CN113856728A - Preparation method of tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst - Google Patents
Preparation method of tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 39
- 239000010439 graphite Substances 0.000 title claims abstract description 39
- HNQQQCFYQACVAM-UHFFFAOYSA-N [Bi].[Sn]=S Chemical compound [Bi].[Sn]=S HNQQQCFYQACVAM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 36
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 28
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 20
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 19
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 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 description 16
- 238000001816 cooling Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 9
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 3
- 238000001782 photodegradation Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- ALRFTTOJSPMYSY-UHFFFAOYSA-N tin disulfide Chemical compound S=[Sn]=S ALRFTTOJSPMYSY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 2
- 238000007669 thermal treatment Methods 0.000 claims 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 4
- 108091006149 Electron carriers Proteins 0.000 abstract description 3
- 230000004298 light response Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract description 2
- 229910001432 tin ion Inorganic materials 0.000 abstract description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 10
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention discloses a preparation method and application of a tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst. The main technical characteristics are as follows: preparing graphite phase carbon nitride nanosheets by a calcining method; and preparing the tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst by an in-situ growth method. According to the invention, tin ions are doped with bismuth sulfide and compounded with graphite-phase carbon nitride to form a Z-type heterostructure by an in-situ growth method, and good visible light response characteristics of bismuth base and carbon nitride base and Sn are utilized4+The characteristic of higher electron carrier content accelerates the photo-generated carriers at the interfaceThe redox capability of the photo-excited electrons and holes is maintained, so that the composite photocatalyst shows good stability and catalytic performance. The preparation method is simple, the conditions are easy to control, the production cost is low, the environment is protected, and the method has important significance in the aspect of photocatalytic degradation of organic pollutants.
Description
Technical Field
The invention relates to a preparation method of a tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst, belongs to the technical field of photocatalysts, and particularly relates to preparation of an in-situ growth type tin ion doped bismuth sulfide/carbon nitride composite material and application of the composite material in degradation of phenol organic pollutants.
Background
The problem of environmental pollution is a big problem which puzzles the human survival development for a long time, and harmful pollutants released into water resources and air in production and life are treated before causing harm to organisms. Semiconductor-based photocatalytic technology has shown significant advantages in addressing environmental pollution as an ideal candidate for the past few decades. Therefore, there is an urgent need to develop a photocatalyst having high photocatalytic activity to achieve industrial applications. In the semiconductor photocatalysts studied, g-C3N4Exhibit excellent activity under visible light irradiation, however, g-C3N4The carrier has inherent defects, such as low carrier partition and fluidity and insufficient sunlight utilization, which hinder the practical application. Therefore, the improvement of the charge distribution and migration of photogenerated carriers and the utilization of sunlight is improving g-C3N4The method has important significance in the aspect of the availability ratio. The construction of heterojunctions and homojunctions is considered to be an effective way to promote distribution and migration of photoexcited carriers in a number of optimization schemes, such as band gap tuning, defect control, micro-topography control, surface sensitization, promoters and heterostructures, and the like.
Bismuth-based semiconductors have a visible light response characteristic, are chemically inert, non-toxic, and large in available amount, and thus are attracting much attention. The valence band of bismuth-based semiconductors consists of mixed orbitals of Bi 6s and O2 p, with well-dispersed Bi 6s orbitals leading to band gap narrowing and enhanced transport of photo-generated charge carriers. It is observed that bismuth-based semiconductors generally have a band gap of about 3.0 eV, and therefore, almost all bismuth-based semiconductors can be used as visible light-responsive photocatalysts.
This patent selects Sn4+As a doping element, Sn is a dual-ionization donor, which can provide donor ions, achieve higher electron carrier contents, and even improve the band gap and optical properties of the photocatalyst. And bismuth sulfide (Bi)2S3) Has a narrow band gap (1.3-1.7 eV), and can absorb light with a wavelength of 800 nm. The bismuth sulfide/carbon nitride heterostructure may cause photo-generated electrons to be in C3N4Is enriched in the Conduction Band (CB) of (A) and is in Bi2S3The Valence Band (VB) of (a) retains holes, thereby achieving rapid distribution of photogenerated light, and in addition, the redox ability of photoexcited electrons and holes can be maintained. The experimental result proves that Bi2S3The construction of the base heterostructure obviously promotes the distribution of the light excitation carrier and improves the utilization rate of sunlight.
Disclosure of Invention
The present invention is directed to the above g-C3N4The preparation method of the tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst is designed, is used for degrading 2, 4-dichlorophenol (2, 4-DCP) under visible light, and shows great development potential in the field of environmental remediation.
The invention is realized by the following technical scheme:
1. a preparation method of a tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst comprises the following steps:
(1) calcination method for preparing graphite phase carbon nitride powder
And (3) mixing the components in a mass ratio of 7.5: 1.5: placing 0.1 part of potassium chloride, melamine and ammonium chloride in a crucible with a cover, heating to 500-600 ℃ at a heating rate of 5-10 ℃/min, and keeping for 4-6 hours; cooling to room temperature, fully grinding the obtained product, respectively filtering and washing with ultrasonic water and absolute ethyl alcohol for multiple times, transferring to a porcelain boat, and calcining for 2-4 h at 300-500 ℃; obtaining yellow graphite-phase carbon nitride powder;
(2) preparation of tin-doped bismuth sulfide/graphite phase carbon nitride composite photocatalyst precursor
Respectively dissolving bismuth nitrate pentahydrate, tin chloride pentahydrate and thioacetamide in 10-30 mL of ethylene glycol, fully stirring at room temperature until the bismuth nitrate, the tin chloride pentahydrate and the thioacetamide are completely dissolved, and respectively recording as bismuth nitrate liquid, tin chloride liquid and thioacetamide liquid; adding graphite-phase carbon nitride powder prepared by a calcination method into bismuth nitrate solution, continuously stirring at room temperature to uniformly disperse the graphite-phase carbon nitride powder, and recording the mixture as solution A; adding tin chloride solution into the solution A, and stirring at room temperature for 60-90 min to obtain uniform suspension, and recording the suspension as solution B; adding the thioacetamide solution into the solution B, stirring at room temperature for 60-90 min to obtain a uniform suspension, and recording the uniform suspension as solution C; the molar ratio of the bismuth nitrate pentahydrate to the tin chloride pentahydrate to the thioacetamide is 1: 1: 2-4; the molar ratio of the bismuth nitrate pentahydrate to the tin chloride pentahydrate to the thioacetamide to the graphite-phase carbon nitride is 1: 1: 2-4: 0.25 to 1;
(3) preparation of tin-doped bismuth sulfide/graphite phase carbon nitride composite photocatalyst
Placing the solution C in a high-pressure reaction kettle with a polytetrafluoroethylene lining, then placing the reaction kettle in a forced air drying oven, heating and continuously reacting, wherein the reaction temperature is 120-180 ℃, and the reaction time is 15-21 h; after the reaction is finished, cooling the reaction kettle to room temperature, taking out a sample, sequentially washing the sample with deionized water and absolute ethyl alcohol for 3-5 times respectively, drying the sample for 16-48 hours at the temperature of 30-60 ℃, and then grinding the sample to obtain the tin-doped bismuth sulfide/graphite phase carbon nitride composite photocatalyst;
the tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst has the advantages that the tin bismuth sulfide is uniformly dispersed on the surface of the graphite phase carbon nitride, the graphite phase carbon nitride exists in a stacked smooth flaky mode, and Sn is added4+The doping of (a) causes the tin bismuth sulfide/graphite phase carbon nitride composite material to behave in the form of a short rod.
2. The application of the tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst prepared by the preparation method in degrading organic pollutants comprises the following steps:
a 300W xenon lamp is adopted to simulate sunlight and is provided with a 420 nm optical filter to obtain simulated visible light; 100 mg of photocatalyst is added into 100 mL of 2, 4-dichlorophenol solution with the concentration of 150 mg/L, and the catalytic performance of the photocatalyst is evaluated by carrying out photodegradation reaction for 150 min under the irradiation of simulated visible light.
The invention has the advantages and effects that:
1. the preparation method of the tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst has the advantages of simple preparation process, cheap reactants, high yield, environmental friendliness and the like; the carbon nitride prepared by the calcination method can obtain graphite-phase carbon nitride nanosheets with high specific surface area and uniform pore size distribution, and is more beneficial to the compounding of other materials and the distribution of photon-generated carriers; the narrow band gap of the tin bismuth sulfide, the wide absorption range and the higher electron carrier content are utilized, the separation and the migration of photogenerated electricity and hole pairs can be accelerated, so that the composite photocatalyst has high stability and excellent photocatalytic performance, has high degradation capability on 2, 4-dichlorophenol, and has wide application prospect in the aspect of photocatalytic degradation of organic pollutants.
2. According to the preparation method of the tin-doped bismuth sulfide/graphite phase carbon nitride composite photocatalyst, the ethylene glycol is used as a solvent, and the combination of sulfide ions decomposed from thioacetamide and metal ions is promoted.
3. Compared with the in-situ growth method and the hydrothermal method for synthesizing the tin-doped bismuth sulfide/graphite phase carbon nitride composite photocatalyst, the composite material synthesized by the in-situ growth method has the advantages of regular shape, higher yield and higher catalytic efficiency.
4. The tin-doped bismuth sulfide/graphite phase carbon nitride composite photocatalyst accords with the characteristics of a Z-shaped heterostructure after being analyzed, and is the main reason for greatly improving the catalytic efficiency.
Drawings
FIG. 1 is an XRD diagram of a bismuth stannic sulfide/graphite phase carbon nitride composite photocatalyst;
FIG. 2 is an SEM image of a bismuth tin sulfide/graphite phase carbon nitride composite photocatalyst;
fig. 3 is a total number spectrogram of an element distribution diagram of the tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst.
Detailed Description
Example 1
A preparation method of a tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst comprises the following steps:
(1) weighing the components in a mass ratio of 7.5: 1.5: 0.1 of potassium chloride, melamine and ammonium chloride are placed in a crucible with a cover, heated to 500 ℃ at the heating rate of 5 ℃/min and kept for 4 hours; cooling to room temperature, fully grinding the obtained product, transferring the product into a porcelain boat, heating to 300 ℃ at the heating rate of 10 ℃/min, and calcining for 2 h at 300 ℃ to obtain yellow graphite-phase carbon nitride powder;
(2) weighing 1.5 g of bismuth nitrate pentahydrate, 1.5 g of stannic chloride pentahydrate and 3 g of thioacetamide, respectively dissolving in 10 mL of ethylene glycol, fully stirring at room temperature until completely dissolving, and respectively recording as bismuth nitrate liquid, stannic chloride liquid and thioacetamide liquid; adding graphite-phase carbon nitride powder prepared by a calcination method into bismuth nitrate solution, continuously stirring at room temperature to uniformly disperse the graphite-phase carbon nitride powder, and recording the mixture as solution A; adding tin chloride solution into solution A, stirring at room temperature for 60 min to obtain uniform suspension, and recording as solution B; adding the thioacetamide solution into the solution B, stirring at room temperature for 60 min to obtain a uniform suspension, and recording the suspension as solution C;
(3) placing the solution C in a high-pressure reaction kettle with a polytetrafluoroethylene lining, then placing the reaction kettle in a forced air drying oven, heating for continuous reaction, wherein the reaction temperature is 120 ℃, and the reaction time is 15 hours; after the reaction is finished, cooling the reaction kettle to room temperature, taking out a sample, sequentially washing the sample by deionized water and absolute ethyl alcohol for 3 times respectively, drying the sample for 16 hours at the temperature of 30 ℃, and then grinding the sample to obtain the tin-doped bismuth sulfide/graphite phase carbon nitride composite photocatalyst; preparing composite photocatalysts with different mass percentages by controlling the component ratios of the raw materials, wherein the mass ratio of the graphite-phase carbon nitride to the bismuth nitrate pentahydrate is respectively 25 wt%, 50 wt%, 75 wt% and 100 wt% by taking the mass of the bismuth nitrate pentahydrate as a reference;
(4) under the irradiation of simulated visible light, the composite photocatalyst with the mass ratio of 75 wt% has the strongest removal capability on 2, 4-dichlorophenol within 180 min, and the photocatalytic degradation rate is respectively improved by 1.75 times and 2.76 times compared with that of bismuth sulfide and graphite-phase carbon nitride single components before compounding.
Example 2
A preparation method of a tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst comprises the following steps:
(1) weighing the components in a mass ratio of 7.5: 1.5: 0.1 of potassium chloride, melamine and ammonium chloride are placed in a crucible with a cover, heated to 550 ℃ at the heating rate of 5 ℃/min and kept for 4 hours; cooling to room temperature, fully grinding the obtained product, transferring the product into a porcelain boat, heating to 400 ℃ at the heating rate of 10 ℃/min, and calcining for 2 h at 400 ℃ to obtain yellow graphite-phase carbon nitride powder;
(2) weighing 1.5 g of bismuth nitrate pentahydrate, 1.5 g of stannic chloride pentahydrate and 4 g of thioacetamide, respectively dissolving in 20 mL of ethylene glycol, fully stirring at room temperature until the bismuth nitrate, the stannic chloride and the thioacetamide are completely dissolved, and respectively recording as bismuth nitrate liquid, stannic chloride liquid and thioacetamide liquid; adding graphite-phase carbon nitride powder prepared by a calcination method into bismuth nitrate solution, continuously stirring at room temperature to uniformly disperse the graphite-phase carbon nitride powder, and recording the mixture as solution A; adding tin chloride solution into solution A, stirring at room temperature for 70 min to obtain uniform suspension, and recording as solution B; adding the thioacetamide solution into the solution B, stirring at room temperature for 70 min to obtain a uniform suspension, and recording the uniform suspension as solution C;
(3) placing the solution C in a high-pressure reaction kettle with a polytetrafluoroethylene lining, then placing the reaction kettle in a forced air drying oven, heating for continuous reaction, wherein the reaction temperature is 140 ℃, and the reaction time is 17 hours; after the reaction is finished, cooling the reaction kettle to room temperature, taking out a sample, sequentially washing the sample by deionized water and absolute ethyl alcohol for 3 times respectively, drying the sample for 24 hours at the temperature of 40 ℃, and then grinding the sample to obtain the tin-doped bismuth sulfide/graphite phase carbon nitride composite photocatalyst; preparing composite photocatalysts with different mass percentages by controlling the component ratios of the raw materials, wherein the mass ratio of the graphite-phase carbon nitride to the bismuth nitrate pentahydrate is respectively 25 wt%, 50 wt%, 75 wt% and 100 wt% by taking the mass of the bismuth nitrate pentahydrate as a reference;
(4) under the irradiation of simulated visible light, the composite photocatalyst with the mass ratio of 75 wt% has the strongest removal capability on 2, 4-dichlorophenol within 180 min, and the photocatalytic degradation rate is respectively improved by 2.96 times and 3.72 times compared with that of bismuth sulfide and graphite-phase carbon nitride single components before compounding.
Example 3
A preparation method of a tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst comprises the following steps:
(1) weighing the components in a mass ratio of 7.5: 1.5: 0.1 of potassium chloride, melamine and ammonium chloride are placed in a crucible with a cover, heated to 550 ℃ at the heating rate of 10 ℃/min and kept for 5 hours; cooling to room temperature, fully grinding the obtained product, transferring the product into a porcelain boat, heating to 400 ℃ at the heating rate of 15 ℃/min, and calcining for 3 h at 400 ℃ to obtain yellow graphite-phase carbon nitride powder;
(2) weighing 1.5 g of bismuth nitrate pentahydrate, 1.5 g of stannic chloride pentahydrate and 5 g of thioacetamide, respectively dissolving in 20 mL of ethylene glycol, fully stirring at room temperature until the bismuth nitrate, the stannic chloride and the thioacetamide are completely dissolved, and respectively recording as bismuth nitrate liquid, stannic chloride liquid and thioacetamide liquid; adding graphite-phase carbon nitride powder prepared by a calcination method into bismuth nitrate solution, continuously stirring at room temperature to uniformly disperse the graphite-phase carbon nitride powder, and recording the mixture as solution A; adding tin chloride solution into solution A, stirring at room temperature for 80 min to obtain uniform suspension, and recording as solution B; adding the thioacetamide solution into the solution B, stirring for 80 min at room temperature to obtain a uniform suspension, and recording the suspension as solution C;
(3) placing the solution C in a high-pressure reaction kettle with a polytetrafluoroethylene lining, then placing the reaction kettle in a forced air drying oven, heating for continuous reaction, wherein the reaction temperature is 160 ℃, and the reaction time is 19 hours; after the reaction is finished, cooling the reaction kettle to room temperature, taking out a sample, sequentially washing the sample by deionized water and absolute ethyl alcohol for 3 times respectively, drying the sample for 36 hours at the temperature of 50 ℃, and then grinding the sample to obtain the tin-doped bismuth sulfide/graphite phase carbon nitride composite photocatalyst; preparing composite photocatalysts with different mass percentages by controlling the component ratios of the raw materials, wherein the mass ratio of the graphite-phase carbon nitride to the bismuth nitrate pentahydrate is respectively 25 wt%, 50 wt%, 75 wt% and 100 wt% by taking the mass of the bismuth nitrate pentahydrate as a reference;
(4) under the irradiation of simulated visible light, the composite photocatalyst with the mass ratio of 75 wt% has the strongest removal capability on 2, 4-dichlorophenol within 180 min, and the photocatalytic degradation rate is respectively improved by 4.25 times and 5.33 times compared with that of bismuth sulfide and graphite-phase carbon nitride single components before compounding.
Example 4
A preparation method of a tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst comprises the following steps:
(1) weighing the components in a mass ratio of 7.5: 1.5: 0.1 of potassium chloride, melamine and ammonium chloride are placed in a crucible with a cover, heated to 600 ℃ at the heating rate of 10 ℃/min and kept for 6 hours; cooling to room temperature, fully grinding the obtained product, transferring the product into a porcelain boat, heating to 500 ℃ at the heating rate of 20 ℃/min, and calcining at 500 ℃ for 4 h to obtain yellow graphite-phase carbon nitride powder;
(2) weighing 1.5 g of bismuth nitrate pentahydrate, 1.5 g of stannic chloride pentahydrate and 6 g of thioacetamide, respectively dissolving in 30 mL of ethylene glycol, weighing 1.5 g of bismuth nitrate pentahydrate, 1.5 g of stannic chloride pentahydrate and 5 g of thioacetamide, respectively dissolving in 20 mL of ethylene glycol, fully stirring at room temperature until completely dissolving, and respectively recording as bismuth nitrate liquid, tin chloride liquid and thioacetamide liquid; adding graphite-phase carbon nitride powder prepared by a calcination method into bismuth nitrate solution, continuously stirring at room temperature to uniformly disperse the graphite-phase carbon nitride powder, and recording the mixture as solution A; adding tin chloride solution into solution A, stirring at room temperature for 90 min to obtain uniform suspension, and recording as solution B; adding the thioacetamide solution into the solution B, stirring for 90 min at room temperature to obtain a uniform suspension, and recording the suspension as solution C;
(3) placing the solution C in a high-pressure reaction kettle with a polytetrafluoroethylene lining, then placing the reaction kettle in a forced air drying oven, heating for continuous reaction, wherein the reaction temperature is 180 ℃, and the reaction time is 21 h; after the reaction is finished, cooling the reaction kettle to room temperature, taking out a sample, sequentially washing the sample by deionized water and absolute ethyl alcohol for 3 times respectively, drying the sample for 48 hours at the temperature of 60 ℃, and then grinding the sample to obtain the tin-doped bismuth sulfide/graphite phase carbon nitride composite photocatalyst; preparing composite photocatalysts with different mass percentages by controlling the component ratios of the raw materials, wherein the mass ratio of the graphite-phase carbon nitride to the bismuth nitrate pentahydrate is respectively 25 wt%, 50 wt%, 75 wt% and 100 wt% by taking the mass of the bismuth nitrate pentahydrate as a reference;
(4) under the irradiation of simulated visible light, the composite photocatalyst with the mass ratio of 75 wt% has the strongest removal capability on 2, 4-dichlorophenol within 180 min, and the photocatalytic degradation rate is respectively improved by 4.25 times and 5.33 times compared with that of bismuth sulfide and graphite-phase carbon nitride single components before compounding.
Claims (6)
1. A preparation method of a tin bismuth sulfide/graphite phase carbon nitride composite photocatalyst is characterized by comprising the following process steps:
(1) preparation of the precursor
Respectively dissolving bismuth nitrate pentahydrate, tin chloride pentahydrate and thioacetamide in 10-30 mL of ethylene glycol, fully stirring at room temperature until the bismuth nitrate, the tin chloride pentahydrate and the thioacetamide are completely dissolved, and respectively recording as bismuth nitrate liquid, tin chloride liquid and thioacetamide liquid;
adding graphite-phase carbon nitride powder prepared by a calcination method into bismuth nitrate solution, continuously stirring at room temperature to uniformly disperse the graphite-phase carbon nitride powder, and recording the mixture as solution A; adding tin chloride solution into the solution A, and stirring at room temperature for 60-90 min to obtain uniform suspension, and recording the suspension as solution B; adding the thioacetamide solution into the solution B, stirring at room temperature for 60-90 min to obtain a uniform suspension, and recording the uniform suspension as solution C;
(2) thermal treatment
Placing the solution C in a high-pressure reaction kettle with a polytetrafluoroethylene lining, then placing the reaction kettle in a forced air drying oven, heating and continuously reacting, wherein the reaction temperature is 120-180 ℃, and the reaction time is 15-21 h; and after the reaction is finished, cooling the reaction kettle to room temperature, taking out a sample, sequentially washing the sample with deionized water and absolute ethyl alcohol for 3-5 times respectively, drying the sample for 16-48 hours at the temperature of 30-60 ℃, and then grinding the sample to obtain the tin-doped bismuth sulfide/graphite phase carbon nitride composite photocatalyst.
2. The method for preparing the bismuth sulfide tin/graphite phase carbon nitride composite photocatalyst according to claim 1, wherein the molar ratio of bismuth nitrate pentahydrate, tin chloride pentahydrate and thioacetamide is 1: 1: 2 to 4.
3. The method for preparing the bismuth sulfide tin/graphite phase carbon nitride composite photocatalyst according to claim 1, wherein the molar ratio of bismuth nitrate pentahydrate, tin chloride pentahydrate, thioacetamide and graphite phase carbon nitride is 1: 1: 2-4: 0.25 to 1.
4. The method for preparing the bismuth sulfide tin/graphite-phase carbon nitride composite photocatalyst according to claim 1, wherein the bismuth sulfide tin/graphite-phase carbon nitride composite photocatalyst is prepared by uniformly dispersing bismuth sulfide tin on the surface of graphite-phase carbon nitride, and the graphite-phase carbon nitride exists in the form of stacked smooth sheets, namely Sn4+The doping of (a) causes the tin bismuth sulfide/graphite phase carbon nitride composite material to behave in the form of a short rod.
5. The use of the bismuth stannic sulfide/graphite phase carbon nitride composite photocatalyst prepared by the preparation method according to claim 1 for degrading organic pollutants.
6. Use according to claim 5 for degrading organic contaminants, wherein the organic contaminants are 2, 4-dichlorophenol; a 300W xenon lamp is adopted to simulate sunlight and is provided with a 420 nm optical filter to obtain simulated visible light; 100 mg of photocatalyst is added into 100 mL of 2, 4-dichlorophenol solution with the concentration of 150 mg/L, and the catalytic performance of the photocatalyst is evaluated by carrying out photodegradation reaction for 150 min under the irradiation of simulated visible light.
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