CN111804317A - Method for directly growing high-density cobalt phosphide nano-wire electrocatalyst on conductive substrate and application thereof - Google Patents
Method for directly growing high-density cobalt phosphide nano-wire electrocatalyst on conductive substrate and application thereof Download PDFInfo
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- 239000010941 cobalt Substances 0.000 title claims abstract description 108
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- 239000002243 precursor Substances 0.000 claims abstract description 16
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 11
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- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
Abstract
The invention belongs to the technical field of nano material preparation, and discloses a method for directly growing a high-density cobalt phosphide nano wire electrocatalyst on a conductive substrate, which comprises the following steps: s1, growing a cobalt phosphide nanowire precursor on the surface of the conductive substrate by a hydrothermal method; carrying out a phosphating reaction on the cobalt phosphide nanowire precursor obtained from S2 and S1 to obtain a cobalt phosphide nanowire electrocatalyst; wherein, the raw materials of the hydrothermal method in the step S1 are cobalt nitrate hexahydrate, urea and ammonium fluoride, and the molar ratio is 5: 20: 6. the invention grows cobalt phosphide nano-wires on a conductive substrate by a hydrothermal method and a phosphorization method and is used as an electrocatalyst. The method greatly improves the adhesion of the cobalt phosphide and the conductive substrate, and is beneficial to the transmission of electrons between the substrate and the electrocatalyst. Meanwhile, the high-density cobalt phosphide nanowire can expose more catalytic active sites, and the electrocatalytic performance of the high-density cobalt phosphide nanowire can be further improved. In addition, the method has the advantages of low temperature requirement, simple preparation process and convenience for large-scale popularization and application.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a method for directly growing a high-density cobalt phosphide nano wire electro-catalyst on a conductive substrate and application thereof.
Background
The increasingly deteriorating environment and depleted fossil energy have prompted researchers to find a sustainable energy conversion technology with high efficiency and low cost. Hydrogen energy has received much attention because of its high energy density and its combustion does not produce new pollutants. The search for an efficient method for preparing hydrogen is urgently needed. Among the hydrogen production methods, the hydrogen production by water electrolysis is the most potential hydrogen production technology in the future, and the key point of the technology is to prepare a high-efficiency electrocatalyst.
In recent years, the most widely studied non-noble metal HER electrocatalysts include transition metal carbides, selenides, nitrides, and phosphides. Among these electrocatalysts, Transition Metal Phosphide (TMP) has received much attention due to its low cost, high activity and durability at all pH values. Of these TMPs, cobalt phosphide has attracted much interest due to its specific electronic structure and high catalytic performance. However, cobalt phosphide nanowires were basically prepared by a hydrothermal method. Therefore, in the electrocatalytic hydrogen production test, the cobalt phosphide nanowires need to be stuck on a conductive substrate by using a Nafion solution, which affects the transfer of electrons between the substrate and the electrocatalyst, thereby affecting the electrocatalytic activity thereof. The problem of electron transfer at the interface can be effectively solved by directly growing the electrocatalyst on the conductive substrate. To date, few researchers have attempted to grow cobalt phosphide nanowires directly on conductive substrates. However, the density of cobalt phosphide nanowires on the conductive substrate is not high and the growth is not uniform, which can greatly reduce the catalytic active sites of cobalt phosphide. The high-density cobalt phosphide nanowire synthesized on the conductive substrate can expose more catalytic active sites, so that the electrocatalytic activity of cobalt phosphide is greatly improved.
Therefore, the development of a method for directly growing the high-density cobalt phosphide nanowire on the conductive substrate has important research significance and application value.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention firstly provides a method for directly growing a high-density cobalt phosphide nano-wire electrocatalyst on a conductive substrate.
The second purpose of the invention is to provide the cobalt phosphide nanowire electrocatalyst obtained by the method.
The third purpose of the invention is to provide the application of the cobalt phosphide nanowire electrocatalyst.
The purpose of the invention is realized by the following technical scheme:
a method for growing a high density cobalt phosphide nanowire electrocatalyst directly on an electrically conductive substrate, comprising the steps of:
s1, growing a cobalt phosphide nanowire precursor on the surface of the conductive substrate by a hydrothermal method;
carrying out a phosphating reaction on the cobalt phosphide nanowire precursor obtained from S2 and S1 to obtain a cobalt phosphide nanowire electrocatalyst;
the raw materials of the hydrothermal method in the step S1 are cobalt nitrate hexahydrate, urea and ammonium fluoride, wherein the molar ratio of the cobalt nitrate hexahydrate to the urea to the ammonium fluoride is 5: 20: 6.
the invention grows cobalt phosphide nano-wires on a conductive substrate by a hydrothermal method and a phosphorization method and is used as an electrocatalyst. The method greatly improves the adhesion of the cobalt phosphide and the conductive substrate, and is beneficial to the transmission of electrons between the substrate and the electrocatalyst. Meanwhile, the high-density cobalt phosphide nanowire can expose more catalytic active sites, and the electrocatalytic performance of the high-density cobalt phosphide nanowire can be further improved. In addition, the method requires lower temperature and has simple preparation process.
In the reaction process, the molar ratio of the raw materials of cobalt nitrate hexahydrate, urea and ammonium fluoride needs to be strictly controlled so as to obtain high-density ordered cobalt phosphide nanowires, and the high-density ordered cobalt phosphide nanowires have a large specific surface area so as to expose more catalytic active sites.
Preferably, in the above preparation method, the conductive substrate is FTO and carbon cloth.
More preferably, the conductive substrate is pretreated before hydrothermal reaction, and the pretreatment is to remove organic and inorganic contaminants on the substrate so as to facilitate the growth of cobalt sulfide on the surface of the substrate.
As a preferred embodiment, the pretreatment comprises cleaning and drying, wherein the cleaning is to sequentially perform ultrasonic treatment on the conductive substrate in acetone, ethanol and deionized water for 10-20 min, the ultrasonic power is 180W, and the frequency is 40 KHz.
Preferably, in the above preparation method, the operation of step S1 is: and (3) obliquely leaning the conductive substrate in the reaction kettle, putting the reaction kettle into an oven for hydrothermal reaction, wherein the reaction temperature is 110-150 ℃, and the reaction time is 3-8 h.
Preferably, in the preparation method, the reaction in the step S2 is performed in a tubular furnace, the phosphatization raw material is sodium hypophosphite, the molar number of the sodium hypophosphite is the same as that of cobalt nitrate hexahydrate, the phosphatization reaction temperature is 300-350 ℃, the temperature is maintained for 120-180 min, and the phosphatization raw material is naturally cooled to room temperature after being phosphated.
More preferably, in the process of the phosphating reaction, the temperature of the tubular furnace is increased to 300 ℃ according to the speed of 2-5 ℃/min.
The invention also provides an electrocatalytic electrode comprising a high density cobalt phosphide nanowire electrocatalyst grown directly on an electrically conductive substrate obtained by the method of any one of claims 1 to 7.
The invention also provides the cobalt phosphide nanowire electrocatalyst obtained by the method.
The invention also provides the application of the cobalt phosphide nanowire electrocatalyst in the aspect of electrocatalysis; the cobalt phosphide nanowire electrocatalyst is favorably used for electrocatalysis, and the performance of electrocatalysis (such as electrocatalysis hydrogen production) can be obviously improved.
Compared with the prior art, the invention has the following beneficial effects:
the invention grows cobalt phosphide nano-wires on a conductive substrate by a hydrothermal method and a phosphorization method and is used as an electrocatalyst. The method greatly improves the adhesion of the cobalt phosphide and the conductive substrate, and is beneficial to the transmission of electrons between the substrate and the electrocatalyst. Meanwhile, the high-density cobalt phosphide nanowire can expose more catalytic active sites, and the electrocatalytic performance of the high-density cobalt phosphide nanowire can be further improved. In addition, the method has the advantages of low temperature requirement, simple preparation process and convenience for large-scale popularization and application.
Drawings
FIG. 1 is a flow chart of a method of fabricating high density cobalt phosphide nanowires directly grown on a conductive substrate in accordance with the present invention;
FIG. 2 is a diagram of the phosphating procedure in a preparation method for directly growing high-density cobalt phosphide nanowires on a conductive substrate provided in example 1;
FIG. 3 is an SEM image of high density cobalt phosphide nanowires on FTO obtained in example 1, at a magnification of 10000 times;
FIG. 4 is an XRD pattern of cobalt phosphide nanowires on FTO obtained in example 1;
FIG. 5 is a linear voltammetric scan of cobalt phosphide nanowires of different growth densities on FTO obtained in example 1;
FIG. 6 is an SEM image of high density cobalt phosphide nanowires on carbon cloth obtained in example 2, at 500X magnification;
FIG. 7 is an SEM image of high density cobalt phosphide nanowires on carbon cloth obtained in example 2, at 2000X magnification;
FIG. 8 is an XRD pattern of high density cobalt phosphide nanowires on carbon cloth obtained in example 2;
FIG. 9 is a plot of the linear voltammetric scan of high density cobalt phosphide nanowires on carbon cloth obtained in example 2;
FIG. 10 is an SEM image of cobalt phosphide nanowires on FTO obtained in comparative example 1, at a magnification of 10000 times;
fig. 11 is an SEM image of cobalt phosphide nanowires on carbon cloth obtained in comparative example 2, at a magnification of 1500;
fig. 12 is an SEM image of cobalt phosphide nanowires on carbon cloth obtained in comparative example 2, at a magnification of 2600 times.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The test methods used in the following experimental examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
Example 1
As shown in fig. 1, the present example provides a method of growing cobalt phosphide nanowires directly on FTO, comprising the steps of:
step 101, cleaning of the FTO: carrying out ultrasonic treatment on FTO for 10min respectively according to the sequence of acetone, ethanol and deionized water, wherein the ultrasonic power is 180W, and the frequency is 40 KHz;
step 102, drying the FTO: heating the treated FTO on a heating table for 30 min;
103, growing a cobalt phosphide nanowire precursor on FTO by a hydrothermal method:
(1) dissolving 1.576g of cobalt nitrate hexahydrate (AR, 99%, avadin reagent), 1.2g of urea (AR, 99%, avadin reagent) and 0.222g of ammonium fluoride (AR, 99%, avadin reagent) in 35mL of deionized water, and then stirring at room temperature for 30min to obtain a mixed solution; the above mixed solution was poured into a 50mL reaction vessel, and the treated FTO was leaned against the reaction vessel.
(2) Next, the reaction vessel was placed in an oven, and the reaction temperature was set to 120 ℃ and reacted at this temperature for 6 hours. And after the reaction is finished, taking the FTO out of the reaction kettle, washing the FTO with deionized water and absolute ethyl alcohol for three times respectively, and drying the FTO for 12 hours at the temperature of 60 ℃ to obtain a cobalt phosphide precursor.
104, putting the cobalt phosphide precursor in a tube furnace for phosphorization: FTO with cobalt precursor growing on the surface is placed in a corundum boat, and 0.5g of sodium hypophosphite is placed in another corundum boat. The experiment required a three temperature zone tube furnace (OtFeke Crystal Material technology Co., Ltd., OTF-1200X-III). Sodium hypophosphite is placed at the center of the first temperature zone, and a cobalt precursor is placed at the center of the second temperature zone.
In the phosphating process, the pressure is normal pressure, and high-purity argon (99.999%) is introduced at the flow rate of 400sccm for cleaning for 20 min.
The temperature of three temperature zones in the phosphating process is set as follows: the temperature was increased from room temperature (30 ℃) to 300 ℃ over 135min and maintained for 120min (temperature control procedure shown in FIG. 2). And naturally cooling to room temperature after the phosphorization is finished.
Airflow regulation during the phosphating process: argon gas is introduced into the whole phosphating process, and the flow rate is 100 sccm.
The experimental result is shown in fig. 3, which is an SEM image of the cobalt phosphide nanowire prepared in this example, and it can be known from the figure that the cobalt phosphide nanowire is vertical to the substrate and uniformly and orderly grown, and the density of the nanowire is high, and the nanowire has a large specific surface area, so that more catalytic active sites can be exposed.
Fig. 4 is an XRD pattern of the cobalt phosphide nanowire prepared in this example. According to standard card PDF #29-0497, the diffraction peaks at 31.6, 36.3, 48.1 and 56.7 degrees in the figure correspond to the (011), (111), (211) and (301) crystal planes of cobalt phosphide, respectively. Therefore, we can know that the cobalt phosphide nanowire is successfully prepared.
FIG. 5 is a linear voltammetry scan of different density cobalt phosphide nanowires on FTO, and the test condition is a three-electrode system (electrolyte solution is 0.5M H)2SO4AgCl/Ag as reference electrode, graphite carbon rod as counter electrode, and cobalt phosphide nanowire prepared in this example as working electrode). As can be seen from FIG. 5, the electrocatalytic activity of the ordered and high-density cobalt phosphide nanowire is significantly better than that of the disordered and low-density cobalt phosphide nanowire at 10mA/cm2When the overvoltage is higher than the threshold value, the overpotential of the ordered high-density cobalt phosphide is only-86 mV, which indicates thatThe high density cobalt phosphide nanowires did possess more catalytically active sites.
Example 2
The embodiment provides a method for directly growing uniform and ordered cobalt phosphide nanowires on carbon cloth, which comprises the following steps:
step 101, cleaning of carbon cloth: performing ultrasonic treatment on the carbon cloth for 20min respectively according to the sequence of acetone, ethanol and deionized water, wherein the ultrasonic power is 180W, and the frequency is 40 KHz;
step 102, drying the carbon cloth: heating the treated carbon cloth on a heating table for 30 min;
103, growing a cobalt phosphide nanowire precursor on the carbon cloth by a hydrothermal method:
(1) dissolving 1.576g of cobalt nitrate hexahydrate (AR, 99%, avadin reagent), 1.2g of urea (AR, 99%, avadin reagent) and 0.222g of ammonium fluoride (AR, 99%, avadin reagent) in 35mL of deionized water, and then stirring at room temperature for 30min to obtain a mixed solution; the above mixed solution was poured into a 50mL reaction vessel, and the treated carbon cloth was leaned against the reaction vessel.
(2) Next, the reaction vessel was placed in an oven, and the reaction temperature was set at 150 ℃ and reacted at this temperature for 8 hours. And after the reaction is finished, taking the carbon cloth out of the reaction kettle, washing the carbon cloth with deionized water and absolute ethyl alcohol for three times respectively, and drying the carbon cloth for 12 hours at the temperature of 60 ℃ to obtain a cobalt phosphide precursor.
104, putting the cobalt phosphide precursor in a tube furnace for phosphorization: carbon cloth with a cobalt precursor growing on the surface is placed in one corundum boat, and 0.5g of sodium hypophosphite is placed in the other corundum boat. The experiment required a three temperature zone tube furnace (OtFeke Crystal Material technology Co., Ltd., OTF-1200X-III). Sodium hypophosphite is placed at the center of the first temperature zone, and a cobalt precursor is placed at the center of the second temperature zone.
In the phosphating process, the pressure is normal pressure, and high-purity argon (99.999%) is introduced at the flow rate of 400sccm for cleaning for 20 min.
The temperature of three temperature zones in the phosphating process is set as follows: the mixture was heated from room temperature (30 ℃) to 350 ℃ over 135min and held for 180 min. And naturally cooling to room temperature after the phosphorization is finished.
Airflow regulation during the phosphating process: argon gas is introduced into the whole phosphating process, and the flow rate is 100 sccm.
Referring to fig. 6 and 7, SEM images of the cobalt phosphide nanowires prepared in this example show that the cobalt phosphide nanowires were successfully prepared. And the density of the cobalt phosphide nanowire is high and the growth is uniform.
Referring to FIG. 8, the XRD pattern of the cobalt phosphide nanowires prepared in this example also shows diffraction peaks consistent with those of cobalt phosphide standard (PDF #29-0497 standard card), indicating that the cobalt phosphide nanowires were successfully prepared.
FIG. 9 is a linear voltammetry scan of cobalt phosphide nanowires of different densities on carbon cloth according to the present invention, and the test condition is a three-electrode system (electrolyte solution is 0.5M H)2SO4AgCl/Ag as reference electrode, graphite carbon rod as counter electrode, and cobalt phosphide nanowire prepared in this example as working electrode). As can be seen from FIG. 9, the electrocatalytic activity of the ordered and high-density cobalt phosphide nanowire is significantly better than that of the disordered and low-density cobalt phosphide nanowire at 10mA/cm2The overpotential of the ordered high-density cobalt phosphide is only-75 mV, which indicates that the high-density cobalt phosphide nanowire really has more catalytic active sites.
Comparative example 1
This comparative example provides a method for growing cobalt phosphide nanowires directly on FTO, and the method provided by this comparative example is identical to example 1 except that the amounts of cobalt nitrate hexahydrate, urea and ammonium fluoride in step 103 were set to 0.291g, 0.300g and 0.074g, respectively.
The experimental results are shown in fig. 10, which shows SEM images of the cobalt phosphide nanowires prepared in the comparative example, and it can be seen that disordered cobalt phosphide nanowires were prepared in the comparative example, and the density of the nanowires was not high.
Comparative example 2
The present comparative example provides a method for directly growing cobalt phosphide nanowires on carbon cloth, and the remaining steps and conditions are the same as those of comparative example 1 except that FTO in steps 101, 102 and 103 is replaced with carbon cloth.
SEM images of the cobalt phosphide nanowires prepared in the present comparative example are shown in fig. 11 and 12, and cobalt phosphide is a flower-like nanowire on the carbon cloth, but the growth was not uniform and the density was not high.
Claims (10)
1. A method for directly growing a high-density cobalt phosphide nanowire electrocatalyst on an electrically conductive substrate, comprising the steps of:
s1, growing a cobalt phosphide nanowire precursor on the surface of the conductive substrate by a hydrothermal method;
carrying out a phosphating reaction on the cobalt phosphide nanowire precursor obtained from S2 and S1 to obtain a cobalt phosphide nanowire electrocatalyst;
the raw materials of the hydrothermal method in the step S1 are cobalt nitrate hexahydrate, urea and ammonium fluoride, wherein the molar ratio of the cobalt nitrate hexahydrate to the urea to the ammonium fluoride is 5: 20: 6.
2. the method of growing high density cobalt phosphide nanowire electrocatalysts directly on conductive substrates according to claim 1, wherein the conductive substrates are FTO and carbon cloth.
3. The method of growing a high density cobalt phosphide nanowire electrocatalyst directly on an electrically conductive substrate according to claim 2, wherein the electrically conductive substrate is pre-treated prior to undergoing the hydrothermal reaction.
4. The method for directly growing the high-density cobalt phosphide nano-wire electrocatalyst on the conductive substrate according to claim 3, wherein the pretreatment comprises cleaning and drying, the cleaning is to sequentially subject the conductive substrate to ultrasonic treatment in acetone, ethanol and deionized water for 10-20 min, the ultrasonic power is 180W, and the frequency is 40 KHz.
5. The method for growing high density cobalt phosphide nanowire electrocatalysts directly on conductive substrates according to claim 4, wherein step S1 is operated as: and (3) obliquely leaning the conductive substrate in the reaction kettle, putting the reaction kettle into an oven for hydrothermal reaction, wherein the reaction temperature is 110-150 ℃, and the reaction time is 3-8 h.
6. The method for directly growing the high-density cobalt phosphide nano-wire electrocatalyst on the conductive substrate according to claim 5, wherein the reaction of the step S2 is carried out in a tube furnace, the raw material for phosphorization is sodium hypophosphite with the same mole number as cobalt nitrate hexahydrate, the temperature for phosphorization is 300-350 ℃, the temperature is kept for 120-180 min, and the product is naturally cooled to room temperature after phosphorization is finished.
7. The method for directly growing the high-density cobalt phosphide nano-wire electrocatalyst on the conductive substrate according to claim 6, wherein the temperature of the tubular furnace is raised to 300 ℃ at a rate of 2-5 ℃/min during the phosphating reaction.
8. An electrocatalytic electrode comprising a high density cobalt phosphide nanowire electrocatalyst grown directly on an electrically conductive substrate obtained by the method of any one of claims 1 to 7.
9. A cobalt phosphide nanowire electrocatalyst obtained by a method for growing a high-density cobalt phosphide nanowire electrocatalyst directly on an electrically conductive substrate, obtained by the method according to any one of claims 1 to 7.
10. The use of the cobalt phosphide nanowire electrocatalyst according to claim 9 in electrocatalysis.
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| CN112921352A (en) * | 2021-01-21 | 2021-06-08 | 徐志军 | Preparation method of cobalt phosphide nano-particles |
| CN113249739A (en) * | 2021-06-04 | 2021-08-13 | 中国科学技术大学 | Metal phosphide-loaded monatomic catalyst, preparation method thereof and application of metal phosphide-loaded monatomic catalyst as hydrogen evolution reaction electrocatalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112921352A (en) * | 2021-01-21 | 2021-06-08 | 徐志军 | Preparation method of cobalt phosphide nano-particles |
| CN113249739A (en) * | 2021-06-04 | 2021-08-13 | 中国科学技术大学 | Metal phosphide-loaded monatomic catalyst, preparation method thereof and application of metal phosphide-loaded monatomic catalyst as hydrogen evolution reaction electrocatalyst |
| CN113249739B (en) * | 2021-06-04 | 2022-07-15 | 中国科学技术大学 | Metal phosphide-loaded monatomic catalyst, preparation method thereof and application of metal phosphide-loaded monatomic catalyst as hydrogen evolution reaction electrocatalyst |
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Application publication date: 20201023 |