is used as a working electrode, a carbon rod is used as a counter electrode, and Hg/HgO is used as a reference electrode; electrochemical performance testing was performed in a standard three-electrode system at room temperature, normal pressure and room temperature.
Compared with the prior art, the invention provides the preparation method and the application of the metal organic framework electrocatalyst treated by the argon plasma, which has the following beneficial effects:
(1) Surface modification: the argon plasma can alter the catalyst surface properties, thereby adjusting the activity and selectivity of the catalyst, which provides the possibility to tailor the catalyst to specific reaction conditions.
(2) High degree of controllability: the conditions of the argon plasma treatment can realize a highly controllable preparation process by adjusting parameters such as gas composition, electric field strength and the like, and are favorable for accurately controlling the structure and the performance of the catalyst. According to the invention, through plasma treatment, a large number of oxygen vacancies are generated on the surface of the Ni-MOF-BA-P/NF catalyst, so that the electronic valence state of a metal nickel site on the surface of the catalyst is reduced, the electronic structure of an active site on the surface of the catalyst is regulated, the adsorption and desorption of an OER reaction intermediate are facilitated, and the catalytic activity is further improved.
(3) The invention uses argon plasma treatment, which is an environment-friendly and efficient surface modification technology, and the process can be carried out at room temperature without additional chemical reagents, and a large number of unsaturated coordination nickel sites with oxygen vacancies can be constructed on the surface of the catalyst by the pre-catalyst prepared by the argon plasma treatment, thereby being beneficial to the adsorption and desorption of OER reaction intermediates and further improving the catalytic activity.
(4) The invention provides a simple, economical and efficient synthesis method, and the nickel metal organic framework catalyst with excellent electrocatalytic OER activity, selectivity and stability is synthesized through argon plasma treatment. This has important practical implications for the development of clean energy conversion devices such as water baths, metal air batteries, fuel cells and the like.
Drawings
FIG. 1 is a scanning electron microscope image of the catalyst prepared in examples 1,2 and 3 of the present invention, wherein the image (a, b) is a scanning electron microscope image of Ni-MOF/NF, the image (c) is a scanning electron microscope image of Ni-MOF-BA/NF, and the image (d) is a scanning electron microscope image of Ni-MOF-BA-P/NF;
FIG. 2 shows an X-ray diffraction pattern, a Raman spectrum, an X-ray photoelectron spectrum and an electron paramagnetic resonance spectrum of the catalyst prepared by the three embodiments of the invention in sequence;
FIG. 3 shows, in order, a linear sweep voltammogram (a), an electrochemical impedance diagram (b), an electric double layer capacitance diagram (c), and a conversion frequency diagram (d) of the catalysts prepared in three examples of the present invention;
Fig. 4 is a faraday efficiency chart (a) and a stability test chart (b) of the catalyst in the third embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present invention.
In order to more clearly describe the preparation method of the plasma-treated metal-organic framework electrocatalyst provided by the embodiment of the invention in detail, the following description will be made with reference to specific embodiments.
Example 1
The embodiment provides a preparation method of a plasma-treated metal organic framework electrocatalyst, which comprises the following detailed steps:
1. Foam nickel pretreatment: cutting out foam Nickel (NF) with the specification of 2cm x 4cm, sequentially using 5M HCl, absolute ethyl alcohol and deionized water for ultrasonic treatment for 15min for removing oxides and organic impurities, and drying for later use.
2.1 MmoL Ni (NO 3)2·6H2 O is placed in a clean beaker with a magnetic rotor) is accurately weighed by a high-precision electronic balance, 32mL of N, N-Dimethylformamide (DMF), 2mL of ethanol and 2mL of deionized water are respectively measured by a liquid-transfering gun, the beaker is added, the beaker is sealed by a preservative film, and the solution is stirred by a magnetic stirrer for 10min under the condition of 700r/min, so that the solution is fully dissolved.
3. 1MmoL terephthalic acid (H 2 BDC) is weighed by a high-precision electronic balance and added into the solution in the step 2, and the solution is stirred for 10min by magnetic force at the speed of 700r/min, so that the solution is uniformly mixed.
4. After stirring uniformly, the solution obtained in step 3 was transferred to a 50mL reactor liner, the pretreated NF was immersed in the solution, the autoclave was sealed and maintained at 120℃for 12 hours (heating rate 1 ℃/min). And cooling to room temperature along with the furnace, thoroughly flushing the product with ethanol and deionized water, and then drying in a vacuum drying oven at 50 ℃ to obtain the Ni-MOF/NF.
Taking the prepared Ni-MOF/NF as a working electrode, 1MKOH as electrolyte, a carbon rod as a counter electrode and Hg/HgO as a reference electrode; electrochemical performance testing was performed in a standard three-electrode system at room temperature, normal pressure and room temperature.
Example two
The embodiment provides a preparation method of a plasma-treated metal organic framework electrocatalyst, which comprises the following detailed steps:
1. Foam nickel pretreatment: cutting out foam Nickel (NF) with the specification of 2cm x 4cm, sequentially using 5M HCl, absolute ethyl alcohol and deionized water for ultrasonic treatment for 15min for removing oxides and organic impurities, and drying for later use.
2.1 MmoL Ni (NO 3)2·6H2 O is placed in a clean beaker with a magnetic rotor) is accurately weighed by a high-precision electronic balance, 32mL of N, N-Dimethylformamide (DMF), 2mL of ethanol and 2mL of deionized water are respectively measured by a liquid-transfering gun, the beaker is added, the beaker is sealed by a preservative film, and the solution is stirred by a magnetic stirrer for 10min under the condition of 700r/min, so that the solution is fully dissolved.
3. 0.6MmoL terephthalic acid (H 2 BDC) and 0.4mmoL Benzoic Acid (BA) are weighed by a high-precision electronic balance and added into the solution in the step2, and the solution is stirred for 10min by magnetic force at the speed of 700r/min, so that the solution is uniformly mixed.
4. After stirring uniformly, the solution obtained in step 3 was transferred to a 50mL reactor liner, the pretreated NF was immersed in the solution, the autoclave was sealed and maintained at 120℃for 12 hours (heating rate 1 ℃/min). Cooling to room temperature along with the furnace, thoroughly flushing the product with ethanol and deionized water, and then drying in a vacuum drying oven at 50 ℃ to obtain the Ni-MOF-BA/NF.
Taking the prepared Ni-MOF-BA/NF as a working electrode, 1MKOH as electrolyte, a carbon rod as a counter electrode and Hg/HgO as a reference electrode; electrochemical performance testing was performed in a standard three-electrode system at room temperature, normal pressure and room temperature.
Example III
The embodiment provides a preparation method of a plasma-treated metal organic framework electrocatalyst, which comprises the following detailed steps:
1. Foam nickel pretreatment: cutting out foam Nickel (NF) with the specification of 2cm x 4cm, sequentially using 5M HCl, absolute ethyl alcohol and deionized water for ultrasonic treatment for 15min for removing oxides and organic impurities, and drying for later use.
2.1 MmoL Ni (NO 3)2·6H2 O is placed in a clean beaker with a magnetic rotor) is accurately weighed by a high-precision electronic balance, 32mL of N, N-Dimethylformamide (DMF), 2mL of ethanol and 2mL of deionized water are respectively measured by a liquid-transfering gun, the beaker is added, the beaker is sealed by a preservative film, and the solution is stirred by a magnetic stirrer for 10min under the condition of 700r/min, so that the solution is fully dissolved.
3. 0.6MmoL terephthalic acid (H 2 BDC) and 0.4mmoL Benzoic Acid (BA) are weighed by a high-precision electronic balance and added into the solution in the step2, and the solution is stirred for 10min by magnetic force at the speed of 700r/min, so that the solution is uniformly mixed.
4. After stirring uniformly, the solution obtained in step 3 was transferred to a 50mL reactor liner, the pretreated NF was immersed in the solution, the autoclave was sealed and maintained at 120℃for 12 hours (heating rate 1 ℃/min). Cooling to room temperature along with the furnace, thoroughly flushing the product with ethanol and deionized water, and then drying in a vacuum drying oven at 50 ℃ to obtain the Ni-MOF-BA/NF.
5. Placing the Ni-MOF-BA/NF obtained in the step 4 into a plasma generator, vacuumizing for 5 minutes, introducing argon for 5 minutes, starting the plasma generator, keeping the power at 80W, and irradiating for 5 minutes to obtain the Ni-MOF-BA-P/NF.
Taking the prepared Ni-MOF-BA-P/NF as a working electrode, 1MKOH as electrolyte, a carbon rod as a counter electrode and Hg/HgO as a reference electrode; electrochemical performance testing was performed in a standard three-electrode system at room temperature, normal pressure and room temperature.
The scanning electron microscope SEM in FIG. 1 shows that Ni-MOF/NF shows ultra-thin nanoplatelet morphology, and that Ni-MOF-BA-P/NF shows rough porous morphology after argon plasma treatment.
The X-ray diffraction pattern in fig. 2 shows that after plasma treatment, the position of the diffraction peak is shifted to the left, i.e., lattice expansion is generated. The lattice expansion can cause the change of the electronic structure of the adsorption site on the surface of the catalyst, thereby affecting the adsorption capacity of the intermediate in the reaction and improving the reaction rate and selectivity. At the same time, lattice expansion can also alter the pore structure inside the catalyst, affecting the mass transfer properties of the reactants and products. The raman spectrum shows that the intensity of the diffraction peak decreases after plasma treatment. This is probably due to the fact that a large number of oxygen vacancies are generated on the catalyst surface after the plasma treatment, resulting in a decrease in crystallization properties of the crystals. The X-ray photoelectron spectrum shows that after plasma treatment, the peak of bivalent nickel moves to low binding energy and the electronic structure is changed. This is because after plasma treatment, a large number of oxygen vacancies are generated on the catalyst surface, facilitating electron transfer from oxygen to nickel, and reducing the valence state of nickel. This electron transfer affects the electronic structure of the catalyst, thereby promoting the formation of reaction intermediates and regulating the activity of the catalyst. Electron paramagnetic resonance spectra show that after plasma treatment, a stronger oxygen vacancy peak is generated.
As can be seen from the results shown in FIG. 3, (a) the resulting Ni-MOF-BA-P/NF catalyst modified electrode had the optimal oxygen evolution catalytic activity in 1.0M KOH alkaline solution. At a current density of 100mA cm -2, the overpotential was 300mV, which is superior to the catalytic activity of the commercial RuO 2 catalyst. This indicates that the OER activity of the catalyst can be effectively improved after the plasma treatment.
(B) The Ni-MOF-BA-P/NF catalyst obtained by the test has the lowest charge transfer resistance, which shows that the Ni-MOF-BA-P/NF catalyst has better conductivity. This shows that the charge transfer capacity is significantly improved after plasma treatment. Meanwhile, the reduction of the charge transfer resistance means that electrons are easier to transfer between the surfaces of the catalysts, the loss of the electrons on the surfaces of the catalysts can be reduced, more electrons can effectively participate in catalytic reaction, the active centers of the catalysts can fully participate in the reaction, and the catalytic activity is improved.
(C) The Ni-MOF-BA-P/NF with the highest electrochemically active area (ECSA) is able to expose more catalytically active sites. This suggests that after plasma treatment, the Ni-MOF-BA-P/NF has more active sites to participate in the catalytic reaction, and more surface area provides more reaction centers to help adsorb and activate reactants, thus improving the reaction rate.
(D) Ni-MOF-BA-P/NF with higher conversion frequency (TOF) has higher intrinsic catalytic activity. This suggests that Ni-MOF-BA-P/NF reflects a more efficient catalyst active site after plasma treatment, which means that the catalyst is able to convert reactants more efficiently, improving catalytic activity.
As shown in FIG. 4, the Ni-MOF-BA-P/NF produced in example 3 had an OER Faraday efficiency of 99.2%, which represents a high OER selectivity. And the Ni-MOF-BA-P/NF catalyst is subjected to a stability test for 250 hours under the current density of 100mA cm -2, and the catalytic activity is not obviously degraded, so that the Ni-MOF-BA-P/NF catalyst prepared by the method has very excellent electrochemical stability. Stable catalysts are capable of maintaining their catalytic activity over a longer period of time and are less prone to deactivation, which is particularly critical for long-run catalytic reactions, especially in industrial production.
Therefore, the Ni-MOF-BA-P/NF catalyst prepared by plasma treatment has excellent OER activity, stability and selectivity, and provides a new idea and insight for designing and developing a novel efficient, stable and low-cost catalyst.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting thereof; although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (9)
1. The preparation method of the plasma-treated metal organic framework electrocatalyst is characterized by comprising the following steps:
step 1, foam nickel pretreatment: removing oxides and organic matters on the surface of the foam nickel, and drying for later use;
step 2, preparing Ni-MOF-BA/NF on the treated foam nickel, which comprises the following steps:
Step 2.1: adding Ni (NO 3)2·6H2 O into a mixed solution containing N, N-dimethylformamide, ethanol and deionized water, and fully dissolving;
step 2.2: adding terephthalic acid and benzoic acid into the solution obtained in the step 2.1, and uniformly mixing;
Step 2.3: transferring the solution obtained in the step 2.2 into a reaction kettle, immersing the pretreated foam nickel into the solution for reaction, washing the product after the reaction is finished by ethanol and deionized water, and drying to obtain Ni-MOF-BA/NF;
And 3, placing the Ni-MOF-BA/NF obtained in the step two in a plasma generator, vacuumizing, introducing argon, starting the ion generator to ionize the argon into plasma, and modifying the Ni-MOF-BA/NF by using high-energy particles to obtain the Ni-MOF-BA-P/NF.
2. The method for preparing the plasma-treated metal-organic framework electrocatalyst according to claim 1, wherein in step 1, HCl, absolute ethyl alcohol and deionized water are sequentially used for ultrasonic cleaning for 15-20 min, and the metal-organic framework electrocatalyst is dried for standby.
3. The method for preparing a plasma-treated metal-organic framework electrocatalyst according to claim 1, wherein the molar ratio of Ni (NO 3)2·6H2 O, terephthalic acid, and benzoic acid) is 1 to 1.1:0.6 to 0.7:0.4 to 0.5.
4. A method of preparing a plasma treated metal organic framework electrocatalyst according to claim 2 or 3, wherein the volume ratio of N, N-dimethylformamide, ethanol and deionized water is from 16 to 20:1:1.
5. The method for preparing a plasma-treated metal-organic framework electrocatalyst according to claim 4, wherein the solutions in step 2.1 and step 2.2 are each stirred with a magnetic stirrer at 700-800r/min for 10-15 min.
6. The method for preparing a plasma-treated metal-organic framework electrocatalyst according to claim 4, wherein in step 2.3, the solution is sealed in an autoclave at 120 ℃ for 12 hours.
7. The method for preparing a plasma-treated metal-organic framework electrocatalyst according to claim 1, wherein in step 3, after vacuumizing for 5min and introducing argon for 5min, the plasma generator is turned on, and the power is maintained at 80W and irradiated for 5min.
8. A metal organic framework electrocatalyst prepared by the method of any one of claims 1 to 7.
9. Use of a metal organic framework electrocatalyst according to claim 8 wherein the MOF catalyst prepared is used as a working electrode, a carbon rod is used as a counter electrode and Hg/HgO is used as a reference electrode; electrochemical performance testing was performed in a standard three-electrode system at room temperature, normal pressure and room temperature.
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