CN106492870A - A kind of photochemical catalyst of doped metallic oxide and preparation method thereof - Google Patents
A kind of photochemical catalyst of doped metallic oxide and preparation method thereof Download PDFInfo
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- CN106492870A CN106492870A CN201610902315.4A CN201610902315A CN106492870A CN 106492870 A CN106492870 A CN 106492870A CN 201610902315 A CN201610902315 A CN 201610902315A CN 106492870 A CN106492870 A CN 106492870A
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- oxide
- metal oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 39
- 238000006731 degradation reaction Methods 0.000 claims abstract description 20
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 20
- 230000015556 catabolic process Effects 0.000 claims abstract description 16
- 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 claims abstract description 9
- 229940012189 methyl orange Drugs 0.000 claims abstract description 9
- 230000007704 transition Effects 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910002804 graphite Inorganic materials 0.000 claims description 26
- 239000010439 graphite Substances 0.000 claims description 26
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 239000002270 dispersing agent Substances 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 18
- 229910052796 boron Inorganic materials 0.000 claims description 14
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 14
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- -1 dicyanodiamine Chemical compound 0.000 claims description 8
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 238000002329 infrared spectrum Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 6
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 4
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 4
- 229910001923 silver oxide Inorganic materials 0.000 claims description 4
- IOWOAQVVLHHFTL-UHFFFAOYSA-N technetium(vii) oxide Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Tc+7].[Tc+7] IOWOAQVVLHHFTL-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 2
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 239000000987 azo dye Substances 0.000 abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 22
- 239000012071 phase Substances 0.000 description 21
- 230000001699 photocatalysis Effects 0.000 description 18
- 230000000694 effects Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000103 photoluminescence spectrum Methods 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 238000007146 photocatalysis Methods 0.000 description 11
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 7
- 230000009102 absorption Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 239000002516 radical scavenger Substances 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 102000016938 Catalase Human genes 0.000 description 4
- 108010053835 Catalase Proteins 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229940005561 1,4-benzoquinone Drugs 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000015424 sodium Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- CZCSLHYZEQSUNV-UHFFFAOYSA-N [Na].OB(O)O Chemical compound [Na].OB(O)O CZCSLHYZEQSUNV-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention provides a kind of photochemical catalyst of doped metallic oxide, and the preparation method there is provided the photochemical catalyst, which passes through in g C3N4Middle doping nonmetalloid forms the g C of nonmetal doping3N4Afterwards, then Second Transition oxide is particularly with metal oxide to be doped, codope g C are obtained3N4Photochemical catalyst, the photochemical catalyst are significantly improved to the degradation rate of azo dyes under visible light, and by taking methyl orange as an example, with its catalytic degradation under ultraviolet light, the degradation rate after 1 hour reaches more than 80%.
Description
Technical field
The invention belongs to photocatalysis field, is related to CN photochemical catalysts of a kind of doped metallic oxide and preparation method thereof.
Background technology
Graphite phase carbon nitride (abbreviation g-C3N4) so that its photocatalytic activity is higher, good stability, cost of material are cheap, make it
Become a kind of new catalysis material, however, single phase catalyst generally makes its photocatalysis performance table because quantum efficiency is low
Existing not ideal enough.g-C3N4Material photo-generate electron-hole recombination rate is higher, causes its catalytic efficiency relatively low, so as to limit it
Application in terms of photocatalysis.
In order to improve g-C3N4Catalysis activity, recent years, people have studied a lot of method of modifying.At present, generally make
With nonmetalloid to g-C3N4It is modified, mainly includes S, B, F, P etc. for modified nonmetalloid, it is considered that this
A little nonmetalloids instead of C in 3-s- triazine structural units, N, H element, so as to form g-C3N4Lattice defect causes photoproduction
Electron-hole pair is efficiently separated, and effectively improves its photocatalysis performance.
Zhang etc. is by dicyandiamide and BmimPF6(ionic liquid) mixes, and obtains P doping g-C after high-temperature calcination3N4Urge
Through XPS analysis, agent, shows that P element instead of C in construction unit, although a small amount of P doping can not change g-C3N4Skeleton knot
Structure, but, which substantially changes g-C3N4Electronic structure, photogenerated current is also apparently higher than no doping g-C3N4.
The mixture using heat resolve melamine with boron oxide such as Yan is prepared for B doping g-C3N4, through XPS spectrum
Analysis shows B instead of g-C3N4H in structure, photocatalytic degradation of dye research show that B adulterates while improve catalyst to light
Absorption, therefore, which is also improved to rhodamine B photocatalytic degradation efficiency.
Liu etc. is by g-C3N4In H2It is prepared for unique electronic structure S element doping g- in 450 DEG C of calcinings in S atmosphere
C3N4CNS catalyst, XPS analysis show S instead of g-C3N4N in structure.The S doping g-C as λ ＞ 300 and 420nm3N4Light
Catalytic decomposition aquatic products hydrogen catalysis efficiency is respectively than single g-C3N4Improve 7.2 and 8.0 times.
Wang etc. reports B, F doping g-C3N4Research, they use NH4F is obtained F element doping g- as F sources with DCDA
C3N4Catalyst (CNF).Its result of study shows that F elements have mixed g-C3N4Skeleton in, define C F keys so as in one
Part sp2C is converted into sp3C, so that cause g-C3N4Planar structure is irregular.In addition, with F element doping increasing numbers, CNF
Absorption region in visible region also expands therewith, and its corresponding band-gap energy drops to 2.63eV by 2.69eV.
Use BH3NH3As the g-C that boron source prepares B element doping3N4Catalyst (CNB), characterizes discovery B element to which and mixes
Instead of g-C3N4C element in construction unit.
Lin etc. while B is mixed, and causes g-C because of the effect of benzene leaving group using tetraphenylboron sodium as B sources3N4
Laminate structure is formed, the thickness of its layer is 2～5nm, reduces light induced electron and reach the energy consumed required for catalyst surface,
Therefore photocatalysis efficiency is improved.
However, there presently does not exist the g-C of metal oxide and nonmetalloid codope3N4Research.
Content of the invention
In order to solve the above problems, present inventor has performed studying with keen determination, as a result find：In g-C3N4Middle doping is nonmetallic
Element forms the g-C of nonmetal doping3N4Afterwards, then it is particularly Second Transition oxide with metal oxide to be mixed
Miscellaneous, codope g-C is obtained3N4Photochemical catalyst, the photochemical catalyst are significantly improved to the degradation rate of azo dyes under visible light,
By taking methyl orange as an example, with its catalytic degradation under ultraviolet light, the degradation rate after 1 hour reaches more than 80%, so as to complete this
Invention.
It is an object of the invention to provide following aspect：
In a first aspect, the present invention provides a kind of photochemical catalyst of doped metallic oxide, it is characterised in that the photocatalysis
Carbonitride of the agent by metal oxide with nonmetal doping is composited, wherein,
The metal oxide is transition metal oxide, preferably Second Transition oxide；
The nonmetalloid is selected from boron, sulphur, phosphorus, fluorine etc., preferably boron.
Second aspect, the present invention also provide a kind of method of the photochemical catalyst for preparing above-mentioned doped metallic oxide, and which is special
Levy and be, the method is comprised the following steps：
Step 1, prepares the graphite phase carbon nitride of nonmetal doping；
Step 2, the graphite phase carbon nitride of nonmetal doping obtained in step 1 and metal oxide are combined.
Description of the drawings
Fig. 1 illustrates the infrared spectrogram of sample；
Fig. 2 illustrates sample ultraviolet catalytic ability stability analysis figure；
Fig. 3 illustrates the UV-Vis DRS spectrogram of sample；
Fig. 4 illustrates sample photoluminescence spectra figure；
Fig. 5 illustrates sample ultraviolet catalytic activity figure；
Fig. 6 illustrates that sample ultraviolet catalytic activity changes over figure；
Fig. 7 illustrates impact of the scavenger to sample ultraviolet catalytic activity.
Specific embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more with these explanations
For clear, clear and definite.
The present invention described below.
According to the first aspect of the invention, there is provided a kind of photochemical catalyst of doped metallic oxide, wherein, the photocatalysis
Carbonitride of the agent by metal oxide with nonmetal doping is composited.
In the present invention, the metal oxide is transition metal oxide, preferably Second Transition oxide, more
It is preferably chosen from yittrium oxide, zirconium oxide, niobium oxide, molybdenum oxide, technetium oxide, ruthenium-oxide, rhodium oxide, palladium oxide, silver oxide and oxygen
One or more in cadmium, further preferably one or more in yittrium oxide, zirconium oxide, palladium oxide and cadmium oxide,
Such as zirconium oxide.
The inventors discovered that, above-mentioned metal oxide, particularly Second Transition oxide, especially zirconium oxide, tool
There are the premium properties such as high rigidity, high intensity, high tenacity, high wearability, especially there are excellent ambient temperature mechanical properties and resistance to
High temperature, decay resistance, they are in each field such as pottery, refractory material, machinery, electronics, optics, Aero-Space, biology, chemistry
Obtain a wide range of applications.
In the present invention, the metal oxide is nanosize metal oxide particulate, and such as particle diameter is the gold of 1～100nm
Category oxide.
In the present invention, the source of the metal oxide is not specially limited, can is commercial products, or
Made products, when the metal is oxidized to made products, are not specially limited to the method for preparing the metal oxide, can
To be any one prepares nano-metal-oxide in prior art method, such as Hydrolyze method, the precipitation method, hydro-thermal method, colloidal sol-
Gel method, spray pyrolysis, freeze-drying and high-energy ball milling method etc..
In the present invention, the nonmetalloid in photochemical catalyst is doped in selected from boron, sulphur, phosphorus, fluorine etc., preferably boron.
The inventors discovered that, the light absorbs of graphite phase carbon nitride after the above-mentioned nonmetalloid that adulterates in graphite phase carbon nitride
Efficiency is significantly improved.
The inventors discovered that, the graphite phase carbon nitride and above-mentioned metal oxide doped with above-mentioned nonmetalloid is compound,
The composite photo-catalyst photocatalysis efficiency for obtaining is high, and which can be reached to the degradation rate of methyl orange after ultraviolet light 1 hour
82.5%.
In the present invention, the photochemical catalyst of the doped metallic oxide, according to its infrared spectrum, is 814cm in wave number-1、1244cm-1、1409cm-1、1638cm-1And 650cm-1There is absworption peak in position.
In the present invention, the photochemical catalyst of the doped metallic oxide, wherein, metal oxide and nonmetal doping
The weight ratio of graphite phase carbon nitride is 0.1:100～20:100, preferably 0.2:100～1.5:100, such as 0.25:100、0.5:
100、0.75:100、1.25:100.
In the present invention, when the photochemical catalyst of the doped metallic oxide is prepared, itrogenous organic substance with contain non-gold
Weight of the weight ratio of the compound of category element for itrogenous organic substance:The weight of the compound containing nonmetalloid=(1.0～
20.0)g:(0.5～50.0) mg, preferably (3.0～18.0) g:(1.0～45.0) mg, more preferably (5.0～15.0) g:
(1.5～40.0) mg, more preferably (8.0～12.0) g:(2.0～35.0) mg, much further preferably from (9.0～
11.0)g:(2.0～30.0) mg, such as 10.0g:6mg.
According to the second aspect of the invention, there is provided a kind of method of the photochemical catalyst for preparing kind of doped metallic oxide,
Characterized in that, the method comprising the steps of：
Step 1, prepares the graphite phase carbon nitride of nonmetal doping, specifically includes following sub-step：
Sub-step 1-1, the compound containing nonmetalloid is scattered in the first dispersant, then is added in system and contained
Nitrogen organic, removes the first dispersant after being well mixed；
Sub-step 1-2, the system that sub-step 1-1 is obtained is calcined, and optionally, is crushed after firing.
In the present invention, the itrogenous organic substance refers to the small organic molecule while containing nitrogen and carbon, special
The nitrogenous small organic molecule that in a heated condition can decompose is not referred to, which is in graphite phase carbon nitride is prepared both as nitrogen source
Material is again as carbon source material.
The inventors discovered that, the use of carbon-nitrogen ratio is 1:3～3:The itrogenous organic substance of 1 small-molecular-weight as raw material, preferably
The use of carbon-nitrogen ratio is 1:2 small-molecular-weight itrogenous organic substance as raw material, such as cyanamide, dicyanodiamine, melamine, urea,
Guanidine hydrochloride etc., preferably urea.
In the present invention, the nonmetalloid being doped in graphite phase carbon nitride is selected from boron, sulphur, phosphorus, fluorine etc., preferably
Boron.
The compound containing nonmetalloid that the present invention is selected is selected from the corresponding oxide of the nonmetalloid, containing should
The acid of nonmetalloid or the salt containing the metallic element.
When the nonmetalloid is boron element, the compound containing nonmetalloid is selected from boron oxide, boric acid, boric acid
Sodium, potassium borate, potassium tetraphenylboron and/or sodium tetraphenylborate etc., preferably sodium tetraphenylborate.
The present invention selects the weight ratio of itrogenous organic substance and the compound containing nonmetalloid for the weight of itrogenous organic substance
Amount:The weight of the compound containing nonmetalloid=(1.0～20.0) g:(0.5～50.0) mg, preferably (3.0～18.0)
g:(1.0～45.0) mg, more preferably (5.0～15.0) g:(1.5～40.0) mg, more preferably (8.0～12.0) g:
(2.0～35.0) mg, much further preferably from (9.0～11.0) g:(2.0～30.0) mg, such as 10.0g:6mg.
The inventors discovered that, itrogenous organic substance and compound containing nonmetalloid are placed in liquid-phase system and are mixed,
Can make above two material mixing fully, nonmetal doping graphite phase carbon nitride pattern is homogeneous obtained in calcining.
The present invention is not specially limited to the first dispersant, preferably uses pure water, deionized water and/or distilled water, excellent
Elect distilled water as.
The inventors discovered that, remove in itrogenous organic substance and the compound mixture place system containing nonmetalloid
First dispersant can significantly shorten calcination time, and therefore, the present invention selects to remove the first dispersant before calcination, and the present invention is right
The mode for removing the first dispersant is not specially limited, and in prior art, any mode for removing the first dispersant can make
With, such as normal temperature volatilization, normal heating, vacuum distillation etc., the present invention to except first remove dispersant when temperature do not do especially limit yet
Fixed, the compound not make itrogenous organic substance and containing nonmetalloid is decomposed into preferably, such as 30 DEG C～200 DEG C, more preferably
50 DEG C～150 DEG C, more preferably 60 DEG C～120 DEG C, such as 80 DEG C.
Optionally, the mixture removed after the first dispersant is dried, the inventors discovered that, dried mixture
Which is easier to react under conditions of high-temperature calcination, can substantially shorten the reaction time, and the product morphology for obtaining is good, grain
Footpath is homogeneous.
In sub-step 1-2 of the present invention, the mode for cooling down is not specially limited, can be adopted any one in prior art
Plant the mode cooled down by pressed powder, such as natural cooling and artificial pressure cooling method etc., it is preferred to use natural cooling.
In sub-step 1-2 of the present invention, the material after above-mentioned calcining is cooled to 10 DEG C～50 DEG C preferably, more preferably 15
DEG C～40 DEG C, more preferably 20 DEG C～35 DEG C, such as 25 DEG C.
Itrogenous organic substance can generate non-gold when calcining at 400 DEG C～800 DEG C with the compound containing nonmetalloid
The graphite phase carbon nitride of category element doping, i.e. CNB, and also obtained product morphology is homogeneous, and preferred calcination temperature of the present invention is 400
DEG C～800 DEG C, more preferably 450 DEG C～600 DEG C, such as 550 DEG C.
Present inventors have further discovered that, calcination time is fully can to react for 1～5 hour, and therefore, the present invention is preferably selected
Calcination time is 1～5 hour, preferably 1.5～4 hours, more preferably 2～3.5 hours, such as 2 hours.
In the present invention, optionally, by calcining after material cooled down, and crushed.
Step 2, the graphite phase carbon nitride of nonmetal doping obtained in step 1 and metal oxide are combined,
Specifically, including following sub-step：
Sub-step 2-1, the graphite phase carbon nitride of nonmetal doping obtained in step 1 is mixed with metal oxide, is added
Second dispersant is disperseed, and removes the second dispersant after dispersion fully；
Sub-step 2-2, the system that sub-step 2-1 is obtained is calcined, and optionally, is carried out cooling down calcined product, powder
Broken.
In the present invention, the metal oxide is transition metal oxide, preferably Second Transition oxide, more
It is preferably chosen from yittrium oxide, zirconium oxide, niobium oxide, molybdenum oxide, technetium oxide, ruthenium-oxide, rhodium oxide, palladium oxide, silver oxide and oxygen
One or more in cadmium, further preferably one or more in yittrium oxide, zirconium oxide, palladium oxide and cadmium oxide,
Such as zirconium oxide.
The inventors discovered that, above-mentioned metal oxide, particularly Second Transition oxide, especially zirconium oxide, tool
There are the premium properties such as high rigidity, high intensity, high tenacity, high wearability, especially there are excellent ambient temperature mechanical properties and resistance to
High temperature, decay resistance, they are widely used in pottery, refractory material, machinery, electronics, optics, Aero-Space, biology, chemistry
Etc. each field.
In the present invention, the metal oxide is nanosize metal oxide particulate, and such as particle diameter is the gold of 1～100nm
Category oxide.
In sub-step 2-1 of the present invention, the metal oxide preferable particle size is the nano zircite particle of 1～100nm.
In sub-step 2-1 of the present invention, metal oxide is nitrogenized with the graphite-phase of nonmetal doping obtained in step 1
The weight ratio of carbon is 0.1:100～20:100, preferably 0.2:100～1.5:100, such as 0.25:100、0.5:100、0.75:
100、1.25:100.
In sub-step 2-2 of the present invention, second dispersant is organic solvent, preferably methyl alcohol, ethanol, dichloromethane
Alkane, chloroform etc., more preferably methyl alcohol, ethanol, more preferably ethanol, such as absolute ethyl alcohol.
The inventors discovered that, use above-mentioned organic solvent as the second dispersant, metal oxide is mixed with nonmetalloid
Miscellaneous graphite phase carbon nitride uniformly can be sufficiently mixed, and make a small amount of metal oxide be homogeneously dispersed in nonmetalloid and mix
In miscellaneous graphite phase carbon nitride, so that the photochemical catalyst of obtained doped metallic oxide has good pattern and uniform journey
Degree.
In step 2 of the present invention, after the graphite phase carbon nitride of nonmetal doping is mixed with metal oxide fully, remove
Second dispersant, the present invention are not specially limited to the method for removing the second dispersant, it is possible to use any one in prior art
The method for planting separation of solid and liquid, such as filter, evaporate, being evaporated under reduced pressure etc., it is preferable that holding mixing during the second dispersant is removed
Operation.
Optionally, after the second dispersant is removed, mixed system is dried.
In sub-step 2-2 of the present invention, system obtained in sub-step 2-1 is calcined, preferred calcination temperature of the present invention
For 450 DEG C～700 DEG C, more preferably 400 DEG C～600 DEG C, such as 550 DEG C.
Present inventors have further discovered that, calcination time is fully can to react for 1～5 hour, and therefore, the present invention is preferably selected
Calcination time is 1～5 hour, and preferably this is 1.5～4 hours, more preferably 2～3.5 hours, such as 3 hours.
In the present invention, optionally, by calcining after material cooled down, and crushed.
The photochemical catalyst of doped metallic oxide obtained in step 2 of the present invention, according to its infrared spectrum, in wave number be
814cm-1、1244cm-1、1409cm-1、1638cm-1And 650cm-1There is absworption peak in position；
Wherein, metal oxide is 0.1 with the weight ratio of the graphite phase carbon nitride of nonmetal doping:100～20:100, excellent
Elect 0.2 as:100～1.5:100, such as 0.25:100、0.5:100、0.75:100、1.25:100；
Wherein, weight of the weight ratio of itrogenous organic substance and the compound containing nonmetalloid for itrogenous organic substance:Contain
There is weight=(1.0～20.0) g of the compound of nonmetalloid:(0.5～50.0) mg, preferably (3.0～18.0) g:
(1.0～45.0) mg, more preferably (5.0～15.0) g:(1.5～40.0) mg, more preferably (8.0～12.0) g:
(2.0～35.0) mg, much further preferably from (9.0～11.0) g:(2.0～30.0) mg, such as 10.0g:6mg；
Which can reach 82.5% to the degradation rate of methyl orange after ultraviolet light 1 hour.
Photochemical catalyst of doped metallic oxide provided according to the present invention and preparation method thereof, with following beneficial effect
Really：
(1) in the photochemical catalyst that the present invention is provided, doped metallic oxide amount is few, low cost；
(2) photochemical catalyst can be reached to the degradation rate of azo dyes, particularly methyl orange under ultraviolet light
More than more than 80%, or even 82.5%；
(3) preparation method that the present invention is provided is simple, it is easy to operate, the high income of photochemical catalyst product；
(4) the method environmental protection, non-environmental-pollution.
Embodiment
Embodiment 1～7
6mg tetraphenylboron sodiums are accurately weighed, is put in the small beaker of dried and clean, add 10mL distilled water to dissolve which, so
Add the urea 10.0g of precise afterwards, then be added thereto to 10mL distilled water and be completely dissolved, when heating water bath extremely
When 80 DEG C, this beaker is put in water-bath, in the crucible that sample is proceeded to after water is evaporated dried and clean, is placed in chamber type electric resistance furnace
Interior, and in 550 DEG C of roasting temperature 2h, be placed in after cooling finely ground in mortar, you can CNB finished products are obtained.
Accurately weigh the above-mentioned CNB samples of seven parts of 0.4g to be put in the small beaker of seven dried and cleans, numbering is respectively 1,2,
3,4,5,6,7, then accurately weigh the ZrO of seven parts of different qualities2, quality be respectively 0.0040g, 0.0030g, 0.0020g,
0.0010g, 0.0004g, 0.0051g and 0.0061g, then which is sequentially added in order in above-mentioned seven small beakers, finally
10mL ethanol is separately added into in seven beakers successively, when heating water bath is to 80 DEG C, beaker is put in water-bath.
Sample is proceeded to after ethanol is evaporated in the crucible of dried and clean and numbered, be subsequently placed in chamber type electric resistance furnace, and
In 550 DEG C of roasting temperature 3h, it is placed in after roasting in mortar and grinds, is then charged into sealing in pouch, seals.
Can be prepared by the ZrO of different quality percentage2- CNB composite photo-catalyst (ZrO2In ZrO2Weight percent in-CNB
Than being respectively 1% (embodiment 1), 0.75% (embodiment 2), 0.5% (embodiment 3), 0.25% (embodiment 4), 0.1% (reality
Apply example 5), 1.25% (embodiment 6), 1.5% (embodiment 7)), be labeled as 1%ZrO2- CNB, 0.75%ZrO2- CNB, 0.5%
ZrO2- CNB, 0.25%ZrO2- CNB, 0.1%ZrO2- CNB, 1.25%ZrO2- CNB, 1.5%ZrO2-CNB.
Comparative example
Comparative example 1
This comparative example specimen in use is obtained CNB in embodiment 1～7.
Comparative example 2
This comparative example specimen in use is ZrO used in embodiment 1～72.
Comparative example 3
Weigh 10.0g urea to be placed in crucible, be put in chamber type electric resistance furnace in 550 after roasting 4h, by product cooling extremely
Room temperature, is placed in grinding 20min in agate mortar, and then, loading sample sack, as graphite phase carbon nitride sample are designated as CN.
Experimental example
The infrared spectrum characterization of 1 sample of experimental example
This experimental example specimen in use is obtained by embodiment 1～7 and comparative example 2.
Infrared spectrum be for measure sample be subject to consecutive variations frequency Infrared irradiation when, molecule absorption some frequency
The radiation of rate, and caused the change of dipole moment by its oscillating movement or bending motion, cause jump of the energy level from ground state to excitation state
Move, so as to form molecular absorption spectrum.
Above-mentioned sample powder on a small quantity is taken, is separately added in potassium bromide powder, then be ground to and be well mixed, be pressed into thin slice, then
Infrared spectrum characterization is carried out to catalyst with FTIS, as a result as shown in figure 1, wherein
Curve a represents ZrO2Infrared spectrogram；
Curve b represents that embodiment 2 is obtained the infrared spectrogram of sample；
Curve c represents that embodiment 3 is obtained the infrared spectrogram of sample；
Curve d represents that embodiment 4 is obtained the infrared spectrogram of sample；
Curve e represents that embodiment 5 is obtained the infrared spectrogram of sample；
Curve f represents that embodiment 1 is obtained the infrared spectrogram of sample；
Curve g represents that embodiment 6 is obtained the infrared spectrogram of sample；
Curve h represents that embodiment 7 is obtained the infrared spectrogram of sample；
Curve i represents the infrared spectrogram of CNB samples.
From curve i in Fig. 1, in 814cm-1The absworption peak of position should belong to the flexural vibrations of triazine ring, 1244cm-1And 1409cm-1Neighbouring absworption peak should belong to the characteristic absorption peak of CNB, 1638cm-1The absworption peak at place should be C=N double bonds
Stretching vibration；
In Fig. 1, curve a understands, in 650cm-1There is ZrO in position2Characteristic absorption peak,
In Fig. 1, curve b～curve h understands that ZrO occurs in composite photo-catalyst obtained in each embodiment2Feature with CNB
Absworption peak, illustrates ZrO2It has been compound on CNB by said method.
The stability analysis of 2 sample of experimental example
This experimental example specimen in use is obtained by embodiment 2.
By above-mentioned photochemical catalyst sample is added to methyl orange solution illumination 6 hours under ultraviolet light, then return
Photochemical catalyst sample is received, repeating carries out ultraviolet degradation methyl orange experiment, is repeated 4 times, and determines above-mentioned photochemical catalyst sample
Photocatalysis stability, as a result as shown in Figure 2.
As shown in Figure 2, the sample is being recycled and reused during 4 times, and its photo-catalysis capability does not occur significant change.
The UV-Vis DRS of 3 sample of experimental example is characterized
This experimental example specimen in use is that embodiment 1～7 and comparative example 1 and 2 are obtained.
Take above-mentioned photochemical catalyst sample (powder) on a small quantity, sample should be pressed fine and close with slide as far as possible, to keep sample
Surface smooth, each catalyst sample is characterized using UV-Vis DRS spectrometer, test wavelength 250-700nm,
As a result as shown in figure 3, wherein,
Curve 1 represents that embodiment 2 is obtained the UV-Vis DRS spectrum of sample；
Curve 2 represents that embodiment 3 is obtained the UV-Vis DRS spectrum of sample；
Curve 3 represents that embodiment 4 is obtained the UV-Vis DRS spectrum of sample；
Curve 4 represents that embodiment 1 is obtained the UV-Vis DRS spectrum of sample；
Curve 5 represents that embodiment 7 is obtained the UV-Vis DRS spectrum of sample；
Curve 6 represents that comparative example 1 is obtained the UV-Vis DRS spectrum of sample.
From the figure 3, it may be seen that ZrO2- CNB types photochemical catalyst can absorb ultraviolet light and visible ray, and simple CNB is almost only
Ultraviolet light can be absorbed.
With ZrO in photochemical catalyst2The increase of load capacity, photochemical catalyst gradually weaken to the absorption of ultraviolet light, and this may
It is because substantial amounts of ZrO2Hamper absorptions of the CNB to ultraviolet light.
Also know that from Fig. 3, ZrO2- CNB types catalyst to the absorbability order of ultraviolet light is：0.75%ZrO2-CNB>
0.5%ZrO2-CNB>0.25%ZrO2-CNB>1.0%ZrO2-CNB>1.5%ZrO2-CNB>CNB.
Also know that from Fig. 3, the size order of photochemical catalyst absworption peak red shift is：0.75%ZrO2-CNB>0.5%ZrO2-
CNB>0.25%ZrO2-CNB>1.0%ZrO2-CNB>1.5%ZrO2-CNB>CNB.
Above-mentioned catalyst is condensed to the absorbability of ultraviolet light and two aspects of degree of red shift occur, further demonstrated that
The ultraviolet catalytic of photochemical catalyst is active to be sequentially：
0.75%ZrO2-CNB>0.5%ZrO2-CNB>0.25%ZrO2-CNB>1.0%ZrO2-CNB>1.5%ZrO2-CNB
>CNB.
The photoluminescence spectra of 4 sample of experimental example is characterized
This experimental example specimen in use is that embodiment 1～7 and comparative example 1 are obtained.
Photoluminescence spectra (PL) is the effective ways for studying semiconductor nano material electronic structure and optical property.Can
Disclose architectural characteristic and the photo-generated carriers (electron-hole pair) such as surface defect and the surface Lacking oxygen of semiconductor nano material
Separation and the information such as compound, so as to being to prepare and the high semiconductor functional material of utility provides strong foundation.
Take above-mentioned catalyst fines respectively to be placed in sample cell on a small quantity, carry out compressing tablet, as far as possible sample should be pressed fine and close,
To keep the smooth of sample surfaces, using the photoluminescence performance of the various catalyst samples of XRF detection, as a result such as Fig. 4
Shown, wherein,
Curve 1 represents the photoluminescence spectra of sample obtained in embodiment 5；
Curve 2 represents the photoluminescence spectra of sample obtained in embodiment 4；
Curve 3 represents the photoluminescence spectra of sample obtained in embodiment 7；
Curve 4 represents the photoluminescence spectra of sample obtained in embodiment 6；
Curve 5 represents the photoluminescence spectra of sample obtained in embodiment 1；
Curve 6 represents the photoluminescence spectra of sample obtained in embodiment 3；
Curve 7 represents the photoluminescence spectra of sample obtained in embodiment 2；
Curve 8 represents the photoluminescence spectra of sample obtained in comparative example 1；
As seen from Figure 4, embodiment and photochemical catalyst sample obtained in comparative example in the range of the wavelength 400-600nm
(powder) all shows not only strong but also wide luminous signal.
For 0.75%ZrO2- CNB catalyst samples (powder), are that signal peak is most in the range of 400-600nm in wavelength
Weak.
The catalysis activity of semiconductor light-catalyst is relevant with the recombination probability of photo-generate electron-hole pair, it is, in general, that PL light
The intensity of spectrum is less, and the recombination probability of photo-generate electron-hole pair is lower, and the catalysis activity of semiconductor light-catalyst is just higher.
In this regard, figure 4, it is seen that the activity order of photochemical catalyst is 0.75%ZrO2- CNB catalyst
Activity is most strong, 0.5%ZrO2- CNB and 1%ZrO2- CNB catalyst activities take second place, CNB catalyst active minimum, this with aforementioned
The catalyst activity order that experiment is measured also is consistent.
The photocatalytic activity of 5 sample of experimental example is determined
This experimental example specimen in use is that embodiment 1～7 and comparative example 1～3 are obtained.
Above-mentioned photocatalyst powder each 0.050g is accurately weighed respectively in quartz ampoule, and numbering is 1～10.Add respectively successively
Enter 40mL concentration for 5.00mg L-1Methyl orange solution, and respectively add a little magneton, quartz ampoule is put into photochemical reaction
In instrument, under continuous stirring, dark reaction processes 30min, and its absorbance A is surveyed in sampling centrifugation respectively0.Lamp power supply is opened, purple is carried out
Outer photo-irradiation treatment 1h, sampling centrifugation, surveys its absorbance A respectivelyt, calculate degradation rate W (%)=(A0-At)/A0 × 100%, root
According to the UV active figure that gained degradation rate draws out different catalysts sample, as a result as shown in figure 5, wherein,
A () illustrates 1%ZrO2The ultraviolet catalytic activity of-CNB；
B () illustrates 0.75%ZrO2The ultraviolet catalytic activity of-CNB；
C () illustrates 0.5%ZrO2The ultraviolet catalytic activity of-CNB；
D () illustrates 0.25%ZrO2The ultraviolet catalytic activity of-CNB；
E () illustrates 0.1%ZrO2The ultraviolet catalytic activity of-CNB；
F () illustrates 1.25%ZrO2The ultraviolet catalytic activity of-CNB；
G () illustrates 1.25%ZrO2The ultraviolet catalytic activity of-CNB；
H () illustrates ZrO2Ultraviolet catalytic activity；
I () illustrates the ultraviolet catalytic activity of CNB.
As shown in Figure 5, ZrO2The degradation rate of-CNB photochemical catalysts is with ZrO2In ZrO2The increase of the weight fraction in-CNB by
Cumulative big, work as ZrO2In ZrO2When weight fraction in-CNB is 0.75%, the degradation rate of photochemical catalyst reaches highest, reaches
82.5%, then its ultraviolet catalytic activity is again with ZrO2In ZrO2Weight fraction in-CNB increases and reduces.
The ZrO being combined as seen from Figure 52The photocatalytic activity of-CNB photochemical catalysts is higher than pure ZrO2, pure CNB or simple
The photocatalytic activity of CN.
The photocatalytic activity of 6 sample of experimental example changes over feature
Specimen in use is that embodiment 1～7 and comparative example 1 are obtained.
Experimental technique is similar to experimental example 5, differ only in first sample time be between 30min, then the time of sub-sampling
It is divided into 20min, i.e. separately sampled when 0min, 30min, 50min, 70min, 90min and 110min, determines its absorbance, as a result
As shown in Figure 6.
Wherein, blank represents blank assay, i.e. be added without any photochemical catalyst in test system；
It will be appreciated from fig. 6 that photocatalyst activity order is:0.75%ZrO2-CNB>0.5%ZrO2-CNB>1%ZrO2-CNB>
1.25%ZrO2-CNB>1.5%ZrO2-CNB>0.25%ZrO2-CNB>0.1%ZrO2-CNB>CNB>blank.
Impact of 7 scavenger of experimental example to sample photocatalytic activity
This experimental example specimen in use is obtained by embodiment 2.
Accurately weigh the above-mentioned photocatalyst powder of five parts of 0.050g to be respectively placed in 5 quartz ampoules, numbering 1,2,3,4,5,
40mL concentration is separately added into successively for 10.00mg L-1Methyl orange solution.
Any scavenger is added without in No. 1 pipe, is designated as no,
5.000 μ L isopropanols are added in No. 2 pipes, are designated as IPA,
0.004g ammonium oxalate is added in No. 3 pipes, AO is designated as,
0.004g 1,4-benzoquinone is added in No. 4 pipes, BQ is designated as,
3.800 μ L catalases are added in No. 5 pipes, are designated as CAT,
A little magneton is added in each test tube.Quartz ampoule is put in photochemical reaction instrument, under continuous stirring, dark place
Reason 30min, sampling centrifugation, surveys its absorbance A respectively0.Light source is opened, ultraviolet lighting processes 1h, and its absorbance is surveyed in sampling centrifugation
At, calculate degradation rate W (%)=(A0-At)/A0× 100%, drafting pattern, as a result as shown in Figure 7.
This experiment studies 0.75%ZrO with methyl orange as model compound by introducing various free radical scavengers2-
The photocatalysis mechanism of CNB photochemical catalysts.
Add isopropanol (IPA) and play a part of OH generations in inhibition system degradation process, add ammonium oxalate (AO) and rise
The h in inhibition system degradation process+The effect of generation, adds 1,4-benzoquinone (BQ) and plays O in inhibition system degradation process2-Produce
Effect, add catalase (CAT) play H in inhibition system degradation process2O2The effect of generation.
As seen from Figure 7, in the case where other conditions are constant：
(1) compared with without scavenger, after adding scavenger, the activity of catalyst decreases；
(2) in the case of other conditions identical, the addition of ammonium oxalate (AO) is to the active shadow of catalyst ultraviolet catalytic
Maximum is rung, illustrates that OH is topmost active specy during photo-catalytic degradation of methyl-orange under ultraviolet light；
(3), after adding ammonium oxalate (AO), isopropanol (IPA), the activity of catalyst has more obvious reduction, ammonium oxalate
(AO) addition causes the activity of catalyst to drop minimum.That is h+, OH play substantially work in Photocatalytic Degradation Process
With especially h+Play main effect in photocatalytic process.
The present invention is described in detail above in association with specific embodiment and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Multiple equivalencings, modification or improvement can be carried out to technical solution of the present invention and embodiments thereof, these each fall within the present invention
In the range of.Protection scope of the present invention is defined by claims.
Claims (10)
1. a kind of photochemical catalyst of doped metallic oxide, it is characterised in that the photochemical catalyst is by metal oxide and non-gold
The carbonitride of category element doping is composited.
2. photochemical catalyst according to claim 1, it is characterised in that
The metal oxide is transition metal oxide, preferably Second Transition oxide, is more preferably selected from aoxidizing
One kind in yttrium, zirconium oxide, niobium oxide, molybdenum oxide, technetium oxide, ruthenium-oxide, rhodium oxide, palladium oxide, silver oxide and cadmium oxide or
Multiple, further preferably in yittrium oxide, zirconium oxide, palladium oxide and cadmium oxide one or more, such as zirconium oxide；And/or
The nonmetalloid in photochemical catalyst is doped in selected from boron, sulphur, phosphorus, fluorine etc., preferably boron；And/or
The photochemical catalyst of the doped metallic oxide, wherein, the graphite phase carbon nitride of metal oxide and nonmetal doping
Weight ratio is 0.1:100～20:100, preferably 0.2:100～1.5:100, such as 0.25:100、0.5:100、0.75:100、
1.25:100.
3. photochemical catalyst according to claim 1 and 2, it is characterised in that in the light for preparing the doped metallic oxide
During catalyst, the weight of the weight ratio of itrogenous organic substance and the compound containing nonmetalloid for itrogenous organic substance:Containing non-
The weight of the compound of metallic element=(1.0～20.0) g:(0.5～50.0) mg, preferably (3.0～18.0) g:(1.0～
45.0) mg, more preferably (5.0～15.0) g:(1.5～40.0) mg, more preferably (8.0～12.0) g:(2.0～
35.0) mg, much further preferably from (9.0～11.0) g:(2.0～30.0) mg, such as 10.0g:6mg；And/or
According to its infrared spectrum, it is 814cm in wave number-1、1244cm-1、1409cm-1、1638cm-1And 650cm-1Position is present inhales
Receive peak.
4. a kind of method of the photochemical catalyst of the doped metallic oxide prepared described in one of claims 1 to 3, its feature exist
In the method is comprised the following steps：
Step 1, prepares the graphite phase carbon nitride of nonmetal doping；
Step 2, the graphite phase carbon nitride of nonmetal doping obtained in step 1 and metal oxide are combined.
5. method according to claim 4, it is characterised in that step 1 includes following sub-step：
Sub-step 1-1, the compound containing nonmetalloid is scattered in the first dispersant, then is added in system and nitrogenous had
Machine thing, removes the first dispersant after being well mixed；
Sub-step 1-2, the system that sub-step 1-1 is obtained is calcined, and optionally, is crushed after firing；And/or
Step 2 includes following sub-step：
Sub-step 2-1, the graphite phase carbon nitride of nonmetal doping obtained in step 1 is mixed with metal oxide, adds second
Dispersant is disperseed, and removes the second dispersant after dispersion fully；
Sub-step 2-2, the system that sub-step 2-1 is obtained is calcined, and optionally, calcined product is carried out cooling down, crushed.
6. the method according to claim 4 or 5, it is characterised in that the itrogenous organic substance is referred to while containing nitrogen
And the small organic molecule of carbon, preferably carbon-nitrogen ratio is 1:3～3:The itrogenous organic substance of 1 small-molecular-weight, more carbon-nitrogen ratio
For 1:2 small-molecular-weight itrogenous organic substance, especially preferably cyanamide, dicyanodiamine, melamine, urea, guanidine hydrochloride etc., excellent
Elect urea as；And/or
The nonmetalloid in graphite phase carbon nitride is doped in selected from boron, sulphur, phosphorus, fluorine etc., preferably boron；And/or
Compound containing nonmetalloid selected from the corresponding oxide of the nonmetalloid, containing the nonmetalloid acid or
Person contains the salt of the metallic element.
7. the method according to one of claim 4～6, it is characterised in that in sub-step 1-1,
Weight of the weight ratio of itrogenous organic substance and the compound containing nonmetalloid for itrogenous organic substance:Containing nonmetallic unit
Weight=(1.0～20.0) g of the compound of element:(0.5～50.0) mg, preferably (3.0～18.0) g:(1.0～45.0)
Mg, more preferably (5.0～15.0) g:(1.5～40.0) mg, more preferably (8.0～12.0) g:(2.0～35.0) mg,
Much further preferably from (9.0～11.0) g:(2.0～30.0) mg, such as 10.0g:6mg；And/or
First dispersant preferably uses pure water, deionized water and/or distilled water, preferably distilled water；And/or
In sub-step 1-2,
Calcining heat is 400 DEG C～800 DEG C, more preferably 450 DEG C～600 DEG C, such as 550 DEG C；And/or
Calcination time is 1～5 hour, preferably 1.5～4 hours, more preferably 2～3.5 hours, such as 2 hours.
8. the method according to one of claim 4～7, it is characterised in that in sub-step 2-1,
The metal oxide is transition metal oxide, preferably Second Transition oxide, is more preferably selected from aoxidizing
One kind in yttrium, zirconium oxide, niobium oxide, molybdenum oxide, technetium oxide, ruthenium-oxide, rhodium oxide, palladium oxide, silver oxide and cadmium oxide or
Multiple, further preferably in yittrium oxide, zirconium oxide, palladium oxide and cadmium oxide one or more, such as zirconium oxide；And/or
The metal oxide is nanosize metal oxide particulate, and such as particle diameter is the metal oxide of 1～100nm；And/or
The metal oxide preferable particle size is the nano zircite particle of 1～100nm；And/or
Metal oxide is 0.1 with the weight ratio of the graphite phase carbon nitride of nonmetal doping obtained in step 1:100～20:
100, preferably 0.2:100～1.5:100, such as 0.25:100、0.5:100、0.75:100、1.25:100.
9. the method according to one of claim 4～8, it is characterised in that in sub-step 2-2,
Second dispersant is organic solvent, preferably methyl alcohol, ethanol, dichloromethane, chloroform etc., more preferably first
Alcohol, ethanol, more preferably ethanol, such as absolute ethyl alcohol；And/or
Calcining heat is 450 DEG C～700 DEG C, more preferably 400 DEG C～600 DEG C, such as 550 DEG C；And/or
Calcination time is 1～5 hour, and preferably this is 1.5～4 hours, more preferably 2～3.5 hours, such as 3 hours.
10. the method according to one of claim 4～9, it is characterised in that doped metallic oxide obtained in step 2
Photochemical catalyst,
According to its infrared spectrum, it is 814cm in wave number-1、1244cm-1、1409cm-1、1638cm-1And 650cm-1Position is present inhales
Receive peak；And/or
Wherein, metal oxide is 0.1 with the weight ratio of the graphite phase carbon nitride of nonmetal doping:100～20:100, preferably
0.2:100～1.5:100, such as 0.25:100、0.5:100、0.75:100、1.25:100；And/or
Wherein, weight of the weight ratio of itrogenous organic substance and the compound containing nonmetalloid for itrogenous organic substance:Containing non-
The weight of the compound of metallic element=(1.0～20.0) g:(0.5～50.0) mg, preferably (3.0～18.0) g:(1.0～
45.0) mg, more preferably (5.0～15.0) g:(1.5～40.0) mg, more preferably (8.0～12.0) g:(2.0～
35.0) mg, much further preferably from (9.0～11.0) g:(2.0～30.0) mg, such as 10.0g:6mg；And/or
Which can reach 82.5% to the degradation rate of methyl orange after ultraviolet light 1 hour.
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