CN108355669B - Magnetic nano onion carbon loaded Bi2WO6Photocatalyst and preparation method and application thereof - Google Patents
Magnetic nano onion carbon loaded Bi2WO6Photocatalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN108355669B CN108355669B CN201810074928.2A CN201810074928A CN108355669B CN 108355669 B CN108355669 B CN 108355669B CN 201810074928 A CN201810074928 A CN 201810074928A CN 108355669 B CN108355669 B CN 108355669B
- Authority
- CN
- China
- Prior art keywords
- mcnos
- magnetic nano
- photocatalyst
- onion carbon
- nano onion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 241000234282 Allium Species 0.000 title claims abstract description 27
- 235000002732 Allium cepa var. cepa Nutrition 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000006731 degradation reaction Methods 0.000 claims description 24
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 23
- 230000015556 catabolic process Effects 0.000 claims description 22
- 229940043267 rhodamine b Drugs 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000975 dye Substances 0.000 claims description 9
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 239000002131 composite material Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/33—
-
- B01J35/39—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a magnetic nano onion carbon loaded Bi2WO6The photocatalyst and the preparation method and the application thereof. The invention takes magnetic nano onion carbon (MCNOs) as a carrier to prepare magnetic Bi by a hydrothermal method2WO6the/MCNOs composite photocatalyst. The raw materials are cheap and easy to obtain, and the preparation process is simple; the prepared composite photocatalyst is uniform in carrying, active components are not easy to fall off, the stability is high, and secondary pollution to the environment is avoided; the obtained composite photocatalyst can efficiently adsorb and mineralize target pollutants under the condition of visible light; the nano onion carbon inhibits Bi to a great extent2WO6The photo-generated electrons and holes of the photocatalyst are compounded, so that the photocatalytic activity of the photocatalyst is improved, and the difficulty of low quantum yield in practical application of a photocatalytic technology is effectively solved; the catalyst is more convenient and efficient to separate and recycle, and is expected to solve the problem that photocatalytic powder is difficult to recycle in a suspension system.
Description
Technical Field
The invention relates to a magnetic nano onion carbon loaded Bi2WO6Belonging to the technical field of photocatalyst and preparation thereof.
Background
In recent years, energy has become more and more serious due to environmental problemsIncreasingly, the development of clean energy for treating environmental pollution is urgent, and the photocatalysis technology is widely concerned at home and abroad due to the potential application of the photocatalysis technology in solving the problems of energy shortage and environmental pollution. The traditional photocatalytic material generally adopts metal oxide or sulfide with larger band gap, and has the following defects in practical application: (1) the light response range is narrow; TiO as conventional semiconductor photocatalysts2The forbidden band width of the photocatalyst is 3.2eV, and the photocatalyst only has photocatalytic activity in an ultraviolet light region (only accounting for 4% of the sunlight capacity); (2) the quantum yield is low; due to the limitation of the material, the quantity of photo-generated electrons to holes is less or the recombination is easy; (3) the catalyst has poor separation and recovery performance; the traditional photocatalytic particles are difficult to recover in a liquid phase, so that the application of the traditional photocatalytic particles is greatly limited. Therefore, how to develop a photocatalytic material with high activity, wide spectrum response and easy solid-liquid separation is a precondition and a key for promoting the wide application of the photocatalytic technology in the field of pollution control.
Bismuth tungstate (Bi)2WO6) The perovskite-type solar cell is of a layered structure with a perovskite plate, a valence band is formed by hybridization of Bi6s and O2p orbitals, and strong interaction between the orbitals reduces symmetry to generate a relevant dipole, so that the perovskite-type solar cell has wider visible light wavelength response, higher oxidation activity and higher charge mobility. However, the existing Bi2WO6The material has two problems in environmental application, namely, the catalyst is difficult to separate and recover; secondly, the yield of the photoproduction quantum is low, the degradation efficiency is low due to easy recombination of photoproduction electron-hole, and the existing Bi is needed2WO6Further improvements were investigated to obtain photocatalytic materials that are easily recyclable and highly efficient.
Disclosure of Invention
The invention aims to provide a magnetic nano onion carbon loaded Bi2WO6By reacting narrow band gap Bi2WO6The active component is loaded on the magnetic nano onion carbon carrier, so that the visible light absorption performance and the solid-liquid separation and recovery performance are improved.
The invention adopts Magnetic Nano onion Carbon (MCNOs), which is a novel Nano material, and the unique hollow structure of the Nano material provides a channel for the transmission of electrons; the larger specific surface area can also enhance the adsorption and ion exchange performance of the dye and accelerate the degradation of the organic dye; in addition, CNOs with Fe-Ni nuclei have good saturation magnetization, and can realize magnetic separation of catalyst and dye. Thus, MCNOs are excellent catalyst supports, can improve the degradation efficiency of the photocatalyst, and can achieve magnetic recovery of the photocatalyst.
The invention provides a magnetic nano onion carbon loaded Bi2WO6The photocatalyst of (2) with Bi2WO6Taking magnetic nano onion carbon as a carrier and Bi as an active component2WO6The active component is loaded on a magnetic nano onion carbon carrier to form; the catalyst comprises the following components in parts by weight:
magnetic nano onion carbon MCNOs: 10 to 20wt% of a surfactant,
Bi2WO6：80~90wt%。
the invention provides the magnetic nano onion carbon loaded Bi2WO6The preparation method of the photocatalyst comprises the following steps:
(1) adding Bi (NO)3）3·5H2Dissolving O in nitric acid to form a transparent solution A (2.5-3.5 mmol/L), and adding Na2WO4·2H2Dissolving O in deionized water to form a transparent solution B (1.25-1.75 mmol/L), wherein Bi (NO) is dissolved in the deionized water3）3·5H2O and Na2WO4·2H2The molar ratio of O is 1.5: 1-2: 1;
(2) dropwise adding the solution B into the solution A at a speed of 1-2 mL/min to form a white suspension, adjusting the pH value with NaOH, and magnetically stirring for 25-35 min;
(3) adding 0.11-0.21 g of MCNOs into 30-50mL of surfactant, and performing ultrasonic dispersion for 25-35 min to form MCNOs dispersion liquid;
(4) adding the dispersed MCNOs dispersion liquid into the suspension obtained in the step (2), and magnetically stirring for 25-35 min;
(5) transferring the solution into a high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction in an oven;
(6) after the reaction kettle is cooled to room temperature, taking the product in the reaction kettle, alternately cleaning with water and absolute ethyl alcohol, centrifuging and drying to obtain the magnetic Bi2WO6a/MCNOs catalyst.
As a preferable preparation scheme, the pH value in the step (2) is adjusted to 1-3.
The amount of MCNOs in the step (3) is theoretical Bi2WO610-20% of the mass.
And (4) the surfactant in the step (3) is glycol.
The hydrothermal reaction temperature, namely the temperature of the oven in the step (5), is set to be 140-180 ℃, and the reaction time is 1-6 h.
The cleaning in the step (6) is to alternately clean the glass substrate for 3-5 times by using deionized water and absolute ethyl alcohol; the centrifugal rotating speed is 6000 to 8000r/min, and the centrifugal time is 8 to 10 min; the drying mode is drying by an oven, the temperature is set at 60-80 ℃, and the drying time is 6-8 h.
The invention provides the magnetic nano onion carbon loaded Bi2WO6The photocatalyst is applied to the catalytic degradation of organic dyes under the condition of visible light.
The organic dye is rhodamine B (RhB). In the degradation process, the concentration of RhB is 10mg/L, and Bi2WO6The addition amount of the/MCNOs composite catalyst is 1.0-1.5 g/L.
Bi of the present invention2WO6The removal rate of the/MCNOs composite catalyst to the organic dye within 2 hours can reach more than 80%.
The composite material prepared by the invention has superparamagnetism, and the magnetic recovery of the catalyst can be completed by adding a magnet. The catalyst is convenient to recover and is beneficial to reuse.
The invention has the beneficial effects that:
(1) the present application provides a photocatalytically active component Bi2WO6Loaded to MCNOSOn the surface, on one hand, the problem of catalyst loss in the photocatalysis process is effectively solved, and the stability of the photocatalyst is improved;on the other hand, the large specific surface area of the carrier is utilized to provide more active sites, so that more micro chemical reaction sites are provided for a photocatalytic system, and the photocatalytic activity is further improved in a synergistic manner.
(2) The catalyst prepared by the invention is a high-efficiency photocatalyst easy for magnetic recovery, and is pure Bi2WO6Compared with the prior art, the catalyst has greatly improved adsorption performance and catalytic degradation performance.
(3) When the photocatalyst is used for treating RhB, pollutants in water can be completely degraded after photoreaction is carried out for 2 hours, and after the reaction is finished, the catalyst can be separated by using a magnet.
(4) The photocatalyst prepared by the method is simple to operate and easy to implement, and can be popularized and used in water pollution treatment.
Drawings
FIG. 1 shows Bi in example 12WO6MCNOs, MCNOs and Bi2WO6An XRD pattern of (a);
FIG. 2 shows Bi in example 12WO6SEM and EDS of/MCNOs;
FIG. 3 shows Bi in example 12WO6Hysteresis curves for/MCNOs and MCNOs;
FIG. 4 shows Bi in example 12WO6MCNOs, MCNOs and Bi2WO6Ultraviolet to visible diffuse reflectance spectrogram;
FIG. 5 is a UV-vis scan of RhB solution of example 1 for different degradation times;
FIG. 6 is a graph showing the effect of magnetic photocatalysts added at different MCNOs on the degradation of 10mg/L RhB.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
magnetic nano carbon onion doped bismuth tungstate (Bi)2WO6The preparation method of the/MCNOs) catalyst comprises the following specific steps:
firstly, 1.455g of bismuth nitrate is weighed and dissolved in 6mL of HNO with 2mol/L3Dissolving 0.495g of sodium tungstate in 6mL of deionized water to form a transparent solution A, and dissolving the transparent solution B in the deionized water to form a transparent solution B; dropwise adding the solution B into the solution A to form a white suspension, adjusting the pH to 3 by using NaOH, and magnetically stirring for 30 min; then 0.19g of MCNOs is weighed and added into a surfactant glycol, and ultrasonic dispersion is carried out for 30min to form MCNOs dispersion liquid; adding the dispersed MCNOs dispersion liquid into the suspension with the adjusted pH, and magnetically stirring for 30min to form a precursor; then transferring the precursor into a high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction at 150 ℃ for 2 h; after the reaction kettle is cooled to room temperature, taking a product in the reaction kettle, washing the product with deionized water and absolute ethyl alcohol for 3 times respectively, and drying the product at 80 ℃ for 8 hours to obtain the magnetic Bi2WO6a/MCNOs photocatalyst.
200mL of 10mg/L rhodamine B is prepared, and then 0.2g of Bi is added2WO6MCNOs magnetic photocatalyst, and is magnetically stirred for 20min after ultrasonic dispersion for 10min in a dark condition to achieve adsorption balance; and then, a 300W xenon lamp is adopted, a 420 nm optical filter is added as a visible light source, the reaction time is 120min, a sample is taken every 20min, and the absorbance is measured after centrifugation. And then, drawing a curve by taking the time (t) as an abscissa and the removal rate as an ordinate, and reflecting the degradation performance of the magnetic photocatalyst (see figure 6), wherein the degradation rate of the catalyst prepared by the method to rhodamine B can reach 91.1% within 2 h.
Shown in FIG. 1 is Bi2WO6MCNOs, MCNOs and Bi2WO6The XRD pattern of (A) is compared with a standard card (PDF number 73-1126), and Bi is shown2WO6MCNOs and Bi2WO6Shows a uniform crystal structure and crystallinity, and further, in Bi2WO6The XRD pattern of the/MCNOs shows characteristic peaks of the MCNOs, which indicates that the MCNOs are successfully compounded into Bi2WO6In (1).
FIG. 2 shows Bi2WO6SEM image of/MCNOs composite, it can be seen that Bi2WO6Has a flaky shape and has better dispersion performance.
FIG. 3 shows Bi2WO6Hysteresis loops of/MCNOs, two samples can be seenAll have good superparamagnetism, which indicates that the purpose of magnetically separating the compound can be achieved by adding a magnet.
FIG. 4 shows Bi2WO6MCNOs, MCNOs and Bi2WO6Ultraviolet-visible diffuse reflectance spectrum of (B), Bi2WO6The light absorption edge was about 445nm, indicating that Bi2WO6The forbidden band width of (A) is 2.75 eV. In addition, Bi2WO6the/MCNOs compound has larger absorption of light in a visible light region, and can accelerate the generation of photogenerated electrons and holes.
FIG. 5 is a UV-vis scan of RhB solution at different degradation times, the peak intensity at 554nm gradually decreases and blue shift occurs as the reaction proceeds, and the color of the solution gradually changes from rose bengal to colorless, indicating that the degradation of RhB is completed.
FIG. 6 is a graph showing the degradation effect of magnetic photocatalysts with different addition amounts of MCNOs on 10mg/L RhB, which shows that the degradation effect of the photocatalyst on RhB reaches the maximum when the addition amount of MCNOs is 18wt%, and the specific meanings are described in the following examples.
Example 2:
firstly, 1.455g of bismuth nitrate is weighed and dissolved in 6mL of HNO with 2mol/L3Dissolving 0.495g of sodium tungstate in 6mL of deionized water to form a transparent solution A, and dissolving the transparent solution B in the deionized water to form a transparent solution B; dropwise adding the solution B into the solution A to form a white suspension, adjusting the pH to 3 by using NaOH, and magnetically stirring for 30 min; then 0.17g of MCNOs is weighed and added into a surfactant glycol, and ultrasonic dispersion is carried out for 30min to form MCNOs dispersion liquid; adding the dispersed MCNOs dispersion liquid into the suspension with the adjusted pH, and magnetically stirring for 30min to form a precursor; then transferring the precursor into a high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction at 150 ℃ for 2 h; after the reaction kettle is cooled to room temperature, taking a product in the reaction kettle, washing the product with deionized water and absolute ethyl alcohol for 3 times respectively, and drying the product at 80 ℃ for 8 hours to obtain Bi2WO6the/MCNOs magnetic photocatalyst.
200mL of 10mg/L rhodamine B is prepared, and then 0.2g of Bi is added2WO6The MCNOs magnetic photocatalyst is obtained by ultrasonic dispersion for 10min in a dark condition and magnetic stirring for 20minCarrying out adsorption balance; and then, a 300W xenon lamp is adopted, a 420 nm optical filter is added as a visible light source, the reaction time is 120min, a sample is taken every 20min, and the absorbance is measured after centrifugation. And then, drawing a curve by taking the time (t) as an abscissa and the removal rate as an ordinate, and reflecting the degradation performance of the magnetic photocatalyst (see figure 6), wherein the degradation rate of the catalyst prepared by the method to rhodamine B can reach 88.6% within 2 h.
Example 3:
firstly, 1.455g of bismuth nitrate is weighed and dissolved in 6mL of HNO with 2mol/L3Dissolving 0.495g of sodium tungstate in 6mL of deionized water to form a transparent solution A, and dissolving the transparent solution B in the deionized water to form a transparent solution B; dropwise adding the solution B into the solution A to form a white suspension, adjusting the pH to 3 by using NaOH, and magnetically stirring for 30 min; then 0.15g of MCNOs is weighed and added into a surfactant glycol, and ultrasonic dispersion is carried out for 30min to form MCNOs dispersion liquid; adding the dispersed MCNOs dispersion liquid into the suspension with the adjusted pH, and magnetically stirring for 30min to form a precursor; then transferring the precursor into a high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction at 150 ℃ for 2 h; after the reaction kettle is cooled to room temperature, taking a product in the reaction kettle, washing the product with deionized water and absolute ethyl alcohol for 3 times respectively, and drying the product at 80 ℃ for 8 hours to obtain Bi2WO6the/MCNOs magnetic photocatalyst.
200mL of 10mg/L rhodamine B is prepared, and then 0.2g of Bi is added2WO6MCNOs magnetic photocatalyst, and is magnetically stirred for 20min after ultrasonic dispersion for 10min in a dark condition to achieve adsorption balance; and then, a 300W xenon lamp is adopted, a 420 nm optical filter is added as a visible light source, the reaction time is 120min, a sample is taken every 20min, and the absorbance is measured after centrifugation. And then, drawing a curve by taking the time (t) as an abscissa and the removal rate as an ordinate, and reflecting the degradation performance of the magnetic photocatalyst (see figure 6), wherein the degradation rate of the catalyst prepared by the method to rhodamine B can reach 89.4% within 2 h.
Example 4:
firstly, 1.455g of bismuth nitrate is weighed and dissolved in 6mL of HNO with 2mol/L3Dissolving 0.495g of sodium tungstate in 6mL of deionized water to form a transparent solution A, and dissolving the transparent solution B in the deionized water to form a transparent solution B; adding the solution B dropwise into the solutionForming a white suspension in the solution A, adjusting the pH to 3 by using NaOH, and magnetically stirring for 30 min; then 0.13g of MCNOs is weighed and added into a surfactant glycol, and ultrasonic dispersion is carried out for 30min to form MCNOs dispersion liquid; adding the dispersed MCNOs dispersion liquid into the suspension with the adjusted pH, and magnetically stirring for 30min to form a precursor; then transferring the precursor into a high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction at 150 ℃ for 2 h; after the reaction kettle is cooled to room temperature, taking a product in the reaction kettle, washing the product with deionized water and absolute ethyl alcohol for 3 times respectively, and drying the product at 80 ℃ for 8 hours to obtain Bi2WO6the/MCNOs magnetic photocatalyst.
200mL of 10mg/L rhodamine B is prepared, and then 0.2g of Bi is added2WO6MCNOs magnetic photocatalyst, and is magnetically stirred for 20min after ultrasonic dispersion for 10min in a dark condition to achieve adsorption balance; and then, a 300W xenon lamp is adopted, a 420 nm optical filter is added as a visible light source, the reaction time is 120min, a sample is taken every 20min, and the absorbance is measured after centrifugation. And then, drawing a curve by taking the time (t) as an abscissa and the removal rate as an ordinate, and reflecting the degradation performance of the magnetic photocatalyst (see figure 6), wherein the degradation rate of the catalyst prepared by the method to rhodamine B can reach 83.5% within 2 h.
Example 5:
firstly, 1.455g of bismuth nitrate is weighed and dissolved in 6mL of HNO with 2mol/L3Dissolving 0.495g of sodium tungstate in 6mL of deionized water to form a transparent solution A, and dissolving the transparent solution B in the deionized water to form a transparent solution B; dropwise adding the solution B into the solution A to form a white suspension, adjusting the pH to 3 by using NaOH, and magnetically stirring for 30 min; then 0.11g of MCNOs is weighed and added into a surfactant glycol, and ultrasonic dispersion is carried out for 30min to form MCNOs dispersion liquid; adding the dispersed MCNOs dispersion liquid into the suspension with the adjusted pH, and magnetically stirring for 30min to form a precursor; then transferring the precursor into a high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction at 150 ℃ for 2 h; after the reaction kettle is cooled to room temperature, taking a product in the reaction kettle, washing the product with deionized water and absolute ethyl alcohol for 3 times respectively, and drying the product at 80 ℃ for 8 hours to obtain Bi2WO6the/MCNOs magnetic photocatalyst.
Preparation 10mg/L rhodamine B200 mL, then add 0.2g Bi2WO6MCNOs magnetic photocatalyst, and is magnetically stirred for 20min after ultrasonic dispersion for 10min in a dark condition to achieve adsorption balance; and then, a 300W xenon lamp is adopted, a 420 nm optical filter is added as a visible light source, the reaction time is 120min, a sample is taken every 20min, and the absorbance is measured after centrifugation. And then, drawing a curve by taking the time (t) as an abscissa and the removal rate as an ordinate, and reflecting the degradation performance of the magnetic photocatalyst (see figure 6), wherein the degradation rate of the catalyst prepared by the method to rhodamine B can reach 76.8% within 2 h.
Claims (9)
1. Magnetic nano onion carbon loaded Bi2WO6The photocatalyst according to (1), characterized in that: with Bi2WO6Taking magnetic nano onion carbon as a carrier and Bi as an active component2WO6The active component is loaded on a magnetic nano onion carbon carrier to form; the catalyst comprises the following components in percentage by weight:
magnetic nano onion carbon MCNOs: 10 to 20wt% of a surfactant,
Bi2WO6：80~90 wt%；
the magnetic nano onion carbon loaded Bi2WO6The preparation method of the photocatalyst comprises the following steps:
(1) adding Bi (NO)3）3·5H2Dissolving O in nitric acid to obtain transparent solution A with concentration of 2.5-3.5mmol/L, adding Na2WO4·2H2Dissolving O in deionized water to form a transparent solution B with the concentration of 1.25-1.75mmol/L, wherein Bi (NO) is added3）3·5H2O and Na2WO4·2H2The molar ratio of O is 1.5: 1-2: 1;
(2) dropwise adding the solution B into the solution A at a speed of 1-2 mL/min to form a white suspension, adjusting the pH value with NaOH, and magnetically stirring for 25-35 min;
(3) adding 0.11-0.21 g of MCNOs into 30-50mL of surfactant, and performing ultrasonic dispersion for 25-35 min to form MCNOs dispersion liquid;
(4) adding the dispersed MCNOs dispersion liquid into the suspension obtained in the step (2), and magnetically stirring for 25-35 min;
(5) transferring the solution into a high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction in an oven;
(6) after the reaction kettle is cooled to room temperature, taking the product in the reaction kettle, alternately cleaning the product with water and absolute ethyl alcohol, centrifuging and drying to obtain the magnetic Bi2WO6a/MCNOs catalyst.
2. The magnetic nano onion carbon supported Bi of claim 12WO6The photocatalyst according to (1), characterized in that: and (3) adjusting the pH value in the step (2) to 1-3.
3. The magnetic nano onion carbon supported Bi of claim 12WO6The photocatalyst according to (1), characterized in that: the amount of MCNOs in the step (3) is theoretical Bi2WO610 to 20% by mass.
4. The magnetic nano onion carbon supported Bi of claim 12WO6The photocatalyst according to (1), characterized in that: the surfactant is ethylene glycol.
5. The magnetic nano onion carbon supported Bi of claim 12WO6The photocatalyst according to (1), characterized in that: the hydrothermal reaction temperature, namely the temperature of the oven in the step (5), is set to be 140-180 ℃, and the reaction time is 1-6 h.
6. The magnetic nano onion carbon supported Bi of claim 12WO6The photocatalyst according to (1), characterized in that: the cleaning in the step (6) is to alternately clean the glass substrate for 3-5 times by using deionized water and absolute ethyl alcohol; the centrifugal rotating speed is 6000 to 8000r/min, and the centrifugal time is 8 to 10 min; the drying mode is drying by an oven, the temperature is set at 60-80 ℃, and the drying time is 6-8 h.
7. The magnetic nano onion carbon supported Bi of claim 12WO6The photocatalyst is applied to the catalytic degradation of organic dyes under the condition of visible light.
8. Use according to claim 7, characterized in that: the organic dye is rhodamine B, the concentration of the rhodamine B is 10mg/L in the degradation process, and Bi is added2WO6The addition amount of the/MCNOs catalyst is 1.0-1.5 g/L.
9. Use according to claim 8, characterized in that: the Bi2WO6The removal rate of the organic dye rhodamine B by the MCNOs catalyst reaches more than 80 percent within 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810074928.2A CN108355669B (en) | 2018-01-25 | 2018-01-25 | Magnetic nano onion carbon loaded Bi2WO6Photocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810074928.2A CN108355669B (en) | 2018-01-25 | 2018-01-25 | Magnetic nano onion carbon loaded Bi2WO6Photocatalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108355669A CN108355669A (en) | 2018-08-03 |
| CN108355669B true CN108355669B (en) | 2020-09-08 |
Family
ID=63007084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810074928.2A Active CN108355669B (en) | 2018-01-25 | 2018-01-25 | Magnetic nano onion carbon loaded Bi2WO6Photocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108355669B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109248678B (en) * | 2018-09-29 | 2021-05-14 | 沈阳理工大学 | Preparation method of light bismuth tungstate purification material |
| CN111068656A (en) * | 2019-11-04 | 2020-04-28 | 江苏大学 | Bi2WO6HRP (horse radish peroxidase) coupled artificial catalyst as well as preparation method and application thereof |
| CN111036252A (en) * | 2019-12-05 | 2020-04-21 | 太原理工大学 | Bismuth tungstate quantum dot/magnetic nano onion carbon magnetic composite photocatalyst and preparation method and application thereof |
| CN111450823A (en) * | 2020-04-24 | 2020-07-28 | 南京奇安威尔环境科技有限公司 | Composite catalyst GQD/Bi for degrading NO2WO6And method for preparing the same |
| CN113893840B (en) * | 2021-08-31 | 2023-04-14 | 浙江树人学院（浙江树人大学） | Composite photocatalyst, preparation method and application in dye wastewater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008091102A (en) * | 2006-09-29 | 2008-04-17 | Sanyo Electric Co Ltd | Fuel electrode catalyst for fuel cell, electrode/membrane assembly, fuel cell equipped with electrode/membrane assembly, and fuel cell system |
| CN107349927A (en) * | 2017-08-30 | 2017-11-17 | 陕西科技大学 | A kind of laurustinus tufted bismuth tungstate/charcoal composite photocatalyst material and its preparation method and application |
-
2018
- 2018-01-25 CN CN201810074928.2A patent/CN108355669B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008091102A (en) * | 2006-09-29 | 2008-04-17 | Sanyo Electric Co Ltd | Fuel electrode catalyst for fuel cell, electrode/membrane assembly, fuel cell equipped with electrode/membrane assembly, and fuel cell system |
| CN107349927A (en) * | 2017-08-30 | 2017-11-17 | 陕西科技大学 | A kind of laurustinus tufted bismuth tungstate/charcoal composite photocatalyst material and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 非贵金属助剂在光催化制氢中的应用;肖凌峰 等;《2017全国光催化材料及创新应用学术研讨会摘要集》;20170930;第17页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108355669A (en) | 2018-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108355669B (en) | Magnetic nano onion carbon loaded Bi2WO6Photocatalyst and preparation method and application thereof | |
| CN107456991B (en) | g-C3N4Preparation method of quantum dot supported bismuth tungstate nanosheet photocatalyst | |
| CN110152711B (en) | CeO (CeO)2@MoS2/g-C3N4Ternary composite photocatalyst and preparation method thereof | |
| CN108435194B (en) | Bismuth ferrite/bismuth tungstate heterojunction photocatalysis material and preparation method thereof | |
| CN108686665B (en) | Preparation method of nanorod zinc ferrite in-situ composite lamellar titanium dioxide photocatalytic material | |
| CN106944074B (en) | A kind of visible-light response type composite photo-catalyst and its preparation method and application | |
| CN106693996B (en) | Preparation method and application of bismuth sulfide-bismuth ferrite composite visible-light-driven photocatalyst | |
| CN110368962A (en) | A kind of BiOI/WO3Preparation method, product and the application of hetero-junctions efficient photoelectricity treater catalysis electrode | |
| CN110302826B (en) | Basic bismuth nitrate and bismuth oxyiodide composite photocatalyst and preparation method and application thereof | |
| WO2023108950A1 (en) | PREPARATION METHOD FOR Z-SCHEME α-FE2O3/ZNIN2S4 COMPOSITE PHOTOCATALYST AND USE THEREOF | |
| CN113578313B (en) | Manganese-doped sillenite photocatalyst, preparation method thereof and application thereof in synchronous degradation of hexavalent chromium and organic pollutants | |
| CN116196944A (en) | Preparation method and application of biomass nitrogen-doped carbon quantum dot coupled ultrathin BiOBr nano-sheet composite photocatalyst | |
| CN115608367A (en) | Zn1-xCuxO/TiO with core-shell structure 2 Preparation method and application of photocatalytic composite material | |
| CN113578368B (en) | g-C 3 N 4 /Ag 3 PO 4 /BiFeO 3 Preparation method and application of composite visible light catalyst | |
| CN115845832A (en) | ZIF-8-derivatized ZnO/BiVO 4 Preparation method and application of heterojunction compound | |
| CN110624532B (en) | TiO 22-BiVO4-graphene ternary composite photocatalytic material and preparation method thereof | |
| CN111659429B (en) | Preparation method of cadmium sulfide-cesium phosphotungstate composite material and application of composite material as visible-light-driven photocatalyst to hydrogen preparation | |
| CN111468133B (en) | Preparation method of potassium niobate/alpha-ferric oxide heterogeneous photocatalyst | |
| CN111111639B (en) | ZnO/InOOH heterogeneous Z-type photocatalytic material and preparation method thereof | |
| CN110075879B (en) | Carbon-coated ferroferric oxide magnetic microsphere modified bismuth oxyiodide composite photocatalytic material and preparation method and application thereof | |
| CN109701518B (en) | Composite photocatalyst, preparation method thereof and application of composite photocatalyst in degradation of organic dye | |
| CN113578296A (en) | Lamellar gray TiO2 photocatalytic material and preparation method thereof | |
| CN113019375A (en) | double-Z type photocatalyst NiO/NiFe2O4/Fe2O3And uses thereof | |
| CN113101954B (en) | Bi 5 O 7 I/Bi 2 MoO 6 Composite photocatalyst and preparation method and application thereof | |
| CN115138354B (en) | Core-shell structure Cs 0.32 WO 3 /BiVO 4 Heterojunction, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230719 Address after: No. 3, Beihai Road, Tuolingtou Park, Yangquan Economic and Technological Development Zone, Yangquan City, Shanxi Province 045000 Patentee after: Shanxi Zhongxing Science and Technology Group Co.,Ltd. Address before: 030024 No. 79 West Main Street, Wan Berlin District, Shanxi, Taiyuan, Yingze Patentee before: Taiyuan University of Technology |