CN108295907B - Composite visible light photocatalystAgent Ag2CO3/TiO2/UiO-66-(COOH)2Preparation method and application thereof - Google Patents
Composite visible light photocatalystAgent Ag2CO3/TiO2/UiO-66-(COOH)2Preparation method and application thereof Download PDFInfo
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- CN108295907B CN108295907B CN201810121578.0A CN201810121578A CN108295907B CN 108295907 B CN108295907 B CN 108295907B CN 201810121578 A CN201810121578 A CN 201810121578A CN 108295907 B CN108295907 B CN 108295907B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- WIKQEUJFZPCFNJ-UHFFFAOYSA-N carbonic acid;silver Chemical compound [Ag].[Ag].OC(O)=O WIKQEUJFZPCFNJ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 title claims description 42
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 title claims description 36
- 238000000034 method Methods 0.000 title description 13
- 239000011941 photocatalyst Substances 0.000 claims abstract description 50
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 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 9
- 230000000593 degrading effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 71
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 31
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 229960000583 acetic acid Drugs 0.000 claims description 21
- 239000012362 glacial acetic acid Substances 0.000 claims description 21
- 239000003446 ligand Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 14
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 14
- 239000013207 UiO-66 Substances 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 12
- 239000004408 titanium dioxide Substances 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 11
- 239000012621 metal-organic framework Substances 0.000 description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 10
- 229910052796 boron Inorganic materials 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 229910001958 silver carbonate Inorganic materials 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 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 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 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
- 230000004298 light response Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007598 dipping method Methods 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
- 230000007613 environmental effect Effects 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
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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
- 238000002054 transplantation Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- 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
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- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
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- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- 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
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- A—HUMAN NECESSITIES
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- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
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- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Catalysts (AREA)
Abstract
The invention relates to a composite visible light photocatalyst, in particular to modified Ag2CO3/TiO2/UiO‑66‑(COOH)2Visible light photocatalyst and its application in degrading organic rhodamine and formaldehyde. The supported photocatalyst disclosed by the invention is wide in application, simple to manufacture, low in cost and good in stability, can effectively degrade rhodamine and formaldehyde organic matters within 20min, and greatly improves the degradation efficiency of the visible-light photocatalyst.
Description
Technical Field
The invention relates to a preparation method of a composite visible light photocatalyst, in particular to modified Ag2CO3/TiO2/UiO-66-(COOH)2A preparation method of a visible light photocatalyst and application thereof.
Background
Environmental pollution and energy crisis have gradually endangered human survival. Photocatalytic technology is considered to be the most effective and promising approach to energy and environmental problems. TiO22Has the advantages of high efficiency, no toxicity, stable chemical property and the like, and is the current researchThe most widespread being photocatalysts. The TiO can be improved by doping modification or compounding with narrow-band semiconductor2The response to visible light is still low, and the visible light activity is far away from practical application. There is therefore a need to develop new photocatalysts with high visible light activity.
Ag2CO3Has strong visible light photocatalytic activity and has wide application prospect in the fields of environmental pollution treatment, clean energy conversion and the like. However, during photocatalytic degradation, Ag2CO3Is easily corroded by light, Ag2CO3The silver ions are easily reduced into silver by photo-generated electrons, so that the activity of the catalyst is gradually reduced, and the practical application of the catalyst is severely restricted. Thus, Ag is increased2CO3Is an important research direction.
Although the nano TiO2 has high photocatalytic activity, the nano TiO2 is easy to agglomerate in a solution, difficult to separate and recover and easy to cause secondary pollution, and the photocatalyst is easy to inactivate and has low recycling rate, so the popularization and the application of the photocatalytic technology are seriously restricted. To solve these problems, researchers have realized or carried out metal element doping, such as silver, non-metal ion doping, such as N, C; rare earth element Re is doped, or titanium dioxide and other visible light response substances are compounded, such as TdS, ZnO and the like, so that the visible light response performance of the titanium dioxide is improved, and the energy level of the photocatalyst is increased.
The supported nano TiO2 photocatalyst greatly increases the specific surface area of the TiO2 photocatalyst, and has a certain positive effect on inhibiting the agglomeration of crystal grains and the transformation of crystal phases. And because the carrier is an active adsorption material, the porous carrier can firstly adsorb organic pollutants in a dark place to achieve adsorption dissociation balance, and then under illumination, the organic pollutants can have a more efficient photocatalytic effect with TiO2, so that the photocatalytic activity of TiO2 is improved. In addition, the high dispersion of the nano TiO2 on the carrier can also improve the light utilization rate.
At present, the widely applied carriers at home and abroad comprise silica gel, alumina, glass fiber, graphene, activated carbon and some natural minerals such as diatomite, zeolite and the like. Due to its rich pore structure and high stability, zeolite is one of the most widely used supports for catalysts. However, zeolites also have a number of disadvantages, such as limited adsorption capacity for microporous materials, particularly in solution, where macromolecular solvents do not enter the pores. Therefore, a carrier with adjustable pore size and wider adjustable range is needed, however, the porous material MOF can meet the needs of the present research. At present, only SBA-15 molecular sieve is used as a carrier of a nano TiO2 photocatalyst, and the research has attracted extensive attention and interest of scholars at home and abroad.
The immobilization method of the TiO2 photocatalyst can be divided into two main types, namely a physical loading method and a chemical loading method. The physical loading method does not involve chemical reaction, so the experimental operation is simpler than the chemical loading method, but the TiO2 loaded photocatalyst synthesized by the chemical loading method has higher hydrothermal stability and more stable chemical property.
Currently, the chemical methods for synthesizing supported TiO 2/carrier mainly include direct synthesis and post-synthesis. Firstly synthesizing a carrier material, and then dispersing TiO2 into silica gel, alumina, glass fiber, graphene, activated carbon or a molecular sieve by an impregnation method, a deposition method or a transplantation method to synthesize the TiO 2/carrier. The advantage of this process is the high hydrothermal stability of the TiO 2/support, the disadvantage is the poor dispersibility of TiO2 and the amount of TiO2 is not well controlled. However, the post-synthesis method is generally used in many cases, and the disadvantage of poor dispersibility of TiO2 can be compensated for by a method of modifying the carrier.
In recent years, the research on doping modification of the supported titanium dioxide by the transition metal or the heavy metal is more and more emphasized, and the photocatalytic effect of the doped supported titanium dioxide is greatly improved, and the application range is wide. In order to ensure good stability of the supported titanium dioxide photocatalyst, the researchers doped TiO2/SBA-15 with Au element to synthesize Au/TiO2/SBA-15, and also doped and modified M/TiO2/SBA-15 photocatalyst by using metal Cu and Bi, but still have the problems that the titanium dioxide has general dispersion performance and the catalyst cannot be stabilized for a long time.
Disclosure of Invention
The MOFs metal organic framework is a coordination polymer which develops rapidly in recent years, has a three-dimensional pore structure, generally takes metal ions as connecting points, is supported into a space 3D extension by organic ligands, is another important novel porous material besides zeolite and carbon nanotubes, has the performances of high void ratio, low density, large specific surface area, regular pore channels, adjustable pore diameter and the like, is a rigid MOFs material with high stability, and the stability of the MOFs is mainly determined by the stability of an inorganic metal unit and the strength of the binding force between metal and ligands. A key disadvantage of most MOFs is that the thermal stability is not high, and in general, the thermal stability of MOFs is 400 ℃ at 350-. UiO-66 is an MOF with ultra-high stability, and the chemical formula is Zr6O4(OH)4(CO2)12Its skeleton collapse temperature is higher than 500 deg.C, and its stability comes from highly symmetrical inorganic metal unit Zr6O4(OH)4And Zr as such6Strong interaction of the octahedral nucleus with the carboxyl oxygen O in the ligand. One Zr6The octahedral nucleus is coordinated with 12 terephthalic acid ligands to form tetrahedral and octahedral hole cages, and eight faces of each octahedral cage are connected with a tetrahedral cage in a manner that the connection mode continuously extends in three-dimensional space, thereby forming a hole cage with three dimensions
MOFs of pore size. In addition, chemical stability tests show that UiO-66 has good water resistance and acid resistance.
In order to overcome the defects of the prior art, the invention firstly carries out carboxylic acid modification on the carrier UiO-66- (Zr) to form UiO-66- (COOH)2The specific surface area of the carrier UiO-66 is increased, and the dispersion point of the titanium dioxide is increased, thereby being beneficial to controlling the dispersion performance and TiO2The amount of the supported.
In order to make the UiO-66 be better combined with titanium dioxide and make the titanium dioxide attached on the UiO-66, the replacement can keep the structure of the UiO-66 basically unchanged and improve the hydrothermal stability of the UiO-66, and the acid attachment points are increased to make the titanium uniformly dispersed.
The preparation method comprises the steps of doping metal salt silver carbonate of titanium dioxide, compounding AgCO3 and TiO2 which have the same visible light activity, simply and effectively exerting the synergistic photocatalytic performance of the AgCO3 and the TiO2, forming advantage complementation, and in order to enable active components to form good dispersion, increase the stability and prolong the service life of the photocatalyst, firstly carrying out acid modification on a metal organic framework UiO-66(Zr) with ultrahigh stability, improving the carboxylic acid loading point of a carrier, thereby improving the active component distribution point of the catalyst, enabling the service life and the photocatalytic activity of the catalyst to be simultaneously optimized, wherein a ligand is 1, 2, 4, 5-benzenetetracarboxylic acid (namely H4BETA) and also 1, 2, 4, 5-benzenetetracarboxylic acid. At present, no similar report exists for preparing the synthetic photocatalyst with the structure of Ag2CO3/TiO2/ UiO-66-(COOH)2。
The composite visible light catalyst of the invention has the structure of Ag2CO3/TiO2/UiO-66-(COOH)2The preparation method comprises the following steps:
(1) weighing tetrabutyl titanate according to the mass ratio of 1: 3-5, dissolving the tetrabutyl titanate in glacial acetic acid to prepare a mixed solution, and dissolving the mixed solution in absolute ethyl alcohol to obtain a solution A;
(2) weighing a template agent triethanolamine and dissolving the template agent triethanolamine in absolute ethyl alcohol, wherein the mass ratio of the template agent to the absolute ethyl alcohol is 1: 5-25, so as to obtain a solution B;
(3) mixing the solution A and the solution B, adding 1/30-1/20 volume of distilled water of the mixed solution of the solution A and the solution B, stirring for 10-24 hours to obtain a clear solution, standing for 12 hours at 60-120 ℃ to form gel, and drying for 5-24 hours at 50-90 ℃;
(4) calcining the dried substance at 350-600 ℃ for 1-5 hours to remove the template agent, then soaking the dried substance in isopropanol, stirring and centrifugally separating to obtain the nano TiO2。
(5) The prepared nano TiO is2Ultrasonically dispersing in water, adjusting pH value of the solution, and adding silver nitrate AgNO3Stirring the solution evenly, and then adding Na2CO3Generating a precipitate, washing the solid, drying at the temperature of 100-2CO3/TiO2。
(6) Synthesis of UiO-66- (COOH)2: synthesis of Carboxylic acid modified UIO-66- (COOH) Using ligand 1, 2, 4, 5 benzenetetracarboxylic acid2Porous material: ZrCl4 and glacial acetic acid are dissolved in a solvent DMF in a reaction kettle, ultrasonic dispersion is carried out for 10min-2h, then ligand 1, 2, 4, 5-benzenetetracarboxylic acid is put into the solution, stirring is carried out, crystallization reaction is carried out for 10-24 h at the temperature of 100-150 ℃, cooling is carried out after the reaction is finished, centrifugal filtration, washing and drying are carried out. Wherein the molar ratio of the components is ZrCl4, the ligand and the template agent glacial acetic acid is 1: 1-2: 20-30.
(7) Adding Ag in the step (5)2CO3/TiO2Dividing into two parts, firstly, a part of Ag2CO3/TiO2Ultrasonically dispersing in water, transferring into inner container of polytetrafluoroethylene high-pressure reaction kettle, controlling temperature at 60-90 deg.C, adding UiO-66- (COOH)2 carrier material, soaking for 1-3 hr, drying at 80-100 deg.C for 1-3 hr, and drying the rest Ag2CO3/TiO2Adding, stirring, performing second impregnation reaction for 1-3 hours, standing for 2-5 hours, washing, and drying at 80-100 ℃ for 1-3 hours to obtain Ag2CO3/TiO2/UiO-66-(COOH)2A composite photocatalyst is provided. Ag in composite photocatalyst2CO3∶TiO2∶UiO-66-(COOH)2The mass ratio of the components is 1-20: 20-50: 30-40.
Preferably, the concentration of the silver nitrate in the step (5) is 0.2-1mol/l, and the addition amount is 10-20 ml; the concentration of sodium carbonate is 0.5-2mol/l, preferably 0.5-1 mol/l. The ultrasonic dispersion time in the step (5) is 20-30 min.
Preferably, the dipping reaction in the step (7) is carried out for 1 to 3 hours, then the mixture is kept still for 2 to 5 hours and washed, preferably at 70 to 100 DEG C
The composite visible-light-induced photocatalyst prepared by the preparation method of the composite visible-light-induced photocatalyst is applied to degradation of organic rhodamine, formaldehyde and the like.
The invention firstly passes through the templateThe sol-gel method of the agent is used for preparing uniform titanium dioxide nano particles, which have good crystal form stability, larger length-diameter ratio, smaller diameter and uniform pore structure, and then the uniform titanium dioxide nano particles are further mixed with Ag2CO3The preparation of the composite photocatalyst is carried out, because the silver carbonate has the property of high-temperature decomposition, the reaction temperature and the drying condition need to be controlled in the compounding process of the silver carbonate and can not exceed 250 ℃, moreover, the invention adopts a simple ion precipitation method, the silver carbonate product can be effectively formed by controlling the ph of the system and the adding concentration of the sodium carbonate and the silver nitrate, the two mutually promote the separation of electron-hole, which is beneficial to the rapid generation of photoelectron, and on the basis, the Ag is used2CO3/TiO2Soaking in carboxylic acid modified UiO-66, forming a plurality of octahedral and tetrahedral three-dimensional structures due to Zr-embedded pore cage structure in the metal organic framework porous material, and forming Ag2CO3、TiO2The embedding or the loading on the carrier shows that the transmission and the generation of the photo-electric ions are accelerated in a specific three-dimensional structure, and the photocatalysis efficiency is improved.
In addition, the traditional UiO-66 modification usually adopts-NH 2, -CH3 and the like, the invention adopts 1, 2, 4, 5-benzene tetracarboxylic acid as a ligand to replace other ligands, and adopts a simple hydrothermal solvent method to prepare the porous material, so that the porous material has good stability, high temperature resistance and pore structure performance. In addition, in the impregnation process, the method adopts a mode of combining step-by-step impregnation and partial impregnation, a part of active components are impregnated, then the second impregnation is carried out, and the two impregnations can ensure that the Ag is impregnated by two times2CO3、TiO2Fully embedded cage structure or UiO-66- (COOH)2In the active site, the catalyst is fully impregnated, which is beneficial to Ag2CO3、TiO2Fully dispersed and effectively exerts the composite photocatalytic performance.
Further, the invention also carries out more in-depth research, and adds the steps of B doping, and the specific steps are as follows:
(1) weighing tetrabutyl titanate according to the mass ratio of 1: 3-5, dissolving the tetrabutyl titanate in glacial acetic acid to prepare a mixed solution, and dissolving the mixed solution in absolute ethyl alcohol to obtain a solution A;
(2) weighing a template agent triethanolamine and a boron-containing component boric acid, and dissolving the template agent triethanolamine and the boron-containing component boric acid in absolute ethyl alcohol, wherein the mass ratio of the template agent to the absolute ethyl alcohol is 1: 5-25, so as to obtain a solution B;
(3) mixing the solution A and the solution B, adding 1/30-1/20 volume of distilled water of the mixed solution of the solution A and the solution B, stirring for 10-24 hours to obtain a clear solution, standing for 12 hours at 60-120 ℃ to form gel, and drying for 5-24 hours at 50-90 ℃;
(4) calcining the dried substance at 350-600 ℃ for 1-5 hours to remove the template agent, then soaking the dried substance in isopropanol, stirring and centrifugally separating to obtain the B-containing nano TiO2。
(5) The prepared B-containing nano TiO2Ultrasonically dispersing in water, adjusting pH value of the solution, and adding silver nitrate AgNO3Stirring the solution evenly, and then adding Na2CO3Generating a precipitate, washing the solid, drying at 100-150 ℃ to obtain the boron-containing Ag2CO3/TiO2。
(6) Synthesis of UIO-66- (COOH)2: ZrCl4 and glacial acetic acid are dissolved in a solvent DMF in a reaction kettle, ultrasonic dispersion is carried out for 10min-2h, then ligand 1, 2, 4, 5-benzenetetracarboxylic acid is put into the solution, stirring is carried out, crystallization reaction is carried out for 10-24 h at the temperature of 100-150 ℃, cooling is carried out after the reaction is finished, centrifugal filtration, washing and drying are carried out. Wherein the molar ratio of the components is ZrCl4, the ligand and the template agent glacial acetic acid is 1: 1-2: 20-30.
(7) Adding the Ag containing B in the step (5)2CO3/TiO2Dividing into two parts, firstly, a part of B-Ag2CO3/TiO2Dispersing in water by ultrasonic, transferring into inner container of polytetrafluoroethylene high-pressure reaction kettle, controlling temperature at 60-90 deg.C, adding UIO-66- (COOH)2The carrier material is first impregnated for 1-3 hours, dried at 80-100 ℃ for 1-3 hours, and then the rest of the B-Ag is added2CO3/TiO2Adding, stirring, performing second impregnation reaction for 1-3 hours, standing for 2-5 hours, washing, and drying at 80-100 ℃ for 1-3 hours to obtain Ag2CO3/TiO2/ UiO-66-(COOH)2A composite photocatalyst is provided. Ag in composite photocatalyst2CO3∶TiO2∶UiO-66-(COOH)2The mass ratio of the boron to the boron is 1-20: 20-50: 30-40, and the doping amount of the boron is 1-10 wt% based on the catalyst.
In the technical scheme, the metal salt silver carbonate and the nonmetal B ions are simultaneously doped, so that a synergistic effect can be formed, and a strong hole-electron is formed, thereby further improving the photocatalytic activity.
The prepared composite photocatalyst is applied to the degradation process of organic rhodamine and formaldehyde, a 3 mu L organic culture dish is put into a closed glass box, the photocatalyst is coated on the glass box, and the concentration of organic gas in the box is 1.8mg/m3And continuously irradiating a 30W fluorescent lamp, and inspecting the degradation rate of rhodamine and formaldehyde.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1
(1) Weighing tetrabutyl titanate according to the mass ratio of 1: 3, dissolving the tetrabutyl titanate in glacial acetic acid to prepare a mixed solution, and then dissolving the mixed solution in absolute ethyl alcohol to obtain a solution A;
(2) weighing a template agent triethanolamine and dissolving the template agent triethanolamine in absolute ethyl alcohol, wherein the mass ratio of the template agent to the absolute ethyl alcohol is 1: 10, so as to obtain a solution B;
(3) mixing the solution A and the solution B, adding 1/30 volume of distilled water into the mixed solution of the solution A and the solution B, stirring for 10 hours to obtain a clear solution, standing for 12 hours at 60 ℃ to form gel, and drying for 18 hours at 50 ℃;
(4) calcining the dried substance at 400 ℃ for 4 hours to remove the template agent, then soaking the dried substance in isopropanol, stirring and centrifugally separating to obtain the nano TiO2。
(5) The prepared nano TiO is2Ultrasonically dispersing in water, adjusting pH value of the solution, and adding silver nitrate 0.5mol/l AgNO3The solution is stirred evenly and then 1mol/l Na is added2CO3Generating precipitate, washing the solid, drying at 100 ℃ to obtain Ag2CO3/TiO2。
(6) Synthesis of UiO-66- (COOH)2: ZrCl4 and glacial acetic acid are dissolved in a solvent DMF in a reaction kettle, ultrasonic dispersion is carried out for 1h, then ligand 1, 2, 4, 5-benzenetetracarboxylic acid is put into the solution, stirring is carried out, crystallization reaction is carried out for 24 h at 100 ℃, cooling is carried out after the reaction is finished, centrifugal filtration, washing and drying are carried out. Wherein the molar ratio of the components is ZrCl4, the ligand and the template agent glacial acetic acid is 1: 20.
(7) Adding Ag in the step (5)2CO3/TiO2Dividing into two parts, firstly, a part of Ag2CO3/TiO2Dispersing in water by ultrasonic wave, transferring into inner container of polytetrafluoroethylene high-pressure reaction kettle, controlling temperature at 90 deg.C, adding UiO-66- (COOH)2The support material is first impregnated for 1 hour, dried at 80 ℃ for 3 hours and then the remainder of the Ag2CO3/TiO2Adding, stirring, soaking for 1 hr, standing for 2 hr, washing, and drying at 80 deg.C for 3 hr to obtain Ag2CO3/TiO2/UiO-66-(COOH)2A composite photocatalyst is provided. Ag in composite photocatalyst2CO3∶TiO2∶UiO-66-(COOH)2The mass ratio of (A) to (B) is 20: 40.
Example 2
(1) Weighing tetrabutyl titanate according to the mass ratio of 1: 4, dissolving the tetrabutyl titanate in glacial acetic acid to prepare a mixed solution, and then dissolving the mixed solution in absolute ethyl alcohol to obtain a solution A;
(2) weighing a template agent triethanolamine and dissolving the template agent triethanolamine in absolute ethyl alcohol, wherein the mass ratio of the template agent to the absolute ethyl alcohol is 1: 15, so as to obtain a solution B;
(3) mixing the solution A and the solution B, adding 1/20 volume of distilled water into the mixed solution of the solution A and the solution B, stirring for 12 hours to obtain a clear solution, standing for 12 hours at 100 ℃ to form gel, and drying for 6 hours at 80 ℃;
(4) calcining the dried substance at 600 deg.C for 1 hr to remove template agent, soaking in isopropanol, stirring, and centrifuging to obtain nanometer TiO2。
(5) The prepared nano TiO is2Dispersing in water by ultrasonic wave, and mixingAdding silver nitrate 1mol/l AgNO according to the pH value of the solution320ml of the solution is stirred evenly and then 1mol/l of Na is added2CO3Generating precipitate, washing the solid, drying at 120 ℃ to obtain Ag2CO3/TiO2。
(6) Synthesis of UiO-66- (COOH)2: ZrCl4 and glacial acetic acid are dissolved in a solvent DMF in a reaction kettle, ultrasonic dispersion is carried out for 30min, then ligand 1, 2, 4, 5-benzenetetracarboxylic acid is put into the solution, stirring is carried out, crystallization reaction is carried out for 10 hours at 150 ℃, cooling is carried out after the reaction is finished, centrifugal filtration, washing and drying are carried out. Wherein the molar ratio of the components is ZrCl4, the ligand and the template agent glacial acetic acid is 1: 20.
(7) Adding Ag in the step (5)2CO3/TiO2Dividing into two parts, firstly, a part of Ag2CO3/TiO2Dispersing in water by ultrasonic wave, transferring into inner container of polytetrafluoroethylene high-pressure reaction kettle, controlling temperature at 90 deg.C, adding UiO-66- (COOH)2The support material is first impregnated for 2 hours, dried at 80 ℃ for 2 hours and then the remainder of the Ag2CO3/TiO2Adding, stirring, soaking for 2 hr, standing for 3 hr, washing, and drying at 80 deg.C for 2 hr to obtain Ag2CO3/TiO2/UiO-66-(COOH)2A composite photocatalyst is provided. Ag in composite photocatalyst2CO3∶TiO2∶UiO-66-(COOH)2The mass ratio of (A) to (B) is 15: 50: 35.
Example 3
(1) Weighing tetrabutyl titanate according to the mass ratio of 1: 5, dissolving the tetrabutyl titanate in glacial acetic acid to prepare a mixed solution, and then dissolving the mixed solution in absolute ethyl alcohol to obtain a solution A;
(2) weighing a template agent triethanolamine and dissolving the template agent triethanolamine in absolute ethyl alcohol, wherein the mass ratio of the template agent to the absolute ethyl alcohol is 1: 25, so as to obtain a solution B;
(3) mixing the solution A and the solution B, adding 1/20 volume of distilled water into the mixed solution of the solution A and the solution B, stirring for 12 hours to obtain a clear solution, standing for 12 hours at 100 ℃ to form gel, and drying for 12 hours at 60 ℃;
(4) will dryCalcining the dried substance at 350-600 ℃ for 1-5 hours to remove the template agent, then soaking the dried substance in isopropanol, stirring and centrifugally separating to obtain the nano TiO2。
(5) The prepared nano TiO is2Ultrasonically dispersing in water, regulating pH to 9-11, adding silver nitrate 0.5mol/l AgNO3The solution is stirred evenly and then 1mo/l Na is added2CO3Generating a precipitate, washing the solid, drying at the temperature of 100-2CO3/TiO2。
(6) Synthesis of UiO-66- (COOH)2: ZrCl4 and glacial acetic acid are dissolved in a solvent DMF in a reaction kettle, ultrasonic dispersion is carried out for 1h, then ligand 1, 2, 4, 5-benzenetetracarboxylic acid is put into the solution, stirring is carried out, crystallization reaction is carried out for 12 h at 120 ℃, cooling is carried out after the reaction is finished, centrifugal filtration, washing and drying are carried out. Wherein the molar ratio of the components is ZrCl4, the ligand and the template agent glacial acetic acid is 1: 2: 30.
(7) Adding Ag in the step (5)2CO3/TiO2Dividing into two parts, firstly, a part of Ag2CO3/TiO2Dispersing in water by ultrasonic wave, transferring into inner container of polytetrafluoroethylene high-pressure reaction kettle, controlling temperature at 60-90 deg.C, adding UiO-66- (COOH)2The support material is first impregnated for 3 hours, dried at 100 ℃ for 2 hours and then the remainder of the Ag2CO3/TiO2Adding, stirring uniformly, carrying out second impregnation reaction for 3 hours, standing for 3 hours, washing, and drying at 100 ℃ for 2 hours to obtain Ag2CO3/TiO2/UiO-66-(COOH)2A composite photocatalyst is provided. Ag in composite photocatalyst2CO3∶TiO2∶UiO-66-(COOH)2The mass ratio of (A) to (B) is 10: 50: 40.
Example 4
(1) Weighing tetrabutyl titanate according to the mass ratio of 1: 5, dissolving the tetrabutyl titanate in glacial acetic acid to prepare a mixed solution, and then dissolving the mixed solution in absolute ethyl alcohol to obtain a solution A;
(2) weighing a template agent triethanolamine and a boron-containing component boric acid, and dissolving the template agent triethanolamine and the boron-containing component boric acid in absolute ethyl alcohol, wherein the mass ratio of the template agent to the absolute ethyl alcohol is 1: 10, so as to obtain a solution B;
(3) mixing the solution A and the solution B, adding 1/20 volume of distilled water into the mixed solution of the solution A and the solution B, stirring for 10 hours to obtain a clear solution, standing for 12 hours at 60 ℃ to form gel, and drying for 5 hours at 90 ℃;
(4) calcining the dried substance at 600 ℃ for 1 hour to remove the template agent, then soaking the dried substance in isopropanol, stirring and centrifugally separating to obtain the B-containing nano TiO2。
(5) The prepared B-containing nano TiO2Ultrasonically dispersing in water, adjusting pH value of the solution, and adding silver nitrate AgNO3Stirring the solution evenly, and then adding Na2CO3Generating precipitate, washing the solid, drying at 100 ℃ to obtain the boron-containing Ag2CO3/TiO2。
(6) Synthesis of UiO-66- (COOH)2: ZrCl4 and glacial acetic acid are dissolved in a solvent DMF in a reaction kettle, ultrasonic dispersion is carried out for 30min, then ligand 1, 2, 4, 5-benzenetetracarboxylic acid is put into the solution, stirring is carried out, crystallization reaction is carried out for 12 hours at 120 ℃, cooling is carried out after the reaction is finished, centrifugal filtration, washing and drying are carried out. Wherein the molar ratio of the components is ZrCl4, the ligand and the template agent glacial acetic acid is 1: 30.
(7) Adding the Ag containing B in the step (5)2CO3/TiO2Dividing into two parts, firstly, a part of B-Ag2CO3/TiO2Dispersing in water by ultrasonic wave, transferring into inner container of polytetrafluoroethylene high pressure reaction kettle, controlling temperature at 60-90 deg.C, adding UiO-66- (COOH)2The support material is first impregnated for 3 hours, dried at 100 ℃ for 2 hours and the remainder of the B-Ag is then dried2CO3/TiO2Adding, stirring, soaking for 3 hr, standing for 4 hr, washing, and drying at 100 deg.C for 2 hr to obtain Ag2CO3/TiO2/UIO-66-(COOH)2A composite photocatalyst is provided. Ag in composite photocatalyst2CO3∶TiO2∶UiO-66-(COOH)2The mass ratio of (A) to (B) is 10: 50: 40. The doping amount of boron is 10 wt% of the catalyst.
Comparative example 1
Without using a carrierBody, preparation of Ag only2CO3/TiO2The composite photocatalyst has the same experimental parameters as those in example 1.
Comparative example 2
Impregnating Ag with carrier alumina2CO3/TiO2Ag was obtained in the same manner as in example 1 except for the other experimental parameters2CO3/TiO2/Al2O3A load type composite photocatalyst.
Comparative example 3
Soaking Ag in carrier SBA-15 molecular sieve2CO3/TiO2Ag was obtained in the same manner as in example 1 except for the other experimental parameters2CO3/TiO2SBA-15 supported composite photocatalyst.
Comparative example 4
Adopting a UiO-66(Zr) carrier which is not modified by carboxylic acid to load impregnated Ag2CO3/TiO2Ag was obtained in the same manner as in example 1 except for the other experimental parameters2CO3/TiO2the/UiO-66 load type composite photocatalyst.
Comparative example 5
The Ag obtained by one-step impregnation is obtained by adopting simple one-step impregnation and other parameters are the same as those of the example 12CO3/TiO2/UiO-66-(COOH)2A load type composite photocatalyst.
Application example
The composite visible light photocatalyst prepared in the examples and the comparative examples is used for degrading organic matters such as rhodamine, formaldehyde and the like, a 3 mu L organic matter culture dish is put into a closed glass box and is coated with the photocatalyst, and the concentration of organic matter gas in the box is 1.8mg/m3The degradation rates of rhodamine and formaldehyde under the continuous irradiation of 30W fluorescent lamp are shown in the following table 1.
The results show that the supported visible light composite catalyst still has the excellent effect that the adsorption rate of rhodamine and formaldehyde organic matters is more than 98 percent under the conditions of small catalyst dosage and short illumination time (less than 20min), and has important significance for greatly improving the efficiency of photodegradation of organic matters by compounding nano carbon dioxide with silver carbonate and modifying a carrier. And the preparation process of the catalyst is simple, and the catalyst is expected to be subjected to industrial tests and popularization.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be made by those skilled in the art without inventive work within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (3)
1. The preparation method of the composite visible light photocatalyst is characterized in that the photocatalyst is made of Ag2CO3/TiO2/UiO-66-(COOH)2The preparation method comprises the following steps:
(1) weighing tetrabutyl titanate according to the mass ratio of 1: 3, dissolving the tetrabutyl titanate in glacial acetic acid to prepare a mixed solution, and then dissolving the mixed solution in absolute ethyl alcohol to obtain a solution A;
(2) weighing a template agent triethanolamine and dissolving the template agent triethanolamine in absolute ethyl alcohol, wherein the mass ratio of the template agent to the absolute ethyl alcohol is 1: 10, so as to obtain a solution B;
(3) mixing the solution A and the solution B, adding 1/30 volume of distilled water into the mixed solution of the solution A and the solution B, stirring for 10 hours to obtain a clear solution, standing for 12 hours at 60 ℃ to form gel, and drying for 18 hours at 50 ℃;
(4) calcining the dried substance at 400 ℃ for 4 hours to remove the template agent, then soaking the dried substance in isopropanol, stirring and centrifugally separating to obtain the nano TiO2；
(5) The prepared nano TiO is2Ultrasonically dispersing in water, adjusting pH value of the solution, and adding silver nitrate 0.5mol/l AgNO3The solution is stirred evenly and then 1mol/l Na is added2CO3Generating precipitate, washing the solid, drying at 100 ℃ to obtain Ag2CO3/TiO2；
(6) Synthesis of UiO-66- (COOH)2: ZrCl4 and glacial acetic acid are dissolved in a solvent DMF in a reaction kettle, ultrasonic dispersion is carried out for 1h, then ligand 1, 2, 4, 5-benzenetetracarboxylic acid is put into the solution, stirring is carried out, crystallization reaction is carried out for 24 h at 100 ℃, cooling is carried out after the reaction is finished, centrifugal filtration, washing and drying are carried out; wherein the molar ratio of the components is ZrCl4, the ligand and the template agent glacial acetic acid is 1: 20;
(7) adding Ag in the step (5)2CO3/TiO2Dividing into two parts, firstly, a part of Ag2CO3/TiO2Dispersing in water by ultrasonic wave, transferring into inner container of polytetrafluoroethylene high-pressure reaction kettle, controlling temperature at 90 deg.C, adding UiO-66- (COOH)2The support material is first impregnated for 1 hour, dried at 80 ℃ for 3 hours and then the remainder of the Ag2CO3/TiO2Adding, stirring, soaking for 1 hr, standing for 2 hr, washing, and drying at 80 deg.C for 3 hr to obtain Ag2CO3/TiO2/UiO-66-(COOH)2Composite photocatalyst and Ag in composite photocatalyst2CO3∶TiO2∶UiO-66-(COOH)2The mass ratio of (A) to (B) is 20: 40.
2. The application of the composite visible light photocatalyst prepared by the preparation method according to claim 1 in degrading organic rhodamine and formaldehyde.
3. The use of claim 2, wherein the culture dish containing 3 μ L organic substances and the photocatalyst coated on the culture dish are contained in a sealed glass box, and the concentration of organic substance gas in the box is 1.8mg/m3And continuously irradiating the 30W fluorescent lamp.
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