CN106622295A - Cobalt disulfide/graphene-graphene nanoribbon composite aerogel and preparation method and application thereof - Google Patents
Cobalt disulfide/graphene-graphene nanoribbon composite aerogel and preparation method and application thereof Download PDFInfo
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- CN106622295A CN106622295A CN201611219601.7A CN201611219601A CN106622295A CN 106622295 A CN106622295 A CN 106622295A CN 201611219601 A CN201611219601 A CN 201611219601A CN 106622295 A CN106622295 A CN 106622295A
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 100
- 239000004964 aerogel Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002074 nanoribbon Substances 0.000 title abstract 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract description 4
- 238000004108 freeze drying Methods 0.000 claims abstract description 3
- 239000002127 nanobelt Substances 0.000 claims description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- 239000007788 liquid Substances 0.000 claims description 35
- 239000006185 dispersion Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000009938 salting Methods 0.000 claims description 14
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 241000209094 Oryza Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- 239000000126 substance Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 description 13
- 239000010439 graphite Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/23—
-
- 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
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
Abstract
The invention relates to cobalt disulfide/graphene-graphene nanoribbon composite aerogel and a preparation method and application thereof. The aerogel is prepared through in-situ growth of cobalt disulfide particles on graphene-graphene nanoribbon composite aerogel. The preparation method includes a freeze-drying ice template method and a solvothermal method. The prepared graphene-graphene nanoribbon composite aerogel has the advantages of the large specific area, excellent electrical conductivity, stable chemical properties, good mechanical properties and the like, and is a high-performance electro-catalysis material.
Description
Technical field
The invention belongs to transient metal sulfide-material with carbon element field, more particularly to a kind of cobalt disulfide/Graphene-graphite
Alkene nanobelt composite aerogel and its preparation method and application.
Background technology
With the increase of energy-output ratio, the active demand of cleaning and regenerative resource promotes people for the spy of Hydrogen Energy
Rope.Sustainable hydrogen manufacturing is the essential condition of following hydrogen economy, and electrolysis water is considered as the hydrogen producing technology for most having future.Generally
Electrode material be precious metal material, such as platinum is expensive.And highly active base metal and its compound, due to its cost
Low, efficiency high advantage is by extensive concern.
Graphene is the graphite of monolithic layer, by sp2Carbon atom Hexagonal array is formed, and possesses higher inside carrier mobility
Rate, good thermal conductivity, high-specific surface area, and excellent mechanical strength, therefore all have broad application prospects in many aspects.
But in practical application, because the very strong π-π of graphene film interlayer interact, easily again stacking forms the knot of class graphite to lamella
Structure, makes the excellent performance of Graphene to be fully used.Graphene nanobelt is accurate one-dimensional c-based nanomaterial, and it has
Excellent physical and chemical performance, it is more flexibly more adjustable than Graphene, CNT that its special edge effect causes it to have
Property.The two is combined and prepares Graphene-graphene aerogel composite aerogel, the three-dimensional formed with high-specific surface area is more
Pore network structure, so as to effectively suppress being stacked between graphene sheet layer and graphene nanobelt, is conducive to the biography of electronics
The migration of defeated and ion.
Pyrite phase transient metal sulfide (MX2, M=Fe, Co, Ni, X=S, Se) is because it is in acid and alkalescence condition
Under all embody electro-chemical activity and cause extensive concern.Wherein, with other semiconductor pyrite phase material (curing nickel and two sulphur
Change iron) to compare, the electric conductivity of cobalt disulfide is more excellent, thus becomes good liberation of hydrogen catalyst material.But, pure cobalt disulfide is use up
Pipe has low-resistivity, good catalysis activity and chemical stability, but easily occurs from reuniting, and avtive spot cannot fully expose,
Affect the cyclical stability of its catalysis characteristics and energy stores.And Graphene-graphene nanobelt composite aerogel has
Superior electrical conductivity, high porosity, high-specific surface area and good stability, are a kind of outstanding matrix materials, and two kinds of materials are entered
Row is compound, can reach the purpose of the two functional combination, finally improves catalytic efficiency.
The content of the invention
The technical problem to be solved is to provide a kind of compound gas of cobalt disulfide/Graphene-graphene nanobelt
Gel and its preparation method and application, the aeroge have larger specific surface area, excellent electric conductivity, it is stable chemically
The advantages of matter, good mechanical property, be a kind of high performance electrocatalysis material.
A kind of cobalt disulfide/Graphene-graphene nanobelt composite aerogel of the present invention, is received by Graphene-Graphene
Rice is obtained with growth in situ cobalt disulfide particle on composite aerogel.
A kind of preparation method of the cobalt disulfide/Graphene-graphene nanobelt composite aerogel of the present invention, including：
(1) by graphene nanobelt dispersion liquid and graphene oxide dispersion in mass ratio 2:1～1:2 stirring mixing, shape
Into homogeneous dispersion liquid, freeze-drying is then carried out, obtain Graphene-graphene nanobelt composite aerogel；
(2) cobalt salt and sulfosalt are dissolved in solvent, obtain homogeneous salting liquid；By salting liquid and above-mentioned Graphene-graphite
Alkene nanobelt composite aerogel, carries out solvent thermal reaction, obtains final product cobalt disulfide/Graphene-graphene nanobelt composite aerogel.
Graphene oxide dispersion concentration in the step (1) is 2-5mg/mL.
Graphene nanobelt dispersion liquid concentration in the step (1) is 2-5mg/mL.
Cobalt salt in the step (2) is one or more in cobalt chloride, cobalt nitrate, cobalt acetate；Cobalt salt is molten in salt
Concentration in liquid is 2～20mg/mL.
Sulfosalt in the step (2) is one or more in thiocarbamide, thioacetamide, vulcanized sodium；Sulfosalt is molten in salt
Concentration in liquid is 3～35mg/mL.
Solvent in the step (2) is water or N,N-dimethylformamide.
Graphene-graphene nanobelt composite aerogel in the step (2) is 1 with the mass ratio of cobalt salt:1.5-2.
Solvent thermal reaction temperature in the step (2) is 150～200 DEG C, and the reaction time is 10～24h.
A kind of application of cobalt disulfide/Graphene-graphene nanobelt composite aerogel of the present invention, is applied to electricity and urges
Change.
Beneficial effect
(1) preparation process of the present invention is simple, environmental protection, it is easy to operate, and is a kind of effective efficiently preparation method.
(2) Graphene and quasi-one-dimensional graphene nanobelt of two dimension are combined and prepare composite aerogel material by the present invention
Material so that high conductivity, the Graphene of high-specific surface area and the graphene nanobelt phase with unique draw ratio and marginal texture
Connect and run through, increase the specific surface area of composite, effectively constructed multilevel hierarchy.
(3) with aerogel composite as substrate, by a step solvent heat growth in situ cobalt disulfide particle, effectively press down
The reunion of cobalt disulfide is made, and has successfully constructed the composite with multilevel hierarchy and active site.
(4) cobalt disulfide/Graphene-graphene nanobelt aerogel composite prepared by the present invention, can be used as analysis
Hydrogen, oxygen reduction catalyst material, are a kind of preferable high-performance electric catalysis materials.
Description of the drawings
Fig. 1 is the SEM figures of the cobalt disulfide/Graphene-graphene nanobelt aerogel composite of embodiment 1；Wherein,
(A) it is Graphene-graphene nanobelt composite aerogel；(B) it is the compound airsetting of cobalt disulfide/Graphene-graphene nanobelt
Glue material.
Fig. 2 is the XRD of the cobalt disulfide/Graphene-graphene nanobelt aerogel composite of embodiment 1；
Fig. 3 is the electrochemistry Hydrogen Evolution Performance figure of cobalt disulfide/Graphene-graphene nanobelt aerogel composite；Its
In, (A) material for embodiment 1 scans volt-ampere curve (LSV) in acidic electrolyte bath lower linear, and (B) material for embodiment 1 exists
Tafel curves under acidic electrolyte bath, (C) for embodiment 4 material alkaline electrolyte lower linear scanning volt-ampere curve (LSV),
(D) material of embodiment 4 Tafel curves under alkaline electrolyte, (E) material for embodiment 1-4 is offline in acidic electrolyte bath
Property scanning volt-ampere curve (LSV), (F) for embodiment 1-4 material alkaline electrolyte lower linear scanning volt-ampere curve (LSV).
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
(1) graphite oxide is scattered in deionized water, ultrasound obtains the graphene oxide point of the stable dispersion of 4mg/mL
Dispersion liquid；
(2) graphene nanobelt is dispersed in water, obtains the uniform graphene nanobelt dispersion liquid of 4mg/mL；
(3) by step (1) and step (2) resulting solution respectively by volume 1:1,1:2,2:1 ratio is well mixed；
(4) mixed liquor obtained by step (3) is placed in into liquid nitrogen frozen, places into freeze drier and be dried, obtain oxygen
Graphite alkene-graphene nanobelt composite aerogel；
(5) 79mg cobalt chlorides and 127mg thiocarbamides are dissolved in 36mL deionized waters, ultrasonic 5min is prepared homogeneous
Salting liquid；
(6) graphene oxide-graphene nanobelt of the different proportion for obtaining the salting liquid for preparing and step (4)
(graphene oxide-graphene nanobelt composite aerogel is 1 with the mass ratio of cobalt chloride for composite aerogel mixing:2), it is put into
In Teflon hydrothermal reaction kettles, 12h is reacted under the conditions of 200 DEG C, after Temperature fall, take out product, and deionized water is anti-
Multiple cleaning is repeatedly and dry, prepares molybdenum bisuphide/Graphene-graphene nanobelt aerogel composite, is designated as respectively
G/GNR@CoS2-2、G/GNR2@CoS2-2、G2/GNR@CoS2-2。
In electro-chemical test, using three electrode test systems, it is with the glass-carbon electrode that prepared hybrid material is modified
Working electrode, saturated calomel electrode is reference electrode, and graphite rod is that, to electrode, acidic electrolysis bath is 0.5M H2SO4, alkaline electrolysis
Liquid is 1M KOH.Before testing, in advance by the logical nitrogen 30min of electrolyte.Using institute in the linear sweep voltammetry research present invention
The electrocatalytic hydrogen evolution reactivity of the hybrid material of preparation.
Characterize the present invention using SEM (SEM), X-ray diffractometer (XRD), electrochemical workstation to be obtained
Cobalt disulfide/Graphene-graphene nanobelt aerogel composite structure and morphology and as liberation of hydrogen catalysis electrode
Chemical property, its result is as follows：
1. SEM test results show：Prepared cobalt disulfide/Graphene-graphene nanobelt aerogel composite
There is multi-stage pore structure, graphene sheet layer is built into the skeleton structure of three networks with graphene nanobelt jointly, and Graphene is received
Rice band is through between graphene sheet layer.And have clear and definite steamed bun shape CoS in aspect2Exist, in each synusia plane
It is distributed, takes full advantage of the high-specific surface area and high conductivity of aerogel composite, effectively inhibits cobalt disulfide certainly
The reunion of body so as to which electro-chemical activity site is fully exposed.Referring to Fig. 1.
2. XRD test results show：Prepared cobalt disulfide/Graphene-graphene nanobelt aerogel composite
In 2 θ=28.4 °, 32.8 °, 36.7 °, 40.4 °, 46.9 ° and 55.5 ° or so there is respectively obvious diffraction maximum, correspond to respectively vertical
(111), (200), (210), (211) of square phase cobalt disulfide, (220), (311) crystal face (JCPDS No.41-1471), it was demonstrated that
Cobalt disulfide is supported on well on Graphene-graphene nanobelt composite aerogel.Referring to Fig. 2.
3. electro-chemical test shows that prepared cobalt disulfide/Graphene-graphene nanobelt aerogel composite exists
Under acid and alkaline electrolyte, excellent electrochemical catalysis Hydrogen Evolution Performance is respectively provided with.Under the conditions of acidic electrolyte bath, referring to Fig. 3
(E), the present embodiment has more excellent electrochemical catalysis Hydrogen Evolution Performance, and from Fig. 3 (B), its Tafel slope is 62mV
dec-1, it is much better than the performance of pure molybdenum bisuphide.
Embodiment 2
(1) graphite oxide is scattered in deionized water, ultrasound obtains the graphene oxide point of the stable dispersion of 4mg/mL
Dispersion liquid；
(2) graphene nanobelt is dispersed in water, obtains the uniform graphene nanobelt dispersion liquid of 4mg/mL；
(3) by step (1) and step (2) resulting solution respectively by volume 1:1,1:2,2:1 ratio is well mixed；
(4) mixed liquor obtained by step (3) is placed in into liquid nitrogen frozen, places into freeze drier and be dried, obtain oxygen
Graphite alkene-graphene nanobelt composite aerogel；
(5) 40mg cobalt chlorides and 64mg thiocarbamides are dissolved in 36mL deionized waters, ultrasonic 5min is prepared homogeneous
Salting liquid；
(6) graphene oxide-graphene nanobelt of the different proportion for obtaining the salting liquid for preparing and step (4)
(graphene oxide-graphene nanobelt composite aerogel is 1 with the mass ratio of cobalt chloride for composite aerogel mixing:2), it is put into
In Teflon hydrothermal reaction kettles, 12h is reacted under the conditions of 200 DEG C, after Temperature fall, take out product, and deionized water is anti-
Multiple cleaning is repeatedly and dry, prepares molybdenum bisuphide/Graphene-graphene nanobelt aerogel composite, is designated as respectively
G/GNR@CoS2-1、G/GNR2@CoS2-1、G2/GNR@CoS2-1。
Embodiment 3
(1) graphite oxide is scattered in deionized water, ultrasound obtains the graphene oxide point of the stable dispersion of 4mg/mL
Dispersion liquid；
(2) graphene nanobelt is dispersed in water, obtains the uniform graphene nanobelt dispersion liquid of 4mg/mL；
(3) by step (1) and step (2) resulting solution respectively by volume 1:1,1:2,2:1 ratio is well mixed；
(4) mixed liquor obtained by step (3) is placed in into liquid nitrogen frozen, places into freeze drier and be dried, obtain oxygen
Graphite alkene-graphene nanobelt composite aerogel；
(5) 158mg cobalt chlorides and 254mg thiocarbamides are dissolved in 36mL deionized waters, ultrasonic 5min is prepared homogeneous
Salting liquid；
(6) graphene oxide-graphene nanobelt of the different proportion for obtaining the salting liquid for preparing and step (4)
(graphene oxide-graphene nanobelt composite aerogel is 1 with the mass ratio of cobalt chloride for composite aerogel mixing:2), it is put into
In Teflon hydrothermal reaction kettles, 12h is reacted under the conditions of 200 DEG C, after Temperature fall, take out product, and deionized water is anti-
Multiple cleaning is repeatedly and dry, prepares molybdenum bisuphide/Graphene-graphene nanobelt aerogel composite, is designated as respectively
G/GNR@CoS2-3、G/GNR2@CoS2-3、G2/GNR@CoS2-3。
Embodiment 4
(1) graphite oxide is scattered in deionized water, ultrasound obtains the graphene oxide point of the stable dispersion of 4mg/mL
Dispersion liquid；
(2) graphene nanobelt is dispersed in water, obtains the uniform graphene nanobelt dispersion liquid of 4mg/mL；
(3) by step (1) and step (2) resulting solution respectively by volume 1:1,1:2,2:1 ratio is well mixed；
(4) mixed liquor obtained by step (3) is placed in into liquid nitrogen frozen, places into freeze drier and be dried, obtain oxygen
Graphite alkene-graphene nanobelt composite aerogel；
(5) 60mg cobalt chlorides and 96mg thiocarbamides are dissolved in 36mL deionized waters, ultrasonic 5min is prepared homogeneous
Salting liquid；
(6) graphene oxide-graphene nanobelt of the different proportion for obtaining the salting liquid for preparing and step (4)
(graphene oxide-graphene nanobelt composite aerogel is 1 with the mass ratio of cobalt chloride for composite aerogel mixing:2), it is put into
In Teflon hydrothermal reaction kettles, 12h is reacted under the conditions of 200 DEG C, after Temperature fall, take out product, and deionized water is anti-
Multiple cleaning is repeatedly and dry, prepares molybdenum bisuphide/Graphene-graphene nanobelt aerogel composite, is designated as respectively
G/GNR@CoS2-4、G/GNR2@CoS2-4、G2/GNR@CoS2-4.Under the conditions of alkaline electrolyte, referring to Fig. 3 (F), this enforcement
Example has more excellent electrochemical catalysis Hydrogen Evolution Performance, and from Fig. 3 (D), its Tafel slope is 87mV dec-1, it is much better than pure
The performance of molybdenum bisuphide.
Claims (10)
1. a kind of cobalt disulfide/Graphene-graphene nanobelt composite aerogel, it is characterised in that：Received by Graphene-Graphene
Rice is obtained with growth in situ cobalt disulfide particle on composite aerogel.
2. a kind of preparation method of cobalt disulfide/Graphene-graphene nanobelt composite aerogel, including：
(1) by graphene nanobelt dispersion liquid and graphene oxide dispersion in mass ratio 2:1～1:2 stirring mixing, form equal
One dispersion liquid, then carries out freeze-drying, obtains Graphene-graphene nanobelt composite aerogel；
(2) cobalt salt and sulfosalt are dissolved in solvent, obtain homogeneous salting liquid；Salting liquid is received with above-mentioned Graphene-Graphene
Rice band composite aerogel, carries out solvent thermal reaction, obtains final product cobalt disulfide/Graphene-graphene nanobelt composite aerogel.
3. the preparation side of a kind of cobalt disulfide/Graphene-graphene nanobelt composite aerogel according to claim 2
Method, it is characterised in that：Graphene oxide dispersion concentration in the step (1) is 2-5mg/mL.
4. the preparation side of a kind of cobalt disulfide/Graphene-graphene nanobelt composite aerogel according to claim 2
Method, it is characterised in that：Graphene nanobelt dispersion liquid concentration in the step (1) is 2-5mg/mL.
5. the preparation side of a kind of cobalt disulfide/Graphene-graphene nanobelt composite aerogel according to claim 2
Method, it is characterised in that：Cobalt salt in the step (2) is one or more in cobalt chloride, cobalt nitrate, cobalt acetate；Cobalt salt
Concentration in salting liquid is 2～20mg/mL.
6. the preparation side of a kind of cobalt disulfide/Graphene-graphene nanobelt composite aerogel according to claim 2
Method, it is characterised in that：Sulfosalt in the step (2) is one or more in thiocarbamide, thioacetamide, vulcanized sodium；Sulfosalt
Concentration in salting liquid is 3～35mg/mL.
7. the preparation side of a kind of cobalt disulfide/Graphene-graphene nanobelt composite aerogel according to claim 2
Method, it is characterised in that：Solvent in the step (2) is water or N,N-dimethylformamide.
8. the preparation side of a kind of cobalt disulfide/Graphene-graphene nanobelt composite aerogel according to claim 2
Method, it is characterised in that：Graphene-graphene nanobelt composite aerogel in the step (2) is 1 with the mass ratio of cobalt salt:
1.5-2。
9. the preparation side of a kind of cobalt disulfide/Graphene-graphene nanobelt composite aerogel according to claim 2
Method, it is characterised in that：Solvent thermal reaction temperature in the step (2) is 150～200 DEG C, and the reaction time is 10～24h.
10. a kind of application of cobalt disulfide/Graphene-graphene nanobelt composite aerogel as claimed in claim 1, it is special
Levy and be：It is applied to electro-catalysis.
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| CN116247169B (en) * | 2023-04-01 | 2024-01-19 | 中国矿业大学 | CoS containing Se doping 2 Preparation method of sodium ion battery serving as negative electrode |
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