CN114181068A - Cerium-doped copper oxalate nano material and preparation method thereof - Google Patents
Cerium-doped copper oxalate nano material and preparation method thereof Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 87
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 118
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 99
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 36
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 33
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 33
- 239000013110 organic ligand Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 30
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000000975 co-precipitation Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 150000000703 Cerium Chemical class 0.000 claims abstract description 15
- 150000001879 copper Chemical class 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 24
- 229940039748 oxalate Drugs 0.000 claims description 21
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 15
- 229940039790 sodium oxalate Drugs 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 5
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical group C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims 1
- SKEYZPJKRDZMJG-UHFFFAOYSA-N cerium copper Chemical compound [Cu].[Ce] SKEYZPJKRDZMJG-UHFFFAOYSA-N 0.000 abstract description 8
- 210000003743 erythrocyte Anatomy 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 20
- 239000013078 crystal Substances 0.000 description 20
- 229910052684 Cerium Inorganic materials 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 18
- 238000009210 therapy by ultrasound Methods 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000012046 mixed solvent Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- -1 e.g. Chemical compound 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000003921 particle size analysis Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229960001759 cerium oxalate Drugs 0.000 description 2
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 238000010276 construction Methods 0.000 description 1
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- 210000000267 erythroid cell Anatomy 0.000 description 1
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- 238000007210 heterogeneous catalysis Methods 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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Images
Classifications
-
- 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
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
Abstract
The invention relates to the technical field of nano materials, and discloses a preparation method of a cerium-doped copper oxalate nano material, which comprises the following steps: (1) dissolving water-soluble cerium salt and water-soluble copper salt as metal sources in a solvent, and completely dissolving to obtain a solution A; dissolving water-soluble oxalate and hexamethylenetetramine as organic ligands in a solvent, and completely dissolving to obtain a solution B; the solvent is a mixed solution of deionized water and ethylene glycol; (2) and pouring the solution B into the solution A, keeping the stirring state for coprecipitation reaction, decompressing, filtering, and drying to obtain the cerium-doped copper oxalate nano material. The nano material prepared by the method has a specific geometric structure, namely a disc-shaped copper-cerium-containing nano structure with concave middle parts on two sides similar to red blood cells of a human body, the obtained product is a cerium-doped copper oxalate structure, the crystallinity is high, the uniformity is good, and the important application prospect is expected to be played in the fields of catalysis and the like.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a nano-microstructure regulation and control technology of a rare earth element-containing material, and more particularly relates to a cerium-doped copper oxalate nano material and a preparation method thereof.
Background
Cerium (Ce) is the light rare earth element with the highest earth abundance, and the special outer layer 4f orbital electronic structure (4f15d16s2) of the cerium (Ce) enables Ce to be reversibly converted between Ce3+ and Ce4+
Shows stronger oxidation-reduction capability. When Ce is used as the central atom of the complex, the remaining multiple electron orbitals can form new chemical bonds with other substances, and the characteristic makes rare earth elements called 'industrial vitamins' have important application scenes, wherein the material containing the rare earth element Ce shows excellent characteristics in various fields (J.Am.chem.Soc.,2003,125(6): 1494-1495.).
However, the preparation of the cerium nano-material containing the rare earth element in the prior art has a technical shortness, namely the preparation process is complex and often needs a high-temperature high-pressure reaction process, and the prepared product has a single micro-geometric structure and is mostly in a spherical, sheet or rod structure, so that the exertion of specific functions of the material is limited.
Therefore, the development of a simple, efficient, economical and environment-friendly method for preparing the copper-cerium-element-containing nanomaterial with a special regular geometric structure is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a controllable preparation method of a disc-shaped cerium-doped copper oxalate nanostructure having a shape similar to human erythrocytes, i.e., having a concave shape in the middle of two sides, and aims to solve the problems of design and construction of a novel nanostructure containing rare earth element Ce. The preparation method has the characteristics of simplicity, high efficiency, low cost, environmental friendliness and the like, the nano material containing the copper and cerium elements with the regular geometric structure is prepared, the obtained product has a human-body-like erythrocyte shape, is uniform in size and good in dispersity, and an effective strategy is provided for developing the copper and cerium structural material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a cerium-doped copper oxalate nano material comprises the following steps:
(1) dissolving water-soluble cerium salt and water-soluble copper salt as metal sources in a solvent, and completely dissolving to obtain a solution A;
dissolving water-soluble oxalate and hexamethylenetetramine as organic ligands in a solvent, and completely dissolving to obtain a solution B;
the solvent is a mixed solution of deionized water and ethylene glycol;
(2) and pouring the solution B into the solution A, keeping the stirring state for coprecipitation reaction, decompressing, filtering, and drying to obtain the cerium-doped copper oxalate nano material.
Has the advantages that: the method comprises the steps of respectively preparing a solution containing copper and cerium metal ions and a solution containing oxalate and hexamethylenetetramine by using a coprecipitation method and using a mixed solution of deionized water and ethylene glycol as a solvent, and fully mixing the solutions without adding any other organic additives to prepare the erythrocyte-like cerium-doped copper oxalate nano material. The method does not need a high-temperature high-pressure reaction environment, has a simple preparation process, has the characteristics of low production cost, no toxicity, no pollution and high yield, and is suitable for large-scale production. The nano material prepared by the method has a specific geometric structure, namely a disc-shaped copper-cerium-containing nano structure with concave middle parts on two sides similar to red blood cells of a human body, and the obtained product is a cerium-doped copper oxalate structure with high crystallinity and good uniformity. The structure is reported for the first time, and is expected to play an important application prospect in the fields of catalysis and the like.
As a preferable technical scheme of the invention, the mass ratio of the copper salt to the cerium salt in the metal source in the step (1) is 30: 1-4: 1, the mass ratio of the oxalate to the hexamethylenetetramine in the organic ligand is 1: 1-10: 1, and the mass ratio of the metal source to the organic ligand is 0.32: 1-2.4: 1. In the coprecipitation reaction, oxalate provides oxalate in an equimolar amount, and oxalate is combined with metal ions to form a solid product to be precipitated, wherein the amount of oxalate is greater than or equal to that of the metal ions. Hexamethylenetetramine is used as a surfactant, the main function of the hexamethylenetetramine is to regulate and control the surface tension of a solvent, the hexamethylenetetramine does not participate in the production of solid product materials, and the hexamethylenetetramine is only required to be kept at a moderate concentration.
As a preferable technical scheme of the invention, the concentration of metal ions in the solution A in the step (1) is 1.0-50 g/L; the concentration of the organic ligand in the solution B is 0.4-40 g/L, and the volume ratio of deionized water to ethylene glycol in the solvent is 53: 2-40: 15.
Has the advantages that: the mixed solution of deionized water and ethylene glycol is used as a solvent, and the viscosity of the solvent can be effectively increased due to the addition of the ethylene glycol, so that the mixed solution and the ethylene glycol are in a proper proportion, and the mixed solution is suitable for substance nucleation in the coprecipitation growth process, thereby realizing the generation of a target product. When the concentration of the metal ions in the reaction system is too small, the yield of the target product is too low; and if the concentration is too high and the kinetic reaction rate is too high, the agglomeration phenomenon in the growth and nucleation process can be caused, and the erythroid cell structure can not be formed.
More preferably, the mass ratio of the copper salt to the cerium salt in the metal source in the step (1) is 16:1, the mass ratio of the oxalate salt to hexamethylenetetramine in the organic ligand is 3:1, and the mass ratio of the metal source to the organic ligand is 1.28: 1; the concentration of metal ions in the solution A is 7.73 g/L; the concentration of the organic ligand in the solution B is 5.91g/L, and the volume ratio of the deionized water to the ethylene glycol in the solvent is 50: 5.
As the preferable technical scheme of the invention, the coprecipitation reaction temperature in the step (2) is 5-50 ℃, and the time is 10-120 min.
More preferably, the coprecipitation reaction temperature in the step (2) is 25 ℃ and the time is 30 min.
Has the advantages that: the temperature of the coprecipitation reaction is lower than 5 ℃, a solvent area is solidified, the solubility of a solute is reduced, and the precipitation is easy; the temperature is higher than 50 ℃, the reaction kinetics in the coprecipitation process is accelerated, the formation of a specific structure of a product is not facilitated, and the reaction condition of 25 ℃ close to room temperature is selected, so that the energy consumption can be reduced, and the reaction can be promoted to be carried out mildly. For the reaction time, when the reaction time is less than 10min, the microstructure of the product is not completely formed, and the reaction time exceeds 120min, the nucleation reaction in the reaction system is continuously carried out, so that the size of the obtained nano-particles is increased, the nano-particles do not belong to the nano-material category, and the appearance are changed.
As a preferable technical scheme of the invention, the step (2) is leached by absolute ethyl alcohol during decompression and suction filtration.
As a preferable technical scheme of the invention, the stirring speed of the step (2) is 800 rpm; the temperature of the drying was 60 ℃.
As a preferable technical solution of the present invention, the cerium salt is selected from one or more of cerium nitrate, cerium sulfate and cerium chloride; the copper salt is selected from one or more of copper nitrate, copper sulfate and copper chloride; the oxalate is selected from one or more of sodium oxalate, potassium oxalate and ammonium oxalate.
According to experimental mechanism, for the selection of metal source species, only the reagent raw material is required to provide metal ions with the same valence state, and the metal ions are not related to the anion species, such as obvious copper sulfate and copper chloride, the functions of the reagent raw material and the copper chloride are completely the same, and the reagent raw material and the copper chloride can be further mixed for use. Similarly, when an organic ligand is selected, it is only necessary to ensure that the oxalate selected provides oxalate, e.g., sodium oxalate and potassium oxalate, which are fully functional, may be used in combination.
More preferably, the cerium salt is cerium nitrate; the copper salt is copper sulfate; the oxalate is sodium oxalate.
The invention also aims to provide the cerium-doped copper oxalate nano material prepared by the preparation method. The nano material is light blue solid powder and is marked as Ce-CuC2O4Having a human erythrocyte-like structure, i.e., a discoid structure with a depression in the middle of both faces, andthe crystal structure is copper oxalate, and the size is uniform and the dispersibility is good.
Compared with the prior art, the invention discloses a preparation method of a cerium-doped copper oxalate nano material and a product thereof. The cerium-doped copper oxalate nano material with a specific geometric structure is prepared by a coprecipitation method, a high-temperature and high-pressure environment is not needed, the preparation process is simple, the adopted solvents are non-toxic, harmless and low-cost ethylene glycol and water, and in addition, any organic matter additive is not needed to be added, so that the prepared material is less in impurities, and the product purity is improved. The technical parameters provided by the invention can realize the preparation of the disc-shaped cerium-doped copper oxalate nano material with the human-body-like erythrocyte shape, namely, the middle concave parts on the two surfaces, and the preparation of the nano material with the specific geometric structure with different copper and cerium contents can be realized by regulating and controlling the feeding proportion of the metal salt in the reaction process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic Scanning Electron Microscope (SEM) illustration of a cerium-doped copper oxalate nanomaterial prepared in example 1 of the present invention, wherein a and b are SEM photographs of a sample at different magnifications, respectively;
FIG. 2 is a scanning electron microscopy (SEM-EDS) energy spectrum analysis diagram of the cerium-doped copper oxalate nano-material prepared in example 1 of the present invention;
FIG. 3 is a diagram of X-ray diffraction (XRD) patterns of cerium-doped copper oxalate nanomaterial prepared in example 1 of the present invention;
FIG. 4 is a graph showing a particle size analysis of a cerium-doped copper oxalate nanomaterial prepared in example 1 of the present invention;
FIG. 5 is a nitrogen adsorption desorption (BET) graph of cerium-doped copper oxalate nanomaterial prepared in example 1 of the present invention;
FIG. 6 is a thermogravimetric analysis (TGA) of cerium doped copper oxalate nanomaterial prepared in example 1 of the present invention;
fig. 7 is a Scanning Electron Microscope (SEM) image of a cerium-doped copper oxalate nanomaterial prepared in example 5 of the present invention, wherein a, b, c, and d are SEM photographs of the resulting material when X is 0, 0.1, 0.15, and 0.2, respectively);
FIG. 8 is a Scanning Electron Microscope (SEM) image of the copper oxalate nano-material prepared in example 6 of the present invention;
FIG. 9 is a Scanning Electron Microscope (SEM) image of a cerium oxalate nanomaterial prepared in example 7 of the present invention;
FIG. 10 is a Scanning Electron Microscope (SEM) image of the cobalt-doped copper oxalate nanomaterial prepared in example 8 of the present invention;
fig. 11 is a Scanning Electron Microscope (SEM) image of the nickel-doped copper oxalate nanomaterial prepared in example 9 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
A preparation method of a cerium-doped copper oxalate nano material comprises the following steps:
(1) dissolving water-soluble cerium salt and water-soluble copper salt as metal sources in a solvent, and completely dissolving to obtain a solution A;
dissolving water-soluble oxalate and hexamethylenetetramine as organic ligands in a solvent, and completely dissolving to obtain a solution B;
the solvent is a mixed solution of deionized water and ethylene glycol;
(2) and pouring the solution B into the solution A, keeping the stirring state for coprecipitation reaction, decompressing, filtering, and drying to obtain the cerium-doped copper oxalate nano material.
As a preferable technical scheme of the invention, the mass ratio of the copper salt to the cerium salt in the metal source in the step (1) is 30: 1-4: 1, the mass ratio of the oxalate to the hexamethylenetetramine in the organic ligand is 1: 1-10: 1, and the mass ratio of the metal source to the organic ligand is 0.32: 1-2.4: 1.
As a preferable technical scheme of the invention, the concentration of metal ions in the solution A in the step (1) is 1.0-50 g/L; the concentration of the organic ligand in the solution B is 0.4-40 g/L, and the volume ratio of deionized water to ethylene glycol in the solvent is 53: 2-40: 15.
More preferably, the mass ratio of the copper salt to the cerium salt in the metal source in the step (1) is 16:1, the mass ratio of the oxalate salt to hexamethylenetetramine in the organic ligand is 3:1, and the mass ratio of the metal source to the organic ligand is 1.28: 1; the concentration of metal ions in the solution A is 7.73 g/L; the concentration of the organic ligand in the solution B is 5.91g/L, and the volume ratio of the deionized water to the ethylene glycol in the solvent is 50: 5.
As the preferable technical scheme of the invention, the coprecipitation reaction temperature in the step (2) is 5-50 ℃, and the time is 10-120 min.
More preferably, the coprecipitation reaction temperature in the step (2) is 25 ℃ and the time is 30 min.
As a preferable technical scheme of the invention, the step (2) is leached by absolute ethyl alcohol during decompression and suction filtration.
As a preferable technical scheme of the invention, the stirring speed of the step (2) is 800 rpm; the temperature of the drying was 60 ℃.
As a preferable technical solution of the present invention, the cerium salt is selected from one or more of cerium nitrate, cerium sulfate and cerium chloride; the copper salt is selected from one or more of copper nitrate, copper sulfate and copper chloride; the oxalate is selected from one or more of sodium oxalate, potassium oxalate and ammonium oxalate.
More preferably, the cerium salt is cerium nitrate; the copper salt is copper sulfate; the oxalate is sodium oxalate.
Example 1
A preparation method of a cerium-doped copper oxalate nano material comprises the following steps:
(1) preparing a reaction solution containing a metal source: and (3) accurately adding 50mL of deionized water and 5mL of ethylene glycol into a 200mL beaker, then adding accurately weighed 0.8g of copper sulfate pentahydrate and 0.05g of cerium nitrate into the mixed solvent, carrying out ultrasonic treatment at normal temperature, and marking as a solution A when the crystals are completely dissolved.
Preparing a reaction solution containing an organic ligand: and (3) accurately adding 50mL of deionized water and 5mL of ethylene glycol into a 100mL beaker, accurately weighing 0.5g of sodium oxalate and 0.16g of Hexamethylenetetramine (HMT), and carrying out ultrasonic treatment at normal temperature until crystals are completely dissolved, wherein the solution is marked as solution B.
(2) Preparing a copper-cerium-containing nano structure by a coprecipitation method: slowly pouring the prepared solution B into the solution A, starting timing when the solution B is completely poured into the solution A, keeping the room temperature and stirring for reaction for 30min, wherein the stirring speed is 800 rpm. After the reaction time was over, the reaction mixture was rapidly filtered under reduced pressure, rinsed with absolute ethanol during the filtration, and then dried at 60 ℃ to obtain a sample, which was a cerium-doped copper oxalate nanomaterial prepared in this example and was denoted as Ce-CuC2O4。
Example 2
A preparation method of a cerium-doped copper oxalate nano material comprises the following steps:
(1) preparing a reaction solution containing a metal source: and (3) accurately adding 40mL of deionized water and 15mL of ethylene glycol into a 200mL beaker, then adding accurately weighed 0.104g of copper sulfate pentahydrate and 0.006g of cerium nitrate into the mixed solvent, carrying out ultrasonic treatment, and marking as a solution A when the crystals are completely dissolved.
Preparing a reaction solution containing an organic ligand: and (3) accurately adding 40mL of deionized water and 15mL of ethylene glycol into a 100mL beaker, accurately weighing 0.034g of sodium oxalate and 0.012g of Hexamethylenetetramine (HMT), and carrying out ultrasonic treatment until crystals are completely dissolved, wherein the solution is marked as solution B.
(2) Preparing a copper-cerium-containing nano structure by a coprecipitation method: and (3) cooling the solution to 5 ℃, then slowly pouring the prepared solution B into the solution A, starting timing when the solution B is completely poured into the solution A, and keeping stirring for reaction for 10 min. After the reaction time has been cut off, quicklyPerforming rapid vacuum filtration, leaching with absolute ethanol during the filtration, and drying the obtained sample at 60 ℃ to obtain light blue powder, which is the cerium-doped copper oxalate nano material prepared in the embodiment and is recorded as Ce-CuC2O4。
Example 3
A preparation method of a cerium-doped copper oxalate nano material comprises the following steps:
(1) preparing a reaction solution containing a metal source: and (3) accurately adding 53mL of deionized water and 2mL of ethylene glycol into a 200mL beaker, then adding accurately weighed 4.4g of copper sulfate pentahydrate and 1.1g of cerium nitrate into the mixed solvent, carrying out ultrasonic treatment at normal temperature, and marking as a solution A when the crystals are completely dissolved.
Preparing a reaction solution containing an organic ligand: a beaker with the specification of 100mL is taken, 53mL of deionized water and 2mL of ethylene glycol are accurately added, 14.1g of sodium oxalate and 2.95g of Hexamethylenetetramine (HMT) are accurately weighed and added, and ultrasonic treatment is carried out at normal temperature until crystals are completely dissolved, so that the solution B is marked.
(2) Preparing a copper-cerium-containing nano structure by a coprecipitation method: heating the solution to 50 ℃, then slowly pouring the prepared solution B into the solution A, starting timing when the solution B is completely poured into the solution A, and keeping stirring for reaction for 120 min. After the reaction time was over, the reaction mixture was rapidly filtered under reduced pressure, rinsed with absolute ethanol during the filtration, and then dried at 60 ℃ to obtain a sample, which was a cerium-doped copper oxalate nanomaterial prepared in this example and was denoted as Ce-CuC2O4。
Example 4
A preparation method of a cerium-doped copper oxalate nano material comprises the following steps:
(1) preparing a reaction solution containing a metal source: and (3) accurately adding 50mL of deionized water and 5mL of ethylene glycol into a 200mL beaker, then adding accurately weighed 0.8g of copper chloride dihydrate and 0.05g of cerium nitrate into the mixed solvent, carrying out ultrasonic treatment at normal temperature, and marking as a solution A when the crystals are completely dissolved.
Preparing a reaction solution containing an organic ligand: accurately adding 50mL of deionized water and 5mL of ethylene glycol into a 100mL beaker, accurately weighing 0.25g of potassium oxalate, 0.25g of sodium oxalate and 0.16g of Hexamethylenetetramine (HMT), and carrying out ultrasonic treatment at normal temperature until crystals are completely dissolved, wherein the solution is marked as solution B.
(2) Preparing a copper-cerium-containing nano structure by a coprecipitation method: slowly pouring the prepared solution B into the solution A, starting timing when the solution B is completely poured into the solution A, and keeping the room temperature to stir for reaction for 30 min. After the reaction time was over, the reaction mixture was rapidly filtered under reduced pressure, rinsed with absolute ethanol during the filtration, and then dried at 60 ℃ to obtain a sample, which was a cerium-doped copper oxalate nanomaterial prepared in this example and was denoted as Ce-CuC2O4。
Example 5:
a preparation method of a cerium-doped copper oxalate nano material comprises the following steps:
(1) preparing a reaction solution containing a metal source: accurately adding 50mL of deionized water and 5mL of ethylene glycol into a 200mL beaker, then adding accurately weighed 0.8g of copper sulfate pentahydrate and X g (X is 0, 0.10, 0.15 and 0.20) of cerium nitrate into the mixed solvent, carrying out ultrasonic treatment at normal temperature, and marking as a solution A when the crystals are completely dissolved.
Preparing a reaction solution containing an organic ligand: and (3) accurately adding 50mL of deionized water and 5mL of ethylene glycol into a 100mL beaker, accurately weighing 0.5g of sodium oxalate and 0.16g of Hexamethylenetetramine (HMT), and carrying out ultrasonic treatment at normal temperature until crystals are completely dissolved, wherein the solution is marked as solution B.
(2) Preparing a copper-cerium-containing nano structure by a coprecipitation method: slowly pouring the prepared solution B into the solution A, starting timing when the solution B is completely poured into the solution A, and keeping the room temperature to stir for reaction for 30 min. After the reaction time was over, the reaction mixture was rapidly filtered under reduced pressure, rinsed with absolute ethanol during the filtration, and then dried at 60 ℃ to obtain a sample, which was a cerium-doped copper oxalate nanomaterial prepared in this example and was denoted as Ce-CuC2O4。
Example 6:
a preparation method of a copper oxalate nano material comprises the following steps:
(1) preparing a reaction solution containing a metal source: and (3) accurately adding 50mL of deionized water and 5mL of ethylene glycol into a 200mL beaker, then adding accurately weighed 0.8g of pentahydrate and copper sulfate into the mixed solvent, carrying out ultrasonic treatment at normal temperature, and marking as a solution A when the crystals are completely dissolved.
Preparing a reaction solution containing an organic ligand: and (3) accurately adding 50mL of deionized water and 5mL of ethylene glycol into a 100mL beaker, accurately weighing 0.5g of sodium oxalate and 0.16g of Hexamethylenetetramine (HMT), and carrying out ultrasonic treatment at normal temperature until crystals are completely dissolved, wherein the solution is marked as solution B.
(2) Preparing a copper-containing nano structure by a coprecipitation method: slowly pouring the prepared solution B into the solution A, starting timing when the solution B is completely poured into the solution A, and keeping the room temperature to stir for reaction for 30 min. After the reaction time was over, the reaction mixture was rapidly filtered under reduced pressure, rinsed with absolute ethanol during the filtration, and then the resulting sample was dried at 60 ℃ to obtain a light blue powder, which was the copper-containing nanomaterial prepared in this example and was designated as CuC2O4。
Example 7:
a preparation method of a cerium-containing nano material comprises the following steps:
(1) preparing a reaction solution containing a metal source: and (3) accurately adding 50mL of deionized water and 5mL of ethylene glycol into a 200mL beaker, then adding accurately weighed 0.8g of cerium nitrate into the mixed solvent, carrying out ultrasonic treatment at normal temperature, and marking as a solution A when the crystals are completely dissolved.
Preparing a reaction solution containing an organic ligand: and (3) accurately adding 50mL of deionized water and 5mL of ethylene glycol into a 100mL beaker, accurately weighing 0.5g of sodium oxalate and 0.16g of Hexamethylenetetramine (HMT), and carrying out ultrasonic treatment at normal temperature until crystals are completely dissolved, wherein the solution is marked as solution B.
(2) Preparing a copper-containing nano structure by a coprecipitation method: slowly pouring the prepared solution B into the solution A, starting timing when the solution B is completely poured into the solution A, and keeping the room temperature to stir for reaction for 30 min. After the reaction time was over, the reaction mixture was rapidly filtered under reduced pressure, rinsed with absolute ethanol during the filtration, and then dried at 60 ℃ to obtain a white powder, which is the cerium-containing nanomaterial prepared in this example and is designated as CeC2O4。
Example 8:
a preparation method of a cobalt and copper containing nano material comprises the following steps:
(1) preparing a reaction solution containing a metal source: and (3) accurately adding 50mL of deionized water and 5mL of ethylene glycol into a 200mL beaker, then adding accurately weighed 0.8g of copper sulfate pentahydrate and 0.05g of cobalt nitrate hexahydrate into the mixed solvent, carrying out ultrasonic treatment at normal temperature, and marking as a solution A when the crystals are completely dissolved.
Preparing a reaction solution containing an organic ligand: and (3) accurately adding 50mL of deionized water and 5mL of ethylene glycol into a 100mL beaker, accurately weighing 0.5g of sodium oxalate and 0.16g of Hexamethylenetetramine (HMT), and carrying out ultrasonic treatment at normal temperature until crystals are completely dissolved, wherein the solution is marked as solution B.
(2) Preparing a copper-containing nano structure by a coprecipitation method: slowly pouring the prepared solution B into the solution A, starting timing when the solution B is completely poured into the solution A, and keeping the room temperature to stir for reaction for 30 min. After the reaction time was over, the reaction mixture was rapidly filtered under reduced pressure, rinsed with absolute ethanol during the filtration, and then dried at 60 ℃ to obtain a sample, which was a cobalt and copper containing nanostructure prepared in this example and was designated as Co-CuC2O4。
Example 9:
a method for preparing a nano material containing nickel and copper comprises the following steps:
(1) preparing a reaction solution containing a metal source: and (3) accurately adding 50mL of deionized water and 5mL of ethylene glycol into a 200mL beaker, then adding accurately weighed 0.8g of copper sulfate pentahydrate and 0.05g of nickel nitrate hexahydrate into the mixed solvent, carrying out ultrasonic treatment at normal temperature, and marking as a solution A when the crystals are completely dissolved.
Preparing a reaction solution containing an organic ligand: and (3) accurately adding 50mL of deionized water and 5mL of ethylene glycol into a 100mL beaker, accurately weighing 0.5g of sodium oxalate and 0.16g of Hexamethylenetetramine (HMT), and carrying out ultrasonic treatment at normal temperature until crystals are completely dissolved, wherein the solution is marked as solution B.
(2) Preparing a copper-containing nano structure by a coprecipitation method: slowly pouring the prepared solution B into the solution A, starting timing when the solution B is completely poured into the solution A, and keeping the room temperature to stir for reaction for 30 min.After the reaction time was over, the reaction mixture was rapidly filtered under reduced pressure, rinsed with absolute ethanol during the filtration, and then dried at 60 ℃ to obtain a sample, which was a nickel and copper-containing nanostructure prepared in this example and was denoted as Ni-CuC2O4。
Effect example 1
The nano-materials prepared in the above examples are scanned by an electron microscope, and all the cerium-doped copper oxalate nano-materials obtained in examples 1 to 5 have a quasi-erythrocyte structure. Wherein, the scanning electron microscope picture of the embodiment 1 refers to an attached figure 1, the scanning electron microscope picture of the embodiment 5 refers to an attached figure 7, the scanning electron microscope picture of the embodiment 6 refers to an attached figure 8, the scanning electron microscope picture of the embodiment 7 refers to an attached figure 9, the scanning electron microscope picture of the embodiment 8 refers to an attached figure 10, and the scanning electron microscope picture of the embodiment 9 refers to an attached figure 11; the nanomaterial prepared in example 1 was subjected to energy spectrum analysis (see fig. 2), X-ray diffraction analysis (see fig. 3), particle size analysis (see fig. 4), nitrogen adsorption/desorption analysis (see fig. 5), and thermogravimetric analysis (see fig. 6).
As shown in the accompanying drawing 1, the Scanning Electron Microscope (SEM) shows that the obtained cerium-doped copper oxalate nano-material is a flat disc-shaped structure, and the upper and lower surfaces of the nano-material are concave in the middle, similar to the human erythrocyte structure. The nano material shown in the photo has uniform particle size, and the scanning electron microscope photo under a high power lens shows that the particle surface is a flat sphere formed by self-assembling flakes.
As shown in the energy spectrum test analysis result (SEM-EDS) of fig. 2, the obtained product cerium-doped copper oxalate nanomaterial contains copper as the main metal component and a small amount of cerium, wherein the atomic number (at.ratio) ratio of the copper to the cerium is 3.7: 1. It can be seen that the material is rich in carbon and oxygen elements, which are derived from oxalate ions in the reaction, and the oxalate ions and metal ions combine to form a precipitate in the solution system.
As shown in the X-ray diffraction result (XRD) of the attached figure 3, the content of cerium in the obtained cerium-doped copper oxalate nano material is too low, so that a single cerium oxalate precipitate cannot be formed, and cerium exists in the copper oxalate crystal structure only in a doped form.
As can be seen from the particle size analysis result of FIG. 4, the obtained cerium-doped copper oxalate nano-material has a narrow particle size distribution, which indicates that the particle size uniformity is high, and the average particle size of the particles is 340 nm.
As shown in the nitrogen adsorption-desorption graph (BET) of FIG. 5, the specific surface area of the obtained cerium-doped copper oxalate nano material is 0.47m2(ii) in terms of/g. Further, the hysteresis loop in the figure is known to correspond to the H4 type adsorption isotherm, indicating that the obtained product itself contains abundant microporous structure, and the abundant pore structure helps the material to expose more active sites in the heterogeneous catalysis process, and promotes the combination and desorption rate of reactants and products.
From the results of thermogravimetric analysis (TGA) test shown in fig. 6, the organic structure in the obtained cerium-doped copper oxalate nanomaterial gradually decomposes from 100 ℃ and completely decomposes at 300 ℃, and the mass loss of the material is 49%, which indicates that the content of metal element in the product is about 50%. In addition, when the temperature is gradually raised to 450-600 ℃, a small amount of mass increase of the material occurs, which is caused by a small amount of oxidation of the residual metal components.
As can be seen from FIG. 7, the ratio of the metal sources copper and cerium in the initial stage of material preparation can be adjusted to realize the nano-structure materials with different copper-cerium ratios. When the feeding (g) ratio of the copper sulfate pentahydrate to the cerium nitrate is 0.8:0 (figure 7-a), 0.8:0.1 (figure 7-b), 0.8:0.15 (figure 7-c) and 0.8:0.2 (figure 7-d), respectively. As can be seen, when no metal cerium source is added, the obtained product is in the form of amorphous granules, as shown in FIG. 7 (a); when a source of metallic cerium is added in an amount, the resulting product exhibits a red cell-like structure, as shown in fig. 7 (b-d), indicating that the formation of this particular geometry is due to the combined action of the metallic elements copper and cerium.
As can be seen from FIG. 8, when only a single metal source, Cu source, is added, and no Ce source is added, the morphology of the obtained product is characterized by irregular shrivelled spherical structure, and no erythrocyte-like structure is formed. As can be seen from FIG. 9, when only the metal Ce source is added, the morphology of the resulting product is irregular and plate-like. Therefore, under the reaction conditions of the invention, the metal Cu dominates the formation of the spherical structure, and the metal Ce dominates the formation of the sheet structure, when the ratio of the two structures is within a certain interval, the shrivelled spherical structure with the self-assembled sheet shape and the depressed middle part can be formed, namely the human erythrocyte-like nano structure.
As can be seen from FIG. 10, when Co is used instead of Ce, the morphology of the obtained product is characterized by an ellipsoidal particle structure. As shown in FIG. 11, when Ni is further used to replace Ce, the morphology of the product is also characterized by a spherical particle structure. Both fail to form erythroid structures. It is further shown that the formation of this particular geometry is closely related to the reaction conditions described herein and the presence of the metallic elements Cu and Ce.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A preparation method of a cerium-doped copper oxalate nano material is characterized by comprising the following steps:
(1) dissolving water-soluble cerium salt and water-soluble copper salt as metal sources in a solvent, and completely dissolving to obtain a solution A;
dissolving water-soluble oxalate and hexamethylenetetramine as organic ligands in a solvent, and completely dissolving to obtain a solution B;
the solvent is a mixed solution of deionized water and ethylene glycol;
(2) and pouring the solution B into the solution A, keeping the stirring state for coprecipitation reaction, decompressing, filtering, and drying to obtain the cerium-doped copper oxalate nano material.
2. The method for preparing the cerium-doped copper oxalate nanomaterial according to claim 1, wherein the mass ratio of the copper salt to the cerium salt in the metal source in the step (1) is 30: 1-4: 1, the mass ratio of the oxalate to hexamethylenetetramine in the organic ligand is 1: 1-10: 1, and the mass ratio of the metal source to the organic ligand is 0.32: 1-2.4: 1.
3. The method according to claim 2, wherein the concentration of metal ions in the solution A in the step (1) is 1.0-50 g/L; the concentration of the organic ligand in the solution B is 0.4-40 g/L, and the volume ratio of deionized water to ethylene glycol in the solvent is 53: 2-40: 15.
4. The method for preparing the cerium-doped copper oxalate nanomaterial according to claim 3, wherein the mass ratio of the copper salt to the cerium salt in the metal source in the step (1) is 16:1, the mass ratio of the oxalate to hexamethylenetetramine in the organic ligand is 3:1, and the mass ratio of the metal source to the organic ligand is 1.28: 1;
the concentration of metal ions in the solution A is 7.73 g/L; the concentration of the organic ligand in the solution B is 5.91g/L, and the volume ratio of the deionized water to the ethylene glycol in the solvent is 50: 5.
5. The method for preparing a cerium-doped copper oxalate nanomaterial according to claim 1, wherein the coprecipitation reaction in step (2) is carried out at a temperature of 5-50 ℃ for 10-120 min.
6. The method according to claim 5, wherein the temperature of the coprecipitation reaction in step (2) is 25 ℃ and the time is 30 min.
7. The method for preparing the cerium-doped copper oxalate nanomaterial according to claim 1, wherein the cerium salt is selected from one or more of cerium nitrate, cerium sulfate and cerium chloride; the copper salt is selected from one or more of copper nitrate, copper sulfate and copper chloride; the oxalate is selected from one or more of sodium oxalate, potassium oxalate and ammonium oxalate.
8. The cerium-doped copper oxalate nanomaterial prepared by the preparation method according to any one of claims 1 to 7, wherein the cerium-doped copper oxalate nanomaterial has a human erythrocyte-like structure, i.e., a discoid structure with two concave sides.
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