CN113060770A - 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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- 239000002073 nanorod Substances 0.000 title claims abstract description 166
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title abstract description 8
- 229960002173 citrulline Drugs 0.000 claims abstract description 74
- RHGKLRLOHDJJDR-BYPYZUCNSA-N L-citrulline Chemical compound NC(=O)NCCC[C@H]([NH3+])C([O-])=O RHGKLRLOHDJJDR-BYPYZUCNSA-N 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000007740 vapor deposition Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 71
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 44
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 230000002194 synthesizing effect Effects 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 19
- 238000004073 vulcanization Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 description 44
- 239000000843 powder Substances 0.000 description 36
- 239000000203 mixture Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 21
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 19
- 239000012467 final product Substances 0.000 description 19
- 239000012153 distilled water Substances 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 229910052573 porcelain Inorganic materials 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- 238000001816 cooling Methods 0.000 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 238000012546 transfer Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- RHGKLRLOHDJJDR-UHFFFAOYSA-N Ndelta-carbamoyl-DL-ornithine Natural products OC(=O)C(N)CCCNC(N)=O RHGKLRLOHDJJDR-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000013477 citrulline Nutrition 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
The invention discloses a preparation method of a heterojunction CoO/CoS porous nanorod, 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 through a 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)2O→O2+H2) And (4) generating. However, in OER (4OH → 2H) due to anodic oxygen evolution reaction2O+4e-+O2) The process has complex mechanism, slow dynamics and high required overpotential; the need to develop an efficient electrocatalyst is particularly critical. Currently, IrO is commercialized2And RuO2Is a highly efficient OER catalyst, but its high price and rare content prevent widespread use. 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 purpose of the invention is as follows: 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)6H13N3O3) As a coordination agent, synthesizing a cobalt-citrulline nanorod precursor through a hydrothermal reaction; and then calcining and oxidizing the nanorod, and vulcanizing by a vapor deposition method to obtain the heterojunction CoO/CoS porous nanorod.
And when L-citrulline is replaced by other kinds of amino acids, the 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 calcining treatment comprises the step of carrying out oxidation heat treatment on the cobalt-citrulline nanorods, 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 structure3O4And (4) nanorods. 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; the inert atmosphere comprises Ar and Ar/H2、N2At least one of; the heating rate is 1-10 ℃/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)2Or CoCl2。
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 the 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 RuO2Better 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, cobalt salt is used as a metal source, L-citrulline is used as a coordination agent to prepare a light pink Co-citrulline precursor, and the precursor is calcined and oxidized to obtain black porous Co3O4And 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) The pore channels are effectively introduced during organic splitting, 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) The test result shows that the prepared heterojunction CoO/CoS porous nanorod catalyst shows higher 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 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; (a) SEM pictures and TEM pictures.
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 invention3O4Pictures of nanorods; (a) SEM pictures and TEM pictures.
FIG. 4 is porous Co prepared according to the present invention3O4X-ray diffraction pattern (XRD) of nanorods.
FIG. 5 is a TEM spectrum of the heterojunction CoO/CoS porous nanorod prepared according to the invention, wherein (a) is a low power electron microscope image, and (b) is a high power electron microscope image.
FIG. 6 is an SEM spectrum of heterojunction CoO/CoS porous nanorods prepared according to the present invention; (a) is SEM image, and (b) is magnified SEM image.
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 present invention3O4Porous nanorods and commercial RuO2Comparative 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)2Dissolved 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 410 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm and N is arranged at the position2Heating 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 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)2Dissolved 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 treatmentThen keeping the temperature for 1h to obtain black Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 410 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm and N is arranged at the position2Heating 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 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)2Dissolved 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 415 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm, and N is arranged at the position2Heating 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 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)2Dissolved 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 with a water-alcohol mixed solution for several times, and drying in vacuum to obtain the productPink 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 415 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm, and N is arranged at the position2Heating 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 5:
a preparation method of a heterojunction CoO/CoS porous nanorod comprises the following steps:
1) synthesizing a Co-citrulline nanorod precursor: 5mmol L-citrulline and 1mmol Co (NO)3)2Dissolved 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: 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 410 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm and N is arranged at the position2Heating 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 L-citrulline and 1mmol Co (NO)3)2Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 160 ℃ for 8 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 410 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm and N is arranged at the position2Heating 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)2Dissolved 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 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 410 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm and N is arranged at the position2Heating 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 L-citrulline and 1mmol Co (NO)3)2Dissolved 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 410 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm and N is arranged at the position2Heating 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)2Dissolved 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 410 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm and N is arranged at the position2Heating 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 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)2Dissolved 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 410 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm and N is arranged at the position2Heating 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 11:
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)2Dissolved 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: the light pink powder prepared in the step 1) is put in the air atmosphereHeating to 350 deg.C at a temperature of 10 deg.C/min for oxidation heat treatment, and maintaining at the temperature for 1 hr to obtain black Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 410 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm and N is arranged at the position2Heating 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 12:
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)2Dissolved 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 410 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm and N is arranged at the position2Heating 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)2Dissolved in 35mL of distilled water to form a pink clear solution, transferred to a 50mL autoclave, and reacted at 160 ℃ for 5 hours. Mixing with water and alcoholMixing the solution, centrifugally washing for several times, and drying 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 410 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm and N is arranged at the position2Heating 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)2Dissolved 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 410 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm and N is arranged at the position2Heating 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 L-citrulline and 1mmol Co (NO)3)2Dissolved 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 410 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm and N is arranged at the position2Heating 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 L-citrulline and 1mmol Co (NO)3)2Dissolved 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3O418 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm, and N is arranged at the position2Heating to 350 deg.C at 2 deg.C/min under atmosphere, and heatingThe temperature was maintained for 0.5h and then cooled to give 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 L-citrulline and 1mmol Co (NO)3)2Dissolved 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 Co3O4A porous nanorod.
3) Black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3 O 420 times of) is arranged at the two ends of the porcelain boat at the interval of 3cm, and N is arranged at the position2Heating 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.
And physically characterizing the heterojunction CoO/CoS porous nanorod prepared in the example by using characterization means such as TEM, SEM and XRD. From FIG. 1(SEM and TEM spectra), it can be seen that the prepared Co-citrulline precursor has a rod-like structure with a diameter of about 100-200 nm. FIG. 2 is an XRD pattern of Co-citrulline, vs. Co (CO)3)0.5(OH)·0.11H2O 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), the calcined and oxidized sample and Co can be seen3O4The 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 heterojunction CoO/CoS porous nanorods, and it is observed from the images that the size of the catalyst after sulfidation is uniform, the original morphology is maintained, a rough surface is formed, mass transfer channels are added,the CoO and CoS heterostructure interfaces are mutually permeated, and charges among different components are transferred, so that the conductivity is improved. The XRD patterns 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 RuO2From Co in addition3O4The 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 L-citrulline and 1mmol Co (NO)3)2Dissolved 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 Co3O4A porous nanorod.
3) Mixing the black Co obtained in the step 2)3O4Porous nanorod and thiourea (mass of Co)3O45 times of) are arranged at the two ends of the porcelain boat at intervals of 3cm, and the spacing is N2Heating 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.
It was found by testing that the final product of this comparative example was not a heterojunction CoO/CoS porous nanorod, but a CoO nanorod.
Claims (10)
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; and then calcining and oxidizing the nanorod, and vulcanizing by a vapor deposition method to obtain the heterojunction CoO/CoS porous nanorod.
2. The preparation method of the heterojunction CoO/CoS porous nanorod according to claim 1, characterized in that: 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.
3. The preparation method of the heterojunction CoO/CoS porous nanorod according to claim 1, characterized in that: the calcining treatment comprises the step of carrying out oxidation heat treatment on the cobalt-citrulline nano-rods, wherein the heat treatment temperature is 300-500 ℃, and the heat treatment time is 0.5-3 h.
4. The preparation method of the heterojunction CoO/CoS porous nanorod according to claim 1, characterized in that: the vulcanization treatment comprises the steps of carrying out vapor deposition vulcanization on the calcined product and thiourea, and carrying out heat treatment in an inert atmosphere; the heating temperature is 300-400 ℃, and the heating time is 0.5-2 h.
5. The preparation method of the heterojunction CoO/CoS porous nanorod according to claim 1, characterized in that: the mol ratio of the L-citrulline to the cobalt salt is 0.1-10: 1.
6. The preparation method of the heterojunction CoO/CoS porous nanorod according to claim 1, characterized in that: the cobalt salt being Co (NO)3)2Or CoCl2。
7. The preparation method of the heterojunction CoO/CoS porous nanorod according to claim 3, characterized in that: the heating rate is 0.5-10 ℃/min.
8. The method of claim 4, wherein the preparation method of the heterojunction CoO/CoS porous nanorod is characterized in that: the mass ratio of the calcined product to the thiourea is 1: 10-20.
9. The heterojunction CoO/CoS porous nanorod prepared by the preparation method of any one of claims 1 to 8.
10. Use of the heterojunction CoO/CoS porous nanorods according to claim 9 as anode catalyst for water electrolysis.
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