CN110773239A - Ag-C co-doped TiO 2-perchloric acid pyranyl salt photocatalyst and preparation method thereof - Google Patents
Ag-C co-doped TiO 2-perchloric acid pyranyl salt photocatalyst and preparation method thereof Download PDFInfo
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- CN110773239A CN110773239A CN201911023035.6A CN201911023035A CN110773239A CN 110773239 A CN110773239 A CN 110773239A CN 201911023035 A CN201911023035 A CN 201911023035A CN 110773239 A CN110773239 A CN 110773239A
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 106
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 44
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 33
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 32
- -1 benzaldehyde compound Chemical class 0.000 claims abstract description 29
- IQTIKBNBZPMRCC-UHFFFAOYSA-N 2H-pyran-1-ium perchlorate Chemical compound [O-][Cl](=O)(=O)=O.C1[OH+]C=CC=C1 IQTIKBNBZPMRCC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- DTUQWGWMVIHBKE-UHFFFAOYSA-N Benzeneacetaldehyde Natural products O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 claims abstract description 13
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 13
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940100595 phenylacetaldehyde Drugs 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 43
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 12
- 239000008103 glucose Substances 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000008247 solid mixture Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229940079593 drug Drugs 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 7
- 230000005281 excited state Effects 0.000 abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000005283 ground state Effects 0.000 abstract description 3
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 3
- 238000010791 quenching Methods 0.000 abstract description 3
- 230000000171 quenching effect Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- TXDCDOVILUDCMT-UHFFFAOYSA-N 2,4,6-tribromobenzaldehyde Chemical compound BrC1=CC(Br)=C(C=O)C(Br)=C1 TXDCDOVILUDCMT-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- HWFUMAYINFTNSZ-UHFFFAOYSA-N 2,4,6-trinitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(C=O)C([N+]([O-])=O)=C1 HWFUMAYINFTNSZ-UHFFFAOYSA-N 0.000 description 1
- CPJXFDTWPWFJKF-UHFFFAOYSA-N 2-(2,4,6-trinitrophenyl)acetaldehyde Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(CC=O)C([N+]([O-])=O)=C1 CPJXFDTWPWFJKF-UHFFFAOYSA-N 0.000 description 1
- SBIYHGVIQIMBMG-UHFFFAOYSA-N 2-(3,5-dichlorophenyl)acetaldehyde Chemical compound ClC1=CC(Cl)=CC(CC=O)=C1 SBIYHGVIQIMBMG-UHFFFAOYSA-N 0.000 description 1
- VTYPJQNTKRSFKD-UHFFFAOYSA-N 2-(3,5-dinitrophenyl)acetaldehyde Chemical compound C(=O)CC1=CC(=CC(=C1)[N+]([O-])=O)[N+]([O-])=O VTYPJQNTKRSFKD-UHFFFAOYSA-N 0.000 description 1
- ZLDMZIXUGCGKMB-UHFFFAOYSA-N 3,5-dibromobenzaldehyde Chemical compound BrC1=CC(Br)=CC(C=O)=C1 ZLDMZIXUGCGKMB-UHFFFAOYSA-N 0.000 description 1
- CASRSOJWLARCRX-UHFFFAOYSA-N 3,5-dichlorobenzaldehyde Chemical compound ClC1=CC(Cl)=CC(C=O)=C1 CASRSOJWLARCRX-UHFFFAOYSA-N 0.000 description 1
- YCTNWTBGSOCMRO-UHFFFAOYSA-N 3,5-dinitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC(C=O)=CC([N+]([O-])=O)=C1 YCTNWTBGSOCMRO-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of chemical reaction photocatalysts and discloses Ag-C co-doped TiO
2The perchlorate pyran salt photocatalyst and the preparation method thereof comprise the following formula raw materials: benzaldehyde compound, phenylacetaldehyde compound, phosphorus oxychloride and Ag-C co-doped TiO
2. The Ag-C co-doped TiO
2A perchlorate photocatalyst and a preparation method thereof, when absorbing solar energy, the perchlorate absorbs electrons to form an excited state and has strong oxidation property, and C atoms replace TiO in the calcination process
2The O atoms in the lattice interstitial spaces form Ti-C bonds and C-O bonds with stronger bond energy and shorter bond length, which can inhibit the growth of the crystal lattice to a certain extentTiO
2Grain growth of TiO
2Has larger specific surface area and active site, Ag
+Electrons are easy to be abstracted in a reaction system, and the generated negative charges are used for a reduction quenching process in the catalysis process of the perchloric acid pyran salt derivative, so that the excited state of the perchloric acid pyran salt can absorb the charges and reduce the charges to a ground state, and the circulation process of the catalyst is completed.
Description
Technical Field
The invention relates to the technical field of chemical reaction photocatalysts, in particular to Ag-C co-doped TiO
2-a perchlorate photocatalyst and a process for producing the same.
Background
The search for simple, efficient, green and mild chemical reactions is a goal continuously pursued by chemical scientists, solar energy is used as clean energy and becomes an important component of energy used by human beings, sunlight is used as abundant clean energy to drive organic chemical reactions, chemical reactions driven by visible light can become a green and efficient synthesis strategy and serve the production and life of human beings, although human beings are aware of the fact that visible light can be applied to chemical reactions, chemical reactions driven by sunlight are relatively slow in development, on one hand, most of classical photochemical reactions are carried out under the action of biological harmful light ultraviolet light, and the reactions need to be carried out by means of complex instruments and equipment, on the other hand, most of compounds cannot directly absorb visible light, so that the wide application of sunlight to chemical reactions is limited, how to convert the light energy of sunlight into chemical energy to drive the chemical reaction is a hot spot of chemical research in recent years.
At present, most of photoreactions need to add visible light catalysts, mainly comprise noble metal photocatalysts such as Ru (II), Ir (III) complex and the like, and organic dye photocatalysts comprise Rose Bengal, eosin Y, Mes-Acr
+ClO
2The photocatalyst has good photocatalytic activity and is widely applied to photoreaction organic synthesis, but the noble metal photocatalyst is difficult to prepare and expensive, while the organic dye photocatalyst has narrow light absorption waveband and low oxidation-reduction potential, so that the photocatalytic performance is poor, and the organic dye photocatalyst easily causes environmental pollution, thereby limiting the practical application of the organic dye photocatalyst.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an Ag-C co-doped TiO
2The perchlorate pyranoid salt photocatalyst and the preparation method thereof solve the problems of the organic dye photocatalyst that the light absorption waveband is narrow, the oxidation-reduction potential is low and the photocatalysis performance is poor, and simultaneously solve the problems of difficult recovery and easy environmental pollution of the organic dye photocatalyst.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: Ag-C co-doped TiO
2The perchlorate pyran salt photocatalyst and the preparation method thereof comprise the following formula raw materials in parts by weight: 3-5 parts of benzaldehyde compound, 6-10 parts of phenylacetaldehyde compound, 36-60 parts of phosphorus oxychloride and 25-55 parts of Ag-C co-doped TiO
2The preparation method comprises the following experimental medicines: glucose, isopropyl titanate, absolute ethyl alcohol, silver nitrate, hexadecyl trimethyl ammonium bromide, dilute hydrochloric acid and anhydrous acetonitrile.
Preferably, the amount concentration of the dilute hydrochloric acid substance is 5-8mol/L, and the mass fraction is 17-25%.
Preferably, the preparation method of the Ag-C co-doped TiO2 comprises the following steps: adding 200-80 mL of anhydrous ethanol into a hydrothermal synthesis automatic reaction kettle, adding 3-5 parts of silver nitrate, stirring at a constant speed for dissolving, sequentially adding 70-82 parts of isopropyl titanate, 10-15 parts of glucose and 5-10 parts of hexadecyltrimethylammonium bromide, stirring at a constant speed for dissolving, slowly dropwise adding dilute hydrochloric acid to adjust the pH value of the solution to 3-4, setting the temperature of the automatic reaction kettle to be 120-130 ℃, stirring at a constant speed for reacting for 5-7 hours, removing the ethanol from the materials through concentration under reduced pressure after the reaction is finished, placing a solid mixture into a tubular resistance furnace, heating at a rate of 5 ℃/min to 520-550 ℃, maintaining the temperature for calcining for 4-6 hours, placing the calcined product into a high-energy planetary ball mill, setting a revolution rate of 50-80rpm and a rotation rate of 600-630rpm for ball milling, until the materials completely pass through a 800-mesh sieve, washing the ball-milled product by using a proper amount of distilled water, placing the ball-milled product in an oven, heating and fully drying the ball-milled product to obtain the Ag-C co-doped TiO
2。
Preferably, the benzaldehyde compound has a general formula
R
1The group is any one of 2,4, 6-trinitro, 3, 5-dinitro, 2,4, 6-tribromo, 3, 5-tribromo, 2,4, 6-trichloro and 3, 5-dichloro.
Preferably, the phenylacetaldehyde compound has a general formula
R
2The group is any one of 2,4, 6-trinitro, 3, 5-dinitro, 2,4, 6-tribromo, 3, 5-tribromo, 2,4, 6-trichloro and 3, 5-dichloro.
Preferably, the perchlorate salt derivative is any one of the following compounds:
the preparation method comprises the following steps: (1) adding a reflux device into the three-necked bottle, and introducing N
2Discharging the air in the reaction device, sequentially adding 300-800mL of anhydrous acetonitrile, 3-5 parts of benzaldehyde compound and 6-10 parts of phenylacetaldehyde compound, stirring uniformly, adding 36-60 parts of phosphorus oxychloride, placing the three-necked bottle in a constant-temperature water bath kettle, heating to 75-80 ℃ under the condition of N
2Stirring at constant speed for reaction for 24-30h in the atmosphere, after the reaction is finished, concentrating the materials under reduced pressure to remove anhydrous acetonitrile, washing the concentrated mixture by using a proper amount of anhydrous diethyl ether to obtain a perchloric acid pyranyl salt derivative, wherein the reaction equation is as follows:
preferably, the mass ratio of the benzaldehyde compound to the phenylacetaldehyde compound to the phosphorus oxychloride is 1:2-2.5: 12-15.
Preferably, the Ag-C co-doped TiO
2The preparation method of the perchlorate photocatalyst comprises the following steps: adding 300-500mL of absolute ethanol into a reaction bottle, and sequentially adding 25-55 parts of Ag-C co-doped TiO
2And perchloric acid pyran salt derivative, stirring, placing the reaction bottle in an ultrasonic disperser, heating to 45-50 ℃, performing ultrasonic dispersion for 2-3h at the ultrasonic frequency of 22-28KHz, transferring the solution into a high-speed centrifuge at the centrifugal speed of 12000-15000rpm, removing the upper layer of absolute ethanol solution, placing the solid in an oven, heating to 60-70 ℃, and drying to obtain the Ag-C co-doped TiO
2-a perchlorate photocatalyst.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
1. the Ag-C co-doped TiO
2A perchlorate photocatalyst and a process for producing the same, wherein the perchlorate derivative has an ultraviolet absorption spectrum peak of 395-510nm when absorbing sunlightThe catalyst can absorb electrons to form an excited state, which is equivalent to a traditional organic dye photocatalyst, and has very high oxidation potential, strong oxidizability, and can oxidize inert substances, promote the forward progress of chemical reaction, and realize the generation of sunlight-driven chemical reaction, and meanwhile, the perchlorate derivative contains a plurality of electron-withdrawing groups of nitryl or Br and Cl atoms, thereby reducing the electron cloud density of a pyran ring and an even triphenyl bonding C atom, leading the polarity of the perchlorate derivative to be larger, greatly increasing the catalytic activity of the perchlorate derivative, leading the structural stability and the chemical stability of the perchlorate derivative to be greatly improved due to a highly symmetrical structure, avoiding the phenomenon that the catalyst is decomposed in a reaction system in the using process, and improving the practicability and the service life of the catalyst.
2. The Ag-C co-doped TiO
2-perchloric acid pyranyl salt photocatalyst and preparation method thereof, and Ag-C co-doped TiO
2，TiO
2Has full absorption band of ultraviolet visible spectrum, increases the performance of catalyst for absorbing light energy, and realizes Ag-C co-doping TiO by calcination method
2With appropriate amounts of C atoms replacing TiO at elevated temperatures
2The O atoms in the lattice interstitial form Ti-C bonds and C-O bonds with stronger bond energy and shorter bond length, and can inhibit TiO to a certain extent
2Grain growth of modified TiO
2And melamine pyrolysis produces trace amounts of NH
3And NH
4 +In TiO
2The surface of the crystal forms a topological structure, and the growth and agglomeration of crystal nucleus are inhibited, thereby reducing TiO
2Grain size of the crystals to TiO
2The material has larger specific surface area and active sites, enhances the performance of the material in absorbing light energy, and simultaneously, the larger specific surface area can lead the perchlorate derivative to be better loaded on TiO
2The surface of (2) inhibits the agglomeration of perchlorate into large particles to a certain extent, thereby reducing the catalytic performance, and Ag is doped with TiO
2Middle, Ag
+Has strong oxidation performance, can be used as a synergistic catalytic system, and Ag
+Electrons in the reaction system are easy to be abstracted in the reaction system, and the generated negative charge is used for the perchloric acid pyran salt derivativeIn the reduction quenching process in the catalysis process, the excited state of the perchloric acid pyran salt can absorb charges and reduce the charges to a ground state, so that the catalyst circulation process is completed, and the photocatalysis effect of the catalyst is greatly improved.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: Ag-C co-doped TiO
2The perchlorate pyran salt photocatalyst and the preparation method thereof comprise the following formula raw materials in parts by weight: 3-5 parts of benzaldehyde compound, 6-10 parts of phenylacetaldehyde compound, 36-60 parts of phosphorus oxychloride and 25-55 parts of Ag-C co-doped TiO
2The preparation method comprises the following experimental medicines: glucose, isopropyl titanate, absolute ethyl alcohol, silver nitrate, hexadecyl trimethyl ammonium bromide, dilute hydrochloric acid and anhydrous acetonitrile, wherein the amount concentration of the dilute hydrochloric acid is 5-8mol/L, and the mass fraction is 17-25%.
The preparation method of the Ag-C co-doped TiO2 comprises the following steps: adding 200-80 mL of anhydrous ethanol into a hydrothermal synthesis automatic reaction kettle, adding 3-5 parts of silver nitrate, stirring at a constant speed for dissolving, sequentially adding 70-82 parts of isopropyl titanate, 10-15 parts of glucose and 5-10 parts of hexadecyltrimethylammonium bromide, stirring at a constant speed for dissolving, slowly dropwise adding dilute hydrochloric acid to adjust the pH value of the solution to 3-4, setting the temperature of the automatic reaction kettle to be 120-130 ℃, stirring at a constant speed for reacting for 5-7 hours, removing the ethanol from the materials through concentration under reduced pressure after the reaction is finished, placing a solid mixture into a tubular resistance furnace, heating at a rate of 5 ℃/min to 520-550 ℃, maintaining the temperature for calcining for 4-6 hours, placing the calcined product into a high-energy planetary ball mill, setting a revolution rate of 50-80rpm and a rotation rate of 600-630rpm for ball milling, until the materials completely pass through a 800-mesh sieve, washing the ball-milled product by using a proper amount of distilled water, placing the ball-milled product in an oven, heating and fully drying the ball-milled product to obtain the Ag-C co-doped TiO
2。
The benzaldehyde compound has the general formula
R
1The group is any one of 2,4, 6-trinitro, 3, 5-dinitro, 2,4, 6-tribromo, 3, 5-tribromo, 2,4, 6-trichloro and 3, 5-dichloro, and the phenylacetaldehyde compound is generally usedIs of the formula
R
2The group is any one of 2,4, 6-trinitro, 3, 5-dinitro, 2,4, 6-tribromo, 3, 5-tribromo, 2,4, 6-trichloro and 3, 5-dichloro.
The perchloric acid pyran salt derivative is any one of the following compounds:
the preparation method comprises the following steps: (1) adding a reflux device into the three-necked bottle, and introducing N
2Discharging the air in the reaction device, sequentially adding 300-800mL of anhydrous acetonitrile, 3-5 parts of benzaldehyde compound and 6-10 parts of phenylacetaldehyde compound, uniformly stirring, then adding 36-60 parts of phosphorus oxychloride, wherein the mass ratio of the benzaldehyde compound to the phenylacetaldehyde compound to the phosphorus oxychloride is 1:2-2.5:12-15, placing the three-neck bottle in a constant-temperature water bath kettle, heating to 75-80 ℃, and placing the bottle in a N-shaped constant-temperature water bath kettle
2Stirring at constant speed for reaction for 24-30h in the atmosphere, after the reaction is finished, concentrating the materials under reduced pressure to remove anhydrous acetonitrile, washing the concentrated mixture by using a proper amount of anhydrous diethyl ether to obtain a perchloric acid pyranyl salt derivative, wherein the reaction equation is as follows:
Ag-C codoped TiO
2The preparation method of the perchlorate photocatalyst comprises the following steps: adding 300-500mL of absolute ethanol into a reaction bottle, and sequentially adding 25-55 parts of Ag-C co-doped TiO
2And perchloric acid pyran salt derivative, stirring, placing the reaction bottle in an ultrasonic disperser, heating to 45-50 ℃, performing ultrasonic dispersion for 2-3h at the ultrasonic frequency of 22-28KHz, transferring the solution into a high-speed centrifuge at the centrifugal speed of 12000-15000rpm, removing the upper layer of absolute ethanol solution, placing the solid in an oven, heating to 60-70 ℃, and drying to obtain the Ag-C co-doped TiO
2-a perchlorate photocatalyst.
Example 1:
(1) the preparation method of the Ag-C co-doped TiO2 comprises the following steps: adding 200mL of absolute ethyl alcohol into a hydro-thermal synthesis automatic reaction kettle, adding 3 parts of silver nitrate, stirring at a constant speed for dissolving, sequentially adding 82 parts of isopropyl titanate, 10 parts of glucose and 5 parts of hexadecyl trimethyl ammonium bromide, stirring at a constant speed for dissolving, slowly dropwise adding dilute hydrochloric acid to adjust the pH value of the solution to 3, setting the temperature of the automatic reaction kettle to 120 ℃, stirring at a constant speed for reaction for 5 hours, removing ethanol from the materials after the reaction is finished by decompression and concentration, placing the solid mixture in a tubular resistance furnace, heating at the rate of 5 ℃/min to 520 ℃, maintaining the temperature for calcination for 4 hours, placing the calcined product in a high-energy planetary ball mill, setting the revolution rate to be 50rpm and the rotation rate to be 600rpm for ball milling until the materials completely pass through a 800-mesh screen, washing the ball milling product by using a proper amount of distilled water, and placing the ball milling product in an oven to be heated and fully dried to obtain the Ag-C co-doped TiO.
2And (3) component 1.
(2) Preparation of a perchlorate derivative: adding a reflux device into the three-necked bottle, and introducing N
2Discharging the air in the reaction device, sequentially adding 300mL of anhydrous acetonitrile, 3 parts of 2,4, 6-trinitrobenzaldehyde and 6 parts of 2,4, 6-trinitrophenylacetaldehyde, stirring uniformly, adding 36 parts of phosphorus oxychloride, placing the three-necked bottle in a constant-temperature water bath kettle, heating to 75 ℃ in an N-shaped water bath kettle
2Stirring at a constant speed for reaction for 24h in the atmosphere, concentrating the materials under reduced pressure after the reaction is finished to remove anhydrous acetonitrile, washing the concentrated mixture by using a proper amount of anhydrous diethyl ether to obtain a perchlorate pyran salt derivative component 1, wherein the reaction equation is as follows:
(3) preparation of Ag-C codoped TiO
2-a perchlorate photocatalyst: adding 300mL of absolute ethyl alcohol into a reaction bottle, and sequentially adding 55 parts of Ag-C co-doped TiO prepared in the step (1)
2Uniformly stirring the component 1 and the perchloric acid pyran salt derivative component 1 prepared in the step (2), placing a reaction bottle in an ultrasonic disperser, heating to 45 ℃, performing ultrasonic dispersion for 2 hours at the ultrasonic frequency of 22KHz,then transferring the solution into a high-speed centrifuge, removing the upper layer of absolute ethyl alcohol solution at the centrifugal rotation speed of 12000rpm, placing the solid in an oven, heating to 60 ℃ and drying to obtain the Ag-C co-doped TiO
2Perchlorate photocatalyst 1.
Example 2:
(1) the preparation method of the Ag-C co-doped TiO2 comprises the following steps: adding 200mL of absolute ethyl alcohol into a hydro-thermal synthesis automatic reaction kettle, adding 3 parts of silver nitrate, stirring at a constant speed for dissolving, sequentially adding 82 parts of isopropyl titanate, 10 parts of glucose and 5 parts of hexadecyl trimethyl ammonium bromide, stirring at a constant speed for dissolving, slowly dropwise adding dilute hydrochloric acid to adjust the pH value of the solution to 3, setting the temperature of the automatic reaction kettle to 130 ℃, stirring at a constant speed for reaction for 5 hours, removing ethanol from the materials after the reaction is finished by decompression and concentration, placing the solid mixture in a tubular resistance furnace, heating at the rate of 5 ℃/min to 520 ℃, maintaining the temperature for calcination for 4 hours, placing the calcined product in a high-energy planetary ball mill, setting the revolution rate to be 80rpm and the rotation rate to be 600rpm for ball milling until the materials completely pass through a 800-mesh screen, washing the ball-milled product by using a proper amount of distilled water, and placing the ball-milled product in an oven for heating and fully drying the water to obtain the Ag-C co-doped TiO.
2And (3) component 2.
(2) Preparation of a perchlorate derivative: adding a reflux device into the three-necked bottle, and introducing N
2Discharging the air in the reaction device, sequentially adding 600mL of anhydrous acetonitrile, 3 parts of 3, 5-dinitrobenzaldehyde and 6 parts of 3, 5-dinitrophenylacetaldehyde, uniformly stirring, then adding 36 parts of phosphorus oxychloride, placing the three-necked bottle in a constant-temperature water bath kettle, heating to 75 ℃ in an N-shaped solution
2Stirring at constant speed for reaction for 30h in the atmosphere, after the reaction is finished, concentrating the materials under reduced pressure to remove anhydrous acetonitrile, washing the concentrated mixture by using a proper amount of anhydrous diethyl ether to obtain a perchlorate pyran salt derivative component 2, wherein the reaction equation is as follows:
(3) preparation of Ag-C codoped TiO
2-a perchlorate photocatalyst: adding 300mL of absolute ethyl alcohol into the reaction bottle, and addingSequentially adding 55 parts of Ag-C co-doped TiO prepared in the step (1)
2Uniformly stirring the component 2 and the perchloric acid pyran salt derivative component 2 prepared in the step (2), placing a reaction bottle in an ultrasonic disperser, heating to 45 ℃, performing ultrasonic dispersion for 2 hours at the ultrasonic frequency of 22KHz, transferring the solution into a high-speed centrifuge, removing the upper layer of absolute ethanol solution, placing the solid in an oven, heating to 60 ℃, and drying to obtain the Ag-C co-doped TiO
2Perchlorate photocatalyst 2.
Example 3:
(1) the preparation method of the Ag-C co-doped TiO2 comprises the following steps: adding 300mL of absolute ethyl alcohol into a hydro-thermal synthesis automatic reaction kettle, adding 4 parts of silver nitrate, stirring at a constant speed for dissolving, sequentially adding 77 parts of isopropyl titanate, 12 parts of glucose and 7 parts of hexadecyl trimethyl ammonium bromide, stirring at a constant speed for dissolving, slowly dropwise adding dilute hydrochloric acid to adjust the pH value of the solution to 4, setting the temperature of the automatic reaction kettle to 130 ℃, stirring at a constant speed for reaction for 6 hours, removing ethanol from the materials after the reaction is finished by decompression and concentration, placing the solid mixture in a tubular resistance furnace, heating at the rate of 5 ℃/min to 530 ℃, maintaining the temperature for calcination for 6 hours, placing the calcined product in a high-energy planetary ball mill, setting the revolution rate to be 60rpm and the rotation rate to be 600rpm for ball milling until the materials completely pass through a 800-mesh screen, washing the ball-milled product by using a proper amount of distilled water, and placing the ball-milled product in an oven for heating and fully drying the water to obtain the Ag-C co-doped TiO.
2And (3) component.
(2) Preparation of a perchlorate derivative: adding a reflux device into the three-necked bottle, and introducing N
2Discharging the air in the reaction device, sequentially adding 600mL of anhydrous acetonitrile, 4 parts of 2,4, 6-tribromobenzaldehyde and 8 parts of 2,4, 6-tribromophenylacetaldehyde, stirring uniformly, adding 50 parts of phosphorus oxychloride, placing the three-necked bottle in a constant-temperature water bath kettle, heating to 80 ℃, and adding N
2Stirring at constant speed for reaction for 27h in the atmosphere, after the reaction is finished, concentrating the materials under reduced pressure to remove anhydrous acetonitrile, washing the concentrated mixture by using a proper amount of anhydrous diethyl ether to obtain a perchlorate pyran salt derivative component 3, wherein the reaction equation is as follows:
(3) preparation of Ag-C codoped TiO
2-a perchlorate photocatalyst: adding 400mL of absolute ethyl alcohol into a reaction bottle, and sequentially adding 38 parts of Ag-C co-doped TiO prepared in the step (1)
2Uniformly stirring the component 3 and the perchloric acid pyran salt derivative component 3 prepared in the step (2), placing a reaction bottle in an ultrasonic disperser, heating to 50 ℃, performing ultrasonic dispersion for 3 hours at the ultrasonic frequency of 22KHz, transferring the solution into a high-speed centrifuge, centrifuging at the rotating speed of 15000rpm, removing the upper layer of absolute ethanol solution, placing the solid in an oven, heating to 70 ℃, and drying to obtain the Ag-C co-doped TiO
2Perchlorate photocatalyst 3.
Example 4:
(1) the preparation method of the Ag-C co-doped TiO2 comprises the following steps: adding 500mL of absolute ethyl alcohol into a hydro-thermal synthesis automatic reaction kettle, adding 5 parts of silver nitrate, stirring at a constant speed for dissolving, sequentially adding 70 parts of isopropyl titanate, 15 parts of glucose and 10 parts of hexadecyl trimethyl ammonium bromide, stirring at a constant speed for dissolving, slowly dropwise adding dilute hydrochloric acid to adjust the pH value of the solution to 4, setting the temperature of the automatic reaction kettle to 130 ℃, stirring at a constant speed for reaction for 6 hours, removing ethanol from the materials after the reaction is finished by decompression and concentration, placing the solid mixture in a tubular resistance furnace, heating at the rate of 5 ℃/min to 550 ℃, maintaining the temperature for calcination for 6 hours, placing the calcined product in a high-energy planetary ball mill, setting the revolution rate to be 80rpm and the rotation rate to be 630rpm for ball milling until the materials completely pass through a 800-mesh screen, washing the ball milling product by using a proper amount of distilled water, and placing the ball milling product in an oven to be heated and fully dried to obtain the Ag-C co-doped TiO.
2And (4) component.
(2) Preparation of a perchlorate derivative: adding a reflux device into the three-necked bottle, and introducing N
2Discharging the air in the reaction device, sequentially adding 600mL of anhydrous acetonitrile, 4 parts of 3, 5-dibromobenzaldehyde and 9 parts of 3, 5-dibromoacetaldehyde, stirring uniformly, then adding 51 parts of phosphorus oxychloride, placing the three-necked bottle in a constant-temperature water bath kettle, heating to 80 ℃ in an N-N reaction kettle
2Stirring and reacting at uniform speed in atmosphereAnd (3) after the reaction is finished, removing anhydrous acetonitrile from the materials through reduced pressure concentration, washing and concentrating the mixture by using a proper amount of anhydrous diethyl ether, and obtaining a perchloric acid pyranyl salt derivative component 4, wherein the reaction equation is as follows:
(3) preparation of Ag-C codoped TiO
2-a perchlorate photocatalyst: adding 500mL of absolute ethyl alcohol into a reaction bottle, and sequentially adding 36 parts of Ag-C co-doped TiO prepared in the step (1)
2Uniformly stirring the component 4 and the perchlorate pyran salt derivative component 4 prepared in the step (2), placing a reaction bottle in an ultrasonic disperser, heating to 50 ℃, performing ultrasonic dispersion for 3 hours at the ultrasonic frequency of 26KHz, transferring the solution into a high-speed centrifuge, removing the upper layer of absolute ethanol solution, placing the solid in an oven, heating to 65 ℃, and drying to obtain the Ag-C co-doped TiO salt derivative component 4
2A perchlorate photocatalyst 4.
Example 5:
(1) the preparation method of the Ag-C co-doped TiO2 comprises the following steps: adding 500mL of absolute ethanol into a hydrothermal synthesis automatic reaction kettle, adding 5 parts of silver nitrate, stirring at a constant speed for dissolving, sequentially adding 70 parts of isopropyl titanate, 15 parts of glucose and 10 parts of hexadecyltrimethylammonium bromide, stirring at a constant speed for dissolving, slowly and dropwise adding dilute hydrochloric acid to adjust the pH value of the solution to 4, setting the temperature of the automatic reaction kettle to 130 ℃, stirring at a constant speed for reacting for 5-7 hours, concentrating the materials under reduced pressure after the reaction is finished to remove the ethanol, placing the solid mixture into a tubular resistance furnace, heating at a heating rate of 5 ℃/min to 550 ℃, maintaining the temperature for calcining for 6 hours, placing the calcined product into a high-energy planetary ball mill, setting the revolution rate of 80rpm and the rotation rate of 630rpm for ball milling until the materials all pass through a 800-mesh screen, washing the ball-milled product with a proper amount of distilled water, placing the ball-milled product into an oven, to obtain Ag-C co-doped TiO
2And (5) component.
(2) Preparation of a perchlorate derivative: adding a reflux device into the three-necked bottle, and introducing N
2Discharging the air in the reaction device, sequentially adding 800mL of anhydrous acetonitrile, 5 parts of 2,4, 6-tribromobenzaldehyde and 10 parts of 2,4, 6-tribromophenylacetaldehyde, stirring uniformly, adding 60 parts of phosphorus oxychloride, placing the three-necked bottle in a constant-temperature water bath kettle, heating to 80 ℃, and adding N
2Stirring at constant speed for reaction for 30h in the atmosphere, after the reaction is finished, concentrating the materials under reduced pressure to remove anhydrous acetonitrile, washing the concentrated mixture by using a proper amount of anhydrous diethyl ether to obtain a perchlorate pyran salt derivative component 5, wherein the reaction equation is as follows:
(3) preparation of Ag-C codoped TiO
2-a perchlorate photocatalyst: adding 500mL of absolute ethyl alcohol into a reaction bottle, and sequentially adding 25 parts of Ag-C co-doped TiO prepared in the step (1)
2Uniformly stirring the component 5 and the perchloric acid pyran salt derivative component 5 prepared in the step (2), placing a reaction bottle in an ultrasonic disperser, heating to 50 ℃, performing ultrasonic dispersion for 3 hours at the ultrasonic frequency of 28KHz, transferring the solution into a high-speed centrifuge, removing the upper layer of absolute ethanol solution, placing the solid in an oven, heating to 70 ℃, and drying to obtain the Ag-C co-doped TiO
2A perchlorate photocatalyst 5.
Example 6:
(1) the preparation method of the Ag-C co-doped TiO2 comprises the following steps: adding 500mL of absolute ethanol into a hydrothermal synthesis automatic reaction kettle, adding 5 parts of silver nitrate, stirring at a constant speed for dissolving, sequentially adding 70 parts of isopropyl titanate, 15 parts of glucose and 10 parts of hexadecyltrimethylammonium bromide, stirring at a constant speed for dissolving, slowly and dropwise adding dilute hydrochloric acid to adjust the pH of the solution to 4, setting the temperature of the automatic reaction kettle to 130 ℃, stirring at a constant speed for reacting for 7 hours, concentrating the material under reduced pressure after the reaction is finished to remove the ethanol, placing the solid mixture into a tubular resistance furnace, heating at a rate of 5 ℃/min to 550 ℃, maintaining the temperature for calcining for 6 hours, placing the calcined product into a high-energy planetary ball mill, setting a revolution rate of 80rpm, performing ball milling at a rotation rate of 630rpm until the material completely passes through a 800-mesh screen, and using a proper amount of silver nitrateWashing the ball-milled product with distilled water, heating in an oven to fully dry the water to obtain the Ag-C co-doped TiO
2And (6) component.
(2) Preparation of a perchlorate derivative: adding a reflux device into the three-necked bottle, and introducing N
2Discharging the air in the reaction device, sequentially adding 800mL of anhydrous acetonitrile, 5 parts of 3, 5-dichlorobenzaldehyde and 10 parts of 3, 5-dichlorophenylacetaldehyde, uniformly stirring, adding 60 parts of phosphorus oxychloride, placing the three-necked bottle in a constant-temperature water bath kettle, heating to 80 ℃ in an N-shaped container, and adding a solvent to obtain a solution
2Stirring at constant speed for reaction for 30h in the atmosphere, after the reaction is finished, concentrating the materials under reduced pressure to remove anhydrous acetonitrile, washing the concentrated mixture by using a proper amount of anhydrous diethyl ether to obtain a perchlorate pyran salt derivative component 6, wherein the reaction equation is as follows:
(3) preparation of Ag-C codoped TiO
2-a perchlorate photocatalyst: adding 500mL of absolute ethyl alcohol into a reaction bottle, and sequentially adding 25 parts of Ag-C co-doped TiO prepared in the step (1)
2Uniformly stirring the component 6 and the perchloric acid pyran salt derivative component 6 prepared in the step (2), placing a reaction bottle in an ultrasonic disperser, heating to 50 ℃, performing ultrasonic dispersion for 2 hours at the ultrasonic frequency of 28KHz, transferring the solution into a high-speed centrifuge, removing the upper layer of absolute ethanol solution, placing the solid in an oven, heating to 70 ℃, and drying to obtain the Ag-C co-doped TiO
2A perchlorate photocatalyst 6.
In summary, the Ag-C co-doped TiO
2The ultraviolet absorption spectrum peak of the perchlorate derivative is 395-510nm, when absorbing the corresponding wave band of sunlight, the perchlorate derivative can absorb electrons to form an excited state, is equivalent to the traditional organic dye photocatalyst, has high oxidation potential, has strong oxidizability, can oxidize inert substances, promotes the forward progress of chemical reaction, realizes the generation of sunlight-driven chemical reaction, and simultaneously contains a plurality of electron-withdrawing groupsNitro or Br, Cl atom, reduced the pyran ring and the electronic cloud density of the homogeneous triphenyl bonding C atom, make the polarity of the pyrochloride derivative bigger, has increased its catalytic activity by a wide margin, and the pyrochloride derivative highly symmetrical structure makes its structural stability and chemical stability improve by a wide margin, has avoided the catalyst to decompose the phenomenon in the reaction system in the use, has improved the practicality and life of catalyst.
The Ag-C co-doped TiO
2-perchloric acid pyranyl salt photocatalyst and preparation method thereof, and Ag-C co-doped TiO
2，TiO
2Has full absorption band of ultraviolet visible spectrum, increases the performance of catalyst for absorbing light energy, and realizes Ag-C co-doping TiO by calcination method
2With appropriate amounts of C atoms replacing TiO at elevated temperatures
2The O atoms in the lattice interstitial form Ti-C bonds and C-O bonds with stronger bond energy and shorter bond length, and can inhibit TiO to a certain extent
2Grain growth of modified TiO
2And melamine pyrolysis produces trace amounts of NH
3And NH
4 +In TiO
2The surface of the crystal forms a topological structure, and the growth and agglomeration of crystal nucleus are inhibited, thereby reducing TiO
2Grain size of the crystals to TiO
2The material has larger specific surface area and active sites, enhances the performance of the material in absorbing light energy, and simultaneously, the larger specific surface area can lead the perchlorate derivative to be better loaded on TiO
2The surface of (2) inhibits the agglomeration of perchlorate into large particles to a certain extent, thereby reducing the catalytic performance, and Ag is doped with TiO
2Middle, Ag
+Has strong oxidation performance, can be used as a synergistic catalytic system, and Ag
+Electrons in the reaction system are easy to capture in the reaction system, and the generated negative charges are used in a reduction quenching process in the catalysis process of the perchlorate derivative, so that the excited state of the perchlorate can absorb the charges to be reduced to a ground state, the circulation process of the catalyst is completed, and the photocatalysis effect of the catalyst is greatly improved.
Claims (8)
1. Ag-C co-doped TiO
2-pyranyl perchlorate lightThe catalyst and the preparation method thereof comprise the following formula raw materials in parts by weight, and are characterized in that: 3-5 parts of benzaldehyde compound, 6-10 parts of phenylacetaldehyde compound, 36-60 parts of phosphorus oxychloride and 25-55 parts of Ag-C co-doped TiO
2The preparation method comprises the following experimental medicines: glucose, isopropyl titanate, absolute ethyl alcohol, silver nitrate, hexadecyl trimethyl ammonium bromide, dilute hydrochloric acid and anhydrous acetonitrile.
2. Ag-C co-doped TiO according to claim 1
2-a perchlorate photocatalyst and a process for producing the same, characterized in that: the quantity concentration of the dilute hydrochloric acid substance is 5-8mol/L, and the mass fraction is 17-25%.
3. Ag-C co-doped TiO according to claim 1
2-a perchlorate photocatalyst and a process for producing the same, characterized in that: the preparation method of the Ag-C co-doped TiO2 comprises the following steps: adding 200-80 mL of anhydrous ethanol into a hydrothermal synthesis automatic reaction kettle, adding 3-5 parts of silver nitrate, stirring at a constant speed for dissolving, sequentially adding 70-82 parts of isopropyl titanate, 10-15 parts of glucose and 5-10 parts of hexadecyltrimethylammonium bromide, stirring at a constant speed for dissolving, slowly dropwise adding dilute hydrochloric acid to adjust the pH value of the solution to 3-4, setting the temperature of the automatic reaction kettle to be 120-130 ℃, stirring at a constant speed for reacting for 5-7 hours, removing the ethanol from the materials through concentration under reduced pressure after the reaction is finished, placing a solid mixture into a tubular resistance furnace, heating at a rate of 5 ℃/min to 520-550 ℃, maintaining the temperature for calcining for 4-6 hours, placing the calcined product into a high-energy planetary ball mill, setting a revolution rate of 50-80rpm and a rotation rate of 600-630rpm for ball milling, until the materials completely pass through a 800-mesh sieve, washing the ball-milled product by using a proper amount of distilled water, placing the ball-milled product in an oven, heating and fully drying the ball-milled product to obtain the Ag-C co-doped TiO
2。
4. Ag-C co-doped TiO according to claim 1
2-a perchlorate photocatalyst and a process for producing the same, characterized in that: the general formula of the benzaldehyde compound is
R
1The group is any one of 2,4, 6-trinitro, 3, 5-dinitro, 2,4, 6-tribromo, 3, 5-tribromo, 2,4, 6-trichloro and 3, 5-dichloro.
5. Ag-C co-doped TiO according to claim 1
2-a perchlorate photocatalyst and a process for producing the same, characterized in that: the general formula of the phenylacetaldehyde compound is
R
2The group is any one of 2,4, 6-trinitro, 3, 5-dinitro, 2,4, 6-tribromo, 3, 5-tribromo, 2,4, 6-trichloro and 3, 5-dichloro.
6. Ag-C co-doped TiO according to claim 1
2-a perchlorate photocatalyst and a process for producing the same, characterized in that: the perchloric acid pyran salt derivative is any one of the following compounds:
the preparation method comprises the following steps: (1) adding a reflux device into the three-necked bottle, and introducing N
2Discharging the air in the reaction device, sequentially adding 300-800mL of anhydrous acetonitrile, 3-5 parts of benzaldehyde compound and 6-10 parts of phenylacetaldehyde compound, stirring uniformly, adding 36-60 parts of phosphorus oxychloride, placing the three-necked bottle in a constant-temperature water bath kettle, heating to 75-80 ℃ under the condition of N
2Stirring at constant speed for reaction for 24-30h in the atmosphere, after the reaction is finished, concentrating the materials under reduced pressure to remove anhydrous acetonitrile, washing the concentrated mixture by using a proper amount of anhydrous diethyl ether to obtain a perchloric acid pyranyl salt derivative, wherein the reaction equation is as follows:
7. Ag-C co-doped TiO according to claim 4
2-a perchlorate photocatalyst and a process for producing the same, characterized in that: the mass ratio of the benzaldehyde compound to the phenylacetaldehyde compound to the phosphorus oxychloride is 1:2-2.5: 12-15.
8. Ag-C co-doped TiO according to claim 1
2-a perchlorate photocatalyst and a process for producing the same, characterized in that: the Ag-C co-doped TiO
2The preparation method of the perchlorate photocatalyst comprises the following steps: adding 300-500mL of absolute ethanol into a reaction bottle, and sequentially adding 25-55 parts of Ag-C co-doped TiO
2And perchloric acid pyran salt derivative, stirring, placing the reaction bottle in an ultrasonic disperser, heating to 45-50 ℃, performing ultrasonic dispersion for 2-3h at the ultrasonic frequency of 22-28KHz, transferring the solution into a high-speed centrifuge at the centrifugal speed of 12000-15000rpm, removing the upper layer of absolute ethanol solution, placing the solid in an oven, heating to 60-70 ℃, and drying to obtain the Ag-C co-doped TiO
2-a perchlorate photocatalyst.
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