WO2019047602A1 - Method for preparing bismuth sulfide-modified gold nanoparticles/sodium dioxide nanotube structure and application thereof - Google Patents
Method for preparing bismuth sulfide-modified gold nanoparticles/sodium dioxide nanotube structure and application thereof Download PDFInfo
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- WO2019047602A1 WO2019047602A1 PCT/CN2018/093955 CN2018093955W WO2019047602A1 WO 2019047602 A1 WO2019047602 A1 WO 2019047602A1 CN 2018093955 W CN2018093955 W CN 2018093955W WO 2019047602 A1 WO2019047602 A1 WO 2019047602A1
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- Prior art keywords
- titanium dioxide
- strontium sulfide
- tio
- nanotube structure
- modified gold
- Prior art date
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- 239000002071 nanotube Substances 0.000 title claims abstract description 180
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910052797 bismuth Inorganic materials 0.000 title abstract description 10
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 title abstract 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 193
- -1 bismuth sulfide-modified gold Chemical class 0.000 claims abstract description 92
- 239000010931 gold Substances 0.000 claims abstract description 68
- 239000002245 particle Substances 0.000 claims abstract description 65
- 229910052737 gold Inorganic materials 0.000 claims abstract description 58
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 57
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 37
- 239000008103 glucose Substances 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 230000015556 catabolic process Effects 0.000 claims abstract description 9
- 238000006731 degradation reaction Methods 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 104
- 239000004408 titanium dioxide Substances 0.000 claims description 84
- 239000000243 solution Substances 0.000 claims description 70
- 229910052712 strontium Inorganic materials 0.000 claims description 47
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000010936 titanium Substances 0.000 claims description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- 229910052719 titanium Inorganic materials 0.000 claims description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000002048 anodisation reaction Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- ZEGFMFQPWDMMEP-UHFFFAOYSA-N strontium;sulfide Chemical compound [S-2].[Sr+2] ZEGFMFQPWDMMEP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000007743 anodising Methods 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
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- 230000002255 enzymatic effect Effects 0.000 abstract description 11
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 abstract description 9
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- 239000000463 material Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract 3
- 238000007781 pre-processing Methods 0.000 abstract 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- DUDJJJCZFBPZKW-UHFFFAOYSA-N [Ru]=S Chemical compound [Ru]=S DUDJJJCZFBPZKW-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- 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 10
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 10
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 10
- 235000010323 ascorbic acid Nutrition 0.000 description 10
- 229960005070 ascorbic acid Drugs 0.000 description 10
- 239000011668 ascorbic acid Substances 0.000 description 10
- 229960000907 methylthioninium chloride Drugs 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 229940116269 uric acid Drugs 0.000 description 10
- 229910021607 Silver chloride Inorganic materials 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 7
- 229910052707 ruthenium Inorganic materials 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000003115 supporting electrolyte Substances 0.000 description 7
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 238000003491 array Methods 0.000 description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
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- 238000005215 recombination Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
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- 229910052709 silver Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- IBRMAPJCHQJDMT-UHFFFAOYSA-N [Au].[Bi]=S Chemical compound [Au].[Bi]=S IBRMAPJCHQJDMT-UHFFFAOYSA-N 0.000 description 3
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- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
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- 150000001408 amides Chemical class 0.000 description 2
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- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- XEIPQVVAVOUIOP-UHFFFAOYSA-N [Au]=S Chemical compound [Au]=S XEIPQVVAVOUIOP-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/0207—Pretreatment of the support
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Definitions
- the invention relates to the technical field of materials, in particular to a preparation method of a ternary structure of strontium sulfide modified gold nanoparticles/titanium dioxide nanotubes, a non-enzymatic glucose sensor and a composite material thereof and the application thereof in the field of photocatalytic degradation of organic pollutants such as pollutants .
- Titanium dioxide TiO 2
- TiO 2 a semiconductor material
- Titanium dioxide (TiO 2 ) has excellent chemical stability, photoelectric properties, biocompatibility and corrosion resistance. It has been widely used in photocatalytic degradation of pollutants, fuel sensitized solar cells, biomedical materials, gas sensors and photolysis. Water hydrogen production and other aspects.
- nano-TiO 2 has its special properties, especially catalytic properties.
- One-dimensional TiO 2 nanostructures wires, rods, strips, and tubes
- beneficial geometric effects such as directional charge transport and orthogonal electron-hole separation.
- the morphology of TiO 2 NTs has been studied intensively.
- TiO 2 nanoparticle TiO 2 nanotube arrays it has large specific surface area, high surface energy, easy recycling and load of electrons and holes. The advantage is lower.
- TiO 2 nanotube arrays still have some disadvantages, which limits its application in many aspects.
- TiO 2 has a wide band gap (3.2 eV for anatase and 3.0 eV for rutile), and can only absorb 3-5% of solar energy ( ⁇ ⁇ 387 nm), and the utilization rate is low; The recombination rate of photogenerated electron-hole pairs in TiO2 nanotubes is still high and the photocatalytic activity is low.
- the object of the present invention is to provide a method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure, which solves the above problems.
- a method for preparing a strontium sulfide modified gold nanoparticle/titanium dioxide nanotube structure comprising the following steps:
- the TiO 2 nanotube array is placed in the composite solution of strontium sulfide and gold particles, and the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure is obtained by an oven method.
- the substrate is a titanium sheet
- the titanium sheet is pure titanium or a titanium alloy
- the substrate is pretreated to ultrasonically clean the substrate with dilute nitric acid, acetone, ethanol and deionized water for 20-40 min.
- the preparation of the TiO 2 nanotube array on the substrate by the two anodizing methods specifically comprises: using a pretreated substrate as an anode, a platinum sheet as a cathode, and simultaneously inserting an electrolyte into the anode for two anodization, the anode Oxidation produces a primary TiO 2 nanotube array, and the primary TiO 2 nanotube array is calcined to obtain an anatase TiO 2 nanotube array.
- the electrolyte is an ethylene glycol solution of ammonium fluoride and water.
- the mass percentage concentration of ammonium fluoride is 0.2-0.8 wt%
- the volume percentage concentration of water is 2.0-4.0.
- v% in the two anodizations, the voltage during the first anodization is 40-60V, the time is 1-3h, and the voltage during the second anodization is 40-60V, the time is 3 At -10 min, the calcination temperature is 400-500 ° C, the calcination time is 1-3 h, and the calcination heating and cooling rates are both 3-8 ° C / min.
- the obtaining the gold particles by the reduction comprises: stirring with a HAuCl 4 oil bath, adding sodium citrate after boiling, changing the time to obtain a solution of AuNPs.
- the preparation of the composite solution of strontium sulfide and gold particles comprises adding thioacetamide and cesium acetate to the AuNPs solution, and reacting in an oven to obtain a composite solution of strontium sulfide and gold particles.
- the TiO 2 nanotube array is placed in the strontium sulfide and gold particle composite solution, and the strontium sulfide modified gold nanoparticle/titanium dioxide nanotube structure is obtained by an oven method, including: the TiO 2 nanotube After pre-treatment of the array, the array was immersed in the composite solution of strontium sulfide and gold particles, and then placed in an oven and heated at 37 ° C for 4 h to obtain a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure.
- strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in the above manner can be applied to an organic dye pollutant degradation catalyst.
- strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in the above manner can also be applied to a composite material.
- strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in the above manner can also be applied to a non-glucose sensor.
- the invention provides a preparation method of a strontium sulfide modified gold nanoparticle/titanium dioxide nanotube structure, wherein the prepared strontium sulfide modified gold nanoparticle/titanium dioxide nanotube structure improves the photoelectric effect of the TiO 2 nanotube structure on the one hand; On the one hand, the catalytic ability of the titanium dioxide nanotube structure is improved to achieve degradation of organic pollutants such as methylene blue under visible light irradiation and for producing a non-enzymatic glucose sensor. Compared with unmodified TiO 2 nanotubes, the TiO 2 nanotube structure of strontium sulfide modified gold nanoparticles has significantly improved photoelectric properties, and has good chemical stability and recyclability.
- FIG. 1 is a schematic flow chart of a method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure of the present invention
- FIG. 2 is an SEM image of a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared by the present invention, wherein (a), (b), and (c) are respectively immersed in a gold sulfide nanoparticle solution having a concentration of 0.02. SEM images of %, 0.01%, 0.005% strontium sulfide modified gold nanoparticles supported titanium dioxide nanotube structures;
- a, b are SEM images of the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in Example 1 of the present invention, and c is the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in Example 1.
- the EDS diagram, d is the elemental distribution map of the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in Example 1;
- FIG. 4 is a TEM image, HRTEM image, and mapping of the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in Example 1.
- Views (a), (b), and (c) are TEM images of strontium sulfide-modified gold nanoparticles/titanium dioxide nanotube structures
- views (d) and (e) are HRTEMs of strontium sulfide-modified gold nanoparticles/titanium dioxide nanotube structures.
- Figure, view (f) is the mapping of view (c);
- FIG. 5 is an XPS diagram of an unmodified TiO 2 nanotube array, a ruthenium sulfide nanoparticle-modified TiO 2 nanotube array, a simple gold particle modified TiO 2 nanotube array, and a simple ruthenium sulfide modified TiO 2 in Example 1.
- Figure (a) is a full spectrum, and Figures (b), (c) and (d) are narrow, gold, bismuth and sulfur spectra of the strontium sulfide-modified gold nanoparticles/titanium dioxide nanotube structures prepared in Example 1;
- FIG. 6 is a fluorescence diagram of an unmodified TiO 2 nanotube array, a different concentration of ruthenium sulfide nanoparticle-modified TiO 2 nanotube array, a simple gold particle modified TiO 2 nanotube array, and a simple ruthenium sulfide modified TiO 2 in Example 1. Spectrum;
- Example 7 is unmodified in Example 1 TiO 2 nanotube array embodiment, different concentrations of bismuth sulfide-modified gold nanoparticles TiO 2 nanotube array, pure gold particles modified TiO 2 nanotube array and pure bismuth sulfide nanotubes modified TiO 2 Photocurrent response diagram of the array;
- Example 8 is an oxidation curve of a TiO 2 nanotube array modified with sulfided gold particles in Example 1 for different concentrations of glucose solution;
- Example 9 is a response step curve of a TiO 2 nanotube array modified with sulfided gold particles in Example 1 for different concentrations of glucose solution;
- Example 10 is a step graph of interference effects of ascorbic acid, uric acid, etc. in a non-enzymatic glucose sensor of a TiO 2 nanotube array modified with a ruthenium sulfide particle in Example 1;
- FIG. 11 is an unmodified TiO 2 nanotube array, a ruthenium sulfide particle modified TiO 2 nanotube array, a gold modified TiO 2 nanotube array, and a ruthenium sulfide modified TiO 2 nanotube array in Example 1 in ultraviolet light and visible light.
- the efficiency map for degrading methylene blue; views b, d are the views of the sample, a, c corresponding to the ultraviolet absorption wavelength of the sample.
- the present invention performs a series of modification treatments on the titanium dioxide nanotube array to optimize its own disadvantages such as doping metal, non-metal, and semiconductor nanoparticles in combination with a TiO 2 nanotube array.
- TiO 2 in order to maintain the charge transfer performance and excellent light resistance, the use of narrow band gap semiconductor NTs are easy to make the photosensitive TiO 2, so chalcogenide attention recently, bismuth-based semiconductor has attracted considerable attention.
- Bismuth sulfide (Bi 2 S 3 ) is a photo-responsive semiconductor with a narrow band gap ( ⁇ 1.3eV), a layered semiconductor with high absorption coefficient, and Bi 2 S 3 has potential in the fields of catalysis, sensors, optoelectronic nanodevices and lithium ion batteries. Applications.
- the dispersion of noble metal nanoparticles (Ag, Cu, Pt) on the surface of TiO 2 nanotubes can assist in the capture of photogenerated electrons, accelerate the separation of electron holes, and inhibit the recombination of photogenerated electrons and holes.
- noble metal nanoparticles Au, Cu, Pt
- the combination of Au nanoparticles can also act as an electron trap, contribute to charge separation, and sensitize TiO 2 under visible light due to local surface plasmon resonance (LSPR) effects.
- LSPR local surface plasmon resonance
- the addition of Au nanoparticles between two semiconductors (Bi 2 S 3 -TiO 2 ) can reduce the trap state Auger rate and partially compensate for the negative effects of surface trap sites, thereby improving the light conversion efficiency.
- FIG. 1 is a schematic flow chart of a method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure according to the present invention.
- the present invention provides a method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure, comprising the following steps:
- the TiO 2 nanotube array is placed in the composite solution of strontium sulfide and gold particles, and the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure is obtained by an oven method.
- a method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure comprising:
- Step 1 The substrate may be made of titanium, and the titanium sheet is pretreated;
- this step can be performed as follows: the titanium sheet is cleaned.
- the titanium sheet is pure titanium or titanium alloy, and its size is 1.5 cm ⁇ 3.0 cm.
- the titanium sheet was ultrasonically cleaned by dilute nitric acid, acetone, ethanol and deionized water for 20-40 min.
- Step two preparing an TiO2 nanotube array by anodization
- the step may be specifically performed by using a cleaned titanium sheet as an anode, a platinum sheet as a cathode, an ammonium fluoride and water in an ethylene glycol solution as an electrolyte, applying a certain voltage, and performing the anode twice. Oxidation, anodization to obtain a TiO 2 nanotube array, and then calcined to obtain a better crystalline anatase TiO 2 nanotube array.
- the mass percentage concentration of ammonium fluoride is 0.2-0.8 wt%, and the volume percentage concentration of water is 2.0-4.0 v%.
- the voltage for the first anodization is 40-60 V for 1-3 h, and the voltage for the second anodization is 40-60 V for 3-10 min.
- the prepared TiO 2 nanotube array was calcined in air at a calcination temperature of 400-500 ° C, a calcination time of 1-3 h, and a calcination temperature rise and a temperature drop rate of 3-8 ° C/min. By calcination, a more crystalline anatase-type TiO 2 nanotube array is obtained.
- this step can be specifically carried out as follows: using HAuCl 4 (60 ml, 0.01 wt%, 0.02 wt%, 0.005 wt%), stirring in an oil bath (130 ° C), boiling and adding sodium citrate (600 ml, 1 wt) %) Change time (0.5 h, 1 h, 1.5 h, 2 h) to obtain AuNPs solution.
- Step 4 preparing a mixed solution of strontium sulfide and gold particles
- the step may be specifically carried out by adding 0.003 g of 400 ⁇ L of thioacetamide and 0.0038 g of 100 ⁇ L of cesium acetate to the AuNPs solution, and reacting in an oven at 80 ° C for 10 hours to obtain a mixed solution of strontium sulfide and gold particles.
- Step 5 Pretreatment of TiO 2 NTs
- this step can be specifically carried out by placing TiO 2 NTs in a solution of MPTs (3-mercaptopropyltrimethoxysilane 150 ⁇ L) and NH 4 OH (30 ⁇ L, 27%) in 15 ml of ethanol in the dark. 24h 25°C, protected from light by aluminum foil.
- MPTs 3-mercaptopropyltrimethoxysilane 150 ⁇ L
- NH 4 OH 30 ⁇ L, 27%)
- Step 6 Based on the prepared mixed solution of barium sulfide and gold particles, the barium sulfide and gold particles are loaded onto the structure of TiO2NTs to obtain a structure of barium sulfide modified gold nanoparticles/titanium dioxide nanotubes.
- the step may be specifically performed as follows: the treated titanium sheet (the secondary anodized titanium tube) is immersed in a solution of the gold/barium sulfide composite solution, and placed in an oven at 37 ° C for 4 hours. A strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure is obtained.
- the structure of the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube was completed. After these six steps, the structure can also be tested.
- Step 7 The performance test of photocatalytic degradation of organic dye contaminants by using the prepared novel photocatalyst.
- the unmodified TiO 2 nanotube array, the ruthenium sulfide particle modified TiO 2 nanotube array, the gold modified TiO 2 nanotube array, and the yttrium sulfide modified titanium dioxide nanotube array were respectively immersed at an initial concentration of 10 mg/ In an aqueous solution of L methylene blue, after standing for 0.5 hour in a dark environment to reach an equilibrium state of adsorption, it was irradiated for 0-120 min under ultraviolet light and visible light, respectively, at intervals of 30 min. The UV spectral absorbance of the contaminated solution was tested at each time interval.
- the prepared substrate can be used as an electrode and can be widely used in the field of non-enzymatic glucose sensors.
- the performance test of the non-enzymatic glucose sensor was performed using the prepared working electrode.
- the cycle voltage is -1V-1V
- the number of scanning turns is 5-15 turns
- the scan rate is 20-100 mV/s.
- the glucose concentration was 0-0.05 M
- the interference curve the glucose drop concentration was 0-10 mM
- the ascorbic acid and uric acid drop concentrations were 2 mM.
- FIG. 2 is an SEM image of the structure of the strontium sulfide-modified gold nanoparticles/titanium dioxide nanotubes prepared by the present invention, wherein (a), (b), and (c) are respectively impregnated ruthenium-doped gold nanoparticles solution. SEM images of ruthenium sulfide modified gold nanoparticles supported titanium dioxide nanotubes at concentrations of 0.02%, 0.01%, and 0.005%. As shown in Fig.
- the diameter of the nanotubes in the ruthenium sulfide modified gold particles/titanium dioxide nanotube array is 80-100 nm, the wall thickness is 10-20 nm, and the size of the ruthenium sulfide-modified gold nanoparticles is 15-20 nm, which is uniform.
- the wall thickness is 10-20 nm, and the size of the ruthenium sulfide-modified gold nanoparticles is 15-20 nm, which is uniform.
- titanium dioxide nanotubes On titanium dioxide nanotubes.
- an embodiment or “an embodiment” as used herein refers to a particular feature, structure, or characteristic that can be included in at least one implementation of the invention.
- TiO 2 nanotube array by pretreatment of titanium sheet and secondary anodization.
- the titanium substrate was ultrasonically washed with acetone, absolute ethanol and deionized water for 15 min.
- acetone, absolute ethanol and deionized water for 15 min.
- platinum plate electrode as the cathode
- an electrolyte solution containing 98v% ethylene glycol (0.35% by weight of ammonium fluoride) and 2v% water anodizing with a voltage of 50V for 1.5h, and after ultrasonically peeling off the film layer, continue to apply 50V voltage.
- a TiO 2 nanotube array was prepared and then heat treated at 450 ° C for 2 h to transform from an amorphous state to a better crystalline anatase.
- TiO 2 NTs were placed in a solution of MPTs (3-mercaptopropyltrimethoxysilane 150 ⁇ L) and NH 4 OH (30 ⁇ L, 27%) in 15 ml of ethanol and covered with aluminum foil for 24 h at 25 °C.
- the soaked titanium piece was placed in a 15 ml solution of gold/barium sulfide in a reaction solution of 4 h at 37 °C.
- strontium sulfide modified gold nanoparticle/titanium dioxide nanotube array was obtained.
- FIG. 2 is an SEM image of the structure of the strontium sulfide-modified gold nanoparticles/titanium dioxide nanotubes prepared by the present invention, wherein (a), (b), and (c) are respectively impregnated ruthenium-doped gold nanoparticles solution.
- SEM images of ruthenium sulfide modified gold nanoparticles supported titanium dioxide nanotubes at concentrations of 0.02%, 0.01%, and 0.005%.
- 15-20 nm of barium sulfide-modified gold nanoparticles are uniformly deposited on the surface and inside of the nanotube.
- a, b of FIG. 3 is an SEM image of a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in Example 1 of the present invention
- c is a strontium sulfide-modified gold nanoparticle prepared in Example 1.
- / EDS map of titanium dioxide nanotube structure d is the elemental distribution map of the ruthenium sulfide modified gold nanoparticle / titanium dioxide nanotube structure prepared in Example 1.
- the strontium sulfide-modified gold particle/titanium dioxide nanotube structure mainly contains Ti, O, S, Bi, and Au elements.
- FIG. 4 is a TEM image, HRTEM image, and mapping of the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in Example 1.
- Views (a), (b), and (c) are TEM images of strontium sulfide-modified gold nanoparticles/titanium dioxide nanotube structures
- views (d) and (e) are HRTEMs of strontium sulfide-modified gold nanoparticles/titanium dioxide nanotube structures.
- Figure, view (f) is the mapping of view (c).
- Figure 4 further shows that the strontium sulfide-modified gold nanoparticles are uniformly distributed on the surface and inside of the TiO 2 nanotubes with a particle size of about 15 nm; the HRTEM and SAED images show that the TiO 2 anatase (101) crystal lattice spacing is 0.352 nm. The spacing of the gold (111) plane is 0.23 nm, and the interplanar spacing of ruthenium sulfide (221) is 0.286 nm, which is in agreement with the XRD test results of FIG.
- FIG. 5 is an unmodified TiO 2 nanotube array, a ruthenium sulfide nanoparticle modified TiO 2 nanotube array, a simple gold particle modified TiO 2 nanotube array, and a simple ruthenium sulfide modified TiO 2 in Example 1.
- XPS diagram wherein (a) is a full spectrum, and (b), (c), (d) are gold, antimony, sulfur of the strontium sulfide-modified gold nanoparticles/titanium dioxide nanotube structure prepared in Example 1. Narrow spectrum. As shown in Fig.
- FIG. 6 is unmodified in Example 1 TiO 2 nanotube array embodiment, different concentrations of bismuth sulfide-modified gold nanoparticles TiO 2 nanotube array, pure gold particles modified TiO 2 nanotube array and pure bismuth sulfide Fluorescence spectrum of modified TiO 2 .
- the unmodified TiO 2 nanotube array has the highest fluorescence intensity, and the fluorescence intensity decreases after loading Bi 2 S 3 and Au, further indicating that the recombination of free electrons and holes is hindered.
- FIG. 7 in Example 1 is an unmodified TiO 2 nanotube array embodiment, different concentrations of bismuth sulfide-modified gold nanoparticles TiO 2 nanotube array, pure gold particles modified TiO 2 nanotube array and pure bismuth sulfide
- the photocurrent response diagram of the modified TiO 2 nanotube array shows that the photocurrent of 0.01% Au/Bi 2 S 3 @TiO 2 is the best, the carrier separation efficiency is increased, and the recombination of electron-hole pairs is suppressed.
- the oxidation curve of the ruthenium sulfide modified gold particle/titanium dioxide nanotube array in a sodium hydroxide solution of different concentrations of glucose is supported by a 0.1 M sodium hydroxide solution as a supporting electrolyte, wherein -
- the peak of about 0.23V is the electrochemical oxidation of glucose adsorbed on the surface of the electrode
- the peak of about 0.1V is the further oxidation of the intermediate produced during the electrochemical oxidation of glucose on the surface of the electrode.
- a peak of about 0.45 V is caused by the direct oxidation of glucose in the solution phase to the electrode. As the glucose concentration continues to increase, the peak value also increases.
- FIG. 9 is a response step curve of the TiO 2 nanotube array modified by the sulfided gold particles in Example 1 for different concentrations of glucose solution, and 2 ml of the glucose solution is injected every 25 seconds. It can be seen from the figure that as soon as the glucose solution is added, the current value will become smaller, and as the time increases, it is stepped, indicating that the electrode is more sensitive to the glucose concentration.
- FIG. 10 is a graph showing the influence of interference effects of ascorbic acid and uric acid on the non-enzymatic glucose sensor of the TiO 2 nanotube array modified by the ruthenium sulfide particles in Example 1. It can be seen from Fig. 11 that the influence rate of glucose on current density is 100%, the influence rate of ascorbic acid on current density is about 40%, and the influence rate of uric acid on current density is about 30%.
- FIG. 11a and FIG. 1 are respectively an unmodified TiO 2 nanotube array under ultraviolet light and visible light, a ruthenium sulfide particle modified TiO 2 nanotube array, and a gold modified TiO 2 nanotube array in Example 1.
- Figure a is the efficiency diagram of degradation of methylene blue under ultraviolet light irradiation.
- the degradation effect of Au/Bi 2 S 3 @TiO 2 is preferably about 30%.
- Figure c is the efficiency diagram of degradation of methylene blue under visible light irradiation, Au/Bi 2 S
- the degradation effect of 3 @TiO 2 is preferably about 40%.
- TiO 2 nanotube array by pretreatment of titanium sheet and secondary anodization.
- the titanium substrate was ultrasonically washed with acetone, absolute ethanol and deionized water for 15 min.
- acetone, absolute ethanol and deionized water for 15 min.
- platinum plate electrode as the cathode, inserting an electrolyte solution containing 97v% ethylene glycol (ammonium fluoride 0.4wt%) and 3v% water, anodizing with a voltage of 40V for 1h, and after ultrasonically peeling off the film layer, continue to apply a voltage of 40V anode.
- the TiO 2 nanotube array was prepared and then heat treated at 450 ° C for 2 h to transform from an amorphous state to a better crystalline anatase.
- the soaked titanium piece was placed in a 15 ml solution of gold/barium sulfide in a reaction solution of 4 h at 37 °C. Finally, a strontium sulfide modified gold nanoparticle/titanium dioxide nanotube array was obtained.
- TiO 2 NTs were placed in a solution of MPTs (3-mercaptopropyltrimethoxysilane 150 ⁇ L) and NH 4 OH (30 ⁇ L, 27%) in 15 ml of ethanol and covered with aluminum foil for 24 h at 25 °C.
- the soaked titanium piece was placed in a 15 ml solution of gold/barium sulfide in a reaction solution of 4 h at 37 °C.
- strontium sulfide modified gold nanoparticle/titanium dioxide nanotube array was obtained.
- the beneficial effects of the present invention are: the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure of the invention improves the photoelectric effect of the TiO 2 nanotube array on the one hand, and improves the titanium dioxide nanotube array on the other hand. Catalytic ability to achieve degradation of organic contaminants such as methylene blue under visible light illumination and for the production of non-enzymatic glucose sensors. Compared with unmodified TiO 2 nanotubes, the TiO 2 nanotube structure of strontium sulfide modified gold nanoparticles has significantly improved photoelectric properties, and has good chemical stability and recyclability.
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Abstract
A method for preparing bismuth sulfide-modified gold nanoparticles/a sodium dioxide nanotube structure and an application thereof, the method comprising: selecting a substrate, and pre-processing the substrate; preparing a TiO2 nanotube array on the substrate by means of two-step anodic oxidation; obtaining gold particles by means of reduction; preparing a bismuth sulfide and gold particle compound solution; placing the TiO2 nanotube array into the bismuth sulfide and gold particle compound solution, and preparing bismuth sulfide-modified gold nanoparticles/a sodium dioxide nanotube structure by means of an oven method. The bismuth sulfide-modified gold nanoparticles/sodium dioxide nanotube structure prepared by the foregoing method may be applied to organic pollutant degradation catalysts, compound materials and non-enzymatic glucose sensors.
Description
本发明涉及材料技术领域，具体涉及一种硫化铋修饰金纳米颗粒/二氧化钛纳米管三元结构的制备方法、非酶葡萄糖传感器和复合材料及其在光催化降解污染物等有机污染物领域的应用。The invention relates to the technical field of materials, in particular to a preparation method of a ternary structure of strontium sulfide modified gold nanoparticles/titanium dioxide nanotubes, a non-enzymatic glucose sensor and a composite material thereof and the application thereof in the field of photocatalytic degradation of organic pollutants such as pollutants .
绿色环保，清洁能源的需求已经成为当今世界的一个主流趋势，半导体光催化作为处理全球能源危机和环境污染的潜在解决方案引起了广泛的关注。许多科学家纷纷开展了用于光催化降解污染物的纳米结构材料的研究。作为半导体材料的二氧化钛(TiO
2)在科学家中受到暴风雨般的欢迎。二氧化钛(TiO
2)具有优异的化学稳定性、光电特性、生物相容性及抗腐蚀性等特点，已经广泛应用于光催化降解污染物、燃料敏化太阳能电池、生物医用材料、气体传感器和光解水制氢等方面。纳米TiO
2除了具有与普通纳米材料一样的表面效应、低尺寸效应、量子尺寸效应和宏观量子隧道效应外，还具有其特殊的性质，尤其是催化性能。一维TiO
2纳米结构(电线，棒，带和管)，由于有益的几何效应，如定向电荷传输和正交电子-空穴分离，引起了相当大的关注。其中，由于其制造和控制的容易性，已经深入研究了TiO
2NTs的形态，较TiO
2纳米颗粒TiO
2纳米管阵列具有比表面积大、表面能高、易回收利用以及电子和空穴的负荷率较低等优点。但是，TiO
2纳米管阵列仍存在着一些缺点，限制了它在很多方面的应用。如，(1)TiO
2的禁带宽度较宽(锐钛矿为3.2eV，金红石为3.0eV)，只能吸收3-5％的太阳光能(λ＜387nm)，利用率低；(2)TiO2纳米管的光生电子空穴对的复合率仍然较高，光催化活性低。
Green environmental protection, the demand for clean energy has become a mainstream trend in the world today, and semiconductor photocatalysis has attracted widespread attention as a potential solution to the global energy crisis and environmental pollution. Many scientists have carried out research on nanostructured materials for photocatalytic degradation of pollutants. Titanium dioxide (TiO 2 ), a semiconductor material, has been tempered by scientists. Titanium dioxide (TiO 2 ) has excellent chemical stability, photoelectric properties, biocompatibility and corrosion resistance. It has been widely used in photocatalytic degradation of pollutants, fuel sensitized solar cells, biomedical materials, gas sensors and photolysis. Water hydrogen production and other aspects. In addition to the same surface effect, low size effect, quantum size effect and macroscopic quantum tunneling effect as nano-materials, nano-TiO 2 has its special properties, especially catalytic properties. One-dimensional TiO 2 nanostructures (wires, rods, strips, and tubes) have attracted considerable attention due to beneficial geometric effects such as directional charge transport and orthogonal electron-hole separation. Among them, due to the ease of manufacture and control, the morphology of TiO 2 NTs has been studied intensively. Compared with TiO 2 nanoparticle TiO 2 nanotube arrays, it has large specific surface area, high surface energy, easy recycling and load of electrons and holes. The advantage is lower. However, TiO 2 nanotube arrays still have some disadvantages, which limits its application in many aspects. For example, (1) TiO 2 has a wide band gap (3.2 eV for anatase and 3.0 eV for rutile), and can only absorb 3-5% of solar energy (λ < 387 nm), and the utilization rate is low; The recombination rate of photogenerated electron-hole pairs in TiO2 nanotubes is still high and the photocatalytic activity is low.
发明内容Summary of the invention
本发明目的是提供一种硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法，解决上述问题。The object of the present invention is to provide a method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure, which solves the above problems.
本发明的技术方案是：The technical solution of the present invention is:
一种硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法，该方法包括如下步骤：A method for preparing a strontium sulfide modified gold nanoparticle/titanium dioxide nanotube structure, the method comprising the following steps:
选择基底，对所述基底预处理；Selecting a substrate to pretreat the substrate;
两次阳极氧化法在所述基底上制备TiO
2纳米管阵列；
Preparing a TiO 2 nanotube array on the substrate by two anodization methods;
通过还原获得金颗粒；Obtaining gold particles by reduction;
配制硫化铋和金颗粒复合溶液；Formulating a composite solution of strontium sulfide and gold particles;
将所述TiO
2纳米管阵列放入所述硫化铋和金颗粒复合溶液中，通过烘箱法制得硫化铋修饰金纳米颗粒/二氧化钛纳米管结构。
The TiO 2 nanotube array is placed in the composite solution of strontium sulfide and gold particles, and the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure is obtained by an oven method.
进一步的，所述基底为钛片，所述钛片为纯钛或者钛合金，所述基底预处理为依次采用稀硝酸、丙酮、乙醇和去离子水超声清洗所述基底20-40min。Further, the substrate is a titanium sheet, the titanium sheet is pure titanium or a titanium alloy, and the substrate is pretreated to ultrasonically clean the substrate with dilute nitric acid, acetone, ethanol and deionized water for 20-40 min.
进一步的，所述两次阳极氧化法在所述基底上制备TiO
2纳米管阵列具体包括：以经过预处理的基底作为阳极，铂片作为阴极，同时插入电解液中进行两次阳极氧化，阳极氧化制得初级TiO
2纳米管阵列，将所述初级TiO
2纳米管阵列煅烧获得锐钛矿型TiO
2纳米管阵列。
Further, the preparation of the TiO 2 nanotube array on the substrate by the two anodizing methods specifically comprises: using a pretreated substrate as an anode, a platinum sheet as a cathode, and simultaneously inserting an electrolyte into the anode for two anodization, the anode Oxidation produces a primary TiO 2 nanotube array, and the primary TiO 2 nanotube array is calcined to obtain an anatase TiO 2 nanotube array.
进一步的，所述电解液为氟化铵和水的乙二醇溶液，所述乙二醇溶液中，氟化铵的质量百分比浓度为0.2-0.8wt％，水的体积百分比浓度为2.0-4.0v％，所述两次阳极氧化中，在进行第一次阳极氧化时的电压为40-60V，时间为1-3h，在进行第二次阳极氧化时的电压为40-60V，时间为3-10min，所述煅烧的温度为400-500℃，煅烧的时间为1-3h，煅烧的升温和降温速率均为3-8℃/min。Further, the electrolyte is an ethylene glycol solution of ammonium fluoride and water. In the ethylene glycol solution, the mass percentage concentration of ammonium fluoride is 0.2-0.8 wt%, and the volume percentage concentration of water is 2.0-4.0. v%, in the two anodizations, the voltage during the first anodization is 40-60V, the time is 1-3h, and the voltage during the second anodization is 40-60V, the time is 3 At -10 min, the calcination temperature is 400-500 ° C, the calcination time is 1-3 h, and the calcination heating and cooling rates are both 3-8 ° C / min.
进一步的，所述通过还原获得金颗粒包括：用HAuCl4油浴搅拌，煮沸后加柠檬酸钠，改变时间,得到AuNPs溶液。Further, the obtaining the gold particles by the reduction comprises: stirring with a HAuCl 4 oil bath, adding sodium citrate after boiling, changing the time to obtain a solution of AuNPs.
进一步的，所述配制硫化铋和金颗粒复合溶液包括在AuNPs溶液中加硫代乙酰胺和醋酸铋，放入烘箱中反应，得到硫化铋和金颗粒复合溶液。Further, the preparation of the composite solution of strontium sulfide and gold particles comprises adding thioacetamide and cesium acetate to the AuNPs solution, and reacting in an oven to obtain a composite solution of strontium sulfide and gold particles.
进一步的，所述将所述TiO
2纳米管阵列放入所述硫化铋和金颗粒复合溶液中，通过烘箱法制得硫化铋修饰金纳米颗粒/二氧化钛纳米管结构包括：将所述TiO
2纳米管阵列经前处理后，浸入所述硫化铋和金颗粒复合溶液中，然后放入烘箱中，在37℃的条件下加热4h，得到硫化铋修饰金纳米颗粒/二氧化钛纳米管结构。
Further, the TiO 2 nanotube array is placed in the strontium sulfide and gold particle composite solution, and the strontium sulfide modified gold nanoparticle/titanium dioxide nanotube structure is obtained by an oven method, including: the TiO 2 nanotube After pre-treatment of the array, the array was immersed in the composite solution of strontium sulfide and gold particles, and then placed in an oven and heated at 37 ° C for 4 h to obtain a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure.
上述方式所制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构能够应用于有机染料污染物降解催化剂。The strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in the above manner can be applied to an organic dye pollutant degradation catalyst.
上述方式所制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构还能够应用在复合材料中。The strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in the above manner can also be applied to a composite material.
上述方式所制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构还能够应用于非葡萄糖传感器中。The strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in the above manner can also be applied to a non-glucose sensor.
本发明提供了一种硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法，其所制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构一方面提高了TiO
2纳米管结构的光电效应；另一方面提高二氧化钛纳米管结构的催化能力，以达到在可见光照射下对亚甲基蓝等有机污染物 的降解以及用于制作非酶葡萄糖传感器。与未修饰的TiO
2纳米管比较，硫化铋修饰金纳米颗粒的TiO
2纳米管结构光电性能显著提高，同时具备良好的化学稳定性能和重复利用性。
The invention provides a preparation method of a strontium sulfide modified gold nanoparticle/titanium dioxide nanotube structure, wherein the prepared strontium sulfide modified gold nanoparticle/titanium dioxide nanotube structure improves the photoelectric effect of the TiO 2 nanotube structure on the one hand; On the one hand, the catalytic ability of the titanium dioxide nanotube structure is improved to achieve degradation of organic pollutants such as methylene blue under visible light irradiation and for producing a non-enzymatic glucose sensor. Compared with unmodified TiO 2 nanotubes, the TiO 2 nanotube structure of strontium sulfide modified gold nanoparticles has significantly improved photoelectric properties, and has good chemical stability and recyclability.
为了更清楚地说明本发明实施例的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其它的附图。其中，In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the present invention, Those skilled in the art can also obtain other drawings based on these drawings without paying any inventive labor. among them,
图1为本发明的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法的流程示意图；1 is a schematic flow chart of a method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure of the present invention;
图2为本发明制得的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的SEM图，其中，(a)、(b)、(c)、分别为浸渍硫化铋金纳米颗粒溶液的浓度为0.02％、0.01％、0.005％的硫化铋修饰金纳米颗粒负载二氧化钛纳米管结构的SEM图；2 is an SEM image of a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared by the present invention, wherein (a), (b), and (c) are respectively immersed in a gold sulfide nanoparticle solution having a concentration of 0.02. SEM images of %, 0.01%, 0.005% strontium sulfide modified gold nanoparticles supported titanium dioxide nanotube structures;
图3中a，b为本发明实施例1中制得的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的SEM图，c为实施例1中制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的EDS图，d为实施例1中制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的元素分布图谱；3, a, b are SEM images of the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in Example 1 of the present invention, and c is the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in Example 1. The EDS diagram, d is the elemental distribution map of the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in Example 1;
图4为实施例1中制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的TEM图、HRTEM图和mapping。视图(a)、(b)、(c)为硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的TEM图，视图(d)、(e)为硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的HRTEM图，视图(f)为视图(c)的mapping；4 is a TEM image, HRTEM image, and mapping of the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in Example 1. Views (a), (b), and (c) are TEM images of strontium sulfide-modified gold nanoparticles/titanium dioxide nanotube structures, and views (d) and (e) are HRTEMs of strontium sulfide-modified gold nanoparticles/titanium dioxide nanotube structures. Figure, view (f) is the mapping of view (c);
图5为实施例1中未经修饰的TiO
2纳米管阵列、硫化铋金纳米颗粒修饰的TiO
2纳米管阵列、单纯金颗粒修饰TiO
2纳米管阵列和单纯硫化铋修饰TiO
2的XPS图，其中图(a)为全谱图，图(b)、(c)、(d)为实施例1中制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的金、铋、硫窄谱图；
5 is an XPS diagram of an unmodified TiO 2 nanotube array, a ruthenium sulfide nanoparticle-modified TiO 2 nanotube array, a simple gold particle modified TiO 2 nanotube array, and a simple ruthenium sulfide modified TiO 2 in Example 1. Figure (a) is a full spectrum, and Figures (b), (c) and (d) are narrow, gold, bismuth and sulfur spectra of the strontium sulfide-modified gold nanoparticles/titanium dioxide nanotube structures prepared in Example 1;
图6为实施例1中未经修饰的TiO
2纳米管阵列、不同浓度硫化铋金纳米颗粒修饰的TiO
2纳米管阵列、单纯金颗粒修饰TiO
2纳米管阵列和单纯硫化铋修饰TiO
2的荧光光谱图；
6 is a fluorescence diagram of an unmodified TiO 2 nanotube array, a different concentration of ruthenium sulfide nanoparticle-modified TiO 2 nanotube array, a simple gold particle modified TiO 2 nanotube array, and a simple ruthenium sulfide modified TiO 2 in Example 1. Spectrum;
图7为实施例1中未经修饰的TiO
2纳米管阵列、不同浓度硫化铋修饰金纳米颗粒的TiO
2纳米管阵列、单纯金颗粒修饰TiO
2纳米管阵列和单纯硫化铋修饰TiO
2纳米管阵列的光电流响应图；
7 is unmodified in Example 1 TiO 2 nanotube array embodiment, different concentrations of bismuth sulfide-modified gold nanoparticles TiO 2 nanotube array, pure gold particles modified TiO 2 nanotube array and pure bismuth sulfide nanotubes modified TiO 2 Photocurrent response diagram of the array;
图8为实施例1中经硫化铋金颗粒修饰的TiO
2纳米管阵列对不同浓度葡萄糖溶液的氧化曲线；
8 is an oxidation curve of a TiO 2 nanotube array modified with sulfided gold particles in Example 1 for different concentrations of glucose solution;
图9为实施例1中经硫化铋金颗粒修饰的TiO
2纳米管阵列对不同浓度葡萄糖溶液的响应 阶梯曲线；
9 is a response step curve of a TiO 2 nanotube array modified with sulfided gold particles in Example 1 for different concentrations of glucose solution;
图10为实施例1中硫化铋金颗粒修饰的TiO
2纳米管阵列做非酶葡萄糖传感器时对抗坏血酸、尿酸等的干扰影响阶梯曲线图；
10 is a step graph of interference effects of ascorbic acid, uric acid, etc. in a non-enzymatic glucose sensor of a TiO 2 nanotube array modified with a ruthenium sulfide particle in Example 1;
图11为实施例1中未经修饰的TiO
2纳米管阵列、硫化铋金颗粒修饰的TiO
2纳米管阵列、金修饰TiO
2纳米管阵列和硫化铋修饰的二氧化钛纳米管阵列在紫外光和可见光下降解亚甲基蓝的效率图；视图b，d分别为视图a，c对应样品的紫外吸收波长图。
11 is an unmodified TiO 2 nanotube array, a ruthenium sulfide particle modified TiO 2 nanotube array, a gold modified TiO 2 nanotube array, and a ruthenium sulfide modified TiO 2 nanotube array in Example 1 in ultraviolet light and visible light. The efficiency map for degrading methylene blue; views b, d are the views of the sample, a, c corresponding to the ultraviolet absorption wavelength of the sample.
本发明对二氧化钛纳米管阵进行一系列改性处理来优化它本身的缺点如掺杂金属、非金属以及半导体纳米粒子与TiO
2纳米管阵列结合。为了保持TiO
2极好的电荷转移性能和光腐蚀性，使用窄带隙半导体来使TiO
2NTs易于感光，因此硫族化合物引起重视，最近，对铋基半导体已经引起了相当大的关注。硫化铋(Bi
2S
3)是具有窄带隙(～1.3eV)的光响应半导体，高吸收系数的层状半导体，Bi
2S
3在催化、传感器、光电纳米器件和锂离子电池等领域具有潜在的应用。贵金属纳米颗粒(Ag、Cu、Pt)分散在TiO
2纳米管表面可协助捕获光生电子，加速电子空穴的分离，进而抑制光生电子和空穴复合。在检测葡萄糖方面的应用，具有更优越的催化性能，对于几乎所有的人类历史，黄金因其天然美丽，不变性和独特的延展性和耐久性的平衡而被追捧。Au纳米颗粒的结合也可以作为电子阱，有助于电荷分离，并且由于局部表面等离子共振(LSPR)效应，在可见光下对TiO
2进行敏化。在两个半导体(Bi
2S
3-TiO2)之间添加Au纳米颗粒能够减少陷阱状态俄歇率，并部分补偿表面陷阱位点的负面影响，从而提高光转换效率。
The present invention performs a series of modification treatments on the titanium dioxide nanotube array to optimize its own disadvantages such as doping metal, non-metal, and semiconductor nanoparticles in combination with a TiO 2 nanotube array. TiO 2 in order to maintain the charge transfer performance and excellent light resistance, the use of narrow band gap semiconductor NTs are easy to make the photosensitive TiO 2, so chalcogenide attention recently, bismuth-based semiconductor has attracted considerable attention. Bismuth sulfide (Bi 2 S 3 ) is a photo-responsive semiconductor with a narrow band gap (~1.3eV), a layered semiconductor with high absorption coefficient, and Bi 2 S 3 has potential in the fields of catalysis, sensors, optoelectronic nanodevices and lithium ion batteries. Applications. The dispersion of noble metal nanoparticles (Ag, Cu, Pt) on the surface of TiO 2 nanotubes can assist in the capture of photogenerated electrons, accelerate the separation of electron holes, and inhibit the recombination of photogenerated electrons and holes. For the detection of glucose, it has superior catalytic properties. For almost all human history, gold is sought after for its natural beauty, invariance and unique balance of ductility and durability. The combination of Au nanoparticles can also act as an electron trap, contribute to charge separation, and sensitize TiO 2 under visible light due to local surface plasmon resonance (LSPR) effects. The addition of Au nanoparticles between two semiconductors (Bi 2 S 3 -TiO 2 ) can reduce the trap state Auger rate and partially compensate for the negative effects of surface trap sites, thereby improving the light conversion efficiency.
请参阅图1，图1为本发明的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法的流程示意图。如图1所示，本发明提供一种硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法，包括以下步骤：Please refer to FIG. 1. FIG. 1 is a schematic flow chart of a method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure according to the present invention. As shown in FIG. 1 , the present invention provides a method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure, comprising the following steps:
选择基底，对所述基底预处理；Selecting a substrate to pretreat the substrate;
两次阳极氧化法在所述基底上制备TiO
2纳米管阵列；
Preparing a TiO 2 nanotube array on the substrate by two anodization methods;
通过还原获得金颗粒；Obtaining gold particles by reduction;
配制硫化铋和金颗粒复合溶液；Formulating a composite solution of strontium sulfide and gold particles;
将所述TiO
2纳米管阵列放入所述硫化铋和金颗粒复合溶液中，通过烘箱法制得硫化铋修饰金纳米颗粒/二氧化钛纳米管结构。
The TiO 2 nanotube array is placed in the composite solution of strontium sulfide and gold particles, and the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure is obtained by an oven method.
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合具体实施方式对本发明作进一步详细的说明。The above described objects, features and advantages of the present invention will become more apparent from the detailed description.
一种硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法，包括：A method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure, comprising:
步骤一：基底可选用钛片，先对钛片预处理；Step 1: The substrate may be made of titanium, and the titanium sheet is pretreated;
在一个实施例中，该步骤可以具体如下执行：对钛片进行清洗。其中，所述钛片为纯钛或钛合金，其尺寸为1.5cm×3.0cm。依次采用稀硝酸、丙酮、乙醇和去离子水对钛片超声清洗20-40min。In one embodiment, this step can be performed as follows: the titanium sheet is cleaned. Wherein, the titanium sheet is pure titanium or titanium alloy, and its size is 1.5 cm×3.0 cm. The titanium sheet was ultrasonically cleaned by dilute nitric acid, acetone, ethanol and deionized water for 20-40 min.
步骤二：阳极氧化法制备TiO2纳米管阵列；Step two: preparing an TiO2 nanotube array by anodization;
在一个实施例中，该步骤可以具体如下执行：以清洗后的钛片作为阳极，铂片作为阴极，氟化铵和水的乙二醇溶液中作为电解液，施加一定电压，进行两次阳极氧化，阳极氧化制得TiO
2纳米管阵列，再煅烧以获得晶型更好的锐钛矿型TiO
2纳米管阵列。
In one embodiment, the step may be specifically performed by using a cleaned titanium sheet as an anode, a platinum sheet as a cathode, an ammonium fluoride and water in an ethylene glycol solution as an electrolyte, applying a certain voltage, and performing the anode twice. Oxidation, anodization to obtain a TiO 2 nanotube array, and then calcined to obtain a better crystalline anatase TiO 2 nanotube array.
其中，乙二醇溶液中，氟化铵的质量百分比浓度为0.2-0.8wt％，水的体积百分比浓度为2.0-4.0v％。进行第一次阳极氧化的电压为40-60V，时间为1-3h，第二次阳极氧化的电压为40-60V，时间为3-10min。将制得的TiO
2纳米管阵列在空气中进行煅烧，煅烧的温度为400-500℃，锻烧的时间为1-3h，煅烧的升温和降温速率均为3-8℃/min。通过煅烧，得到晶型更好的锐钛矿型TiO
2纳米管阵列。
Among them, in the ethylene glycol solution, the mass percentage concentration of ammonium fluoride is 0.2-0.8 wt%, and the volume percentage concentration of water is 2.0-4.0 v%. The voltage for the first anodization is 40-60 V for 1-3 h, and the voltage for the second anodization is 40-60 V for 3-10 min. The prepared TiO 2 nanotube array was calcined in air at a calcination temperature of 400-500 ° C, a calcination time of 1-3 h, and a calcination temperature rise and a temperature drop rate of 3-8 ° C/min. By calcination, a more crystalline anatase-type TiO 2 nanotube array is obtained.
步骤三：采用柠檬酸钠还原金颗粒Step 3: Reduction of gold particles with sodium citrate
在一个实施例中，该步骤可以具体如下执行：用HAuCl
4(60ml，0.01wt％、0.02wt％、0.005wt％)，油浴(130℃)搅拌，煮沸后加柠檬酸钠(600ml，1wt％)改变时间(0.5h，1h，1.5h，2h),得到AuNPs溶液。
In one embodiment, this step can be specifically carried out as follows: using HAuCl 4 (60 ml, 0.01 wt%, 0.02 wt%, 0.005 wt%), stirring in an oil bath (130 ° C), boiling and adding sodium citrate (600 ml, 1 wt) %) Change time (0.5 h, 1 h, 1.5 h, 2 h) to obtain AuNPs solution.
步骤四：配制硫化铋和金颗粒的混合溶液；Step 4: preparing a mixed solution of strontium sulfide and gold particles;
在一个实施例中，该步骤可以具体如下执行：AuNPs溶液中加0.003g 400μL硫代乙酰胺和0.0038g 100μL醋酸铋，放入80℃烘箱中反应10h，得到硫化铋和金颗粒的混合溶液。In one embodiment, the step may be specifically carried out by adding 0.003 g of 400 μL of thioacetamide and 0.0038 g of 100 μL of cesium acetate to the AuNPs solution, and reacting in an oven at 80 ° C for 10 hours to obtain a mixed solution of strontium sulfide and gold particles.
步骤五：TiO
2NTs进行前处理；
Step 5: Pretreatment of TiO 2 NTs;
在一个实施例中，该步骤可以具体如下执行：将TiO
2NTs放入MPTs(3-巯丙基三甲氧基硅烷150μL)和NH
4OH(30μL，27％)的15ml乙醇溶液中避光反应24h 25℃，避光方式如用铝箔覆盖。
In one embodiment, this step can be specifically carried out by placing TiO 2 NTs in a solution of MPTs (3-mercaptopropyltrimethoxysilane 150 μL) and NH 4 OH (30 μL, 27%) in 15 ml of ethanol in the dark. 24h 25°C, protected from light by aluminum foil.
步骤六：基于制得的硫化铋和金颗粒混合溶液，将硫化铋和金颗粒负载到TiO2NTs结构上去，制得硫化铋修饰金纳米颗粒/二氧化钛纳米管结构。Step 6: Based on the prepared mixed solution of barium sulfide and gold particles, the barium sulfide and gold particles are loaded onto the structure of TiO2NTs to obtain a structure of barium sulfide modified gold nanoparticles/titanium dioxide nanotubes.
在一个实施例中，该步骤可以具体如下执行：将处理后的钛片(二次阳极氧化后的钛管)浸入金/硫化铋的复合溶液的溶液中，放入37℃烘箱内加热4h，得到硫化铋修饰金纳米颗粒/二氧化钛纳米管结构。In one embodiment, the step may be specifically performed as follows: the treated titanium sheet (the secondary anodized titanium tube) is immersed in a solution of the gold/barium sulfide composite solution, and placed in an oven at 37 ° C for 4 hours. A strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure is obtained.
在上述六个步骤后，完成制作硫化铋修饰金纳米颗粒/二氧化钛纳米管结构。在这六个步 骤后，还可以对结构进行测试。After the above six steps, the structure of the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube was completed. After these six steps, the structure can also be tested.
步骤七：利用制备好的新型光电催化剂进行光催化降解有机染料污染物的性能测试。Step 7: The performance test of photocatalytic degradation of organic dye contaminants by using the prepared novel photocatalyst.
具体地，将未经修饰的TiO
2纳米管阵列、硫化铋金颗粒修饰的TiO
2纳米管阵列、金修饰TiO
2纳米管阵列和硫化铋修饰的二氧化钛纳米管阵列分别浸渍于初始浓度为10mg/L的亚甲基蓝的水溶液中，在黑暗环境中静置0.5小时达到吸附平衡状态后，分别在紫外光和可见光下照射0-120min，时间间隔为30min。每次时间间隔时，测试污染溶液的紫外光谱吸收值。
Specifically, the unmodified TiO 2 nanotube array, the ruthenium sulfide particle modified TiO 2 nanotube array, the gold modified TiO 2 nanotube array, and the yttrium sulfide modified titanium dioxide nanotube array were respectively immersed at an initial concentration of 10 mg/ In an aqueous solution of L methylene blue, after standing for 0.5 hour in a dark environment to reach an equilibrium state of adsorption, it was irradiated for 0-120 min under ultraviolet light and visible light, respectively, at intervals of 30 min. The UV spectral absorbance of the contaminated solution was tested at each time interval.
上述制备好的基底可作为电极使用，可在非酶葡萄糖传感器领域得到广泛应用。The prepared substrate can be used as an electrode and can be widely used in the field of non-enzymatic glucose sensors.
利用制备好的工作电极进行非酶葡萄糖传感器的性能测试。The performance test of the non-enzymatic glucose sensor was performed using the prepared working electrode.
具体地，循环电压为-1V-1V，扫描圈数在5-15圈，扫描速率在20-100mV/S。氧化曲线中，葡萄糖浓度为0-0.05M，干扰性曲线中，葡萄糖滴加浓度为0-10mM，抗坏血酸和尿酸滴加浓度为2mM。Specifically, the cycle voltage is -1V-1V, the number of scanning turns is 5-15 turns, and the scan rate is 20-100 mV/s. In the oxidation curve, the glucose concentration was 0-0.05 M, and in the interference curve, the glucose drop concentration was 0-10 mM, and the ascorbic acid and uric acid drop concentrations were 2 mM.
请参阅图2，图2为本发明制得的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的SEM图，其中，(a)、(b)、(c)分别为浸渍硫化铋金纳米颗粒溶液的浓度为0.02％、0.01％、0.005％的硫化铋修饰金纳米颗粒负载二氧化钛纳米管结构的SEM图。如图2所示，硫化铋修饰金颗粒/二氧化钛纳米管阵列中纳米管管径为80-100nm，管壁厚度为10-20nm，硫化铋修饰的金纳米颗粒粒径为15-20nm，均匀生在二氧化钛纳米管上。Please refer to FIG. 2. FIG. 2 is an SEM image of the structure of the strontium sulfide-modified gold nanoparticles/titanium dioxide nanotubes prepared by the present invention, wherein (a), (b), and (c) are respectively impregnated ruthenium-doped gold nanoparticles solution. SEM images of ruthenium sulfide modified gold nanoparticles supported titanium dioxide nanotubes at concentrations of 0.02%, 0.01%, and 0.005%. As shown in Fig. 2, the diameter of the nanotubes in the ruthenium sulfide modified gold particles/titanium dioxide nanotube array is 80-100 nm, the wall thickness is 10-20 nm, and the size of the ruthenium sulfide-modified gold nanoparticles is 15-20 nm, which is uniform. On titanium dioxide nanotubes.
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图和实施例进一步说明本发明的技术方案。但是本发明不限于所列出的实施例，还应包括在本发明所要求的权利范围内其他任何公知的改变。The above described objects, features and advantages of the present invention will become more apparent from the aspects of the appended claims. However, the invention is not limited to the embodiments shown, but also includes any other known changes within the scope of the claims.
首先，此处所称的“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例，也不是单独的或选择性的与其他实施例互相排斥的实施例。First, "an embodiment" or "an embodiment" as used herein refers to a particular feature, structure, or characteristic that can be included in at least one implementation of the invention. The appearances of the "in one embodiment", "a" or "an"
其次，本发明利用结构示意图等进行详细描述，在详述本发明实施例时，为便于说明，示意图会不依一般比例作局部放大，而且所述示意图只是实例，其在此不应限制本发明保护的范围。此外，在实际制作中应包含长度、宽度及深度的三维空间。The present invention will be described in detail with reference to the accompanying drawings and the like. The scope. In addition, the actual production should include three-dimensional space of length, width and depth.
另外，本发明中所讲的字母简称，均为本领域固定简称，其中部分字母文解释如下：SEM图：电子扫描显像图；TEM图：透射电子扫面显像图；HRTEM图：高分辨率透射电子扫面显像图；EDS图：能谱图；XRD图：X射线衍射图；XPS谱图：X射线光电子能谱分析谱图。In addition, the abbreviations of the letters mentioned in the present invention are fixed abbreviations in the field, and some of the letters are explained as follows: SEM image: electronic scanning image; TEM image: transmission electron scanning image; HRTEM image: high resolution Rate transmission electron scanning imaging; EDS diagram: energy spectrum; XRD pattern: X-ray diffraction pattern; XPS spectrum: X-ray photoelectron spectroscopy spectrum.
实施例1Example 1
本实施案例按如下步骤展示一种硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法：In this embodiment, a preparation method of a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure is demonstrated as follows:
(1)钛片的预处理及二次阳极氧化法制备TiO
2纳米管阵列。对钛片基底用丙酮、无水乙醇、去离子水依次超声清洗15min。以铂片电极为阴极，同时插入含有98v％乙二醇(氟化铵0.3wt％)和2v％水的电解质溶液中，施加50V电压阳极氧化1.5h，超声脱落膜层后，继续施加50V电压阳极氧化6min，制得TiO
2纳米管阵列，再经450℃热处理2h，从无定型状态转变成晶型较好的锐钛矿。
(1) Preparation of TiO 2 nanotube array by pretreatment of titanium sheet and secondary anodization. The titanium substrate was ultrasonically washed with acetone, absolute ethanol and deionized water for 15 min. Taking the platinum plate electrode as the cathode, inserting an electrolyte solution containing 98v% ethylene glycol (0.35% by weight of ammonium fluoride) and 2v% water, anodizing with a voltage of 50V for 1.5h, and after ultrasonically peeling off the film layer, continue to apply 50V voltage. After anodizing for 6 min, a TiO 2 nanotube array was prepared and then heat treated at 450 ° C for 2 h to transform from an amorphous state to a better crystalline anatase.
(2)通过HAuCl
4(0.001g 10ml)油浴搅拌，煮沸后加柠檬酸钠(1g 99g去离子水)反应1-2小时得到AuNPs溶液，50ml的Au NPs溶液中加0.003g 400μL硫代乙酰胺和0.0038g 100μL醋酸铋，放入80℃烘箱反应10h，得到金/硫化铋的复合溶液。将TiO
2NTs放入MPTs(3-巯丙基三甲氧基硅烷150μL)和NH4OH(30μL，27％)的15ml乙醇溶液中用铝箔覆盖24h 25℃。再将浸泡过的钛片放入15ml的金/硫化铋的复合溶液中，反应条件为4h 37℃。最后得到硫化铋修饰金纳米颗粒/二氧化钛纳米管阵列。
(2) Stirring with HAuCl 4 (0.001 g 10 ml) in an oil bath, boiling and adding sodium citrate (1 g of 99 g of deionized water) for 1-2 hours to obtain AuNPs solution, and adding 50 g of Au NPs solution to 0.003 g of 400 μL of thioethane. The amide and 0.0038 g of 100 μL of cesium acetate were placed in an oven at 80 ° C for 10 hours to obtain a gold/ruthenium sulfide composite solution. TiO 2 NTs were placed in a solution of MPTs (3-mercaptopropyltrimethoxysilane 150 μL) and NH 4 OH (30 μL, 27%) in 15 ml of ethanol and covered with aluminum foil for 24 h at 25 °C. The soaked titanium piece was placed in a 15 ml solution of gold/barium sulfide in a reaction solution of 4 h at 37 °C. Finally, a strontium sulfide modified gold nanoparticle/titanium dioxide nanotube array was obtained.
(3)对制备好的硫化铋修饰金颗粒/二氧化钛纳米管阵列作光电及测试：配置0.1M的亚硫酸钠做支持电解液，硫化铋修饰金颗粒/二氧化钛纳米管阵列作工作电极，铂片作对电极，银/氯化银作参比电极，利用电化学工作站的计时电位法检测光电级相应，其中有无光照时间间隔为30s。(3) Photoelectric and test for prepared ruthenium sulfide modified gold particles/titanium dioxide nanotube array: 0.1M sodium sulfite was used as supporting electrolyte, strontium sulfide modified gold particles/titanium dioxide nanotube array was used as working electrode, and platinum plate was used as counter electrode. Silver/silver chloride was used as the reference electrode, and the photoelectric potential level was detected by the chronopotentiometry of the electrochemical workstation, and the time interval between the illumination and the illumination was 30 s.
(4)对制备好的硫化铋修饰金颗粒/二氧化钛纳米管阵列作光催化降解有机污染物的应用：将未经修饰的TiO
2纳米管阵列、硫化铋金颗粒修饰的TiO
2纳米管阵列、金修饰TiO
2纳米管阵列和硫化铋修饰的二氧化钛纳米管阵列分别浸渍于初始浓度为10mg/L的亚甲基蓝，首先在黑暗环境中静置0.5小时达到吸附平衡状态后，分别在紫外光和可见光下照射0-120min。时间间隔分别为30min。每个时间间隔，取对应溶液测试紫外光谱吸收值。
(4) prepared bismuth sulfide particles modified with the gold / titania nanotube arrays for photocatalytic degradation of organic pollutants applications: the unmodified TiO 2 nanotube array, bismuth sulfide gold particles modified TiO 2 nanotube array, The gold-modified TiO 2 nanotube array and the ruthenium sulfide-modified TiO 2 nanotube array were respectively immersed in methylene blue at an initial concentration of 10 mg/L, and first allowed to stand in a dark environment for 0.5 hour to reach an equilibrium state of adsorption, respectively under ultraviolet light and visible light. Irradiation 0-120 min. The time interval is 30 min. At each time interval, the corresponding solution was tested for UV absorbance.
(5)对制备好的硫化铋修饰金颗粒/二氧化钛纳米管阵列作非酶葡萄糖传感器应用：配置0.1M的氢氧化钠溶液做支持电解液，硫化铋修饰金颗粒/二氧化钛纳米管阵列作工作电极，铂片作对电极，银/氯化银作参比电极，利用电化学工作站的循环伏安曲线检测葡萄糖，其中葡萄糖依次添加浓度5mM，进一步地，电极性能干扰性检测，测试制备电极对抗坏血酸、尿酸的干扰性，其中葡萄糖添加浓度为2-10mM，尿酸、抗坏血酸添加浓度为2mM。(5) Application of prepared non-enzymatic glucose sensor for strontium sulfide modified gold particles/titanium dioxide nanotube array: 0.1M sodium hydroxide solution is used as supporting electrolyte, strontium sulfide modified gold particles/titanium dioxide nanotube array is used as working electrode The platinum plate is used as the counter electrode, and the silver/silver chloride is used as the reference electrode. The glucose is detected by the cyclic voltammetry curve of the electrochemical workstation, wherein the glucose is sequentially added with a concentration of 5 mM, and further, the electrode performance interference detection is performed, and the electrode is tested for ascorbic acid. The interference of uric acid, wherein the glucose addition concentration is 2-10 mM, and the concentration of uric acid and ascorbic acid is 2 mM.
上述实施例所制得的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构具体结论如下：The specific conclusions of the structure of the strontium sulfide-modified gold nanoparticles/titanium dioxide nanotubes prepared in the above examples are as follows:
请参阅图2，图2为本发明制得的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的SEM图，其中，(a)、(b)、(c)分别为浸渍硫化铋金纳米颗粒溶液的浓度为0.02％、0.01％、0.005％的硫化铋修饰金纳米颗粒负载二氧化钛纳米管结构的SEM图。从图2可知，15-20nm的硫化铋修饰金纳米颗粒均匀地沉积在纳米管表面和内部。Please refer to FIG. 2. FIG. 2 is an SEM image of the structure of the strontium sulfide-modified gold nanoparticles/titanium dioxide nanotubes prepared by the present invention, wherein (a), (b), and (c) are respectively impregnated ruthenium-doped gold nanoparticles solution. SEM images of ruthenium sulfide modified gold nanoparticles supported titanium dioxide nanotubes at concentrations of 0.02%, 0.01%, and 0.005%. As can be seen from Fig. 2, 15-20 nm of barium sulfide-modified gold nanoparticles are uniformly deposited on the surface and inside of the nanotube.
请参阅图3，图3中a，b为本发明实施例1中制得的硫化铋修饰金纳米颗粒/二氧化钛纳 米管结构的SEM图，c为实施例1中制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的EDS图，d为实施例1中制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的元素分布图谱。如图3所示，硫化铋修饰金颗粒/二氧化钛纳米管结构主要含有Ti、O、S、Bi和Au元素。Referring to FIG. 3, a, b of FIG. 3 is an SEM image of a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in Example 1 of the present invention, and c is a strontium sulfide-modified gold nanoparticle prepared in Example 1. / EDS map of titanium dioxide nanotube structure, d is the elemental distribution map of the ruthenium sulfide modified gold nanoparticle / titanium dioxide nanotube structure prepared in Example 1. As shown in FIG. 3, the strontium sulfide-modified gold particle/titanium dioxide nanotube structure mainly contains Ti, O, S, Bi, and Au elements.
请参阅图4，图4为实施例1中制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的TEM图、HRTEM图和mapping。视图(a)、(b)、(c)为硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的TEM图，视图(d)、(e)为硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的HRTEM图，视图(f)为视图(c)的mapping。图4进一步表明硫化铋修饰的金纳米颗粒均匀分布在TiO
2纳米管表面和内部，颗粒尺寸大约为15nm；HRTEM和SAED图显示TiO
2锐钛矿型(101)晶面晶格间距为0.352nm，金(111)晶面间距为0.23nm，硫化铋(221)的晶面间距为0.286nm,与图4的XRD测试结果相吻合。
Please refer to FIG. 4. FIG. 4 is a TEM image, HRTEM image, and mapping of the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared in Example 1. Views (a), (b), and (c) are TEM images of strontium sulfide-modified gold nanoparticles/titanium dioxide nanotube structures, and views (d) and (e) are HRTEMs of strontium sulfide-modified gold nanoparticles/titanium dioxide nanotube structures. Figure, view (f) is the mapping of view (c). Figure 4 further shows that the strontium sulfide-modified gold nanoparticles are uniformly distributed on the surface and inside of the TiO 2 nanotubes with a particle size of about 15 nm; the HRTEM and SAED images show that the TiO 2 anatase (101) crystal lattice spacing is 0.352 nm. The spacing of the gold (111) plane is 0.23 nm, and the interplanar spacing of ruthenium sulfide (221) is 0.286 nm, which is in agreement with the XRD test results of FIG.
请参阅图5，图5为实施例1中未经修饰的TiO
2纳米管阵列、硫化铋金纳米颗粒修饰的TiO
2纳米管阵列、单纯金颗粒修饰TiO2纳米管阵列和单纯硫化铋修饰TiO
2的XPS图，其中图(a)为全谱图，图(b)、(c)、(d)为实施例1中制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的金、铋、硫窄谱图。如图5所示，除了O 1s(530.3eV),Ti 2p(458.3eV、464.2ev)和C 1s(283.8eV)峰，Bi 4f和S 2p和Au 4f峰的存在证明了硫化铋修饰金纳米颗粒/二氧化钛纳米管阵列。从Bi 4f和S 2p的高分辨XPS图谱c和d中可看出，Bi 4f
5/2(158.0eV)和Bi 4f
7/2(162.6eV)及S 2p
3/2(158.0eV)和S 2p
1/2(163.2eV)，证明硫化铋的存在，Au 4f
7/2(83.9eV)和Au 4f
5/2(87.3eV)能量间隙为3.4eV证明了金单质的存在。
Please refer to FIG. 5. FIG. 5 is an unmodified TiO 2 nanotube array, a ruthenium sulfide nanoparticle modified TiO 2 nanotube array, a simple gold particle modified TiO 2 nanotube array, and a simple ruthenium sulfide modified TiO 2 in Example 1. XPS diagram, wherein (a) is a full spectrum, and (b), (c), (d) are gold, antimony, sulfur of the strontium sulfide-modified gold nanoparticles/titanium dioxide nanotube structure prepared in Example 1. Narrow spectrum. As shown in Fig. 5, in addition to O 1s (530.3 eV), Ti 2p (458.3 eV, 464.2 ev) and C 1s (283.8 eV) peaks, the presence of Bi 4f and S 2p and Au 4f peaks proves that ruthenium sulfide-modified gold nanoparticles Particle/titanium dioxide nanotube array. It can be seen from the high-resolution XPS spectra c and d of Bi 4f and S 2p that Bi 4f 5/2 (158.0 eV) and Bi 4f 7/2 (162.6 eV) and S 2p 3/2 (158.0 eV) and S 2p 1/2 (163.2 eV), demonstrating the presence of strontium sulfide, Au 4f 7/2 (83.9 eV) and Au 4f 5/2 (87.3 eV) with an energy gap of 3.4 eV demonstrates the presence of gold.
请参阅图6，图6为实施例1中未经修饰的TiO
2纳米管阵列、不同浓度硫化铋金纳米颗粒修饰的TiO
2纳米管阵列、单纯金颗粒修饰TiO
2纳米管阵列和单纯硫化铋修饰TiO
2的荧光光谱图。如图6所示，未经修饰的TiO
2纳米管阵的荧光强度最高，通过负载Bi
2S
3和Au后，荧光强度降低，进一步说明阻碍了自由电子和空穴的重组。
Refer to FIG. 6, FIG. 6 is unmodified in Example 1 TiO 2 nanotube array embodiment, different concentrations of bismuth sulfide-modified gold nanoparticles TiO 2 nanotube array, pure gold particles modified TiO 2 nanotube array and pure bismuth sulfide Fluorescence spectrum of modified TiO 2 . As shown in Fig. 6, the unmodified TiO 2 nanotube array has the highest fluorescence intensity, and the fluorescence intensity decreases after loading Bi 2 S 3 and Au, further indicating that the recombination of free electrons and holes is hindered.
请参阅图7，图7为实施例1中未经修饰的TiO
2纳米管阵列、不同浓度硫化铋修饰金纳米颗粒的TiO
2纳米管阵列、单纯金颗粒修饰TiO
2纳米管阵列和单纯硫化铋修饰TiO
2纳米管阵列的光电流响应图，由图可知0.01％Au/Bi
2S
3@TiO
2的光电流最好，增加载流子分离效率，抑制电子空穴对的重组。
Please refer to FIG. 7, FIG. 7 in Example 1 is an unmodified TiO 2 nanotube array embodiment, different concentrations of bismuth sulfide-modified gold nanoparticles TiO 2 nanotube array, pure gold particles modified TiO 2 nanotube array and pure bismuth sulfide The photocurrent response diagram of the modified TiO 2 nanotube array shows that the photocurrent of 0.01% Au/Bi 2 S 3 @TiO 2 is the best, the carrier separation efficiency is increased, and the recombination of electron-hole pairs is suppressed.
请参阅图8，如图8所示，以0.1M的氢氧化钠溶液为支持电解液，硫化铋修饰金颗粒/二氧化钛纳米管阵列在不同浓度葡萄糖的氢氧化钠溶液中的氧化曲线，其中-0.23V左右的峰为电极表面吸附葡萄糖的电化学氧化，0.1V左右的峰是电极表面吸附葡萄糖电化学氧化过程中产生的中间体的进一步氧化。0.45V左右的峰为溶液体相中的葡萄糖扩散至电极上进行直接氧化引起的。随着葡萄糖浓度的不断增大，峰值也逐渐增大。Please refer to FIG. 8. As shown in FIG. 8, the oxidation curve of the ruthenium sulfide modified gold particle/titanium dioxide nanotube array in a sodium hydroxide solution of different concentrations of glucose is supported by a 0.1 M sodium hydroxide solution as a supporting electrolyte, wherein - The peak of about 0.23V is the electrochemical oxidation of glucose adsorbed on the surface of the electrode, and the peak of about 0.1V is the further oxidation of the intermediate produced during the electrochemical oxidation of glucose on the surface of the electrode. A peak of about 0.45 V is caused by the direct oxidation of glucose in the solution phase to the electrode. As the glucose concentration continues to increase, the peak value also increases.
请参阅图9，图9为实施例1中经硫化铋金颗粒修饰的TiO
2纳米管阵列对不同浓度葡萄糖溶液的响应阶梯曲线，每隔25秒注射2ml葡萄糖溶液。从图中可知，一加入葡萄糖溶液，电流值会变小，随着时间的增加，呈阶梯状，说明此电极对葡萄糖浓度响应较敏锐。
Please refer to FIG. 9. FIG. 9 is a response step curve of the TiO 2 nanotube array modified by the sulfided gold particles in Example 1 for different concentrations of glucose solution, and 2 ml of the glucose solution is injected every 25 seconds. It can be seen from the figure that as soon as the glucose solution is added, the current value will become smaller, and as the time increases, it is stepped, indicating that the electrode is more sensitive to the glucose concentration.
请参阅图10，图10为实施例1中硫化铋金颗粒修饰的TiO
2纳米管阵列做非酶葡萄糖传感器时对抗坏血酸、尿酸等的干扰影响阶梯曲线图。从图11中可以看出，葡萄糖对电流密度的影响率为100％，抗坏血酸对电流密度的影响率为40％左右，尿酸对电流密度的影响率为30％左右。
Please refer to FIG. 10. FIG. 10 is a graph showing the influence of interference effects of ascorbic acid and uric acid on the non-enzymatic glucose sensor of the TiO 2 nanotube array modified by the ruthenium sulfide particles in Example 1. It can be seen from Fig. 11 that the influence rate of glucose on current density is 100%, the influence rate of ascorbic acid on current density is about 40%, and the influence rate of uric acid on current density is about 30%.
请参阅图11，图11a、c分别为实施例1中在紫外光和可见光下未经修饰的TiO
2纳米管阵列、硫化铋金颗粒修饰的TiO
2纳米管阵列、金修饰TiO
2纳米管阵列和硫化铋修饰的二氧化钛纳米管阵列在紫外光和可见光下降解亚甲基蓝的效率图；视图b，d分别为视图a，c对应的硫化铋修饰金颗粒/二氧化钛纳米管阵列的紫外吸收波长图。图a为在紫外光照射下的降解亚甲基蓝效率图，Au/Bi
2S
3@TiO
2降解效果最好为30％左右，图c为在可见光照射下降解亚甲基蓝的效率图，Au/Bi
2S
3@TiO
2降解效果最好为40％左右。
Please refer to FIG. 11. FIG. 11a and FIG. 1 are respectively an unmodified TiO 2 nanotube array under ultraviolet light and visible light, a ruthenium sulfide particle modified TiO 2 nanotube array, and a gold modified TiO 2 nanotube array in Example 1. And the efficiency of degrading methylene blue in the ultraviolet and visible light of the yttria-modified titanium dioxide nanotube array; the views b and d are the ultraviolet absorption wavelengths of the yttrium sulfide modified gold particles/titanium dioxide nanotube array corresponding to the views a and c, respectively. Figure a is the efficiency diagram of degradation of methylene blue under ultraviolet light irradiation. The degradation effect of Au/Bi 2 S 3 @TiO 2 is preferably about 30%. Figure c is the efficiency diagram of degradation of methylene blue under visible light irradiation, Au/Bi 2 S The degradation effect of 3 @TiO 2 is preferably about 40%.
实施例2Example 2
本实施案例按如下步骤展示一种硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法：In this embodiment, a preparation method of a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure is demonstrated as follows:
(1)钛片的预处理及二次阳极氧化法制备TiO
2纳米管阵列。对钛片基底用丙酮、无水乙醇、去离子水依次超声清洗15min。以铂片电极为阴极，同时插入含有97v％乙二醇(氟化铵0.4wt％)和3v％水的电解质溶液中，施加40V电压阳极氧化1h，超声脱落膜层后，继续施加40V电压阳极氧化8min，制得TiO
2纳米管阵列，再经450℃热处理2h，从无定型状态转变成晶型较好的锐钛矿。
(1) Preparation of TiO 2 nanotube array by pretreatment of titanium sheet and secondary anodization. The titanium substrate was ultrasonically washed with acetone, absolute ethanol and deionized water for 15 min. Taking the platinum plate electrode as the cathode, inserting an electrolyte solution containing 97v% ethylene glycol (ammonium fluoride 0.4wt%) and 3v% water, anodizing with a voltage of 40V for 1h, and after ultrasonically peeling off the film layer, continue to apply a voltage of 40V anode. After oxidation for 8 min, the TiO 2 nanotube array was prepared and then heat treated at 450 ° C for 2 h to transform from an amorphous state to a better crystalline anatase.
(2)通过HAuCl
4(0.002g 10ml)油浴搅拌，煮沸后加柠檬酸钠(1g 99g去离子水)反应1-2小时得到AuNPs溶液，50ml的AuNPs溶液中加0.003g 400μL硫代乙酰胺和0.0038g 100μL醋酸铋，放入80℃烘箱反应10h，得到金/硫化铋的复合溶液。将TiO
2NTs放入MPTs(3-巯丙基三甲氧基硅烷150μL)和NH
4OH(30μL，27％)的15ml乙醇溶液中用铝箔覆盖24h 25℃。再将浸泡过的钛片放入15ml的金/硫化铋的复合溶液中，反应条件为4h 37℃。最后得到硫化铋修饰金纳米颗粒/二氧化钛纳米管阵列。
(2) Stir in HAuCl 4 (0.002g 10ml) oil bath, boil and add sodium citrate (1g 99g deionized water) for 1-2 hours to obtain AuNPs solution, add 0.003g of 400μL thioacetamide to 50ml of AuNPs solution. And 0.0038 g of 100 μL of cesium acetate was placed in an oven at 80 ° C for 10 hours to obtain a gold/ruthenium sulfide composite solution. TiO 2 NTs were placed in a solution of MPTs (3-mercaptopropyltrimethoxysilane 150 μL) and NH 4 OH (30 μL, 27%) in 15 ml of ethanol and covered with aluminum foil for 24 h at 25 °C. The soaked titanium piece was placed in a 15 ml solution of gold/barium sulfide in a reaction solution of 4 h at 37 °C. Finally, a strontium sulfide modified gold nanoparticle/titanium dioxide nanotube array was obtained.
(3)对制备好的硫化铋修饰金颗粒/二氧化钛纳米管阵列作光电及测试：配置0.1M的亚硫酸钠做支持电解液，硫化铋修饰金颗粒/二氧化钛纳米管阵列作工作电极，铂片作对电极，银/氯化银作参比电极，利用电化学工作站的计时电位法检测光电级相应，其中有无光照时间间隔为30s。(3) Photoelectric and test for prepared ruthenium sulfide modified gold particles/titanium dioxide nanotube array: 0.1M sodium sulfite was used as supporting electrolyte, strontium sulfide modified gold particles/titanium dioxide nanotube array was used as working electrode, and platinum plate was used as counter electrode. Silver/silver chloride was used as the reference electrode, and the photoelectric potential level was detected by the chronopotentiometry of the electrochemical workstation, and the time interval between the illumination and the illumination was 30 s.
(4)对制备好的硫化铋修饰金颗粒/二氧化钛纳米管阵列作光催化降解有机污染物的应用：将未经修饰的TiO
2纳米管阵列、硫化铋金颗粒修饰的TiO
2纳米管阵列、金修饰TiO
2纳米管阵列和硫化铋修饰的二氧化钛纳米管阵列分别浸渍于初始浓度为10mg/L的亚甲基蓝，首先在黑暗环境中静置1小时达到吸附平衡状态后，分别在紫外光和可见光下照射0-120min。时间间隔分别为30min。每个时间间隔，取对应溶液测试紫外光谱吸收值。
(4) prepared bismuth sulfide particles modified with the gold / titania nanotube arrays for photocatalytic degradation of organic pollutants applications: the unmodified TiO 2 nanotube array, bismuth sulfide gold particles modified TiO 2 nanotube array, The gold-modified TiO 2 nanotube array and the yttrium sulfide-modified TiO 2 nanotube array were respectively immersed in methylene blue at an initial concentration of 10 mg/L, and first allowed to stand in a dark environment for 1 hour to reach an equilibrium state of adsorption, respectively under ultraviolet light and visible light. Irradiation 0-120 min. The time interval is 30 min. At each time interval, the corresponding solution was tested for UV absorbance.
(5)对制备好的硫化铋修饰金颗粒/二氧化钛纳米管阵列作非酶葡萄糖传感器应用：配置0.1M的氢氧化钠溶液做支持电解液，硫化铋修饰金颗粒/二氧化钛纳米管阵列作工作电极，铂片作对电极，银/氯化银作参比电极，利用电化学工作站的循环伏安曲线检测葡萄糖，其中葡萄糖依次添加浓度10mM，进一步地，电极性能干扰性检测，测试制备电极对抗坏血酸、尿酸的干扰性，其中葡萄糖添加浓度为5-10mM，尿酸、抗坏血酸添加浓度为5mM。(5) Application of prepared non-enzymatic glucose sensor for strontium sulfide modified gold particles/titanium dioxide nanotube array: 0.1M sodium hydroxide solution is used as supporting electrolyte, strontium sulfide modified gold particles/titanium dioxide nanotube array is used as working electrode The platinum plate is used as the counter electrode, and the silver/silver chloride is used as the reference electrode. The glucose is detected by the cyclic voltammetry curve of the electrochemical workstation, wherein the glucose is sequentially added with a concentration of 10 mM, and further, the electrode performance interference detection is performed, and the electrode is tested for ascorbic acid. The interference of uric acid, wherein the concentration of glucose added is 5-10 mM, and the concentration of uric acid and ascorbic acid is 5 mM.
实施例3Example 3
本实施案例按如下步骤展示一种硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法：In this embodiment, a preparation method of a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure is demonstrated as follows:
(1)钛片的预处理及二次阳极氧化法制备TiO
2纳米管阵列。对纯钛片基底用稀硝酸、丙酮、无水乙醇、去离子水依次超声清洗25min。以铂片电极为阴极，同时插入含有99v％乙二醇(氟化铵0.1wt％)和1v％水的电解质溶液中，施加60V电压阳极氧化1小时，超声脱落膜层后，继续施加60V电压阳极氧化5min，制得TiO
2纳米管阵列，再450℃煅烧1h，使其从无定型状态转变成锐钛矿。
(1) Preparation of TiO 2 nanotube array by pretreatment of titanium sheet and secondary anodization. The pure titanium substrate was ultrasonically washed with dilute nitric acid, acetone, absolute ethanol and deionized water for 25 min. Taking the platinum plate electrode as the cathode, inserting an electrolyte solution containing 99v% ethylene glycol (0.15% by weight of ammonium fluoride) and 1v% water, anodizing with a voltage of 60V for 1 hour, and after ultrasonically peeling off the film layer, continue to apply 60V voltage. After anodizing for 5 min, an array of TiO 2 nanotubes was prepared and calcined at 450 ° C for 1 h to convert it from an amorphous state to anatase.
(2)通过HAuCl
4(0.0005g 10ml)油浴搅拌，煮沸后加柠檬酸钠(1g 99g去离子水)反应1-2小时得到AuNPs溶液，50ml的Au NPs溶液中加0.003g 400μL硫代乙酰胺和0.0038g 100μL醋酸铋，放入80℃烘箱反应10h，得到金/硫化铋的复合溶液。将TiO
2NTs放入MPTs(3-巯丙基三甲氧基硅烷150μL)和NH
4OH(30μL，27％)的15ml乙醇溶液中用铝箔覆盖24h 25℃。再将浸泡过的钛片放入15ml的金/硫化铋的复合溶液中，反应条件为4h 37℃。最后得到硫化铋修饰金纳米颗粒/二氧化钛纳米管阵列。
(2) Stir in HAuCl 4 (0.0005g 10ml) oil bath, boil and add sodium citrate (1g 99g deionized water) for 1-2 hours to obtain AuNPs solution, add 50g of Au NPs solution to add 0.003g 400μL thioethane The amide and 0.0038 g of 100 μL of cesium acetate were placed in an oven at 80 ° C for 10 hours to obtain a gold/ruthenium sulfide composite solution. TiO 2 NTs were placed in a solution of MPTs (3-mercaptopropyltrimethoxysilane 150 μL) and NH 4 OH (30 μL, 27%) in 15 ml of ethanol and covered with aluminum foil for 24 h at 25 °C. The soaked titanium piece was placed in a 15 ml solution of gold/barium sulfide in a reaction solution of 4 h at 37 °C. Finally, a strontium sulfide modified gold nanoparticle/titanium dioxide nanotube array was obtained.
(3)对制备好的硫化铋修饰金颗粒/二氧化钛纳米管阵列作光电及测试：配置0.1M的亚硫酸钠做支持电解液，硫化铋修饰金颗粒/二氧化钛纳米管阵列作工作电极，铂片作对电极，银/氯化银作参比电极，利用电化学工作站的计时电位法检测光电级相应，其中有无光照时间间隔为30s。(3) Photoelectric and test for prepared ruthenium sulfide modified gold particles/titanium dioxide nanotube array: 0.1M sodium sulfite was used as supporting electrolyte, strontium sulfide modified gold particles/titanium dioxide nanotube array was used as working electrode, and platinum plate was used as counter electrode. Silver/silver chloride was used as the reference electrode, and the photoelectric potential level was detected by the chronopotentiometry of the electrochemical workstation, and the time interval between the illumination and the illumination was 30 s.
(4)对制备好的硫化铋修饰金颗粒/二氧化钛纳米管阵列作光催化降解有机污染物的应用：将未经修饰的TiO
2纳米管阵列、硫化铋金颗粒修饰的TiO
2纳米管阵列、金修饰TiO
2纳米管阵列和硫化铋修饰的二氧化钛纳米管阵列分别浸渍于初始浓度为10mg/L的亚甲基蓝， 首先在黑暗环境中静置1小时达到吸附平衡状态后，分别在紫外光和可见光下照射0-120min。时间间隔分别为30min。每个时间间隔，取对应溶液测试紫外光谱吸收值。
(4) prepared bismuth sulfide particles modified with the gold / titania nanotube arrays for photocatalytic degradation of organic pollutants applications: the unmodified TiO 2 nanotube array, bismuth sulfide gold particles modified TiO 2 nanotube array, The gold-modified TiO 2 nanotube array and the ruthenium sulfide-modified TiO 2 nanotube array were respectively immersed in methylene blue at an initial concentration of 10 mg/L, and first allowed to stand in a dark environment for 1 hour to reach an equilibrium state of adsorption, respectively under ultraviolet light and visible light. Irradiation 0-120 min. The time interval is 30 min. At each time interval, the corresponding solution was tested for UV absorbance.
(5)对制备好的硫化铋修饰金颗粒/二氧化钛纳米管阵列作非酶葡萄糖传感器应用：配置0.1M的氢氧化钠溶液做支持电解液，硫化铋修饰金颗粒/二氧化钛纳米管阵列作工作电极，铂片作对电极，银/氯化银作参比电极，利用电化学工作站的循环伏安曲线检测葡萄糖，其中葡萄糖依次添加浓度3mM，进一步地，电极性能干扰性检测，测试制备电极对抗坏血酸、尿酸的干扰性，其中葡萄糖添加浓度为1-5mM，尿酸、抗坏血酸添加浓度为1mM。(5) Application of prepared non-enzymatic glucose sensor for strontium sulfide modified gold particles/titanium dioxide nanotube array: 0.1M sodium hydroxide solution is used as supporting electrolyte, strontium sulfide modified gold particles/titanium dioxide nanotube array is used as working electrode The platinum plate is used as the counter electrode, and the silver/silver chloride is used as the reference electrode. The glucose is detected by the cyclic voltammetry curve of the electrochemical workstation, wherein the glucose is sequentially added with a concentration of 3 mM, and further, the electrode performance interference detection is performed, and the electrode is tested for ascorbic acid. The interference of uric acid, wherein the glucose addition concentration is 1-5 mM, and the concentration of uric acid and ascorbic acid is 1 mM.
与现有技术相比，本发明的有益效果是：本发明的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构一方面提高了TiO
2纳米管阵列的光电效应；另一方面提高二氧化钛纳米管阵列的催化能力，以达到在可见光照射下对亚甲基蓝等有机污染物的降解以及用于制作非酶葡萄糖传感器。与未修饰的TiO
2纳米管比较，硫化铋修饰金纳米颗粒的TiO
2纳米管结构光电性能显著提高，同时具备良好的化学稳定性能和重复利用性。
Compared with the prior art, the beneficial effects of the present invention are: the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure of the invention improves the photoelectric effect of the TiO 2 nanotube array on the one hand, and improves the titanium dioxide nanotube array on the other hand. Catalytic ability to achieve degradation of organic contaminants such as methylene blue under visible light illumination and for the production of non-enzymatic glucose sensors. Compared with unmodified TiO 2 nanotubes, the TiO 2 nanotube structure of strontium sulfide modified gold nanoparticles has significantly improved photoelectric properties, and has good chemical stability and recyclability.
应说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，其均应涵盖在本发明的权利要求范围当中。It should be noted that the above embodiments are only used to explain the technical solutions of the present invention, and the present invention is not limited thereto. Although the present invention is described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention can be Modifications or equivalents are intended to be included within the scope of the appended claims.
Claims (10)
- 硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法，其特征在于，该方法包括如下步骤：A method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure, characterized in that the method comprises the following steps:选择基底，对所述基底预处理；Selecting a substrate to pretreat the substrate;两次阳极氧化法在所述基底上制备TiO 2纳米管阵列； Preparing a TiO 2 nanotube array on the substrate by two anodization methods;通过还原获得金颗粒；Obtaining gold particles by reduction;配制硫化铋和金颗粒复合溶液；Formulating a composite solution of strontium sulfide and gold particles;将所述TiO 2纳米管阵列放入所述硫化铋和金颗粒复合溶液中，通过烘箱法制得硫化铋修饰金纳米颗粒/二氧化钛纳米管结构。 The TiO 2 nanotube array is placed in the composite solution of strontium sulfide and gold particles, and the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure is obtained by an oven method.
- 根据权利要求1所述的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法，其特征在于：所述基底为钛片，所述钛片为纯钛或者钛合金，所述基底预处理为依次采用稀硝酸、丙酮、乙醇和去离子水超声清洗所述基底20-40min。The method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure according to claim 1, wherein the substrate is a titanium sheet, the titanium sheet is pure titanium or a titanium alloy, and the substrate is pretreated The substrate was ultrasonically washed with dilute nitric acid, acetone, ethanol and deionized water in sequence for 20-40 min.
- 根据权利要求1所述的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法，其特征在于，所述两次阳极氧化法在所述基底上制备TiO 2纳米管阵列具体包括：以经过预处理的基底作为阳极，铂片作为阴极，同时插入电解液中进行两次阳极氧化，阳极氧化制得初级TiO 2纳米管阵列，将所述初级TiO 2纳米管阵列煅烧获得锐钛矿型TiO 2纳米管阵列。 The method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure according to claim 1, wherein the anodic oxidation method for preparing a TiO 2 nanotube array on the substrate comprises: The treated substrate serves as an anode, the platinum plate serves as a cathode, and is simultaneously inserted into the electrolytic solution for two anodization, anodizing to obtain a primary TiO 2 nanotube array, and the primary TiO 2 nanotube array is calcined to obtain anatase TiO 2 . Nanotube array.
- 根据权利要求3所述的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法，其特征在于：所述电解液为氟化铵和水的乙二醇溶液，所述乙二醇溶液中，氟化铵的质量百分比浓度为0.2-0.8wt％，水的体积百分比浓度为2.0-4.0v％，所述两次阳极氧化中，在进行第一次阳极氧化时的电压为40-60V，时间为1-3h，在进行第二次阳极氧化时的电压为40-60V，时间为3-10min，所述煅烧的温度为400-500℃，煅烧的时间为1-3h，煅烧的升温和降温速率均为3-8℃/min。The method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure according to claim 3, wherein the electrolyte is an ethylene glycol solution of ammonium fluoride and water, in the ethylene glycol solution, The mass percentage concentration of ammonium fluoride is 0.2-0.8 wt%, and the volume percentage concentration of water is 2.0-4.0 v%. In the two anodizations, the voltage at the time of the first anodization is 40-60 V, time. For 1-3h, the voltage during the second anodization is 40-60V, the time is 3-10min, the calcination temperature is 400-500 ° C, the calcination time is 1-3h, the heating and cooling of the calcination The rate is 3-8 ° C / min.
- 根据权利要求1所述的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法，其特征在于，所述通过还原获得金颗粒包括：用HAuCl 4油浴搅拌，煮沸后加柠檬酸钠，改变时间，得到AuNPs溶液。 The method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure according to claim 1, wherein the obtaining the gold particles by reduction comprises: stirring with a HAuCl 4 oil bath, adding sodium citrate after boiling, and changing At time, a solution of AuNPs was obtained.
- 根据权利要求1所述的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法，其特征在于，所述配制硫化铋和金颗粒复合溶液包括在AuNPs溶液中加硫代乙酰胺和醋酸铋，放入烘箱中反应，得到硫化铋和金颗粒复合溶液。The method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure according to claim 1, wherein the preparing a composite solution of strontium sulfide and gold particles comprises adding thioacetamide and cesium acetate to the AuNPs solution. The reaction was carried out in an oven to obtain a composite solution of strontium sulfide and gold particles.
- 根据权利要求1所述的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法，其特征在于，所述将所述TiO 2纳米管阵列放入所述硫化铋和金颗粒复合溶液中，通过烘箱法制 得硫化铋修饰金纳米颗粒/二氧化钛纳米管结构包括：将所述TiO 2纳米管阵列经前处理后，浸入所述硫化铋和金颗粒复合溶液中，然后放入烘箱中，在37℃的条件下加热4h，得到硫化铋修饰金纳米颗粒/二氧化钛纳米管结构。 The method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure according to claim 1, wherein the TiO 2 nanotube array is placed in the composite solution of strontium sulfide and gold particles, and passed through The cerium sulfide modified gold nanoparticle/titanium dioxide nanotube structure prepared by the oven method comprises: pretreating the TiO 2 nanotube array, immersing in the composite solution of strontium sulfide and gold particles, and then placing it in an oven at 37 ° C The mixture was heated for 4 h to obtain a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure.
- 根据权利要求1-7所述的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法所制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构在有机染料污染物降解催化剂中的应用。The method for preparing a strontium sulfide modified gold nanoparticle/titanium dioxide nanotube structure prepared according to claim 1-7, wherein the strontium sulfide modified gold nanoparticle/titanium dioxide nanotube structure is used in an organic dye contaminant degradation catalyst.
- 根据权利要求1-7所述的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法所制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构在复合材料中的应用。The use of the strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure prepared by the method for preparing a strontium sulfide-modified gold nanoparticle/titanium dioxide nanotube structure according to claims 1-7 in a composite material.
- 根据权利要求1-7所述的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构的制备方法所制备的硫化铋修饰金纳米颗粒/二氧化钛纳米管结构在非葡萄糖传感器中的应用。The method for preparing a strontium sulfide modified gold nanoparticle/titanium dioxide nanotube structure prepared according to claims 1-7, wherein the strontium sulfide modified gold nanoparticle/titanium dioxide nanotube structure is used in a non-glucose sensor.
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