CN107715894A - Bismuth sulfide modifies the preparation method and application of gold nano grain/titania nanotube structure - Google Patents
Bismuth sulfide modifies the preparation method and application of gold nano grain/titania nanotube structure Download PDFInfo
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- CN107715894A CN107715894A CN201710803182.XA CN201710803182A CN107715894A CN 107715894 A CN107715894 A CN 107715894A CN 201710803182 A CN201710803182 A CN 201710803182A CN 107715894 A CN107715894 A CN 107715894A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 277
- 239000002071 nanotube Substances 0.000 title claims abstract description 182
- 239000010931 gold Substances 0.000 title claims abstract description 152
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 142
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 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 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000012986 modification Methods 0.000 claims abstract description 94
- 230000004048 modification Effects 0.000 claims abstract description 85
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 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
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007743 anodising Methods 0.000 claims abstract description 10
- 238000004073 vulcanization Methods 0.000 claims abstract description 9
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 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 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
- 230000008859 change Effects 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 8
- 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
- 230000015556 catabolic process Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- 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
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 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 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 230000002255 enzymatic effect Effects 0.000 abstract 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 abstract description 4
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- 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
- 230000009467 reduction Effects 0.000 abstract description 2
- 235000013339 cereals Nutrition 0.000 description 99
- 239000000243 solution Substances 0.000 description 55
- 239000004408 titanium dioxide Substances 0.000 description 30
- 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
- 229940116269 uric acid Drugs 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- 235000010323 ascorbic acid Nutrition 0.000 description 8
- 229960005070 ascorbic acid Drugs 0.000 description 8
- 239000011668 ascorbic acid Substances 0.000 description 8
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000005622 photoelectricity Effects 0.000 description 7
- 239000003115 supporting electrolyte Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910052709 silver Inorganic materials 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
- 239000013078 crystal Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 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 5
- 230000001699 photocatalysis Effects 0.000 description 5
- WKLWZEWIYUTZNJ-UHFFFAOYSA-K diacetyloxybismuthanyl acetate Chemical class [Bi+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WKLWZEWIYUTZNJ-UHFFFAOYSA-K 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000004044 response Effects 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000005030 aluminium foil Substances 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
- 238000007598 dipping method Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 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 2
- -1 Bismuthino Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 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
- 241000790917 Dioxys <bee> Species 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
- 206010070834 Sensitisation Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
Classifications
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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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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a kind of preparation method and application of bismuth sulfide modification gold nano grain/titania nanotube structure.It includes：Substrate is selected, to the substrate pretreatment；Anodizing prepares TiO on the substrate twice2Nano-tube array；Gold grain is obtained by reducing；Formulating vulcanization bismuth and gold grain composite solution；By the TiO2Nano-tube array is put into bismuth sulfide and the gold grain composite solution, and bismuth sulfide, which is made, by Oven Method modifies gold nano grain/titania nanotube structure.Bismuth sulfide modification gold nano grain/titania nanotube structure of the present invention is formed by reduction of sodium citrate gold grain, has huge potential in the organic pollution 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 modifies gold nano grain/nano titania
Preparation method, non-enzymatic glucose sensor and the composite of pipe ternary structural and its in organic dirt such as photocatalytic pollutant degradation
Contaminate the application in thing field.
Background technology
Green, 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
It is used for the research of the nano structural material of photocatalytic pollutant degradation.Titanium dioxide as semi-conducting material（TiO2）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-TiO2Except with the surface effect as common nano material
Answer, outside low dimensional effect, quantum size effect and macro quanta tunnel effect, also with its special property, be especially catalyzed
Performance.One-dimensional TiO2Nanostructured（Electric wire, rod, band and pipe）, due to beneficial geometric effect, such as orient electric charge transmission and orthogonal
Electron-hole separates, and causes sizable concern.Wherein, due to the easiness of its manufacture and control, have extensively studied
TiO2NTs form, compared with TiO2Nano particle TiO2Nano-tube array have specific surface area is big, surface energy is high, it is easy to be recycled with
And the rate of load condensate in electronics and hole it is relatively low the advantages that.But TiO2Nano-tube array there are still some shortcomings, limit it
Very many applications.Such as,（1）TiO2Energy gap it is wider (anatase is 3.2 eV, and rutile is 3.0 eV), can only inhale
3-5% solar energy (nm of λ ＜ 387) is received, utilization rate is low；（2）TiO2The recombination rate of the photo-generate electron-hole pair of nanotube is still
So higher, photocatalytic activity is low.
The content of the invention
It is an object of the present invention to provide a kind of preparation side of bismuth sulfide modification gold nano grain/titania nanotube structure
Method, solve the above problems.
The technical scheme is that：
A kind of preparation method of bismuth sulfide modification gold nano grain/titania nanotube structure, this method comprise the following steps：
Substrate is selected, to the substrate pretreatment；
Anodizing prepares TiO on the substrate twice2Nano-tube array；
Gold grain is obtained by reducing；
Formulating vulcanization bismuth and gold grain composite solution；
By the TiO2Nano-tube array is put into bismuth sulfide and the gold grain composite solution, and bismuth sulfide is made by Oven Method
Modify 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, ethanol and deionized water.
Further, the anodizing twice prepares TiO on the substrate2Nano-tube array specifically includes：With
As anode, platinized platinum inserts and anodic oxidation twice, anodic oxygen is carried out in electrolyte substrate by pretreatment as negative electrode
Change and primary TiO is made2Nano-tube array, by the primary TiO2Nano-tube array calcining obtains Detitanium-ore-type TiO2Nanotube battle array
Row.
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
Press as 40-60V, time 3-10min, the temperature of the calcining is 400-500 DEG C, and time of calcining is 1-3h, the liter of calcining
Gentle rate of temperature fall is 3-8 DEG C/min.
Further, it is described to be included by reducing acquisition gold grain：Use HAuCl4Oil bath is stirred, and boils rear adding citric acid
Sodium, change the time, obtain AuNPs solution.
Further, the formulating vulcanization bismuth and gold grain composite solution, which are included in AuNPs solution, adds thioacetamide
And bismuth acetate, it is put into baking oven and reacts, obtains bismuth sulfide and gold grain composite solution.
Further, it is described by the TiO2Nano-tube array is put into bismuth sulfide and the gold grain composite solution, is led to
Crossing the obtained bismuth sulfide modification gold nano grain/titania nanotube structure of Oven Method includes：By the TiO2Nano-tube array
After pre-treatment, immerse in bismuth sulfide and the gold grain composite solution, be then placed in baking oven, heated under conditions of 37 DEG C
4h, obtain bismuth sulfide modification gold nano grain/titania nanotube structure.
Bismuth sulfide modification gold nano grain/titania nanotube structure prepared by aforesaid way can be applied to organic
Dyestuff contaminant degradation catalyst.
Bismuth sulfide modification gold nano grain/titania nanotube structure prepared by aforesaid way can also be applied multiple
In condensation material.
Bismuth sulfide modification gold nano grain/titania nanotube structure prepared by aforesaid way can also be applied to non-
In glucose sensor.
The invention provides a kind of bismuth sulfide modification gold nano grain/titania nanotube structure preparation method, its
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 degraded of the organic pollutions 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.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill of field, without having to pay creative labor, it can also be obtained according to these accompanying drawings other
Accompanying drawing.Wherein,
Fig. 1 is the flow signal that the bismuth sulfide of the present invention modifies the preparation method of gold nano grain/titania nanotube structure
Figure；
Fig. 2 is the SEM figures that bismuth sulfide produced by the present invention modifies gold nano grain/titania nanotube structure, wherein, (a),
(b), the bismuth sulfide that (c), the concentration of respectively dipping bismuth sulfide gold nano grain solution are 0.02%, 0.01%, 0.005% is modified
The SEM figures of gold-nanoparticle-supported titania nanotube structure；
A in Fig. 3, b are that obtained bismuth sulfide modifies gold nano grain/titania nanotube structure in the embodiment of the present invention 1
SEM schemes, and c is the EDS figures that the bismuth sulfide prepared in embodiment 1 modifies gold nano grain/titania nanotube structure, and d is real
Apply the Elemental redistribution collection of illustrative plates of the bismuth sulfide modification gold nano grain/titania nanotube structure prepared in example 1；
Fig. 4 is TEM figures, the HRTEM that the bismuth sulfide prepared in embodiment 1 modifies gold nano grain/titania nanotube structure
Figure and mapping.View (a), (b), the TEM figures that (c) is bismuth sulfide modification gold nano grain/titania nanotube structure,
View (d), (e) are the HRTEM figures that bismuth sulfide modifies gold nano grain/titania nanotube structure, and view (f) is view
(c) mapping；
Fig. 5 is TiO unmodified in embodiment 12The TiO of nano-tube array, bismuth sulfide gold nano particle modification2Nanotube battle array
Row, simple gold grain modification TiO2Nano-tube array and simple bismuth sulfide modification TiO2XPS figure, wherein figure (a) be full spectrogram,
Figure (b), (c), (d) be the gold, bismuth that the bismuth sulfide for preparing modifies gold nano grain/titania nanotube structure in embodiment 1,
The narrow spectrogram of sulphur；
Fig. 6 is TiO unmodified in embodiment 12The TiO of nano-tube array, various concentrations bismuth sulfide gold nano particle modification2
Nano-tube array, simple gold grain modification TiO2Nano-tube array and simple bismuth sulfide modification TiO2Fluorescence spectra；
Fig. 7 is TiO unmodified in embodiment 12The TiO of nano-tube array, various concentrations bismuth sulfide modification gold nano grain2
Nano-tube array, simple gold grain modification TiO2Nano-tube array and simple bismuth sulfide modification TiO2The photoelectric current of nano-tube array
Response diagram；
Fig. 8 is the TiO modified in embodiment 1 through bismuth sulfide gold grain2Oxygen of the nano-tube array to different glucose solution
Change curve；
Fig. 9 is the TiO modified in embodiment 1 through bismuth sulfide gold grain2Sound of the nano-tube array to different glucose solution
Answer staircase curve；
Figure 10 is the TiO that bismuth sulfide gold grain is modified in embodiment 12Nano-tube array resists bad when doing non-enzymatic glucose sensor
The interference effect staircase curve figure of hematic acid, uric acid etc.；
Figure 11 is TiO unmodified in embodiment 12Nano-tube array, the TiO of bismuth sulfide gold grain modification2Nano-tube array,
Gold modification TiO2Nano-tube array and the Nano tube array of titanium dioxide of bismuth sulfide modification are degraded Asia under ultraviolet light and visible ray
The efficiency chart of methyl blue；View b, d are respectively view a, the UV absorption wavelength graph of c counter samples.
Embodiment
The present invention carries out a series of the shortcomings that modifications are to optimize itself to titania nanotube battle array and such as adulterates gold
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 with narrow band gap（〜1.3eV）Photoresponse half
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）It is dispersed in TiO2Nanotube surface can assist to capture photoproduction electricity
Son, accelerate the separation of electron hole, and then suppress light induced electron and hole-recombination.Application in terms of glucose is detected, has
More superior catalytic performance, for almost all of human history, gold is because it is natural beautiful, consistency and unique ductility
Pursued with the balance of durability.The combination of Au nano particles can also be used as electron trap, contribute to separation of charge, and by
In surface plasmon resonance（LSPR）Effect, under visible light to TiO2It is sensitized.In two semiconductors（Bi2S3-
TiO2）Between addition Au nano particles can reduce trapping state Auger rate, and part compensates the negative shadow in surface trap site
Ring, so as to improve light conversion efficiency
Referring to Fig. 1, Fig. 1, which is the bismuth sulfide of the present invention, modifies the preparation method of gold nano grain/titania nanotube structure
Schematic flow sheet.As shown in figure 1, the present invention provides a kind of bismuth sulfide modification gold nano grain/titania nanotube structure
Preparation method, comprise the following steps：
Substrate is selected, to the substrate pretreatment；
Anodizing prepares TiO on the substrate twice2Nano-tube array；
Gold grain is obtained by reducing；
Formulating vulcanization bismuth and gold grain composite solution；
By the TiO2Nano-tube array is put into bismuth sulfide and the gold grain composite solution, and bismuth sulfide is made by Oven Method
Modify gold nano grain/titania nanotube structure.
In order to facilitate the understanding of the purposes, features and advantages of the present invention, with reference to embodiment
The present invention is further detailed explanation.
A kind of preparation method of bismuth sulfide modification gold nano grain/titania nanotube structure, including：
Step 1：Titanium sheet is can be selected in substrate, and first titanium sheet is pre-processed；
In one embodiment, the step can be with execution specific as follows：Titanium sheet is cleaned.Wherein, the titanium sheet is pure titanium
Or titanium alloy, its size are the cm of 1.5 cm × 3.0.Successively using dust technology, acetone, ethanol and deionized water to titanium sheet ultrasound
Clean 20-40min.
Step 2：Anodizing prepares TiO2Nano-tube array；
In one embodiment, the step can be with execution specific as follows：Using the titanium sheet after cleaning as anode, platinized platinum is as cloudy
Electrolyte is used as in the ethylene glycol solution of pole, ammonium fluoride and water, applies certain voltage, carries out anodic oxidation twice, anodic oxidation
TiO is made2Nano-tube array, then calcine to obtain the more preferable Detitanium-ore-type TiO of crystal formation2Nano-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%.The voltage for carrying out first time anodic oxidation is 40-60V, time 1-3h, second of anodic oxidation
Voltage is 40-60V, time 3-10min.By obtained TiO2Nano-tube array is calcined in atmosphere, the temperature of calcining
For 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 more preferable Detitanium-ore-type TiO of crystal formation2Nano-tube array.
Step 3：Using reduction of sodium citrate gold grain
In one embodiment, the step can be with execution specific as follows：Use HAuCl4（60 ml, 0.01wt%、0.02wt%、
0.005wt%,）Oil bath（130℃）Stirring, boils rear adding citric acid sodium（600ml, 1wt%）Change the time（0.5h, 1h,
1.5h, 2h）, obtain AuNPs solution.
Step 4：The mixed solution of formulating vulcanization bismuth and gold grain；
In one embodiment, the step can be with execution specific as follows：Add the μ L thioacetamides of 0.003g 400 in AuNPs solution
With the μ L bismuth acetates of 0.0038g 100, it is put into 80 DEG C of baking ovens and reacts 10h, obtain the mixed solution of bismuth sulfide and gold grain.
Step 5：TiO2NTs carries out pre-treatment；
In one embodiment, the step can be with execution specific as follows：By TiO2NTs is put into MPTs（3- mercapto propyl trimethoxies
The μ L of silane 150）And NH425 DEG C of 24h of lucifuge reaction in OH (30 μ L, 27%) 15ml ethanol solutions, lucifuge mode such as uses aluminium
Paper tinsel covers.
Step 6：Based on obtained bismuth sulfide and gold grain mixed solution, bismuth sulfide and gold grain are loaded into TiO2
NTs structures get on, and bismuth sulfide modification gold nano grain/titania nanotube structure is made.
In one embodiment, the step can be with execution specific as follows：By the titanium sheet after processing（After two-step anodization
Titanium tube）Immerse in the solution of the composite solution of gold/bismuth sulfide, be put into heating 4h in 37 DEG C of baking ovens, obtain bismuth sulfide modification Jenner
Rice grain/titania nanotube structure.
After above-mentioned six steps, complete to make bismuth sulfide modification gold nano grain/titania nanotube structure.At this
After six steps, structure can also be tested.
Step 7：The performance that photocatalytically degradating organic dye pollutant is carried out using the novel photoelectric catalyst prepared is surveyed
Examination.
Specifically, by unmodified TiO2Nano-tube array, the TiO of bismuth sulfide gold grain modification2Nano-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 the aqueous solution in, after in dark surrounds standing 0.5 hour and reaching adsorption equilibrium state, respectively in ultraviolet light and
0-120 min are irradiated under visible ray, time interval is 30 min.During each time interval, the ultraviolet spectra of foul solution is tested
Absorption value.
The above-mentioned substrate prepared can use as electrode, 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 the scanning number of turns 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, disturb in linearity curve, it is 0-10mM, ascorbic acid and uric acid drop that concentration, which is added dropwise, in glucose
It is 2mM to add concentration.
Referring to Fig. 2, Fig. 2, which is bismuth sulfide produced by the present invention, modifies gold nano grain/titania nanotube structure
SEM schemes, wherein, (a), (b), (c), be respectively dipping bismuth sulfide gold nano grain solution concentration for 0.02%, 0.01%,
0.005% bismuth sulfide modifies the SEM figures of gold-nanoparticle-supported titania nanotube structure.As shown in Fig. 2 bismuth sulfide is repaiied
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 particle diameter of modification is 15-20 nm, uniformly raw on titania nanotube.
In order to facilitate the understanding of the purposes, features and advantages of the present invention, with reference to the accompanying drawings and examples
Further illustrate technical scheme.But the invention is not restricted to listed embodiment, it should also be included in institute of the present invention
It is required that interest field in other any known change.
First, " one embodiment " or " embodiment " referred to herein refers to may be included at least one realization side of the present invention
Special characteristic, structure or characteristic in formula." in one embodiment " that different places occur in this manual not refers both to
Same embodiment, nor the single or selective embodiment mutually exclusive with other embodiment.
Secondly, the present invention is described in detail using structural representation etc., when the embodiment of the present invention is described in detail, for ease of saying
Bright, schematic diagram can disobey general proportion and make partial enlargement, and the schematic diagram is example, and it should not limit the present invention herein
The scope of protection.In addition, the three dimensions 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 area is fixed referred to as, which part letter text is explained such as
Under：SEM schemes：Electron scanning imaging figure；TEM schemes：Transmitted electron surface sweeping imaging figure；HRTEM schemes：High-resolution transmitted electron is swept
Face imaging figure；EDS schemes：Energy spectrum diagram；XRD：X-ray diffractogram；XPS spectrum figure：X-ray photoelectron spectroscopic analysis spectrogram.
Embodiment 1
The implementation case shows a kind of preparation of bismuth sulfide modification gold nano grain/titania nanotube structure as follows
Method：
（1）The pretreatment of titanium sheet and two-step electrochemical anodizing method prepare TiO2Nano-tube array.To titanium sheet substrate acetone, anhydrous second
Alcohol, deionized water are cleaned by ultrasonic 15min successively.Using platinum plate electrode as negative electrode, while insertion contains 98v% ethylene glycol（Ammonium fluoride
0.3wt%）In the electrolyte solution of 2v% water, apply 50V ultors oxidation 1.5h, ultrasound comes off after film layer, continued to
50V ultors aoxidize 6 min, and TiO is made2Nano-tube array, then through 450 DEG C of heat treatment 2h, be transformed into from unformed state
The preferable anatase of crystal formation.
（2）Pass through HAuCl4（0.001g 10ml）Oil bath is stirred, and it is anti-to boil rear adding citric acid sodium (1g 99g deionized waters)
Answer 1-2 hours to obtain AuNPs solution, add the μ L thioacetamides of 0.003g 400 and 0.0038g in 50ml Au NPs solution
100 μ L bismuth acetates, 80 DEG C of baking oven reaction 10h are put into, obtain the composite solution of gold/bismuth sulfide.By TiO2NTs is put into MPTs（3-
The μ L of mercaptopropyl trimethoxysilane 150）And NH4In OH (30 μ L, 27%) 15ml ethanol solutions 24h 25 is covered with aluminium foil
℃.The titanium sheet soaked is put into the 15ml composite solution of gold/bismuth sulfide 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 grain/Nano tube array of titanium dioxide prepared：Configuration 0.1
M sodium sulfite does supporting electrolyte, and bismuth sulfide modification gold grain/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 level of electrochemical workstation, wherein having
No light time interval is 30s.
（4）Photocatalytic degradation organic contamination is made to the bismuth sulfide modification gold grain/Nano tube array of titanium dioxide prepared
The application of thing：By unmodified TiO2Nano-tube array, the TiO of bismuth sulfide gold grain modification2Nano-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, after first in dark surrounds standing 0.5 hour and reaching adsorption equilibrium state, shone respectively under ultraviolet light and visible ray
Penetrate 0-120 min.Time interval is respectively 30 min.Each time interval, corresponding solution is taken to test ultraviolet spectra absorption value.
（5）Making non-enzymatic glucose sensor to the bismuth sulfide modification gold grain/Nano tube array of titanium dioxide prepared should
With：The sodium hydroxide solution for configuring 0.1 M does supporting electrolyte, and bismuth sulfide modification gold grain/Nano tube array of titanium dioxide is made
Working electrode, platinized platinum are made to make reference electrode to electrode, silver/silver chlorate, are detected using the cyclic voltammetry curve of electrochemical workstation
Glucose, wherein glucose add the mM of concentration 5 successively, and further, electrode performance interference detection, test prepares electrode pair
The interference of ascorbic acid, uric acid, wherein glucose addition concentration are 2-10mM, and uric acid, ascorbic acid addition concentration are 2mM.
Bismuth sulfide modification gold nano grain/specific conclusion of titania nanotube structure obtained by above-described embodiment is such as
Under：
Referring to Fig. 2, Fig. 2 is the SEM that bismuth sulfide produced by the present invention modifies gold nano grain/titania nanotube structure
Figure, wherein, (a), (b), (c), the concentration of respectively dipping bismuth sulfide gold nano grain solution are 0.02%, 0.01%, 0.005%
Bismuth sulfide modify the SEM figures of gold-nanoparticle-supported titania nanotube structure.As can be seen from Figure 2,15-20 nm vulcanization
Bismuth modification gold nano grain is uniformly deposited on nanotube surface and inside.
Referring to Fig. 3, a in Fig. 3, b are that obtained bismuth sulfide modifies gold nano grain/titanium dioxide in the embodiment of the present invention 1
The SEM figures of titanium nano tube structure, c are that the bismuth sulfide prepared in embodiment 1 modifies gold nano grain/titania nanotube structure
EDS figures, d is the distribution diagram of element that the bismuth sulfide for preparing modifies gold nano grain/titania nanotube structure in embodiment 1
Spectrum.As shown in figure 3, bismuth sulfide modification gold grain/titania nanotube structure mainly contains Ti, O, S, Bi and Au element.
Referring to Fig. 4, Fig. 4, which is 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 figures of structure, view (d), (e) they are the HRTEM figures that bismuth sulfide modifies gold nano grain/titania nanotube structure, 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 figures are shown between TiO2 Detitanium-ore-types (101) crystal face lattice
Away from for 0.352 nm, gold（111）Interplanar distance is 0.23 nm, bismuth sulfide（221）Interplanar distance be 0.286 nm, with Fig. 4's
XRD test results match.
Referring to Fig. 5, Fig. 5 is TiO unmodified in embodiment 12Nano-tube array, bismuth sulfide gold nano particle modification
TiO2Nano-tube array, simple gold grain modification TiO2Nano-tube array and simple bismuth sulfide modification TiO2XPS figure, wherein
It is full spectrogram to scheme (a), 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 tubular construction.As shown in figure 5, except O 1s (530.3 eV), Ti 2p (458.3 eV,
464.2ev) and C 1s (283.8 eV) peak, the presence at Bi 4f and S 2p and Au 4f peaks demonstrate bismuth sulfide modification gold nano
Particle/Nano tube array of titanium dioxide.It can be seen that from Bi 4f and S 2p high-resolution XPS collection of illustrative plates c and d, 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 TiO unmodified in embodiment 12Nano-tube array, various concentrations bismuth sulfide gold nano
The TiO of particle modification2Nano-tube array, simple gold grain modification TiO2Nano-tube array and simple bismuth sulfide modification TiO2It is glimmering
Light spectrogram.As shown in fig. 6, the fluorescence intensity highest of unmodified TiO2 nanotube battle arrays, by loading Bi2S3It is glimmering after Au
Luminous intensity reduces, and further illustrates the restructuring for hindering free electron and hole.
Referring to Fig. 7, Fig. 7 is TiO unmodified in embodiment 12Nano-tube array, various concentrations bismuth sulfide modification gold
The TiO of nano particle2Nano-tube array, simple gold grain modification TiO2Nano-tube array and simple bismuth sulfide modification 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, suppress the restructuring of electron hole pair.
Referring to Fig. 8, as shown in figure 8, using 0.1 M sodium hydroxide solution as supporting electrolyte, bismuth sulfide modifies gold
Oxidation curve of the grain/Nano tube array of titanium dioxide in the sodium hydroxide solution of different glucose, wherein -0.23V is left
The peak that right peak adsorbs the electrochemical oxidation, 0.1 V or so of glucose for electrode surface is that electrode surface adsorbs glucose electrification
Learn the further oxidation of caused intermediate in oxidizing process.0.45 V or so peak is that the glucose in solution body phase diffuses to
Carried out on electrode caused by direct oxidation.With the continuous increase of concentration of glucose, peak value also gradually increases.
Referring to Fig. 9, Fig. 9 is the TiO modified in embodiment 1 through bismuth sulfide gold grain2Nano-tube array is to various concentrations
The response staircase curve of glucose solution, 2ml glucose solutions were injected every 25 seconds.It can be seen that an addition glucose is molten
Liquid, current value can diminish, increase over time, stepped, illustrate that the response of this electrode pair concentration of glucose is sharper.
Referring to Fig. 10, Figure 10 is the TiO that bismuth sulfide gold grain is modified in embodiment 12Nano-tube array does non-enzymatic grape
The interference effect staircase curve figure of Ascorbic Acid, uric acid etc. during 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
For 30% or so.
Figure 11 is referred to, Figure 11 a, c are respectively TiO unmodified under ultraviolet light and visible ray in embodiment 12Nanometer
Pipe array, the TiO of bismuth sulfide gold grain modification2Nano-tube array, gold modification TiO2Nano-tube array and the dioxy of bismuth sulfide modification
Change the efficiency chart of titanium nano-tube array degradation of methylene blue under ultraviolet light and visible ray；View b, d are respectively view a, and c is corresponding
Bismuth sulfide modification gold grain/Nano tube array of titanium dioxide UV absorption wavelength graph.It is the drop under ultraviolet light to scheme a
Solve methylene blue efficiency chart, Au/Bi2S3@TiO2Degradation effect is preferably 30% or so, and figure c is sub- for degraded 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 preparation of bismuth sulfide modification gold nano grain/titania nanotube structure as follows
Method：
（1）The pretreatment of titanium sheet and two-step electrochemical anodizing method prepare TiO2Nano-tube array.To titanium sheet substrate acetone, anhydrous second
Alcohol, deionized water are cleaned by ultrasonic 15 min successively.Using platinum plate electrode as negative electrode, while insertion contains 97v% ethylene glycol（Ammonium fluoride
0.4wt%）In the electrolyte solution of 3v% water, apply 40 V ultors and aoxidize 1 h, ultrasound comes off after film layer, continued to
40 V ultors aoxidize 8 min, and TiO is made2Nano-tube array, then through 450 DEG C of heat treatment 2h, be transformed into from unformed state
The preferable anatase of crystal formation.
（2）Pass through HAuCl4（0.002g 10ml）Oil bath is stirred, and it is anti-to boil rear adding citric acid sodium (1g 99g deionized waters)
Answer 1-2 hours to obtain AuNPs solution, add the μ L thioacetamides of 0.003g 400 and 0.0038g in 50ml Au NPs solution
100 μ L bismuth acetates, 80 DEG C of baking oven reaction 10h are put into, obtain the composite solution of gold/bismuth sulfide.By TiO2NTs is put into MPTs（3-
The μ L of mercaptopropyl trimethoxysilane 150）And NH4In OH (30 μ L, 27%) 15ml ethanol solutions 24h 25 is covered with aluminium foil
℃.The titanium sheet soaked is put into the 15ml composite solution of gold/bismuth sulfide 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 grain/Nano tube array of titanium dioxide prepared：Configuration 0.1
M sodium sulfite does supporting electrolyte, and bismuth sulfide modification gold grain/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 level of electrochemical workstation, wherein having
No light time interval is 30s.
（4）Photocatalytic degradation organic contamination is made to the bismuth sulfide modification gold grain/Nano tube array of titanium dioxide prepared
The application of thing：By unmodified TiO2Nano-tube array, the TiO of bismuth sulfide gold grain modification2Nano-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, after first in dark surrounds standing 1 hour and reaching adsorption equilibrium state, irradiated respectively under ultraviolet light and visible ray
0-120min.Time interval is respectively 30min.Each time interval, corresponding solution is taken to test ultraviolet spectra absorption value.
（5）Making non-enzymatic glucose sensor to the bismuth sulfide modification gold grain/Nano tube array of titanium dioxide prepared should
With：Configuration 0.1M sodium hydroxide solution is supporting electrolyte, bismuth sulfide modification gold grain/Nano tube array of titanium dioxide workmanship
Make electrode, platinized platinum is made to make reference electrode to electrode, silver/silver chlorate, and Portugal is detected using the cyclic voltammetry curve of electrochemical workstation
Grape sugar, wherein glucose adds concentration 10mM successively, and further, electrode performance interference detection, test prepares electrode confrontation
The interference of bad hematic acid, uric acid, wherein glucose addition concentration are 5-10mM, and uric acid, ascorbic acid addition concentration are 5 mM.
Embodiment 3
The implementation case shows a kind of preparation of bismuth sulfide modification gold nano grain/titania nanotube structure as follows
Method：
（1）The pretreatment of titanium sheet and two-step electrochemical anodizing method prepare TiO2Nano-tube array.To pure titanium sheet substrate dust technology, third
Ketone, absolute ethyl alcohol, deionized water are cleaned by ultrasonic 25 min successively.Using platinum plate electrode as negative electrode, while insertion contains 99v% second two
Alcohol（Ammonium fluoride 0.1wt%）In the electrolyte solution of 1v% water, apply 60 V ultors and aoxidize 1 hour, ultrasonic dezidua
After layer, continue to 60 V ultors and aoxidize 5 min, TiO is made2Nano-tube array, then 450 DEG C of 1 h of calcining, make it from nothing
Stabilized condition is transformed into anatase.
（2）Pass through HAuCl4（0.0005g 10ml）Oil bath is stirred, and boils rear adding citric acid sodium (1g 99g deionized waters)
Reaction 1-2 hours obtain AuNPs solution, add the μ L thioacetamides of 0.003g 400 and 0.0038g in 50ml Au NPs solution
100 μ L bismuth acetates, 80 DEG C of baking oven reaction 10h are put into, obtain the composite solution of gold/bismuth sulfide.By TiO2NTs is put into MPTs（3-
The μ L of mercaptopropyl trimethoxysilane 150）And NH4In OH (30 μ L, 27%) 15ml ethanol solutions 24h 25 is covered with aluminium foil
℃.The titanium sheet soaked is put into the 15ml composite solution of gold/bismuth sulfide 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 grain/Nano tube array of titanium dioxide prepared：Configuration 0.1
M sodium sulfite does supporting electrolyte, and bismuth sulfide modification gold grain/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 level of electrochemical workstation, wherein having
No light time interval is 30s.
（4）Photocatalytic degradation organic contamination is made to the bismuth sulfide modification gold grain/Nano tube array of titanium dioxide prepared
The application of thing：By unmodified TiO2Nano-tube array, the TiO of bismuth sulfide gold grain modification2Nano-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, after first in dark surrounds standing 1 hour and reaching adsorption equilibrium state, irradiated respectively under ultraviolet light and visible ray
0-120 min.Time interval is respectively 30 min.Each time interval, corresponding solution is taken to test ultraviolet spectra absorption value.
（5）Making non-enzymatic glucose sensor to the bismuth sulfide modification gold grain/Nano tube array of titanium dioxide prepared should
With：The sodium hydroxide solution for configuring 0.1 M does supporting electrolyte, and bismuth sulfide modification gold grain/Nano tube array of titanium dioxide is made
Working electrode, platinized platinum are made to make reference electrode to electrode, silver/silver chlorate, are detected using the cyclic voltammetry curve of electrochemical workstation
Glucose, wherein glucose add the mM of concentration 3 successively, and further, electrode performance interference detection, test prepares electrode pair
The interference of ascorbic acid, uric acid, wherein glucose addition concentration are 1-5 mM, and uric acid, ascorbic acid addition concentration are 1 mM.
Compared with prior art, the beneficial effects of the invention are as follows：Bismuth sulfide modification gold nano grain/titanium dioxide of the present invention
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 row, to reach the degraded to organic pollutions 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 embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to preferable
The present invention is described in detail embodiment, it will be understood by those within the art that, can be to the technology of the present invention
Scheme is modified or equivalent substitution, and without departing from the spirit and scope of technical solution of the present invention, it all should cover in this hair
Among bright right.
Claims (10)
1. bismuth sulfide modifies the preparation method of gold nano grain/titania nanotube structure, it is characterised in that this method includes
Following steps：
Substrate is selected, to the substrate pretreatment；
Anodizing prepares TiO on the substrate twice2Nano-tube array；
Gold grain is obtained by reducing；
Formulating vulcanization bismuth and gold grain composite solution；
By the TiO2Nano-tube array is put into bismuth sulfide and the gold grain composite solution, and bismuth sulfide is made by Oven Method
Modify gold nano grain/titania nanotube structure.
2. the preparation method of bismuth sulfide modification gold nano grain/titania nanotube structure according to claim 1, its
It is characterised by：The substrate is titanium sheet, and the titanium sheet is pure titanium or titanium alloy, and the substrate pretreatment is to use dilute nitre successively
Acid, acetone, ethanol and deionized water are cleaned by ultrasonic the substrate 20-40min.
3. the preparation method of bismuth sulfide modification gold nano grain/titania nanotube structure according to claim 1, its
It is characterised by, the anodizing twice prepares TiO on the substrate2Nano-tube array specifically includes：With by pre- place
As anode, platinized platinum inserts and anodic oxidation twice is carried out in electrolyte the substrate of reason as negative electrode, and anodic oxidation is made just
Level TiO2Nano-tube array, by the primary TiO2Nano-tube array calcining obtains Detitanium-ore-type TiO2Nano-tube array.
4. the preparation method of bismuth sulfide modification gold nano grain/titania nanotube structure according to claim 3, its
It is characterised by：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 during 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 time of calcining is 1-3h, the heating and cooling of calcining
Speed is 3-8 DEG C/min.
5. the preparation method of bismuth sulfide modification gold nano grain/titania nanotube structure according to claim 1, its
It is characterised by, it is described to be included by reducing acquisition gold grain：Use HAuCl4Oil bath is stirred, and boils rear adding citric acid sodium, during change
Between, obtain AuNPs solution.
6. the preparation method of bismuth sulfide modification gold nano grain/titania nanotube structure according to claim 1, its
It is characterised by, the formulating vulcanization bismuth and gold grain composite solution are included in AuNPs solution plus thioacetamide and bismuth acetate,
It is put into baking oven and reacts, obtains bismuth sulfide and gold grain composite solution.
7. the preparation method of bismuth sulfide modification gold nano grain/titania nanotube structure according to claim 1, its
It is characterised by, it is described by the TiO2Nano-tube array is put into bismuth sulfide and the gold grain composite solution, passes through Oven Method
Bismuth sulfide modification gold nano grain/titania nanotube structure, which is made, to be included：By the TiO2Nano-tube array is through pre-treatment
Afterwards, immerse in bismuth sulfide and the gold grain composite solution, be then placed in baking oven, heat 4h under conditions of 37 DEG C, obtain
Bismuth sulfide modifies gold nano grain/titania nanotube structure.
8. the preparation method of bismuth sulfide modification gold nano grain/titania nanotube structure according to claim 1-7
Prepared bismuth sulfide modifies gold nano grain/titania nanotube structure in organic dye pollutant degradation catalyst
Using.
9. the preparation method of bismuth sulfide modification gold nano grain/titania nanotube structure according to claim 1-7
The prepared bismuth sulfide modification gold nano grain/application of titania nanotube structure in the composite.
10. the preparation side of bismuth sulfide modification gold nano grain/titania nanotube structure according to claim 1-7
Bismuth sulfide modification gold nano grain/application of the titania nanotube structure in non-glucose sensor prepared by method.
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| PCT/CN2018/093955 WO2019047602A1 (en) | 2017-09-08 | 2018-07-02 | Method for preparing bismuth sulfide-modified gold nanoparticles/sodium dioxide nanotube structure and application thereof |
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| CN108525667A (en) * | 2018-04-10 | 2018-09-14 | 苏州大学 | Metal organic frame derives the preparation method of the TiO 2 nanotubes modified array of cobaltosic oxide |
| CN108760857A (en) * | 2018-06-01 | 2018-11-06 | 徐州医科大学 | A kind of titanium dioxide nanofiber enzyme electrode of decorated by nano-gold and its preparation method and application |
| WO2019047602A1 (en) * | 2017-09-08 | 2019-03-14 | 南通纺织丝绸产业技术研究院 | Method for preparing bismuth sulfide-modified gold nanoparticles/sodium dioxide nanotube structure 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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