CN113903929A - Porous carbon coated Fe-doped CoP particle/carbon nanotube oxygen evolution electrocatalytic composite material and preparation method and application thereof - Google Patents
Porous carbon coated Fe-doped CoP particle/carbon nanotube oxygen evolution electrocatalytic composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a porous carbon coated Fe doped CoP particle/carbon nano tube oxygen evolution electrocatalytic composite material and a preparation method and application thereof, belonging to the field of electrocatalytic oxygen evolution. The preparation steps of the composite material are as follows: a. uniformly growing a ZnCo bimetallic zeolite imidazole framework compound on the surface of the carboxylated carbon nanotube by adopting a liquid phase method to serve as a precursor; b. loading a Prussian blue crystal containing Fe on the surface of a precursor by an ion exchange method to form a ZIFs @ PBA/CNTs composite precursor; c. carrying out high-temperature annealing treatment in an inert atmosphere to generate a porous carbon-coated Fe-doped metal Co particle/carbon nanotube composite; d. and finally, pre-oxidizing the compound, and performing heat treatment reaction in a quartz tube furnace by using sodium hypophosphite crystals as a phosphorus source to obtain the porous carbon coated Fe doped CoP particles/carbon nano tube oxygen evolution electrocatalytic composite material. The composite material has good conductivity and electrocatalytic stability.
Description
Technical Field
The invention belongs to the field of electrocatalytic oxygen evolution, and particularly relates to a porous carbon-coated Fe-doped CoP particle/carbon nano tube oxygen evolution electrocatalytic composite material and a preparation method thereof.
Background
Oxygen Evolution Reactions (OERs) have received extensive attention from researchers over the past decades due to their key role in sustainable energy technologies such as carbon dioxide abatement, water splitting, metal-air batteries, etc. However, the complex multiple electron/proton conversion step (2H) experienced by electrocatalytic OER2O→O2 + 4H+ + 4e–) Resulting in slow kinetics and requiring higher overpotentials; while having a noble metal group (IrO) with excellent OER catalytic performance2Or RuO2) The expensive price and instability of the material severely hamper its large-scale practical application. Therefore, it is urgent to develop a high-activity oxygen evolution electrocatalyst by preparing a non-noble metal-based material with low price.
Cobalt phosphide (CoP) has high theoretical activity and low cost, and thus has become a hot research point in the energy field in recent years. However, the OER activity of bulk phase CoP is not high and not stable enough in alkaline electrolytes and high overpotentials, mainly due to: (1) active sites of the block structure are concentrated at the edge of the block structure, so that the block structure is easy to stack, and exposed active sites are too few; (2) the conductivity of the material is poor; (3) the corrosion resistance is poor and the corrosion resistance is unstable in alkaline medium.
Disclosure of Invention
The invention aims to provide a porous carbon coated Fe-doped CoP particle/carbon nanotube composite material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme.
The invention provides a preparation method of a porous carbon coated Fe-doped CoP particle/carbon nanotube composite material, which specifically comprises the following steps:
(1) 12 mL of a solution containing 0.366 g of Zn (NO)3)2·6H2O (nitre hexahydrateZinc salt) and Co (NO)3)2·6H2Pouring the methanol solution of O (cobalt nitrate hexahydrate) mixed metal salt into 20 mL of methanol solution containing 0.811 g of 2-methylimidazole, stirring for 10 s, adding 8 mL of methanol/water mixed solution (methanol volume/water volume =4: 1) containing PVP (polyvinylpyrrolidone) and carboxylated carbon nanotubes, continuously stirring for 3 h, centrifugally cleaning the obtained precipitate with methanol, and drying to obtain zeolite imidazole framework compound/carbon nanotubes (namely ZIFs/CNTs) powder;
(2) weighing 40 mg of ZIFs/CNTs powder, stirring and dispersing in 36 mL of ethanol, and dropwise adding 4 mL of K3[Fe(CN)6]Stirring the (potassium ferricyanide) water solution for 2 hours, centrifugally cleaning and drying the obtained precipitate by using water and ethanol to obtain zeolite imidazole framework compound @ Prussian blue/carbon nano tube (namely ZIFs @ PBA/CNTs) powder;
(3) weighing 120 mg of ZIFs @ PBA/CNTs powder, placing the powder in a tube furnace, keeping a high-purity Ar (argon) atmosphere, setting a temperature program and carrying out high-temperature heat treatment to obtain porous carbon-coated Fe-doped Co particle/carbon nanotube (Fe-Co @ PNC/CNTs) powder;
(4) weighing 50 mg of Fe-Co @ PNC/CNTs powder, pre-oxidizing in a muffle furnace, and mixing with 300 mg of NaH2PO2·H2O (sodium hypophosphite) crystal powder is respectively placed in two separated positions in a tube furnace, wherein NaH is used2PO2·H2And (3) keeping the O crystal powder at the upstream, keeping a high-purity Ar atmosphere, and performing high-temperature phosphating treatment by setting a temperature program to obtain the black porous carbon coated Fe-doped CoP particle/carbon nano tube composite material (namely Fe-CoP @ PNC/CNTs).
Preferably, the composition contains 0.366 g Zn (NO)3)2·6H2O and Co (NO)3)2·6H2The metal salt mass ratio of the methanol solution of O mixed metal salt is Zn (NO)3)2·6H2O：Co(NO3)2·6H2O =3:7 to 7: 3. More preferably, the metal salt mass ratio is Zn (NO)3)2·6H2O：Co(NO3)2·6H2O=5:5。
Preferably, the mass of PVP in the methanol/water mixed solution containing PVP and the carboxylated carbon nano tube is 100-300 mg, and the mass of the carboxylated carbon nano tube is 10-30 mg.
Preferably, said K3[Fe(CN)6]The concentration of the aqueous solution is 2.5-7.5 mg/mL–1。
Preferably, in the step (3), the parameters of the high-temperature heat treatment performed by the set temperature program are as follows: at 5 ℃ min–1The temperature rising rate is increased from room temperature to 650-950 ℃, then the temperature is kept for 1-3 h, and finally the natural cooling is carried out;
preferably, in the step (4), the parameters of the pre-oxidation treatment are as follows: at 5 ℃ min–1The temperature rising rate is increased from room temperature to 250-350 ℃, then the temperature is kept for 5-30 min, and finally the natural cooling is carried out.
Preferably, in the step (4), the parameters of the high-temperature phosphating treatment performed by the set temperature program are as follows: at 2 ℃ min–1The temperature rising rate is increased from room temperature to 300-400 ℃, then the temperature is kept for 1-3 h, and finally the natural cooling is carried out.
The porous carbon-coated Fe-doped CoP particle/carbon nanotube composite material provided by the invention is prepared by adopting the method. The porous carbon coated Fe-doped CoP particle/carbon nanotube composite material can be used as an electrocatalyst for the electrolysis water oxygen evolution reaction.
The heterogeneous atom doping can regulate and control the electronic structure of the semiconductor and enhance the capability of the reaction sites of the semiconductor to adsorb active substances; the porous carbon coating can improve the conductivity and protect the inner layer structure, and is also beneficial to enhancing the mass transfer dynamics of reactants and products on the surface of the material; and complexing with carbon nanotubes can further increase the exposure of active sites of the semiconductor material. The three components are compounded with CoP, the CoP particles are doped with Fe element and coated by porous carbon, so that the Fe element and the CoP particles uniformly grow on the surface of the carbon nano tube, the active sites of the carbon nano tube can be obviously enhanced and exposed, and the CoP and the composite carbon material are tightly combined, thereby comprehensively improving the oxygen evolution electrocatalytic activity and stability of the catalyst.
Compared with the prior art, the invention has the following advantages:
hair brushThe preparation method is simple, strong in repeatability, and cheap and easily available in raw materials; the prepared porous carbon-coated Fe-doped CoP particle/carbon nanotube composite material has good conductivity, the unique porous carbon-coated structure provides enhanced attachment sites for mass transfer of electrolytic base liquid/products, and the carbon nanotubes providing supporting load obviously expose a large amount of catalytic active sites; the novel composite material shows high-efficiency activity when applied to electrolytic water oxygen evolution reaction, and particularly generates 10 mA cm–2Very low overpotential (226 mV) and very small Tafel slope (48.4 mV dec)–1) (ii) a The composite material still keeps stable activity and structure after continuous catalytic oxygen generation for 20 hours. The invention provides a new idea for developing a non-noble metal-based catalyst with high performance and low cost.
Drawings
Fig. 1 is an XRD pattern of the porous carbon coated Fe doped CoP particle/carbon nanotube composite of example 1.
FIG. 2 is an EDX-Mapping plot of the porous carbon coated Fe-doped CoP particle/carbon nanotube composite of example 1.
Fig. 3 is an SEM image of the porous carbon coated Fe doped CoP particle/carbon nanotube composite of example 1.
Fig. 4 is a TEM image of the porous carbon coated Fe doped CoP particle/carbon nanotube composite of example 1.
Fig. 5 is a linear sweep voltammetry polarization curve of the porous carbon coated Fe doped CoP particle/carbon nanotube composite of example 2 as an electrocatalyst in 1M KOH.
Fig. 6 is a tafel slope curve fitted from a polarization curve for the porous carbon coated Fe doped CoP particle/carbon nanotube composite of example 2 as an electrocatalyst.
FIG. 7 shows that the porous carbon coated Fe-doped CoP particle/carbon nanotube composite material of example 2 is used as an electrocatalyst at a constant current of 10 mA cm–2The chronopotentiometric curve was tested for 20 h at current density.
Fig. 8 is an SEM image of the porous carbon coated Fe doped CoP particle/carbon nanotube composite of example 2 after 20 h chronopotentiometric stability test as electrocatalyst.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and thus the present invention is not limited to the specific embodiments disclosed below.
The preparation method of the porous carbon coated Fe-doped CoP particle/carbon nanotube composite material comprises the following steps:
a. uniformly growing ZnCo bimetallic zeolite imidazole framework compounds (ZIFs/CNTs) on the surface of the carboxylated carbon nanotube by adopting a liquid phase method to serve as precursors;
b. loading a Prussian blue crystal containing Fe on the surface of a precursor by an ion exchange method to form a ZIFs @ PBA/CNTs composite precursor;
c. carrying out high-temperature annealing treatment in an inert atmosphere to generate a porous carbon-coated Fe-doped metal Co particle/carbon nanotube composite (Fe-Co @ PNC/CNTs);
d. and finally, pre-oxidizing the compound, and performing heat treatment reaction in a quartz tube furnace by using sodium hypophosphite crystals as a phosphorus source to obtain the porous carbon coated Fe doped CoP particles/carbon nano tube oxygen evolution electrocatalytic composite material (Fe-CoP @ PNC/CNTs).
The crystal structure of the product prepared by the invention is measured by an X-ray diffractometer (XRD), the appearance of the material is measured by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), the element composition is measured by energy dispersive X-ray spectrometer imaging (EDX-mapping), and the catalytic activity of electrolysis water for oxygen evolution is measured on Shanghai Chenghua electrochemical workstation.
Example 1
The preparation process and steps in this example are as follows:
(1) 12 mL of a solution containing 0.366 g of Zn (NO)3)2·6H2O and Co (NO)3)2·6H2Pouring 20 mL of mixed metal salt methanol solution with the O mass ratio of 5:5 into the reactor, wherein the mixed metal salt methanol solution contains 0Adding 811 g of 2-methylimidazole in methanol solution, stirring for 10 s, adding 8 mL of methanol/water mixed solution (methanol volume/water volume =4: 1) containing 200 mg of PVP and 20 mg of carboxylated carbon nanotubes, continuously stirring for 3 h, centrifugally cleaning the obtained precipitate with methanol, and drying to obtain zeolite imidazole framework compound/carbon nanotube (ZIFs/CNTs) powder;
(2) weighing 40 mg ZIFs/CNTs powder, stirring and dispersing in 36 mL ethanol, and dropwise adding 4 mL of 5 mg/mL–1K of3[Fe(CN)6]Stirring the aqueous solution for 2 hours, centrifugally cleaning and drying the obtained precipitate by using water and ethanol to obtain zeolite imidazole framework compound @ Prussian blue/carbon nano tube (namely ZIFs @ PBA/CNTs) powder;
(3) weighing 120 mg of ZIFs @ PBA/CNTs powder, placing the powder in a tube furnace, keeping a high-purity Ar atmosphere, setting a temperature program to carry out high-temperature heat treatment, wherein the parameters are as follows: at 5 ℃ min–1The temperature rise rate is increased from room temperature to 800 ℃, then the temperature is kept for 3 h, and finally the porous carbon-coated Fe-doped Co particles/carbon nano tubes (namely Fe-Co @ PNC/CNTs) powder is obtained after natural cooling;
(4) weighing 50 mg of Fe-Co @ PNC/CNTs powder, and performing pre-oxidation treatment in a muffle furnace, wherein the parameters are as follows: at 5 ℃ min–1The temperature rising rate is increased from room temperature to 350 ℃, then the temperature is kept for 10 min, and finally the natural cooling is carried out; and then 300 mg NaH2PO2·H2O crystal powder is respectively placed in two separated positions in a tube furnace, wherein NaH2PO2·H2Keeping the O crystal powder at the upstream, keeping the high-purity Ar atmosphere, setting a temperature program to perform high-temperature phosphating treatment, wherein the parameters are as follows: at 2 ℃ min–1The temperature rise rate is increased from room temperature to 350 ℃, then the temperature is kept for 2h, and finally the composite material is naturally cooled to obtain the black porous carbon coated Fe doped CoP particles/carbon nano tubes (namely Fe-CoP @ PNC/CNTs).
The X-ray powder diffraction (XRD) analysis in fig. 1 reveals that the resulting Fe-CoP @ PNC/CNTs composite contains orthorhombic CoP crystalline phases, whereas doped Fe elements and amorphous carbon materials are not detectable by XRD instruments, but the energy dispersive X-ray spectrometer imaging (EDX-mapping, see fig. 2) analysis demonstrates that Fe, Co, P, N, and C elements are uniformly distributed in the composite. Scanning electron micrographs (see fig. 3) show that the composite material is formed by cross-assembly of a large number of one-dimensional nanotube-like substances, and the surface of the composite material is rich in rough porous structures. The TEM (see FIG. 4) shows that a large number of Fe-doped CoP particles are coated with porous carbon, which are further uniformly attached to the carbon nanotubes, constituting a heterogeneous Fe-CoP @ PNC/CNTs composite.
Example 2
The performance test of the porous carbon coated Fe doped CoP particle/carbon nano tube composite material as the catalyst for the electrolytic water oxygen evolution reaction:
(1) preparing an electrocatalyst working electrode:
adding 5 mg of porous carbon coated Fe doped CoP particle/carbon nano tube composite material powder and 40 mul of 5 wt% nafion solution into 960 mul of ethanol, and performing ultrasonic treatment for 30 min to form uniform catalyst ink; 8 mul of catalyst ink is transferred and coated on the surface of a glassy carbon electrode (with the diameter of 3 mm), and the glassy carbon electrode is naturally dried and then is to be measured.
(2) Electrochemical performance study:
the electrochemical properties of the prepared samples were tested on the CHI 760E electrochemical workstation (chenhua instrument, shanghai, china). A traditional three-electrode system, namely a graphite electrode as a counter electrode, a Saturated Calomel Electrode (SCE) as a reference electrode and a catalyst modified glassy carbon electrode as a working electrode is used. 1 mol. L–1Aqueous KOH solution is used as the supporting electrolyte. Unless otherwise indicated, all potentials in the tests were converted to reversible hydrogen electrode potentials according to the Nernst equation (E RHE). OverpotentialηThis can be further obtained by the following formula:η = E RHE – 1.23 V.
FIG. 5 shows that the content of the porous carbon-coated Fe-doped CoP particle/carbon nanotube composite material as an electrocatalyst is 1 mol.L–1Linear sweep voltammetric polarization curves in KOH. The graph shows that the porous carbon coated Fe-doped CoP particle/carbon nano tube composite material has good electrocatalytic activity, and the electrocatalytic decomposition water oxygen evolution reaction initial potential (defined as obtaining the current density of 1 mA-cm)–2The overpotential of) is only 173 mV,and generates 10 mA cm–2The reference current density (equivalent to the current density produced by a 12.3% efficient solar water splitting plant) requires only 226 mV overpotential.
Fig. 6 is a tafel slope curve of a porous carbon coated Fe doped CoP particle/carbon nanotube composite as an electrocatalyst. The porous carbon-coated Fe-doped CoP particle/carbon nanotube composite material is shown to have a lower Tafel slope (only 48.4 mV dec)–1) It is shown that the oxygen evolution reaction rate is accelerated sharply with the increase of the overpotential.
FIG. 7 shows that the porous carbon-coated Fe-doped CoP particle/carbon nanotube composite material is used as an electrocatalyst at 10 mA cm–1Chronopotentiometric curve at current density. At constant current density (10 mA cm)–1) During the continuous test for 20 hours, the overpotential only needs to be applied not more than 232 mV; fig. 8 is a scanning electron microscope photograph of the composite as an electrocatalyst after being subjected to a potentiostatic test for 20 h, showing that it still maintains a morphology similar to the initial state. These reflect the high electrocatalytic activity and structural stability of the material in alkaline electrolytes.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a porous carbon-coated Fe-doped CoP particle/carbon nanotube composite material is characterized by comprising the following steps:
(1) 12 mL of a solution containing 0.366 g of Zn (NO)3)2·6H2O and Co (NO)3)2·6H2Mixing O with metal salt in methanol, pouring into 20 mL of methanol solution containing 0.811 g 2-methylimidazole, stirring for 10 s, adding 8 mL of methanol/water mixture containing PVP and carboxylated carbon nanotubes (methanol volume/water volume =4: 1), stirring for 3 h, centrifuging the obtained precipitate with methanol, and collecting precipitateCleaning and drying to obtain a zeolite imidazole framework compound/carbon nano tube, namely ZIFs/CNTs powder;
(2) weighing 40 mg of ZIFs/CNTs powder, stirring and dispersing in 36 mL of ethanol, and dropwise adding 4 mL of K3[Fe(CN)6]Stirring the aqueous solution for 2 hours, centrifugally cleaning and drying the obtained precipitate by using water and ethanol to obtain a zeolite imidazole framework compound @ Prussian blue/carbon nano tube, namely ZIFs @ PBA/CNTs powder;
(3) weighing 120 mg of ZIFs @ PBA/CNTs powder, placing the powder in a tube furnace, keeping a high-purity Ar atmosphere, setting a temperature program and carrying out high-temperature heat treatment to obtain porous carbon-coated Fe-doped Co particles/carbon nano tubes, namely Fe-Co @ PNC/CNTs powder;
(4) weighing 50 mg of Fe-Co @ PNC/CNTs powder, pre-oxidizing in a muffle furnace, and mixing with 300 mg of NaH2PO2·H2O crystal powder is respectively placed in two separated positions in a tube furnace, wherein NaH2PO2·H2And (3) keeping the O crystal powder at the upstream, keeping a high-purity Ar atmosphere, and performing high-temperature phosphating treatment by setting a temperature program to obtain a black porous carbon coated Fe-doped CoP particle/carbon nano tube composite material, namely Fe-CoP @ PNC/CNTs.
2. The method of claim 1, wherein said Zn (NO) is present in an amount of 0.366 g3)2·6H2O and Co (NO)3)2·6H2The mass ratio of the metal salt in the methanol solution of the O mixed metal salt is 3: 7-7: 3.
3. The method according to claim 1, wherein the mass of PVP in the methanol/water mixture containing PVP and carboxylated carbon nanotubes is 100-300 mg, and the mass of carboxylated carbon nanotubes is 10-30 mg.
4. The method of claim 1, wherein K is3[Fe(CN)6]The concentration of the aqueous solution is 2.5-7.5 mg/mL–1。
5. The method of claim 1, wherein the set temperature program performs the high temperature heat treatment with parameters of: at 5 ℃ min–1The temperature rising rate is increased from room temperature to 650-950 ℃, then the temperature is kept for 1-3 h, and finally the product is naturally cooled.
6. The method according to claim 1, wherein the pre-oxidation treatment parameters are: at 5 ℃ min–1The temperature rising rate is increased from room temperature to 250-350 ℃, then the temperature is kept for 5-30 min, and finally the natural cooling is carried out.
7. The method according to claim 1, wherein the set temperature program is used for carrying out high-temperature phosphating treatment with the following parameters: at 2 ℃ min–1The temperature rising rate is increased from room temperature to 300-400 ℃, then the temperature is kept for 1-3 h, and finally the natural cooling is carried out.
8. The porous carbon coated Fe-doped CoP particle/carbon nanotube composite material prepared by the method according to any one of claims 1-7.
9. Use of the porous carbon coated Fe doped CoP particle/carbon nanotube composite according to claim 8.
10. The use according to claim 9, wherein the porous carbon coated Fe doped CoP particle/carbon nanotube composite is used as an electrocatalyst for the electrolysis water oxygen evolution reaction.
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