CN110935449A - Efficient environment-friendly black titanium dioxide-based photocatalyst and preparation method thereof - Google Patents
Efficient environment-friendly black titanium dioxide-based photocatalyst and preparation method thereof Download PDFInfo
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- CN110935449A CN110935449A CN201811108414.0A CN201811108414A CN110935449A CN 110935449 A CN110935449 A CN 110935449A CN 201811108414 A CN201811108414 A CN 201811108414A CN 110935449 A CN110935449 A CN 110935449A
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- titanium dioxide
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- based photocatalyst
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 246
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 98
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 239000000463 material Substances 0.000 claims description 85
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 71
- 239000000758 substrate Substances 0.000 claims description 61
- 230000001699 photocatalysis Effects 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 26
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 15
- -1 polypropylene Polymers 0.000 claims description 15
- 238000011068 loading method Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 229910052755 nonmetal Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000007146 photocatalysis Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 238000001228 spectrum Methods 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002073 nanorod Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000002121 nanofiber Substances 0.000 claims description 6
- 239000002070 nanowire Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 239000002071 nanotube Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
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- 150000002500 ions Chemical class 0.000 description 17
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000003980 solgel method Methods 0.000 description 14
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 12
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- 239000002243 precursor Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 230000031700 light absorption Effects 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 230000032683 aging Effects 0.000 description 8
- 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 description 8
- 230000015556 catabolic process Effects 0.000 description 8
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- 238000000862 absorption spectrum Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000012808 vapor phase Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
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- 239000003795 chemical substances by application Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 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 6
- 229940012189 methyl orange Drugs 0.000 description 6
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- 238000000926 separation method Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000004887 air purification Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
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- 230000000295 complement effect Effects 0.000 description 3
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
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- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
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- 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 description 2
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000003903 river water pollution Methods 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
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- 230000004048 modification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
-
- 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
- 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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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a high-efficiency environment-friendly black titanium dioxide-based photocatalyst and a preparation method thereof.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a high-efficiency environment-friendly black titanium dioxide-based photocatalyst and a preparation method thereof.
Background
Atmospheric pollution, water eutrophication, biodiversity drastic reduction and persistent organic pollutants are diffused globally, the global ecological environment crisis is the primary challenge facing human fate communities, and the environmental protection of the ecological environment becomes the work focus of people. Solar energy is an inexhaustible ideal energy which is known at present, and how to efficiently convert the solar energy into high-efficiency energy which is directly used by human beings becomes a popular research target. The photocatalytic technology is an efficient, safe and environment-friendly scientific technology which can activate a photocatalyst by using sunlight as an energy source to drive an oxidation-reduction reaction, and the photocatalyst is not consumed in the reaction process, and has been accepted by the international academia in the fields of clean energy and environment.
TiO2The photocatalyst has good corrosion resistance and high catalytic activity, is stable in performance, cheap and easily available, and is nontoxic and harmless, so that the photocatalyst is the best photocatalyst recognized at present. The technology has great potential in the aspects of hydrogen energy and wastewater purification treatment, and also has wide application prospect in the aspect of air purification. However, the traditional titanium dioxide can only absorb 5% of sunlight due to the larger forbidden bandwidth (anatase type, 3.2eV), and the sunlight utilization rate is lower, so that most energy sources of sunlight cannot be efficiently utilized. Secondly, the rapid recombination of photogenerated electrons and holes results in TiO2The quantum efficiency of photocatalysis is low, and then TiO is influenced2Catalytic activity of semiconductor photocatalysts. How to effectively expand the light absorption response spectrum of titanium dioxide, improve the photocatalytic quantum efficiency, improve the photocatalytic activity of titanium dioxide and apply the titanium dioxide to the practical life is the key point and the difficulty of the current research, which also has important promoting significance for the popularization of the photocatalytic technology to the commercial application.
Disclosure of Invention
Face to faceThe invention aims to provide a high-efficiency environment-friendly black titanium dioxide-based photocatalyst material, a preparation method and application thereof, aiming at effectively expanding the light absorption response spectrum of the traditional titanium dioxide, promoting the photocatalytic quantum efficiency and improving the photocatalytic activity of the titanium dioxide, improving the photocatalytic efficiency under ultraviolet light and enabling TiO to be also used in the prior titanium dioxide photocatalysis technology2The absorption spectrum is expanded to a visible light region, the recombination of photo-generated electrons and holes is inhibited, and the photocatalyst has high-efficiency photocatalytic performance under the illumination condition.
In one aspect, the present invention provides a black titanium dioxide-based photocatalyst, which includes a loading substrate and co-doped black titanium dioxide loaded on the loading substrate, where the loading substrate is at least one of a one-dimensional nanotube, a one-dimensional nanowire, a one-dimensional nanorod, a one-dimensional nanofiber, and a two-dimensional layered material.
In the invention, the black titanium dioxide-based photocatalyst comprises a load substrate composed of a one-dimensional nanotube, a one-dimensional nanowire, a one-dimensional nanorod, a one-dimensional nanofiber or a two-dimensional layered material and co-doped black titanium dioxide loaded on the load substrate, wherein the TiO is improved by the synergistic effect of the load substrate and co-doped ions2Photocatalytic activity of (1). On the one hand, ion co-doping can cause TiO2The forbidden bandwidth is reduced or a new doping energy level is formed to form an impurity energy level, so that the absorption range of the solar spectrum is widened, on the other hand, the defects caused by the loading substrate and the doping are beneficial to the separation of photo-generated electron hole pairs, the recombination of the electron hole pairs is inhibited, and the black titanium dioxide-based photocatalyst material with excellent photocatalytic performance is realized under the synergistic effect.
The mass ratio of the co-doped black titanium dioxide to the load substrate can be 1 (0.5-5), and preferably 1 (2-4).
In the co-doped black titanium dioxide, co-doping element and TiO2The molar ratio of (1): to (0.01): to 0.15), preferably (0.05): to 0.10).
The doping element in the co-doped black titanium dioxide can be a metal doping element and/or a non-metal doping element, namely the co-doping can be in the form of metal ionsAnd the ion and the metal ion are co-doped, the metal ion and the nonmetal are co-doped, and the nonmetal are co-doped. The metal doping element can be at least one of Fe, Co, Ni, Cu, Zn, W, Ti, Ru, Nb, La, Gd, Sm and Nd, and the nonmetal doping element can be at least one of H, B, C, N, P, S, I, F. The advantages of each doped ion in the co-doped black titanium dioxide of the high-quality load substrate material are complementary, so that the photocatalysis efficiency under ultraviolet light is improved, and TiO is also enabled to be2The absorption spectrum extends into the visible region; meanwhile, the load substrate is beneficial to accelerating the effective separation of the photo-generated electrons and the holes, inhibiting the recombination of the photo-generated electrons and the holes and improving the photocatalytic capacity of the photo-generated electrons and the holes under sunlight.
Preferably, the load substrate is at least one of a carbon nanotube, a carbon fiber, a titanium dioxide nanowire, a zinc oxide nanorod, a tin oxide nanowire, graphene oxide, boron nitride and molybdenum disulfide.
On the other hand, the invention also discloses a preparation method of the black titanium dioxide-based photocatalyst, which comprises the following steps:
preparing co-doped black titanium dioxide;
mixing the co-doped black titanium dioxide, a load substrate and a solvent to obtain a mixture; and stirring the mixture, soaking for more than 12 hours, drying and then carrying out heat treatment to obtain the black titanium dioxide-based photocatalyst.
According to the invention, the black titanium dioxide-based photocatalyst is obtained by mixing the prepared co-doped black titanium dioxide, a load substrate and a solvent, soaking for a certain time and then carrying out heat treatment. On one hand, the black titanium dioxide-based photocatalyst material prepared by the method improves the photocatalytic efficiency under ultraviolet light and further enables TiO to be2The absorption spectrum extends into the visible region; on the other hand, good interface contact can be formed, separation of photogenerated electron-hole pairs is facilitated, and recombination of the photogenerated electron-hole pairs is inhibited. In addition, the preparation method is simple in preparation process and easy to control in preparation process, and the material can be applied to the fields of hydrogen energy preparation, water pollutant treatment, air purification and the like。
Preferably, the solvent is at least one of ethanol, N-methyl pyrrolidone and water.
Preferably, the temperature of the heat treatment is 400 to 500 ℃.
The heat treatment process can be protected by gas. The passing protective gas can be one or more of hydrogen, nitrogen and argon, and the flow rate can be 100-1000 sccm.
Preferably, the time for immersion is 12 to 48 hours, preferably 12 to 18 hours.
The drying temperature can be 60-80 ℃.
The preparation method of the co-doped black titanium dioxide can be prepared by a sol-gel method or a sol-gel method and a gas phase CVD method. Wherein, the sol-gel method is used for preparing co-doped black TiO2The method can comprise the following steps: mixing a chelating agent, a co-doping source and a solvent a, stirring for 5-15 minutes, and adjusting the pH value to 1-4 to obtain a mixed solution A; mixing a titanium dioxide precursor, a stabilizer and a solvent B, and stirring for 10-20 minutes to obtain a mixed solution B; adding the mixed solution B into the mixed solution A under an ice bath condition, stirring for 2-4 h in the process to obtain yellow transparent sol, and then aging for 6-10 h to obtain gel; drying at the temperature of 80-100 ℃ to obtain light yellow powder; and placing the obtained light yellow powder at 400-600 ℃ for heat treatment for a period of time to finally obtain co-doped black TiO2。
The solvent a and/or the solvent b can be at least one of ethanol, water, ethylene glycol and n-butanol.
The stabilizer can be acetylacetone, triethanolamine, etc.
The chelating agent can be glacial acetic acid, citric acid, tartaric acid, etc.
The Co-doping source (doping element source) may include metal element doping sources such as nitrates and chlorides of metal elements (Fe, Co, Ni, Cu, Zn, W, Ti, Ru, Nb, La, Gd, Sm, Nd), NH4Cl, phosphoric acid, H2S, sodium borohydride, thiourea, glucose, CH4、NH3、H2、N2One or more of the non-metal element doping sourcesA compound (I) is provided.
The titanium dioxide precursor may be n-butyl titanate (tetrabutyl titanate), butyl titanate, titanium tetrachloride or tetraisobutyl titanate.
The mass ratio of the titanium dioxide precursor, the solvent a, the solvent b, the chelating agent and the stabilizing agent can be 1 (0.4-1): 1-20): 0.2-0.8): 0.1-0.2. In one example, n-butyl titanate is used as a precursor, a solvent a is water and ethanol, a solvent b is ethanol, glacial acetic acid is used as a chelating agent, acetylacetone is used as a stabilizer, and the mass ratio of the n-butyl titanate, the water, the ethanol, the glacial acetic acid and the acetylacetone is 1 (0.6-1) to (1-6) to (0.4-0.6) to (0.1-0.2).
Co-doped TiO2The "sol-gel method + vapor phase CVD" is similar to the sol-gel method, except that the doping elements in the sol-gel method can be added during the preparation of the titanium dioxide precursor, while the doping elements in the "sol-gel method + vapor phase CVD" are doped by the vapor phase method during the heat treatment. In addition, the co-doping element may be doped in the vapor-phase heat treatment in both the "sol-gel method + vapor-phase CVD" and the sol-gel method.
In another aspect, the present invention further provides a mesh-shaped porous photocatalytic belt material, which comprises a mesh-shaped substrate and any one of the black titanium dioxide-based photocatalysts loaded on the mesh-shaped substrate.
The mesh substrate may be a polymeric fabric or an inorganic porous material. The polymer fabric may be one selected from polypropylene, polytetrafluoroethylene, polyethylene, polyvinylidene fluoride, and polyamide mesh.
In another aspect, the present invention provides a method for preparing a mesh-shaped porous photocatalytic belt material, comprising mixing a mesh-shaped porous photocatalytic belt material with a solvent c to obtain a dispersion; and applying the dispersion to a mesh substrate.
The coating method can be a pulling method, a dipping method, a spraying method and the like.
The solvent c can be one or a mixture of several of absolute ethyl alcohol, N-methyl pyrrolidone and water. A binder may be added to the dispersion. The binder may comprise one or a mixture of several of a curing agent, phenolic resin/polyacrylamide, polyacrylic acid/potassium persulfate (ammonium persulfate), carboxymethylcellulose, and the like.
In another aspect, the invention further provides an application of any one of the black titanium dioxide-based photocatalyst materials in the field of photocatalysis, especially in the field of full-solar-spectrum-enhanced photocatalysis, including air purification, sewage treatment and the like.
According to the invention, the black titanium dioxide-based photocatalyst material with excellent performance can be prepared, can be applied to effectively decompose pollutants such as formaldehyde, toluene, xylene, ammonia and the like, and can effectively carry out photocatalytic reaction in wastewater treatment such as dye wastewater, organic phosphorus compounds, polycyclic aromatic hydrocarbons, pesticide wastewater, cyanide wastewater and the like, and the final reaction products are carbon dioxide, water and other harmless substances, so that secondary pollution is avoided. The material has the characteristics of high efficiency and environmental protection, and can be widely used in the field of environmental purification.
Drawings
Fig. 1 shows a photograph of a real object of the co-doped titanium dioxide prepared in example 1 of the present invention and conventional P25 (white titanium dioxide) (white on the left is the conventional material P25, black on the right is the co-doped titanium dioxide);
FIG. 2 shows the UV-VIS spectra of the high-efficiency and environmentally friendly black titanium dioxide-based photocatalyst material prepared in example 3 of the present invention and a conventional P25 material;
FIG. 3 shows the degradation of the high-efficiency environment-friendly black titanium dioxide-based photocatalyst material prepared in example 4 of the present invention under sunlight compared with the degradation of methyl orange as a traditional P25 material;
FIG. 4 shows a photograph of a mesh-shaped photocatalytic belt material prepared in example 5 of the present invention;
FIG. 5 shows a comparison of water samples taken before and after two weeks of wastewater treatment under sunlight for the mesh photocatalytic zone material prepared in example 6 of the present invention.
Detailed Description
The present invention is further described below in conjunction with the following embodiments, which are intended to illustrate and not to limit the present invention.
The invention provides a high-efficiency environment-friendly black titanium dioxide-based photocatalyst material and a preparation method and application thereof, aiming at effectively expanding the light absorption response spectrum of the traditional titanium dioxide, promoting the photocatalytic quantum efficiency and improving the photocatalytic activity of the titanium dioxide. The present inventors used a co-doped black titanium dioxide (hereinafter, sometimes referred to as "co-doped ion-modified TiO") supporting a substrate and a high-quality substrate supporting material2OR codoped TiO2") synergistic effect to enhance TiO2The black titanium dioxide base photocatalyst material with excellent photocatalytic performance is obtained through the photocatalytic activity. Here, "co-doping" means that the doping element is 2 or more. In addition, the invention discloses a reticular porous photocatalytic belt material, and the efficient environment-friendly black titanium dioxide-based photocatalyst material is loaded on a reticular substrate. The material disclosed by the invention has the characteristics of high efficiency and environmental protection, and can be applied to the fields of treating pollutants in water, purifying air and the like.
Hereinafter, the black titanium dioxide-based photocatalyst material according to the present invention, the preparation method and the application thereof are exemplarily described.
(Black titanium dioxide based photocatalyst Material)
The black titanium dioxide-based photocatalyst material comprises a load substrate and codoped ion modified TiO loaded on the load substrate2. The loading substrate can adopt one-dimensional nanotubes, nanowires, nanorods, nanofibers, two-dimensional layered materials and the like. One-dimensional nanotubes, nanowires, nanorods, nanofibers include, but are not limited to, carbon nanotubes, carbon fibers, titanium dioxide nanowires, zinc oxide nanorods, tin oxide nanowires, and the like. Two-dimensional layered materials include, but are not limited to, graphene oxide, boron nitride, molybdenum disulfide, and the like.
Co-doped ion modified TiO2The mass ratio of the support substrate to the support substrate can be 1 (0.5-5), and preferably 1 (2-4). Doping elements (i.e., co-doping elements, or also "co-doping ions") with TiO2The molar ratio of (1): to (0.01): to 0.15), preferably (0.05): to 0.10).
The co-doping element may be a metal doping element and/or a non-metal doping element,that is, the co-doping may be in the form of at least one of co-doping of metal ions with metal ions, co-doping of metal ions with non-metal ions, and co-doping of non-metal with non-metal ions. Metallic doping elements include, but are not limited to, Fe, Co, Ni, Cu, Zn, W, Ti, Ru, Nb, La, Gd, Sm, Nd. Non-metal doping elements include, but are not limited to H, B, C, N, P, S, I, F. High-quality co-doped ion modified TiO loaded on substrate material2The advantages of each doped ion are complementary, thereby not only improving the photocatalytic efficiency under ultraviolet light, but also leading TiO to be2The absorption spectrum extends into the visible region; meanwhile, the load substrate is beneficial to accelerating the effective separation of the photo-generated electrons and the holes, inhibiting the recombination of the photo-generated electrons and the holes and improving the photocatalytic capacity of the photo-generated electrons and the holes under sunlight.
(preparation of a black titanium dioxide-based photocatalyst material).
First, co-doped ion modified TiO is prepared2. The codoped ion modified TiO can be prepared by a sol-gel method or a sol-gel method and a gas phase CVD method2。
Sol-gel method for preparing co-doped black TiO2The method can comprise the following steps: mixing a chelating agent, a co-doping source and a solvent a, stirring for 5-15 minutes, and adjusting the pH value to 1-4 to obtain a mixed solution A; mixing a titanium dioxide precursor, a stabilizer and a solvent B, and stirring for 10-20 minutes to obtain a mixed solution B; adding the mixed solution B into the mixed solution A under an ice bath condition, stirring for 2-4 h in the process to obtain yellow transparent sol, and then aging for 6-10 h to obtain gel; drying at the temperature of 80-100 ℃ to obtain light yellow powder; and placing the obtained light yellow powder at 400-600 ℃ for heat treatment for a period of time to finally obtain the co-doped TiO2. The heat treatment can be carried out under gas protection. The passing protective gas can be one or more of hydrogen, nitrogen and argon, and the flow rate can be 100-1000 sccm.
Co-doped TiO2The "sol-gel method + vapor phase CVD" of (a) is similar to the sol-gel method, except that one doping element may be added during the preparation of the titanium dioxide precursor, while the other doping element is doped by a vapor phase method during the heat treatment. In addition, it is also possibleSo that both codopant elements are doped during the gas-phase heat treatment. The gas phase heat treatment can be performed in the atmosphere of methane, acetylene, ethylene, propane, ammonia gas, etc., with a flow rate of 100-1000 sccm.
The solvent a and/or the solvent b may be at least one of ethanol (absolute ethanol), water, ethylene glycol, and n-butanol. The stabilizer can be acetylacetone, triethanolamine, etc. The chelating agent can be glacial acetic acid, citric acid, tartaric acid, etc. The Co-doping source (Co-doping element source) includes but is not limited to metal element doping sources such as nitrates and chlorides of metal elements (Fe, Co, Ni, Cu, Zn, W, Ti, Ru, Nb, La, Gd, Sm, Nd, etc.), NH4Cl, phosphoric acid, H2S, sodium borohydride, thiourea, glucose, CH4、NH3、H2、N2And doping source of non-metal element. The titanium dioxide precursor may be n-butyl titanate (tetrabutyl titanate), butyl titanate, titanium tetrachloride or tetraisobutyl titanate.
The mass ratio of the titanium dioxide precursor, the solvent a, the solvent b, the chelating agent and the stabilizing agent can be 1 (0.4-1): 1-20): 0.2-0.8): 0.1-0.2. In one example, n-butyl titanate is used as a precursor, a solvent a is water and ethanol, a solvent b is ethanol, glacial acetic acid is used as a chelating agent, acetylacetone is used as a stabilizer, and the mass ratio of the n-butyl titanate, the water, the ethanol, the glacial acetic acid and the acetylacetone is 1 (0.6-1) to (1-6) to (0.4-0.6) to (0.1-0.2).
Then, co-doped ions are modified into TiO2Mixing the supporting substrate and the solvent d to obtain a mixture. Solvents d include, but are not limited to, ethanol, N-methylpyrrolidone, water. The order of mixing is not particularly limited, and co-doped TiO can be used2The dispersion liquid is dropwise added into the load substrate dispersion liquid, and the codopant ion modified TiO can also be added2And the supporting substrate is dispersed in the solvent d. By co-doping with TiO2In the case of dropwise addition of the dispersion to a dispersion of a supporting substrate, the codoped TiO is added dropwise2Mixing with a solvent e to obtain codoped TiO2Dispersing liquid, mixing the load substrate with a solvent f to obtain co-doped TiO2And (3) dispersing the mixture. Solvents e and/or f include, but are not limited to, ethanol, N-methylpyrroleAlkanone, water. The supporting substrate may be a commercially available or a self-made material. The method for preparing the supporting substrate is not particularly limited, and can be prepared by a method known in the art. Co-doped ion modified TiO2The mass ratio of the support substrate to the support substrate can be 1 (0.5-5), and preferably 1 (2-4).
Then, the mixture is stirred, dipped for a period of time, dried and then heat-treated. The stirring time can be 1-6 h. The time for immersion is 12 hours or more, preferably 12 to 48 hours, and the like, preferably 12 to 18 hours. The drying can be carried out at 60-80 ℃.
The temperature of the heat treatment can be 400-500 ℃, preferably 450-550 ℃, and the time of the heat treatment can be 1-5 hours. The heat treatment process can be protected by gas. The passing protective gas can be one or more of hydrogen, nitrogen and argon, and the flow rate can be 100-1000 sccm.
Thus, co-doping of TiO was completed2And compounding with a load substrate. On one hand, the black titanium dioxide-based photocatalyst material prepared by the method improves the photocatalytic efficiency under ultraviolet light and further enables TiO to be2The absorption spectrum extends into the visible region; on the other hand, good interface contact can be formed, separation of photogenerated electron-hole pairs is facilitated, and recombination of the photogenerated electron-hole pairs is inhibited.
The high-efficiency environment-friendly black titanium dioxide-based photocatalyst material can be applied to photocatalysis, especially full-solar-spectrum-enhanced photocatalysis, including air purification, sewage treatment and the like.
(mesh-like porous photocatalytic belt Material)
The mesh-shaped porous photocatalytic belt material of one embodiment of the invention comprises a mesh-shaped substrate (or a porous substrate) and a high-efficiency environment-friendly black titanium dioxide-based photocatalyst material loaded on the mesh-shaped substrate. The mass ratio of the mesh substrate to the black titanium dioxide based photocatalyst material can be (9-1): 7-3.
The mesh substrate may be a polymer fabric (polymer net) or an inorganic porous material. Polymeric fabrics include, but are not limited to, polypropylene, polytetrafluoroethylene, polyethylene, polyvinylidene fluoride, polyamide mesh.
(preparation of a reticulated porous photocatalytic tape material).
First, a mesh-like porous photocatalytic belt material is mixed with a solvent c to obtain a dispersion. The dispersing solvent c can be one or a mixture of several of absolute ethyl alcohol, N-methyl pyrrolidone and water. A binder may be added to the dispersion. Binders include, but are not limited to, curatives, phenolic resins/polyacrylamides, polyacrylic acids/potassium persulfate (ammonium persulfate), carboxymethylcellulose.
Next, the dispersion is coated on a mesh substrate. The coating method can be a pulling method, a dipping method, a spraying method and the like. Further, the coating may also include: doctor blade method and roll coating method.
According to the invention, the mesh-shaped photocatalytic belt material has the performance of the high-efficiency environment-friendly black titanium dioxide-based photocatalyst material, solves the problem that titanium dioxide powder is difficult to completely recover in a photocatalytic technology for a long time, and is more directly, simply and conveniently applied to the photocatalytic technology. Fig. 4 shows an experimental diagram of the mesh-shaped photocatalytic belt material used for black and odorous river channel treatment. It can be seen that the photocatalytic net is arranged in water to carry out photocatalysis. Fig. 5 shows a comparative graph of river water sampling before and after the mesh photocatalytic belt material is used for treatment. It can be seen that the river water pollution before treatment is serious, and the change of the river water after treatment is obvious, wherein various indexes of the sewage such as COD (103), TP (1), TN (5), NH3-N (6) are reduced to COD (30), TP (0.23), TN (1.5) and NH3-N (1.0).
The invention has the beneficial effects that:
according to the invention, in the black titanium dioxide-based photocatalyst material, a load substrate and high-quality co-doped ion modified TiO loaded on the substrate material2The advantages of the doped ions are complementary, thereby not only improving the photocatalytic efficiency under ultraviolet light, but also enabling TiO to be2The absorption spectrum extends into the visible region; meanwhile, the load substrate is beneficial to accelerating the effective separation of the photo-generated electrons and the holes and inhibiting the recombination of the photo-generated electrons and the holes, and has high-efficiency photocatalysis performance under the illumination condition;
the preparation method has simple technical process and easy control of the preparation process, and the black titanium dioxide-based photocatalyst material with excellent performance is prepared, can be applied to effectively decompose pollutants such as formaldehyde, toluene, xylene, ammonia and the like, can effectively carry out photocatalytic reaction in the treatment of wastewater such as dye wastewater, organic phosphorus compounds, polycyclic aromatic hydrocarbons, pesticide wastewater, cyanide wastewater and the like, and can not generate secondary pollution because the final reaction products are carbon dioxide, water and other harmless substances. The material has the characteristics of high efficiency and environmental protection, and can be widely used in the field of environmental purification.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Co-doped TiO2The preparation of (1): (1) adding 4ml of glacial acetic acid, 0.18g of cobalt chloride, 0.08g of thiourea and 6ml of deionized water into 20ml of absolute ethyl alcohol, stirring for 15 minutes, and adjusting the pH value to 3; (2) adding 10ml of tetrabutyl titanate dropwise into an ethanol (20ml) solution of acetylacetone (1ml), and stirring rapidly for 20 minutes; (3) dropwise adding the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1) under an ice bath condition, rapidly stirring for 2 hours in the process to obtain yellow transparent sol, and then aging for 10 hours to obtain gel; (4) drying at 100 deg.C to obtain light yellow powder; (5) placing the obtained light yellow powder at 500 ℃ for heat treatment for 1.5h to finally obtain co-doped TiO2. FIG. 1 shows the preparation of co-doped TiO2Physical photograph, different from white color of traditional P25, the co-doped TiO prepared by the method2The appearance is black, indicating that it can absorb visible light in the solar spectrum; co-doped TiO2Preparing with a load substrate: 0.5g of the codoped TiO prepared above was doped2And 2g of graphene oxide prepared by the Hummers method were dispersed in an aqueous solution, stirred for 6 hours, and thenDipping for 16h, drying at 80 ℃, and finally carrying out heat treatment under the condition of 550 ℃ and the protection of argon gas with the flow of 300sccm for 1h to obtain the final high-efficiency environment-friendly black titanium dioxide-based photocatalyst material. Taking a 0.1g black titanium dioxide-based photocatalyst material sample to carry out degradation test on 10mg/l methyl orange, wherein the decomposition can reach more than 95% in 4 min;
the material can be prepared in batches according to a proportion, 5Kg of the black titanium dioxide-based photocatalyst material is dispersed in 1L of ethanol solution, 10g of curing agent is added at the same time, the mixture is stirred for 20 hours, and the visible light absorption mesh-shaped photocatalytic belt can be constructed by loading the mixture on a polypropylene net through an impregnation method.
Example 2
Co-doped TiO2The preparation of (1): (1) adding 3ml of glacial acetic acid, 0.09g of cobalt chloride, 0.10g of nickel nitrate and 6ml of deionized water into 20ml of absolute ethyl alcohol, stirring for 30 minutes, and adjusting the pH value to 4; (2) adding 10ml of tetrabutyl titanate dropwise into an ethanol (20ml) solution of acetylacetone (1ml), and stirring rapidly for 15 minutes; (3) dropwise adding the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1) under an ice bath condition, rapidly stirring for 2 hours in the process to obtain yellow transparent sol, and then aging for 8 hours to obtain gel; (4) drying at 90 deg.C to obtain light yellow powder; (5) placing the obtained light yellow powder at 500 ℃ under the protection of nitrogen with the flow of 300sccm for heat treatment for 1.5h to finally obtain the co-doped TiO2；
Co-doped TiO2Preparing with a load substrate: 0.4g of the codoped TiO prepared above was doped2And 0.8g of single-walled carbon nanotube is dispersed in an ethanol solution, stirred for 8 hours, then soaked for 14 hours, dried at 90 ℃, and finally thermally treated under the protection of nitrogen at 500 ℃ for 1 hour to obtain the final high-efficiency environment-friendly black titanium dioxide-based photocatalyst material. Taking a 0.1g black titanium dioxide-based photocatalyst material sample to carry out degradation test on 10mg/l methyl orange, wherein the decomposition can reach more than 98% in 4 min;
the material can be prepared in batches according to a proportion, 5Kg of the black titanium dioxide-based photocatalyst material is dispersed in 1L of aqueous solution, 20g of low molecular weight phenolic resin is added at the same time, the mixture is stirred for 20 hours, and the visible light absorption mesh-shaped photocatalytic belt can be constructed by being loaded on a polypropylene net through a spraying method.
Example 3
Co-doped TiO2The preparation of (1): (1) adding 4ml of glacial acetic acid, 0.01ml of phosphoric acid, 0.08g of thiourea and 6ml of deionized water into 20ml of absolute ethyl alcohol, stirring for 60 minutes, and adjusting the pH value to 2; (2) adding 10ml of tetrabutyl titanate dropwise into an ethanol (20ml) solution of acetylacetone (1ml), and stirring rapidly for 20 minutes; (3) dropwise adding the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1) under an ice bath condition, rapidly stirring for 1h in the process to obtain yellow transparent sol, and then aging for 7h to obtain gel; (4) drying at 90 deg.C to obtain light yellow powder; (5) placing the obtained light yellow powder at 500 ℃ for heat treatment for 1.5h to finally obtain co-doped TiO2；
Co-doped TiO2Preparing with a load substrate: 0.4g of the codoped TiO prepared above was doped2And dispersing 1.2g of tin oxide nanowires in an N-methyl pyrrolidone solution, stirring for 8h, then soaking for 14h, drying at 90 ℃, and finally performing heat treatment under the condition of 500 ℃ and the nitrogen protection of 200sccm for 1.5h to obtain the final efficient and environment-friendly black titanium dioxide-based photocatalyst material. Fig. 2 is a graph of ultraviolet-visible absorption spectrums of the high-efficiency environment-friendly black titanium dioxide-based photocatalyst material and the conventional P25 material, and it can be seen that the high-efficiency environment-friendly black titanium dioxide-based photocatalyst material disclosed by the present invention completely absorbs visible light in a solar spectrum, whereas the conventional P25 material mainly responds under ultraviolet light. Taking a 0.1g black titanium dioxide-based photocatalyst material sample to carry out degradation test on 10mg/l methyl orange, wherein the decomposition can reach more than 95% in 3 min;
the material can be prepared in batches according to a proportion, 5Kg of the black titanium dioxide-based photocatalyst material is dispersed in 1L N-methyl pyrrolidone solution, 10g of curing agent is added at the same time, the mixture is stirred for 20 hours, and the visible light absorption mesh-shaped photocatalytic belt can be constructed by loading the mixture on a polypropylene net through an impregnation method.
Example 4
Co-doped TiO2The preparation of (1): (1) adding 6ml of glacial acetic acid, 0.02g of ferric nitrate and 8ml of deionized water into 24ml of absolute ethyl alcohol, stirring for 20 minutes, and adjusting the pH value to 2; (2) adding 10ml of tetrabutyl titanate dropwise into an ethanol (20ml) solution of acetylacetone (1ml), and stirring rapidly for 20 minutes; (3) dropwise adding the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1) under an ice bath condition, rapidly stirring for 1.5h in the process to obtain yellow transparent sol, and then aging for 6h to obtain gel; (4) drying at 80 deg.C to obtain light yellow powder; (5) placing the obtained faint yellow powder in the methane atmosphere with the flow of 100sccm at 550 ℃ for heat treatment for 2h to finally obtain Fe and C co-doped TiO2；
Co-doped TiO2Preparing with a load substrate: co-doped TiO prepared as above2Dropwise adding the dispersion into the prepared boron nitride nanosheet dispersion, stirring for 6 hours, then soaking for 14 hours, and finally carrying out heat treatment under the condition of 500 ℃ under the protection of argon for 1 hour to obtain the final efficient and environment-friendly black titanium dioxide-based photocatalyst material; fig. 3 shows that the prepared high-efficiency environment-friendly black titanium dioxide-based photocatalyst material is degraded in sunlight and compared with a traditional P25 material methyl orange, after 15min, the degradation of the high-efficiency environment-friendly black titanium dioxide-based photocatalyst is completely degraded, while the degradation of the traditional material P25 is slow, which indicates that the high-efficiency environment-friendly black titanium dioxide-based photocatalyst material has excellent photocatalytic performance. The material can be prepared in batches according to a proportion, 5Kg of the black titanium dioxide-based photocatalyst material is dispersed in 1L N-methyl pyrrolidone solution, 10g of curing agent is added at the same time, the mixture is stirred for 20 hours, and the visible light absorption mesh-shaped photocatalytic belt can be constructed by loading the mixture on a polypropylene net through an impregnation method.
Example 5
Co-doped TiO2The preparation of (1): (1) adding 4ml of glacial acetic acid, 0.01ml of phosphoric acid, 0.08g of thiourea and 6ml of deionized water into 20ml of absolute ethyl alcohol, stirring for 60 minutes, and adjusting the pH value to 2; (2) adding 10ml of tetrabutyl titanate dropwise into an ethanol (20ml) solution of acetylacetone (1ml), and stirring rapidly for 20 minutes; (3) dropwise adding the mixed liquid obtained in the step (2) into the mixed liquid obtained in the step (1) under ice bath conditionIn the solution, rapidly stirring for 1h in the process to obtain yellow transparent sol, and then aging for 7h to obtain gel; (4) drying at 90 deg.C to obtain light yellow powder; (5) placing the obtained light yellow powder in an ammonia gas atmosphere with the flow of 100sccm at 500 ℃ for 2h to obtain P, N co-doped TiO2；
Co-doped TiO2Preparing with a load substrate: 0.4g of the codoped TiO prepared above was doped2And 0.6g of molybdenum sulfide nanosheet is dispersed in an ethanol solution, stirred for 8 hours, then soaked for 14 hours, dried at 90 ℃, and finally thermally treated under the protection of nitrogen at 500 ℃ for 1 hour to obtain the final efficient and environment-friendly black titanium dioxide-based photocatalyst material. Taking 0.1g of a black titanium dioxide-based photocatalyst material sample to carry out degradation test on 10mg/l of methyl orange, wherein the decomposition can reach more than 99% in 3 min;
the material can be prepared in batches according to a proportion, 5Kg of the black titanium dioxide-based photocatalyst material is dispersed in 1L N-methyl pyrrolidone solution, 10g of curing agent is added at the same time, the mixture is stirred for 20 hours, and the visible light absorption mesh-shaped photocatalytic belt can be constructed by loading the mixture on a polypropylene net through an impregnation method. FIG. 4 is a photograph of a mesh photocatalytic belt material.
Example 6
Co-doped TiO2The preparation of (1): (1) adding 4ml of glacial acetic acid, 0.01g of glucose, 0.08g of thiourea and 6ml of deionized water into 20ml of absolute ethyl alcohol, stirring for 60 minutes, and adjusting the pH value to 2; (2) adding 10ml of tetrabutyl titanate dropwise into an ethanol (20ml) solution of acetylacetone (1ml), and stirring rapidly for 20 minutes; (3) dropwise adding the mixed solution obtained in the step (2) into the mixed solution obtained in the step (1) under an ice bath condition, rapidly stirring for 1h in the process to obtain yellow transparent sol, and then aging for 7h to obtain gel; (4) drying at 90 deg.C to obtain light yellow powder; (5) placing the obtained light yellow powder in 100sccm ammonia gas atmosphere at 500 ℃ for heat treatment for 1.5h to finally obtain C, N co-doped TiO2；
Co-doped TiO2Preparing with a load substrate: 0.4g of the codoped TiO prepared above was doped2And 1.6g of carbonDispersing the nano-fibers in an N-methyl pyrrolidone solution, stirring for 8 hours, then soaking for 14 hours, drying at 90 ℃, and finally performing heat treatment under the protection of nitrogen at 500 ℃ for 1 hour to obtain the final high-efficiency environment-friendly black titanium dioxide-based photocatalyst material;
the material can be prepared in batches according to a proportion, 5Kg of the black titanium dioxide-based photocatalyst material is dispersed in 1L N-methyl pyrrolidone solution, 10g of curing agent is added at the same time, the mixture is stirred for 20 hours, and the visible light absorption mesh-shaped photocatalytic belt can be constructed by loading the mixture on a polypropylene net through an impregnation method. The water samples of the reticular photocatalytic belt material prepared in the figure 5 are compared before and after wastewater treatment, and it can be seen that river water pollution before treatment is serious, and the appearance is obviously improved after treatment.
Claims (10)
1. The black titanium dioxide-based photocatalyst is characterized by comprising a loading substrate and co-doped black titanium dioxide loaded on the loading substrate, wherein the loading substrate is at least one of a one-dimensional nanotube, a one-dimensional nanowire, a one-dimensional nanorod, a one-dimensional nanofiber and a two-dimensional layered material.
2. The black titanium dioxide-based photocatalyst according to claim 1, wherein the mass ratio of the co-doped black titanium dioxide to the supporting substrate is 1 (0.5-5).
3. The black titanium dioxide-based photocatalyst according to claim 1 or 2, wherein the co-doped black titanium dioxide is co-doped with an element and TiO2The molar ratio of (1) to (0.01-0.15).
4. The black titanium dioxide-based photocatalyst according to any one of claims 1 to 3, wherein the doping element in the co-doped black titanium dioxide is a metal doping element and/or a non-metal doping element; the metal doping element is at least one of Fe, Co, Ni, Cu, Zn, W, Ti, Ru, Nb, La, Gd, Sm and Nd, and the nonmetal doping element is at least one of H, B, C, N, P, S, I, F.
5. The black titanium dioxide-based photocatalyst according to any one of claims 1 to 4, wherein the supporting substrate is at least one of carbon nanotubes, carbon fibers, titanium dioxide nanowires, zinc oxide nanorods, tin oxide nanowires, graphene oxide, boron nitride, and molybdenum disulfide.
6. A method for preparing the black titanium dioxide-based photocatalyst according to any one of claims 1 to 5, comprising:
preparing co-doped black titanium dioxide;
mixing the co-doped black titanium dioxide, a load substrate and a solvent to obtain a mixture; and
and stirring the mixture, soaking for more than 12 hours, drying and then carrying out heat treatment to obtain the black titanium dioxide-based photocatalyst.
7. The method according to claim 6, wherein the solvent is at least one of ethanol, N-methylpyrrolidone, and water;
the temperature of the heat treatment is 400-500 ℃.
8. A mesh-like porous photocatalytic belt material characterized by comprising a mesh-like substrate and the black titanium oxide-based photocatalyst according to any one of claims 1 to 5 supported on the mesh-like substrate.
9. The reticulated porous photocatalytic belt material of claim 8, wherein the reticulated substrate is a polymeric fabric or an inorganic porous material; the polymer fabric is selected from one of polypropylene, polytetrafluoroethylene, polyethylene, polyvinylidene fluoride and polyamide net.
10. Use of the black titanium dioxide-based photocatalyst according to any one of claims 1 to 5 in the field of photocatalysis, in particular full solar spectrum enhancement.
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