CN110227559B - Ligand-protected Ag nano-cluster-sensitized titanium dioxide photocatalyst and preparation method and application thereof - Google Patents
Ligand-protected Ag nano-cluster-sensitized titanium dioxide photocatalyst and preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 60
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 101
- 239000002904 solvent Substances 0.000 claims abstract description 77
- 238000005406 washing Methods 0.000 claims abstract description 75
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 47
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000011068 loading method Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000001704 evaporation Methods 0.000 claims abstract description 26
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 230000015556 catabolic process Effects 0.000 claims abstract description 7
- 238000006731 degradation reaction Methods 0.000 claims abstract description 7
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 114
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 80
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000001291 vacuum drying Methods 0.000 claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003344 environmental pollutant Substances 0.000 claims description 4
- 231100000719 pollutant Toxicity 0.000 claims description 4
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 claims description 4
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- 229940012189 methyl orange Drugs 0.000 claims description 3
- 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 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- JBTHDAVBDKKSRW-UHFFFAOYSA-N chembl1552233 Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 JBTHDAVBDKKSRW-UHFFFAOYSA-N 0.000 claims description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229940098221 silver cyanide Drugs 0.000 claims description 2
- 229940096017 silver fluoride Drugs 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229960001516 silver nitrate Drugs 0.000 claims description 2
- 229940073450 sudan red Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 20
- 238000002156 mixing Methods 0.000 description 19
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 18
- ZMRFRBHYXOQLDK-UHFFFAOYSA-N 2-phenylethanethiol Chemical compound SCCC1=CC=CC=C1 ZMRFRBHYXOQLDK-UHFFFAOYSA-N 0.000 description 18
- 125000003944 tolyl group Chemical group 0.000 description 9
- 239000000975 dye Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- 108010024636 Glutathione Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004471 energy level splitting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960003180 glutathione Drugs 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
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- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/33—
-
- B01J35/39—
-
- 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
Abstract
The invention provides a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst, a preparation method and application thereof, and the preparation method comprises the following steps: (1) dissolving silver salt in a solvent, adding an organophosphorus ligand, uniformly stirring the mixed solution, centrifuging, washing and drying; (2) dissolving the dried product obtained in the step (1) in a solvent, adding mercaptan, uniformly stirring, adding sodium borohydride, stirring, evaporating to remove the solvent, washing and extracting the product to obtain an Ag nano-cluster solution protected by a ligand; (3) and (3) loading the Ag nanocluster obtained in the step (2) on titanium dioxide to obtain the Ag nanocluster sensitized titanium dioxide photocatalyst. The catalyst is used for degrading organic pollutants in water by visible light catalysis. The catalytic process uses oxygen as an oxidant and visible light as a driving force, and has the characteristics of high degradation efficiency, simplicity in operation, recyclable catalyst, long service life of the catalyst, environmental friendliness and the like.
Description
Technical Field
The invention relates to the field of environmental photocatalytic treatment, in particular to a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst, and a preparation method and application thereof.
Background
With the development of chemical industry, environmental pollution is becoming more serious. The discharge of printing and dyeing wastewater is one of the important causes of water pollution. Every year, a large amount of commercial dyes are discharged, and the dyes are stable in chemical property and cause great damage to the ecological environment. By utilizing the characteristic that the semiconductor oxide material can be activated under the irradiation of sunlight, organic matters can be effectively oxidized and degraded into carbon dioxide, water and other small molecules. Compared with the traditional purification method, the semiconductor photocatalysis technology has the advantages of mild reaction conditions, no secondary pollution, simple operation, obvious degradation effect and the like. Titanium dioxide is one of the most interesting photocatalysts, which is low-toxic, low-cost, durable, superhydrophilic and has excellent photochemical stability. However, the titanium dioxide has a wide forbidden band (rutile 3.0 e V, anatase 3.2 eV), which makes it only absorb ultraviolet light, and the ultraviolet light only accounts for 6% of sunlight, which greatly inhibits the application of titanium dioxide in the field of photocatalysis.
There are three main ways to widen the light absorption range of titanium dioxide: doping other metal elements to reduce TiO2The forbidden band width of the nano material; II, using inorganic or organic compounds to react with TiO2Sensitizing is carried out to improve the optical activity of the dye in a visible light region; third, coupling surface plasma resonance metal-TiO2. Among them, the dye sensitization method has become one of the effective methods due to its wide absorption of visible light. Is used as nano TiO2Organic dyes of sensitizers which are generally transition metal complexes with low excited states, such as polypyridine complexes, phthalocyanines and metalloporphyrins. The metal ions are usually Ru (II), Fe (II), Mg (II), Zn (II) and Al (III), and the ligands are nitrogen heterocycles with delocalized pi orbitals or aromatic ring systems. However, pure titanium dioxide sensitized with phthalocyanine or porphyrin has low sensitizing efficiency, and the sensitizer is easily aggregated and deactivated or the sensitizer itself is degraded by light, so that the use of the dye sensitizing method is limited.
Therefore, the development of a sensitizer with excellent visible light response and stable structure has great significance, and has potential application prospect in visible light degradation of pollutants in water.
Disclosure of Invention
The invention provides a ligand-protected Ag nano-cluster sensitized titanium dioxide photocatalyst, a preparation method and application thereof, wherein the size of the Ag nano-cluster is about 1nm, and due to quantum size effect and energy level splitting of the Ag nano-cluster, a HOMO-LUMO (highest occupied molecular orbital) track appears and visible light is well absorbed.
The technical scheme for realizing the invention is as follows:
a method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
(1) dissolving silver salt in a solvent, adding an organophosphorus ligand, uniformly stirring the mixed solution, centrifuging, washing and drying;
(2) dissolving the dried product obtained in the step (1) in a solvent, adding mercaptan, uniformly stirring, adding sodium borohydride, stirring, evaporating to remove the solvent, washing and extracting the product to obtain an Ag nano-cluster solution protected by a ligand;
(3) and (3) loading the Ag nanocluster obtained in the step (2) on titanium dioxide to obtain the Ag nanocluster sensitized titanium dioxide photocatalyst.
The silver salt in the step (1) is one of silver nitrate, silver fluoride and silver cyanide, and the concentration of the silver salt solution is 0.01-1 mol.L-1(ii) a The organophosphorus ligand is one of trimethylphosphine, 1, 3-bis (diphenylphosphino) propane and tricyclohexylphosphine, and the concentration of the mixed solution is 0.01-25 mol.L-1Stirring for 0.5-10h, centrifuging, washing, and drying at 80 ℃ for 10 h.
The solvent is one or more of water, tetrahydrofuran, ethanol, toluene, dichloromethane, acetonitrile and N, N-dimethylformamide.
After the dried product in the step (2) is dissolved in the solvent, the concentration of Ag in the solution is 0.01-1 mol.L-1The concentration of mercaptan after mercaptan addition is 0.001-10 mol.L-1Stirring for 0.5-5h, adding sodium borohydride, wherein the concentration of the sodium borohydride in the mixed solution is 0.001-100 mol.L-1Stirring for 0.5-10h, evaporating to remove the solvent, washing the product with one or more of n-hexane, acetone and acetonitrile, and finally extracting with one or more of dichloromethane, acetonitrile and ethanol to obtain the ligand-protected Ag nanocluster.
In the step (2), the mercaptan is 2-phenethyl mercaptan, thiophenol, hexanethiol, glutathione, 2-naphthalene mercaptan, 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane.
And (3) adding titanium dioxide into the Ag nano-cluster solution in the step (3), wherein the loading capacity of Ag is 0.01-5 wt%, stirring for 1-12 h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
The Ag nanocluster sensitized titanium dioxide photocatalyst protected by the ligand prepared by the preparation method is provided.
The size of the Ag nanocluster is 0.8-3 nm.
The ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst is applied to visible light catalytic degradation of organic pollutants in water, the wavelength of a used light source is 400-800 nm, the illumination time is 1-20 h, and the pollutants are rhodamine, methyl orange, methyl blue or Sudan red.
The titanium dioxide photocatalyst is repeatedly used for 3-5 times, and the degradation rate is more than 90%.
The invention has the beneficial effects that: the catalyst is used for degrading organic pollutants in water by visible light catalysis. The catalytic process uses oxygen as an oxidant and visible light as a driving force, and has the characteristics of high degradation efficiency, simplicity in operation, recyclable catalyst, long service life of the catalyst, environmental friendliness and the like. And synthesizing the Ag nanocluster protected by the ligand through an experiment, and then loading the Ag nanocluster on titanium dioxide to obtain the Ag nanocluster sensitized titanium dioxide catalyst protected by the ligand. The titanium dioxide enhances the separation efficiency of the electrons and the holes of the Ag nanocluster and increases the stability of the Ag nanocluster. The catalyst can effectively utilize visible light to catalyze and degrade organic pollutants in water.
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, 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 the drawings without creative efforts.
Fig. 1 is an electron microscope image of Ag nanoclusters prepared in example 1 of the present invention.
FIG. 2 is a graph showing the effect of the catalyst of example 7 in repeated use.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 0.5 h, centrifuging, washing, and drying at 80 deg.C for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is toluene, and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 0.01 wt%, stirring for 1h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 2
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3DissolutionIn water, AgNO3Is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.01mol.L-1Stirring for 10h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is toluene, and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 0.05 wt%, stirring for 3h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 3
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 0.01mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is toluene, and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 1 wt%, stirring for 5h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 4
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 0.01mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.25 mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is toluene, and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 2 wt%, stirring for 6h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 5
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in ethanol, AgNO3Is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is dichloromethane, and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 3 wt%, stirring for 8h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 6
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolving in water + ethanol (volume ratio 1:1), AgNO3Is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 25mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is toluene, and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 4 wt%, stirring for 10h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 7
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 1mol.L-1. Adding a certain amount of PPh thereto3The concentration is 0.1 mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is ethanol and DMF (volume ratio is 1:1), and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the sodium borohydride isThe concentration of sodium chloride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 5 wt%, stirring for 12h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 8
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is ethanol and DMF (volume ratio is 1:1), and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.5mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 0.08 wt%, stirring for 6h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 9
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent of ethanol + DMF (dimethyl formamide)Product ratio of 1:1), the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 1.5 wt%, stirring for 8h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 10
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is ethanol and DMF (volume ratio is 1:1), and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 0.5 h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 2.5 wt%, stirring for 10h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 11
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 1mol.L-1. Adding intoAmount of PPh3At a concentration of 0.1 mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is ethanol and DMF (volume ratio is 1:1), and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 5h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 3.5 wt%, stirring for 12h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 12
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is ethanol and DMF (volume ratio is 1:1), and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 0.5 h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 4.5 wt%, stirring for 10h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 13
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is ethanol and DMF (volume ratio is 1:1), and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 10h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 5 wt%, stirring for 12h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 14
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is ethanol and DMF (volume ratio is 1:1), and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of hexanethiol into the mixture, wherein the concentration of the hexanethiol is 0.01mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 1.5 wt%, stirring for 12h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 15
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is ethanol and DMF (volume ratio is 1:1), and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of hexanethiol into the mixture, wherein the concentration of the hexanethiol is 0.01mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with dichloromethane and ethanol (volume ratio is 1:1) to obtain the ligand-protected Ag nano-cluster.
Adding titanium dioxide (P25) into the obtained Ag nano-cluster solution, wherein the loading capacity of Ag is 2 wt%, stirring for 12h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 16
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Has a concentration of 5mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 25mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is ethanol and DMF (volume ratio is 1:1), and the concentration of Ag is 0.01mol.L-1. Adding a certain amount of hexanethiol into the mixture, wherein the concentration of the hexanethiol is 0.01mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydrideThe concentration is 100mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (P25) into the obtained Ag nano-cluster solution, wherein the loading capacity of Ag is 5 wt%, stirring for 12h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 17
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 0.01mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 1h, centrifuging, washing, and drying at 80 ℃ for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is ethanol and DMF (volume ratio is 1:1), and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of hexanethiol into the mixture, wherein the concentration of the hexanethiol is 100mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (P25) into the obtained Ag nano-cluster solution, wherein the loading capacity of Ag is 3 wt%, stirring for 10h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 18
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
AgF is dissolved in water, and the concentration of AgF is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 0.5 h, centrifuging, washing, and drying at 80 deg.C for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is toluene, and the concentration of Ag is 0.1 mol.L-1. To the direction ofWherein a certain amount of 2-phenethyl mercaptan is added, and the concentration of the mercaptan is 0.001mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 0.01 wt%, stirring for 1h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 19
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
dissolving AgCN in water, wherein the concentration of AgCN is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 0.5 h, centrifuging, washing, and drying at 80 deg.C for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is toluene, and the concentration of Ag is 0.1 mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 0.01 wt%, stirring for 1h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 20
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 0.5 h, centrifuging, washing, and drying at 80 deg.CDrying for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is toluene, and the concentration of Ag is 1mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 0.01 wt%, stirring for 1h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
Example 21
A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst comprises the following steps:
mixing AgNO3Dissolved in water, AgNO3Is 1mol.L-1. Adding a certain amount of PPh thereto3At a concentration of 0.1 mol.L-1Stirring for 0.5 h, centrifuging, washing, and drying at 80 deg.C for 10 h.
Dissolving the product obtained in the last step in a solvent, wherein the solvent is toluene, and the concentration of Ag is 1mol.L-1. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 0.001mol.L-1. Stirring for 1h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.01mol.L-1. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain the ligand-protected Ag nanocluster.
Adding titanium dioxide (anatase) into the obtained Ag nano-cluster solution, wherein the loading amount of Ag is 0.01 wt%, stirring for 1h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
The ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst prepared in examples 1-21 is used, rhodamine, methyl orange and methyl blue are used as pollutants, tests are carried out under the conditions that the light source wavelength is 400-800 nm and the illumination time is 1-20 h, and the test results are shown in Table 1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A method for preparing a ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst is characterized by comprising the following steps:
(1) dissolving silver salt in a solvent, adding an organophosphorus ligand, uniformly stirring the mixed solution, centrifuging, washing and drying;
(2) dissolving the dried product obtained in the step (1) in a solvent, adding mercaptan, uniformly stirring, adding sodium borohydride, stirring, evaporating to remove the solvent, washing and extracting the product to obtain an Ag nano-cluster solution protected by a ligand; wherein the mercaptan is 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane;
(3) and (3) loading the Ag nanocluster obtained in the step (2) on titanium dioxide to obtain the Ag nanocluster sensitized titanium dioxide photocatalyst.
2. The method for preparing the ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst as claimed in claim 1, wherein: the silver salt in the step (1) is one of silver nitrate, silver fluoride and silver cyanide, and the concentration of the silver salt solution is 0.01-1 mol.L-1(ii) a And the organophosphorus ligand is one of trimethylphosphine, 1, 3-bis (diphenylphosphino) propane and tricyclohexylphosphine, stirring for 0.5-10h, centrifuging, washing and drying for 10h at 80 ℃.
3. The method for preparing the ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst as claimed in claim 1, wherein: the solvent is one or more of water, tetrahydrofuran, ethanol, toluene, dichloromethane, acetonitrile and N, N-dimethylformamide.
4. The method for preparing the ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst as claimed in claim 1, wherein: after the dried product in the step (2) is dissolved in the solvent, the concentration of Ag in the solution is 0.01-1 mol.L-1The concentration of mercaptan after mercaptan addition is 0.001-10 mol.L-1Stirring for 0.5-5h, adding sodium borohydride, wherein the concentration of the sodium borohydride in the mixed solution is 0.001-100 mol.L-1Stirring for 0.5-10h, evaporating to remove the solvent, washing the product with one or more of n-hexane, acetone and acetonitrile, and finally extracting with one or more of dichloromethane, acetonitrile and ethanol to obtain the ligand-protected Ag nanocluster.
5. The method for preparing the ligand-protected Ag nanocluster-sensitized titanium dioxide photocatalyst as claimed in claim 1, wherein: and (3) adding titanium dioxide into the Ag nano-cluster solution in the step (3), wherein the loading capacity of Ag is 0.01-5 wt%, stirring for 1-12 h, centrifuging, washing, and vacuum drying at 80 ℃ for 10 h.
6. The titanium dioxide photocatalyst sensitized with Ag nanoclusters protected with ligands prepared by the preparation method of any one of claims 1 to 5.
7. The ligand-protected Ag nanoclustered sensitized titanium dioxide photocatalyst as claimed in claim 6, characterized in that: the size of the Ag nanocluster is 0.8-3 nm.
8. The use of the ligand-protected Ag nanoclustered sensitized titanium dioxide photocatalyst of claim 6 in visible light photocatalytic degradation of organic pollutants in water, characterized in that: the wavelength of the used light source is 400-800 nm, the illumination time is 1-20 h, and the pollutants are rhodamine, methyl orange, methyl blue or Sudan red.
9. The use of the ligand-protected Ag nanoclustered sensitized titanium dioxide photocatalyst of claim 8 in visible light photocatalytic degradation of organic pollutants in water, characterized in that: the titanium dioxide photocatalyst is repeatedly used for 3-5 times, and the degradation rate is more than 90%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301861A (en) * | 2013-06-29 | 2013-09-18 | 上海荣富新型材料有限公司 | Preparation method of trace silver phosphate sensitized titanium dioxide photocatalyst |
| CN106862584A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of synthetic method of atom number and the controllable silver nanoclusters of particle size |
| CN107935103A (en) * | 2017-12-25 | 2018-04-20 | 李雪琴 | A kind for the treatment of process of silver-based composite photocatalyst for degrading dyeing waste water |
| CN109420774A (en) * | 2017-08-28 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of preparation of the controllable AgAu alloy nanocluster of atom number, size |
-
2019
- 2019-07-01 CN CN201910584786.9A patent/CN110227559B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301861A (en) * | 2013-06-29 | 2013-09-18 | 上海荣富新型材料有限公司 | Preparation method of trace silver phosphate sensitized titanium dioxide photocatalyst |
| CN106862584A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of synthetic method of atom number and the controllable silver nanoclusters of particle size |
| CN109420774A (en) * | 2017-08-28 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of preparation of the controllable AgAu alloy nanocluster of atom number, size |
| CN107935103A (en) * | 2017-12-25 | 2018-04-20 | 李雪琴 | A kind for the treatment of process of silver-based composite photocatalyst for degrading dyeing waste water |
Non-Patent Citations (3)
| Title |
|---|
| A facile UV-light mediated synthesis of l-histidine stabilized silver nanocluster for efficient photodegradation of methylene blue;Nabin Kumar Pal，et al.;《Journal of Molecular Catalysis A: Chemical》;20150414;第404-405卷;27-35 * |
| TiO2-supported Ag nanoclusters with enhanced visible light activity for the photocatalytic removal of NO;Yanyan Duan，et al.;《Applied Catalysis B: Environmental》;20180421;第234卷;206-212 * |
| 银促进的TiO2光催化降解甲基橙;尤先锋等;《催化学报》;20060331;第27卷(第3期);270-274 * |
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