CN109529825A - One kind being based on sylphon shape TiO2Nano bionic Photoreactor and its preparation method and application - Google Patents
One kind being based on sylphon shape TiO2Nano bionic Photoreactor and its preparation method and application Download PDFInfo
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- CN109529825A CN109529825A CN201811419500.3A CN201811419500A CN109529825A CN 109529825 A CN109529825 A CN 109529825A CN 201811419500 A CN201811419500 A CN 201811419500A CN 109529825 A CN109529825 A CN 109529825A
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- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 126
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 claims abstract description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 51
- 229910052749 magnesium Inorganic materials 0.000 claims description 51
- 239000011777 magnesium Substances 0.000 claims description 50
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 43
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 230000003197 catalytic effect Effects 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 11
- 229910010273 TiOF2 Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- -1 aza porphyrin compound Chemical class 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims description 5
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 230000004044 response Effects 0.000 abstract description 4
- 230000003595 spectral effect Effects 0.000 abstract description 4
- 239000000356 contaminant Substances 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 238000006053 organic reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000010931 gold Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 23
- 229910045601 alloy Inorganic materials 0.000 description 21
- 239000000956 alloy Substances 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 19
- 239000010949 copper Substances 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 229910002710 Au-Pd Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910002708 Au–Cu Inorganic materials 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 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
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- LOZHPJDATPAKCA-UHFFFAOYSA-N [Mg].C(CCC)O Chemical compound [Mg].C(CCC)O LOZHPJDATPAKCA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- 150000004032 porphyrins Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MYPNFKKWGMMNMA-UHFFFAOYSA-N [Mg].N1=CC=CC2=CC=CC=C12 Chemical compound [Mg].N1=CC=CC2=CC=CC=C12 MYPNFKKWGMMNMA-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [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 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- RZUBARUFLYGOGC-MTHOTQAESA-L acid fuchsin Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=C(N)C(C)=CC(C(=C\2C=C(C(=[NH2+])C=C/2)S([O-])(=O)=O)\C=2C=C(C(N)=CC=2)S([O-])(=O)=O)=C1 RZUBARUFLYGOGC-MTHOTQAESA-L 0.000 description 1
- QGKVXWDADKTZHW-UHFFFAOYSA-N azaporphyrin Chemical compound C1=C(N=2)C=CC=2C=C(N=2)C=CC=2C=C(N2)C=CC2=CC2=CNC1=N2 QGKVXWDADKTZHW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013528 metallic particle Substances 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 238000001953 recrystallisation Methods 0.000 description 1
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- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to nano bionic Photoreactor photocatalysis organic reaction technical fields, are related to a kind of based on sylphon shape TiO2Nano bionic Photoreactor and its preparation method and application.The method comprises the steps of firstly, preparing sylphon shape TiO2As carrier, then pass through metal deposit, Thio-tetraazaporphyrin compound and sylphon shape TiO2Self assembly is carried out, this structure has certain bionic function, widened spectral response range, directly can carry out catalysis reactive organic molecule using visible light, and has good selectivity in carrying out catalysis reactive organic molecule and stability.The nano bionic Photoreactor photocatalytic activity with higher holds out broad prospects in terms of photocatalysis reactive organic molecule and degradation environmental contaminants.
Description
Technical field
The invention belongs to nano bionic Photoreactor photocatalysis organic reaction technical fields, are related to a kind of based on sylphon shape
TiO2Nano bionic Photoreactor and its preparation method and application.
Background technique
Nowadays, organic pollutant causes various harm to the health and environment of the mankind.Through studying, photochemical catalytic oxidation is point
The effective means of organic pollutant is solved, and studied, develop and implemented the various Photocatalytic Oxidations of decades.?
Light-catalysed field has many people to propose and is more advantageous to light-catalysed reaction unit, for example, publication number is CN206457270U
Utility model patent in propose it is a kind of can be to the device that pollutant photocatalytic degradation product is separated and detected in real time, this is filled
Setting can be detected and be separated to the product after degradation, easy to operate.But since such device figure is huge, reaction condition is severe
It carves, it has not been convenient to carry.
Currently, some research discovery supported catalysts, bionic catalyst can form one kind by self assembly in the solution
Advantageous, separation, stable nanostructure formation nano-reactor, these nano-reactors formed in solution, not only
Substrate reactions rate is improved, prevents the catalyst functional group's degradation for loading or encapsulating or inactivation, and be advantageous to reactor
Recovery and recycle.
Nano-TiO2Hollow structure because it has many advantages, such as biggish specific surface area, low-density and permeability, show
Gone out its excellent performance, it has been reported that there are also TiO2Nanotube, TiO2Nano-hollow ball, TiO2Nano-hollow box and
Nano-TiO2Nucleocapsid structure etc..
Summary of the invention
The object of the present invention is to provide one kind to be based on sylphon shape TiO2Nano bionic Photoreactor and preparation method thereof, this
The bionical Photoreactor of invention preparation has certain bionic function and good stability, and can be visible in near-infrared-- purple
Photocatalysis reactive organic molecule is carried out under outer wide spectral range, while there is regular structure, higher photocatalytic activity, good
Stability and selectivity.
To achieve the goals above, the technical solution adopted by the present invention is that:
One kind being based on sylphon shape TiO2Nano bionic Photoreactor, the nano bionic Photoreactor is with sylphon shape TiO2
For carrier, carrier surface load has metal and/or Thio-tetraazaporphyrin compound.
Further, the metal is Cu, Pd and/or Au.
Further, the above-mentioned bionical Photoreactor is prepared by following methods:
(1) sylphon shape TiO is prepared2；
(2) it weighs metal salt to be scattered in distilled water, adjusts its pH value to 8-9 with NaOH solution, be then added thereto
Sylphon shape TiO2, in 50-90 DEG C of water-bath, after being stirred to react 3-20h, it is filtered, washed, is dried overnight, dried product exhibited dispersion
In distilled water, then NaBH is added thereto4Solution is stirred to react after 6-12h and filters, wash, be dried to obtain bionical light reaction
Device；
The metal salt is mantoquita, palladium salt and/or gold salt, it is preferred that the mantoquita is CuSO4, the palladium salt is PdCl2,
The gold salt is HAuCl4；
The metal salt and sylphon shape TiO2Mass ratio be 1:(1-8).
Further, the metal salt be mass ratio 3:(1-8) CuSO4And HAuCl4Or the metal salt is quality
Than 3:(1-8) PdCl2And HAuCl4。
Further, sylphon shape TiO is being added thereto in the step (2)2While, sulfur-bearing four is added into system
Aza porphyrin compound, the Thio-tetraazaporphyrin compound additional amount are the 1%-8% of metal salt quality, preferably
2.5%.
Further, the Thio-tetraazaporphyrin compound is the aza porphyrin free ligand of sulfur-bearing four, four nitrogen of sulfur-bearing
One of miscellaneous porphyrin magnesium and Thio-tetraazaporphyrin aluminium, preferably Thio-tetraazaporphyrin magnesium.
Further, when Thio-tetraazaporphyrin compound and metal salt is added simultaneously into system, the metal salt
For HAuCl4, the metal salt and sylphon shape TiO2Mass ratio be 1:1-4.
Further, when being added without Thio-tetraazaporphyrin compound in system, the step (2) is in 60-80 DEG C of water
In bath (preferably 75 DEG C), after being stirred to react 3-7h, it is filtered, washed, is dried overnight, dried product exhibited is scattered in distilled water,
NaBH is added thereto again4Solution is stirred to react after 8-12h and filters, wash, be dried to obtain bionical Photoreactor.
Further, when being added without Thio-tetraazaporphyrin compound in system, the metal salt and sylphon shape TiO2
Mass ratio be 1:(1-4).
Further, when Thio-tetraazaporphyrin compound is added in system, the step (2) is in 70-90 DEG C of water-bath
In (preferably 90 DEG C), after being stirred to react 10-20h, be filtered, washed, be dried overnight, dried product exhibited is scattered in distilled water,
NaBH is added thereto again4Solution is stirred to react after 8-12h and filters, wash, be dried to obtain bionical Photoreactor.
Further, the above-mentioned bionical Photoreactor is prepared by following methods:
(A) Thio-tetraazaporphyrin compound is prepared；
(B) by TiOF2, dehydrated alcohol and Thio-tetraazaporphyrin compound be placed in autoclave, in 150-250 after sealing
32h-60h is reacted at DEG C, is cooled to room temperature after reaction, after rotary evaporation is concentrated, is dried overnight, and product sulfur-bearing is obtained
Tetraazatetradecane porphyrin@sylphon shape TiO2Bionical Photoreactor；
The TiOF2Mass ratio with Thio-tetraazaporphyrin compound is 300:(1-8).
Further, the TiOF2Mass ratio with Thio-tetraazaporphyrin compound is 300:(1-4), preferably
300:2。
Further, 32h-48h is reacted at 200 DEG C after sealing in above-mentioned steps (B), preferably react at 200 DEG C
48h。
Further, the condition of the drying is to be dried in vacuo at 60-120 DEG C, is dried in vacuo at preferably 60 DEG C.
Further, the NaBH4The concentration of solution is 2wt%.
Further, the TiOF2With sylphon shape TiO2The preparation method is as follows:
(1) it is slowly added to hydrofluoric acid (concentration 44wt%) into glacial acetic acid, stirs evenly, titanium is then added thereto
Sour four butyl esters, stir evenly, obtain white suspension, white suspension is transferred in the liner of autoclave later, close
Be honored as a queen at 200 DEG C and react 12h, after reaction, cooled to room temperature, remove supernatant liquid, with dehydrated alcohol wash to
Neutrality is filtered with the organic filter membrane decompression of micropore later, dry, obtains TiOF2；The amount ratio of the butyl titanate and hydrofluoric acid
For 15g:5mL；
(2) TiOF is added in a high pressure reaction kettle2And dehydrated alcohol, ultrasound make its dispersion, are put into baking oven after sealing,
12h is reacted at 200 DEG C, after reaction, removes supernatant liquor, is successively used dehydrated alcohol and distillation water washing to neutrality, is filtered,
It is put into 60 DEG C of baking ovens dry 12h, obtains sylphon shape TiO2。
Further, the Thio-tetraazaporphyrin compound is Thio-tetraazaporphyrin free ligand, four azepine of sulfur-bearing
One of porphyrin magnesium and Thio-tetraazaporphyrin aluminium, preferably Thio-tetraazaporphyrin magnesium.
Further, the Thio-tetraazaporphyrin magnesium the preparation method is as follows: n-butanol and magnesium are added in there-necked flask,
Iodine initiation reaction is added into system, is heated to reflux under nitrogen protection for magnetic agitation, and reaction obtains n-butanol magnesium solution, to
After reaction solution is cooled to room temperature, 2,3- dicyano -5- methylol-- two thiophene English of Isosorbide-5-Nitrae is dissolved in n-butanol, is slowly dropped to above-mentioned
In n-butanol magnesium solution, under nitrogen protection, 120 DEG C of reflux, revolving crosses chromatographic column, after recrystallization, obtains Thio-tetraazaporphyrin
Magnesium；
The additional amount ratio of two thiophene English of the n-butanol, magnesium and 2,3- dicyano -5- methylol -1,4- is 50mL:3-
4mmol:10mmol.
The present invention also provides application of the above-mentioned bionical Photoreactor in the reaction of photochemical catalytic oxidation benzylamine.
The present invention also provides application of the above-mentioned bionical Photoreactor in organic pollutant degradation.
Further, the organic pollutant is rhodamine B, methyl orange, acid fuchsin, mercaptobenzothiazoler or diformazan
Phenol orange, preferably rhodamine B.
Compared with prior art, technical solution of the present invention is had the following advantages and beneficial effects:
The present invention is prepared for a kind of based on TiO2Sylphon shape nano bionic Photoreactor, Metal Supported is in sylphon shape TiO2Table
Not only there is photoresponse in face in ultra-violet (UV) band, also has photoresponse in visible region；Thio-tetraazaporphyrin compound is sensitized sylphon shape
TiO2Afterwards, also there is photoresponse in near-infrared region.Therefore, nano bionic Photoreactor prepared by the present invention has wider spectrum
Response range, near infrared light, visible light, ultraviolet light can excite, and can effectively solve TiO2Only to caused by ultraviolet light response too
The problem of sunlight major part energy cannot efficiently use.Nano bionic Photoreactor has preferable photocatalytic activity in the present invention
With certain bionic function, reactor is provided for reactive organic molecule well, organic molecule is carried out under the conditions of light-catalysed
Reaction, had both reached good catalytic effect, and had also improved yield, using this nano bionic Photoreactor in catalysis organic molecule
Reaction aspect has remarkable effect, easy to operate.
The method comprises the steps of firstly, preparing sylphon shape TiO2As carrier, then pass through metal deposit, Thio-tetraazaporphyrin chemical combination
Object and sylphon shape TiO2Self assembly is carried out, this structure has certain bionic function, widened spectral response range, can be directly sharp
Catalysis reactive organic molecule is carried out with visible light, and has good selectivity and stablizes in carrying out catalysis reactive organic molecule
Property.The nano bionic Photoreactor photocatalytic activity with higher, in photocatalysis reactive organic molecule and degradation environmental pollution
Object space face holds out broad prospects.
Detailed description of the invention
Fig. 1 is the schematic diagram that nano bionic Photoreactor of the invention widens spectral response；
Fig. 2 is the schematic diagram that nano bionic Photoreactor of the invention is catalyzed reactive organic molecule；
Fig. 3 is Au (10)-Cu@TiO prepared by embodiment 12Nanometer Photoreactor and sylphon shape TiO2SEM figure；
Fig. 4 is Au (10)-Cu@TiO prepared by embodiment 12The EDS energy spectrum diagram of nanometer Photoreactor；
Fig. 5 is nanometer Photoreactor (binary Au-Cu alloy@sylphon shape TiO prepared by embodiment 12) XRD diagram；
Fig. 6 is Au (10)-Pd@TiO prepared by embodiment 22The TEM figure of nanometer Photoreactor；
Fig. 7 is Au (10)-Pd@TiO prepared by embodiment 22The SEM figure of nanometer Photoreactor；
Fig. 8 is nanometer Photoreactor (binary Au-Pd alloy@sylphon shape TiO prepared by embodiment 22) UV-vis figure；
Fig. 9 is Thio-tetraazaporphyrin magnesium@sylphon shape TiO prepared by embodiment 32(1) SEM of nano bionic Photoreactor
Figure；
Figure 10 is nano bionic Photoreactor (Thio-tetraazaporphyrin magnesium@sylphon shape TiO prepared by embodiment 32) XRD
Figure；
It is nano bionic Photoreactor (Thio-tetraazaporphyrin magnesium@sylphon shape TiO shown in Figure 112) and 1 step of embodiment
Suddenly the sylphon shape TiO of (1) preparation2Photocatalytic degradation RhB activity curve figure.
Figure 12 is nano bionic Photoreactor (ternary Au- Thio-tetraazaporphyrin magnesium@sylphon shape prepared by embodiment 4
TiO2) UV-vis figure；
Figure 13 is nano bionic Photoreactor (ternary Au- Thio-tetraazaporphyrin magnesium@sylphon shape prepared by embodiment 4
TiO2) photocatalytic degradation RhB activity curve figure.
Figure 14 is ternary Au- Thio-tetraazaporphyrin magnesium@TiO prepared by embodiment 42(3) nano bionic Photoreactor light
The activity curve figure of catalytic degradation RhB circulation experiment.
Specific embodiment
Technical solution of the present invention and technical effect are described in further details below with reference to embodiment and attached drawing.
Embodiment 1: one kind being based on sylphon shape TiO2Nano bionic Photoreactor, be prepared by following methods:
(1) sylphon shape TiO2Preparation: measure 30mL glacial acetic acid in polytetrafluoroethylene beaker, be slowly added to thereto
5mL HF (concentration 44wt%), stirs evenly, and 15.00g butyl titanate (TBT) then is added thereto again, stirs 30min
Afterwards, white suspension is obtained, is later transferred to white suspension in the liner of 100mL autoclave, after sealing reaction kettle,
12h is reacted at 200 DEG C.After reaction, cooled to room temperature, removes the liquid on upper layer, and obtained solid is precipitated with anhydrous
Ethanol washing is filtered with (0.4 μm, the similarly hereinafter) decompression of the organic filter membrane of micropore, obtained solid vacuum at 60 DEG C is dry later to neutrality
Dry 6 hours, obtain white powder TiOF2。
Weigh 1g TiOF2In 100mL autoclave liner, 40mL dehydrated alcohol is added thereto, ultrasound makes its point
It dissipates, after sealing reaction kettle, puts it into baking oven, 12h is reacted at 200 DEG C, after reaction, after removing supernatant liquor, successively
With dehydrated alcohol and distillation water washing to neutral, suction filtration, obtained solid is put into 60 DEG C of baking ovens and is dried in vacuo 12h, obtains white
Powder TiO2To get arrive sylphon shape TiO2。
(2) binary Au-Cu alloy@sylphon shape TiO2Preparation: weigh 30mg CuSO4With 10mg HAuCl4It is scattered in
In 100mL distilled water, magnetic agitation is opened, adjusts its pH value to 8-9, then by its turn with the 0.2mol/L NaOH prepared
It moves on in 250mL round-bottomed flask, 0.1214g sylphon shape TiO is added thereto2, in 75 DEG C of water-baths, it is stirred to react after 5h with having
Machine membrane filtration is put into 60 DEG C of baking ovens and is dried in vacuum overnight, will dry after obtained solid uses a large amount of distillation water washings to neutrality
Product afterwards is added in 100mg distilled water, and after being uniformly dispersed, the NaBH of 20mL 2wt% is added thereto4Solution is (existing in ice water
Match, similarly hereinafter), it is filtered after being stirred to react 8h, obtained solid is washed with distilled water to neutrality, after filtering, is put into 60 DEG C of baking ovens true
Sky is dry, obtains the Au-Cu alloy@sylphon shape TiO that average grain diameter is 290nm or so2Nano bionic Photoreactor Au (10)-
Cu@TiO2。
(3) Au (10)-Cu@TiO is used2The reaction of photochemical catalytic oxidation benzylamine is carried out as catalyst: in a clean 50mL
Au (10)-Cu@TiO of 25mg above-mentioned steps (2) preparation is sequentially added in light reaction bottle2With the acetonitrile of 25mL, ultrasound makes to be catalyzed
Agent is evenly dispersed in acetonitrile；Then the benzylamine (1mmol) of 0.11mL is added thereto, stirs 15min under dark condition.
Then xenon lamp (visible light, power 350W) light source is opened, electric current is adjusted to 9.0A, continuous illumination 6h after illumination, takes 4mL
Sample carries out gas chromatographic analysis, the results are shown in Table 1 after centrifuge is centrifuged 10min.
The parameter setting of gas-chromatography: (1) temperature and pressure of injection port is respectively 250 DEG C and 9.0 pas, and operational mode is
" shunting ", wherein split ratio is set as 10:1, and bypass flow is set as 20mL/min.(2) detector parameters are set, temperature setting
It is 270 DEG C, air mass flow is set as 300mL/min, and hydrogen gas flow is set as 40mL/min, make-up gas flow (N2)
30mL/min, column flow 2mL/min, flame 134.1Pa.(3) post case parameter setting, opening temperature are 50 DEG C, when balance
Between 0.5min, highest post case temperature be 325 DEG C.
According to the method for above-mentioned steps (1) and step (2), by HAuCl4Additional amount be changed to 20mg, 30mg, 40mg respectively
Respectively obtain three nano bionic Photoreactors: Au (20)-Cu@TiO2、Au(30)-Cu@TiO2With Au (40)-Cu@TiO2。
Then it is utilized respectively the product being prepared and carries out binary Au-Cu alloy@sylphon shape TiO according to above-mentioned steps (3)2
In addition above-mentioned nano bionic Photoreactor (i.e. catalyst) quality such as is changed to as a result such as table 1 by the reaction of photochemical catalytic oxidation benzylamine
The sylphon shape TiO of step (1) preparation2The reaction of photochemical catalytic oxidation benzylamine is carried out, as a result such as table 1.
Fig. 3 is the sylphon shape TiO of step (1) preparation2With Au (10)-Cu@TiO2The SEM figure of nanometer Photoreactor, wherein
Top two is sylphon shape TiO2SEM figure, lower section two is Au (10)-Cu@TiO2SEM figure, Cong Tuzhong sees relative to sky
Box-like TiO2, Au (10)-Cu@TiO2Surface be distributed uniform metallic particles, while surface there are many smaller aperture and is compared
Coarse, which increase the surface areas of nanometer Photoreactor, are conducive to organic molecule entrance and are wherein reacted.
Fig. 4 is Au (10)-Cu@TiO2The EDS energy spectrum diagram of nanometer Photoreactor, the prepared sample known to Surface scan figure
In contain O, Ti, Au, Cu element, wherein O element and Ti element are uniformly distributed, Au element be more than Cu element, Surface scan figure and SEM
The shape of figure is quite similar.As it can be seen that there is the peak of Ti, O, Au, Cu element to occur from spot scan figure, illustrate Au-Cu alloy@sylphon
Shape TiO2Nano bionic Photoreactor is successfully prepared.
Fig. 5 is the sylphon shape TiO of each nanometer Photoreactor manufactured in the present embodiment and step (1) preparation2XRD diagram.
It as can be seen from the figure is diffraction maximum occur at 25.18 °, 38.55 °, 47.80 °, 55.06 °, 62.56 °, 69.80 ° in 2 θ,
It is typical Detitanium-ore-type sylphon shape TiO2Characteristic peak.Wherein 2 θ are the diffraction of Cu occur at 43.35 °, 50.85 °, 74.25 °
Peak illustrates that copper nanoparticle loads successfully.Compare TiO2With Au-Cu alloy@sylphon shape TiO2As it can be seen that being to have at 17.25 ° in 2 θ
Faint diffraction maximum, as the ratio of Au increases, diffraction maximum is more and more obvious, and illustrates sylphon shape TiO2Area load has gold nano
Particle.
The comparison of 1 each nanometer of Photoreactor photochemical catalytic oxidation benzylamine reactivity of table
Note: TiO in table2For the sylphon shape TiO of step (1) preparation2, xenon lamp (optical filter) refers to the light for filtering λ >=420nm
The experimental result carried out behind source, respectively the flow that is passed through of oxygen source is 0.4m in experiment3/s。
As shown in Table 1, when light source is visible light, after reacting 6h in air, imines has selectively reached 99% or more.This
The prepared Au-Cu alloy sylphon shape TiO come out of invention2With very strong photochemical catalytic oxidation selectivity, benzylamine is oxidized to phase
The imines answered, and the conversion ratio of its photocatalysis benzylamine is significantly higher than sylphon shape TiO2。
When with Au-Cu alloy@sylphon shape TiO2As catalyst light source be ultraviolet light (light source for filtering λ >=420nm),
In atmosphere after photocatalysis 6h, Au-Cu alloy@sylphon shape TiO2The conversion ratio of photocatalysis benzylamine compared to visible light under
Drop.It is worth noting that, the conversion ratio that benzylamine occurs is 94.5% and selectivity is 99% or more when oxygen source is pure oxygen, say
Bright Au-Cu alloy@sylphon shape TiO2It has good selectivity.
Embodiment 2: one kind being based on sylphon shape TiO2Nano bionic Photoreactor, be prepared by following methods:
(1) sylphon shape TiO is prepared according to the method for 1 step of embodiment (1)2。
(2) binary Au-Pd alloy@sylphon shape TiO2Preparation: weigh the HAuCl of 10mg4With 30mg PdCl2It is scattered in
In 100mL distilled water, magnetic agitation is opened, adjusts its pH value to 8-9, then by its turn with the NaOH of the 0.2mol/L prepared
It moves on in 250mL round-bottomed flask, 0.1214g sylphon shape TiO is added thereto2, in 75 DEG C of water-baths, it is stirred to react after 5h with having
Machine membrane filtration is put into 60 DEG C of baking ovens and is dried in vacuum overnight after obtained solid uses a large amount of distillation water washings to neutrality.It will dry
Product is added in 100mg distilled water afterwards, and after being uniformly dispersed, the NaBH of 20mL 2wt% is added thereto4Solution is stirred to react 8h
After filter, obtained solid is washed with distilled water to neutrality, is put into after filtering in baking oven and is dried in vacuo at 60 DEG C, obtains binary
Au-Pd alloy@sylphon shape TiO2, as Au (10)-Pd@TiO2, average grain diameter 290nm.
Binary Au-Pd alloy@sylphon shape TiO2Photochemical catalytic oxidation benzylamine reaction: in a clean 50mL light reaction bottle
Sequentially add catalyst Au (10)-Pd@TiO of 25mg2With the acetonitrile of 25mL, ultrasound makes catalyst be evenly dispersed in acetonitrile
In；Then the benzylamine (1mmol) of 0.11mL is added thereto, stirs 15min under dark condition.Opening xenon lamp, (power 350W, can
It is light-exposed) light source, electric current is adjusted to 9.0A, continuous illumination 6h, after illumination, 4mL sample is taken, after centrifuge is centrifuged 10min, into
Promoting the circulation of qi analysis of hplc.
According to the method for above-mentioned steps (1) and step (2), by HAuCl4Additional amount be changed to 20mg, 30mg, 40mg respectively
Respectively obtain Au (20)-Pd@TiO2Photoreactor, Au (30)-Pd@TiO2Photoreactor and Au (40)-Pd@TiO2Photoreactor.
Then binary Au-Pd alloy@sylphon shape TiO is carried out respectively2The reaction of photochemical catalytic oxidation benzylamine, it is in addition that above-mentioned light is anti-
Device (i.e. catalyst) is answered to be changed to the sylphon shape TiO of equal quality steps (1) preparation2Carry out the reaction of photochemical catalytic oxidation benzylamine.
It is a nanometer Photoreactor (Au (10)-Pd@TiO shown in Fig. 62) TEM figure.As can be seen from the figure sylphon shape TiO2
Area load have equally distributed Au, Pd nano particle, the lesser nano particle of these sizes is evenly distributed and quantity is more,
Partial size is relatively uniform.
It is a nanometer Photoreactor (Au (10)-Pd@TiO shown in Fig. 72) SEM figure.As can be seen from the figure sylphon shape TiO2
It is made of six faces, and surface is smooth, pattern is more unified and regular, consistent with TEM figure.Au, Pd nano particle uniformly divide
Cloth is in sylphon shape TiO2Surface, it can be enhanced in the photoresponse of visible light, to preferably be catalyzed under visible light organic
Molecule reaction.
Fig. 8 show each nanometer Photoreactor manufactured in the present embodiment (Au-Pd alloy@sylphon shape TiO2) UV-vis
Figure.As can be seen from the figure sylphon shape TiO2Only there is UV Absorption peak in 400nm or less.After having loaded Au-Pd alloy,
560nm nearby occurs compared with strong absworption peak, this is mainly absorption peak of the Au in visible region.
The comparison of 2 each nanometers of Photoreactor photochemical catalytic oxidation benzylamine reactivities of table
Note: TiO in table2For the sylphon shape TiO of step (1) preparation2, xenon lamp (optical filter) refers to the light for filtering λ >=420nm
The experimental result carried out behind source, each flow that is passed through for testing oxygen source is 0.4m3/s。
As shown in Table 2, when light source is visible light, after reacting 6h in air, imines has selectively reached 99% or more.This
The prepared sylphon shape TiO come out of invention2With very strong photochemical catalytic oxidation benzylamine selectivity.And Au-Pd alloy@sylphon shape
TiO2The conversion ratio of photochemical catalytic oxidation benzylamine is significantly higher than sylphon shape TiO2And conversion ratio can reach 95% or more.
When with Au-Pd alloy@sylphon shape TiO2It is that ultraviolet light (filters the light of λ >=420nm in light source as catalyst
Source), in atmosphere after photocatalysis 6h, Au-Pd alloy@sylphon shape TiO2The conversion ratio of photocatalysis benzylamine compared to visible light
Decline.It is worth noting that, the conversion ratio that benzylamine occurs is 93.6% and selectivity is 99% or more when oxygen source is pure oxygen,
Illustrate Au-Pd alloy@sylphon shape TiO2It has good selectivity.
Embodiment 3: one kind being based on sylphon shape TiO2Nano bionic Photoreactor, be prepared by following methods:
(1) TiOF is prepared according to (1) method the step of embodiment 12, spare.
(2) 50ml n-butanol and 0.075g the preparation of Thio-tetraazaporphyrin magnesium: are added in 100ml there-necked flask
The initiation reaction of 0.1g iodine is added into system, is heated to reflux under nitrogen protection for (3.13mmol) magnesium powder, magnetic agitation, reacts
After 20 hours, n-butanol magnesium solution is obtained, is cooled to room temperature, then by 2, the 3- dicyano -5- hydroxyl of 2.0g (10mmol)
Methyl-1 is slowly dropped in above-mentioned n-butanol magnesium solution, the color of reaction solution is gradually after bis- thiophene English of 4- is dissolved in 10ml n-butanol
Deepen, finally in blackish green, after dripping, flow back 20 hours under 120 DEG C, nitrogen protection, then rotate, obtain black-and-blue solid
Body is that eluant, eluent crosses silicagel column with the chloroform of volume ratio 20:1 and methanol mixed solvent, obtained principal product methylene chloride and
The mixed solvent (volume ratio 1:1) of isopropanol recrystallizes, and obtains Thio-tetraazaporphyrin magnesium.FT-IR(KBr)3401(-OH),
3286 (N-H), 2919 (C-H), 1702 (C-O), 1635 (C=N), 1472 (C=C), 1403,1304,1202,1035 (C-C),
874,791cm-1；1H NMR(d-DMSO):δ-3.36(s,2H,NH),2.89(m,4H,S-CH2),3.76(m,8H,S-CH2),
4.03(m,8H,CH2-OH),4.23(m,4H,OH)。
(3) Thio-tetraazaporphyrin magnesium@sylphon shape TiO2Preparation: by 300mg TiOF2, 70mL dehydrated alcohol and 1mg contain
Sulphur tetraazatetradecane porphyrin magnesium is placed in 100mL teflon lined autoclave, reacts 48h after sealing at 200 DEG C, and reaction terminates
Afterwards, it is cooled to room temperature to reaction solution, after rotary evaporation is concentrated, is dried in vacuum overnight at 60 DEG C, obtain product containing thia four
Nitrogen porphyrin magnesium@TiO2(1), average grain diameter 312nm.
According to above-mentioned steps (1)-(3) method, the additional amount of Thio-tetraazaporphyrin magnesium is changed to 2mg, 5mg points respectively
Thio-tetraazaporphyrin magnesium@TiO is not obtained2(2), Thio-tetraazaporphyrin magnesium@TiO2(5)。
With the above-mentioned Thio-tetraazaporphyrin magnesium@sylphon shape TiO prepared2Photocatalytic degradation effect is carried out as photochemical catalyst
Fruit test: under visible light illumination, using organic dyestuff RhB as target contaminant, to the photocatalytic activity of prepared sample into
Evaluation is gone.
Detailed process is as follows: being 5 × 10 by 50mg photochemical catalyst and 50mL initial concentration-4It is anti-that the RhB of mol/L is added to light
Answer in bottle, then by mixed solution shaken overnight in the dark, after reaching adsorption equilibrium, by with optical filter (λ >
For 210W xenon lamp irradiation system 420nm) to ensure only to start light-catalyzed reaction by radiation of visible light, system is passed through condensed water
It is cooling, it is used to keep system at room temperature.Every 20min collects 3.5mL aliquot, and centrifugation removes catalyst granules and is used for
Analysis.The RhB concentration of different time points is detected by uv-vis spectra, all measurements carry out at room temperature.
Above-mentioned Photoreactor (i.e. catalyst) is in addition changed to etc. to the sylphon shape of 1 step of embodiment (1) preparation of quality
TiO2Photocatalytic degradation effect test is carried out, as a result such as Figure 11.
It is nano bionic Photoreactor (Thio-tetraazaporphyrin magnesium@TiO shown in Fig. 92(1)) SEM figure.It can be with from figure
Find out Thio-tetraazaporphyrin@sylphon shape TiO2Sample is empty box like structure, and the hairy antenna of Thio-tetraazaporphyrin magnesium is covered on
Sylphon shape TiO2Surface, increase the surface area of bionical Photoreactor, be more advantageous to photocatalytic degradation reaction.
It is nano bionic Photoreactor (Thio-tetraazaporphyrin magnesium@sylphon shape TiO shown in Figure 102) and 1 step of embodiment
Suddenly the sylphon shape TiO of (1) preparation2XRD diagram.For all samples, it observes the broad peak at 2 θ=25.37 °, corresponds to sharp
Titanium ore TiO2{ 101 } face diffraction (JCPDS No.21-1272).With sylphon shape TiO2It compares, Thio-tetraazaporphyrin magnesium@sylphon
Shape TiO2The diffraction maximum of { 101 } and { 200 } crystal face become more sharp, show that crystallinity is higher.The four azepine porphin of sulfur-bearing in figure
Quinoline magnesium@sylphon shape TiO2Other characteristic diffraction peaks do not show displacement or peak shape variation, this shows four azepine porphin of sulfur-bearing
The modification and sensitization of quinoline magnesium do not change sylphon shape TiO2Crystal structure.
It is nano bionic Photoreactor (Thio-tetraazaporphyrin magnesium@sylphon shape TiO shown in Figure 112) and 1 step of embodiment
Suddenly the sylphon shape TiO of (1) preparation2When photocatalytic degradation RhB in reaction solution RhB concentration and its initial concentration ratio time graph
Figure.Show Thio-tetraazaporphyrin magnesium@TiO in figure2(2) degradation rate of the sample in 2h reaches 98.4%, has optimal light
Catalytic activity.In this process, the sequence of degradation rate is Thio-tetraazaporphyrin magnesium@TiO2(2) > Thio-tetraazaporphyrin
Magnesium@TiO2(1) > Thio-tetraazaporphyrin magnesium@TiO2(5) > sylphon shape TiO2。
Embodiment 4: one kind being based on sylphon shape TiO2Nano bionic Photoreactor, be prepared by following methods:
(1) sylphon shape TiO is prepared according to (1) method the step of embodiment 12, spare.
(2) preparation of Thio-tetraazaporphyrin magnesium: with (2) the step of embodiment 3.
(3) ternary Au- Thio-tetraazaporphyrin magnesium@sylphon shape TiO2Preparation: weigh the HAuCl of 40mg4It is steamed in 100mL
In distilled water, magnetic agitation is opened, its pH value is adjusted to 8-9 with the 0.2mol/L NaOH solution prepared, transfers it to
In 250mL round-bottomed flask, 1mg Thio-tetraazaporphyrin magnesium and 0.1214g sylphon shape TiO are added thereto2, in 90 DEG C of water-baths
In, after being stirred to react 15h, with organic membrane filtration, obtained solid, to neutrality, is put into 60 DEG C of baking ovens with a large amount of distillation water washings
It is dried in vacuum overnight.Dried product exhibited is added in 100mg distilled water, after being uniformly dispersed, is added 20mL 2wt%'s thereto
NaBH4Solution filters after being stirred to react 8h, and obtained solid is washed with distilled water to neutrality, after filtering, is put into 60 DEG C of baking ovens true
Sky is dried to obtain ternary metal-Thio-tetraazaporphyrin magnesium@sylphon shape TiO2, i.e. Au- Thio-tetraazaporphyrin magnesium@TiO2(1),
Its average grain diameter is 315nm.
According to above-mentioned steps (1)-(3) method, the additional amount of Thio-tetraazaporphyrin magnesium is changed to 3mg, 5mg points respectively
Au- Thio-tetraazaporphyrin magnesium@TiO is not obtained2(3) Photoreactor, Au- Thio-tetraazaporphyrin magnesium@TiO2(5) Photoreactor.
Then nano bionic Photoreactor (ternary Au- Thio-tetraazaporphyrin magnesium@sylphon shape TiO is carried out respectively2) light urges
Change degradation effect test: under visible light illumination, using organic dyestuff RhB as target contaminant, the light of prepared sample is urged
Change activity to be evaluated.Detailed process is as follows: by 50mg ternary Au- Thio-tetraazaporphyrin magnesium@sylphon shape TiO2With with
50mL initial concentration is 5 × 10-4The RhB of mol/L is added in light reaction bottle, then vibrates mixed solution in the dark
Night.After reaching adsorption equilibrium, by being ensured with the 210W xenon lamp irradiation system with optical filter (λ > 420nm) only by visible
Light irradiates to carry out light-catalyzed reaction, and condensed water is cooling, is used to keep system at room temperature.In given time interval,
3.5mL aliquot is collected, then centrifugation removes catalyst granules for analyzing.When detecting different by uv-vis spectra
Between the RhB concentration put.
The sylphon shape TiO of the step of above-mentioned Photoreactor (i.e. catalyst) such as is changed at the quality (1) preparation2Carry out photocatalysis
Degradation effect test, as a result such as Figure 13.
Figure 12 is nano bionic Photoreactor (Au- Thio-tetraazaporphyrin magnesium@sylphon shape TiO2) UV-vis figure.From figure
In as can be seen that the sylphon shape TiO after Au and Thio-tetraazaporphyrin magnesium is added2Absorption peak red shift is to visible region and close red
The area Wai Guang.And with the increase of Thio-tetraazaporphyrin content of magnesium, all Au- Thio-tetraazaporphyrin magnesium@sylphon shape TiO2?
The absorption intensity of near-infrared region gradually increases.
Figure 13 is nano bionic Photoreactor (Au- Thio-tetraazaporphyrin magnesium@sylphon shape TiO2) photocatalytic degradation RhB when
The time plot of RhB concentration and its initial concentration ratio in reaction solution.Show Au- Thio-tetraazaporphyrin magnesium@TiO in figure2
(3) degradation rate of the sample in 2h reaches 99%, has optimal photocatalytic activity.In this process, the sequence of degradation rate
It is Au- Thio-tetraazaporphyrin magnesium@TiO2(3) > Au- Thio-tetraazaporphyrin magnesium@TiO2(1) > Au- Thio-tetraazaporphyrin magnesium@
TiO2(5) > sylphon shape TiO2。
Figure 14 is nano bionic Photoreactor (Au- Thio-tetraazaporphyrin magnesium@TiO2(3)) 5 times of photocatalytic degradation RhB
The activity curve figure of circulation experiment.After first set reaction, catalyst is filtered out, in identical condition after washing, drying
Under carry out above-mentioned catalysis reaction again, this is one cycle, altogether carry out four times circulation, totally 5 times experiment, it can be seen that 5 times experiment after
Catalyst catalytic efficiency still with higher, with good stability, after circulation four times, catalytic efficiency is declined, can
It can be that parting particle falls off and causes in the middle part of cyclic process, but generally, the stability of catalyst is very high, can be repeated several times
It uses.
Claims (10)
1. one kind is based on sylphon shape TiO2Nano bionic Photoreactor, which is characterized in that the nano bionic Photoreactor is with sky
Box-like TiO2For carrier, carrier surface load has metal and/or Thio-tetraazaporphyrin compound.
2. nano bionic Photoreactor according to claim 1, which is characterized in that the metal is Cu, Pd and/or Au.
3. nano bionic Photoreactor according to claim 2, which is characterized in that the bionical Photoreactor is by with lower section
Method is prepared:
(1) sylphon shape TiO is prepared2；
(2) it weighs metal salt to be scattered in distilled water, adjusts its pH value to 8-9 with NaOH solution, sylphon is then added thereto
Shape TiO2, in 50-90 DEG C of water-bath, after being stirred to react 3-20h, it is filtered, washed, is dried overnight, dried product exhibited is scattered in steaming
In distilled water, then NaBH is added thereto4 Solution is stirred to react after 6-12h and filters, wash, be dried to obtain bionical Photoreactor；
The metal salt is CuSO4、PdCl2And/or HAuCl4；
The metal salt and sylphon shape TiO2The mass ratio of additional amount is 1:1-8.
4. nano bionic Photoreactor according to claim 3, which is characterized in that the metal salt is mass ratio 3:(1-
8) CuSO4And HAuCl4Or the metal salt is mass ratio 3:(1-8) PdCl2And HAuCl4。
5. nano bionic Photoreactor according to claim 3, which is characterized in that adding thereto in the step (2)
Enter sylphon shape TiO2While, Thio-tetraazaporphyrin compound, the Thio-tetraazaporphyrin compound are added into system
Additional amount is the 1%-8% of metal salt quality.
6. nano bionic Photoreactor according to claim 5, which is characterized in that when being added sulfur-bearing four simultaneously into system
When aza porphyrin compound and metal salt, the metal salt is HAuCl4。
7. nano bionic Photoreactor according to claim 1, which is characterized in that the bionical Photoreactor is by with lower section
Method is prepared:
(A) Thio-tetraazaporphyrin compound is prepared；
(B) by TiOF2, dehydrated alcohol and Thio-tetraazaporphyrin compound be placed in autoclave, after sealing at 150-250 DEG C
32-60h is reacted, is cooled to room temperature, after rotary evaporation is concentrated, is dried overnight after reaction, obtain bionical Photoreactor；
The TiOF2Mass ratio with Thio-tetraazaporphyrin compound is 300:1-8.
8. nano bionic Photoreactor according to claim 1-7, which is characterized in that the four azepine porphin of sulfur-bearing
Quinoline compound is one of Thio-tetraazaporphyrin free ligand, Thio-tetraazaporphyrin magnesium and Thio-tetraazaporphyrin aluminium.
9. nano bionic Photoreactor according to claim 1-7, which is characterized in that the condition of the drying is
It is dried in vacuo at 60-120 DEG C.
10. a kind of described in any item nano bionic Photoreactors of claim 1-7 answering in the reaction of photochemical catalytic oxidation benzylamine
With；
A kind of application of described in any item nano bionic Photoreactors of claim 1-7 in organic pollutant degradation.
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