CN115364855A - Preparation method of cuprous oxide/titanium dioxide/graphene oxide ternary nano compound - Google Patents
Preparation method of cuprous oxide/titanium dioxide/graphene oxide ternary nano compound Download PDFInfo
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- CN115364855A CN115364855A CN202210907984.6A CN202210907984A CN115364855A CN 115364855 A CN115364855 A CN 115364855A CN 202210907984 A CN202210907984 A CN 202210907984A CN 115364855 A CN115364855 A CN 115364855A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 62
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 52
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 52
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 150000001875 compounds Chemical class 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 27
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 24
- 239000012153 distilled water Substances 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 23
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 239000001632 sodium acetate Substances 0.000 claims abstract description 17
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000002114 nanocomposite Substances 0.000 claims abstract description 14
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006479 redox reaction Methods 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000010949 copper Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000005485 electric heating Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000006303 photolysis reaction Methods 0.000 description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000011206 ternary composite Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/39—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of a cuprous oxide/titanium dioxide/graphene oxide ternary nano compound, which is characterized by comprising the following steps of: the method comprises the following steps: s1: sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to the molar ratio of 1; s2: adding graphene oxide into the mixed solution A, and controlling the mass ratio of the graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B; s3: and then transferring the suspension B into a hydrothermal reaction kettle, sealing, carrying out forced hydrolysis reaction and hydrothermal redox reaction at 160-200 ℃, reacting for 3-20 h, then naturally cooling, centrifugally separating, washing and vacuum drying to obtain the cuprous oxide/titanium dioxide/graphene oxide ternary nano composite. The invention has the advantages of simple preparation process, good operability, no pollution, no side reaction, high product purity, easily obtained raw materials and the like.
Description
Technical Field
The invention belongs to the field of synthesis of nano composite materials, and particularly relates to a preparation method of a cuprous oxide/titanium dioxide/graphene oxide ternary nano composite.
Background
Clean hydrogen energy is an important energy source in the future, hydrogen production is efficiently carried out at low cost, and especially hydrogen production by water photolysis is an important research direction for researchers. Since the titanium dioxide semiconductor is discovered to have the performance of hydrogen production by photolysis of water in 1972, the hydrogen production by photolysis of water has been paid attention and attention to by academia and industry. Under the irradiation of light with energy larger than or equal to the forbidden bandwidth of a semiconductor, electrons in the valence band of the photocatalytic material absorb the energy of incident photons and jump to a conduction band to form an electron/hole pair, holes and electrons migrate to the surface of the material to undergo redox reaction with water molecules adsorbed on the surface, namely, the electrons and water undergo reduction reaction to generate hydrogen, and the holes oxidize the water to generate oxygen. However, titanium dioxide, which is a wide band gap n-type semiconductor, is excited only by ultraviolet light and cannot effectively use energy of visible light, and in order to effectively use solar energy, it would be of great importance to develop a high-performance photocatalyst having visible light activity. Meanwhile, because electrons are negatively charged and holes are positively charged, electrons/holes generated by illumination in the photocatalytic material are easy to recombine, so that the photon efficiency is low, and the development of hydrogen production by water photolysis is seriously hindered. Therefore, how to prevent the recombination of 'electron/hole' and improve the efficiency of photocatalytic hydrogen production becomes one of the major challenges in the current international photocatalytic research field, and is also a bottleneck problem restricting the practicability of the photocatalytic hydrogen production technology. Therefore, in the practical application of the photocatalytic technology, the photocatalytic material is the core, and the activity and stability of the photocatalytic material are the key for determining whether the photocatalytic technology can be practically applied.
As is well known, cuprous oxide is an ideal visible light type photocatalytic material, has an energy band gap of about 2.17eV, can fully utilize visible light energy, is non-toxic and simple to prepare, and belongs to a narrow band gap p-type semiconductor. At present, the preparation method of cuprous oxide is various. Among them, the liquid phase reduction method is one of the most commonly used methods for preparing nano cuprous oxide, and cuprous oxide is usually prepared by reducing bivalent copper with reducing agents such as ascorbic acid, glucose, formaldehyde, hydrazine hydrate, sodium borohydride and the like under certain conditions. Although the preparation methods have respective advantages, reducing agents such as formaldehyde, hydrazine hydrate and the like have large toxicity, can cause certain pollution to the environment, and do not accord with the guiding idea of green chemistry. Meanwhile, in the liquid phase reduction method, the reducing agent is usually excessive, so that further reduction side reaction is easy to occur, the reaction is complex, and the condition is not easy to control. Therefore, researchers are always striving to find a new preparation method which is green and environment-friendly and has a simple process. Meanwhile, the recombination efficiency of the photoproduction electrons and the photoproduction holes of the single cuprous oxide pure phase is high, the visible light photocatalytic activity is restricted, but the recombination of the semiconductor material is one of effective ways for reducing the recombination of the photoproduction electron-hole pairs.
Aiming at the defects existing in the prior art for preparing cuprous oxide, the invention aims to disclose a novel preparation method of a cuprous oxide/titanium dioxide/graphene oxide ternary nano compound. In addition, graphene is used as a two-dimensional material and has good semiconductor performance and chemical stability, so that the graphene oxide, titanium dioxide and cuprous oxide are compounded to prepare a ternary heterojunction compound, separation of a photon-generated carrier is facilitated, and the photocatalytic efficiency of the composite photocatalyst is improved; meanwhile, the graphene is used as a carrier, so that the migration growth of titanium dioxide and cuprous oxide can be effectively inhibited, so that the nanoscale titanium dioxide and cuprous oxide can be obtained, and the photocatalytic performance of the ternary composite material is further improved through the synergistic effect of the three components.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the preparation method of the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite, which is green and environment-friendly, simple in process, free of side reaction and easy in obtaining of raw materials.
In order to solve the technical problems, the invention utilizes the reducing groups such as hydroxyl, epoxy and the like carried by the surface of graphene oxide to carry out hydrothermal oxidation-reduction reaction on bivalent copper (Cu) under hydrothermal conditions 2+ ) Reduction to monovalent copper (Cu) + ) And (3) in-situ deposition of cuprous oxide on the surface of the graphene oxide is carried out, and migration growth of the cuprous oxide is effectively inhibited, so that the in-situ deposited nano-scale cuprous oxide is obtained. Meanwhile, nano titanium dioxide is deposited on the surface of the graphene oxide in situ through forced hydrolysis and hydrothermal crystallization.
The technical scheme of the invention is summarized as follows:
a preparation method of a cuprous oxide/titanium dioxide/graphene oxide ternary nano compound comprises the following steps:
s1: sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to the molar ratio of 1;
s2: adding graphene oxide into the mixed solution A, and controlling the mass ratio of the graphene oxide to copper sulfate to be 5:1, stirring uniformly to obtain a suspension B;
s3: and then transferring the suspension B into a hydrothermal reaction kettle, sealing, performing forced hydrolysis reaction (reaction formula (1)) and hydrothermal redox reaction (reaction formula (2)) at 160-200 ℃, reacting for 3-20 h, naturally cooling, centrifugally separating, washing, and drying in vacuum to obtain the cuprous oxide/titanium dioxide/graphene oxide ternary nano composite.
Preferably, the concentration of copper sulfate in the mixed solution A is 0.005 to 0.02mol/L.
Preferably, the lining of the hydrothermal reaction kettle is made of polyphenyl.
Preferably, the forced hydrolysis reaction equation is:
preferably, the hydrothermal redox reaction equation is:
preferably, the washing method specifically comprises: the product was washed 2 times with distilled water and 1 time with anhydrous ethanol.
Preferably, the temperature of the vacuum drying is 85 ℃ and the time is 2h.
The invention has the beneficial effects that:
(1) The invention adopts a simple one-pot hydrothermal synthesis technology, has simple operation and is easy for industrial production.
(2) According to the invention, copper sulfate, titanium sulfate, sodium acetate and graphene oxide are used as raw materials, a toxic reducing agent is not needed, the ternary heterojunction photocatalyst can be efficiently synthesized, and the raw materials are easy to obtain, pollution-free and environment-friendly.
(3) The cuprous oxide/titanium dioxide/graphene oxide ternary nano compound prepared by the method has no side reaction and high product purity.
(4) The sodium acetate is weak acid strong base salt and is used as a medium pH control agent to promote forced hydrolysis reaction and hydrothermal redox reaction to proceed in a forward reaction direction; meanwhile, the existence of sodium acetate can maintain the pH value of the reaction system and prevent Cu + Disproportionation reaction is carried out, and the product is used as a protective agent of cuprous oxide to avoid excessive reduction of cuprous oxide into elemental copper, so that the yield and the product purity of the ternary nano-composite are obviously improved.
(5) According to the invention, the graphene oxide, titanium dioxide and cuprous oxide are compounded to prepare the ternary heterojunction compound, so that the separation efficiency of a photon-generated carrier is effectively improved, and the photocatalytic efficiency of the composite photocatalyst is further improved; meanwhile, the graphene is used as a carrier, so that the migration growth of titanium dioxide and cuprous oxide can be effectively inhibited, and then the nano-scale titanium dioxide and cuprous oxide are deposited on the surface of the graphene in situ, and the photocatalytic performance of the ternary composite material is further improved through the synergistic effect of the three components and the Fermi level difference.
Drawings
FIG. 1 is an X-ray diffraction pattern of the products prepared in examples 1-3.
FIG. 2 is an X-ray diffraction pattern of the products prepared in examples 1, 4-6.
FIG. 3 is an X-ray diffraction pattern of the products prepared in examples 1, 7-8 and comparative example.
Fig. 4 is a scanning electron microscope image of the product made in example 1.
FIG. 5 is a flow chart of the preparation method of the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite of the present invention.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example 1
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a mol ratio of 1;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of the graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
and transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl lining, sealing the reaction kettle, putting the reaction kettle into an electric heating box, preserving the heat for 6 hours at 160 ℃, naturally cooling to room temperature, centrifugally separating, washing the product with distilled water for 2 times, washing the product with absolute ethyl alcohol for 1 time, and drying in vacuum for 2 hours at 85 ℃ to obtain the product.
The product prepared in example 1 was analyzed by X-ray diffraction, and the phase composition thereof was a cuprous oxide/titanium dioxide/graphene oxide ternary complex, which was calculated using the scherrer equation to obtain an average grain size of cuprous oxide of about 27nm and an average grain size of titanium dioxide of about 13nm.
Example 2
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a mol ratio of 1;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of the graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
and transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl lining, sealing the reaction kettle, putting the reaction kettle into an electric heating box, preserving the heat for 6 hours at 180 ℃, naturally cooling to room temperature, centrifugally separating, washing the product with distilled water for 2 times, washing the product with absolute ethyl alcohol for 1 time, and drying in vacuum for 2 hours at 85 ℃ to obtain the product.
The product prepared in example 2 was analyzed by X-ray diffraction, and the phase composition thereof was a cuprous oxide/titanium dioxide/graphene oxide ternary complex, which was calculated using the scherrer equation to obtain an average grain size of cuprous oxide of about 40nm and an average grain size of titanium dioxide of about 17nm.
Example 3
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to the mol ratio of 1;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of the graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
and transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl lining, sealing the reaction kettle, putting the reaction kettle into an electric heating box, preserving the heat for 6 hours at 200 ℃, naturally cooling to room temperature, centrifugally separating, washing the product with distilled water for 2 times, washing the product with absolute ethyl alcohol for 1 time, and drying in vacuum for 2 hours at 85 ℃ to obtain the product.
The product prepared in example 3 was subjected to X-ray diffraction analysis, and the phase composition thereof was a cuprous oxide/titanium dioxide/graphene oxide ternary complex, and the average grain size of cuprous oxide was about 72nm and the average grain size of titanium dioxide was about 23nm, which were calculated using the scherrer equation.
Example 4
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a mol ratio of 1;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of the graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
and transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl lining, sealing the reaction kettle, putting the reaction kettle into an electric heating box, preserving the heat for 3 hours at 160 ℃, naturally cooling to room temperature, centrifugally separating, washing the product with distilled water for 2 times, washing the product with absolute ethyl alcohol for 1 time, and drying in vacuum for 2 hours at 85 ℃ to obtain the product.
The product prepared in example 4 was subjected to X-ray diffraction analysis, and the phase composition thereof was a cuprous oxide/titanium dioxide/graphene oxide ternary complex, and the average grain size of cuprous oxide was about 23nm and the average grain size of titanium dioxide was about 11nm, which were calculated using the scherrer equation.
Example 5
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a mol ratio of 1;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of the graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
and transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl lining, sealing the reaction kettle, putting the reaction kettle into an electric heating box, preserving the heat for 10 hours at 160 ℃, naturally cooling to room temperature, centrifugally separating, washing the product with distilled water for 2 times, washing the product with absolute ethyl alcohol for 1 time, and drying in vacuum for 2 hours at 85 ℃ to obtain the product.
The product prepared in example 5 was analyzed by X-ray diffraction, and the phase composition thereof was a cuprous oxide/titanium dioxide/graphene oxide ternary complex, which was calculated using the scherrer equation to obtain an average grain size of cuprous oxide of about 32nm and an average grain size of titanium dioxide of about 14nm.
Example 6
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to the mol ratio of 1;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of the graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
and transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl lining, sealing the reaction kettle, putting the reaction kettle into an electric heating box, preserving the heat for 20 hours at 160 ℃, naturally cooling to room temperature, centrifugally separating, washing the product with distilled water for 2 times, washing the product with absolute ethyl alcohol for 1 time, and drying in vacuum for 2 hours at 85 ℃ to obtain the product.
The product prepared in example 6 was analyzed by X-ray diffraction, and the phase composition thereof was a cuprous oxide/titanium dioxide/graphene oxide ternary complex, which was calculated using the scherrer equation to obtain an average grain size of cuprous oxide of about 41nm and an average grain size of titanium dioxide of about 19nm.
Example 7
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a molar ratio of 1;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of the graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
and transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polystyrene lining, sealing the reaction kettle, putting the reaction kettle into an electric heating box, preserving heat for 6 hours at 160 ℃, naturally cooling to room temperature, performing centrifugal separation, washing the product with distilled water for 2 times, washing the product with absolute ethyl alcohol for 1 time, and performing vacuum drying for 2 hours at 85 ℃ to obtain the product.
The product prepared in example 7 was subjected to X-ray diffraction analysis, and the phase composition thereof was a cuprous oxide/titanium dioxide/graphene oxide ternary complex, and the average grain size of cuprous oxide was about 26nm and the average grain size of titanium dioxide was about 13nm, which were calculated using the scherrer equation.
Example 8
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a mol ratio of 1;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of the graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
and transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl lining, sealing the reaction kettle, putting the reaction kettle into an electric heating box, preserving the heat for 6 hours at 160 ℃, naturally cooling to room temperature, centrifugally separating, washing the product with distilled water for 2 times, washing the product with absolute ethyl alcohol for 1 time, and drying in vacuum for 2 hours at 85 ℃ to obtain the product.
The product prepared in example 8 was subjected to X-ray diffraction analysis, and the phase composition thereof was a cuprous oxide/titanium dioxide/graphene oxide ternary complex, and the average grain size of cuprous oxide was about 29nm and the average grain size of titanium dioxide was about 14nm, which were calculated using the scherrer equation.
Comparative example
The difference from example 1 is that: sodium acetate is not contained in the reaction system, and the details are as follows:
sequentially dissolving copper sulfate and titanium sulfate in distilled water according to a mol ratio of 1;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of the graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
and transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl lining, sealing the reaction kettle, putting the reaction kettle into an electric heating box, preserving the heat for 6 hours at 160 ℃, naturally cooling to room temperature, centrifugally separating, washing the product with distilled water for 2 times, washing the product with absolute ethyl alcohol for 1 time, and drying in vacuum for 2 hours at 85 ℃ to obtain the product.
X-ray diffraction analysis is carried out on the product prepared by the comparative example, and a strong elemental copper characteristic diffraction peak exists in a diffraction pattern, which shows that bivalent copper can be reduced into elemental copper when sodium acetate does not exist in the reaction raw material.
The products obtained in examples 1 to 3 were analyzed by X-ray diffraction, and the results are shown in FIG. 1. The analysis result shows that: the average grain size was calculated using the scherrer equation, indicating that the average grain size of the product gradually increased as the hydrothermal reaction temperature increased.
The products obtained in examples 1, 4 to 6 were analyzed by X-ray diffraction, and the results are shown in FIG. 2. The analysis result shows that: the average grain size was calculated using the scherrer equation, indicating that the average grain size of the product increased slightly as the hydrothermal reaction time was extended.
The products obtained in examples 1, 7 to 8 and comparative example were subjected to X-ray diffraction analysis, and the results are shown in FIG. 3. The analysis result shows that: as the copper ion concentration increases, the average grain size of the product increases slightly, but without sodium acetate in the raw material, divalent copper can be over-reduced to elemental copper.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (7)
1. A preparation method of a cuprous oxide/titanium dioxide/graphene oxide ternary nano compound is characterized by comprising the following steps: the method comprises the following steps:
s1: sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to the molar ratio of 1;
s2: adding graphene oxide into the mixed solution A, and controlling the mass ratio of the graphene oxide to copper sulfate to be 5:1, stirring uniformly to obtain a suspension B;
s3: and then transferring the suspension B into a hydrothermal reaction kettle, sealing, carrying out forced hydrolysis reaction and hydrothermal redox reaction at 160-200 ℃, reacting for 3-20 h, then naturally cooling, centrifugally separating, washing and vacuum drying to obtain the cuprous oxide/titanium dioxide/graphene oxide ternary nano composite.
2. The preparation method of the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite according to claim 1, wherein the preparation method comprises the following steps: the concentration of the copper sulfate in the mixed solution A is 0.005-0.02 mol/L.
3. The preparation method of the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite according to claim 1, wherein the preparation method comprises the following steps: the lining of the hydrothermal reaction kettle is made of polyphenyl.
4. The preparation method of the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite according to claim 1, wherein the preparation method comprises the following steps: the forced hydrolysis reaction equation is:
5. the preparation method of the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite according to claim 1, wherein the preparation method comprises the following steps: the hydrothermal oxidation-reduction reaction is to utilize the reducing groups, including hydroxyl and epoxy, carried by the surface of graphene oxide to react with Cu under the hydrothermal condition 2+ Reduction to Cu + The reaction equation is as follows:
6. the preparation method of the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite compound according to claim 1, wherein the preparation method comprises the following steps: the washing method specifically comprises the following steps: the product was washed 2 times with distilled water and 1 time with absolute ethanol.
7. The preparation method of the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite according to claim 1, wherein the preparation method comprises the following steps: the temperature of the vacuum drying is 85 ℃ and the time is 2h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101322939A (en) * | 2008-07-25 | 2008-12-17 | 华中师范大学 | Functional nano Ti2O/Cu2O heterophase Fenton thin film and preparation method as well as use |
| CN102350334A (en) * | 2011-08-08 | 2012-02-15 | 江苏大学 | Graphene/mesoporous titanium dioxide visible light catalyst and preparation method |
| CN103331159A (en) * | 2013-07-10 | 2013-10-02 | 中南大学 | Cu2O-TiO2/reduced graphene oxide ternary complex, and preparation method and applications thereof |
| CN103373739A (en) * | 2012-04-18 | 2013-10-30 | 宁波大学 | Hydrothermal preparation method of cuprous oxide crystal |
| CN106732591A (en) * | 2016-11-30 | 2017-05-31 | 浙江理工大学 | A kind of graphene-supported p N-shapeds Cu2O‑TiO2The preparation method of heterojunction nanometer material |
-
2022
- 2022-07-29 CN CN202210907984.6A patent/CN115364855B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101322939A (en) * | 2008-07-25 | 2008-12-17 | 华中师范大学 | Functional nano Ti2O/Cu2O heterophase Fenton thin film and preparation method as well as use |
| CN102350334A (en) * | 2011-08-08 | 2012-02-15 | 江苏大学 | Graphene/mesoporous titanium dioxide visible light catalyst and preparation method |
| CN103373739A (en) * | 2012-04-18 | 2013-10-30 | 宁波大学 | Hydrothermal preparation method of cuprous oxide crystal |
| CN103331159A (en) * | 2013-07-10 | 2013-10-02 | 中南大学 | Cu2O-TiO2/reduced graphene oxide ternary complex, and preparation method and applications thereof |
| CN106732591A (en) * | 2016-11-30 | 2017-05-31 | 浙江理工大学 | A kind of graphene-supported p N-shapeds Cu2O‑TiO2The preparation method of heterojunction nanometer material |
Non-Patent Citations (2)
| Title |
|---|
| KEXING LIU等: ""Influence of pH on Hydrothermal Synthesis of Photoactive Cu2O Films in an Acetate Solution"", INT. J. ELECTROCHEM. SCI. * |
| WANG ZHANG等: ""Rose rock-shaped nano Cu2O anchored graphene for high-performance supercapacitors via solvothermal route"", JOURNAL OF POWER SOURCES * |
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