CN112023952A - Cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material and preparation method and application thereof - Google Patents
Cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material and preparation method and application thereof Download PDFInfo
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- -1 Cobalt selenide-molybdenum selenide Chemical compound 0.000 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000004964 aerogel Substances 0.000 title claims abstract description 29
- 239000002071 nanotube Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 25
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 229910018864 CoMoO4 Inorganic materials 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 17
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 13
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 11
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 11
- 238000007710 freezing Methods 0.000 claims abstract description 9
- 230000008014 freezing Effects 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229930182478 glucoside Natural products 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- 229930182470 glycoside Natural products 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 238000004873 anchoring Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000001816 cooling Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000000017 hydrogel Substances 0.000 abstract 1
- 238000010257 thawing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 34
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 6
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 description 6
- 239000003929 acidic solution Substances 0.000 description 5
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/23—
-
- B01J35/33—
-
- B01J35/40—
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material and a preparation method and application thereof. The technical scheme is as follows: ultrasonically dispersing graphene oxide in deionized water, adding ascorbic acid and alkyl glucoside, stirring, transferring into a hydrothermal reaction kettle, reacting at 80 ℃ for 12h, taking out reduced graphene oxide hydrogel (GH), cooling at room temperature, completely freezing at-18 ℃ for 6h, thawing at room temperature, and drying at 60 ℃ to obtain the reduced graphene oxide aerogel(GA). Mixing CoMoO4Dispersing in deionized water, adding selenium powder, hydrazine hydrate and GA, stirring uniformly, transferring into a hydrothermal reaction kettle, reacting at 180 ℃ for 24h, and drying to obtain the MS-CS NTs/GA composite material. The preparation method is simple, green and pollution-free, and the prepared catalyst has high hydrogen production performance and practical applicability.
Description
Technical Field
The invention is applied to the technical field of hydrogen production by electrolyzing water, relates to a preparation method and application of a cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material, and belongs to the technical field of micro-nano preparation.
Background
With the continuous increase of global population and the continuous development of society, the demand of human beings for energy is increasing, and the production and life of human beings are threatened by the environmental problems caused by energy shortage and energy consumption. The hydrogen is used as a novel clean energy source, is an ideal choice for replacing the traditional fossil fuel, and the hydrogen can be used as an ideal secondary energy source, so that the hydrogen has a very wide application prospect. The current industrial hydrogen production process mainly comprises petrochemical catalytic cracking and natural gas steam reforming hydrogen production, and the process does not conform to the current strategy of 'green sustainable development', so that the key point is to find an efficient, clean and sustainable method for preparing hydrogen.
Among the hydrogen production methods, the electrochemical catalysis method for preparing hydrogen is clean, pollution-free, convenient and fast. Among the catalysts used for electrochemical catalytic hydrogen production, noble metal catalysts such as platinum and the like have extremely low overpotential and very good hydrogen evolution effect, but the noble metal catalysts are expensive, have low self storage capacity and high cost, so that the development and the application of the noble metal catalysts in the aspect of hydrogen production by water electrolysis are limited. Transition metal chalcogenide (TMD) materials are receiving increasing attention and are being extensively and intensively studied in the aspect of electrocatalytic hydrogen evolution. However, the single TMD material is easy to agglomerate, so that the exposed active sites are reduced, the overpotential is large in the process of electrolyzing water, and the hydrogen evolution effect is greatly reduced. By anchoring the TMD material on the reduced graphene oxide aerogel, the problem of excessive agglomeration of the TMD material can be avoided. The use of reduced graphene oxide aerogel (GA) as a carrier allows the TMD material to be uniformly dispersed on the aerogel, thereby exposing more active sites. In addition, the reduced graphene oxide aerogel has excellent conductivity and a highly porous structure, and can further accelerate the transmission of electrolyte and the transfer of electrons.
Disclosure of Invention
The invention aims to provide preparation and application of a cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material (MS-CS NTs/GA composite material)4Adding selenium powder, hydrazine hydrate and GA as a precursor, and anchoring the cobalt selenide-molybdenum selenide hollow nanotube on the GA.
In order to achieve the purpose, the technical scheme of the invention is as follows: a cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material is prepared by using CoMoO as raw material4Adding selenium powder, hydrazine hydrate and GA as a precursor to react, and anchoring the cobalt selenide-molybdenum selenide hollow nanotube on the GA to obtain the cobalt selenide-molybdenum selenide hollow nanotube.
A preparation method of a cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material comprises the following steps:
1) dissolving graphene oxide prepared by an improved Hummers method in deionized water, performing ultrasonic dispersion for 30-60min, adding ascorbic acid and alkyl glucoside, stirring, transferring into a hydrothermal reaction kettle for hydrothermal reaction to obtain GH, freezing, and drying to obtain GA;
2) mixing CoMoO4Ultrasonically dispersing in deionized water, then adding selenium powder, hydrazine hydrate and GA, stirring uniformly, transferring into a hydrothermal reaction kettle for hydrothermal reaction, and drying to obtain MS-CS NTs/GA.
Preferably, in the preparation method of the cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material, the weight ratio of graphene oxide: ascorbic acid: alkyl glycoside ═ 1: 1-3: 1-3.
Preferably, in the preparation method of the cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material, in the step 1), the stirring speed is 2500-.
Preferably, in the preparation method of the cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material, in the step 1), the hydrothermal reaction temperature is 70-90 ℃, and the reaction time is 10-15 hours.
Preferably, in the preparation method of the cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material, in the step 2), the CoMoO is added4The mol ratio of the selenium powder to the selenium powder is 1:1-1: 6.
Preferably, in the preparation method of the cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material, in the step 2), the mass ratio of the CoMoO is4Hydrazine hydrate, wherein GA is 10-30: 1: 5-10.
Preferably, in the preparation method of the cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material, in the step 2), the temperature of the hydrothermal reaction is 170-.
The cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material is applied to hydrogen production by electrocatalysis decomposition of water.
The invention fully utilizes the unique layered structure of the molybdenum selenide to form a structure in which the molybdenum selenide and the cobalt selenide are mutually staggered, thereby preventing the molybdenum selenide and the cobalt selenide from excessively agglomerating. The cobalt selenide-molybdenum selenide composite material prepared by the invention has a hollow nano tubular structure, and the conductivity of the cobalt selenide-molybdenum selenide composite material is improved by taking GA as a carrier and adjusting the size of pores of the GA.
The invention has the beneficial effects that:
1) the cobalt selenide-molybdenum selenide composite material prepared by the invention is in a hollow nano tube shape, and provides a large number of active sites for electrocatalytic water decomposition. Meanwhile, cobalt selenide and molybdenum selenide have synergistic effect, so that the material has better electrocatalysis effect and stability.
2) In the preparation process, the cobalt selenide-molybdenum selenide composite material is anchored on the GA, and the GA as a carrier does not participate in chemical reaction and can be directly used as a working electrode so as to facilitate subsequent application and test.
3) The MS-CS NTs/GA composite material prepared by the invention has good electrocatalytic water decomposition effect, and the current density is-10 mA/cm2The overpotential of the voltage is 167mV, and the overpotential is smaller. In contrast to other materials, e.g. MoS2/GA、CoSe2/GA、MoSe2-CoSe2The material of the invention has smaller overpotential, which shows better electrocatalysis effect, greatly reduces the energy required by water electrolysis and improves the problem of larger overpotential existing in water electrolysis.
4) The material obtained by adopting specific reaction conditions and raw materials through a one-pot hydrothermal method has a good electrocatalytic water decomposition effect, and the preparation method is simple and low in cost. Easy to realize industrial production.
In conclusion, the catalyst prepared by the invention has better electrocatalytic water decomposition capability and lower overpotential, and the synthesis method is simple and has practical and reliable applicability.
Drawings
FIG. 1a is CoMoO in example 1 of the present invention4XRD pattern of (a).
FIG. 1b is a CoMoO representation of the invention in example 14Scanning electron micrograph (c).
FIG. 1c is a scanning electron micrograph of MS-CS NTs in example 1 of the present invention.
FIG. 1d is a scanning electron micrograph of GA in example 1 of the present invention
FIG. 1e is a scanning electron micrograph of MS-CS NTs/GA in example 1 of the present invention.
FIG. 1f is an XRD pattern of MS-CS NTs/GA, GA and MS-CS NTs in example 1 of the present invention.
FIG. 2 is a graph showing the electrocatalytic performance test of MS-CS NTs/GA in example 1 of the present invention.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
Example 1
Preparing graphene oxide: 1g of graphite powder, 3g of potassium permanganate and 60mL of concentrated sulfuric acid are respectively frozen at the temperature of minus 18 ℃ for 30 min. Then mixing the materials in a flask, and stirring for 2 hours in an ice-water bath; and moving the solution into an oil bath at 50 ℃ to stir for 6h, then slowly adding 120mL of deionized water, adding hydrogen peroxide (30%) until no bubbles are generated in the solution, finally centrifuging the solution until the pH value is 7, and drying the solution to obtain the graphene oxide.
CoMoO4The preparation of (1): 0.4839g of sodium molybdate dihydrate, 0.5821g of cobalt nitrate hexahydrate and deionized water are taken and stirred at room temperature, then the mixture is moved into a hydrothermal reaction kettle to react for 12 hours at 180 ℃, the mixture is cooled to room temperature and then filtered, and the CoMoO is obtained after drying at 60 DEG C4。
Preparing an MS-CS NTs composite material: 110mg of CoMoO4Dispersing in 64mL deionized water, then adding 158mg selenium powder and 6mL hydrazine hydrate, stirring uniformly, transferring into a hydrothermal reaction kettle, reacting for 24h at 180 ℃, and drying at 60 ℃ to obtain MS-CS NTs.
Preparation of MS-CS NTs/GA composite (r ═ 3500):
1) ultrasonically dispersing 120mg of graphene oxide in 10mL of deionized water for 60min, adding 240mg of ascorbic acid, then adding 240mg of alkyl glycoside, stirring for 5min at 3500rpm, then transferring into a hydrothermal reaction kettle, reacting for 12h at 80 ℃ to obtain GH, taking out the GH, cooling at room temperature, completely freezing for 6h at-18 ℃, unfreezing at room temperature, and then drying at 60 ℃ to obtain GA.
2) 110mg of CoMoO4Dispersing in 64mL deionized water, then adding 158mg selenium powder, 6mL hydrazine hydrate and 40mg GA, stirring uniformly, transferring into a hydrothermal reaction kettle, reacting for 24h at 180 ℃, and drying at 60 ℃ to obtain MS-CS NTs/GA.
And (3) detection:
FIG. 1a is CoMoO4XRD pattern of (a). The successful synthesis of the material is shown by comparison with a standard spectrogram.
FIG. 1b is CoMoO4Scanning electron micrograph (c). CoMoO4Has a long linear shape and a smooth surface.
FIG. 1c is a scanning electron micrograph of GA. As can be seen from the figure, there are many large pores with a diameter of 100-300um, which is more favorable for the uniform distribution of MS-CS NTs in GA.
FIG. 1d is a scanning electron micrograph of MS-CS NTs. As can be seen from the figure, the cobalt selenide and molybdenum selenide composite material presents a hollow tubular shape, and more active sites can be exposed.
FIG. 1e is a scanning electron micrograph of MS-CS NTs/GA. As can be seen from the figure, the aerogel prepared by adding the alkyl glycoside and stirring has large pores with the pore diameter of about 100-300um, so that the MS-CS NTs are uniformly distributed in the pores, and the agglomeration phenomenon does not occur.
FIG. 1f is an XRD pattern of GA, MS-CS NTs and MS-CS NTs/GA. After comparison with a standard spectrogram, peaks at 30.7, 34.5, 35.9, 47.7, 50.2 and 63.3 respectively correspond to (101), (111), (120), (211), (002) and (122) crystal lattice planes of cobalt selenide, and a small peak at 14.4 is a (002) crystal lattice plane of molybdenum selenide, which indicates that the material is successfully prepared.
FIG. 2 is a graph showing the electrocatalytic performance test of MS-CS NTs/GA in example 1 of the present invention.
Example 2 preparation of MS-CS NTs/GA composite (r. 2500)
1) And ultrasonically dispersing 120mg of graphene oxide in 10mL of deionized water, adding 240mg of ascorbic acid, adding 240mg of alkyl glycoside, stirring for 5min at 2500rpm, transferring into a hydrothermal reaction kettle, reacting at 80 ℃ for 12h to obtain GH, taking out the GH, cooling at room temperature, completely freezing at-18 ℃ for 6h, unfreezing at room temperature, and drying at 60 ℃ to obtain GA.
2) 110mg of CoMoO4Dispersing in 64mL of deionized water, then adding 158mg of selenium powder, 6mL of hydrazine hydrate and 40mg of GA, stirring uniformly, transferring into a hydrothermal reaction kettle, reacting for 24h at 180 ℃, and drying at 60 ℃ to obtain MS-CS NTs/GA.
Example 3 preparation of MS-CS NTs/GA composite (r. 3000)
1) And ultrasonically dispersing 120mg of graphene oxide in 10mL of deionized water, adding 240mg of ascorbic acid, adding 240mg of alkyl glycoside, stirring at 3000rpm for 5min, transferring into a hydrothermal reaction kettle, reacting at 80 ℃ for 12h, taking out GH, cooling at room temperature, completely freezing at-18 ℃ for 6h, unfreezing at room temperature, and drying at 60 ℃ to obtain GA.
2) 110mg of CoMoO4Dispersing in a certain amount of deionized water, then adding 158mg of selenium powder, 6mL of hydrazine hydrate and 40mg of GA, stirring uniformly, transferring into a hydrothermal reaction kettle, reacting for 24h at 180 ℃, and drying at 60 ℃ to obtain MS-CS NTs/GA.
Example 4 preparation of MS-CS NTs/GA composite (r ═ 4000)
1) And ultrasonically dispersing 120mg of graphene oxide in 10mL of deionized water, adding 240mg of ascorbic acid, adding 240mg of alkyl glycoside, stirring at 4000rpm for 5min, transferring into a hydrothermal reaction kettle, reacting at 80 ℃ for 12h, taking out GH, cooling at room temperature, completely freezing at-18 ℃ for 6h, unfreezing at room temperature, and drying at 60 ℃ to obtain GA.
2) 110mg of CoMoO4Dispersing in a certain amount of deionized water, then adding 158mg of selenium powder, 6mL of hydrazine hydrate and 40mg of GA, stirring uniformly, transferring into a hydrothermal reaction kettle, reacting for 24h at 180 ℃, and drying at 60 ℃ to obtain MS-CS NTs/GA.
Example 5 preparation of MS-CS NTs/GA composite (r 4500)
1) And ultrasonically dispersing 120mg of graphene oxide in 10mL of deionized water, adding 240mg of ascorbic acid, adding 240mg of alkyl glycoside, stirring for 5min at 4500rpm, transferring into a hydrothermal reaction kettle, reacting at 80 ℃ for 12h, taking out GH, cooling at room temperature, completely freezing at-18 ℃ for 6h, unfreezing at room temperature, and drying at 60 ℃ to obtain GA.
2) 110mg of CoMoO4Dispersing in a certain amount of deionized water, then adding 158mg of selenium powder, 6mL of hydrazine hydrate and 40mg of GA, stirring uniformly, transferring into a hydrothermal reaction kettle, reacting for 24h at 180 ℃, and drying at 60 ℃ to obtain MS-CS NTs/GA.
Example 6 preparation of MS-CS NTs/GA composite (r ═ 5000)
1) And ultrasonically dispersing 120mg of graphene oxide in 10mL of deionized water, adding 240mg of ascorbic acid, adding 240mg of alkyl glycoside, stirring for 5min at 5000rpm, transferring into a hydrothermal reaction kettle, reacting at 80 ℃ for 12h, taking out GH, cooling at room temperature, completely freezing at-18 ℃ for 6h, unfreezing at room temperature, and drying at 60 ℃ to obtain GA.
2) 110mg of CoMoO4Dispersing in a certain amount of deionized water, then adding 158mg of selenium powder, 6mL of hydrazine hydrate and 40mg of GA, stirring uniformly, transferring into a hydrothermal reaction kettle, reacting for 24h at 180 ℃, and drying at 60 ℃ to obtain MS-CS NTs/GA.
Example 7 electrochemical Performance testing of MS-CS NTs/GA composite materials
The test method is as follows:
constructing a standard three-electrode system, taking 4mg of the MS-CS NTs/GA (r is 3500) material prepared in example 1, 50 mu L of Nafion solution, 200 mu L of deionized water and 750 mu L of absolute ethyl alcohol, carrying out ultrasonic treatment to a completely dispersed state, and then taking 10 mu L of the solution to drop on a glassy carbon electrode to serve as a working electrode; the graphite rod is a counter electrode; the reference electrode is a saturated calomel electrode; electrolyte of 0.5mol/L H2SO4And (3) solution. The test equipment employed is an electrochemical workstation.
FIG. 2 is a graph showing the electrocatalytic performance test curve of MS-CS NTs/GA prepared in example 1 at-10 mA/cm2The overpotential at this time was 167 mV. Compared with other invention materials (MoS disclosed in patent No. CN 107670679A)2the/rGO-CN is at-10 mA/cm2The overpotential at time was 203 mV; Ag-CoSe disclosed in patent No. CN106563813B2At-10 mA/cm2Overpotential of time is 320mV), and the electrocatalyst prepared by MS-CS NTs/GA at 3500rpm shows higher catalytic performance in an acidic solution. It can be seen from the figure that the catalytic performance of the materials synthesized at different stirring speeds is also different. The overpotential is the largest at 2500r because the pore size of GA is smaller when the rotation speed is smaller, and the flow of electrolyte is hindered because the pore channels are blocked by the agglomeration of MS-CS NTs. The overpotential is the minimum at 3500r, which shows that the pore size of GA at the rotation speed not only ensures the electrolyte solution to flow on the surface of the electrode, but also prevents the MS-CS NTs from excessively agglomerating, thereby exposing more active sites. When the rotating speed exceeds 3500At r, the pore size of GA increases with the increase of the rotation speed, but the excessive pore size accelerates the flow of the electrolyte solution on the electrode surface, but also causes the MS-CS NTs to be excessively agglomerated together, so that the number of exposed active sites is reduced, and the catalytic performance is reduced. When the rotating speed is low and the rotating speed is high, the overpotential is increased, which shows that the flowing of the electrolyte solution on the electrode surface and the quantity of exposed active sites have important influence on the catalytic performance.
Example 8
In contrast to example 7, 4mg of the MS-CS NTs/GA material (r. 2500) prepared in example 2 was used for electrochemical performance testing, and the MS-CS NTs/GA material prepared in example 2 was used at a current density of-10 mA/cm2The overpotential under (1) is 269mV compared to other materials (Ag-CoSe disclosed in patent No. CN 106563813B)2At-10 mA/cm2The overpotential at this time was 320mV), indicating that the electrocatalyst made at 2500rpm also exhibited higher catalytic performance in acidic solution.
Example 9
In contrast to example 7, 4mg of the MS-CS NTs/GA material prepared in example 3 (r 3000) was used for electrochemical performance testing, and the MS-CS NTs/GA material prepared in example 3 was used at a current density of-10 mA/cm2The overpotential under (1) was 201mV compared with other materials (Ag-CoSe disclosed in patent No. CN 106563813B)2At-10 mA/cm2The overpotential of time was 320mV), the material prepared by the present invention has a lower overpotential, indicating that the electrocatalyst prepared at 3000rpm also exhibits higher catalytic performance in acidic solution.
Example 10
In contrast to example 7, 4mg of the material prepared in example 4 was used for electrochemical performance testing, and the MS-CS NTs/GA material prepared in example 4 (r: 4000) was used at a current density of-10 mA/cm2The overpotential under (1) is 221mV compared with other materials (Ag-CoSe disclosed in patent No. CN 106563813B)2At-10 mA/cm2The overpotential of the time is 320mV), the material prepared by the invention has lower overpotential, and the condition that the electrocatalyst prepared at 4000rpm is acidic is shownThe solution also shows higher catalytic performance.
Example 11
In contrast to example 7, 4mg of the MS-CS NTs/GA material prepared in example 5 (r 4500) was used for electrochemical performance testing, and the material prepared in example 5 was used at a current density of-10 mA/cm2The overpotential under (1) is 231mV compared with the material used (Ag-CoSe disclosed in patent No. CN 106563813B)2At-10 mA/cm2The overpotential of time was 320mV), the material prepared by the present invention had a lower overpotential, indicating that the electrocatalyst prepared at 4500rpm also exhibited higher catalytic performance in acidic solution.
Example 12
In contrast to example 7, 4mg of the MS-CS NTs/GA material prepared in example 6 (r: 5000) was used for electrochemical performance testing, and the material prepared in example 6 was used at a current density of-10 mA/cm2The overpotential under (1) is 251mV compared with other materials (Ag-CoSe disclosed in patent No. CN 106563813B)2At-10 mA/cm2The overpotential of time was 320mV), the material prepared by the present invention has a lower overpotential, indicating that the electrocatalyst prepared at 5000rpm also exhibits higher catalytic performance in acidic solution.
Claims (9)
1. The cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material is characterized in that the composite material is CoMoO4Adding selenium powder, hydrazine hydrate and GA as a precursor to react, and anchoring the cobalt selenide-molybdenum selenide hollow nanotube on the GA to obtain the cobalt selenide-molybdenum selenide hollow nanotube.
2. A preparation method of a cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material is characterized by comprising the following steps:
1) dissolving graphene oxide prepared by an improved Hummers method in deionized water, performing ultrasonic dispersion for 30-60min, adding ascorbic acid and alkyl glucoside, stirring, transferring into a hydrothermal reaction kettle for hydrothermal reaction to obtain GH, freezing, and drying to obtain GA;
2) mixing CoMoO4Ultrasonically dispersing in deionized water, then adding selenium powder, hydrazine hydrate and GA, stirring uniformly, transferring into a hydrothermal reaction kettle for hydrothermal reaction, and drying to obtain MS-CS NTs/GA.
3. The method for preparing the cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material as claimed in claim 2, wherein the method comprises the following steps: according to the mass ratio, the graphene oxide: ascorbic acid: alkyl glycoside ═ 1: 1-3: 1-3.
4. The method for preparing the cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material as claimed in claim 2, wherein the method comprises the following steps: in the step 1), the stirring speed is 2500-.
5. The method for preparing the cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material as claimed in claim 2, wherein the method comprises the following steps: in the step 1), the temperature of the hydrothermal reaction is 70-90 ℃, and the reaction time is 10-15 h.
6. The method for preparing the cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material as claimed in claim 2, wherein the method comprises the following steps: in step 2), CoMoO4The mol ratio of the selenium powder to the selenium powder is 1:1-1: 6.
7. The method for preparing the cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material as claimed in claim 2, wherein the method comprises the following steps: in the step 2), according to the mass ratio, CoMoO4Hydrazine hydrate, wherein GA is 10-30: 1: 5-10.
8. The method for preparing the cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite material as claimed in claim 2, wherein the method comprises the following steps: in the step 2), the temperature of the hydrothermal reaction is 170-190 ℃, and the reaction time is 20-30 h.
9. The use of the cobalt selenide-molybdenum selenide hollow nanotube/reduced graphene oxide aerogel composite as claimed in claim in the electrocatalytic decomposition of water to produce hydrogen.
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