CN114934293A - Preparation method of CoPS/black phosphorus alkene vertical heterostructure material, CoPS/black phosphorus alkene composite material and application - Google Patents
Preparation method of CoPS/black phosphorus alkene vertical heterostructure material, CoPS/black phosphorus alkene composite material and application Download PDFInfo
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- -1 black phosphorus alkene Chemical class 0.000 title claims abstract description 84
- 239000000463 material Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002135 nanosheet Substances 0.000 claims abstract description 18
- JHYNEQNPKGIOQF-UHFFFAOYSA-N 3,4-dihydro-2h-phosphole Chemical compound C1CC=PC1 JHYNEQNPKGIOQF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 206010034962 Photopsia Diseases 0.000 claims abstract description 13
- 229910000065 phosphene Inorganic materials 0.000 claims abstract description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001868 cobalt Chemical class 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000137 annealing Methods 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 3
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 230000001808 coupling effect Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 9
- 238000004321 preservation Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 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
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The invention belongs to the field of catalysts for electrocatalytic water decomposition, and particularly relates to a preparation method of a CoPS/black phosphorus alkene vertical heterostructure material, a CoPS/black phosphorus alkene composite material and application. The method comprises the following steps: (1) stirring black phosphorus alkene, soluble cobalt salt and ammonia water in water for reaction, and performing solid-liquid separation to obtain Co (OH) 2 A black phosphorus alkene heterostructure material; (2) mixing said Co (OH) 2 Black phospholene heterostructure material and P 2 S 5 And carrying out atmosphere protection annealing at 300-450 ℃ to obtain the CoPS/black phosphorus alkene vertical heterostructure material. According to the invention, CoPS nanosheets are vertically loaded on black phosphene, a CoPS/black phosphene vertical heterostructure with a stable structure is constructed, and a large number of active sites can be provided for a catalyst by utilizing a strong coupling effect between heterogeneous interfaces, so thatThereby improving the electrocatalytic performance of the material.
Description
Technical Field
The invention belongs to the field of catalysts for electrocatalytic water decomposition, and particularly relates to a preparation method of a CoPS/black phosphorus alkene vertical heterostructure material, a CoPS/black phosphorus alkene composite material and application.
Background
At present, precious metal catalysts are mainly used for electrocatalytic decomposition of water, but the expensive and scarce precious metal catalysts seriously restrict large-scale industrial application of hydrogen energy, and the development of novel high-efficiency non-precious metal electrocatalysts is the key for realizing the sustainable development of the hydrogen energy industry.
In recent years, the application potential of cobalt phosphosulfurized (CoPS) in the field of electrocatalytic decomposition of water has received much attention. For example, chinese patent application publication No. CN114105113A discloses a method for preparing cobalt nickel phosphide sulfide heterostructure nanosheets, which can be obtained by hydrothermal reaction and phosphating. However, in the practical application process, the single CoPS catalyst is easy to agglomerate to weaken the catalytic performance of the single CoPS catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of a CoPS/black phospholene vertical heterostructure material, and the obtained material can enhance the structural stability, avoid agglomeration of CoPS nanosheets and improve the electrocatalytic performance by constructing a BP heterostructure.
The second purpose of the invention is to provide the CoPS/black phosphorus alkene composite material prepared by the scheme.
The third purpose of the invention is to provide the material obtained by the preparation method of the CoPS/black phosphorus alkene vertical heterostructure material and the application of the CoPS/black phosphorus alkene composite material.
In order to achieve the purpose, the preparation method of the CoPS/black phosphorus alkene vertical heterostructure material adopts the following technical scheme:
a preparation method of a CoPS/black phosphorus alkene vertical heterostructure material comprises the following steps:
(1) stirring the black phosphorus alkene, soluble cobalt salt and ammonia water in water for reaction, and performing solid-liquid separation to obtain Co (OH) 2 A black phosphorus alkene heterostructure material; the molar weight of Co in the soluble cobalt salt is 0.004-0.01 mol per 40-100 mg of black phosphorus alkene;
(2) mixing said Co (OH) 2 Black phosphorus alkene heterostructure material and P 2 S 5 And carrying out atmosphere protection annealing at 300-450 ℃ to obtain the CoPS/black phosphorus alkene vertical heterostructure material.
According to the preparation method of the CoPS/black phosphene vertical heterostructure material, CoPS nanosheets are vertically loaded on black phosphene, a CoPS/black phosphene vertical heterostructure with a stable structure is constructed, and a large number of active sites can be provided for a catalyst by utilizing a strong coupling effect between heterogeneous interfaces, so that the electrocatalysis performance of the material is improved.
In order to better achieve uniform mixing of the substances, preferably, in the step (1), the aqueous dispersion of the black phosphorus alkene, the aqueous solution of the soluble cobalt salt and the ammonia water are mixed to obtain a mixed solution, and the mixed solution is subjected to the stirring reaction. The stirring reaction time is 3-10 min. The stirring speed is 800-1000 r/min.
More preferably, every 20-50 mL of the black phosphorus alkene dispersion liquid corresponds to 40-100 mg of black phosphorus alkene, the amount of the soluble cobalt salt aqueous solution is 20-30 mL, and the amount of the ammonia water is 4-6 mL. More preferably, the black phosphorus alkene is prepared by an electrochemical stripping method; the soluble cobalt salt is cobalt sulfate.
Can utilize P 2 S 5 Is a source of phosphorus and sulfur, made of Co (OH) 2 The heterogeneous structure of the black phosphene is converted into CoPS/black phosphene, and P can be controlled to realize full conversion 2 S 5 Relative excess, preferably, in step (2), Co (OH) 2 Black phospholene heterostructure material and P 2 S 5 The mass ratio of (1): (1-2).
Preferably, in the step (2), the heat preservation time at 300-450 ℃ is 1-2 h. Further preferably, in the step (2), the rate of heating to 300-450 ℃ is 2-4 ℃/min.
The technical scheme of the CoPS/black phosphorus alkene composite material is as follows:
the CoPS/black phosphorus alkene composite material comprises a black phosphorus alkene matrix and a CoPS nanosheet vertically loaded on the black phosphorus alkene matrix, wherein the molar quantity of Co in the CoPS nanosheet is 0.004-0.01 mol per 40-100 mg of black phosphorus alkene.
The CoPS/black phosphorus alkene composite material constructs a black phosphorus alkene and CoPS nanosheet heterostructure, and the CoPS nanosheet is vertically loaded on a black phosphorus alkene sheet layer, so that the unique heterostructure has good structural stability, and is proved to have low over potential and excellent hydrogen evolution and oxygen evolution bifunctional electrocatalysis characteristics.
The material obtained by the preparation method of the CoPS/black phosphorus alkene vertical heterostructure material and the application of the CoPS/black phosphorus alkene composite material as an electrocatalytic decomposition water catalyst.
The material has a stable structure, a regular shape, a lower overpotential and excellent electrocatalytic properties with double functions of hydrogen evolution and oxygen evolution, and is a hydrogen evolution/oxygen evolution double-function fully-decomposed hydroelectric catalyst with great application potential.
Preferably, the electrocatalytic water splitting catalyst is a hydrogen and/or oxygen evolution catalyst.
Drawings
FIG. 1 is a diagram of the process for fabricating a CoPS/black phospholene vertical heterostructure fabricated in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a CoPS/black phosphorus alkene vertical heterostructure prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of a CoPS/black phospholene vertical heterostructure prepared in example 1 of the present invention;
FIG. 4 shows the high resolution transmission electron microscopy characterization results of the CoPS/black phosphorus alkene vertical heterostructure prepared in example 1 of the present invention;
FIG. 5 is a hydrogen evolution linear voltammogram of a CoPS/black phospholene vertical heterostructure prepared in example 1 of the present invention;
FIG. 6 is an oxygen evolution linear voltammogram of a CoPS/black phospholene vertical heterostructure prepared in example 1 of the present invention.
Detailed Description
Aiming at the current situation that the prior CoPS catalyst is easy to agglomerate to weaken the catalytic performance of the CoPS catalyst, the invention constructs the heterostructure electrocatalyst based on dimensional materials to avoid the problems. The strong coupling effect between heterogeneous interfaces can provide a large number of active sites for the catalyst, and the intrinsic catalytic activity of the catalyst can be enhanced by reconstructing the electronic structure of the material.
Two-dimensional layered black phosphorus alkene (BP) has stronger intrinsic hydrophilicity than graphene, can adjust the valence state of a load element, and can form a heterogeneous interface with CoPS through a chemical bond.
The step (1) of the invention is to strip the block black phosphorus into thin-layer black phosphorus alkene by adopting an electrochemical stripping method, and Co (OH) is obtained by a chemical precipitation method 2 The nano-sheets are uniformly and vertically loaded on the surface of the black phosphorus alkene. In the step, the molar weight of Co in the soluble cobalt salt corresponding to each 40-100 mg of the black phosphorus alkene is controlled to be 0.004-0.01 mol. For 40-100 mg of black phosphorus alkene, CoSO 4 ·7H 2 The amount of O is preferably 1 to 3g, more preferably 1.4 to 2.811g, and CoSO is prepared by using water 4 The volume of the solution is preferably 20-30 mL. The dosage of the ammonia water is preferably 4-6 mL. During the stirring reaction, the rotation speed is preferably 800-1000 r/min, and the stirring time is preferably 4-6 min.
And (2) preparing the CoPS/black phosphorus alkene vertical heterostructure by an atmosphere protection annealing method. In this step, P 2 S 5 And Co (OH) 2 The mass ratio of the/black phosphorus alkene heterostructure material is preferably (1-2): 1. The heat preservation temperature is preferably 350-450 ℃. The heat preservation time is preferably 1-2 h.
The following describes the practice of the present invention in detail with reference to specific examples. In the following examples, the procedure of preparing thin-layer black phospholene by electrochemical stripping was carried out according to the previous research results (CN111252806B) of the inventors. The obtained thin-layer black phosphorus alkene is a black phosphorus alkene nano-sheet, and the thickness of the black phosphorus alkene nano-sheet is 4-8 nm; the two-dimensional size is (2.8 to 3.2) × (1.5 to 2.6) μm.
First, specific embodiment of preparation method of CoPS/black phosphorus alkene vertical heterostructure material
Example 1
The preparation method of the CoPS/black phosphorus alkene vertical heterostructure material of the embodiment is shown in fig. 1, and comprises the following steps:
(1) 100mg of black phosphenes (nanoplatelets) were dispersed in 20mL of deionized water to form 20mL of black phosphene dispersion. The mass of the CoSO was 2.811g 4 ·7H 2 The O powder was dissolved in 30mL of deionized water to form a cobalt sulfate solution. Adding a cobalt sulfate solution into 20mL of black phosphorus dispersion liquid at a stirring speed of 900r/min to form a mixed solution; dropwise adding 5mL of ammonia water (the mass fraction is 25%) into the mixed solution, continuously stirring for 5min, repeatedly carrying out centrifugal cleaning on a precipitation product, drying, and collecting to obtain Co (OH) 2 a/BP heterostructure powder.
(2) Control P 2 S 5 Powder with Co (OH) 2 The mass ratio of the black phosphorus alkene heterostructure powder is 2:1, and P is added 2 S 5 Placing the powder in the inlet of a tube furnace, and adding Co (OH) 2 Putting the black phosphorus alkene heterostructure powder at the gas outlet of a tubular furnace, introducing argon gas as protective atmosphere, controlling the heating rate to be 2 ℃/min, the heat preservation temperature to be 350 ℃, keeping the heat preservation time to be 2h, cooling to the room temperature along with the furnace, and finally obtaining the CoPS/BP vertical heterostructure powder.
Example 2
The preparation method of the CoPS/black phosphorus alkene vertical heterostructure material of the embodiment comprises the following steps:
(1) 50mg of black phosphorus alkene was dispersed in 20mL of deionized water to form 20mL of black phosphorus alkene dispersion. CoSO with the mass of 1.4g 4 ·7H 2 The O powder was dissolved in 30mL of deionized water to form a cobalt sulfate solution. Adding the mixture into 20mL of black phosphorus alkene dispersion liquid at a stirring speed of 800r/min to form a mixed solution; dropwise adding 6mL of ammonia water into the mixed solution, continuously stirring for 6min, repeatedly performing centrifugal cleaning and drying on the precipitate, and collecting to obtain Co (OH) 2 a/BP heterostructure powder.
(2) By P 2 S 5 Preparation of CoPS/BP vertical heterostructure as phosphorus and sulfur source, P 2 S 5 Powder with Co (OH) 2 The mass ratio of the/BP heterostructure powder is 1: 1. In the step, the heating rate is controlled to be 3 ℃/min, the heat preservation temperature is controlled to be 400 ℃, and the temperature is keptThe temperature and time are 1.5h, and CoPS/BP vertical heterostructure powder can be obtained finally.
Example 3
The preparation method of the CoPS/black phosphorus alkene vertical heterostructure material of the embodiment comprises the following steps:
(1) 75mg of black phosphene was dispersed in 20mL of deionized water to form 20mL of black phosphene dispersion. 2.1g of CoSO 4 ·7H 2 Dissolving O powder in 30mL of deionized water; slowly adding the mixture into 20mL of black phosphorus alkene dispersion liquid at a stirring speed of 1000r/min to form a mixed solution; dropwise adding 4mL of ammonia water into the mixed solution, continuously stirring for 4min, repeatedly performing centrifugal cleaning and drying on the precipitate, and collecting to obtain Co (OH) 2 a/BP heterostructure powder;
(2) by P 2 S 5 Preparation of CoPS/BP vertical heterostructure as phosphorus source and sulfur source, P 2 S 5 Powder with Co (OH) 2 The mass ratio of the black phosphorus alkene heterostructure powder is 2: 1. In the step, the heating rate is 4 ℃/min, the heat preservation temperature is 450 ℃, the heat preservation time is 1h, and finally the CoPS/BP vertical heterostructure powder can be obtained.
Specific examples of two, CoPS/Black Phosphorenes composite materials
Example 4
The CoPS/black phosphorus alkene composite material of this embodiment is a product obtained by the method of embodiment 1, and includes a black phosphorus alkene substrate and a CoPS nanosheet vertically loaded on the black phosphorus alkene substrate, where a ratio of a mass of the black phosphorus alkene to a molar weight of Co in the CoPS nanosheet is 100 mg: 0.01 mol.
SEM analysis was performed on the CoPS/black phospholene vertical heterostructure material prepared by the method of example 1, and the corresponding SEM image is shown in FIG. 2. As can be seen from FIG. 2, thin and small CoPS nanosheets are uniformly and vertically coated on the surface of the black phospholene, so that a heterostructure is formed, and the agglomeration phenomenon of the CoPS nanosheets is effectively avoided.
XRD analysis of the CoPS/black phospholene vertical heterostructure material obtained by the method of example 1 is shown in FIG. 3. The diffraction peaks in FIG. 3 correspond to the (021) plane of BP and the (111), (200), (210), (211), (220) and (311) planes of CoPS, respectively, confirming that the two phases of BP and CoPS coexist in the material.
The CoPS/black phosphorus alkene vertical heterostructure material prepared by the method of example 1 is observed by a transmission electron microscope, and the result is shown in fig. 4. As can be seen from FIG. 4, the CoPS nanosheets are uniformly coated on the surface of the black phospholene, which is consistent with the characterization result of a scanning electron microscope.
Specific examples of application of CoPS/black phosphorus alkene composite material
Example 5
The application of the CoPS/black phosphorus alkene composite material of this embodiment is to use the CoPS/black phosphorus alkene composite material obtained in example 1 as a hydrogen evolution catalyst, specifically, 4mg of CoPS/black phosphorus alkene vertical heterostructure material and 1mg of acetylene black are uniformly ground in a mortar and poured into a 1.5mL sample bottle, 900 μ L of isopropanol, 70 μ L of deionized water and 30 μ L of 5 wt.% Nafion solution are sequentially added, after the mixed solution is subjected to ultrasound for 1.5h, 5 μ L of suspension is dropped on a common platinum carbon electrode (diameter is 3mm), and the suspension is naturally dried to form a film, which is used as a working electrode. And (3) performing electrochemical performance test in a three-phase electrolytic cell at room temperature by using the Shanghai Chenghua CHI650 electrochemical workstation.
When the catalyst is used as a hydrogen evolution electrocatalyst, the counter electrode is a graphite rod, the reference electrode is a saturated Ag/AgCl electrode, the electrolyte is a 1M KOH solution, the test speed of the current potential volt-ampere characteristic curve is 5mV/s, and the test range is-0.8 to-1.7V vs Ag/AgCl.
Example 6
The CoPS/black phosphorus composite material of the present example is applied by using the CoPS/black phosphorus composite material obtained in example 1 as an oxygen evolution catalyst, and is different from example 5 in that: when the graphene oxide material is used as an oxygen evolution electrocatalyst, the counter electrode is a graphite rod, the reference electrode is a saturated Hg/HgO electrode, the electrolyte is a 1M KOH solution, the current potential volt-ampere characteristic curve testing speed is 5mV/s, and the testing range is 0-0.8V vs Hg/HgO.
Fourth, example of experiment
Due to the influence of factors such as activation potential barrier, solution resistance, contact resistance and ion migration in the reaction process, the application of voltage exceeding the theoretical potential is required to promote hydrogen evolution and oxygen evolutionThe process occurs, and the potential exceeding the theoretical voltage is the overpotential. Generally, the current density can be measured by measuring 10 or 20mA cm -2 Time required overpotential (η) 10 Or η 20 ) The higher the overpotential is, the higher the catalytic activity of the material is.
Experimental example 1 Hydrogen evolution Performance test
The hydrogen evolution performance test was carried out under the conditions of example 5, and the hydrogen evolution linear voltammograms for the different materials are shown in FIG. 5. Wherein 1.22g of CoPS powder (0.01 mol; prepared according to the method of example 1) was ground with 100mg of black phospholene nanoplatelet powder (BP; same as example 1), ultrasonically mixed for 1h, and dried. Subsequently, 4mg of the mixed powder (CoPS + BP) was taken out for the sampling and hydrogen/oxygen evolution performance test of the catalyst sample.
As can be seen from fig. 5, the hydrogen evolution catalytic performance of the CoPS/black phospholene vertical heterostructure prepared in example 1 is significantly improved compared with that of BP, CoPS and CoPS + BP mixed samples, which indicates that the hydrogen evolution performance of the perpendicular heterostructure for electrocatalytic decomposition of water is excellent.
The composite material of example 1 was used as a hydrogen evolution catalyst at a current density of 10 or 20mA cm -2 The overpotential at time is 190mV or 231 mV.
Experimental example 2 oxygen evolution Performance test
The oxygen evolution performance test was performed under the conditions of example 6, and the oxygen evolution linear voltammograms of the different materials are shown in FIG. 6.
As can be seen from fig. 6, the oxygen evolution catalytic performance of the CoPS/black phospholene vertical heterostructure prepared in example 1 is significantly improved compared with that of BP, CoPS and CoPS + BP mixed samples, which indicates that the oxygen evolution performance of the perpendicular heterostructure prepared in example 1 through electrocatalysis excellent in water decomposition.
The composite material of example 1 was used as an oxygen evolution catalyst at a current density of 10 or 20mA cm -2 The overpotential at time was 314mV or 344 mV.
Claims (10)
1. A preparation method of a CoPS/black phosphorus alkene vertical heterostructure material is characterized by comprising the following steps:
(1) mixing black phosphorus alkene, soluble cobalt salt and ammonia waterStirring the mixture in water to react, and performing solid-liquid separation to obtain Co (OH) 2 A black phosphorus alkene heterostructure material; the molar weight of Co in the soluble cobalt salt is 0.004-0.01 mol per 40-100 mg of black phosphorus alkene;
(2) mixing said Co (OH) 2 Black phospholene heterostructure material and P 2 S 5 And carrying out atmosphere protection annealing at 300-450 ℃ to obtain the CoPS/black phosphorus alkene vertical heterostructure material.
2. The method according to claim 1, wherein in the step (1), the aqueous dispersion of black phosphene, the aqueous solution of soluble cobalt salt, and ammonia water are mixed to obtain a mixture, and the mixture is subjected to the stirring reaction.
3. The method for preparing a CoPS/black phosphorus alkene vertical heterostructure material according to claim 2, wherein each 20-50 mL of black phosphorus alkene dispersion solution corresponds to 40-100 mg of black phosphorus alkene, 20-30 mL of aqueous solution corresponding to soluble cobalt salt, and 4-6 mL of aqueous ammonia.
4. The method of claim 3, wherein the black phosphene is produced by electrochemical lift-off; the soluble cobalt salt is cobalt sulfate.
5. The method of claim 1, wherein in step (2), Co (OH) is added to form a CoPS/black phospholene vertical heterostructure material 2 Black phosphorus alkene heterostructure material and P 2 S 5 The mass ratio of (1): (1-2).
6. The method for preparing a CoPS/black phosphorus alkene vertical heterostructure material of claim 1 or 5, wherein in the step (2), the holding time at 300-450 ℃ is 1-2 h.
7. The method for preparing a CoPS/black phosphorus alkene vertical heterostructure material according to claim 6, wherein in the step (2), the rate of heating to 300-450 ℃ is 2-4 ℃/min.
8. The CoPS/black phosphorus alkene composite material is characterized by comprising a black phosphorus alkene matrix and CoPS nanosheets vertically loaded on the black phosphorus alkene matrix, wherein the molar quantity of Co in each 40-100 mg of black phosphorus alkene corresponding to the CoPS nanosheets is 0.004-0.01 mol.
9. The material obtained by the preparation method of the CoPS/black phosphorus alkene vertical heterostructure material according to any one of claims 1-7 and the application of the CoPS/black phosphorus alkene composite material according to claim 8 as an electrocatalytic decomposition water catalyst.
10. Use according to claim 9, wherein the electrocatalytic water splitting catalyst is a hydrogen and/or oxygen evolution catalyst.
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