CN113769779B - Photocatalyst for treating sewage containing amine organic matters, and preparation method and application thereof - Google Patents
Photocatalyst for treating sewage containing amine organic matters, and preparation method and application thereof Download PDFInfo
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- CN113769779B CN113769779B CN202110938957.0A CN202110938957A CN113769779B CN 113769779 B CN113769779 B CN 113769779B CN 202110938957 A CN202110938957 A CN 202110938957A CN 113769779 B CN113769779 B CN 113769779B
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- photocatalyst
- amine
- lanthanum
- treating
- bso
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 99
- 150000001412 amines Chemical class 0.000 title claims abstract description 71
- 239000010865 sewage Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052788 barium Inorganic materials 0.000 claims abstract description 120
- 229940071182 stannate Drugs 0.000 claims abstract description 112
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000001699 photocatalysis Effects 0.000 claims abstract description 37
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 30
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000005416 organic matter Substances 0.000 claims abstract description 26
- 239000013543 active substance Substances 0.000 claims abstract description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 42
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 38
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 38
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 35
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 34
- 229910001626 barium chloride Inorganic materials 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000004729 solvothermal method Methods 0.000 claims description 19
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 11
- 239000002351 wastewater Substances 0.000 claims description 11
- MCQCLFYYAUYINZ-UHFFFAOYSA-N [Sn].[La] Chemical compound [Sn].[La] MCQCLFYYAUYINZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- 150000002603 lanthanum Chemical class 0.000 claims description 6
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 31
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000003504 photosensitizing agent Substances 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 229910052718 tin Inorganic materials 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 238000004321 preservation Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 19
- 239000000843 powder Substances 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000007790 solid phase Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 230000000875 corresponding effect Effects 0.000 description 11
- 238000010304 firing Methods 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- 238000011049 filling Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 235000000621 Bidens tripartita Nutrition 0.000 description 7
- 240000004082 Bidens tripartita Species 0.000 description 7
- 208000006637 fused teeth Diseases 0.000 description 7
- 230000006798 recombination Effects 0.000 description 7
- 238000005215 recombination Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 6
- 238000003892 spreading Methods 0.000 description 6
- 230000007480 spreading Effects 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000003421 catalytic decomposition reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229940031098 ethanolamine Drugs 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 230000001443 photoexcitation Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- BEVKFMGKUSSAGX-UHFFFAOYSA-J O.O.O.O.O.O.[Cl-].[Zr+4].[Cl-].[Cl-].[Cl-] Chemical compound O.O.O.O.O.O.[Cl-].[Zr+4].[Cl-].[Cl-].[Cl-] BEVKFMGKUSSAGX-UHFFFAOYSA-J 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002546 full scan Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
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- B01J35/39—
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
- B01J31/0232—Halogen-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0228
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a photocatalyst for treating amine-containing organic matter sewage, and a preparation method and application thereof. The photocatalyst comprises an eosin dye and a photocatalytic active substance, wherein the mass ratio of the eosin dye to the photocatalytic active substance is (1-7): 7, and the photocatalytic active substance is barium stannate or lanthanum doped barium stannate. The photocatalyst for treating the amine-containing organic matter sewage uses eosin dye and photocatalytic active substances as raw materials, wherein the photocatalytic active substances are barium stannate or lanthanum doped barium stannate, the problem that the visible light catalytic activity of a photosensitizer is low under the condition of no noble metal load of the existing photocatalyst is solved pertinently, and the photocatalyst has high photocatalytic activity and stability for treating the amine-containing organic matter sewage.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a photocatalyst for treating amine-containing organic matter sewage, and a preparation method and application thereof.
Background
The solar photocatalytic water splitting to produce hydrogen is a simulation of photosynthesis in nature, which is a process of converting absorbed carbon dioxide into oxygen and organic matters by a complex catalytic reaction of green plants under illumination. The photocatalytic water splitting hydrogen production reaction is an energy conversion process that a photocatalyst converts solar energy into chemical energy under illumination, and the photocatalyst is not consumed along with the progress of the reaction. Fujishima and Honda have realized TiO for the first time since 1972 2 Photoelectrochemical decomposition of water by semiconductor photoelectrodes to obtain H 2 And O 2 After that, the photocatalytic water splitting hydrogen production technology attracts the interests of a plurality of researchers at home and abroad. For nearly half a century, research into photocatalytic materials has been replayed in conventional semiconductor materials, such as TiO 2 、Fe 2 O 3 、g-C 3 N 4 CdS, etc. Although photocatalytic hydrogen production technology has been developed rapidly in the last half century of research, many difficult problems, such as complex synthesis routes, low photocatalytic performance, etc., remain to be found in the course of the research.
After photo-excitation to generate photo-generated electrons and photo-generated holes, the electrons and the holes react respectively. Typically, the photogenerated electrons will reduce protons to hydrogen, known as hydrogen-generating half reactions; and the photogenerated holes oxidize the oxygen element to oxygen, known as an oxygen generating half reaction. The oxygen-generating half reaction is a four-electron process, so that the kinetics is slow, the photo-generated holes cannot be consumed in time, the whole photocatalytic reaction process is slowed down, and the hydrogen production rate is influenced. Oxygen, on the other hand, is a good electron acceptor, its presence inhibits the rate of hydrogen-producing half reactions and also produces uncontrolled reactive oxygen radicals. At the same time, oxygen has limited commercial value and the cost of separating it from hydrogen is high. Therefore, if a substance capable of self-sacrificing and rapidly absorbing holes is added into the photocatalytic system, the surface chemical reaction can be quickened, and the hydrogen production capacity of the system can be improved. Such materials are referred to as "sacrificial agents". The sacrificial agent has the main functions of promoting charge separation, inhibiting surface reverse reaction, prolonging the service life of corresponding photo-generated holes or electrons, improving the photocatalysis performance from the aspect of dynamics and accelerating the half reaction.
The amine-containing organic matter is a chemical raw material with wide application, is used as a surfactant, a wetting agent for textiles and cosmetics, a dispersing agent for resin and rubber, and the like, and has wide application in modern industrial production. At present, most of waste water similar to amine-containing organic pollutants adopts a biochemical treatment method or a method combining chemical pretreatment and biochemistry, such as a method for treating methyl diethanolamine-containing waste water by a microwave photochemical catalytic oxidation method, a method for treating high-concentration organic amine waste water by a multi-stage physicochemical treatment and biochemical combination process, a method for treating amine-containing organic waste water by a complex extraction method, and a method for treating alcohol amine-like waste water by an ion exchange method and a Fenton oxidation method.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a photocatalyst for treating amine-containing organic matter sewage, and a preparation method and application thereof. The photocatalyst for treating the amine-containing organic matter sewage uses eosin dye and photocatalytic active substances as raw materials, wherein the photocatalytic active substances are barium stannate or lanthanum doped barium stannate, the problem that the visible light catalytic activity of the photosensitizer is low under the condition of no noble metal load of the existing photocatalyst is solved pertinently, and the photocatalyst has high amine-containing organic matter photocatalytic activity and stability.
In order to solve the technical problems, the invention adopts the following technical scheme: the photocatalyst for treating the amine-containing organic matter sewage is characterized by comprising an eosin dye and a photocatalytic active substance, wherein the mass ratio of the eosin dye to the photocatalytic active substance is (1-7): 7, and the photocatalytic active substance is barium stannate or lanthanum doped barium stannate.
The photocatalyst for treating the sewage containing the amine organic matters is characterized in that in the barium stannate, ba 2+ With Sn 2 + The ratio of the amounts of the substances is 1:1; in the lanthanum-doped barium stannate, ba 2+ 、Sn 2+ And La (La) 2+ The ratio of the amounts of the substances was 10:9.5:0.5.
The photocatalyst for treating the amine-containing organic matter sewage is characterized in that the preparation method of the barium stannate comprises the following steps:
adding soluble tin salt into hydrogen peroxide solution containing citric acid monohydrate and barium chloride, and stirring until the soluble tin salt is dissolved to obtain tin precursor solution;
step two, dropwise adding ammonia water into the tin precursor solution in the step one until the pH value of the system is 9-11, so as to obtain tin-containing suspension;
stirring the tin-containing suspension in the step II at 50-70 ℃ for 0.5-3 h, cooling, washing, drying, grinding and roasting to obtain barium stannate.
The photocatalyst for treating the amine-containing organic matter sewage is characterized in that the preparation method of the hydrogen peroxide solution containing citric acid monohydrate and barium chloride in the step one comprises the following steps: citric acid monohydrate was added to the hydrogen peroxide solution, followed by the addition of barium chloride to obtain a hydrogen peroxide solution containing citric acid monohydrate and barium chloride.
The photocatalyst for treating the sewage containing the amine organic matters is characterized in that the mass of the citric acid monohydrate is 0.2-1 times of the mass of the soluble tin salt, and the mass of the hydrogen peroxide is 30-70 times of the mass of the citric acid monohydrate; the soluble tin salt is tin chloride or tin nitrate.
The photocatalyst for treating the sewage containing the amine organic matters is characterized in that the mass percentage of the ammonia water in the second step is 25% -28%, and the dropping speed of the ammonia water is 16-24 mL/min; and step three, the temperature rising rate of the roasting is 4-6 ℃/min, and the roasting temperature is 520-580 ℃.
The photocatalyst for treating the amine-containing organic matter sewage is characterized in that the preparation method of lanthanum-doped barium stannate comprises the following steps:
adding soluble tin salt and soluble lanthanum salt into hydrogen peroxide solution containing citric acid monohydrate and barium chloride, and stirring until the soluble tin salt and the soluble lanthanum salt are dissolved to obtain tin precursor solution containing lanthanum; the soluble lanthanum salt is lanthanum nitrate;
Step two, dropwise adding ammonia water into the tin precursor solution containing lanthanum in the step one until the pH value of the system is 9-11, so as to obtain lanthanum-tin suspension;
and thirdly, stirring the lanthanum-tin-containing suspension in the second step at 50-70 ℃ for 0.5-3 h, cooling, washing, drying, grinding and roasting to obtain lanthanum-doped barium stannate.
In addition, the invention also provides a method for preparing the photocatalyst for treating the sewage containing the amine organic matters, which is characterized by comprising the following steps of: and carrying out solvothermal reaction on the eosin dye and the photocatalytic active substance to prepare the photocatalyst for treating the amine-containing organic matter sewage.
The method is characterized in that the solvent of the solvothermal reaction is absolute ethyl alcohol, and the temperature of the solvothermal reaction is 110-130 ℃; the solvothermal reaction is carried out in a polytetrafluoroethylene hydrothermal kettle liner sleeved with a stainless steel outer liner.
Furthermore, the invention also provides a method for treating the amine-containing organic pollutants by using the photocatalyst for treating the amine-containing organic matter sewage, which is characterized in that the amine-containing organic pollutants comprise dye-containing pollutants or ethanol amine-containing pollutants.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a method for preparing a photocatalyst by using eosin dye and a photocatalytic active substance as raw materials, wherein the photocatalytic active substance is stannoic acidPhotocatalyst for treating amine-containing organic matter sewage by doping barium or lanthanum with barium stannate, which aims at solving the problem that the visible light catalytic activity of the photosensitizer is low under the condition of no noble metal load of the existing photocatalyst, and the photocatalytic activity of the catalytic amine-containing organic matter can reach 60 mu mol h -1 g -1 Has high photocatalytic activity and stability for treating the sewage containing the amine organic matters.
2. The invention adopts the photocatalyst which comprises eosin dye and photocatalytic active substances as raw materials, can couple degradation pollutants with hydrogen production, and finally generates two products of hydrogen and solar chemicals, thereby improving energy efficiency and reducing cost.
3. The invention provides a method for preparing photocatalyst for treating amine-containing organic matter sewage, which comprises the steps of carrying out solvothermal reaction on eosin dye and photocatalytic active substances to prepare the photocatalyst for treating amine-containing organic matter sewage, wherein the solvent is absolute ethyl alcohol, the solvothermal reaction temperature is 110-130 ℃, the reactant systems are fully contacted, the reaction is complete, the generation of photo-generated carriers can be effectively promoted, the transmission efficiency of the photo-generated carriers is improved, and the defect of serious photo-generated carrier recombination is overcome.
4. According to the preparation method, an electron transport material in a solar cell is expanded and applied to construction of a composite photocatalyst, wherein carboxyl groups of eosin dye and barium stannate or lanthanum-doped barium stannate form double-tooth bridging configuration coordination bonds, in the process of photocatalytic degradation of amine-containing organic matters, eosin is taken as a light absorber to absorb light to generate carriers, electrons are directionally transported to the electron transport material barium stannate or lanthanum-doped barium stannate through the double-tooth bridging configuration coordination bonds, and react with hydrogen ions in a solution to generate hydrogen, and photo-generated holes react with the amine-containing organic matters in the solution, so that the effect of efficiently degrading organic pollutants is achieved.
The technical scheme of the invention is further described in detail below with reference to the accompanying drawings and the examples.
Drawings
FIG. 1 shows XRD patterns of Barium Stannate (BSO), lanthanum doped barium stannate (LBSO), a photocatalyst (EY/BSO) based on barium stannate, and a photocatalyst (EY/LBSO) based on lanthanum doped barium stannate.
FIG. 2 is a UV-Vis spectrum of Barium Stannate (BSO), lanthanum doped barium stannate (LBSO), barium stannate based photocatalyst (EY/BSO), and lanthanum doped barium stannate based photocatalyst (EY/LBSO).
FIG. 3 is an SEM photograph of Barium Stannate (BSO) and a photocatalyst (EY/BSO) using barium stannate as a raw material.
Fig. 4 is a TEM and EDX elemental scan (Mapping) picture of the product: (a) Barium Stannate (BSO); (b) a photocatalyst (EY/BSO) comprising barium stannate as a raw material; (c) EY/MOF of comparative example 1.
FIG. 5 shows XPS spectra of Barium Stannate (BSO) and a photocatalyst (EY/BSO) using barium stannate as a raw material. Wherein, (a) XPS broad spectrum of Barium Stannate (BSO) and photocatalyst (EY/BSO) using barium stannate as raw material; (b) XPS Br 3d spectrum of photocatalyst (EY/BSO) with barium stannate as raw material; (c) XPS C1 s spectra of Barium Stannate (BSO) and photocatalyst (EY/BSO) prepared from barium stannate; (d) XPS O1 s spectra of Barium Stannate (BSO) and photocatalyst (EY/BSO) using barium stannate as raw material; (e) XPS Ba 3d spectra of Barium Stannate (BSO) and photocatalyst (EY/BSO) using barium stannate as raw material; (c) XPS Sn 3d spectra of Barium Stannate (BSO) and photocatalyst (EY/BSO) using barium stannate as raw material.
Fig. 6 is FTIR spectra of each sample.
FIG. 7 is a graph of the thermogravimetric curves of samples of a photocatalyst (EY/BSO) starting with barium stannate and a photocatalyst (EY/LBSO) starting with lanthanum doped barium stannate.
Fig. 8 shows electrochemical ac impedance spectra of Barium Stannate (BSO), lanthanum doped barium stannate (LBSO), a photocatalyst (EY/BSO) based on barium stannate, and a photocatalyst (EY/LBSO) based on lanthanum doped barium stannate.
FIG. 9 is a graph showing the activity of visible light catalytic decomposition of triethanolamine, wherein (a) is a graph showing the activity of the sample in the absence of a promoter in the visible light catalytic decomposition of triethanolamine, and (b) is a histogram showing the rate of decomposition of triethanolamine.
Detailed Description
All chemical reagents were purchased from national pharmaceutical group chemical reagent limited, pure chemical; the water used was self-made and had a resistance of 18.25mΩ.
Example 1
The embodiment provides a preparation method of barium stannate, which comprises the following steps:
step one, preparing a hydrogen peroxide solution containing citric acid monohydrate and barium chloride: adding 5mmol of citric acid monohydrate into 170mL of 30% hydrogen peroxide solution, stirring until the solution is colorless and transparent, adding 10mmol of barium chloride, and stirring until the solution is completely dissolved to obtain a hydrogen peroxide solution containing citric acid monohydrate and barium chloride;
step two, adding 10mmol of tin chloride into the hydrogen peroxide solution containing citric acid monohydrate and barium chloride in the step one, and stirring until the tin chloride is completely dissolved to obtain a tin precursor solution;
step three, dropwise adding ammonia water into the tin precursor solution in the step two, and stopping dropwise adding until the pH value of the system is 10, so as to obtain milky tin-containing suspension; the mass percentage of the ammonia water is 26%, and the dropping speed of the ammonia water is 20mL/min;
Transferring the tin-containing suspension in the step three into a water bath kettle with the temperature of 50 ℃ for heat preservation and stirring reaction for 1h, taking out, cooling to room temperature, washing with deionized water until the pH value of the supernatant is 7, then placing into a baking oven with the temperature of 60 ℃ for drying for 6h, grinding, spreading 1g of ground powder in a 25mL ceramic crucible, placing the ceramic crucible with the powder into a muffle furnace, heating to 520 ℃ at the heating rate of 4 ℃/min for heat preservation and firing for 1h, stopping heating, and naturally cooling to obtain barium stannate white powder; the room temperature is 20-25 ℃; as a possible embodiment, the deionized water washing is performed in a centrifuge at 5000rpm for 5min each.
Example 2
This example is the same as example 1 except that tin nitrate is used in step two and the firing temperature in step four is 550 ℃.
Example 3
This example is the same as example 1, except that tin nitrate is used in step two and the firing temperature in step four is 580 ℃.
Example 4
The embodiment provides a preparation method of barium stannate, which comprises the following steps:
step one, preparing a hydrogen peroxide solution containing citric acid monohydrate and barium chloride: adding 2mmol of citric acid monohydrate into 100mL of hydrogen peroxide solution with the mass percentage content of 30%, stirring until the solution is colorless and transparent, then adding 10mmol of barium chloride, and stirring until the solution is completely dissolved to obtain hydrogen peroxide solution containing citric acid monohydrate and barium chloride;
Step two, adding 10mmol of tin chloride into the hydrogen peroxide solution containing citric acid monohydrate and barium chloride in the step one, and stirring until the tin chloride is completely dissolved to obtain a tin precursor solution;
step three, dropwise adding ammonia water into the tin precursor solution in the step two, and stopping dropwise adding when the pH value of the system is 9, so as to obtain milky tin-containing suspension; the mass percentage of the ammonia water is 25%, and the dropping speed of the ammonia water is 16mL/min;
transferring the tin-containing suspension in the step three into a water bath kettle with the temperature of 60 ℃ for heat preservation and stirring reaction for 0.5h, taking out, cooling to room temperature, washing with deionized water until the pH value of the supernatant is 7, then placing into a baking oven with the temperature of 60 ℃ for drying for 10h, grinding, spreading 1g of ground powder in a 25mL ceramic crucible, placing the ceramic crucible with the powder into a muffle furnace, heating to 520 ℃ at a heating rate of 5 ℃/min for heat preservation and firing for 1h, stopping heating, and naturally cooling to obtain barium stannate white powder; the room temperature is 20-25 ℃; as a possible implementation, deionized water washing in a centrifuge, the rotation speed is 7000rpm, each centrifugal time is 4 minutes.
Example 5
The embodiment provides a preparation method of barium stannate, which comprises the following steps:
Step one, preparing a hydrogen peroxide solution containing citric acid monohydrate and barium chloride: adding 10mmol of citric acid monohydrate into 210mL of hydrogen peroxide solution with the mass percentage of 30%, stirring until the solution is colorless and transparent, adding 10mmol of barium chloride, and stirring until the solution is completely dissolved to obtain hydrogen peroxide solution containing citric acid monohydrate and barium chloride;
step two, adding 10mmol of tin chloride into the hydrogen peroxide solution containing citric acid monohydrate and barium chloride in the step one, and stirring until the tin chloride is completely dissolved to obtain a tin precursor solution;
step three, dropwise adding ammonia water into the tin precursor solution in the step two, and stopping dropwise adding when the pH value of the system is 11, so as to obtain milky tin-containing suspension; the mass percentage of the ammonia water is 28%, and the dropping speed of the ammonia water is 24mL/min;
transferring the tin-containing suspension in the step three into a water bath kettle with the temperature of 70 ℃ for heat preservation and stirring reaction for 3 hours, taking out, cooling to room temperature, washing with deionized water until the pH value of the supernatant is 7, then placing into a baking oven with the temperature of 60 ℃ for drying for 8 hours, grinding, spreading 1g of ground powder in a 25mL ceramic crucible, placing the ceramic crucible with the powder into a muffle furnace, heating to 520 ℃ at the heating rate of 6 ℃/min for heat preservation and firing for 1 hour, stopping heating, and naturally cooling to obtain barium stannate white powder; the room temperature is 20-25 ℃; as a possible embodiment, the deionized water washing was performed in a centrifuge at 6000rpm for 3min each.
Example 6
The embodiment provides a preparation method of lanthanum-doped barium stannate, which specifically comprises the following steps:
step one, preparing a hydrogen peroxide solution containing citric acid monohydrate and barium chloride: adding 5mmol of citric acid monohydrate into 170mL of 30% hydrogen peroxide solution, stirring until the solution is colorless and transparent, adding 10mmol of barium chloride, and stirring until the solution is completely dissolved to obtain a hydrogen peroxide solution containing citric acid monohydrate and barium chloride;
adding 9.5mmol of tin chloride and 0.5mmol of lanthanum nitrate into the hydrogen peroxide solution containing citric acid monohydrate and barium chloride in the first step, and stirring until the solution is completely dissolved to obtain a tin precursor solution containing lanthanum;
step three, dropwise adding ammonia water into the lanthanum-containing tin precursor solution in the step two until the pH value of the system is 10, and stopping dropwise adding to obtain milky lanthanum-tin suspension; the mass percentage of the ammonia water is 26%, and the dropping speed of the ammonia water is 20mL/min;
transferring the lanthanum-tin-containing suspension in the step three into a water bath kettle at 60 ℃ for heat preservation and stirring reaction for 1h, taking out, cooling to room temperature, washing with deionized water until the pH value of the supernatant is 7, then placing into a baking oven at 60 ℃ for drying for 8h, grinding, spreading 1g of ground powder in a 25mL ceramic crucible, placing the ceramic crucible filled with the powder into a muffle furnace, heating to 520 ℃ at a heating rate of 5 ℃/min for heat preservation and firing for 1h, stopping heating, and naturally cooling to obtain lanthanum-doped barium stannate white powder; the room temperature is 20-25 ℃; as a possible embodiment, the deionized water washing was performed in a centrifuge at 6000rpm for 4min each.
Example 7
The present embodiment is the same as in example 6, except that tin nitrate is used in the second step and the firing temperature in the fourth step is 550 ℃.
Example 8
The present embodiment is the same as in example 6, except that tin nitrate is used in the second step and the firing temperature in the fourth step is 580 ℃.
Example 9
The embodiment provides a preparation method of lanthanum-doped barium stannate, which specifically comprises the following steps:
step one, preparing a hydrogen peroxide solution containing citric acid monohydrate and barium chloride: adding 10mmol of citric acid monohydrate into 210mL of hydrogen peroxide solution with the mass percentage of 30%, stirring until the solution is colorless and transparent, adding 10mmol of barium chloride, and stirring until the solution is completely dissolved to obtain hydrogen peroxide solution containing citric acid monohydrate and barium chloride;
adding 9.5mmol of tin chloride and 0.5mmol of lanthanum nitrate into the hydrogen peroxide solution containing citric acid monohydrate and barium chloride in the first step, and stirring until the solution is completely dissolved to obtain a tin precursor solution containing lanthanum;
step three, dropwise adding ammonia water into the lanthanum-containing tin precursor solution in the step two until the pH value of the system is 9, and stopping dropwise adding to obtain milky lanthanum-tin suspension; the mass percentage of the ammonia water is 28%, and the dropping speed of the ammonia water is 24mL/min;
Transferring the lanthanum-tin-containing suspension in the step three into a water bath kettle with the temperature of 50 ℃ for heat preservation and stirring reaction for 3 hours, taking out, cooling to room temperature, washing with deionized water until the pH value of the supernatant is 7, then placing into a baking oven with the temperature of 60 ℃ for drying for 10 hours, grinding, spreading 1g of ground powder in a 25mL ceramic crucible, placing the ceramic crucible with the powder into a muffle furnace, heating to 520 ℃ at the heating rate of 4 ℃/min for heat preservation and firing for 1 hour, stopping heating, and naturally cooling to obtain lanthanum-doped barium stannate white powder; the room temperature is 20-25 ℃; as a possible embodiment, the deionized water washing is performed in a centrifuge at 5000rpm for 3min each.
Example 10
The embodiment provides a preparation method of lanthanum-doped barium stannate, which specifically comprises the following steps:
step one, preparing a hydrogen peroxide solution containing citric acid monohydrate and barium chloride: adding 2mmol of citric acid monohydrate into 100mL of hydrogen peroxide solution with the mass percentage content of 30%, stirring until the solution is colorless and transparent, then adding 10mmol of barium chloride, and stirring until the solution is completely dissolved to obtain hydrogen peroxide solution containing citric acid monohydrate and barium chloride;
adding 9.5mmol of tin chloride and 0.5mmol of lanthanum nitrate into the hydrogen peroxide solution containing citric acid monohydrate and barium chloride in the first step, and stirring until the solution is completely dissolved to obtain a tin precursor solution containing lanthanum;
Step three, dropwise adding ammonia water into the lanthanum-containing tin precursor solution in the step two until the pH value of the system is 11, and stopping dropwise adding to obtain milky lanthanum-tin suspension; the mass percentage of the ammonia water is 25%, and the dropping speed of the ammonia water is 16mL/min;
transferring the lanthanum-tin-containing suspension in the step three into a water bath kettle with the temperature of 70 ℃ for heat preservation and stirring reaction for 0.5h, taking out, cooling to room temperature, washing with deionized water until the pH value of the supernatant is 7, then placing the supernatant into a baking oven with the temperature of 60 ℃ for drying for 6h, grinding, spreading 1g of ground powder in a 25mL ceramic crucible, placing the ceramic crucible with the powder into a muffle furnace, heating to 520 ℃ at the heating rate of 6 ℃/min for heat preservation and firing for 1h, stopping heating, and naturally cooling to obtain lanthanum-doped barium stannate white powder; the room temperature is 20-25 ℃; as a possible implementation, deionized water washing in a centrifuge, the rotation speed is 7000rpm, each centrifugal time is 5 minutes.
Example 11
The barium stannate of the example 1 is directly used as a raw material of a photocatalyst for treating the sewage containing the amine organic matters, and the raw material of the photocatalyst for treating the sewage containing the amine organic matters further comprises eosin dye, wherein the mass ratio of the eosin dye to the barium stannate is 3:7.
The embodiment also provides a method for preparing the photocatalyst for treating the sewage containing the amine organic matters by using the raw materials, which comprises the following steps:
adding 300mg of eosin dye and 700mg of barium stannate of example 1 into a hydrothermal kettle liner filled with 20mL of ethanol, performing ultrasonic treatment for 20min, filling into a stainless steel outer liner for sealing, then placing into a 120 ℃ oven for heat preservation for 24h solvothermal reaction, and naturally cooling to room temperature;
and step two, washing the solid phase substance cooled in the step one by deionized water until the washing liquid is colorless and transparent, and drying the washed solid phase in a 60 ℃ oven for 10 hours to obtain the photocatalyst for treating the sewage containing the amine organic matters.
Comparative example 1
The comparative example provides a method for preparing a photocatalyst by taking eosin dye and MOF as raw materials, wherein the mass ratio of the eosin dye to the MOF is 3:7, and the preparation method comprises the following steps:
step one, synthesizing MOFs: 0.3g of zirconium chloride hexahydrate is added into a polytetrafluoroethylene hydrothermal kettle liner containing 30mL of N, N-Dimethylformamide (DMF), and the mixture is subjected to ultrasonic treatment for 20min until the zirconium chloride is completely dissolved;
step two, dropwise adding 5mL of concentrated hydrochloric acid, then adding 0.3g of 2-amino terephthalic acid (H2 APTA) and 20mL of DMF, and continuing to carry out ultrasonic treatment for 20min;
step three, filling the mixture into a stainless steel water heating kettle shell for sealing, and preserving heat for 24 hours in a 100 ℃ oven;
After the reaction is completed, centrifugally separating the obtained light yellow suspension, washing the precipitate with DMF for 3 times, and then washing with methanol for 3 times;
step five, drying a yellow sample obtained after methanol washing at 85 ℃ to obtain MOF;
step six, adding 300mg of eosin dye and 700mg of MOF into a hydrothermal kettle liner filled with 20mL of ethanol, ultrasonically treating for 20min, filling into a stainless steel outer liner for sealing, then placing into a 120 ℃ oven for heat preservation for 24h, and naturally cooling to room temperature;
and step seven, washing the solid phase substance cooled in the step six with deionized water until the washing liquid is colorless and transparent, and drying the solid phase substance in a 60 ℃ oven for 10 hours to obtain the photocatalyst for treating the sewage containing the amine organic matters.
Comparative example 2
This comparative example provides a method for preparing a photocatalyst from eosin dye and commercially available titanium dioxide (P25), wherein the mass ratio of eosin dye to P25 is 3:7; the preparation method comprises the following steps:
adding 300mg of eosin dye and 700mg of P25 into a hydrothermal kettle liner filled with 20mL of ethanol, performing ultrasonic treatment for 20min, filling into a stainless steel outer liner, sealing, then placing into a 120 ℃ oven for heat preservation for 24h, and naturally cooling to room temperature;
and step two, washing the solid phase substance cooled in the step one by deionized water until the washing liquid is colorless and transparent, and drying the washed solid phase in a 60 ℃ oven for 10 hours to obtain the photocatalyst EY/P25 for treating the sewage containing the amine organic matters.
Example 12
The barium stannate of example 4 is directly used as a raw material of a photocatalyst for treating the sewage containing the amine organic matters, and the raw material of the photocatalyst for treating the sewage containing the amine organic matters further comprises eosin dye, wherein the mass ratio of the eosin dye to the barium stannate is 1:7.
The embodiment also provides a method for preparing the photocatalyst for treating the sewage containing the amine organic matters by using the raw materials, which comprises the following steps:
step one, adding 100mg of eosin dye and 700mg of barium stannate of example 4 into a hydrothermal kettle liner filled with 20mL of ethanol, ultrasonically treating for 20min, filling into a stainless steel outer liner for sealing, then placing into a 110 ℃ oven for heat preservation for 24h solvothermal reaction, and naturally cooling to room temperature;
and step two, washing the solid phase substance cooled in the step one by deionized water until the washing liquid is colorless and transparent, and drying the washed solid phase in a 50 ℃ oven for 12 hours to obtain the photocatalyst for treating the sewage containing the amine organic matters.
Example 13
The barium stannate of example 5 is directly used as a raw material of a photocatalyst for treating the sewage containing the amine organic matters, and the raw material of the photocatalyst for treating the sewage containing the amine organic matters further comprises an eosin dye, wherein the mass ratio of the eosin dye to the barium stannate is 1:1.
The embodiment also provides a method for preparing the photocatalyst for treating the sewage containing the amine organic matters by using the raw materials, which comprises the following steps:
adding 700mg of eosin dye and 700mg of barium stannate of example 5 into a hydrothermal kettle liner filled with 20mL of ethanol, performing ultrasonic treatment for 20min, filling into a stainless steel outer liner for sealing, then placing into a 115 ℃ oven for heat preservation for 24h solvothermal reaction, and naturally cooling to room temperature;
and step two, washing the solid phase substance cooled in the step one by deionized water until the washing liquid is colorless and transparent, and drying the washed solid phase in a 55 ℃ oven for 11 hours to obtain the photocatalyst for treating the sewage containing the amine organic matters.
Example 14
The lanthanum-doped barium stannate of example 6 is directly used as a raw material of a photocatalyst for treating the amine-containing organic matter sewage, the raw material of the photocatalyst for treating the amine-containing organic matter sewage further comprises eosin dye, and the mass ratio of the eosin dye to the lanthanum-doped barium stannate is 3:7.
The embodiment also provides a method for preparing the photocatalyst for treating the sewage containing the amine organic matters by using the raw materials, which comprises the following steps:
adding 300mg of eosin dye and 700mg of lanthanum-doped barium stannate of example 6 into a hydrothermal kettle liner filled with 20mL of ethanol, performing ultrasonic treatment for 20min, filling into a stainless steel outer liner for sealing, then placing into a 130 ℃ oven for heat preservation for 24h solvothermal reaction, and naturally cooling to room temperature;
And step two, washing the solid phase substance cooled in the step one by deionized water until the washing liquid is colorless and transparent, and drying the washed solid phase in a 60 ℃ oven for 10 hours to obtain the photocatalyst for treating the sewage containing the amine organic matters.
Example 15
The lanthanum-doped barium stannate of example 9 is directly used as a raw material of a photocatalyst for treating the amine-containing organic matter sewage, the raw material of the photocatalyst for treating the amine-containing organic matter sewage further comprises eosin dye, and the mass ratio of the eosin dye to the lanthanum-doped barium stannate is 1:7.
The embodiment also provides a method for preparing the photocatalyst for treating the sewage containing the amine organic matters by using the raw materials, which comprises the following steps:
adding 100mg of eosin dye and 700mg of lanthanum-doped barium stannate of example 9 into a hydrothermal kettle liner filled with 20mL of ethanol, ultrasonically treating for 20min, filling into a stainless steel outer liner for sealing, then placing into a 120 ℃ oven for heat preservation for 24h solvothermal reaction, and naturally cooling to room temperature;
and step two, washing the solid phase substance cooled in the step one by deionized water until the washing liquid is colorless and transparent, and drying the washed solid phase in a 60 ℃ oven for 10 hours to obtain the photocatalyst for treating the sewage containing the amine organic matters.
Example 16
The lanthanum-doped barium stannate of example 10 was directly used as a raw material of a photocatalyst for treating wastewater containing amine-containing organic matters, which further includes eosin dye, wherein the mass ratio of eosin dye to lanthanum-doped barium stannate is 1:1.
The embodiment also provides a method for preparing the photocatalyst for treating the sewage containing the amine organic matters by using the raw materials, which comprises the following steps:
adding 700mg of eosin dye and 700mg of lanthanum-doped barium stannate of example 10 into a hydrothermal kettle liner filled with 20mL of ethanol, performing ultrasonic treatment for 20min, filling into a stainless steel outer liner for sealing, then placing into a 125 ℃ oven for heat preservation for 24h solvothermal reaction, and naturally cooling to room temperature;
and step two, washing the solid phase substance cooled in the step one by deionized water until the washing liquid is colorless and transparent, and drying the washed solid phase in a 50 ℃ oven for 12 hours to obtain the photocatalyst for treating the sewage containing the amine organic matters.
Application example 1
This example provides a method for treating an amine-containing organic contaminant with the photocatalyst for treating an amine-containing organic wastewater of any one of examples 11 to 16, wherein the method of application calculates the degradation rate of triethanolamine by detecting the amount of hydrogen produced to obtain the amount of triethanolamine consumed. The application method analyzes and calculates the output of photocatalytic reaction gas through a photocatalytic testing device for measuring side irradiation, and the device comprises the following steps: the gas test equipment consists of a Pyrex glass reactor with the volume of 240mL, a 300W xenon lamp (model: LF 300B-F) provided with a 420nm cut-off filter, a magnetic stirrer and a circulating cooling water system, a gas chromatograph (with the capacity of 0-500 mu L), a gas chromatograph (with high-purity argon as carrier gas, a molecular sieve chromatographic column of TDX-01 type, a heat conduction detector) and a computer system.
The specific operation is as follows:
(1) The 420nm optical filter is arranged at a light outlet of the xenon lamp, and a power supply of the xenon lamp is started to preheat for more than 15 minutes, so that the current, the voltage and the light intensity of the xenon lamp are kept stable in the test process;
(2) Dispersing photocatalyst into a reaction bottle filled with pollutants containing ethanolamine substances according to a preset amount (10 mg-100 mg), and adding H 2 PtCl 4 (0-5%wt Pt), purging with Ar for 15min, exhausting impurity gas in the reactor, and taking no oxygen as a standard in a gas test; the pollutant containing the ethanolamine substance is 186mL 10vol% triethanolamine solution;
(3) The plane of the side illumination of the reaction bottle is opposite to the light outlet of the xenon lamp, a circulating cooling water power supply is turned on, so that the reactor maintains constant temperature, a magnetic stirrer is turned on, the rotation speed is regulated to be fixed, and the photocatalyst is dispersed in the triethanolamine solution;
(4) After the reaction starts, sampling the gas in the reactor from the silica gel plug above by using a microsyringe every 1h, extracting 200 mu L of gas, injecting the gas into a gas chromatograph, testing the hydrogen content and recording;
(5) After the test is completed, the xenon lamp, the magnetic stirrer and the power supply of the circulating water machine are turned off, and the used reactor is cleaned and stored.
Evaluation of performance:
XRD patterns of the barium stannate BSO of example 1, the lanthanum doped barium stannate LBSO of example 6, the barium stannate-based photocatalyst EY/BSO of example 11, and the lanthanum doped barium stannate-based photocatalyst EY/LBSO of example 14 are shown in FIG. 1. As can be seen from FIG. 1, first, the BSO samples have three distinct diffraction peaks at 30.6 °, 43.9 ° and 54.5 °, corresponding to the (110), (200) and (211) plane diffraction peaks in the barium stannate 01-089-2488 cards, respectively, and all the samples can clearly observe the above three characteristic diffraction peaks of barium stannate, indicating that the samples contain a large amount of barium stannate before and after BSO recombination EY.
In addition, as can be seen by comparing XRD patterns of the BSO and EY/BSO samples, the intensity of the characteristic diffraction peak of barium stannate in EY/BSO is obviously reduced, and besides the characteristic diffraction peak of barium stannate, new diffraction peaks appear at 23.9 degrees, 34.2 degrees, 42.0 degrees and 46.8 degrees, and the diffraction peaks are attributed to BaCO 3 (cards 00-001-0506), which shows that during the BSO compounding EY, part of BSO is chemically reacted and converted into BaCO 3 The method comprises the steps of carrying out a first treatment on the surface of the The same phenomenon was observed in EY/LBSO samples, indicating that the same conversion to BaCO occurred during LBSO compounding EY 3 Is a chemical reaction of (a) and (b).
In addition, from the characteristic peak intensities corresponding to barium stannate, in BSO and LBSO, the characteristic peak is stronger in LBSO than in BSO, and the characteristic peak is stronger in EY/BSO than in EY/LBSO, which indicates that the chemical conversion reaction of LBSO occurs in a larger amount before and after solvothermal process, which is probably due to the introduction of defects in BSO caused by La doping, the presence of defects promotes the conversion of BSO into BaCO 3 。
FIG. 2 is a UV-Vis plot of sample of barium stannate BSO of example 1, lanthanum doped barium stannate LBSO of example 6, barium stannate-based photocatalyst EY/BSO of example 11, and lanthanum doped barium stannate-based photocatalyst EY/LBSO of example 14. As is evident from FIG. 2, the BSO absorption edge alone is about 400nm and is not substantially capable of absorbing visible light, which is consistent with the literature report, the BSO absorption edge after La doping is slightly red shifted, the light absorption capacity is enhanced, and the comparison shows that: before EY is compounded, BSO and LBSO can only absorb ultraviolet light below 400nm, after EY solvothermal compounding, the light absorption range of the BSO and LBSO is expanded from 400nm to about 600nm, the ultraviolet light region is expanded to the visible light region, and the light absorption capacity is obviously improved.
In order to study the mode of BSO composite EY from microscopic morphology, scanning electron microscope image analysis is carried out on the barium stannate BSO of the example 1 and the photocatalyst EY/BSO taking barium stannate as a raw material of the example 11, and an SEM image is shown in figure 3, and it can be seen from the image that BSO and EY/BSO are nano particles with smaller diameters, and the microscopic morphology of a sample is not obviously different before and after BSO is compounded with EY.
To study the binding pattern of BSO to EY microscopically, samples were subjected to TEM characterization as shown in fig. 4. As can be seen from FIG. 4a, the nanocrystals were about 20nm before BSO recombination EY, and the nanocrystals still agglomerated together after BSO recombination EY (FIG. 4 b) showed no substantial change in apparent morphology. To confirm whether EY was successfully bound to BSO, TEM Mapping characterization was performed, and by elemental confirmation of the distribution of BSO and EY, it can be seen from the TEM Mapping diagram of fig. 4 that the location of BSO distribution substantially detected the characteristic element Br of EY, which indicates that EY was uniformly distributed on the crystals of BSO, indicating that the solvothermal process achieved the binding of EY to BSO.
The XPS characterization results of the barium stannate BSO of example 1 and the barium stannate-based photocatalyst EY/BSO of example 11 are shown in FIG. 5. As can be seen from the full-scan spectrum of fig. 5a, characteristic peaks of Ba, sn and O elements exist in the samples before and after BSO compounding EY, which indicates that the main bodies before and after compounding are BSO; the presence of a characteristic peak of Br in the compounded sample, which is also demonstrated by the presence of EY in the compounded sample, as demonstrated by the high resolution profile of Br element of FIG. 5 b. FIG. 5C is a C1s XPS spectrum of BSO and EY/BSO, the BSO having three C1s characteristic peaks at 284.8, 286.0, 288.8eV, corresponding to graphite carbon ((CH) respectively 2 ) n ) C-O bonds and O-c=o bonds. EY/BSO has four characteristic peaks of C1s, one in addition to three contained in BSOThe newly added characteristic peak at 290.1eV corresponds to the large pi bond in the benzene ring in EY. Of the three peaks of both BSO and EY/BSO, the peak area of the C-O bond in EY/BSO increases significantly, probably because EY contains more C-O bonds. FIG. 5d is an O1s XPS spectrum of BSO and EY/BSO, the BSO having three characteristic peaks of O1s at 529.5, 531.6, 533.4eV, corresponding to lattice oxygen (O 2- ) Oxygen vacancy (O) 2 - )、CO 3 2- Or the carboxyl group of EY. The signal peak of lattice oxygen is not substantially detected in EY/BSO because EY attaches to the surface of BSO, affecting the detection of the signal of lattice oxygen in BSO. FIG. 5e is a Ba 3d XPS spectrum, ba 3d 5/2 The orbital corresponding binding energy is a signal peak at 779.4eV, ba 3d 3/2 The orbitals correspond to the signal peaks at binding energy 794.7eV, indicating that Ba is +2 valent. FIG. 5f is a Sn 3d XPS spectrum, sn 3d 5/2 The orbital corresponding binding energy is 486.3eV of signal peak, sn 3d 3/2 The orbitals correspond to the signal peaks at a binding energy of 494.8eV, indicating that Sn is +4 valent. In samples before and after BSO and EY, the signal peaks of Sn and Ba are very obvious. In the high-resolution spectra of Sn 3d and Ba 3d, it can be clearly distinguished that the characteristic peak of the sample shifts after BSO is compounded with EY, the characteristic peak of Ba 3d shifts to the high binding energy direction by 1.0eV, and the characteristic peak of Sn 3d shifts to the high binding energy direction by 1.4eV, which means that the chemical environment of Ba and Sn changes to a certain extent, presumably because the carboxyl groups in Ba, sn and EY form a double-tooth bridging structure in the BSO compounding EY process, and the EY is a nonmetallic element with high electronegativity, and after the Ba, sn and EY are bonded, electrons of Ba and Sn are more attractive by EY and the valence state is corrected, so that the characteristic peaks of Ba and Sn shift to the high binding energy direction.
In order to more fully analyze the structure between EY and BSO, infrared spectroscopic tests were further performed on the barium stannate BSO of example 1, the lanthanum doped barium stannate LBSO of example 6, the barium stannate-based photocatalyst EY/BSO of example 11, the lanthanum doped barium stannate-based photocatalyst EY/LBSO sample of example 14, and the eosin dye EY, and the results are shown in fig. 6. First, by comparing the infrared spectra of the high wavenumber portion of FIG. 6a, it can be seen that EY is present in the high wavenumber portionAt 3460cm -1 There is a sharp characteristic peak, which is attributed to the stretching vibration of free hydroxyl O-H, which is consistent with the structure containing free hydroxyl in EY; other samples at 3500-3200cm -1 The wave number range has a broad absorption peak corresponding to the stretching vibration of intermolecular hydrogen bonds O-H. In the low wavenumber portion of FIG. 6b, the characteristic peaks of BSO and LBSO are mainly 1430cm -1 And 645cm -1 Two absorption peaks at the location, corresponding to the vibration absorption sum of M-OH (SnO) 3 ) 2- Vibration absorption of the group, the presence of infrared absorption peaks of these two features in the sample after BSO complexation EY, is a sufficient indication that the sample after BSO complexation EY still contains a significant amount of BSO crystals.
In addition, several special absorption peaks can be found in the samples before and after EY and BSO complex EY in the low wave number fraction, and 1552cm are contained in the EY, EY/BSO and EY/LBSO samples -1 、1244cm -1 、1090cm -1 、978cm -1 、760cm -1 、692cm -1 Absorption peak of 1552cm -1 The absorption peak at which corresponds to (COO) - Asymmetric vibration absorption peaks of the group; 1244cm -1 Vibration corresponding to the C-C bond; 1090cm -1 Vibration corresponding to ether linkage; 760cm -1 And 692cm -1 From these several signal peaks, it was confirmed that signal peaks of organic EY appear in EY/BSO and EY/LBSO samples, indicating that EY is indeed contained in the samples after BSO recombination of EY. Although the characteristic peaks of several EY described above were found in the sample after BSO complexing EY, the strong absorption peak of part of EY was not found in the sample after BSO complexing EY, probably because: 1. some characteristic peaks of EY are partially masked by the signal peaks of BSO, e.g., 1464cm -1 The characteristic peak at the position is covered by the M-OH peak of BSO; 2. part of the characteristic peaks are not recognized due to the change of the chemical environment of the group, such as 1207cm -1 -OH peak at.
Again, in addition to the characteristic peaks of BSO and EY, new signal peaks appear in the EY/BSO and EY/LBSO samples at 1352cm -1 A new characteristic peak appears at the position, and the peak corresponds toIn the characteristic peak of the double-tooth bridging structure, the double-tooth bridging structure means that two oxygen atoms on the carboxyl of EY are respectively connected with one metal atom in BSO, so as to form the double-tooth bridging structure, and the structure can enable EY to be fixed on the BSO in a chemical bonding mode, so that a transmission channel of a photo-generated carrier is constructed between the BSO and EY, and the transmission of photo-generated electrons is enhanced. 1352cm of careful comparison of EY/BSO and EY/LBSO -1 Infrared signal peak and 1430cm -1 The relative intensity of the infrared signal peak at 1352cm in EY/LBSO can be seen -1 The infrared signal peak is relatively strong, which indicates that more double-tooth bridging structures are formed in EY/LBSO than in EY/BSO, and more carrier transmission channels are formed.
To investigate the difference in EY content of the BSO and LBSO composites, thermal re-testing was performed on samples of the barium stannate-based photocatalyst EY/BSO of example 11 and the lanthanum doped barium stannate-based photocatalyst EY/LBSO of example 14, as shown in FIG. 7, where the EY/BSO and EY/LBSO were substantially identical in mass, indicating that the EY content was substantially identical in EY/BSO and EY/LBSO, probably due to the physical adsorption between EY and BSO when BSO and EY were composited.
BSO and LBSO are electron transport materials themselves, which are one of the materials of solar cells, and therefore, in order to explore the difference in electron transport properties between BSO and BSO, BSO and LBSO powders were fabricated into photoelectrodes for electrochemical impedance spectroscopy analysis. The electrochemical impedance spectra before and after the combination EY of BSO and LBSO are shown in fig. 8, and it can be clearly seen from the graph that LBSO has a smaller impedance radius than BSO, which indicates that the bulk phase impedance of LBSO is relatively small, and the migration rate of photo-generated carriers in bulk phase is relatively fast, indicating that La doping increases the electron transport performance of BSO. Compared with EY/BSO and EY/LBSO samples, the impedance radius of the EY/LBSO is obviously smaller, which proves that the EY/LBSO has smaller resistance, and the photo-generated electrons generated by EY photo-excitation are easier to transmit, so that the visible light catalytic performance of the EY/LBSO is improved. Combining the electrochemical impedance spectroscopy results of BSO, LBSO and FTIR characterization, the reason why EY/LBSO resistance is smaller may be: 1. the resistance of LBSO is smaller than that of BSO, the two-tooth bridging structure formed by LBSO and EY is more, the photo-generated carrier transmission path is more, and the resistance is smaller. Comparing the samples before and after BSO recombination EY can clearly see that the impedance after BSO recombination EY is significantly smaller than that of BSO, which is probably because the resistance of BSO is reduced after EY is bonded with BSO, so the impedance is reduced.
The activity of the visible light-catalyzed degradation of triethanolamine of EY/BSO (100 mg), EY/LBSO (100 mg) samples in the above examples and EY/P25 (100 mg), EY (30 mg), BSO+EY (70 mg BSO+30mg EY) samples of comparative example 2 as a control is shown in FIG. 9. As can be seen from FIG. 9, first, the photosensitizer EY itself has a certain activity of degrading triethanolamine by visible light catalysis, which is 1.0. Mu. Mol.h -1 After EY is loaded on different carriers, the catalyst has different activities of catalyzing and decomposing triethanolamine by visible light, wherein the highest photocatalytic activity is an EY/LBSO sample, and the visible light catalytic activity reaches 4.8 mu mol.h -1 4.8 times of pure EY, and then EY/BSO sample, the activity of the visible light catalytic decomposition of triethanolamine is 3.9 mu mol.h -1 3.8 times of pure EY, and the lowest EY/P25 sample has photocatalytic activity of only 0.9 mu mol.h -1 Photocatalytic activity below EY. This shows that BSO is more suitable than the usual P25 as an electron transport material for use in photocatalysts without the addition of a cocatalyst. In addition, LBSO has a smaller impedance, better electron transport properties, and better visible light catalytic properties than BSO, indicating that the photocatalytic activity of the photocatalyst is positively correlated with electron transport properties. In addition, EY/BSO has higher visible light catalytic activity than the EY and BSO mixed sample (BSO+EY), which shows that the interaction force between the photosensitizer EY and the carrier BSO in the solvothermal process is stronger and the carrier transmission effect is better.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent structural changes of the above embodiment according to the technical matter of the present invention still fall within the scope of the technical solution of the present invention.
Claims (8)
1. A photocatalyst for treating sewage containing amine organic matters is characterized by comprising eosin dye and photocatalytic activityThe mass ratio of the eosin dye to the photocatalytic active material is (1-7): 7, and the photocatalytic active material is barium stannate or lanthanum doped barium stannate; in the barium stannate, ba 2+ With Sn 2+ The ratio of the amounts of the substances is 1:1; in the lanthanum-doped barium stannate, ba 2+ 、Sn 2+ And La (La) 2+ The ratio of the amounts of the substances is 10:9.5:0.5; the preparation method of the photocatalyst for treating the sewage containing the amine organic matters comprises the following steps: and carrying out solvothermal reaction on the eosin dye and the photocatalytic active substance to prepare the photocatalyst for treating the amine-containing organic matter sewage.
2. The photocatalyst for treating an amine-containing organic matter-containing sewage according to claim 1, wherein the preparation method of the barium stannate comprises:
adding soluble tin salt into hydrogen peroxide solution containing citric acid monohydrate and barium chloride, and stirring until the soluble tin salt is dissolved to obtain tin precursor solution;
Step two, dropwise adding ammonia water into the tin precursor solution in the step one until the pH value of the system is 9-11, so as to obtain tin-containing suspension;
and thirdly, stirring the tin-containing suspension in the second step at 50-70 ℃ for 0.5-3 hours, cooling, washing, drying, grinding and roasting to obtain barium stannate.
3. The photocatalyst for treating an amine-containing organic matter-containing wastewater according to claim 2, wherein the preparation method of the hydrogen peroxide solution containing citric acid monohydrate and barium chloride in the step one comprises: citric acid monohydrate was added to the hydrogen peroxide solution, followed by the addition of barium chloride to obtain a hydrogen peroxide solution containing citric acid monohydrate and barium chloride.
4. The photocatalyst for treating an amine-containing organic matter-containing sewage according to claim 3, wherein the amount of the substance of citric acid monohydrate is 0.2 to 1 times the amount of the substance of soluble tin salt, and the mass of hydrogen peroxide is 30 to 70 times the mass of citric acid monohydrate; the soluble tin salt is tin chloride or tin nitrate.
5. The photocatalyst for treating wastewater containing amine organic matters according to claim 2, wherein the mass percentage of the ammonia water in the second step is 25% -28%, and the dropping speed of the ammonia water is 16-24 mL/min; and step three, the temperature rising rate of the roasting is 4-6 ℃/min, and the roasting temperature is 520-580 ℃.
6. The photocatalyst for treating wastewater containing amine-containing organic matters according to claim 1, wherein the preparation method of the lanthanum-doped barium stannate comprises the following steps:
adding soluble tin salt and soluble lanthanum salt into hydrogen peroxide solution containing citric acid monohydrate and barium chloride, and stirring until the soluble tin salt and the soluble lanthanum salt are dissolved to obtain tin precursor solution containing lanthanum; the soluble lanthanum salt is lanthanum nitrate;
step two, dropwise adding ammonia water into the tin precursor solution containing lanthanum in the step one until the pH value of the system is 9-11, so as to obtain lanthanum-tin suspension;
and thirdly, stirring the lanthanum-tin-containing suspension in the second step at 50-70 ℃ for 0.5-3 hours, cooling, washing, drying, grinding and roasting to obtain lanthanum-doped barium stannate.
7. The photocatalyst for treating wastewater containing amine organic matters according to claim 1, wherein the solvent of the solvothermal reaction is absolute ethyl alcohol, and the temperature of the solvothermal reaction is 110-130 ℃; the solvothermal reaction is carried out in a polytetrafluoroethylene hydrothermal kettle liner sleeved with a stainless steel outer liner.
8. A method for treating an amine-containing organic contaminant using the photocatalyst for treating an amine-containing organic wastewater according to claim 1, wherein the amine-containing organic contaminant comprises a dye-containing contaminant or an ethanolamine-containing contaminant.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489329A (en) * | 2011-11-17 | 2012-06-13 | 华东理工大学 | Catalysis system for hydrogen generation by catalytic reduction of water with visible light, and preparation method thereof |
| CN107611225A (en) * | 2017-09-28 | 2018-01-19 | 福州大学 | A kind of double surface treatment methods for improving barium stannate radical dye sensitization solar battery electricity conversion |
| CN108479759A (en) * | 2018-04-24 | 2018-09-04 | 吉林建筑大学 | A kind of visible-light response type La doped wolframic acid bismuth catalyst and preparation method thereof |
| CN108607588A (en) * | 2018-03-26 | 2018-10-02 | 南昌航空大学 | A kind of preparation method of La doped class graphite phase carbon nitride catalysis material |
| CN108987125A (en) * | 2018-08-13 | 2018-12-11 | 云南大学 | Ca-Ti ore type stannate electrode material for super capacitor with high-specific capacitance super and preparation method thereof |
| CN110961156A (en) * | 2019-11-06 | 2020-04-07 | 西安交通大学 | Dye solvent thermal-sensitized MOFs photocatalyst and preparation method and application thereof |
| CN111204707A (en) * | 2020-01-14 | 2020-05-29 | 福建师范大学福清分校 | Application of perovskite material in dye-sensitized photolysis water-splitting hydrogen production |
| CN112871209A (en) * | 2021-02-18 | 2021-06-01 | 上海应用技术大学 | High-efficiency photocatalytic hydrogen production catalytic system and preparation method thereof |
-
2021
- 2021-08-16 CN CN202110938957.0A patent/CN113769779B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489329A (en) * | 2011-11-17 | 2012-06-13 | 华东理工大学 | Catalysis system for hydrogen generation by catalytic reduction of water with visible light, and preparation method thereof |
| CN107611225A (en) * | 2017-09-28 | 2018-01-19 | 福州大学 | A kind of double surface treatment methods for improving barium stannate radical dye sensitization solar battery electricity conversion |
| CN108607588A (en) * | 2018-03-26 | 2018-10-02 | 南昌航空大学 | A kind of preparation method of La doped class graphite phase carbon nitride catalysis material |
| CN108479759A (en) * | 2018-04-24 | 2018-09-04 | 吉林建筑大学 | A kind of visible-light response type La doped wolframic acid bismuth catalyst and preparation method thereof |
| CN108987125A (en) * | 2018-08-13 | 2018-12-11 | 云南大学 | Ca-Ti ore type stannate electrode material for super capacitor with high-specific capacitance super and preparation method thereof |
| CN110961156A (en) * | 2019-11-06 | 2020-04-07 | 西安交通大学 | Dye solvent thermal-sensitized MOFs photocatalyst and preparation method and application thereof |
| CN111204707A (en) * | 2020-01-14 | 2020-05-29 | 福建师范大学福清分校 | Application of perovskite material in dye-sensitized photolysis water-splitting hydrogen production |
| CN112871209A (en) * | 2021-02-18 | 2021-06-01 | 上海应用技术大学 | High-efficiency photocatalytic hydrogen production catalytic system and preparation method thereof |
Non-Patent Citations (7)
| Title |
|---|
| Accelerating electron transport in Eosin Y by bidentately bridging on BaSnO3 for noble-metal-free photocatalytic H2 production;Shi Jinwen 等;《Energy Storage and Saving》;第2卷(第1期);第328-335页 * |
| BaSnO3染料敏化太阳能电池的制备及其性能研究;郭福安;《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》(第12期);C042-206 * |
| Colloidally prepared La-doped BaSnO3 electrodes for efficient, photostable perovskite solar cells;Shin Seong Sik 等;《SCIENCE》;第356卷(第6334期);第169页右栏第1段，补充材料图S9 * |
| Dye-sensitized photocatalyst for effective water splitting catalyst;Motonori Watanabe 等;《Science and Technology of Advanced Materials》;第18卷(第1期);第707页左栏第3段、右栏第1-2段 * |
| Eosin Y bidentately bridged on UiO-66-NH2 by solvothermal treatment towards enhanced visible-light-driven photocatalytic H2 production;Shi Jinwen 等;《APPLIED CATALYSIS B-ENVIRONMENTAL》;第280卷;第2页2.1.2，第8页左栏第2段、Scheme 1 * |
| Nanosized BaSnO3 as Electron Transport Promoter Coupled with g-C3N4 toward Enhanced Photocatalytic H2 Production;Kang Xing 等;《ADVANCED SUSTAINABLE SYSTEMS》;第5卷(第9期);第7页左栏第1段，第8页左栏第3段，补充材料的材料制备部分 * |
| 张新华.钙钛矿型MSnO3（Ca,Sr,Ba）纳米材料的两步固相化学合成及光催化性能研究.《中国优秀硕士学位论文全文数据库 工程科技I辑》.2019,(第12期),B014-255. * |
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