CN107715894B - Bismuth sulfide modifies gold nano grain/titania nanotube structure preparation method and application - Google Patents
Bismuth sulfide modifies gold nano grain/titania nanotube structure preparation method and application Download PDFInfo
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- CN107715894B CN107715894B CN201710803182.XA CN201710803182A CN107715894B CN 107715894 B CN107715894 B CN 107715894B CN 201710803182 A CN201710803182 A CN 201710803182A CN 107715894 B CN107715894 B CN 107715894B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 263
- 239000002071 nanotube Substances 0.000 title claims abstract description 171
- 239000010931 gold Substances 0.000 title claims abstract description 139
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 129
- 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 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 62
- 238000012986 modification Methods 0.000 claims abstract description 56
- 230000004048 modification Effects 0.000 claims abstract description 54
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 38
- 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 36
- 239000008103 glucose Substances 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004073 vulcanization Methods 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 7
- RBWFXUOHBJGAMO-UHFFFAOYSA-N sulfanylidenebismuth Chemical class [Bi]=S RBWFXUOHBJGAMO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 29
- 229910052719 titanium Inorganic materials 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 13
- 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
- 238000006731 degradation reaction Methods 0.000 claims description 11
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 230000015556 catabolic process Effects 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 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 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- OQUFOZNPBIIJTN-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium Chemical compound [Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OQUFOZNPBIIJTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 150000002343 gold Chemical class 0.000 claims 1
- 230000002255 enzymatic effect Effects 0.000 abstract description 11
- 238000007743 anodising Methods 0.000 abstract description 8
- 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 abstract description 5
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- FYNVXASLFHXUBV-UHFFFAOYSA-K [Au+3].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+] Chemical compound [Au+3].C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+] FYNVXASLFHXUBV-UHFFFAOYSA-K 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 55
- 235000013339 cereals Nutrition 0.000 description 53
- 239000004408 titanium dioxide Substances 0.000 description 30
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 18
- IBRMAPJCHQJDMT-UHFFFAOYSA-N [Au].[Bi]=S Chemical compound [Au].[Bi]=S IBRMAPJCHQJDMT-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 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
- 238000012360 testing method Methods 0.000 description 10
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- 235000010323 ascorbic acid Nutrition 0.000 description 9
- 229960005070 ascorbic acid Drugs 0.000 description 9
- 239000011668 ascorbic acid Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 230000005622 photoelectricity Effects 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000003115 supporting electrolyte Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 229960004756 ethanol Drugs 0.000 description 6
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000005030 aluminium foil Substances 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002211 ultraviolet spectrum Methods 0.000 description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- WKLWZEWIYUTZNJ-UHFFFAOYSA-K diacetyloxybismuthanyl acetate Chemical class [Bi+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WKLWZEWIYUTZNJ-UHFFFAOYSA-K 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
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- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- -1 Bismuthino Chemical group 0.000 description 2
- CLSVJBIHYWPGQY-UHFFFAOYSA-N [3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1-azaspiro[4.5]dec-3-en-4-yl] ethyl carbonate Chemical compound CCOC(=O)OC1=C(C=2C(=CC=C(C)C=2)C)C(=O)NC11CCC(OC)CC1 CLSVJBIHYWPGQY-UHFFFAOYSA-N 0.000 description 2
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- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 101000878457 Macrocallista nimbosa FMRFamide Proteins 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
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- XRURWBKRKZLENR-UHFFFAOYSA-N azane;ethane-1,2-diol Chemical compound N.OCCO XRURWBKRKZLENR-UHFFFAOYSA-N 0.000 description 1
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- 239000003574 free electron Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses a kind of bismuth sulfides to modify gold nano grain/titania nanotube structure preparation method and application.Comprising: substrate be selected, to the substrate pretreatment；Anodizing prepares TiO on the substrate twice2Nano-tube array；Gold particle is obtained by reduction；Formulating vulcanization bismuth and gold particle composite solution；By the TiO2Nano-tube array is put into the bismuth sulfide and gold particle composite solution, and bismuth sulfide is made by Oven Method and modifies gold nano grain/titania nanotube structure.Bismuth sulfide modification gold nano grain/titania nanotube structure of the invention is formed by reduction of sodium citrate gold particle, has huge potential in the organic pollutants such as non-enzymatic glucose sensor and photocatalytic degradation methylene blue field.
Description
Technical field
The present invention relates to field of material technology, and in particular to a kind of bismuth sulfide modification gold nano grain/nano titania
Preparation method, non-enzymatic glucose sensor and the composite material of pipe ternary structural and its in organic dirt such as photocatalytic pollutant degradation
Contaminate the application in object field.
Background technique
Environmentally protective, the demand of clean energy resource has become a main trend of the world today, and conductor photocatalysis is made
Potential solution for processing global energy crisis and environmental pollution causes extensive concern.Many scientists carry out one after another
The research of nano structural material for photocatalytic pollutant degradation.Titanium dioxide (TiO as semiconductor material2) in section
By welcome like the tempest in scholar.Titanium dioxide (TiO2) there is excellent chemical stability, photoelectric characteristic, bio-compatible
The features such as property and corrosion resistance, have been widely used for photocatalytic pollutant degradation, fuel sensitization solar battery, bio-medical
Material, gas sensor and photolysis water hydrogen etc..Nano-TiO2In addition to having the surface effect as common nano material
It answers, outside low dimensional effect, quantum size effect and macro quanta tunnel effect, also there is its special property, be especially catalyzed
Performance.One-dimensional TiO2Nanostructure (electric wire, stick, band and pipe) such as orients charge transmission and orthogonal due to beneficial geometric effect
Electron-hole separation, causes sizable concern.Wherein, it due to the easiness of its manufacture and control, has had extensively studied
TiO2The form of NTs, compared with TiO2Nano particle TiO2Nano-tube array have large specific surface area, surface can it is high, easy to be recycled with
And electrons and holes rate of load condensate it is lower the advantages that.But TiO2Nano-tube array there are still some disadvantages, limit it
Very various applications.Such as, (1) TiO2Forbidden bandwidth it is wider (anatase be 3.2 eV, rutile be 3.0 eV), can only inhale
The solar energy (387 nm of λ <) of 3-5% is received, utilization rate is low；(2) TiO2The recombination rate of the photo-generate electron-hole pairs of nanotube is still
So higher, photocatalytic activity is low.
Summary of the invention
It is an object of the present invention to provide a kind of bismuth sulfides to modify gold nano grain/titania nanotube structure preparation side
Method solves the above problems.
The technical scheme is that
A kind of bismuth sulfide modification gold nano grain/titania nanotube structure preparation method, this method include as follows
Step:
Substrate is selected, to the substrate pretreatment；
Anodizing prepares TiO on the substrate twice2Nano-tube array；
Gold particle is obtained by reduction；
Formulating vulcanization bismuth and gold particle composite solution；
By the TiO2Nano-tube array is put into the bismuth sulfide and gold particle composite solution, and sulphur is made by Oven Method
Change bismuth and modifies gold nano grain/titania nanotube structure.
Further, the substrate is titanium sheet, and the titanium sheet is pure titanium or titanium alloy, and the substrate pretreatment is successively
The substrate 20-40min is cleaned by ultrasonic using dust technology, acetone, ethyl alcohol and deionized water.
Further, the anodizing twice prepares TiO on the substrate2Nano-tube array specifically includes: with
By pretreated substrate as anode, platinized platinum is inserted into electrolyte as cathode and carries out anodic oxidation twice, anodic oxygen
Change and primary TiO is made2Nano-tube array, by the primary TiO2Nano-tube array calcining obtains Detitanium-ore-type TiO2Nanotube battle array
Column.
Further, the electrolyte is the ethylene glycol solution of ammonium fluoride and water, in the ethylene glycol solution, ammonium fluoride
Mass percent concentration is 0.2-0.8wt%, and the concentration of volume percent of water is 2.0-4.0v%, the anodic oxidation twice
In, the voltage when carrying out first time anodic oxidation is 40-60V, time 1-3h, the electricity when carrying out second of anodic oxidation
Pressure is 40-60V, and time 3-10min, the temperature of the calcining is 400-500 DEG C, and the time of calcining is 1-3h, the liter of calcining
Mild rate of temperature fall is 3-8 DEG C/min.
Further, it is described by reduction obtain gold particle include: to use HAuCl4Oil bath stirring, boils rear adding citric acid
Sodium changes the time, obtains AuNPs solution.
Further, the formulating vulcanization bismuth and gold particle composite solution, which are included in AuNPs solution, adds thioacetamide
And bismuth acetate, it is put into baking oven and reacts, obtain bismuth sulfide and gold particle composite solution.
Further, described by the TiO2Nano-tube array is put into the bismuth sulfide and gold particle composite solution, is led to
Crossing Oven Method and bismuth sulfide modification gold nano grain/titania nanotube structure is made includes: by the TiO2Nano-tube array
It after pre-treatment, immerses in the bismuth sulfide and gold particle composite solution, is then placed in baking oven, heated under conditions of 37 DEG C
4h obtains bismuth sulfide modification gold nano grain/titania nanotube structure.
The modification of bismuth sulfide prepared by aforesaid way gold nano grain/titania nanotube structure can be applied to organic
Dyestuff contaminant degradation catalyst.
The modification of bismuth sulfide prepared by aforesaid way gold nano grain/titania nanotube structure can also be applied multiple
In condensation material.
The modification of bismuth sulfide prepared by aforesaid way gold nano grain/titania nanotube structure can also be applied to non-
In glucose sensor.
The present invention provides a kind of bismuth sulfides to modify gold nano grain/titania nanotube structure preparation method,
On the one hand prepared bismuth sulfide modification gold nano grain/titania nanotube structure improves TiO2The light of nano tube structure
Electrical effect；On the other hand the catalytic capability of titania nanotube structure is improved, to reach under visible light illumination to methylene
The degradation of the organic pollutants such as indigo plant and for making non-enzymatic glucose sensor.With unmodified TiO2Nanotube compares, sulphur
Change the TiO of bismuth modification gold nano grain2Nano tube structure photoelectric properties significantly improve, and are provided simultaneously with good chemical stability
And reusing.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill of field, without any creative labor, it can also be obtained according to these attached drawings other
Attached drawing.Wherein,
Fig. 1 is the process that bismuth sulfide of the invention modifies gold nano grain/titania nanotube structure preparation method
Schematic diagram；
Fig. 2 is that bismuth sulfide produced by the present invention modifies gold nano grain/titania nanotube structure SEM figure, wherein
(a), (b), (c), be respectively dipping bismuth sulfide gold nano grain solution concentration be 0.02%, 0.01%, 0.005% bismuth sulfide
Modify the SEM figure of gold-nanoparticle-supported titania nanotube structure；
A in Fig. 3, b are bismuth sulfide modification gold nano grain/titania nanotube knot obtained in the embodiment of the present invention 1
The SEM of structure schemes, and c is that the bismuth sulfide prepared in embodiment 1 modifies gold nano grain/titania nanotube structure EDS figure, d
Bismuth sulfide to prepare in embodiment 1 modifies gold nano grain/titania nanotube structure Elemental redistribution map；
Fig. 4 be in embodiment 1 bismuth sulfide for preparing modify gold nano grain/titania nanotube structure TEM figure,
HRTEM figure and mapping.View (a), (b), (c) are that bismuth sulfide modifies gold nano grain/titania nanotube structure
TEM figure, view (d), (e) are that bismuth sulfide modifies gold nano grain/titania nanotube structure HRTEM figure, and view (f) is
The mapping of view (c)；
Fig. 5 is unmodified TiO in embodiment 12The TiO of nano-tube array, bismuth sulfide gold nano particle modification2Nanometer
Pipe array, simple gold particle modify TiO2Nano-tube array and simple bismuth sulfide modify TiO2XPS figure, wherein figure (a) is full spectrum
Figure, figure (b), (c), (d) be in embodiment 1 bismuth sulfide for preparing modify gold nano grain/titania nanotube structure gold,
The narrow spectrogram of bismuth, sulphur；
Fig. 6 is unmodified TiO in embodiment 12Nano-tube array, various concentration bismuth sulfide gold nano particle modification
TiO2Nano-tube array, simple gold particle modify TiO2Nano-tube array and simple bismuth sulfide modify TiO2Fluorescence spectra；
Fig. 7 is unmodified TiO in embodiment 12Nano-tube array, various concentration bismuth sulfide modify gold nano grain
TiO2Nano-tube array, simple gold particle modify TiO2Nano-tube array and simple bismuth sulfide modify TiO2The light of nano-tube array
Current-responsive figure；
Fig. 8 is the TiO modified in embodiment 1 through bismuth sulfide gold particle2Nano-tube array is to different glucose solution
Oxidation curve；
Fig. 9 is the TiO modified in embodiment 1 through bismuth sulfide gold particle2Nano-tube array is to different glucose solution
Response staircase curve；
Figure 10 is the TiO of bismuth sulfide gold particle modification in embodiment 12When nano-tube array does non-enzymatic glucose sensor pair
The interference effect staircase curve figure of ascorbic acid, uric acid etc.；
Figure 11 is unmodified TiO in embodiment 12The TiO that nano-tube array, bismuth sulfide gold particle are modified2Nanotube battle array
Column, gold modification TiO2Nano-tube array and the Nano tube array of titanium dioxide of bismuth sulfide modification are degraded under ultraviolet light and visible light
The efficiency chart of methylene blue；View b, d are respectively view a, the UV absorption wavelength graph of c counter sample.
Specific embodiment
The present invention carries out a series of modifications to titania nanotube battle array such as to adulterate gold the shortcomings that optimizing itself
Category, nonmetallic and semi-conductor nano particles and TiO2Nano-tube array combines.In order to keep TiO2Fabulous electric charge transfer performance
With photoetch, make TiO using narrow gap semiconductor2NTs is easy to photosensitive, therefore chalcogenide draws attention, recently, right
Bismuthino semiconductor has caused sizable concern.Bismuth sulfide (Bi2S3) it is the photoresponse half with narrow band gap (1.3eV)
Conductor, the layered semiconductor of high absorption coefficient, Bi2S3In fields such as catalysis, sensor, photoelectric nano device and lithium ion batteries
With potential application.Noble metal nano particles (Ag, Cu, Pt) are dispersed in TiO2Nanotube surface can assist capture photoproduction electricity
Son accelerates the separation of electron hole, and then inhibits light induced electron and hole-recombination.Application in terms of detecting glucose, has
More superior catalytic performance, for almost all of human history, gold is because it is natural beautiful, invariance and unique ductility
It is pursued with the balance of durability.The combination of Au nano particle can also be used as electron trap, facilitate separation of charge, and by
In surface plasmon resonance (LSPR) effect, under visible light to TiO2It is sensitized.In two semiconductor (Bi2S3-
TiO2) between addition Au nano particle can reduce trapping state Auger rate, and part compensates the negative shadow in surface trap site
It rings, to improve light conversion efficiency
Referring to Fig. 1, Fig. 1 is that bismuth sulfide of the invention modifies the preparation of gold nano grain/titania nanotube structure
The flow diagram of method.As shown in Figure 1, the present invention provides a kind of bismuth sulfide modification gold nano grain/titania nanotube
The preparation method of structure, comprising the following steps:
Substrate is selected, to the substrate pretreatment；
Anodizing prepares TiO on the substrate twice2Nano-tube array；
Gold particle is obtained by reduction；
Formulating vulcanization bismuth and gold particle composite solution；
By the TiO2Nano-tube array is put into the bismuth sulfide and gold particle composite solution, and sulphur is made by Oven Method
Change bismuth and modifies gold nano grain/titania nanotube structure.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, With reference to embodiment
The present invention is described in further detail.
A kind of bismuth sulfide modification gold nano grain/titania nanotube structure preparation method, comprising:
Step 1: titanium sheet can be selected in substrate, first pre-processes to titanium sheet；
In one embodiment, which specific as follows can execute: clean to titanium sheet.Wherein, the titanium sheet is
Pure titanium or titanium alloy, having a size of the cm of 1.5 cm × 3.0.Successively using dust technology, acetone, ethyl alcohol and deionized water to titanium sheet
It is cleaned by ultrasonic 20-40min.
Step 2: anodizing prepares TiO2Nano-tube array；
In one embodiment, which specific as follows can execute: using the titanium sheet after cleaning as anode, platinized platinum is made
For cathode, it is used as electrolyte in the ethylene glycol solution of ammonium fluoride and water, applies certain voltage, carries out anodic oxidation twice, anode
It aoxidizes and TiO is made2Nano-tube array, then calcine to obtain the better Detitanium-ore-type TiO of crystal form2Nano-tube array.
Wherein, in ethylene glycol solution, the mass percent concentration of ammonium fluoride is 0.2-0.8wt%, the percent by volume of water
Concentration is 2.0-4.0v%.Carry out first time anodic oxidation voltage be 40-60V, time 1-3h, second of anodic oxidation
Voltage is 40-60V, time 3-10min.By TiO obtained2Nano-tube array is calcined in air, the temperature of calcining
It is 400-500 DEG C, the time of calcination is 1-3h, and the heating of calcining and rate of temperature fall are 3-8 DEG C/min.By calcining, obtain
The better Detitanium-ore-type TiO of crystal form2Nano-tube array.
Step 3: reduction of sodium citrate gold particle is used
In one embodiment, which specific as follows can execute: use HAuCl4(60 ml, 0.01wt%,
0.02wt%, 0.005wt%) (130 DEG C) of oil bath stirrings, boil rear adding citric acid sodium (600ml, 1wt%) the change time (0.5h,
1h, 1.5h, 2h), obtain AuNPs solution.
Step 4: the mixed solution of formulating vulcanization bismuth and gold particle；
In one embodiment, which specific as follows can execute: add the 400 thio second of μ L of 0.003g in AuNPs solution
100 μ L bismuth acetate of amide and 0.0038g, is put into 80 DEG C of baking ovens and reacts 10h, obtain the mixed solution of bismuth sulfide and gold particle.
Step 5: TiO2NTs carries out pre-treatment；
In one embodiment, which specific as follows can execute: by TiO2NTs is put into MPTs(3- mercapto propyl front three
150 μ L of oxysilane) and NH425 DEG C for 24 hours are protected from light in the 15ml ethanol solution of OH (30 μ L, 27%), is protected from light mode such as
It is covered with aluminium foil.
Step 6: it is based on bismuth sulfide obtained and gold particle mixed solution, bismuth sulfide and gold particle are loaded into TiO2
NTs structure gets on, and bismuth sulfide is made and modifies gold nano grain/titania nanotube structure.
In one embodiment, which specific as follows can execute: will treated titanium sheet (after two-step anodization
Titanium tube) it immerses in the solution of gold/bismuth sulfide composite solution, it is put into 37 DEG C of baking ovens and heats 4h, obtain bismuth sulfide modification Jenner
Rice grain/titania nanotube structure.
After above-mentioned six steps, bismuth sulfide modification gold nano grain/titania nanotube structure is completed the production.At this
After six steps, structure can also be tested.
Step 7: it is surveyed using the performance that the novel photoelectric catalyst prepared carries out photocatalytically degradating organic dye pollutant
Examination.
Specifically, by unmodified TiO2The TiO that nano-tube array, bismuth sulfide gold particle are modified2Nano-tube array, gold
Modify TiO2It is 10 mg/L that nano-tube array and the Nano tube array of titanium dioxide of bismuth sulfide modification are impregnated in initial concentration respectively
Methylene blue aqueous solution in, stood after reaching adsorption equilibrium state within 0.5 hour in a dark environment, respectively in ultraviolet light and
0-120 min is irradiated under visible light, time interval is 30 min.When each time interval, the ultraviolet spectra of foul solution is tested
Absorption value.
The above-mentioned substrate prepared can be used as electrode use, can be used widely in non-enzymatic glucose sensor field.
The performance test of non-enzymatic glucose sensor is carried out using the working electrode prepared.
Specifically, cyclical voltage is -1V-1V, and scanning circle number is enclosed in 5-15, and sweep speed is in 20-100 mV/S.Oxidation is bent
In line, concentration of glucose 0-0.05M is interfered in linearity curve, and it is 0-10mM, ascorbic acid and uric acid drop that concentration, which is added dropwise, in glucose
Adding concentration is 2mM.
Referring to Fig. 2, Fig. 2 is that bismuth sulfide produced by the present invention modifies gold nano grain/titania nanotube structure
SEM figure, wherein (a), (b), (c), be respectively dipping bismuth sulfide gold nano grain solution concentration be 0.02%, 0.01%,
0.005% bismuth sulfide modifies the SEM figure of gold-nanoparticle-supported titania nanotube structure.As shown in Fig. 2, bismuth sulfide is repaired
Nanotube caliber is 80-100 nm in gilding particle/Nano tube array of titanium dioxide, and pipe thickness is 10-20 nm, bismuth sulfide
The gold nano grain partial size of modification is 15-20 nm, uniformly raw on titania nanotube.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawings and examples
Further illustrate technical solution of the present invention.But the present invention is not limited to listed embodiments, should also be included in institute of the present invention
It is required that interest field in other any well known change.
Firstly, " one embodiment " or " embodiment " referred to herein, which refers to, may be included at least one realization side of the invention
A particular feature, structure, or characteristic in formula." in one embodiment " that different places occur in the present specification not refers both to
The same embodiment, nor the individual or selective embodiment mutually exclusive with other embodiments.
Secondly, the present invention is described in detail using structural schematic diagram etc., when describing the embodiments of the present invention, for convenient for saying
Bright, schematic diagram can disobey general proportion and make partial enlargement, and the schematic diagram is example, should not limit the present invention herein
The range of protection.In addition, the three-dimensional space of length, width and depth should be included in actual fabrication.
In addition, the letter said in the present invention is referred to as, it is that this field is fixed referred to as, part of letter text is explained such as
Under: SEM figure: electron scanning imaging figure；TEM figure: transmitted electron surface sweeping imaging figure；HRTEM figure: high-resolution transmitted electron is swept
Face imaging figure；EDS figure: energy spectrum diagram；XRD diagram: X-ray diffractogram；XPS spectrum figure: X-ray photoelectron spectroscopic analysis spectrogram.
Embodiment 1
The implementation case shows a kind of bismuth sulfide modification gold nano grain/titania nanotube structure as follows
Preparation method:
(1) pretreatment of titanium sheet and two-step electrochemical anodizing method prepare TiO2Nano-tube array.To titanium sheet substrate acetone, nothing
Water-ethanol, deionized water are successively cleaned by ultrasonic 15min.Using platinum plate electrode as cathode, while being inserted into containing (the fluorination of 98v% ethylene glycol
Ammonium 0.3wt%) and the electrolyte solution of 2v% water in, apply 50V ultor and aoxidize 1.5h, ultrasound falls off after film layer, continue to apply
Add 50V ultor to aoxidize 6 min, TiO is made2Nano-tube array, then through 450 DEG C of heat treatment 2h, change from unformed state
At the preferable anatase of crystal form.
(2) pass through HAuCl4(0.001g 10ml) oil bath stirring, it is anti-to boil rear adding citric acid sodium (1g 99g deionized water)
It answers and obtains within 1-2 hours AuNPs solution, 400 μ L thioacetamide of 0.003g and 0.0038g are added in the Au NPs solution of 50ml
100 μ L bismuth acetates are put into 80 DEG C of baking oven reaction 10h, obtain gold/bismuth sulfide composite solution.By TiO2NTs is put into MPTs(3-
150 μ L of mercaptopropyl trimethoxysilane) and NH4With aluminium foil covering for 24 hours 25 in the 15ml ethanol solution of OH (30 μ L, 27%)
℃.The titanium sheet impregnated is put into gold/bismuth sulfide composite solution of 15ml again, reaction condition is 37 DEG C of 4h.Finally
Gold nano grain/Nano tube array of titanium dioxide is modified to bismuth sulfide.
(3) photoelectricity and test are made to the bismuth sulfide modification gold particle/Nano tube array of titanium dioxide prepared: configuration 0.1
The sodium sulfite of M does supporting electrolyte, and bismuth sulfide modification gold particle/Nano tube array of titanium dioxide makees working electrode, and platinized platinum is made
To electrode, silver/silver chlorate makees reference electrode, corresponding using the chronoptentiometry detection photoelectricity grade of electrochemical workstation, wherein having
No light time interval is 30s.
(4) photocatalytic degradation organic contamination is made to the bismuth sulfide modification gold particle/Nano tube array of titanium dioxide prepared
The application of object: by unmodified TiO2The TiO that nano-tube array, bismuth sulfide gold particle are modified2Nano-tube array, gold modification
TiO2Nano-tube array and the Nano tube array of titanium dioxide of bismuth sulfide modification are impregnated in the Asia that initial concentration is 10 mg/L respectively
Methyl blue shines under ultraviolet light and visible light respectively after standing reaches adsorption equilibrium state in 0.5 hour in a dark environment first
Penetrate 0-120 min.Time interval is respectively 30 min.Each time interval takes corresponding solution to test ultraviolet spectra absorption value.
(5) the bismuth sulfide modification gold particle/Nano tube array of titanium dioxide prepared is answered as non-enzymatic glucose sensor
With: the sodium hydroxide solution of 0.1 M of configuration does supporting electrolyte, and bismuth sulfide is modified gold particle/Nano tube array of titanium dioxide and made
Working electrode, platinized platinum are made to electrode, and silver/silver chlorate makees reference electrode, are detected using the cyclic voltammetry curve of electrochemical workstation
Glucose, wherein glucose successively adds 5 mM of concentration, and further, electrode performance interference detection, test prepares electrode pair
The interference of ascorbic acid, uric acid, wherein glucose addition concentration is 2-10mM, and uric acid, ascorbic acid addition concentration are 2mM.
Bismuth sulfide obtained by above-described embodiment modifies gold nano grain/specific conclusion of titania nanotube structure such as
Under:
Referring to Fig. 2, Fig. 2 is that bismuth sulfide produced by the present invention modifies gold nano grain/titania nanotube structure
SEM figure, wherein (a), (b), (c), be respectively dipping bismuth sulfide gold nano grain solution concentration be 0.02%, 0.01%,
0.005% bismuth sulfide modifies the SEM figure of gold-nanoparticle-supported titania nanotube structure.As can be seen from Figure 2,15-20 nm
Bismuth sulfide modification gold nano grain be uniformly deposited on nanotube surface and inside.
Referring to Fig. 3, a in Fig. 3, b are bismuth sulfide modification gold nano grain/titanium dioxide obtained in the embodiment of the present invention 1
The SEM of titanium nano tube structure schemes, and c is that the bismuth sulfide prepared in embodiment 1 modifies gold nano grain/titania nanotube structure
EDS figure, d is that the bismuth sulfide for preparing modifies gold nano grain/titania nanotube structure distribution diagram of element in embodiment 1
Spectrum.As shown in figure 3, bismuth sulfide modification gold particle/titania nanotube structure mainly contains Ti, O, S, Bi and Au element.
Referring to Fig. 4, Fig. 4 is that the bismuth sulfide prepared in embodiment 1 modifies gold nano grain/titania nanotube structure
TEM figure, HRTEM figure and mapping.View (a), (b), (c) are that bismuth sulfide modifies gold nano grain/titania nanotube
The TEM of structure schemes, and view (d), (e) they are that bismuth sulfide modifies gold nano grain/titania nanotube structure HRTEM figure, depending on
Scheme the mapping that (f) is view (c).Fig. 4 further demonstrates that the gold nano grain of bismuth sulfide modification is evenly distributed on TiO2 nanometers
Pipe surface and inside, particle size are about 15 nm；HRTEM and SAED figure is shown between TiO2 Detitanium-ore-type (101) crystal face lattice
Away from for 0.352 nm, golden (111) interplanar distance is 0.23 nm, and the interplanar distance of bismuth sulfide (221) is 0.286 nm, with Fig. 4's
XRD test result matches.
Referring to Fig. 5, Fig. 5 is unmodified TiO in embodiment 12Nano-tube array, bismuth sulfide gold nano particle modification
TiO2Nano-tube array, simple gold particle modify TiO2Nano-tube array and simple bismuth sulfide modify TiO2XPS figure, wherein
Scheming (a) is full spectrogram, and figure (b), (c), (d) are that the bismuth sulfide prepared in embodiment 1 modifies gold nano grain/nano titania
The narrow spectrogram of gold, bismuth, sulphur of pipe structure.As shown in figure 5, in addition to O 1s (530.3 eV), Ti 2p (458.3 eV,
464.2ev) and the peak C 1s (283.8 eV), the presence at the peak Bi 4f and S 2p and Au 4f demonstrate bismuth sulfide modification gold nano
Particle/Nano tube array of titanium dioxide.It can be seen that from high-resolution XPS the map c and d of Bi 4f and S 2p, Bi 4f5/2
(158.0 eV) and Bi 4f7/2 (162.6 eV) and S 2p3/2(158.0 eV) and S 2p1/2(163.2 eV), it was demonstrated that vulcanization
The presence of bismuth, Au 4f7/2(83.9 eV) and Au 4f5/2(87.3 eV) energy gap is that 3.4 eV demonstrate golden simple substance
In the presence of.
Referring to Fig. 6, Fig. 6 is unmodified TiO in embodiment 12Nano-tube array, various concentration bismuth sulfide gold nano
The TiO of particle modification2Nano-tube array, simple gold particle modify TiO2Nano-tube array and simple bismuth sulfide modify TiO2It is glimmering
Light spectrogram.As shown in fig. 6, the fluorescence intensity highest of unmodified TiO2 nanotube battle array, by loading Bi2S3It is glimmering after Au
Luminous intensity reduces, and further explanation hinders the recombination in free electron and hole.
Referring to Fig. 7, Fig. 7 is unmodified TiO in embodiment 12Nano-tube array, various concentration bismuth sulfide modification gold
The TiO of nano particle2Nano-tube array, simple gold particle modify TiO2Nano-tube array and simple bismuth sulfide modify TiO2Nanometer
The photocurrent response figure of pipe array, as seen from the figure 0.01% Au/Bi2S3@TiO2Photoelectric current it is best, increase carrier separation effect
Rate inhibits the recombination of electron hole pair.
Referring to Fig. 8, as shown in figure 8, bismuth sulfide modifies gold using the sodium hydroxide solution of 0.1 M as supporting electrolyte
Oxidation curve of the grain/Nano tube array of titanium dioxide in the sodium hydroxide solution of different glucose, wherein -0.23V is left
Right peak is the electrochemical oxidation that electrode surface adsorbs glucose, and the peak of 0.1 V or so is electrode surface absorption glucose electrification
Learn the further oxidation of the intermediate generated in oxidation process.The peak of 0.45 V or so is that the glucose in solution body phase diffuses to
It is carried out caused by direct oxidation on electrode.With the continuous increase of concentration of glucose, peak value is also gradually increased.
Referring to Fig. 9, Fig. 9 is the TiO modified in embodiment 1 through bismuth sulfide gold particle2Nano-tube array is to various concentration
The response staircase curve of glucose solution, every 25 seconds injection 2ml glucose solutions.It can be seen that an addition glucose is molten
Liquid, current value can become smaller, as time increases, stepped, and it is sharper to illustrate that this electrode responds concentration of glucose.
Referring to Fig. 10, Figure 10 is the TiO of bismuth sulfide gold particle modification in embodiment 12Nano-tube array does non-enzymatic grape
The interference effect staircase curve figure of Ascorbic Acid, uric acid etc. when sugared sensor.It can be seen from fig. 11 that glucose is to electric current
The contributive rate of density is 100%, and ascorbic acid is 40% or so to the contributive rate of current density, contributive rate of the uric acid to current density
It is 30% or so.
Please refer to Figure 11, Figure 11 a, c be respectively in embodiment 1 under ultraviolet light and visible light unmodified TiO2Nanometer
The TiO that pipe array, bismuth sulfide gold particle are modified2Nano-tube array, gold modification TiO2The dioxy of nano-tube array and bismuth sulfide modification
Change the efficiency chart of titanium nano-tube array degradation of methylene blue under ultraviolet light and visible light；View b, d are respectively view a, and c is corresponding
Bismuth sulfide modify gold particle/Nano tube array of titanium dioxide UV absorption wavelength graph.Scheming a is the drop under ultraviolet light
Solve methylene blue efficiency chart, Au/Bi2S3@TiO2Degradation effect is preferably 30% or so, and figure c is that degradation is sub- under visible light illumination
The efficiency chart of methyl blue, Au/Bi2S3@TiO2Degradation effect is preferably 40% or so.
Embodiment 2
The implementation case shows a kind of bismuth sulfide modification gold nano grain/titania nanotube structure as follows
Preparation method:
(1) pretreatment of titanium sheet and two-step electrochemical anodizing method prepare TiO2Nano-tube array.To titanium sheet substrate acetone, nothing
Water-ethanol, deionized water are successively cleaned by ultrasonic 15 min.Using platinum plate electrode as cathode, while being inserted into and containing 97v% ethylene glycol (fluorine
Change ammonium 0.4wt%) and the electrolyte solution of 3v% water in, apply 40 V ultors and aoxidize 1 h, ultrasound falls off after film layer, continuation
Apply 40 V ultors and aoxidize 8 min, TiO is made2Nano-tube array, then through 450 DEG C of heat treatment 2h, turn from unformed state
Become the preferable anatase of crystal form.
(2) pass through HAuCl4(0.002g 10ml) oil bath stirring, it is anti-to boil rear adding citric acid sodium (1g 99g deionized water)
It answers and obtains within 1-2 hours AuNPs solution, 400 μ L thioacetamide of 0.003g and 0.0038g are added in the Au NPs solution of 50ml
100 μ L bismuth acetates are put into 80 DEG C of baking oven reaction 10h, obtain gold/bismuth sulfide composite solution.By TiO2NTs is put into MPTs(3-
150 μ L of mercaptopropyl trimethoxysilane) and NH4With aluminium foil covering for 24 hours 25 in the 15ml ethanol solution of OH (30 μ L, 27%)
℃.The titanium sheet impregnated is put into gold/bismuth sulfide composite solution of 15ml again, reaction condition is 37 DEG C of 4h.Finally
Gold nano grain/Nano tube array of titanium dioxide is modified to bismuth sulfide.
(3) photoelectricity and test are made to the bismuth sulfide modification gold particle/Nano tube array of titanium dioxide prepared: configuration 0.1
The sodium sulfite of M does supporting electrolyte, and bismuth sulfide modification gold particle/Nano tube array of titanium dioxide makees working electrode, and platinized platinum is made
To electrode, silver/silver chlorate makees reference electrode, corresponding using the chronoptentiometry detection photoelectricity grade of electrochemical workstation, wherein having
No light time interval is 30s.
(4) photocatalytic degradation organic contamination is made to the bismuth sulfide modification gold particle/Nano tube array of titanium dioxide prepared
The application of object: by unmodified TiO2The TiO that nano-tube array, bismuth sulfide gold particle are modified2Nano-tube array, gold modification
TiO2Nano-tube array and the Nano tube array of titanium dioxide of bismuth sulfide modification are impregnated in the Asia that initial concentration is 10 mg/L respectively
Methyl blue irradiates under ultraviolet light and visible light respectively after standing reaches adsorption equilibrium state in 1 hour in a dark environment first
0-120min.Time interval is respectively 30min.Each time interval takes corresponding solution to test ultraviolet spectra absorption value.
(5) the bismuth sulfide modification gold particle/Nano tube array of titanium dioxide prepared is answered as non-enzymatic glucose sensor
With: the sodium hydroxide solution for configuring 0.1M does supporting electrolyte, and bismuth sulfide modifies gold particle/Nano tube array of titanium dioxide workmanship
Make electrode, platinized platinum is made to electrode, and silver/silver chlorate makees reference electrode, detects Portugal using the cyclic voltammetry curve of electrochemical workstation
Grape sugar, wherein glucose successively adds concentration 10mM, and further, electrode performance interference detection, test prepares electrode confrontation
The interference of bad hematic acid, uric acid, wherein glucose addition concentration is 5-10mM, and uric acid, ascorbic acid addition concentration are 5 mM.
Embodiment 3
The implementation case shows a kind of bismuth sulfide modification gold nano grain/titania nanotube structure as follows
Preparation method:
(1) pretreatment of titanium sheet and two-step electrochemical anodizing method prepare TiO2Nano-tube array.To the dilute nitre of pure titanium sheet substrate
Acid, acetone, dehydrated alcohol, deionized water are successively cleaned by ultrasonic 25 min.Using platinum plate electrode as cathode, while insertion contains 99v%
In the electrolyte solution of ethylene glycol (ammonium fluoride 0.1wt%) and 1v% water, applies 60 V ultors and aoxidize 1 hour, ultrasound is de-
After falling film layer, continues to 60 V ultors and aoxidize 5 min, TiO is made2Nano-tube array, then 450 DEG C of 1 h of calcining, make it
It is transformed into anatase from unformed state.
(2) pass through HAuCl4(0.0005g 10ml) oil bath stirring, boils rear adding citric acid sodium (1g 99g deionized water)
Reaction obtains AuNPs solution for 1-2 hours, adds 400 μ L thioacetamide of 0.003g and 0.0038g in the Au NPs solution of 50ml
100 μ L bismuth acetates are put into 80 DEG C of baking oven reaction 10h, obtain gold/bismuth sulfide composite solution.By TiO2NTs is put into MPTs(3-
150 μ L of mercaptopropyl trimethoxysilane) and NH4With aluminium foil covering for 24 hours 25 in the 15ml ethanol solution of OH (30 μ L, 27%)
℃.The titanium sheet impregnated is put into gold/bismuth sulfide composite solution of 15ml again, reaction condition is 37 DEG C of 4h.Finally
Gold nano grain/Nano tube array of titanium dioxide is modified to bismuth sulfide.
(3) photoelectricity and test are made to the bismuth sulfide modification gold particle/Nano tube array of titanium dioxide prepared: configuration 0.1
The sodium sulfite of M does supporting electrolyte, and bismuth sulfide modification gold particle/Nano tube array of titanium dioxide makees working electrode, and platinized platinum is made
To electrode, silver/silver chlorate makees reference electrode, corresponding using the chronoptentiometry detection photoelectricity grade of electrochemical workstation, wherein having
No light time interval is 30s.
(4) photocatalytic degradation organic contamination is made to the bismuth sulfide modification gold particle/Nano tube array of titanium dioxide prepared
The application of object: by unmodified TiO2The TiO that nano-tube array, bismuth sulfide gold particle are modified2Nano-tube array, gold modification
TiO2Nano-tube array and the Nano tube array of titanium dioxide of bismuth sulfide modification are impregnated in the Asia that initial concentration is 10 mg/L respectively
Methyl blue irradiates under ultraviolet light and visible light respectively after standing reaches adsorption equilibrium state in 1 hour in a dark environment first
0-120 min.Time interval is respectively 30 min.Each time interval takes corresponding solution to test ultraviolet spectra absorption value.
(5) the bismuth sulfide modification gold particle/Nano tube array of titanium dioxide prepared is answered as non-enzymatic glucose sensor
With: the sodium hydroxide solution of 0.1 M of configuration does supporting electrolyte, and bismuth sulfide is modified gold particle/Nano tube array of titanium dioxide and made
Working electrode, platinized platinum are made to electrode, and silver/silver chlorate makees reference electrode, are detected using the cyclic voltammetry curve of electrochemical workstation
Glucose, wherein glucose successively adds 3 mM of concentration, and further, electrode performance interference detection, test prepares electrode pair
The interference of ascorbic acid, uric acid, wherein glucose addition concentration is 1-5 mM, and uric acid, ascorbic acid addition concentration are 1 mM.
Compared with prior art, the beneficial effects of the present invention are: bismuth sulfide of the invention modifies gold nano grain/titanium dioxide
On the one hand titanium nano tube structure improves TiO2The photoelectric effect of nano-tube array；On the other hand titania nanotube battle array is improved
The catalytic capability of column, to reach the degradation to organic pollutants such as methylene blues under visible light illumination and for making non-enzymatic
Glucose sensor.With unmodified TiO2Nanotube compares, and bismuth sulfide modifies the TiO of gold nano grain2Nano tube structure photoelectricity
Performance significantly improves, and is provided simultaneously with good chemical stability and reusing.
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferable
Embodiment describes the invention in detail, those skilled in the art should understand that, it can be to technology of the invention
Scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered in this hair
In bright scope of the claims.
Claims (5)
1. bismuth sulfide modifies gold nano grain/titania nanotube structure preparation method, which is characterized in that this method includes
Following steps:
Substrate is selected, the substrate is titanium sheet, and the titanium sheet is pure titanium or titanium alloy, successively uses dust technology, acetone, ethyl alcohol
It is cleaned by ultrasonic the substrate 20-40min with deionized water；
Using by pretreated substrate, as anode, platinized platinum is inserted into electrolyte as cathode and carries out anodic oxidation twice,
Primary TiO is made in anodic oxidation2Nano-tube array, by the primary TiO2Nano-tube array calcining obtains Detitanium-ore-type TiO2It receives
Mitron array；
Gold particle is obtained by reduction: using HAuCl4Oil bath stirring, boils rear adding citric acid sodium, changes the time, it is molten to obtain AuNPs
Liquid；
Formulating vulcanization bismuth and gold particle composite solution: adding thioacetamide and bismuth acetate in AuNPs solution, is put into baking oven anti-
It answers, obtains bismuth sulfide and gold particle composite solution；
By the TiO2Nano-tube array is put into the bismuth sulfide and gold particle composite solution, and bismuth sulfide is made by Oven Method
Modify gold nano grain/titania nanotube structure: by the TiO2Nano-tube array immerses the vulcanization after pre-treatment
It in bismuth and gold particle composite solution, is then placed in baking oven, heats 4h under conditions of 37 DEG C, obtain bismuth sulfide modification gold nano
Particle/titania nanotube structure.
2. bismuth sulfide according to claim 1 modifies gold nano grain/titania nanotube structure preparation method,
Be characterized in that: the electrolyte is the ethylene glycol solution of ammonium fluoride and water, in the ethylene glycol solution, the quality percentage of ammonium fluoride
Specific concentration is 0.2-0.8wt%, and the concentration of volume percent of water is 2.0-4.0v%, in the anodic oxidation twice, is being carried out
Voltage when first time anodic oxidation is 40-60V, time 1-3h, and the voltage when carrying out second of anodic oxidation is 40-
60V, time 3-10min, the temperature of the calcining are 400-500 DEG C, and the time of calcining is 1-3h, the heating and cooling of calcining
Rate is 3-8 DEG C/min.
3. described in any item bismuth sulfides modify gold nano grain/titania nanotube structure system according to claim 1-2
Bismuth sulfide prepared by Preparation Method is modified gold nano grain/titania nanotube structure and is catalyzed in organic dye pollutant degradation
Application in agent.
4. described in any item bismuth sulfides modify gold nano grain/titania nanotube structure system according to claim 1-2
Bismuth sulfide prepared by Preparation Method modifies the gold nano grain/application of titania nanotube structure in the composite.
5. described in any item bismuth sulfides modify gold nano grain/titania nanotube structure system according to claim 1-2
Bismuth sulfide prepared by Preparation Method modifies gold nano grain/titania nanotube structure answering in non-glucose sensor
With.
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| CN108760857B (en) * | 2018-06-01 | 2020-09-29 | 徐州医科大学 | Nanogold-modified titanium dioxide nano-cellulase electrode and preparation method and application thereof |
| CN111203235A (en) * | 2020-02-28 | 2020-05-29 | 南京理工大学 | Au/NCDs/Bi2S3Composite photocatalyst and preparation method and application thereof |
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| CN101187043A (en) * | 2007-09-17 | 2008-05-28 | 西北有色金属研究院 | Preparation method for super long titanium dioxide nanotube array with photocatalytic performance |
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| CN107715894B (en) * | 2017-09-08 | 2019-08-06 | 南通纺织丝绸产业技术研究院 | Bismuth sulfide modifies gold nano grain/titania nanotube structure preparation method and application |
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| CN101187043A (en) * | 2007-09-17 | 2008-05-28 | 西北有色金属研究院 | Preparation method for super long titanium dioxide nanotube array with photocatalytic performance |
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| CN102125837A (en) * | 2011-01-11 | 2011-07-20 | 湖南大学 | Metal-graphene-titanium dioxide nanotube array photocatalyst and preparation and application method thereof |
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