CN114736388B - Fe-doped novel two-dimensional Co-MOFs composite material, and preparation method and application thereof - Google Patents

Fe-doped novel two-dimensional Co-MOFs composite material, and preparation method and application thereof Download PDF

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CN114736388B
CN114736388B CN202210392712.7A CN202210392712A CN114736388B CN 114736388 B CN114736388 B CN 114736388B CN 202210392712 A CN202210392712 A CN 202210392712A CN 114736388 B CN114736388 B CN 114736388B
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刘宇奇
代思玉
王新颖
李玮
金楠皓
李杨华
陈寒
赵越
刘小铭
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Kunming University of Science and Technology
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Abstract

The invention provides a Fe-doped novel two-dimensional Co-MOFs composite material, a preparation method and application thereof. The composite material takes a novel two-dimensional Co-MOFs crystal material as a carrier, fe element doping is distributed on the carrier, and after Fe element doping is carried out on a Co-based metal organic framework material with a two-dimensional framework crystal structure, the obtained composite material has an amorphous structure, and Co element and Fe element are uniformly distributed in the amorphous structure. The composite material has good electrochemical catalytic oxygen evolution performance under alkaline conditions, is stable after 11 hours of circulation, and can be used as an alkaline OER electrocatalyst.

Description

Fe-doped novel two-dimensional Co-MOFs composite material, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrochemical materials, and particularly relates to a novel Fe-doped two-dimensional Co-MOFs composite material, a preparation method and application thereof, in particular to application of the composite material as an alkaline OER electrocatalyst.
Background
The Metal-organic frameworks (Metal-Organic Frameworks, MOFs) are used as unique porous coordination polymers, have the characteristics of various structures, high specific surface area, adjustable pore surface, adjustable pore size and the like, and are crystalline porous materials which are rapidly developed in recent years. Recently, metal Organic Frameworks (MOFs) have attracted increasing attention in energy-related applications due to their tunable porosity and diversity of coordination bonds between metal ions and organic ligands.
Electrochemical water splitting hydrogen production is key to developing sustainable energy conversion and storage technologies. However, oxygen Evolution (OER) kinetics are retarded, severely limiting hydrogen production efficiency. The catalysts currently used in commercial applications are still limited to Ir or Ru-based materials, but these noble metal materials have the disadvantages of high cost and small reserves. On the other hand, the poor stability of these noble metal-based catalysts further hinders the efficiency of energy conversion, all of which limit their large-scale application. It is therefore highly desirable to develop electrocatalysts that are efficient, inexpensive and stable to promote the catalytic reactions. However, the transition metal cobalt has a rich reserve, is low in cost, and contains various variable valence states, so that the cobalt-based material-based electrocatalyst has been receiving great attention from researchers. Furthermore, the abundant active metal sites in the metal organic framework structure not only can be used as high active sites in electrocatalysis and show high adsorption affinity and catalytic activity, but also can provide accommodation space for electrolyte. Among the many metal framework materials, in particular cobalt-based metal organic framework materials (Co-MOFs), it not only combines the porosity of MOF materials, but also has high theoretical catalytic activity of metallic cobalt and low binding energy to H, and these unique advantages make Co-MOFs and their derivatives widely used in the field of electrocatalysis.
And researches also show that by introducing other transition metal elements to form the bimetallic cobalt-based material, the active site distribution and charge transfer rate of the material can be effectively improved, and the material has more excellent electrocatalytic activity than single cobalt-based material. Furthermore, synergistic bimetallic centres have been shown theoretically and experimentally to adsorb intermediates such as OH, O and OOH during electrocatalysis, and MOFs with active bimetallic nodes are therefore considered to be excellent electrocatalysts. However, for bulk bimetallic MOFs, most of the metal sites are buried deep within the material and cannot contact the electrolyte, severely affecting the catalytic effect of the catalyst. To address these problems, elaborate structures (e.g., amorphous materials) are needed to significantly enhance the surface area and porous structure of the conductive MOF, which can maximize the number of exposed bimetallic active sites while facilitating contact of these active species with the electrolyte to achieve efficient electrocatalysis.
Disclosure of Invention
The invention aims to provide a novel Fe-doped two-dimensional Co-MOFs composite material and a preparation method thereof, which have excellent alkaline OER electrocatalytic activity and stability and can be applied as an alkaline OER electrocatalyst.
The technical scheme provided by the invention is as follows: the Fe-doped novel two-dimensional Co-MOFs composite material has an amorphous structure, and Fe atoms are uniformly distributed in novel two-dimensional Co-MOFs crystals;
the novel two-dimensional Co-MOFs crystal is a two-dimensional supermolecular material based on tetrazine and V-type carboxylic acid double ligands, and the chemical molecular formula of the novel two-dimensional Co-MOFs crystal is { [ Co (bptz) 2 (oba) 2 ]·2DMF} n Wherein bpdz is 3, 6-bis (pyridin-3-yl) -1,2,4, 5-tetrazine with two protons removed, oba is 4, 4' -dicarboxydiphenyl ether with two protons removed; said { [ Co (bptz) 2 (oba) 2 ]·2DMF} n The crystal structure of (2) belongs to monoclinic crystal form, the space group is P21/c, and the unit cell parameters are as follows:
Figure BDA0003597610530000021
α＝γ＝90.00°，β＝111.41°。
the preparation method of the composite material mainly comprises the steps of taking novel two-dimensional Co-MOFs crystals as a carrier, doping transition metal element Fe by a mechanical grinding method, dissolving cobalt acetate, 4 '-dicarboxyl diphenyl ether and 3, 6-bis (pyridine-3-yl) -1,2,4, 5-tetrazine in N, N' -Dimethylformamide (DMF) solution, transferring the obtained solution to a reaction kettle, and carrying out crystallization reaction; after the temperature is reduced to room temperature, washing and drying are carried out to obtain the novel two-dimensional Co-MOFs crystal; ferrous sulfate is added into the obtained Co-MOFs crystal material, and Fe doped composite material Fe@Co-MOFs is obtained by grinding under the participation of ethanol. The method specifically comprises the following steps:
(1) Adding 3, 6-bis (pyridin-3-yl) -1,2,4, 5-tetrazine into DMF solution, stirring uniformly, and then adding 4, 4' -dicarboxyl diphenyl ether solution dissolved in DMF solution under stirring to obtain mixed solution;
(2) Adding cobalt acetate dissolved in DMF solution into the mixed solution in the step (1), and stirring to obtain a reaction solution;
(3) Transferring the reaction liquid obtained in the step (2) to a reaction kettle for crystallization reaction; cooling to room temperature by a program to obtain a mixed solution a, filtering the mixed solution a, washing and drying to obtain the novel two-dimensional Co-MOFs crystal material;
(4) In step (3)FeSO is added into the obtained Co-MOFs crystal material 4 ·7H 2 O, grinding under the participation of ethanol to obtain Fe@Co-MOFs of the Fe doped composite material.
Preferably, the molar ratio of cobalt acetate, 3, 6-bis (pyridin-3-yl) -1,2,4, 5-tetrazine and 4, 4' -dicarboxydiphenyl ether is 1, based on 0.05mmol of cobalt acetate: 1:1.
preferably, the three DMF solutions in steps (1) - (2) are used in the same amount, and the total amount is 6mL.
Preferably, the crystallization reaction in the step (3) is carried out at a temperature of 85 ℃ for 48-72 hours.
Preferably, in the step (3), the temperature is reduced at a speed of 5 ℃/h.
Preferably, in the step (4), co-MOFs crystals and FeSO 4 ·7H 2 The molar ratio of O is 1 (0.3-1).
The composite material has excellent OER electrocatalytic activity and stability under alkaline conditions, and can be used as an alkaline OER catalyst with excellent performance:
(1) The overpotential (overpotential) is extremely low
The alkaline OER electrocatalytic test shows that the catalyst is used for preparing the catalyst at 50 mA.cm -2 The overpotential of Fe@Co-MOFs of the Fe-doped novel two-dimensional Co-MOFs composite material is between 250 and 290mV, wherein the overpotential is between 50mA cm -2 The overpotential at current density is only 248mV.
(2) Has good stability
The Fe@Co-MOFs of the composite material is 50 mA.cm -2 Can be stabilized for 11 hours under the current density of (2), and compares the Linear Sweep Voltammetry (LSV) curves before and after the test, and discovers that the Fe@Co-MOFs of the material after the stability test is 50mA cm -2 The OER overpotential increases by only 22mV at the current density of (a).
The beneficial effects are that: according to the invention, the novel two-dimensional Co-MOFs crystal material is doped with metallic iron, so that the synergistic effect of multiple metals can be realized, the electronic structure of the metal center can be regulated, defects can be introduced in the structure, and the OER performance of the material can be improved. The grinding method can keep the morphological advantages of the matrix MOFs, and in the grinding process, the MOFs can be peeled into smaller sizes, a large amount of lattice distortion and interfaces are generated, the electrocatalytic performance of the material is enhanced, and the material can be applied as an alkaline OER catalyst with excellent performance.
Drawings
FIG. 1 is a diagram showing the coordination environment of the novel two-dimensional Co-based metal organic frameworks (Co-MOFs) prepared in example 1, example 2, and example 3 of the present invention.
FIG. 2 is a two-dimensional block diagram of a novel two-dimensional Co-based metal organic frameworks (Co-MOFs) prepared in example 1, example 2, and example 3 of the present invention.
FIG. 3 is a diagram showing the structure of supermolecule of Co-MOFs prepared in example 1, example 2, and example 3 of the present invention.
FIG. 4 is an XRD pattern of a Fe-doped novel two-dimensional Co-MOFs composite prepared in example 1, example 2, and example 3 of the present invention.
FIG. 5 is a High Resolution Transmission Electron Microscope (HRTEM) image of Fe@Co-MOFs-3 of the Fe-doped novel two-dimensional Co-MOFs composite material prepared in example 3 of the present invention.
FIG. 6 is a mapping image of dark field High Resolution Transmission Electron Microscope (HRTEM) of Fe@Co-MOFs-3 of the Fe-doped novel two-dimensional Co-MOFs composite material prepared in example 3 of the present invention.
FIG. 7 is a linear sweep voltammetric LSV curve for the Fe-doped novel two-dimensional Co-MOFs composite prepared in example 1, example 2, example 3, according to the present invention.
FIG. 8 is a linear sweep voltammetric LSV curve before and after 11h electrochemical stability testing of the Fe@Co-MOFs-3 composite material Fe@Co-MOFs-3 prepared in example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
The Fe-doped novel two-dimensional Co-MOFs composite material provided by the invention, wherein the novel two-dimensional Co-MOFs crystal is a two-dimensional supermolecular material based on tetrazine and V-type carboxylic acid double ligands, and the chemical molecular formula of the novel two-dimensional Co-MOFs composite material is { [ Co (bptz) 2 (oba) 2 ]·2DMF} n Wherein bpdz is 3, 6-bis (pyridin-3-yl) -1,2,4, 5-tetrazine with two protons removed, and oba is 4, 4' -dicarboxydiphenyl ether with two protons removed.
Wherein { [ Co (bptz) 2 (oba) 2 ]·2DMF} n The crystal structure of (2) belongs to monoclinic crystal form, the space group is P21/c, and the unit cell parameters are as follows:
Figure BDA0003597610530000041
α＝γ＝90.00°，β＝111.41°。
the composite material has an amorphous structure, and Fe atoms are uniformly distributed in the novel two-dimensional Co-MOFs crystal. As shown in FIG. 1, { [ Co (bptz) 2 (oba) 2 ]·2DMF} n Each Co of (C) 2+ In hexacoordinated mode with two pyridine N atoms from two tetrazine ligands and four O atoms from three carboxylic acid ligands, a distorted octahedral structure is formed. In one aspect, the carboxylic acid group at one end of each carboxylic acid ligand is chelated to one Co 2+ The carboxylic acid group at the other end is represented by mu 2 Bridging means connecting two adjacent Co 2+ On the other hand, the pyridine rings at both ends of each tetrazine ligand also bridge two Co 2+ . This connection is repeated from cycle to cycle, and finally the tetrazine ligand and the carboxylic acid ligand center Co 2+ The connection forms a two-dimensional network structure as shown in fig. 2. The abundant hydrogen bonds in turn expand the two-dimensional network into a three-dimensional supramolecular structure, as shown in fig. 3.
The preparation route of the Fe doped composite material Fe@Co-MOFs takes a novel two-dimensional Co-MOFs as a matrix, and is implemented specifically according to the following steps:
example 1
(1) 3, 6-bis (pyridin-3-yl) -1,2,4, 5-tetrazine (bptz) (0.0118 g,0.05 mmol) was added to a 2mL DBMF solution, stirred well, followed by the addition of 4, 4' -dicarboxydiphenyl ether (H) dissolved in 2mL DBMF with stirring 2 oba) (0.0129 g,0.05 mmol) to give a mixture;
(2) After the step (1), cobalt acetate (Co (OAc)) dissolved in 2mL of DMF was added to the mixture 2 ·6H 2 O) (0.0125 g,0.05 mmol), and stirring for 30 min to obtain reaction solution;
(3) Transferring the reaction solution obtained in the step (2) into a polytetrafluoroethylene hydrothermal reaction kettle, and reacting at a constant temperature of 85 ℃ for 72 hours; cooling to room temperature at a speed of 5 ℃/h to obtain a mixed solution a;
(4) Filtering the mixed solution a obtained in the step (3), washing the obtained solid substance with deionized water and DMF in sequence, and finally drying in an oven to obtain a novel Co-based two-dimensional metal organic frame material (Co-MOFs);
(5) Adding ferrous sulfate FeSO to Co-MOFs (0.065 g,0.1 mmol) obtained in step (4) 4 ·7H 2 O (0.0092 g,0.033 mmol) is ground for 60min under the participation of 2mL of ethanol to obtain the Fe@Co-MOFs-1 of the novel Fe-doped two-dimensional Co-MOFs composite material.
The coordination environment diagram, the two-dimensional structure diagram and the three-dimensional supermolecular structure diagram of the novel Co-based two-dimensional metal organic frameworks (Co-MOFs) prepared in the steps (1) - (4) are shown in the figures 1,2 and 3.
XRD of the Fe-doped composite material Fe@Co-MOFs-1 prepared in the step (5) is shown in figure 4.
OER performance test is carried out on the composite material prepared by the method, and the test method is as follows:
(1) Firstly, preparing composite material Fe@Co-MOFs-1 ink, wherein the preparation method specifically comprises the following steps: 5mg of the composite Fe@Co-MOFs-1 was transferred to a mixed solution of deionized water (200. Mu.L) and 0.5% Nafion ethanol solution (300. Mu.L), and sonicated for 30 minutes to obtain a mauve ink.
(2) Catalyst ink (25. Mu.L) was supported on foam nickel (0.5 cm) by drop coating 2 ) The electrode was formed thereon, and dried slowly at room temperature.
(3) The three-electrode battery test is adopted, the glassy carbon electrode is a working electrode, the counter electrode is a platinum wire, the reference electrode is Hg/HgO (0.925V vs. RHE), the electrolyte is 1M KOH, and the test voltage range is 1.0-1.8V vs. RHE.
The test result shows that the composite material Fe@Co-MOFs-1 of the embodiment is 50mA cm -2 The overpotential is between 280 and 290mV, as shown in fig. 7.
Example 2
In this example, the preparation of novel two-dimensional Co-based metal organic frameworks (Co-MOFs) was identical to that of example 1The same procedure as in example 1 was followed except that the reaction mixture was reacted at a constant temperature of 85℃for 48 hours in a hydrothermal reaction vessel of polytetrafluoroethylene, and the doping method was the same as that of example 1, except that ferrous sulfate FeSO was doped 4 ·7H 2 The amount of O was 0.0184g (0.067 mmol).
XRD of the Fe-doped novel two-dimensional Co-MOFs composite (Fe@Co-MOFs-2) prepared above is shown in figure 4.
The prepared composite material Fe@Co-MOFs-2 is subjected to OER performance test, the test method is the same as that in the example 1, and the test result shows that the composite material Fe@Co-MOFs-2 of the example is 50mA cm -2 The overpotential is between 270 and 290mV, as shown in fig. 7.
Example 3
In this example, the preparation method of the novel two-dimensional Co-based metal organic frameworks (Co-MOFs) is exactly the same as that in example 1, and the doping method is also the same as that in example 1, except that the doped ferrous sulfate FeSO 4 ·7H 2 The amount of O was 0.0278g (0.1 mmol).
XRD of the Fe-doped novel two-dimensional Co-MOFs composite material (Fe@Co-MOFs-3) prepared above is shown in figure 4. With the increase of the doping amount of Fe, the crystallinity of the prepared composite material gradually decreases until the composite material becomes amorphous material Fe@Co-MOFs-3.
The dark field High Resolution Transmission Electron Microscope (HRTEM) diagram (200 nm and 2 nm) of the prepared composite material Fe@Co-MOsFs-3 is shown in FIG. 5, and the 2nm diagram clearly reflects that Fe@Co-MOFs-3 is of an amorphous structure.
As shown in fig. 6, the mapping image of the dark field High Resolution Transmission Electron Microscope (HRTEM) obtained above shows that Co element and Fe element are uniformly distributed in the amorphous structure.
The prepared composite material Fe@Co-MOFs-3 is subjected to OER performance test, the test method is the same as that in the example 1, and the test result shows that the composite material Fe@Co-MOFs-3 of the example is 50mA cm -2 The overpotential is only 240 to 250mV, as shown in fig. 7, and can be stabilized for 11 hours or more.
The electrochemical stability test of the Fe@Co-MOFs-3 of the prepared composite material is carried out, the Linear Sweep Voltammetry (LSV) curves before and after the cyclic test are shown in figure 8, and the amorphous material Fe@Co-MOFs-3 is found to be 50mA cm after 11h of cyclic test -2 The OER overpotential at current density is only 22mV higher, with excellent stability.
Therefore, the Fe doped amorphous material Fe@Co-MOFs-3 can be used as an alkaline OER electrocatalyst, and has excellent catalytic performance and stability.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.

Claims (8)

1. A Fe-doped two-dimensional Co-MOFs composite material is characterized in that: the composite material has an amorphous structure, takes two-dimensional Co-MOFs crystals as a carrier, carries out Fe doping of a transition metal element by a mechanical grinding method, and Fe atoms are uniformly distributed in the two-dimensional Co-MOFs crystals;
the method specifically comprises the following steps:
(1) Adding 3, 6-bis (pyridin-3-yl) -1,2,4, 5-tetrazine into DMF solution, stirring uniformly, and then adding 4, 4' -dicarboxyl diphenyl ether solution dissolved in DMF solution under stirring to obtain mixed solution;
(2) Adding cobalt acetate dissolved in DMF solution into the mixed solution in the step (1), and stirring to obtain a reaction solution;
(3) Transferring the reaction liquid obtained in the step (2) to a reaction kettle for crystallization reaction; cooling to room temperature by a program to obtain a mixed solution a, filtering the mixed solution a, washing and drying to obtain the two-dimensional Co-MOFs crystal material;
(4) Adding FeSO into the Co-MOFs crystal material obtained in the step (3) 4 ·7H 2 O, co-MOFs crystal and FeSO 4 ·7H 2 The molar ratio of O is 1:1, grinding under the participation of ethanol to obtain Fe@Co-MOFs of a Fe-doped two-dimensional Co-MOFs composite material;
the two-dimensional Co-MOFs crystal is a two-dimensional supermolecular material based on tetrazine and V-type carboxylic acid double ligands, and the chemical molecular formula of the two-dimensional Co-MOFs crystal is { [ Co (bptz) 2 (oba) 2 ]·2DMF} n Wherein bpdz is 3, 6-bis (pyridin-3-yl) -1,2,4, 5-tetrazine with two protons removed, oba is 4, 4' -dicarboxydiphenyl ether with two protons removed; said { [ Co (bptz) 2 (oba) 2 ]·2DMF} n The crystal structure of (2) belongs to monoclinic crystal form, the space group is P21/c, and the unit cell parameters are as follows: a= 13.942 (2) a, b= 13.186 (19) a, c= 18.636 (3) a, α=γ=90.00°, β= 111.41 °.
2. The Fe-doped two-dimensional Co-MOFs composite according to claim 1, wherein: based on 0.05mmol of cobalt acetate, the molar ratio of the cobalt acetate to the 3, 6-bis (pyridin-3-yl) -1,2,4, 5-tetrazine to the 4, 4' -dicarboxydiphenyl ether is 1:1:1.
3. the Fe-doped two-dimensional Co-MOFs composite according to claim 1, wherein: the three DMF solutions in the steps (1) - (2) are the same in dosage, and the total amount is 6mL.
4. The Fe-doped two-dimensional Co-MOFs composite according to claim 1, wherein: the crystallization reaction temperature in the step (3) is 85 ℃ and the time is 48-72 h.
5. The Fe-doped two-dimensional Co-MOFs composite according to claim 1, wherein: and (3) performing program cooling at a speed of 5 ℃/h in the step (3).
6. Use of the Fe-doped two-dimensional Co-MOFs composite material as claimed in claim 1 as an alkaline OER electrocatalyst.
7. The method of claim 6, wherein the current density is 50mA DEGcm -2 The overpotential of the Fe-doped two-dimensional Co-MOFs composite material is 240 mV-250 mV.
8. The method according to claim 7, wherein the current density is 50mA cm -2 After 11h electrochemical stability test, the OER overpotential of the composite material of the Fe doped two-dimensional Co-MOFs is increased by 22mV.
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