CN113060770B - Preparation method of heterojunction CoO/CoS porous nanorod, obtained material and application - Google Patents
Preparation method of heterojunction CoO/CoS porous nanorod, obtained material and application Download PDFInfo
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Abstract
The invention discloses a preparation method of a heterojunction CoO/CoS porous nanorod as well as an obtained material and application thereof, wherein a cobalt salt is used as a metal source, L-citrulline is used as a coordination agent, and the cobalt-citrulline nanorod is synthesized by hydrothermal reaction; and then calcining and oxidizing the nano rod, and finally vulcanizing by a vapor deposition method to obtain the heterojunction CoO/CoS porous nano rod with loose porosity and rough surface. The heterojunction CoO/CoS porous nanorod catalyst prepared by the method shows high catalytic activity and stability to the electrochemical reaction (OER) of oxygen, is a high-stability anode oxygen precipitation catalyst which can be well applied to water electrolysis, and has a wide application prospect in the future energy industry.
Description
Technical Field
The invention relates to the field of catalysts, in particular to an anode catalyst and a preparation method and application thereof.
Background
Energy crisis and environmental pollution are two major problems, and the development of new technology and new energy is the key to solve the two problems and is also a research hotspot in the scientific research field, and a series of new energy such as solar energy, wind energy, biomass energy and the like are generated at the same time. Hydrogen energy is a renewable energy source with abundant reserves, cleanness and no pollution, and hydrogen can pass through electrolyzed water (2H) 2 O→O 2 +H 2 ) And (4) generating. However, in OER (4 OH → 2H) due to anodic oxygen evolution reaction 2 O+4e - +O 2 ) The process mechanism is complex, the dynamics of slow motion is high, and the required overpotential is high; the need to develop an efficient electrocatalyst is particularly critical. Currently, irO is commercialized 2 And RuO 2 Is an efficient OER catalyst, but has high price and rare contentPreventing wide application. Therefore, it has become a trend to explore non-noble metal OER electrocatalysts that are both economical and efficient to replace these noble metals.
In recent years, transition metal-based oxides (TMOs) have received attention as a potential class of noble metal oxygen catalyst alternatives. However, single transition metal oxides are less conductive and it is difficult to achieve lower OER overpotentials.
Disclosure of Invention
The invention aims to: the invention aims to provide a preparation method of a heterojunction CoO/CoS porous nanorod, and an obtained material and application thereof.
The technical scheme is as follows: the invention provides a preparation method of a heterojunction CoO/CoS porous nanorod, which takes cobalt salt as a metal source and adopts L-citrulline (C) 6 H 13 N 3 O 3 ) As a coordination agent, synthesizing a cobalt-citrulline nanorod precursor through a hydrothermal reaction; and then carrying out calcination oxidation treatment on the nanorod, and carrying out vulcanization treatment by a vapor deposition method to obtain the heterojunction CoO/CoS porous nanorod.
And when L-citrulline is replaced by other amino acids, nanorods cannot be synthesized.
Wherein the hydrothermal reaction comprises the steps of dissolving L-citrulline and cobalt salt in water to obtain a mixed solution, and carrying out a solvothermal reaction; the reaction temperature is 140-200 ℃, and the reaction time is 4-8 h; thereby obtaining the nano rod with smooth surface.
The calcination treatment comprises the steps of carrying out oxidation heat treatment on the cobalt-citrulline nano rod, wherein the heat treatment temperature is 300-500 ℃, and the heat treatment time is 0.5-3 h; the heat treatment is carried out in air atmosphere, and porous Co is obtained without destroying the original structure 3 O 4 A nano-rod. Wherein the heating rate is 0.5-10 ℃/min.
The vulcanization treatment comprises mixing the calcined product with thiourea, and performing heat treatment in an inert atmosphere; the heating temperature is 300-400 ℃, and the heating time is 0.5-2 h; inert atmosphereComprises Ar, ar/H 2 、N 2 At least one of (a); the heating rate is 1-10 deg.C/min. The heterojunction CoO/CoS porous nanorod with loose porous surface roughness is obtained by keeping the existing structure.
Preferably, the mol ratio of the L-citrulline to the cobalt salt is 0.1-10: 1; the mass ratio of the calcined product to the thiourea is 1: 10-20. Wherein the cobalt salt is Co (NO) 3 ) 2 Or CoCl 2 。
The invention provides a heterojunction CoO/CoS porous nanorod prepared by the preparation method. The prepared nano rod has the advantages of uniform shape, looseness, porosity, rough surface, composite structure, synergistic effect, multiple active sites and the like, and has high-efficiency oxygen precipitation catalytic activity and stability. The method has simple process and easy operation, and can realize large-scale production.
The invention also provides application of the heterojunction CoO/CoS porous nanorod as an anode catalyst for water electrolysis. The heterojunction CoO/CoS porous nanorod is suitable for serving as an anode catalyst of electrolyzed water and has higher RuO ratio than that of commercialized RuO 2 Better OER electrocatalytic activity and stability.
Since a single cobalt-based catalyst has a large charge transfer resistance and limited active sites, a higher overpotential is still required to generate oxygen. The invention can effectively reduce the phenomenon by adopting a designed heterostructure and an adjusted electronic structure, and can utilize the synergistic effect of the heterostructure and the mutual coupling of different interfaces, thereby increasing the active sites and the electrical conductivity of the catalyst and improving the electrocatalytic oxidation performance of the material.
In the preparation process, after calcination and vulcanization treatment, the catalyst can still keep the original nanorod structure, and a loose and porous structure is formed due to gas generated by decomposition of citrulline during heating, and the nanorod heterojunction structure has a rough surface, so that active sites and mass transfer channels of the catalyst are increased, and the performance of the catalyst is improved due to interface charge transfer induced by the heterostructure and the coupling effect among different components.
Has the advantages that: in the preparation method of the invention, cobalt salt is used as a metal source, L-citrulline is used as a coordination agent,preparing a light pink Co-citrulline precursor, and calcining and oxidizing the precursor to obtain black porous Co 3 O 4 And sulfurizing the nano rod by using a vapor deposition method to obtain the heterojunction CoO/CoS porous nano rod. The material has a heterogeneous structure formed by two substances, has a porous structure, has rich active sites on a rough surface, and improves the mass transfer efficiency. The preparation process has clear and reliable mechanism, the preparation condition is mild and easy to operate, and the electrochemical reaction (OER) to oxygen shows higher catalytic activity and stability. The method specifically comprises the following steps:
1) The rough surface structure of the nano rod provides abundant mass transfer channels, increases active sites and is beneficial to gas diffusion and electrolyte transmission.
2) During organic splitting, the pore channels are effectively introduced, the morphology of the pore channels is kept, and a larger specific surface area is exposed.
3) The interfaces of the heterogeneous structures with uniform CoO and CoS distribution are mutually permeated, so that the strong synergistic effect is achieved, and the conductivity and the electron transfer are increased.
4) Test results show that the prepared heterojunction CoO/CoS porous nanorod catalyst shows high catalytic activity and stability to the electrochemical reaction (OER) of oxygen, is a high-stability anode oxygen precipitation catalyst which can be well applied to water electrolysis, and has a wide application prospect in the future energy industry.
5) The preparation method is simple and economical, and can realize large-scale production.
Drawings
FIG. 1 is a picture of a Co-citrulline complex precursor prepared according to the present invention; the SEM pictures are taken in (a) and TEM pictures are taken in (b).
Fig. 2 is an X-ray diffraction pattern (XRD) of a Co-citrulline complex precursor prepared according to the method of the present invention.
FIG. 3 is porous Co prepared according to the present invention 3 O 4 Pictures of nanorods; the SEM pictures are taken in (a) and TEM pictures are taken in (b).
FIG. 4 is porous Co prepared according to the invention 3 O 4 The nanorod X-ray diffraction pattern (XRD).
FIG. 5 is TEM spectra of heterojunction CoO/CoS porous nanorods prepared according to the present invention (a) is low magnification electron microscopy image, and (b) is high magnification electron microscopy image.
FIG. 6 is an SEM spectrum of heterojunction CoO/CoS porous nanorods prepared according to the present invention; the SEM image is shown in (a) and the magnified SEM image is shown in (b).
FIG. 7 is an XRD spectrum of the heterojunction CoO/CoS porous nanorod prepared according to the invention.
FIG. 8 is a heterojunction CoO/CoS porous nanorod material, co, prepared according to the invention 3 O 4 Porous nanorods and commercial RuO 2 Comparative OER curves in 1M KOH solution.
FIG. 9 is an OER curve before and after ADT testing of heterojunction CoO/CoS porous nanorod materials prepared according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
The starting materials and reagents in the following examples are all commercially available.
Example 1:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 2mmol L-citrulline and 1mmol Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 160 ℃ for 5 hours. Then, centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ by a program of 0.5 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorods and thiourea (mass Co) 3 O 4 10 times of the total length of the porcelain boat) are arranged at the two ends of the porcelain boat at intervals of 3cm and N 2 Heating to 350 deg.C at 2 deg.C/min under atmosphere, and maintaining at the temperatureHolding for 1h, and then cooling to obtain the final product.
Example 2:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 0.1mmol L-citrulline and 1mmol Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 160 ℃ for 5 hours. Then centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ by a program of 0.5 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorods and thiourea (mass Co) 3 O 4 10 times of) is arranged at the two ends of the porcelain boat at intervals of 3cm, N is 2 Heating to 350 deg.C at 2 deg.C/min under atmosphere, maintaining at the temperature for 1h, and cooling to obtain final product.
Example 3:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 10mmol L-citrulline and 1mmol Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 160 ℃ for 5 hours. Then centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ at a temperature of 0.5 ℃/min in air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Will be described in detail2) Obtained black Co 3 O 4 Porous nanorod and thiourea (mass of Co) 3 O 4 15 times of the total length of the porcelain boat) are arranged at the two ends of the porcelain boat at intervals of 3cm and N 2 Heating to 350 deg.C at 2 deg.C/min under atmosphere, maintaining at the temperature for 1h, and cooling to obtain final product.
Example 4:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 2mmol L-citrulline and 1mmol Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 140 ℃ for 5 hours. Then, centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ by a program of 0.5 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorods and thiourea (mass Co) 3 O 4 15 times of the total length of the porcelain boat) are arranged at the two ends of the porcelain boat at intervals of 3cm and N 2 Heating to 350 deg.C at 2 deg.C/min under atmosphere, maintaining at the temperature for 1h, and cooling to obtain final product.
Example 5:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 5mmol of L-citrulline and 1mmol of Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 200 ℃ for 4 hours. Then, centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: will be described in detail1) Heating the prepared light pink powder to 350 ℃ in an air atmosphere at a temperature of 0.5 ℃/min for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorod and thiourea (mass of Co) 3 O 4 10 times of) is arranged at the two ends of the porcelain boat at intervals of 3cm, N is 2 Heating to 350 deg.C with a program of 2 deg.C/min under atmosphere, maintaining at the temperature for 1h, and cooling to obtain the final product.
Example 6:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 5mmol of L-citrulline and 1mmol of Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 160 ℃ for 8h. Then centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ by a program of 0.5 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorods and thiourea (mass Co) 3 O 4 10 times of the total length of the porcelain boat) are arranged at the two ends of the porcelain boat at intervals of 3cm and N 2 Heating to 350 deg.C with a program of 2 deg.C/min under atmosphere, maintaining at the temperature for 1h, and cooling to obtain the final product.
Example 7:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: adding 8mmol L-citrulline and 1mmol Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, which was transferred to a 50mL autoclaveAnd reacting at 160 ℃ for 5h. Then centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 300 ℃ by a program of 0.5 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorod and thiourea (mass of Co) 3 O 4 10 times of) is arranged at the two ends of the porcelain boat at intervals of 3cm, N is 2 Heating to 350 deg.C with a program of 2 deg.C/min under atmosphere, maintaining at the temperature for 1h, and cooling to obtain the final product.
Example 8:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 9mmol of L-citrulline and 1mmol of Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 160 ℃ for 5 hours. Then, centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 400 ℃ by a program of 0.5 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorod and thiourea (mass of Co) 3 O 4 10 times of) is arranged at the two ends of the porcelain boat at intervals of 3cm, N is 2 Heating to 350 deg.C with a program of 2 deg.C/min under atmosphere, maintaining at the temperature for 1h, and cooling to obtain the final product.
Example 9:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 2mmol L-citrulline and 1mmol Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 160 ℃ for 5 hours. Then centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ by a program of 0.5 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 0.5h to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorod and thiourea (mass of Co) 3 O 4 10 times of) is arranged at the two ends of the porcelain boat at intervals of 3cm, N is 2 Heating to 350 deg.C at 2 deg.C/min under atmosphere, maintaining at the temperature for 1h, and cooling to obtain final product.
Example 10:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 2mmol L-citrulline and 1mmol Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 160 ℃ for 5 hours. Then centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ by a program of 0.5 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 3 hours to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorod and thiourea (mass of Co) 3 O 4 10 times of) is arranged at the two ends of the porcelain boat at intervals of 3cm, N is 2 Under the atmosphere, at the speed of 2 ℃/minThe temperature is raised to 350 ℃ for heat treatment, and the temperature is kept for 1h, and then the product is cooled to obtain the final product.
Example 11:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 2mmol of L-citrulline and 1mmol of Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 160 ℃ for 5 hours. Then, centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ by a program of 10 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorod and thiourea (mass of Co) 3 O 4 10 times of) is arranged at the two ends of the porcelain boat at intervals of 3cm, N is 2 Heating to 350 deg.C at 2 deg.C/min under atmosphere, maintaining at the temperature for 1h, and cooling to obtain final product.
Example 12:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 2mmol of L-citrulline and 1mmol of Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, which was transferred to a 50mL autoclave and reacted at 160 ℃ for 5 hours. Then centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ by a program of 0.5 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 Porous nanoparticlesA rod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorod and thiourea (mass of Co) 3 O 4 10 times of) is arranged at the two ends of the porcelain boat at intervals of 3cm, N is 2 Heating to 300 ℃ with a program of 2 ℃/min under the atmosphere for heat treatment, keeping the temperature for 1h, and then cooling to obtain the final product.
Example 13:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 2mmol L-citrulline and 1mmol Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 160 ℃ for 5 hours. Then centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ by a program of 0.5 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorod and thiourea (mass of Co) 3 O 4 10 times of) is arranged at the two ends of the porcelain boat at intervals of 3cm, N is 2 Heating to 400 ℃ with a program of 2 ℃/min under the atmosphere for heat treatment, keeping the temperature for 1h, and then cooling to obtain the final product.
Example 14:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 2mmol L-citrulline and 1mmol Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, which was transferred to a 50mL autoclave and reacted at 160 ℃ for 5 hours. Then centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ by a program of 0.5 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorod and thiourea (mass of Co) 3 O 4 10 times of) is arranged at the two ends of the porcelain boat at intervals of 3cm, N is 2 Heating to 350 deg.C with a program of 1 deg.C/min under atmosphere, maintaining at the temperature for 1h, and cooling to obtain the final product.
Example 15:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 2mmol of L-citrulline and 1mmol of Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 160 ℃ for 5 hours. Then centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ by a program of 0.5 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorods and thiourea (mass Co) 3 O 4 10 times of the total length of the porcelain boat) are arranged at the two ends of the porcelain boat at intervals of 3cm and N 2 Heating to 350 deg.C with a program of 10 deg.C/min under atmosphere, maintaining at the temperature for 1h, and cooling to obtain the final product.
Example 16:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 2mmol of L-citrulline and 1mmol of Co (NO) 3 ) 2 Dissolved in 35mL of distilled waterA pink clear solution is formed in the reaction kettle, and the solution is transferred to a 50mL high-pressure reaction kettle and reacts for 5 hours at 160 ℃. Then, centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ at a temperature of 0.5 ℃/min in air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorods and thiourea (mass Co) 3 O 4 18 times of) are arranged at the two ends of the porcelain boat at intervals of 3cm, and the space is N 2 Heating to 350 deg.C with a program of 2 deg.C/min under atmosphere, maintaining at the temperature for 0.5h, and cooling to obtain the final product.
Example 17:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 2mmol of L-citrulline and 1mmol of Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 160 ℃ for 5 hours. Then centrifugally washing the mixture for several times by using a water-alcohol mixed solution, and drying the mixture in vacuum to obtain light pink powder, namely a Co-citrulline nanorod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ by a program of 0.5 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Black Co obtained in the step 2) 3 O 4 Porous nanorod and thiourea (mass of Co) 3 O 4 20 times of the total length of the porcelain boat) are arranged at the two ends of the porcelain boat at intervals of 3cm and N 2 Heating to 350 deg.C at 2 deg.C/min under atmosphere, maintaining at the temperature for 2 hr, and cooling to obtain final product.
Using the characterization means of TEM, SEM and XRD, etcThe heterojunction CoO/CoS porous nanorods prepared in the above example were physically characterized. From FIG. 1 (SEM and TEM spectra), it can be seen that the prepared Co-citrulline precursor has a rod-like structure and a diameter of about 100-200nm. FIG. 2 is an XRD pattern of Co-citrulline, with Co (CO) 3 ) 0.5 (OH)·0.11H 2 O standard cards are identical. FIG. 3 is SEM and TEM images of the calcined and oxidized precursor, and not only the porous structure is formed, but also the rod-like structure can be maintained. From the XRD spectrum (FIG. 4), it can be seen that the calcined and oxidized sample is mixed with Co 3 O 4 The one-to-one correspondence of the standard cards of (a) also indicates the successful oxidation of the precursor. FIGS. 5 and 6 are TEM and SEM images of the heterojunction CoO/CoS porous nanorod, and it is observed from the images that the size of the catalyst after sulfurization is uniform, the original appearance is maintained, a rough surface is formed, a mass transfer channel is added, coO and CoS heterostructure interfaces are mutually permeated, and the electric charge transfer between different components improves the conductivity. The XRD spectra of the heterojunction CoO/CoS porous nanorods in FIG. 7 are also consistent with the standard cards of CoO (PDF # 65-2502) and CoS (PDF # 65-8977), respectively, further confirming the heterostructure thereof. FIG. 8 is the LSV curve of the heterojunction CoO/CoS porous nanorod tested in 1M KOH solution, and it can be seen that the overpotential of the catalyst is significantly lower than that of the commercial RuO 2 From Co in addition 3 O 4 The obvious comparison of LSV curves of the porous nanorod and the heterojunction CoO/CoS porous nanorod shows that the introduction of S greatly improves the electrocatalytic performance of the catalyst. In addition, an accelerated durability test (fig. 9) was also performed, and after 1000 cycles of CV scanning, the overpotential of the heterojunction CoO/CoS porous nanorod was increased by only 10mV, confirming its better stability.
Comparative example:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) Synthesizing a Co-citrulline nanorod precursor: 2mmol of L-citrulline and 1mmol of Co (NO) 3 ) 2 Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 160 ℃ for 5 hours. Then centrifugally washing for several times by using a water-alcohol mixed solution, and drying in vacuum to obtain light pink powder, namely Co-citrulline nano-particlesA rod precursor;
2) Preparing a heterojunction CoO/CoS porous nanorod: heating the light pink powder prepared in the step 1) to 350 ℃ by a program of 0.5 ℃/min in the air atmosphere for oxidation heat treatment, and keeping the temperature for 1h to obtain black Co 3 O 4 A porous nanorod.
3) Mixing the black Co obtained in the step 2) 3 O 4 Porous nanorods and thiourea (mass Co) 3 O 4 5 times of the total length of the porcelain boat) are arranged at the two ends of the porcelain boat at intervals of 3cm and N 2 Heating to 350 deg.C with a program of 2 deg.C/min under atmosphere, maintaining at the temperature for 2h, and cooling to obtain the final product.
The final product of this comparative example was found by testing not to be a heterojunction CoO/CoS porous nanorod, but a CoO nanorod.
Claims (6)
1. A preparation method of a heterojunction CoO/CoS porous nanorod is characterized in that: taking cobalt salt as a metal source and L-citrulline as a coordination agent, and synthesizing a cobalt-citrulline nanorod by a hydrothermal reaction; then calcining and oxidizing the nano rod, and vulcanizing by a vapor deposition method to obtain a heterojunction CoO/CoS porous nano rod; the hydrothermal reaction comprises the steps of dissolving L-citrulline and cobalt salt in water to obtain a mixed solution, and carrying out a solvothermal reaction; the calcination treatment comprises the steps of carrying out oxidation heat treatment on the cobalt-citrulline nano-rods, wherein the heat treatment temperature is 300-500 ℃, the heat treatment time is 0.5-3h, the reaction temperature is 140-200 ℃, the reaction time is 4-8h, and the vulcanization treatment comprises the steps of carrying out vapor deposition vulcanization on the calcination products and thiourea, and carrying out heat treatment in an inert atmosphere; the heating temperature is 300 to 400 ℃, the heating time is 0.5 to 2h, and the molar ratio of the L-citrulline to the cobalt salt is 0.1 to 10:1.
2. the method of preparing the heterojunction CoO/CoS porous nanorod of claim 1, wherein the method comprises the following steps: the cobalt salt being Co (NO) 3 ) 2 Or CoCl 2 。
3. The preparation method of the heterojunction CoO/CoS porous nanorod according to claim 1, characterized in that: the heating rate is 0.5 to 10 ℃/min.
4. The preparation method of the heterojunction CoO/CoS porous nanorod according to claim 1, characterized in that: the mass ratio of the calcined product to the thiourea is 1:10 to 20.
5. A heterojunction CoO/CoS porous nanorod prepared by the preparation method of any one of claims 1 to 4.
6. Use of the heterojunction CoO/CoS porous nanorods according to claim 5 as anode catalyst for electrolyzing water.
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