CN109107611A - A kind of polypyrrole/biomass carbon/SnO2-xThe preparation method of nano composite photocatalytic material - Google Patents
A kind of polypyrrole/biomass carbon/SnO2-xThe preparation method of nano composite photocatalytic material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000002028 Biomass Substances 0.000 title claims abstract description 61
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 40
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910006702 SnO2-x Inorganic materials 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 19
- 235000005979 Citrus limon Nutrition 0.000 claims abstract description 4
- 244000131522 Citrus pyriformis Species 0.000 claims abstract description 4
- 240000000560 Citrus x paradisi Species 0.000 claims abstract description 4
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 4
- 240000008790 Musa x paradisiaca Species 0.000 claims abstract description 4
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims abstract description 4
- 239000010903 husk Substances 0.000 claims abstract description 4
- 244000183278 Nephelium litchi Species 0.000 claims abstract description 3
- 235000015742 Nephelium litchi Nutrition 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 96
- 238000013019 agitation Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000003760 magnetic stirring Methods 0.000 claims description 20
- 239000010813 municipal solid waste Substances 0.000 claims description 20
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 230000002045 lasting effect Effects 0.000 claims description 17
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 16
- JALQQBGHJJURDQ-UHFFFAOYSA-L bis(methylsulfonyloxy)tin Chemical compound [Sn+2].CS([O-])(=O)=O.CS([O-])(=O)=O JALQQBGHJJURDQ-UHFFFAOYSA-L 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 150000003233 pyrroles Chemical class 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
- 239000001384 succinic acid Substances 0.000 claims description 10
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 8
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229960003237 betaine Drugs 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 41
- 238000007146 photocatalysis Methods 0.000 abstract description 18
- 230000007547 defect Effects 0.000 abstract description 9
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 229920000620 organic polymer Polymers 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 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 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910003107 Zn2SnO4 Inorganic materials 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- JKYKXTRKURYNGW-UHFFFAOYSA-N 3,4-dihydroxy-9,10-dioxo-9,10-dihydroanthracene-2-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=C(O)C(S(O)(=O)=O)=C2 JKYKXTRKURYNGW-UHFFFAOYSA-N 0.000 description 1
- MPVDXIMFBOLMNW-ISLYRVAYSA-N 7-hydroxy-8-[(E)-phenyldiazenyl]naphthalene-1,3-disulfonic acid Chemical compound OC1=CC=C2C=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1\N=N\C1=CC=CC=C1 MPVDXIMFBOLMNW-ISLYRVAYSA-N 0.000 description 1
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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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
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- 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
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/38—Organic compounds containing nitrogen
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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
A kind of polypyrrole/biomass carbon/SnO2‑xThe preparation method of nano composite photocatalytic material, by rich defect tin oxide and biomass carbon heterojunction semiconductor, load is scattered in nanocomposite obtained from conductive organic polymer by way of chemical bond is complexed；SnO2‑xSelected from SnO, SnO/Sn3O4、Sn3O4、SnO/Sn3O4/SnO2Or Sn3O4/SnO2；Biomass carbon is from life production waste, the biomass carbon network structure as made from the biomass castoffs such as coconut husk, lychee exocarp, fallen leaves, banana skin, orange peel, pomelo peel, lemon peel.The present invention utilizes SnO2‑xVisible light photocatalysis redox characteristic, the superior electrical conductivity of biomass carbon, polypyrrole light conduction and electric conductivity and three components between there is the heterojunction structure of chemical bonding, sufficiently inhibit the photo-generate electron-hole in its light-catalyzed reaction compound, to be conducive to improve the performance of its photocatalytic redox degradation of contaminant and photocatalysis Decomposition aquatic products hydrogen.Meanwhile the characteristics of polypyrrole easy plastotype, can effectively avoid the recycling difficult problem of powder body material.
Description
Technical field
The present invention relates to a kind of preparation method of nano composite photocatalytic material, in particular to a kind of polypyrrole/biomass
Carbon/SnO2-xThe preparation method of nano composite photocatalytic material.
Background technique
In mankind nowadays are produced and lived, catalyst may not only be applied to traditional Chemical Manufacture, and in environment
It administers, function of human body is adjusted and the fields such as energy stores are also widely used.Meanwhile as society is constantly progressive and environmental problem
It is increasingly prominent, developing cheap, environmental-friendly efficient green catalyst becomes the research hotspot of related researcher.
Rich defect tin oxide (SnO2-x) there is good visible light photocatalysis redox ability, biomass carbon has good
Good electric conductivity and unique carbon backbone structure performance, polypyrrole have good visible absorption property and excellent electric conductivity
Energy.By SnO2-x, biomass carbon and polypyrrole carry out it is compound after can have the synergistic effect of enhancing electronics transfer.Polypyrrole and life
The collaboration of substance carbon is compound in SnO2-xBoth it can be used as SnO2-xThe support carrier of composite catalyst, also can effectively improve SnO2-x
The photoelectric conversion efficiency of composite material is to help to obtain excellent photocatalysis performance.
SnO2It is a kind of important N-shaped wide band gap semiconducter, it has excellent photoelectric characteristic, gas-sensitive property, chemistry steady
Qualitative and environment friendly, thus be widely used in drug delivery, energy storage, magnetic storage medium material, solar battery,
The fields such as electrode material, gas sensing materials, electrocatalysis material and catalysis material.In catalyst field, SnO2It is used extensively
In degradation orange G, cloth Lille indigo plant, alizarin red S, methylene blue, the organic dyestuff such as rhodamine B [Wang, X., Fan, H., Ren,
P.,et al.Homogeneous SnO2 core-shell microspheres:Microwave-assisted
hydrothermal synthesis,morphology control and photocatalytic properties[J]
.Materials Research Bulletin,2014,50:191-196.].Monovalent state SnO2Biggish forbidden bandwidth leads to it
Ultraviolet light, which can only be absorbed and utilized, just can be carried out light-catalyzed reaction, but UV energy only accounts for the deficiency of solar energy gross energy
5%.In order to improve SnO2The light absorption and photocatalysis performance of material, most simple and effective strategy are exactly to construct mixed valence or non-
The tin-oxide of stoichiometric ratio reduces its forbidden bandwidth [the Zhu member of Imperial Academy, beam condition oxygen defect type while increasing internal defects
SnO2Research [J] the chemistry of nano particle visible light catalytic performance is notified to, 2016,79 (4): 327-331.].And deficiency
Tin oxide SnO2-xIn oxygen vacancies may advantageously facilitate the separation of photo-generate electron-hole as electronics trap center, to promote oxygen
[Shi Leyu, LIU MEILING, Li Xintong wait the preparation of non-stoichiometry oxidation tin and photocatalysis performance to grind for the light-catalyzed reaction of change tin
Study carefully the Shandong [J] chemical industry, 2016,45 (6): 7-8.].Sn auto-dope SnO2-xThe presence of nanocrystalline middle oxygen defect can effectively improve light
The separation of raw electron-hole pair, thus obtain excellent dyestuff Photocatalytic Degradation Property [Han, D., Jiang, B., Feng,
J.,Yin,Y.,Wang,W.Photocatalytic Self-Doped SnO2-x Nanocrystals Drive Visible-
Light-Responsive Color Switching[J].Angewandte Chemie International Edition,
2017,56(27):7792-7796.].The design feature of oxygen-enriched vacancy defect makes SnO2-xNano particle show than P25 and
ZnO all excellent photocatalytic water H2-producing capacity (133.8 μm of olh-1·g-1)[Li,M.,Hu,Y.,Xie,S.,Huang,Y.,
Tong,Y.,Lu,X.Heterostructured ZnO/SnO2-x nanoparticles for efficient
photocatalytic hydrogen production[J].Chemical Communications,2014,50(33):
4341-4343.]。
SnO is improved in order to realize2The photocatalysis performance of material, various SnO2Composite photo-catalyst is designed, is prepared for out
Come, such as graphene/SnO2[Seema,H.,Kemp,K.C.,Chandra,V.,et al.Graphene-SnO2 composites
for highly efficient photocatalytic degradation of methylene blue under
sunlight[J].Nanotechnology,2012,23(35):355705.]、CdS/SnO2[Liu,Y.,Zhang,P.,
Tian,B.,et al.Core-shell structural CdS@SnO2 nanorods with excellent visible-
light photocatalytic activity for the selective oxidation of benzyl alcohol
to benzaldehyde[J].ACS Applied Materials&Interfaces,2015,7(25):13849-13858.]、
Zn2SnO4/SnO2[Sun,L.,Han,X.,Jiang,Z.,et al.Fabrication of cubic Zn2SnO4/SnO2
complex hollow structures and their sunlight-driven photocatalytic activity
[J].Nanoscale,2016,8(26):12858-12862.]、MoS2/SnO2[Huang,Y.,Miao,Y.E.,Zhang,L.,
et al.Synthesis of few-layered MoS2 nanosheet-coated electrospun SnO2 nanotube
heterostructures for enhanced hydrogen evolution reaction[J].Nanoscale,2014,6
] and Fe (18): 10673-10679.2O3/SnO2[Niu,M.,Huang,F.,Cui,L.,et al.Hydrothermal
synthesis,structural characteristics,and enhanced photocatalysis of SnO2/α-
Fe2O3semiconductor nanoheterostructures[J].ACS Nano,2010,4(2):681-688.].More than
Composite material is by the SnO of broad stopband width2The semiconductor material progress of low energy gap width is compound, promotes to a certain extent
SnO2The separation of photo-generate electron-hole in semiconductor material, has expanded the light abstraction width from ultraviolet to visible, to obtain
Certain raising of photocatalysis performance, but the above composite material can not solve the energy level between different composite component to the maximum extent
The problem of structure matches, thus it is unable to get SnO2The maximization of based composites photo-generate electron-hole separation.
The tin-oxide composite material for the different stoichiometric ratios that level structure matches is conducive to improve photo-generated carrier
Separation rate and obtain excellent photocatalysis performance.Such as SnO/Sn3O4Heterojunction structure has than one pack system SnO and one pack system Sn3O4More
Add excellent rhodamine B Photocatalytic Degradation Property [Cui Lei, Yang Lijuan, Gao Jiansen, Gu Shipu .SnO/Sn3O4The system of heterojunction structure
Standby and its photocatalysis performance functional material, 2017,48 (1), 1159-1162.].And SnO/Sn3O4Heterojunction structure passes through energy level
Effective charge between the interface that structure matches shifts and has superior photocatalytic degradation rhodamine B performance than one pack system
[Xia,W.,Wang,H.,Zeng,X.,Han,J.,Zhu,J.,Zhou,M.,&Wu,S.High-efficiency
photocatalytic activity of type II SnO/Sn3O4 heterostructures via interfacial
charge transfer.CrystEngComm,2014,16(30),6841-6847.].But the above tin-oxide heterojunction structure
Photo-generate electron-hole separation rate still not no being optimal, and have the defects that stability is not high enough, thus inhibit
The further increasing of its photocatalysis performance.
Polypyrrole is typical conducting polymer, and environmental stability is good, nontoxic, conductivity is high, is readily synthesized, in high score
In terms of the functional materials such as sub-conductor, electronics and optical device, chemical sensor, electrochromic display device (ECD), anti-corrosion material and device
There are many potential applications.Biomass carbon is as electron donor, it may have safe and non-toxic, gap is flourishing, absorption property is good, intensity
The design features such as the advantages that high, easy regeneration, economy and durability, both can be used as the support carrier of catalyst, also can effectively improve
The catalytic efficiency of catalyst, thus it is primarily used to the adsorption cleaning processing of drinking water, alcoholic, beverage, trade effluent.Polypyrrole
Have good visible absorption property with biomass carbon, can be used as the visible light modified material in photochemical catalyst.By poly- pyrrole
It coughs up, biomass carbon and SnO2-xCarry out it is compound after can significantly increase composite material electronics transfer synergistic effect, to be conducive to
Improve its photocatalysis performance.
It is existing that in relation to polypyrrole/carbon/semiconductor composite preparation method, mainly there are several types of: self assemblies to combine
[preparation of Zheng field carbon nano-tube/poly pyrroles/metal oxide composite nano-line and catalytic property research [D] are lucky for hydro-thermal process
Woods university, 2013.], hydro-thermal method [Liang Y, Li S, Du M.Synthesis of polymer/rGO/SnO2,
hierarchical structure and its photodegradation of organic pollutants[J]
.Colloid&Polymer Science, 2015,293 (12): 3499-3504.], hydro-thermal method combination chemistry polymerizing in situ method [Lee
Qin, Li Chuan, Wang Bing wait a kind of noble metal platinum deposition of-polypyrrole sensitization agent of hollow form titanium dioxide nano photocatalysis and its system
Preparation Method, CN102989514A [P] .2013.], in situ chemical oxidative polymerization method [Li, Juan, University X, et
al.Synthesis and characterization of a novel tube-in-tube nanostructured PPy/
MnO2/CNTs composite for supercapacitor[J].Materials Research Bulletin,2013,48
(2): 747-751.] etc..These preparation methods all have the advantages that its uniqueness, but are disadvantageous in that the inadequate environment of reaction raw materials
Close friend, complex steps, and material reuniting effect obtained are obvious etc..
Summary of the invention
The purpose of the present invention is to provide a kind of polypyrrole/biomass carbon/SnO2-xThe preparation of nano composite photocatalytic material
It is close to prepare high morphology controllable, degree of scatter, homogeneous grain diameter and interface cohesion using wet-chemical in-situ synthesis for method
Polypyrrole/biomass carbon/SnO2-xNano composite photocatalytic material.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
1) by biomass castoff under nitrogen or argon atmosphere, with the heating rate of 2~10 DEG C/min from room temperature
To 100~400 DEG C of 0.5~10h of heat preservation, reaction terminates to be cooled to room temperature to obtain biomass carbon skeleton；
2) analytically pure the stannous methanesulfonate ((CH of 1mmol is taken respectively3SO3)2) and the methanesulfonic acid of 0.5~5.2mmol Sn
(CH4O3S it) is completely dissolved in the dehydrated alcohol of 3~12mL, sequentially adds the dodecyl ethyoxyl sulphur of 0.5~7mmol later
The deionized water of base glycine betaine and 5~25mL obtains solution A after being completely dissolved；
3) the biomass carbon skeleton for taking 0.5~6g polished is added in solution A and obtains mixed liquid B；
4) mixed liquid B is transferred in the water heating kettle of polytetrafluoroethyllining lining, then water heating kettle is put into constant temperature oven
In 80~160 DEG C of 48~72h of heat preservation, reaction terminates to be cooled to room temperature to obtain containing precipitated product SnO2-xMixed liquor C；
5) pyrroles (C is controlled4H5N stannous methanesulfonate ((CH used) and in step 2)3SO3)2Sn molar ratio) is (0.01
~0.1): 1, by pyrroles (C4H5N it) is completely dissolved in dehydrated alcohol in closed container, obtains solution D, mixed liquor C is slow
It is added in solution D, adjusts rapid sealing container after its pH value is 1~3 with succinic acid solution, will hold after 0.5~2h of magnetic agitation
Device is transferred in -10~10 DEG C of cryostat, stands 48~72h；
6) cooled to room temperature after reaction, product is centrifuged, and successively uses deionized water and nothing
Water-ethanol respectively washs, finally at 30~70 DEG C and vacuum degree is 10-1~10-3Poly- pyrrole is dried to obtain in the vacuum oven of Pa
Cough up/biomass carbon/SnO2-xNano composite photocatalytic material.
The biomass castoff is coconut husk, lychee exocarp, fallen leaves, banana skin, orange peel, pomelo peel or lemon peel.
The step 2,3,5) whole process under the condition of ice bath of trash ice and water using constant-temperature magnetic stirring device to it
Lasting magnetic agitation is carried out at -10~10 DEG C.
Step 4) the packing ratio is 40~70%.
The concentration of step 5) the succinic acid solution is 0.5~10mol/L.
The step 6) is respectively washed 3~8 times using deionized water and dehydrated alcohol.
Step 6) the drying time is 1~12h.
The present invention utilizes carbon backbone structure and electric conductivity, the light conduction of polypyrrole, electrical conductance and the easily modeling of biomass carbon
Type characteristic, and rich defect tin oxide (SnO2-x) visible light photocatalysis redox ability, by from a wealth of sources, environmental compatible
The biomass such as cheap pericarp be raw material, turn waste into wealth, successfully prepared using green synthesis method with controlled architecture,
Polypyrrole/biomass carbon/SnO of recyclable characteristic and excellent photocatalysis performance2-xNano composite photocatalytic material.Using high temperature
Carbonization, the self assembly of ice bath low temperature and hydrothermal crystallization three-step approach be prepared for the polypyrrole/biomass carbon with excellent photocatalysis performance/
SnO2-xTernary nano composite material.Stable, safe and non-toxic using the tin oxide chemical property of metallic tin and non-stoichiometric,
Resourceful, price economy and good conductivity and be conducive to photo-generate electron-hole to isolated advantage, to obtain superior light
Catalytic performance.
Compared with traditional preparation methods, the present invention the polypyrrole/life that is prepared of Low Temperature Wet chemistry in-situ synthesis
Substance carbon/SnO2-xNano composite photocatalytic material can effectively avoid hard aggregation, and composite material obtained has stability height, divides
Dissipate property is good, particle diameter distribution is narrow, crystal development is complete, pattern and size are controllable, simple process is efficient and interface cohesion closely etc. it is excellent
Point effectively overcomes the problem of level structure does not match that between different component in tin-oxide composite photocatalyst material, effectively promotees
Into the quick separating of photo-generate electron-hole pair, more efficient photocatalysis performance is obtained.
The beneficial effects of the present invention are embodied in:
1) polypyrrole/biomass carbon/SnO of the invention2-xThe preparation method technology controlling and process letter of nano composite photocatalytic material
Single, cost is relatively low, and preparation temperature is low and does not need Post isothermal treatment, avoids Post isothermal treatment to a certain extent and in the process may
The defects of caused crystal grain is grown up, is roughened or crimped.
2) polypyrrole/biomass carbon/SnO proposed by the present invention2-xNano composite photocatalytic material, using different component it
Between good physical chemistry compatibility and the level structure to match, be able to achieve in close interface cohesion and interfacial structure
The separation of efficient photo-generate electron-hole pair, to obtain 95% or more light in 180min under the conditions of sunlight irradiation
The efficiency of catalyzing oxidizing degrading rhodamine B.
3) wet-chemical in-situ synthesis proposed by the present invention realize morphology controllable, polymolecularity, interface cohesion it is close and
Polypyrrole/biomass carbon/SnO of homogeneous grain diameter2-xNanostructure composite photocatalyst material.
Detailed description of the invention
Fig. 1 is polypyrrole/biomass carbon/SnO prepared by the embodiment of the present invention 22-xThe scanning of nano composite photocatalytic material
Electron microscope (SEM) photo.
Specific embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings.
Embodiment 1:
1) in a nitrogen atmosphere by biomass castoff coconut husk, with the heating rate of 2 DEG C/min from room temperature to 100 DEG C
10h is kept the temperature, reaction terminates to be cooled to room temperature to obtain biomass carbon skeleton；
2) analytically pure the stannous methanesulfonate ((CH of 1mmol is taken respectively3SO3)2) and the methanesulfonic acid (CH of 0.5mmol Sn4O3S)
It is completely dissolved in the dehydrated alcohol of 3mL, sequentially adds the dodecyl ethyoxyl sulfobetaines and 5mL of 0.5mmol later
Deionized water, whole process under the condition of ice bath of trash ice and water using constant-temperature magnetic stirring device to its at -10 DEG C into
The lasting magnetic agitation of row obtains solution A after being completely dissolved；
3) the biomass carbon skeleton for taking 0.5g polished is added in solution A under the condition of ice bath of trash ice and water using perseverance
Warm magnetic stirring apparatus carries out lasting magnetic agitation at -10 DEG C to it and obtains mixed liquid B；
4) mixed liquid B is transferred in the water heating kettle of polytetrafluoroethyllining lining by 70% packing ratio, then by water heating kettle
It is put into constant temperature oven in 80 DEG C of heat preservation 72h, reaction terminates to be cooled to room temperature to obtain containing precipitated product SnO2-xMixed liquor C；
5) lasting magnetic agitation is carried out using constant-temperature magnetic stirring device under -10 DEG C of trash ice and the condition of ice bath of water
Under conditions of, control pyrroles (C4H5N stannous methanesulfonate ((CH used) and in step 2)3SO3)2Sn molar ratio) is 0.01:
1, by pyrroles (C4H5N it) is completely dissolved in dehydrated alcohol in closed container, obtains solution D, mixed liquor C is slowly added to molten
In liquid D, rapid sealing container after its pH value is 3 is adjusted with the succinic acid solution of 0.5mol/L, turns container after magnetic agitation 2h
It moves in -10 DEG C of cryostat, stands 72h；
6) cooled to room temperature after reaction, product is centrifuged, and successively uses deionized water and nothing
Water-ethanol respectively washs 3 times, finally at 30 DEG C and vacuum degree is 10-3Dry 12h obtains polypyrrole/life in the vacuum oven of Pa
Substance carbon/SnO2-xNano composite photocatalytic material.
Embodiment 2:
1) under an argon atmosphere by biomass castoff fallen leaves, with the heating rate of 6 DEG C/min from room temperature to 260 DEG C
5h is kept the temperature, reaction terminates to be cooled to room temperature to obtain biomass carbon skeleton；
2) analytically pure the stannous methanesulfonate ((CH of 1mmol is taken respectively3SO3)2) and the methanesulfonic acid (CH of 3.2mmol Sn4O3S)
It is completely dissolved in the dehydrated alcohol of 8mL, sequentially adds the dodecyl ethyoxyl sulfobetaines and 16mL of 3.5mmol later
Deionized water, whole process carries out it using constant-temperature magnetic stirring device under the condition of ice bath of trash ice and water at 0 DEG C
Lasting magnetic agitation obtains solution A after being completely dissolved；
3) the biomass carbon skeleton for taking 3g polished is added in solution A uses constant temperature under the condition of ice bath of trash ice and water
Magnetic stirring apparatus carries out lasting magnetic agitation at 0 DEG C to it and obtains mixed liquid B；
4) mixed liquid B is transferred in the water heating kettle of polytetrafluoroethyllining lining by 66% packing ratio, then by water heating kettle
It is put into constant temperature oven in 120 DEG C of heat preservation 56h, reaction terminates to be cooled to room temperature to obtain containing precipitated product SnO2-xMixed liquor
C；
5) lasting magnetic agitation is carried out using constant-temperature magnetic stirring device under 0 DEG C of trash ice and the condition of ice bath of water
Under the conditions of, control pyrroles (C4H5N stannous methanesulfonate ((CH used) and in step 2)3SO3)2Sn molar ratio) is 0.06:1,
By pyrroles (C4H5N it) is completely dissolved in dehydrated alcohol in closed container, obtains solution D, mixed liquor C is slowly added to solution D
In, rapid sealing container after its pH value is 2 is adjusted with the succinic acid solution of 3mol/L, container is transferred to 0 after magnetic agitation 1h
DEG C cryostat in, stand 60h；
6) cooled to room temperature after reaction, product is centrifuged, and successively uses deionized water and nothing
Water-ethanol respectively washs 6 times, finally at 66 DEG C and vacuum degree is 10-2Dry 6h obtains polypyrrole/life in the vacuum oven of Pa
Substance carbon/SnO2-xNano composite photocatalytic material.
As seen from Figure 1, the component for composite material being made includes polypyrrole, biomass carbon skeleton and SnO2-x, organize and divide it
Between be tightly combined, wherein biomass carbon present skeleton structure, matrix porosity diameter is about 200nm, and polypyrrole is uniform with SnO2-x
And it is closely distributed among biomass carbon skeleton.
Embodiment 3:
1) in a nitrogen atmosphere by biomass castoff banana skin, with the heating rate of 10 DEG C/min from room temperature extremely
400 DEG C of heat preservation 0.5h, reaction terminate to be cooled to room temperature to obtain biomass carbon skeleton；
2) analytically pure the stannous methanesulfonate ((CH of 1mmol is taken respectively3SO3)2) and the methanesulfonic acid (CH of 5.2mmol Sn4O3S)
It is completely dissolved in the dehydrated alcohol of 12mL, sequentially adds the dodecyl ethyoxyl sulfobetaines and 25mL of 7mmol later
Deionized water, whole process carries out it using constant-temperature magnetic stirring device under the condition of ice bath of trash ice and water at 10 DEG C
Lasting magnetic agitation obtains solution A after being completely dissolved；
3) the biomass carbon skeleton for taking 6g polished is added in solution A uses constant temperature under the condition of ice bath of trash ice and water
Magnetic stirring apparatus carries out lasting magnetic agitation at 10 DEG C to it and obtains mixed liquid B；
4) mixed liquid B is transferred in the water heating kettle of polytetrafluoroethyllining lining by 70% packing ratio, then by water heating kettle
It is put into constant temperature oven in 160 DEG C of heat preservation 48h, reaction terminates to be cooled to room temperature to obtain containing precipitated product SnO2-xMixed liquor
C；
5) lasting magnetic agitation is carried out using constant-temperature magnetic stirring device under 10 DEG C of trash ice and the condition of ice bath of water
Under conditions of, control pyrroles (C4H5N stannous methanesulfonate ((CH used) and in step 2)3SO3)2Sn molar ratio) is 0.1:1,
By pyrroles (C4H5N it) is completely dissolved in dehydrated alcohol in closed container, obtains solution D, mixed liquor C is slowly added to solution D
In, rapid sealing container after its pH value is 1 is adjusted with the succinic acid solution of 10mol/L, shifts container after magnetic agitation 0.5h
Into 10 DEG C of cryostats, 48h is stood；
6) cooled to room temperature after reaction, product is centrifuged, and successively uses deionized water and nothing
Water-ethanol respectively washs 8 times, finally at 70 DEG C and vacuum degree is 10-1Dry 3h obtains polypyrrole/life in the vacuum oven of Pa
Substance carbon/SnO2-xNano composite photocatalytic material.
Embodiment 4:
1) under an argon atmosphere by biomass castoff orange peel, with the heating rate of 4 DEG C/min from room temperature to 300
DEG C heat preservation 6h, reaction terminate be cooled to room temperature to obtain biomass carbon skeleton；
2) analytically pure the stannous methanesulfonate ((CH of 1mmol is taken respectively3SO3)2) and the methanesulfonic acid (CH of 1mmol Sn4O3S it) fills
Divide and be dissolved in the dehydrated alcohol of 5mL, sequentially adds the dodecyl ethyoxyl sulfobetaines of 1mmol and going for 10mL later
Ionized water, whole process continue it using constant-temperature magnetic stirring device under the condition of ice bath of trash ice and water at -5 DEG C
Magnetic agitation be completely dissolved after obtain solution A；
3) the biomass carbon skeleton for taking 2g polished is added in solution A uses constant temperature under the condition of ice bath of trash ice and water
Magnetic stirring apparatus carries out lasting magnetic agitation at -5 DEG C to it and obtains mixed liquid B；
4) mixed liquid B is transferred in the water heating kettle of polytetrafluoroethyllining lining by 40% packing ratio, then by water heating kettle
It is put into constant temperature oven in 100 DEG C of heat preservation 66h, reaction terminates to be cooled to room temperature to obtain containing precipitated product SnO2-xMixed liquor
C；
5) lasting magnetic agitation is carried out using constant-temperature magnetic stirring device under -5 DEG C of trash ice and the condition of ice bath of water
Under conditions of, control pyrroles (C4H5N stannous methanesulfonate ((CH used) and in step 2)3SO3)2Sn molar ratio) is 0.03:
1, by pyrroles (C4H5N it) is completely dissolved in dehydrated alcohol in closed container, obtains solution D, mixed liquor C is slowly added to molten
In liquid D, rapid sealing container after its pH value is 2 is adjusted with the succinic acid solution of 5mol/L, shifts container after magnetic agitation 1h
Into -5 DEG C of cryostat, 56h is stood；
6) cooled to room temperature after reaction, product is centrifuged, and successively uses deionized water and nothing
Water-ethanol respectively washs 5 times, finally at 40 DEG C and vacuum degree is 102Dry 1h obtains polypyrrole/life in the vacuum oven of Pa
Substance carbon/SnO2-xNano composite photocatalytic material.
Embodiment 5:
1) in a nitrogen atmosphere by biomass castoff pomelo peel, with the heating rate of 8 DEG C/min from room temperature to 200
DEG C heat preservation 8h, reaction terminate be cooled to room temperature to obtain biomass carbon skeleton；
2) analytically pure the stannous methanesulfonate ((CH of 1mmol is taken respectively3SO3)2) and the methanesulfonic acid (CH of 4mmol Sn4O3S it) fills
Divide in the dehydrated alcohol of dissolution 10mL, sequentially adds the dodecyl ethyoxyl sulfobetaines of 4mmol and going for 20mL later
Ionized water, whole process continue it using constant-temperature magnetic stirring device under the condition of ice bath of trash ice and water at 5 DEG C
Magnetic agitation be completely dissolved after obtain solution A；
3) the biomass carbon skeleton for taking 1g polished is added in solution A uses constant temperature under the condition of ice bath of trash ice and water
Magnetic stirring apparatus carries out lasting magnetic agitation at 5 DEG C to it and obtains mixed liquid B；
4) mixed liquid B is transferred in the water heating kettle of polytetrafluoroethyllining lining by 60% packing ratio, then by water heating kettle
It is put into constant temperature oven in 140 DEG C of heat preservation 52h, reaction terminates to be cooled to room temperature to obtain containing precipitated product SnO2-xMixed liquor
C；
5) lasting magnetic agitation is carried out using constant-temperature magnetic stirring device under 5 DEG C of trash ice and the condition of ice bath of water
Under the conditions of, control pyrroles (C4H5N stannous methanesulfonate ((CH used) and in step 2)3SO3)2Sn molar ratio) is 0.05:1,
By pyrroles (C4H5N it) is completely dissolved in dehydrated alcohol in closed container, obtains solution D, mixed liquor C is slowly added to solution D
In, rapid sealing container after its pH value is 3 is adjusted with the succinic acid solution of 8mol/L, is transferred to container after magnetic agitation 1.5h
In 5 DEG C of cryostat, 64h is stood；
6) cooled to room temperature after reaction, product is centrifuged, and successively uses deionized water and nothing
Water-ethanol respectively washs 4 times, finally at 60 DEG C and vacuum degree is 10-3Dry 8h obtains polypyrrole/life in the vacuum oven of Pa
Substance carbon/SnO2-xNano composite photocatalytic material.
Embodiment 6:
1) under an argon atmosphere by biomass castoff lemon peel, with the heating rate of 5 DEG C/min from room temperature to 350
DEG C heat preservation 2h, reaction terminate be cooled to room temperature to obtain biomass carbon skeleton；
2) analytically pure the stannous methanesulfonate ((CH of 1mmol is taken respectively3SO3)2) and the methanesulfonic acid (CH of 2mmol Sn4O3S it) fills
Divide and be dissolved in the dehydrated alcohol of 6mL, sequentially adds the dodecyl ethyoxyl sulfobetaines of 6mmol and going for 18mL later
Ionized water, whole process continue it using constant-temperature magnetic stirring device under the condition of ice bath of trash ice and water at 0 DEG C
Magnetic agitation be completely dissolved after obtain solution A；
3) the biomass carbon skeleton for taking 5g polished is added in solution A uses constant temperature under the condition of ice bath of trash ice and water
Magnetic stirring apparatus carries out lasting magnetic agitation at 0 DEG C to it and obtains mixed liquid B；
4) mixed liquid B is transferred in the water heating kettle of polytetrafluoroethyllining lining by 50% packing ratio, then by water heating kettle
It is put into constant temperature oven in 90 DEG C of heat preservation 70h, reaction terminates to be cooled to room temperature to obtain containing precipitated product SnO2-xMixed liquor C；
5) lasting magnetic agitation is carried out using constant-temperature magnetic stirring device under 0 DEG C of trash ice and the condition of ice bath of water
Under the conditions of, control pyrroles (C4H5N stannous methanesulfonate ((CH used) and in step 2)3SO3)2Sn molar ratio) is 0.08:1,
By pyrroles (C4H5N it) is completely dissolved in dehydrated alcohol in closed container, obtains solution D, mixed liquor C is slowly added to solution D
In, rapid sealing container after its pH value is 1 is adjusted with the succinic acid solution of 1mol/L, container is transferred to 0 after magnetic agitation 2h
DEG C cryostat in, stand 70h；
6) cooled to room temperature after reaction, product is centrifuged, and successively uses deionized water and nothing
Water-ethanol respectively washs 7 times, finally at 50 DEG C and vacuum degree is 10-1Dry 10h obtains polypyrrole/life in the vacuum oven of Pa
Substance carbon/SnO2-xNano composite photocatalytic material.
Claims (7)
1. a kind of polypyrrole/biomass carbon/SnO2-xThe preparation method of nano composite photocatalytic material, it is characterised in that including with
Lower step:
1) by biomass castoff under nitrogen or argon atmosphere, with the heating rate of 2~10 DEG C/min from room temperature to 100
~400 DEG C of 0.5~10h of heat preservation, reaction terminate to be cooled to room temperature to obtain biomass carbon skeleton；
2) analytically pure the stannous methanesulfonate ((CH of 1mmol is taken respectively3SO3)2) and the methanesulfonic acid of 0.5~5.2mmol Sn
(CH4O3S it) is completely dissolved in the dehydrated alcohol of 3~12mL, sequentially adds the dodecyl ethyoxyl sulphur of 0.5~7mmol later
The deionized water of base glycine betaine and 5~25mL obtains solution A after being completely dissolved；
3) the biomass carbon skeleton for taking 0.5~6g polished is added in solution A and obtains mixed liquid B；
4) mixed liquid B is transferred in the water heating kettle of polytetrafluoroethyllining lining, then water heating kettle is put into constant temperature oven 80
~160 DEG C of 48~72h of heat preservation, reaction terminate to be cooled to room temperature to obtain containing precipitated product SnO2-xMixed liquor C；
5) pyrroles (C is controlled4H5N stannous methanesulfonate ((CH used) and in step 2)3SO3)2Sn molar ratio) be (0.01~
0.1): 1, by pyrroles (C4H5N it) is completely dissolved in dehydrated alcohol in closed container, obtains solution D, mixed liquor C is slowly added
Enter in solution D, rapid sealing container after its pH value is 1~3 is adjusted with succinic acid solution, by container after 0.5~2h of magnetic agitation
It is transferred in -10~10 DEG C of cryostat, stands 48~72h；
6) cooled to room temperature after reaction, product is centrifuged, and successively uses deionized water and anhydrous second
Alcohol respectively washs, finally at 30~70 DEG C and vacuum degree is 10-1~10-3Polypyrrole/life is dried to obtain in the vacuum oven of Pa
Substance carbon/SnO2-xNano composite photocatalytic material.
2. polypyrrole/biomass carbon/SnO according to claim 12-xThe preparation method of nano composite photocatalytic material,
Be characterized in that: the biomass castoff is coconut husk, lychee exocarp, fallen leaves, banana skin, orange peel, pomelo peel or lemon peel.
3. polypyrrole/biomass carbon/SnO according to claim 12-xThe preparation method of nano composite photocatalytic material,
Be characterized in that: the step 2,3,5) whole process under the condition of ice bath of trash ice and water using constant-temperature magnetic stirring device to it
Lasting magnetic agitation is carried out at -10~10 DEG C.
4. polypyrrole/biomass carbon/SnO according to claim 12-xThe preparation method of nano composite photocatalytic material,
Be characterized in that: the step 4) packing ratio is 40~70%.
5. polypyrrole/biomass carbon/SnO according to claim 12-xThe preparation method of nano composite photocatalytic material,
Be characterized in that: the concentration of step 5) the succinic acid solution is 0.5~10mol/L.
6. polypyrrole/biomass carbon/SnO according to claim 12-xThe preparation method of nano composite photocatalytic material,
Be characterized in that: the step 6) is respectively washed 3~8 times using deionized water and dehydrated alcohol.
7. polypyrrole/biomass carbon/SnO according to claim 12-xThe preparation method of nano composite photocatalytic material,
Be characterized in that: the step 6) drying time is 1~12h.
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|---|---|---|---|---|
| CN111747747A (en) * | 2020-07-17 | 2020-10-09 | 重庆大学 | Preparation method, product and application of carbon-based material with bionic fractal structure based on shaddock peel |
| CN115608381A (en) * | 2022-09-27 | 2023-01-17 | 华南理工大学 | Molybdenum disulfide/tin oxide composite photocatalyst and preparation method and application thereof |
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2018
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747747A (en) * | 2020-07-17 | 2020-10-09 | 重庆大学 | Preparation method, product and application of carbon-based material with bionic fractal structure based on shaddock peel |
| CN115608381A (en) * | 2022-09-27 | 2023-01-17 | 华南理工大学 | Molybdenum disulfide/tin oxide composite photocatalyst and preparation method and application thereof |
| CN115608381B (en) * | 2022-09-27 | 2023-11-24 | 华南理工大学 | Molybdenum disulfide/tin oxide composite photocatalyst and preparation method and application thereof |
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