CN107469864B - Nano-copper/cyclized polyacrylonitrile composite photocatalyst and preparation method thereof - Google Patents
Nano-copper/cyclized polyacrylonitrile composite photocatalyst and preparation method thereof Download PDFInfo
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- CN107469864B CN107469864B CN201710816048.3A CN201710816048A CN107469864B CN 107469864 B CN107469864 B CN 107469864B CN 201710816048 A CN201710816048 A CN 201710816048A CN 107469864 B CN107469864 B CN 107469864B
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 149
- 239000010949 copper Substances 0.000 title claims abstract description 127
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 126
- 239000002131 composite material Substances 0.000 title claims abstract description 102
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 126
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001879 copper Chemical class 0.000 claims abstract description 17
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- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 14
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 7
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- 238000001914 filtration Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 22
- 230000009467 reduction Effects 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
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- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
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- 238000006243 chemical reaction Methods 0.000 description 2
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- 229920001059 synthetic polymer Polymers 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a nano-copper/cyclized polyacrylonitrile composite photocatalyst and a preparation method thereof, relates to the technical field of photocatalysts, and aims to solve the technical problems of low catalytic efficiency and unstable properties of the existing photocatalyst. The preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst comprises the following steps: respectively dissolving polyacrylonitrile and copper salt in N, N-dimethylformamide, mixing the two solutions, adding water to obtain a copper simple substance, adding ethanol to obtain a nano-copper/polyacrylonitrile composite precursor, and finally carrying out heat treatment on the nano-copper/polyacrylonitrile composite precursor in an inert atmosphere to obtain the nano-copper/cyclized polyacrylonitrile composite photocatalyst. The preparation method has the advantages of simple steps, easy operation and low cost, and the prepared composite photocatalyst has the properties of both cyclized polyacrylonitrile and nano-copper and has the advantages of high photocatalytic efficiency, stability and low price.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a nano-copper/cyclized polyacrylonitrile composite photocatalyst and a preparation method thereof.
Background
A photocatalyst generally refers to a chemical substance that is capable of catalyzing upon excitation by photons. In recent years, most research focuses on the development and development of semiconductor photocatalysts, but the semiconductor photocatalysts generally have the problems of narrow light influence range, easy recombination of photogenerated electrons and photogenerated holes and the like, so that the photocatalytic efficiency is low, and the development and application of a photocatalytic technology are limited to a great extent. Therefore, research and development of a photocatalyst having high catalytic efficiency, stability and low cost is urgently required.
Polyacrylonitrile (PAN) is a synthetic polymer widely used in industry, and is a polymer containing a large amount of strongly electronegative cyano groups, and the cyano groups can perform complex reaction with many metal ions. As the temperature increases, PAN undergoes cyclization and is converted to a semiconducting conjugated "ladder" polymer by polymerization of unreacted cyano groups to produce cyclized polyacrylonitrile. The cyclized polyacrylonitrile as the catalyst carrier has a large specific surface area, can increase the adsorption capacity of the photocatalyst, has excellent conductivity, can make photoproduction electrons move rapidly, is beneficial to inhibiting the recombination of the photoproduction electrons and photoproduction holes, and is beneficial to improving the photocatalytic efficiency.
The nano copper particles have wide application, low price, sterilization, deodorization, catalysis and other properties, but the independently prepared nano copper has obvious agglomeration and oxidation trends and unstable properties. Therefore, the research on how to improve the agglomeration and oxidation phenomena of the nano-copper and how to fully utilize the characteristics of the nano-copper and the cyclized polyacrylonitrile to develop the photocatalyst has important significance.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a nano-copper/cyclized polyacrylonitrile composite photocatalyst, so as to solve the technical problems of low catalytic efficiency and unstable property of the existing photocatalyst. According to the method, the nano-copper and the cyclized polyacrylonitrile are compounded, so that the agglomeration and oxidation phenomena of the nano-copper can be improved, and the obtained nano-copper/cyclized polyacrylonitrile composite photocatalyst can have the catalytic performances of both the cyclized polyacrylonitrile and the nano-copper.
The second purpose of the invention is to provide the photocatalyst prepared by the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst, which has the properties of both cyclized polyacrylonitrile and nano-copper, and has the advantages of high photocatalytic efficiency, stability and low price.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a preparation method of a nano-copper/cyclized polyacrylonitrile composite photocatalyst, which comprises the following steps:
respectively dissolving polyacrylonitrile and copper salt in N, N-dimethylformamide, mixing the two solutions, adding water to obtain a copper simple substance, adding ethanol to obtain a nano-copper/polyacrylonitrile composite precursor, and finally carrying out heat treatment on the nano-copper/polyacrylonitrile composite precursor in an inert atmosphere to obtain the nano-copper/cyclized polyacrylonitrile composite photocatalyst.
Optionally, in the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst, the ratio of the mass of the polyacrylonitrile to the volume of the N, N-dimethylformamide is (0.5-1):50 g/mL; preferably, the mass of polyacrylonitrile is 0.5-1g, and the volume of N, N-dimethylformamide is 50 mL.
Optionally, in the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst, the copper salt includes copper nitrate trihydrate, copper nitrate or copper acetate; the ratio of the mass of the copper salt to the volume of the N, N-dimethylformamide is (0.1-0.3) to 10 g/mL; preferably, the mass of the copper salt is 0.1-0.3g and the volume of N, N-dimethylformamide is 10 mL.
Optionally, in the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst, water is deionized water, and the amount of water is 1-3 mL.
Optionally, in the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst, the amount of ethanol is 10-20mL, and the ethanol is added dropwise.
Optionally, in the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst, the heat treatment temperature is 513-573K, and the heat treatment time is 2-4 h.
Optionally, the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst provided by the invention comprises the following steps:
(a) dissolving polyacrylonitrile by using N, N-dimethylformamide;
(b) dissolving copper salt with N, N-dimethylformamide;
(c) mixing the solutions of step (a) and step (b), and then keeping the temperature at a constant temperature;
(d) adding water to the solution obtained in step (c) and maintaining the temperature at a constant temperature;
(e) adding ethanol into the solution obtained in the step (d) to obtain flocculate, and then filtering and vacuum-drying the flocculate to obtain a nano copper/polyacrylonitrile composite precursor;
(f) and carrying out heat treatment on the nano-copper/polyacrylonitrile composite precursor in an inert atmosphere at the temperature of 513-573K for 2-4h to obtain the nano-copper/polyacrylonitrile composite photocatalyst.
Optionally, in the step (c), the constant temperature is 333-.
Optionally, in the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst, in the step (d), the constant temperature is 333-.
Meanwhile, the invention also provides a nano-copper/cyclized polyacrylonitrile composite photocatalyst, which is prepared by the preparation method and is black.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst has the advantages of simple steps, easy operation and low cost, fully utilizes the good complexation property between polyacrylonitrile and copper ions, and ensures that the copper ions can still be well dispersed in a polyacrylonitrile carrier after being reduced into nano-copper, thereby improving the agglomeration and oxidation phenomena of the nano-copper; meanwhile, the cyclized polyacrylonitrile has better surface adsorption performance and photocatalytic performance as a semiconductor material, and is compounded with the nano-copper, so that the excellent performance of the cyclized polyacrylonitrile as a catalyst carrier and the catalytic performance of the nano-copper can be fully exerted, and the prepared nano-copper/cyclized polyacrylonitrile composite photocatalyst can have the properties of both cyclized polyacrylonitrile and nano-copper, and has the advantages of high photocatalytic efficiency, stability and low price.
(2) The nano-copper/cyclized polyacrylonitrile composite photocatalyst has the properties of both cyclized polyacrylonitrile and nano-copper, and has the advantages of high photocatalytic efficiency, stability and low price.
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, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an XRD (X-ray diffraction) diagram of a nano-copper/cyclized polyacrylonitrile composite photocatalyst;
FIG. 2 is an SEM image of cyclized polyacrylonitrile;
FIG. 3 is an SEM image of the nano-copper/cyclized polyacrylonitrile composite photocatalyst prepared in example 1;
FIG. 4 is an activity analysis diagram of photocatalytic reduction of Cr (VI) by the nano-copper/cyclized polyacrylonitrile composite photocatalyst prepared in example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The embodiment does not indicate specific conditions, and the method is carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
According to one aspect of the invention, the embodiment of the invention provides a preparation method of a nano-copper/cyclized polyacrylonitrile composite photocatalyst, which comprises the following steps: respectively dissolving polyacrylonitrile and copper salt in N, N-dimethylformamide, mixing the two solutions, adding water to obtain a copper simple substance, adding ethanol to obtain a nano-copper/polyacrylonitrile composite precursor, and finally carrying out heat treatment on the nano-copper/polyacrylonitrile composite precursor in an inert atmosphere to obtain the nano-copper/cyclized polyacrylonitrile composite photocatalyst.
Specifically, the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst provided by the embodiment of the invention comprises the steps of respectively dissolving polyacrylonitrile and copper nitrate trihydrate in N, N-dimethylformamide, mixing the two solutions to enable copper ions to carry out a complex reaction with cyano groups in the polyacrylonitrile, reducing the copper ions into copper simple substances by the N, N-dimethylformamide in the presence of water, adding ethanol for flocculation to obtain a nano-copper/polyacrylonitrile composite precursor, and then carrying out heat treatment on the nano-copper/polyacrylonitrile composite precursor in an inert atmosphere to obtain the nano-copper/cyclized polyacrylonitrile composite photocatalyst.
Compared with the prior art, the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst provided by the embodiment of the invention has the beneficial effects that:
the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst provided by the embodiment of the invention has the advantages of simple steps, easy operation and lower cost, fully utilizes the good complexation property between polyacrylonitrile and copper ions, and ensures that the copper ions can still be well dispersed in a polyacrylonitrile carrier after being reduced into nano-copper, thereby improving the agglomeration and oxidation phenomena of the nano-copper; meanwhile, the cyclized polyacrylonitrile has better surface adsorption performance and photocatalytic performance as a semiconductor material, and is compounded with the nano-copper, so that the excellent performance of the cyclized polyacrylonitrile as a catalyst carrier and the catalytic performance of the nano-copper can be fully exerted, and the prepared nano-copper/cyclized polyacrylonitrile composite photocatalyst can have the properties of both cyclized polyacrylonitrile and nano-copper, and has the advantages of high photocatalytic efficiency, stability and low price.
Alternatively, in the present invention, the inert atmosphere refers to a protective environment formed in an inert gas, typically but not limited to nitrogen or helium.
Optionally, in the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst provided by the embodiment of the invention, the ratio of the mass of polyacrylonitrile to the volume of N, N-dimethylformamide is (0.5-1):50 g/mL; preferably, the mass of polyacrylonitrile is 0.5-1g, and the volume of N, N-dimethylformamide is 50 mL.
Alternatively, the ratio of the mass of polyacrylonitrile to the volume of N, N-dimethylformamide is typically, but not limited to, 0.5:50g/mL, 0.6:50g/mL, 0.7:50g/mL, 0.8:50g/mL, 0.9:50g/mL, or 1:50 g/mL.
Alternatively, the mass of polyacrylonitrile is typically but not limited to 0.5g, 0.6g, 0.7g, 0.8g, 0.9 or 1g, and the volume of N, N-dimethylformamide is 50 mL; other values adjusted according to the mass-to-volume ratio are also possible, for example, the mass of polyacrylonitrile is 2g, the volume of N, N-dimethylformamide is 100mL, and 50mL is taken after dissolving polyacrylonitrile in N, N-dimethylformamide and is ready for use.
Optionally, in the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst provided by the embodiment of the present invention, the copper salt includes copper nitrate trihydrate, copper nitrate or copper acetate; the ratio of the mass of the copper salt to the volume of the N, N-dimethylformamide is (0.1-0.3) to 10 g/mL; preferably, the mass of the copper salt is 0.1-0.3g and the volume of N, N-dimethylformamide is 10 mL.
Alternatively, the ratio of the mass of the copper salt to the volume of N, N-dimethylformamide is typically, but not limited to, 0.1:10g/mL, 0.2:10g/mL, or 0.3:10 g/mL.
Alternatively, the mass of the copper salt is typically, but not limited to, 0.1g, 0.2g, or 0.3g, and the volume of N, N-dimethylformamide is 10 mL; other values adjusted according to the mass-to-volume ratio are also possible, for example, the mass of copper nitrate trihydrate is 0.6g, the volume of N, N-dimethylformamide is 20mL, and 10mL of solution is taken for standby after dissolving the copper nitrate trihydrate in the N, N-dimethylformamide; when the polyacrylonitrile fiber is used, 50mL of polyacrylonitrile is dissolved in N, N-dimethylformamide solution, 10mL of copper nitrate trihydrate is dissolved in the N, N-dimethylformamide solution, and the mixture is subjected to heat preservation at constant temperature and then the subsequent steps are carried out.
Optionally, in the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst provided by the embodiment of the invention, water is deionized water, and the amount of water is 1-3 mL.
Alternatively, the amount of water used is typically, but not limited to, 1mL, 1.5mL, 2mL, 2.5mL, or 3 mL.
Optionally, in the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst provided by the embodiment of the invention, the amount of ethanol is 10-20mL, and the ethanol is added dropwise. The ethanol is added in a dropwise manner, so that the flocculation effect can be promoted, and the yield of the nano copper/polyacrylonitrile composite precursor can be improved.
Alternatively, the amount of ethanol used is typically, but not limited to, 10mL, 11mL, 12mL, 13mL, 14mL, 15mL, 16mL, 17mL, 18mL, 19mL, or 20 mL.
Optionally, in the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst provided by the embodiment of the invention, in the step (f), the heat treatment temperature is 513-.
Alternatively, in step (f), the temperature of the heat treatment is typically, but not limited to, 513K, 515K, 518K, 523K, 525K, 528K, 533K, 535K, 538K, 543K, 545K, 548K, 553K, 555K, 558K, 563K, 565K, 568K, or 573K; the time of the heat treatment is 2h, 2.5h, 3h, 3.5h or 4 h.
Optionally, in the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst provided by the embodiment of the invention, the heat treatment temperature is 513-573K, and the heat treatment time is 2-4 h.
Alternatively, the temperature of the heat treatment is typically, but not limited to, 513K, 515K, 518K, 523K, 525K, 528K, 533K, 535K, 538K, 543K, 545K, 548K, 553K, 555K, 558K, 563K, 565K, 568K, or 573K; the time of the heat treatment is 2h, 2.5h, 3h, 3.5h or 4 h.
Optionally, the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst provided by the embodiment of the invention comprises the following steps:
(a) dissolving polyacrylonitrile by using N, N-dimethylformamide;
(b) dissolving copper nitrate trihydrate with N, N-dimethylformamide;
(c) mixing the solutions of step (a) and step (b), and then keeping the temperature at a constant temperature;
(d) adding water to the solution obtained in step (c) and maintaining the temperature at a constant temperature;
(e) adding ethanol into the solution obtained in the step (d) to obtain flocculate, and then filtering and vacuum-drying the flocculate to obtain a nano copper/polyacrylonitrile composite precursor;
(f) and (3) carrying out heat treatment on the nano-copper/polyacrylonitrile composite precursor in an inert atmosphere at the temperature of 513-573K for 2-4h to obtain the nano-copper/polyacrylonitrile composite photocatalyst.
Specifically, the solution obtained in step (c) is a black solution.
Optionally, in the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst provided by the embodiment of the invention, in the step (c), the constant temperature is 333-.
Alternatively, in step (c), the constant temperature is typically, but not limited to, 333K, 334K, 335K, 336K, 337K, 338K, 339K, 340K, 341K, 342K, or 343K; the incubation time is typically, but not limited to, 3h, 4h, 5h, 6h, 7h, 8h or 9 h.
Optionally, in the preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst provided by the embodiment of the invention, in the step (d), the constant temperature is 333-.
Optionally, in step (d), the constant temperature is typically, but not limited to, 333K, 334K, 335K, 336K, 337K, 338K, 339K, 340K, 341K, 342K, or 343K; the incubation time is typically, but not limited to, 2h, 2.2h, 2.5h, 2.7h or 3 h.
Preferably, the embodiment of the invention provides a preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst, which comprises the following steps:
(1) dissolving 0.5-1g of polyacrylonitrile by using 50mL of N, N-dimethylformamide;
(2) dissolving 0.1-0.3g of copper nitrate trihydrate with 10mL of N, N-dimethylformamide;
(3) mixing the solutions in the step (1) and the step (2), and then preserving the heat for 3-9h at the constant temperature of 333-343K;
(4) adding 1-3mL of deionized water into the solution obtained in the step (3), and then preserving heat for 2-3h at the constant temperature of 333-343K;
(5) dropwise adding 10-20mL of ethanol into the solution obtained in the step (4) to obtain flocculates, and then filtering and vacuum-drying the flocculates to obtain a nano copper/polyacrylonitrile composite precursor;
(f) and carrying out heat treatment on the nano-copper/polyacrylonitrile composite precursor in an inert atmosphere at the temperature of 513-573K for 2-4h to obtain the nano-copper/polyacrylonitrile composite photocatalyst.
Alternatively, in the above embodiment of the preferred production method, the order of step (1) and step (2) may be interchanged.
According to another aspect of the invention, the embodiment of the invention provides a nano-copper/cyclized polyacrylonitrile composite photocatalyst, which is prepared by the method and is black.
The nano-copper/cyclized polyacrylonitrile composite photocatalyst provided by the embodiment of the invention has the properties of both cyclized polyacrylonitrile and nano-copper, and has the advantages of high photocatalytic efficiency, stability and low price.
The present invention will be further described with reference to the following examples.
Example 1
0.5g polyacrylonitrile was dissolved with 50ml of N, N-dimethylformamide; 0.2g of copper nitrate trihydrate was dissolved in 10ml of N, N-dimethylformamide; mixing the two solutions; keeping the temperature of the mixed solution at 343K for 6 h; adding 3ml of deionized water into the mixed solution, and keeping the temperature at 343K for 2.5 hours; then, 20ml of ethanol is dripped into the mixed solution to obtain flocculate, and the flocculate is filtered, washed and dried in vacuum to obtain the nano-copper/cyclized polyacrylonitrile composite precursor; and (3) carrying out heat treatment on the nano-copper/cyclized polyacrylonitrile composite precursor for 2 hours at 573K to obtain the nano-copper/cyclized polyacrylonitrile composite photocatalyst.
Example 2
0.8g polyacrylonitrile was dissolved with 50ml of N, N-dimethylformamide; 0.2g of copper nitrate trihydrate was dissolved in 10ml of N, N-dimethylformamide; mixing the two solutions; keeping the temperature of the mixed solution at 333K for 3 h; adding 2ml of deionized water into the mixed solution, and keeping the temperature at 333K for 2 hours; then, dropwise adding 15ml of ethanol into the mixed solution to obtain flocculate, filtering, washing and vacuum drying the flocculate to obtain a nano copper/cyclized polyacrylonitrile composite precursor; and (3) carrying out heat treatment on the nano-copper/cyclized polyacrylonitrile composite precursor for 2.5h at 563K to obtain the nano-copper/cyclized polyacrylonitrile composite photocatalyst.
Example 3
Dissolving 1g of polyacrylonitrile by using 50ml of N, N-dimethylformamide; 0.3g of copper nitrate trihydrate was dissolved in 10ml of N, N-dimethylformamide; mixing the two solutions; keeping the temperature of the mixed solution at 343K for 4 hours; adding 1ml of deionized water into the mixed solution, and keeping the temperature at 333K for 2 hours; then, dropwise adding 15ml of ethanol into the mixed solution to obtain flocculate, filtering, washing and vacuum drying the flocculate to obtain a nano copper/cyclized polyacrylonitrile composite precursor; and carrying out heat treatment on the nano-copper/cyclized polyacrylonitrile composite precursor for 2.5h at 563K to obtain the nano-copper/cyclized polyacrylonitrile composite photocatalyst.
And (3) performing characterization and analysis on the nano-copper/cyclized polyacrylonitrile composite photocatalyst prepared in the embodiment 1-3.
FIG. 1 is an XRD (X-ray diffraction) pattern of a nano-copper/cyclized polyacrylonitrile composite photocatalyst.
As shown in fig. 1, the three composite materials prepared in examples 1 to 3 respectively have characteristic peaks at 43 ° and 51 °, and compared with PDF #04-0836 card, the characteristic peaks of Cu are 43 ° and 51 °, and the corresponding crystal plane indices are (110) and (200), so that it can be determined that the composite materials prepared in examples 1 to 3 all contain elemental copper, and meanwhile, the diffraction peak has a certain width, and it can be seen that the elemental copper is in a nanoscale state; the three composite materials have a steamed bread peak at 25-35 degrees, which is the peak of polyacrylonitrile in the composite material, and the high polymer materials are all represented as steamed bread peaks.
FIG. 2 is an SEM image of cyclized polyacrylonitrile; FIG. 3 is an SEM image of the nano-copper/cyclized polyacrylonitrile composite photocatalyst prepared in example 1.
As shown in fig. 2 and fig. 3, the cyclized polyacrylonitrile carrier is in a sheet shape, and in the SEM image of the nano-copper/cyclized polyacrylonitrile composite photocatalyst, many small particles, namely copper nanoparticles, can be seen on the cyclized polyacrylonitrile sheet-shaped carrier.
FIG. 4 is an activity analysis diagram of photocatalytic reduction of Cr (VI) by the nano-copper/cyclized polyacrylonitrile composite photocatalyst prepared in example 1.
As shown in FIG. 4, the nano-copper/cyclized polyacrylonitrile composite photocatalyst prepared in example 1 has good effects of catalytically reducing Cr (VI) under visible light, and the photocatalytic reduction rates of five times of photocatalytic reduction of Cr (VI) are η1＝99.89％,、η2＝99.89％、η3＝98.47％、η4＝92.22％,、η580.56%. From the photocatalytic reduction rate, the photocatalytic reduction rate of the first three photocatalytic reductions of cr (vi) is high, cr (vi) is almost completely reduced, and the photocatalytic reduction rates of the last two photocatalytic reductions decrease in sequence until the photocatalytic reduction rate is less than 90% when the former two photocatalytic reductions are repeatedly used for the fifth time. From the data, the nano-copper/cyclized polyacrylonitrile composite photocatalyst prepared by the invention has excellent effect of photocatalytic reduction of Cr (VI) and excellent recycling performance.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (12)
1. A preparation method of a nano-copper/cyclized polyacrylonitrile composite photocatalyst is characterized by comprising the following steps:
respectively dissolving polyacrylonitrile and copper salt in N, N-dimethylformamide, mixing the two solutions, adding water to obtain a copper simple substance, adding ethanol to obtain a nano-copper/polyacrylonitrile composite precursor, and finally carrying out heat treatment on the nano-copper/polyacrylonitrile composite precursor in an inert atmosphere to obtain the nano-copper/cyclized polyacrylonitrile composite photocatalyst.
2. The method for preparing the nano-copper/cyclized polyacrylonitrile composite photocatalyst according to claim 1, wherein the ratio of the mass of polyacrylonitrile to the volume of N, N-dimethylformamide is (0.5-1):50 g/mL.
3. The method for preparing the nano-copper/cyclized polyacrylonitrile composite photocatalyst according to claim 2, wherein the mass of polyacrylonitrile is 0.5-1g, and the volume of N, N-dimethylformamide is 50 mL.
4. The method for preparing the nano-copper/cyclized polyacrylonitrile composite photocatalyst according to claim 2, wherein the copper salt comprises copper nitrate trihydrate, copper nitrate or copper acetate;
the ratio of the mass of the copper salt to the volume of the N, N-dimethylformamide is (0.1-0.3):10 g/mL.
5. The method for preparing the nano-copper/cyclized polyacrylonitrile composite photocatalyst according to claim 4, wherein the mass of the copper salt is 0.1-0.3g, and the volume of the N, N-dimethylformamide is 10 mL.
6. The method for preparing the nano-copper/cyclized polyacrylonitrile composite photocatalyst according to claim 4, wherein the water is deionized water, and the amount of the water is 1-3 mL.
7. The preparation method of the nano-copper/cyclized polyacrylonitrile composite photocatalyst as claimed in claim 6, wherein the amount of the ethanol is 10-20mL, and the ethanol is added dropwise.
8. The method for preparing the nano-copper/cyclized polyacrylonitrile composite photocatalyst as claimed in claim 1 or 7, wherein the heat treatment temperature is 513-573K, and the heat treatment time is 2-4 h.
9. The method for preparing the nano-copper/cyclized polyacrylonitrile composite photocatalyst as claimed in claim 8, wherein the method comprises the following steps:
(a) dissolving polyacrylonitrile by using N, N-dimethylformamide;
(b) dissolving copper salt with N, N-dimethylformamide;
(c) mixing the solutions of step (a) and step (b), and then keeping the temperature at a constant temperature;
(d) adding water to the solution obtained in step (c) and maintaining the temperature at a constant temperature;
(e) adding ethanol into the solution obtained in the step (d) to obtain flocculate, and then filtering and vacuum-drying the flocculate to obtain a nano copper/polyacrylonitrile composite precursor;
(f) and carrying out heat treatment on the nano-copper/polyacrylonitrile composite precursor in an inert atmosphere at the temperature of 513-573K for 2-4h to obtain the nano-copper/polyacrylonitrile composite photocatalyst.
10. The method for preparing the nano-copper/cyclized polyacrylonitrile composite photocatalyst as claimed in claim 9, wherein in the step (c), the constant temperature is 333-.
11. The method for preparing the nano-copper/cyclized polyacrylonitrile composite photocatalyst as claimed in claim 9, wherein in the step (d), the constant temperature is 333-.
12. A nano-copper/cyclized polyacrylonitrile composite photocatalyst is characterized by being prepared by the method of any one of claims 1 to 11, and the nano-copper/cyclized polyacrylonitrile composite photocatalyst is black.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451762A (en) * | 2010-11-01 | 2012-05-16 | 上海大学 | Preparation method of cyclizing polyacrylonitrile compound multi-metal oxide |
| CN103521225A (en) * | 2013-10-31 | 2014-01-22 | 内蒙古工业大学 | Method for preparing carbon fiber copper-carried catalyst for reaction of preparing ethanediol through oxalic ester |
| CN105126917A (en) * | 2015-09-02 | 2015-12-09 | 河北科技大学 | Preparation method for copper/cuprous oxide/cyclized polyacrylonitrile visible-light-driven photocatalyst |
| US9399243B1 (en) * | 2015-08-09 | 2016-07-26 | Shenzhen Eigen-Equation Graphene Technology Co., Ltd. | Method of preparing carbon-coated cuprous oxide |
| CN106068161A (en) * | 2014-03-11 | 2016-11-02 | 日东电工株式会社 | Photocatalysis element |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451762A (en) * | 2010-11-01 | 2012-05-16 | 上海大学 | Preparation method of cyclizing polyacrylonitrile compound multi-metal oxide |
| CN103521225A (en) * | 2013-10-31 | 2014-01-22 | 内蒙古工业大学 | Method for preparing carbon fiber copper-carried catalyst for reaction of preparing ethanediol through oxalic ester |
| CN106068161A (en) * | 2014-03-11 | 2016-11-02 | 日东电工株式会社 | Photocatalysis element |
| US9399243B1 (en) * | 2015-08-09 | 2016-07-26 | Shenzhen Eigen-Equation Graphene Technology Co., Ltd. | Method of preparing carbon-coated cuprous oxide |
| CN105126917A (en) * | 2015-09-02 | 2015-12-09 | 河北科技大学 | Preparation method for copper/cuprous oxide/cyclized polyacrylonitrile visible-light-driven photocatalyst |
Non-Patent Citations (1)
| Title |
|---|
| 环化聚丙烯腈修饰氧化锌的紫外光催化性能;刘彦彦等;《河北科技大学学报》;20160630;第37卷(第3期);第238-244页 * |
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