CN113830755A - Method for electrochemically preparing cobalt simple substance-graphene intercalation compound by one-step method - Google Patents
Method for electrochemically preparing cobalt simple substance-graphene intercalation compound by one-step method Download PDFInfo
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- CN113830755A CN113830755A CN202111076773.4A CN202111076773A CN113830755A CN 113830755 A CN113830755 A CN 113830755A CN 202111076773 A CN202111076773 A CN 202111076773A CN 113830755 A CN113830755 A CN 113830755A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C01B32/19—Preparation by exfoliation
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- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
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Abstract
The invention discloses a method for electrochemically preparing a cobalt simple substance-graphene intercalation compound by a one-step method. The method adopts an anode electrochemical stripping method, firstly, hexanitrocobalt anion is inserted into a graphite layer to generate electrochemical reaction, so that exfoliated graphite particles are suspended in electrolyte and gradually migrate to a cathode to generate reduction reaction, and finally, cobalt ions in the layer are reduced into a cobalt simple substance. Compared with the stripping mode of high-voltage excited plasma in the prior art, the stripping method adopts the double graphite sheets to replace the noble metal pole piece, and uses the aqueous electrolyte, thereby avoiding the use of expensive polluting solutions such as organic solvents, ionic liquids and the like. The electrolyte in the acidic environment can keep the stability of sodium hexanitrocobaltate anions; anionic surfactants can enhance anionic wetting and dispersion. The method has the advantages of mild stripping conditions, low equipment requirements, low energy consumption, simple operation and short stripping time, and conforms to a green chemical synthesis route.
Description
The technical field is as follows:
the invention belongs to the technical field of carbon composite material preparation, and particularly relates to a method for electrochemically preparing a cobalt simple substance-graphene intercalation compound (Co-GIC) by a one-step method.
Background art:
with the increasingly sharp problems of energy and environmental pollution, people pursue a cheap and environment-friendly synthetic route in the preparation of materials. And the graphene intercalation compound has great potential application value in the fields of catalysts, magnetic materials, conductive materials, secondary batteries and the like, and how to prepare the graphene intercalation compound is a short plate. Therefore, the preparation method of the cobalt simple substance-graphene intercalation compound (Co-GIC) attracts people to pay attention.
At present, the preparation method of Co-GIC is mainly a Co-reduction method, which needs to firstly prepare Graphene Oxide (GO) by using a Hummer method, and aims to introduce more oxygen-containing functional groups such as carboxyl, hydroxyl and the like on the surface of the graphene oxide so as to exchange ions with later-added cobalt salt, and finally carry out Co-reduction by using a reducing agent or high-temperature reduction. The prepared material is easy to gather a large number of cobalt particles on the edge of graphene, and the preparation process is complex, high in danger coefficient, time-consuming and energy-consuming. Therefore, a brand new more economic, rapid and green preparation method is particularly important.
The invention content is as follows:
the invention provides a method for electrochemically preparing a cobalt simple substance-graphene intercalation compound by a one-step method, aiming at solving the problems in the prior art.
The method for electrochemically preparing the cobalt simple substance-graphene intercalation compound by the one-step method comprises the following steps:
(1) adding sodium hexanitrocobaltate, weak acid and anionic surfactant into deionized water to prepare electrolyte;
(2) one or more pairs of graphite sheets connected with a direct current power supply in pairs are relatively and vertically immersed into electrolyte, a direct current power supply is adopted for stripping for 2-4h at constant current, ice bath is added during stripping, and the ice bath time is not less than two thirds of the stripping time;
(3) carrying out vacuum filtration on the suspension after reaction by using deionized water and washing; dispersing the cleaned product in DMF for water bath ultrasonic treatment; standing after ultrasonic treatment, centrifuging by using a centrifugal machine, and freeze-drying a lower-layer product to obtain the cobalt simple substance-graphene intercalation compound.
And (4) calcining the cobalt simple substance-graphene intercalation compound obtained in the step (3) for 2-6h at the temperature of 500-600 ℃ in an oxygen-free atmosphere. To improve the graphene quality and the fineness of the cobalt particles.
The concentration of the sodium hexanitrocobaltate in the electrolyte is 0.01-0.05 mol/L.
The weak acid is one or more of acetic acid, boric acid, citric acid and nitrous acid; when the weak acid is liquid at normal temperature, the addition amount of the weak acid is 8-12% of the volume of the electrolyte; when the weak acid is solid at normal temperature, the addition amount of the weak acid is 20-40 g/L.
The anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, sodium dioctyl sulfosuccinate, ammonium dodecyl sulfonate, ammonium dodecyl benzene sulfonate, ammonium dodecyl sulfate, ammonium hexadecyl sulfate, ammonium octadecyl sulfate and ammonium dioctyl sulfosuccinate; the addition amount of the anionic surfactant is 0.05-0.5 g/L.
The thickness of the graphite flake is 0.1-2mm, and the distance between every two graphite flakes connected with the direct current power supply is 2-4 cm.
The constant current is 0.5-0.7A.
The cathode graphite sheet stripped in the step (3) can be reused.
The standing is not less than 12h, and the centrifuge is centrifuged for 20-40min at 3000-.
The invention adopts an anode electrochemical stripping method, wherein high-purity graphite flakes are used as a cathode and an anode, firstly, hexanitrocobalt anion is inserted into a graphite layer to generate electrochemical reaction, so that exfoliated graphite particles are suspended in electrolyte and gradually migrate to a cathode to generate reduction reaction, and finally, cobalt ions in the layer are reduced into a cobalt simple substance. Compared with the stripping mode of high-voltage excited plasma in the prior art, the stripping method adopts the double graphite sheets to replace the noble metal pole piece, and uses the aqueous electrolyte, thereby avoiding the use of expensive polluting solutions such as organic solvents, ionic liquids and the like. The electrolyte in the acidic environment can keep the stability of sodium hexanitrocobaltate anions; anionic surfactants can enhance anionic wetting and dispersion. The method has the advantages of mild stripping conditions, low equipment requirements, low energy consumption, simple operation and short stripping time, and conforms to a green chemical synthesis route.
Description of the drawings:
fig. 1 is an XRD pattern of the elemental cobalt-graphene intercalation compound prepared in example 1 and the product of comparative example 1;
FIG. 2 is a scanning electron microscope image of elemental cobalt-graphene intercalation compound prepared in example 1;
FIG. 3 is a blue shift comparison of Raman G peak of the cobalt elemental-graphene intercalation compound prepared in example 1 and the product of comparative example 1;
FIG. 4 is a XPS Co 2p high resolution plot of elemental cobalt-graphene intercalation compounds prepared in example 1;
fig. 5 is an XRD pattern of the elemental cobalt-graphene intercalation compound prepared in example 2.
The specific implementation mode is as follows:
the following detailed description of the embodiments of the present invention will be provided in conjunction with the accompanying drawings, which are only a part of the embodiments and are not intended to be exhaustive.
Example 1
(1) 0.403g of sodium hexanitrocobaltate, 12mL of acetic acid and 0.01g of sodium dodecyl sulfate are added into a small beaker and stirred to prepare 100mL of electrolyte;
(2) mixing 4X 2X 0.1cm3The two graphite sheets are connected with a direct current power supply and then are parallelly immersed into the electrolyte, the immersion depth of the electrolyte is 2cm, and the distance between the two graphite sheets connected with the direct current power supply is 3 cm; stripping at constant current of 0.6A for 3.5 hr, and maintaining the stripping processKeeping an ice bath;
(3) carrying out vacuum filtration on the reacted suspension, washing the suspension by using 300mL of deionized water, and dispersing the obtained black filter cake in DMF (dimethyl formamide) for water bath ultrasound for 30min to obtain black liquid; standing the product after ultrasonic treatment overnight, centrifuging the product for 30min at 4000rpm of a centrifuge, and freeze-drying the black product of the lower layer to obtain a black powdery cobalt simple substance-graphene intercalation compound.
(4) Calcining the freeze-dried cobalt simple substance-graphene intercalation compound for 4 hours at 550 ℃ in a tubular furnace under the atmosphere of high-purity argon to obtain the refined cobalt simple substance-graphene intercalation compound with low oxygen content.
Comparative example 1
The sodium hexanitrocobaltate is removed from the electrolyte in the step (1) in the above example 1, a cobalt wire with the diameter of 1mm is wound on an anode graphite sheet, other conditions are the same as those in the example 1, and finally the freeze-dried product is calcined in an argon-hydrogen mixed gas containing 8% hydrogen at 550 ℃ for 4 hours by using a tubular furnace for thermal reduction to obtain a product of which the cobalt metal is loaded on the surface of the graphene.
The typical cubic structure of the simple substance cobalt and the (002) crystal plane of the graphene of the simple substance cobalt-graphene intercalation compound prepared in example 1 can be seen from the X-ray diffraction (XRD) pattern of fig. 1.
From the Scanning Electron Micrograph (SEM) of fig. 2, it can be seen that the elemental cobalt-graphene intercalation compound prepared in example 1 has a wrinkled graphene sheet shape, and no significant cobalt particle aggregation, indicating good dispersibility and a size of only less than two nanometers.
The blue shift comparison diagram of the Raman G peak of example 1 and comparative example 1 in fig. 3 shows that the cobalt simple substance-graphene intercalation compound prepared in example 1 has an obvious charge transfer phenomenon, has a chemical effect, and meets the characteristics of a donor graphene intercalation compound.
From the Co 2p XPS high resolution spectrum of example 1 of fig. 4, it can be seen that the peak position of cobalt shifts significantly to the high binding energy, because the cobalt provides electrons to the graphene due to the chemical action of the cobalt simple substance-graphene intercalation compound.
According to the characteristics, the cobalt simple substance-graphene intercalation prepared by an electrochemical method is adopted in the inventionThe layer compound is a donor intercalation compound, namely the intercalation agent cobalt simple substance needs to provide electrons to the parent graphene, so that a Raman G peak is obviously blue-shifted, and XPS Co 2p also enables Co to be subjected to blue-shift0The electron binding energy is shifted to a high level, but the original lattice structure of the cobalt simple substance is retained. The difference between the composite material and other supported cobalt simple substances/graphene composite materials is that the supported composite materials basically do not generate charge transfer, so that a Raman G peak does not generate a large blue shift or red shift but can generate a shift of several wave numbers under the influence of a doping effect, and a narrow spectrum diagram of XPS Co 2p generates an obvious cobalt simple substance peak near 778-779 eV. The characterization of example 1 demonstrates that the solution of the invention is feasible. In addition, the cobalt simple substance-graphene intercalation compound is directly prepared in the water-based electrolyte by a one-step method, and the method completely accords with the chemical synthesis route with economic benefit and environmental protection.
Example 2
(1) Adding 0.403g of sodium hexanitrocobaltate, 3g of boric acid and 0.01g of sodium dodecyl sulfate into a small beaker, and stirring to prepare 100mL of electrolyte;
(2) mixing 4X 2X 0.1cm3The two graphite sheets are connected with a direct current power supply and then are parallelly immersed into the electrolyte, the immersion depth of the electrolyte is 2cm, and the distance between the two graphite sheets connected with the direct current power supply is 3 cm; stripping for 3.5h at constant current of 0.6A, and keeping ice bath in the stripping process;
(3) carrying out vacuum filtration on the reacted suspension, washing the suspension by using 300mL of deionized water, and dispersing the obtained black filter cake in DMF (dimethyl formamide) for water bath ultrasound for 30min to obtain black liquid; standing the product after ultrasonic treatment overnight, centrifuging the product for 30min at 4000rpm of a centrifuge, and freeze-drying the black product of the lower layer to obtain a black powdery cobalt simple substance-graphene intercalation compound.
(4) Calcining the freeze-dried cobalt simple substance-graphene intercalation compound for 4 hours at 550 ℃ in a tubular furnace under the atmosphere of high-purity argon to obtain the refined cobalt simple substance-graphene intercalation compound with low oxygen content.
From the XRD pattern of example 2 of fig. 5, it can be seen that the formed cobalt simple substance is a face-centered hexagonal structure.
Claims (9)
1. A method for electrochemically preparing a cobalt simple substance-graphene intercalation compound by a one-step method is characterized by comprising the following specific steps:
(1) adding sodium hexanitrocobaltate, weak acid and anionic surfactant into deionized water to prepare electrolyte;
(2) one or more pairs of graphite sheets connected with a direct current power supply in pairs are relatively and vertically immersed into electrolyte, a direct current power supply is adopted for stripping for 2-4h at constant current, ice bath is added during stripping, and the ice bath time is not less than two thirds of the stripping time;
(3) carrying out vacuum filtration on the suspension after reaction by using deionized water and washing; dispersing the cleaned product in DMF for water bath ultrasonic treatment; standing after ultrasonic treatment, centrifuging by using a centrifugal machine, and freeze-drying a lower-layer product to obtain the cobalt simple substance-graphene intercalation compound.
2. The method as claimed in claim 1, wherein the elemental cobalt-graphene intercalation compound obtained in step (3) is calcined at 500-600 ℃ for 2-6h in an oxygen-free atmosphere.
3. The method of claim 1, wherein the concentration of sodium hexanitrocobaltate in the electrolyte is 0.01-0.05 mol/L.
4. The method according to claim 1, wherein the weak acid is one or more of acetic acid, boric acid, citric acid and nitrous acid; when the weak acid is liquid at normal temperature, the addition amount of the weak acid is 8-12% of the volume of the electrolyte; when the weak acid is solid at normal temperature, the addition amount of the weak acid is 20-40 g/L.
5. The method of claim 1, wherein the anionic surfactant is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, sodium dioctyl sulfosuccinate, ammonium dodecyl sulfonate, ammonium dodecyl benzene sulfonate, ammonium dodecyl sulfate, ammonium hexadecyl sulfate, ammonium octadecyl sulfate, and ammonium dioctyl sulfosuccinate; the addition amount of the anionic surfactant is 0.05-0.5 g/L.
6. The method of claim 1, wherein the graphite sheets have a thickness of 0.1-2mm and the distance between two graphite sheets of each pair connected to a dc power supply is 2-4 cm.
7. The method of claim 1, wherein the constant current is 0.5-0.7A.
8. The method of claim 1, wherein the stripped cathode graphite sheet of step (3) is reusable.
9. The method as claimed in claim 1, wherein the standing is not less than 12h, and the centrifuge is centrifuged at 3000 and 5000rpm for 20-40 min.
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