CN113013426B - Niobium monoatomic catalyst, preparation method and application thereof - Google Patents

Niobium monoatomic catalyst, preparation method and application thereof Download PDF

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CN113013426B
CN113013426B CN202110203235.0A CN202110203235A CN113013426B CN 113013426 B CN113013426 B CN 113013426B CN 202110203235 A CN202110203235 A CN 202110203235A CN 113013426 B CN113013426 B CN 113013426B
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CN113013426A (en
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袁涛
郑时有
蒋必志
杨俊和
庞越鹏
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University of Shanghai for Science and Technology
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    • H01M4/90—Selection of catalytic material
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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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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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Abstract

The invention provides a preparation method of a niobium monoatomic catalyst, which comprises the following steps: adding zeolite imidazole framework material ZIF-8 powder into an organic solution, and stirring for a first predetermined time to fully disperse the zeolite imidazole framework material ZIF-8 powder to obtain a solution I; adding a niobium compound into the solution I, and continuously stirring for a second preset time to obtain a solution II; adding a surfactant into the solution II, continuously stirring for a third preset time, and then centrifugally drying to obtain a white solid powdery precursor material; and (2) placing the precursor material in an inert atmosphere or a reducing atmosphere for high-temperature annealing treatment to obtain the niobium monatomic catalyst, wherein the mass ratio of the niobium compound to the ZIF-8 powder is 0.005-0.05: 1, the mass ratio of the ZIF-8 powder to the surfactant is 1: 0.5-3, in the step 4, the temperature range of the annealing treatment is 800-1200 ℃, and the heat preservation time is 1-24 hours. The invention also provides a niobium monoatomic catalyst prepared by the preparation method and application of the niobium monoatomic catalyst in a catalytic battery cathode.

Description

Niobium monoatomic catalyst, preparation method and application thereof
Technical Field
The invention belongs to the field of materials science, and particularly relates to a niobium monoatomic catalyst, and a preparation method and application thereof.
Background
With the energy crisis and the global warming becoming more severe, the development of clean, sustainable new energy conversion and storage devices has become very urgent. Among these advanced energy technologies, fuel cells are considered to be a promising energy conversion technology with advantages of low emission, high conversion efficiency, and convenience in operation; metal-air batteries are one of the most ideal energy storage technologies due to their high energy density, low cost, and long life. However, the slow kinetics of oxygen reduction or oxygen evolution reactions at these energy technology cathodes has become a critical limiting step. Therefore, the development of efficient and durable electrocatalysts is one of the major research directions in electrochemical energy technology. Currently, platinum-based catalysts are consistently considered the most advanced catalyst materials due to their higher current density and lower overpotential. However, the platinum-based catalyst has poor durability and high cost, which hinders the application of new renewable energy conversion and energy storage devices. For this reason, efforts have been made to design and synthesize inexpensive, durable, highly active non-noble metal catalysts.
Among the non-noble metal catalysts currently under study, the monatomic type catalysts exhibit extraordinary catalytic performance due to their size, structural effect, and strong metal-support interactions. In this novel monatomic catalyst, a metal monatomic is coordinated to N or C to become a catalytic active center. Although many types of monatomic catalysts have been reported, achieving both good activity and stability remains a major problem. The presence of a monatomic catalyst, such as the most common Fe/Co-based catalysts, results in dissolution of the active metal sites due to H2O2 attack, resulting in poor stability under high pressure conditions. Therefore, further research on the transition metal in the symmetric coordination M-N-C system has important significance for improving the efficiency and durability of electrocatalysis.
According to the Sabatier principle, the catalytic center should have a suitable binding energy with oxygen and reaction intermediates, neither too strong nor too weak. Niobium thus belongs to the fifth subgroup 4d transition metals of the periodic table of the elements, whose electronic structure has various coordination numbers from +1 to + 5. And the tunability of the metallic d-band center of niobium in the vicinity of the electron-withdrawing carbon is a prerequisite for obtaining catalytic activity and stability. However, the synthesis of niobium as a monatomic catalyst and its catalytic activity have been rarely reported.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a niobium monoatomic catalyst, a method for producing the same, and an application thereof.
The invention provides a preparation method of a niobium monatomic catalyst, which is characterized by comprising the following steps: step 1, adding zeolite imidazole framework material ZIF-8 powder into an organic solution, and stirring for a first predetermined time to fully disperse the zeolite imidazole framework material ZIF-8 powder to obtain a solution I; step 2, adding a niobium compound into the solution I, and continuously stirring for second preset time to obtain a solution II; step 3, adding a surfactant into the solution II, continuously stirring for a third preset time, and then centrifugally drying to obtain a white solid powdery precursor material; and 4, placing the precursor material in an inert atmosphere or a reducing atmosphere for high-temperature annealing treatment to obtain the niobium monatomic catalyst, wherein the mass ratio of the niobium compound to the ZIF-8 powder is 0.005-0.05: 1, the mass ratio of the ZIF-8 powder to the surfactant is 1: 0.5-3, the annealing treatment temperature range in the step 4 is 800-1200 ℃, and the heat preservation time is 1-24 h.
In the preparation method of the niobium monatomic catalyst provided by the invention, the niobium monatomic catalyst can also have the following characteristics: wherein the organic solution in the step 1 is one of methanol, ethanol, N-N dimethylformamide DMF and N-N dimethylacetamide DEF, and the first predetermined time is 1-10 hours.
In the preparation method of the niobium monatomic catalyst provided by the invention, the niobium monatomic catalyst can also have the following characteristics: wherein the niobium compound in the step 2 is one of niobium pentachloride, niobium pentafluoride and niobium ethoxide, and the second preset time is 1-10 hours.
In the preparation method of the niobium monatomic catalyst provided by the invention, the niobium monatomic catalyst can also have the following characteristics: the surfactant in the step 3 is one or a combination of pluronic F127, Sodium Dodecyl Sulfate (SDS), bromohexadecyl trimethylamine (CTAB) and polyvinylpyrrolidone (PVP), and the third preset time is 1-10 h.
In the preparation method of the niobium monatomic catalyst provided by the invention, the niobium monatomic catalyst can also have the following characteristics: the inert atmosphere or the reducing atmosphere in the step 4 is one of argon, nitrogen, helium, a first mixed gas of argon and hydrogen and a second mixed gas of nitrogen and hydrogen, and the volume percentage content of hydrogen in the first mixed gas and the second mixed gas is 10-40%.
The invention also provides a niobium monoatomic catalyst prepared by the preparation method of the niobium monoatomic catalyst.
The invention also provides an application of the niobium monoatomic catalyst in a catalytic battery cathode.
Action and Effect of the invention
According to the preparation method of the niobium monoatomic catalyst, the composite material with the transition metal niobium monoatomic dispersed on the surface of the metal organic framework material is prepared for the first time by adopting a surfactant-assisted dispersion method and is used for oxygen reduction and oxygen precipitation of the niobium monoatomic catalyst. In alkaline solution, the niobium monatomic catalyst material shows good surface morphology and catalytic activity, and the electrocatalytic activity of the niobium monatomic catalyst material greatly exceeds that of a commercial platinum-carbon catalyst.
Further, the preparation method realizes uniform dispersion of Nb monoatomic atoms by liquid phase diffusion and surfactant polar group-assisted dispersion, and forms coordination with nitrogen and carbon atoms on the surface of ZIF-8, thereby showing excellent oxygen reduction and oxygen precipitation catalytic activity and electrochemical stability of the catalyst. In addition, the preparation method is simple, green and efficient, no too severe experimental conditions are adopted in the process of synthesizing the niobium monoatomic catalyst, no too expensive chemical material is used, the efficient utilization of the niobium monoatomic catalyst is realized, and the concept of green chemistry is met. In addition, the prepared niobium monatomic catalyst has good controllability and is suitable for large-scale industrial production.
Drawings
FIG. 1 is an electron micrograph of a niobium monoatomic catalyst synthesized in example 1 of the present invention; wherein, a is a scanning electron microscope picture; b is a transmission electron microscope photograph;
FIG. 2 is an X-ray diffraction spectrum of a niobium monatomic catalyst material synthesized in example 1 of the invention;
FIG. 3 is an oxygen reduction CV curve of the niobium monatomic catalyst material synthesized in example 1 of the present invention;
FIG. 4 is an oxygen reduction LSV test curve for the niobium monatomic catalyst material synthesized in example 1 of the present invention;
FIG. 5 is an oxygen evolution LSV test curve for the testing of niobium monatomic catalyst material synthesized in example 2 of the present invention;
FIG. 6 is a laser Raman spectroscopy test curve of the niobium monatomic catalyst material synthesized in example 3 of the present invention;
fig. 7 is an oxygen evolution LSV test curve for the testing of niobium monatomic catalyst material synthesized in example 3 of the present invention.
Detailed Description
In order to make the technical means and functions of the present invention easily understood, the present invention will be specifically described below with reference to the embodiments and the accompanying drawings.
The invention provides a preparation method of a niobium monoatomic catalyst, which comprises the following steps:
step 1, adding zeolite imidazole framework material ZIF-8 powder into an organic solution, and stirring for 1-10 hours to fully disperse the zeolite imidazole framework material ZIF-8 powder to obtain a solution I.
In the invention, the organic solution is one of methanol, ethanol, N-N dimethylformamide DMF and N-N dimethylacetamide DEF.
And 2, adding a niobium compound into the solution I, and continuously stirring for 1-10 h to obtain a solution II.
And 3, adding a surfactant into the solution II, continuously stirring for 1-10 h, and then centrifugally drying to obtain a white solid powdery precursor material.
In the invention, the surfactant is one or a combination of more of pluronic F127, Sodium Dodecyl Sulfate (SDS), bromohexadecyl trimethylamine (CTAB) and polyvinylpyrrolidone (PVP), and the mass ratio of the ZIF-8 powder to the surfactant is 1: 0.5-3.
And 4, placing the precursor material in an inert atmosphere or a reducing atmosphere for high-temperature annealing treatment to obtain the niobium monatomic catalyst.
In the invention, the inert atmosphere or the reducing atmosphere is one of argon, nitrogen, helium, a first mixed gas of argon and hydrogen and a second mixed gas of nitrogen and hydrogen, and the volume percentage content of the hydrogen in the first mixed gas and the second mixed gas is 10-40%.
In the invention, the temperature range of annealing treatment is 800-1200 ℃, and the heat preservation time is 1-24 h.
The invention also provides a niobium monoatomic catalyst prepared by the preparation method of the niobium monoatomic catalyst.
The invention also provides an application of the niobium monoatomic catalyst in a catalytic battery cathode.
The organic solution, the surfactant, and the inert atmosphere or the reducing atmosphere listed above are not all exemplified in the following examples, and the organic solution, the surfactant, and the inert atmosphere or the reducing atmosphere not shown in the examples can achieve the same technical effects as the organic solution, the surfactant, and the inert atmosphere or the reducing atmosphere listed in the examples.
< example 1>
The synthesis, the structural characterization and the electrochemical catalytic performance test of the Nb-N-C @ F127 monoatomic catalyst material.
200mg of prepared ZIF-8 was dissolved in 20ml of a methanol solution, ultrasonically dispersed for 30 minutes, and then 4mg of niobium pentachloride-containing yellow powder taken out of the glove box was dissolved in 3ml of a methanol solution, followed by pouring into the above-mentioned methanol solution containing ZIF-8. The mixed solution is placed on a stirring table for stirring. After stirring for 10 hours, 100mg of the surfactant F127, which was sufficiently ground, was further added to the mixed and stirred solution. And then stirring the mixed solution added with the F127 for 3 hours to obtain the niobium pentachloride doped metal frame composite material with the surface uniformly coated with the surfactant. And centrifugally drying the composite material, placing the dried composite material in a tubular furnace in Ar atmosphere, heating the temperature to 800 ℃ from room temperature at a speed of 5 ℃/min, preserving the temperature for 1h, and naturally cooling to obtain the surface carbon-coated niobium monoatomic dispersion metal-air battery cathode catalyst.
Fig. 1 is an electron micrograph of a niobium monoatomic catalyst synthesized in example 1 of the present invention, in which fig. 1(a) is a scanning electron micrograph and fig. 1(b) is a transmission electron micrograph.
The scanning electron micrograph of the calcined surfactant-coated niobium monatomic catalyst is shown in fig. 1(a), and it can be seen from fig. 1(a) that the niobium monatomic catalyst has a very uniform morphology and is a regular dodecahedron. Fig. 1(b) is a transmission electron micrograph of the calcined surfactant-coated niobium monatomic catalyst, and it can be seen from fig. 1(b) that the niobium monatomic catalyst particles are intact, are in the shape of a regular hexagon under a transmission electron microscope, correspond to the spatial structure of a regular dodecahedron, and have a particle size of about 250 nm. And it can be seen that the surface is coated with a layer of carbon material, which is the surfactant F127.
Fig. 2 is an X-ray diffraction spectrum of the niobium monatomic catalyst material synthesized in example 1 of the present invention, and the crystalline phases of niobium and carbon were analyzed by X-ray diffraction (XRD).
As shown in fig. 2, the sample exhibited two broad carbon peaks, indicating that the catalyst precursor had fully carbonized after pyrolysis. Similar to other reported monatomic catalysts, no diffraction peak associated with the crystalline niobium species was found in the XRD pattern.
Fig. 3 is an oxygen reduction CV curve of the niobium monatomic catalyst material synthesized in example 1 of the present invention, fig. 4 is an oxygen reduction LSV test curve of the niobium monatomic catalyst material synthesized in example 1 of the present invention, the abscissa in fig. 3 represents the potential converted to the standard hydrogen electrode, the ordinate represents the current, the abscissa in fig. 4 represents the potential converted to the standard hydrogen electrode, and the ordinate represents the current density.
After grinding the prepared catalyst, 5mg of the catalyst is weighed and dissolved in 950 mu l of absolute ethyl alcohol to form a mixed solution, and then 50 mu l of Nafion solution is added into the mixed solution to prepare the ink containing solution. Then the ink solution is subjected to ultrasonic treatment for 30min to prepare a 5mg/ml catalyst ink solution. And dropwise adding 5 mu l of catalyst ink solution on a rotating disc ring electrode for four times, and after the solution is naturally dried on the electrode, installing the electrode on a catalyst test system to perform Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV) tests. The results of the test in 0.1M KOH solution are shown in FIG. 3, and the oxygen reduction peak potential of Nb-N-C @ F127 is 0.883V (vs. Reversible Hydrogen Electrode (RHE)). As shown in FIG. 4, Nb-N-C @ F127 has an oxygen reduction peak potential of 0.854V (vs. RHE) which exceeds commercial 20% Pt/C (E.R) 1/2 0.838V (vs. rhe)) catalyst, exhibiting excellent electrocatalytic activity.
< example 2>
The synthesis of a niobium monoatomic catalyst (Nb-N-C @ SDS) material and the electrochemical catalytic performance test thereof.
200mg of prepared ZIF-8 was dissolved in 20ml of ethanol solution, ultrasonically dispersed for 30 minutes, and then 4mg of niobium pentachloride powder taken out of the glove box was dissolved in 5ml of ethanol solution, followed by pouring into the above ZIF-8 ethanol solution. The mixed solution is placed on a stirring table for stirring. After stirring for 10 hours, 200mg of SDS, which was sufficiently ground, was further added to the mixed and stirred solution. And then stirring the mixed solution added with the SDS for 3 hours to ensure that the ZIF-8 with the surface adsorbed with the niobium pentachloride is uniformly coated by the SDS, thus obtaining the niobium pentachloride doped metal framework composite material with the surface uniformly coated with the surfactant. And then centrifugally drying the composite material, placing the dried composite material in a tubular furnace in Ar atmosphere, heating to 900 ℃ at the speed of 5 ℃/min, preserving the temperature for 2h, and naturally cooling to obtain the carbon material with the surface coated with carbon and niobium monoatomic dispersion, wherein the carbon material is used as a fuel cell cathode catalyst.
Fig. 5 is an oxygen evolution LSV test curve of the niobium monatomic catalyst material test synthesized in example 2 of the present invention, wherein the abscissa represents the potential converted to a standard hydrogen electrode and the ordinate represents the current density.
The fired Nb-N-C @ SDS monatomic catalyst an ink solution was prepared as in example 1, and the same amount was dropped onto a rotating disk electrode to conduct an LSV test. The results of the test in 1M KOH solution are shown in FIG. 5, when the current density is 10mA cm -2 The overpotential of Nb-N-C @ SDS is 1.530V (vs. RHE), which is superior to that of commercial IrO 2 1.533V (vs. rhe) of the catalyst, exhibiting excellent oxygen evolution catalytic performance.
< example 3>
The method comprises the following steps of synthesis, structural characterization and electrochemical catalytic performance test of a niobium monatomic catalyst (Nb-N-C @ PVP) material.
200mg of prepared ZIF-8 was dissolved in 20ml of DEF solution, ultrasonically dispersed for 30 minutes, and then 10mg of niobium ethoxide powder taken out of the glove box was dissolved in 3ml of DEF solution, followed by pouring into the above-mentioned DEF solution of ZIF-8. The mixed solution is placed on a stirring table for stirring. After stirring for 10 hours, 600mg of fully ground PVP was added to the mixed and stirred solution. Then will addAdding the mixed solution of PVP and stirring for 10 hours to ensure that the ZIF-8 with the niobium ethoxide adsorbed on the surface is uniformly coated by the PVP, thus obtaining the niobium ethoxide doped metal framework composite material with the surface uniformly coated with the surfactant. Then the composite material is placed in H with the volume ratio of 1:9 after being centrifugally dried 2 And (3) heating to 1200 ℃ at the temperature of 5 ℃/min in a tubular furnace with/Ar mixed atmosphere, preserving the temperature for 12h, and naturally cooling to obtain the carbon material with the surface coated with carbon and niobium monoatomic dispersion, which is used as a fuel cell cathode catalyst.
Fig. 6 is a laser raman spectrum test curve of the niobium monatomic catalyst material synthesized in example 3 of the present invention, wherein the abscissa represents the spectral range of raman and the ordinate represents the spectral intensity.
The calcined Nb-N-C @ PVP monatomic catalyst was subjected to laser Raman spectroscopy, as shown in FIG. 6, catalyst I D /I G 1.61, it can be seen that after high temperature annealing at 1200 ℃, the catalyst has been carbonized completely, the degree of carbon disordering is also very high, and a large number of electrocatalytic active sites can be provided.
Fig. 7 is an oxygen evolution LSV test curve of the niobium monatomic catalyst material test synthesized in example 3 of the present invention, wherein the abscissa represents the potential converted to a standard hydrogen electrode and the ordinate represents the current density.
The fired Nb-N-C @ PVP monatomic catalyst was used to prepare an ink solution according to the method of example 1, and the same amount was dropped onto a rotating disk electrode for oxygen evolution LSV testing. The results of the test in 1M KOH solution are shown in FIG. 7 when the current density is 10mA cm -2 The overpotential of Nb-N-C @ PVP is 1.530V (vs. RHE), which is superior to that of commercial IrO 2 1.533V (vs. rhe) of the catalyst, exhibiting excellent oxygen evolution catalytic activity.
Effects and effects of the embodiments
As can be seen from examples 1 to 3, the composite material in which the transition metal niobium is monoatomic-dispersed on the surface of the metal organic framework material is prepared for the first time by the surfactant-assisted dispersion method in the preparation method of the niobium monoatomic catalyst according to the above examples, and is used for the oxygen reduction and oxygen precipitation catalyst. In alkaline solution, the niobium monoatomic catalyst material shows good surface appearance and catalytic activity, and the electrocatalytic activity of the niobium monoatomic catalyst material greatly exceeds that of a commercial platinum-carbon catalyst.
Further, according to the preparation method, uniform dispersion of Nb monoatomic atoms is realized through liquid phase diffusion and surfactant polar group auxiliary dispersion methods, coordination is formed between the Nb monoatomic atoms and nitrogen and carbon atoms on the surface of ZIF-8, and excellent oxygen reduction and oxygen precipitation catalytic activity and electrochemical stability of the catalyst are further shown. In addition, the preparation method is simple, green and efficient, too harsh experimental conditions are not used in the process of synthesizing the niobium monatomic catalyst, too expensive chemical materials are not used, the efficient utilization of the niobium monatomic is realized, and the green chemical concept is met. In addition, the prepared niobium monatomic catalyst has good controllability and is suitable for large-scale industrial production.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.

Claims (7)

1. The preparation method of the niobium monatomic catalyst is characterized by comprising the following steps of:
step 1, adding zeolite imidazole framework material ZIF-8 powder into an organic solution, and stirring for a first predetermined time to fully disperse the organic solution to obtain a solution I;
step 2, adding a niobium compound into the solution I, and continuously stirring for a second preset time to obtain a solution II;
step 3, adding a surfactant into the solution II, continuously stirring for a third preset time, and then centrifugally drying to obtain a white solid powdery precursor material;
step 4, placing the precursor material in an inert atmosphere or a reducing atmosphere for high-temperature annealing treatment to obtain a niobium monoatomic catalyst,
wherein the mass ratio of the niobium compound to the ZIF-8 powder is 0.005-0.05: 1,
the mass ratio of the ZIF-8 powder to the surfactant is 1: 0.5-3,
in the step 4, the temperature range of the annealing treatment is 800-1200 ℃, the heat preservation time is 1-24 h,
in the niobium monoatomic catalyst, niobium atoms are uniformly dispersed in a monoatomic form, and the niobium atoms as active center atoms coordinate with carbon elements and nitrogen elements on the surface of the zeolitic imidazolate framework material ZIF-8.
2. The method for preparing a niobium monatomic catalyst according to claim 1, wherein:
wherein the organic solution in the step 1 is one of methanol, ethanol, N-N dimethylformamide DMF and N-N dimethylacetamide DEF,
the first preset time is 1-10 h.
3. The method for preparing a niobium monoatomic catalyst according to claim 1, wherein:
wherein the niobium compound in the step 2 is one of niobium pentachloride, niobium pentafluoride and niobium ethoxide,
the second preset time is 1-10 h.
4. The method for preparing a niobium monatomic catalyst according to claim 1, wherein:
wherein, in the step 3, the surfactant is one or a combination of pluronic F127, sodium dodecyl sulfate SDS, bromohexadecyl trimethylamine CTAB and polyvinylpyrrolidone PVP,
the third preset time is 1-10 h.
5. The method for preparing a niobium monatomic catalyst according to claim 1, wherein:
wherein the inert atmosphere or the reducing atmosphere in the step 4 is one of argon, nitrogen, helium, a first mixed gas of argon and hydrogen, and a second mixed gas of nitrogen and hydrogen,
the volume percentage content of hydrogen in the first mixed gas and the second mixed gas is 10-40%.
6. A niobium monoatomic catalyst produced by the method for producing a niobium monoatomic catalyst according to claim 1 to 5.
7. Use of the niobium monoatomic catalyst according to claim 6 in a cathode of a catalytic cell.
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