CN115121264A - Room temperature preparation method of water-soluble silver tin sulfur nanocrystalline photocatalyst - Google Patents
Room temperature preparation method of water-soluble silver tin sulfur nanocrystalline photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 75
- IXIAPNSTBDTWBC-UHFFFAOYSA-N [Ag]=S.[Sn] Chemical compound [Ag]=S.[Sn] IXIAPNSTBDTWBC-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229940012189 methyl orange Drugs 0.000 claims abstract description 26
- 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 abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims abstract description 11
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims abstract description 11
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940054334 silver cation Drugs 0.000 claims abstract description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000011859 microparticle Substances 0.000 claims abstract description 7
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 claims abstract description 7
- -1 sulfhydryl compound Chemical class 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 38
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 19
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 19
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 19
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 19
- 239000001119 stannous chloride Substances 0.000 claims description 19
- 235000011150 stannous chloride Nutrition 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940071536 silver acetate Drugs 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 2
- 229940071127 thioglycolate Drugs 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000002159 nanocrystal Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- YNXRTZDUPOFFKZ-UHFFFAOYSA-N [In].[Ag]=S Chemical compound [In].[Ag]=S YNXRTZDUPOFFKZ-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 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 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940079101 sodium sulfide Drugs 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 1
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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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
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
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Abstract
The invention relates to a room temperature preparation method of a water-soluble silver tin sulfur nanocrystalline photocatalyst, belonging to the field of water-soluble nanocrystalline photocatalysts. The preparation operation is as follows; (1) uniformly mixing a tin source, hydrochloric acid, a sulfhydryl compound, a silver cation precursor and water, and adding sodium hydroxide or potassium hydroxide until the solution is clarified to form a precursor solution; (2) and adding sodium sulfide nonahydrate, adjusting the pH value by using an acid solution, stirring, centrifuging, and drying the precipitate to obtain the dark gray powdery water-soluble silver tin sulfur nanocrystalline photocatalyst. The size of the powdery microparticles of the water-soluble silver tin sulfur nanocrystalline photocatalyst is 1-5 nanometers; under the condition of visible light irradiation, 0.8-1.6 mg of water-soluble silver tin sulfur nanocrystalline photocatalyst is used for catalyzing 10-20 ml of methyl orange solution with the concentration of 0.1 mg/ml for 2-5 minutes, and 93-99% of methyl orange in the methyl orange solution is degraded. The catalyst disclosed by the invention is lower in toxicity, green and environment-friendly; the preparation cost is lower, no rare metal is contained, and the raw materials are rich.
Description
Technical Field
The invention belongs to the technical field of water-soluble nanocrystalline photocatalysts, and particularly relates to a water-soluble silver tin sulfur nanocrystalline photocatalyst and a room temperature preparation method thereof.
Background
The environmental pollution problem becomes a major problem to be solved urgently in the present society, wherein organic dyes such as methyl orange, rhodamine B, methylene blue and the like cause serious water pollution, the natural degradation speed of the organic dyes in water is very slow, the organic dyes have biological accumulation, the health of human beings and offspring is seriously threatened, and the water pollution treatment is urgent. Photocatalytic degradation utilizes sunlight to excite a semiconductor to generate electrons and holes, and organic pollutants are oxidized into H on the surface of the semiconductor 2 O and CO 2 And compared with biological and physical removal technologies, the organic dye in the industrial wastewater can be more effectively degraded by the inorganic matters. The activity of the nanocrystalline photocatalyst with the particle size range in the nanometer size is obviously stronger than that of a bulk material under the influence of the distance of a transmission path, so that the photocatalytic activity can be effectively improved by preparing the nanocrystalline photocatalytic material. Cadmium-containing water-soluble nanocrystals (such as cadmium sulfide, zinc cadmium sulfide and the like) have been reported as photocatalysis, but the application of the cadmium-containing water-soluble nanocrystals in the future is severely limited due to the fact that the cadmium-containing water-soluble nanocrystals contain a highly toxic element. The silver indium sulfide nanocrystalline can also degrade organic pollutants by a photocatalyst, but indium is a rare element and is expensive, so that the research focus is on finding candidate materials for replacing the silver indium sulfide nanocrystalline. The silver tin sulfur nanocrystalline is a I-IV-VI transition metal sulfide,the composite material has the advantages of silver sulfide and tin sulfide, the band gap of the composite material can be adjusted at will between 1.1 eV and 2.35 eV, and the composite material has strong corrosion resistance, and moreover, the price cost of tin is far less than that of indium, so that the composite material has a great application prospect in the field of photodegradation. Compared with the oil-soluble nanocrystalline photocatalyst, the water-soluble nanocrystalline photocatalyst can carry out photocatalytic degradation reaction without ligand exchange, has simple steps and mild reaction conditions, does not need expensive and toxic organic reagents, and has very wide development prospect in the field of photocatalytic degradation.
At present, most of the preparation processes of the silver tin sulfur nanocrystals need to be carried out by heating in a reaction kettle, a three-mouth bottle and other containers, and are limited by a plurality of factors, such as small volume of the reaction container (several milliliters to tens of milliliters), high reaction temperature (generally over 100 ℃) and long reaction time (several hours to tens of hours). Although the photocatalyst is not consumed in the process of degrading the organic dye theoretically, the industrial wastewater treatment capacity is large, the concentration is high, the scale of the existing preparation method is small, the macro preparation cannot be realized, and the practical application of degrading the organic pollutants by the photocatalysis is difficult to realize. In view of this, it is very necessary to develop a water-soluble silver tin sulfur nanocrystalline photocatalyst which can be rapidly and massively prepared at room temperature and has high photocatalytic degradation efficiency.
Disclosure of Invention
The invention provides a room temperature preparation method of a water-soluble silver tin sulfur nanocrystalline photocatalyst, aiming at solving the problems of higher toxicity of a cadmium-based catalyst, overhigh cost of a silver indium sulfur nanocrystalline photocatalyst, small capacity of a reaction container, high reaction temperature, longer reaction time and the like in the preparation process of the existing nanocrystalline photocatalyst.
The room temperature preparation operation steps of the water-soluble silver tin sulfur nanocrystalline photocatalyst are as follows:
(1) adding a tin source and hydrochloric acid into water according to a ratio, wherein the molar ratio of the tin source to the hydrochloric acid is 1: 0.4-1: 1.5; adding a ligand, adding a silver cation precursor, wherein the adding amount of the ligand is 1-8 times of the total molar amount of the silver cation precursor and the tin source, and adding sodium hydroxide or potassium hydroxide until the solution is clear to form a precursor solution; the molar ratio of the silver cation precursor to the tin source in the precursor solution is 1: 9-4: 1;
the tin source is one of stannous chloride or stannous sulfate;
the ligand is one of 3-mercaptopropionic acid or thioglycolic acid or citric acid or thiomalic acid;
the silver cation precursor is one of silver acetate or silver nitrate or silver sulfate;
(2) adding sodium sulfide nonahydrate into the precursor solution, wherein the addition amount of the sodium sulfide nonahydrate is 1-10 times of the total molar amount of the silver cation precursor and the tin cation precursor in the precursor solution; adjusting the pH value to 3-6 by using an acid solution, stirring at room temperature for 5-30 minutes to obtain a water-soluble silver tin sulfur nanocrystalline photocatalyst solution, centrifuging, and drying precipitates to obtain a powdery water-soluble silver tin sulfur nanocrystalline photocatalyst;
the water-soluble silver tin sulfur nanocrystalline photocatalyst is dark gray powdery microparticles, and the size of the microparticles is 1-5 nanometers;
under the condition of visible light irradiation, 0.8-1.6 mg of water-soluble silver tin sulfur nanocrystalline photocatalyst is used for catalyzing 10-20 ml of methyl orange solution with the concentration of 0.1 mg/ml for 2-5 minutes, and 93-99% of methyl orange in the methyl orange solution is degraded.
The further technical scheme is as follows:
in the step (2), the acid solution is one of 3-mercaptopropionic acid, thioglycolic acid, amine thioglycolate, citric acid, thiomalic acid, diluted hydrochloric acid or diluted nitric acid.
The visible light is visible light with a wavelength of more than 420 nanometers.
The beneficial technical effects of the invention are embodied in the following aspects:
1. the preparation process of the invention does not need reaction vessels such as a reaction kettle, a three-neck flask and the like, and is not limited by an experimental field and an experimental vessel; the method can be quickly synthesized in the air atmosphere at room temperature, does not generate the agglomeration phenomenon caused by austenite curing, has high experimental reproducibility, is suitable for large-scale production, and greatly reduces the preparation cost.
2. The silver-tin-sulfur photocatalyst selected by the invention can directly absorb visible light, and the energy utilization rate is high; the photocatalyst can be directly used for photocatalytic degradation without being loaded on other materials, and the preparation process is simple.
3. The water-soluble nanocrystalline photocatalyst prepared by the invention has no long-chain organic ligand, can be directly used for photocatalytic hydrogen production and organic dye degradation without complex ligand exchange, is simple to operate, and is easy to realize industrialization.
4. Compared with a cadmium-based photocatalyst, the water-soluble silver tin sulfur nanocrystalline photocatalyst prepared by the method is lower in toxicity, green and environment-friendly; compared with the silver-indium-sulfur nanocrystalline photocatalyst, the water-soluble silver-tin-sulfur nanocrystalline photocatalyst prepared by the invention has the advantages of lower cost, no rare metal and rich raw material yield.
5. The silver tin sulfur nanocrystalline photocatalyst prepared by the invention belongs to the nano particle size, has a large light absorption coefficient and a short exciton diffusion distance, is more beneficial to separation of current carriers compared with bulk phase materials, and realizes efficient photocatalytic degradation reaction.
6. Fig. 1 is a degradation diagram of methyl orange degraded by using a silver tin sulfide photocatalyst prepared by the invention, and fig. 2 is an ultraviolet-visible absorption spectrum of methyl orange degraded by using the silver tin sulfide photocatalyst prepared by the invention. From the figure, 1.6 mg of the photocatalyst of the invention is used for photocatalytic degradation of an aqueous solution containing 2 mg of methyl orange under visible light, the highest degradation efficiency can reach 99% within 5 minutes, and the degradation speed of the photocatalyst is far higher.
Drawings
Fig. 1 is a degradation diagram of methyl orange degraded by the water-soluble nanocrystalline photocatalyst prepared in example 1, wherein the molar ratios of the cations to the sulfur source are 1:2, 1:3, 1:4, 1:5 and 1:6, respectively.
Fig. 2 is a transmission electron microscope photograph of the nanocrystalline photocatalyst of example 2.
FIG. 3 is the UV-VIS absorption spectrum of methyl orange degraded by the nano-crystalline photocatalyst of example 2.
Fig. 4 is a graph of the degradation of nanocrystalline photocatalytic methyl orange prepared from reaction precursor solutions of different pH values in example 3.
Fig. 5 is a degradation diagram of nanocrystalline photocatalytic methyl orange prepared at different silver-tin ratios in examples.
Detailed Description
For a further understanding of the present invention, reference will now be made to the following preferred embodiments of the invention in conjunction with the examples, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention and is not intended to limit the scope of the claims which follow.
Example 1
The preparation operation steps of the water-soluble silver tin sulfur nanocrystalline photocatalyst are as follows:
(1) taking 5 beakers, adding materials into each beaker according to a formula, and mixing, wherein the materials in each beaker comprise 15 ml of deionized water, 1.9 mg of stannous chloride, 0.18 mg of hydrochloric acid, 26 mg of 3-mercaptopropionic acid and 3.4 mg of silver nitrate, and the molar ratio of the stannous chloride to the hydrochloric acid is 2: 1; the adding amount of the 3-mercaptopropionic acid is 8 times of the total molar amount of the silver nitrate and the stannous chloride; sodium hydroxide was added until the solution was clear, yielding five identical precursor solutions.
The molar ratio of silver nitrate to stannous chloride in the precursor solution is 2: 1.
(2) adding 7.2 mg, 14.4 mg, 21.6 mg, 28.8 mg and 36 mg of sodium sulfide nonahydrate into the five parts of precursor solution respectively, wherein the adding amount of the five parts of sodium sulfide nonahydrate is respectively 1 time, 2 times, 3 times, 4 times and 5 times of the molar total amount of the sodium sulfide required by the silver nitrate and the stannous chloride in the precursor solution; and then adjusting the pH value of the five parts of reaction precursor solution to 4.0 by using 3-mercaptopropionic acid, reacting for 15 minutes under the stirring condition to obtain five parts of silver-tin-sulfur water-soluble nanocrystalline photocatalyst solutions, centrifuging the solutions, and drying precipitates to obtain five parts of powdered water-soluble silver-tin-sulfur nanocrystalline photocatalysts, wherein the water-soluble silver-tin-sulfur nanocrystalline photocatalysts are dark gray powdered micro-particles, and the size of the micro-particles is 1-5 nanometers.
Methyl orange cannot be degraded in natural environment, and can be rapidly degraded under the condition of visible light after the water-soluble silver tin sulfur nanocrystalline photocatalyst prepared in the embodiment 1 is added. Fig. 1 is a graph showing the degradation of methyl orange by five parts of water-soluble silver tin sulfur nanocrystalline photocatalysts prepared in example 1 by using different molar ratios of cation/sulfur source, and 20 ml of methyl orange solution with a concentration of 0.1 mg/ml is degraded by using 1.6 mg of water-soluble silver tin sulfur nanocrystalline photocatalyst, as can be seen from fig. 1, the rate of photocatalytic degradation increases gradually with the increase of the ratio of cation/sulfur source initially, reaches the maximum at the time of cation/sulfur source =1/4, 99% of methyl orange in solution can be degraded in 5 minutes, and then the rate of photocatalytic degradation does not increase significantly any more.
Example 2
The preparation operation steps of the water-soluble silver tin sulfur nanocrystalline photocatalyst are as follows:
(1) taking 1 50 ml beaker, adding materials into the beaker according to the formula, mixing, adding the materials in each beaker into the beaker 15 ml of deionized water, 1.9 mg of stannous chloride, 0.18 mg of hydrochloric acid, 26 mg of 3-mercaptopropionic acid and 3.4 mg of silver nitrate in sequence, mixing, and adding sodium hydroxide until the solution is clear to obtain the nanocrystal reaction precursor solution.
(2) Respectively adding 28.8 mg of sodium sulfide nonahydrate into the reaction precursor solution, then adjusting the pH value of the reaction precursor solution to 4.0 by using 3-mercaptopropionic acid, reacting for 15 minutes under the stirring condition to obtain a water-soluble silver tin sulfur nanocrystalline photocatalyst solution, centrifuging the solution, and drying to obtain water-soluble silver tin sulfur nanocrystalline photocatalyst powder.
Methyl orange cannot be degraded in natural environment, and can be rapidly degraded under the condition of visible light after the water-soluble silver-tin-sulfur nanocrystalline photocatalyst prepared in the embodiment 2 is added. Fig. 2 is a transmission electron microscope image of the water-soluble silver tin sulfur nanocrystalline photocatalyst in this example 2, and it can be seen from fig. 2 that the powder size distribution of the water-soluble silver tin sulfur nanocrystalline photocatalyst is narrow, no agglomeration phenomenon occurs, and the average diameter of the powder particles is about 3 nm. Fig. 3 is an ultraviolet-visible absorption spectrum of methyl orange degraded by the water-soluble silver tin sulfur nanocrystalline photocatalyst in this example 2, and methyl orange with a concentration of 0.1 mg/ml is degraded by 10 ml using 0.8 mg of the water-soluble silver tin sulfur nanocrystalline photocatalyst, and it can be seen from fig. 3 that methyl orange is degraded by the water-soluble silver tin sulfur nanocrystalline photocatalyst at a fast speed, and 95% of methyl orange can be degraded in 4 minutes. This indicates that the nanocrystals did not experience a decrease in the rate of catalytic degradation due to the amplification reaction.
Example 3
The preparation operation steps of the water-soluble silver tin sulfur nanocrystalline photocatalyst are as follows:
(1) taking 5 beakers, adding materials into the beakers according to the formula, mixing, adding the materials into the 5 beakers in sequence, wherein the materials in each beaker are 15 ml of deionized water, 1.9 mg of stannous chloride, 0.18 mg of hydrochloric acid, 26 mg of 3-mercaptopropionic acid and 3.4 mg of silver nitrate, mixing, and adding sodium hydroxide until the solution is clear to obtain five parts of the same nanocrystal reaction precursor solution.
(2) Adding 28.8 milligrams of sodium sulfide nonahydrate into the five parts of reaction precursor solution respectively, then adjusting the pH values of the five parts of nanocrystal reaction precursor solution to 4.0, 5.0, 6.0, 7.0 and 8.0 respectively by using 3-mercaptopropionic acid, reacting for 15 minutes under the stirring condition to obtain five parts of silver tin sulfur water-soluble nanocrystal photocatalyst solutions, centrifuging and drying the solutions to obtain five parts of silver water-soluble tin sulfur nanocrystal photocatalysts with different pH values, wherein the five parts of water-soluble tin sulfur nanocrystal photocatalysts are all in powder form.
Methyl orange cannot be degraded in natural environment, and can be rapidly degraded under the condition of visible light after the water-soluble silver tin sulfur nanocrystalline photocatalyst prepared in the embodiment 3 is added. Fig. 4 is a degradation diagram of methyl orange degraded by water-soluble tin-sulfur nanocrystalline photocatalyst with different pH values in this example 3, 10 ml of methyl orange with a concentration of 0.1 mg/ml is degraded by using 1.6 mg of water-soluble tin-sulfur nanocrystalline photocatalyst, as can be seen from fig. 4, the rate of photocatalytic degradation of nanocrystals tends to increase with the continuous decrease of pH value, when the pH of the precursor solution =4, the catalytic degradation rate of water-soluble tin-sulfur nanocrystalline photocatalyst reaches the maximum, and 99% of methyl orange in the solution can be degraded in 2 minutes.
Example 4
The preparation operation steps of the water-soluble silver tin sulfur nanocrystalline photocatalyst are as follows:
(1) taking 5 beakers, respectively marking as No. one beaker to No. five beakers, adding the materials into each beaker according to the formula, and mixing; 15 ml of deionized water was added to each beaker, and 2.84 mg of stannous chloride, 0.2732 mg of hydrochloric acid, 26 mg of 3-mercaptopropionic acid and 2.55 mg of silver nitrate were added to beaker one; wherein the molar ratio of the silver nitrate to the stannous chloride is 1:1.
Adding 3.79 mg of stannous chloride, 0.3646 mg of hydrochloric acid, 26 mg of 3-mercaptopropionic acid and 1.69 mg of silver nitrate to a No. two beaker; wherein the molar ratio of the silver nitrate to the stannous chloride is 2: 1.
Adding 4.26 mg of stannous chloride, 0.4106 mg of hydrochloric acid, 26 mg of 3-mercaptopropionic acid and 1.27 mg of silver nitrate to a No. three beaker; wherein the molar ratio of silver nitrate to stannous chloride is 3: 1.
Adding 4.55 mg of stannous chloride, 0.438 mg of hydrochloric acid, 26 mg of 3-mercaptopropionic acid and 1.02 mg of silver nitrate into a No. four beaker; wherein the molar ratio of silver nitrate to stannous chloride is 4: 1.
Adding 4.74 mg of stannous chloride, 0.4563 mg of hydrochloric acid, 26 mg of 3-mercaptopropionic acid and 0.85 mg of silver nitrate to a No. five beaker; wherein the molar ratio of the silver nitrate to the stannous chloride is 5: 1.
And respectively adding sodium hydroxide into the five beakers until the solution is clear to obtain five parts of nanocrystal reaction precursor solutions.
(2) And adding 9 mg, 6.78 mg, 12.25 mg, 12.6 mg and 13.33 mg of sodium sulfide nonahydrate into the five nanocrystal reaction precursor solutions respectively, adjusting the pH value to 4.0 by using 3-mercaptopropionic acid, and reacting for 15 minutes under the stirring condition to obtain five water-soluble silver tin sulfur nanocrystal photocatalyst solutions.
Methyl orange cannot be degraded in natural environment, and can be rapidly degraded under the condition of visible light after the water-soluble silver-tin-sulfur nanocrystalline photocatalyst prepared in the embodiment 4 is added. Fig. 5 is a degradation graph of methyl orange degraded by the water-soluble silver tin sulfide nanocrystalline photocatalyst prepared according to different silver tin ratios in the embodiment 4, and it can be seen from the graph that when the silver/tin ratio is 1/2, the photocatalytic degradation rate reaches the maximum, and 93.1% of methyl orange in the solution can be degraded in 2 minutes.
Example 5
The preparation operation steps of the water-soluble silver tin sulfur nanocrystalline photocatalyst are as follows:
(1) adding materials according to the formula into a 50 ml beaker, mixing the materials, namely 15 ml of deionized water, 2.26 mg of stannous sulfide, 0.2174 mg of hydrochloric acid, 26 mg of 3-mercaptopropionic acid and 2.55 mg of silver nitrate, uniformly mixing the materials, and adding sodium hydroxide until the solution is clear to obtain a nanocrystal reaction precursor solution.
(2) Adding 36 mg of sodium sulfide nonahydrate into the nanocrystal reaction precursor solution, then adjusting the pH value to 4.0 by using 3-mercaptopropionic acid, and reacting for 15 minutes under the stirring condition to obtain the water-soluble silver tin sulfide nanocrystal photocatalyst solution.
Claims (3)
1. A room temperature preparation method of a water-soluble silver tin sulfur nanocrystalline photocatalyst is characterized by comprising the following operation steps:
(1) adding a tin source and hydrochloric acid into water according to a ratio, wherein the molar ratio of the tin source to the hydrochloric acid is 1: 0.4-1: 1.5; adding a ligand, adding a silver cation precursor, wherein the adding amount of the ligand is 1-8 times of the total molar amount of the silver cation precursor and the tin source, and adding sodium hydroxide or potassium hydroxide until the solution is clarified to form a precursor solution; the molar ratio of the silver cation precursor to the tin source in the precursor solution is 1: 9-4: 1;
the tin source is one of stannous chloride or stannous sulfate;
the ligand is one of 3-mercaptopropionic acid or thioglycolic acid or citric acid or thiomalic acid;
the silver cation precursor is one of silver acetate or silver nitrate or silver sulfate;
(2) adding sodium sulfide nonahydrate into the precursor solution, wherein the addition amount of the sodium sulfide nonahydrate is 1-10 times of the total molar amount of the silver cations and the tin cations in the precursor solution; adjusting the pH value to 3-6 by using an acid solution, stirring at room temperature for 5-30 minutes to obtain a water-soluble silver tin sulfur nanocrystalline photocatalyst solution, centrifuging, and drying precipitates to obtain a powdery water-soluble silver tin sulfur nanocrystalline photocatalyst;
the water-soluble silver tin sulfur nanocrystalline photocatalyst is dark gray powdery microparticles, and the size of the microparticles is 1-5 nanometers;
under the condition of visible light irradiation, 0.8-1.6 mg of water-soluble silver tin sulfur nanocrystalline photocatalyst is used for catalyzing 10-20 ml of methyl orange solution with the concentration of 0.1 mg/ml for 2-5 minutes, and 93% -99% of methyl orange in the methyl orange solution is degraded.
2. The room temperature preparation method of the water-soluble silver tin sulfur nanocrystalline photocatalyst according to claim 1, characterized in that: in the step (2), the acid solution is one of 3-mercaptopropionic acid, thioglycolic acid, amine thioglycolate, citric acid, thiomalic acid, diluted hydrochloric acid or diluted nitric acid.
3. The room temperature preparation method of the water-soluble silver tin sulfur nanocrystalline photocatalyst according to claim 2, characterized in that: the visible light is visible light with a wavelength of more than 420 nanometers.
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