CN109126821A - A kind of preparation method of biomass carbon Base Metal modification auto-dope richness defect tin oxide nano composite photocatalyst material - Google Patents
A kind of preparation method of biomass carbon Base Metal modification auto-dope richness defect tin oxide nano composite photocatalyst material Download PDFInfo
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- CN109126821A CN109126821A CN201811093626.6A CN201811093626A CN109126821A CN 109126821 A CN109126821 A CN 109126821A CN 201811093626 A CN201811093626 A CN 201811093626A CN 109126821 A CN109126821 A CN 109126821A
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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 58
- 239000000463 material Substances 0.000 title claims abstract description 56
- 230000007547 defect Effects 0.000 title claims abstract description 54
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000010953 base metal Substances 0.000 title claims abstract description 26
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 26
- 238000012986 modification Methods 0.000 title claims abstract description 14
- 230000004048 modification Effects 0.000 title claims abstract description 14
- 239000011941 photocatalyst Substances 0.000 title claims description 28
- 230000001699 photocatalysis Effects 0.000 claims abstract description 32
- 230000000694 effects Effects 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 95
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 48
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- 239000010813 municipal solid waste Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- 239000011780 sodium chloride Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 238000003760 magnetic stirring Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 8
- 244000269722 Thea sinensis Species 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 8
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 8
- 235000013824 polyphenols Nutrition 0.000 claims description 8
- 239000001119 stannous chloride Substances 0.000 claims description 8
- 235000011150 stannous chloride Nutrition 0.000 claims description 8
- 206010001497 Agitation Diseases 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 230000002045 lasting effect Effects 0.000 claims description 7
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 235000005979 Citrus limon Nutrition 0.000 claims description 3
- 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
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 239000010903 husk Substances 0.000 claims description 3
- 244000183278 Nephelium litchi Species 0.000 claims description 2
- 235000015742 Nephelium litchi Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 244000276331 Citrus maxima Species 0.000 claims 1
- 235000001759 Citrus maxima Nutrition 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002131 composite material Substances 0.000 abstract description 16
- 239000001301 oxygen Substances 0.000 abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 abstract description 16
- 238000000926 separation method Methods 0.000 abstract description 11
- 239000002082 metal nanoparticle Substances 0.000 abstract description 9
- 239000002105 nanoparticle Substances 0.000 abstract description 9
- 239000004065 semiconductor Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 52
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 11
- 239000010931 gold Substances 0.000 description 10
- 229910006702 SnO2-x Inorganic materials 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 3
- 238000007540 photo-reduction reaction Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000010944 silver (metal) Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 240000000560 Citrus x paradisi Species 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910003081 TiO2−x Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- -1 CuS Chemical class 0.000 description 1
- 229910015675 MoO3−x Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000000969 carrier Substances 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
- 230000009514 concussion Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 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
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000002784 hot electron Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
A kind of preparation method of biomass carbon Base Metal modification auto-dope richness defect tin oxide nano composite material, by the auto-dope richness defect tin oxide semiconductor hetero-junctions of metal-modified, load is scattered in that biomass is carbon-based to obtain photocatalysis composite by way of chemical bond is complexed；Auto-dope richness defect tin oxide is selected from the non-stoichiometric of Sn doping or the tin oxide of the oxygen-enriched defect of mixed valence；The auto-dope richness defect tin oxide of metal-modified is carried on the metal nanoparticle with plasma resonance effect on auto-dope richness defect tin oxide nanoparticles.The present invention utilizes the heterojunction structure between the visible light photocatalysis redox characteristic of auto-dope richness defect tin oxide, the plasma resonance effect of metal nanoparticle, the electric conductivity of biomass carbon sill and three components with chemical bonding, the photo-generate electron-hole separation rate in its light-catalyzed reaction is sufficiently improved, to be conducive to improve the performance of its photocatalytic redox degradation of contaminant and photocatalysis Decomposition aquatic products hydrogen.
Description
Technical field
The present invention relates to a kind of preparation method of tin oxide nano composite material, especially a kind of biomass carbon Base Metal modification
The preparation method of auto-dope richness defect tin oxide nano composite photocatalyst material.
Background technique
Carbon nanomaterial has the characteristic of good photo induced electron transfer and two-photon absorption, in the design side of photochemical catalyst
Face possibly serves for powerful energy converter, degradation environment in harmful substance, produce the fields such as hydrogen energy source have it is wide
Application prospect.But currently, the carbon material photocatalysis efficiency of single structure is unsatisfactory, it is made to receive pole in practical applications
It is big to restrict.Thus the new structural carbon-based composite photo-catalyst of development and exploration seems particularly important.Nano-noble metal is due to its etc.
Ion resonance effect shows strong absorption in visible region, has received widespread attention.Auto-dope richness defect tin oxide
(SnO2-x) there is considerable visible light photocatalysis redox ability.Will efficiently using sunlight carbon-based material with it is expensive
Auto-dope richness defect tin oxide after metal-modified is mutually compound, and the composite material of preparation can obtain the complementation of these three material advantages
Comprehensive excellent properties, and realize the abundant inhibition compound to photo-generated carrier.Meanwhile using life production waste as biomass
The raw material of carbon realize waste utilization, can effectively mitigate environmental pressure.
Auto-dope richness defect tin oxide SnO2-xIn oxygen vacancies may advantageously facilitate light induced electron-as electronics trap center
The separation in hole, thus promote tin oxide light-catalyzed reaction [Shi Leyu, LIU MEILING, Li Xintong, wait non-stoichiometry aoxidize
The preparation of tin and the Shandong Photocatalytic Performance Study [J] chemical industry, 2016,45 (6): 7-8.].The design feature of oxygen-enriched vacancy defect
Make SnO2-xNano particle shows the photocatalytic water H2-producing capacity all more excellent than P25 and ZnO (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.].Sn auto-dope SnO2-xThe presence of nanocrystalline middle oxygen defect can have
Effect improve photo-generate electron-hole pair separation, 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.].Meanwhile the band gap of the tin-oxide of non-stoichiometric or mixed valence is wide
Degree is than monovalent state SnO2Band gap width it is smaller, thus show superior photocatalysis performance, such as Sn2O3、Sn3O4With
Sn5O6.In document report, stannous oxide (SnO) has strong reducing property, be used to prepare catalyst and reducing agent etc., in plating
For preparing stannous fluoboric acid and other soluble tin salts.The Sn of multi-level nano-structure3O4Realize solar irradiation in 30min
Penetrate condition Methyl Orange 30% degradation [Song, H., Son, S.Y., Kim, S.K., G.Y.A facile
synthesis of hierarchical Sn3O4 nanostructures in an acidic aqueous solution
and their strong visible-light-driven photocatalytic activity.Nano Research,
2015,8(11),3553-3561.]。
In order to obtain the closer composite material of level structure, the tin-oxide composite photocatalyst material of different stoichiometric ratios
Material is designed to be prepared for out.SnO/Sn3O4Heterojunction structure has than one pack system SnO and one pack system Sn3O4More excellent Luo Dan
Bright B Photocatalytic Degradation Property [Cui Lei, Yang Lijuan, Gao Jiansen, Gu Shipu .SnO/Sn3O4The preparation and its photocatalysis of heterojunction structure
Performance functional material, 2017,48 (1), 1159-1162.].And SnO/Sn3O4Heterojunction structure is matched by level structure
Between interface effective charge transfer and than one pack system have superior photocatalytic degradation rhodamine B performance [Xia, W., Wang,
H.,Zeng,X.,Han,J.,Zhu,J.,Zhou,M.,&Wu,S.High-efficiency photocatalytic
activity of type II SnO/Sn3O4heterostructures via interfacial charge
transfer.CrystEngComm,2014,16(30),6841-6847.]。
But the photo-generate electron-hole separation rate of the above material still not no being optimal, and there is stability not
Enough high defects, thus inhibit further increasing for its photocatalysis performance.
Local surface plasma resonance (Localized Surface Plasmon Resonance, LSPR)
[(Boerigter,C.,Campana,R.,Morabito,M.,Linic,S.Evidence and implications of
direct charge excitation as the dominant mechanism in plasmon-mediated
Photocatalysis [J] .Nature communications, 2016,7:10545.] [Shi Jianjian, Liu little Ming, Tang Xinghua,
The preparation of Li Shuai dragon novel plasma photochemical catalyst nanogold-metatitanic acid zinc complexes and photolysis water hydrogen performance [J] application
Learn, 2016,33 (5): 583-590.] it is that nano particle is illuminated by the light the concussion effect of free carrier collective caused by excitation, cause
Nano material has the unique physical that selective light absorbs and near field enhances.Plasmon based on LSPR induces current-carrying
Son separation (Plasmon-Induced Carriers Separation, PICS) [Clavero, C.Plasmon-induced
hot-electron generation at nanoparticle/metal-oxide interfaces for
Photovoltaic and photocatalytic devices [J] .Nature Photonics, 2014,8 (2): 95.] energy
Effectively inhibit the photo-generated carrier in semiconductor material compound.In addition, LSPR effect can also improve the photothermal conversion effect of semiconductor
Rate, can accelerate activated reactant molecule, so improve light-catalyzed reaction rate [Meng, X., Liu, L., Ouyang, S., Xu,
H.,Wang,D.,Zhao,N.,Ye,J.Nanometals for Solar‐to‐Chemical Energy Conversion:
From Semiconductor‐Based Photocatalysis to Plasmon‐Mediated Photocatalysis
and Photo‐Thermocatalysis[J].Advanced Materials,2016,28(32):6781-6803.].Zhang Tie
The preparation method using plasma resonance effect and the nanocluster with electron-transport synergistic effect has been invented by sharp seminar, obtains
Having arrived has good photoelectric composite photocatalyst material [Zhang Tierui, Cao Yinhu, Wu Lizhu waits to utilize surface plasma
The nanocluster photochemical catalyst and its preparation method and application of resonance effects and electron-transport synergistic effect:, CN104437561A
[P].2015.].Currently, the material with stronger LSPR effect mainly includes the metal nanoparticles such as Pt, Au, Ag and Cu, part
Nonmetallic compound (such as CuS, WO3-xAnd MoO3-xDeng) although can also show LSPR effect and cost is relatively low, low carrier
Concentration makes its effective PICS relatively difficult to achieve.Metal nanoparticle (such as Pt, Au, Ag and Cu etc.) is selected to prepare plasma resonance
The SnO of photosensitizer metal-modified2-xComposite material environmental-friendly, catalytic activity be strong and the aspects such as stability is high have it is many excellent
Gesture.
In recent years, the light that the synergistic effect of plasma resonance and Lacking oxygen defect significantly promotes some semiconductor materials is urged
Change reaction.Hong Kong Chinese University Wang Jianfang professor knows that professor is prepared for Au/BiOCl plasma resonance with Central China Normal University Zhang Li
Photochemical catalyst [Li, H., Qin, F., Yang, Z., Cui, X., Wang, J., Zhang, L.New reaction pathway
induced by plasmon for selective benzyl alcohol oxidation on BiOCl possessing
oxygen vacancies[J].Journal of the American Chemical Society,2017,139(9):
3513-3521.], BiOCl Lacking oxygen promotes a nanometer separation for the surface Au hot carrier, and plasma by capturing thermoelectron
The internal field of resonance effects induction enhances the fast transfer of interface light induced electron, realizes the photocatalytic-oxidation of efficient benzyl alcohol
Change.BiVO of Dalian Polytechnic University professor Dong Xiaoli to oxygen-enriched vacancy4Photo-reduction load [the Shi Chun of Ag nanoparticle is carried out
Scape, Dong Xiaoli, Wang Xiuying, Ma Hongchao, it is close red that the pucherite that Zhang Xiufang silver nanoparticle deposition contains Lacking oxygen can be improved it
Outer photocatalysis performance [J] is catalyzed journal, 2017,39 (1): 128-137.], the plasma resonance effect of Ag enhances material
It is visible light-responded, BiVO4Lacking oxygen effectively captures electronics and then promotes the separation of photo-generated carrier.Chinese Academy of Sciences king passes justice and grinds
Ag/TiO has been made by photo-reduction and subsequent heat treatment in the person of studying carefully2-x[Duan,Y.,Zhang,M.,Wang,L.,Wang,F.,
Yang,L.,Li,X.,Wang,C.Plasmonic Ag-TiO2-x nanocomposites for the photocatalytic
removal of NO under visible light with high selectivity:The role of oxygen
Vacancies [J] .Applied Catalysis B:Environmental, 2017,204:67-77.], plasma resonance effect
It should be made to have excellent visible light-responded and efficient photo-generated carrier separation rate, while TiO2-xLacking oxygen defect promotes
The photo-reduction of NO, realizing Lacking oxygen defect and plasma resonance enhances the collaboration that NO photocatalysis removes.The above research table
Bright metal plasma resonance and the coupling of semiconductor material Lacking oxygen defect help to enhance the photocatalytic of composite material
Energy.
In order to make the plasma resonance effect of metal nanoparticle realize that plasmon induces current-carrying by photoelectric effect
Son separation maximizes, and selection coincides with metal nanoparticle plasma resonance light abstraction width and photoelectricity transmission and photochemistry are steady
Qualitative excellent semiconductor material is most important.Auto-dope richness defect tin oxide is thought due to having above-mentioned advantage, the person of being applied
It is most potential the light-catalysed ideal semiconductor material of high-efficiency solar wide spectrum to be realized by plasma resonance photosensitizer at present
One of.In view of Lacking oxygen defect can make auto-dope richness defect tin oxide have excellent photoelectricity transmission ability and be conducive to photodissociation
The level structure and plasma resonance effect of aquatic products hydrogen expand the significant work of catalyst visible light and near infrared light responding ability
With the coupling of metal nanoparticle plasma resonance and auto-dope richness defect tin oxide Lacking oxygen defect will be conducive to
Enhance the solar energy photocatalytic performance of metal-modified auto-dope richness defect tin oxide.
Biomass carbon is as electron donor, it may have it is safe and non-toxic, gap is flourishing, absorption property is good, intensity is high, easily again
The design features such as the advantages that life, economy and durability, both can be used as the support carrier of catalyst, and also can effectively improve catalyst
Catalytic efficiency, thus it is primarily used to the adsorption cleaning processing of drinking water, alcoholic, beverage, trade effluent.Biomass carbon also has
Good visible absorption property can be used as the visible light modified material in photochemical catalyst.Using biomass carbon as a kind of group
Composite wood can be significantly increased after dividing the progress of the auto-dope richness defect tin oxide of material and plasma resonance effect metal-modified compound
The synergistic effect of the electronics transfer of material, to be conducive to further increase its photocatalysis performance.
Currently, mainly there are several types of solvent heat knots for preparation method in relation to nanocarbon/metal support type semiconductor composite
Light combination chemical synthesis [the peak Xu Jian carbon material/noble metal enhancing TiO2The Zhejiang research [D] of base composite photocatalyst is big
Learn, 2016.], ultrasonic wave composite algorithm [preparation of military tinkling of pieces of jades carbon dots/noble metal composite construction and its visible light catalytic performance [D]
Northcentral University, 2014.], [Zhong Xing, Wang Jianguo, village Guilin one kind are net for air for sodium borohydride reduction combination air roasting method
Surface plasma resonance enhancing photochemical catalyst and its preparation method and application of change:, CN105289685A [P] .2016.], micro emulsion
Liquid self assembly mating surface activating agent is carbonized, and [Liu Wenxian, Liu Zhiying, crown male, wait carbon coating Au/TiO to two-step method2It is mesoporous micro-
Ball: a kind of new selective photochemical catalyst [J] .Science China.Materials Chinese science: material science (English),
2017 (5): 438-448.], hard template and chemical reduction method [Li Y, CaoS, Zhang A, et al.Carbon and
Nitrogen Co-doped Bowl-like Au/TiO2,Nanostructures with Tunable Size for
Enhanced Visible-Light-Driven Photocatalysis[J].Applied Surface Science,
2018.] etc..The above preparation method all has the advantages that its uniqueness, but shortcoming be mostly preparation process it is complicated,
Need multistep reaction, raw material environment is unfriendly, carried metal is easy to fall off etc..
Summary of the invention
The purpose of the present invention is to provide a kind of biomass carbon Base Metal modification auto-dope richness defect tin oxide nano is compound
The preparation method of catalysis material prepares morphology controllable, degree of scatter height, homogeneous grain diameter using wet-chemical in-situ synthesis
And the close biomass carbon Base Metal of interface cohesion modifies auto-dope richness defect tin oxide nano composite photocatalyst 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 2~8 DEG C/min from room temperature extremely
200~400 DEG C of 0.5~5h of heat preservation, reaction terminate to be cooled to room temperature to obtain biomass carbon skeleton；
2) the analytically pure stannous chloride (SnCl of 1mmol is taken respectively2) and the citric acid of 5~12mmol be completely dissolved in 8~
In 20mL dehydrated alcohol, NaOH solution is used after sequentially adding the tea polyphenols of 2~10mmol and the deionized water of 10~25mL later
It adjusts its pH value and obtains solution A for 4~8；
3) the analytically pure chloroplatinic acid (H of 0~1mmol is taken2PtCl6), 0~2mmol gold chloride (HAuCl4), 0~5mmol nitre
Sour silver (AgNO3), 0~10mmol copper nitrate (Cu (NO3)2) and 1~15mmol citric acid be completely dissolved in 8~20mL go from
Sub- water is uniformly mixed and obtains solution B；
4) solution B is added dropwise in solution A with 30~60 drops/minute speed, obtains solution C, 0.01~3g is taken to walk
The rapid biomass carbon skeleton 1) obtained is added in solution C and obtains hydro-thermal reaction precursor liquid；
5) precursor liquid is transferred to the air-flow in the water heating kettle of polytetrafluoroethyllining lining with 0.1~0.5Mpa into precursor liquid
Uniformly be passed through nitrogen after seal water heating kettle immediately, then by reaction kettle be put into constant temperature oven 100~200 DEG C keep the temperature 24~
72h；
6) to the end of hydro-thermal reaction and reaction system cooled to room temperature, product is centrifuged, and successively makes
It is washed with deionized water and dehydrated alcohol, finally at 35~65 DEG C and vacuum degree is 10-1~10-3It is done in the vacuum oven of Pa
The dry biomass carbon Base Metal modification auto-dope richness defect tin oxide nano composite photocatalyst material obtained based on LSPR effect.
The biomass castoff is coconut husk, lychee exocarp, fallen leaves, banana skin, orange peel, pomelo peel or lemon peel.
The concentration of the step 2) NaOH solution is 2~8mol/L.
Step 2) the whole process uses constant-temperature magnetic stirring device to it -20 in the ice salt bath of NaCl and trash ice
~10 DEG C of progress continuing magnetic force stirrings.
The step 3) is completely dissolved in after deionized water to be stirred in the ice salt bath of NaCl and trash ice using constant temperature magnetic force again
Device is mixed to it in -20~10 DEG C of lasting magnetic agitations, is uniformly mixed and obtains solution B.
Step 4) the whole process uses constant-temperature magnetic stirring device to it -20 in the ice salt bath of NaCl and trash ice
~10 DEG C of progress continuing magnetic force stirrings.
Step 5) the packing ratio is 40~70%.
The time that the step 5) is passed through nitrogen is 10~60min.
The step 6) is respectively washed 3~8 times using deionized water and dehydrated alcohol.
Step 6) the drying time is 2~10h.
The present invention utilizes the light transfer characteristic and electric conductivity of biomass carbon, the single component metals such as Pt, Au, Ag, Cu or conjunction
The light absorption expansion capability of the metal nanoparticle plasma resonance effect of gold and the visible light of auto-dope richness defect tin oxide
Photocatalytic redox ability, to obtain superior photocatalysis performance.
Compared with traditional preparation methods, it is rich that biomass carbon Base Metal prepared by preparation method of the invention modifies auto-dope
Defect tin oxide nano composite photocatalyst material have stability height, good dispersion, particle diameter distribution is narrow, crystal development is complete, shape
The advantages that looks and size are controllable, simple process is efficient and interface cohesion is close, effectively overcomes conventional metals support type semiconductor
The problem of metallic is easy movement, falls off in composite photocatalyst material, obtains more efficient photocatalysis performance.
The beneficial effects of the present invention are embodied in:
1) preparation method technology controlling and process of the invention is simple, and energy consumption is lower, cost is relatively low, and preparation temperature is low and after not needing
Phase Crystallizing treatment, the crystal grain that avoid may cause during Post isothermal treatment to a certain extent grow up, are roughened or crimps etc. scarce
It falls into.
2) biomass carbon Base Metal prepared by the present invention modifies auto-dope richness defect tin oxide nano composite photocatalyst material,
It is rich using the visible light absorption and electric conductivity of biomass carbon, the plasma resonance effect of metal nanoparticle and auto-dope
The visible light photocatalysis redox characteristic of defect tin oxide, these three effects are mutually coupled, and are realized in intimate interfacial structure
The separation of efficient photo-generate electron-hole pair, and the composite photocatalyst material with sunlight wide spectrum light absorpting ability, thus
Obtain the photocatalysis performance of excellent hydrogen production by water decomposition and degradation of organic substances.
Detailed description of the invention
Fig. 1 is that the carbon-based Pt/Au of biomass prepared by the embodiment of the present invention 2 modifies auto-dope richness defect tin oxide (SnO2‐x)
Scanning electron microscope (SEM) map of nanocomposite.
Specific embodiment
The present invention is made with reference to the accompanying drawing further detailed.
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 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 chloride (SnCl of 1mmol is taken respectively2) and the citric acid of 5mmol to be completely dissolved in 8mL anhydrous
In ethyl alcohol, sequentially adds adjust its pH with the NaOH solution of 2mol/L after the tea polyphenols of 2mmol and the deionized water of 10mL later
Value is 8 to obtain solution A, whole process in the ice salt bath of NaCl and trash ice using constant-temperature magnetic stirring device to its 10 DEG C into
The stirring of row continuing magnetic force；
3) the analytically pure chloroplatinic acid (H of 0.1mmol is taken2PtCl6), 3mmol silver nitrate (AgNO3) and 5mmol citric acid it is abundant
It is dissolved in the deionized water of 8mL, then it is held at 10 DEG C using constant-temperature magnetic stirring device in the ice salt bath of NaCl and trash ice
Continuous magnetic agitation is uniformly mixed and obtains solution B；
4) solution B is added dropwise in solution A with 30 drops/minute speed, obtains solution C, 0.01g step 1) is taken to obtain
Biomass carbon skeleton, be added solution C in obtain hydro-thermal reaction precursor liquid, whole process makes in the ice salt bath of NaCl and trash ice
Continuing magnetic force stirring is carried out at 10 DEG C to it with constant-temperature magnetic stirring device；
5) precursor liquid is transferred to the air-flow in the water heating kettle of polytetrafluoroethyllining lining with 0.2Mpa by 70% packing ratio
Water heating kettle is sealed immediately after being uniformly passed through nitrogen 50min into precursor liquid, and then reaction kettle is put into constant temperature oven at 100 DEG C
Heat preservation is for 24 hours；
6) to the end of hydro-thermal reaction and reaction system cooled to room temperature, product is centrifuged, and successively makes
3 times are respectively washed with deionized water and dehydrated alcohol, finally at 35 DEG C and vacuum degree is 10-3It is dry in the vacuum oven of Pa
10h obtains the modification auto-dope richness defect tin oxide nano composite photocatalyst material of the biomass carbon Base Metal based on LSPR effect.
Embodiment 2:
1) under an argon atmosphere by biomass castoff fallen leaves, with the heating rate of 4 DEG C/min from room temperature to 300 DEG C
3h is kept the temperature, reaction terminates to be cooled to room temperature to obtain biomass carbon skeleton；
2) the analytically pure stannous chloride (SnCl of 1mmol is taken respectively2) and the citric acid of 8mmol to be completely dissolved in 14mL anhydrous
In ethyl alcohol, sequentially adds adjust its pH with the NaOH solution of 5mol/L after the tea polyphenols of 6mmol and the deionized water of 21mL later
Value is 6 to obtain solution A, whole process in the ice salt bath of NaCl and trash ice using constant-temperature magnetic stirring device to its 0 DEG C into
The stirring of row continuing magnetic force；
3) the analytically pure chloroplatinic acid (H of 0.3mmol is taken2PtCl6), 2mmol gold chloride (HAuCl4) and 8mmol citric acid fill
Divide the deionized water for being dissolved in 15mL, then uses constant-temperature magnetic stirring device to it at 0 DEG C in the ice salt bath of NaCl and trash ice
Lasting magnetic agitation is uniformly mixed and obtains solution B；
4) solution B is added dropwise in solution A with 40 drops/minute speed, obtains solution C, 1.5g step 1) is taken to obtain
Biomass carbon skeleton, be added solution C in obtain hydro-thermal reaction precursor liquid, whole process makes in the ice salt bath of NaCl and trash ice
Continuing magnetic force stirring is carried out at 0 DEG C to it with constant-temperature magnetic stirring device；
5) precursor liquid is transferred to the air-flow in the water heating kettle of polytetrafluoroethyllining lining with 0.25Mpa by 60% packing ratio
Water heating kettle is sealed immediately after being uniformly passed through nitrogen 30min into precursor liquid, and then reaction kettle is put into constant temperature oven at 150 DEG C
Keep the temperature 48h；
6) to the end of hydro-thermal reaction and reaction system cooled to room temperature, product is centrifuged, and successively makes
6 times are respectively washed with deionized water and dehydrated alcohol, finally at 45 DEG C and vacuum degree is 10-2Dry 6h in the vacuum oven of Pa
Obtain the biomass carbon Base Metal modification auto-dope richness defect tin oxide nano composite photocatalyst material based on LSPR effect.
As seen from Figure 1, the composite material is by biomass carbon, auto-dope richness defect tin oxide and Pt/Au alloy three
Group is grouped as, and three components are combined closely, and it is more close to be rendered as combination for auto-dope richness defect tin oxide in the composite material
Nano particle, particle diameter are about 5~10nm, and Pt/Au is rendered as alloy nanoparticle cluster pattern, and cluster diameter dimension is about
For 3~50nm, biomass carbon is rendered as carbon skeleton microstructure, and matrix porosity diameter is about 200nm~700nm.
Embodiment 3:
1) in a nitrogen atmosphere by biomass castoff banana skin, with the heating rate of 8 DEG C/min from room temperature to 400
DEG C heat preservation 0.5h, reaction terminate be cooled to room temperature to obtain biomass carbon skeleton；
2) the analytically pure stannous chloride (SnCl of 1mmol is taken respectively2) and 12mmol citric acid be completely dissolved in 20mL without
In water-ethanol, sequentially adds adjust it with the NaOH solution of 8mol/L after the tea polyphenols of 10mmol and the deionized water of 25mL later
PH value obtains solution A for 4, and whole process uses constant-temperature magnetic stirring device to it at 10 DEG C in the ice salt bath of NaCl and trash ice
Carry out continuing magnetic force stirring；
3) 1mmol silver nitrate (AgNO is taken3), 6mmol copper nitrate (Cu (NO3)2) and 13mmol citric acid be completely dissolved in
The deionized water of 20mL, then use constant-temperature magnetic stirring device to it in 10 DEG C of lasting magnetic in the ice salt bath of NaCl and trash ice
Power is uniformly mixed to obtain solution B；
4) solution B is added dropwise in solution A with 60 drops/minute speed, obtains solution C, 3g step 1) is taken to obtain
Biomass carbon skeleton is added in solution C and obtains hydro-thermal reaction precursor liquid, and whole process uses in the ice salt bath of NaCl and trash ice
Constant-temperature magnetic stirring device is to it in 10 DEG C of progress continuing magnetic force stirrings；
5) precursor liquid is transferred to the air-flow in the water heating kettle of polytetrafluoroethyllining lining with 0.5Mpa by 40% packing ratio
Water heating kettle is sealed immediately after being uniformly passed through nitrogen 15min into precursor liquid, and then reaction kettle is put into constant temperature oven at 200 DEG C
Heat preservation is for 24 hours；
6) to the end of hydro-thermal reaction and reaction system cooled to room temperature, product is centrifuged, and successively makes
8 times are respectively washed with deionized water and dehydrated alcohol, finally at 65 DEG C and vacuum degree is 10-1Dry 2h in the vacuum oven of Pa
Obtain the biomass carbon Base Metal modification auto-dope richness defect tin oxide nano composite photocatalyst material based on LSPR effect.
Embodiment 4:
1) under an argon atmosphere by biomass castoff orange peel, with the heating rate of 5 DEG C/min from room temperature to 250
DEG C heat preservation 4h, reaction terminate be cooled to room temperature to obtain biomass carbon skeleton；
2) the analytically pure stannous chloride (SnCl of 1mmol is taken respectively2) and 10mmol citric acid be completely dissolved in 17mL without
In water-ethanol, sequentially adds adjust it with the NaOH solution of 4mol/L after the tea polyphenols of 8mmol and the deionized water of 20mL later
PH value obtains solution A for 5, and whole process uses constant-temperature magnetic stirring device to it -20 in the ice salt bath of NaCl and trash ice
DEG C carry out continuing magnetic force stirring；
3) the analytically pure chloroplatinic acid (H of 0.5mmol is taken2PtCl6), 1mmol gold chloride (HAuCl4), 2mmol silver nitrate
(AgNO3), 3mmol copper nitrate (Cu (NO3)2) and 1mmol citric acid be completely dissolved in the deionized water of 13mL, then in NaCl and
It is uniformly mixed using constant-temperature magnetic stirring device in -20 DEG C of lasting magnetic agitations in the ice salt bath of trash ice and obtains solution B；
4) solution B is added dropwise in solution A with 35 drops/minute speed, obtains solution C, 0.5g step 1) is taken to obtain
Biomass carbon skeleton, be added solution C in obtain hydro-thermal reaction precursor liquid, whole process makes in the ice salt bath of NaCl and trash ice
Continuing magnetic force stirring is carried out at -20 DEG C to it with constant-temperature magnetic stirring device；
5) precursor liquid is transferred to the air-flow in the water heating kettle of polytetrafluoroethyllining lining with 0.1Mpa by 50% packing ratio
Water heating kettle is sealed immediately after being uniformly passed through nitrogen 10min into precursor liquid, and then reaction kettle is put into constant temperature oven at 130 DEG C
Keep the temperature 72h；
6) to the end of hydro-thermal reaction and reaction system cooled to room temperature, product is centrifuged, and successively makes
5 times are respectively washed with deionized water and dehydrated alcohol, finally at 40 DEG C and vacuum degree is 10-1Dry 5h in the vacuum oven of Pa
Obtain the biomass carbon Base Metal modification auto-dope richness defect tin oxide nano composite photocatalyst material based on LSPR effect.
Embodiment 5:
1) in a nitrogen atmosphere by biomass castoff pomelo peel, with the heating rate of 3 DEG C/min from room temperature to 350
DEG C heat preservation 1h, reaction terminate be cooled to room temperature to obtain biomass carbon skeleton；
2) the analytically pure stannous chloride (SnCl of 1mmol is taken respectively2) and the citric acid of 6mmol to be completely dissolved in 10mL anhydrous
In ethyl alcohol, sequentially adds adjust its pH with the NaOH solution of 6mol/L after the tea polyphenols of 5mmol and the deionized water of 13mL later
Value obtains solution A for 7, and whole process uses constant-temperature magnetic stirring device to it at -10 DEG C in the ice salt bath of NaCl and trash ice
Carry out continuing magnetic force stirring；
3) the analytically pure chloroplatinic acid (H of 0.8mmol is taken2PtCl6), 0.5mmol gold chloride (HAuCl4), 4mmol silver nitrate
(AgNO3), 8mmol copper nitrate (Cu (NO3)2) and 10mmol citric acid be completely dissolved in the deionized water of 18mL, then in NaCl and
It is uniformly mixed using constant-temperature magnetic stirring device in -10 DEG C of lasting magnetic agitations in the ice salt bath of trash ice and obtains solution B；
4) solution B is added dropwise in solution A with 45 drops/minute speed, obtains solution C, 1g step 1) is taken to obtain
Biomass carbon skeleton is added in solution C and obtains hydro-thermal reaction precursor liquid, and whole process uses in the ice salt bath of NaCl and trash ice
Constant-temperature magnetic stirring device is to it in -10 DEG C of progress continuing magnetic force stirrings；
5) precursor liquid is transferred to the air-flow in the water heating kettle of polytetrafluoroethyllining lining with 0.4Mpa by 65% packing ratio
Water heating kettle is sealed immediately after being uniformly passed through nitrogen 60min into precursor liquid, and then reaction kettle is put into constant temperature oven at 180 DEG C
Keep the temperature 36h；
6) to the end of hydro-thermal reaction and reaction system cooled to room temperature, product is centrifuged, and successively makes
7 times are respectively washed with deionized water and dehydrated alcohol, finally at 50 DEG C and vacuum degree is 10-2Dry 8h in the vacuum oven of Pa
Obtain the biomass carbon Base Metal modification auto-dope richness defect tin oxide nano composite photocatalyst material based on LSPR effect.
Embodiment 6:
1) by biomass castoff lemon peel under nitrogen or argon atmosphere, with the heating rate of 6 DEG C/min from room temperature liter
To 300 DEG C of heat preservation 2h, reaction terminates to be cooled to room temperature to obtain biomass carbon skeleton temperature；
2) the analytically pure stannous chloride (SnCl of 1mmol is taken respectively2) and the citric acid of 9mmol to be completely dissolved in 15mL anhydrous
In ethyl alcohol, sequentially adds adjust its pH with the NaOH solution of 3mol/L after the tea polyphenols of 7mmol and the deionized water of 16mL later
Value is 6 to obtain solution A, whole process in the ice salt bath of NaCl and trash ice using constant-temperature magnetic stirring device to its 5 DEG C into
The stirring of row continuing magnetic force；
3) the analytically pure chloroplatinic acid (H of 1mmol is taken2PtCl6), 1.5mmol gold chloride (HAuCl4), 5mmol silver nitrate
(AgNO3), 10mmol copper nitrate (Cu (NO3)2) and 15mmol citric acid be completely dissolved in the deionized water of 10mL, then in NaCl
Solution B is obtained with being uniformly mixed to it in 5 DEG C of lasting magnetic agitations in the ice salt bath of trash ice using constant-temperature magnetic stirring device；
4) solution B is added dropwise in solution A with 50 drops/minute speed, obtains solution C, 2g step 1) is taken to obtain
Biomass carbon skeleton is added in solution C and obtains hydro-thermal reaction precursor liquid, and whole process uses in the ice salt bath of NaCl and trash ice
Constant-temperature magnetic stirring device is to it in 5 DEG C of progress continuing magnetic force stirrings；
5) precursor liquid is transferred to the air-flow in the water heating kettle of polytetrafluoroethyllining lining with 0.3Mpa by 55% packing ratio
Water heating kettle is sealed immediately after being uniformly passed through nitrogen 40min into precursor liquid, and then reaction kettle is put into constant temperature oven at 160 DEG C
Keep the temperature 60h；
6) to the end of hydro-thermal reaction and reaction system cooled to room temperature, product is centrifuged, and successively makes
4 times are respectively washed with deionized water and dehydrated alcohol, finally at 55 DEG C and vacuum degree is 10-3Dry 4h in the vacuum oven of Pa
Obtain the biomass carbon Base Metal modification auto-dope richness defect tin oxide nano composite photocatalyst material based on LSPR effect.
Claims (10)
1. a kind of preparation method of biomass carbon Base Metal modification auto-dope richness defect tin oxide nano composite photocatalyst material,
It is characterized in that:
1) by biomass castoff under nitrogen or argon atmosphere, with the heating rate of 2~8 DEG C/min from room temperature to 200
~400 DEG C of 0.5~5h of heat preservation, reaction terminate to be cooled to room temperature to obtain biomass carbon skeleton；
2) the analytically pure stannous chloride (SnCl of 1mmol is taken respectively2) and 5~12mmol citric acid be completely dissolved in 8~20mL without
In water-ethanol, sequentially adds adjust it with NaOH solution after the tea polyphenols of 2~10mmol and the deionized water of 10~25mL later
PH value obtains solution A for 4~8；
3) the analytically pure chloroplatinic acid (H of 0~1mmol is taken2PtCl6), 0~2mmol gold chloride (HAuCl4), 0~5mmol silver nitrate
(AgNO3), 0~10mmol copper nitrate (Cu (NO3)2) and 1~15mmol citric acid be completely dissolved in the deionized water of 8~20mL
It is uniformly mixed and obtains solution B；
4) solution B is added dropwise in solution A with 30~60 drops/minute speed, obtains solution C, take 0.01~3g step 1)
Obtained biomass carbon skeleton is added in solution C and obtains hydro-thermal reaction precursor liquid；
5) by precursor liquid be transferred to the air-flow in the water heating kettle of polytetrafluoroethyllining lining with 0.1~0.5Mpa into precursor liquid uniformly
Water heating kettle is sealed immediately after being passed through nitrogen, and then reaction kettle is put into constant temperature oven in 100~200 DEG C of 24~72h of heat preservation；
6) to the end of hydro-thermal reaction and reaction system cooled to room temperature, product is centrifuged, and successively using going
Ionized water and dehydrated alcohol washing, finally at 35~65 DEG C and vacuum degree is 10-1~10-3It is dry in the vacuum oven of Pa
Auto-dope richness defect tin oxide nano composite photocatalyst material is modified to the biomass carbon Base Metal based on LSPR effect.
2. biomass carbon Base Metal according to claim 1 modifies auto-dope richness defect tin oxide nano composite photocatalyst material
The preparation method of material, it is characterised in that: the biomass castoff is coconut husk, lychee exocarp, fallen leaves, banana skin, orange peel, shaddock
Sub- skin or lemon peel.
3. biomass carbon Base Metal according to claim 1 modifies auto-dope richness defect tin oxide nano composite photocatalyst material
The preparation method of material, it is characterised in that: the concentration of the step 2) NaOH solution is 2~8mol/L.
4. biomass carbon Base Metal according to claim 1 modifies auto-dope richness defect tin oxide nano composite photocatalyst material
The preparation method of material, it is characterised in that: the step 2) whole process uses constant temperature magnetic force in the ice salt bath of NaCl and trash ice
Agitating device is to it in -20~10 DEG C of progress continuing magnetic force stirrings.
5. biomass carbon Base Metal modification auto-dope richness defect tin oxide nano according to claim 1 answers photocatalytic synthesis material
The preparation method of material, it is characterised in that: the step 3) is completely dissolved in after deionized water again in the ice salt bath of NaCl and trash ice
It is middle using constant-temperature magnetic stirring device to it in -20~10 DEG C of lasting magnetic agitations, be uniformly mixed and obtain solution B.
6. biomass carbon Base Metal according to claim 1 modifies auto-dope richness defect tin oxide nano composite photocatalyst material
The preparation method of material, it is characterised in that: the step 4) whole process uses constant temperature magnetic force in the ice salt bath of NaCl and trash ice
Agitating device is to it in -20~10 DEG C of progress continuing magnetic force stirrings.
7. biomass carbon Base Metal according to claim 1 modifies auto-dope richness defect tin oxide nano composite photocatalyst material
The preparation method of material, it is characterised in that: the step 5) packing ratio is 40~70%.
8. biomass carbon Base Metal according to claim 1 modifies auto-dope richness defect tin oxide nano composite photocatalyst material
The preparation method of material, it is characterised in that: the time that the step 5) is passed through nitrogen is 10~60min.
9. biomass carbon Base Metal according to claim 1 modifies auto-dope richness defect tin oxide nano composite photocatalyst material
The preparation method of material, it is characterised in that: the step 6) is respectively washed 3~8 times using deionized water and dehydrated alcohol.
10. biomass carbon Base Metal according to claim 1 modifies auto-dope richness defect tin oxide nano composite photocatalyst
The preparation method of material, it is characterised in that: the step 6) drying time is 2~10h.
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Cited By (3)
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| CN110064386A (en) * | 2019-05-30 | 2019-07-30 | 济南大学 | A kind of three tin nanometer sheet composite photocatalyst materials of oxidation of tool Lacking oxygen four and preparation method of tin nanoparticles modification |
| CN113136602A (en) * | 2021-04-19 | 2021-07-20 | 西北师范大学 | Preparation and application of bismuth vanadate/Vo-FeNiOOH composite photo-anode |
| CN115153279A (en) * | 2022-05-16 | 2022-10-11 | 浙江飞剑工贸有限公司 | Titanium cup with function of supplementing trace elements and preparation method thereof |
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2018
- 2018-09-19 CN CN201811093626.6A patent/CN109126821A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110064386A (en) * | 2019-05-30 | 2019-07-30 | 济南大学 | A kind of three tin nanometer sheet composite photocatalyst materials of oxidation of tool Lacking oxygen four and preparation method of tin nanoparticles modification |
| CN110064386B (en) * | 2019-05-30 | 2021-08-24 | 济南大学 | Tin nanoparticle modified composite photocatalytic material with oxygen vacancy stannic oxide nanosheets and preparation method thereof |
| CN113136602A (en) * | 2021-04-19 | 2021-07-20 | 西北师范大学 | Preparation and application of bismuth vanadate/Vo-FeNiOOH composite photo-anode |
| CN115153279A (en) * | 2022-05-16 | 2022-10-11 | 浙江飞剑工贸有限公司 | Titanium cup with function of supplementing trace elements and preparation method thereof |
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