CN115364855B - Preparation method of cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite - Google Patents
Preparation method of cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 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 51
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 51
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 42
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 37
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 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
- 238000000034 method Methods 0.000 claims abstract description 22
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000001632 sodium acetate Substances 0.000 claims abstract description 18
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 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 14
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 14
- 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
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 238000006479 redox reaction Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000011941 photocatalyst Substances 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 15
- 239000002131 composite material Substances 0.000 description 10
- 238000005485 electric heating Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 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
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 description 3
- 230000008569 process Effects 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
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 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
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000011206 ternary composite Substances 0.000 description 2
- 239000004593 Epoxy Chemical group 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
- 239000002253 acid Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 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
- 229910001431 copper ion Inorganic materials 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
- 238000006386 neutralization reaction Methods 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000035484 reaction time Effects 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
- 238000012546 transfer Methods 0.000 description 1
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- 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
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
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Abstract
The invention discloses a preparation method of a cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite, 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 a molar ratio of 1:0.5:10 to obtain a mixed solution A; 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 transferring the suspension B into a hydrothermal reaction kettle, sealing, performing forced hydrolysis reaction and hydrothermal oxidation-reduction reaction at 160-200 ℃, reacting for 3-20 h, and 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, easy obtainment of raw materials and the like.
Description
Technical Field
The invention belongs to the field of nanocomposite synthesis, and particularly relates to a preparation method of a cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite.
Background
Under the background of 'carbon peak and carbon neutralization', clean hydrogen energy is an important energy source in the future, and high-efficiency and low-cost hydrogen production, especially water photolysis hydrogen production, is an important research direction for researchers. Since the discovery in 1972 that titanium dioxide semiconductors have the ability to produce hydrogen by photolysis of water, hydrogen production by photolysis of water has been receiving attention and importance from academia and industry. Under the irradiation of light with energy greater than or equal to the semiconductor forbidden band width, electrons in the valence band of the photocatalytic material absorb the energy of incident photons and transfer to a conduction band to form electron/hole pairs, the holes and the electrons migrate to the surface of the material and undergo oxidation-reduction reaction with water molecules adsorbed on the surface, namely, the electrons undergo reduction reaction with water to generate hydrogen, and the hole oxidation water generates oxygen. However, titanium dioxide, which is a wide band gap n-type semiconductor, can only be excited by ultraviolet light and cannot effectively utilize energy of visible light, and in order to effectively utilize solar energy, it would be of great importance to develop a high-performance photocatalyst having visible light activity. Meanwhile, electrons are negatively charged, and holes are positively charged, so that electrons/holes generated by illumination in the photocatalytic material are easily combined, the light quantum efficiency is low, and the development of hydrogen production by water photocatalytic reaction is seriously hindered. Therefore, how to prevent the recombination of electrons and holes and improve the photocatalytic hydrogen production efficiency becomes one of the great challenges in the field of the current international photocatalytic research and is also a bottleneck problem for restricting the practical application of the photocatalytic hydrogen production technology. Therefore, in practical use of the photocatalytic technology, the photocatalytic material will be the core, and the activity and stability of the photocatalytic material are key to determine whether the photocatalytic technology can be practically used.
As is known, cuprous oxide is used as a p-type semiconductor with a narrow band gap, the band gap is about 2.17eV, the energy of visible light can be fully utilized, and the p-type semiconductor is nontoxic and simple to prepare, and belongs to an ideal visible light type photocatalytic material. 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 usually, reducing agents such as ascorbic acid, glucose, formaldehyde, hydrazine hydrate, sodium borohydride and the like are adopted to reduce bivalent copper under certain conditions to prepare cuprous oxide. Although the preparation methods have respective advantages, the reducing agents such as formaldehyde, hydrazine hydrate and the like have larger toxicity, cause certain pollution to the environment and do not accord with the guiding thought of green chemistry. Meanwhile, in the liquid phase reduction method, the reducing agent is usually excessive, further reduction side reaction is easy to occur, the reaction is complex, and the conditions are not easy to control. Researchers are continually striving to find new preparation methods which are environment-friendly and simple in process. Meanwhile, the single cuprous oxide pure-phase photo-generated electron and photo-generated hole have high recombination efficiency, so that the visible light photocatalytic activity is restricted, but the recombination of the semiconductor material is one of effective ways for reducing the photo-generated electron-hole pair recombination.
Aiming at the defects of the preparation of cuprous oxide in the prior art, the invention aims to disclose a novel preparation method of a ternary nano-composite of cuprous oxide/titanium dioxide/graphene oxide, wherein in the preparation process, a reducing agent is not required to be added in addition to three reaction raw materials of copper sulfate, titanium sulfate and graphene oxide and a medium pH value control agent sodium acetate, so that the preparation method is simple in process flow, raw materials are easy to obtain, and environment-friendly. In addition, graphene is taken as a two-dimensional material, and has good semiconductor performance and chemical stability, so that the ternary heterojunction compound is prepared by compositing graphene oxide with titanium dioxide and cuprous oxide, separation of photogenerated carriers is facilitated, and photocatalysis efficiency of a composite photocatalyst is improved; meanwhile, the graphene is used as a carrier, so that migration and growth of titanium dioxide and cuprous oxide can be effectively inhibited, 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 a preparation method of a cuprous oxide/titanium dioxide/graphene oxide ternary nano-composite, which is environment-friendly, simple in process, free of side reaction and easy to obtain raw materials.
In order to solve the technical problems, the invention utilizes the reducing groups such as hydroxyl, epoxy and the like which are self-contained on the surface of graphene oxide to react with bivalent copper (Cu) through hydrothermal oxidation-reduction under hydrothermal conditions 2+ ) Reduction to monovalent copper (Cu) + ) And the cuprous oxide is in-situ deposited on the surface of the graphene oxide, and migration and growth of the cuprous oxide are effectively inhibited, so that the in-situ deposited nanoscale 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:
the preparation method of the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite comprises the following steps:
s1: sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a molar ratio of 1:0.5:10 to obtain a mixed solution A;
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: transferring the suspension B into a hydrothermal reaction kettle, sealing, performing forced hydrolysis reaction (reaction formula (1)) and hydrothermal oxidation-reduction reaction (reaction formula (2)) at 160-200 ℃, reacting for 3-20 h, naturally cooling, centrifugally separating, washing, and vacuum drying to obtain the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite.
Preferably, the concentration of copper sulfate in the mixed solution A is 0.005-0.02 mol/L.
Preferably, the lining material of the hydrothermal reaction kettle is para-polyphenyl.
Preferably, the forced hydrolysis reaction equation is:
preferably, the hydrothermal oxidation-reduction reaction equation is:
preferably, the washing method specifically comprises the following steps: the product was washed 2 times with distilled water and 1 time with absolute ethanol.
Preferably, the temperature of the vacuum drying is 85 ℃ and the time is 2 hours.
The invention has the beneficial effects that:
(1) The invention adopts a simple one-pot hydrothermal synthesis technology, is simple to operate and is easy for industrial production.
(2) According to the method, copper sulfate, titanium sulfate, sodium acetate and graphene oxide are used as raw materials, a toxic reducing agent is not needed, and the ternary heterojunction photocatalyst can be synthesized efficiently.
(3) The cuprous oxide/titanium dioxide/graphene oxide ternary nano-composite prepared by the method has no side reaction and high product purity.
(4) The sodium acetate is weak acid and strong alkali salt, and is used as a medium pH value control agent to promote the forced hydrolysis reaction and the hydrothermal oxidation-reduction reaction to proceed towards the positive 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 to serve as a protective agent of cuprous oxide, so that the cuprous oxide is prevented from being excessively reduced into elemental copper, and the yield and the product purity of the ternary nano-composite are remarkably improved.
(5) According to the invention, the ternary heterojunction compound is prepared by compositing graphene oxide with titanium dioxide and cuprous oxide, so that the separation efficiency of photogenerated carriers is effectively improved, and the photocatalysis efficiency of the composite photocatalyst is further improved; meanwhile, the graphene is used as a carrier, so that migration and growth of titanium dioxide and cuprous oxide can be effectively inhibited, nanoscale titanium dioxide and cuprous oxide are further 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 three components and the fermi level difference.
Drawings
FIG. 1 is an X-ray diffraction pattern of the product made in examples 1-3.
FIG. 2 is an X-ray diffraction pattern of the products produced in examples 1, 4-6.
FIG. 3 shows the X-ray diffraction patterns of the products of examples 1, 7-8 and comparative examples.
Fig. 4 is a scanning electron microscope image of the product made in example 1.
Fig. 5 is a flow chart of a preparation method of the ternary nano composite of cuprous oxide/titanium dioxide/graphene oxide.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
Example 1
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a molar ratio of 1:0.5:10 to obtain a mixed solution A containing 0.01mol/L copper sulfate;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl liner, sealing the reaction kettle, placing the reaction kettle into an electric heating box, preserving heat for 6 hours at 160 ℃, naturally cooling to room temperature, centrifugally separating, washing a 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 subjected to X-ray diffraction analysis, and its phase composition was a ternary cuprous oxide/titanium dioxide/graphene oxide composite, and the average crystal grain size of cuprous oxide was about 27nm and the average crystal grain size of titanium dioxide was about 13nm as calculated by using the scherrer formula.
Example 2
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a molar ratio of 1:0.5:10 to obtain a mixed solution A containing 0.01mol/L copper sulfate;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl liner, sealing the reaction kettle, placing the reaction kettle into an electric heating box, preserving heat for 6 hours at 180 ℃, naturally cooling to room temperature, centrifugally separating, washing a product with distilled water for 2 times, washing the product with absolute ethyl alcohol for 1 time, and drying in vacuum at 85 ℃ for 2 hours to obtain the product.
The product prepared in example 2 was subjected to X-ray diffraction analysis, and its phase composition was a ternary cuprous oxide/titanium dioxide/graphene oxide composite, and the average crystal grain size of cuprous oxide was about 40nm and the average crystal grain size of titanium dioxide was about 17nm as calculated by using the scherrer formula.
Example 3
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a molar ratio of 1:0.5:10 to obtain a mixed solution A containing 0.01mol/L copper sulfate;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl liner, sealing the reaction kettle, placing the reaction kettle into an electric heating box, preserving heat for 6 hours at 200 ℃, naturally cooling to room temperature, centrifugally separating, washing a product with distilled water for 2 times, washing the product with absolute ethyl alcohol for 1 time, and drying in vacuum at 85 ℃ for 2 hours to obtain the product.
The product prepared in example 3 was subjected to X-ray diffraction analysis, and its phase composition was a ternary cuprous oxide/titanium dioxide/graphene oxide composite, and the average crystal grain size of cuprous oxide was about 72nm and the average crystal grain size of titanium dioxide was about 23nm as calculated by using the scherrer formula.
Example 4
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a molar ratio of 1:0.5:10 to obtain a mixed solution A containing 0.01mol/L copper sulfate;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl liner, sealing the reaction kettle, placing the reaction kettle into an electric heating box, preserving heat for 3 hours at 160 ℃, naturally cooling to room temperature, centrifugally separating, washing a product with distilled water for 2 times, washing the product with absolute ethyl alcohol for 1 time, and drying in vacuum at 85 ℃ for 2 hours to obtain the product.
The product prepared in example 4 was subjected to X-ray diffraction analysis, and its phase composition was a ternary cuprous oxide/titanium dioxide/graphene oxide composite, and the average crystal grain size of cuprous oxide was about 23nm and the average crystal grain size of titanium dioxide was about 11nm as calculated by using the scherrer equation.
Example 5
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a molar ratio of 1:0.5:10 to obtain a mixed solution A containing 0.01mol/L copper sulfate;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl liner, sealing the reaction kettle, placing the reaction kettle into an electric heating box, preserving heat for 10 hours at 160 ℃, naturally cooling to room temperature, centrifugally separating, washing a product with distilled water for 2 times, washing the product with absolute ethyl alcohol for 1 time, and vacuum drying at 85 ℃ for 2 hours to obtain the product.
The product prepared in example 5 was subjected to X-ray diffraction analysis, and its phase composition was a ternary cuprous oxide/titanium dioxide/graphene oxide composite, and the average crystal grain size of cuprous oxide was about 32nm and the average crystal grain size of titanium dioxide was about 14nm as calculated by using the scherrer equation.
Example 6
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a molar ratio of 1:0.5:10 to obtain a mixed solution A containing 0.01mol/L copper sulfate;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl liner, sealing the reaction kettle, placing the reaction kettle into an electric heating box, preserving heat for 20 hours at 160 ℃, naturally cooling to room temperature, centrifugally separating, washing a product with distilled water for 2 times, washing the product with absolute ethyl alcohol for 1 time, and vacuum drying at 85 ℃ for 2 hours to obtain the product.
The product prepared in example 6 was subjected to X-ray diffraction analysis, and its phase composition was a ternary cuprous oxide/titanium dioxide/graphene oxide composite, and the average crystal grain size of cuprous oxide was about 41nm and the average crystal grain size of titanium dioxide was about 19nm as calculated by using the scherrer formula.
Example 7
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a molar ratio of 1:0.5:10 to obtain a mixed solution A containing 0.005mol/L copper sulfate;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl liner, sealing the reaction kettle, placing the reaction kettle into an electric heating box, preserving heat for 6 hours at 160 ℃, naturally cooling to room temperature, centrifugally separating, washing a 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 7 was subjected to X-ray diffraction analysis, and its phase composition was a ternary cuprous oxide/titanium dioxide/graphene oxide composite, and the average crystal grain size of cuprous oxide was about 26nm and the average crystal grain size of titanium dioxide was about 13nm as calculated by using the scherrer formula.
Example 8
Sequentially dissolving copper sulfate, titanium sulfate and sodium acetate in distilled water according to a molar ratio of 1:0.5:10 to obtain a mixed solution A containing 0.02mol/L copper sulfate;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl liner, sealing the reaction kettle, placing the reaction kettle into an electric heating box, preserving heat for 6 hours at 160 ℃, naturally cooling to room temperature, centrifugally separating, washing a 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 its phase composition was a ternary cuprous oxide/titanium dioxide/graphene oxide composite, and the average crystal grain size of cuprous oxide was about 29nm and the average crystal grain size of titanium dioxide was about 14nm as calculated by using the scherrer equation.
Comparative example
The difference from example 1 is that: the reaction system is free of sodium acetate, and the specific steps are as follows:
sequentially dissolving copper sulfate and titanium sulfate in distilled water according to a molar ratio of 1:0.5 to obtain a mixed solution A containing 0.01mol/L copper sulfate;
at room temperature, adding graphene oxide into 30mL of mixed solution A, and controlling the mass ratio of graphene oxide to copper sulfate to be 5:1, uniformly stirring to obtain a suspension B;
transferring the suspension B into a 50mL hydrothermal reaction kettle with a para-polyphenyl liner, sealing the reaction kettle, placing the reaction kettle into an electric heating box, preserving heat for 6 hours at 160 ℃, naturally cooling to room temperature, centrifugally separating, washing a 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 when sodium acetate is not contained in the reaction raw materials, bivalent copper can be reduced into elemental copper.
The products obtained in examples 1-3 above were subjected to X-ray diffraction analysis, the results of which are shown in FIG. 1. The analysis results show 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 and 4-6 were subjected to X-ray diffraction analysis, and the results are shown in FIG. 2. The analysis results show that: the average grain size was calculated using the scherrer equation, indicating that the average grain size of the product slightly increased as the hydrothermal reaction time was extended.
The products obtained in examples 1, 7-8 and comparative example were subjected to X-ray diffraction analysis, and the results are shown in FIG. 3. The analysis results show that: as the copper ion concentration increases, the average grain size of the product increases slightly, but without sodium acetate in the feed, the cupric ion can be over-reduced to elemental copper.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (6)
1. A preparation method of a cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite photocatalyst 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 a molar ratio of 1:0.5:10 to obtain a mixed solution A, wherein the concentration of the copper sulfate in the mixed solution A is 0.005-0.02 mol/L;
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 transferring the suspension B into a hydrothermal reaction kettle, sealing, performing forced hydrolysis reaction and hydrothermal oxidation-reduction reaction at 160-200 ℃, reacting for 3-20 h, and then naturally cooling, centrifugally separating, washing and vacuum drying to obtain the cuprous oxide/titanium dioxide/graphene oxide ternary nano-composite.
2. The method for preparing the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite photocatalyst according to claim 1, wherein the method comprises the following steps: the lining material of the hydrothermal reaction kettle is para-polyphenyl.
3. The method for preparing the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite photocatalyst according to claim 1, wherein the method comprises the following steps: the forced hydrolysis reaction equation is:
4. the method for preparing the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite photocatalyst according to claim 1, wherein the method comprises the following steps: the hydrothermal oxidation-reduction reaction is to utilize the self-contained reducing groups on the surface of graphene oxide, including hydroxyl and epoxy groups, to carry out Cu under the hydrothermal condition 2+ Reduction to Cu + The reaction equation is:
5. the method for preparing the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite photocatalyst according to claim 1, wherein the 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.
6. The method for preparing the cuprous oxide/titanium dioxide/graphene oxide ternary nanocomposite photocatalyst according to claim 1, wherein the method comprises the following steps: the temperature of the vacuum drying is 85 ℃ and the time is 2 hours.
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