CN112958134A - Ag modified N-doped porous carbon loaded TiO2Composite material and method of making - Google Patents
Ag modified N-doped porous carbon loaded TiO2Composite material and method of making Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 137
- 239000000463 material Substances 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims description 66
- 239000008367 deionised water Substances 0.000 claims description 62
- 229910021641 deionized water Inorganic materials 0.000 claims description 62
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 57
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 238000002156 mixing Methods 0.000 claims description 47
- 238000001035 drying Methods 0.000 claims description 44
- 239000002243 precursor Substances 0.000 claims description 39
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 36
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 33
- 238000003763 carbonization Methods 0.000 claims description 30
- HBQUOLGAXBYZGR-UHFFFAOYSA-N 2,4,6-triphenyl-1,3,5-triazine Chemical compound C1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 HBQUOLGAXBYZGR-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000007833 carbon precursor Substances 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 22
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 20
- 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 19
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 19
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 18
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 14
- 229910052573 porcelain Inorganic materials 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000012300 argon atmosphere Substances 0.000 claims description 9
- 238000010000 carbonizing Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Natural products CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 46
- 239000004408 titanium dioxide Substances 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000011941 photocatalyst Substances 0.000 abstract description 6
- 229910052709 silver Inorganic materials 0.000 abstract description 6
- 239000004332 silver Substances 0.000 abstract description 6
- 239000012855 volatile organic compound Substances 0.000 abstract description 6
- 238000004887 air purification Methods 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000031700 light absorption Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 32
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- 230000015556 catabolic process Effects 0.000 description 8
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- 239000000047 product Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 7
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- 239000011812 mixed powder Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 208000000044 Amnesia Diseases 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 208000026139 Memory disease Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
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- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000006984 memory degeneration Effects 0.000 description 1
- 208000023060 memory loss Diseases 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- B01J35/23—
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
Abstract
The invention relates to the technical field of air purification, and discloses Ag modified N-doped porous carbon loaded TiO2The composite material is characterized in that titanium dioxide is one of the most promising catalysts for VOCs pollutants in photocatalysis, toluene can be decomposed into carbon dioxide and water under mild conditions, the porous carbon material has large specific surface area, good chemical stability, high conductivity and high electron mobility, the electron-hole pair recombination under ultraviolet illumination can be inhibited, meanwhile, the porous carbon has certain adsorbability for toluene, and nitrogen atoms are doped to ensure that electrons around pores of the porous carbon have certain adsorbabilityThe cloud density is increased, the electrostatic attraction of the p-toluene is improved, the metal silver has a large optical cross section in a visible light region, has a surface plasma resonance effect, is doped on the photocatalyst, enables the light absorption of the titanium dioxide to move towards a long wave direction, and improves the light absorption range and the light-generated electron-hole separation efficiency in the photocatalysis process.
Description
Technical Field
The invention relates to the technical field of air purification, in particular to Ag modified N-doped porous carbon loaded TiO2Composite materials and methods of preparation.
Background
With the rapid development of social economy, the quality of life of people is improved to a great extent, but the problem of environmental pollution brought by people is not small and varies while people pursue life of substances, so that people pay more attention to the problem of environmental pollution, wherein the air quality is closely related to the life of people, in the current society, the air pollution is more and more serious, the life of people is greatly influenced, meanwhile, the body health of people is also influenced to a great extent, Volatile Organic Compounds (VOCs) in the air pollution are main components of air pollutants which are most harmful to human bodies and comprise various aromatic hydrocarbons, aldehydes, halogenated hydrocarbons and the like, how to solve the pollution is achieved, the aim of air purification is fulfilled, and the air purification device has high research value and practical significance.
Toluene is taken as a common pollutant in VOCs, has wide sources in life, such as various detergents, solvents, paints, fuels and the like, can seriously damage the nervous system after being absorbed by a human body, causes memory loss, can cause diseases such as anemia and leukemia after long-term contact, is a substance with high toxicity, has important function on air purification by removing toluene in the air, has the advantages of environmental protection, no secondary pollution, single reaction, high stability and the like by being taken as a common photocatalyst in VOCs treatment, but has lower catalytic degradation efficiency, is easy to generate electron-hole pair recombination under the irradiation of ultraviolet light, has the characteristics of excellent chemical stability, electrical conductivity, rich pore structure, large specific surface area and the like, can well inhibit the electron-hole pair recombination generated by the excitation of titanium dioxide under the irradiation of ultraviolet light, the nitrogen atoms can increase the electron cloud density around the porous carbon pores, and have strong capacity on adjusting the electronic property and the conductivity of carbon and an electron donor, and simultaneously improve the electrostatic attraction of the toluene, so that the adsorption speed of the toluene is improved, the photocatalytic performance of the catalyst is improved to a great extent, and the absorption range of light and the separation efficiency of photo-generated electrons and holes can be improved in the photocatalytic process by doping metal element metal silver onto the photocatalyst, new energy levels are generated in the photocatalytic forbidden band, and the formed composite material shows good degradation efficiency and excellent toluene removal capacity.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides Ag modified N-doped porous carbon loaded TiO2The composite material solves the problems of slow degradation efficiency and low degradation rate of a single titanium dioxide component in the toluene photocatalysis process.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: ag modified N-doped porous carbon loaded TiO2A composite material of Ag modified N-doped porous carbon loaded with TiO2The composite material and the preparation method are as follows:
(1) adding a 1, 2-dichloroethane solvent into a flask, adding 2,4, 6-triphenyl-1, 3, 5-triazine, stirring and mixing uniformly, adding dimethanol formal and ferric trichloride in a nitrogen atmosphere, heating, carrying out a hypercrosslinking reaction on the 2,4, 6-triphenyl-1, 3, 5-triazine in a mixing system, cooling to room temperature after the reaction is finished, filtering, washing with methanol, and drying after the washing is finished to obtain a nitrogen-containing porous carbon precursor;
(2) adding a nitrogen-containing porous carbon precursor into a porcelain boat, placing the porcelain boat into a tubular furnace, carbonizing at high temperature in an argon atmosphere, cooling to room temperature after carbonization is finished, washing with ethanol and deionized water, centrifuging after washing, and drying to obtain nitrogen-containing porous carbon;
(3) adding deionized water and lithium hydroxide into a beaker, uniformly mixing, dropwise adding tetrabutyl titanate, ultrasonically dispersing, uniformly mixing, adding nitrogen-containing porous carbon, transferring into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction in a drying box, cooling to room temperature after the reaction is finished, washing with deionized water to be neutral, and using dilute sulfurSoaking in acid solution, washing with deionized water to neutrality, and drying to obtain N-doped porous carbon loaded TiO2A precursor;
(4) loading N-doped porous carbon with TiO2Adding the precursor into a crucible, transferring the crucible into a muffle furnace, and roasting to obtain the N-doped porous carbon loaded hollow nano TiO2；
(5) Adding deionized water into a beaker, adding pyrrole monomer, stirring and mixing uniformly, and then adding silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Forming a solution A, preparing a mixed solution B of deionized water, ferric nitrate and sodium bromide, dropwise adding the solution B into the solution A, stirring and mixing to perform polymerization reaction, washing with deionized water and ethanol after the reaction is finished, centrifuging, precipitating and drying to obtain the Ag modified N-doped porous carbon loaded TiO2A precursor;
(6) modifying Ag with N-doped porous carbon loaded TiO2Adding the precursor into a crucible, placing the crucible in a muffle furnace for roasting, and obtaining Ag modified N-doped porous carbon loaded TiO after roasting and sintering2A composite material.
Preferably, the mass ratio of the 2,4, 6-triphenyl-1, 3, 5-triazine, the dimethanol formal and the ferric trichloride in the step (1) is 100:150-175: 345-360.
Preferably, the temperature of the hypercrosslinking reaction in the step (1) is 75-85 ℃, and the time of the hypercrosslinking reaction is 15-24 h.
Preferably, the temperature rise rate of the carbonization in the step (2) is 1-3 ℃/min, the carbonization temperature is 700-900 ℃, and the carbonization time is 2-4 h.
Preferably, the mass ratio of the lithium hydroxide, the tetrabutyl titanate and the nitrogen-containing porous carbon in the step (3) is 180-320:100: 9-15.
Preferably, the temperature of the hydrothermal reaction in the step (3) is 150-.
Preferably, the roasting temperature in the step (4) is 300-350 ℃, and the roasting time is 3-5 h.
Preferably, in the step (5), pyrrole, silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Miao (Chinese character of 'ao' (Chinese character))The mass ratio of the ferric iron to the sodium bromide is 0.6-1.5:85-90:100:680-720: 50-65.
Preferably, the temperature of the polymerization reaction in the step (5) is 70-80 ℃, and the time of the polymerization reaction is 2-6 h.
Preferably, the roasting temperature in the step (6) is 400-450 ℃, and the roasting time is 1-4 h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the Ag modified N-doped porous carbon loaded TiO2In the synthesis process of the composite material, 2,4, 6-triphenyl-1, 3, 5-triazine is subjected to a hypercrosslinking reaction under the action of dimethyl formal and ferric trichloride to generate a nitrogen-containing porous carbon precursor, under the high-temperature condition, a polymer is used as a carbon source and a carbon source to carry out carbonization treatment to obtain the nitrogen-containing porous carbon, tetrabutyl titanate is firstly reacted with deionized water in a solution to generate the precursor, under the ultrasonic condition, the generated precursor is reacted with lithium hydroxide, the nitrogen-containing porous carbon is added before hydrothermal reaction, the generated titanium dioxide precursor uniformly grows on the porous carbon substrate, the agglomeration of nano particle titanium dioxide is effectively avoided, and after calcination, the N-doped porous carbon loaded hollow nano TiO is obtained2Pyridine is used as a monomer, silver nitrate is used as a silver source, and chemical oxidative polymerization is carried out to obtain the polypyrrole-doped silver-coated N-doped porous carbon-loaded hollow nano TiO2After high-temperature roasting, polypyrrole is removed, and the obtained simple substance silver long-N-doped porous carbon loaded hollow nano TiO2Therefore, the heterojunction is formed, and the separation efficiency of the photo-generated electron-hole pairs of the semiconductor is effectively promoted.
The Ag modified N-doped porous carbon loaded TiO2The composite material, titanium dioxide is an effective semiconductor material, is one of the most promising catalysts for VOCs pollutants in photocatalysis, can decompose toluene into carbon dioxide and water under mild conditions, but the titanium dioxide generates electron-hole pairs under the action of illumination to be compounded on the photocatalyst, so that the light quantum efficiency is low, and the porous carbon material is used, so that the porous carbon material has a large specific surface areaMeanwhile, the carbon material has the advantages of good chemical stability, conductivity, high electron mobility and the like, after being compounded with titanium dioxide, the carbon material can inhibit electron-hole pair recombination under the condition of ultraviolet irradiation, meanwhile, the porous carbon has certain adsorbability to toluene, the nitrogen atom-doped porous carbon is contained, so that the electron cloud density around the pores of the porous carbon is increased to a certain extent, the electronic property and the conductivity of the carbon and the electron donor capacity are improved, the electrostatic attraction to the toluene is improved, the adsorption speed to the toluene is improved, the photocatalytic performance of the catalyst is improved to a great extent, the metallic silver has a large optical cross section in a visible light region, has a surface plasmon resonance effect, is doped on the photocatalyst, the light absorption of the titanium dioxide is moved to a long wave direction, the light absorption range in the photocatalytic process and the separation efficiency to the photoelectron-hole are improved, the obtained composite catalyst has excellent degradation rate and degradation capability.
Drawings
FIG. 1 is a scheme diagram of a nitrogen-containing porous carbon precursor synthesized by a2, 4, 6-triphenyl-1, 3, 5-triazine hypercrosslinking reaction.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: ag modified N-doped porous carbon loaded TiO2The composite material and the preparation method are as follows:
(1) adding a 1, 2-dichloroethane solvent into a flask, adding 2,4, 6-triphenyl-1, 3, 5-triazine, stirring and mixing uniformly, then adding dimethanol formal and ferric trichloride in a nitrogen atmosphere, slowly heating the mixture at a mass ratio of 100:150 plus 175:345 plus 360 in the mixed system, carrying out a hypercrosslinking reaction on the added 2,4, 6-triphenyl-1, 3, 5-triazine at a temperature of 75-85 ℃ for 15-24h, cooling to room temperature after the reaction is finished, filtering, collecting filter residues, repeatedly washing the filter residues by using methanol until the filtrate is clear, drying in a vacuum drying box after the washing is finished, obtaining a nitrogen-containing porous carbon precursor;
(2) adding a nitrogen-containing porous carbon precursor into a porcelain boat, fully grinding until the nitrogen-containing porous carbon precursor is uniformly mixed, transferring the mixed powder into a tubular furnace, carbonizing at the high temperature of 700-900 ℃ in the argon atmosphere, wherein the temperature rise rate of carbonization is 1-3 ℃/min, the carbonization time is 2-4h, cooling to room temperature after the carbonization is finished, washing with ethanol and deionized water, centrifuging after washing, and drying to obtain nitrogen-containing porous carbon;
(3) adding deionized water and lithium hydroxide into a beaker, uniformly mixing, dropwise adding tetrabutyl titanate, performing ultrasonic dispersion, uniformly mixing, then adding nitrogen-containing porous carbon, wherein the mass ratio of the lithium hydroxide to the tetrabutyl titanate to the nitrogen-containing porous carbon is 180-+Washing the mixture to be neutral by using deionized water, and drying to obtain the N-doped porous carbon loaded TiO2A precursor;
(4) adding N-doped porous carbon loaded TiO into crucible2Transferring the precursor into a muffle furnace, roasting at the temperature of 300-350 ℃, and roasting for 3-5h to obtain the N-doped porous carbon loaded hollow nano TiO2；
(5) Adding deionized water into a beaker, adding pyrrole monomer, stirring and mixing uniformly, adding silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Forming solution A, preparing mixed solution B of deionized water, ferric nitrate and sodium bromide, and adding pyrrole, silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Dropwise adding the solution B into the solution A at 70-80 ℃, stirring and mixing to generate a polymerization reaction, wherein the polymerization reaction temperature is 70-80 ℃, the polymerization reaction time is 2-6h, after the reaction is finished, washing with deionized water and ethanol, centrifuging, precipitating, and drying the product in an oven to obtain the Ag modified N doped porous carbon loaded TiO2A precursor;
(6) adding Ag modified N-doped porous carbon loaded TiO into crucible2Precursor is put in a muffle furnaceRoasting at the temperature of 400-450 ℃ for 1-4h to obtain the Ag modified N-doped porous carbon loaded TiO after roasting and sintering2A composite material.
Example 1
(1) Adding a 1, 2-dichloroethane solvent into a flask, adding 2,4, 6-triphenyl-1, 3, 5-triazine, stirring and mixing uniformly, then adding dimethanol formal and ferric trichloride in a nitrogen atmosphere, wherein the mass ratio of the added 2,4, 6-triphenyl-1, 3, 5-triazine to dimethanol formal to ferric trichloride is 100:150:345, slowly heating the mixture under the condition of water bath, carrying out a hypercrosslinking reaction on the 2,4, 6-triphenyl-1, 3, 5-triazine in the mixture system at the temperature of 75 ℃ for 15 hours, cooling the mixture to room temperature after the reaction is finished, filtering, collecting filter residues, repeatedly washing the filter residues with methanol until the filtrate is clear, drying the filter residues in a vacuum drying box after the washing is finished, and obtaining a nitrogen-containing porous carbon precursor;
(2) adding a nitrogen-containing porous carbon precursor into a porcelain boat, fully grinding until the nitrogen-containing porous carbon precursor is uniformly mixed, transferring the mixed powder into a tubular furnace, carbonizing at a high temperature of 700 ℃ in an argon atmosphere, wherein the temperature rise rate of carbonization is 1 ℃/min, the carbonization time is 2h, cooling to room temperature after the carbonization is finished, washing with ethanol and deionized water, centrifuging after washing, and drying to obtain nitrogen-containing porous carbon;
(3) adding deionized water and lithium hydroxide into a beaker, uniformly mixing, dropwise adding tetrabutyl titanate, performing ultrasonic dispersion, uniformly mixing, then adding nitrogen-containing porous carbon, wherein the mass ratio of the lithium hydroxide to the tetrabutyl titanate to the nitrogen-containing porous carbon is 180:100:9, transferring the mixture into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction in a drying box at the temperature of 150 ℃ for 36 hours, cooling to room temperature after the reaction is finished, washing the obtained sample with deionized water to be neutral, soaking the sample with a dilute sulfuric acid solution, and washing to remove Li+Washing the mixture to be neutral by using deionized water, and drying to obtain the N-doped porous carbon loaded TiO2A precursor;
(4) adding N-doped porous carbon loaded TiO into crucible2Transferring the precursor into a muffle furnace, roasting at 300 ℃ for 3h,obtaining the N-doped porous carbon loaded hollow nano TiO2；
(5) Adding deionized water into a beaker, adding pyrrole monomer, stirring and mixing uniformly, adding silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Forming solution A, preparing mixed solution B of deionized water, ferric nitrate and sodium bromide, and adding pyrrole, silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Dropwise adding the solution B into the solution A, stirring and mixing to generate a polymerization reaction, wherein the polymerization reaction temperature is 70 ℃, the polymerization reaction time is 2 hours, after the reaction is finished, washing with deionized water and ethanol, centrifuging, precipitating, and drying the product in an oven to obtain the Ag modified N doped porous carbon loaded TiO2A precursor;
(6) adding Ag modified N-doped porous carbon loaded TiO into crucible2Placing the precursor in a muffle furnace for roasting at 400 ℃ for 1h to obtain the Ag modified N-doped porous carbon loaded TiO after roasting and sintering2A composite material.
Example 2
(1) Adding a 1, 2-dichloroethane solvent into a flask, adding 2,4, 6-triphenyl-1, 3, 5-triazine, stirring and mixing uniformly, then adding dimethanol formal and ferric trichloride in a nitrogen atmosphere, wherein the mass ratio of the added 2,4, 6-triphenyl-1, 3, 5-triazine to dimethanol formal to ferric trichloride is 100:155:350, slowly heating the mixture under the condition of water bath, carrying out a hypercrosslinking reaction on the 2,4, 6-triphenyl-1, 3, 5-triazine in the mixture system at the temperature of 78 ℃ for 18 hours, cooling the mixture to room temperature after the reaction is finished, filtering, collecting filter residues, repeatedly washing the filter residues with methanol until the filtrate is clear, drying the filter residues in a vacuum drying box after the washing is finished, and obtaining a nitrogen-containing porous carbon precursor;
(2) adding a nitrogen-containing porous carbon precursor into a porcelain boat, fully grinding until the nitrogen-containing porous carbon precursor is uniformly mixed, transferring the mixed powder into a tubular furnace, carbonizing at high temperature of 750 ℃ in an argon atmosphere, wherein the temperature rise rate of carbonization is 2 ℃/min, the carbonization time is 3h, cooling to room temperature after carbonization is finished, washing with ethanol and deionized water, centrifuging after washing, and drying to obtain nitrogen-containing porous carbon;
(3) adding deionized water and lithium hydroxide into a beaker, uniformly mixing, dropwise adding tetrabutyl titanate, performing ultrasonic dispersion, uniformly mixing, then adding nitrogen-containing porous carbon, wherein the mass ratio of the lithium hydroxide to the tetrabutyl titanate to the nitrogen-containing porous carbon is 200:100:10, transferring the mixture into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction in a drying box at the temperature of 160 ℃ for 40 hours, cooling to room temperature after the reaction is finished, washing the obtained sample with deionized water to be neutral, soaking the sample with a dilute sulfuric acid solution, and washing to remove Li+Washing the mixture to be neutral by using deionized water, and drying to obtain the N-doped porous carbon loaded TiO2A precursor;
(4) adding N-doped porous carbon loaded TiO into crucible2Transferring the precursor into a muffle furnace, roasting at 310 ℃ for 4h to obtain the N-doped porous carbon loaded hollow nano TiO2；
(5) Adding deionized water into a beaker, adding pyrrole monomer, stirring and mixing uniformly, adding silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Forming solution A, preparing mixed solution B of deionized water, ferric nitrate and sodium bromide, and adding pyrrole, silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Dropwise adding the solution B into the solution A, stirring and mixing to generate a polymerization reaction, wherein the polymerization reaction temperature is 72 ℃, the polymerization reaction time is 3 hours, after the reaction is finished, washing with deionized water and ethanol, centrifuging, precipitating, and drying the product in an oven to obtain the Ag modified N doped porous carbon loaded TiO2A precursor;
(6) adding Ag modified N-doped porous carbon loaded TiO into crucible2The precursor is placed in a muffle furnace for roasting, the roasting temperature is 410 ℃, the roasting time is 2 hours, and after the roasting and sintering, the Ag modified N-doped porous carbon loaded TiO is obtained2A composite material.
Example 3
(1) Adding a 1, 2-dichloroethane solvent into a flask, adding 2,4, 6-triphenyl-1, 3, 5-triazine, stirring and mixing uniformly, then adding dimethanol formal and ferric trichloride in a nitrogen atmosphere, wherein the mass ratio of the added 2,4, 6-triphenyl-1, 3, 5-triazine to dimethanol formal to ferric trichloride is 100:160:350, slowly heating the mixture under the condition of water bath, carrying out a hypercrosslinking reaction on the 2,4, 6-triphenyl-1, 3, 5-triazine in the mixture system at the temperature of 80 ℃ for 20 hours, cooling the mixture to room temperature after the reaction is finished, filtering, collecting filter residues, repeatedly washing the filter residues with methanol until the filtrate is clear, drying the filter residues in a vacuum drying box after the washing is finished, and obtaining a nitrogen-containing porous carbon precursor;
(2) adding a nitrogen-containing porous carbon precursor into a porcelain boat, fully grinding until the nitrogen-containing porous carbon precursor is uniformly mixed, transferring the mixed powder into a tubular furnace, carbonizing at a high temperature of 800 ℃ in an argon atmosphere, wherein the temperature rise rate of carbonization is 2 ℃/min, the carbonization time is 3h, cooling to room temperature after the carbonization is finished, washing with ethanol and deionized water, centrifuging after washing, and drying to obtain nitrogen-containing porous carbon;
(3) adding deionized water and lithium hydroxide into a beaker, uniformly mixing, dropwise adding tetrabutyl titanate, performing ultrasonic dispersion, uniformly mixing, then adding nitrogen-containing porous carbon, wherein the mass ratio of the lithium hydroxide to the tetrabutyl titanate to the nitrogen-containing porous carbon is 250:100:12, transferring the mixture into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction in a drying box at the temperature of 170 ℃ for 42 hours, cooling to room temperature after the reaction is finished, washing the obtained sample with deionized water to be neutral, soaking the sample with a dilute sulfuric acid solution, and washing to remove Li+Washing the mixture to be neutral by using deionized water, and drying to obtain the N-doped porous carbon loaded TiO2A precursor;
(4) adding N-doped porous carbon loaded TiO into crucible2Transferring the precursor into a muffle furnace, roasting at 320 ℃ for 4h to obtain the N-doped porous carbon loaded hollow nano TiO2；
(5) Adding deionized water into a beaker, adding pyrrole monomer, stirring and mixing uniformly, adding silver nitrate and N-doped porous carbon-loaded hollow nano TiO2To form solution APreparing a B mixed solution of deionized water, ferric nitrate and sodium bromide, and adding pyrrole, silver nitrate and N-doped porous carbon loaded hollow nano TiO2Dropwise adding the solution B into the solution A, stirring and mixing to generate a polymerization reaction, wherein the polymerization reaction temperature is 75 ℃, the polymerization reaction time is 4 hours, after the reaction is finished, washing with deionized water and ethanol, centrifuging, precipitating, and drying the product in an oven to obtain the Ag modified N doped porous carbon loaded TiO2A precursor;
(6) adding Ag modified N-doped porous carbon loaded TiO into crucible2Placing the precursor in a muffle furnace for roasting at the roasting temperature of 420 ℃ for 3h to obtain Ag modified N-doped porous carbon loaded TiO after roasting and sintering2A composite material.
Example 4
(1) Adding a 1, 2-dichloroethane solvent into a flask, adding 2,4, 6-triphenyl-1, 3, 5-triazine, stirring and mixing uniformly, then adding dimethanol formal and ferric trichloride in a nitrogen atmosphere, wherein the mass ratio of the added 2,4, 6-triphenyl-1, 3, 5-triazine to dimethanol formal to ferric trichloride is 100:165:355, slowly heating the mixture under the condition of water bath, carrying out a hypercrosslinking reaction on the 2,4, 6-triphenyl-1, 3, 5-triazine in the mixture system at the temperature of 80 ℃ for 22 hours, cooling the mixture to room temperature after the reaction is finished, filtering, collecting filter residues, repeatedly washing the filter residues with methanol until the filtrate is clear, drying the filter residues in a vacuum drying box after the washing is finished, and obtaining a nitrogen-containing porous carbon precursor;
(2) adding a nitrogen-containing porous carbon precursor into a porcelain boat, fully grinding until the nitrogen-containing porous carbon precursor is uniformly mixed, transferring the mixed powder into a tubular furnace, carbonizing at a high temperature of 850 ℃ in an argon atmosphere, wherein the temperature rise rate of carbonization is 2 ℃/min, the carbonization time is 3h, cooling to room temperature after the carbonization is finished, washing with ethanol and deionized water, centrifuging after washing, and drying to obtain nitrogen-containing porous carbon;
(3) adding deionized water and lithium hydroxide into a beaker, uniformly mixing, dropwise adding tetrabutyl titanate, ultrasonically dispersing, uniformly mixing, then adding nitrogen-containing porous carbon,transferring the lithium hydroxide, tetrabutyl titanate and nitrogen-containing porous carbon into a polytetrafluoroethylene reaction kettle in a mass ratio of 310:100:13, carrying out hydrothermal reaction in a drying box at the temperature of 170 ℃ for 45h, cooling to room temperature after the reaction is finished, washing the obtained sample with deionized water, washing to neutrality, soaking with dilute sulfuric acid solution to wash and remove Li+Washing the mixture to be neutral by using deionized water, and drying to obtain the N-doped porous carbon loaded TiO2A precursor;
(4) adding N-doped porous carbon loaded TiO into crucible2Transferring the precursor into a muffle furnace, roasting at 3340 ℃ for 4h to obtain the N-doped porous carbon-loaded hollow nano TiO2；
(5) Adding deionized water into a beaker, adding pyrrole monomer, stirring and mixing uniformly, adding silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Forming solution A, preparing mixed solution B of deionized water, ferric nitrate and sodium bromide, and adding pyrrole, silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Dropwise adding the solution B into the solution A, stirring and mixing to generate a polymerization reaction, wherein the polymerization reaction temperature is 75 ℃, the polymerization reaction time is 5 hours, after the reaction is finished, washing with deionized water and ethanol, centrifuging, precipitating, and drying the product in an oven to obtain the Ag modified N doped porous carbon loaded TiO2A precursor;
(6) adding Ag modified N-doped porous carbon loaded TiO into crucible2The precursor is placed in a muffle furnace for roasting, the roasting temperature is 440 ℃, the roasting time is 3 hours, and after the roasting and sintering, the Ag modified N-doped porous carbon loaded TiO is obtained2A composite material.
Example 5
(1) Adding a 1, 2-dichloroethane solvent into a flask, adding 2,4, 6-triphenyl-1, 3, 5-triazine, stirring and mixing uniformly, then adding dimethanol formal and ferric trichloride in a nitrogen atmosphere, wherein the mass ratio of the added 2,4, 6-triphenyl-1, 3, 5-triazine to dimethanol formal to ferric trichloride is 100:175:360, slowly heating the mixture in a water bath condition, carrying out a hypercrosslinking reaction on the 2,4, 6-triphenyl-1, 3, 5-triazine in the mixture system at the temperature of 85 ℃ for 24 hours, cooling the mixture to room temperature after the reaction is finished, filtering, collecting filter residues, repeatedly washing the filter residues with methanol until the filtrate is clear, drying the filter residues in a vacuum drying oven after the washing is finished, and obtaining a nitrogen-containing porous carbon precursor;
(2) adding a nitrogen-containing porous carbon precursor into a porcelain boat, fully grinding until the nitrogen-containing porous carbon precursor is uniformly mixed, transferring the mixed powder into a tubular furnace, carbonizing at high temperature of 900 ℃ in an argon atmosphere, wherein the temperature rise rate of carbonization is 3 ℃/min, the carbonization time is 4h, cooling to room temperature after carbonization is finished, washing with ethanol and deionized water, centrifuging after washing, and drying to obtain nitrogen-containing porous carbon;
(3) adding deionized water and lithium hydroxide into a beaker, uniformly mixing, dropwise adding tetrabutyl titanate, performing ultrasonic dispersion, uniformly mixing, then adding nitrogen-containing porous carbon, wherein the mass ratio of the lithium hydroxide to the tetrabutyl titanate to the nitrogen-containing porous carbon is 320:100:15, transferring the mixture into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction in a drying box at the temperature of 180 ℃ for 48 hours, cooling to room temperature after the reaction is finished, washing the obtained sample with deionized water to be neutral, soaking the sample with a dilute sulfuric acid solution, and washing to remove Li+Washing the mixture to be neutral by using deionized water, and drying to obtain the N-doped porous carbon loaded TiO2A precursor;
(4) adding N-doped porous carbon loaded TiO into crucible2Transferring the precursor into a muffle furnace, roasting at 350 ℃ for 5h to obtain the N-doped porous carbon loaded hollow nano TiO2；
(5) Adding deionized water into a beaker, adding pyrrole monomer, stirring and mixing uniformly, adding silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Forming solution A, preparing mixed solution B of deionized water, ferric nitrate and sodium bromide, and adding pyrrole, silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Dropwise adding the solution B into the solution A at a mass ratio of 1.5:90:100:720:65, stirring and mixingAnd (2) carrying out polymerization reaction at the temperature of 80 ℃ for 6h, washing with deionized water and ethanol after the reaction is finished, centrifuging, precipitating, and drying the product in an oven to obtain the Ag modified N-doped porous carbon loaded TiO2A precursor;
(6) adding Ag modified N-doped porous carbon loaded TiO into crucible2The precursor is placed in a muffle furnace for roasting, the roasting temperature is 450 ℃, the roasting time is 4 hours, and after the roasting and sintering, the Ag modified N-doped porous carbon loaded TiO is obtained2A composite material.
Comparative example 1
(1) Adding a 1, 2-dichloroethane solvent into a flask, adding 2,4, 6-triphenyl-1, 3, 5-triazine, stirring and mixing uniformly, then adding dimethanol formal and ferric trichloride in a nitrogen atmosphere, wherein the mass ratio of the added 2,4, 6-triphenyl-1, 3, 5-triazine to dimethanol formal to ferric trichloride is 100:120:305, slowly heating under the condition of water bath, carrying out a hypercrosslinking reaction on the 2,4, 6-triphenyl-1, 3, 5-triazine in a mixing system at the temperature of 80 ℃ for 18 hours, cooling to room temperature after the reaction is finished, filtering, collecting filter residues, repeatedly washing with methanol until the filtrate is clear, drying in a vacuum drying oven after the washing is finished, and obtaining a nitrogen-containing porous carbon precursor;
(2) adding a nitrogen-containing porous carbon precursor into a porcelain boat, fully grinding until the nitrogen-containing porous carbon precursor is uniformly mixed, transferring the mixed powder into a tubular furnace, carbonizing at a high temperature of 800 ℃ in an argon atmosphere, wherein the temperature rise rate of carbonization is 2 ℃/min, the carbonization time is 3h, cooling to room temperature after the carbonization is finished, washing with ethanol and deionized water, centrifuging after washing, and drying to obtain nitrogen-containing porous carbon;
(3) adding deionized water and lithium hydroxide into a beaker, uniformly mixing, dropwise adding tetrabutyl titanate, performing ultrasonic dispersion, uniformly mixing, then adding nitrogen-containing porous carbon, wherein the mass ratio of the lithium hydroxide to the tetrabutyl titanate to the nitrogen-containing porous carbon is 120:100:5, transferring the mixture into a polytetrafluoroethylene reaction kettle, performing hydrothermal reaction in a drying box, the temperature of the hydrothermal reaction is 160 ℃, the time of the hydrothermal reaction is 42 hours, cooling to room temperature after the reaction is finished, and using waste waterWashing the obtained sample with ionized water to neutrality, and soaking in dilute sulfuric acid solution to remove Li+Washing the mixture to be neutral by using deionized water, and drying to obtain the N-doped porous carbon loaded TiO2A precursor;
(4) adding N-doped porous carbon loaded TiO into crucible2Transferring the precursor into a muffle furnace, roasting at 320 ℃ for 4h to obtain the N-doped porous carbon loaded hollow nano TiO2；
(5) Adding deionized water into a beaker, adding pyrrole monomer, stirring and mixing uniformly, adding silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Forming solution A, preparing mixed solution B of deionized water, ferric nitrate and sodium bromide, and adding pyrrole, silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Dropwise adding the solution B into the solution A, stirring and mixing to generate a polymerization reaction, wherein the polymerization reaction temperature is 75 ℃, the polymerization reaction time is 5 hours, after the reaction is finished, washing with deionized water and ethanol, centrifuging, precipitating, and drying the product in an oven to obtain the Ag modified N doped porous carbon loaded TiO2A precursor;
(6) adding Ag modified N-doped porous carbon loaded TiO into crucible2Placing the precursor in a muffle furnace for roasting at the roasting temperature of 420 ℃ for 2h to obtain Ag modified N-doped porous carbon loaded TiO after roasting and sintering2A composite material.
A300W xenon lamp is used as a light source, and the obtained composite material is used in a photoreactor to carry out a toluene degradation experiment, wherein the method comprises the following steps: ag modified N-doped porous carbon loaded TiO prepared by uniformly dispersing on quartz plate2The composite material photocatalyst is placed at the bottom of a photoreactor, oxygen and 0.5 mu L of toluene are introduced into the reactor, a xenon lamp is used for irradiating the catalyst, circulating cooling water is used for cooling the reactor, stable catalytic reaction temperature is kept, reaction is continued for 1h, products are detected by an online PA201S photoacoustic gas detector, and the concentration of generated carbon dioxide is detected to obtain the corresponding toluene amount and degradation rate.
Claims (10)
1. Ag modified N-doped porous carbon loaded TiO2A composite material characterized by: the Ag modified N-doped porous carbon loaded TiO2The composite material and the preparation method are as follows:
(1) adding a 1, 2-dichloroethane solvent into a flask, adding 2,4, 6-triphenyl-1, 3, 5-triazine, stirring and mixing uniformly, adding dimethanol formal and ferric trichloride in a nitrogen atmosphere, heating, carrying out a hypercrosslinking reaction on the 2,4, 6-triphenyl-1, 3, 5-triazine in a mixing system, cooling to room temperature after the reaction is finished, filtering, washing with methanol, and drying after the washing is finished to obtain a nitrogen-containing porous carbon precursor;
(2) adding a nitrogen-containing porous carbon precursor into a porcelain boat, placing the porcelain boat into a tubular furnace, carbonizing at high temperature in an argon atmosphere, cooling to room temperature after carbonization is finished, washing with ethanol and deionized water, centrifuging after washing, and drying to obtain nitrogen-containing porous carbon;
(3) adding deionized water and lithium hydroxide into a beaker, uniformly mixing, dropwise adding tetrabutyl titanate, ultrasonically dispersing, uniformly mixing, adding nitrogen-containing porous carbon, transferring into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction in a drying box, cooling to room temperature after the reaction is finished, washing with deionized water to be neutral, soaking with a dilute sulfuric acid solution, washing with deionized water to be neutral, and drying to obtain the N-doped porous carbon loaded TiO2A precursor;
(4) loading N-doped porous carbon with TiO2Adding the precursor into a crucible, transferring the crucible into a muffle furnace, and roasting to obtain the N-doped porous carbon loaded hollow nano TiO2；
(5) Adding deionized water into a beaker, adding pyrrole monomer, stirring and mixing uniformly, and then adding silver nitrate and N-doped porous carbon-loaded hollow nano TiO2Forming solution A, preparing deionized water, ferric nitrate and sodium bromide, and mixingMixing the solution, dropwise adding the solution B into the solution A, stirring and mixing to perform polymerization reaction, washing with deionized water and ethanol after the reaction is finished, centrifuging, precipitating, and drying to obtain the Ag modified N-doped porous carbon loaded TiO2A precursor;
(6) modifying Ag with N-doped porous carbon loaded TiO2Adding the precursor into a crucible, placing the crucible in a muffle furnace for roasting, and obtaining Ag modified N-doped porous carbon loaded TiO after roasting and sintering2A composite material.
2. The Ag modified N-doped porous carbon-loaded TiO2 composite material according to claim 1, wherein the composite material comprises: the mass ratio of the 2,4, 6-triphenyl-1, 3, 5-triazine, the dimethyl formal and the ferric trichloride in the step (1) is 100:150-175: 345-360.
3. The Ag-modified N-doped porous carbon-loaded TiO of claim 12A composite material characterized by: the temperature of the hypercrosslinking reaction in the step (1) is 75-85 ℃, and the time of the hypercrosslinking reaction is 15-24 h.
4. The Ag-modified N-doped porous carbon-loaded TiO of claim 12A composite material characterized by: the temperature rise rate of carbonization in the step (2) is 1-3 ℃/min, the carbonization temperature is 700-900 ℃, and the carbonization time is 2-4 h.
5. The Ag-modified N-doped porous carbon-loaded TiO of claim 12A composite material characterized by: the mass ratio of the lithium hydroxide, the tetrabutyl titanate and the nitrogen-containing porous carbon in the step (3) is 180-320:100: 9-15.
6. The Ag-modified N-doped porous carbon-loaded TiO of claim 12A composite material characterized by: the temperature of the hydrothermal reaction in the step (3) is 150-180 ℃, and the time of the hydrothermal reaction is 36-48 h.
7. According toThe Ag-modified N-doped porous carbon-loaded TiO of claim 12A composite material characterized by: the roasting temperature in the step (4) is 300-350 ℃, and the roasting time is 3-5 h.
8. The Ag-modified N-doped porous carbon-loaded TiO of claim 12A composite material characterized by: in the step (5), pyrrole, silver nitrate and N-doped porous carbon-loaded hollow nano TiO2The mass ratio of the ferric nitrate to the sodium bromide is 0.6-1.5:85-90:100:680-720: 50-65.
9. The Ag-modified N-doped porous carbon-loaded TiO of claim 12A composite material characterized by: the temperature of the polymerization reaction in the step (5) is 70-80 ℃, and the time of the polymerization reaction is 2-6 h.
10. The Ag-modified N-doped porous carbon-loaded TiO of claim 12A composite material characterized by: the roasting temperature in the step (6) is 400-450 ℃, and the roasting time is 1-4 h.
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