CN110180594B - Preparation method of electrocatalyst - Google Patents
Preparation method of electrocatalyst Download PDFInfo
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- CN110180594B CN110180594B CN201910579629.9A CN201910579629A CN110180594B CN 110180594 B CN110180594 B CN 110180594B CN 201910579629 A CN201910579629 A CN 201910579629A CN 110180594 B CN110180594 B CN 110180594B
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title description 14
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 28
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 5
- -1 wherein M is Co Substances 0.000 claims abstract description 4
- IGHSXWNAVWDWTI-UHFFFAOYSA-N 2,3,6,7,10,11-hexahydrotriphenylene Chemical group C1CC=C2C3=CCCC=C3C3=CCCC=C3C2=C1 IGHSXWNAVWDWTI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000006230 acetylene black Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002073 nanorod Substances 0.000 claims description 3
- 239000002060 nanoflake Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000013110 organic ligand Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AYESKMWPTSCYSJ-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol;hydrochloride Chemical compound [Cl-].OC[PH+](CO)CO AYESKMWPTSCYSJ-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- QMLILIIMKSKLES-UHFFFAOYSA-N triphenylene-2,3,6,7,10,11-hexol Chemical group C12=CC(O)=C(O)C=C2C2=CC(O)=C(O)C=C2C2=C1C=C(O)C(O)=C2 QMLILIIMKSKLES-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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Abstract
Embodiments of the present disclosure provide a method for preparing an electrocatalyst, the method including: first, 2,3,6,7,10, 11-hexahydrotriphenylene (HHTP) and M (OAc)2·4H2Adding O into deionized water to obtain a mixed solution, wherein M is Co, Ni or Cu; then, carrying out ultrasonic treatment on the mixed solution through an ultrasonic device to enable the mixed solution to react to obtain a reacted solution, wherein the reacted solution comprises solid M3(HHTP)2(ii) a Then, the M is separated from the reacted solution3(HHTP)2. Thus, the electrocatalyst material M can be obtained simply and quickly by using the ultrasonic action3(HHTP)2。
Description
Technical Field
One or more embodiments of the present disclosure relate to the field of preparing electrocatalytic electrode materials, and more particularly, to a method of preparing an electrocatalyst by an ultrasonic method.
Background
The total amount of resources on earth is constant, but in recent years, with the increasing population, energy problems have become a topic of interest naturally. Meanwhile, sustainability and clean non-pollution of energy become intrinsic requirements for finding new energy (Chen J, et al. ACS applied materials & interfaces,2016,8(21): 13378-13383.). Fuel cells are not limited by the carnot cycle, and therefore, they are efficient and free from noise pollution, and therefore, the emission of harmful gases is one of the most promising power generation technologies. However, the cathode kinetics are relatively slow and require a catalyst for catalysis. Among them, the Pt/C catalyst is an optimum catalyst for oxygen reduction reaction and is used for commercial use because of its low overpotential and good stability. However, the excessive price, scarce reserves and low stability of Pt prevent its large-scale commercial application (Wu M, et al. ACS Catalysis,2017,7(9): 6082-. Therefore, the development of efficient, cheap and stable ORR catalysts is of great importance for the successful commercialization of these green energy sources.
Metal Organic Frameworks (MOFs) have been developed in the last two decades and are a kind of inorganic-organic hybrid materials with porous structure formed by coordination of Metal ions (clusters) and organic ligands. The MOFs material has the advantages of high specific surface area, uniform pore diameter, adjustable structure and the like, and is widely concerned by people. The MOFs material has three positions on the structure which can be used as catalytic active centers, namely, central ions, organic ligands and structural pores (Tianyuxue, et al applied chemical industry, 2018 (4)). The central ion is an unsaturated coordination site of the catalytic reaction active center, the organic ligand is a functional group existing in the catalytic reaction active center, or a new active center is formed after the organic ligand is modified and modified, the structural pores of the MOFs are sites or carriers for catalytic reaction, and the MOFs and derivative materials thereof are widely researched in the field of electrocatalysis.
Currently, hydrothermal methods (Usov P M, et. al.2016,4(43): 16818-. Metal-catalysts (M-CATs) Materials are a class of MOFs with one-dimensional pore channels in a layered structure, have stability and good electrical conductivity, and are potentially excellent electrocatalysts (Hmadeh M, et al. chemistry of Materials,2012,24(18): 3511-) -3513.). The one-step ultrasonic synthesis method provided by the invention for synthesizing the M-CATs has the advantages of simple operation, no need of a heat source, rapid synthesis and time saving, and the shape of the material can be controlled by the ultrasonic time, so that a new method is provided for different requirements.
Disclosure of Invention
One or more embodiments of the present specification describe a method of preparing an electrocatalyst that obviates at least one of the above-described disadvantages of the prior art.
According to a first aspect, there is provided a method of preparing an electrocatalyst, the method comprising: 2,3,6,7,10, 11-hexahydroxy tris (hydroxymethyl) phosphonium chloride is used as a catalystPhenylene (HHTP) and M (OAc)2·4H2Adding O into deionized water to obtain a mixed solution, wherein M is Co, Ni or Cu; carrying out ultrasonic treatment on the mixed solution through an ultrasonic device to enable the mixed solution to react to obtain a reacted solution, wherein the reacted solution comprises solid M3(HHTP)2(ii) a Separating said M from said reacted solution3(HHTP)2Used for manufacturing the electrocatalyst.
In one possible implementation, the mass volume concentration of HHTP in the mixed solution is 0.35g/L to 23.33g/L, and the M (OAc)2·4H2The mass volume concentration of O is 0.5g/L to 33.33 g/L.
In a possible implementation manner, the ultrasonic treatment of the mixed solution by an ultrasonic device to react the mixed solution to obtain a reacted solution includes: controlling the duration of the ultrasonic treatment to be 50-80min to obtain M in the reacted solution3(HHTP)2The shape of the material is in a nanometer rod shape.
In a possible implementation manner, the ultrasonic treatment of the mixed solution by an ultrasonic device to react the mixed solution to obtain a reacted solution includes: controlling the duration of the ultrasonic treatment at 160-200min to obtain M in the reacted solution3(HHTP)2The material is in a nanometer sheet shape.
In one possible implementation, the separation of the M from the post-reaction solution3(HHTP)2The method comprises the following steps: centrifuging the reacted solution; washing the precipitate obtained by the centrifugal treatment; drying the washed precipitate to obtain M3(HHTP)2。
In one possible implementation manner, the centrifuging the reacted solution includes: and centrifuging the solution after the reaction at the rotating speed of 3000-8000 r/min.
In a possible implementation manner, the washing of the precipitate obtained by the centrifugation includes: the precipitate obtained from the centrifugation was washed several times with deionized water and acetone.
In one possible implementation manner, the drying process of the washed precipitate includes: and drying the washed precipitate in an air drying oven or a vacuum drying oven, wherein the drying temperature set by the air drying oven or the vacuum drying oven is 25-60 ℃.
In one possible implementation, the method further includes: the M is added3(HHTP)2Adding the mixture and acetylene black into absolute ethyl alcohol, and performing ultrasonic dispersion treatment to obtain M3(HHTP)2-CB for use as an electrocatalyst, wherein CB represents the acetylene black.
In one possible implementation, the M3(HHTP)2And acetylene black in a mass ratio of 3: 7, the time of ultrasonic dispersion treatment is 30-90 min.
The preparation method of the electrocatalyst provided by the embodiment of the specification can be used for simply, quickly and energy-saving preparation of the electrocatalyst material with more excellent performance by utilizing the ultrasonic action, and can be used for controlling the microscopic morphology of the electrocatalyst material by controlling the time of the ultrasonic action, so that the electrocatalyst material has different characteristics correspondingly, and can be suitable for different electrocatalysis scenes.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows a flow diagram of a method of making an electrocatalyst according to one embodiment;
FIG. 2 shows Co prepared in example one of the present specification3(HHTP)2XRD profile of (1);
FIG. 3 shows an implementation of the present descriptionExample one preparation of the resulting Co3(HHTP)2SEM picture of (1);
FIG. 4 shows Co prepared in example one of the present specification3(HHTP)2And Co3(HHTP)2-linear sweep voltammogram of CB;
FIG. 5 shows Ni prepared in example two of the present specification3(HHTP)2XRD profile of (1);
FIG. 6 shows Ni prepared in example two of the present specification3(HHTP)2SEM picture of (1);
FIG. 7 shows Ni prepared in example two of the present specification3(HHTP)2And Ni3(HHTP)2-linear sweep voltammogram of CB;
FIG. 8 shows Co prepared in example III of this specification3(HHTP)2SEM picture of (1);
FIG. 9 shows Ni prepared in example four of the present specification3(HHTP)2SEM image of (d).
Detailed Description
It is to be understood that the scope of the invention is not to be limited to the specific embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments, and is not intended to limit the scope of the present invention; in the description and claims of the present application, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, 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. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
As mentioned above, MOFs materials are inorganic-organic hybrid materials with porous structures formed by coordination of metal ions (clusters) and organic ligands, and M-CATs materials are MOFs with one-dimensional pore channels with layered structures, have stability and good conductivity, and are potential excellent electrocatalysts.
However, hydrothermal method, microwave synthesis method, etc. are mostly adopted in the currently used M-CATs synthesis method, and these methods have several disadvantages, including high-cost high-temperature heating and long reaction time, complicated morphology control conditions, and the requirement for sealed and pressure-rated containers.
Based on the above, the inventor provides a preparation method of M-CATs material, which can realize simple, rapid and energy-saving preparation of the electrocatalyst material with more excellent performance by utilizing the ultrasonic action, and can control the micro-morphology of the electrocatalyst material by controlling the time of the ultrasonic action, and the electrocatalyst material has different characteristics correspondingly and can be suitable for different electrocatalysis scenes.
In the examples disclosed in this specification, M (OAc) is used2·4H2O provides metal ions, wherein M can be Co, Ni, Cu or the like, 2,3,6,7,10, 11-hexahydrotriphenylene (HHTP) is used for providing organic ligands, and a corresponding M-CATs material, namely M, is synthesized3(HHTP)2。
The implementation steps of the method are described below. The method comprises the following specific steps:
fig. 1 shows a flow diagram of a method of making an electrocatalyst according to one embodiment. As shown in fig. 1, the method specifically includes the following steps: step S110, 2,3,6,7,10, 11-hexahydroxytriphenylene (HHTP) and M (OAc)2·4H2Adding O into deionized water to obtain a mixed solution, wherein M is Co, Ni or Cu; step S120, carrying out ultrasonic treatment on the mixed solution through an ultrasonic device to enable the mixed solution to react to obtain a reacted solution, wherein the reacted solution comprises solid M3(HHTP)2(ii) a Step S130 of separating the M from the reacted solution3(HHTP)2Used for manufacturing the electrocatalyst. The steps are as follows:
first, in step S110, HHTP and M (OAc)2·4H2And adding O into deionized water to obtain a mixed solution.
Specifically, M (OAc) mentioned above2·4H2M in O may be Co, Ni, Cu, or the like. The mixed solution is preferably prepared using deionized water, and may be prepared using distilled water or the like as an aqueous solvent.
In one embodiment, the mixed solution has a mass volume concentration of HHTP of 0.35g/L to 23.33g/L, and M (OAc)2·4H2The mass volume concentration of O is 0.5g/L to 33.33 g/L. In a specific embodiment, the HHTP has a mass of 70-350mg, M (OAc)2·4H2The mass of O is 100-500mg, and the volume of the deionized water is 15-200 ml.
After the mixed solution is obtained, in step S120, the mixed solution is subjected to ultrasonic treatment by an ultrasonic device to react the mixed solution, so as to obtain a reacted solution, wherein the reacted solution includes solid M3(HHTP)2。
In one embodiment, the ultrasonic device may be an ultrasonic cleaning apparatus.
In one embodiment, the ultrasonic treatment is carried out for 30-300min, the power is 250W, and the frequency is 40-80 KHz.
In one embodiment, the resulting M may be controlled by controlling the duration of sonication3(HHTP)2The micro-morphology of (2). In a specific embodiment, the mixed solution is subjected to ultrasonic treatment for 50-80min to obtain M3(HHTP)2The shape of the material is in a nanometer rod shape. In another specific embodiment, the mixed solution is subjected to ultrasonic treatment for 160-3(HHTP)2The material is in a nanometer sheet shape.
After the post-reaction solution is obtained as above, the M is separated from the post-reaction solution in step S1303(HHTP)2For making electricityA catalyst.
In one embodiment, this step may include: firstly, carrying out centrifugal treatment on the solution after the reaction; then washing the precipitate obtained by the centrifugal treatment; then drying the washed precipitate to obtain the M3(HHTP)2。
Further, in a specific embodiment, the centrifuging the reacted solution may include: and centrifuging the solution after the reaction at the rotating speed of 3000-8000 r/min.
In a specific embodiment, the washing the precipitate obtained by the centrifugation may include: the precipitate obtained from the centrifugation was washed several times with deionized water and acetone.
In a specific embodiment, the drying process of the washed precipitate may include: and drying the washed precipitate in an air drying oven or a vacuum drying oven, wherein the drying temperature set by the air drying oven or the vacuum drying oven is 25-60 ℃.
M can be obtained in step S130 as described above3(HHTP)2In one aspect, in one embodiment, dried M can be directly applied3(HHTP)2As an electrocatalyst.
On the other hand, in one embodiment, M can also be increased by adding acetylene black3(HHTP)2Is used for the electrical conductivity of (1). Specifically, after step S130, step S140 may be further included: the M is added3(HHTP)2Adding the mixture and acetylene black into absolute ethyl alcohol, and performing ultrasonic dispersion treatment to obtain M3(HHTP)2-CB for use as an electrocatalyst, wherein CB represents the acetylene black.
In a specific implementation, where M3(HHTP)2And acetylene black in a mass ratio of 3: 7.
in one specific implementation, the time of the ultrasonic dispersion treatment can be 30-90 min.
From the above, by the preparation method of the M-CATs material disclosed in the embodiments of the present specification, the electrocatalyst material with better performance can be prepared simply, rapidly and energy-saving by using the ultrasonic action, and the micro-morphology of the electrocatalyst material can be controlled by controlling the time of the ultrasonic action, so that the material has different characteristics, and is suitable for different electrocatalysis scenes.
Further, the implementation steps and the beneficial effects of the method are described below with reference to more specific examples.
Example one
The preparation stage comprises the following steps:
1. 140mg of HHTP and 200mg of Co (OAc) were weighed out on an analytical balance2·4H2O was mixed in 30ml of deionized water to obtain a mixed solution.
2. Sealing and placing in an ultrasonic cleaner for reaction for 180min by ultrasonic treatment.
3. The product is sequentially centrifuged, washed by water, washed by acetone and dried in vacuum to obtain the catalyst material Co for the oxygen reduction reaction3(HHTP)2。
4. 3mg Co weighed by an analytical balance3(HHTP)2Mixing with 7mg acetylene black, dissolving in 1.25ml absolute ethanol, and ultrasonically dispersing for 30min to obtain final electrode material Co3(HHTP)2-CB。
And (3) a testing stage:
1. XRD test was carried out on the centrifuged product after vacuum drying to obtain the XRD profile shown in FIG. 2, and analysis of the XRD profile revealed that the centrifuged product had a composition of Co3(HHTP)2Therefore, the M-CATs material is successfully prepared by the method provided by the embodiment of the specification.
2. Scanning electron microscope was used to photograph Co prepared in example one3(HHTP)2Obtaining the SEM image, as shown in FIG. 3, in which Co is shown3(HHTP)2The material presents the appearance of a nano sheet.
3. To Co on electrochemical workstation3(HHTP)2And Co3(HHTP)2The CB test is carried out, and the Linear Sweep Voltammogram (LSV) at the optimum loading is shown in FIG. 4. From FIG. 4Therefore, the M-CATs material obtained by the ultrasonic method has good oxygen reduction performance.
Example two
The preparation stage comprises the following steps:
1. 140mg of HHTP and 200mg of Ni (OAc) were weighed out with an analytical balance2·4H2O was mixed in 30ml of deionized water to obtain a mixed solution.
2. Sealing and placing in an ultrasonic cleaner for reaction for 180min by ultrasonic treatment.
3. The product is sequentially centrifuged, washed by water, washed by acetone and dried in vacuum to obtain the catalyst material Ni for the oxygen reduction reaction3(HHTP)2。
4. 3mg Ni weighed by an analytical balance3(HHTP)2Mixing with 7mg acetylene black, dissolving in 1.25ml absolute ethyl alcohol, and performing ultrasonic treatment for 30min to disperse uniformly to obtain the final electrode material Ni3(HHTP)2-CB。
And (3) a testing stage:
1. XRD test was carried out on the centrifuged product after vacuum drying to obtain the XRD profile shown in FIG. 5, and analysis of the XRD profile revealed that the centrifuged product had Ni as a component3(HHTP)2Therefore, the M-CATs material is successfully prepared by the method provided by the embodiment of the specification.
2. Scanning Electron microscope imaging of Ni prepared in example one3(HHTP)2Obtaining SEM image, as shown in FIG. 6, showing Ni3(HHTP)2The material presents the appearance of a nano sheet.
3. On electrochemical workstation to Ni3(HHTP)2And Ni3(HHTP)2The CB test is carried out, and the Linear Sweep Voltammogram (LSV) at the optimum loading is shown in FIG. 7. As can be seen from FIG. 7, the M-CATs material obtained by the ultrasonic method has good oxygen reduction performance.
EXAMPLE III
The preparation stage comprises the following steps:
1. 70mg of HHTP and 100mg of Co (OAc) were weighed out on an analytical balance2·4H2O was mixed in 20ml (or 15ml) of deionized water to obtain a solution.
2. Sealing and placing in an ultrasonic cleaner for reaction for 60min by ultrasonic treatment.
3. The product is sequentially centrifuged, washed by water, washed by acetone and dried in vacuum to obtain the catalyst material Co for the oxygen reduction reaction3(HHTP)2。
3.3 mg of M-CATs and 7mg of acetylene black are weighed by an analytical balance, mixed and dissolved in 1.25ml of absolute ethyl alcohol, and uniformly dispersed by ultrasonic for 30min to obtain the final electrode material Co3(HHTP)2-CB。
And (3) a testing stage:
scanning Electron microscope imaging of Co prepared in example two3(HHTP)2Obtaining the SEM image, as shown in FIG. 8, of Co3(HHTP)2The material is in a shape of a nano rod and has the shape of a rod-shaped stacked sheet.
Example four
The preparation stage comprises the following steps:
1. 70mg of HHTP and 100mg of Ni (OAc) were weighed out on an analytical balance2·4H2O was mixed in 20ml (or 15ml) of deionized water to obtain a solution.
2. Sealing and placing in an ultrasonic cleaner for reaction for 60min by ultrasonic treatment.
3. The product is sequentially centrifuged, washed by water, washed by acetone and dried in vacuum to obtain the catalyst material Ni for the oxygen reduction reaction3(HHTP)2。
3.3 mg of M-CATs and 7mg of acetylene black are weighed by an analytical balance, mixed and dissolved in 1.25ml of absolute ethyl alcohol, and uniformly dispersed by ultrasonic for 30min to obtain the final electrode material Ni3(HHTP)2-CB。
And (3) a testing stage:
scanning Electron microscope imaging of Ni prepared in example two3(HHTP)2Obtaining the SEM image thereof, as shown in FIG. 9, Ni3(HHTP)2The material is in a shape of a nano rod and has the shape of a rod-shaped stacked sheet.
In summary, by the preparation method of the M-CATs material disclosed in the embodiments of the present disclosure, the electrocatalyst material with better performance can be prepared simply, rapidly and energy-saving by using the ultrasonic action, and the micro-morphology of the electrocatalyst material can be controlled by controlling the time of the ultrasonic action, and accordingly, the preparation method has different characteristics, and can be applied to different electrocatalysis scenarios.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (6)
1. A method of preparing an electrocatalyst, the method comprising:
HHTP of 2,3,6,7,10, 11-hexahydrotriphenylene and M (OAc)2·4H2Adding O into deionized water to obtain a mixed solution, wherein M is Co, Ni or Cu;
carrying out ultrasonic treatment on the mixed solution through an ultrasonic device to enable the mixed solution to react to obtain a reacted solution, wherein the reacted solution comprises solid M3(HHTP)2(ii) a Wherein, the duration of the ultrasonic treatment is controlled to be 50-80min, and then the M in the solution after the reaction is obtained3(HHTP)2The shape of the material is in a nano rod shape; controlling the duration of the ultrasonic treatment at 160-200min to obtain M in the reacted solution3(HHTP)2The shape of the material is nano-flake;
separating said M from said reacted solution3(HHTP)2；
The M is added3(HHTP)2Adding the mixture and acetylene black into absolute ethyl alcohol, and performing ultrasonic dispersion treatment to obtain M3(HHTP)2-CB for use as an electrocatalyst, wherein CB represents the acetylene black; wherein, M is3(HHTP)2And acetylene black in a mass ratio of 3: 7, the time of ultrasonic dispersion treatment is 30-90 min.
2. According to the rightThe method of claim 1, wherein the HHTP is present in the mixed solution at a concentration of 0.35g/L to 23.33g/L by mass volume, and wherein M (OAc)2·4H2The mass volume concentration of O is 0.5g/L to 33.33 g/L.
3. The method of claim 1, wherein said separating said M from said reacted solution3(HHTP)2The method comprises the following steps:
centrifuging the reacted solution;
washing the precipitate obtained by the centrifugal treatment;
drying the washed precipitate to obtain M3(HHTP)2。
4. The method of claim 3, wherein the centrifuging the post-reaction solution comprises:
and centrifuging the solution after the reaction at the rotating speed of 3000-8000 r/min.
5. The method of claim 3, wherein the washing the precipitate from the centrifugation comprises:
the precipitate obtained from the centrifugation was washed several times with deionized water and acetone.
6. The method of claim 3, wherein the drying the washed precipitate comprises:
and drying the washed precipitate in an air drying oven or a vacuum drying oven, wherein the drying temperature set by the air drying oven or the vacuum drying oven is 25-60 ℃.
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