CN112892536A - Preparation method of composite photocatalyst, composite photocatalyst and degradation method of dye wastewater - Google Patents
Preparation method of composite photocatalyst, composite photocatalyst and degradation method of dye wastewater Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 239000002351 wastewater Substances 0.000 title claims abstract description 24
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000015556 catabolic process Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 42
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 19
- 239000010439 graphite Substances 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 230000000593 degrading effect Effects 0.000 claims abstract description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 11
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052603 melanterite Inorganic materials 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 239000000975 dye Substances 0.000 abstract description 17
- 239000000987 azo dye Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000003911 water pollution Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000001044 red dye Substances 0.000 description 8
- 238000004042 decolorization Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 239000012798 spherical particle Substances 0.000 description 5
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 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 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 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 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- -1 iron ion Chemical class 0.000 description 2
- 239000001048 orange dye Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J23/745—Iron
-
- 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
- B01J35/33—Electric or magnetic properties
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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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention provides a preparation method of a composite photocatalyst, the composite photocatalyst and a degradation method of dye wastewater, and belongs to the field of water pollution treatment. The preparation method of the composite photocatalyst comprises the following steps: mixing butyl titanate, hydrochloric acid and graphite in ethanol solution, performing ultrasonic treatment to obtain gel, drying the gel, grinding the gel into powder, and calcining the powder to obtain graphite-TiO2(ii) a Then adding graphite-TiO2The nanoparticles are dispersed in a solvent containingFe3O4Adding NaOH and polyethylene glycol into the mixed solution to react to obtain the composite photocatalyst graphite-TiO2@Fe3O4. The composite photocatalyst has strong catalytic activity and high recovery rate. The composite photocatalyst is graphite-TiO2@Fe3O4The method can be used for degrading azo dyes which are difficult to degrade, such as alizarin red, with the degradation rate reaching more than 90 percent.
Description
Technical Field
The invention relates to the field of water pollution treatment, in particular to a preparation method of a composite photocatalyst, the composite photocatalyst and a degradation method of dye wastewater.
Background
Azo dyes are widely used in paper printing, textile and leather manufacturing processes, and pose significant risks to the ecological environment due to their high toxicity, carcinogenicity and mutagenicity. Most azo dyes are difficult to degrade due to their complex structure, for example alizarin red is an anthraquinone dye, and the solid form is powdery, easily soluble in water, highly toxic, but difficult to degrade. Therefore, the photocatalytic oxidation technology has become one of the hot spots for treating the azo dye wastewater.
TiO2The photocatalyst has the advantages of stability, high oxidation capacity, ecological friendliness and the like, and is widely applied to the photocatalytic technology. Due to TiO2TiO with forbidden band width (3.0-3.2eV)2Rapid recombination of photogenerated electron-hole (e/h) pairs confined to the ultraviolet portion results in low quantum yield and recovery of powdered TiO from treated wastewater2The catalyst is difficult and expensive.
The persulfate can be activated to generate SO in aqueous solution by various ways such as UV, heat, transition metal and the like4 -It has a more stable structure, longer half-life and stronger redox potential than OH. However, the traditional activation method has the problems of narrow pH application range, easy generation of iron mud in the reaction process, incapability of recycling the catalyst and the like.
Light reported so farThe preparation of the catalyst is not easy to recover, and the method for activating the persulfate has the problems of high energy consumption, complex steps, easy generation of secondary pollution and the like. For example, patent (cn202010356595.x) "a method for treating dye wastewater by activating persulfate through UV heating" can activate persulfate, but is limited to ultraviolet condition, and electrons and holes generated by light irradiation of photocatalyst are easy to recombine, reducing catalytic efficiency, and the photocatalyst is not easy to recover. In addition, as proposed in patent (CN 111153485 a), "a composition for efficiently activating persulfate and its application" uses a composition of nano metal sulfide and iron ion to activate persulfate to treat polychlorinated biphenyl wastewater. However, Fe2+The solution is difficult to store and is easy to be oxidized by dissolved oxygen and the like to lose effectiveness, thereby causing low utilization rate. In addition, PP @ Au-TiO in visible light as reported2Degrading alizarin red of 20mg/L, wherein the degradation efficiency is only 80% after 3 h; ce3+/Ce4+/Bi2O3The Vis degrades alizarin red with 20mg/L, and the degradation efficiency is only 78% after 2 h; all the reports show that the degradation time is longer and the degradation efficiency is low under the condition of lower alizarin red concentration.
In view of the above, the present application provides a preparation method of a composite photocatalyst, and a degradation method of dye wastewater.
Disclosure of Invention
The invention aims to provide a composite photocatalyst and a preparation method thereof.
The second purpose of the invention is to provide a method for degrading dye wastewater, which can inhibit TiO2The electrons and the holes in the dye are recombined to generate hydroxyl radicals, and persulfate can be activated to generate sulfate radicals, so that the dye organic wastewater can be efficiently treated under visible light, and the catalyst can be recycled.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the present invention provides a preparation method of a composite photocatalyst, which comprises:
mixing ethyl titanate, hydrochloric acid and graphite in an ethanol solution, performing ultrasonic treatment to obtain gel, drying the gel, grinding the gel into powder, and calcining the powder at 400-500 ℃ for 2-4 hours to obtain graphite-TiO2A nanoparticle;
will contain FeSO4·7H2O and Fe2(SO4)3The mixed solution is placed in water bath at the temperature of 55-65 ℃ for heating to obtain the Fe-containing iron3O4The graphite-TiO is mixed with2Dispersing the nano particles in the mixed solution, adding NaOH and polyethylene glycol, continuously reacting for 20-40 minutes at 55-65 ℃, washing to be neutral, and drying to obtain the composite photocatalyst graphite-TiO2@Fe3O4。
Further, in a preferred embodiment of the present invention, the molar ratio of the graphite to the ethyl titanate is 0.007 to 0.06: 1.
further, in a preferred embodiment of the present invention, the graphite-TiO is prepared2In the process of nanoparticles, the preparation method of the gel comprises the following steps: ultrasonically dispersing the graphite in absolute ethyl alcohol to obtain a first solution; adding the butyl titanate and the hydrochloric acid into absolute ethyl alcohol, and then adding the first solution to obtain a second solution; and adding water into the second solution, stirring until the solution is converted into sol, and performing ultrasonic treatment to obtain gel.
Further, in a preferred embodiment of the present invention, the graphite-TiO is2@Fe3O4In (b), the Fe3O4With the TiO mentioned2The molar ratio of (A) to (B) is 0.2 to 1: 1.
In a second aspect, the invention provides a composite photocatalyst graphite-TiO2@Fe3O4Which is prepared by the preparation method.
In a third aspect, the present invention provides a method for degrading dye wastewater, comprising:
after the pH value of the dye wastewater is adjusted to 3-7, the composite photocatalyst graphite-TiO is sequentially added2@Fe3O4And persulfate is subjected to light-shielding reaction and then placed under visible light for reaction for 1-3 hours.
Further, in a preferred embodiment of the present invention, the dye wastewater contains alizarin red, and the alizarin red and the graphite-TiO are mixed together2@Fe3O4The mass ratio of (A) to (B) is 1: 2-3.
Further, in a preferred embodiment of the present invention, the persulfate is potassium persulfate, and a molar ratio of the alizarin red to the potassium persulfate is 1: 16-17.
The invention has the following effects:
the composite photocatalyst graphite-TiO provided by the invention2@Fe3O4And its preparation method, mixing graphite with TiO2The doped graphite has conductivity and can effectively inhibit TiO in the photoreaction process2Recombination of electrons and holes on the surface is carried out, so that more holes participate in the photoreaction process, and the photocatalytic activity of the composite catalyst is improved; at the same time, Fe3O4Has magnetic property, and is prepared from Fe3O4The photocatalyst dispersed in the reaction solvent can be rapidly recovered by being loaded on the surface of the photocatalyst, so that the residual loss is reduced, and the photocatalyst is favorable for recycling. The composite photocatalyst has high degradation efficiency on azo dyes, and particularly has a degradation rate of 93.9% on dyes which are difficult to degrade, such as alizarin red.
The invention further provides a degradation method of dye wastewater, which is to subject the composite photocatalyst graphite-TiO to degradation2@Fe3O4The method can be used for effectively degrading azo dyes such as alizarin red in a synergistic manner with persulfate, and has the following principle and beneficial effects:
1. composite photocatalyst graphite-TiO2@Fe3O4The medium graphite has conductive effect, and under the irradiation of visible light, the graphite-TiO2Holes generated by the excitation of visible light on the surface and OH in the solution-Or H2O forms OH, S2O8 2-With graphite-TiO2Electronic reaction of surfaces to produce SO4 -At the same time S2O8 2-Can also be mixed with Fe3O4Fe of the surface2+Reaction to produce raw SO4 -Of, graphite-TiO2With Fe3O4The combination of the two can generate two free radicals to synergistically degrade the dye wastewater.
2. Composite photocatalyst graphite-TiO2@Fe3O4Fe of the surface2+Can rapidly generate an activation reaction with persulfate to generate SO4 -Produced Fe3+The electrons which can be rapidly led out are reduced into Fe2+The probability of side reaction is reduced, the higher utilization rate of persulfate is ensured, and the secondary pollution to the water body caused by dissolution of a large amount of iron ions is avoided.
3. Due to a part of electrons and S2O8 2-React to generate SO4 -Thus, graphite-TiO2The recombination of electrons and holes generated by the excitation of visible light on the surface is reduced, and the recombination of electrons and holes is also inhibited.
4. Composite photocatalyst graphite-TiO2@Fe3O4 Medium TiO 22With Fe3O4All are nano spherical particles and have certain adsorbability, so that organic dye in water can be effectively adsorbed, and the photocatalytic reaction rate is improved.
Drawings
FIG. 1 shows a composite photocatalyst graphite-TiO2@Fe3O4X-ray diffraction patterns of (a);
FIG. 2 shows a composite photocatalyst graphite-TiO2@Fe3O4A transmission electron microscope photograph of (a);
FIG. 3 shows a composite photocatalyst graphite-TiO2@Fe3O4The effect graph of activated persulfate to degrade alizarin red for decolorization;
FIG. 4 is a graph of the effect of initial pH values of different alizarin reds on alizarin red decolorization;
FIG. 5 is a graph showing the effect of adding persulfate at different concentrations on alizarin red decolorization;
FIG. 6 is a diagram showing the effect of the composite photocatalyst on activating persulfate to degrade waste water containing different dyes.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
This example provides a composite photocatalyst graphite-TiO2@Fe3O4The preparation method comprises the following steps:
(1) 6ml of butyl titanate and 0.6ml of 2mol/L hydrochloric acid were transferred and added to 40ml of absolute ethanol, and the mixture was magnetically stirred for 2 minutes. And (3) putting 0.012g of graphite in 4ml of ethanol, performing ultrasonic treatment for 1 minute, pouring the graphite into the solution, and performing ultrasonic treatment for 3-5 minutes. Finally, 3ml of deionized water is added and stirred at a constant speed on a magnetic stirrer until the mixture is changed into sol, and then the sol is changed into gel by ultrasound. Drying at room temperature, grinding, placing the ground powder into a muffle furnace, and calcining at 450 deg.C for 3 hr to obtain graphite-TiO2Spherical nanoparticles (G-TiO)2)。
(2) In N2Under the protection of (3), 7.125g of FeSO4·7H2O and 3.525g Fe2(SO4)3Dissolving in 75ml deionized water respectively, heating in 60 deg.C water bath under magnetic stirring, and mixing with the prepared graphite-TiO2Rapidly adding the nano spherical particles into the mixed solution, uniformly mixing, dropwise adding 50ml of 1mol/L NaOH solution, and then adding 1.5ml of polyethylene glycol-400 to prepare Fe3O4Curing for 30 minutes, cooling the obtained black product particles to room temperature, depositing the black product particles at the bottom of the reactor through precipitation, washing the reactor to be neutral, and drying the reactor in an oven at 60 ℃ to obtain the composite photocatalyst graphite-TiO2@Fe3O4(G-TiO2@Fe3O4)。
For the G-TiO obtained2@Fe3O4The material characterization was performed, and the results are shown in fig. 1 and 2:
FIG. 1 shows a composite photocatalyst G-TiO2@Fe3O4FIG. 1 shows a transmission electron micrograph of G-TiO2@Fe3O4On flake graphite, Fe3O4And TiO2Attached by coulomb electrostatic forces and mixed in the form of nanoparticle aggregates.
FIG. 2 shows a composite photocatalyst G-TiO2@Fe3O4X-ray diffraction pattern of (A), G-TiO, as can be seen from FIG. 22@Fe3O4Not only having anatase TiO2The characteristic peak (standard card JCPDS 00-021-3O4The diffraction peaks of (1), 35.4, 43.2, 54.0, 56.8 and 62.5 corresponding to the (220), (311), (400), (422), (511) and (440) crystal planes, and Fe in the standard card JCPDS 00-019-6293O4The characteristic peaks are consistent, which shows that Fe3O4Has been successfully loaded on G-TiO2The above. Diffraction peak of graphene is TiO2Screening due to the crystallinity of graphite compared to TiO2Much lower.
Example 2
This example provides a composite photocatalyst graphite-TiO2@Fe3O4The preparation method comprises the following steps:
(1) transfer 12ml of butyl titanate and 1.2ml of 2mol/L hydrochloric acid into 80ml of absolute ethanol, and magnetically stir for 2 minutes. And (3) putting 0.024g of graphite into 4ml of ethanol, performing ultrasonic treatment for 1 minute, pouring into the solution, and performing ultrasonic treatment for 3-5 minutes. Finally, 6ml of deionized water is added and stirred at a constant speed on a magnetic stirrer until the mixture is changed into sol, and then the sol is changed into gel by ultrasound. Drying at room temperature, grinding, placing the ground powder into a muffle furnace, and calcining at 450 deg.C for 3 hr to obtain graphite-TiO2Spherical nanoparticles (i.e., G-TiO)2)。
(2) In N2Under the protection of (3), 9.5g of FeSO4·7H2O and 4.75g Fe2(SO4)3Dissolving in 100ml respectively for separationHeating in 60 deg.C water bath under magnetic stirring to obtain graphite-TiO2Rapidly adding the nano spherical particles into the mixed solution, uniformly mixing, dropwise adding 200ml of 1mol/L NaOH solution, and then adding 2ml of polyethylene glycol-400 to prepare Fe3O4Curing for 30 minutes, cooling the obtained black product particles to room temperature, depositing the black product particles at the bottom of the reactor through precipitation, washing the reactor to be neutral, and drying the reactor in an oven at 60 ℃ to obtain the composite photocatalyst graphite-TiO2@Fe3O4(i.e., G-TiO)2@Fe3O4)。
Example 3
This example provides a composite photocatalyst graphite-TiO2@Fe3O4The preparation method comprises the following steps:
(1) transfer 12ml of butyl titanate and 1.2ml of 2mol/L hydrochloric acid into 80ml of absolute ethanol, and magnetically stir for 2 minutes. Taking 0.024g of graphite, putting the graphite in 4ml of ethanol, carrying out ultrasonic treatment for 1 minute, pouring the graphite into the solution, and carrying out ultrasonic treatment for 3 minutes. Finally, 6ml of deionized water is added and stirred at a constant speed on a magnetic stirrer until the mixture is changed into sol, and then the sol is changed into gel by ultrasound. Drying at room temperature, grinding, placing the ground powder into a muffle furnace, and calcining at 500 deg.C for 2 hr to obtain graphite-TiO2Spherical nanoparticles (i.e., G-TiO)2)。
(2) In N2Under the protection of (3), 9.5g of FeSO4·7H2O and 4.75gFe2(SO4)3Dissolving in 100ml deionized water respectively, heating in water bath at 65 deg.C under magnetic stirring, and mixing with the prepared graphite-TiO2Rapidly adding the nano spherical particles into the mixed solution, uniformly mixing, dropwise adding 200ml of 1mol/L NaOH solution, and then adding 2ml of polyethylene glycol-400 to prepare Fe3O4Curing for 20 minutes, cooling the obtained black product particles to room temperature, depositing the black product particles at the bottom of the reactor through precipitation, washing the reactor to be neutral, and drying the reactor in an oven at the temperature of 55 ℃ to obtain the composite photocatalyst graphite-TiO2@Fe3O4(i.e., G-TiO)2@Fe3O4)。
Example 4
This example provides a composite photocatalyst graphite-TiO2@Fe3O4The preparation method comprises the following steps:
(1) transfer 12ml of butyl titanate and 1.2ml of 2mol/L hydrochloric acid into 80ml of absolute ethanol, and magnetically stir for 2 minutes. 0.0028g of graphite is put into 4ml of ethanol for 1 minute of ultrasonic treatment, poured into the solution and subjected to ultrasonic treatment for 5 minutes. Finally, 6ml of deionized water is added and stirred at a constant speed on a magnetic stirrer until the mixture is changed into sol, and then the sol is changed into gel by ultrasound. Drying at room temperature, grinding, placing the ground powder into a muffle furnace, and calcining at 400 ℃ for 3 hours to obtain graphite-TiO2Spherical nanoparticles (i.e., G-TiO)2)。
(2) In N2Under the protection of (2.375 g) of FeSO4·7H2O and 1.1875g Fe2(SO4)3Dissolving in 100ml deionized water respectively, heating in 55 deg.C water bath under magnetic stirring, and mixing with the prepared graphite-TiO2Rapidly adding the nano spherical particles into the mixed solution, uniformly mixing, dropwise adding 200ml of 1mol/L NaOH solution, and then adding 2ml of polyethylene glycol-400 to prepare Fe3O4Curing for 40 minutes, cooling the obtained black product particles to room temperature, depositing the black product particles at the bottom of the reactor through precipitation, washing the reactor to be neutral, and drying the reactor in a 65 ℃ oven to obtain the composite photocatalyst graphite-TiO2@Fe3O4(i.e., G-TiO)2@Fe3O4)。
Example 5
The embodiment provides a degradation method of dye wastewater, which comprises the following steps:
adding 0.25g/L of graphite-TiO prepared in example 1 into 100ml of alizarin red dye wastewater with the concentration of 100mg/L, pH being 32@Fe3O4Adding 6mmol of potassium persulfate, turning on a magnetic stirrer to perform dark reaction for 1 hour, turning on a visible light source to perform reaction for 1 hour, and finally enabling the removal rate of the alizarin red dye to reach 100%.
The following description will be made with reference to experimental data to demonstrate the effects of the present invention:
experimental example 1
The degradation efficiency of alizarin red by four different catalytic systems is compared:
a persulfate system, namely adding 6mmol of potassium persulfate into a reaction solution, adjusting the pH value of the solution to 3, and turning on a light source after dark reaction for 1 hour;
“TiO2@Fe3O4"system: adding 0.25g/L of photocatalyst TiO2@Fe3O4Adding the mixture into a reaction solution, adjusting the pH value of the solution to 3, and turning on a light source after dark reaction for 1 h;
the composite photocatalyst system comprises: adding 0.25G/L of composite photocatalyst G-TiO2@Fe3O4Adding the mixture into a reaction solution, adjusting the pH value of the solution to 3, and turning on a light source after dark reaction for 1 h;
the composite photocatalyst activates persulfate system: adding 0.25g/L composite photocatalyst graphite-TiO2@Fe3O4Adding the solution into a reaction solution, adding 6mmol of PS, adjusting the pH value of the solution to 3, carrying out dark reaction for 1 hour, and then turning on a light source;
100mL of alizarin red dye solution with the concentration of 100mg/L is respectively treated by the three catalytic systems. The results are shown in FIG. 3.
And (4) analyzing results: "persulfate" systems, "TiO2@Fe3O4The system, the composite photocatalyst system and the composite photocatalyst activated persulfate system correspond to curves 1, 2, 3 and 4 in sequence. After reacting for 2 hours, under the action of only a persulfate system, the decoloring rate of alizarin red is only 7.2 percent; secondly, in "TiO2@Fe3O4Under the action of the system, the decolorization rate of alizarin red is 71.9 percent; under the action of a composite photocatalysis system, the decoloring rate of alizarin red is 93.9 percent; in the composite photocatalyst activated persulfate system, the decolorization rate of alizarin red is increased to 100%, but the composite photocatalyst activated persulfate system has a faster reaction rate constant.
Thus, the composite photocatalyst activates a persulfate system with "TiO2@Fe3O4Compared with a system, a composite photocatalyst system and a persulfate system, the system has the function of decoloring alizarin redRemarkable synergistic effect.
Experimental example 2
Comparing the influence of different pH values on the degradation efficiency of the composite photocatalyst activated persulfate system, namely the pH value on the degradation efficiency of the composite photocatalyst activated persulfate system:
under the condition of normal temperature, the initial pH values of alizarin red dye solution with the concentration of 100mg/L are adjusted to be 3, 4, 5.5, 6 and 7, 0.6mmol of PS is added, and the reaction is carried out under visible light, and the result is shown in figure 4.
Analysis of the results, when the initial pH values were 3, 4, 5.5, 6 and 7, curves 5, 6, 7, 8 and 9 were corresponded in this order. The decoloring rates of alizarin red after 2 hours of reaction are respectively 100%, 97.0%, 89.7%, 82.0% and 9.3%, so that the composite photocatalyst activated persulfate has higher catalytic activity under an acidic condition.
Experimental example 3
The influence of the addition amount of persulfate on the degradation efficiency of the composite photocatalyst activated persulfate system is compared:
under the condition of normal temperature, the initial concentration of alizarin red solution is 100mg/L, the initial pH value is 3, and graphite-TiO2@Fe3O4The addition amount of (A) was 0.25g/L, and the addition amounts of potassium persulfate were 0, 2, 4, 6, 8, and 10mmol, respectively. The reaction was carried out under visible light, and the results are shown in FIG. 5.
As a result, when the amount of potassium persulfate to be added was 0, 2, 4, 6, 8 and 10mmol, curves 10, 11, 12, 13, 14 and 15 were sequentially assigned. The decolorization rates of the alizarin red after 2 hours of reaction are respectively 94%, 93.9%, 95.9%, 100%, 97.9% and 95.1%, and the decolorization rate of the alizarin red is increased and then decreased along with the increase of the addition amount of the potassium persulfate, so that 6mmol is the optimal addition amount of the potassium persulfate.
Experimental example 4
Compared with the influence of a composite photocatalyst activated persulfate system on the degradation efficiency of different azo dyes:
at normal temperature, adjusting the concentration of methyl orange dye solution to be 10mg/L, Congo red dye solution to be 50mg/L and alizarin red dye solution to be 100mg/L, and respectively adding 0.25g/L of composite photocatalyst graphite-TiO2@Fe3O4Adding the solution into a reaction solution, adding 6mmol of PS, adjusting the pH value of the solution to 3, carrying out dark reaction for 60min, and turning on a light source;
as a result, the degradation of methyl orange dye at 10mg/L, Congo red dye at 50mg/L and alizarin red dye at 100mg/L correspond to curves 16, 17 and 18, respectively, in this order. The decoloring rates after the reaction for 2 hours are respectively 93.1%, 97.6% and 100%, so that the composite photocatalyst activated persulfate system has higher catalytic activity on methyl orange, congo red and alizarin red.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention shall fall within the protection scope defined by the claims of the present invention.
Claims (8)
1. A preparation method of a composite photocatalyst is characterized by comprising the following steps:
mixing butyl titanate, hydrochloric acid and graphite in an ethanol solution, performing ultrasonic treatment to obtain gel, drying the gel, grinding the gel into powder, calcining the powder at 400-500 ℃ for 2-4 h to obtain graphite-TiO2A nanoparticle;
will contain FeSO4·7H2O and Fe2(SO4)3The mixed solution is placed in water bath at the temperature of 55-65 ℃ for heating to obtain the Fe-containing iron3O4The graphite-TiO is mixed with2Dispersing the nano particles in the mixed solution, adding NaOH and polyethylene glycol, continuously reacting at 55-65 ℃ for 20-40 min, washing to be neutral, and drying to obtain the composite photocatalyst graphite-TiO2@Fe3O4。
2. The preparation method of the composite photocatalyst as claimed in claim 1, wherein the molar ratio of the graphite to the butyl titanate is 0.007-0.06: 1.
3. the method for preparing the composite photocatalyst as claimed in claim 1, wherein the graphite-TiO is prepared2In the process of nanoparticles, the preparation method of the gel comprises the following steps: ultrasonically dispersing the graphite in absolute ethyl alcohol to obtain a first solution; adding the butyl titanate and the hydrochloric acid into absolute ethyl alcohol, and then adding the first solution to obtain a second solution; and adding water into the second solution, stirring until the solution is converted into sol, and performing ultrasonic treatment to obtain gel.
4. The method for preparing the composite photocatalyst as claimed in claim 1, wherein the graphite-TiO is2@Fe3O4In (b), the Fe3O4With the TiO mentioned2The molar ratio of (A) to (B) is 0.2 to 1: 1.
5. Composite photocatalyst graphite-TiO2@Fe3O4Characterized in that it is prepared by the preparation method according to any one of claims 1 to 5.
6. A degradation method of dye wastewater is characterized by comprising the following steps:
after the pH value of the dye wastewater is adjusted to 3-7, the composite photocatalyst graphite-TiO of claim 5 is sequentially added2@Fe3O4And persulfate is subjected to light-shielding reaction and then placed under visible light for reaction for 1-3 hours.
7. The method for degrading dye wastewater according to claim 6, wherein the dye wastewater contains alizarin red, and the alizarin red and the graphite-TiO are2@Fe3O4The mass ratio of (A) to (B) is 1: 2-3.
8. The degradation method of dye wastewater according to claim 7, wherein the persulfate is potassium persulfate, and the molar ratio of the alizarin red to the potassium persulfate is 1: 16-17.
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