CN111129524A - Ce-Zr bimetallic cluster MOF-based oxygen reduction electrocatalyst and preparation method and application thereof - Google Patents
Ce-Zr bimetallic cluster MOF-based oxygen reduction electrocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Ce-Zr bimetallic cluster MOF-based oxygen reduction electrocatalyst, a preparation method and application thereof, and belongs to the field of proton exchange membrane fuel cell catalysts. Dispersing metal salt in a solvent, adding organic acid and a macrocyclic compound, carrying out ultrasonic treatment for 10-30min at 20-40 ℃, reacting for 6-12h at 120-150 ℃, carrying out suction filtration, washing until filtrate is colorless, drying, and carrying out high-temperature pyrolysis carbonization to obtain the bimetallic cluster MOF-based electrocatalyst. The method is simple to operate, easy to control and environment-friendly, and the prepared bimetallic cluster MOF-based electrocatalyst has high oxygen reduction activity and can be used for proton exchange membrane fuel cells.
Description
Technical Field
The invention belongs to the field of proton exchange membrane fuel cell electro-catalysts, and relates to a Ce-Zr bimetallic cluster MOF-based oxygen reduction electro-catalyst, and a preparation method and application thereof.
Background
In the present generation, rapid consumption of primary energy such as fossil fuel causes a series of problems such as global energy crisis, global warming and environmental deterioration. Therefore, the development of environment-friendly, sustainable, safe and efficient energy technology is urgent. Proton Exchange Membrane Fuel Cells (PEMFCs) have received extensive attention from researchers due to their advantages of high power density, high energy conversion efficiency, fast start-up, environmental friendliness, and the like.
The redox reaction at the cathode side of a Proton Exchange Membrane Fuel Cell (PEMFC) requires an electrocatalyst with excellent performance to accelerate the oxygen reduction process at the cathode side due to problems such as slow reaction kinetics, complex reaction process, and poor reversibility of the reaction. Researchers have studied the relationship between the bond energy of oxygen adsorbed on the surface of electrocatalysts of different metals and the oxygen reduction activity, and found that the bond energy and the oxygen reduction activity are presented as a volcano-type curve, and the most excellent oxygen reduction activity of the noble metal platinum (Pt) compared with other metals is obtained (Journal of Physical Chemistry B,2004,108: 17886-17892.). Currently, a noble metal Pt-based electrocatalyst is one of the core materials of PEMFCs, but the large amount of Pt used, the low global reserves and the high price limit the progress of commercialization of PEMFCs. The development of non-noble metal catalysts (NPMCs) with high activity, high stability and low price to replace Pt-based electrocatalysts is one of the key technical schemes for promoting the large-scale development of PEMFCs. Over the past decades, researchers have struggled to discover metal nitrogen carbon electrocatalysts (M-N/C, mainly M-N)4As an active site, M ═ transition metals such as Fe, Co, etc.) have excellent oxygen reduction activity and durability, and are expected to promote further development of fuel cells instead of commercial Pt-based electrocatalysts.
Since the first discovery by Jasinski in 1964, N was pyrolyzed by high temperature4The chelate of cobalt phthalocyanine, and the discovery that it has oxygen reduction activity in alkaline systems (Nature,1964,201, 1212-. The Wei group obtained electrocatalysts with higher oxygen reduction activity and better durability by loading ferriporphyrin on carbon materials through covalent bonds (angelw. chem.,2014,126, 6777-6781). However, these non-noble metal electrocatalysts prepared solely from metal macrocyclic compounds such as metal phthalocyanines or metalloporphyrins as precursors generally produce H2O2By two-electron oxygen reduction process of (A), and H2O2Will destroy the electrocatalysisThe active sites of the agent severely reduce the useful life and activity of the electrocatalyst. Therefore, there is a need for a strategy to improve the oxygen reduction activity and durability of metal macrocycle electrocatalysts.
Metal Organic Frameworks (MOFs), also known as Porous Coordination Polymers (PCPs), are highly crystalline materials formed by ionic bonding of metal ions or clusters and multifunctional organic ligands, and have many advantages such as porous structure, easily adjustable structure, high specific surface area, controllable morphology, and adjustable chemical composition. The MOFs has stable structure and good thermal stability, and after the MOFs are pyrolyzed and carbonized at high temperature, the conductivity of the MOFs can be greatly improved and the porous characteristic of the MOFs can be kept, so that the pyrolyzed MOFs are still beneficial to mass transfer and diffusion. The application of MOFs in oxygen reduction electrocatalysts, whose many excellent properties contribute to O2Will have the ability to readily undergo a four electron oxygen reduction process to increase oxygen reduction activity and reduce H2O2Thereby improving the service life of the electrocatalyst.
Zr produced by 2017 Zingiber officinale Kimura group with Zr metal salt6The cluster, with meso-tetra (4-carboxyphenyl) porphine (TCPP) as a ligand, synthesizes PCN-224 with stable structure, then obtains the electrocatalyst with stable structure through the metallization of Fe and Co metal salt, high-temperature pyrolysis carbonization and acid cleaning etching, and the durability of the electrocatalyst is greatly improved (ChemSusChem,2017,10, 1-7). In 2018, the team also takes Zr6The catalyst is a metal cluster, the ligands are changed into TCCP and Fe-TCCP, and the proportion of the two ligands is adjusted to synthesize the Fe-based monatomic catalyst, which improves the activity of the catalyst on the basis of keeping the original stability (Angew. chem. int. Ed.2018,57, 8525-. By introducing the MOF structure, Zr is added, although the activity and durability of the metal macrocyclic compound is extremely large6The metal cluster MOF has the advantages that zirconium element in the MOF is difficult to remove, the activity of an electrocatalyst is influenced to a certain extent, complex processes such as acid washing and etching are needed, the preparation process is complex, and the MOF is difficult to apply to proton exchange membrane fuel cells.
In recent years, researchers have found that cerium, like zirconium, can form a second building block of six-cluster metal nuclei (J.Am. chem. Soc.2019,141,8306-8314), and Martin Lammert et al have found that cerium clusters can produce MOFs with different steric configurations with a variety of different ligands (Crystal. growth Des.2017,17, 1125-1131). In 2017, researchers load Pt on Ce-MOF to prepare an electrocatalyst with good performance and stable structure (Electrochimica Acta,2018,266.), and in 18 years Zhang Zhong et al prepare an oxygen reduction electrocatalyst with catalytic performance superior to that of commercial Pt/C by taking BTCPA containing carboxyl as a ligand (ACS Applied Materials & Interfaces,2018: acsami.8b03742.). Although the introduction of cerium can improve the activity of the oxygen-reducing electrocatalyst, when the content of cerium is too high, the oxygen vacancy is increased, which is somewhat detrimental to the progress of the reaction.
Disclosure of Invention
The invention aims to provide a Ce-Zr bimetallic cluster MOF-based oxygen reduction electrocatalyst, and a preparation method and application thereof. The double metal cluster MOF-based oxygen reduction electrocatalyst is prepared by Ce6、Zr6The two metal clusters are formed, a porous high-crystallinity material is grown between a side chain group of a metal macrocyclic compound with oxygen reduction catalytic capability and the metal clusters through the action of a coordination ionic bond, and then the target electrocatalyst is prepared through high-temperature pyrolysis carbonization. The prepared bimetallic cluster MOF-based oxygen reduction electrocatalyst has better oxygen reduction comprehensive performance and can be used for proton exchange membrane fuel cells.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a Ce-Zr bimetallic cluster MOF-based oxygen reduction electrocatalyst comprises the following steps:
uniformly dispersing two metal salts in a solvent, adding a macrocyclic compound and an organic acid, carrying out ultrasonic treatment for 10-30min at the temperature of 20-40 ℃, reacting for 6-12h at the temperature of 120-150 ℃, carrying out suction filtration, washing until the filtrate is colorless, drying, and carrying out high-temperature pyrolysis carbonization for 1-3h at the temperature of 600-900 ℃ to obtain the Ce-Zr bimetallic cluster MOF oxygen reduction electrocatalyst.
The two metal salts are zirconium salt and cerium salt, and the mass ratio of the zirconium salt to the cerium salt is 1-9: 1;
the mass ratio of the macrocyclic compound to the total metal salt (Ce salt + Zr salt) is 0.3-0.5: 1.
The mass ratio of the organic acid to the total metal salt (Ce salt + Zr salt) is 30-50: 1.
Based on the technical scheme, preferably, the zirconium salt comprises ZrCl4、ZrOCl2·8H2O、ZrO(NO3)2·H2One or more than two of O.
Based on the above technical solution, preferably, the cerium salt comprises Ce (NO)3)3·6H2O、Ce(NH4)2(NO3)6One or two of them.
Based on the technical scheme, preferably, the organic acid comprises CH2O2、C2H4O2、C2HF3O2、C3H6O2、C4H8O2、C2H2Cl2O2、C7H6O2、C8H8O2One or a mixture of two or more of them.
Based on the technical scheme, preferably, the macrocyclic compound comprises porphyrin or phthalocyanine with side chains containing tetracarboxyl; wherein the center of the macrocyclic compound is free of metal elements or comprises metal elements, and the metal comprises iron, cobalt, copper and manganese.
Based on the above technical scheme, preferably, the solvent comprises one or a mixture of more than two of water, methanol, ethanol, propanol, isopropanol, dichloromethane, acetonitrile, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), and N, N-Dimethylacetamide (DMAC).
The invention also relates to a method for protecting the Ce-Zr bimetallic cluster MOF-based oxygen reduction electrocatalyst prepared by the preparation method.
The invention also relates to application of the Ce-Zr bimetallic cluster MOF-based oxygen reduction electrocatalyst in a proton exchange membrane fuel cell.
The preparation method of the electrocatalyst is simplified and optimized, the zirconium element is partially replaced by the cerium element, and the solvothermal method is also adopted to prepare the Ce-Zr bimetallic cluster MOF-based oxygen reduction electrocatalyst which shows better oxygen reduction activity and stability.
Compared with the prior art, the invention has the beneficial effects that: 1) zr element is partially replaced, the acid-washing etching step is omitted, and the preparation process is simplified; 2) the introduction of Ce metal does not destroy the structure of MOFs; 3) oxides of cerium metal, such as: CeO (CeO)2Can be H2O2Is advantageous for reducing H produced2O2Attack porphyrin ring and prolong the service life of the catalyst. 4) The method is simple to operate, easy to control and environment-friendly, and the prepared bimetallic cluster MOF-based electrocatalyst has high oxygen reduction activity and can be used for proton exchange membrane fuel cells.
Drawings
FIG. 1 thermogravimetric analysis (TG) curve of the product obtained in example 1 of the invention;
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of the product obtained in example 1 of the present invention;
FIG. 3 is an oxygen reduction polarization (LSV) curve of the product obtained in example 1 of the present invention.
Detailed Description
The invention is further described in the following with reference to the drawings and examples, which are provided only for the purpose of illustrating the invention more clearly, but the scope of the invention as claimed is not limited to the scope of the embodiments presented below.
Comparative example 1
41.5mg of ZrOCl2·8H2Dispersing O in 8mL of DMF solution, adding 474mg of benzoic acid and 34mg of meso-tetra (4-carboxyphenyl) porphine ferric chloride (Fe-TCPP), carrying out ultrasonic treatment at 25 ℃ for 10min, reacting at 120 ℃ for 12h, carrying out suction filtration, washing until filtrate is colorless, drying at 65 ℃, and pyrolyzing at 700 ℃ for 1h to finally obtain black powder solid which is recorded as Zr-MOF electrocatalyst.
Comparative example 2
56.0mg of Ce (NO)3)3·6H2Dispersing O (Ce-MOF) in 8mL of DMF solution, adding 474mg of benzoic acid and 34mg of meso-tetra (4-carboxyphenyl) porphin ferric chloride (Fe-TCPP), carrying out ultrasonic treatment at 25 ℃ for 10min, reacting at 120 ℃ for 12h, carrying out suction filtration, washing until the filtrate is colorless, drying at 65 ℃, and pyrolyzing at 700 ℃ for 1h to finally obtain a black powder solid which is recorded as a Ce-MOF electrocatalyst.
Example 1
37.5mg of ZrOCl2·8H2O，5.6mg Ce(NO3)3·6H2Dispersing O in 8mL of DMF solution, adding 474mg of benzoic acid and 34mg of meso-tetra (4-carboxyphenyl) porphine ferric chloride (Fe-TCPP), carrying out ultrasonic treatment at 25 ℃ for 10min, reacting at 120 ℃ for 12h, carrying out suction filtration, washing until filtrate is colorless, drying at 65 ℃, and pyrolyzing at 700 ℃ for 1h to finally obtain black powder solid which is recorded as 20% Ce-Zr-MOF electrocatalyst.
As shown in fig. 1, thermogravimetric analysis shows that the Ce-Zr-MOF electrocatalyst in this example has better thermal stability, and the detailed description of its weight loss stage is shown in the figure, and its weight loss stage is divided into five stages; a free water loss stage (20 ℃ -120 ℃); cl-The loss phase (120 ℃ to 350 ℃); the loss stage of macrocyclic side chain group (350-500 deg.C); macrocyclic compound rupture stage (500 ℃ -540 ℃); metal oxidation stage (540-800 ℃).
As shown in fig. 2, the morphology of the Ce-Zr-MOF electrocatalyst in this example is spindle-shaped, the length is about 2um, the width is about 500nm, and the introduction of Ce does not affect the MOF structure.
Referring to fig. 3, the electrochemical performance of the oxygen reduction reaction test is measured by a standard three-electrode method, the catalyst is made into a thin-film working electrode, and the test conditions are as follows: potential sweep tests were performed at a sweep rate of 10mV/s in 0.1M KOH saturated with oxygen at 25 ℃ and at a voltage of 0-1.2V (vs RHE), with electrode rotation at 1600 r/min. The polarization curve shows the half-wave potential (E) of the non-noble metal (Ce-Zr-MOF) electrocatalyst obtained in example 11/2) 0.88V, better than commercial 20% Pt/C (E)1/20.86V), has excellent oxygen reduction catalytic activity. In addition, it can be seen from the figure thatCe. When Zr is introduced into MOFs simultaneously, the activity of the catalyst is better than that of the single Zr-MOF electrocatalyst (E) in comparative example 11/20.85V) and the Ce-MOF electrocatalyst (E) in comparative example 21/2＝0.82V)。
Example 2
39.5mg of ZrOCl2·8H2O，2.8mg Ce(NO3)3·6H2Dispersing O in 8mL of DMF solution, adding 474mg of benzoic acid and 34mg of meso-tetra (4-carboxyphenyl) porphine ferric chloride (Fe-TCPP), carrying out ultrasonic treatment at 25 ℃ for 10min, reacting at 120 ℃ for 12h, carrying out suction filtration, washing until the filtrate is colorless, drying at 65 ℃, and pyrolyzing at 700 ℃ for 1h to finally obtain a black powder solid. The morphology and performance of the catalyst obtained in example 2 are similar to those of the sample in example 1, and the catalyst has better comprehensive oxygen reduction performance.
Example 3
33.5mg of ZrOCl2·8H2O，11.2mg Ce(NO3)3·6H2Dispersing O in 8mL of DMF solution, adding 474mg of benzoic acid and 34mg of meso-tetra (4-carboxyphenyl) porphine ferric chloride (Fe-TCPP), carrying out ultrasonic treatment at 25 ℃ for 10min, reacting at 120 ℃ for 12h, carrying out suction filtration, washing until the filtrate is colorless, drying at 65 ℃, and pyrolyzing at 700 ℃ for 1h to finally obtain a black powder solid. The morphology and performance of the catalyst obtained in example 3 are similar to those of the sample in example 1, and the catalyst has better comprehensive oxygen reduction performance.
Example 4
41mg of ZrOCl2·8H2O，0.575mg Ce(NO3)3·6H2Dispersing O in 8mL of DMF solution, adding 474mg of benzoic acid and 34mg of meso-tetra (4-carboxyphenyl) porphine ferric chloride (Fe-TCPP), carrying out ultrasonic treatment at 25 ℃ for 10min, reacting at 120 ℃ for 12h, carrying out suction filtration, washing until the filtrate is colorless, drying at 65 ℃, and pyrolyzing at 700 ℃ for 1h to finally obtain a black powder solid. The morphology and performance of the catalyst obtained in example 4 are similar to those of the sample in example 1, and the catalyst has better comprehensive oxygen reduction performance.
Example 5
35.5mg of ZrOCl2·8H2O，8.4mg Ce(NO3)3·6H2O in 8mL DMAdding 474mg of benzoic acid and 34mg of meso-tetra (4-carboxyphenyl) porphin ferric chloride (Fe-TCPP) into the F solution, carrying out ultrasonic treatment at 25 ℃ for 10min, reacting at 120 ℃ for 12h, carrying out suction filtration, washing until the filtrate is colorless, drying at 65 ℃, and pyrolyzing at 700 ℃ for 1h to finally obtain a black powder solid. The morphology and performance of the catalyst obtained in example 5 are similar to those of the sample in example 1, and the catalyst has better comprehensive oxygen reduction performance.
Claims (8)
1. A preparation method of a Ce-Zr bimetallic cluster MOF-based oxygen reduction electrocatalyst is characterized by comprising the following steps:
uniformly dispersing metal salt in a solvent, adding a macrocyclic compound and an organic acid, carrying out ultrasonic treatment for 10-30min at the temperature of 20-40 ℃, reacting for 6-12h at the temperature of 120-150 ℃, carrying out suction filtration, washing until the filtrate is colorless, drying, and pyrolyzing for 1-3h at the temperature of 600-900 ℃ to obtain the Ce-Zr double metal cluster MOF oxygen reduction electrocatalyst;
the metal salt is zirconium salt and cerium salt, and the mass ratio of the zirconium salt to the cerium salt is 1-9: 1;
the mass ratio of the macrocyclic compound to the metal salt is 0.1-0.5: 1.
The mass ratio of the organic acid to the metal salt is 30-50: 1.
2. The method for preparing the Ce-Zr bi-metal cluster MOF-based oxygen reduction electrocatalyst according to claim 1, characterized in that the organic acid is CH2O2、C2H4O2、C2HF3O2、C3H6O2、C4H8O2、C2H2Cl2O2、C7H6O2、C8H8O2One or a mixture of two or more of them.
3. The method for preparing a Ce-Zr double metal cluster MOF-based oxygen reduction electrocatalyst according to claim 1 or 2, characterized in that said macrocyclic compound is porphyrin or phthalocyanine with side chain containing tetracarboxyl group; wherein the center of the macrocyclic compound contains no metal element or comprises a metal element, and the metal is iron, cobalt, copper or manganese.
4. The method according to claim 1, wherein the zirconium salt is ZrCl4、ZrOCl2·8H2O、ZrO(NO3)2·H2One or more than two of O.
5. The method of claim 1, wherein the cerium salt is Ce (NO)3)3·6H2O、Ce(NH4)2(NO3)6One or two of them.
6. The method for preparing the Ce-Zr double-metal cluster MOF-based oxygen reduction electrocatalyst according to claim 1, wherein the solvent is one or a mixture of more than two of water, methanol, ethanol, propanol, isopropanol, dichloromethane, acetonitrile, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
7. The Ce-Zr bimetallic cluster MOF-based oxygen reduction electrocatalyst prepared by the preparation method of any one of claims 1 to 6.
8. The application of the Ce-Zr bimetallic cluster MOF-based oxygen reduction electrocatalyst in claim 7 to proton exchange membrane fuel cells.
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| CN111841547A (en) * | 2020-07-31 | 2020-10-30 | 青岛创启汇能新材料科技有限公司 | Composite material, preparation method thereof and catalyst prepared from composite material |
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| CN113506904A (en) * | 2021-06-02 | 2021-10-15 | 华南理工大学 | Proton exchange membrane and preparation method and application thereof |
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Application publication date: 20200508 |