CN109107612A - A kind of poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO2-xThe preparation method of nanocomposite - Google Patents
A kind of poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO2-xThe preparation method of nanocomposite Download PDFInfo
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- CN109107612A CN109107612A CN201811093630.2A CN201811093630A CN109107612A CN 109107612 A CN109107612 A CN 109107612A CN 201811093630 A CN201811093630 A CN 201811093630A CN 109107612 A CN109107612 A CN 109107612A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910006702 SnO2-x Inorganic materials 0.000 claims abstract description 24
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 80
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 29
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 239000010813 municipal solid waste Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003760 magnetic stirring Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 238000012546 transfer Methods 0.000 claims description 9
- -1 decyl dimethyl hydroxypropyl Chemical group 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 244000131522 Citrus pyriformis Species 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 240000008790 Musa x paradisiaca Species 0.000 claims description 3
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims description 3
- 239000010903 husk Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 240000000560 Citrus x paradisi Species 0.000 claims description 2
- 244000183278 Nephelium litchi Species 0.000 claims description 2
- 235000015742 Nephelium litchi Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 32
- 230000001699 photocatalysis Effects 0.000 abstract description 29
- 238000007146 photocatalysis Methods 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 35
- 239000002131 composite material Substances 0.000 description 13
- 229910001887 tin oxide Inorganic materials 0.000 description 9
- 230000007547 defect Effects 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000013019 agitation Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 238000011160 research 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
- 238000003786 synthesis reaction Methods 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
- 230000007812 deficiency Effects 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000011065 in-situ storage Methods 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
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910003107 Zn2SnO4 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 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
- 239000002699 waste material Substances 0.000 description 2
- 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
- 239000005977 Ethylene Substances 0.000 description 1
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- 229910006698 SnO2-Fe2O3 Inorganic materials 0.000 description 1
- SXMUSCUQMMSSKP-UHFFFAOYSA-N [O].C=1C=CSC=1 Chemical compound [O].C=1C=CSC=1 SXMUSCUQMMSSKP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 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
- 125000002704 decyl 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])* 0.000 description 1
- 239000006185 dispersion Substances 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
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007641 inkjet printing 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
- 239000011159 matrix material Substances 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
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 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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- 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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- 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 poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO2‑xThe preparation method of nanocomposite, by SnO2‑xLoad is scattered in nanocomposite obtained from poly- 3,4- ethylenedioxy thiophene by way of chemical bond is complexed with biomass carbon heterojunction semiconductor.The present invention utilizes SnO2‑xVisible light photocatalysis redox characteristic, biomass carbon superior electrical conductivity, poly- 3, there is the heterojunction structure of chemical bonding between the electric conductivity and component of 4- ethylenedioxy thiophene, 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 conductive organic matter easy plastotype, can effectively avoid the recycling difficult problem of powder body material, thus, poly- 3,4-ethylene dioxythiophene (PEDOT)/biomass carbon/SnO produced by the present invention2‑xNanocomposite is a kind of novel environment friendly catalysis material convenient for recycling.
Description
Technical field
The present invention relates to a kind of preparation methods of nano composite photocatalytic material, and in particular to a kind of poly- 3,4- ethylene two
Oxygen thiophene/biomass carbon/SnO2-xThe preparation method of nanocomposite.
Background technique
Environmental pollution, shortage of resources have become two major issues of puzzlement world economy social sustainable development, and
This two problems seem especially prominent for China.Simultaneously with social development, the increased speed of waste is gradually accelerated,
Biomass castoff is turned waste into wealth, biomass carbon is made and realizes re-using, also can effectively mitigate environmental pressure.Rich defect
Tin oxide (SnO2-x) since there is great potential in photocatalysis field with excellent visible light photocatalysis responding ability.So
And the rich defect tin oxide (SnO of single component2-x) that there is optical response ranges is relatively narrow, solar energy utilization ratio is low and quantum effect
The low deficiency of rate, seriously limits its practical application.
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 (18): 10673-10679.] and Fe2O3/SnO2 [Niu,M.,Huang,F.,
Cui,L.,et al.Hydrothermal synthesis, structural characteristics,and enhanced
photocatalysis of SnO2/α-Fe2O3 semiconductor nanoheterostructures[J].ACS Nano,
2010,4(2):681-688.].The above composite material is by the SnO of broad stopband width2The semiconductor material of low energy gap width carries out
It is compound, SnO is promoted to a certain extent2The separation of photo-generate electron-hole, has been expanded from ultraviolet to visible in semiconductor material
Light abstraction width, to obtain certain raising of photocatalysis performance, but the above composite material can not solve to the maximum extent
The problem of never matching with the level structure between compounding ingredients, thus it is unable to get SnO2Based composites light induced electron-
The maximization of 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 Sn3O4
More excellent rhodamine B Photocatalytic Degradation Property [Cui Lei, Yang Lijuan, Gao Jiansen, Gu Shipu .SnO/Sn3O4Heterojunction structure
Preparation and its photocatalysis performance functional material, 2017,48 (1), 1159-1162.].And SnO/Sn3O4Heterojunction structure passes through energy
Effective charge between the interface that level 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.
Poly- 3,4- ethylenedioxy thiophene (PEDOT) is due to conductivity with higher, preferable environmental stability, nontoxic
Advantage and film become one of most deep, most widely used conducting polymer of research at present to the high transmittance of visible light.
And in antistatic coating, conductive film, supercapacitor, electrochromic device, Organic Light Emitting Diode, organic solar electricity
The fields such as pond, electromagnetic shielding material and ink jet printing, which are shown, to have broad application prospects.Biomass carbon as electron donor,
Have many advantages, such as the design features such as safe and non-toxic, gap is flourishing, absorption property is good, intensity is high, easy regeneration, economy and durability, both may be used
Using the support carrier as catalyst, the catalytic efficiency of catalyst also can effectively improve, thus be primarily used to drinking water, system
The adsorption cleaning processing of wine, beverage, trade effluent.Polypyrrole and biomass carbon have good visible absorption property, can be with
As the visible light modified material in photochemical catalyst.By poly- 3,4- ethylenedioxy thiophene (PEDOT), biomass carbon and SnO2-xInto
The synergistic effect that the electronics transfer of composite material can be significantly increased after row is compound, to be conducive to improve its photocatalysis performance.
Mainly have in relation to poly- 3,4- ethylenedioxy thiophene (PEDOT)/carbon/semiconductor composite preparation method following several
Kind: [the preparation and property of the super of Wang Min poly- (3,4- ethylenedioxy thiophene) and graphene, carbon nano tube compound material of graft method
Can research [D] Xinjiang University, 2016.], chemical polymerization [the poly- 3,4- ethylenedioxy thiophene of the peak Lu Feng, Wu Xinkai, He Gu
(PEDOT) application [J] the semiconductor optoelectronic of-graphene oxide combination electrode in Organic Light Emitting Diode, 2015,36 (1):
81-84.] [preparation, characterization and performance study [D] the Donghua University of poly- (3,4- ethylenedioxy thiophene) composite material of He Lu,
2014.] etc..These preparation methods all have the advantages that its uniqueness, but are disadvantageous in that reaction raw materials are not environmental-friendly enough, walk
It is rapid cumbersome, and material reuniting effect obtained is obvious etc.,
Summary of the invention
The purpose of the present invention is to provide an a kind of poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO2-xNano combined material
The preparation method of material is prepared high morphology controllable, degree of scatter, homogeneous grain diameter and interface using wet-chemical in-situ synthesis and is tied
Close closely poly- 3,4- ethylenedioxy thiophene (PEDOT)/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) the analytically pure stannous oxalate (C of 1mmol is taken2O4) and the oxalic acid (H of 0.2~4mmol Sn2C2O4) it is completely dissolved in 4
In the dehydrated alcohol of~15mL, sequentially add later 3~14mmol decyl dimethyl hydroxypropyl sulfobetaines and 13~
The deionized water of 23mL obtains solution A after being completely dissolved；
3) the biomass carbon skeleton for taking 0.5~6g polished, which is added to be uniformly mixed in solution A, obtains mixed liquid B；
4) by the water heating kettle of mixed liquid B transfer polytetrafluoroethyllining lining, then reaction kettle is put into constant temperature oven
120~200 DEG C of 48~72h of heat preservation, reaction terminate to be cooled to room temperature to obtain the SnO containing precipitated product2-xMixed liquor C；
5) by stannous oxalate (C used in 3,4- ethylenedioxy thiophene (EDOT) and step 2)2O4Sn molar ratio) is
(0.01~0.1): 1,3,4-ethylene dioxythiophene (EDOT) is completely dissolved in the anhydrous of 120~250ml in closed container
Solution D is obtained in the mixed solution of ethyl alcohol, PSS and DMSO, wherein the volume ratio of dehydrated alcohol, PSS and DMSO be 1:(0.5~
1.6): (0.6~1.8)；Mixed liquor C is slowly added in solution D, is adjusted after its pH value is 3~5 with propionic acid solution and is sealed rapidly
Container is transferred to 48~72h of standing in -10~10 DEG C of cryostat after 0.5~2h of magnetic agitation by container；
6) product is centrifuged, and at 30~70 DEG C after successively respectively being washed using deionized water and dehydrated alcohol
And vacuum degree is 10-1~10-3Poly- 3,4- ethylenedioxy thiophene (PEDOT)/biomass is drying to obtain in the vacuum oven of Pa
Carbon/SnO2-xNanocomposite.
The biomass castoff is coconut husk, lychee exocarp, fallen leaves, banana skin, orange peel, pomelo peel or lemon peel.
Step 2) the whole process in the ice salt bath of sodium chloride and trash ice using constant-temperature magnetic stirring device to its
- 10~10 DEG C of continuing magnetic forces are stirred to being completely dissolved.
Step 3) the whole process under the condition of ice bath of trash ice and water using constant-temperature magnetic stirring device to its-
10~10 DEG C of continuing magnetic forces are stirred to uniformly mixed.
Step 4) the packing ratio is 40~70%.
Step 5) the whole process carries out continuing magnetic force stirring in -10~10 DEG C of trash ice and the ice bath of water.
The concentration of the step 5) propionic 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 is from environment/resources sustainable development angle, with environmental protection and biomass resource higher value application
Made by comprehensively utilizing the advantage of three kinds of materials using biomass carbon and poly- 3,4-ethylene dioxythiophene (PEDOT) for target
For the good conductor of electricity, it can be effectively conducted the characteristic of light induced electron, to improve the service life of material photo-generated carrier, help to obtain excellent
Different photocatalysis performance.The easy plastotype feature of poly- 3,4- ethylenedioxy thiophene (PEDOT) is also beneficial to realize the composite catalyst material
The recycling and reusing of material can effectively avoid powder body material difficulty from recycling and the adverse effect caused by environment.Biomass carbon and poly- 3,
4- ethylenedioxy thiophene (PEDOT) material is to have from a special microstructural nanometer light material, in environmental protection, catalysis
The fields such as agent carrier have a extensive future.
In order to advanced optimize tin-oxide heterojunction structure, further increases the separation of its photo-generated carrier and photocatalysis is steady
It is qualitative, the present invention using metallic tin and non-stoichiometric tin oxide chemical property is stable, safe and non-toxic, resourceful, valence
Lattice economy and good conductivity and be conducive to photo-generate electron-hole to isolated advantage, to obtain superior photocatalysis performance.
Compared with traditional preparation methods, Low Temperature Wet chemistry in-situ synthesis proposed by the invention be prepared poly- 3,4-
Ethylenedioxy thiophene (PEDOT)/biomass carbon/SnO2-xNano composite photocatalytic material can effectively avoid hard aggregation, obtained multiple
Condensation material have stability height, good dispersion, particle diameter distribution is narrow, crystal development is complete, pattern and size are controllable, simple process is high
The advantages that effect and interface cohesion are close effectively overcomes in tin-oxide composite photocatalyst material between different component level structure not
The problem of matching has effectively facilitated the quick separating of photo-generate electron-hole pair, obtains more efficient photocatalysis performance.
The beneficial effects of the present invention are embodied in:
1) poly- 3,4- ethylenedioxy thiophene (PEDOT)/biomass carbon/SnO of the invention2-xThe preparation of nanocomposite
Method and process control is simple, and cost is relatively low, and preparation temperature is low and does not need Post isothermal treatment, avoids later period heat to a certain extent
The defects of crystal grain that may cause in treatment process is grown up, is roughened or crimped.
2) poly- 3,4- ethylenedioxy thiophene (PEDOT)/biomass carbon/SnO of the invention2-xNanocomposite, using not
With physical chemistry compatibility good between component and the level structure to match, it is able to achieve close interface cohesion and boundary
The separation of efficient photo-generate electron-hole pair in the structure of face, to obtain 95% in 120min under the conditions of sunlight irradiation
The efficiency of above photocatalytic oxidation degradation rhodamine B.
3) the wet-chemical in-situ synthesis that uses of the present invention realize morphology controllable, polymolecularity, interface cohesion it is close and
The Sn/SnO of homogeneous grain diameter2-x/SnO2Nanostructure composite photocatalyst material.
Detailed description of the invention
Fig. 1 is poly- 3,4- ethylenedioxy thiophene (PEDOT)/biomass carbon/SnO prepared by the embodiment of the present invention 22-xNanometer
Scanning electron microscope (SEM) photo of composite photocatalyst material.
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) the analytically pure stannous oxalate (C of 1mmol is taken2O4) and the oxalic acid (H of 0.2mmol Sn2C2O4) it is completely dissolved in 4mL's
In dehydrated alcohol, the deionized water of the decyl dimethyl hydroxypropyl sulfobetaines and 13mL that sequentially add 3mmol later is whole
A process in the ice salt bath of sodium chloride and trash ice using constant-temperature magnetic stirring device to its -10 DEG C of continuing magnetic forces stir to
Solution A is obtained after being completely dissolved；
3) the biomass carbon skeleton for taking 0.5g polished is added in solution A, ice bath item of the whole process in trash ice and water
It is stirred in -10 DEG C of continuing magnetic forces to uniformly mixed using constant-temperature magnetic stirring device under part and obtains mixed liquid B；
4) then reaction kettle is put by the water heating kettle of mixed liquid B transfer polytetrafluoroethyllining lining by 70% packing ratio
Enter in 120 DEG C of heat preservation 72h in constant temperature oven, reaction terminates to be cooled to room temperature to obtain the SnO containing precipitated product2-xMixed liquor
C；
5) under the spare part for carrying out continuing magnetic force stirring in -10 DEG C of trash ice and the ice bath of water, by 3,4- enedioxy thiophene
Stannous oxalate (C used in pheno (EDOT) and step 2)2O4Sn molar ratio) is 0.01:1, by 3,4-ethylene dioxythiophene
(EDOT) it is completely dissolved in closed container in the mixed solution of the dehydrated alcohol of 120ml, PSS and DMSO and obtains solution D,
The volume ratio of middle dehydrated alcohol, PSS and DMSO is 1:0.5:0.6；Mixed liquor C is slowly added in solution D, 0.5mol/L is used
Propionic acid solution to adjust its pH value be rapid sealing container after 5, container is transferred to after magnetic agitation 2h -10 DEG C of cryogenic thermostat
72h is stood in case；
6) product is centrifuged, and at 30 DEG C after successively respectively washing 3 times using deionized water and dehydrated alcohol
And vacuum degree is 10-3In the vacuum oven of Pa dry 12h to get poly- 3,4-ethylene dioxythiophene (PEDOT)/biomass carbon/
SnO2-xNanocomposite.
Embodiment 2:
1) under an argon atmosphere by biomass castoff fallen leaves, with the heating rate of 5 DEG C/min from room temperature to 200 DEG C
5h is kept the temperature, reaction terminates to be cooled to room temperature to obtain biomass carbon skeleton；
2) the analytically pure stannous oxalate (C of 1mmol is taken2O4) and the oxalic acid (H of 3mmol Sn2C2O4) it is completely dissolved in 12mL's
In dehydrated alcohol, the deionized water of the decyl dimethyl hydroxypropyl sulfobetaines and 20mL that sequentially add 8mmol later is whole
A process stirs to complete it in 0 DEG C of continuing magnetic force using constant-temperature magnetic stirring device in the ice salt bath of sodium chloride and trash ice
Solution A is obtained after fully dissolved；
3) the biomass carbon skeleton for taking 3g polished is added in solution A, condition of ice bath of the whole process in trash ice and water
Lower stirred in 0 DEG C of continuing magnetic force to uniformly mixed using constant-temperature magnetic stirring device to it obtains mixed liquid B；
4) then reaction kettle is put by the water heating kettle of mixed liquid B transfer polytetrafluoroethyllining lining by 60% packing ratio
Enter in 160 DEG C of heat preservation 36h in constant temperature oven, reaction terminates to be cooled to room temperature to obtain the SnO containing precipitated product2-xMixed liquor
C；
5) under the spare part for carrying out continuing magnetic force stirring in 0 DEG C of trash ice and the ice bath of water, by 3,4-ethylene dioxythiophene
(EDOT) stannous oxalate (C used and in step 2)2O4Sn molar ratio) is 0.1:1, and 3,4-ethylene dioxythiophene (EDOT) is existed
It is completely dissolved in closed container in the mixed solution of the dehydrated alcohol of 150ml, PSS and DMSO and obtains solution D, wherein anhydrous second
The volume ratio of alcohol, PSS and DMSO is 1:0.7:0.87；Mixed liquor C is slowly added in solution D, it is molten with the propionic acid of 10mol/L
It is rapid sealing container after 3 that liquid, which adjusts its pH value, is transferred to container in 0 DEG C of cryostat and stands after magnetic agitation 0.5h
48h；
6) product is centrifuged, and at 70 DEG C after successively respectively washing 8 times using deionized water and dehydrated alcohol
And vacuum degree is 10-1In the vacuum oven of Pa dry 1h to get poly- 3,4-ethylene dioxythiophene (PEDOT)/biomass carbon/
SnO2-xNanocomposite.
As seen from Figure 1, the component of composite material obtained includes poly- 3,4-ethylene dioxythiophene, biomass carbon skeleton
And SnO2-x, it is tightly combined between component, wherein skeleton structure is presented in biomass carbon, and matrix porosity diameter is about the μ of 100nm~3
M, poly- 3,4-ethylene dioxythiophene and SnO2-xIt uniformly and 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) the analytically pure stannous oxalate (C of 1mmol is taken2O4) and the oxalic acid (H of 4mmol Sn2C2O4) it is completely dissolved in 15mL's
In dehydrated alcohol, the deionized water of the decyl dimethyl hydroxypropyl sulfobetaines and 23mL that sequentially add 14mmol later is whole
A process stirs to complete it in 10 DEG C of continuing magnetic forces using constant-temperature magnetic stirring device in the ice salt bath of sodium chloride and trash ice
Solution A is obtained after fully dissolved；
3) the biomass carbon skeleton for taking 6g polished is added in solution A, condition of ice bath of the whole process in trash ice and water
Lower stirred in 10 DEG C of continuing magnetic forces to uniformly mixed using constant-temperature magnetic stirring device to it obtains mixed liquid B；
4) then reaction kettle is put by the water heating kettle of mixed liquid B transfer polytetrafluoroethyllining lining by 70% packing ratio
Enter in 200 DEG C of heat preservation 48h in constant temperature oven, reaction terminates to be cooled to room temperature to obtain the SnO containing precipitated product2-xMixed liquor
C；
5) under the spare part for carrying out continuing magnetic force stirring in 10 DEG C of trash ice and the ice bath of water, by 3,4-ethylene dioxythiophene
(EDOT) stannous oxalate (C used and in step 2)2O4Sn molar ratio) is 0.1:1, and 3,4-ethylene dioxythiophene (EDOT) is existed
It is completely dissolved in closed container in the mixed solution of the dehydrated alcohol of 170ml, PSS and DMSO and obtains solution D, wherein anhydrous second
The volume ratio of alcohol, PSS and DMSO is 1:0.8:1；Mixed liquor C is slowly added in solution D, with the propionic acid solution tune of 10mol/L
Saving its pH value is rapid sealing container after 3, is transferred to container in 10 DEG C of cryostat and stands after magnetic agitation 0.5h
48h；
6) product is centrifuged, and at 70 DEG C after successively respectively washing 8 times using deionized water and dehydrated alcohol
And vacuum degree is 10-1In the vacuum oven of Pa dry 1h to get poly- 3,4-ethylene dioxythiophene (PEDOT)/biomass carbon/
SnO2-xNanocomposite.
Embodiment 4:
1) under an argon atmosphere by biomass castoff orange peel, with the heating rate of 3 DEG C/min from room temperature extremely
300 DEG C of heat preservation 2h, reaction terminate to be cooled to room temperature to obtain biomass carbon skeleton；
2) the analytically pure stannous oxalate (C of 1mmol is taken2O4) and the oxalic acid (H of 1mmol Sn2C2O4) it is completely dissolved in the nothing of 7mL
In water-ethanol, the deionized water of the decyl dimethyl hydroxypropyl sulfobetaines and 15mL that sequentially add 6mmol later is entire
Process stirs to complete it in -5 DEG C of continuing magnetic forces using constant-temperature magnetic stirring device in the ice salt bath of sodium chloride and trash ice
Solution A is obtained after dissolution；
3) the biomass carbon skeleton for taking 1g polished is added in solution A, condition of ice bath of the whole process in trash ice and water
Lower stirred in -5 DEG C of continuing magnetic forces to uniformly mixed using constant-temperature magnetic stirring device to it obtains mixed liquid B；
4) then reaction kettle is put by the water heating kettle of mixed liquid B transfer polytetrafluoroethyllining lining by 40% packing ratio
Enter in 180 DEG C of heat preservation 56h in constant temperature oven, reaction terminates to be cooled to room temperature to obtain the SnO containing precipitated product2-xMixed liquor
C；
5) under the spare part for carrying out continuing magnetic force stirring in -5 DEG C of trash ice and the ice bath of water, by 3,4-ethylene dioxythiophene
(EDOT) stannous oxalate (C used and in step 2)2O4Sn molar ratio) is 0.05:1, by 3,4-ethylene dioxythiophene (EDOT)
It is completely dissolved in closed container in the mixed solution of the dehydrated alcohol of 180ml, PSS and DMSO and obtains solution D, wherein anhydrous
The volume ratio of ethyl alcohol, PSS and DMSO is 1:0.9:1.2；Mixed liquor C is slowly added in solution D, it is molten with the propionic acid of 1mol/L
It is rapid sealing container after 4 that liquid, which adjusts its pH value, is transferred to container in -5 DEG C of cryostat and stands after magnetic agitation 1h
56h；
6) product is centrifuged, and at 50 DEG C after successively respectively washing 5 times using deionized water and dehydrated alcohol
And vacuum degree is 10-2In the vacuum oven of Pa dry 5h to get poly- 3,4-ethylene dioxythiophene (PEDOT)/biomass carbon/
SnO2-xNanocomposite.
Embodiment 5:
1) in a nitrogen atmosphere by biomass castoff lemon peel, with the heating rate of 8 DEG C/min from room temperature extremely
260 DEG C of heat preservation 8h, reaction terminate to be cooled to room temperature to obtain biomass carbon skeleton；
2) the analytically pure stannous oxalate (C of 1mmol is taken2O4) and the oxalic acid (H of 2mmol Sn2C2O4) it is completely dissolved in 10mL's
In dehydrated alcohol, the deionized water of decyl the dimethyl hydroxypropyl sulfobetaines and 18mL of 10mmol is sequentially added later
Whole process in the ice salt bath of sodium chloride and trash ice using constant-temperature magnetic stirring device to its 5 DEG C of continuing magnetic forces stir to
Solution A is obtained after being completely dissolved；
3) the biomass carbon skeleton for taking 4g polished is added in solution A, condition of ice bath of the whole process in trash ice and water
Lower stirred in 5 DEG C of continuing magnetic forces to uniformly mixed using constant-temperature magnetic stirring device to it obtains mixed liquid B；
4) then reaction kettle is put by the water heating kettle of mixed liquid B transfer polytetrafluoroethyllining lining by 50% packing ratio
Enter in 140 DEG C of heat preservation 64h in constant temperature oven, reaction terminates to be cooled to room temperature to obtain the SnO containing precipitated product2-xMixed liquor
C；
5) under the spare part for carrying out continuing magnetic force stirring in 5 DEG C of trash ice and the ice bath of water, by 3,4-ethylene dioxythiophene
(EDOT) stannous oxalate (C used and in step 2)2O4Sn molar ratio) is 0.08:1, by 3,4-ethylene dioxythiophene (EDOT)
It is completely dissolved in closed container in the mixed solution of the dehydrated alcohol of 250ml, PSS and DMSO and obtains solution D, wherein anhydrous
The volume ratio of ethyl alcohol, PSS and DMSO is 1:1.6:1.8；Mixed liquor C is slowly added in solution D, it is molten with the propionic acid of 5mol/L
It is rapid sealing container after 5 that liquid, which adjusts its pH value, is transferred to container in 5 DEG C of cryostat and stands after magnetic agitation 1.5h
64h；
6) product is centrifuged, and at 60 DEG C after successively respectively washing 6 times using deionized water and dehydrated alcohol
And vacuum degree is 10-3In the vacuum oven of Pa dry 8h to get poly- 3,4-ethylene dioxythiophene (PEDOT)/biomass carbon/
SnO2-xNanocomposite.
Claims (9)
1. a kind of poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO2-xThe preparation method of nanocomposite, it is characterised in that
The following steps are included:
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) the analytically pure stannous oxalate (C of 1mmol is taken2O4) and the oxalic acid (H of 0.2~4mmol Sn2C2O4) it is completely dissolved in 4~
In the dehydrated alcohol of 15mL, sequentially add later 3~14mmol decyl dimethyl hydroxypropyl sulfobetaines and 13~
The deionized water of 23mL obtains solution A after being completely dissolved；
3) the biomass carbon skeleton for taking 0.5~6g polished, which is added to be uniformly mixed in solution A, obtains mixed liquid B；
4) by the water heating kettle of mixed liquid B transfer polytetrafluoroethyllining lining, then reaction kettle is put into constant temperature oven 120~
200 DEG C of 48~72h of heat preservation, reaction terminate to be cooled to room temperature to obtain the SnO containing precipitated product2-xMixed liquor C；
5) by stannous oxalate (C used in 3,4- ethylenedioxy thiophene (EDOT) and step 2)2O4Sn molar ratio) be (0.01~
0.1): 1,3,4-ethylene dioxythiophene (EDOT) is completely dissolved in the dehydrated alcohol of 120~250ml, PSS in closed container
With solution D is obtained in the mixed solution of DMSO, wherein the volume ratio of dehydrated alcohol, PSS and DMSO be 1:(0.5~1.6): (0.6
~1.8)；Mixed liquor C is slowly added in solution D, adjusts rapid sealing container after its pH value is 3~5, magnetic force with propionic acid solution
Container is transferred to 48~72h of standing in -10~10 DEG C of cryostat after 0.5~2h of stirring；
6) product is centrifuged, and after successively respectively wash using deionized water and dehydrated alcohol at 30~70 DEG C and very
Reciprocal of duty cycle is 10-1~10-3Be drying to obtain in the vacuum oven of Pa poly- 3,4- ethylenedioxy thiophene (PEDOT)/biomass carbon/
SnO2-xNanocomposite.
2. poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO according to claim 12-xThe preparation of nanocomposite
Method, it is characterised in that: the biomass castoff is coconut husk, lychee exocarp, fallen leaves, banana skin, orange peel, pomelo peel or lemon
Lemon skin.
3. poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO according to claim 12-xThe preparation of nanocomposite
Method, it is characterised in that: the step 2) whole process is filled in the ice salt bath of sodium chloride and trash ice using temperature constant magnetic stirring
It sets and it is stirred in -10~10 DEG C of continuing magnetic forces to being completely dissolved.
4. poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO according to claim 12-xThe preparation of nanocomposite
Method, it is characterised in that: the step 3) whole process uses constant-temperature magnetic stirring device under the condition of ice bath of trash ice and water
It is stirred in -10~10 DEG C of continuing magnetic forces to uniformly mixed.
5. poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO according to claim 12-xThe preparation of nanocomposite
Method, it is characterised in that: the step 4) packing ratio is 40~70%.
6. poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO according to claim 12-xThe preparation of nanocomposite
Method, it is characterised in that: the step 5) whole process carries out continuing magnetic force in -10~10 DEG C of trash ice and the ice bath of water and stirs
It mixes.
7. poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO according to claim 12-xThe preparation of nanocomposite
Method, it is characterised in that: the concentration of the step 5) propionic acid solution is 0.5~10mol/L.
8. poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO according to claim 12-xThe preparation of nanocomposite
Method, it is characterised in that: the step 6) is respectively washed 3~8 times using deionized water and dehydrated alcohol.
9. poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO according to claim 12-xThe preparation of nanocomposite
Method, it is characterised in that: the step 6) drying time is 1~12h.
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