CN105561975A - Preparation method of nanometer mesoporous SiO2/TiO2 photocatalytic composite material doped with metal ions - Google Patents
Preparation method of nanometer mesoporous SiO2/TiO2 photocatalytic composite material doped with metal ions Download PDFInfo
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- CN105561975A CN105561975A CN201610056111.3A CN201610056111A CN105561975A CN 105561975 A CN105561975 A CN 105561975A CN 201610056111 A CN201610056111 A CN 201610056111A CN 105561975 A CN105561975 A CN 105561975A
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- titanium
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract description 62
- 239000000377 silicon dioxide Substances 0.000 title abstract description 31
- 230000001699 photocatalysis Effects 0.000 title abstract description 8
- 229910052681 coesite Inorganic materials 0.000 title abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 title abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 title abstract 2
- 229910052682 stishovite Inorganic materials 0.000 title abstract 2
- 229910052905 tridymite Inorganic materials 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 55
- 239000011941 photocatalyst Substances 0.000 claims description 40
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 229910052750 molybdenum Inorganic materials 0.000 claims description 22
- 239000011733 molybdenum Substances 0.000 claims description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 20
- -1 silane compound Chemical class 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 9
- 239000011609 ammonium molybdate Substances 0.000 claims description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-O azanium;hydron;hydroxide Chemical compound [NH4+].O VHUUQVKOLVNVRT-UHFFFAOYSA-O 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical class CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000003916 acid precipitation Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 230000002421 anti-septic effect Effects 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- JEZFASCUIZYYEV-UHFFFAOYSA-N chloro(triethoxy)silane Chemical compound CCO[Si](Cl)(OCC)OCC JEZFASCUIZYYEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- SOBXOQKKUVQETK-UHFFFAOYSA-H titanium(3+);trisulfate Chemical compound [Ti+3].[Ti+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O SOBXOQKKUVQETK-UHFFFAOYSA-H 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- GDXTWKJNMJAERW-UHFFFAOYSA-J molybdenum(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mo+4] GDXTWKJNMJAERW-UHFFFAOYSA-J 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000001239 high-resolution electron microscopy Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005314 correlation function Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C09D7/61—Additives non-macromolecular inorganic
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Abstract
The invention relates to a preparation method of a nanometer mesoporous SiO2/TiO2 photocatalytic composite material doped with metal ions. The method is simple in procedure, high in operability, low in cost and suitable for batched preparation and has industrial production probability and wide application prospects. In addition, the method has another important advantage that due to the fact that the whole reaction system only uses water as solvent without using other organic solvent such as alcohol, the pollution to the environment is effectively reduced and the safety of production links is improved.
Description
Technical field
The invention belongs to inorganic, metal oxide preparation field, particularly the mesoporous nano SiO of doped metal ion
2-TiO
2the preparation method of composite photocatalyst material.
Background technology
Nano-TiO
2as functional inorganic material, be with a wide range of applications at numerous areas such as coating, opto-electronic conversion, catalysis, function ceramics, anti-biotic materials, its synthesis and application study are the emphasis of correlation function Material Field research always.This wherein, be a kind of emerging green technology effectively removing chemical pollutant using nano-titanium oxide as the Photocatalitic Technique of Semiconductor of photochemical catalyst, it can accelerate the degradation process of oxynitrides and sulfide.Namely the hole utilizing solid semiconductor catalysis material to produce by optical excitation, captures NO
xelectronics in system, makes it activate and be oxidized to NO
3 -stay catalyst surface, thus the NO of solidification haze
xsource.At road traffic space application photocatalytic degradation material, modification is carried out as utilized catalysis material road pavement material, or produce coating by catalysis material, what can make road paint, road equipment material possesses harmful substance in degrading tail gas, reducing tail gas to the pollution effects of air, is the effective ways of the end treatment of moving source tail gas clean-up.
Research shows, at TiO
2a small amount of metal ion is mixed in lattice, can at TiO
2surface produces defect, and what this defect became light induced electron and hole catches trap, can effectively reduce light induced electron and hole-recombination, improve photo-generated carrier efficiency.In addition, because doped metal ion can at TiO
2the doped energy-band that between valence band and conduction band, formation one is new, reduces TiO
2energy gap, and then strengthen the visible light activity of catalyst.
But conductor photocatalysis is by NO
xbe oxidized to NO
3 -reaction, through many intermediate steps, have some harmful intermediate products and generate, the NO as part is oxidized to NO
2, and be released, this is harmful to environment, can promote the formation of photochemical fog.And photocatalysis technology and adsorption technology are combined, be the primary solutions addressed this problem.High-absorption material is to NO and NO
2absorption, makes the NO generated through Photocatalytic Oxidation With Semiconductors NO
2namely also NO is oxidized to further by absorption in the moment produced
3 -, thus avoid intermediate product NO
2release.
At present, for mainly comprising the material such as active carbon, molecular sieve with the high adsorption material of nano-titanium oxide compound, but absorbent charcoal material is due to light tight, lower to the utilization rate of load catalysis material.And adopt molecular sieve as carrier, there is cost higher, back loading technique is easy to the problem of blocking pipe simultaneously.Therefore, the high-performance nano silica-titania composite photocatalyst material of direct synthesizing blender metal ion has important Research Significance.At present, associated materials synthetic method generally adopts respectively synthetic silica and titania meterial, then the technique of compound, and step is numerous and diverse, and there is subsequent oxidation silicon and titanium oxide cannot the problem of effective compound.Its main cause is, titanium oxide crystallization needs high temperature sintering usually, and silica generally can in liquid phase direct hydrolysis, and therefore, liquid phase is directly synthesized composite construction and had difficulties.
Summary of the invention
According to an aspect of the present invention, one object of the present invention is to provide a kind of simple and easy to control, respond well, is suitable for the mesoporous nano SiO preparing doped metal ion of large-scale industrial production
2-TiO
2the method of composite photocatalyst material.
In order to realize above-mentioned purpose of the present invention, the mesoporous nano SiO of doped metal ion of the present invention
2-TiO
2the preparation method of composite photocatalyst material comprises the following steps:
1) controlled hydrolysis prepares the ortho-titanic acid precipitation of doped metal ion
Using Ti-inorganic salt and the metal inorganic salt as adulterant jointly soluble in water, form mixed solution, wherein the molar ratio of doped metal ion and titanium ion is 0.002: 1 to 0.3: 1, and by the Ti in mixed solution
4+ion concentration is adjusted to 0.01 ~ 0.50mol/L; Joined in described mixed solution by inorganic base, the pH value making mixed solution is 5 ~ 11, obtains the co-precipitation of metal hydroxides and ortho-titanic acid, the precipitation obtained purified process removing impurity.
2) hydrogen peroxide-ammino-complex preparation
Hydrogenperoxide steam generator dispersion steps 1 with mass percentage concentration is 10% to 60%) metal hydroxides that obtains becomes solution state with the co-precipitation of ortho-titanic acid, wherein H
2o
2control 1 to 25 with total molecule mol ratio of metal ion and Ti; In obtained titanium peroxide solution, add ammonium hydrate, form metal/titanium-peroxidating-ammonia Compound complex solution, wherein NH
4 +control 1 to 25 with total molecule mol ratio of metal ion and Ti.
3) the mesoporous nano SiO of doped metal ion is prepared
2-TiO
2composite photocatalyst material
It is 0 ~ 100 DEG C in reaction temperature, preferably 10 ~ 90 DEG C, under being more preferably 60 ~ 80 DEG C of stirrings, to step 2) add organic silane compound in metal/titanium-peroxidating-ammonia Compound complex solution of preparing and react, wherein, the volume ratio of organic silane compound and metal/titanium-peroxidating-ammonia Compound complex solution is 10: 1 to 1: 10, heat time controls between 0.5 hour to 12 hours, between being preferably 1 hour to 8 hours, be more preferably between 3 hours to 6 hours, after having reacted, through filtering, washing, drying waits post-processing step, obtain the mesoporous nano SiO of doped metal ion
2-TiO
2composite photocatalyst material.
Wherein, step 1) in titanium liquid in Ti
4+ion concentration is for being preferably 0.1 ~ 0.3mol/L, more preferably 0.2 ~ 0.3mol/L.Described inorganic base is selected from least one in the group of sodium carbonate, sodium acid carbonate, potash, saleratus, NaOH, potassium hydroxide, ammoniacal liquor alkali electroless reagent place composition, is preferably NaOH, potassium hydroxide or ammoniacal liquor.
The described metal inorganic salt as adulterant is the inorganic salts such as ammonium salt being selected from the hydrochloride of d0 race metal, sulfate, nitrate, metal, is preferably the ammonium salt of hydrochloride or metal, most preferably is ammonium molybdate; Described d0 race metal can one or more for being selected from chromium (Cr), molybdenum (Mo), tungsten (W), vanadium (V), niobium (Nb), tantalum (Ta), be preferably in chromium (Cr), molybdenum (Mo), tungsten (W) and vanadium (V) one or more, more preferably molybdenum (Mo), tungsten (W) or vanadium (V), most preferably be molybdenum (Mo).
Step 1) in Ti-inorganic salt can be ilmenite, metatitanic acid compounds, titanium tetrachloride, titanium sulfate, titanium sesquisulfate or titanyl sulfate etc., be preferably titanium tetrachloride or titanyl sulfate.Described purge process can by method removing impurity such as frozen recrystallizations.
Step 2) in the mass percentage concentration of hydrogenperoxide steam generator be preferably 20% to 40%, be more preferably 30%; H
2o
2preferably control 1 to 25 with total molecule mol ratio of metal ion and Ti, be preferably 5 to 10; The mass percentage concentration of described ammonium hydrate is 0.1% to 10%, is preferably 1% to 6%, is more preferably 2% to 8%.NH
4 +preferably control 5 to 20 with total molecule mol ratio of metal ion and Ti.Described ammonium hydrate is preferably ammoniacal liquor, ammonium chloride etc.
Step 3) in described organic silane compound structure be RR
1r
2r
3si; Wherein: R is C
1~ C
18oxyalkyl chain, R
1, R
2, R
3independently be selected from C
1~ C
18one in oxyalkyl chain, chlorine, amino, sulfonic group, wherein said C
1~ C
18oxyalkyl chain is preferably C
2~ C
8oxyalkyl chain, is more preferably C
3~ C
6oxyalkyl chain, more specifically, described organic silane compound can be four own TMOSs, four butoxy silanes, triethoxy chloro silane etc.
According to an aspect of the present invention, one object of the present invention is the mesoporous nano SiO providing a kind of high activity doped metal ion
2-TiO
2composite photocatalyst material, described composite photocatalyst material is prepared by above method.
According to an aspect of the present invention, one object of the present invention is to provide a kind of coating, described in comprise mesoporous nano SiO according to doped metal ion of the present invention
2-TiO
2composite photocatalyst material, and other conventional paint ingredient, such as resin, antiseptic, levelling agent, pigment etc., as long as described conventional paint ingredient can not to the mesoporous nano SiO of described doped metal ion
2-TiO
2the catalytic performance of composite photocatalyst material causes adverse effect.Coating according to the present invention can adopt the modes such as spraying, roller coating, brushing directly to apply in addition.
Beneficial effect
The present invention is compared with the preparation method of bibliographical information, and method flow of the present invention is simple, workable, simultaneously less expensive, is applicable to batch preparation, possesses the possibility of suitability for industrialized production, be with a wide range of applications.Another considerable advantage of the present invention is that whole reaction system all only uses water as solvent in addition, and not with an organic solvent, such as alcohol etc., thus efficiently reduce the pollution to environment, improve the security of production link.
Accompanying drawing explanation
Fig. 1 a is the transmission electron microscope photo of nano meso-porous titanium dioxide/silica composite photocatalyst material of the doped metal ion prepared according to the embodiment of the present invention 1.
Fig. 1 b is the high resolution electron microscopy photo of nano meso-porous titanium dioxide/silica composite photocatalyst material of the doped metal ion prepared according to the embodiment of the present invention 1.
Fig. 2 is the X-ray diffraction spectrogram according to the nano meso-porous titanium dioxide/silica composite photocatalyst material of the doping molybdenum metal ion of embodiment 1 preparation and the nano meso-porous titanium dioxide/silica composite photocatalyst material according to the non-doping molybdenum metal ion of comparative example 1 preparation.
Fig. 3 is the UV-vis DRS spectrum according to the nano meso-porous titanium dioxide/silica composite photocatalyst material of the doping molybdenum metal ion of embodiment 1 preparation and the nano meso-porous titanium dioxide/silica composite photocatalyst material according to the non-doping molybdenum metal ion of comparative example 1 preparation.
Fig. 4 is the photocatalysis result according to embodiment 1 and the doping molybdenum metal ion of comparative example 1 preparation and the nano meso-porous titanium dioxide/silica composite photocatalyst material of non-doping molybdenum metal ion.
Detailed description of the invention
The present invention mainly utilizes the water-based complex formed by compound and the ammonia complexing of water-soluble titanium peroxide precursor and metal ion, catalysis organic silane compound forms silica with great specific surface area at titanium peroxide and the hydrolysis of peroxidating metal surface, further heat treatment makes titanium per-compound and peroxidating metal crystallization subsequently, thus forms the mesoporous nano SiO of high activity doped metal ion based on one kettle way technique
2-TiO
2composite photocatalyst material.
Coating according to the present invention may be used for the substrate surfaces such as outdoor and indoor wall, ground, brick face and strong adhesion.Such as can by coatings according to the present invention on the surface of floor tile, for outdoor road surfacing; Or after freeway guardrail dope lacquerer sequence completes, described coating is directly coated on skin of paint, thus realizes the NO to air middle and high concentration
xdecompose.And also can directly be coated on the surface of external wall according to coating of the present invention, effectively realize pollutants in air (NO
x, SOx, VOCs etc.) degraded and the absorption of the small particles of pollution thing such as PM2.5.
Following examples are only enumerate as the example of embodiment of the present invention, do not form any restriction to the present invention, it will be appreciated by those skilled in the art that the amendment in the scope not departing from essence of the present invention and design all falls into protection scope of the present invention.
Hereinafter, describe in detail with reference to the accompanying drawings preferred embodiment of the present disclosure.Before described, the term used in description and claims should be understood, and should not be construed as and be confined to general and dictionary meaning, but the principle of term suitably should be defined based on allowing the artificially best explanation of invention, make an explanation based on the meaning and concept corresponding to the technology of the present invention aspect.Therefore, at this description only preferred embodiment for the purpose of illustration, and be not mean to limit the scope of the invention, it is therefore to be understood that, can be made other equivalently to implement and amendment under without departing from the spirit and scope of the present invention.
Embodiment 1
First use 500ml deionized water dissolving 100g titanyl sulfate and 0.5g ammonium molybdate, obtain the mixed aqueous solution of titanyl sulfate and ammonium molybdate; By mass concentration be 36% ammonia water titration mixed aqueous solution be 9 be precipitated thing to PH, spend deionized water 3 times, obtain molybdenum hydroxide and ortho-titanic acid mixture.The molybdenum hydroxide obtained with the aqueous hydrogen peroxide solution dissolving 5g that 5ml mass percentage concentration is 30% and ortho-titanic acid mixture, thus obtain the aqueous solution of the titanium peroxide of doping metals molybdenum, then regulate the pH of the titanium peroxide aqueous solution of above-mentioned doping metals molybdenum to be about 10 with the ammoniacal liquor that mass percentage concentration is 2.5%; At temperature is 80 DEG C, add the four own TMOSs that 5ml mass percentage concentration is 28%, mechanical agitation back flow reaction 4 hours, after having reacted, product is through filtering, washing, and the process such as drying obtain the nano meso-porous titanium dioxide/silica composite photocatalyst material of doped metal ion.
Comparative example 1
Except not adding the ammonium molybdate as adulterant, prepare the nano meso-porous titanium dioxide/silica composite photocatalyst material of non-doped metal ion according to the mode that embodiment 1 is identical.
Fig. 1 a is the transmission electron microscope photo of nano meso-porous titanium dioxide/silica composite photocatalyst material of the doping molybdenum metal ion prepared according to embodiment 1, and Fig. 1 b is the high resolution electron microscopy photo of the nano meso-porous titanium dioxide/silica composite photocatalyst material of the doping molybdenum metal ion prepared according to embodiment 1.As can be seen from Fig. 1 a, the titania/silica particle of prepared doping molybdenum ion has good dispersiveness, particle size is about 25nm, as can be seen from the high resolution electron microscopy photo of Fig. 1 b, prepared sample has obvious lattice fringe, illustrates that prepared sample has good crystal formation.
Fig. 2 is the X-ray diffraction spectrogram according to the nano meso-porous titanium dioxide/silica composite photocatalyst material of the doping molybdenum metal ion of embodiment 1 preparation and the nano meso-porous titanium dioxide/silica composite photocatalyst material according to the non-doping molybdenum metal ion of comparative example 1 preparation.As can be seen from the figure, non-doping molybdenum metal ion titania/silica composite and be doped with molybdenum titania/silica composite in TiO
2all remain Anatase, do not occur other assorted peak, this illustrates that the molybdenum example of doping does not change the crystalline structure of sample.
Fig. 3 is the UV-vis DRS spectrum according to the nano meso-porous titanium dioxide/silica composite photocatalyst material of the doping molybdenum metal ion of embodiment 1 preparation and the nano meso-porous titanium dioxide/silica composite photocatalyst material according to the non-doping molybdenum metal ion of comparative example 1 preparation.Can find out that the absorption region of not titania-doped/silica to light is at 200 to 400nm, mainly concentrates on UV light region, does not almost absorb the visible ray being greater than 400nm.And doping molybdenum metal ion can make photochemical catalyst absorption band edge there occurs obvious red shift, and be improved significantly in visible region (400 to 800nm) absorption intensity.This shows that the nano meso-porous titanium dioxide/silica composite photocatalyst material of doping molybdenum metal ion may have certain photocatalytic activity under visible light illumination.
Embodiment 2
With 500ml deionized water dissolving 100g titanyl sulfate and 0.5g ammonium molybdate, obtain the mixed aqueous solution of titanyl sulfate and ammonium molybdate; The mixed aqueous solution obtained by the ammonia water titration that mass concentration is 36% is 9 be precipitated thing to PH, spends deionized water 3 times, obtains molybdenum hydroxide and ortho-titanic acid mixture.The molybdenum hydroxide obtained with the aqueous hydrogen peroxide solution dissolving 10g that 10ml mass percentage concentration is 30% and ortho-titanic acid mixture, thus obtain the aqueous solution of the titanium peroxide of doping metals molybdenum, regulate the pH of the titanium peroxide aqueous solution of above-mentioned doping metals molybdenum to be about 5 with the ammoniacal liquor that mass percentage concentration is 2.5%; At temperature is 50 DEG C, add four butoxy silanes that 5ml mass percentage concentration is 28%, mechanical agitation back flow reaction 12 hours, after having reacted, product is through filtering, washing, and the process such as drying obtain the nano meso-porous titanium dioxide/silica composite photocatalyst material being doped with molybdenum ion.
Embodiment 3
With 500ml deionized water dissolving 100g titanyl sulfate and 0.5g ammonium molybdate, obtain the mixed aqueous solution of titanyl sulfate and ammonium molybdate; By mass concentration be 36% ammonia water titration mixed aqueous solution be 9 be precipitated thing to PH, spend deionized water 3 times, obtain molybdenum hydroxide and ortho-titanic acid mixture.The molybdenum hydroxide obtained with the aqueous hydrogen peroxide solution dissolving 5g that 5ml mass percentage concentration is 30% and ortho-titanic acid mixture, thus obtain the aqueous solution of the titanium peroxide of doping metals molybdenum, regulate the pH of the titanium peroxide aqueous solution of above-mentioned doping metals molybdenum to be about 7 with the ammoniacal liquor that mass percentage concentration is 2.5%; At temperature is 100 DEG C, add four TMOSs that 5ml mass percentage concentration is 28%, mechanical agitation back flow reaction 4 hours, after having reacted, product is through filtering, washing, and the process such as drying obtain the nano meso-porous titanium dioxide/silica composite photocatalyst material being doped with molybdenum ion.
EXPERIMENTAL EXAMPLE: NO
xdegradation experiment
The composite titania/silica photocatalyst material being doped with molybdenum ion obtained is carried out NO
xdegradation experiment, described experiment is carried out as follows:
Respectively by according to embodiment 1 and the composite titania/silica photocatalyst Material coating being doped with molybdenum ion and not being doped with molybdenum ion prepared according to comparative example 1 on the glass plate of 10cm × 20cm, the consumption of described composite photocatalyst material is 0.5g, then with 2 μ w/cm
2white light light intensity when irradiating, flow through this glass plate with the air-flow of NO containing 1ppm, gas flow rate is 800ml/min.In addition, select the situation not applying catalytic treatment to test as blank, do same experiment as a comparison.Result is shown in the diagram.
As can be seen from the result of Fig. 4, when not using catalyst, the NO in gas
xsubstantially without degraded.Under white light conditions, the photocatalytic activity of the titania/silica catalysis material of non-doping molybdenum metal ion is lower, it is 15% to the conversion ratio of NO, and under the same conditions, the composite titania/silica photocatalyst material of doping molybdenum metal ion is 60% to the conversion ratio of NO.
Claims (10)
1. the mesoporous nano SiO of a doped metal ion
2-TiO
2the preparation method of composite photocatalyst material, it comprises the following steps:
1) controlled hydrolysis prepares the ortho-titanic acid precipitation of doped metal ion
Using Ti-inorganic salt and the metal inorganic salt as adulterant jointly soluble in water, form mixed solution, wherein the molar ratio of doped metal ion and titanium ion is 0.002: 1 to 0.3: 1, and by the Ti in mixed solution
4+ion concentration is adjusted to 0.01 ~ 0.50mol/L; Joined in described mixed solution by inorganic base, the pH value making mixed solution is 5 ~ 11, obtains the co-precipitation of metal hydroxides and ortho-titanic acid, the precipitation obtained purified process removing impurity;
2) hydrogen peroxide-ammino-complex preparation
Hydrogenperoxide steam generator dispersion steps 1 with mass percentage concentration is 10% to 60%) metal hydroxides that obtains becomes solution state with the co-precipitation of ortho-titanic acid, wherein H
2o
2control 1 to 25 with total molecule mol ratio of metal ion and Ti, in obtained titanium peroxide solution, add ammonium hydrate, form metal/titanium-peroxidating-ammonia Compound complex solution, wherein NH
4 +control 1 to 25 with total molecule mol ratio of metal ion and Ti;
3) the mesoporous nano SiO of doped metal ion is prepared
2-TiO
2composite photocatalyst material
It is 0 ~ 100 DEG C in reaction temperature, preferably 10 ~ 90 DEG C, under being more preferably 60 ~ 80 DEG C of stirrings, to step 2) add organic silane compound in metal/titanium-peroxidating-ammonia Compound complex solution of preparing and react, wherein, the volume ratio of organic silane compound and metal/titanium-peroxidating-ammonia Compound complex solution is 10: 1 to 1: 10, heat time controls between 0.5 hour to 12 hours, between being preferably 1 hour to 8 hours, be more preferably between 3 hours to 6 hours, after having reacted, through filtering, washing, drying waits post-processing step, obtain the mesoporous nano SiO of doped metal ion
2-TiO
2composite photocatalyst material.
2. preparation method according to claim 1, is characterized in that, step 1) in titanium liquid in Ti
4+ion concentration is for being preferably 0.1 ~ 0.3mol/L, more preferably 0.2 ~ 0.3mol/L.
3. preparation method according to claim 1, it is characterized in that, step 1) described in inorganic base be selected from sodium carbonate, sodium acid carbonate, potash, saleratus, NaOH, potassium hydroxide, ammoniacal liquor alkali electroless reagent place composition group at least one, be preferably NaOH, potassium hydroxide or ammoniacal liquor.
4. preparation method according to claim 1, it is characterized in that, the described metal inorganic salt as adulterant is the inorganic salts such as ammonium salt being selected from the hydrochloride of d0 race metal, sulfate, nitrate, metal, is preferably the ammonium salt of hydrochloride or metal, most preferably is ammonium molybdate; Described d0 race metal can one or more for being selected from chromium (Cr), molybdenum (Mo), tungsten (W), vanadium (V), niobium (Nb), tantalum (Ta), be preferably in chromium (Cr), molybdenum (Mo), tungsten (W) and vanadium (V) one or more, more preferably molybdenum (Mo), tungsten (W) or vanadium (V), most preferably be molybdenum (Mo).
5. preparation method according to claim 1, is characterized in that, step 1) in Ti-inorganic salt can be ilmenite, metatitanic acid compounds, titanium tetrachloride, titanium sulfate, titanium sesquisulfate or titanyl sulfate etc., be preferably titanium tetrachloride or titanyl sulfate.Described purge process can by method removing impurity such as frozen recrystallizations.
6. preparation method according to claim 1, is characterized in that, step 2) in the mass percentage concentration of described hydrogenperoxide steam generator be preferably 20% to 40%, be more preferably 30%; H
2o
2preferably control 1 to 25 with total molecule mol ratio of metal ion and Ti, be preferably 5 to 10; The mass percentage concentration of described ammonium hydrate is 0.1% to 10%, is preferably 1% to 6%, is more preferably 2% to 8%.NH
4 +preferably control 5 to 20 with total molecule mol ratio of metal ion and Ti: described ammonium hydrate is preferably ammoniacal liquor, ammonium chloride etc.
7. preparation method according to claim 1, is characterized in that, step 3) in described organic silane compound structure be RR
1r
2r
3si; Wherein: R is C
1~ C
18oxyalkyl chain, R
1, R
2, R
3independently be selected from C
1~ C
18one in oxyalkyl chain, chlorine, amino, sulfonic group, wherein said C
1~ C
18oxyalkyl chain is preferably C
2~ C
8oxyalkyl chain, is more preferably C
3~ C
6oxyalkyl chain, more specifically, described organic silane compound can be four own TMOSs, four butoxy silanes, triethoxy chloro silane etc.
8. the mesoporous nano SiO of a doped metal ion
2-TiO
2composite photocatalyst material, described composite photocatalyst material is prepared by the method in claim 1 to 7 described in any one.
9. a coating, it comprises the mesoporous nano SiO of doped metal ion according to claim 8
2-TiO
2composite photocatalyst material, and other conventional paint ingredient.
10. coating according to claim 9, is characterized in that, described conventional paint ingredient comprises resin, antiseptic, levelling agent and/or pigment.
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| CN106564904A (en) * | 2016-11-07 | 2017-04-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Tungsten-doped nanometer silicon dioxide and preparation method thereof |
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| CN108273487A (en) * | 2018-02-09 | 2018-07-13 | 纳琦环保科技有限公司 | The preparation method of titanium oxide/calcium oxide/silica composite photocatalyst material of hollow structure |
| CN110366444A (en) * | 2018-02-09 | 2019-10-22 | 纳琦环保科技有限公司 | A kind of synthetic method of the composite photocatalyst material with photo-thermal synergistic effect |
| CN110366444B (en) * | 2018-02-09 | 2022-04-26 | 纳琦环保科技有限公司 | Synthetic method of composite photocatalytic material with photo-thermal synergistic effect |
| CN113083342A (en) * | 2021-02-25 | 2021-07-09 | 深圳市环保科技集团有限公司 | Composite photocatalyst, preparation method and application thereof |
| CN113083342B (en) * | 2021-02-25 | 2023-09-05 | 深圳市环保科技集团股份有限公司 | Composite photocatalyst, preparation method and application thereof |
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