CN110252353A - A kind of BiOI/Bi/TiO of ternary heterojunction structure2Composite photocatalyst material and its preparation and application - Google Patents
A kind of BiOI/Bi/TiO of ternary heterojunction structure2Composite photocatalyst material and its preparation and application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 127
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 230000007547 defect Effects 0.000 claims abstract description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 11
- 239000010935 stainless steel Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- UOZDOLIXBYLRAC-UHFFFAOYSA-L [2-hydroxy-3-(trimethylazaniumyl)propyl]-trimethylazanium;diiodide Chemical compound [I-].[I-].C[N+](C)(C)CC(O)C[N+](C)(C)C UOZDOLIXBYLRAC-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011229 interlayer Substances 0.000 claims abstract description 4
- 239000008187 granular material Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000010936 titanium Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 claims description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- LGPJVNLAZILZGQ-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCC[N+](C)(C)C LGPJVNLAZILZGQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 235000009518 sodium iodide Nutrition 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 23
- 239000002184 metal Substances 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000002708 enhancing effect Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 229960000935 dehydrated alcohol Drugs 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000004044 response Effects 0.000 description 4
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- 238000001291 vacuum drying Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004054 benzoquinones Chemical class 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 241000894007 species Species 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010020466 Hunger Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910010251 TiO2(B) Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- 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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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The present invention relates to a kind of BiOI/Bi/TiO of ternary heterojunction structure2Composite photocatalyst material, TiO2For the nanometer chip architecture of exposure { 001 } and { 101 } crystal face simultaneously, there are Lacking oxygens and unsaturation Ti on surface3+Defect sites；BiOI partial size is uniformly dispersed in TiO in 50~200nm or so2{ 001 } on crystal face；Metal Bi granule interlayer is in BiOI and TiO2Between the interface of contact position.Preparation includes: first to prepare while exposing { 001 } and { 101 } crystal face, and there are Lacking oxygens and unsaturation Ti on surface3+The TiO of defect sites2Nanometer sheet；Then by TiO2In nanometer sheet and bismuth source dispersion organic solution, the organic solution containing propiodal is instilled with vigorous stirring, continues to stir；It is transferred in stainless steel autoclave, 12~36h is reacted in 140~170 DEG C；It is cooled to room temperature, is filtered, washed, is dried in vacuo.The present invention passes through TiO2The dispersibility of strong interaction enhancing BiOI between BiOI, and metal Bi is formed in situ between contact interface, quantum yield can be improved, light induced electron and hole is made to possess stronger redox ability, there is preferable catalytic activity.
Description
Technical field
The invention belongs to visible-light photocatalysis material field more particularly to a kind of BiOI/Bi/ of ternary heterojunction structure
TiO2Composite photocatalyst material and its preparation and application.
Background technique
The two-dimentional TiO of exposure { 001 } and { 101 } crystal face altogether2Nanometer sheet is because its unique photo-generate electron-hole is to separation energy
Power has become TiO2The research hotspot in base optic catalytic field.However, TiO2It is a kind of broad-band gap (~3.2eV) n-type semiconductor,
It can only be by ultraviolet excitation.In order to promote it in the photoresponse ability of visible light region, an effective method is by TiO2With
A kind of narrow gap semiconductor is compounded to form heterojunction structure catalyst.The TiO reported before2In base heterojunction structure catalyst, metal
The hetero-junctions (metal-mediated heterojunctions, MMHs) of mediation is due to its higher quantum yield by wide
General concern.But metal mediate heterojunction structure preparation process it is relative complex, related metal be usually noble metal Au, Ag,
Pd.Noble metal is replaced with base metal, exploitation MMHs photochemical catalyst has great importance and the trend of current development.
BiOI is a kind of narrow band gap (1.94eV) p-type semiconductor, can be by excited by visible light, unique anisotropy stratiform
Structure is conducive to electron-transport, becomes building BiOI/TiO2The appropriate candidate materials of anisotropy heterojunction structure.However,
In actual fabrication process, the BiOI separate microspheres easy to reunite for growing into micron-scale greatly reduce heterojunction boundary and connect
Contacting surface product.In addition, the quantum efficiency of BiOI is lower, this is because the body that electron-hole corresponds to object, which mutually slowly migrates, leads to photoproduction
Caused by the Quick Casting of carrier.By reducing the partial size of BiOI, it is improved in TiO2Dispersibility in nanometer sheet, by Fermi
The lower metal of energy level introduces transmission medium of the heterojunction boundary as photo-generated carrier, is expected to solve disadvantages mentioned above.
Summary of the invention
The purpose of the present invention is to provide a kind of BiOI/Bi/TiO of simple and feasible ternary heterojunction structure2Complex light is urged
The preparation method and application for changing material, the BiOI/Bi/TiO of ternary heterojunction structure is provided by the method one-step synthesis2It is compound
Catalysis material uses metal Bi that noble metal (Au, Ag, Pt etc.) is replaced to mediate as metal, the light induced electron of modulation composite material
With the transfer path in hole, the separative efficiency of photo-generate electron-hole pairs is improved；The oxidation-reduction potential for adjusting semiconductor material, mentions
The redox ability of high composite material, it is of the existing technology to solve the problems, such as.
A kind of BiOI/Bi/TiO of ternary heterojunction structure2Composite photocatalyst material, TiO2For simultaneously exposure { 001 } and
{ 101 } the nanometer chip architecture of crystal face, there are Lacking oxygens and unsaturation Ti on surface3+Defect sites；BiOI is uniformly dispersed in TiO2
{ 001 } on crystal face；Metal Bi granule interlayer is in BiOI and TiO2Between the interface of contact position.Based on TiO2On nanometer sheet { 001 } crystal face
There are Lacking oxygens abundant and unsaturation Ti3+Defect sites can pass through TiO2Strong interaction enhancing between BiOI
The dispersibility of BiOI, and metal Bi is formed in situ between contact interface.Nanometer sheet is made in titanium dioxide, is exposed
{ 001 } high energy planar defect is relatively more, and furthermore { 001 } crystal face and { 101 } crystal face may make up surface heterogeneous medium knot.Ti3+It is that Lacking oxygen lures
It is derived, there is Lacking oxygen, oxygen atom abjection leaves two electronics, electronics transfer to two neighbouring Ti4+Become two Ti3+。
Ti3+Electronics can be provided and play reduction.
Further, the BiOI/Bi/TiO of the ternary heterojunction structure2Existed simultaneously in composite photocatalyst material BiOI,
Bi and TiO2Three kinds of object phases.
The BiOI/Bi/TiO of above-mentioned ternary heterojunction structure2The preparation method of composite photocatalyst material mainly includes following step
It is rapid:
(1) TiO prepared2Nanometer sheet exposes { 001 } and { 101 } crystal face simultaneously, and there are Lacking oxygens and unsaturation on surface
Ti3+Defect sites；
(2) under conditions of 26~28 DEG C, by TiO obtained by step (1)2Nanometer sheet and bismuth source are scattered in organic solution,
It instills the organic solution containing propiodal dropwise with vigorous stirring, continues 60~90min of stirring；Mixing speed is 500~600r/
min
(3) suspension obtained in step (2) is transferred in stainless steel autoclave, controlled at 140~170
DEG C, the reaction time is 12~36h；
(4) it is cooled to room temperature, solid product is obtained by filtration, product be dried in vacuo after sufficiently washing in 50~90 DEG C
8~for 24 hours；Washing is first to be washed 3~5 times with dehydrated alcohol, then be washed with deionized 3~5 times.
Further, step (1) TiO2The preparation of nanometer sheet mainly comprises the steps that
(S1) under conditions of 26~28 DEG C, under intense agitation, pattern directed agents HF aqueous solution is instilled dropwise
In titanium source, holding is vigorously stirred 60~120min；Mixing speed is 500~1000r/min；
(S2) mixed liquor obtained by step (S1) is transferred in stainless steel autoclave, controlled at 180~240 DEG C,
Reaction time is 12~36h；
(S3) it is cooled to room temperature, the solid was filtered product, product is carried out to be dried in vacuo 8 in 50~90 DEG C after sufficiently washing
~for 24 hours, obtain primary TiO of the surface containing F2Nanometer sheet；Washing is first to be washed 3~5 times with dehydrated alcohol, then use deionized water
Washing 3~5 times；
(S4) the primary TiO by surface obtained in step (S3) containing F2Nanometer sheet, which is placed in tube furnace, calcines defluorinate, control
Temperature processed is 500~600 DEG C, and calcination atmosphere is air, inertia or reducing atmosphere, and calcination time is 2~4h.Calcination atmosphere is
One of air, helium, argon gas, nitrogen, hydrogen are a variety of.
Further, organic solvent include ethylene glycol, glycol monoethyl ether, glycerine one or more；Institute
State the one or more that bismuth source includes five nitric hydrate bismuths, bismuthyl carbonate, bismuth sulfate；The propiodal includes potassium iodide, iodate
The one or more of sodium, cetyl trimethyl ammonium iodide.
Further, the molar ratio of the bismuth source and propiodal is 1:1.
Further, described HF, H2The volume ratio of O and titanium source is 3:2:25.
Further, the titanium source is one of butyl titanate, titanium tetrachloride, isopropyl titanate or a variety of.
The BiOI/Bi/TiO of above-mentioned ternary heterojunction structure2The application of composite photocatalyst material, which is characterized in that can be used as
The photodegradative catalyst of organic dyestuff
Compared with prior art, the present invention is based on TiO2There are Lacking oxygen abundant and insatiable hungers on nanometer sheet { 001 } crystal face
And Ti3+Defect sites utilize TiO2The dispersibility of strong interaction enhancing BiOI between surface defect position and BiOI, and
BiOI and TiO2Metal Bi is formed in situ between the contact interface of nanometer sheet.The generated in-situ metal Bi particle gold of the present invention
Belonging to Bi replaces noble metal (Au, Ag, Pt etc.) to mediate as metal, reduces the cost for introducing metallic intermediate layer, modulation composite wood
The light induced electron of material and the transfer path in hole, improve the separative efficiency of photo-generate electron-hole pairs；Adjust the oxygen of semiconductor material
Change reduction potential, improves the redox ability of composite material.The present invention is constructed using one step of solvent-thermal process method with three
The BiOI/Bi/TiO of first heterojunction structure2Composite photocatalyst material；The composite material prepared, which has, is different from tradition BiOI/
TiO2The electronics transfer path of binary heterojunction structure meets Z-scheme electron-transport mechanism, and the light quantum that material can be improved produces
Rate makes light induced electron and hole possess stronger redox ability；Compared with BiOI/TiO2Binary heterojunction structure has higher urge
Change activity.
Detailed description of the invention
Fig. 1 is embodiment 1, (a) TiO made from embodiment 2 and embodiment 32NBs、(b)TiO2MSs、 (c)TiO2NSs-
a、(d)0.20BiOI/TiO2NBs、(e)0.20BiOI/TiO2MSs and (f) 0.20 BiOI/Bi/TiO2The X of NSs-a sample is penetrated
Line powder diffractogram；
Fig. 2 is (a) TiO of embodiment 1, sample made from embodiment 2 and embodiment 32NBs、(b)0.20 BiOI/
TiO2NBs、(c)TiO2MSs、(d)0.20BiOI/TiO2MSs、(e)TiO2NSs-a and (f) 0.20BiOI/Bi/TiO2NSs-a
Field emission scanning electron microscope figure；
Fig. 3 is the ultraviolet-visible diffusing reflection spectrogram of embodiment 1, sample made from embodiment 2 and embodiment 3；
Fig. 4 is the photocatalytic activity figure of embodiment 1, sample made from embodiment 2 and embodiment 3；
Fig. 5 is the photoluminescence spectra figure of embodiment 1, sample made from embodiment 2 and embodiment 3；
(a) and (b) in Fig. 6 is 0.20BiOI/Bi/TiO made from embodiment 12NSs-a tri compound semiconductor light is urged
Change the transmission electron microscope picture of material；
Fig. 7 is 0.20BiOI/Bi/TiO made from embodiment 12The X of NSs-a tri compound conductor photocatalysis material is penetrated
Photoelectron spectra spectrogram；
Fig. 8 is 0.20BiOI/Bi/TiO made from embodiment 12The freedom of NSs-a tri compound conductor photocatalysis material
Base captures assay activity figure.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing
Step ground detailed description.
Embodiment 1
The molar ratio of Bi:Ti is the BiOI/Bi/TiO of 0.20:12Nanometer sheet (calcines) tri compound semiconductor under air atmosphere
Catalysis material.
(1) at 28 DEG C, 9mL HF (40wt%) and 6mL deionized water are mixed, under intense agitation (500~
1000r/s), it is added dropwise in 25mL butyl titanate dropwise, holding is vigorously stirred 60min；
(2) suspension obtained by step (1) is transferred in 100mL stainless steel autoclave, 240 DEG C of reactions are for 24 hours；
(3) it is cooled to room temperature, solid product is collected by filtration, washed 3~5 times with deionized water and dehydrated alcohol respectively, in
80 DEG C of vacuum drying 12h, obtain primary TiO of the surface containing F2Nanometer sheet；
(4) the primary TiO by surface obtained in step (3) containing F2Nanometer sheet, which is placed in tube furnace, calcines defluorinate, in sky
The lower 500 DEG C of calcinings 2h of gas atmosphere obtains surface with Lacking oxygen abundant and unsaturation Ti3+The TiO of defect sites2Nanometer sheet.
(5) at 28 DEG C, TiO obtained in 2mmol step (4)2Nanometer sheet and 0.4mmol Bi (NO3)3·5H2O dispersion
In 20mL ethylene glycol, under intense agitation (500~1000r/s), 20mL ethylene glycol and 0.4mmol KI are instilled dropwise
Mixed solution, continue stir 60min；
(6) suspension obtained in (5) is transferred in 100mL stainless steel autoclave, 160 DEG C of reactions are for 24 hours；
(7) it is cooled to room temperature, solid product is obtained by filtration, washed 3~5 times with deionized water and dehydrated alcohol respectively, in
80 DEG C of vacuum drying 12h.Sample obtained is named as 0.20BiOI/Bi/TiO2NSs-a。
0.20BiOI/Bi/TiO2The XRD spectra of NSs-a shown in f, occurs at 25.3 °, 37.8 °, 48.04 ° as shown in figure 1
Characteristic peak belong to Anatase TiO2(101), (004), (200) face, at 29.3 ° and 31.6 ° occur characteristic peak
Belong to (012) and (110) face of BiOI.The characteristic peak occurred at 27.1 ° belongs to (012) face of metal Bi, this shows
Successfully construct BiOI/Bi/TiO2NSs-a ternary heterojunction structure.It is worth noting that, d and e are respectively BiOI/TiO2NBs and
BiOI/TiO2The XRD spectrogram of MSs, wherein not being found the presence of metal Bi, this illustrates two-dimensional TiO2Nanometer sheet surface is only
Some Lacking oxygens and unsaturation Ti3+Defect sites inducing metal Bi is formed.
0.20BiOI/Bi/TiO2(c), (d) shown, original TiO in the SEM spectrogram such as Fig. 2 of NSs-a2NSs-a is simultaneously
Eight { 101 } faces in two square { 001 } faces and surrounding above and below exposure, surface is smooth, and corner angle are clearly demarcated；After loading BiOI,
TiO2There are many little particle (as shown in circles in figure) for growth on NSs-a { 001 } face, turn out to be BiOI, the partial size of BiOI through TEM
Only tens nanometers.
0.20BiOI/Bi/TiO2Shown in TEM spectrogram such as Fig. 6 (a) and Fig. 6 (b) of NSs-a, TiO2NSs-a's and BiOI
Lattice fringe spacing is respectively 0.355nm and 0.285nm, and the lattice fringe of metal Bi is 0.330 nm, appear in BiOI and
TiO2Between the lattice fringe of NSs-a, illustrate TiO2NSs-a, BiOI and metal Bi are existed simultaneously in composite material, and metal
Bi is mixed in BiOI and TiO2Between the contact interface of NSs-a.
0.20BiOI/Bi/TiO2The XPS spectrum figure of NSs-a as shown in fig. 7, in Fig. 7 (a) and Fig. 7 (b), 457.5eV and
The peak occurred at 457.9eV is Ti3+Characteristic peak, in Fig. 7 (d), at 531.8eV occur peak be Lacking oxygen characteristic peak,
Illustrate TiO2There are Lacking oxygens and unsaturation Ti on the surface NSs-a3+Defect sites.Gold is not detected in Fig. 7 (e) and Fig. 7 (f)
Belong to the characteristic peak of Bi, this is because XPS detection is limited to the region of several nm deeps of sample surfaces, superficial layer does not have metal Bi's
Characteristic peak illustrates that metal Bi is to be located at BiOI and TiO2Between the interlayer of NSs-a.
0.20BiOI/Bi/TiO2The UV-vis spectrogram of NSs-a as shown in figure 3, its to the light table within the scope of 400-650nm
Reveal strong response, while the light for being greater than 650nm wave band to wavelength still has response, compared with 0.20 BiOI/TiO2NBs and
0.20BiOI/TiO2MSs shows better visible light absorption capacity.
0.20BiOI/Bi/TiO2The photocatalytic activity figure of NSs-a is as shown in figure 4,0.20BiOI/Bi/TiO2NSs-a exists
Optimal catalytic activity is shown in light degradation RhB reaction, degradation rate reaches 97.27% after illumination 4h, hence it is evident that is higher than
0.20BiOI/TiO2The 86.38% and 0.20BiOI/TiO of NBs2The 86.60% of MSs.
0.20BiOI/Bi/TiO2The PL spectrogram of NSs-a is as shown in figure 5,0.20BiOI/Bi/TiO2The transmitting of NSs-a
Intensity is lower than 0.20BiOI/TiO2NBs-a and 0.20BiOI/TiO2MSs illustrates BiOI/Bi/TiO2Ternary heterojunction structure can
It is effective to inhibit photo-generated carrier compound.
Embodiment 2
Using the method reported in document before, TiO is prepared2Nanobelt then prepares 0.20 BiOI/TiO2It receives
Rice band binary composite semiconductor light-catalyst material.
(1) under the conditions of 28 DEG C, magnetic agitation (500~600r/s), the Degussa P25 of 0.4g is scattered in 60mL's
In the aqueous solution of NaOH (10M), magnetic agitation 60min；
(2) suspension obtained in step (1) is transferred in 100mL stainless steel autoclave, 180 DEG C of reaction 72h；
(3) solid sediment is collected by filtration, is washed 3~5 times with deionized water and dehydrated alcohol respectively.Obtained solid precipitating
Object is scattered in again in HCl (0.1M) aqueous solution of 50mL, static 48h；
(4) solid sediment is collected by filtration, is washed 3~5 times with deionized water and dehydrated alcohol respectively, the vacuum at 80 DEG C
After dry 12h, with the further 600 DEG C of calcinings 2h of Muffle furnace, TiO is obtained2Nanobelt；
(5) at 28 DEG C, TiO obtained in 2mmol step (4)2Nanobelt and 0.4mmol Bi (NO3)3·5H2O dispersion
In 20mL ethylene glycol, (500~1000r/s) instills 20mL ethylene glycol and 0.4mmol KI dropwise under intense agitation
Mixed solution continues to stir 60min；
(6) suspension obtained in (5) is transferred in 100mL stainless steel autoclave, 160 DEG C of reactions are for 24 hours；
(7) it is cooled to room temperature, solid product is obtained by filtration, washed 3~5 times with deionized water and dehydrated alcohol respectively, in
80 DEG C of vacuum drying 12h.Sample obtained is named as 0.20BiOI/TiO2NBs
0.20BiOI/TiO2The XRD diagram of NBs is as shown in Figure 1, the characteristic peak occurred at 25.3 °, 37.8 °, 48.04 ° is returned
Belong to Anatase TiO2(101), (004), (200) face, at 29.3 ° and 31.6 ° occur characteristic peak belong to BiOI
(012) and (110) face, at 44.3 ° occur peak can belong to TiO2(B), this is because crystallization in recrystallization process
Caused by not exclusively.There is no the characteristic diffraction peak of metal Bi to exist in figure, illustrates that the sample is BiOI/TiO2NBs binary is different
Matter structure.
0.20BiOI/TiO2The SEM of NBs schemes as shown in Fig. 2, in Fig. 2 (a), original TiO2The surface NBs is smooth flat
Whole, length is generally 1-3 microns, and width is that 50-300nm is differed, with a thickness of 25-40nm；In Fig. 2 (b), after loading BiOI,
TiO2The surface NBs grows the non-uniform BiOI thin slice of one layer of size.
0.20BiOI/TiO2UV-vis figure such as Fig. 3 of NBs shows, strong response is shown between 400-650nm, but
It is weaker than 0.20BiOI/Bi/TiO2NSs-a, the light to wavelength greater than 650nm do not have absorbability.
0.20BiOI/TiO2The photocatalytic activity figure of NBs is as shown in figure 4,0.20BiOI/TiO2The degradation rate of NBs is
86.38%, it is lower than 0.20BiOI/Bi/TiO2The 97.27% of NSs-a.
0.20BiOI/TiO2The PL spectrogram of NBs is as shown in figure 5,0.20BiOI/TiO2The emissive porwer highest of NBs, light
Raw carrier is most easily compound.
Embodiment 3
TiO is prepared using the method reported in document before2Micron ball prepares BiOI/TiO2Micron ball binary is multiple
Close semiconductor light-catalyst material.
(1) under the conditions of 28 DEG C, magnetic agitation (500~600r/s), the concentrated sulfuric acid (98%) of 0.33mL and 0.3mL's
H2It is instilled in the butyl titanate of 15mL and the mixed solution of 75mL dehydrated alcohol dropwise after O mixing, continues magnetic agitation
30min；
(2) suspension obtained in step (1) is transferred in 100mL stainless steel autoclave, 180 DEG C of reaction 4h；
(3) solid sediment is collected by filtration, is washed 3~5 times with deionized water and dehydrated alcohol respectively, it is dry in 80 DEG C of vacuum
After dry 12h, with the further 600 DEG C of calcinings 2h of Muffle furnace, TiO is obtained2Micron ball；
(4) at 28 DEG C, TiO obtained in 2mmol step (3)2Microballoon and 0.4mmol Bi (NO3)3·5H2O is scattered in
In 20mL ethylene glycol, (500~1000r/s) instills the mixed of 20mL ethylene glycol and 0.4mmol KI dropwise under intense agitation
Solution is closed, continues to stir 60min；
(5) suspension obtained in (4) is transferred in 100mL stainless steel autoclave, 160 DEG C of reactions are for 24 hours；
(6) it is cooled to room temperature, solid product is obtained by filtration, washed 3~5 times with deionized water and dehydrated alcohol respectively, in
80 DEG C of vacuum drying 12h.Sample obtained is named as 0.20BiOI/TiO2MSs
0.20BiOI/TiO2The XRD diagram of MSs is as shown in Figure 1, the characteristic peak occurred at 25.3 °, 37.8 °, 48.04 ° is returned
Belong to Anatase TiO2(101), (004), (200) face, at 29.3 ° and 31.6 ° occur characteristic peak belong to BiOI
(012) and (110) face.There is no the characteristic diffraction peak of metal Bi to exist in figure, illustrates that the sample is BiOI/TiO2MSs bis-
First heterojunction structure.
0.20BiOI/TiO2The SEM of MSs schemes as shown in Fig. 2, in Fig. 2 (e), original TiO23-4 microns of NBs diameter,
By many tiny TiO2Nanometer rods composition, there are many holes on surface, comparatively smooth；In Fig. 2 (f), after loading BiOI,
TiO2The external BiOI for growing one layer of MSs, surface become very coarse, hole further expansion.
0.20BiOI/TiO2UV-vis figure such as Fig. 3 of MSs shows, strong response is shown between 400-650nm, but
It is weaker than 0.20BiOI/Bi/TiO2NSs-a and 0.20BiOI/TiO2NBs, the light to wavelength greater than 650 nm do not have absorbability.
0.20BiOI/TiO2The photocatalytic activity figure of MSs is as shown in figure 4,0.20BiOI/TiO2The degradation rate of NBs is
86.60%, it is lower than 0.20BiOI/Bi/TiO2The 97.27% of NSs-a.
0.20BiOI/TiO2The PL spectrogram of MSs is as shown in figure 5,0.20BiOI/TiO2The emissive porwer of NBs is higher than
0.20BiOI/Bi/TiO2NSs-a, photo-generated carrier compound ability are better than 0.20BiOI/Bi/TiO2 NSs-a。
Embodiment 4
Circulation experiment is carried out by probe reaction of light degradation rhodamine B, probes into 0.20 BiOI/Bi/ being prepared
TiO2The photocatalytic activity of NSs-a.As shown in figure 4, original BiOI and TiO2The catalytic effect of NSs-a is unsatisfactory, only
65.52% and 51.84%.After loading BiOI, 0.20BiOI/Bi/TiO2The disposal efficiency of NSs-a is apparently higher than
0.20BiOI/TiO2NBs and 0.20BiOI/TiO2MSs reaches 97.27%, this shows the BiOI/Bi/ of ternary heterojunction structure
TiO2The catalytic activity of composite photocatalyst material is better than BiOI/TiO2Binary heterojunction structure.
Embodiment 5
It is respectively O with benzoquinones, isopropanol, EDTA-2Na2-, OH and h+Sacrifice agent, probe into BiOI/Bi/TiO2It receives
The electron-transport mechanism of rice piece tri compound conductor photocatalysis material.As shown in figure 8, in Fig. 8 (a) and 8 (b), EDTA-
The addition of 2Na makes original BiOI and TiO2The catalytic efficiency of NSs-a is greatly reduced, and the addition of benzoquinones and isopropanol is to original
BiOI and TiO2The catalytic efficiency of NSs-a influences less, to illustrate h+It is key reaction species, O2-Play the role of with OH
Less, this is because BiOI and TiO2Conduction band positions be lower than O2/·O2-Oxidation-reduction potential (- 0.28eV).In Fig. 8 (c)
In, the addition of benzoquinones greatly reduces 0.20BiOI/Bi/TiO2The catalytic efficiency of NSs-a, and OH and h+To catalytic efficiency
Influence is also enhanced, this shows O2-As key reaction active specy, the reason is that due to BiOI/Bi/TiO2NSs-a is heterogeneous
After structure is formed, valence band buckling phenomenon, the conduction band and TiO of BiOI occurs2The valence band of NSs-a distinguishes raising and lowering, BiOI's
Conduction band oxidation-reduction potential is more negative than O2/·O2-Oxidation-reduction potential (- 0.28eV), metal Bi plays electron-transport wherein
The effect of mediation, after catalyst is excited by light, TiO2Light induced electron on NSs-a conduction band is transmitted to the valence of BiOI by metal Bi
It takes and hole-recombination, final electron rich is on the conduction band of BiOI, with absorption O2Generate O2-, hole-rich is in TiO2
In the valence band of NSs-a, OH and h+Oxidability enhancing.
Embodiment 6
According to the method for embodiment 1, the molar ratio for preparing Bi:Ti is respectively the BiOI/Bi/ of 0.10:1 and 0.30:1
TiO2Nanometer sheet (calcines) tri compound conductor photocatalysis material under air atmosphere, then detect degradation rate, as a result such as 1 institute of table
Show.When the molar ratio of Bi:Ti is 0.20 as can be seen from Table 1, there is highest degradation rate.
The BiOI/Bi/TiO of the molar ratio of 1 difference Bi:Ti of table2The comparison of the degradation rate of nanometer sheet
Claims (9)
1. a kind of BiOI/Bi/TiO of ternary heterojunction structure2Composite photocatalyst material, which is characterized in that TiO2For exposure simultaneously
{ 001 } and the nanometer chip architecture of { 101 } crystal face, there are Lacking oxygens and unsaturation Ti on surface3+Defect sites；BiOI uniformly disperses
In TiO2{ 001 } on crystal face；Metal Bi granule interlayer is in BiOI and TiO2Between the interface of contact position.
2. the BiOI/Bi/TiO of ternary heterojunction structure according to claim 12Composite photocatalyst material, which is characterized in that institute
State the BiOI/Bi/TiO of ternary heterojunction structure2BiOI, Bi and TiO are existed simultaneously in composite photocatalyst material2Three kinds of object phases.
3. the BiOI/Bi/TiO of ternary heterojunction structure according to claim 1 or claim 22The preparation method of composite photocatalyst material,
It is characterized in that, mainly comprising the steps that
(1) TiO prepared2Nanometer sheet exposes { 001 } and { 101 } crystal face simultaneously, and there are Lacking oxygens and unsaturation Ti on surface3+It lacks
Fall into site；
(2) under conditions of 26~28 DEG C, by TiO obtained by step (1)2Nanometer sheet and bismuth source are scattered in organic solution, violent
The organic solution containing propiodal is instilled under stirring dropwise, continues 60~90min of stirring；
(3) suspension obtained in step (2) is transferred in stainless steel autoclave, controlled at 140~170 DEG C, instead
It is 12~36h between seasonable；
(4) be cooled to room temperature, solid product be obtained by filtration, to product carry out sufficiently wash after in 50~90 DEG C be dried in vacuo 8~
24h。
4. preparation method according to claim 3, which is characterized in that step (1) described TiO2The preparation of nanometer sheet mainly includes
Following steps:
(S1) under conditions of 26~28 DEG C, under intense agitation, pattern directed agents HF aqueous solution is instilled into titanium source dropwise
In, holding is vigorously stirred 60~120min；
(S2) mixed liquor obtained by step (S1) is transferred in stainless steel autoclave, controlled at 180~240 DEG C, reaction
Time is 12~36h；
(S3) it is cooled to room temperature, the solid was filtered product, carry out after sufficiently washing being dried in vacuo 8 in 50~90 DEG C to product~
For 24 hours, primary TiO of the surface containing F is obtained2Nanometer sheet；
(S4) the primary TiO by surface obtained in step (S3) containing F2Nanometer sheet, which is placed in tube furnace, calcines defluorinate, controls temperature
It is 500~600 DEG C, calcination atmosphere is air, inertia or reducing atmosphere, and calcination time is 2~4h.
5. preparation method according to claim 3, which is characterized in that organic solvent include ethylene glycol, ethylene glycol list first
The one or more of ether, glycerine；The bismuth source include five nitric hydrate bismuths, bismuthyl carbonate, bismuth sulfate it is a kind of or more
Kind；The propiodal includes the one or more of potassium iodide, sodium iodide, cetyl trimethyl ammonium iodide.
6. preparation method according to claim 3, which is characterized in that the molar ratio of the bismuth source and propiodal is 1:1.
7. preparation method according to claim 4, which is characterized in that described HF, H2The volume ratio of O and titanium source is 3:2:25.
8. preparation method according to claim 4, which is characterized in that the titanium source is butyl titanate, titanium tetrachloride, isopropyl
One of alcohol titanium is a variety of.
9. the BiOI/Bi/TiO of ternary heterojunction structure according to claim 1 or claim 22The application of composite photocatalyst material, it is special
Sign is, can be used as the photodegradative catalyst of organic dyestuff.
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