CN112871215B - Preparation method and application of iron-doped cobalt imidazolide hollow nano catalytic material - Google Patents

Preparation method and application of iron-doped cobalt imidazolide hollow nano catalytic material Download PDF

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CN112871215B
CN112871215B CN202110038854.9A CN202110038854A CN112871215B CN 112871215 B CN112871215 B CN 112871215B CN 202110038854 A CN202110038854 A CN 202110038854A CN 112871215 B CN112871215 B CN 112871215B
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cobalt
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imidazolate
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CN112871215A (en
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林健健
赵清云
郑德华
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Qingdao University of Science and Technology
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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    • B01J2531/84—Metals of the iron group
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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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Abstract

The invention discloses a preparation method of an iron-doped cobalt imidazolide nano catalytic material, which comprises the following steps: dissolving a proper amount of cobalt nitrate, ferric nitrate, an organic ligand and an organic acid in an organic solvent, and stirring the mixture at 70 ℃ to obtain a mixed reaction solution; 2) Transferring the mixed reaction solution into a high-pressure reaction kettle, and preserving the temperature until the reaction is complete; 3) And after the high-pressure reaction kettle is cooled to room temperature, centrifugally washing to obtain brown precipitate, and purifying the brown precipitate to obtain the iron-doped cobalt imidazolate nano material.

Description

Preparation method and application of iron-doped cobalt imidazolide hollow nano catalytic material
The technical field is as follows:
the invention relates to the technical field of new material synthesis, in particular to the technical field of electrocatalytic water decomposition, and particularly relates to a preparation method and application of an iron-doped cobalt imidazolate hollow nanorod catalytic material.
Background art:
the continuous use of fossil fuels causes problems such as energy crisis and environmental pollution. Therefore, there is an urgent need to develop sustainable alternative clean energy, and hydrogen is widely used in many fields as a clean energy. Currently, hydrogen is mainly produced by direct electrolysis of water, which is a green technology with low energy consumption, but the slow kinetics of the Oxygen Evolution Reaction (OER) in the electrolysis of water may hinder efficient water electrolysis. Noble metal catalyst IrO 2 And RuO 2 OER is effectively promoted, but their high price and low availability limit their wide range of applications. Therefore, research into non-noble metal catalysts, such as hydroxides, metal oxides, perovskites, and the like, is receiving attention. Several strategies have been proposed to improve the electrochemical performance of catalysts, such as increasing the number of electrochemically active sites and improving the intrinsic activity of the catalyst.
Metal Organic Frameworks (MOFs) have large surface areas, high porosity and structures that can be easily tuned by changing the metal active center and ligands, and can meet the requirements for developing efficient OER catalysts. However, large MOFs crystals often have the disadvantages of poor conductivity and active sites hindered by organic ligands, and the calcination process at high temperatures may also result in degradation of active sites and loss of organic ligands, which greatly limits the OER performance of MOF catalyst materials. One strategy to address this problem is to increase the crystal structure of the MOF crystals by adding heteroatoms or ligands and creating unsaturated coordination centers, thereby increasing the number of exposed active sites.
Amorphous MOF (MOF) nanomaterials have gained increasing attention as new catalysts for electrochemical applications, with enormous application potential. However, aMOFs are generally prepared under severe conditions, and aMOFs having a complicated composition and structure are rarely reported. Recently, the bear loyalty et al synthesized an aMOF-based nanocomposite (aMOF-NC) having a structure and a composition complexity by a simple method, proposed an amorphization/competitive coordination mechanism based on experimental and density functional theory calculation results, prepared an aMOF-NC having a core-shell structure, including an iron-rich FeCo-aMOF core and a cobalt-rich FeCo-aMOF core-shell in a nanorod having a core-shell structure, and amorphous Co (OH) 2 The nanosheet serves as the outer layer. The aMOF-NC benefits from structural and compositional heterogeneity, shows excellent oxygen release reactivity, and proves that the structural and compositional heterogeneity is beneficial to the improvement of electrochemical performance. Zeixin et al proposed to modify the electronic structure of MOFs by introducing missing linkers to improve the performance of OER.
In general, the active segments in amorphous MOFs can only be observed in a small fraction of the structure, with irregular boundaries and a predominantly random distribution of atoms. This structural feature provides a number of crystal structure defects that can act as electrochemically active sites, facilitate mass transport and improve OER performance. Therefore, it is of great interest to prepare amorphous catalysts for efficient OER.
Through the above analysis, the problems and defects of the prior art are as follows: the noble metal-based catalyst is not suitable for mass production due to its high price and small storage amount.
The invention content is as follows:
aiming at the problem of high cost caused by the fact that a catalyst needs to use noble metals in the prior art, the invention provides the iron-doped cobalt imidazolate hollow nanorod catalytic material, and as the storage capacity of transition metals is large, the price is low and the materials are easy to obtain, and the synthesis raw materials of iron-cobalt nano materials are all prepared from mass-produced fine chemicals, the time and the cost can be well saved.
The invention provides a preparation method and application of an iron-doped cobalt imidazolate hollow nanorod catalytic material, which comprises the following steps:
1) Dissolving a proper amount of cobalt nitrate, ferric nitrate, an organic ligand and an organic acid in an organic solvent, and stirring the mixture at 70 ℃ to obtain a mixed reaction solution;
2) Transferring the mixed reaction solution into a high-pressure reaction kettle, and preserving the temperature until the reaction is complete;
3) And after the high-pressure reaction kettle is cooled to room temperature, centrifugally washing to obtain brown precipitate, and purifying the brown precipitate to obtain the iron-doped cobalt imidazolate nano material.
In one embodiment according to the present invention, step 1) further comprises:
a) Fully dissolving a proper amount of ferric nitrate and cobalt nitrate in an organic solvent at 70 ℃ to obtain a uniformly mixed solution I; preferably, the mass ratio of the ferric nitrate to the cobalt nitrate in the step a) is 1:2.5-6; and (2) taking the ratio of g: the ratio of ferric nitrate to organic solvent is 1:140-210;
b) Fully dissolving a proper amount of organic ligand in the organic solvent 1, and fully stirring to obtain a uniformly mixed solution II; preferably, the mass ratio of ferric nitrate to organic ligand in step b) is 1:11 to 18; and g: and the ratio of the organic ligand to the organic solvent is 1:11 to 19;
c) Slowly injecting the solution I into the solution II, and fully stirring and reacting at 70 ℃ for 20-30 minutes to obtain a mixed solution;
d) Adding 50-100 mu L of organic acid solution into the mixed solution, and uniformly mixing to obtain a mixed reaction solution.
In one embodiment according to the present invention, in step 1), the organic ligand is selected from one of vinyl imidazole, dimethyl imidazole or terephthalic acid;
in one embodiment according to the present invention, in step 1), the organic solvent is selected from one of methanol, ethanol, or N-N dimethylformamide.
In one embodiment according to the present invention, in step 1), the organic acid is selected from one of glacial acetic acid, citric acid and ethylenediaminetetraacetic acid.
In one embodiment according to the present invention, in the step 2), the autoclave maintaining reaction is carried out by transferring the autoclave to a maintaining device at 100-180 ℃ for 10-20 hours.
In one embodiment according to the invention, said purification in step 3) is achieved by a process comprising the steps of:
and (3) performing ultrasonic dispersion treatment on the brown precipitate, washing the brown precipitate for a plurality of times by using absolute ethyl alcohol, collecting the precipitate by centrifuging after washing, and finally performing vacuum drying in a vacuum drying oven for 5-10 hours.
The invention also provides the iron-doped cobalt imidazolate nano material prepared by the method; preferably, the iron-doped cobalt imidazolate nano material is in a hollow rod shape.
The invention also provides application of the iron-doped cobalt imidazolate nano material in preparation of catalysts, electrodes or batteries. Preferably, the catalyst is used for catalyzing electrochemical decomposition of water to produce hydrogen.
The invention has the beneficial effects that:
according to the invention, an organic solvent which is easy to obtain and low in price is used as a solvent, the hollow nano-rod-shaped iron-doped cobalt imidazolide nano-material with excellent OER performance is obtained by regulating and controlling the feeding ratio of an iron source precursor and a cobalt source precursor added before reaction, and as the transition metal storage capacity is large and the price is low and easy to obtain, the synthesis raw materials of the iron-cobalt nano-material provided by the invention are all prepared from mass-produced fine chemicals, so that the time and the cost can be well saved.
Drawings
Fig. 1 is a flow chart of a preparation method of an iron-doped cobalt imidazolate nanomaterial according to an embodiment of the present invention.
Fig. 2 is a fourier infrared spectrum of an iron-doped cobalt imidazolate nanomaterial provided by the embodiment of the invention.
FIG. 3 is a Scanning Electron Microscope (SEM) spectrum of AFC-MOFs (1/4) prepared in example 1 provided by the present invention, and the obtained iron-doped cobalt imidazolate nano-material is in the shape of hollow nanorods.
FIG. 4 is a transmission electron microscope and high resolution transmission electron microscope spectra provided in the present invention to see the morphology and lattice distribution of the Fe/Co (1/4) material prepared in example 1.
Fig. 5 is a transmission electron microscope element distribution chart provided by the embodiment of the invention, and the uniform distribution of several elements can be seen.
FIG. 6 shows the iron-doped cobalt imidazolate nanomaterial prepared in example 1 and commercial IrO 2 Performance of the noble metal catalysts is compared.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the embodiment of the invention provides a preparation method of an iron-doped cobalt imidazolate nano material.
As shown in fig. 1, a preparation method of an iron-doped cobalt imidazolate nanomaterial provided by an embodiment of the present invention includes the following steps:
1) Fully dissolving ferric nitrate and cobalt nitrate in a certain amount of organic solvent at 70 ℃, and stirring for dissolving to obtain a solution I; dissolving an organic ligand in a certain amount of organic solvent, and fully stirring to obtain a solution II; and slowly pouring the solution I into the solution II, adding the organic acid, and fully stirring to obtain a mixed solution.
2) Transferring the obtained mixed solution into a stainless steel high-pressure reaction kettle, preserving heat for a period of time, and naturally cooling;
3) Centrifuging to obtain a brown product, washing the brown product with ethanol under ultrasonic treatment, and drying in a vacuum drying oven to obtain the nano material.
The preparation method of the iron-doped cobalt imidazolate nano material provided by the embodiment of the invention specifically comprises the following steps:
the first step is as follows: fully dissolving 0.05-0.07g of ferric nitrate and 0.2-0.3g of cobalt nitrate in 10-15ml of organic solvent at 70 ℃, and fully stirring to form a uniform solution I;
the second step is that: fully dissolving 0.8-0.9g of organic ligand in 10-15ml of organic solution, and fully stirring to form a uniform solution II;
the third step: slowly introducing the solution I into the solution II, and fully stirring for 20-30 minutes at 70 ℃;
the fourth step: adding 50-100 mu L of organic acid solution into the mixed solution to form uniform solution;
the fifth step: transferring the solution into a stainless steel high-pressure reaction kettle, transferring the high-pressure reaction kettle into an oven, adjusting the temperature to 100-180 ℃, and keeping the temperature for 10-20 hours;
and a sixth step: and after the high-pressure reaction kettle is naturally cooled to room temperature, centrifugally washing the mixture to obtain a brown precipitate, ultrasonically dispersing the obtained brown precipitate, washing the precipitate for a plurality of times by using absolute ethyl alcohol, centrifugally collecting the precipitate, and transferring the product into a vacuum drying oven to be dried in vacuum for 5-10 hours to obtain a brown product.
Furthermore, in the reaction process, the mixing ratio of the volume of the organic acid, the volume of the organic solvent, the mass of the ferric nitrate, the mass of the cobalt nitrate and the mass of the organic ligand is a: b: c: d: e, wherein a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 30, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 5, and e is more than or equal to 0 and less than or equal to 10.
Further, the organic solvent in the first step is any one selected from methanol, ethanol, and N-N dimethylformamide.
Further, the magnetic stirring speed in the first step is 500-1000 r/min.
Further, the organic ligand in the second step is selected from one of vinylimidazole, dimethylimidazole and terephthalic acid.
Further, the organic acid in the fourth step is selected from one of glacial acetic acid, citric acid and ethylenediamine tetraacetic acid.
Further, in the centrifugal collecting process in the sixth step, the centrifugal rotating speed is 6000 rpm/min-10000 rpm, and the centrifugal time is 1-10 minutes.
Further, the temperature of vacuum drying in the sixth step is 50-80 ℃, and the drying time is 5-10 hours.
In a preferred embodiment of the present invention, wherein the magnetic stirring speed in the first step is 500-1000 rpm.
The technical solution of the present invention is further described with reference to the following specific examples.
Example 1:
the preparation method of the iron-doped cobalt imidazolate nano material provided by the embodiment of the invention comprises the following steps of:
first, 0.066g of ferric nitrate and 0.218g of cobalt nitrate were dissolved in 15mL of an organic solvent and sufficiently stirred to form a first solution. 0.98g of organic ligand was dissolved in 15mL of organic solvent and stirred well to form solution two. Slowly pouring the solution I into the solution II to form a mixed solution, adding 100 mu L of organic acid, then rapidly magnetically stirring the mixed solution at room temperature for 15min, transferring the mixture into a stainless steel high-pressure reaction kettle, putting the high-pressure reaction kettle into a drying oven at 160 ℃, and keeping for 12h; and finally, cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a brown precipitate, ultrasonically dispersing the brown precipitate, washing the precipitate for a plurality of times by using absolute ethyl alcohol, centrifugally collecting the precipitate, and drying the precipitate in a vacuum drier for 6 hours to obtain a brown product. The yield of the product is 20%, and the content ratio of the iron to the cobalt is about 1:5, the purity is about more than 95 percent.
Example 2:
the preparation method of the iron-doped cobalt imidazolate nano material provided by the embodiment of the invention comprises the following steps of:
first, 0.06g of ferric nitrate and 0.174g of cobalt nitrate were dissolved in 15mL of an organic solvent and sufficiently stirred to form a first solution. 0.98g of organic ligand was dissolved in 15mL of organic solvent and stirred well to form solution two. Slowly pouring the solution I into the solution II to form a mixed solution, adding 100 mu L of organic acid, then rapidly magnetically stirring the mixed solution at room temperature for 15min, transferring the mixture into a stainless steel high-pressure reaction kettle, putting the high-pressure reaction kettle into a drying oven at 160 ℃, and keeping for 12h; and finally, cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a brown precipitate, ultrasonically dispersing the brown precipitate, washing the precipitate for a plurality of times by using absolute ethyl alcohol, centrifugally collecting the precipitate, and drying the precipitate in a vacuum drier for 6 hours to obtain a brown product. The yield of the product is 20%, and the content ratio of two metal elements of iron and cobalt is about 1:4, the purity is about more than 95 percent.
Example 3:
the preparation method of the iron-doped cobalt imidazolate nano material provided by the embodiment of the invention comprises the following steps of:
first, 0.06g of ferric nitrate and 0.131g of cobalt nitrate were dissolved in 15mL of an organic solvent and sufficiently stirred to form a first solution. 0.98g of organic ligand was dissolved in 15mL of organic solvent and stirred well to form solution two. Slowly pouring the solution I into the solution II to form a mixed solution, adding 100 mu L of organic acid, then quickly and magnetically stirring the mixed solution at room temperature for 15min, then transferring the mixture into a stainless steel high-pressure reaction kettle, putting the high-pressure reaction kettle into a drying oven at 160 ℃, and keeping for 12h; and finally, cooling the temperature of the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain brown precipitate, ultrasonically dispersing the brown precipitate, washing the brown precipitate for a plurality of times by using absolute ethyl alcohol, centrifugally collecting the brown precipitate, and drying the brown precipitate in a vacuum drying machine for 6 hours to obtain a brown product. The yield of the product is 20%, and the content ratio of the iron to the cobalt is about 1:3, the purity is about more than 95 percent.
Example 4: performance detection
Electrochemical testing of all samples was performed in 1.0M KOH at room temperature using an electrochemical workstation with a standard three-electrode system. The working electrode on the rotating disk electrode (GC) was made of AFC-MOFs catalyst. Adding 750 mu L of deionized water, 250 mu L of isopropanol and 40 mu L of Nafion117 solution into 5mg of sample catalyst and 5mg of carbon powder, adding a proper amount of zirconium beads, ball-milling for 24 hours on a ball mill, taking out, carrying out ultrasonic treatment in an ultrasonic machine for 30 minutes, dropping 10 mu L of the solution on a clean GC electrode, carrying out calibration with reference to a reference, and converting the solution into a Reversible Hydrogen Electrode (RHE) by a formula.
E RHE ＝E (Hg/HgO) +0.89
The three-electrode system was bubbled with high purity oxygen for 30 minutes prior to each OER test. To explore the OER activity, linear sweep voltammetry tests were performed at a rate of 5mV/s over a voltage range of 0V to-0.9V. Electrochemical Impedance Spectroscopy (EIS) measurements were obtained at a voltage of 0.61V and fitted by the Zview software. An Hg/HgO electrode in 1M aqueous KOH was used as a reference electrode.
As shown in FIG. 6, the iron-doped cobalt imidazolate catalysts obtained in examples 1-3 of the present invention. Linear Sweep Voltammetry (LSV) showed higher efficiency of AFC-MOFs than Fe-aMOF or Co-cMOF (FIG. 6 a). At 10mA cm -2 The lowest overpotential of the AFC-MOF (1 2 (270 mV) and Fe-aMOF (374 mV), co-cMOF (320 mV), AFC MOF (1). The OER kinetics were studied with the corresponding Tafle slope, with AFC-MOFs (1. The electrochemical impedance plot demonstrates that AFC-MOFs (1. By Cyclic Voltammetry (CV) at a scan rate of 20 to 100mV s -1 The electrochemical surface area (ECSA) was investigated and the results showed that when going from single metal MOF to double metal MOF (Fe-aMOF (3.32mF. Cm.) -2 )、Co-cMOF(5.02mF.cm -2 )、AFC-MOFs(1:5)(13.63mF.cm -2 )、AFC-MOFs(1:3)(15.63mF.cm -2 ) And AFC-MOFs (1) (30.37mf.cm -2 ) As Cdl value gradually increased, the AFC-MOFs (1). In addition to excellent electrocatalytic properties, the stability of the catalyst material is a very important measure of its overall suitability. The long-term durability of AFC-MOFs (1). At 10 mA-cm -2 The voltage remained close to 1.485v after 60h, indicating that it had good OER stability. The results show that the iron-doped cobalt imidazolate catalyst is an ideal electrochemical catalytic material.
Compared with the prior art, the iron-doped cobalt imidazolide catalyst is synthesized in one step by co-heating ferric nitrate, cobalt nitrate and dimethyl imidazole in an organic solvent. The results presented herein may provide a new strategy for designing composite MOF materials with different morphologies and new opportunities for developing new MOF water electrolysis electrocatalyst materials that are efficient and low cost.
The above summary and the detailed description are intended to demonstrate the practical application of the technical solutions provided by the present invention, and should not be construed as limiting the scope of the present invention. Various modifications, equivalent substitutions, or improvements may be made by those skilled in the art within the spirit and principles of the invention. The scope of the invention is to be determined by the appended claims.

Claims (7)

1. A preparation method of an iron-doped cobalt imidazolide nano catalytic material is characterized by comprising the following steps:
1) Dissolving a proper amount of cobalt nitrate, ferric nitrate, an organic ligand and an organic acid in an organic solvent, and stirring the mixture at 70 ℃ to obtain a mixed reaction solution;
2) Transferring the mixed reaction solution into a high-pressure reaction kettle, and preserving the temperature until the reaction is complete;
3) After the high-pressure reaction kettle is cooled to room temperature, carrying out centrifugal washing to obtain brown precipitate, and purifying the brown precipitate to obtain the iron-doped cobalt imidazolate nano material;
the step 1) further comprises the following steps:
a) Fully dissolving a proper amount of ferric nitrate and cobalt nitrate in an organic solvent at 70 ℃ to obtain a uniformly mixed solution I; in the step a), the mass ratio of ferric nitrate to cobalt nitrate is 1:2.5-6; and (2) taking the ratio of g: the ratio of ferric nitrate to organic solvent is 1:140-210;
b) Fully dissolving a proper amount of organic ligand in the organic solvent 1, and fully stirring to obtain a uniformly mixed solution II; the mass ratio of ferric nitrate to organic ligand in the step b) is 1:11-18; and (2) taking the ratio of g: and the ratio of the organic ligand to the organic solvent is 1:11 to 19;
c) Slowly injecting the solution I into the solution II, and fully stirring and reacting at 70 ℃ for 20-30 minutes to obtain a mixed solution;
d) Adding 50-100 mu L of organic acid solution into the mixed solution, and uniformly mixing to obtain a mixed reaction solution;
in the step 1), the organic ligand is selected from one of vinyl imidazole, dimethyl imidazole or terephthalic acid;
the organic solvent is selected from one of methanol, ethanol or N-N dimethylformamide;
the organic acid is selected from one of glacial acetic acid, citric acid and ethylenediamine tetraacetic acid.
2. The preparation method of claim 1, wherein in the step 2), the high-pressure reaction kettle is transferred to a heat preservation device and is kept at the temperature of 100-180 ℃ for 10-20 hours.
3. The method of claim 1, wherein the purification in step 3) is achieved by a method comprising the steps of:
and (3) performing ultrasonic dispersion treatment on the brown precipitate, washing the brown precipitate for a plurality of times by using absolute ethyl alcohol, collecting the precipitate by centrifuging after washing, and finally performing vacuum drying in a vacuum drying oven for 5-10 hours.
4. An iron-doped cobalt imidazolate nanomaterial prepared according to the method of any one of claims 1 to 3.
5. The iron-doped cobalt imidazolate nanomaterial of claim 4 wherein the iron-doped cobalt imidazolate nanomaterial is hollow rod-shaped.
6. Use of the iron-doped cobalt imidazolate nanomaterial according to claim 4 or 5 in the preparation of catalysts, electrodes or batteries.
7. The use according to claim 6, wherein the catalyst is used for catalyzing the electrochemical decomposition of water to produce hydrogen.
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