CN104645967A - Preparation and application of Y3-xNdxNbO7-zeolite composite porous nano catalytic material - Google Patents
Preparation and application of Y3-xNdxNbO7-zeolite composite porous nano catalytic material Download PDFInfo
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- CN104645967A CN104645967A CN201410841665.5A CN201410841665A CN104645967A CN 104645967 A CN104645967 A CN 104645967A CN 201410841665 A CN201410841665 A CN 201410841665A CN 104645967 A CN104645967 A CN 104645967A
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- 239000000463 material Substances 0.000 title claims abstract description 66
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 59
- 239000010457 zeolite Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 53
- 239000001257 hydrogen Substances 0.000 claims abstract description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 49
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 34
- 229950001664 phoxim Drugs 0.000 claims abstract description 32
- ATROHALUCMTWTB-OWBHPGMISA-N phoxim Chemical compound CCOP(=S)(OCC)O\N=C(\C#N)C1=CC=CC=C1 ATROHALUCMTWTB-OWBHPGMISA-N 0.000 claims abstract description 32
- 229960005404 sulfamethoxazole Drugs 0.000 claims abstract description 32
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 21
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000000593 degrading effect Effects 0.000 claims abstract description 14
- 239000002086 nanomaterial Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 40
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 230000015556 catabolic process Effects 0.000 claims description 21
- 238000006731 degradation reaction Methods 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000000354 decomposition reaction Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 230000001699 photocatalysis Effects 0.000 claims description 19
- IQEXKXOUCPUHHH-UHFFFAOYSA-N [Nb].[Nd].[Y] Chemical compound [Nb].[Nd].[Y] IQEXKXOUCPUHHH-UHFFFAOYSA-N 0.000 claims description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 18
- 230000005693 optoelectronics Effects 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 13
- 239000010955 niobium Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000007146 photocatalysis Methods 0.000 claims description 12
- 239000002351 wastewater Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 239000002114 nanocomposite Substances 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000009841 combustion method Methods 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 4
- 239000003344 environmental pollutant Substances 0.000 claims description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 241000370738 Chlorion Species 0.000 claims description 3
- 229910003023 Mg-Al Inorganic materials 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 230000019771 cognition Effects 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 238000005286 illumination Methods 0.000 abstract description 31
- 239000007864 aqueous solution Substances 0.000 abstract description 15
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 10
- 230000003287 optical effect Effects 0.000 abstract description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052753 mercury Inorganic materials 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 2
- XQAXGZLFSSPBMK-UHFFFAOYSA-M [7-(dimethylamino)phenothiazin-3-ylidene]-dimethylazanium;chloride;trihydrate Chemical compound O.O.O.[Cl-].C1=CC(=[N+](C)C)C=C2SC3=CC(N(C)C)=CC=C3N=C21 XQAXGZLFSSPBMK-UHFFFAOYSA-M 0.000 abstract 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 12
- 230000005855 radiation Effects 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000356 contaminant Substances 0.000 description 10
- 238000005273 aeration Methods 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 230000033558 biomineral tissue development Effects 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000003912 environmental pollution Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 229910017116 Fe—Mo Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
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- 238000004070 electrodeposition Methods 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
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- 239000013067 intermediate product Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
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- 239000012535 impurity Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- SRUWWOSWHXIIIA-UKPGNTDSSA-N Cyanoginosin Chemical compound N1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@@H](C)[C@H](C(O)=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)C(=C)N(C)C(=O)CC[C@H](C(O)=O)N(C)C(=O)[C@@H](C)[C@@H]1\C=C\C(\C)=C\[C@H](C)[C@@H](O)CC1=CC=CC=C1 SRUWWOSWHXIIIA-UKPGNTDSSA-N 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
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- 230000003851 biochemical process Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 108010067094 microcystin Proteins 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002821 niobium Chemical class 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 238000007254 oxidation reaction Methods 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RLBIQVVOMOPOHC-UHFFFAOYSA-N parathion-methyl Chemical group COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C=C1 RLBIQVVOMOPOHC-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a novel material of a nano structure, wherein the grain size of Y3-xNdxNbO7 (x is greater than or equal to 0.5 and less than or equal to 1) is 0.15-0.3 microns and the grain sizes of Y3-xNdxNbO7 (x is greater than or equal to 0.5 and less than or equal to 1) and Y3-xNdxNbO7 (x is greater than or equal to 0.5 but less than or equal to 1)-zeolite composite material are 0.2-0.4 microns. The invention further relates to a Y3-xNdxNbO7 (x is greater than or equal to 0.5 but less than or equal to 1)/hydrogen bridge mixture composite modified optical electrode. The novel catalytic materials can be applied to degrading organic pollutants (including phoxim (C12H15N2O3PS)), methylene blue (C16H18ClN3S), sulfamethoxazole (C10H11N3O3S) and the like under a visible light condition by taking Y3-xNdxNbO7 (x is greater than or equal to 0.5 but less than or equal to 1) and the Y3-xNdxNbO7 (x is greater than or equal to 0.5 but less than or equal to 1)-zeolite composite material as optical catalysts. A light source is an xenon lamp, and an edge filter (lambda is greater than 420nm) is used; under the visible light or ultraviolet light condition, water is decomposed to produce hydrogen, Pt, NiO and RuO2 cocatalysts are respectively loaded on the surface of catalyst powder, the light source is the xenon lamp or a high voltage mercury lamp, and the edge filter (lambda is greater than 420nm or greater than 390nm) is used. The catalyst powder is uniformly distributed in an aqueous solution, and the whole illumination reaction is carried out under a closed light-tight environment.
Description
Technical field
The present invention relates to two kinds of novel photocatalysts and a kind of novel photoelectric pole, preparations and applicatio, especially powder catalytic material Y
3-xnd
xnbO
7(0.5≤x≤1), Y
3-xnd
xnbO
7the compound porous nano catalytic material of (0.5≤x≤1)-zeolite and Y
3-xnd
xnbO
7the composite modified optoelectronic pole of (0.5≤x≤1)/hydrogen bridge mixed thing, preparation technology, removes the application of the organic pollution in water body through photocatalysis, and the application of photochemical catalyzing hydrogen making.
Background technology
In the last few years, along with expanding economy, dyeing waste water, agricultural chemicals, chemical pharmaceutical etc. enter the waters such as river, lake in a large number, and the toxic organic pollutant environmental pollution problem caused thus has become ten significant problems paid close attention in the world.At present, people generally process organic wastewater with biochemical process process.But for the water body that toxic organic pollutant pollutes, traditional method does not almost have removal effect to it, because the Recalcitrant chemicals such as the methylene blue in water, sulfamethoxazole, Microcystin, chlopyrifos and parathion-methyl can suppress biologically active, destroy the stability of biochemical treatment system.Above conventional method is difficult to the pollutant removed, in the world of greatest concern, application potential is maximum is that (photochemical catalyst of normal employing is TiO for photocatalysis technology illumination is penetrated under
2semiconductor).The energy of global scale, environmental problem are more and more outstanding in recent years.The carbon dioxide that a large amount of burnings of fossil fuel produce, oxynitrides, oxygen sulfur compound have caused serious problem of environmental pollution; and the exhaustion of fossil resource simultaneously result also in energy crisis; in order to alleviate problem of environmental pollution and reply energy crisis, hydrogen causes World Focusing as clear energy sources.But the production of current Hydrogen Energy also mainly relies on the reformation of coal, natural gas to obtain, and this will inevitably aggravate the consumption of non-regeneration energy and bring problem of environmental pollution.Utilizing light-catalysed water decomposition to be then direct is Hydrogen Energy by light energy conversion, is one of desirable route fundamentally solving the energy and problem of environmental pollution, is called as " technology of 21 century dream ", receives showing great attention to of domestic and international scientist.
Two difficult challenges that current photocatalysis field exists how to realize visible light-responded and photo-quantum efficiency raising problem.The exploitation of catalyst has 2 kinds of implementation methods: the first is that Doped anions or cation are to change TiO
2character, exploitation band gap is close to the New raxa semiconductor of ideal catalyst band gap.The second is the catalyst of exploitation New raxa.Titanium dioxide is the most frequently used, because his stable chemical nature, and also nontoxic, cheap; Shortcoming is that the forbidden band of titanium dioxide is too wide, and cause its valence-band electrons transition difficulty of excited by visible light, although can reach visible light-responded by doping, efficiency comparison is low.In addition, TiO
2light induced electron and hole-recombination probability very high, cause its photocatalysis efficiency lower.Therefore, researcher also starts the catalyst developing New raxa, and achieves a series of remarkable achievement: CaBi
2o
4that degrade acetaldehyde and methylene blue effect are fine; The generation of secondary pollution formaldehyde can be suppressed by the BiOCl meso-porous nano structure that Pt is noble metal decorated; There is the CeO of meso-hole structure
2-Bi
2o
3compound nanometer photocatalyst can rhodamine B effectively in degradation of dye; Li Can project team system is for spinel structure compound ZnIn2S4, and this material can absorb visible ray and decomposing N a2S-Na2SO3 aqueous solution releasing hydrogen gas; The Gal-xZnxO1-xNx material of Domen seminar exploitation, by supported co-catalyst Rh
2-xcr
xo
3in the quantum efficiency of 420nm place acquisition 59%, this fully shows the development potentiality that solar energy photocatalytic hydrogen manufacturing attracts people's attention.
Multivariant oxide is that a class has the novel narrow band gap catalysis material enriching the Nomenclature Composition and Structure of Complexes, has larger research and development to be worth, compd A
xb
yo
7it is exactly one of focus of Recent study.A
xb
yo
7be a kind of Open architecture, by the doping of other ions, for the migration of oxygen atom, proton or electronics provides hole, or hole concentration can be increased, thus provide a possibility for developing visible-light response type catalyst.Through forefathers' research, with such photochemical catalyst of metal ion doping, there is potential degradation of contaminant and photolysis water hydrogen ability.
Generally adopt solid phase method to A at present
xb
yo
7the structural material of series synthesizes, and by metal oxide as raw material, forms through high-temperature calcination.But because solid phase synthesis temperature is high, time powder that is long, that generate is uneven, therefore progressively by hydro-thermal method, sol-gal process replace.But the A of said method gained
xb
yo
7there is dispersed, size distribution poor-performing problem in powder, this greatly have impact on the photocatalysis performance of such material.Therefore, find suitable element doping, optimize the effective way that the preparation method of itself and relevant nano composite material and technique become exploitation visible light responsive photocatalyst.In the preparation process of nano catalytic material, we find, have good catalytic performance with such catalyst of neodymium, yttrium and niobium doping, therefore this project is intended to by research containing neodymium, yttrium and niobium class A
xb
yo
7novel nano catalysis material and technology of preparing thereof, carry out the degree of depth and excavate their Photocatalytic Activity for Degradation organic contamination solution and the ability of photocatalytic water hydrogen making.Not only can produce significant economic benefit, and huge environmental benefit and social benefit can also be produced.
Summary of the invention
The object of the invention is: propose two kinds of powder catalytic material Y
3-xnd
xnbO
7(0.5≤x≤1) and preparation were established and method, performance characterization and application.And a kind of Y is proposed
3-xnd
xnbO
7the compound porous nano catalytic material of (0.5≤x≤1)-zeolite and Y
3-xnd
xnbO
7the preparation technology of (0.5≤x≤1) novel photoelectric pole, performance characterization and application.
Technical scheme of the present invention is: powder catalytic material Y
3-xnd
xnbO
7the preparation of (0.5≤x≤1), adopt salt to help solution combustion method and liquid-phase catalysis phase inversion, the particle diameter of powder is 0.15 ~ 0.3 micron.
Y
3-xnd
xnbO
7the preparation of (0.5≤x≤1)-Zeolite composite materials, sized zeolite particles is 0.5 ~ 3 micron, Y
3-xnd
xnbO
7particle diameter 0.2 ~ 0.4 micron after (0.5≤x≤1)-Zeolite composite materials parcel.
Y
3-xnd
xnbO
7the preparation of the composite modified optoelectronic pole of (0.5≤x≤1)/hydrogen bridge mixed thing, Y
2ndNbO
7the electricity conversion of optoelectronic pole is 8.55%.
The application of powder catalytic material, passes through Y
3-xnd
xnbO
7(0.5≤x≤1) powder is catalyst, the methylene blue (Cl in degrading waste water
6h
18clN
3s), sulfamethoxazole (C
10h
11n
3o
3s), phoxim.Light source is xenon lamp, mixes edge filter (λ > 420nm).In experimentation, maintaining catalyst fines by the mode of magnetic stirring apparatus and oxygenic aeration is suspended state.Whole illumination reaction carries out under airtight lighttight environment.
Y
3-xnd
xnbO
7the application of (0.5≤x≤1)-Zeolite composite materials, passes through Y
3-xnd
xnbO
7(0.5x≤1) powder is catalyst, the methylene blue (Cl in degrading waste water
6h
18clN
3s), sulfamethoxazole (C
10h
11n
3o
3s), phoxim.Light source is xenon lamp, mixes edge filter (λ > 420nm).In experimentation, maintaining catalyst fines by the mode of magnetic stirring apparatus and oxygenic aeration is suspended state.Whole illumination reaction carries out under airtight lighttight environment.
1, novel nano-material Y
3-xnd
xnbO
7the preparation method of (0.5≤x≤1): it is characterized in that adopting salt to help solution combustion method:
A. reagent prepares: agents useful for same mainly contains Y (NO
3)
36H
2o (AR), NdCl
3(AR), NbCl
5(AR), glycine (AR), KCI (AR), deionized water (AR) etc.
B. instrument prepares: electronic balance, magnetic temp controlling heater, Muffle furnace, drying box etc.
C. the preparation of catalyst material: by Y
3-xnd
xnbO
7atomic molar in (0.5≤x≤1) molecular formula is than being (3-x): x: 1, takes appropriate Y (NO respectively with electronic balance
3)
36H
2o, NdCl
3, NbCl
5, put grinding in mortar into and evenly, until grinding particle diameter reaches 3 ~ 5 microns, then fine silt transferred in quartz beaker, add a certain amount of deionized water and medicine is dissolved, then add glycine and the KCI of stoichiometric proportion, form mixed solution.Be positioned over by quartz beaker on magnetic temp controlling heater, heat at 60 DEG C, after reaction 3 ± 1h, solution temperature rises to about 110 DEG C gradually, and in the process, solution becomes transparent gradually and evaporated.After above-mentioned solution evaporation completely, gained viscous fluid cognition expands. and then discharge gas.Rapid generation self-propagating solution combustion reaction, generates loose powder, burning gained powder is put into muffle furnace calcining 3 ~ 4h, cooling.Then sample distilled water is washed 3 times, then use absolute ethanol washing 2 times, put into drying box dry, drying box temperature is set to 60 DEG C, takes out sample grinding pack, obtains end product.
Novel nano-material Y
3-xnd
xnbO
7the preparation method of (0.5≤x≤1): it is characterized in that adopting liquid-phase catalysis phase inversion:
A. reagent prepares: agents useful for same mainly contains Y (NO
3)
36H
2o (AR), NdCl
3(AR), NbCl
5(AR), FeCl
24H
2o (AR), NaOH (AR), deionized water (AR) etc.
B. solution is prepared: by Y
3-xnd
xnbO
7atomic molar ratio in (0.5≤x≤1) molecular formula is (3-x): x: 1 takes appropriate Y (NO respectively with electronic balance
3)
36H
2o, NdCl
3, NbCl
5, put grinding in mortar into and evenly, until grinding particle diameter reaches 3 ~ 5 microns, then transfer in quartz beaker by fine silt, respectively add a certain amount of deionized water and medicine is dissolved, obtained yttrium neodymium niobium mixes molten 50mL.NaOH6.00g is taken, FeCl with electronic balance
24H
2o 4.98g, with deionized water dissolving, each gets 3mol/L NaOH solution 50mL, 0.5mol/L FeCl
2solution 50mL.
C. the preparation of catalyst material: pH value to 9.5 ~ 10.5 regulating yttrium neodymium niobium mixing solution system by the NaOH solution of 3.0mol/L, add the FeCl of 1.0mol/L
2solution as catalyst, Fe
2+with Fe
3+the ratio of material amount be 0.02: 1; PH value to 9.5 ~ 10.5 of careful regulation system again, then boiling reflux 2h, then carry out centrifugation to it, spend deionized water 4 ~ 5 times again, finally by obtained Y
3-xnd
xnbO7 (0.5≤x≤1) nanoparticle dispersion is for subsequent use in deionized water, and the solid content of dispersion liquid is 40 ~ 55g/L.
2, Y
3-xnd
xnbO
7the preparation method of the compound porous nano catalytic material of (0.5≤x≤1)-zeolite: it is characterized in that: adopt Mg-Al hydrolysis and coprecipitation method:
A. reagent prepares: agents useful for same mainly contains Y (NO
3)
36H
2o (AR), NdCl
3(AR), NbCl
5(AR), FeCl
24H
2o (AR); Sodium pyrophosphate (AR), sulfuric acid (AR), absolute ethyl alcohol (CP), methyl orange (AR), deionized water (AR) etc.
B. the preparation of zeolite suspension: first, zeolite is ground and sieves, and take 5g sieve after particulate zeolite, to join in 50g water after soaked overnight, magnetic agitation 2h, the ore pulp of obtained 10%, in wherein adding the sodium pyrophosphate of 0.15g, mechanical agitation (450r/min) 0.5h, leaves standstill 2 h hypsokinesis precipitation upper strata suspension for subsequent use.
C. yttrium neodymium niobium mixed solution preparation: by Y
3-xnd
xnbO
7atomic molar in (0.5≤x≤1) molecular formula is than being (3-x): x: 1, the Y (NO dividing another name appropriate with electronic balance
3)
36H
2o, NdCl
3, NbCl
5make mixed solution 50mL, obtain 0.1mol/L yttrium neodymium niobium mixed solution for subsequent use.
D.Y
3-xnd
xnbO
7the preparation of (0.5≤x≤1)-Zeolite Nanocomposite: get zeolite suspension 50mL and heat in water-bath and be stirred to 85 DEG C, use 10% sulfuric acid adjust ph to 2.0 respectively, add 20g urea, the 0.1mol/L yttrium neodymium niobium mixed solution configuring 50mL is slowly at the uniform velocity instilled in zeolite suspension, after yttrium neodymium niobium mixed solution all drips off, stop stirring and heat and take out hydrolytic precipitation colloid, with distilled water and absolute ethyl alcohol repeatedly centrifuge washing extremely without chlorion.By the deposit after washing in 80 DEG C of dry acquisition Y
3-xnd
xnbO
7(0.5≤x≤1)/Zeolite Nanocomposite.
3, Y
3-xnd
xnbO
7the preparation method of the composite modified optoelectronic pole of (0.5≤x≤1)/hydrogen bridge mixed thing: it is characterized in that: adopt electrodeposition process preparation:
A. reagent prepares: agents useful for same mainly contains Y (NO
3)
36H
2o (AR), NdCl
3(AR), NbCl
5(AR), EuO (4N), HNO
3(5N) etc.The Y of configuration
3+, Nd
3+, Nb
5+solution is respectively 0.15mmol/L, 0.15mmol/L, 0.15mmol/L, and experimental water is secondary quartz distilled water, during each electrochemistry experiment, and logical N in advance
2gas 10min is except O
2gas, and the N keeping electrolytic cell
2atmospheric condition, then measures, and all experiments are carried out all at ambient temperature.
B. instrument prepares: SK2200HP type ultrasonic cleaner, PB.10 type acidometer, JSM-6701 type field emission electron flying-spot microscope etc.
The preparation of c.Eu-Fe-Mo cyanogen bridge mixed thing modified electrode: when preparation Eu-Fe-Mo cyanogen bridge mixed thing modifies glassy carbon electrode, adopt three-electrode system: take platinum filament as auxiliary electrode, saturated calomel (SCE) electrode is reference electrode.Glassy carbon electrode (Φ=3mm) is used 0.3 and 0.05 μm of Al successively
2o
3, suspension is polished to minute surface, uses absolute ethyl alcohol and each 1min of water ultrasonic cleaning respectively.The electrode handled well is placed in m (Eu
3+): m (MoO
4 2-): m (K
3fe (CN)
6): m (C
6h
4(COO)
2hK)=12:3: 3: 1, separately adds appropriate 0.5mol/L KNO
3, 1% triton and 0.2mol/L-monoxone cushioning liquid, regulate pH=1.83 constant volume in the decorating liquid of 50mL volumetric flask, modify with potential range interscan 2 circle of the sweep speed of 84mV/s at-0.28 ~ 0.54V (rise and sweep current potential 0.50V).Electrode after modification is separately placed in 0.16mol/L dipotassium hydrogen phosphate, in the potential range of 0 ~ 1.2V CV scanning make electrode reach stable, finally by electrode taking-up redistilled water rinse, for subsequent use.
D.Y
3-xnd
xnbO
7the preparation of (0.5≤x≤1) composite modified optoelectronic pole: Y
3-xnd
xnbO
7the preparation of (0.5≤x≤1) composite modified optoelectronic pole adopts potentiostatic electrodeposition method.With the cyanogen bridge mixed thing modified electrode prepared for working electrode, respectively get the Y of certain volume by a certain percentage
3+, Nd
3+, Nb
5+solution, adds appropriate natrium citricum and sodium sulphate in addition respectively as complexing agent and supporting electrolyte, also adds HNO simultaneously
3using as oxygen donor.Regulate the pH value of electroplate liquid between 1.5 ~ 1.7 with hydrochloric acid, constant volume is in the deposit fluid of 25.0mL, and under agitation, sentence constant potential mode one single deposition 8s in-0.38eV, accumulation repeated deposition 16 times, can obtain Y
3-xnd
xnbO
7(0.5≤x≤1) composite modified optoelectronic pole.
The invention has the beneficial effects as follows: help solution combustion method by salt, liquid-phase catalysis phase inversion successfully prepared novel photocatalysis material Y
3-xnd
xnbO
7(0.5≤x≤1) powder, has prepared Y simultaneously
3-xnd
xnbO
7(0.5≤x≤1)-Zeolite composite materials and Y
3-xnd
xnbO
7the composite modified optoelectronic pole of (0.5≤x≤1)/hydrogen bridge mixed thing.And a series of sign has been carried out to it, have studied above-mentioned novel photocatalysis material contaminated Organic Pollutants In Water of degrading under visible light illumination and (comprise methylene blue (C
16h
18clN
3s), sulfamethoxazole (C
10h
11n
3o
3s), phoxim (C
12h
15n
2o
3pS) efficiency) and mechanism of degradation, study efficiency and the optical activity of decomposition water hydrogen making under visible ray or UV-irradiation.Final beneficial effect of the present invention makes the clearance of above-mentioned organic pollution reach 99.9%, and above-mentioned organic pollution total organic Carbon removal reaches 99.5%.
Accompanying drawing explanation
Fig. 1 .Y
2ndNbO
7actual measurement XRD data
Y is learnt by figure
2ndNbO
7for single-phase, and experiment original material high purity, without any impurity phase.
Fig. 2 .Y
2ndNbO
7transmission electron microscope picture spectrogram
Learn that catalyst is irregular pattern by figure, particle size range is 0.15 ~ 0.3 micron.
Fig. 3 .Y
2ndNbO
7diffuse reflection absorb collection of illustrative plates
Y is learnt by figure
2ndNbO
7band gap width be 2.09eV.
Fig. 4 .Y
2ndNbO
7band structure
Y as seen from the figure
2ndNbO
7band structure, conduction band is by the 4d track of Y, and the 4d track of the 4f track of Nd and Nb is formed, and valence band is made up of the 2p track of O.
Detailed description of the invention
Prepare powder catalytic material Y
3-xnd
xnbO
7(0.5≤x≤1), Y
3-xnd
xnbO
7the compound porous nano catalytic material of (0.5≤x≤1)-zeolite and Y
3-xnd
xnbO
7the composite modified optoelectronic pole of (0.5≤x≤1)/hydrogen bridge mixed thing.Degrade under visible light in the process of methylene blue, sulfamethoxazole and phoxim persistent organic pollutants in water body, by liquid chromatography/mass spectrometry (LC/MS) combined instrument and ion chromatograph, test the intermediate product and end product followed the tracks of in the above-mentioned organic pollution process of degraded, obtain the possible approaches of Some Organic Pollutants in water body of degrading under visible light illumination, disclose the degradation mechanism of methylene blue in water body, sulfamethoxazole and phoxim organic pollution.Take light source as xenon lamp or high-pressure sodium lamp, or difference supporting Pt, NiO and R
uo
2cocatalyst, carries out decomposition water hydrogen making at airtight by the glass piping interior lighting reactor of multiple Valve controlling.
(1) preparation can at the novel photocatalyst Y of visible light wave range response
3-xnd
xnbO
7(0.5≤x≤1); Preparation can at the Y of visible light wave range response
3-xnd
xnbO
7the compound porous nano catalytic material of (0.5≤x≤1)-zeolite.Adopt ultraviolet-visible spectrophotometer and UV-Vis diffuse reflection spectroscopy instrument to measure the absorption spectra that the new catalyst of above-mentioned preparation produces under visible ray (or ultraviolet light) irradiates, characterize its optical absorption property.Determine above-mentioned new catalyst x-ray photoelectron power spectrum (XPS), inquire into the transport mechanism in electronics and hole in the electron structure feature on above-mentioned new catalyst surface and photocatalyst crystals, analyze each microregion element composition of catalyst, and binding isotherm result of calculation analyzes level structure and the density of electronic states of above-mentioned new catalyst.
(2) X-ray diffractometer (XRD) is adopted to carry out material phase analysis to the invention described above catalyst; Transmission electron microscope (TEM) is adopted to analyze the microstructure characteristic of the invention described above catalyst; The one-tenth utilizing x-ray photoelectron power spectrum (XPS) to determine them is grouped into, and discloses the electron structure feature of catalyst surface.Profound level discloses the microstructure of novel photocatalyst to the affecting laws of photocatalysis degradation organic contaminant efficiency.
Degrade in the process of the persistent organic pollutants such as methylene blue, sulfamethoxazole, phoxim in water body under visible light illumination, by liquid chromatography/mass spectrometry (LC/MS) combined instrument and ion chromatograph, test the intermediate product and end product followed the tracks of in the above-mentioned organic pollution process of degraded, obtain under the effect of new catalyst particle, to degrade under visible light illumination the possible approaches of Some Organic Pollutants in water body, disclose the degradation mechanism of the organic pollutions such as methylene blue in water body, sulfamethoxazole, phoxim.
To adopt in Single wavelength radiation of visible light water body the persistent organic pollutants such as methylene blue, sulfamethoxazole, phoxim, photogenerated charge (light induced electron or the photohole) quantity participating in photocatalytic degradation reaction is successfully derived by experimental study and theory calculate, and then derive the light photon number participating in reaction, in conjunction with the total number of photons of the incident light calculated, finally draw the photo-quantum efficiency of the organic pollutions such as water body methylene orchid, sulfamethoxazole, phoxim of degrading under the effect of Single wavelength visible ray.
Detailed description of the invention
1, novel nano-material Y
3-xnd
xnbO
7the preparation were established of (0.5≤x≤1) is as follows:
(1) salt is adopted to help solution combustion method to prepare Y
3-xnd
xnbO
7(0.5≤x≤1) photocatalytic powder material:
A. with Y (NO
3)
36H
2o (AR), NdCl
3(AR), NbCl
5(AR) be raw material, by Y, Nd and Nb with the atomic molar of described molecular formula ratio (3-x): the Y (NO of x: 1
3)
36H
2o (AR), NdCl
3(AR), NbCl
5(AR) be transferred in quartz beaker after grinding, add-quantitative deionized water makes medicine dissolve, then adds glycine and the KCI of stoichiometric proportion, formation mixed solution.
B. the above-mentioned quartz beaker filling mixed solution is positioned on magnetic temp controlling heater. heat at 60 DEG C, after reaction 3 ± 1h, solution temperature rises to about 110 DEG C gradually, and in the process, solution becomes transparent gradually and evaporated.After above-mentioned solution evaporation completely, gained viscous fluid cognition expands. and then discharge gas. and there is rapidly the reaction of self-propagating solution combustion, generate the powder loosened, burning gained powder is put into muffle furnace calcining 3 ~ 4h, cooling.Then sample distilled water is washed 3 times, then use absolute ethanol washing 2 times, put into drying box dry, drying box temperature is set to 60 DEG C, takes out sample grinding pack, obtains end product.
(2) liquid-phase catalysis phase inversion is adopted to prepare Y
3-xnd
xnbO
7(0.5≤x≤1) photocatalytic powder material:
A. Y is pressed
3-xnd
xnbO
7the atomic molar ratio of (0.5≤x≤1) molecular formula gets raw material Y (NO
3)
36H
2o (AR), NdCl
3(AR), NbCl
5(AR) grind, namely the mol ratio of Y, Nd and Nb is (3-x): x: 1 (0.5≤x≤1), transfer in quartz beaker by the fine silt after grinding, add a certain amount of deionized water and medicine is dissolved, obtained yttrium neodymium niobium mixes molten 50mL.
B. NaOH 6.00g is taken, FeCl with electronic balance
24H
20 4.98g, with deionized water dissolving, each gets 3mol/L NaOH solution 50mL, 0.5mol/L FeCl
2solution 50mL.
C. regulate pH value to 9.5 ~ 10.5 of yttrium neodymium niobium mixing solution system by above-mentioned obtained NaOH solution, add the FeCl of 1.0mol/L
2solution as catalyst, Fe
2+with Fe
3+the ratio of material amount be 0.02: 1; PH value to 9.5 ~ 10.5 of careful regulation system again, then boiling reflux 2h, then carry out centrifugation to it, spend deionized water 4 ~ 5 times again, finally by obtained Y
3-xnd
xnbO
7(0.5≤x≤1) nanoparticle dispersion is for subsequent use in deionized water, and the solid content of dispersion liquid is 40 ~ 55g/L.
2, Y
3-xnd
xnbO
7the preparation were established of the compound porous nano catalytic material of (0.5≤x≤1)-zeolite is as follows:
Adopt Mg-Al hydrolysis and coprecipitation legal system standby:
A. the preparation of zeolite suspension: first, zeolite is ground and sieves, and take 5g sieve after particulate zeolite, to join in 50g water after soaked overnight, magnetic agitation 2h, the ore pulp of obtained 10%, in wherein adding the sodium pyrophosphate of 0.15g, mechanical agitation (450r/min) 0.5h, leaves standstill 2h hypsokinesis precipitation upper strata suspension for subsequent use.
B. yttrium neodymium niobium mixed solution preparation: by Y
3-xnd
xnbO
7the atomic ratio of molecular formula is (3-x): x: 1 (0.5≤x≤1), takes appropriate Y (NO respectively with electronic balance
3)
36H
2o (AR), NdCl
3(AR), NbCl
5(AR) make mixed solution 50mL, obtain 0.1mol/L yttrium neodymium niobium mixed solution for subsequent use.
C.Y
3-xnd
xnbO
7the preparation of (0.5≤x≤1)-Zeolite Nanocomposite: get zeolite suspension 50mL and heat in water-bath and be stirred to 85 DEG C, use 10% sulfuric acid adjust ph to 2.0 respectively, add 20g urea, the 0.1mol/L yttrium neodymium niobium mixed solution configuring 50mL is slowly at the uniform velocity instilled in zeolite suspension, after yttrium neodymium niobium mixed solution all drips off, stop stirring and heat and take out hydrolytic precipitation colloid, with distilled water and absolute ethyl alcohol repeatedly centrifuge washing extremely without chlorion.By the deposit after washing in 80 DEG C of dry acquisition Y
3-xnd
xnbO
7(0.5≤x≤1)-Zeolite Nanocomposite.
3, Y
3-xnd
xnbO
7the preparation method of the composite modified optoelectronic pole of (0.5≤x≤1)/hydrogen bridge mixed thing:
Prepared by employing electrodeposition process:
A. appropriate raw material Y (NO is respectively got
3)
36H
2o (AR), NdCl
3(AR), NbCl
5(AR), with deionized water dissolving, 100mL Y is configured to
3+, Nd
3+, Nb
5+solution is respectively 0.15mmol/L, 0.15mmol/L, 0.15mmol/L.
B. during each electrochemistry experiment, logical N in advance
2gas 10min is except O
2gas, and the N keeping electrolytic cell
2atmospheric condition, then measures, and all experiments are carried out all at ambient temperature.
The preparation of c.Eu-Fe-Mo cyanogen bridge mixed thing modified electrode: when preparation Eu-Fe-Mo cyanogen bridge mixed thing modifies glassy carbon electrode, adopt three-electrode system: take platinum filament as auxiliary electrode, saturated calomel (SCE) electrode is reference electrode.Glassy carbon electrode (Φ=3mm) is used successively 0.3 μm and 0.05. μm of Al
2o
3, suspension is polished to minute surface, uses absolute ethyl alcohol and each 1min of water ultrasonic cleaning respectively.The electrode handled well is placed in m (Eu
3+): m (MoO
4 2-): m (K
3fe (CN)
6): m (C
6h
4(COO)
2hK)=12: 3: 3: 1, separately add appropriate 0.5mol/L KNO
31% triton and 0.2mol/L-monoxone cushioning liquid, regulate pH=1.83 constant volume in the decorating liquid of 50mL volumetric flask, modifies with potential range interscan 2 circle of the sweep speed of 84mV/s at-0.28 ~ 0.54V (rise and sweep current potential 0.50V).Electrode after modification is separately placed in 0.16mol/L dipotassium hydrogen phosphate, in the potential range of 0 ~ 1.2V CV scanning make electrode reach stable, finally by electrode taking-up redistilled water rinse, for subsequent use.
D.Y
3-xnd
xnbO
7the preparation of (0.5≤x≤1) composite modified optoelectronic pole: Y
3-xnd
xnbO
7the preparation of (0.5≤x≤1) composite modified optoelectronic pole adopts potentiostatic electrodeposition method.With the cyanogen bridge mixed thing modified electrode prepared for working electrode, respectively get the Y of certain volume by a certain percentage
3+, Nd
3+, Nb
5+solution, adds appropriate natrium citricum and sodium sulphate in addition respectively as complexing agent and supporting electrolyte, also adds HNO simultaneously
3using as oxygen donor.Regulate the pH value of electroplate liquid between 1.5 ~ 1.7 with hydrochloric acid, constant volume is in the deposit fluid of 25.0mL, and under agitation, sentence constant potential mode one single deposition 8s in-0.38eV, accumulation repeated deposition 16 times, can obtain Y
3-xnd
xnbO
7(0.5≤x≤1) composite modified optoelectronic pole.
4, the method for building up of light-catalyzed reaction system
The foundation of 4.1 degradation of contaminant light-catalyzed reaction systems
The novel photocatalysis reactor that degradation of contaminant experiment adopts is made up of materials such as xenon lamp and halogen lamp light source, quartz glass device, power-supply controller of electric, steel cage, pump, recirculating cooling water system, various water-filled pipe devices.Utilize the novel powderous Y of above-mentioned preparation
3-xnd
xnbO
7(0.5≤x≤1) and Y
3-xnd
xnbO
7(0.5≤x≤1)-zeolite compound catalyze material as catalyst, the target contaminant under visible light illumination in degrading waste water.Light source is 500W xenon lamp, and in selection water, typical persistent organic pollutants phoxim, methylene blue and sulfamethoxazole are as target contaminant.In experimentation, by Y
3-xnd
xnbO
7(0.5≤x≤1) or Y
3-xnd
xnbO
7(0.5≤x≤1)-zeolite compound catalyze material 0.8g, puts into 300mL phoxim, methylene blue and the sulfamethoxazole aqueous solution and forms suspension system, and the initial concentration of pollutant solution is 0.03mmol L
-1, initial pH value is 7.The xenon lamp choosing 500W irradiates methylene blue solution, mixes edge filter (λ > 420nm).Incident light intensity of illumination is 4.76 × 10-
6einstein L
-1s
-1.In experimentation, maintaining catalyst fines by the mode of magnetic stirring apparatus and oxygenic aeration is suspended state.Whole illumination reaction carries out under airtight lighttight environment.In Degradation of Organo-pollutants in Water with Photo-catalysis phoxim, methylene blue and sulfamethoxazole process, explore Y in conjunction with Modern Analytical Instrument such as GC-MS, LC-MS, HPLC, GC, TOC
3-xnd
xnbO
7the cooperative effect of the photocatalysis quantum efficiency in (0.5≤x≤1)-zeolite-visible ray optimizing disposition technology degraded target organic pollution process, the degradation efficiency of target contaminant, kinetics, photochemical catalytic oxidation, the intermediate product of qualification target contaminant in Photocatalytic Degradation Process and end product, inquire into its Mechanism of Semiconductor Photocatalytic Degradation.
The foundation of 4.2 photochemical catalyzing light-catalyzed reaction systems
Carry out the experiment of decomposition water hydrogen making at airtight by the glass piping interior lighting reactor of multiple Valve controlling, (incident flux is 4.76 × 10 to the xenon lamp of radiation source employing 500W
-6einstein L
-1s
-1, 420nm edge filter) or (incident flux is 6.01 × 10 to adopt 400W
-6einstein L
-1s
-1, 390nm edge filter) high-pressure sodium lamp, at 300mL (16.65mol) pure water and 50mL CH
3powder Y is put in OH
3-xnd
xnbO
7(0.5≤x≤1)
7or Y
3-xnd
xnbO
7(0.5≤x≤1)-zeolite 0.8g.Wherein powder Y
3-xnd
xnbO
7(0.5≤x≤1) supporting Pt, NiO and RuO
2co-catalyst.The hydrogen yield overflowed adopts the gas chromatograph-mass spectrometer (GC-MS) with TCD to measure, and this gas chromatograph-mass spectrometer (GC-MS) is connected with close loop interior lighting reactor.In close loop interior lighting reactor, various gas is removed before reactions, and argon gas is charged this reactor, until oxygen in reactor and nitrogen are completely removed.
5, Y
2ndNbO
7performance characterization
Y is learnt by XRD, XPS result
2ndNbO
7for single-phase (see Fig. 1), and experiment original material high purity, without any impurity phase.From its TEM figure, catalyst is irregular pattern (see Fig. 2).Xray fluorescence spectrometer measures Y
2ndNbO
7average atom molar percentage be Y: Nd: Nb: O=2.00: 0.97: 1.03: 6.96.With Rietveld software to Y
2ndNbO
7xRD result carry out structure refinement, structure refinement factor R P value is RP=9.36%.Y
2ndNbO
7space group be Fd-3m, structure is cubic system, pyrochlore constitution, and cell parameter is
y
2ndNbO
7the indices of crystallographic plane (hkl) of each diffraction maximum are demarcated.Y
2ndNbO
7in catalyst, the space atomic positional parameters of each atom is determined (see table 1).Adopt UV-vis DRS spectrometer to Y
2ndNbO
7the characteristic absorption limit produced under the irradiation of light carries out measuring (see Fig. 3), obtains Y
2ndNbO
7band gap width be 2.09eV.X-ray photoelectron spectroscopy is adopted to measure Y
2ndNbO
7x-ray photoelectron power spectrum (see table 2), the chemical valence of Y, Nd, Nb, O is respectively+3 ,+3 ,+5 ,-2 as shown in Table 2.Obtain Y simultaneously
2ndNbO
7band structure, conduction band is by the 4d track of Y, and the 4d track of the 4f track of Nd and Nb is formed, and valence band is made up of the 2p track of O.(see Fig. 4).
Table 1.Y
2ndNbO
7the locus coordinate of interior each atom
Table 2.Y
2ndNbO
7xPS collection of illustrative plates in each essential element in conjunction with energy peak value (eV)
Application example
1, Y is adopted
2ndNbO
7fine catalyst photocatalytic degradation target contaminant is tested
Phoxim (C in 1.1 degrading waste waters
12h
15n
2o
3pS)
By Y
2ndNbO
7powder 0.8g, puts into the 300mL phoxim aqueous solution and forms suspension system, and the initial concentration of the phoxim aqueous solution is 0.03mmol L
-1, initial pH value is 7.The xenon lamp choosing 500W irradiates phoxim solution, mixes edge filter (λ > 420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, maintaining catalyst fines by the mode of magnetic stirring apparatus and oxygenic aeration is suspended state.Whole illumination reaction carries out under airtight lighttight environment.With Y
2ndNbO
7powder is catalyst, under visible light illumination, along with the prolongation of irradiation time, the concentration of phoxim reduces gradually, total organic carbon (TOC) concentration also reduces gradually, and through 410 minutes, the clearance of phoxim was 100%, the clearance (mineralization rate) of total organic carbon TOC reaches 99.69%, CO
2productive rate be 0.10259mmol, the First order kinetic constant K of phoxim concentration and time
cfor 0.00792min
-1, the First order kinetic constant K of total organic carbon and time
tOCfor 0.0087min
-1.Detailed data are in table 3.
Table 3. is with Y
2ndNbO
7the related data that powder obtains for catalyst degradation phoxim
Methylene blue (C in 1.2 degrading waste waters
16h
18clN
3s)
By Y
2ndNbO
7powder 0.8g, puts into 300mL aqueous solution of methylene blue and forms suspension system, and the initial concentration of aqueous solution of methylene blue is 0.03mmol L
-1, initial pH value is 7.The xenon lamp choosing 500W irradiates methylene blue solution, mixes edge filter (λ > 420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, maintaining catalyst fines by the mode of magnetic stirring apparatus and oxygenic aeration is suspended state.Whole illumination reaction carries out under airtight lighttight environment.With Y
2ndNbO
7powder is catalyst, under visible light illumination, along with the prolongation of irradiation time, the concentration of methylene blue reduces gradually, total organic carbon (TOC) concentration also reduces gradually, and through 320 minutes, the clearance of methylene blue was 100%, the clearance (mineralization rate) of total organic carbon TOC reaches 99.84%, CO
2productive rate be 0.13802mmol, the First order kinetic constant K of methylene blue concentration and time
cfor 0.01611min
-1, the First order kinetic constant K of total organic carbon and time
tOCfor 0.01414min
-1.Detailed data are in table 4.
Table 4. is with Y
2ndNbO
7the related data that powder obtains for catalyst degradation methylene blue
1.3 adopt Y
2ndNbO
7sulfamethoxazole (C in powder degrading waste water
10h
11n
3o
3s)
By Y
2ndNbO
7powder 0.8g, puts into the 300mL sulfamethoxazole aqueous solution and forms suspension system, and the initial concentration of the sulfamethoxazole aqueous solution is 0.03mmol L
-1, initial pH value is 7.The xenon lamp choosing 500W irradiates sulfamethoxazole solution, mixes edge filter (λ > 420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, maintaining catalyst fines by the mode of magnetic stirring apparatus and oxygenic aeration is suspended state.Whole illumination reaction carries out under airtight lighttight environment.With Y
2ndNbO
7powder is catalyst, under visible light illumination, along with the prolongation of irradiation time, the concentration of sulfamethoxazole reduces gradually, total organic carbon (TOC) concentration also reduces gradually, and through 370 minutes, the clearance of sulfamethoxazole was 100%, the clearance (mineralization rate) of total organic carbon TOC reaches 99.23%, CO
2productive rate be 0.08663mmol, the First order kinetic constant K of sulfamethoxazole concentration and time
cfor 0.01009min
-1, the First order kinetic constant K of total organic carbon and time
tOC0.0067 is 0.0067min
-1.Detailed data are in table 5.
Table 5. is with Y
2ndNbO
7the related data that powder obtains for catalyst degradation sulfamethoxazole
2, Y is adopted
2ndNbO
7-zeolite compound catalyze material photocatalytic degradation target contaminant is tested
Phoxim (C in 2.1 degrading waste waters
12h
15n
2o
3pS)
Adopt Y
2ndNbO
7-zeolite compound catalyze material, as catalyst, selects the phoxim of typical difficult degradation in water as target degradation product.The initial concentration of the phoxim aqueous solution is 0.03mmol L
-1, by 0.8g Y
2ndNbO
7-zeolite compound catalyze material powder is put into the 300mL phoxim aqueous solution and is formed suspension system, and initial pH value is 7.The xenon lamp choosing 500W irradiates phoxim solution, mixes edge filter (λ > 420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, adopt oxygenic aeration equally.Whole illumination reaction carries out under airtight lighttight environment.Result shows with Y
2ndNbO
7-zeolite compound catalyze material as catalyst under visible light illumination, along with the prolongation of irradiation time, the concentration of phoxim reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 390 minutes, the clearance of phoxim reaches 100%, and the clearance (mineralization rate) of total organic carbon TOC reaches 99.71%, CO
2productive rate be 0.10368mmol, phoxim concentration and time-level kinetic constant K
cfor 0.00901min
-1, total organic carbon and time-level kinetic constant K
tOCfor 0.00937min
-1.Detailed data are in table 6.
Table 6. adopts Y
2ndNbO
7the related data that-zeolite compound catalyze material obtains for catalyst degradation phoxim
Methylene blue (C in 2.2 degrading waste waters
16h
18clN
3s)
Adopt Y
2ndNbO
7-zeolite compound catalyze material, as catalyst, selects the methylene blue of typical difficult degradation in water as target degradation product.The initial concentration of aqueous solution of methylene blue is 0.03mmol L
-1, by 0.8g Y
2ndNbO
7-zeolite compound catalyze material powder is put into 300mL aqueous solution of methylene blue and is formed suspension system, and initial pH value is 7.The xenon lamp choosing 500W irradiates methylene blue solution, mixes edge filter (λ > 420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, adopt oxygenic aeration equally.Whole illumination reaction carries out under airtight lighttight environment.Result shows with Y
2ndNbO
7-zeolite compound catalyze material as catalyst under visible light illumination, along with the prolongation of irradiation time, the concentration of methylene blue reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 300 minutes, the clearance of methylene blue reaches 100%, and the clearance (mineralization rate) of total organic carbon TOC reaches 99.85%, CO
2productive rate be 0.13803mmol, the First order kinetic constant K of methylene blue concentration and time
cfor 0.01868min
-1, the First order kinetic constant K of total organic carbon and time
tOCfor 0.01577min
-1.Detailed data are in table 7.
Table 7. adopts Y
2ndNbO
7the related data that-zeolite compound catalyze material obtains for catalyst degradation methylene blue
Sulfamethoxazole (C in 2.3 degrading waste waters
10h
11n
3o
3s)
Adopt Y
2ndNbO
7-zeolite compound catalyze material, as catalyst, selects the sulfamethoxazole of typical difficult degradation in water as target degradation product.The initial concentration of the sulfamethoxazole aqueous solution is 0.03mmol L
-1, by 0.8gY
2ndNbO
7-zeolite compound catalyze material powder is put into the 300mL sulfamethoxazole aqueous solution and is formed suspension system, and initial pH value is 7.The xenon lamp choosing 500W irradiates sulfamethoxazole solution, mixes edge filter (λ > 420nm).Incident light intensity of illumination is 4.76 × 10
-6einstein L
-1s
-1.In experimentation, adopt oxygenic aeration equally.Whole illumination reaction carries out under airtight lighttight environment.Result shows with Y
2ndNbO
7-zeolite compound catalyze material as catalyst under visible light illumination, along with the prolongation of irradiation time, the concentration of sulfamethoxazole reduces gradually, total organic carbon (TOC) concentration also reduces gradually, at radiation of visible light after 350 minutes, the clearance of sulfamethoxazole reaches 100%, and the clearance (mineralization rate) of total organic carbon TOC reaches 99.59%, CO
2productive rate be 0.08605mmol, sulfamethoxazole concentration and time-level kinetic constant K
cfor 0.01071min
-1, the First order kinetic constant K of total organic carbon and time
tOCfor 0.00836min
-1.Detailed data are in table 8.
Table 8. adopts Y
2ndNbO
7the related data that-zeolite compound catalyze material obtains for catalyst degradation sulfamethoxazole
3, photochemical catalyzing hydrogen making experimental result and analysis
3.1 adopt Y
2ndNbO
7decomposition water hydrogen making
(1) carry out the experiment of decomposition water hydrogen making at airtight by the glass piping interior lighting reactor of multiple Valve controlling, (incident flux is 4.76 × 10 to the xenon lamp of radiation source employing 500W
-6einstein L
-1s
-1, 420nm edge filter), at 300mL (16.65mol) pure water and 50mL CH
3y is put in OH
2ndNbO
7powder 0.8g.The hydrogen yield overflowed adopts the gas chromatograph-mass spectrometer (GC-MS) with TCD to measure, and this gas chromatograph-mass spectrometer (GC-MS) is connected with close loop interior lighting reactor.In close loop interior lighting reactor, various gas is removed before reactions, and argon gas is charged this reactor, until oxygen in reactor and nitrogen are completely removed.Under xenon lamp irradiates after 24 hours, the output of hydrogen is 10.01 mMs, and the quantum efficiency of decomposition water hydrogen making is 2.42% as calculated.As shown in table 9, along with the prolongation of light application time, the productive rate of hydrogen raises gradually.
Table 9. is with Y
2ndNbO
7powder is catalyst, under visible light illumination the related data that obtains of decomposition water hydrogen making
(2) carry out the experiment of decomposition water hydrogen making at airtight by the glass piping interior lighting reactor of multiple Valve controlling, radiation source adopts 400W, and (incident flux is 6.01 × 10
-6einstein L
-1s
-1, 390nm edge filter) high-pressure sodium lamp, at 300mL (16.65mol) pure water and 50mL CH
3y is put in OH
2ndNbO
7powder 0.8g.The hydrogen yield overflowed adopts the gas chromatograph-mass spectrometer (GC-MS) with TCD to measure, and this gas chromatograph-mass spectrometer (GC-MS) is connected with close loop interior lighting reactor.In close loop interior lighting reactor, various gas is removed before reactions, and argon gas is charged this reactor, until oxygen in reactor and nitrogen are completely removed.Under high voltage mercury lamp radiation after 24 hours, the output of hydrogen is 27.24 mMs.
With Y
2ndNbO
7powder is catalyst, respectively supporting Pt, NiO and RuO
2cocatalyst decomposition water hydrogen making, incident light dominant wavelength is λ=360nm, catalyst 0.8g, pure water 300mL, 50mL CH
3oH, light source is 400W high-pressure sodium lamp, with 0.2wt%-Pt/Y
2ndNbO
7for composite catalyst, after 24 hours, the output of hydrogen is 38.06mmol; With 1.0wt%-NiO/Y
2ndNbO
7for composite catalyst, after 24 hours, the output of hydrogen is 35.27mmol; With 1.0wt%-RuO
2/ Y
2ndNbO
7for composite catalyst, after 24 hours, the output of hydrogen is 32.75mmol, and detailed data are in table 10.
Table 10. is with Y
2ndNbO
7powder is catalyst, the related data that decomposition water hydrogen making obtains under UV-irradiation
3.2 adopt Y
2ndNbO
7-zeolite compound catalyze material decomposition water hydrogen making
(1) carry out the experiment of decomposition water hydrogen making at airtight by the glass piping interior lighting reactor of multiple Valve controlling, (incident flux is 4.76 × 10 to the xenon lamp of radiation source employing 500W
-6einstein L
-1s
-1, 420nm edge filter), at 300mL (16.65mol) pure water and 50mL CH
3y is put in OH
2ndNbO
7-zeolite compound catalyze material powder 0.8g.The hydrogen yield overflowed adopts the gas chromatograph-mass spectrometer (GC-MS) with TCD to measure, and this gas chromatograph-mass spectrometer (GC-MS) is connected with close loop interior lighting reactor.In close loop interior lighting reactor, various gas is removed before reactions, and argon gas is charged this reactor, until oxygen in reactor and nitrogen are completely removed.Under xenon lamp irradiates after 24 hours, the output of hydrogen is 12.13 mMs, and the quantum efficiency of decomposition water hydrogen making is 3.28% as calculated.As shown in table 11, along with the prolongation of light application time, the productive rate of hydrogen raises gradually.
Table 11. is with Y
2ndNbO
7-zeolite compound catalyze material powder is catalyst, under visible light illumination the related data that obtains of decomposition water hydrogen making
(2) carry out the experiment of decomposition water hydrogen making at airtight by the glass piping interior lighting reactor of multiple Valve controlling, radiation source adopts 400W, and (incident flux is 6.01 × 10
-6einstein L
-1s
-1, 390nm edge filter) high-pressure sodium lamp, at 300mL (16.65mol) pure water and 50mL CH
3y is put in OH
2ndNbO
7-zeolite compound catalyze material powder 0.8g.The hydrogen yield overflowed adopts the gas-chromatography with TCD
-gC-MS measures, and this gas chromatograph-mass spectrometer (GC-MS) is connected with close loop interior lighting reactor.In close loop interior lighting reactor, various gas is removed before reactions, and argon gas is charged this reactor, until oxygen in reactor and nitrogen are completely removed.Under high voltage mercury lamp radiation after 24 hours, the output of hydrogen is 31.55 mMs.Detailed data are in table 12.
Table 12. is with Y
2ndNbO
7-zeolite compound catalyze material is catalyst, the related data that decomposition water hydrogen making obtains under UV-irradiation
Claims (7)
1. powder catalytic material, is characterized in that with following structural formula: Y
3-xnd
xnbO
7(0.5≤x≤1), the particle diameter of powder is 0.15 ~ 0.40 micron.
2. the catalysis material of compound porous nanostructured, Y
3-xnd
xnbO
7the compound porous nano catalytic material of (0.5≤x≤1)-zeolite.
3. optoelectronic pole material, Y
3-xnd
xnbO
7the composite modified optoelectronic pole of (0.5≤x≤1)/hydrogen bridge mixed thing.
4. the application of the catalysis material of compound porous nanometer, passes through Y
3-xnd
xnbO
7the compound porous nano material of (0.5≤x≤1)-zeolite is that catalyst is by organic pollution phoxim, methylene blue and the sulfamethoxazole in light-catalyzed reaction system degrading waste water.In addition, with xenon lamp or high-pressure sodium lamp for light source, decomposition water hydrogen making is carried out at airtight by the glass piping interior lighting reactor of multiple Valve controlling.
5. the application of powder catalytic material, with Y
3-xnd
xnbO
7(0.5≤x≤1) powder is catalyst, Degradation of Organo-pollutants in Water with Photo-catalysis phoxim, methylene blue and sulfamethoxazole.In addition, Y
3-xnd
xnbO
7powder or respectively supporting Pt, NiO and RuO
2cocatalyst, with xenon lamp or high-pressure sodium lamp for light source, carries out decomposition water hydrogen making at airtight by the glass piping interior lighting reactor of multiple Valve controlling.
6.Y
3-xnd
xnbO
7the preparation method of (0.5≤x≤1)-Zeolite Nanocomposite: adopt Mg-Al hydrolysis and coprecipitation legal system standby:
A. the preparation of zeolite suspension: first, zeolite is ground and sieves, and take 5g sieve after particulate zeolite, to join in 50g water after soaked overnight, magnetic agitation 2h, the ore pulp of obtained 10%, in wherein adding the sodium pyrophosphate of 0.15g, mechanical agitation (450r/min) 0.5h, leaves standstill 2h hypsokinesis precipitation upper strata suspension for subsequent use.
B. yttrium neodymium niobium mixed solution preparation: by Y
3-xnd
xnbO
7the atomic molar ratio of (0.5≤x≤1) molecular formula is (3-x): x: 1 (0.5≤x≤1), takes appropriate Y (NO respectively with electronic balance
3)
36H
2o (AR), NdCl
3(AR), NbCl
5(AR) make mixed solution 50mL, obtain 0.1mol/L yttrium neodymium niobium mixed solution for subsequent use.
C.Y
3-xnd
xnbO
7the preparation of (0.5≤x≤1)-Zeolite Nanocomposite: get zeolite suspension 50mL and heat in water-bath and be stirred to 85 DEG C, use 10% sulfuric acid adjust ph to 2.0 respectively, add 20g urea, the 0.1mol/L yttrium neodymium niobium mixed solution configuring 50mL is slowly at the uniform velocity instilled in zeolite suspension, after yttrium neodymium niobium mixed solution all drips off, stop stirring and heat and take out hydrolytic precipitation colloid, with distilled water and absolute ethyl alcohol repeatedly centrifuge washing extremely without chlorion.By the deposit after washing in 80 DEG C of dry acquisition Y
3-xnd
xnbO
7(0.5≤x≤1)/Zeolite Nanocomposite.
7. powder catalytic material Y
3-xnd
xnbO
7the preparation method of (0.5≤x≤1): it is characterized in that:
Powder catalytic material Y
3-xnd
xnbO
7the preparation method of (0.5≤x≤1):
(1) salt is adopted to help solution combustion method to prepare Y
3-xnd
xnbO
7(0.5≤x≤1) photocatalytic powder material:
A. with Y (NO
3)
36H
2o (AR), NdCl
3(AR), NbCl
5(AR) be raw material, by Y, Nd and Nb with the atomic molar of described molecular formula ratio (3-x): the Y (NO of x: 1
3)
36H
2o (AR), NdCl
3(AR), NbCl
5(AR) be transferred in quartz beaker after grinding, add a certain amount of deionized water and medicine is dissolved, then add glycine and the KCI of stoichiometric proportion, form mixed solution.
B. the above-mentioned quartz beaker filling mixed solution is positioned on magnetic temp controlling heater.Heat at 60 DEG C, after reaction 3 ± 1h, solution temperature rises to about 110 DEG C gradually, and in the process, solution becomes transparent gradually and evaporated.After above-mentioned solution evaporation completely, gained viscous fluid cognition expands.And then discharge gas, the reaction of self-propagating solution combustion occurs rapidly, generates loose powder, burning gained powder is put into muffle furnace calcining 3 ~ 4h, cooling.Then sample distilled water is washed 3 times, then use absolute ethanol washing 2 times, put into drying box dry, drying box temperature is set to 60 DEG C, takes out sample grinding pack, obtains end product.
(2) liquid-phase catalysis phase inversion is adopted to prepare Y
3-xnd
xnbO
7(0.5≤x≤1) photocatalytic powder material:
A. Y is pressed
3-xnd
xnbO
7the atomic molar ratio of molecular formula gets raw material Y (NO
3)
36H
2o (AR), NdCl
3(AR), NbCl
5(AR) grind, namely the mol ratio of Y, Nd and Nb is (3-x): x: 1 (0.5≤x≤1), transfer in quartz beaker by the fine silt after grinding, add a certain amount of deionized water and medicine is dissolved, obtained yttrium neodymium niobium mixes molten 50mL.
B. NaOH 6.00g is taken, FeCl with electronic balance
24H
2o 4.98g, with deionized water dissolving, each gets 3mol/L NaOH solution 50mL, 0.5mol/L FeCl
2solution 50mL.
C. regulate pH value to 9.5 ~ 10.5 of yttrium neodymium niobium mixing solution system by above-mentioned obtained NaOH solution, add the FeCl of 1.0mol/L
2solution as catalyst, Fe
2+with Fe
3+the ratio of material amount be 0.02: 1; PH value to 9.5 ~ 10.5 of careful regulation system again, then boiling reflux 2h, then carry out centrifugation to it, spend deionized water 4 ~ 5 times again, finally by obtained Y
3-xnd
xnbO
7(0.5≤x≤1) nanoparticle dispersion is for subsequent use in deionized water, and the solid content of dispersion liquid is 40 ~ 55g/L.
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| CN107744807A (en) * | 2017-11-09 | 2018-03-02 | 南京大学（苏州）高新技术研究院 | The preparation and application of a kind of powder catalytic material, compound porous nano catalytic material |
| CN107812527A (en) * | 2017-11-09 | 2018-03-20 | 南京大学（苏州）高新技术研究院 | The preparation and application of a kind of powder catalytic material, graphitiferous phase carbon nitride composite Nano catalysis material |
| CN107744807B (en) * | 2017-11-09 | 2020-11-17 | 南京大学（苏州）高新技术研究院 | Preparation and application of powder catalytic material and composite porous nano catalytic material |
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