CN112023953A - Preparation method of supported nano-gold photocatalyst - Google Patents
Preparation method of supported nano-gold photocatalyst Download PDFInfo
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- 239000010931 gold Substances 0.000 title claims abstract description 84
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 55
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 67
- 238000005406 washing Methods 0.000 claims abstract description 45
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 26
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 22
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000001704 evaporation Methods 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 18
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- 239000004094 surface-active agent Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 238000010335 hydrothermal treatment Methods 0.000 claims description 13
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 12
- 229930195725 Mannitol Natural products 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000594 mannitol Substances 0.000 claims description 12
- 235000010355 mannitol Nutrition 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- ZMRFRBHYXOQLDK-UHFFFAOYSA-N 2-phenylethanethiol Chemical compound SCCC1=CC=CC=C1 ZMRFRBHYXOQLDK-UHFFFAOYSA-N 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 6
- 235000009518 sodium iodide Nutrition 0.000 claims description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- -1 sodium halide Chemical class 0.000 claims description 5
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 2
- 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
- YIJUAFIHCPHXSS-UHFFFAOYSA-N 4-hydroxysulfanylbenzenethiol Chemical compound OSC1=CC=C(S)C=C1 YIJUAFIHCPHXSS-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 108010024636 Glutathione Proteins 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 2
- 235000018417 cysteine Nutrition 0.000 claims description 2
- 229960003180 glutathione Drugs 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 abstract description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 239000002135 nanosheet Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- BXAVKNRWVKUTLY-UHFFFAOYSA-N 4-sulfanylphenol Chemical compound OC1=CC=C(S)C=C1 BXAVKNRWVKUTLY-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005416 organic matter 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- B01J35/39—
-
- B01J35/393—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
Abstract
The invention discloses a preparation method of a supported nano-gold photocatalyst, which comprises the following steps: dissolving HAuCl4.4H2O in a solvent, adding organic mercaptan and sodium borohydride into the solvent, stirring for 0.5-10 h, evaporating the solvent, washing a product, and adding an extracting solution to extract to obtain a nano-gold solution; and adding a carrier into the nano-gold solution to enable the loading amount of Au to be 0.01-5 wt%, stirring for 1-12 h, centrifuging, washing, and drying in vacuum to obtain the supported nano-gold photocatalyst. According to the invention, the ultrathin bismuth oxyhalide nanosheet (2-3 nm) is prepared by hydrothermal method, the oxygen vacancy is exposed out of the bismuth oxyhalide thin layer, and the degree of oxidation of the nano-gold is reduced by utilizing the reducibility of the oxygen vacancy of the ultrathin bismuth oxyhalide nanosheet, so that the photocatalytic stability of the nano-gold is improved, and meanwhile, the catalytic activity of the nano-gold and the bismuth oxyhalide can be improved by virtue of the synergistic effect of the nano-gold and the bismuth oxyhalide.
Description
Technical Field
The invention belongs to the technical field of nano synthesis, and particularly relates to a preparation method of a supported nano Au photocatalyst.
Background
The nano gold has attracted wide attention because of showing excellent catalytic activity in the fields of low-temperature CO oxidation, water vapor transformation, organic synthesis and the like. Due to the surface plasmon resonance (LSPR) effect, the nanogold absorbs visible light strongly, so that the nanogold becomes a potential solar energy conversion and utilization material, and shows excellent catalytic activity in the fields of photocatalytic water splitting hydrogen production, CO2 reduction, pollutant degradation, organic synthesis and the like. However, the gold nanoparticles show obvious size effect in catalysis, namely, the catalytic activity is gradually increased along with the reduction of the size of the nano gold. However, the smaller the gold size, the higher the surface energy and the more unstable. Especially in the photocatalysis reaction, the irradiation can make the nano-gold generate strong oxidative cavity, which is easy to induce the aggregation growth of the nano-gold (Sci. Rep. 6,22742,). The slow and other methods adopt a method of modifying by a reducing organic matter and coating by TiO2 to stabilize the gold nanoparticles, and although the photocatalytic stability is greatly improved, the coating method reduces the catalytic activity of the nano gold. How to effectively improve the photocatalytic stability of the ultra-small nanogold (1 nm) is still a difficult problem in academia. Therefore, the development of the stable nanogold photocatalyst has important significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a supported nano-gold photocatalyst, and the catalytic activity and the photocatalytic stability of the prepared supported nano-gold photocatalyst are obviously improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a supported nano-gold photocatalyst comprises the following steps:
(1) dissolving HAuCl4.4H2O in a solvent, wherein the concentration of HAuCl4.4H2O is 0.01-1 mol/L; adding organic mercaptan, wherein the concentration of the organic mercaptan is 0.01-10 mol/L, stirring for 0.5-5 h, adding sodium borohydride, the final concentration of the sodium borohydride is 0.01-10 mol/L, stirring for 0.5-10 h, evaporating out the solvent, washing the product, and adding an extracting solution to extract to obtain a nano gold solution;
(2) and adding a carrier into the nano-gold solution to enable the loading amount of Au to be 0.01-5 wt%, stirring for 1-12 h, centrifuging, washing, and drying in vacuum to obtain the supported nano-gold photocatalyst.
Further, the solvent in the step (1) is one or more of water, tetrahydrofuran, methanol, ethanol, toluene, dichloromethane, acetonitrile and DMF (N, N-dimethylformamide).
Further, the organic mercaptan in the step (1) is 3-mercaptopropionic acid, 2-phenethyl mercaptan, thiophenol, 4-hydroxythiophenyl mercaptan, hexanethiol, glutathione, cysteine, 2-naphthalene mercaptan, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, or the like.
Further, the washing liquid adopted in the washing in the step (1) is one or more of n-hexane, acetone, acetonitrile and methanol.
Further, the extracting solution in the step (2) is one or more of dichloromethane, acetonitrile, ethanol and water.
Further, the carrier in the step (2) is one or two or more of BiOCl, BiOBr, BiOI and BiOXmYn; wherein X, Y = Cl, Br, I, m and n are not less than 0 but not simultaneously 0.
Further, the preparation method of the carrier comprises the following steps: dissolving Bi (NO3)3 in a mannitol solution, wherein the concentration of Bi (NO3)3 is 0.01-5 mol/L; adding a surfactant with the concentration of 0.05-10 mol/L, stirring for 0.5-5 h, and adding sodium halide with the final concentration of 0.01-10 mol/L; stirring for 0.5-10 h, carrying out hydrothermal treatment at 80-200 ℃ for 1-24 h, cooling, washing and drying to obtain the carrier.
Further, the surfactant is PVP, PVA, or CTAB.
Further, the sodium halide is one or more of sodium chloride, sodium bromide or sodium iodide.
Further, the temperature of vacuum drying in the step (2) is 60-120 ℃, and the time is 2-10 hours.
The catalyst is used for preparing imine by oxidizing and self-coupling primary amine at room temperature, and the specific method comprises the following steps: adding a substrate primary amine, a solvent and a supported nano Au catalyst into a reaction tube, introducing oxygen to replace the internal atmosphere, and reacting for 0.5-10 h under the irradiation of visible light. After the reaction was completed, the catalyst was centrifuged, the solvent was removed by distillation under reduced pressure, and the obtained sample was purified by column separation. The conversion rate of primary amine is 92-100%, and the imine yield is 95-99%. The catalytic process uses oxygen as an oxidant, and has the characteristics of high conversion rate, high selectivity, simple operation, long service life of the catalyst, environmental friendliness and the like, and the catalyst can be recycled for many times.
The invention has the beneficial effects that: according to the invention, the ultrathin bismuth oxyhalide nanosheet (2-3 nm) is prepared by hydrothermal method, the oxygen vacancy is exposed out of the bismuth oxyhalide thin layer, and the degree of oxidation of the nano-gold is reduced by utilizing the reducibility of the oxygen vacancy of the ultrathin bismuth oxyhalide nanosheet, so that the photocatalytic stability of the nano-gold is improved, and meanwhile, the catalytic activity of the nano-gold and the bismuth oxyhalide can be improved by virtue of the synergistic effect of the nano-gold and the bismuth oxyhalide.
Drawings
FIG. 1 is an XRD pattern of supported nano Au and a carrier;
FIG. 2 is a transmission electron microscope image of nano Au;
FIG. 3 is an atomic force microscope image of a support BiOI;
FIG. 4 is a transmission electron microscope image of the supported nano-gold.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
(1) Adding HAuCl4·4H2O dissolved in water, HAuCl4·4H2The concentration of O is 0.01mol/L, and a certain amount of 2-phenethyl mercaptan is added into the O, and the concentration of the mercaptan is 0.01 mol/L. Stirring for 0.5 h, and adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.01 mol/L. Stirring for 0.5 h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain a nano-gold solution;
(2) adding Bi (NO)3)3Dissolving in sweetIn a solution of dew alcohol, Bi (NO)3)3The concentration of (A) is 0.01 mol/L; adding a surface active agent PVP (polyvinyl pyrrolidone) with the concentration of 0.05 mol/L, stirring for 0.5 h, and adding sodium chloride with the final concentration of 0.01 mol/L; stirring for 0.5 h, and performing hydrothermal treatment at 80 ℃ for 24 h. Cooling, washing and drying to obtain the required carrier. And adding a certain amount of carrier into the obtained nano-gold solution, wherein the loading amount of Au is 0.01wt%, stirring for 1h, centrifuging, washing, and vacuum drying at 60 ℃ for 10h to obtain Au/BiOCl.
Example 2
(1) Adding HAuCl4·4H2O dissolved in water, HAuCl4·4H2The concentration of O is 0.05 mol/L, and a certain amount of 2-phenethyl mercaptan is added into the O, and the concentration of the mercaptan is 0.1 mol/L. Stirring for 1h, and then adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol/L. Stirring for 1h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain a nano-gold solution;
(2) adding Bi (NO)3)3Dissolved in a solution of mannitol, Bi (NO)3)3The concentration of (A) is 0.05 mol/L; adding a surface active agent PVP (polyvinyl pyrrolidone) with the concentration of 100 mol/L, stirring for 1h, and adding sodium chloride with the final concentration of 0.1 mol/L; stirring for 1h, and carrying out hydrothermal treatment at 200 ℃ for 24 h. Cooling, washing and drying to obtain the required carrier. And adding a certain amount of carrier into the obtained nano-gold solution, wherein the loading amount of Au is 5wt%, stirring for 12h, centrifuging, washing, and vacuum drying at 120 ℃ for 2h to obtain Au/BiOCl.
Example 3
(1) Adding HAuCl4·4H2O dissolved in water, HAuCl4·4H2The concentration of O was 0.08 mol/L. A certain amount of 2-phenethyl mercaptan is added into the mixture, and the concentration of the mercaptan is 0.5 mol/L. Stirring for 2 hours, and then adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.5 mol/L. Stirring for 3h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain a nano-gold solution;
(2) adding Bi (NO)3)3Dissolved in a solution of mannitol, Bi (NO)3)3The concentration of (A) is 0.1 mol/L; adding a surfactant PVA (polyvinyl alcohol) into the solution, wherein the concentration of the PVA is 0.5mol/L, stirring the solution for 2 hours, and then adding sodium bromide, wherein the final concentration of the sodium bromide is 0.5 mol/L; stirring for 3h, and carrying out hydrothermal treatment at 200 ℃ for 1 h. Cooling, washing and drying to obtain the required carrier. And adding a certain amount of carrier into the obtained nano-gold solution, wherein the loading amount of Au is 2 wt%, stirring for 6h, centrifuging, washing, and vacuum drying at 60 ℃ for 10h to obtain Au/BiOBr.
Example 4
(1) Adding HAuCl4·4H2O dissolved in water, HAuCl4·4H2The concentration of O was 0.1 mol/L. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 1 mol/L. Stirring for 2.5h, and then adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 1 mol/L. Stirring for 5h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain a nano-gold solution;
(2) adding Bi (NO)3)3Dissolved in a solution of mannitol, Bi (NO)3)3The concentration of (A) is 0.5 mol/L; adding a surfactant CTBA (CTBA) into the mixture, wherein the concentration of the CTBA is 1mol/L, stirring the mixture for 2.5 hours, and then adding sodium bromide, wherein the final concentration of the sodium bromide is 1 mol/L; stirring for 5h, and carrying out hydrothermal treatment at 100 ℃ for 20 h. Cooling, washing and drying to obtain the required carrier. And adding a certain amount of carrier into the obtained nano-gold solution, wherein the loading amount of Au is 1wt%, stirring for 8h, centrifuging, washing, and vacuum drying at 100 ℃ for 6h to obtain Au/BiOBr.
Example 5
(1) Adding HAuCl4·4H2O dissolved in ethanol, HAuCl4·4H2The concentration of O was 0.5 mol/L. A certain amount of 2-phenethyl mercaptan is added into the mixture, and the concentration of the mercaptan is 5 mol/L. And stirring for 3 hours, and then adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 5 mol/L. Stirring for 6h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain a nano-gold solution;
(2) adding Bi (NO)3)3Dissolved in a solution of mannitol, Bi (NO)3)3The concentration of (A) is 1 mol/L; adding surface theretoThe concentration of an activating agent PVP is 5mol/L, sodium bromide is added after stirring for 3 hours, and the final concentration of the sodium bromide is 5 mol/L; stirring for 6h, and carrying out hydrothermal treatment at 100 ℃ for 24 h. Cooling, washing and drying to obtain the required carrier. And adding a certain amount of carrier into the obtained nano-gold solution, wherein the loading amount of Au is 0.5wt%, stirring for 1h, centrifuging, washing, and drying in vacuum at 110 ℃ for 4h to obtain Au/BiOBr.
Example 6
(1) Adding HAuCl4·4H2Dissolving O in water + ethanol (volume ratio 1: 1) and HAuCl4·4H2The concentration of O was 0.8 mol/L. Adding a certain amount of 2-phenethyl mercaptan into the mixture, wherein the concentration of the mercaptan is 8 mol/L. Stirring for 4 hours, and then adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 0.1 mol/L. Stirring for 8h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain a nano-gold solution;
(2) adding Bi (NO)3)3Dissolved in a solution of mannitol, Bi (NO)3)3The concentration of (A) is 3 mol/L; adding a surfactant PVA (polyvinyl alcohol) into the solution, wherein the concentration of the PVA is 8mol/L, stirring the solution for 4 hours, and then adding sodium bromide, wherein the final concentration of the sodium bromide is 100 mol/L; stirring for 8h, and carrying out hydrothermal treatment at 150 ℃ for 10 h. Cooling, washing and drying to obtain the required carrier. And adding a certain amount of carrier into the obtained nano-gold solution, wherein the loading amount of Au is 0.05 wt%, stirring for 12h, centrifuging, washing, and vacuum drying at 80 ℃ for 8h to obtain Au/BiOBr.
Example 7
(1) Adding HAuCl4·4H2O dissolved in water, HAuCl4·4H2The concentration of O is 1mol/L, a certain amount of 2-phenethyl mercaptan is added into the O, and the concentration of the mercaptan is 10 mol/L. And stirring for 5 hours, and then adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 10 mol/L. Stirring for 10h, evaporating the solvent, washing the product with n-hexane, and finally extracting with ethanol to obtain a nano-gold solution;
(2) adding Bi (NO)3)3Dissolved in a solution of mannitol, Bi (NO)3)3The concentration of (A) is 5 mol/L; thereto is added the surfactant PVA at a concentration of 10 mol-L, stirring for 5 hours, and then adding sodium chloride, wherein the final concentration of the sodium chloride is 10 mol/L; stirring for 10h, and carrying out hydrothermal treatment at 100 ℃ for 20 h. Cooling, washing and drying to obtain the required carrier. And adding a certain amount of carrier into the obtained nano-gold solution, wherein the loading amount of Au is 0.01wt%, stirring for 12h, centrifuging, washing, and vacuum drying at 90 ℃ for 7 h to obtain Au/BiOCl.
Example 8
(1) Adding HAuCl4·4H2O dissolved in water, HAuCl4·4H2The concentration of O was 1mol/L, and a certain amount of 4 hydroxythiophenol was added thereto, and the concentration of mercaptan was 10 mol/L. And stirring for 5 hours, and then adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 10 mol/L. Stirring for 10h, evaporating the solvent, washing the product with n-hexane, and finally extracting with dichloromethane to obtain a nano-gold solution;
(2) adding Bi (NO)3)3Dissolved in a solution of mannitol, Bi (NO)3)3The concentration of (A) is 5 mol/L; adding a surfactant PVP (polyvinyl pyrrolidone) into the mixture, wherein the concentration of the PVP is 10 mol/L, stirring for 5 hours, and then adding sodium chloride, wherein the final concentration of the sodium chloride is 5 mol/L; stirring for 10h, and carrying out hydrothermal treatment at 160 ℃ for 16 h. Cooling, washing and drying to obtain the required carrier. And adding a certain amount of carrier into the obtained nano-gold solution, wherein the loading amount of Au is 0.01wt%, stirring for 12h, centrifuging, washing, and vacuum drying at 60 ℃ for 10h to obtain Au/BiOCl.
Example 9
(1) Adding HAuCl4·4H2O dissolved in water, HAuCl4·4H2The concentration of O was 1mol/L, and a certain amount of 4 hydroxythiophenol was added thereto, and the concentration of mercaptan was 10 mol/L. And stirring for 5 hours, and then adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 10 mol/L. Stirring for 10h, evaporating the solvent, washing the product with n-hexane, and finally extracting with dichloromethane to obtain a nano-gold solution;
(2) adding Bi (NO)3)3Dissolved in a solution of mannitol, Bi (NO)3)3The concentration of (A) is 5 mol/L; adding PVP as surfactant with concentration of 10 mol/L, stirring for 5 hr, and adding chlorineSodium chloride and sodium bromide are dissolved, and the final concentrations of the sodium chloride and the sodium bromide are respectively 1mol/L and 5 mol/L; stirring for 10h, and carrying out hydrothermal treatment at 160 ℃ for 16 h. Cooling, washing and drying to obtain the required carrier. Adding a certain amount of carrier into the obtained nano-gold solution, wherein the loading amount of Au is 0.01wt%, stirring for 12h, centrifuging, washing, and vacuum drying at 60 ℃ for 10h to obtain Au/BiOCl0.2I。
Example 10
(1) Adding HAuCl4·4H2O dissolved in water, HAuCl4.4H2The concentration of O was 1mol/L, and a certain amount of 4 hydroxythiophenol was added thereto, and the concentration of mercaptan was 10 mol/L. And stirring for 5 hours, and then adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 10 mol/L. Stirring for 10h, evaporating the solvent, washing the product with n-hexane, and finally extracting with dichloromethane to obtain a nano-gold solution;
(2) adding Bi (NO)3)3Dissolved in a solution of mannitol, Bi (NO)3)3The concentration of (A) is 5 mol/L; adding a surfactant PVP (polyvinyl pyrrolidone) into the mixture, wherein the concentration of the PVP is 10 mol/L, stirring for 5 hours, and then adding sodium iodide, wherein the final concentration of the sodium iodide is 5 mol/L; stirring for 10h, and carrying out hydrothermal treatment at 160 ℃ for 16 h. Cooling, washing and drying to obtain the required carrier. Adding a certain amount of carrier into the obtained nano-gold solution, wherein the loading amount of Au is 0.01wt%, stirring for 12h, centrifuging, washing, and vacuum drying at 60 ℃ for 10 h. Obtaining Au/BiOI.
Example 11
(1) Adding HAuCl4·4H2O dissolved in water, HAuCl4.4H2The concentration of O was 1mol/L, and a certain amount of 4 hydroxythiophenol was added thereto, and the concentration of mercaptan was 10 mol/L. And stirring for 5 hours, and then adding a certain amount of sodium borohydride, wherein the concentration of the sodium borohydride is 10 mol/L. Stirring for 10h, evaporating the solvent, washing the product with n-hexane, and finally extracting with dichloromethane to obtain a nano-gold solution;
(2) adding Bi (NO)3)3Dissolved in a solution of mannitol, Bi (NO)3)3The concentration of (A) is 5 mol/L; to this was added the surfactant PVP at a concentration of 10 mol/L, stirring for 5 hours, and then adding sodium chloride, sodium bromide and sodium iodide, wherein the final concentrations of the sodium chloride, the sodium bromide and the sodium iodide are 1mol/L, 5mol/L and 5mol/L respectively; stirring for 10h, and carrying out hydrothermal treatment at 160 ℃ for 16 h. Cooling, washing and drying to obtain the required carrier. Adding a certain amount of carrier into the obtained nano-gold solution, wherein the loading amount of Au is 0.01wt%, stirring for 12h, centrifuging, washing, and vacuum drying at 60 ℃ for 10h to obtain Au/BiOCl0.1Br0.5I0.5。
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A preparation method of a supported nano-gold photocatalyst is characterized by comprising the following steps:
(1) adding HAuCl4 .4H2O in a solvent, HAuCl4·4H2The concentration of O is 0.01-1 mol/L1(ii) a Adding organic mercaptan into the mixture, wherein the concentration of the organic mercaptan is 0.01-10 mol/L1Stirring for 0.5-5 h, and then adding sodium borohydride with the final concentration of 0.01-10 mol.L-1Stirring for 0.5-10 h, evaporating the solvent, washing the product, and adding an extracting solution to extract to obtain a nano gold solution;
(2) and adding a carrier into the nano-gold solution to enable the loading amount of Au to be 0.01-5 wt%, stirring for 1-12 h, centrifuging, washing, and drying in vacuum to obtain the supported nano-gold photocatalyst.
2. The method for preparing the supported nanogold photocatalyst according to claim 1, wherein the method comprises the following steps: the solvent in the step (1) is one or more of water, tetrahydrofuran, methanol, ethanol, toluene, dichloromethane, acetonitrile and DMF.
3. The method for preparing the supported nanogold photocatalyst according to claim 1, wherein the method comprises the following steps: the organic mercaptan in the step (1) is 3-mercaptopropionic acid, 2-phenethyl mercaptan, thiophenol, 4-hydroxythiothiophenol, hexanethiol, glutathione, cysteine, 2-naphthalene mercaptan, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and the like.
4. The method for preparing the supported nanogold photocatalyst according to claim 1, wherein the method comprises the following steps: and (2) the washing liquid adopted in the washing in the step (1) is one or more of normal hexane, acetone, acetonitrile and methanol.
5. The method for preparing the supported nanogold photocatalyst according to claim 1, wherein the method comprises the following steps: the extracting solution in the step (2) is one or more of dichloromethane, acetonitrile, ethanol and water.
6. The method for preparing the supported nanogold photocatalyst according to claim 1, wherein the method comprises the following steps: the carrier in the step (2) is BiOCl, BiOBr, BiOI or BiOXmYnOne or two or more of them; wherein X, Y = Cl, Br, I, m and n are not less than 0 but not simultaneously 0.
7. The method for preparing the supported nanogold photocatalyst according to claim 1 or 6, wherein the method comprises the following steps: the preparation method of the carrier comprises the following steps: adding Bi (NO)3)3Dissolved in a solution of mannitol, Bi (NO)3)3The concentration of (A) is 0.01-5 mol/L1(ii) a Adding a surfactant into the mixture, wherein the concentration of the surfactant is 0.05-10 mol/L1After stirring for 0.5-5 h, adding sodium halide, wherein the final concentration of the sodium halide is 0.01-10 mol.L-1(ii) a Stirring for 0.5-10 h, carrying out hydrothermal treatment at 80-200 ℃ for 1-24 h, cooling, washing and drying to obtainThe vector.
8. The method for preparing the supported nanogold photocatalyst according to claim 7, wherein the method comprises the following steps: the surfactant is PVP, PVA or CTAB.
9. The method for preparing the supported nanogold photocatalyst according to claim 7, wherein the method comprises the following steps: the sodium halide is one or more of sodium chloride, sodium bromide or sodium iodide.
10. The method for preparing the supported nanogold photocatalyst according to claim 1, wherein the method comprises the following steps: and (3) drying in vacuum in the step (2) at the temperature of 60-120 ℃ for 2-10 h.
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