CN111514902B - 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 Nano fiber catalyst and preparation method thereof - Google Patents

2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 Nano fiber catalyst and preparation method thereof Download PDF

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CN111514902B
CN111514902B CN202010442195.0A CN202010442195A CN111514902B CN 111514902 B CN111514902 B CN 111514902B CN 202010442195 A CN202010442195 A CN 202010442195A CN 111514902 B CN111514902 B CN 111514902B
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copper phthalocyanine
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CN111514902A (en
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卢启芳
李康
郭恩言
魏明志
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Qilu University of Technology
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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Abstract

The invention relates to 2,9, 16, 23-tetranitro phthalocyanine copper sensitization NiO/Bi 2 WO 6 The invention relates to a nanofiber catalyst and a preparation method thereof, and NiO/Bi is prepared by an electrostatic spinning technology 2 WO 6 The nano-fiber is loaded on NiO/Bi by combining with the solvothermal technology and loading 2,9, 16, 23-tetranitro copper phthalocyanine (CuTNPc) in a NiO/Bi mode through in-situ growth 2 WO 6 Obtaining the nanofiber photocatalyst on the nanofiber. The nano-fiber catalyst can utilize sunlight to a greater extent, greatly broadens the response range of the catalyst in the solar spectrum, and has the advantages of 2,9, 16, 23-tetranitro copper phthalocyanine sensitization NiO/Bi 2 WO 6 The nanofiber can effectively promote the separation of photon-generated electron-hole pairs, increase the photon-generated carrier quantity and has excellent photocatalytic performance. The photocatalytic performance is enhanced, and the problem that the tetranitro phthalocyanine copper is difficult to recover is effectively solved.

Description

2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 Nano fiber catalyst and preparation method thereof
Technical Field
The invention relates to 2,9, 16, 23-tetranitro phthalocyanine copper sensitization NiO/Bi 2 WO 6 A nano-fiber catalyst and a preparation method thereof belong to the technical field of photocatalysis.
Background
With the rapid development of economy, the environmental pollution problem becomes a great problem facing human beings, especially water pollution, which threatens human health and hinders the development of economy. Therefore, there is an urgent need to find an effective method for solving the pollution of the aqueous environment. In recent years, semiconductor photocatalysis technology is used as a 'green' technology, has low cost and no secondary pollution, can deeply mineralize various pollutants under the condition of illumination, and is rapidly developed.
Among numerous semiconductor photocatalysts, bismuth-based oxides have received much attention because of their high stability, non-toxicity, appropriate band gap structure and excellent photodegradability. Wherein, bismuth tungstate (Bi) 2 WO 6 ) Has Aurivillius layered structure and proper band gap width (2.6-2.8 eV), and has good optical stability. However, bi 2 WO 6 Has a narrow visible light response range (less than 450 nm), and Bi 2 WO 6 The photo-generated electron-hole pairs are easy to recombine, the quantum yield is low, and the photocatalytic performance is limited. Therefore, broadening the photoresponse range and reducing the recombination efficiency of photo-generated electron-hole pairs are key to improving the photocatalytic performance thereof.
Chinese patent document CN104923214A discloses a bismuth tungstate photocatalytic film and a preparation method thereof, which is prepared by the following method: 1) Preparing bismuth tungstate powder: slowly dropwise adding a sodium tungstate solution into a bismuth nitrate solution, dropwise adding a sodium hydroxide solution to adjust the pH value of the solution to 5-7 to obtain a precursor solution, placing the precursor solution into a hydrothermal reaction kettle for hydrothermal reaction, centrifuging the reaction solution after the hydrothermal reaction is finished, separating out solid components, and vacuum-drying to obtain bismuth tungstate powder; 2) Preparing a bismuth tungstate photocatalytic film: pressing bismuth tungstate powder by a dry pressing method to obtain a compact, sintering the compact at a high temperature to obtain a target material required by sputtering, putting the target material into a magnetron sputtering chamber, and performing magnetron sputtering coating by using a quartz glass sheet as a substrate to obtain the bismuth tungstate photocatalytic film. Although the bismuth tungstate photocatalytic film has strong repeatability, the photocatalytic performance is poor.
Nickel oxide (NiO) construction of NiO/Bi due to its unique catalytic, electrical, magnetic properties and high hole mobility 2 WO 6 The heterostructure can effectively promote the separation of the photo-generated electron-hole pairs. As is well known, the one-dimensional nanofiber material has large length-diameter ratio, high photocatalytic activity and good cycle performance, but NiO/Bi 2 WO 6 The nanofiber heterostructure has an absorption range of less than 480nm in the solar spectrum, for TaiThe utilization of sunlight is still low.
Copper phthalocyanine is an important multifunctional polymer material, has good photoelectric properties, and is increasingly leading to extensive research. 2,9, 16, 23-tetranitro copper phthalocyanine (CuTNPc) has good stability and extremely strong absorption on the solar spectrum in the range of 550-750 nm. However, the pure 2,9, 16, 23-tetranitro copper phthalocyanine is a dye and has extremely small particle size, so that the copper phthalocyanine is not beneficial to recycling during recycling and is easy to cause secondary pollution. Sensitization of NiO/Bi by CuTNPc 2 WO 6 The nanofiber can greatly widen the response range of the nanofiber in the solar spectrum, can further increase the quantity of photon-generated carriers and enhance the photocatalytic performance, and the one-dimensional structure is favorable for recycling the photocatalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 A nano-fiber catalyst and a preparation method thereof.
The invention prepares NiO/Bi by electrostatic spinning technology 2 WO 6 The nano-fiber is combined with the solvothermal technology to load 2,9, 16, 23-tetranitro copper phthalocyanine (CuTNPc) on NiO/Bi in an in-situ growth mode 2 WO 6 On the nano-fiber, a novel photocatalytic material with great potential is synthesized, and the photocatalytic performance is excellent.
The invention is realized by the following technical scheme:
2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 The nano-fiber photocatalyst is 2,9, 16, 23-tetranitro copper phthalocyanine (CuTNPc) loaded in NiO/Bi in situ 2 WO 6 On the surface of the nanofiber, 2,9, 16, 23-tetranitro copper phthalocyanine (CuTNPc) and NiO/Bi 2 WO 6 The molar ratio of the nano fibers is (8-15): 100.
2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 The preparation method of the nanofiber photocatalyst comprises the following steps:
1)NiO/Bi 2 WO 6 preparation of nanofibers
Adding ammonium metatungstate, bismuth nitrate pentahydrate and an acid solution into a citric acid solution, adding nickel acetate, and uniformly stirring at room temperature to obtain a solution A; dissolving polyvinylpyrrolidone in absolute ethyl alcohol to obtain a solution B, adding the solution A into the solution B, and uniformly stirring to obtain a precursor solution;
performing electrostatic spinning on the precursor solution at the temperature of 20-30 ℃ and the voltage of 10-30kV, drying after spinning, then heating to 500-700 ℃ in the air atmosphere, preserving the temperature for 1-5h, cooling, soaking in dilute nitric acid solution for 10h, and drying to obtain NiO/Bi 2 WO 6 A nanofiber;
2) 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 Preparation of nanofibers
Adding tetranitrophthalonitrile, copper acetate, ammonium molybdate and glycol into a reaction kettle, and adding NiO/Bi 2 WO 6 Reacting the nano-fibers at 120-200 ℃ for 10-20h, washing and drying the nano-fibers obtained by the reaction to obtain the 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 A nanofiber photocatalyst.
Preferably, according to the invention, the concentration of the citric acid solution in step 1) is between 100 and 200g/L.
According to the present invention, in step 1), the mass ratio of the added amount of ammonium metatungstate to the citric acid in the citric acid solution is: (0.1-0.3): (1-2).
According to the invention, in the step 1), the mass ratio of the added amount of the bismuth nitrate pentahydrate to the ammonium metatungstate is as follows: (0.8-1.0): (0.1-0.3).
According to the invention, in step 1), the mass ratio of the added amount of nickel acetate to ammonium metatungstate is as follows: (0.1-1.0): (0.1-0.3).
Preferably, in step 1), the acid solution is 38% hydrochloric acid solution by mass concentration, and the addition amount of the acid solution is 1-2mL.
Preferably, according to the invention, in step 1), the stirring time to obtain solution A is between 10 and 18h.
According to a preferred embodiment of the invention, in step 1), the concentration of polyvinylpyrrolidone in solution B is from 100 to 200g/L.
Preferably, in step 1), the volume ratio of the solution a to the solution B is: (1-4): (8-12).
Preferably, according to the invention, in step 1), the electrospinning voltage is 20kV and the distance between the spinneret and the receiving plate is 15cm.
Preferably, according to the invention, in step 1), the temperature is raised to 65-700 ℃ at a rate of 1-5 ℃/min, and the dilute nitric acid solution has a pH =5.
Preferably, according to the invention, in step 2), the molar ratio of tetranitrophthalonitrile to copper acetate is (3-6): 1, the mass ratio of copper acetate to ammonium molybdate is as follows: (10-30): (1-5), the mass-to-volume ratio of the tetranitrophthalonitrile to the ethylene glycol is as follows: (5-8): 1, unit: g/L.
Preferably, according to the invention, in step 2), niO/Bi 2 WO 6 The mass ratio of the nano-fiber to the tetranitrophthalonitrile is as follows: 2: (5-8).
2,9, 16, 23-tetranitro phthalocyanine copper sensitization NiO/Bi prepared by the invention 2 WO 6 The nano-fiber photocatalyst has strong absorption in the range of 400-750nm of the solar spectrum, is beneficial to generating more photo-generated electron holes under the irradiation of sunlight, and further enhances the photocatalytic performance.
The invention has the technical characteristics and advantages that:
1. the invention utilizes the nitro group of 2,9, 16, 23-tetranitro copper phthalocyanine to form hydrogen bond connection with the hydroxyl group on the surface of the nanofiber to obtain 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 The nano-fiber can utilize sunlight to a greater extent, greatly broadens the response range of the nano-fiber in the solar spectrum, and has 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 The nanofiber can effectively promote the separation of photon-generated electron-hole pairs, increase the photon-generated carrier quantity and has excellent photocatalytic performance. The photocatalytic performance is enhanced, and the problem that the tetranitro phthalocyanine copper is difficult to recover is effectively solved.
2. The 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi of the invention 2 WO 6 The nano-fiber can efficiently degrade organic matters, has strong reusability, and still has higher catalytic performance after being recycled for four times.
3. The invention adopts an electrostatic spinning method and a solvothermal technology to prepare 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 The nanofiber is simple and convenient to operate, low in price and non-toxic. The prepared nano composite material has strong absorption to sunlight, greatly promotes the separation of photoproduction electron-hole pairs, shows excellent photocatalytic degradation efficiency when being used as a photocatalyst to degrade tetracycline, and is a novel high-efficiency photocatalyst in the field of photocatalysis.
Drawings
FIG. 1 is a NiO/Bi obtained in comparative example 1 2 WO 6 Nanofibers and 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi from example 1 2 WO 6 SEM and EDS images of nanofibers; wherein a and b are NiO/Bi 2 WO 6 SEM image of nanofiber, c is NiO/Bi 2 WO 6 EDS diagram of nanofiber, d and e are 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 SEM image of nanofiber, f is 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 EDS picture of nanofibers.
FIG. 2 shows NiO/Bi obtained in comparative example 1 2 WO 6 Nanofibers (a, b) and 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi obtained in example 1 2 WO 6 TEM image of nanofibers (c, d).
FIG. 3 is a NiO/Bi obtained in comparative example 1 2 WO 6 Nanofibers and 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi prepared in example 1 2 WO 6 XRD spectrum of nanofiber.
FIG. 4 shows NiO/Bi obtained in comparative example 1 2 WO 6 Nanofibers and 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi prepared in example 1 2 WO 6 Diffuse reflectance spectrum (a) and Photoluminescence (PL) spectrum (b) of the nanofibers.
FIG. 5 shows NiO/Bi obtained in comparative example 1 2 WO 6 Nanofibers and 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi from example 1 2 WO 6 A dark reaction adsorption-desorption curve chart (a) when the nano-fiber degrades tetracycline and ultraviolet-visible absorption spectrograms (b, c and d) at different times when the nano-fiber degrades tetracycline solution.
FIG. 6 shows NiO/Bi obtained in comparative example 1 2 WO 6 Nanofibers and 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi prepared in example 1 2 WO 6 The graph (a) is a comparison graph of the photocatalytic degradation rate of the nano-fiber for degrading tetracycline, and the graph (b) is a fitted graph of the photocatalytic reaction kinetics.
FIG. 7 is a NiO/Bi sensitized with 2,9, 16, 23-tetranitro copper phthalocyanine prepared in example 1 2 WO 6 Four-cycle experimental efficiency chart (a) for degrading tetracycline by nano-fiber and four- cycle 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 TEM (b) of nanofibers.
Detailed Description
The invention will be further illustrated with reference to specific examples, but is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available; the equipment used is conventional equipment.
Example 1
2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 The preparation method of the nanofiber photocatalyst comprises the following steps:
(1) At normal temperature, removing 1.0g of citric acid, dissolving in 10mL of deionized water, stirring until the citric acid is dissolved, adding 0.246g of ammonium metatungstate, 0.971g of bismuth nitrate pentahydrate and 1mL of hydrochloric acid solution into the citric acid solution, stirring until the citric acid solution is clarified, adding 0.498g of nickel acetate, and stirring until the citric acid solution is clarified to obtain a solution A; weighing 1.0g of polyvinylpyrrolidone, dissolving in 10mL of absolute ethanol to obtain a solution B, adding 3mL of the solution A into the solution B, and stirring for 15h to obtain a precursor solution;
(2) Transferring the precursor solution obtained in the step (1) into a plastic injector connected with a stainless steel needle, and reacting with the precursor solution 2Connecting a 0kV power supply, wherein the distance between the stainless steel needle and the receiving plate is 15cm, and drying the collected fibers in a drying oven at 60 ℃; heating to 550 ℃ at the heating rate of 1 ℃/min under the air atmosphere after obtaining the gel fiber, preserving heat for 1h, soaking in a dilute nitric acid solution with the pH =5 for 10h after cooling, and drying to obtain NiO/Bi 2 WO 6 A nanofiber;
(3) Taking 20mg of the prepared NiO/Bi 2 WO 6 Adding the nano-fiber, 0.069g of tetranitrophthalonitrile, 0.02g of copper acetate, 0.003g of ammonium molybdate and 10mL of ethylene glycol solution into a 20mL reaction kettle, preserving the temperature at 150 ℃ for 18h, then alternately washing the obtained nano-fiber with deionized water and absolute ethyl alcohol for three times after the reaction kettle is cooled, and drying in a drying oven at 70 ℃ for 10h to obtain 2,9, 16, 23-tetranitrophthalocyanine copper sensitized NiO/Bi 2 WO 6 A nanofiber photocatalyst.
An appropriate amount of photocatalyst is taken to degrade tetracycline under the irradiation of a 300W Xe lamp (simulated sunlight).
Example 2
2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 The preparation method of the nanofiber photocatalyst comprises the following steps:
(1) At normal temperature, dissolving 1.0g of citric acid in 10mL of deionized water, stirring until the citric acid is dissolved, adding 0.246g of ammonium metatungstate, 0.971g of bismuth nitrate pentahydrate and 1mL of hydrochloric acid solution into the citric acid solution, stirring until the citric acid solution is clarified, adding 0.996g of nickel acetate, and stirring until the citric acid solution is clarified to obtain a solution A; weighing 1.0g of polyvinylpyrrolidone, dissolving in 10mL of absolute ethanol to obtain a solution B, adding 3mL of the solution A into the solution B, and stirring for 15h to obtain a precursor solution;
(2) Transferring the precursor solution obtained in the step (1) into a plastic injector connected with a stainless steel needle, connecting the plastic injector with a 20kV power supply, wherein the distance between the stainless steel needle and a receiving plate is 15cm, and drying the collected fibers in a drying oven at 60 ℃; heating to 600 ℃ at the heating rate of 2 ℃/min under the air atmosphere after obtaining the gel fiber, preserving heat for 2h, soaking for 10 hours by using a dilute nitric acid solution with the pH =5 after cooling, and drying to obtain NiO/Bi 2 WO 6 A nanofiber;
(3)taking 20mg of the prepared NiO/Bi 2 WO 6 The nanofibers were added to a 20mL reactor along with 0.069g of tetranitrophthalonitrile, 0.02g of copper acetate, 0.003g of ammonium molybdate, and 10mL of ethylene glycol solution, and the temperature was maintained at 140 ℃ for 20h. Then after the reaction kettle is cooled, the obtained nano-fiber is alternately washed three times by deionized water and absolute ethyl alcohol and dried for 10 hours in a drying oven at the temperature of 70 ℃ to obtain the 2,9, 16, 23-tetranitro phthalocyanine copper sensitized NiO/Bi 2 WO 6 A nanofiber photocatalyst.
Example 3
2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 The preparation method of the nanofiber photocatalyst comprises the following steps:
(1) At normal temperature, removing 1.0g of citric acid, dissolving in 10mL of deionized water, stirring until the citric acid is dissolved, adding 0.246g of ammonium metatungstate, 0.971g of bismuth nitrate pentahydrate and 1mL of hydrochloric acid solution into the citric acid solution, stirring until the citric acid solution is clarified, adding 0.249g of nickel acetate, and stirring until the citric acid solution is clarified to obtain a solution A; weighing 1.0g of polyvinylpyrrolidone, dissolving in 10mL of absolute ethanol to obtain a solution B, adding 3mL of the solution A into the solution B, and stirring for 15h to obtain a precursor solution;
(2) Transferring the precursor solution obtained in the step (1) into a plastic injector connected with a stainless steel needle, connecting the plastic injector with a 20kV power supply, enabling the distance between the stainless steel needle and a receiving plate to be 15cm, drying the collected fibers in a 60 ℃ drying box to obtain gel fibers, heating the gel fibers to 500 ℃ at a heating rate of 3 ℃/min in the air atmosphere, preserving the heat for 2h, cooling, soaking the gel fibers in a dilute nitric acid solution with the pH =5 for 10h, and drying to obtain NiO/Bi 2 WO 6 And (3) nano fibers.
(3) Taking 20mg of the prepared NiO/Bi 2 WO 6 The nanofibers were added to a 20mL reactor along with 0.069g of tetranitrophthalonitrile, 0.02g of copper acetate, 0.003g of ammonium molybdate, and 10mL of ethylene glycol solution, and the temperature was maintained at 160 ℃ for 20h. Then after the reaction kettle is cooled, the obtained nano-fiber is alternately washed three times by deionized water and absolute ethyl alcohol and dried in a drying oven at 70 ℃ for 10 hours to obtain the 2,9, 16, 23-tetranitro phthalocyanine copper sensitized NiO/Bi 2 WO 6 A nanofiber photocatalyst.
Example 4
2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 The preparation method of the nanofiber photocatalyst comprises the following steps:
(1) At normal temperature, dissolving 1.0g of citric acid in 10mL of deionized water, stirring until the citric acid is dissolved, adding 0.246g of ammonium metatungstate, 0.971g of bismuth nitrate pentahydrate and 1mL of hydrochloric acid solution into the citric acid solution, stirring until the citric acid solution is clarified, adding 0.498g of nickel acetate, and stirring until the citric acid solution is clarified to obtain a solution A; weighing 1.0g of polyvinylpyrrolidone, dissolving in 10mL of absolute ethanol to obtain a solution B, adding 3mL of the solution A into the solution B, and stirring for 15 hours to obtain a precursor solution;
(2) Transferring the precursor solution obtained in the step (1) into a plastic injector connected with a stainless steel needle, connecting the plastic injector with a 20kV power supply, enabling the distance between the stainless steel needle and a receiving plate to be 15cm, drying the collected fibers in a 60 ℃ drying box to obtain gel fibers, heating the gel fibers to 550 ℃ at the heating rate of 5 ℃/min in the air atmosphere, preserving the heat for 1h, cooling, soaking the gel fibers in a dilute nitric acid solution with the pH =5 for 10h, and drying to obtain NiO/Bi 2 WO 6 And (3) nano fibers.
(3) Taking 20mg of the prepared NiO/Bi 2 WO 6 The nanofibers were added to a 20mL reactor along with 0.069g of tetranitrophthalonitrile, 0.02g of copper acetate, 0.003g of ammonium molybdate, and 10mL of ethylene glycol solution, and the temperature was maintained at 180 ℃ for 18h. Then after the reaction kettle is cooled, the obtained nano-fiber is alternately washed three times by deionized water and absolute ethyl alcohol and dried for 10 hours in a drying oven at the temperature of 70 ℃ to obtain the 2,9, 16, 23-tetranitro phthalocyanine copper sensitized NiO/Bi 2 WO 6 A nanofiber photocatalyst.
Example 5
2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 The preparation method of the nanofiber photocatalyst comprises the following steps:
(1) At normal temperature, 2.0g of citric acid is dissolved in 10mL of deionized water, the mixture is stirred until the citric acid is dissolved, 0.246g of ammonium metatungstate, 0.971g of bismuth nitrate pentahydrate and 2mL of hydrochloric acid solution are added into the citric acid solution, after the mixture is stirred and clarified, 0.498g of nickel acetate is added, and the mixture is stirred until the mixture is clarified, so that a solution A is obtained; weighing 1.0g of polyvinylpyrrolidone, dissolving in 10mL of absolute ethanol to obtain a solution B, adding 3mL of the solution A into the solution B, and stirring for 15h to obtain a precursor solution;
(2) And (2) transferring the precursor solution obtained in the step (1) into a plastic injector connected with a stainless steel needle, connecting the plastic injector with a 20kV power supply, wherein the distance between the stainless steel needle and a receiving plate is 15cm, and drying the collected fibers in a drying box at 60 ℃. Heating to 500 ℃ at a heating rate of 1 ℃/min under the air atmosphere after obtaining the gel fiber, preserving heat for 2h, soaking in a dilute nitric acid solution with the pH =5 for 10h after cooling, and drying to obtain NiO/Bi 2 WO 6 And (3) nano fibers.
(3) 20mg of the NiO/Bi obtained is taken 2 WO 6 The nanofibers were added to a 20mL reactor along with 0.069g of tetranitrophthalonitrile, 0.02g of copper acetate, 0.003g of ammonium molybdate, and 10mL of ethylene glycol solution, and the temperature was maintained at 160 ℃ for 10h. Then after the reaction kettle is cooled, the obtained nano-fiber is alternately washed three times by deionized water and absolute ethyl alcohol and dried in a drying oven at 70 ℃ for 10 hours to obtain the 2,9, 16, 23-tetranitro phthalocyanine copper sensitized NiO/Bi 2 WO 6 And (3) nano fibers.
Comparative example 1
NiO/Bi 2 WO 6 Preparation of nanofibers
(1) At normal temperature, 1.0g of citric acid is dissolved in 10mL of deionized water, and the solution is stirred until the citric acid is dissolved. 0.246g of ammonium metatungstate, 0.971g of bismuth nitrate pentahydrate and 1mL of hydrochloric acid solution were added to the above solution, and after stirring and clarification, 0.498g of nickel acetate was added and stirred until clarification, to obtain solution A. 1.0g of polyvinylpyrrolidone is weighed and dissolved in 10mL of absolute ethanol, 3mL of the solution A is added, and the mixture is stirred for 15h to be used as a spinnable precursor solution B.
(2) Transferring the solution B obtained in the step (1) into a plastic syringe connected with a stainless steel needle, connecting the plastic syringe with a power supply of 20kV, wherein the distance between the stainless steel needle and a receiving plate is 15cm, and drying the collected fibers in a drying oven at 60 ℃. Heating to 550 ℃ at the heating rate of 1 ℃/min under the air atmosphere after obtaining the gel fiber, preserving heat for 1h, soaking in a dilute nitric acid solution with the pH =5 for 10h after cooling, and drying to obtain the NiO/Bi 2 WO 6 And (3) nano fibers.
Comparative example 2
Preparation method of 2,9, 16, 23-tetranitro copper phthalocyanine
0.069g of tetranitrophthalonitrile, 0.02g of copper acetate, 0.003g of ammonium molybdate and 10mL of ethylene glycol solution were added together in a 20mL reaction vessel and the temperature was maintained at 150 ℃ for 18 hours. And after the reaction kettle is cooled, alternately washing the reaction kettle for three times by using deionized water and absolute ethyl alcohol, and drying the reaction kettle for 10 hours in a drying oven at the temperature of 70 ℃ to obtain a sample.

Claims (7)

1.2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 The nanofiber photocatalyst is 2,9, 16, 23-tetranitro copper phthalocyanine (CuTNPc) loaded on NiO/Bi in situ 2 WO 6 On the surface of the nanofiber, 2,9, 16, 23-tetranitro copper phthalocyanine (CuTNPc) and NiO/Bi 2 WO 6 The molar ratio of the nano fibers is (8-15): 100, respectively;
is prepared by the following method:
1) NiO/Bi 2 WO 6 preparation of nanofibers
Adding ammonium metatungstate, bismuth nitrate pentahydrate and an acid solution into a citric acid solution, adding nickel acetate, and uniformly stirring at room temperature to obtain a solution A; dissolving polyvinylpyrrolidone in absolute ethyl alcohol to obtain a solution B, adding the solution A into the solution B, and uniformly stirring to obtain a precursor solution;
performing electrostatic spinning on the precursor solution at the temperature of 20-30 ℃ and the voltage of 10-30kV, drying after spinning, then heating to 500-700 ℃ in the air atmosphere, preserving the temperature for 1-5h, cooling, soaking in dilute nitric acid solution for 10h, and drying to obtain NiO/Bi 2 WO 6 A nanofiber;
2) 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi 2 WO 6 Preparation of nanofibers
Adding tetranitrophthalonitrile, copper acetate, ammonium molybdate and glycol into a reaction kettle, and adding NiO/Bi 2 WO 6 Reacting the nano-fiber at 120-200 deg.C for 10-20h, washing the obtained nano-fiber, and drying to obtain 2,9, 16, 23-tetranitrateRadical phthalocyanine copper sensitization NiO/Bi 2 WO 6 A nanofiber photocatalyst;
the molar ratio of tetranitrophthalonitrile to copper acetate is (3-6): 1, the mass ratio of copper acetate to ammonium molybdate is as follows: (10-30): (1-5), the mass-to-volume ratio of the tetranitrophthalonitrile to the ethylene glycol is as follows: (5-8): 1, unit: g/L;
NiO/Bi 2 WO 6 the mass ratio of the nano-fiber to the tetranitrophthalonitrile is as follows: 2: (5-8).
2. The 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi of claim 1 2 WO 6 The nanofiber photocatalyst is characterized in that in the step 1), the concentration of a citric acid solution is 100-200g/L, and the mass ratio of the addition amount of ammonium metatungstate to citric acid in the citric acid solution is as follows: (0.1-0.3): (1-2), the mass ratio of the addition amount of the bismuth nitrate pentahydrate to the ammonium metatungstate is as follows: (0.8-1.0): (0.1-0.3).
3. The 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi of claim 1 2 WO 6 The nanofiber photocatalyst is characterized in that in the step 1), the mass ratio of the addition amount of the nickel acetate to the ammonium metatungstate is as follows: (0.1-1.0): (0.1-0.3).
4. The 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi of claim 1 2 WO 6 The nanofiber photocatalyst is characterized in that the acid solution is a hydrochloric acid solution with the mass concentration of 38%, the adding amount of the acid solution is 1-2mL, and the stirring time for obtaining the solution A is 10-18h.
5. The 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi of claim 1 2 WO 6 The nanofiber photocatalyst is characterized in that in the step 1), the concentration of polyvinylpyrrolidone in the solution B is 100-200g/L, and the volume ratio of the solution A to the solution B is as follows: (1-4): (8-12).
6. According to the rightThe 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi according to claim 1 2 WO 6 The nanofiber photocatalyst is characterized in that in the step 1), the electrostatic spinning voltage is 20kV, the distance between a spinning head and a receiving plate is 15cm, the heating rate is 1-5 ℃/min, the temperature is increased to 65-700 ℃, and the pH of a dilute nitric acid solution is =5.
7. The 2,9, 16, 23-tetranitro copper phthalocyanine sensitized NiO/Bi according to claim 1 2 WO 6 The application of the nanofiber photocatalyst is used for the photocatalyst, and the nanofiber photocatalyst has strong absorption in the range of solar spectrum 400-750 nm.
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