CN114933525A - Ferrous oxalate nanowire and preparation method thereof - Google Patents
Ferrous oxalate nanowire and preparation method thereof Download PDFInfo
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- ferrous oxalate
- oxalate
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- 229940062993 ferrous oxalate Drugs 0.000 title claims abstract description 90
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 title claims abstract description 87
- 239000002070 nanowire Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 31
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 26
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims abstract description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 123
- 239000000243 solution Substances 0.000 claims description 50
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 45
- 235000006408 oxalic acid Nutrition 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000012266 salt solution Substances 0.000 claims description 22
- 238000001556 precipitation Methods 0.000 claims description 21
- 239000012046 mixed solvent Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 28
- 230000008569 process Effects 0.000 abstract description 15
- 238000010899 nucleation Methods 0.000 abstract description 6
- 230000006911 nucleation Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000002667 nucleating agent Substances 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000011790 ferrous sulphate Substances 0.000 description 8
- 235000003891 ferrous sulphate Nutrition 0.000 description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000007605 air drying Methods 0.000 description 5
- 235000013980 iron oxide Nutrition 0.000 description 5
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- -1 oxalate ions Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/06—Oxalic acid
- C07C55/07—Salts thereof
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Compounds Of Iron (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a ferrous oxalate nanowire and a preparation method thereof, belonging to the technical field of material synthesis. The invention adopts N, N-diethyl acetamide and polyvinyl alcohol as composite surfactants, and in the process of nucleating ferrous oxalate crystals, the polyvinyl alcohol is used as a nucleating agent to exert a 'template' effect; in the growth process of the ferrous oxalate crystal, N, N-diethyl acetamide is adsorbed on the crystal face of ferrous oxalate to inhibit the crystal growth, polyvinyl alcohol and N, N-diethyl acetamide are coupled to influence the growth direction and growth rate of ferrous oxalate from the angles of crystal nucleation and crystal growth together, and then the ferrous oxalate nanowire with the diameter of 15-100 nm is obtained; and the method is simple and easy to implement.
Description
Technical Field
The invention relates to the technical field of material synthesis, in particular to a ferrous oxalate nanowire and a preparation method thereof.
Background
Ferrous oxalate is used as an important raw material in the industrial fields of minerals, metallurgy, energy and the like, and the shape control of the ferrous oxalate directly influences the service performance of the material. As various iron oxides (hematite alpha-Fe) 2 O 3 Maghemite gamma-Fe 2 O 3 And Fe 3 O 4 ) The shape of the ferrous oxalate can be inherited into the iron oxide as a main precursor of the nano material. Iron oxide is widely concerned with high theoretical specific capacity and is considered as a potential super capacitor negative electrode material, and the nanocrystallization can effectively improve the electrochemical performance of the iron oxide as the super capacitor negative electrode material. Therefore, the iron oxalate is used as a precursor of the iron oxide, and the shape control of the ferrous oxalate is particularly important.
At present, related researches on the shape control of ferrous oxalate have been disclosed, for example, in the invention patent with the publication number of CN103922920A, a polyol-water solution of trivalent ferric salt and oxalic acid is used for sealing and heating to 90-180 ℃, and a one-dimensional ferrous oxalate nanowire with the diameter of 150-300 nanometers and the length of 20-100 micrometers is obtained after reacting for 2-24 hours. However, the method has long reaction time, high reaction temperature and excessively complex preparation method.
Disclosure of Invention
The invention aims to provide a ferrous oxalate nanowire and a preparation method thereof, and the method is simple and easy to implement.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of ferrous oxalate nanowires, which comprises the following steps:
mixing ferrous salt with a polyvinyl alcohol-water mixed solvent to obtain a ferrous salt solution;
mixing oxalic acid with N, N-diethyl acetamide to obtain oxalic acid solution;
and mixing the ferrous salt solution with an oxalic acid solution, and carrying out precipitation reaction to obtain the ferrous oxalate nanowire.
Preferably, the ferrous salt includes one of ferrous sulfate heptahydrate, ferrous chloride, ferrous ammonium sulfate and ferrous nitrate.
Preferably, the mass concentration of the ferrous salt in the ferrous salt solution is 1-10%.
Preferably, the mass concentration of the polyvinyl alcohol in the polyvinyl alcohol-water mixed solvent is 0.1-5%.
Preferably, the mass concentration of the oxalic acid solution is 1-20%.
Preferably, the temperature of the precipitation reaction is 20-40 ℃, and the time of the precipitation reaction is 0.5-2 h.
Preferably, after the precipitation reaction is completed, the obtained precipitation product is sequentially subjected to centrifugal separation, washing and drying to obtain the ferrous oxalate nanowire.
Preferably, the drying temperature is 70-90 ℃, and the drying time is 3-5 h.
The invention provides the ferrous oxalate nanowire prepared by the preparation method of the technical scheme, wherein the ferrous oxalate nanowire is of a network-like structure and has a diameter of 15-100 nm.
The invention provides a preparation method of ferrous oxalate nanowires, which comprises the following steps: mixing ferrous salt with a polyvinyl alcohol-water mixed solvent to obtain a ferrous salt solution; mixing oxalic acid with N, N-diethyl acetamide to obtain oxalic acid solution; and mixing the ferrous salt solution with an oxalic acid solution, and carrying out precipitation reaction to obtain the ferrous oxalate nanowire. The invention adopts N, N-diethyl acetamide and polyvinyl alcohol as composite surfactants, and in the process of nucleating ferrous oxalate crystals, the polyvinyl alcohol is used as a nucleating agent to exert a 'template' effect; in the process of growing the ferrous oxalate crystal, N, N-diethyl acetamide is adsorbed on the crystal face of ferrous oxalate to inhibit the crystal growth, and polyvinyl alcohol and N, N-diethyl acetamide are coupled to influence the growth direction and growth rate of ferrous oxalate from the angles of crystal nucleation and crystal growth together, so as to obtain the network-shaped ferrous oxalate nanowire. The results of the examples show that the standard patterns (PDF #22-0635) of the ferrous oxalate nanowires prepared by the present invention are consistent with that of beta-ferrous oxalate.
In the preparation process of the ferrous oxalate, the particle size of the ferrous oxalate nanowire can be adjusted by controlling the using amount of the polyvinyl alcohol, so that the diameter of the prepared ferrous oxalate nanowire is 15-100 nm.
Furthermore, the method for preparing the ferrous oxalate nanowire at the normal temperature can shorten the reaction time and reduce the reaction temperature, and has important significance for controlling the appearance of the ferrous oxalate nanowire.
Drawings
FIG. 1 is a flow chart of the preparation of ferrous oxalate nanowires of examples 1-3;
fig. 2 is an XRD pattern of the iron oxalate nanowire prepared in example 1;
fig. 3 is an SEM image of the ferrous oxalate nanowires prepared in example 1;
fig. 4 is an XRD pattern of the ferrous oxalate nanowire prepared in example 2;
fig. 5 is an SEM image of the ferrous oxalate nanowires prepared in example 2;
FIG. 6 is an XRD pattern of the ferrous oxalate nanowires prepared in example 3;
fig. 7 is an SEM image of the ferrous oxalate nanowires prepared in example 3;
FIG. 8 is an XRD pattern of ferrous oxalate microparticles prepared in comparative example 1;
FIG. 9 is an SEM image of ferrous oxalate microparticles prepared in comparative example 1;
fig. 10 is an XRD pattern of the iron oxalate nanoparticles prepared in comparative example 2;
fig. 11 is an SEM image of the ferrous oxalate nanoparticles prepared in comparative example 2;
FIG. 12 is an XRD pattern of the ferrous oxalate nanorod prepared in comparative example 3;
FIG. 13 is an SEM image of the ferrous oxalate nanorods prepared in comparative example 3.
Detailed Description
The invention provides a preparation method of ferrous oxalate nanowires, which comprises the following steps:
mixing ferrous salt with a polyvinyl alcohol-water mixed solvent to obtain a ferrous salt solution;
mixing oxalic acid with N, N-diethyl acetamide to obtain oxalic acid solution;
and mixing the ferrous salt solution with an oxalic acid solution, and carrying out precipitation reaction to obtain the ferrous oxalate nanowire.
In the present invention, unless otherwise specified, all the required starting materials for the preparation are commercially available products well known to those skilled in the art.
According to the invention, ferrous salt is mixed with a polyvinyl alcohol-water mixed solvent to obtain a ferrous salt solution. In the present invention, the ferrous salt preferably includes one of ferrous sulfate heptahydrate, ferrous chloride, ferrous ammonium sulfate and ferrous nitrate; more preferably ferrous sulfate heptahydrate, and has low cost and high stability. When the ferrous salts are more than two, the proportion of different ferrous salts is not specially limited, and any proportion can be adopted.
In the present invention, the mass concentration of the polyvinyl alcohol in the polyvinyl alcohol-water mixed solvent is preferably 0.1 to 5%, more preferably 0.1 to 2%, and most preferably 0.5 to 1%. The invention limits the mass concentration of the polyvinyl alcohol-water mixed solvent within the range, can fully carry out the reaction and further improves the purity of the product. The preparation process of the polyvinyl alcohol-water mixed solvent is not particularly limited in the present invention, and the mixed solvent with the above concentration range can be prepared according to the well-known process in the art.
In the invention, the water is preferably deionized water, and the dosage of the water is not particularly limited, so that the mass concentration of the ferrous salt solution is ensured to be within the range. In the invention, the water is used for dissolving polyvinyl alcohol and ferrous salt, ferrous ions and oxalate radicals form a chain structure, the chain structure forms a layered structure, and the water connects layers by the action of hydrogen bonds to support the whole crystal structure. The polyvinyl alcohol is used as a nucleating agent, and serves as a template in the crystal nucleation process of the ferrous oxalate, so that the growth direction and the growth rate of the ferrous oxalate are influenced from the crystal nucleation angle. The invention does not specially limit the dosage of the polyvinyl alcohol, and the mass concentration of the polyvinyl alcohol is ensured to be in the range.
The process of mixing the ferrous salt and the polyvinyl alcohol-water mixed solvent is not particularly limited, and the ferrous salt and the polyvinyl alcohol-water mixed solvent can be fully and uniformly mixed according to the process known in the field.
In the present invention, the mass concentration of the ferrous salt in the ferrous salt solution is preferably 1 to 10%, more preferably 3 to 7%, and most preferably 5%. The invention limits the mass concentration of the ferrous salt solution within the range, can fully carry out the reaction and further improves the purity of the ferrous oxalate product.
According to the invention, oxalic acid and N, N-diethyl acetamide are mixed to obtain an oxalic acid solution. In the invention, the oxalic acid is preferably oxalic acid dihydrate, the cost is low, and the interference and influence of other cations on the reaction system can be avoided. In the present invention, the oxalic acid is used to provide oxalate ions.
In the invention, the mass concentration of the oxalic acid solution is preferably 1-20%, more preferably 3-15%, and most preferably 8%. The invention limits the mass concentration of the oxalic acid solution in the range, can ensure that the reaction is fully performed, and further improves the purity of the product.
In the present invention, the N, N-diethylacetamide is used to dissolve oxalic acid. In the process of growing the ferrous oxalate crystal, N, N-diethyl acetamide molecules and ferrous oxalate structural segments are combined through weak interaction such as hydrogen bonds, van der Waals force and the like, and are adsorbed on the ferrous oxalate crystal to inhibit the growth of the ferrous oxalate crystal, and the growth direction and growth rate of ferrous oxalate are influenced from the crystal growth angle. The dosage of the N, N-diethyl acetamide is not specially limited, and the mass concentration of the oxalic acid solution is ensured to be in the range.
The invention is not limited to the mixing of oxalic acid and N, N-diethyl acetamide, and the materials are mixed uniformly by the process known to those skilled in the art.
After the ferrous salt solution and the oxalic acid solution are obtained, the ferrous salt solution is added into the oxalic acid solution for precipitation reaction.
After a ferrous salt solution and an oxalic acid solution are obtained, the ferrous salt solution and the oxalic acid solution are mixed for precipitation reaction to obtain the ferrous oxalate nanowire.
In the invention, the ferrous salt solution is preferably dripped into the oxalic acid solution, and the dripping time is preferably 60 min; the process of mixing the ferrous salt solution and the oxalic acid solution is preferably carried out under the condition of stirring, the stirring mode is preferably mechanical stirring, and the stirring speed is preferably 250-350 rpm, more preferably 300 rpm; the stirring time is preferably 30-90 min, and more preferably 60 min. The invention limits the stirring speed and time within the range, can promote mass transfer to fully carry out the reaction, further improves the purity and yield of the product, and adjusts the grain size.
In the invention, in the precipitation process, ferrous ions react with oxalate radicals to generate ferrous oxalate precipitates, and the growth direction and growth rate of ferrous oxalate crystals are controlled by the coupling action of polyvinyl alcohol and N, N-diethylacetamide to obtain the ferrous oxalate nanowires.
In the invention, the temperature of the precipitation reaction is preferably 20-40 ℃, more preferably 30 ℃, and the reaction time of the precipitation reaction is preferably 0.5-2 h, more preferably 1 h. In the invention, the precipitation reaction is preferably carried out under a standing condition, and the crystallization is more complete and complete through standing. The invention limits the temperature and time of the precipitation reaction in the range, can fully carry out the reaction, further improves the purity and yield of the product, and simultaneously ensures that the crystallization is more full and complete.
After the precipitation reaction is finished, the invention preferably further comprises the step of sequentially carrying out centrifugal separation, washing and drying on the obtained precipitation product to obtain the ferrous oxalate nanowire. In the present invention, the washing preferably comprises washing with absolute ethanol and deionized water in this order to a solution pH of about 7. The invention has no special limit on the use amount of the absolute ethyl alcohol and the deionized water, and can be adjusted according to actual requirements. The centrifugation process is not particularly limited in the present invention, and may be performed according to a process known in the art. In the present invention, the washing is used to remove water-soluble impurities. In the invention, the drying is preferably carried out in a forced air drying oven, and the drying temperature is preferably 70-90 ℃, more preferably 80 ℃; the drying time is preferably 3-5 h, and more preferably 4 h.
The method adopts polyvinyl alcohol and N, N-diethyl acetamide as composite surfactants to complex ferrous ions, changes crystal face energy, enables growth rates of crystal faces to be different so as to control a crystal growth process, adopts the polyvinyl alcohol as a 'template' in a nucleation process of a ferrous oxalate crystal, adsorbs the N, N-diethyl acetamide on the crystal face of the ferrous oxalate crystal structure, and affects the growth direction and growth rate of the ferrous oxalate from the crystal nucleation and crystal growth angles together so as to obtain the ferrous oxalate nanowire with the diameter of 15-100 nm. The method ensures that the reaction is fully carried out by controlling the reaction steps and the consumption of the raw materials, and improves the purity and the yield of the ferrous oxalate nanowire.
The invention provides the ferrous oxalate nanowire prepared by the preparation method of the technical scheme, wherein the ferrous oxalate nanowire is of a network-like structure and has a diameter of 15-100 nm.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preparation process of the ferrous oxalate nanowires in the embodiments 1-3 is shown in fig. 1: dissolving ferrous salt in a mixed solvent of polyvinyl alcohol and water to obtain a ferrous salt solution; dissolving oxalic acid in N, N-diethyl acetamide to obtain an oxalic acid solution; and dropwise adding the ferrous salt solution into the oxalic acid solution to obtain ferrous oxalate precipitate, and sequentially carrying out centrifugal separation, washing and drying to obtain the ferrous oxalate precipitate.
Example 1
(1) Dissolving 0.077g of polyvinyl alcohol in 77.2mL of deionized water to obtain 0.1 wt% of polyvinyl alcohol-water mixed solvent;
(2) dissolving 3.86g of ferrous sulfate heptahydrate in the polyvinyl alcohol-water mixed solvent in the step (1) to obtain a ferrous sulfate solution with the mass concentration of 5%;
(3) dissolving 1.75g of oxalic acid dihydrate in 21.88mL of N, N-diethyl acetamide to obtain an oxalic acid solution with the mass concentration of 8%;
(4) dropwise adding the ferrous sulfate solution into the oxalic acid solution under the stirring conditions of 25 ℃ and 300rpm, controlling the dropwise adding time to be 60min, standing for 1h at 30 ℃, after centrifugal separation, sequentially washing the precipitate with absolute ethyl alcohol and deionized water until the pH value of the solution is about 7, and then drying for 4h at 80 ℃ in a forced air drying oven to obtain the ferrous oxalate nanowire.
Example 2
The mass of polyvinyl alcohol in step (1) of example 1 was replaced with 0.386g, and the solution was dissolved in 77.2mL of deionized water to obtain a 0.5 wt% polyvinyl alcohol solution, and the procedure was otherwise the same as in example 1.
Example 3
The mass of polyvinyl alcohol in step (1) of example 1 was replaced with 0.772g, and the solution was dissolved in 77.2mL of deionized water to obtain a 1 wt% polyvinyl alcohol solution, with the same parameters as in example 1.
Comparative example 1
(1) Dissolving 3.86g of ferrous sulfate heptahydrate in 77.2mL of deionized water to obtain a ferrous sulfate mixed solution with the mass concentration of 5%;
(2) dissolving 1.75g of oxalic acid dihydrate into 21.88mL of deionized water to obtain an oxalic acid solution with the mass concentration of 8%;
(3) dropwise adding the ferrous sulfate solution into the oxalic acid solution under the stirring conditions of 25 ℃ and 300rpm, controlling the dropwise adding time to be 60min, standing for 1h at 30 ℃, after centrifugal separation, sequentially washing and precipitating with absolute ethyl alcohol and deionized water until the pH value of the solution is 7, and then drying for 4h at 80 ℃ in a forced air drying oven to obtain ferrous oxalate microparticles.
Comparative example 2
(1) Dissolving 3.86g of ferrous sulfate heptahydrate in 77.2mL of deionized water to obtain a ferrous sulfate mixed solution with the mass concentration of 5%;
(2) dissolving 1.75g of oxalic acid dihydrate in 21.88mL of N, N-diethyl acetamide to obtain an oxalic acid solution with the mass concentration of 8%;
(3) dropwise adding the ferrous sulfate solution into the oxalic acid solution under the stirring conditions of 25 ℃ and 300rpm, controlling the dropwise adding time to be 60min, standing for 1h at 30 ℃, carrying out centrifugal separation, sequentially washing and precipitating with absolute ethyl alcohol and deionized water until the pH value of the solution is about 7, and drying for 4h at 80 ℃ in a forced air drying oven to obtain the ferrous oxalate nanoparticles.
Comparative example 3
(1) Dissolving 0.077g of polyvinyl alcohol in 77.2mL of deionized water to obtain a 0.1 wt% polyvinyl alcohol solution, and mixing the 0.1 wt% polyvinyl alcohol solution with 3.86g of ferrous sulfate heptahydrate to obtain a ferrous sulfate solution with the mass concentration of 5%;
(2) dissolving 1.75g of oxalic acid dihydrate into 21.88mL of deionized water to obtain an oxalic acid solution with the mass concentration of 8%;
(3) dropwise adding the ferrous sulfate solution into the oxalic acid solution under the stirring conditions of 25 ℃ and 300rpm, controlling the dropwise adding time to be 60min, standing for 1h at 30 ℃, after centrifugal separation, sequentially washing and precipitating with absolute ethyl alcohol and deionized water until the pH value of the solution is about 7, and then drying for 4h at 80 ℃ in a forced air drying oven to obtain the ferrous oxalate nanorod.
Characterization and Performance testing
1) XRD patterns of the products prepared in examples 1 to 3 and comparative examples 1 to 3 were tested and compared with a standard pattern of beta-ferrous oxalate (PDF #22-0635), and the results are shown in FIGS. 2, 4, 6, 8, 10 and 12. As can be seen from the XRD patterns, the ferrous oxalate prepared by the method is beta-ferrous oxalate.
2) SEM images of the products prepared in examples 1 to 3 and comparative examples 1 to 3 were measured, and the results are shown in FIGS. 3, 5, 7, 9, 11 and 13. From the SEM images, the ferrous oxalate products prepared by the embodiment of the invention are all nanowires with a mesh distribution, the diameter is 15-100 nm, in the preparation process of the ferrous oxalate, the polyvinyl alcohol and the N, N-diethylacetamide are added simultaneously to obtain the ferrous oxalate nanowires, and the particle size of the nanowires can be adjusted by adjusting the dosage of the polyvinyl alcohol. Specifically, when the mass concentration of the polyvinyl alcohol is 0.1 wt%, the diameter of the ferrous oxalate nanowire is about 84nm (fig. 3); when the mass concentration of the polyvinyl alcohol is 0.5 wt%, the diameter of the ferrous oxalate nanowire is about 67nm (fig. 5); when the mass concentration of the polyvinyl alcohol was 1.0 wt%, the diameter of the ferrous oxalate nanowire was about 17nm (fig. 7). In conclusion, the preparation method provided by the invention can obtain the ferrous oxalate nanowire.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of the ferrous oxalate nanowire is characterized by comprising the following steps:
mixing ferrous salt with a polyvinyl alcohol-water mixed solvent to obtain a ferrous salt solution;
mixing oxalic acid with N, N-diethyl acetamide to obtain an oxalic acid solution;
and mixing the ferrous salt solution with an oxalic acid solution, and carrying out precipitation reaction to obtain the ferrous oxalate nanowire.
2. The method according to claim 1, wherein the ferrous salt includes one of ferrous sulfate heptahydrate, ferrous chloride, ferrous ammonium sulfate, and ferrous nitrate.
3. The preparation method according to claim 1, wherein the mass concentration of the ferrous salt in the ferrous salt solution is 1-10%.
4. The method according to claim 1, wherein the polyvinyl alcohol is present in the polyvinyl alcohol-water mixed solvent at a concentration of 0.1 to 5% by mass.
5. The method according to claim 1, wherein the oxalic acid solution has a mass concentration of 1 to 20%.
6. The preparation method according to claim 1, wherein the temperature of the precipitation reaction is 20-40 ℃; the time of the precipitation reaction is 0.5-2 h.
7. The preparation method according to claim 1, wherein after the precipitation reaction is completed, the obtained precipitation product is sequentially subjected to centrifugal separation, washing and drying to obtain the ferrous oxalate nanowires.
8. The preparation method according to claim 7, wherein the drying temperature is 70-90 ℃ and the drying time is 3-5 h.
9. The ferrous oxalate nanowire prepared by the preparation method of any one of claims 1 to 8, wherein the ferrous oxalate nanowire has a network-like structure and a diameter of 15 to 100 nm.
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| CN102344356A (en) * | 2010-08-05 | 2012-02-08 | 中国科学院宁波材料技术与工程研究所 | Battery grade nano ferrous oxalate, its preparation method and application |
| CN102649587A (en) * | 2011-02-24 | 2012-08-29 | 中国科学院兰州化学物理研究所 | Alpha-phase ferric oxide preparation method |
| CN103922920A (en) * | 2014-04-16 | 2014-07-16 | 安徽中医药大学 | Preparation method of one-dimensional ferrous oxalate nanowire |
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| CN102344356A (en) * | 2010-08-05 | 2012-02-08 | 中国科学院宁波材料技术与工程研究所 | Battery grade nano ferrous oxalate, its preparation method and application |
| CN102649587A (en) * | 2011-02-24 | 2012-08-29 | 中国科学院兰州化学物理研究所 | Alpha-phase ferric oxide preparation method |
| CN103922920A (en) * | 2014-04-16 | 2014-07-16 | 安徽中医药大学 | Preparation method of one-dimensional ferrous oxalate nanowire |
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