CN115197591A - Visible light catalytic composite material and preparation method thereof - Google Patents
Visible light catalytic composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 79
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000011574 phosphorus Substances 0.000 claims abstract description 78
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 44
- 230000001699 photocatalysis Effects 0.000 claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- 230000000694 effects Effects 0.000 claims abstract description 32
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 25
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 13
- AKVPUSMVWHWDGW-UHFFFAOYSA-N [C].[N].[P] Chemical compound [C].[N].[P] AKVPUSMVWHWDGW-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 238000006731 degradation reaction Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- PANZTLJCAXSTDN-UHFFFAOYSA-N ethanol;1,3,5-triazine-2,4,6-triamine Chemical compound CCO.NC1=NC(N)=NC(N)=N1 PANZTLJCAXSTDN-UHFFFAOYSA-N 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 150000003672 ureas Chemical class 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000008131 herbal destillate Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 26
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
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- 238000011160 research Methods 0.000 description 5
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- -1 hydroxyl free radical Chemical class 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- NHCSMTQRYWPDDW-UHFFFAOYSA-N [C].[N].[S] Chemical compound [C].[N].[S] NHCSMTQRYWPDDW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
- H02S40/10—Cleaning arrangements
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to a visible light catalytic composite material, which is prepared by doping carbon, nitrogen and phosphorus with nano TiO 2 Material, phosphorus doping Activity g-C 3 N 4 Material and nano SiO 2 Material composition; carbon nitrogen phosphorus doped nano TiO 2 The mass fraction of (A) is 30-45%; phosphorus doping Activity g-C 3 N 4 The mass fraction of the nano SiO is 5 to 15 percent 2 The mass fraction of (A) is 45-60%; the three photocatalytic material components have a photocatalytic synergistic effect, so that the catalytic efficiency of the visible light catalytic composite material is improved. Phosphorus doping Activity of the invention g-C 3 N 4 The polymerization formation and the activated pore-forming are completed simultaneously, and the phosphoric acid is used as an activated catalyst and a phosphorus doping agent simultaneouslySource, simplified phosphorus doping activity g-C 3 N 4 The preparation process of (2). The visible light catalytic composite material can be used for photocatalytic self-cleaning of the surface of a solid and degradation of organic pollutants in air and waste water, and has industrial application prospects.
Description
Technical Field
The invention relates to a visible light catalytic composite material and a preparation method thereof, belonging to the field of environmental functional materials.
Background
Among the existing photocatalytic materials, nano TiO 2 The photocatalyst has the advantages of highest photocatalytic activity, stable chemical property, low price, low toxicity and the like, but the nano TiO 2 The photocatalytic material has the defects of low photocatalytic quantum efficiency, narrow spectral response range, easy agglomeration, easy inactivation and the like. Visible light in solar spectrum accounts for 45%, ultraviolet light only accounts for 3% -5%, and professional tries to reduce nano TiO by means of doping modification and the like 2 Band gap width of semiconductor material, expanded nano TiO 2 The spectral response range of the photocatalytic material enables the photocatalytic material to exert a photocatalytic effect even in the visible light range. The research and development of the high-activity visible light catalytic material are listed as important scientific and engineering technical problems by the nation. The research finds that the nano TiO doped with non-metallic elements of C, N, P, S, F or the mixture thereof 2 The light absorption range can be expanded to a visible light region, and the photocatalytic efficiency of the photocatalyst in an ultraviolet light region can be enhanced. Nano TiO 2 2 With nano SiO 2 Nano carbon dots, nano graphene or graphite phase carbon nitride (g-C) 3 N 4 ) Is made of semiconductor material capable of generating lightCatalytic synergistic effect and multiple promotion of nano TiO 2 The photocatalytic performance of (2).
Graphite phase carbon nitride (g-C) 3 N 4 ) Is a novel non-metal polymer semiconductor material, has a band gap width of 2.7eV, has a layered structure similar to graphite, and can be peeled to form few layers of g-C in a solvent under the action of ultrasonic waves 3 N 4 The material has good chemical stability and thermal stability, and is a nonmetal semiconductor visible light catalytic material with great development potential.
At present, 4000 organizations are engaged in the related research and development of graphite phase carbon nitride materials all over the world, and thousands of research papers are published, and China is at the forefront of the world in the field of research and development of graphite phase carbon nitride materials.
Photocatalysis principle of graphite phase carbon nitride material and nano TiO 2 The principle of photocatalysis is similar, under the condition of irradiation of visible light, a photon-generated carrier can combine with moisture and oxygen to generate a plurality of active oxygen species, including superoxide radical (. O) 2 - ) And hydroxyl free radical (. OH) and the like, can quickly oxidize and decompose organic pollutants in the wastewater, so that the organic pollutants are converted into low-toxicity small molecular compounds which are easy to biochemically degrade and are finally decomposed into carbon dioxide and water.
Chinese patent CN104084229B (2017-02-22) discloses a carbon nitride modified titanium dioxide super-hydrophilic porous film, a preparation method and application thereof, wherein dicyandiamide or melamine is used as a precursor, and carbon nitride nanosheets are prepared by calcining; ultrasonically dispersing carbon nitride nanosheets in absolute ethyl alcohol to obtain carbon nitride dispersion liquid, then adding a titanium dioxide precursor and acetylacetone, uniformly stirring to obtain uniform solution, further processing to obtain carbon nitride/titanium dioxide composite sol, aging for a period of time, coating the carbon nitride/titanium dioxide composite sol on a pretreated substrate, drying and irradiating with ultraviolet rays to obtain the carbon nitride modified titanium dioxide super-hydrophilic porous film. Chinese patent CN107837817B (2020-04-21) discloses a carbon dot/carbon nitride/titanium dioxide composite material and a preparation method and application thereof, wherein carbon nitride has a large surface area, and can just provide a depositable space for a titanium dioxide nanosheet, so that titanium dioxide is not agglomerated, and meanwhile, the narrow forbidden band width of carbon nitride can increase the photoresponse range, thereby increasing the photocatalytic performance. Chinese patent CN112657533A (2021-04-16) discloses a carbon-nitrogen-sulfur co-doped heterojunction photocatalyst and a preparation method and application thereof.
g-C of bulk phase 3 N 4 Due to the limitation of the structure, the photocatalytic efficiency is low due to the fact that the specific surface area is small, the number of active sites is small, the recombination rate of photo-generated electrons and holes is high, the charge mobility is low. Only a few layers g-C stripped to a high specific surface area 3 N 4 So as to exert the specific properties of high specific surface area, high hardness, light transmittance, hydrophobicity and the like.
To improve g-C 3 N 4 The material has the defects that the photocatalytic activity is improved mainly by the following modes: (1) Using nano TiO 2 A modification similar method, which is to perform doping modification of various elements or compounds; (2) Stripping and layering multiple layers of carbon nitride or activating and forming pores by adopting a graphene modification similar method so as to increase the specific surface area of the carbon nitride; researches find that the specific surface area of the few-layer carbon nitride nanosheet obtained by stripping reaches 200-300 m 2 (ii)/g, increased by more than 20 times before stripping; (3) Mixing it with nano TiO 2 Or other semiconductor photocatalytic materials are compounded, the photocatalytic synergistic effect is exerted, and the photocatalyst has good photocatalytic performance in both an ultraviolet region and a visible light region; (4) Adopts the combination modes of doping, activating, compounding and the like to jointly promote the g-C 3 N 4 Performance of the photocatalytic composite material.
Preparation of high specific surface area g-C in the prior art 3 N 4 Mainly adopts complex nano SiO 2 Template method, dissolving away nano SiO by fluoride 2 The pore-forming activation in the manner of (1) does not have environmental technical economy due to the need to consume a large amount of fluoride.
Disclosure of Invention
The invention aims to provide a visible light catalytic composite material which is prepared by doping carbon, nitrogen and phosphorus with nano TiO 2 Material, phosphorus doping Activity g-C 3 N 4 Material and nano SiO 2 Material composition; carbon nitrogen phosphorus doped nano-scaleTiO 2 The mass fraction of (A) is 30-45%; phosphorus doping Activity g-C 3 N 4 The mass fraction of the nano SiO is 5 to 15 percent 2 The mass fraction of (A) is 45-60%; the three photocatalytic material components have a photocatalytic synergistic effect, so that the catalytic efficiency of the visible light catalytic composite material is improved; the nano SiO 2 The material is formed by acidic hydrolysis and polymerization of methyltriethoxysilane and tetraethoxysilane. Can be used for photocatalytic self-cleaning of solid surfaces and degradation of organic pollutants in air and waste water.
Nano TiO in the invention 2 Adopts non-metallic element carbon nitrogen phosphorus doping, and simultaneously leads the carbon nitrogen phosphorus doping and the phosphorus doping to have activity g-C 3 N 4 The performance of the photocatalytic material is greatly improved by compounding, and compared with the prior art which only adopts nano TiO 2 With a body g-C 3 N 4 The two photocatalytic materials are compounded essentially differently. Nano TiO in the prior art 2 And g-C 3 N 4 The photocatalytic response interval of (2) does not include the entire visible light region, and the photocatalytic synergistic effect of the two semiconductor materials is not fully exerted.
The invention relates to nano SiO 2 The material not only can be used as an adhesive and a carrier material of a photocatalytic composite material, but also can enhance carbon, nitrogen and phosphorus doped nano TiO 2 Material and phosphorus doping Activity g-C 3 N 4 The material has synergistic effect of photocatalytic performance.
The invention also aims to provide a preparation method of the visible light catalytic composite material, which comprises the steps of doping carbon, nitrogen and phosphorus with nano TiO 2 Preparation of materials, phosphorus doping Activity g-C 3 N 4 Preparation of material, nano SiO 2 The preparation method comprises four parts of material preparation and visible light catalytic composite material preparation, and comprises the following specific steps:
(1) Neutralizing 2mol/L titanyl sulfate aqueous solution with 4mol/L ammonia water to pH =8-10, filtering and separating white precipitate, and washing with deionized water until no sulfate ions exist; peptizing the white precipitate by using 1mol/L oxalic acid aqueous solution on a water bath with the temperature of 60-80 ℃, and controlling the molar ratio of the raw materials of titanyl sulfate, ammonia water and oxalic acid to be 1:1.5-2.5:0.8 to 1.6 to obtain the nano TiO 2 Hydrosol;
(2) Mixing the mixture with saturated urea aqueous solution, melamine ethanol solution and phosphoric acid aqueous solution, and controlling raw material TiO 2 And the molar ratio of urea to melamine to phosphoric acid is 1:0.5-2:2-10:0.1 to 0.5, refluxing for 4 to 12 hours at the temperature of between 75 and 90 ℃ to form carbon, nitrogen and phosphorus doped nano TiO 2 A mixture of hydrosols; after partial solvent is volatilized, carbon nitrogen phosphorus doped nano TiO containing urea, melamine and phosphoric acid is formed 2 Gelling;
(3) Carbon, nitrogen and phosphorus are doped with nano TiO 2 Drying the gel at 110-160 deg.C; transferring into high temperature furnace at 500-550 deg.C and CO 2 Polymerization under gas protection and product g-C 3 N 4 Activating the material for 4-10h; cooling to form carbon, nitrogen and phosphorus doped nano TiO 2 Doping activity with phosphorus g-C 3 N 4 Mixture, phosphoric acid as g-C 3 N 4 And a source of phosphorus dopant, CO 2 As g-C 3 N 4 A gas activator of the material;
(4) Carbon, nitrogen and phosphorus are doped with nano TiO 2 Doping activity with phosphorus g-C 3 N 4 The mixture is crushed and ground to 100-400 meshes, and then dispersed in ethanol solvent with the solid mass fraction of 5 percent for ultrasonic stripping for 4-12h to form phosphorus doped active g-C 3 N 4 An ethanol dispersion of the material; carbon nitrogen phosphorus doped nano TiO 2 Phosphorus doping activity g-C of particles adsorbed after stripping 3 N 4 C, removing; diluting with ethanol solvent to obtain carbon, nitrogen and phosphorus doped nano TiO with the solid mass fraction of 5% 2 Doping Activity with phosphorus g-C 3 N 4 Visible light catalytic composite material suspension;
(5) Dissolving tetraethoxysilane and methyltriethoxysilane in an ethanol aqueous solution containing a phosphoric acid hydrolytic agent, and controlling the feeding molar ratio as follows: ethyl orthosilicate: methyl triethoxysilane: ethanol: water: phosphoric acid =1:0.1-0.5:10-20: :20-50:0.01-0.1; stirring at room temperature for 2-4h to completely hydrolyze ethyl orthosilicate and methyltriethoxysilane, and aging at room temperature for 12-48h; adjusting the concentration with deionized water to form SiO 2 5% by mass of nano SiO 2 HydrosolNano SiO 2 2 The diameter of the particles is 5-20nm;
(6) Mixing SiO 2 5% by mass of nano SiO 2 Hydrosol and carbon, nitrogen and phosphorus doped nano TiO with solid mass fraction of 5% 2 Doping activity with phosphorus g-C 3 N 4 The photocatalytic composite material suspension was mixed in the ratio of 1:0.2-2, adding into a homogenizer for mixing, then adjusting the pH of the mixed solution to be =4-6 by ammonia water, injecting into a mold, and standing for 0.5-2 h to form gel;
(7) Drying the gel at 110-160 ℃, cooling and crushing to obtain the visible light catalytic composite material with 50-200 meshes, wherein the carbon, nitrogen and phosphorus are doped with the nano TiO 2 The mass fraction of (A) is 30-45%; phosphorus doping Activity g-C 3 N 4 The mass fraction of the nano SiO is 5 to 15 percent 2 The mass fraction of (A) is 45-60%.
Carbon, nitrogen and phosphorus doped nano TiO in the invention 2 The photocatalytic material takes titanyl sulfate as a titanium source, and nanometer TiO is firstly prepared 2 The hydrosol reacts with urea and melamine to form gel, and the gel is subjected to thermochemical reaction at high temperature to form carbon, nitrogen and phosphorus doped nano TiO 2 Carbon, nitrogen and phosphorus doped nano TiO 2 Red shift between light absorbing areas to realize carbon, nitrogen and phosphorus doped nano TiO 2 Visible light is catalyzed, and the photocatalytic efficiency is improved.
Phosphorus doping Activity of the present invention g-C 3 N 4 The photocatalytic material is prepared by polymerizing and activating urea and melamine at high temperature in the presence of phosphoric acid, and then stripping to form high specific surface area active g-C 3 N 4 . Research shows that the urea is used as the raw material to synthesize the doped nano g-C 3 N 4 The yield of (A) is only about 3%, and the specific surface area is 30-50m 2/ g; and the nano g-C synthesized by taking melamine as raw material 3 N 4 The yield of the method is 40 to 60 percent, and the specific surface area is 5 to 15m 2/ g. Research shows that phosphorus doping can reduce g-C 3 N 4 The band gap width of the organic electroluminescent material improves the utilization rate of visible light in the photocatalysis process, and can improve the separation efficiency of photo-generated electrons and holes. The invention selects the mixed raw materials of urea and melamine, integrates the advantages of the two raw materials to form g-C 3 N 4 Specific surface areaModerate, urea as doped modified nano TiO 2 Carbon nitrogen source (c).
The inventor also engaged in research and development of materials with high specific surface areas such as activated carbon and activated graphene, and transferred and applied the idea and method of activating novel carbon materials to activated g-C 3 N 4 In the preparation, phosphoric acid is creatively selected as the bulk g-C 3 N 4 Activating the activated catalyst and the phosphorus dopant which increase the specific surface area of the pore-forming. The principle is phosphoric acid catalytic activation and CO 2 Gas activation of layers g-C capable of forming in polymerization 3 N 4 Oxidation on the surface generates a large number of micropores, greatly increasing the g-C 3 N 4 Specific surface area of (2). Activated pore-forming and phosphorus-doped body g-C 3 N 4 The interlayer acting force in the molecule is obviously weakened, and the few layers g-C with high specific surface area can be easily peeled off under the action of organic solvent and ultrasonic wave 3 N 4 。
The invention creatively dopes carbon, nitrogen and phosphorus with nano TiO 2 Mixing with urea and melamine, and synthesizing phosphorus-doped nano g-C 3 N 4 Carbon, nitrogen and phosphorus doping modified nano TiO generated by decomposing urea and phosphoric acid 2 To make the carbon, the nitrogen and the phosphorus dope with the nano TiO 2 Intercalating phosphorus doped nano g-C 3 N 4 In and out convenient for phosphorus doping with nano g-C 3 N 4 Can be delaminated and retarded by the nano g-C 3 N 4 And (4) agglomeration. Carbon nitrogen phosphorus doped nano TiO 2 The particles are uniformly dispersed in the phosphorus-doped nano g-C 3 N 4 On the surface, close contact with phosphorus doped nano g-C 3 N 4 The surface of the material obviously improves the separation efficiency of photo-generated electron holes, and leads carbon, nitrogen and phosphorus to be doped with nano TiO 2 Doping with phosphorus nano g-C 3 N 4 The compound generates the photocatalysis synergistic effect.
The invention has the beneficial effects that:
(1) Phosphorus doping Activity of the invention g-C 3 N 4 The polymerization reaction and the activation pore-forming are completed at the same time, and the phosphoric acid is simultaneously used as the source of the activation catalyst and the phosphorus doping agent, thereby simplifying the phosphorus doping activity g-C 3 N 4 The preparation process of (1);
(2) Carbon, nitrogen and phosphorus doped nano TiO in the invention 2 As visible light catalytic material, adsorbing active g-C doped with phosphorus 3 N 4 On the surface, a composite visible light catalytic material is formed, the photocatalysis synergistic effect is exerted, and the phosphorus doping activity g-C can be prevented 3 N 4 (ii) agglomeration;
(3) The visible light catalytic composite material is suitable for photocatalytic degradation of organic pollutants on the surface of solid, in air and in waste water, and has industrial application prospect.
The experimental raw materials used in the invention, such as titanyl sulfate, urea, melamine, ammonia water, phosphoric acid, oxalic acid, ethanol, ethyl orthosilicate, methyl triethoxysilane and the like, are all commercially available chemical pure reagents.
Detailed Description
Example 1
50mL of a 2mol/L titanyl sulfate aqueous solution is taken, 50mL of ammonia water of 4mol/L is used for neutralizing until the pH is =9-10, a white precipitate formed is filtered and separated, and the white precipitate is washed by deionized water until no sulfate ions exist. Dispersing the precipitate in 100mL of 1mol/L oxalic acid aqueous solution, heating and peptizing on water bath at 60-80 ℃ to obtain nano TiO 2 130g of hydrosol. Adding saturated urea aqueous solution containing 12 g (0.2 mol/L) of urea, melamine ethanol suspension containing 63g (0.5 mol) of melamine and 4.9g (0.05 mol) of phosphoric acid, and refluxing at 75-90 deg.C for 4-12h to form carbon, nitrogen and phosphorus doped nano TiO 2 Heating 330g of hydrosol to volatilize part of solvent to form carbon nitrogen phosphorus doped nano TiO containing urea, melamine and phosphoric acid 2 97g of gel.
Drying the above mixture at 160 deg.C, transferring into high temperature furnace, and heating at 500-550 deg.C and CO 2 Roasting for 4 hours under the protection of gas, and cooling to form carbon, nitrogen and phosphorus doped nano TiO 2 Doping activity with phosphorus g-C 3 N 4 Mixture 11.1g. Pulverizing, grinding to 100 mesh, dispersing in 200g anhydrous ethanol solvent, ultrasonic stripping for 6 h, diluting with anhydrous ethanol to obtain carbon-nitrogen-phosphorus doped nanometer TiO with solid mass fraction of 5% 2 Doping Activity with phosphorus g-C 3 N 4 Photocatalytic composite222g of a dispersion of the composite material.
Dispersing 104g (0.5 mol) of ethyl orthosilicate and 18.2g (0.1 mol) of methyltriethoxysilane in a mixed aqueous solution containing 2g (0.02 mol) of phosphoric acid hydrolytic agent, 250g (5 mol) of ethanol and 180g (10 mol) of deionized water, stirring at room temperature for 4h to completely hydrolyze the ethyl orthosilicate and the methyltriethoxysilane, aging at room temperature for 48h, and adjusting the concentration with deionized water to form SiO 2 5% by mass of nano SiO 2 Hydrosol, 720g, nanometer SiO therein 2 The particle diameter is 5-20nm.
Carbon, nitrogen and phosphorus doped nano TiO with the solid mass fraction of 5 percent 2 Doping Activity with phosphorus g-C 3 N 4 Dispersion of photocatalytic composite Material 222g, siO 2 5% by mass of nano SiO 2 Mixing 222g of hydrosol in a homogenizer, then adjusting the pH =4-6 of the mixed solution by using ammonia water, injecting the mixed solution into a mold, and standing for 0.5-2 h to form gel; drying the gel at 110-160 ℃, cooling and crushing to obtain 22.2g of visible light catalytic composite material with 50-200 meshes, wherein the nano TiO is doped with carbon, nitrogen and phosphorus 2 The mass fraction of (a) is 36%; phosphorus doping Activity g-C 3 N 4 The mass fraction of (A) is 14 percent, and the SiO is nano 2 Is 50 percent.
Claims (2)
1. A visible light catalytic composite material is characterized in that carbon, nitrogen and phosphorus are doped with nano TiO 2 Material, phosphorus doping Activity g-C 3 N 4 Material and nano SiO 2 Material composition; carbon nitrogen phosphorus doped nano TiO 2 The mass fraction of (A) is 30-45%; phosphorus doping Activity g-C 3 N 4 5-15% of nano SiO 2 The mass fraction of (A) is 45-60%; the three photocatalytic material components have a photocatalytic synergistic effect, so that the catalytic efficiency of the visible light catalytic composite material is improved; the nano SiO 2 The material is formed by acid hydrolysis and polymerization of methyltriethoxysilane and tetraethoxysilane, and can be used for photocatalytic self-cleaning of the surface of a solid and degradation of organic pollutants in air and waste water.
2. The preparation method of the visible light catalytic composite material is characterized by comprising the steps of doping carbon, nitrogen and phosphorus with nano TiO 2 Preparation of materials, phosphorus doping Activity g-C 3 N 4 Preparation of material, nano SiO 2 The preparation method comprises four parts of material preparation and visible light catalytic composite material preparation, and comprises the following specific steps:
(1) Neutralizing a 2mol/L titanyl sulfate aqueous solution with 4mol/L ammonia water to pH =8-10, filtering and separating a formed white precipitate, and washing with deionized water until no sulfate ions exist; peptizing the white precipitate by using a 1mol/L oxalic acid aqueous solution on a water bath with the temperature of 60-80 ℃, and controlling the molar ratio of raw materials of titanyl sulfate, ammonia water and oxalic acid to be 1:1.5-2.5:0.8 to 1.6 to obtain the nano TiO 2 Hydrosol;
(2) Mixing the mixed solution with saturated urea aqueous solution, melamine ethanol solution and phosphoric acid aqueous solution, and controlling raw material TiO 2 Urea, melamine and phosphoric acid in a molar ratio of 1:0.5-2:2-10:0.1 to 0.5, refluxing for 4 to 12 hours at the temperature of between 75 and 90 ℃ to form carbon, nitrogen and phosphorus doped nano TiO 2 A mixture of hydrosols; after partial solvent is volatilized, carbon nitrogen phosphorus doped nano TiO containing urea, melamine and phosphoric acid is formed 2 Gelling;
(3) Carbon, nitrogen and phosphorus are doped with nano TiO 2 Drying the gel at 110-160 deg.C; transferring into high temperature furnace at 500-550 deg.C and CO 2 Carrying out polymerization reaction under the protection of gas, and simultaneously adding the product g-C 3 N 4 Activating the material for 4-10h; cooling to form carbon, nitrogen and phosphorus doped nano TiO 2 Doping activity with phosphorus g-C 3 N 4 Mixing; phosphoric acid as g-C 3 N 4 And a source of phosphorus dopant, CO 2 As g-C 3 N 4 A gas activator of the material;
(4) Carbon, nitrogen and phosphorus doped with nano TiO 2 Doping activity with phosphorus g-C 3 N 4 The mixture is crushed and ground to 100-400 meshes, and then dispersed in ethanol solvent with the solid mass fraction of 5 percent for ultrasonic stripping for 4-12h to form phosphorus doped active g-C 3 N 4 An ethanol dispersion of the material; carbon nitrogen phosphorus doped nano TiO 2 Phosphorus doping by particle adsorption after strippingActivity g-C 3 N 4 The above step (1); diluting with ethanol solvent to obtain carbon, nitrogen and phosphorus doped nano TiO with the solid mass fraction of 5% 2 Doping Activity with phosphorus g-C 3 N 4 Visible light catalytic composite material suspension;
(5) Dissolving ethyl orthosilicate and methyltriethoxysilane in an ethanol water solution containing a phosphoric acid hydrolysis agent, and controlling the feeding molar ratio as follows: ethyl orthosilicate: methyl triethoxysilane: ethanol: water: phosphoric acid =1:0.1-0.5:10-20: :20-50:0.01-0.1; stirring at room temperature for 2-4h to completely hydrolyze ethyl orthosilicate and methyltriethoxysilane, and aging at room temperature for 12-48h; adjusting the concentration with deionized water to form SiO 2 5% by mass of nano SiO 2 Hydrosol, nano SiO 2 The diameter of the particles is 5-20nm;
(6) Mixing SiO 2 5% by mass of nano SiO 2 Hydrosol and carbon, nitrogen and phosphorus doped nano TiO with solid mass fraction of 5% 2 Doping activity with phosphorus g-C 3 N 4 The photocatalytic composite material suspension was mixed in the ratio of 1: adding the mixture into a homogenizer at a mass ratio of 0.2-2, mixing, then adjusting the pH of the mixed solution to be =4-6 by using ammonia water, injecting the mixed solution into a mold, and standing for 0.5-2 h to form gel;
(7) Drying the gel at 110-160 ℃, cooling and crushing to obtain the visible light catalytic composite material with 50-200 meshes, wherein the carbon, nitrogen and phosphorus are doped with the nano TiO 2 The mass fraction of (A) is 30-45%; phosphorus doping Activity g-C 3 N 4 5-15% of nano SiO 2 The mass fraction of (A) is 45-60%.
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| CN103769213A (en) * | 2014-01-07 | 2014-05-07 | 河北科技大学 | Preparation method for phosphor-doped graphite-phase carbon nitride visible-light catalyst |
| CN106391086A (en) * | 2016-09-29 | 2017-02-15 | 中国地质大学（北京） | Preparation method of C3N4/SiO2 heterojunction photocatalyst |
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| CN103769213A (en) * | 2014-01-07 | 2014-05-07 | 河北科技大学 | Preparation method for phosphor-doped graphite-phase carbon nitride visible-light catalyst |
| CN106391086A (en) * | 2016-09-29 | 2017-02-15 | 中国地质大学（北京） | Preparation method of C3N4/SiO2 heterojunction photocatalyst |
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