CN109158122B - Preparation method and application of nitrogen-doped nano-silica photocatalyst - Google Patents
Preparation method and application of nitrogen-doped nano-silica photocatalyst Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 6
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 5
- 239000007790 solid phase Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 28
- 239000003344 environmental pollutant Substances 0.000 claims description 24
- 231100000719 pollutant Toxicity 0.000 claims description 23
- 230000015556 catabolic process Effects 0.000 claims description 14
- 238000006731 degradation reaction Methods 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000005543 nano-size silicon particle Substances 0.000 claims description 10
- 229910052724 xenon Inorganic materials 0.000 claims description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000356 contaminant Substances 0.000 claims description 9
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 5
- 230000005291 magnetic effect Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- ZAMOVMHWSVVCQD-UHFFFAOYSA-N 2-benzyl-3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1CC1=CC=CC=C1 ZAMOVMHWSVVCQD-UHFFFAOYSA-N 0.000 claims description 4
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 4
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000004817 gas chromatography Methods 0.000 claims description 4
- 229960003500 triclosan Drugs 0.000 claims description 4
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 3
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- SVHOVVJFOWGYJO-UHFFFAOYSA-N pentabromophenol Chemical compound OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br SVHOVVJFOWGYJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 150000004827 dibenzo-1,4-dioxins Chemical class 0.000 claims description 2
- 150000003071 polychlorinated biphenyls Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 3
- 239000012071 phase Substances 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 239000004115 Sodium Silicate Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract 1
- 239000012429 reaction media Substances 0.000 abstract 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- ONXPZLFXDMAPRO-UHFFFAOYSA-N decachlorobiphenyl Chemical group ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl ONXPZLFXDMAPRO-UHFFFAOYSA-N 0.000 description 11
- 239000007787 solid Substances 0.000 description 7
- -1 pyrene radical cation Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
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- 238000000926 separation method Methods 0.000 description 4
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- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- NNMHAVGAIQTMRH-UHFFFAOYSA-N 1,2,3,4,6,7,8,9-octafluorodibenzo-p-dioxin Chemical compound FC1=C(F)C(F)=C2OC3=C(F)C(F)=C(F)C(F)=C3OC2=C1F NNMHAVGAIQTMRH-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N CHCl3 Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
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- 239000000741 silica gel Substances 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
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- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000009777 vacuum freeze-drying 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a preparation method and application of a nitrogen-doped nano-silica photocatalyst, and belongs to the technical field of photocatalysis. The preparation method comprises the following steps: mixing a nitrogen source and a sodium silicate solution, adding acid to form a precipitate, and aging, washing, drying, roasting and grinding the precipitate to obtain the nitrogen-doped nano-silica photocatalyst. The catalyst has a spherical shape, the particle size is 100-200 nm, and the doping amount of nitrogen atoms accounts for about 5-6% of the total atomic number. The invention also includes the application of the catalyst in the aspect of photocatalytic degradation of organic pollutants on the surface of a solid phase, and is characterized in that a reaction medium can be a water phase or a gas phase, and simulated natural light irradiation is adopted as a light source. The method adopts a precipitation method to synthesize the nitrogen-doped nano-silica photocatalyst, has the advantages of simplicity, good repeatability and high yield, adopts the simulated sunlight to drive the reaction, and has good catalytic effect on various types of organic pollutants.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a preparation method and application of a nitrogen-doped nano-silica photocatalyst.
Background
Photocatalysis is an advanced oxidation technology for effectively treating pollutants, and the photocatalyst is the key point for efficiently and smoothly carrying out photocatalytic reaction. Metal oxide semiconductor photocatalysts such as TiO2、ZnO、Fe2O3、ZrO2、V2O5、WO3And Bi2O3And the ultraviolet light with the wavelength of below 400 nm is generally needed for excitation to generate the catalytic effect, and if the sunlight wave mainly concentrated in a visible light region is utilized, the electronic structure of the material needs to be changed to improve the visible light catalytic performance. An important and effective method is elemental doping, which incorporates dopants into the crystal lattice of the original catalytic material, altering the elemental composition and atomic arrangement of the material, thereby altering the electronic structure of the material and increasing the photocatalyst activity. The element doping can be divided into two types, namely the doping of metal or transition metal elements, for example, 21 transition metal element doped TiO are evaluated by the system of Choi and the like2Sol oxidation CHCl3And reduction of CCl4Ability of (2) to find Fe3+、Mo5+、Ru3+、Os3+、Re5+、V4+And Rh3+Doping significantly improves TiO2Photocatalytic redox activity. Esterellan et al for preparing Fe-Nb/TiO2Material, the efficiency of which to degrade PFOA is increased by about 6.4 times. Secondly, doping of non-metal elements such as N, S, C, B, P, I, F. Asahi et al comprehensively analyzed F, N, C, S, P and other non-metallic element doped TiO from experimental and theoretical perspectives2Feasibility and superiority of the method, N doping is found to be the design of visible light response TiO2One of the most efficient doping methods for catalysts, N-TiO2At a wavelength of<The visible light region of 500 nm has more obvious absorption, and the photocatalytic degradation efficiency on methyl blue and acetaldehyde is higher. Most of the existing research focuses on modifying TiO2The activity change of the photocatalyst is still little known about other types of photocatalysts doped with elements.
The silica material has wide sourceThe material has the advantages of low price, stable chemical property, high temperature resistance, corrosion resistance, good insulating property and the like, thereby being paid much attention in the field of materials. With the development of nanotechnology, the development and application of silica nanoparticles are of great significance. At present, the application of the silicon dioxide nano material in the field of environmental pollution treatment is mainly embodied in two aspects: firstly, the excellent adsorption performance of the silica nano-material is utilized to adsorb and remove environmental pollutants, for example, Li and the like successfully use the synthesized polyethyleneimine-nano-silica composite material for adsorbing and capturing CO2A gas. Secondly, the silica nano material is used as a carrier of the catalyst or is subjected to surface modification to degrade and remove the pollutants, for example, the Dong et al fixes silver nano particles on fibrous nano silica to be used as a recyclable high-efficiency heterogeneous catalyst for reducing the pollutants. Sarkar et al prepared titanium dioxide and nano-silica extracted from rice hulls into a composite material for degradation of methyl orange. In general, surface modification and modification of silicon dioxide and preparation of composite nano silicon material as a carrier are all helpful for improving catalytic efficiency. Then, whether the silica itself has catalytic activity;
silica is the most important component of atmospheric mine dust and is often used as a model particulate to simulate atmospheric photochemical behavior of organic pollutants, especially Polycyclic Aromatic Hydrocarbons (PAHs). For example, Mao et al found that the photoreaction of pyrene/silica samples involves three major intermediate species, namely pyrene radical cation, superoxide anion radical (O)2•–) And a hydrogen radical, wherein O2•–Is formed by O2Trapping electrons generated at the surface of the silica. Evidence has been provided that indicates the presence of a variety of reactive free radicals, such as silicon-based free radicals, superoxide anion free radicals (O)2•–) Oxygen radical, carbon dioxide radical (CO)2A.) and hydroxyl radical (. OH). Accordingly, we speculate that the photo-oxidation reaction of OH can also occur during the photochemical conversion of organic contaminants adsorbed on the surface of silica particles. However, it is now common for OH radicals to react at the surface of the silicaThe effect is also less well understood.
In recent years, we found that commercial silica gel (silica, the particle size obtained by electron microscope analysis is nano-scale) can generate hydroxyl radicals under simulated sunlight irradiation, decabromodiphenyl oxide can be effectively oxidized and degraded, the generation of the hydroxyl radicals is verified by paramagnetic resonance technology and structural analysis of degradation products, and research work is published in 2017Water ResearchIn the section I. Then, if the nano silicon dioxide is modified (element doped), the catalytic degradation efficiency of pollutants can be improved, and what is the catalytic mechanism;
therefore, it is necessary to study the catalytic degradation efficiency of nano-silica and its modified (element doped) material on pollutants and its catalytic mechanism.
At present, titanium dioxide nanoparticles are produced and applied as the photocatalyst, and the photocatalyst can only utilize ultraviolet light with the wavelength less than 385nm, so that the solar energy utilization rate is low. Some methods for improving the utilization efficiency of visible light, such as doping nonmetal or transition metal ions, sensitizing surface fuel, or modifying noble metal nanoparticles with surface plasmon resonance effect, are also reported in the prior art, and the catalyst system prepared by the methods is unstable, has high production cost, and is difficult to produce on a large scale.
Disclosure of Invention
The invention aims to provide a preparation method and an application range of a nitrogen-doped nano-silica photocatalyst.
The invention adopts the following technical scheme:
a preparation method of a nitrogen-doped nano silicon dioxide photocatalyst comprises the following steps: adding a certain amount of Na2SiO3•9H2Dissolving O in deionized water for later use; dropwise adding a certain amount of nitrogen source aqueous solution into the solution, stirring on a magnetic stirrer, adjusting the pH to about 7-9 by using an acid solution, and stopping adding acid; stirring, aging at 30-80 deg.C for 2-4 hr, washing with deionized water for 3-5 times, and vacuum drying at 30-80 deg.CDrying for more than 10h to ensure that the solid is fully dried, cooling and grinding; then roasting for 6-10h at the temperature of 200-900 ℃, and grinding to obtain the nitrogen-doped nano silicon dioxide photocatalyst.
Furthermore, the nitrogen source is ammonium nitrate or ammonium chloride, and the concentration is 0.5-2 mol/L.
Further, the acid solution is hydrochloric acid or nitric acid, and the concentration is 0.5-2 mol/L.
Further, the baking atmosphere is air.
Further, added Na2SiO3•9H2The molar ratio of the O to the nitrogen source to the acid solution is 1: 0.5: 1.5.
the invention also provides application of the nitrogen-doped nano-silica photocatalyst prepared by the preparation method of the nitrogen-doped nano-silica photocatalyst in degrading organic pollutants on the surface of a solid phase, which comprises the following steps: dissolving a target pollutant in a corresponding solvent, adding a pollutant solution with proper concentration and volume and a catalyst with a corresponding amount into a container together to completely volatilize the solvent, weighing a certain amount of a mixture of the pollutant and the catalyst into a reaction container, reacting under the condition of water or no water, and monitoring the change of the pollutant concentration by using a xenon lamp as a light source at room temperature to calculate the degradation rate of the pollutant.
Still further, the target contaminant is decabromodiphenyl ether, hexabromobenzene, polychlorinated biphenyl, decabromodiphenylethane, polychlorinated diphenyl sulfide, polyfluorinated dibenzo-p-dioxin, pentafluorophenol, pentachlorophenol, pentabromophenol, benzylchlorophenol, triclosan, or tetrabromobisphenol a.
Further, the concentration of the contaminant solution is 1.0 × 10-4mol/kg; the molar ratio of the contaminant to the catalyst is 10-6-10-2: 1; the catalyst is a nitrogen-doped nano-silica photocatalyst calcined at the temperature of 300-500 ℃.
Furthermore, the reaction vessel is a quartz tube, the xenon lamp is a 500W xenon lamp, and the change of the concentration of the pollutants is monitored by utilizing gas chromatography or high performance liquid chromatography.
In the process of the present invention, after obtaining the suspension comprising nitrogen-doped silica, the suspension may be treated using conventional solid-liquid separation means to separate the resulting solid product from the solution, preferably the solid-liquid separation means is centrifugal separation. After solid-liquid separation, the obtained nitrogen-doped silica is washed and dried as required to remove impurities and obtain higher purity. The preferred drying method is one of vacuum freeze drying or vacuum drying.
Compared with the prior art, the invention has the following beneficial effects:
firstly, the method for synthesizing the nitrogen-doped nano-silica photocatalyst by adopting a precipitation method is simple and low in cost, and can be used for small-range operation in a laboratory and large-scale industrial production;
secondly, the invention adopts the simulated sunlight to drive the reaction, is an environment-friendly sustainable environment management method, and has important social significance;
thirdly, the nitrogen-doped nano-silica photocatalyst prepared by the method has good degradation rates on decabromodiphenyl ether, hexabromobenzene, decachlorobiphenyl, decabromodiphenylethane, polychlorinated diphenyl sulfide, octafluoro dibenzo-p-dioxin, pentafluorophenol, pentachlorophenol, pentabromophenol, benzylchlorophenol, triclosan and tetrabromobisphenol A, wherein the removal rate of 6 hours on decabromodiphenyl ether, decachlorobiphenyl, tetrabromobisphenol A, polychlorinated diphenyl sulfide, benzylchlorophenol and triclosan reaches 100% (figure 1).
Drawings
FIG. 1 is a schematic diagram of a nitrogen-doped nanosilica photocatalyst (obtained in example 2) calcined at 300 ℃ for catalytic degradation of various target contaminants under gas phase conditions;
FIG. 2 is a Transmission Electron Micrograph (TEM) of undoped (a), (b) and nitrogen-doped (c), (d) nanosilica materials (calcined at 300 ℃), wherein (b) and (d) are high-power transmission electron micrographs (HRTEM), wherein a and b are pure nanosilica calcined at 300 ℃ in example 1, and c and d are catalysts prepared in example 2;
FIG. 3-a is a full spectrum of X-ray photoelectron spectroscopy (XPS) of an undoped (a) nanosilica (pure nanosilica calcined at 1300 ℃ in example) photocatalyst;
FIG. 3-b is a full spectrum of X-ray photoelectron spectroscopy (XPS) of a nitrogen-doped (b) nanosilica photocatalyst (example calcined at 2300 deg.C);
FIG. 3-c is an XPS spectrum of N1s for the nitrogen doped nano silica photocatalyst obtained by calcination at 2300 deg.C in example;
fig. 4 is a comparison of degradation efficiency curves of N-300 (obtained in example 3) and N-300 (obtained in example 3) doped nano silica materials (calcined at 300 ℃) catalyzed by decachlorobiphenyl, wherein after the doped nano silica materials are doped, the 4h catalytic degradation efficiency is improved from 21% to 97% (4.6 times), which shows that the photocatalytic efficiency of the nano silica can be greatly improved by doping ammonium nitrate as a nitrogen source.
Detailed Description
The present invention is described in further detail below by way of specific embodiments, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Implementation 1: preparation of pure nanosilicon dioxide materials
Taking 1 part of Na2SiO3•9H2Dissolving O in 2 parts of deionized water for later use; to Na2SiO3Dropwise adding 2mol/L hydrochloric acid into the solution, simultaneously stirring on a magnetic stirrer, adjusting the pH value of the solution to about 9, and stopping adding acid; then stirring for 0.5h, aging for 2h at 50 ℃, washing for 3 times by using deionized water, and fully washing off redundant ions in the solution; then vacuum drying at 80 deg.C for more than 10h to ensure solid to be dewatered completely, cooling, and simply grinding to obtain white solid; then roasting in air atmosphere at 200, 300, 500, 700 and 900 ℃ for 6 h; cooling and grinding to obtain the pure nano silicon dioxide material.
Example 2: ammonium chloride is used as nitrogen source
Taking 1 part of Na2SiO3•9H2Dissolving O in 2 parts of deionized water for later use; to Na2SiO3Dropwise adding 0.5 part of 2mol/L ammonium chloride solution into the solution, stirring on a magnetic stirrer, dropwise adding 0.5 mol/L hydrochloric acid solution, adjusting the pH value of the solution to about 9, and stopping adding acid; then stirring for 0.5h, aging for 2h at 50 ℃, washing for 3 times by using deionized water, and fully washing off redundant ions in the solution; then vacuum drying for 12h at 80 ℃ to ensure that the solid is fully dewatered, cooling, and simply grinding to obtain white solid; then roasting in air atmosphere at 200, 300, 500, 700 and 900 ℃ respectively for 6 h; cooling and grinding to obtain the nitrogen-doped nano silicon dioxide material.
The removal rate of decachlorobiphenyl (PCB-209) after the catalysts calcined at different temperatures obtained in examples 1 and 2 were irradiated for 4 hours by a 500W xenon lamp is shown in the following table 1:
TABLE 1 removal of decachlorobiphenyl (PCB-209) after 4 hours of xenon 500W irradiation of the catalysts calcined at different temperatures obtained in examples 1 and 2
Example 3: using ammonium nitrate as nitrogen source
Taking 1 part of Na2SiO3•9H2Dissolving O in 2 parts of deionized water for later use; to Na2SiO3Dropwise adding 0.5 part of 2mol/L ammonium nitrate solution into the solution, stirring on a magnetic stirrer, dropwise adding 0.5 mol/L nitric acid solution, adjusting the pH value of the solution to about 9, and stopping adding acid; then stirring for 0.5h, aging for 2h at 50 ℃, washing for 3 times by using deionized water, and fully washing off redundant ions in the solution; then vacuum drying at 80 deg.C for more than 10h to ensure solid to be dewatered completely, cooling, and simply grinding to obtain white solid; then roasting in air atmosphere at 300 ℃ for 6 h; cooling and grinding to obtain the nitrogen-doped nano silicon dioxide material.
Example 4: experiment for catalyzing degradation of decachlorobiphenyl by nitrogen-doped nano silicon dioxide material
2 mL of a 26 mu mol/L decachlorobiphenyl solution and 1g of the two catalysts obtained in example 1 and example 2 were respectively added into a container to completely volatilize the solvent, 0.05g of a mixture of decachlorobiphenyl and different catalysts was respectively weighed into a 50 mL quartz tube, 40 mL of deionized water was added, a 500W xenon lamp was used as a light source for irradiation, the temperature was room temperature, the change in the concentration of decachlorobiphenyl was monitored by gas chromatography, the degradation rate was calculated, and the catalytic efficiency of the two materials was investigated (Table 1).
Example 5: experiment for catalytically degrading target pollutants by using nitrogen-doped nano-silica photocatalyst
Dissolving a target pollutant in a corresponding solvent, adding 2 mL of a 26 mu mol/L pollutant solution and 1g of the catalyst (calcined at 300 ℃) obtained in example 2 into a container together to completely volatilize the solvent, weighing 0.05g of a mixture of the pollutant and the catalyst into a reaction container, reacting under the condition of water or no water at room temperature, using a 500W xenon lamp as a light source, monitoring the change of the pollutant concentration by using high performance liquid chromatography or gas chromatography, and calculating the degradation rate (figure 1).
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of protection is not limited thereto. The equivalents and modifications of the present invention which may occur to those skilled in the art are within the scope of the present invention as defined by the appended claims.
Claims (4)
1. The application of the nitrogen-doped nano-silica photocatalyst in degrading organic pollutants on the surface of a solid phase is characterized by comprising the following steps of: dissolving a target pollutant in a corresponding solvent, adding a pollutant solution with proper concentration and volume and a catalyst with a corresponding amount into a container together to completely volatilize the solvent, weighing a certain amount of a mixture of the pollutant and the catalyst into a reaction container, reacting under the condition of water or no water, monitoring the change of the pollutant concentration by using a xenon lamp as a light source at room temperature, and calculating the degradation rate of the pollutant;
the target pollutants are decabromodiphenyl ether, hexabromobenzene, polychlorinated biphenyl, decabromodiphenylethane, polychlorinated diphenyl sulfide, polyfluorinated dibenzo-p-dioxin, pentafluorophenol, pentachlorophenol, pentabromophenol, benzylchlorophenol, triclosan or tetrabromobisphenol A;
the preparation method of the nitrogen-doped nano-silica photocatalyst comprises the following steps: adding a certain amount of Na2SiO3·9H2Dissolving O in deionized water for later use; dropwise adding a certain amount of nitrogen source aqueous solution into the solution, stirring on a magnetic stirrer, adjusting the pH to about 7-9 by using an acid solution, and stopping adding acid; aging at 30-80 deg.C for 2-4 hr, washing with deionized water for 3-5 times, vacuum drying at 30-80 deg.C for more than 10 hr, cooling, and grinding; then roasting for 6-10h at the temperature of 300-500 ℃, and grinding to obtain the nitrogen-doped nano silicon dioxide photocatalyst;
wherein the nitrogen source is ammonium nitrate or ammonium chloride, and the concentration is 0.5-2 mol/L;
the acid solution is hydrochloric acid or nitric acid, and the concentration is 0.5-2 mol/L.
2. Use of the nitrogen-doped nanosilica photocatalyst as claimed in claim 1, wherein the concentration of the contaminant solution is 1.0 x 10-4mol/kg; the molar ratio of the contaminant to the catalyst is 10-6-10-2:1;
The reaction vessel is a quartz tube, the xenon lamp is a 500W xenon lamp, and the change of the concentration of the pollutants is monitored by utilizing gas chromatography or high performance liquid chromatography.
3. The use of the nitrogen-doped nanosilica photocatalyst as claimed in claim 1, wherein the calcination atmosphere is air for the degradation of organic contaminants in the solid phase surface.
4. Use of the nitrogen-doped nanosilica photocatalyst as claimed in claim 1 for the degradation of organic contaminants in the surface of a solid phase, characterised by the addition of Na2SiO3·9H2The molar ratio of the O to the nitrogen source to the acid solution is 1: 0.5: 1.5.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1634654A (en) * | 2004-12-02 | 2005-07-06 | 上海大学 | Preparation method of nitrogen doped composite semiconductor photocatalyst |
CN101108336A (en) * | 2007-07-11 | 2008-01-23 | 南开大学 | Method of manufacturing nitrogen of high activity, stannum ion codope nano titanium dioxide photocatalyst |
WO2009052232A1 (en) * | 2007-10-17 | 2009-04-23 | J.M. Huber Corporation | Filtration media for the removal of mercury from flue gas emissions |
KR20110050213A (en) * | 2009-11-06 | 2011-05-13 | 서울대학교산학협력단 | Fabrication of uniform silica/nitrogen-doped titania core/shell nanoparticles by interfacial sol-gel method and application to visible light photocatalyst |
CN106732741A (en) * | 2016-11-29 | 2017-05-31 | 滨州学院 | The visible light catalyst of dyestuff and its preparation and application in a kind of degrading waste water |
-
2018
- 2018-08-24 CN CN201810970605.1A patent/CN109158122B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1634654A (en) * | 2004-12-02 | 2005-07-06 | 上海大学 | Preparation method of nitrogen doped composite semiconductor photocatalyst |
CN101108336A (en) * | 2007-07-11 | 2008-01-23 | 南开大学 | Method of manufacturing nitrogen of high activity, stannum ion codope nano titanium dioxide photocatalyst |
WO2009052232A1 (en) * | 2007-10-17 | 2009-04-23 | J.M. Huber Corporation | Filtration media for the removal of mercury from flue gas emissions |
KR20110050213A (en) * | 2009-11-06 | 2011-05-13 | 서울대학교산학협력단 | Fabrication of uniform silica/nitrogen-doped titania core/shell nanoparticles by interfacial sol-gel method and application to visible light photocatalyst |
CN106732741A (en) * | 2016-11-29 | 2017-05-31 | 滨州学院 | The visible light catalyst of dyestuff and its preparation and application in a kind of degrading waste water |
Non-Patent Citations (2)
Title |
---|
"Solid surface-mediated photochemical transformation of decabromodiphenyl ether (BDE-209) in aqueous solution";Ruijuan Qu et al.;《Water Research》;20170816;第125卷;第114-122页 * |
"掺杂基团对氮改性TiO2紫外光催化活性影响的机理研究";刘会景等;《无机材料学报》;20090531;第24卷(第3期);第443-447页 * |
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