CN111659447A - Photocatalyst for treating dye in high-salinity wastewater and preparation method thereof - Google Patents
Photocatalyst for treating dye in high-salinity wastewater and preparation method thereof Download PDFInfo
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- CN111659447A CN111659447A CN202010647628.6A CN202010647628A CN111659447A CN 111659447 A CN111659447 A CN 111659447A CN 202010647628 A CN202010647628 A CN 202010647628A CN 111659447 A CN111659447 A CN 111659447A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 56
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 40
- 239000010439 graphite Substances 0.000 claims abstract description 40
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000002135 nanosheet Substances 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 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 claims abstract description 8
- 239000000975 dye Substances 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 37
- 239000007787 solid Substances 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 24
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 23
- 229940012189 methyl orange Drugs 0.000 claims description 23
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [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
- 229940043267 rhodamine b Drugs 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229940036358 bismuth subcarbonate Drugs 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 28
- 238000006731 degradation reaction Methods 0.000 abstract description 28
- FWIZHMQARNODNX-UHFFFAOYSA-L dibismuth;oxygen(2-);carbonate Chemical compound [O-2].[O-2].[Bi+3].[Bi+3].[O-]C([O-])=O FWIZHMQARNODNX-UHFFFAOYSA-L 0.000 abstract description 25
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000013032 photocatalytic reaction Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- C02F2101/38—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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physical Water Treatments (AREA)
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Abstract
The invention discloses a photocatalyst for treating dye in high-salinity wastewater and a preparation method thereof, belonging to the field of photocatalysis. The photocatalyst takes a porous graphite phase nitrogen carbide nanosheet as a carrier, and bismuth oxycarbonate nanoparticles are loaded on the porous graphite phase nitrogen carbide nanosheet carrier. The catalyst obtained by the invention can be used for catalytically treating the dye in the high-salinity wastewater under visible light, and has the advantages of response under visible light, low cost and high degradation rate. In the preparation process of the catalyst, graphite-phase nitrogen carbide after hydrothermal treatment is directly ground and roasted with bismuth nitrate, so that bismuthyl carbonate particles can be generated on the surface of a nitrogen carbide carrier in situ, and the catalytic reaction stability of the photocatalyst is improved by utilizing the strong interaction force of the bismuthyl carbonate particles and the bismuth nitrate. In addition, no organic solvent is introduced in the preparation process, so that the method is environment-friendly, simple in process and beneficial to industrial production.
Description
Technical Field
The invention relates to the field of photocatalysis, in particular to a photocatalyst for treating dye in high-salinity wastewater and a preparation method thereof.
Background
1. With the rapid development of textile industrialization, the discharge of a large amount of printing and dyeing wastewater seriously threatens the natural environment and human health. The printing and dyeing wastewater has the characteristics of deep chromaticity, strong toxicity, difficult degradation, large pH value fluctuation and the like, and the content of inorganic salt is very high, so that the printing and dyeing wastewater is difficult to effectively treat by adopting a conventional method.
2. In recent years, the photocatalytic oxidation method is regarded as a pollutant removal technology with the greatest development prospect due to the characteristics of low energy consumption, mild reaction conditions, simple operation, low cost and the like. The TiO2 photocatalyst has the advantages of low price, no toxicity, high activity and the like, but high-concentration Cl < - > in high-salt wastewater has obvious quenching effect on active free radicals OH, so that the photocatalytic effect is seriously reduced.
3. In order to improve the degradation effect of the dye in the high-salt wastewater, the method of organically combining photocatalysis and electrochemistry is adopted in the chinese patent with publication number CN102806075A, which can effectively inhibit the quenching effect of Cl-, but a large amount of electric energy consumed in the photoelectrocatalysis and the adopted TiO2 photocatalyst must work under ultraviolet light, and further development of the technology is still severely restricted.
4. Graphite phase nitrogen carbide (g-C3N4) becomes a novel two-dimensional non-metallic semiconductor material which not only has strong adsorption capacity, but also can respond to visible light due to the unique graphite-shaped lamellar structure and nitrogen substitution doping, and has attracted attention of researchers.
Disclosure of Invention
The invention provides a photocatalyst for treating dye in high-salt wastewater and a preparation method thereof, aiming at making up for the defects of the prior art and solving the problem that the treatment effect of the dye in the high-salt wastewater is not ideal in the prior art.
The technical scheme of the invention is as follows:
a photocatalyst for treating dye in high-salt wastewater takes a porous graphite phase nitrogen carbide nanosheet as a carrier, and bismuth subcarbonate nanoparticles are loaded on the porous graphite phase nitrogen carbide nanosheet carrier.
Preferably, the load of the bismuthyl carbonate nano-particles is 0.1-10.0%.
The preparation method of the photocatalyst for treating the dye in the high-salinity wastewater comprises the following steps:
1) placing the graphite phase nitrogen carbide precursor into a muffle furnace, heating to 400-600 ℃, keeping the temperature for 500min, and cooling to room temperature to obtain yellow powder A;
2) putting the yellow powder A prepared in the step 1) into deionized water, and carrying out ultrasonic treatment for 0.5-3h to obtain a suspension B;
3) placing the suspension B in a hydrothermal kettle, heating at 120-240 ℃ for 6-30h, cooling to room temperature, and centrifuging to obtain a solid substance C;
4) drying the solid matter C to obtain a khaki solid D;
5) mixing and grinding bismuth nitrate and the earthy yellow solid D, then placing the mixture into a muffle furnace, heating the mixture to 400-600 ℃, keeping the temperature for 3-6h, and cooling the mixture to obtain the photocatalyst for treating the dye in the high-salinity wastewater.
Preferably, the graphite-phase nitrogen carbide precursor in step 1) is one or more of urea, cyanamide, dicyandiamide and melamine.
Preferably, in the step 2), the mass fraction of the yellow powder A in the suspension B is 0.5-1.5%.
Preferably, the molar ratio of bismuth nitrate to the yellowish solid D in step 5) is 4X 10-4 to 4X 10-2: 1.
Preferably, the heating rate in the step 1) and the step 5) is 1-5 ℃/min.
The application of the photocatalyst for treating the dye in the high-salt wastewater in treating methyl orange and/or rhodamine B in the high-salt wastewater.
The method for treating the dye in the high-salinity wastewater by adopting the photocatalyst for treating the dye in the high-salinity wastewater comprises the steps of adding the photocatalyst for treating the dye in the high-salinity wastewater into the high-salinity wastewater to be treated; stirring and reacting for 0.2-6h under the irradiation of a light source with the wavelength of 420-800nm, and filtering out the catalyst.
As a preferred scheme, the Cl < - > concentration in the wastewater is 0-6000mg/L, the pH value is 4-11, the dye content is 5-50mg/L, and the addition amount of the catalyst meets the following requirements: 0.6-1.5mg catalyst/mL high salinity wastewater.
The invention has the beneficial effects that:
1) the photocatalyst takes porous graphite phase nitrogen carbide nanosheets as carriers and loads bismuth oxycarbonate nanoparticles. The poly
The porous graphite phase nitrogen carbide has large pore diameter, specific surface and pore volume, and the carrier is favorable for massive adsorption and enrichment of dye molecules on the surface of the nitrogen carbide in a high-salt state, so that abundant raw material preparation is provided for photocatalytic degradation of the photocatalyst; in addition, bismuth subcarbonate and graphite phase nitrogen carbide form a heterostructure, and the heterostructure has strong absorption under visible light, so that the catalyst can be subjected to photocatalysis under visible light, and the operating cost of photocatalysis is reduced.
2) Organic matter, particularly methyl orange and rhodamine B, is degraded by three free radicals for photocatalysts: active free radical OH, photo-generated hole sum 02-and high concentration Cl-have obvious quenching effect on the active free radical OH. The photocatalyst introduced in the patent utilizes bismuth subcarbonate and graphite phase nitrogen carbide to form a heterojunction, so that the photocatalyst can efficiently degrade dyes in high-salt wastewater through a.02- (the electrons on the graphite phase nitrogen carbide are transferred to the surface of the bismuth subcarbonate and directly generated with oxygen in a solution) and photo-generated holes in the graphite phase nitrogen carbide. In addition, because the photo-generated electrons of the graphite phase nitrogen carbide are transferred to the surface of the bismuth oxycarbonate, the graphite phase nitrogen carbide photo-generated electrons and the photo-generated electrons have good separation effect, and the photocatalysis effect is also obviously improved.
3) In the preparation process of the catalyst, graphite-phase nitrogen carbide after hydrothermal treatment is directly ground and roasted with bismuth nitrate, so that bismuthyl carbonate particles can be generated on the surface of a nitrogen carbide carrier in situ, and the catalytic reaction stability of the photocatalyst is improved by utilizing the strong interaction force of the bismuthyl carbonate particles and the bismuth nitrate. In addition, no organic solvent is introduced in the preparation process, so that the method is environment-friendly and simple in process, and is beneficial to industrial production.
4) The photocatalyst of the invention can treat the dye in the high-salinity wastewater under the irradiation of visible light and at room temperature
The degradation is carried out, the reaction condition is mild, the cost is low, and the method is easy to realize.
5) The photocatalyst of the invention is easy to regenerate and use, and has good photocatalytic performance after being regenerated for many times.
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 only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a nitrogen adsorption-desorption isotherm diagram of the photocatalyst for treating dye in high-salt wastewater in example 1.
FIG. 2 is a high power transmission electron micrograph of the photocatalyst for treating the dye in the high salinity wastewater in example 1.
Detailed Description
Example 1
Putting melamine into a crucible with a cover, placing the crucible in a muffle furnace, heating to 400 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 100min, and cooling to room temperature to obtain yellow powder; then mixing the solid with a certain amount of deionized water (the mass percentage of water is 99.5%), carrying out ultrasonic treatment at room temperature for 0.5h, pouring the mixture into a hydrothermal kettle, heating the mixture at 120 ℃ for 6h, cooling the mixture to room temperature, centrifuging the mixture, and drying the obtained solid in an oven at 40 ℃ for 5h to obtain a solid of khaki; then grinding the porous graphite phase nitrogen carbide nanosheets and bismuth subcarbonate (the molar ratio is 1: 4 multiplied by 10 < -4 >), then placing the ground porous graphite phase nitrogen carbide nanosheets and bismuth subcarbonate into a crucible with a cover, heating the crucible to 400 ℃ at the heating speed of 1 ℃/min, keeping the temperature for 3 hours, and cooling the crucible to room temperature to obtain the porous graphite phase nitrogen carbide nanosheets loaded bismuth subcarbonate nanoparticle photocatalyst.
As can be seen from fig. 1, a hysteresis loop appears on the isotherm in the range of 0.5 to 1.0 relative pressure (P/Po) detected by the nitrogen adsorption-desorption technique, indicating that the catalyst has a mesoporous channel structure. This indicates that: the obtained catalyst still maintains the mesoporous structure of the carrier (porous graphite phase nitrogen carbide nanosheet).
From FIG. 2, it can be seen that the lattice fringe spacing is 0.297nm, which corresponds to the bismuth oxycarbonate (100) plane. In addition, it can be found from the figure that the bismuth subcarbonate particles are distributed on the surface of the porous graphite phase nitrogen carbide nanosheet, which will form a heterostructure of bismuth subcarbonate and graphite phase nitrogen carbide, thereby significantly improving the photocatalytic effect.
Evaluation conditions were as follows: in 40mg/L high-salt dye wastewater containing rhodamine B, the Cl < - > concentration is 5700mg/L, the pH value is 4, the adding mass of the catalyst is 0.6mg/mL calculated by the volume of the high-salt dye wastewater, the reaction is stirred at room temperature under the irradiation of a light source with the wavelength of 420-800nm, the photocatalytic reaction time is 1h, and the catalyst is filtered and removed, so that the water body from which the rhodamine B is degraded and removed is obtained.
The results show that: after the porous graphite phase nitrogen carbide nanosheet loaded with the bismuth oxycarbonate photocatalyst is treated, the degradation rate of rhodamine B is 98.4%.
Example 2
Putting melamine into a crucible with a cover, putting the crucible into a muffle furnace, heating to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 500min, and cooling to room temperature to obtain yellow powder; then mixing the solid with a certain amount of deionized water (the mass percentage of water is 98.5%), carrying out ultrasonic treatment at room temperature for 3 hours, pouring the mixture into a hydrothermal kettle, heating the mixture at 240 ℃ for 30 hours, cooling the mixture to room temperature, centrifuging the mixture, and drying the obtained solid in an oven at 100 ℃ for 30 hours to obtain a solid yellowish brown substance; then grinding the porous graphite phase nitrogen carbide nanosheets and bismuth subcarbonate (the molar ratio is 1: 4 multiplied by 10 < -2 >), then placing the ground porous graphite phase nitrogen carbide nanosheets and bismuth subcarbonate into a crucible with a cover, heating to 600 ℃ at the heating speed of 5 ℃/min, keeping the temperature for 6 hours, and cooling to room temperature to obtain the porous graphite phase nitrogen carbide nanosheets loaded bismuth subcarbonate nanoparticle photocatalyst.
Evaluation conditions were as follows: in 40mg/L high-salt dye wastewater containing methyl orange, the Cl < - > concentration is 5700mg/L, the pH value is 11, the adding mass of the catalyst is 1.0mg/mL calculated by the volume of the high-salt dye wastewater, the reaction is stirred at room temperature under the irradiation of a light source with the wavelength of 420-800nm, the photocatalytic reaction time is 1h, and the catalyst is removed by filtration to obtain a water body after the methyl orange is removed by degradation. The results show that: after the photocatalyst of the porous graphite phase nitrogen carbide nanosheet loaded with bismuth oxycarbonate nanoparticles is used for treatment, the degradation rate of methyl orange is 96.8%.
Example 3
Putting melamine into a crucible with a cover, putting the crucible into a muffle furnace, heating to 530 ℃ at a heating rate of 2.5 ℃/min, keeping the temperature for 200min, and cooling to room temperature to obtain yellow powder; then mixing the solid with a certain amount of deionized water (the mass percentage of water is 99.0%), ultrasonically treating the mixture for 1 hour at room temperature, pouring the mixture into a hydrothermal kettle, heating the mixture for 12 hours at 180 ℃, cooling the mixture to room temperature, centrifuging the mixture, and drying the obtained solid in an oven at 70 ℃ for 10 hours to obtain a solid yellowish brown substance; then grinding the porous graphite phase nitrogen carbide nanosheets and bismuth subcarbonate (the molar ratio is 1: 8 multiplied by 10 < -3 >), then placing the ground porous graphite phase nitrogen carbide nanosheets and bismuth subcarbonate (bismuth subcarbonate) into a crucible with a cover, heating to 500 ℃ at the heating speed of 2.5 ℃/min, keeping the temperature for 4 hours, and cooling to room temperature to obtain the porous graphite phase nitrogen carbide nanosheets loaded bismuth subcarbonate nanoparticle photocatalyst.
Evaluation conditions were as follows: in 20mg/L high-salt dye wastewater containing rhodamine B and 20mg/L methyl orange, the Cl < - > concentration is 5700mg/L, the pH value is 7, the adding mass of the catalyst is 1.5mg/mL calculated by the volume of the high-salt dye wastewater, the reaction is stirred at room temperature under the irradiation of a light source with the wavelength of 420-800nm, the photocatalytic reaction time is 1h, and the catalyst is removed by filtration, so that the water body after the rhodamine B and the methyl orange are removed by degradation is obtained.
The results show that: after the porous graphite phase nitrogen carbide nanosheet loaded with the bismuth oxycarbonate nanoparticle photocatalyst is treated, the degradation rate of rhodamine B is 98.2%, and the degradation rate of methyl orange is 97.0%.
Regeneration conditions are as follows: after the photocatalytic reaction is finished, the catalyst precipitate is washed for a plurality of times by deionized water and ethanol in sequence, and the obtained precipitate is dried for 3 hours at 70 ℃. The results show that: the photocatalyst of the photocatalyst with porous graphite phase nitrogen carbide nanosheets loaded with bismuth oxycarbonate nanoparticles still has very good catalytic performance after being reused for four times. The test results are as follows: the catalyst is recycled for the first time, the degradation rate of rhodamine B is 98.1 percent, and the degradation rate of methyl orange is 96.8 percent; the catalyst is recycled for the second time, the degradation rate of rhodamine B is 97.7 percent, and the degradation rate of methyl orange is 96.5 percent; the catalyst is repeatedly utilized for the third time, the degradation rate of rhodamine B is 97.5 percent, and the degradation rate of methyl orange is 96.2 percent; the catalyst is repeatedly used for the fourth time, the degradation rate of rhodamine B is 97.1 percent, and the degradation rate of methyl orange is 96.0 percent.
After the catalyst obtained by the invention is repeatedly utilized for many times, the degradation rate of rhodamine B and methyl orange is still high.
Comparative example 1
Putting melamine into a crucible with a cover, putting the crucible into a muffle furnace, heating to 530 ℃ at a heating rate of 2.5 ℃/min, keeping the temperature for 200min, and cooling to room temperature to obtain yellow powder; then mixing the solid with a certain amount of deionized water (the mass percentage of water is 99.0%), ultrasonically treating the mixture for 1 hour at room temperature, pouring the mixture into a hydrothermal kettle, heating the mixture for 12 hours at 180 ℃, cooling the mixture to room temperature, centrifuging the mixture, and drying the obtained solid in an oven at 70 ℃ for 10 hours to obtain a solid yellowish brown substance; and then putting the mixture into a crucible with a cover, heating to 500 ℃ at the heating speed of 2.5 ℃/min, keeping the temperature for 4 hours, and cooling to room temperature to obtain the photocatalyst of the porous graphite phase nitrogen carbide nanosheet.
Evaluation conditions were as follows: in 20mg/L high-salt dye wastewater containing rhodamine B and 20mg/L methyl orange, the Cl < - > concentration is 5700mg/L, the pH value is 7, the adding mass of the catalyst is 1.5mg/mL calculated by the volume of the high-salt dye wastewater, the reaction is stirred at room temperature under the irradiation of a light source with the wavelength of 420-800nm, the photocatalytic reaction time is 1h, and the catalyst is removed by filtration, so that the water body after the rhodamine B and the methyl orange are removed by degradation is obtained.
The results show that: after the photocatalyst treatment of the porous graphite phase nitrogen carbide nanosheet in the comparative example, the degradation rate of rhodamine B is 23.1%, and the degradation rate of methyl orange is 24.5%.
Comparative example 2
Putting melamine into a crucible with a cover, putting the crucible into a muffle furnace, heating to 530 ℃ at a heating rate of 2.5 ℃/min, keeping the temperature for 200min, and cooling to room temperature to obtain yellow powder; then mixing the solid with a certain amount of deionized water (the mass percentage of water is 99.0%), ultrasonically treating the mixture for 1 hour at room temperature, pouring the mixture into a hydrothermal kettle, heating the mixture for 12 hours at 180 ℃, cooling the mixture to room temperature, centrifuging the mixture, and drying the obtained solid in an oven at 70 ℃ for 10 hours to obtain a solid yellowish brown substance; then grinding the mixture with copper nitrate (the molar ratio is 1: 8 multiplied by 10 < -3 >), placing the mixture into a crucible with a cover, heating the mixture to 500 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 4 hours, and cooling the mixture to room temperature to obtain the photocatalyst of the porous graphite phase nitrogen carbide nanosheet loaded with copper oxide nanoparticles.
Evaluation conditions were as follows: in 20mg/L high-salt dye wastewater containing rhodamine B and 20mg/L methyl orange, the Cl < - > concentration is 5700mg/L, the pH value is 7, the adding mass of the catalyst is 1.5mg/mL calculated by the volume of the high-salt dye wastewater, the reaction is stirred at room temperature under the irradiation of a light source with the wavelength of 420-800nm, the photocatalytic reaction time is 1h, and the catalyst is removed by filtration, so that the water body after the rhodamine B and the methyl orange are removed by degradation is obtained.
The results show that: after the photocatalyst treatment of the porous graphite phase nitrogen carbide nanosheet loaded with copper oxide nanoparticles in the comparative example, the degradation rate of rhodamine B is 35.6%, and the degradation rate of methyl orange is 33.4%.
Comparative example 3
Putting melamine into a crucible with a cover, putting the crucible into a muffle furnace, heating to 530 ℃ at a heating rate of 2.5 ℃/min, keeping the temperature for 200min, and cooling to room temperature to obtain yellow powder; then mixing the solid with a certain amount of deionized water (the mass percentage of water is 99.0%), ultrasonically treating the mixture for 1 hour at room temperature, pouring the mixture into a hydrothermal kettle, heating the mixture for 12 hours at 180 ℃, cooling the mixture to room temperature, centrifuging the mixture, and drying the obtained solid in an oven at 70 ℃ for 10 hours to obtain a solid yellowish brown substance; then grinding the mixture and zinc nitrate (the molar ratio is 1: 8 multiplied by 10 < -3 >), placing the mixture into a crucible with a cover, heating the mixture to 500 ℃ at the heating speed of 2.5 ℃/min, keeping the temperature for 4 hours, and cooling the mixture to room temperature to obtain the photocatalyst of the porous graphite phase nitrogen carbide nanosheet loaded zinc oxide nanoparticles.
Evaluation conditions were as follows: in 20mg/L high-salt dye wastewater containing rhodamine B and 20mg/L methyl orange, the Cl < - > concentration is 5700mg/L, the pH value is 7, the adding mass of the catalyst is 1.5mg/mL calculated by the volume of the high-salt dye wastewater, the reaction is stirred at room temperature under the irradiation of a light source with the wavelength of 420-800nm, the photocatalytic reaction time is 1h, and the catalyst is removed by filtration, so that the water body after the rhodamine B and the methyl orange are removed by degradation is obtained.
The results show that: after the photocatalyst of the porous graphite phase nitrogen carbide nanosheet loaded with zinc oxide nanoparticles is used for treatment, the degradation rate of rhodamine B is 42.7%, and the degradation rate of methyl orange is 39.2%.
Claims (9)
1. A photocatalyst for treating dye in high-salinity wastewater is characterized in that: taking a porous graphite phase nitrogen carbide nanosheet as a carrier, and loading bismuth subcarbonate nanoparticles on the porous graphite phase nitrogen carbide nanosheet carrier; the preparation method of the photocatalyst for treating the dye in the high-salinity wastewater comprises the following steps:
1) placing the graphite phase nitrogen carbide precursor into a muffle furnace, heating to 400-600 ℃, keeping the temperature for 500min, and cooling to room temperature to obtain yellow powder A;
2) putting the yellow powder A prepared in the step 1) into deionized water, and carrying out ultrasonic treatment for 0.5-3h to obtain a suspension B;
3) placing the suspension B in a hydrothermal kettle, heating at 120-240 ℃ for 6-30h, cooling to room temperature, and centrifuging to obtain a solid substance C;
4) drying the solid matter C to obtain a khaki solid D;
5) mixing and grinding bismuth nitrate and the earthy yellow solid D, then placing the mixture into a muffle furnace, heating the mixture to 400-600 ℃, keeping the temperature for 3-6h, and cooling the mixture to obtain the photocatalyst for treating the dye in the high-salinity wastewater.
2. The photocatalyst for treating a dye in high-salinity wastewater as claimed in claim 1, wherein: the load capacity of the bismuthyl carbonate nano-particles is 0.1-10.0%.
3. The photocatalyst for treating a dye in high-salinity wastewater as claimed in claim 1, wherein: the graphite phase nitrogen carbide precursor in the step 1) is one or more of urea, cyanamide, dicyandiamide and melamine.
4. The photocatalyst for treating a dye in high-salinity wastewater as claimed in claim 1, wherein: in the step 2), the mass fraction of the yellow powder A in the suspension B is 0.5-1.5%.
5. The photocatalyst for treating a dye in high-salinity wastewater as defined in claim 1 or 4, wherein: the molar ratio of the bismuth nitrate to the earthy yellow solid D in the step 5) is 4 x 10 < -4 > to 4 x 10 < -2 > to 1.
6. The photocatalyst for treating a dye in high-salinity wastewater as defined in claim 1 or 4, wherein: step 1) and step
5) The medium heating rate is 1-5 ℃/min.
7. The use of the photocatalyst for treating dyes in high-salt wastewater as claimed in claim 1 for treating methyl orange and/or rhodamine B in high-salt wastewater.
8. The method for treating the dye in the high-salinity wastewater by using the photocatalyst for treating the dye in the high-salinity wastewater as claimed in claim 1, wherein the photocatalyst comprises the following steps: adding the photocatalyst for treating the dye in the high-salinity wastewater into the high-salinity wastewater to be treated; stirring and reacting for 0.2-6h under the irradiation of a light source with the wavelength of 420-800nm, and filtering out the catalyst.
9. The method for treating the dye in the high-salinity wastewater according to claim 8, characterized in that: the Cl-concentration in the wastewater is 0-6000mg/L, the pH is 4-11, the dye content is 5-50mg/L, and the addition amount of the catalyst meets the following requirements: 0.6-1.5mg catalyst/mL high salinity wastewater.
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| WO2024088432A1 (en) * | 2023-10-25 | 2024-05-02 | 海南师范大学 | N-doped bismuth oxycarbonate composite graphite-phase carbon nitride material, and preparation method therefor and use thereof |
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