CN108837819B - Zinc ferrite bentonite composite photocatalyst and preparation method and application thereof - Google Patents
Zinc ferrite bentonite composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 112
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 229910000278 bentonite Inorganic materials 0.000 title claims abstract description 77
- 239000000440 bentonite Substances 0.000 title claims abstract description 77
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 75
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 229940092782 bentonite Drugs 0.000 claims abstract description 76
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229940080314 sodium bentonite Drugs 0.000 claims abstract description 66
- 229910000280 sodium bentonite Inorganic materials 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 88
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 229910001868 water Inorganic materials 0.000 claims description 51
- 239000011259 mixed solution Substances 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 30
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 25
- 239000011701 zinc Substances 0.000 claims description 25
- 238000005303 weighing Methods 0.000 claims description 21
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 230000015556 catabolic process Effects 0.000 claims description 11
- 238000006731 degradation reaction Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- -1 iron ions Chemical class 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 6
- 229910052725 zinc Inorganic materials 0.000 claims 6
- 238000001354 calcination Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 25
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- 230000000593 degrading effect Effects 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 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 16
- 229940043267 rhodamine b Drugs 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 9
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KSHPUQQHKKJVIO-UHFFFAOYSA-N [Na].[Zn] Chemical compound [Na].[Zn] KSHPUQQHKKJVIO-UHFFFAOYSA-N 0.000 description 4
- 238000013480 data collection Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B01J35/39—
-
- 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
-
- 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
Abstract
The invention provides a zinc ferrite and bentonite composite photocatalyst as well as a preparation method and application thereof, belonging to the technical field of new photocatalytic materials and environmental protection. The preparation method of the zinc ferrite and bentonite composite photocatalyst provided by the invention has the advantages that the zinc ferrite and bentonite composite photocatalyst with good photocatalytic performance is obtained by adopting a preparation process with simple operation and mild reaction; the nano zinc ferrite is compounded between the layers and on the surface of the sodium bentonite, so that the composite catalyst has good adsorption performance and photocatalytic activity. The purpose of removing environmental pollutants is achieved by utilizing the adsorption property of the bentonite and the light conversion capacity of the nano zinc ferrite; the problems of low photocatalytic activity, difficult recovery and the like of zinc ferrite particles in the process of degrading pollutants are solved, and the application of a photocatalytic technology to actual wastewater is facilitated.
Description
Technical Field
The invention relates to the technical field of new photocatalytic materials and environmental protection, and particularly relates to a zinc ferrite and bentonite composite photocatalyst as well as a preparation method and application thereof.
Background
The traditional water treatment process (such as an adsorption process, a chemical oxidation process, an activated sludge process and a combined process) can not completely degrade organic pollutants which are difficult to degrade (such as dye wastewater). The photocatalysis technology which has mild reaction conditions and does not produce secondary pollution attracts the extensive attention of scientific research. ZnFe of spinel structure2O4Is a metal oxide mainly containing iron oxide, and has proper energy gap structureTherefore, the method has wide application in solar energy conversion and photocatalysis. However, due to ZnFe2O4The rapid recombination of charge carriers causes the problems of relatively low photocatalytic activity, difficult solid-liquid separation and the like, and is not beneficial to ZnFe2O4The method is applied to the aspect of actual wastewater treatment.
Disclosure of Invention
The invention aims to provide a preparation method of a zinc ferrite bentonite composite photocatalyst, and the photocatalyst with higher catalytic efficiency can be prepared by the preparation method.
The second purpose of the invention is to provide the zinc ferrite bentonite composite photocatalyst which has higher photocatalytic efficiency and improves the degradation of environmental pollutants.
The third purpose of the invention is to provide the application of the zinc ferrite bentonite composite photocatalyst in the degradation of environmental pollutants.
In order to achieve the above purpose of the invention, the following technical scheme is adopted:
the preparation method of the zinc ferrite bentonite composite photocatalyst comprises the following steps:
mixing a zinc nitrate solution and a ferric nitrate solution to obtain a zinc ferrite mixed solution;
mixing the zinc ferrite mixed solution with the citric acid solution, and carrying out first stirring and heating in a first water bath to obtain precursor sol;
and mixing the sodium bentonite suspension with the precursor sol, heating in a second water bath, stirring, centrifuging and drying for the second time to obtain the zinc ferrite bentonite composite photocatalyst.
A zinc ferrite and bentonite composite photocatalyst is prepared by the preparation method of the zinc ferrite and bentonite composite photocatalyst.
The zinc ferrite and bentonite composite photocatalyst is applied to degradation of environmental pollutants.
The invention has the beneficial effects that: the preparation method of the zinc ferrite and bentonite composite photocatalyst provided by the invention has the advantages that the zinc ferrite and bentonite composite photocatalyst with good photocatalytic performance is obtained by adopting a preparation process with simple operation and mild reaction; the nano zinc ferrite is compounded between the layers and on the surface of the sodium bentonite, so that the composite catalyst has good adsorption performance and photocatalytic activity. The purpose of removing environmental pollutants is achieved by utilizing the adsorption property of the bentonite and the light conversion capacity of the nano zinc ferrite; the problems of low photocatalytic activity, difficult recovery and the like of zinc ferrite particles in the process of degrading pollutants are solved, and the application of a photocatalytic technology to actual wastewater is facilitated.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 provides an XRD pattern of a catalyst according to Experimental example 1 of the present invention;
FIG. 2 is a graph showing the degradation effect of a visible-light-responsive catalyst on rhodamine B, which is provided in Experimental example 1 of the present invention;
FIG. 3 is a schematic diagram showing the result of degrading chromium wastewater by using the zinc ferrite bentonite composite photocatalyst provided in Experimental example 1 of the present invention;
FIG. 4 is a graph showing the results of degrading rhodamine B for catalysts prepared at different temperatures as provided in Experimental example 2;
FIG. 5 is a graph showing the results of different dosages of catalyst provided in Experimental example 3 for degrading rhodamine B;
FIG. 6 is a graph showing the results of different concentrations of catalyst provided in Experimental example 4 for degrading rhodamine B.
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.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The zinc ferrite bentonite composite photocatalyst, the preparation method and the application thereof according to the embodiment of the invention are specifically described below.
The preparation method of the zinc ferrite bentonite composite photocatalyst comprises the following steps:
mixing a zinc nitrate solution and a ferric nitrate solution to obtain a zinc ferrite mixed solution;
mixing the zinc ferrite mixed solution with the citric acid solution, and carrying out first stirring and heating in a first water bath to obtain precursor sol;
and mixing the sodium bentonite suspension with the precursor sol, heating in a second water bath, stirring, centrifuging and drying for the second time to obtain the zinc ferrite bentonite composite photocatalyst.
Further, in the preferred embodiment of the present invention, the ratio of the number of zinc ions to the number of iron ions in the zinc ferrite mixed solution is 1: 2-4.
Further, in the preferred embodiment of the present invention, after the zinc ferrite mixed solution is mixed with the citric acid solution, the ratio of the number of zinc ions in the mixed solution to the number of citric acid molecules is 1: 5-8.
By reasonably adjusting the proportion of zinc ions, iron ions, citric acid molecules and sodium bentonite, zinc ferrite can be better loaded on the surface of the sodium bentonite to form nano particles, which is beneficial to improving the photocatalytic efficiency.
Further, in the preferred embodiment of the present invention, the temperature of the first water bath and the second water bath is 77-86 ℃; the time of the first water bath is 113-; the time of the second water bath is 55-125 min.
Further, in a preferred embodiment of the present invention, the preparation of a sodium bentonite suspension is further included, including:
weighing sodium bentonite, adding water, stirring at normal temperature for 270-320min, and preparing 5 wt% sodium bentonite suspension.
Further, in the preferred embodiment of the present invention, the second stirring time is 12-15 hours and the temperature is 20-27 ℃.
Further, in the preferred embodiment of the invention, after drying at 80-100 ℃, the zinc ferrite bentonite composite photocatalyst is prepared by roasting at 400-700 ℃ for 1-2 h.
Further, in the preferred embodiment of the present invention, after the sodium bentonite suspension and the precursor sol are mixed, the ratio of the number of zinc ions in the solution to the sodium bentonite is 15-30 mmol/g.
A zinc ferrite and bentonite composite photocatalyst is prepared by the preparation method of the zinc ferrite and bentonite composite photocatalyst.
The zinc ferrite and bentonite composite photocatalyst is applied to degradation of environmental pollutants.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a zinc ferrite bentonite composite photocatalyst, which comprises the following steps:
preparation of precursor sol (zinc ferrite sol):
1.1, respectively weighing zinc nitrate and ferric nitrate to prepare a zinc nitrate solution and a ferric nitrate solution;
1.2 mixing a zinc nitrate solution and a ferric nitrate solution to obtain a zinc ferrite mixed solution; the ratio of the number of zinc ions to the number of iron ions in data collection is 1: 2;
1.3 continuously stirring the zinc ferrite mixed solution at room temperature, and dropwise adding a citric acid solution to the mixed solution, wherein the ratio of the number of zinc ions to the number of citric acid molecules in the mixed solution is 1:5, so as to obtain a dark red mixed solution;
1.4, carrying out a first water bath for 113min on the dark red mixed solution at 77 ℃ to prepare precursor sol.
The preparation method of the sodium bentonite comprises the following steps:
weighing sodium bentonite, adding the sodium bentonite into deionized water, and stirring at normal temperature for 270min to obtain 5 wt% sodium bentonite suspension.
Preparation of the photocatalyst
2.1 dropwise adding 5 wt% of sodium bentonite suspension into the precursor sol according to the proportion of 15mmol/g of zinc ion number and sodium bentonite;
2.2 carrying out a second water bath at the temperature of 77 ℃ for 55 min;
2.3 carrying out second stirring for 12h at the temperature of 20 ℃;
2.4 centrifugally washing the solution for 3-5 times; obtaining a precipitate;
2.5 drying the precipitate at the temperature of 80 ℃, and then roasting at 400 ℃ for 1h to prepare the zinc ferrite bentonite composite photocatalyst.
Example 2
The embodiment provides a preparation method of a zinc ferrite bentonite composite photocatalyst, which comprises the following steps:
preparation of precursor sol (zinc ferrite sol):
1.1, respectively weighing zinc nitrate and ferric nitrate to prepare a zinc nitrate solution and a ferric nitrate solution;
1.2 mixing a zinc nitrate solution and a ferric nitrate solution to obtain a zinc ferrite mixed solution; the ratio of the number of zinc ions to the number of iron ions in data collection is 1: 3;
1.3 continuously stirring the zinc ferrite mixed solution at room temperature, and dropwise adding a citric acid solution to the mixed solution, wherein the ratio of the number of zinc ions in the mixed solution to the number of molecules of the citric acid is 1:6, so as to obtain a dark red mixed solution;
1.4, carrying out a first water bath for 126min at 86 ℃ on the dark red mixed solution to prepare precursor sol.
The preparation method of the sodium bentonite comprises the following steps:
weighing sodium bentonite, adding the sodium bentonite into deionized water, and stirring for 320min at normal temperature to obtain 5 wt% sodium bentonite suspension.
Preparation of the photocatalyst
2.1 dropwise adding 5 wt% of sodium bentonite suspension into the precursor sol according to the proportion of zinc ion number to sodium bentonite of 30 mmol/g;
2.2 carrying out a second water bath at the temperature of 86 ℃ for 125 min;
2.3 second stirring at 27 ℃ for 15 h;
2.4 centrifugally washing the solution for 3-5 times; obtaining a precipitate;
2.5 drying the precipitate at the temperature of 100 ℃, and then roasting at 700 ℃ for 2h to prepare the zinc ferrite bentonite composite photocatalyst.
Example 3
The embodiment provides a preparation method of a zinc ferrite bentonite composite photocatalyst, which comprises the following steps:
preparation of precursor sol (zinc ferrite sol):
1.1, respectively weighing zinc nitrate and ferric nitrate to prepare a zinc nitrate solution and a ferric nitrate solution;
1.2 mixing a zinc nitrate solution and a ferric nitrate solution to obtain a zinc ferrite mixed solution; the ratio of the number of zinc ions to the number of iron ions in data collection is 1: 4;
1.3 continuously stirring the zinc ferrite mixed solution at room temperature, and dropwise adding a citric acid solution to the mixed solution, wherein the ratio of the number of zinc ions in the mixed solution to the number of molecules of the citric acid is 1:8, so as to obtain a dark red mixed solution;
1.4, carrying out a first water bath for 120min at 86 ℃ on the dark red mixed solution to prepare precursor sol.
The preparation method of the sodium bentonite comprises the following steps:
weighing sodium bentonite, adding the sodium bentonite into deionized water, and stirring at normal temperature for 300min to obtain 5 wt% sodium bentonite suspension.
Preparation of the photocatalyst
2.1 dropwise adding 5 wt% of sodium bentonite suspension into the precursor sol according to the proportion of 25mmol/g of zinc ion number and sodium bentonite;
2.2 performing a second water bath at the temperature of 80 ℃ for 120 min;
2.3 carrying out second stirring for 13h at the temperature of 25 ℃;
2.4 centrifugally washing the solution for 3-5 times; obtaining a precipitate;
2.5 drying the precipitate at the temperature of 90 ℃, and then roasting at 500 ℃ for 2h to prepare the zinc ferrite bentonite composite photocatalyst.
Example 4
The embodiment provides a preparation method of a zinc ferrite bentonite composite photocatalyst, which comprises the following steps:
preparation of precursor sol (zinc ferrite sol):
1.1, respectively weighing zinc nitrate and ferric nitrate to prepare a zinc nitrate solution and a ferric nitrate solution;
1.2 mixing a zinc nitrate solution and a ferric nitrate solution to obtain a zinc ferrite mixed solution; the ratio of the number of zinc ions to the number of iron ions in data collection is 1: 2;
1.3 continuously stirring the zinc ferrite mixed solution at room temperature, and dropwise adding a citric acid solution to the mixed solution, wherein the ratio of the number of zinc ions in the mixed solution to the number of molecules of the citric acid is 1:6, so as to obtain a dark red mixed solution;
1.4, carrying out a first water bath for 120min at the temperature of 80 ℃ on the dark red mixed solution to prepare precursor sol.
The preparation method of the sodium bentonite comprises the following steps:
weighing sodium bentonite, adding the sodium bentonite into deionized water, and stirring at normal temperature for 300min to obtain 5 wt% sodium bentonite suspension.
Preparation of the photocatalyst
2.1 dropwise adding 5 wt% of sodium bentonite suspension into the precursor sol according to the proportion of 25mmol/g of zinc ion number and sodium bentonite;
2.2 performing a second water bath at the temperature of 80 ℃ for 120 min;
2.3 carrying out second stirring for 13h at the temperature of 25 ℃;
2.4 centrifugally washing the solution for 3-5 times; obtaining a precipitate;
2.5 drying the precipitate at the temperature of 85 ℃, and then roasting at 600 ℃ for 2h to prepare the zinc ferrite bentonite composite photocatalyst.
Experimental example 1
In this experimental example, the zinc ferrite and bentonite composite photocatalyst is prepared by the preparation method provided in example 4, and the ability and efficiency of the zinc ferrite and bentonite composite photocatalyst for degrading environmental pollutants are verified.
Preparing zinc ferrite sol:
1.1 weighing 2.98gZn (NO)3)2·6H2Dissolving O in 10mL of water to prepare Zn (NO)3)2Solution weighing 8.08gFe (NO)3)3·9H2Dissolving O in 10mL of water to prepare Fe (NO)3)3The solution is prepared by weighing 12.6g of citric acid and dissolving in 30mL of water to prepare a citric acid solution for later use.
1.2 addition of Zn (NO)3)2The solution was added dropwise to Fe (NO)3)3In solution to obtain n [ Zn ]]/n[Fe]1:2 red mixed solution. Adding citric acid solution dropwise into the mixed solution under stirring at room temperature to obtain n [ Fe ]]/n[C6H8O7·H2O]Putting the reddish brown solution at a ratio of 1:3 into a constant-temperature water bath kettle at 80 ℃, and stirring at a constant speed for 2 hours; thus obtaining the reddish-brown precursor sol.
Preparation of sodium bentonite suspension:
0.5g of sodium bentonite is weighed and added into 99.5mL of deionized water, stirred for 5 hours at normal temperature, and fully dispersed to obtain 5 wt% of sodium bentonite suspension for later use.
Preparing a zinc ferrite bentonite composite photocatalyst:
2.1 sodium bentonite suspension of 5 wt% is added drop by drop to the precursor solution prepared in step 1.2 in the ratio Zn/bentonite of 20mmol/g and heated in a magnetic stirring water bath at 80 ℃ for 2 h.
2.2 stirring at constant speed for 13h at 25 ℃ and normal temperature. The resulting solution was centrifuged, washed 2 times with deionized water and 2 times with anhydrous ethanol, and then the precipitate in the centrifuge tube was taken out and placed in a 50mL beaker. Putting the beaker into a drying oven at 100 ℃ for drying, and roasting the dried sample at 600 ℃ for 2 h; obtaining the zinc ferrite and bentonite composite photocatalyst.
The zinc ferrite bentonite composite photocatalyst prepared in this example is detected by XRD, and the detection result is shown in fig. 1, where the 35.3 ° strong peak corresponds to the (311) crystal face of zinc ferrite, and the 26.6 ° strong peak corresponds to the (101) crystal face of bentonite, which indicates that the nano zinc ferrite bentonite composite photocatalyst has been successfully prepared.
In the embodiment, the rhodamine B solution is used as an environmental pollution marker, and the degradation capability of the zinc ferrite sodium bentonite composite catalyst on environmental pollutants is represented by catalytically degrading the rhodamine B solution by the nano zinc ferrite sodium bentonite composite catalyst.
The method comprises the steps of taking a rhodamine B solution (20mg/L) as a target solution, adding 1.0g/L of a sodium zinc ferrite bentonite composite catalyst, adopting a 350W xenon lamp as a light source in an experiment, using a 420nm optical filter to enable the wavelength of irradiation light to be larger than or equal to 420nm, detecting the rhodamine B content in the solution after carrying out photocatalytic reaction for 120min, comparing the change of the rhodamine B content before and after the action of the sodium zinc ferrite bentonite composite catalyst, and calculating the catalytic degradation efficiency of the sodium zinc ferrite bentonite composite catalyst.
The result is shown in fig. 2, and it can be seen that about 90% of rhodamine B is degraded, which indicates that the zinc ferrite sodium bentonite composite catalyst prepared by the invention has better capability of catalyzing and degrading environmental pollution.
In order to further verify the visible light catalytic activity of the zinc ferrite sodium bentonite composite catalyst, heavy metal hexavalent chromium is selected as a target pollutant to perform a degradation experiment. Without changing the above light source conditions, 100mL of potassium dichromate (50mg/L) was weighed into a beaker, and 0.4mL of citric acid solution (20g/L) was added. Adding 0.1g of zinc ferrite sodium bentonite composite catalyst under the dark stirring state, sampling every 30min and centrifuging in a centrifuge. And (3) measuring the absorbance of the solution at 349nm, measuring the concentration of hexavalent chromium in the solution according to a concentration-absorbance standard curve of potassium dichromate, and further calculating the removal rate of the sodium zinc ferrite bentonite composite catalyst to the hexavalent chromium in the photocatalysis process.
As shown in figure 3, in a potassium dichromate degradation experiment, the adding amount of the zinc ferrite sodium bentonite composite catalyst is 1.0g/L, the initial concentration of potassium dichromate is 50mg/L, the wavelength of irradiated light is more than 420nm, and after 120min of reaction, the reduction rate of hexavalent chromium reaches 70%; the photocatalyst shows that the photocatalyst also shows better catalytic activity in the process of reducing hexavalent chromium, and simultaneously shows that the photocatalyst also has better catalytic effect on heavy metal pollutants which are difficult to biodegrade.
Experimental example 2
In this experimental example, the zinc ferrite and bentonite composite photocatalyst is prepared by the preparation method provided in example 4, and the ability and efficiency of the zinc ferrite and bentonite composite photocatalyst for degrading environmental pollutants are verified.
Preparing zinc ferrite sol:
1.1 weighing 2.98gZn (NO)3)2·6H2Dissolving O in 10mL of water to prepare Zn (NO)3)2Solution weighing 8.08gFe (NO)3)3·9H2Dissolving O in 10mL of water to prepare Fe (NO)3)3The solution is prepared by weighing 12.6g of citric acid and dissolving in 30mL of water to prepare a citric acid solution for later use. So that n [ Zn ]]/n[Fe]＝1:2,n[Fe]/n[C6H8O7·H2O]＝1:3。
1.2 addition of Zn (NO)3)2The solution was added dropwise to Fe (NO)3)3In solution to obtain n [ Zn ]]/n[Fe]1:2 red mixed solution. Adding citric acid solution dropwise to the above mixture under continuous stirring at room temperatureAnd mixing the solution. To obtain n [ Fe ]]/n[C6H8O7·H2O]1:3 in reddish brown. And finally, placing the obtained reddish brown solution in a water bath kettle with the constant temperature of 80 ℃, and stirring at a constant speed for 2 hours. So as to obtain the reddish brown zinc ferrite sol.
Preparation of sodium bentonite suspension:
0.5g of sodium bentonite is weighed and added into 99.5mL of deionized water, stirred for 5 hours at normal temperature, and fully dispersed to obtain 5 wt% of sodium bentonite suspension for later use.
Preparing a zinc ferrite bentonite composite photocatalyst:
2.1 adding 5 wt% sodium bentonite suspension into the precursor solution prepared in the step 1.2 drop by drop according to the proportion of Zn/bentonite being 20mmol/g, heating in a magnetic stirring water bath at 80 ℃ for 2h,
2.2 stirring at constant speed for 13h at 25 ℃ and normal temperature. The resulting solution was centrifuged, washed 2 times with deionized water and 2 times with anhydrous ethanol, and then the precipitate in the centrifuge tube was taken out and placed in a 50mL beaker. And (3) putting the beaker into a drying oven at 100 ℃ for drying, and roasting the dried sample at 500 ℃ for 2h to prepare the zinc ferrite bentonite composite photocatalyst.
The zinc ferrite bentonite composite photocatalyst prepared in the experimental example is used for degrading rhodamine B solution (20mg/L), the adding amount of the catalyst is 1.0g/L, a 350W xenon lamp is used as a light source in the experiment, a 420nm optical filter is used for enabling the wavelength of irradiated light to be larger than or equal to 420nm, and the photocatalytic reaction is carried out for 120 min.
The results are shown in FIG. 4, where about 86% of rhodamine B is degraded; the nano zinc ferrite nano bentonite composite catalyst prepared at different roasting temperatures has higher visible light catalytic activity.
Experimental example 3
In this experimental example, the zinc ferrite and bentonite composite photocatalyst is prepared by the preparation method provided in example 4, and the ability and efficiency of the zinc ferrite and bentonite composite photocatalyst for degrading environmental pollutants are verified.
Preparing zinc ferrite sol:
1.1 weighing 2.98gZn (NO)3)2·6H2O dissolved in 10mL of waterIs formulated into Zn (NO)3)2Solution 8.08g Fe (NO) was weighed3)3·H2Dissolving O in 10mL of water to prepare Fe (NO)3)3The solution is prepared by weighing 12.6g of citric acid and dissolving in 30mL of water to prepare a citric acid solution for later use. So that n [ Zn ]]/n[Fe]＝1:2,n[Fe]/n[C6H8O7·H2O]＝1:3。
1.2 addition of Zn (NO)3)2The solution was added dropwise to Fe (NO)3)3In solution to obtain n [ Zn ]]/n[Fe]1:2 red mixed solution. The citric acid solution was added dropwise to the above mixed solution under continuous stirring at room temperature. To obtain n [ Fe ]]/n[C6H8O7·H2O]1:3 in reddish brown. And finally, placing the obtained reddish brown solution in a water bath kettle with the constant temperature of 80 ℃, and stirring at a constant speed for 2 hours. So as to obtain the reddish brown zinc ferrite sol.
Preparation of sodium bentonite suspension:
0.5g of sodium bentonite is weighed and added into 99.5mL of deionized water, stirred for 5 hours at normal temperature, and fully dispersed to obtain 5 wt% of sodium bentonite suspension for later use.
Preparing a zinc ferrite bentonite composite photocatalyst:
2.1 adding 5 wt% sodium bentonite suspension into the precursor solution prepared in the step 1.2 drop by drop according to the proportion of Zn/bentonite being 20mmol/g, heating in a magnetic stirring water bath at 80 ℃ for 2h,
2.2 stirring at constant speed for 13h at 25 ℃ and normal temperature. The resulting solution was centrifuged, washed 2 times with deionized water and 2 times with anhydrous ethanol, and then the precipitate in the centrifuge tube was taken out and placed in a 50mL beaker. And (3) putting the beaker into a drying oven at 100 ℃ for drying, and roasting the dried sample at 600 ℃ for 2h to prepare the zinc ferrite bentonite composite photocatalyst.
The composite photocatalyst prepared in the experimental example is used for degrading rhodamine B solution (20mg/L), the dosage of the catalyst is 0.5g/L, a 350W xenon lamp is used as a light source in the experiment, a 420nm optical filter is used for enabling the wavelength of irradiated light to be larger than or equal to 420nm, and the photocatalytic reaction is carried out for 120 min.
As a result, as shown in FIG. 5, about 73% of rhodamine B was degraded. The nano zinc ferrite sodium bentonite composite catalyst prepared by the method has higher visible light catalytic activity.
Experimental example 4
In this experimental example, the zinc ferrite and bentonite composite photocatalyst is prepared by the preparation method provided in example 4, and the ability and efficiency of the zinc ferrite and bentonite composite photocatalyst for degrading environmental pollutants are verified.
Preparing zinc ferrite sol:
1.1 weighing 2.98gZn (NO)3)2·6H2Dissolving O in 10ml water to prepare Zn (NO)3)2Solution weighing 8.08gFe (NO)3)3·9H2Dissolving O in 10ml water to prepare Fe (NO)3)3The solution is prepared by weighing 12.6g of citric acid and dissolving in 30ml of water to prepare a citric acid solution for later use. So that n [ Zn ]]/n[Fe]＝1:2,n[Fe]/n[C6H8O7·H2O]＝1:3。
1.2 addition of Zn (NO)3)2The solution was added dropwise to Fe (NO)3)3In solution to obtain n [ Zn ]]/n[Fe]1:2 red mixed solution. The citric acid solution was added dropwise to the above mixed solution under continuous stirring at room temperature. To obtain n [ Fe ]]/n[C6H8O7·H2O]1:3 in reddish brown. Finally, placing the obtained reddish brown solution in a water bath kettle with the constant temperature of 80 ℃, and stirring at constant speed for 2 hours; so as to obtain the reddish brown zinc ferrite sol.
Preparation of sodium bentonite suspension:
0.5g of sodium bentonite is weighed and added into 99.5ml of deionized water, stirred for 5 hours at normal temperature, and fully dispersed to obtain 5 wt% of sodium bentonite suspension for later use.
Preparing a zinc ferrite bentonite composite photocatalyst:
2.1 sodium bentonite suspension of 5 wt% is added drop by drop to the precursor solution prepared in step 1.2 in the ratio Zn/bentonite of 20mmol/g and heated in a magnetic stirring water bath at 80 ℃ for 2 h.
2.2 stirring at constant speed for 13h at 25 ℃ and normal temperature. The resulting solution was centrifuged, washed 2 times with deionized water and 2 times with anhydrous ethanol, and after washing, the precipitate in the centrifuge tube was taken out and placed in a 50ml beaker. And (3) putting the beaker into a drying oven at 100 ℃ for drying, and roasting the dried sample at 600 ℃ for 2h to prepare the zinc ferrite bentonite composite photocatalyst.
The composite photocatalyst prepared in the experimental example is used for degrading rhodamine B solution (30mg/L), the dosage of the catalyst is 1g/L, a 350W xenon lamp is used as a light source in the experiment, the wavelength of irradiating light is more than or equal to 420nm by using a 420nm optical filter, and the degradation efficiency is detected after 120min of photocatalytic reaction.
The experimental results are shown in fig. 6, and about 92% of rhodamine B is degraded. The nano zinc ferrite sodium bentonite composite catalyst prepared by the method has higher visible light catalytic activity.
In conclusion, the preparation method of the zinc ferrite sodium bentonite composite catalyst provided by the embodiment of the invention can prepare the catalyst with higher catalytic efficiency through a simple process, can rapidly degrade a large amount of environmental pollutants, and has higher practical application value and better popularization value.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. The preparation method of the zinc ferrite and bentonite composite photocatalyst is characterized by comprising the following steps:
mixing a zinc nitrate solution and a ferric nitrate solution to obtain a zinc ferrite mixed solution;
mixing the zinc ferrite mixed solution with a citric acid solution, and carrying out first stirring and heating in a first water bath to obtain precursor sol;
and mixing the sodium bentonite suspension with the precursor sol, heating in a second water bath, and carrying out second stirring, centrifuging and drying to obtain the zinc ferrite bentonite composite photocatalyst.
2. The method for preparing the zinc ferrite-bentonite composite photocatalyst as claimed in claim 1, wherein the ratio of the number of zinc ions to the number of iron ions in the zinc ferrite mixed solution is 1: 2-4.
3. The method for preparing the zinc ferrite-bentonite composite photocatalyst as claimed in claim 2, wherein after the zinc ferrite mixed solution is mixed with the citric acid solution, the ratio of the number of zinc ions to the number of molecules of the citric acid in the mixed solution is 1: 5-8.
4. The preparation method of the zinc ferrite-bentonite composite photocatalyst as claimed in claim 1, wherein the temperature of the first water bath and the second water bath is 77-86 ℃; the time of the first water bath is 113-126 min; the time of the second water bath is 55-125 min.
5. The preparation method of the zinc ferrite-bentonite composite photocatalyst as claimed in claim 1, further comprising the preparation of the sodium bentonite suspension, comprising:
weighing sodium bentonite, adding water, stirring at normal temperature for 270-320min, and preparing 5 wt% of the sodium bentonite suspension.
6. The preparation method of the zinc ferrite-bentonite composite photocatalyst as claimed in claim 5, wherein the time of the second stirring is 12-15h, and the temperature is 20-27 ℃.
7. The method for preparing the zinc ferrite and bentonite composite photocatalyst as claimed in claim 1, wherein the zinc ferrite and bentonite composite photocatalyst is prepared by drying at 80-100 ℃ and then calcining at 400-700 ℃ for 1-2 h.
8. The preparation method of the zinc ferrite-bentonite composite photocatalyst as claimed in claim 2, wherein after the sodium bentonite suspension and the precursor sol are mixed, the ratio of the number of zinc ions to the amount of sodium bentonite in the solution is 15-30 mmol/g.
9. A zinc ferrite and bentonite composite photocatalyst, which is characterized in that the zinc ferrite and bentonite composite photocatalyst is prepared by the preparation method of the zinc ferrite and bentonite composite photocatalyst as claimed in any one of claims 1 to 8.
10. The use of the zinc ferrite bentonite composite photocatalyst as defined in claim 9 in the degradation of environmental pollutants.
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