CN113903929B - 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 Fe-containing Prussian blue crystal 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 OER 2 O→O 2 + 4H + + 4e – ) Resulting in slow kinetics and requiring higher overpotentials; while having a noble metal group (IrO) with excellent OER catalytic performance 2 Or RuO 2 ) The expensive price and instability of the material seriously hamper the large-scale practical application of the materialThe application is as follows. 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) poor conductivity by itself; (3) poor corrosion resistance and instability 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 contains 0.366 g Zn (NO) 3 ) 2 ·6H 2 O (Zinc nitrate hexahydrate) and Co (NO) 3 ) 2 ·6H 2 Pouring a methanol solution of O (cobalt nitrate hexahydrate) mixed metal salt into a methanol solution of 20 mL containing 0.811 g of 2-methylimidazole, stirring 10 s, adding a methanol/water mixed solution of 8 mL containing PVP (polyvinylpyrrolidone) and carboxylated carbon nanotubes (methanol volume/water volume = 4:1), continuously stirring 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 ZIFs/CNTs powder, stirring and dispersing in 36 mL ethanol, and dropwise adding 4 mL K 3 [Fe(CN) 6 ]Stirring the (potassium ferricyanide) water solution for 2h, centrifugally washing the obtained precipitate with water and ethanol, and drying 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 the atmosphere of high-purity Ar (argon), 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 NaH 2 PO 2 ·H 2 O (sodium hypophosphite) crystal powder is respectively placed in two separated positions in a tube furnace, wherein NaH 2 PO 2 ·H 2 And (3) keeping the O crystal powder at the upstream, keeping the high-purity Ar atmosphere, and setting a temperature program to perform high-temperature phosphating treatment 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 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 The metal salt mass ratio of the methanol solution of O mixed metal salt is Zn (NO) 3 ) 2 ·6H 2 O：Co(NO 3 ) 2 ·6H 2 O = 3. More preferably, the metal salt mass ratio is Zn (NO) 3 ) 2 ·6H 2 O：Co(NO 3 ) 2 ·6H 2 O=5:5。
Preferably, the mass of the PVP in the methanol/water mixed solution containing the 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 K 3 [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 –1 The temperature rising rate is increased from room temperature to 650 to 950 ℃, then the temperature is kept for 1 to 3 hours, and finally the mixture is naturally cooled;
preferably, in the step (4), the parameters of the pre-oxidation treatment are as follows: at 5 ℃ min –1 The temperature rising rate is increased from the room temperature to 250 to 350 ℃, then the temperature is kept for 5 to 30 min, and finally the air 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: to be provided with2℃·min –1 The temperature rising rate is increased from room temperature to 300 to 400 ℃, then the temperature is kept for 1 to 3 hours, and finally the air 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:
the preparation method provided by the invention 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 –2 Very low over-potential (226 mV) and very small tafel slope (48.4 mV dec) –1 ) (ii) a The composite material still keeps stable activity and structure after continuously catalyzing and producing the oxygen 20 h. 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 of example 2 is used as an electrocatalyst at constant value of 10 mA. Cm –2 The chronopotentiometric curve of 20 h was tested at current density.
Fig. 8 is an SEM image of the porous carbon coated Fe doped CoP particle/carbon nanotube composite of example 2 as an electrocatalyst after 20 h chronopotentiometric stability testing.
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 Fe-containing Prussian blue crystal 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 electro-catalytic 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 oxygen evolution of electrolyzed water is measured on an Shanghai Chenhua electrochemical workstation.
Example 1
The preparation process and steps in this example are as follows:
(1) 12 mL contains 0.366 g Zn (NO) 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 Pouring a mixed metal salt methanol solution with the mass ratio of O5:5 into 20 mL methanol solution containing 0.811 g of 2-methylimidazole, stirring 10 s, adding 8 mL methanol/water mixed solution containing 200 mg of PVP and 20 mg carboxylated carbon nanotubes (methanol volume/water volume = 4:1), continuously stirring 3 h, centrifugally washing and drying the obtained precipitate by using methanol to obtain zeolite imidazole framework compound/carbon nanotubes (namely ZIFs/CNTs) powder;
(2) Weighing 40 mg ZIFs/CNTs powder, stirring and dispersing in 36 mL ethanol, and dropwise adding 4 mL with the concentration of 5 mg. ML –1 K of 3 [Fe(CN) 6 ]Stirring the aqueous solution with 2h, centrifuging and cleaning the obtained precipitate with water and ethanol, and drying to obtain zeolite imidazole framework compound @ Prussian blue/carbon nano tube (namely ZIFs @ PBA/CNTs) powder;
(3) Weighing 120 mg ZIFs @ PBA/CNTs powder, placing the powder in a tube furnace, keeping high-purity Ar atmosphere, setting a temperature program to carry out high-temperature heat treatment, wherein the parameters are as follows: at 5 ℃ min –1 The temperature rise rate is increased from room temperature to 800 ℃, then 3 h is kept, and finally natural cooling is carried out, so that the porous carbon-coated Fe-doped Co particle/carbon nanotube (namely Fe-Co @ PNC/CNTs) powder is obtained;
(4) Weighing 50 mg of Fe-Co @ PNC/CNTs powder, and carrying out pre-oxidation treatment in a muffle furnace with the parameters as follows: at 5 ℃ min –1 The 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 NaH 2 PO 2 ·H 2 O crystal powder is respectively placed in two separated positions in a tube furnace, wherein NaH 2 PO 2 ·H 2 Keeping 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 –1 The temperature rise rate is increased from room temperature to 350 ℃, then 2h is kept, and finally natural cooling is carried out, so that the black porous carbon coated Fe-doped CoP particle/carbon nano tube composite material (namely Fe-CoP @ PNC/CNTs) is obtained.
X-ray powder diffraction (XRD) analysis in FIG. 1 reveals that the resulting Fe-CoP @ PNC/CNTs composite material contains an orthorhombic CoP crystalline phase, while the doped Fe element and amorphous carbon material are not detectable by XRD instruments, but energy dispersive X-ray spectrometer imaging (EDX-mapping, see FIG. 2) analysis proves that Fe, co, P, N, C and other elements are uniformly distributed in the composite material. 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. Transmission electron micrographs (see FIG. 4) show that a large number of Fe-doped CoP particles are coated with porous carbon, which are further uniformly attached to 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 porous carbon coated Fe doped CoP particle/carbon nanotube composite material powder and 40 mul 5wt% nafion solution into 960 mul 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 (the diameter is 3 mm) in a dripping way, 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 –1 Aqueous KOH solution is used as the supporting electrolyte. Unless otherwise indicated, all potentials in the test 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 –1 Linear 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) –2 Overpotential) of 173 mV, yielding 10 mA cm –2 The reference current density (equivalent to the current density produced by a 12.3% efficiency solar water splitting plant) only needs 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 graph shows that the porous carbon-coated Fe-doped CoP particle/carbon nanotube composite material has 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 as an electrocatalyst is in the range of 10 mA. Cm –1 Chronopotentiometric curve at current density. Under constant current density (10 mA. Cm) –1 ) During 20 hours of continuous testing, only the applied potential does not exceed 232 mV; FIG. 8 is thatScanning electron micrographs of the composite as an electrocatalyst after being subjected to the 20 h chronopotentiometric stability test showed that it still maintained 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 (4)
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 contains 0.366 g Zn (NO) 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 Mixing metal salt methanol solution with O mass ratio of 5:5, pouring the mixed metal salt methanol solution into 20 mL methanol solution containing 0.811 g of 2-methylimidazole, stirring 10 s, then adding 8 mL methanol/water mixed solution containing 200 mg of PVP and 20 mg carboxylated carbon nano tubes, wherein the methanol volume/water volume =4:1, continuously stirring 3 h, centrifugally washing and drying the obtained precipitate by using methanol, and obtaining a zeolite imidazole framework compound/carbon nano tube, namely ZIFs/CNTs powder;
(2) Weighing 40 mg ZIFs/CNTs powder, stirring and dispersing in 36 mL ethanol, and dropwise adding 4 mL with the concentration of 5 mg. ML –1 K of 3 [Fe(CN) 6 ]Stirring the aqueous solution for 2h, centrifuging and cleaning the obtained precipitate by using water and ethanol, and drying to obtain a zeolite imidazole framework compound @ Prussian blue/carbon nano tube, namely ZIFs @ PBA/CNTs powder;
(3) Weighing 120 mg ZIFs @ PBA/CNTs powder, placing the powder in a tube furnace, keeping high-purity Ar atmosphere, setting a temperature program to carry out high-temperature heat treatment, wherein the parameters are as follows: at 5 ℃ min –1 The temperature rise rate is increased from room temperature to 800 ℃, then 3 h is kept, and finally natural cooling is carried out, thus obtaining the porous carbon-coated Fe-doped Co particle/carbon nano tube, namely Fe-Co @ PNC/CNTs powderGrinding;
(4) Weighing 50 mg of Fe-Co @ PNC/CNTs powder, and carrying out pre-oxidation treatment in a muffle furnace with the parameters as follows: at 5 ℃ min –1 The 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 NaH 2 PO 2 ·H 2 O crystal powder is respectively placed in two separated positions in a tube furnace, wherein NaH 2 PO 2 ·H 2 Keeping 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 –1 The heating rate is increased from room temperature to 350 ℃, then 2h is kept, and finally natural cooling is carried out, so that the black porous carbon coated Fe doped CoP particle/carbon nano tube composite material, namely Fe-CoP @ PNC/CNTs, is obtained.
2. The porous carbon coated Fe-doped CoP particle/carbon nanotube composite material prepared according to the method of claim 1.
3. Use of the porous carbon coated Fe doped CoP particle/carbon nanotube composite according to claim 2.
4. The use according to claim 3, wherein the porous carbon coated Fe-doped CoP particle/carbon nanotube composite is used as an electrocatalyst for the electrolysis of water-to-oxygen evolution reactions.
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