CN108295897B - A kind of compounded visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2And organic matter degradation application - Google Patents
A kind of compounded visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2And organic matter degradation application Download PDFInfo
- Publication number
- CN108295897B CN108295897B CN201810121772.9A CN201810121772A CN108295897B CN 108295897 B CN108295897 B CN 108295897B CN 201810121772 A CN201810121772 A CN 201810121772A CN 108295897 B CN108295897 B CN 108295897B
- Authority
- CN
- China
- Prior art keywords
- tio
- uio
- cooh
- hours
- electrostatic spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 10
- 239000005416 organic matter Substances 0.000 title claims abstract description 10
- 230000015556 catabolic process Effects 0.000 title claims abstract description 9
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 title claims description 40
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 title claims description 37
- WIKQEUJFZPCFNJ-UHFFFAOYSA-N carbonic acid;silver Chemical compound [Ag].[Ag].OC(O)=O WIKQEUJFZPCFNJ-UHFFFAOYSA-N 0.000 title claims description 33
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 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 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 31
- 238000010041 electrostatic spinning Methods 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000003446 ligand Substances 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 239000002121 nanofiber Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 13
- 229960000583 acetic acid Drugs 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 239000012362 glacial acetic acid Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 8
- 239000012876 carrier material Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000001802 infusion Methods 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 206010013786 Dry skin Diseases 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 20
- 239000004408 titanium dioxide Substances 0.000 description 12
- 239000013207 UiO-66 Substances 0.000 description 11
- 239000012621 metal-organic framework Substances 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- -1 Silver ion Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910001958 silver carbonate Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 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
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000021186 dishes Nutrition 0.000 description 1
- LHUKEIJHXACBMW-UHFFFAOYSA-L disilver nitric acid carbonate Chemical compound [Ag+].C([O-])([O-])=O.[N+](=O)(O)[O-].[Ag+] LHUKEIJHXACBMW-UHFFFAOYSA-L 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical compound [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical class OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/30—Accessories for evaporators ; Constructional details thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- B01J35/39—
-
- B01J35/60—
-
- B01J35/61—
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/104—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention relates to a kind of compounded visible light photocatalyst, specifically a kind of Ag of modification2CO3/TiO2/UIO‑66‑(COOH)2Visible-light photocatalyst and its degradation application in organic matter rhodamine, formaldehyde.Loaded photocatalyst of the invention, is widely used, and production is simple, and cost is relatively low, and stability is good, and can effectively degrade rhodamine, formaldehyde organic matter in a short time, improves the degradation efficiency of visible light catalyst.
Description
Technical field
The present invention relates to a kind of compounded visible light photocatalyst, specifically a kind of Ag of modification2CO3/TiO2/ UIO-
66-(COOH)2Visible-light photocatalyst and its application.
Background technique
Environmental pollution and energy crisis have gradually jeopardized the existence of the mankind.Photocatalysis technology is considered as solving the energy and ring
Border problem is most effective, most promising method.TiO2Have many advantages, such as that efficient, nontoxic, chemical property is stablized, is to study at present
Widest photochemical catalyst.By doping vario-property, or with narrow-band semiconductor is the methods of compound can improve TiO2To the sound of visible light
It answers, but its visible light activity is still very low, apart from practical application, there are also very big distances.It is therefore desirable to develop with high visible
Active novel photocatalyst.
Ag2CO3With very strong visible light photocatalysis active, in the fields such as environmental pollution improvement and clean energy resource conversion
Application prospect is very wide.However, in Photocatalytic Degradation Process, Ag2CO3Easily by photoetch, Ag2CO3Silver ion easily quilt
Light induced electron is reduced to silver, and catalyst activity is caused to be gradually reduced, and seriously constrains its practical application.Therefore, Ag is improved2CO3's
Photostability is an important research direction.
Although nano-TiO2Photocatalytic activity it is high, but it is easy to reunite in the solution, and is difficult to separate and recycle, and holds
Secondary pollution, and photochemical catalyst easy in inactivation are easily caused, recycling rate of waterused is low, so seriously constraining pushing away for its photocatalysis technology
It is wide to use.In order to solve these problems, researcher is by making nano-TiO2Particulate load is in structure and all very stable load of property
Metallic element doping, such as silver are realized or carried out on body, it is nonmetallic ion-doped, such as N, C；Rare earth element Re doping,
Or titanium dioxide and other visible light-responded substances progress is compound, such as TdS, ZnO etc., to improve the visible of titanium dioxide
Photo absorption property increases photochemical catalyst energy level.
Nano-TiO2 photocatalyst after load materially increases the specific surface area of TiO2 photochemical catalyst,
And also there is certain positive effect to the transformation of the reunion and crystal phase that inhibit crystal grain.And since carrier sheet is as activated adoption
Material, porous carrier can adsorb organic pollutant first in the dark, reach absorption dissociation equilibrium, then under light illumination, organic dirt
The TiO2 photocatalytic activity that more efficient photocatalysis can occur with TiO2, and then improve for dye object.In addition, nano TiO 2
High degree of dispersion on carrier can also be improved its utilization rate to light.
The present wide carrier of domestic and international application has silica gel, aluminium oxide, glass fibre, graphene, active carbon and one
A little natural minerals such as diatomite, zeolite etc..Because of zeolite pore structure abundant and high stability, become most wide for catalyst
One of general carrier.But zeolite also has many deficiencies, such as poromerics, its limited sorption capacity, especially
In the solution, macromolecular solvent does not enter in hole.It would therefore be desirable to a kind of aperture is adjustable, and adjustable extent it is wider one
Kind carrier, however this porous material of MOF just meets the needs studied now very much.Currently, only SBA-15 molecular sieve conduct is received
Rice TiO2The research of the carrier of photochemical catalyst causes the extensive concern and interest of domestic and foreign scholars.
TiO2The solid support method of photochemical catalyst can be divided into two major classes, first is that physical load method, second is that chemical load method.Object
Reason load method is not related to chemically reacting, thus experimental implementation is simpler than chemical load method, but the TiO2 of chemical load method synthesis
The hydrothermal stability of loaded photocatalyst is higher, and chemical property is more stable.
Currently, synthesis coated TiO2/carrier chemical method mainly has direct synthesis technique and two kinds of post synthesis method.First close
At carrier material then again by infusion process, sedimentation or grafting by TiO2 be distributed to silica gel, aluminium oxide, glass fibre,
Graphene, active carbon or molecular sieve synthesize TiO2/ carrier.The advantages of the method is that the hydrothermal stability of TiO2/ carrier is high, is lacked
Point is that the dispersibility of TiO2 is poor, and the amount of TiO2 poorly controls.But under normal circumstances still using post synthesis method
It is more, and the dispersed poor disadvantage of TiO2 can be made up by the method for modification carrier.
In recent years, the research of transition metal or heavy metal to load type titania doping and modification, is increasingly taken seriously,
And the photocatalysis effect of the load type titania after adulterating is greatly improved, and application range is also very extensive.Have
Scholar mixes TiO2/SBA-15 with Au element in order to which load type titania photocatalyst is with good stability
Au/TiO2/SBA-15 that is miscellaneous, being synthesized, also has and is doped modified synthesis M/TiO2/SBA-15 using Ni metal and Bi
Photochemical catalyst, can be general but there are still dispersability of titanium dioxide, the problem that catalyst cannot be steady in a long-term.
Summary of the invention
MOFs metal organic framework is the very rapid coordination polymer of developed recently, has three-dimensional pore structure, generally
Using metal ion as tie point, it is the another class weight except zeolite and carbon nanotube that organic ligand support extends at space 3D
The novel porous materials wanted have high voidage, low-density, bigger serface, duct rule, performances, the UiO- such as aperture is adjustable
66 be the rigid MOFs material with high stability, and the stability of MOFs is mainly by the stability of inorganic metal unit, Yi Jijin
Belong to the power of the binding force between ligand to determine.A key of most of MOFs is disadvantageous in that thermal stability is not high, one
As for, the thermal stability of MOFs is at 350-400 DEG C.UiO-66 is a kind of MOF with ultrastability, and chemical formula is
Zr6O4(OH)4(CO2)12, for its structure collapse temperature higher than 500 DEG C, the inorganic metal of high degree of symmetry is carried out in its stability source
Unit Zr6O4(OH)4And the Zr6The strong interaction of carboxyl oxygen O in octahedra core and ligand.One Zr6Octahedra core and 12
A terephthalic acid (TPA) ligands form tetrahedron and octahedra two kinds of hole cage, eight faces of each octahedron cage
On, it is connected with a tetrahedron cage, this connection type constantly extends in three-dimensional space, so that being formed hasAperture
MOFs.In addition, chemical stability experiments have shown that, UiO-66 have good water-resistance, acid-resisting.
For overcome the deficiencies in the prior art, the present invention is first by carrying out carboxyl acid modified, shape for carrier UiO-66- (Zr)
At UiO-66- (COOH)2, increase the specific surface area of carrier UiO-66, increase the spaced point of titanium dioxide, to be conducive to control
Dispersion performance and TiO2Load capacity.
In order to enable UiO-66 preferably in conjunction with titanium dioxide, and make the titanium dioxide being attached on UiO-66, this
The structure that kind replacement is able to maintain UiO-66 is basically unchanged, and improves its hydrothermal stability, and sour attachment point increases so that titanium
It can be uniformly dispersed.
The application is answered same AgCO3 and TiO2 with visible light activity by the metal salt dopping to titanium dioxide
It closes, simply and effectively plays the cooperative photocatalysis performance of the two, formed and had complementary advantages, moreover, in order to form active component
Good dispersion increases the stability of photochemical catalyst and improves service life, by the metal organic framework with ultrastability
UiO-66 (Zr) carries out acid modification first, the carboxylic acid load point of carrier is improved, to improve the Active components distribution of catalyst
Point, so that catalyst optimizes in service life with photocatalytic activity simultaneously, there is presently no similar report preparation synthesis photocatalysis
Agent structure is Ag2CO3/TiO2/ UIO-66-(COOH)2。
Composite visible light catalyst of the invention the preparation method is as follows:
(1) by weight, by 5-10 parts of polyvinylpyrrolidones, 80~100 parts of dehydrated alcohols, 50~100 parts of metatitanic acid fourths
After ester mixing, isothermal reaction 2~8 hours, obtains electrostatic spinning solution, using electrostatic spinning under the conditions of 40~90 DEG C of temperature
Technique carries out electrostatic spinning to electrostatic spinning solution, obtains TiO2Nanofiber；
(2) TiO that will be obtained2Nanofiber is dried 1-4 hours at 80~100 DEG C, then with 1 DEG C/min of liter
After warm rate is heated to 500~1000 DEG C, constant temperature 4~8 hours, nano-TiO is obtained2。
(3) nano-TiO that will be prepared2Ultrasonic disperse Yu Shuizhong adjusts solution ph, and silver nitrate AgNO is added3It is molten
Liquid stirs evenly, and Na is then added2CO3, precipitating is generated, takes solid to wash, 100-150 DEG C is dried to obtain Ag2CO3/TiO2。
(4) crystallization synthesis UIO-66- (COOH)2: in a kettle by ZrCl4, glacial acetic acid be dissolved in solvent DMF,
Ultrasonic disperse 10min-2h, then by ligand 1,2,4,5- benzene tertacarbonic acids are put into above-mentioned solution, stirring, at 100-150 DEG C
Crystallization 10-24 hours, cooling down, centrifugal filtration were washed after the reaction was completed, dry.Each component molar ratio ZrCl4: match
Body: template glacial acetic acid=1: 1-2: 20-30.
(5) use infusion process by Ag2CO3/TiO2It is carried on UIO-66- (COOH)2Porous material obtains Ag2CO3/
TiO2/UIO-66-(COOH)2Composite photo-catalyst.
Ag in compounded visible light photocatalyst2CO3∶TiO2∶UIO-66-(COOH)2Mass ratio be 1-20: 30-50:
20-40。
Preferably, the concentration of silver nitrate is 0.2-1mol/L, additional amount 10-20mL/L in step (3)；Sodium carbonate it is dense
Degree is 0.5-2mol/L, preferably 0.5-1mol/L.
Preferably, the dipping of step (5) is by the Ag in step (3)2CO3/TiO2UIO-66- is added with water in dispersion
(COOH)2Carrier material carries out impregnation 1-30 hours, stands 2-5 hours, washs, dry, the preferred 70-100 of drying temperature
℃。
The present invention passes through method of electrostatic spinning first and uniform titanium dioxide nanofiber is prepared, and then dries, grinding
Nanometer titanium dioxide micro-sphere particle is formed, there is good stability of crystal form, there is biggish draw ratio and lesser diameter,
Even pore structure, then further with Ag2CO3The preparation for carrying out composite photo-catalyst, since silver carbonate has pyrolytic
Therefore property in the two recombination process, needs to control reaction temperature and drying condition, no more than 200 DEG C, moreover, this hair
It is bright use simple ion catch electron microscopy can be effective by the ph and sodium carbonate of control system and the addition concentration of silver nitrate
Silver carbonate product is formed, and the two is mutually promoted the separation of electron-hole, is conducive to quickly generate photoelectron, on this basis,
By Ag2CO3/TiO2Carboxyl acid modified UiO-66 is impregnated in, due to being embedded in the hole cage knot of Zr in metal organic framework porous material
Structure forms multiple octahedra, tetrahedral three-dimensional structures, can form Ag2CO3、TiO2Carrier is embedded in or is carried on to show
The transmitting and generation for accelerating photoelectricity ion in specific three-dimensional structure, improve photocatalysis efficiency.
Moreover, traditional UiO-66 is modified to be often use-NH2 ,-CH3 etc., the present invention uses ligand 1,2,4,5- benzene
Tetrabasic carboxylic acid replaces other ligands, and specific ligand is 1,2,4,5- benzene tertacarbonic acids (i.e. H4BETA), i.e., and 1,2,4,5- benzene tetracarboxylic acids.
Porous material is prepared using simple hydro-thermal solvent method, with good stability, heat-resisting quantity and hole structural property.
Further, the step of present invention has also carried out more in-depth study, increases B doping, specific steps: (1)
By weight, after 5-10 parts of polyvinylpyrrolidones, 80~100 parts of dehydrated alcohols, 50~100 parts of butyl titanates being mixed, into
2-5mol/L boric acid is added in one step, and isothermal reaction 2~8 hours, obtains the titanium dioxide of boracic under the conditions of 40~90 DEG C of temperature
Titanium electrostatic spinning solution carries out electrostatic spinning to electrostatic spinning solution using electrostatic spinning process, obtains containing B-TiO2Nanowire
Dimension；
(2) it will obtain containing B-TiO2Nanofiber is dried hour at 80~100 DEG C, then with 1 DEG C/min of liter
After warm rate is heated to 500~1000 DEG C, constant temperature 4~8 hours, a nanometer B Uniform Doped TiO is obtained2 (B-TiO2)。
(3) the nanometer B-TiO that will be prepared2Ultrasonic disperse Yu Shuizhong adjusts solution ph, and silver nitrate AgNO is added3
Solution and, stir evenly, Na be then added2CO3, generate precipitating, take solid to wash, 100-150 DEG C be dried to obtain it is boron doped
Ag2CO3/TiO2。
(4) crystallization synthesis UIO-66- (COOH)2: in a kettle by ZrCl4, glacial acetic acid be dissolved in solvent DMF,
Ultrasonic disperse 10min-2h, then by ligand 1,2,4,5- benzene tertacarbonic acids are put into above-mentioned solution, stirring, at 100-150 DEG C
Crystallization 10-24 hours, cooling down, centrifugal filtration were washed after the reaction was completed, dry.
(5) Ag for being adulterated B using infusion process2CO3/TiO2It is carried on UIO-66- (COOH)2Porous material will contain boron
Ag2CO3/TiO2Dispersion is added UIO-66- (COOH) with water2Carrier material carries out impregnation 1-30 hours, stands 2-5
Hour, washing, 100 DEG C are dried to obtain boron doped Ag2CO3/TiO2/ UIO-66-(COOH)2Composite photo-catalyst.Wherein B mixes
Miscellaneous amount, with catalyst basic calculation 1-10wt%.
Metal salt silver carbonate, nonmetallic B ion are utilized in above-mentioned technical proposal while adulterating, collaboration can be formed and made
With strong hole-electron being formed, to further increase photocatalytic activity.
The composite photo-catalyst of preparation is applied in the degradation process of organic matter rhodamine and formaldehyde by the present invention, closed
Glass box in contain into 3 μ L organic matter culture dishes and be coated with photochemical catalyst, concentration of organic gas is 1.8mg/m in case3,
30W fluorescent lamp Continuous irradiation investigates the degradation rate of rhodamine, formaldehyde.
Specific embodiment
The present invention will be further described in detail with reference to the specific embodiments.
Embodiment 1
(1) by weight, after 5 parts of polyvinylpyrrolidones, 100 parts of dehydrated alcohols, 50 parts of butyl titanates being mixed, 50
Temperature under the conditions of isothermal reaction 3 hours, obtain electrostatic spinning solution, using electrostatic spinning process to electrostatic spinning solution carry out
Electrostatic spinning obtains TiO2Nanofiber；
(2) TiO that will be obtained2Nanofiber is dried 1 hour at 100 DEG C, then with 1 DEG C/min of heating rate
After being heated to 500 DEG C, constant temperature 4 hours, nano-TiO is obtained2.X-ray powder diffraction (XRD) test, shape are carried out to products obtained therefrom
At anatase-type nanometer titanium dioxide.
(3) nano-TiO that will be prepared2Ultrasonic disperse Yu Shuizhong is adjusted solution ph (7-10), and silver nitrate is added
1mol/L AgNO3Solution 10mL/L, stirs evenly, and 1mol/L Na is then added2CO3, precipitating is generated, solid is taken to wash, 100
DEG C it is dried to obtain Ag2CO3/TiO2。
(4) crystallization synthesis UIO-66- (COOH)2: in a kettle by ZrCl4, glacial acetic acid be dissolved in solvent DMF,
Ultrasonic disperse 10min-2h, then by ligand 1,2,4,5- benzene tertacarbonic acids are put into above-mentioned solution, stirring, at 100-150 DEG C
Crystallization 10-24 hours, cooling down, centrifugal filtration were washed after the reaction was completed, dry.Wherein each component molar ratio ZrCl4
: ligand: template glacial acetic acid=1: 1: 20.
(5) use infusion process by Ag2CO3/TiO2It is carried on UIO-66- (COOH)2Porous material, will be in step (3)
Ag2CO3/TiO2Dispersion is added UIO-66- (COOH) with water2Carrier material carries out impregnation 1-30 hours, stands 2-5
Hour, washing, 100 DEG C of dryings obtain Ag2CO3/TiO2/UIO-66-(COOH)2Composite photo-catalyst.Ag2CO3∶TiO2∶UIO-
66-(COOH)2Mass ratio be 15: 45: 40.
Embodiment 2
(1) by weight, after 10 parts of polyvinylpyrrolidones, 100 parts of dehydrated alcohols, 100 parts of butyl titanates being mixed,
Isothermal reaction 6 hours, obtain electrostatic spinning solution under the conditions of 60 DEG C of temperature, using electrostatic spinning process to electrostatic spinning solution
Electrostatic spinning is carried out, TiO is obtained2Nanofiber；
(2) TiO that will be obtained2Nanofiber is dried 2 hours at 100 DEG C, then with 1 DEG C/min of heating rate
After being heated to 900 DEG C, constant temperature 68 hours, nano-TiO is obtained2。
(3) nano-TiO that will be prepared2Ultrasonic disperse Yu Shuizhong is adjusted solution ph (9-10), and 0.5mol/ is added
L silver nitrate AgNO3Solution 20nl, stirs evenly, and the Na of 1mol/L is then added2CO3, precipitating is generated, takes solid to wash, 100-
150 DEG C are dried to obtain Ag2CO3/TiO2。
(4) crystallization synthesis UIO-66- (COOH)2: in a kettle by ZrCl4, glacial acetic acid be dissolved in solvent DMF,
Ultrasonic disperse 10min-2h, then by ligand 1,2,4,5- benzene tertacarbonic acids are put into above-mentioned solution, stirring, at 100-150 DEG C
Crystallization 10-24 hours, cooling down, centrifugal filtration were washed after the reaction was completed, dry.Wherein each component molar ratio ZrCl4
: ligand: template glacial acetic acid=1: 1: 30.
(5) use infusion process by Ag2CO3/TiO2It is carried on UIO-66- (COOH)2Porous material, by Ag2CO3/TiO2Point
It dissipates with water, is added UIO-66- (COOH)2Carrier material carries out impregnation 1-30 hours, stands 2-5 hours, washing, and 100
DEG C it is dried to obtain Ag2CO3/TiO2/UIO-66-(COOH)2Composite photo-catalyst.Ag2CO3∶TiO2∶UIO-66-(COOH)2Matter
Amount is than being 20: 40: 40.
Embodiment 3
(1) by weight, after 10 parts of polyvinylpyrrolidones, 80 parts of dehydrated alcohols, 80 parts of butyl titanates being mixed, 80
DEG C temperature under the conditions of isothermal reaction 2 hours, obtain electrostatic spinning solution, using electrostatic spinning process to electrostatic spinning solution into
Row electrostatic spinning, obtains TiO2Nanofiber；
(2) TiO that will be obtained2Nanofiber is dried 3 hours at 80 DEG C, then is added with 1 DEG C/min of heating rate
Heat obtains nano-TiO to after 9000 DEG C, constant temperature 4 hours2。
(3) nano-TiO that will be prepared2Ultrasonic disperse Yu Shuizhong adjusts solution ph, and silver nitrate 1mol/L is added
AgNO3Solution 20mL/L, stirs evenly, and 1mol/L Na is then added2CO3, precipitating is generated, solid is taken to wash, 100-150 DEG C dry
It is dry to obtain Ag2CO3/TiO2。
(4) crystallization synthesis UIO-66- (COOH)2: in a kettle by ZrCl4, glacial acetic acid be dissolved in solvent DMF,
Ultrasonic disperse 10min-2h, then by ligand 1,2,4,5- benzene tertacarbonic acids are put into above-mentioned solution, stirring, at 100-150 DEG C
Crystallization 15 hours, cooling down, centrifugal filtration were washed after the reaction was completed, dry.Wherein each component molar ratio ZrCl4: match
Body: template glacial acetic acid=1: 1: 20.
(5) by the Ag in step (3)2CO3/TiO2Dispersion is added UIO-66- (COOH) with water2Carrier material is soaked
Stain is reacted 10 hours, stands 2 hours, and washing, 100 DEG C of dryings obtain Ag2CO3/TiO2/ UIO-66-(COOH)2Complex light is urged
Agent.Ag in compounded visible light photocatalyst2CO3∶TiO2∶ UIO-66-(COOH)2Mass ratio be 20: 45: 35.
Embodiment 4
(1) by weight, after 8 parts of polyvinylpyrrolidones, 100 parts of dehydrated alcohols, 100 parts of butyl titanates being mixed, into
5mol/L boric acid is added in one step, and the isothermal reaction 5 hours under the conditions of 60 DEG C of temperature obtains the titanium dioxide electrostatic spinning of boracic
Solution carries out electrostatic spinning to electrostatic spinning solution using electrostatic spinning process, obtains containing B-TiO2Nanofiber；
(2) it will obtain containing B-TiO2Nanofiber is dried 4 hours at 80~100 DEG C, then with 1 DEG C/min
After heating rate is heated to 600 DEG C, constant temperature 4~8 hours, a nanometer B Uniform Doped TiO is obtained2(B-TiO2)。
(3) the nanometer B-TiO that will be prepared2Ultrasonic disperse Yu Shuizhong adjusts solution ph, and 1mol/L silver nitrate is added
AgNO3Solution and, stir evenly, then be added 1mol/L Na2CO3, precipitating is generated, solid is taken to wash, 100-150 DEG C dry
To boron doped Ag2CO3/TiO2。
(4) crystallization synthesis UIO-66- (COOH)2: in a kettle by ZrCl4, glacial acetic acid be dissolved in solvent DMF,
Ultrasonic disperse 10min-2h, then by ligand 1,2,4,5- benzene tertacarbonic acids are put into above-mentioned solution, stirring, at 100-150 DEG C
Crystallization 10-24 hours, cooling down, centrifugal filtration were washed after the reaction was completed, dry.Wherein each component molar ratio ZrCl4
: ligand: template glacial acetic acid=1: 2: 30.
(5) Ag for being adulterated B using infusion process2CO3/TiO2It is carried on UIO-66- (COOH)2Porous material will contain boron
Ag2CO3/TiO2Dispersion is added UIO-66- (COOH) with water2Carrier material carries out impregnation 1-30 hours, stands 2-5
Hour, washing, 100 DEG C are dried to obtain boron doped Ag2CO3/TiO2/ UIO-66-(COOH)2Composite photo-catalyst.Wherein B mixes
Miscellaneous amount, with catalyst basic calculation 10wt%, Ag in composite photo-catalyst2CO3∶TiO2∶UIO-66-(COOH)2Mass ratio be
20∶40∶40。
Comparative example 1
Carrier is not used, Ag is only prepared2CO3/TiO2Composite photo-catalyst, other experiment parameters are the same as embodiment 1.
Comparative example 2
Using alumina catalyst support, Ag is impregnated2CO3/TiO2Other experiment parameters obtain Ag with embodiment 12CO3/TiO2/
Al2O3Supported composite photocatalyst.
Comparative example 3
Using carrier S BA-15 molecular sieve, Ag is impregnated2CO3/TiO2Other experiment parameters obtain Ag with embodiment 12CO3/
TiO2/ SBA-15 supported composite photocatalyst.
Comparative example 4
Using without carboxyl acid modified UiO-66 (Zr) carrier, stain Ag is loaded2CO3/TiO2Other experiment parameters are the same as implementation
Example 1, obtains Ag2CO3/TiO2/ UiO-66 supported composite photocatalyst.
Application examples
Compounded visible light photocatalyst prepared by embodiment and comparative example is used for degradation of organic substances rhodamine, formaldehyde etc.
Organic matter.It is contained in closed glass box into 3uL organic matter culture dish and is coated with photochemical catalyst, concentration of organic gas in case
For 1.8mg/m3, 30W fluorescent lamp Continuous irradiation, degradation rate such as the following table 1 of rhodamine, formaldehyde.
There are the above results to can be seen that support type visible light composite catalyst of the invention small in catalyst amount, illumination
(it is less than 30min) in the case that time is short, still there is the excellent effect of rhodamine, formaldehyde organic matter adsorption rate 98% or more
Fruit, it can be seen that the compound and support modification for carrying out silver carbonate for nanometer titanium dioxide carbon substantially increases light degradation organic matter
Efficiency has great importance.And catalyst preparation process is simple, is expected to carry out commerical test and promote.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those skilled in the art within the technical scope disclosed by the invention, can without the variation that creative work is expected or
Replacement, should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be limited with claims
Subject to fixed protection scope.
Claims (3)
1. a kind of compounded visible light photocatalyst, which is characterized in that the photocatalyst structure is Ag2CO3/TiO2/UIO-66-
(COOH)2, it is specific the preparation method is as follows:
(1) by weight, after 10 parts of polyvinylpyrrolidones, 100 parts of dehydrated alcohols, 100 parts of butyl titanates being mixed, at 60 DEG C
Temperature under the conditions of isothermal reaction 6 hours, obtain electrostatic spinning solution, using electrostatic spinning process to electrostatic spinning solution carry out
Electrostatic spinning obtains TiO2Nanofiber；
(2) TiO that will be obtained2Nanofiber is dried 2 hours at 100 DEG C, then is heated to 1 DEG C/min of heating rate
After 900 DEG C, constant temperature 4~8 hours, nano-TiO is obtained2；
(3) nano-TiO that will be prepared2Ultrasonic disperse Yu Shuizhong adjusts solution ph to 9-10,0.5mol/L nitric acid is added
Silver-colored AgNO3Solution 20mL, stirs evenly, and the Na of 1mol/L is then added2CO3, precipitating is generated, solid is taken to wash, 100-150 DEG C
It is dried to obtain Ag2CO3/TiO2；
(4) crystallization synthesis UIO-66- (COOH)2: in a kettle by ZrCl4, glacial acetic acid be dissolved in solvent DMF, ultrasound
Disperse 10min-2h, then by ligand 1,2,4,5- benzene tertacarbonic acids are put into above-mentioned solution, stirring, the crystallization at 100-150 DEG C
Reaction 10-24 hours, cooling down, centrifugal filtration are washed after the reaction was completed, dry, wherein each component molar ratio ZrCl4: match
Body: template glacial acetic acid=1: 1: 30；
(5) use infusion process by Ag2CO3/TiO2It is carried on UIO-66- (COOH)2Porous material, by Ag2CO3/TiO2Dispersion and water
In, it is added UIO-66- (COOH)2Carrier material carries out impregnation 1-30 hours, stands 2-5 hours, washing, 100 DEG C of dryings
Obtain Ag2CO3/TiO2/UIO-66-(COOH)2Composite photo-catalyst, Ag2CO3∶TiO2∶UIO-66-(COOH)2Mass ratio be
20∶40∶40。
2. application of the compounded visible light photocatalyst as described in claim 1 in degradation of organic substances rhodamine, formaldehyde.
3. application as claimed in claim 2, it is characterised in that: contain in closed glass box into 3 μ L organic matter culture dishes and
Coated with 5g photochemical catalyst, concentration of organic gas is 1.8mg/m in case3, 30W fluorescent lamp Continuous irradiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810121772.9A CN108295897B (en) | 2016-04-25 | 2016-04-25 | A kind of compounded visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2And organic matter degradation application |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610259062.3A CN105879918B (en) | 2016-04-25 | 2016-04-25 | A kind of compounded visible light photocatalyst Ag2CO3/TiO2/ UIO-66-(COOH)2And organic matter degradation application |
| CN201810121772.9A CN108295897B (en) | 2016-04-25 | 2016-04-25 | A kind of compounded visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2And organic matter degradation application |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610259062.3A Division CN105879918B (en) | 2016-04-25 | 2016-04-25 | A kind of compounded visible light photocatalyst Ag2CO3/TiO2/ UIO-66-(COOH)2And organic matter degradation application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108295897A CN108295897A (en) | 2018-07-20 |
| CN108295897B true CN108295897B (en) | 2019-09-13 |
Family
ID=56704425
Family Applications (5)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810121773.3A Active CN108160121B (en) | 2016-04-25 | 2016-04-25 | Composite visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2And application of organic matter degradation |
| CN201810121580.8A Active CN108380244B (en) | 2016-04-25 | 2016-04-25 | Composite visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2And application of organic matter degradation |
| CN201810121772.9A Active CN108295897B (en) | 2016-04-25 | 2016-04-25 | A kind of compounded visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2And organic matter degradation application |
| CN201810121771.4A Active CN108160120B (en) | 2016-04-25 | 2016-04-25 | Composite visible light photocatalyst Ag2CO3/TiO2/ UIO-66-(COOH)2And application of organic matter degradation |
| CN201610259062.3A Expired - Fee Related CN105879918B (en) | 2016-04-25 | 2016-04-25 | A kind of compounded visible light photocatalyst Ag2CO3/TiO2/ UIO-66-(COOH)2And organic matter degradation application |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810121773.3A Active CN108160121B (en) | 2016-04-25 | 2016-04-25 | Composite visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2And application of organic matter degradation |
| CN201810121580.8A Active CN108380244B (en) | 2016-04-25 | 2016-04-25 | Composite visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2And application of organic matter degradation |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810121771.4A Active CN108160120B (en) | 2016-04-25 | 2016-04-25 | Composite visible light photocatalyst Ag2CO3/TiO2/ UIO-66-(COOH)2And application of organic matter degradation |
| CN201610259062.3A Expired - Fee Related CN105879918B (en) | 2016-04-25 | 2016-04-25 | A kind of compounded visible light photocatalyst Ag2CO3/TiO2/ UIO-66-(COOH)2And organic matter degradation application |
Country Status (1)
| Country | Link |
|---|---|
| CN (5) | CN108160121B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582841B (en) * | 2016-11-28 | 2019-08-16 | 深圳大学 | The photochemical catalyst of sponge load and its application |
| CN107051563A (en) * | 2017-03-30 | 2017-08-18 | 常州大学 | A kind of silver carbonate is combined the preparation method of cobalt carbonate photochemical catalyst |
| CN113083268B (en) * | 2021-04-02 | 2023-08-11 | 西安建筑科技大学 | Crystal form controllable TiO 2 Preparation method of photocatalytic material |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10355087A1 (en) * | 2003-11-24 | 2005-06-09 | Basf Ag | Process for the electrochemical preparation of a crystalline porous organometallic framework |
| CN101428209B (en) * | 2007-11-08 | 2010-12-01 | 北京化工大学 | Nano-fibre supported titanium dioxide photocatalyst and preparation method thereof |
| JP5210468B2 (en) * | 2007-12-25 | 2013-06-12 | 株式会社アサカ理研 | Method for producing photocatalyst solution with improved antibacterial properties |
| CN101327438B (en) * | 2008-01-10 | 2010-11-03 | 武汉理工大学 | Method for preparing AgI/TiO2 nano compound photocatalyst |
| CN102626622B (en) * | 2012-03-28 | 2013-10-02 | 武汉理工大学 | Preparation method of Ag/Ag (I)-TiO2 nanocrystalline visual light photochemical catalyst |
| CN103240130B (en) * | 2013-05-21 | 2015-03-11 | 中国石油大学(北京) | TiO2 / MIL-101 composite catalyst for photocatalytic water splitting and preparation method and applications thereof |
| CN103285861B (en) * | 2013-06-24 | 2015-02-11 | 大连民族学院 | An Ag3VO4/TiO2 compound nano-wire having visible light activity, a preparation method and applications thereof |
| CN103611531A (en) * | 2013-12-16 | 2014-03-05 | 长春工业大学 | Preparation method and application of silver oxide/titanium dioxide composite nanofiber photocatalyst |
| CN104324761B (en) * | 2014-10-09 | 2016-04-20 | 济南大学 | The Synthesis and applications that a kind of porous rare earth organic coordination compound is catalyst based |
| CN104324762B (en) * | 2014-10-09 | 2016-06-29 | 济南大学 | A kind of trielement composite material preparation method and application |
| CN104841467A (en) * | 2015-04-21 | 2015-08-19 | 昆明理工大学 | Mesoporous silver carbonate nanorod visible light photocatalyst and preparation method thereof |
| CN104888858B (en) * | 2015-05-22 | 2017-03-01 | 合肥工业大学 | A kind of ternary high efficiency composition visible-light photocatalysis material and preparation method thereof |
| CN104923166B (en) * | 2015-06-17 | 2017-09-08 | 昆明理工大学 | A kind of micropore Fe N MOF materials and its preparation method and application |
| CN105214612B (en) * | 2015-09-18 | 2019-01-04 | 北京化工大学 | A kind of application of metal-organic framework functionalization material |
| CN105170097B (en) * | 2015-09-29 | 2017-12-05 | 安徽工程大学 | A kind of TiO2Nuclear-shell structured nano-composite materials of/ZIF 8 and preparation method thereof |
| CN105195119B (en) * | 2015-10-28 | 2018-06-05 | 内蒙古科技大学 | A kind of basalt fibre-TiO2The preparation method and applications of composite material |
-
2016
- 2016-04-25 CN CN201810121773.3A patent/CN108160121B/en active Active
- 2016-04-25 CN CN201810121580.8A patent/CN108380244B/en active Active
- 2016-04-25 CN CN201810121772.9A patent/CN108295897B/en active Active
- 2016-04-25 CN CN201810121771.4A patent/CN108160120B/en active Active
- 2016-04-25 CN CN201610259062.3A patent/CN105879918B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN108160120B (en) | 2021-02-12 |
| CN105879918B (en) | 2018-06-26 |
| CN105879918A (en) | 2016-08-24 |
| CN108380244A (en) | 2018-08-10 |
| CN108160121A (en) | 2018-06-15 |
| CN108295897A (en) | 2018-07-20 |
| CN108380244B (en) | 2021-01-29 |
| CN108160121B (en) | 2021-02-12 |
| CN108160120A (en) | 2018-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105833918B (en) | A kind of compounded visible light photocatalyst Ag2CO3/TiO2/ UiO-66-(COOH)2Preparation method and applications | |
| Cheng et al. | One-step microwave hydrothermal preparation of Cd/Zr-bimetallic metal–organic frameworks for enhanced photochemical properties | |
| US11345616B2 (en) | Heterojunction composite material consisting of one-dimensional IN2O3 hollow nanotube and two-dimensional ZnFe2O4 nanosheet, and application thereof in water pollutant removal | |
| CN106238100A (en) | The preparation of titanium dioxide nanoplate load MIL 100 (Fe) composite photocatalyst material and application process | |
| CN102145280B (en) | Method for preparing rice hull active carbon/silicon dioxide/titanium dioxide composite material | |
| CN105600828B (en) | A kind of porous nano CuFe2O4Preparation method | |
| CN105502286B (en) | A kind of porous nano NiFe2O4Preparation method | |
| WO2021068570A1 (en) | Composite photocatalyst for degrading tetracycline, preparation method therefor and use thereof | |
| CN105664950B (en) | A kind of porous nano ZnFe2O4Preparation method | |
| CN110882725B (en) | Metal organic framework loaded titanium dioxide photocatalytic material and preparation method thereof | |
| CN108295897B (en) | A kind of compounded visible light photocatalyst Ag2CO3/TiO2/UIO-66-(COOH)2And organic matter degradation application | |
| Yin et al. | Construction of NH 2-MIL-125 (Ti) nanoplates modified Bi 2 WO 6 microspheres with boosted visible-light photocatalytic activity | |
| CN106694050A (en) | Preparation method of visible-light-induced photocatalyst with core-shell structure | |
| CN105435767A (en) | Preparation method of photocatalyst adopting one-dimensional CNF (carbon nanofiber)/TiO2 core-shell structure | |
| CN105833919A (en) | Composite visible-light response catalyst Ag2CO3/TiO2/M-ZIF-8 and application thereof | |
| CN101618342A (en) | Polymer modified high-activity nano titanium dioxide catalyst and preparation method thereof | |
| CN106362742A (en) | Ag/ZnO nano-composite, preparation method thereof and application of composite | |
| CN113441145A (en) | Preparation method of barium titanate/iron oxyhydroxide photocatalyst | |
| CN105854955A (en) | Preparation method and application of compound visible-light responding catalyst Ag2CO3/TiO2/M-ZIF-8 | |
| CN112354559A (en) | Two-dimensional receptor molecule/hierarchical pore TiO2Composite photocatalyst, preparation method and photocatalytic application thereof | |
| CN102658128B (en) | Method for preparing ordered mesoporous Pd-TiO2 heterogeneous catalyst and application thereof | |
| CN113559856B (en) | Preparation method of barium titanate/silver iodate heterojunction photocatalyst | |
| CN104689813A (en) | WXTiO2+3X/SiO2 aerogel compound photocatalyst and preparation method thereof | |
| CN110624532B (en) | TiO 22-BiVO4-graphene ternary composite photocatalytic material and preparation method thereof | |
| CN103170319B (en) | Large-specific-surface-area pure-phase TiO2 photocatalyst and preparation method and applications thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |