CN114665108A - Rare earth metal doped MOF structure oxygen electrocatalyst and preparation method thereof - Google Patents
Rare earth metal doped MOF structure oxygen electrocatalyst and preparation method thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000001301 oxygen Substances 0.000 title claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 26
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 19
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 18
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 16
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 150000001206 Neodymium Chemical class 0.000 claims abstract description 6
- 150000001868 cobalt Chemical class 0.000 claims abstract description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- 239000013110 organic ligand Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 6
- 229910017512 Nd2(CO3)3 Inorganic materials 0.000 claims description 3
- 229910017544 NdCl3 Inorganic materials 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004321 preservation Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 229910017504 Nd(NO3)3 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000012918 MOF catalyst Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- -1 rare earth neodymium salt Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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
- H01M4/88—Processes of manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a rare earth metal doped MOF structure oxygen electro-catalyst and a preparation method thereof, wherein metal ions in a metal organic framework of the catalyst are Co and Nd, and an organic ligand is 2-methylimidazole; wherein the molar ratio of Nd to Co is 1: (4-10), wherein the mass ratio of Co to 2-methylimidazole is 118 (8000-10000); the preparation method comprises (1) dissolving 2-methylimidazole in water to form a solution; (2) dissolving cobalt salt, neodymium salt and hexadecyl trimethyl ammonium bromide in water to form a solution; (3) mixing the solutions prepared in the steps (1) and (2), stirring for 10-60 minutes, washing and drying; (4) heating the product of the step (3) to 600-800 ℃ under the protection of inert gas, and reacting for 1-5 hours in a heat preservation manner to obtain a rare earth metal doped MOF structure oxygen electrocatalyst; the catalyst effectively improves the activity of the catalyst by doping Nd in Co; the preparation method is simple and efficient.
Description
Technical Field
The invention relates to an MOF catalyst, in particular to a rare earth metal doped MOF structure oxygen electrocatalyst and a preparation method thereof.
Background
Facing the problems of energy shortage and environmental pollution, a great deal of scientific and technical personnel are dedicated to the development of clean energy and the development of new energy storage and conversion technology. Among them, rechargeable metal-air batteries have received much attention from people due to their characteristics of high energy density, low cost, environmental friendliness, and the like. The rechargeable zinc-air battery system realizes the generation and storage of electric energy through the oxidation-reduction reaction between the positive electrode and the negative electrode. The Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) on the air cathode correspond to the discharge and charge processes, respectively. However, the slow kinetic progression of ORR and OER is an important factor affecting the energy conversion efficiency of zinc-air batteries. Therefore, the development of the high-efficiency and low-cost bifunctional oxygen electrocatalyst is the key point of the practical application of the rechargeable zinc-air trend.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a rare earth metal doped MOF structure oxygen electro-catalyst with excellent electro-catalytic activity on oxygen electro-reaction; another object of the present invention is to provide a process for preparing the catalyst.
The technical scheme is as follows: according to the rare earth metal doped MOF structure oxygen electrocatalyst, metal ions in a metal organic framework are Co and Nd, and an organic ligand is 2-methylimidazole in (2-MIM); wherein the molar ratio of Nd to Co is 1: (4-10), the mass ratio of Co to 2-methylimidazole is 118: (8000- & lt 10000- & gt).
When the Co content in the catalyst is low, the morphology is poor, metal particles are easy to agglomerate, and the catalytic performance is reduced; when the content of Co is too large, the catalytic performance is lowered.
The catalyst is of a cubic structure.
The preparation method of the catalyst comprises the following steps:
(1) dissolving 2-methylimidazole in water to form a solution;
(2) dissolving cobalt salt, neodymium salt, and cetyltrimethylammonium bromide (CTAB) in water to form a solution;
(3) mixing the solutions prepared in the steps (1) and (2), stirring for 10-60 minutes, washing and drying;
(4) heating the product obtained in the step (3) to 600-800 ℃ under the protection of inert gas, and carrying out heat preservation reaction for 1-5 hours to obtain a rare earth metal doped MOF structure oxygen electrocatalyst;
wherein the mass ratio of the 2-methylimidazole to the hexadecyl trimethyl ammonium bromide is 8000-9000: 5-20.
2-methylimidazole as ligand, whose functional group anchors Co2+Forming a metal organic framework structure. Nd element is introduced by taking neodymium salt as a dopant, and the electronic state of Co is regulated and controlled by utilizing f-orbital electrons of rare earth elements, so that the catalytic performance of the catalyst is improved. CTAB is a morphology directing agent, so that a final product is in a cubic structure, a rhombic dodecahedron structure is obtained without CTAB, the morphology of the catalyst is influenced by the dosage of CTAB, and the undesirable and inhomogeneous morphology is caused by too much or too little dosage of CTAB.
Preferably, the cobalt salt is CoCl2、CoSO4Or Co (NO)3)2。
Preferably, the neodymium salt is Nd (NO)3)3、Nd2(CO3)3Or NdCl3。
Preferably, in the step (4), the temperature rise temperature is 700-800 ℃. Under high temperature environment, Co2+Is reduced into Co simple substance particles by C. The temperature affects the particle size of the Co nanoparticles, and the Co nanoparticles have large particle size and poor performance due to overhigh temperature.
Preferably, in the step (2), the temperature programming rate is 1-10 ℃/min.
The catalyst of the present invention is used as oxygen separating and reducing catalyst.
The invention mechanism is as follows: the invention takes cobalt salt as a cobalt source, 2-methylimidazole (2-MIM) as a ligand and rare earth neodymium salt as a doping agent to synthesize a ZIF-67 precursor containing Nd. When water is used as the reaction solvent, the amine N of 2-MIM is more prone to form hydrogen bonds with hydrated protons, due to the lower dissociation constant of 2-MIM in water, resulting inTo Co2+And a crosslinking effect and a laminated structure are generated between the Nd-ZIF and the 2-MIM, and under the influence of the unique structure and the hydrophobic property of a surfactant CTAB, the nano cubic Nd-ZIF-67 with uniform appearance is finally obtained. Annealing the precursor at high temperature in an inert gas atmosphere, Co2+Is thermally reduced into simple substance particles by C, and Nd is dispersed on the surface of Co nano particles and a carbon substrate in a single atom form, thereby finally obtaining the MOF structure oxygen electro-catalyst doped with the rare earth metal Nd.
The Nd-doped MOF structure oxygen electrocatalyst prepared by the invention has uniform size, controllable appearance and typical cubic structure, and the structure not only enables the catalyst to have excellent mechanical stability, but also provides larger specific surface area on the loose and porous surface, and exposes more active sites. The rare earth Nd element has unique f-orbital electrons, and can perform f-d hybridization with d-orbital electrons of transition metal Co, so that the overall electronic state of the catalyst is optimized, and the catalytic performance is improved.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: (1) the catalyst effectively improves the activity of the catalyst by doping Nd in Co; (2) the catalyst has a typical cubic block structure, uniform size and regular shape, the loose and porous surface of the catalyst effectively increases active sites, and the ORR/OER shows higher catalytic activity and stability; (3) the preparation method is simple and efficient; (4) the catalyst can be well applied to the cathode and anode catalysts of a rechargeable zinc-air battery, and has wide application prospect in the future energy storage industry.
Drawings
FIG. 1 is an SEM image of the catalyst prepared in example 2;
FIG. 2 is a HRTEM image of the catalyst prepared in example 2;
FIG. 3 is a STEM of the catalyst prepared in example 2;
FIG. 4 is an XRD pattern of the catalyst prepared in example 2;
FIG. 5 is an XPS spectrum of the catalyst prepared in example 2;
FIG. 6 is a plot of catalyst OER and ORR polarization.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
The preparation method of the rare earth metal doped MOF structure oxygen electrocatalyst comprises the following steps:
(1) 9g of 2-MIM were weighed out and dissolved in 140mL of H2O, weighing 1.6mmol of CoCl2，0.4mmol NdCl3And 10mg CTAB in 20mL H2O, mixing and stirring the two solutions for 30min, centrifuging, washing and drying;
(2) and (2) heating the precursor prepared in the step (1) to 700 ℃ at a temperature of 5 ℃/min in a nitrogen atmosphere for heat treatment, keeping the temperature for 3h, and cooling to room temperature to obtain a final product.
Example 2
The preparation method of the rare earth metal doped MOF structure oxygen electrocatalyst comprises the following steps:
(1) 9g of 2-MIM were weighed out and dissolved in 140mL of H2O, weighing 2mmol of Co (NO)3)2，0.4mmol Nd(NO3)3And 10mg CTAB in 20mL H2O, mixing and stirring the two solutions for 30min, centrifugally washing and drying;
(2) and (2) heating the precursor prepared in the step (1) to 700 ℃ at a temperature of 5 ℃/min in a nitrogen atmosphere for heat treatment, keeping the temperature for 3h, and cooling to room temperature to obtain a final product.
Example 3
The preparation method of the rare earth metal doped MOF structure oxygen electrocatalyst comprises the following steps:
(1) 9g of 2-MIM were weighed out and dissolved in 140mL of H2O, weighing 2mmol of CoSO4，0.2mmol Nd2(CO3)3And 10mg CTAB in 20mL H2O, mixing and stirring the two solutions for 30min, centrifugally washing and drying;
(2) and (2) heating the precursor prepared in the step (1) to 700 ℃ at a temperature of 5 ℃/min in a nitrogen atmosphere for heat treatment, keeping the temperature for 3h, and cooling to room temperature to obtain a final product.
Example 4
The preparation method of the rare earth metal doped MOF structure oxygen electrocatalyst comprises the following steps:
(1) 8g of 2-MIM are weighed out and dissolved in 140mL of H2O, weighing 2mmol of Co (NO)3)2，0.4mmol Nd(NO3)3And 5mg CTAB in 20mL H2O, mixing and stirring the two solutions for 10min, and drying;
(2) and (2) heating the precursor prepared in the step (1) to 600 ℃ at a temperature of 1 ℃/min in a nitrogen atmosphere for heat treatment, keeping the temperature for 5 hours, and cooling to room temperature to obtain a final product.
Example 5
The preparation method of the rare earth metal doped MOF structure oxygen electrocatalyst comprises the following steps:
(1) 10g of 2-MIM were weighed out and dissolved in 140mL of H2O, weighing 2mmolCo (NO)3)2，0.4mmolNd(NO3)3And 20mg CTAB in 20mL H2O, mixing and stirring the two solutions for 60min, centrifugally washing and drying;
(2) and (2) heating the precursor prepared in the step (1) to 800 ℃ at a program of 10 ℃/min in a nitrogen atmosphere for heat treatment, keeping the temperature for 1h, and cooling to room temperature to obtain a final product.
Comparative example
Based on example 2, Nd (NO) is not added3)3Other conditions were unchanged.
Performance characterization
(1) The catalyst prepared in example 2 was physically characterized using TEM, HAADF-STEM, XRD and XPS.
The prepared catalyst has typical cubic morphology and uniform size as seen by SEM (figure 1) and HRTEM (figure 2).
The presence of Nd monoatomic atoms is shown by the STEM dark field pattern (FIG. 3), which is shown by the circled portion.
As can be seen from the XRD pattern (FIG. 4), numerous diffraction peaks of the catalyst completely coincided with those of a standard card (Co JCPDS: 15-0806), and no diffraction peak of the Nd element was observed, demonstrating that the Nd element exists in a monoatomic form, which is consistent with the results of STEM dark field patterns.
From the XPS spectrum (FIG. 5), it can be seen that Co is present in the catalyst at a valence of +3 as an active center, in addition to zero.
(2) Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) Activity test
Catalyst prepared in example 2, catalyst prepared in comparative example and commercial Pt/C, RuO2For reference to the catalyst, the OER/ORR activity of the different catalysts in alkaline medium was investigated.
As can be seen from the polarization curve of the catalyst of FIG. 6(a) versus OER, the catalyst prepared in example 2 was operated at a current density of 10mA cm-2Has an overpotential of 288mV which is much less than the overpotential of 312mV for the catalyst prepared in the comparative example and the commercial RuO2349mV of overpotential.
As can be seen from the polarization curve of the catalyst to OER in FIG. 6(b), the half-wave potential of the catalyst prepared in example 2 was 0.85V, which is higher than the half-wave potential of the comparative catalyst by 0.80V and the half-wave potential of the commercially available Pt/C by 0.84V.
The OER/ORR activity of the catalyst prepared in example 2 in alkaline electrolyte is much higher than that of the catalyst prepared in comparative example, commercial RuO2And Pt/C catalysts, mainly due to their unique cubic structure and the electronically optimized results from Nd monatomic doping.
Claims (8)
1. A rare earth metal doped MOF structure oxygen electrocatalyst is characterized in that metal ions in a metal organic framework are Co and Nd, and an organic ligand is 2-methylimidazole; wherein the molar ratio of Nd to Co is 1: 4-10, and the mass ratio of Co to 2-methylimidazole is 118: 8000-10000.
2. The catalyst of claim 1 wherein the catalyst is of a cubic structure.
3. A method for preparing the catalyst of claim 1, comprising the steps of:
(1) dissolving 2-methylimidazole in water to form a solution;
(2) dissolving cobalt salt, neodymium salt and hexadecyl trimethyl ammonium bromide in water to form a solution;
(3) mixing the solutions prepared in the steps (1) and (2), stirring for 10-60 minutes, washing and drying;
(4) heating the product of the step (3) to 600-800 ℃ under the protection of inert gas, and calcining for 1-5 hours to obtain the rare earth metal doped MOF structure oxygen electrocatalyst;
wherein the mass ratio of the 2-methylimidazole to the hexadecyl trimethyl ammonium bromide is 8000-9000: 5-20.
4. The method of claim 3, wherein the cobalt salt is CoCl2、CoSO4Or Co (NO)3)2。
5. Method for preparing a catalyst according to claim 3, characterized in that said neodymium salt is Nd (NO)3)3、Nd2(CO3)3Or NdCl3。
6. The method for preparing a catalyst according to claim 3, wherein the temperature of the increase in temperature in the step (4) is 700 to 800 ℃.
7. The method for preparing the catalyst according to claim 3, wherein in the step (4), the temperature increase rate is 1 to 10 ℃/min.
8. Use of the catalyst of claim 1 or 2 as an oxygen evolution and oxygen reduction catalyst.
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