CN112316950A - Supported TiO2Catalyst, preparation method and application thereof - Google Patents
Supported TiO2Catalyst, preparation method and application thereof Download PDFInfo
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- CN112316950A CN112316950A CN202011127771.9A CN202011127771A CN112316950A CN 112316950 A CN112316950 A CN 112316950A CN 202011127771 A CN202011127771 A CN 202011127771A CN 112316950 A CN112316950 A CN 112316950A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 163
- 239000000440 bentonite Substances 0.000 claims abstract description 96
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 95
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000003054 catalyst Substances 0.000 claims abstract description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 38
- 238000001354 calcination Methods 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 230000032683 aging Effects 0.000 claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 17
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 150000002696 manganese Chemical class 0.000 claims abstract description 8
- 230000000593 degrading effect Effects 0.000 claims abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 65
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 239000011941 photocatalyst Substances 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000008367 deionised water Substances 0.000 description 36
- 229910021641 deionized water Inorganic materials 0.000 description 36
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 25
- 229940043267 rhodamine b Drugs 0.000 description 25
- 238000001914 filtration Methods 0.000 description 24
- 239000012043 crude product Substances 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000000926 separation method Methods 0.000 description 14
- 238000001782 photodegradation Methods 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 13
- 239000012065 filter cake Substances 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 12
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 12
- 238000005070 sampling Methods 0.000 description 11
- 238000001132 ultrasonic dispersion Methods 0.000 description 11
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 10
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 10
- 239000011565 manganese chloride Substances 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 239000003480 eluent Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000010457 zeolite Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 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 7
- 229940012189 methyl orange Drugs 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 5
- 239000005909 Kieselgur Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229930003268 Vitamin C Natural products 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 235000019154 vitamin C Nutrition 0.000 description 2
- 239000011718 vitamin C Substances 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to the technical field of photocatalysts, and particularly discloses a supported TiO2A catalyst, a preparation method and application thereof. The preparation method comprises the following steps: adding soluble ferric salt, soluble manganese salt and bentonite into the uniform titanium source solution, adding a precipitator, aging, separating, washing, drying and calcining to obtain iron-manganese doped titanium dioxide loaded by the bentonite; adding the iron-manganese doped titanium dioxide loaded by bentonite into water, stirring andadding reduced graphene oxide, drying after ultrasonic treatment, and calcining to obtain bentonite/iron-manganese doped titanium dioxide/reduced graphene oxide composite material, namely supported TiO2A catalyst. The invention provides a supported TiO2The catalyst has high visible light catalytic activity and excellent adsorbability, can quickly adsorb organic matters and promote the organic matters to be adsorbed on TiO2The particles are enriched around, and the organic pollutants are rapidly explained, so that the aim of rapidly and efficiently degrading the organic matters can be fulfilled.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a supported TiO2A catalyst, a preparation method and application thereof.
Background
With the continuous development of social economy, the problem of environmental pollution is increasingly serious, and how to effectively solve the problem of environmental pollution to realize green development is a problem which is urgently needed to be solved at the present stage. In a plurality of environmental pollution treatment technologies, a semiconductor photocatalytic material represented by titanium dioxide becomes an ideal environmental pollution cleaning material. TiO 22The photocatalyst is low in cost, simple in preparation, high in stability, environment-friendliness and high in efficiency, and can be widely applied to photocatalytic degradation of heavy metals or organic pollutants.
However, TiO2The quantum yield is not high due to self defects of fast recombination of electrons-holes, larger forbidden band width and the like, and TiO2The electrons in the light can only be excited under the ultraviolet light, and the utilization rate of the sunlight is not high. These factors contribute to TiO2The photocatalytic performance of the catalyst is restricted, and the TiO is greatly restricted2Therefore, there is a need for TiO catalysts for a wide range of applications in industry2Modified to promote TiO2The purpose of the photocatalytic performance of (1).
Disclosure of Invention
Aiming at the existing TiO2The invention provides a supported TiO, which has the technical problems2A catalyst, a preparation method and application thereof.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
supported TiO2The preparation method of the catalyst comprises the following steps:
s1: dissolving a titanium source compound in water to obtain a uniform titanium source solution, adding soluble ferric salt, soluble manganese salt and bentonite, then adding a precipitator, carrying out aging reaction, and separating, washing, drying and calcining to obtain iron-manganese doped titanium dioxide loaded on the bentonite;
s2: adding iron-manganese doped titanium dioxide loaded by bentonite into water, stirring and adding reduced graphene oxide, drying after ultrasonic treatment, and calcining to obtain the bentonite/iron-manganese doped titanium dioxide/reduced graphene oxide composite material, namely the loaded TiO2A catalyst.
Compared with the prior art, the supported TiO provided by the invention2The preparation method of the catalyst comprises the steps of firstly taking bentonite as a carrier, and obtaining TiO by in-situ reaction of a titanium source compound with soluble ferric salt and soluble manganese salt2The particles are loaded on the surface of the bentonite, and are helpful for dispersing TiO2The particles avoid agglomeration, and the bentonite has good ion exchange property due to a layered structure formed by the unit cells of the bentonite, and can promote iron ions (Fe)3+) And manganese ion (Mn)2+) To TiO 22Doping of (3). Fe3+And Mn2+To TiO 22The doping of the material enables the response light wave band to be expanded to a visible light region, the utilization rate of photons is obviously improved, and the doping can reduce TiO2Nanoparticle size of material, reduced TiO2The band gap energy of the photocatalyst enhances the capture of electron-hole, thereby obviously improving the photocatalytic activity of the photocatalyst. The iron-manganese doped titanium dioxide (bentonite/Fe-Mn-TiO) loaded by bentonite is added2) Then compounding with reduced graphene oxide (rGO) to obtain bentonite/iron manganese doped titanium dioxide/reduced graphene oxide composite material (bentonite/Fe-Mn-TiO)2/rGO), i.e. supported TiO2A catalyst. The doping of the reduced graphene oxide forms a Ti-O-C chemical bond to further reduce TiO2The forbidden band width of the capacitor; the reduced graphene oxide and the bentonite have the combined action, so that the catalyst has a large specific surface area, more organic molecules can be adsorbed on the surface of the catalyst, and more active sites are provided to contribute to improving the photocatalytic reaction efficiency; high conductivity promoted TiO of reduced graphene oxide2The separation of the photon-generated carriers and the surface plasma resonance phenomenon can effectively prolong the service life of photon-generated electrons and hole pairs and improve the interface migration rate of the carriers. The supported TiO prepared by the invention2The catalyst has excellent adsorbability and photocatalytic performance, and can adsorb organic matters to the surface of the composite material and carry out rapid degradation.
Further, in step S1, the ratio of the amount of the titanium element in the titanium source compound to the amount of the iron element in the soluble iron salt and the manganese element in the soluble manganese salt is 1: 0.2-0.4: 0.3-0.5, and the doping effect is ensured, and meanwhile, the phenomenon that excessive doping becomes a recombination center of an electron-hole pair, which causes the reduction of the photocatalytic activity of the material, is avoided.
Further, in step S1, the mass ratio of the titanium source compound to bentonite is 1: 2.5-3.5, ensuring the growing TiO2Particle density to provide a sufficient amount of photoelectrons for photocatalytic degradation and to ensure that the TiO is not degraded by light2The particle dispersibility, and the combined action of the particles and the reduced graphene oxide improve the adsorption performance of the material, so that the synergistic action of adsorption and catalytic oxidation is achieved, and the organic matter is promoted to be in TiO2The particles are enriched around, and the catalytic efficiency is further improved.
Further, in the step S1, the aging reaction time is 6-8 h; the above-mentionedThe calcining temperature is 500-600 ℃, the time is 1-3 h, the doping effect is ensured, and TiO2Dispersibility of the particles on the surface of bentonite.
Further, in step S1, the titanium source compound is one of titanium sulfate, titanyl sulfate, or titanium tetrachloride.
Further, in step S1, the precipitant is one of sodium hydroxide, sodium carbonate, sodium bicarbonate or ammonia water, and the pH of the system is adjusted to 8-9 to promote the titanium dioxide and iron manganese doping reaction.
Further, in step S1, the soluble iron salt is ferric sulfate or ferric chloride due to Ti4+And Fe3+Radius of (1) is similar, Fe3+Can replace Ti4+Into the TiO2In the internal structure of (2), is effectively dispersed in TiO2Within the crystal lattice. Fe3+Can reduce TiO2Nanoparticle size of material, reduced TiO2The band gap energy of the composite material enhances the capture of electron-hole and improves the visible light catalytic activity of the composite material.
Further, in step S1, the soluble manganese salt is manganese sulfate or manganese chloride, Mn2+Doping to reduce TiO2The band gap forbidden band width, and the light absorption produces the red-shift, promotes visible light absorbing capacity. In addition, due to Mn2+With Fe3+Co-doping to inhibit TiO2The formation of surface metal oxide ensures TiO2And (3) catalytic activity.
Further, in step S2, the mass ratio of the bentonite-loaded iron-manganese doped titanium dioxide to the reduced graphene oxide is 1: 0.05-0.15, the adsorption performance of the material is improved under the combined action of the graphene oxide and bentonite, and the reduced graphene oxide has excellent conductive capacity and can be used as an electron trap to capture TiO2The separation of the photo-generated electron and the photo-generated hole is promoted, the catalytic activity of the catalyst is improved, and the electrons transferred to the reduced graphene oxide and the O adsorbed on the surface of the catalyst2Reaction to generate superoxide radical O2 -。
Furthermore, TiO2Under light irradiation, valence band electrons are excited andand transition to the conduction band to form a photogenerated electron-hole pair (e)-，h+) While, TiO 22With OH and photogenerated holes-The reaction generates hydroxyl radical OH with strong oxidizing property-. At h+、·O2 -、·OH-The purpose of efficiently degrading organic matters is achieved under the combined action of the active substances.
Further, in the step S2, the ultrasonic time is 0.5-1.5 h; the drying temperature is 50-70 ℃, and the drying time is 6-8 h; the calcining temperature is 155-175 ℃, the calcining time is 2-4 hours, and the condition that the reduced graphene oxide and the iron-manganese doped titanium dioxide loaded by bentonite are fully reacted to obtain the loaded TiO is ensured2A catalyst.
The invention also provides a supported TiO2Catalyst consisting of the above-mentioned supported TiO2The catalyst is prepared by the preparation method.
Compared with the prior art, the supported TiO provided by the invention2The catalyst has high visible light catalytic activity and excellent adsorbability, and is helpful for promoting organic matters in TiO2Enrichment around the particles by h+、·O2 -、·OH-The purpose of efficiently degrading organic matters can be realized under the combined action of the active substances.
Correspondingly, the invention also provides the supported TiO2The application of the catalyst in degrading organic pollutants.
Organic contaminants used for degradation include rhodamine B, methylene blue, methyl orange, 2, 4, 6-trichlorophenol, formaldehyde, congo red, p-nitrophenol, toluene, p-xylene, chlorobenzene, and 1, 2-dichlorobenzene.
Drawings
FIG. 1 shows bentonite/Fe-Mn-TiO2Bentonite/Fe-Mn-TiO2rGO and TiO2Ultraviolet-visible diffuse reflectance spectrum of (a).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides supported TiO2The preparation method of the catalyst comprises the following steps:
s1: dissolving a titanium source compound in water to obtain a uniform titanium source solution, adding soluble ferric salt, soluble manganese salt and bentonite, stirring, adding a precipitator, carrying out aging reaction, separating, washing, drying and calcining to obtain bentonite/Fe-Mn-TiO2；
S2: mixing bentonite/Fe-Mn-TiO2Adding the mixture into water, stirring and adding reduced graphene oxide, drying after ultrasonic treatment and calcining to obtain bentonite/Fe-Mn-TiO2/rGO, i.e. supported TiO2A catalyst.
Specifically, bentonite is used as a carrier, a titanium source compound, soluble ferric salt and soluble manganese salt are used as raw materials, and in-situ reaction is carried out to obtain TiO doped with ferrum and manganese2And loading the particles on the surface of the bentonite, and compounding the particles with the reduced graphene oxide to obtain the bentonite/iron-manganese doped titanium dioxide/reduced graphene oxide composite material. TiO capable of ensuring growth by bentonite2Particle density and TiO2The dispersibility of the particles and the combined action of the particles and the reduced graphene oxide improve the adsorption performance of the material to achieve the synergistic action of adsorption and catalytic oxidation, so that the obtained supported TiO2The catalyst has excellent adsorbability and photocatalytic performance, and can efficiently degrade organic pollutants.
The reduced graphene oxide is prepared successfully under green and mild experimental conditions by taking nontoxic and harmless vitamin C as a reducing agent (refer to vitamin C temperature and reduced graphene oxide and characterization), has a higher carbon-oxygen ratio, and is more favorable for improving the conductivity of the catalyst.
To better illustrate the supported TiO provided by the examples of the invention2The preparation of the catalyst is further illustrated by the following examples.
Example 1
Supported TiO2Process for the preparation of catalystsThe method comprises the following steps:
s1: 50mL (0.46mol) of TiCl are added4Dissolved in 500mL of deionized water, rapidly stirred for 10min, and added with 22.4g (0.138mol) of FeCl3，22.7g(0.18mol)MnCl2Continuing stirring, adding 259g of bentonite, stirring, dropwise adding ammonia water until the pH value of the solution is 8.5, aging for 7h, filtering to obtain a crude product, washing the crude product with deionized water for 5 times until the eluent does not contain Cl-Suction filtering, drying the filter cake in a vacuum drying oven at 80 deg.C for 6h, and calcining at 550 deg.C for 2h to obtain bentonite/Fe-Mn-TiO2(280g) Load (Fe-Mn-TiO loaded on the surface of bentonite)2Mass percent with bentonite) is 11.2%;
s2: 250g of the bentonite/Fe-Mn-TiO described above2Adding the mixture into 500mL of deionized water, stirring, adding 25g of reduced graphene oxide, carrying out ultrasonic treatment for 1h, drying at 60 ℃ for 7h, and calcining at 160 ℃ for 3h to obtain bentonite/Fe-Mn-TiO2PerGO (265g), i.e. supported TiO2Catalyst, wherein rGO is complexed (with Fe-Mn-TiO)2Composite rGO and bentonite/Fe-Mn-TiO2In mass percent) was 8%.
The obtained supported TiO2The catalyst degrades rhodamine B. And (2) placing 30mg of photocatalyst in 50mL of 30mg/L rhodamine B solution, sampling once every 30min under the irradiation of sunlight after ultrasonic dispersion, taking supernatant after centrifugal separation, and measuring the rhodamine B content in the solution by using an ultraviolet-visible spectrophotometer, wherein the result shows that the photodegradation rate of rhodamine B in 3 hours is 99%.
Example 2
Supported TiO2The preparation method of the catalyst comprises the following steps:
s1: 120g (0.50mol) of Ti (SO)4)2Dissolved in 600mL deionized water, rapidly stirred for 10min, and added with 20g (0.05mol) of Fe2(SO4)3，22.7g(0.15mol)MnSO4Continuously stirring, adding 300g of bentonite, stirring and dropwise adding a sodium hydroxide solution until the pH value of the solution is 8, ageing and reacting for 6 hours, filtering to obtain a crude product, and performing deionized water treatment on the crude product3 washes until the leacheate is free of SO4 2-Suction filtering, drying the filter cake in a vacuum drying oven at 80 deg.C for 6h, and calcining at 500 deg.C for 3h to obtain bentonite/Fe-Mn-TiO2(325g) Load (Fe-Mn-TiO loaded on the surface of bentonite)2Mass percent with bentonite) is 11.5%;
s2: 300g of the bentonite/Fe-Mn-TiO described above2Adding into 600mL deionized water, stirring, adding 15g reduced graphene oxide, performing ultrasonic treatment for 0.5h, drying at 50 ℃ for 8h, and calcining at 155 ℃ for 4h to obtain bentonite/Fe-Mn-TiO2PerGO (303g), i.e. supported TiO2Catalyst, wherein rGO is complexed (with Fe-Mn-TiO)2Composite rGO and bentonite/Fe-Mn-TiO2In percentage by mass) of 4%.
The obtained supported TiO2The catalyst degrades methyl orange. And (2) placing 30mg of photocatalyst in 50mL of methyl orange solution with the concentration of 30mg/L, performing ultrasonic dispersion, sampling once every 30min under the irradiation of sunlight, performing centrifugal separation, taking supernatant, and measuring the content of methyl orange in the solution by using an ultraviolet-visible spectrophotometer, wherein the result shows that the photodegradation rate of methyl orange in 3 hours is 98%.
Example 3
Supported TiO2The preparation method of the catalyst comprises the following steps:
s1: 50mL (0.46mol) of TiCl are added4Dissolved in 500mL of deionized water, rapidly stirred for 10min, and added with 14.6g (0.09mol) of FeCl3，22.7g(0.18mol)MnCl2Continuing stirring, adding 245g of bentonite, stirring, dropwise adding ammonia water until the pH value of the solution is 8.5, ageing and reacting for 6 hours, filtering to obtain a crude product, washing the crude product with deionized water for 4 times until the eluent does not contain Cl-Suction filtering, drying the filter cake in a vacuum drying oven at 80 deg.C for 4h, and calcining at 550 deg.C for 2h to obtain bentonite/Fe-Mn-TiO2(269g) Load (Fe-Mn-TiO loaded on the surface of bentonite)2Mass percent with bentonite) is 12.5%;
s2: 250g of the bentonite/Fe-Mn-TiO described above2Adding into 500mL deionized water, stirring and addingAdding 25g of reduced graphene oxide, carrying out ultrasonic treatment for 1h, drying at 60 ℃ for 7h, and calcining at 170 ℃ for 2h to obtain bentonite/Fe-Mn-TiO2rGO (263g), i.e. supported TiO2Catalyst, wherein rGO is complexed (with Fe-Mn-TiO)2Composite rGO and bentonite/Fe-Mn-TiO2Mass% of) was 7.3%.
The obtained supported TiO2The catalyst degrades methylene blue. And (2) placing 30mg of photocatalyst in 50mL of methylene blue solution with the concentration of 30mg/L, performing ultrasonic dispersion, sampling once every 30min under the irradiation of sunlight, performing centrifugal separation, taking supernatant, and measuring the content of methylene blue in the solution by using an ultraviolet-visible spectrophotometer, wherein the result shows that the photodegradation rate of methylene blue in 3 hours is 99%.
Example 4
Supported TiO2The preparation method of the catalyst comprises the following steps:
s1: 120g (0.50mol) of Ti (SO)4)2Dissolved in 600mL of deionized water, rapidly stirred for 10min, and added with 30g (0.075mol) of Fe2(SO4)3，22.7g(0.15mol)MnSO4Continuing stirring, adding 420g of bentonite, stirring, dropwise adding a sodium hydroxide solution until the pH value of the solution is 8, ageing and reacting for 7 hours, filtering to obtain a crude product, and washing the crude product with deionized water for 3 times until the eluent does not contain SO4 2-Suction filtering, drying the filter cake in a vacuum drying oven at 80 deg.C for 5h, and calcining at 600 deg.C for 1.5h to obtain bentonite/Fe-Mn-TiO2(447g) Load (Fe-Mn-TiO loaded on the surface of bentonite)2The mass percentage of bentonite) is 8.0%;
s2: 400g of the bentonite/Fe-Mn-TiO described above2Adding the mixture into 650mL of deionized water, stirring and adding 40g of reduced graphene oxide, carrying out ultrasonic treatment for 0.5h, drying at 60 ℃ for 8h, and calcining at 175 ℃ for 2h to obtain bentonite/Fe-Mn-TiO2/rGO (427g), i.e. supported TiO2Catalyst, wherein rGO is complexed (with Fe-Mn-TiO)2Composite rGO and bentonite/Fe-Mn-TiO2Mass% of) was 8.1%.
The obtained supported TiO2The catalyst degrades toluene. And (2) placing 30mg of photocatalyst in 50mL of toluene solution with the concentration of 30mg/L, performing ultrasonic dispersion, sampling once every 30min under the irradiation of sunlight, performing centrifugal separation, taking supernatant, and measuring the toluene content in the solution by using an ultraviolet-visible spectrophotometer, wherein the result shows that the photodegradation rate of toluene in 3 hours is 97%.
Example 5
Supported TiO2The preparation method of the catalyst comprises the following steps:
s1: 50mL (0.46mol) of TiCl are added4Dissolved in 500mL of deionized water, rapidly stirred for 10min, and added with 22.4g (0.138mol) of FeCl3，17.0g(0.135mol)MnCl2Stirring, adding 217g of bentonite, stirring, adding ammonia water dropwise until the pH value of the solution is 8, aging for 6h, filtering to obtain a crude product, washing the crude product with deionized water for 3 times until the eluate contains no Cl-Suction filtering, drying the filter cake in a vacuum drying oven at 80 deg.C for 4.5h, and calcining at 600 deg.C for 2h to obtain bentonite/Fe-Mn-TiO2(240g) Load (Fe-Mn-TiO loaded on the surface of bentonite)2The mass percentage of bentonite) was 14.2%;
s2: 200g of the bentonite/Fe-Mn-TiO2Adding the mixture into 400mL of deionized water, stirring, adding 20g of reduced graphene oxide, carrying out ultrasonic treatment for 0.5h, drying at 50 ℃ for 8h, and calcining at 155 ℃ for 4h to obtain bentonite/Fe-Mn-TiO2PerGO (206g), i.e. supported TiO2Catalyst, wherein rGO is complexed (with Fe-Mn-TiO)2Composite rGO and bentonite/Fe-Mn-TiO2In mass percent) was 8%.
The obtained supported TiO2The catalyst is used for degrading 2, 4, 6-trichlorophenol. 20mg of photocatalyst is placed in 50mL of 2, 4, 6-trichlorophenol solution with the concentration of 30mg/L, samples are taken every 30min under the irradiation of sunlight after ultrasonic dispersion, the supernatant is taken after centrifugal separation, and the content of 2, 4, 6-trichlorophenol in the solution is measured by an ultraviolet-visible spectrophotometer, and the result shows that the photodegradation rate of 2, 4, 6-trichlorophenol in 3 hours is 95%.
Example 6
Supported TiO2The preparation method of the catalyst comprises the following steps:
s1: 50mL (0.46mol) of TiCl are added4Dissolved in 500mL of deionized water, rapidly stirred for 10min, and added with 22.4g (0.138mol) of FeCl3，28.9g(0.23mol)MnCl2Stirring is continued, 270g of bentonite is added, stirring is carried out, ammonia water is added dropwise until the pH value of the solution is 8.5, after aging reaction is carried out for 7 hours, crude products are obtained by filtration, deionized water is used for washing the crude products for 4 times until the eluent does not contain Cl-Suction filtering, drying the filter cake in a vacuum drying oven at 80 deg.C for 3h, and calcining at 600 deg.C for 1h to obtain bentonite/Fe-Mn-TiO2(292g) Load (Fe-Mn-TiO loaded on the surface of bentonite)2The mass percentage of bentonite) is 10.4%;
s2: 250g of the bentonite/Fe-Mn-TiO described above2Adding the mixture into 500mL of deionized water, stirring, adding 25g of reduced graphene oxide, carrying out ultrasonic treatment for 1.5h, drying at 70 ℃ for 6h, and calcining at 160 ℃ for 2.5h to obtain bentonite/Fe-Mn-TiO2/rGO (262g), i.e. supported TiO2Catalyst, wherein rGO is complexed (with Fe-Mn-TiO)2Composite rGO and bentonite/Fe-Mn-TiO2In mass percent) was 8%.
The obtained supported TiO2The catalyst degrades paraxylene. Placing 25mg of photocatalyst in 50mL of p-xylene solution with the concentration of 30mg/L, sampling once every 30min under the irradiation of sunlight after ultrasonic dispersion, taking supernatant after centrifugal separation, and measuring the content of p-xylene in the solution by using an ultraviolet-visible spectrophotometer, wherein the result shows that the photodegradation rate of p-xylene in 3 hours is 98%.
Example 7
Supported TiO2The preparation method of the catalyst comprises the following steps:
s1: 120g (0.50mol) of Ti (SO)4)2Dissolving in 600mL deionized water, stirring rapidly for 10min, adding 40g (0.1mol) Fe2(SO4)3，37.8g(0.25mol)MnSO4Continuing to stirAdding 360g of bentonite, stirring and dropwise adding ammonia water until the pH value of the solution is 9, ageing and reacting for 8 hours, filtering to obtain a crude product, and washing the crude product with deionized water for 3 times until the eluent does not contain SO4 2-Suction filtering, drying the filter cake in a vacuum drying oven at 80 deg.C for 6h, and calcining at 600 deg.C for 1h to obtain bentonite/Fe-Mn-TiO2(375g) Load (Fe-Mn-TiO loaded on the surface of bentonite)2The mass percentage of bentonite) is 8.4%;
s2: 350g of the above bentonite/Fe-Mn-TiO2Adding into 600mL deionized water, stirring, adding 52.5g reduced graphene oxide, performing ultrasonic treatment for 1.5h, drying at 70 ℃ for 6h, and calcining at 175 ℃ for 2h to obtain bentonite/Fe-Mn-TiO2PerGO (394g), i.e. supported TiO2Catalyst, wherein rGO is complexed (with Fe-Mn-TiO)2Composite rGO and bentonite/Fe-Mn-TiO2In mass%) was 12%.
The obtained supported TiO2The catalyst degrades methyl orange. And (2) placing 30mg of photocatalyst in 50mL of methyl orange solution with the concentration of 30mg/L, performing ultrasonic dispersion, sampling once every 30min under the irradiation of sunlight, performing centrifugal separation, taking supernatant, and measuring the content of methyl orange in the solution by using an ultraviolet-visible spectrophotometer, wherein the result shows that the photodegradation rate of methyl orange in 3 hours is 97%.
In order to better illustrate the technical solution of the present invention, further comparison is made below by means of a comparative example and an example of the present invention.
Comparative example 1
Supported TiO2The preparation method of the catalyst is the same as the preparation method of the example 1 except that the bentonite is replaced by the diatomite with the same amount on the basis of the example 1, and comprises the following steps:
s1: 50mL (0.46mol) of TiCl are added4Dissolved in 500mL of deionized water, rapidly stirred for 10min, and added with 22.4g (0.138mol) of FeCl3，22.7g(0.18mol)MnCl2Stirring, adding 259g of diatomite, stirring, adding ammonia water dropwise until the pH value of the solution is 8.5, aging for 7h, filtering to obtain a crude product, and washing the crude product with deionized water for 5 timesWashing until the leacheate is Cl-free-Filtering, drying the filter cake in a vacuum drying oven at 80 deg.C for 6h, and calcining at 550 deg.C for 2h to obtain diatomaceous earth/Fe-Mn-TiO2(276g) Load (Fe-Mn-TiO loaded on the surface of diatomite2Mass percent with diatomite) is 10.4%;
s2: 250g of the above diatomaceous earth/Fe-Mn-TiO2Adding the mixture into 500mL of deionized water, stirring, adding 25g of reduced graphene oxide, carrying out ultrasonic treatment for 1h, drying at 60 ℃ for 7h, and calcining at 160 ℃ for 3h to obtain the diatomite/Fe-Mn-TiO2/rGO (261g), i.e. supported TiO2Catalyst, wherein rGO is complexed (with Fe-Mn-TiO)2Composite rGO and diatomite/Fe-Mn-TiO2In mass%) was 7%.
The obtained supported TiO2The catalyst degrades rhodamine B. And (2) placing 30mg of photocatalyst in 50mL of 30mg/L rhodamine B solution, sampling once every 30min under the irradiation of sunlight after ultrasonic dispersion, taking supernatant after centrifugal separation, and measuring the rhodamine B content in the solution by using an ultraviolet-visible spectrophotometer, wherein the result shows that the photodegradation rate of rhodamine B in 3 hours is 85%. Because the diatomite has no promotion effect on the doping of iron and manganese compared with the bentonite, and the TiO loaded on the surface of the diatomite2The amount of the graphene oxide is reduced, so that the amount of the composite reduced graphene oxide is reduced, and the activity of the catalyst is finally influenced.
Comparative example 2
Supported TiO2The preparation method of the catalyst is the same as the preparation method of the example 1 except that bentonite is replaced by the same amount of activated carbon on the basis of the example 1, and comprises the following steps:
s1: 50mL (0.46mol) of TiCl are added4Dissolved in 500mL of deionized water, rapidly stirred for 10min, and added with 22.4g (0.138mol) of FeCl3，22.7g(0.18mol)MnCl2Continuing stirring, adding 259g of activated carbon, stirring and dropwise adding ammonia water until the pH value of the solution is 8.5, ageing and reacting for 7 hours, filtering to obtain a crude product, and washing the crude product with deionized water for 5 times until the eluent does not contain Cl-Suction filtering, drying the filter cake in a vacuum drying oven at 80 deg.C for 6 hr, and drying in a vacuum drying ovenCalcining at 550 ℃ for 2h to obtain the activated carbon/Fe-Mn-TiO2(278g) Load (Fe-Mn-TiO loaded on the surface of the active carbon)2Mass percentage with activated carbon) was 10.8%;
s2: 250g of the above activated carbon/Fe-Mn-TiO2Adding the mixture into 500mL of deionized water, stirring, adding 25g of reduced graphene oxide, carrying out ultrasonic treatment for 1h, drying at 60 ℃ for 7h, and calcining at 160 ℃ for 3h to obtain activated carbon/Fe-Mn-TiO2rGO (263g), i.e. supported TiO2Catalyst, wherein rGO is complexed (with Fe-Mn-TiO)2Composite rGO and active carbon/Fe-Mn-TiO2Mass% of) was 7.2%.
The obtained supported TiO2The catalyst degrades rhodamine B. And (2) placing 30mg of photocatalyst in 50mL of 30mg/L rhodamine B solution, sampling once every 30min under the irradiation of sunlight after ultrasonic dispersion, taking supernatant after centrifugal separation, and measuring the rhodamine B content in the solution by using an ultraviolet-visible spectrophotometer, wherein the result shows that the photodegradation rate of rhodamine B in 3 hours is 87%. It can be seen that activated carbon is also not as effective as bentonite as a carrier.
Comparative example 3
Supported TiO2The preparation method of the catalyst is the same as the preparation method of the example 1 except that bentonite is replaced by the same amount of zeolite on the basis of the example 1, and comprises the following steps:
s1: 50mL (0.46mol) of TiCl are added4Dissolved in 500mL of deionized water, rapidly stirred for 10min, and added with 22.4g (0.138mol) of FeCl3，22.7g(0.18mol)MnCl2Stirring is continued, 259g of zeolite is added, stirring is carried out, ammonia water is added dropwise until the pH value of the solution is 8.5, after aging reaction for 7 hours, crude products are obtained by filtration, and the crude products are washed by deionized water for 5 times until eluent does not contain Cl-Suction filtering, drying the filter cake in a vacuum drying oven at 80 deg.C for 6h, and calcining at 550 deg.C for 2h to obtain zeolite/Fe-Mn-TiO2(275g) Loading (Fe-Mn-TiO loaded on zeolite surface2Mass percentage with zeolite) was 10.1%;
s2: 250g of the above zeolite/Fe-Mn-TiO2Is added into 500mL of deionized water and then added,stirring and adding 25g of reduced graphene oxide, carrying out ultrasonic treatment for 1h, drying at 60 ℃ for 7h, and calcining at 160 ℃ for 3h to obtain zeolite/Fe-Mn-TiO2PerGO (265g), i.e. supported TiO2Catalyst, wherein rGO is complexed (with Fe-Mn-TiO)2Composite rGO and zeolite/Fe-Mn-TiO2Mass% of) was 7.4%.
The obtained supported TiO2The catalyst degrades rhodamine B. And (2) placing 30mg of photocatalyst in 50mL of 30mg/L rhodamine B solution, sampling once every 30min under the irradiation of sunlight after ultrasonic dispersion, taking supernatant after centrifugal separation, and measuring the rhodamine B content in the solution by using an ultraviolet-visible spectrophotometer, wherein the result shows that the photodegradation rate of rhodamine B in 3 hours is 86%. It can be seen that zeolite also does not perform as well as bentonite as a carrier.
Comparative example 4
Supported TiO2Preparation method of catalyst, MnCl is added on the basis of example 12Replacement with an equal amount of FeCl3Otherwise, the same as in example 1, including the steps of:
s1: 50mL (0.46mol) of TiCl are added4Dissolved in 500mL of deionized water, rapidly stirred for 10min, and 51.6g (0.318mol) of FeCl is added3Stirring, adding 259g of diatomite, stirring, adding ammonia water dropwise until the pH value of the solution is 8.5, aging for 7h, filtering to obtain a crude product, washing the crude product with deionized water for 5 times until the eluent does not contain Cl-Suction filtering, drying the filter cake in a vacuum drying oven at 80 deg.C for 6 hr, calcining at 550 deg.C for 2 hr to obtain diatomite/Fe-TiO2(277g) Load (Fe-TiO loaded on the surface of diatomite2Mass percent with diatomite) is 10.6%;
s2: 250g of the above diatomaceous earth/Fe-Mn-TiO2Adding the mixture into 500mL of deionized water, stirring, adding 25g of reduced graphene oxide, carrying out ultrasonic treatment for 1h, drying at 60 ℃ for 7h, and calcining at 160 ℃ for 3h to obtain the diatomite/Fe-TiO2/rGO (262g), i.e. supported TiO2Catalyst, wherein rGO is complexed (with Fe-TiO)2Composite rGO and diatomaceous earth/Fe-TiO2In percentage by mass of) The content was found to be 7.2%.
The obtained supported TiO2The catalyst degrades rhodamine B. And (2) placing 30mg of photocatalyst in 50mL of 30mg/L rhodamine B solution, sampling once every 30min under the irradiation of sunlight after ultrasonic dispersion, taking supernatant after centrifugal separation, and measuring the rhodamine B content in the solution by using an ultraviolet-visible spectrophotometer, wherein the result shows that the photodegradation rate of rhodamine B in 3 hours is 90%. Since the iron is easily doped in TiO alone2An iron oxide film layer is generated on the surface, and the activity of the catalyst is influenced.
Comparative example 5
Supported TiO2Preparation method of catalyst, FeCl is added on the basis of example 13Replaced by equivalent MnCl2Otherwise, the same as in example 1, including the steps of:
s1: 50mL (0.46mol) of TiCl are added4Dissolved in 500mL of deionized water, rapidly stirred for 10min, and added with 40g (0.318mol) of MnCl2Stirring, adding 259g of diatomite, stirring, adding ammonia water dropwise until the pH value of the solution is 8.5, aging for 7h, filtering to obtain a crude product, washing the crude product with deionized water for 5 times until the eluent does not contain Cl-Suction filtering, drying the filter cake in a vacuum drying oven at 80 deg.C for 6 hr, calcining at 550 deg.C for 2 hr to obtain diatomite/Mn-TiO2(276g) Loading capacity (Mn-TiO loaded on the surface of diatomite2Mass percent with diatomite) is 10.5%;
s2: 250g of the above diatomaceous earth/Mn-TiO2Adding the mixture into 500mL of deionized water, stirring, adding 25g of reduced graphene oxide, carrying out ultrasonic treatment for 1h, drying at 60 ℃ for 7h, and calcining at 160 ℃ for 3h to obtain diatomite/Mn-TiO2rGO (263g), i.e. supported TiO2Catalyst, wherein rGO is complexed (with Mn-TiO)2Composite rGO and diatomite/Mn-TiO2Mass% of) was 7.5%.
The obtained supported TiO2The catalyst degrades rhodamine B. Placing 30mg of photocatalyst in 50mL of 30mg/L rhodamine B solution, ultrasonically dispersing, and taking every 30min under the irradiation of sunlightAnd (3) sampling once, performing centrifugal separation, taking supernatant liquor, and measuring the content of rhodamine B in the solution by using an ultraviolet-visible spectrophotometer, wherein the result shows that the photodegradation rate of rhodamine B in 3 hours is 92%. Because of the single doping of manganese TiO2The visible light catalytic activity is lower.
To better illustrate the supported TiO provided by the examples of the invention2Characterization of the method of preparation of the catalyst, the following is the bentonite/Fe-Mn-TiO prepared in example 12Bentonite/Fe-Mn-TiO2rGO and TiO2The UV-visible diffuse reflectance spectrum analysis was performed, and the results are shown in FIG. 1, for the bentonite/Fe-Mn-TiO obtained in example 12the/rGO shows light absorption red shift, improves the utilization rate of the catalyst to photons, and has good visible light catalytic activity. Supported TiO obtained in examples 2 to 7 of the invention2Catalyst and supported TiO of example 12The catalyst has substantially equivalent technical effects.
From the above data, it can be seen that the supported TiO provided by the embodiments of the present invention2The catalyst has high visible light catalytic activity and excellent adsorbability, can quickly adsorb organic matters and promote the organic matters to be adsorbed on TiO2The particles are enriched around, and the organic pollutants are rapidly explained, so that the purpose of rapidly and efficiently degrading the organic matters can be achieved, and the photodegradation rate of the organic pollutants is up to more than 97% in 3 hours under the irradiation of visible light.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. Supported TiO2The preparation method of the catalyst is characterized by comprising the following steps: the method comprises the following steps:
s1: dissolving a titanium source compound in water to obtain a uniform titanium source solution, adding soluble ferric salt, soluble manganese salt and bentonite, then adding a precipitator, carrying out aging reaction, and separating, washing, drying and calcining to obtain iron-manganese doped titanium dioxide loaded on the bentonite;
s2: adding iron-manganese doped titanium dioxide loaded by bentonite into water, stirring and adding reduced graphene oxide, drying after ultrasonic treatment, and calcining to obtain the bentonite/iron-manganese doped titanium dioxide/reduced graphene oxide composite material, namely the loaded TiO2A catalyst.
2. The supported TiO of claim 12The preparation method of the catalyst is characterized by comprising the following steps: in step S1, the ratio of the amount of the titanium element in the titanium source compound to the amount of the iron element in the soluble iron salt and the manganese element in the soluble manganese salt is 1: 0.2-0.4: 0.3 to 0.5.
3. The supported TiO of claim 12The preparation method of the catalyst is characterized by comprising the following steps: in step S1, the mass ratio of the titanium source compound to bentonite is 1: 2.5 to 3.5.
4. The supported TiO of claim 12The preparation method of the catalyst is characterized by comprising the following steps: in the step S1, the aging reaction time is 6-8 h; the calcination temperature is 500-600 ℃, and the calcination time is 1-3 h.
5. The supported TiO of claim 12The preparation method of the catalyst is characterized by comprising the following steps: in step S1, the titanium source compound is one of titanium sulfate, titanyl sulfate, and titanium tetrachloride.
6. The supported TiO of claim 12The preparation method of the catalyst is characterized by comprising the following steps: in step S1, the precipitant is one of sodium hydroxide, sodium carbonate, sodium bicarbonate, or ammonia water.
7. The supported TiO of claim 12The preparation method of the catalyst is characterized by comprising the following steps: in step S2, the mass ratio of the bentonite-loaded iron-manganese doped titanium dioxide to the reduced graphene oxide is 1: 0.05 to 0.15.
8. The supported TiO of claim 12The preparation method of the catalyst is characterized by comprising the following steps: in the step S2, the ultrasonic time is 0.5-1.5 h; the drying temperature is 50-70 ℃, and the drying time is 6-8 h; the calcining temperature is 155-175 ℃, and the time is 2-4 h.
9. Supported TiO2A catalyst, characterized by: supported TiO according to any one of claims 1 to 82The catalyst is prepared by the preparation method.
10. The supported TiO of claim 92The application of the catalyst in degrading organic pollutants.
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