CN111686763A - Method for preparing magnetic zinc cadmium sulfide composite photocatalyst - Google Patents

Method for preparing magnetic zinc cadmium sulfide composite photocatalyst Download PDF

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CN111686763A
CN111686763A CN202010663022.1A CN202010663022A CN111686763A CN 111686763 A CN111686763 A CN 111686763A CN 202010663022 A CN202010663022 A CN 202010663022A CN 111686763 A CN111686763 A CN 111686763A
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CN111686763B (en
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郝宇
吴廷增
成勇
徐龙君
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Chongqing University
Chongqing Vocational Institute of Engineering
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Abstract

A preparation method of a magnetic zinc cadmium sulfide composite photocatalyst belongs to the field of inorganic catalysts. The invention firstly prepares the Mn-Zn ferrite Mn of the soft magnetic material by a hydrothermal methodxZn1‑xFe2O4And MnxZn1‑xFe2O4and/C, preparing the magnetic cadmium sulfide composite photocatalyst (Mn) by using a dipping precipitation methodxZn1‑xFe2O4/C/Zn0.8Cd0.2S). The method has the advantages of simple preparation process, less used equipment and low energy consumption. Prepared MnxZn1‑xFe2O4/C/Zn0.8Cd0.2The S has stable magnetic property and high photocatalytic activity, 100mL of 10mg/L rhodamine B solution is degraded by using 0.1g of prepared composite magnetic photocatalyst under the irradiation of a simulated sunlight xenon lamp, the degradation rate of the rhodamine B reaches 92.6% in 90min, the photocatalyst is subjected to magnetic recovery under an external magnetic field, and the degradation rate of the rhodamine B is 86.9% after the photocatalyst is repeatedly used for 5 times. The product prepared by the invention can be widely used in the field of photocatalytic degradation of organic pollutants.

Description

Method for preparing magnetic zinc cadmium sulfide composite photocatalyst
Technical Field
The invention relates to a method for preparing a magnetic zinc-cadmium sulfide composite photocatalyst (Mn)xZn1-xFe2O4/C/Zn0.8Cd0.2S) method, belonging to the technical field of inorganic environment photocatalyst.
Background
The CdS photocatalyst has excellent photosensitivity and visible light absorption characteristics, has a direct band gap of 2.4eV, is suitable for absorbing sunlight, and is widely used due to its excellent photocatalytic performance. However, single CdS is not photo-stable and photo-corrosion occurs during the photo-catalysis process. At present, various methods are studied to overcome the defect, such as forming a heterojunction by compounding with other semiconductors and polymers, loading noble metals on the surface, and doping Zn, Mn and other ions to form a solid solution. Solid solution Zn0.8Cd0.2S has excellent photocatalytic activity, and many researchers are working on Zn0.8Cd0.2S solid solution modification to obtain more active photocatalysts, such as NiO/Zn0.8Cd0.2The S solid solution realizes the photocatalytic hydrogen production in pure water. Because the catalytic degradation reaction is mostly carried out in the solution environment, Zn0.8Cd0.2The S photocatalyst has very small particle size and is suspended in a solution to cause the problem of difficult recycling, which not only leads to Zn0.8Cd0.2The loss of the S photocatalyst can also cause serious secondary pollution to the water environment, particularly the CdS contains toxic metal Cd, NiO/Zn0.8Cd0.2S contains heavy metal pollution elements Cd and Ni, which are main factors for restricting the application process of the photocatalyst. The composite magnetic photocatalyst realizes the catalyst by an external magnetic fieldThe recycling can overcome the defects of complex process, large energy consumption and low recovery rate of the conventional filtration and recovery mode. To solve this problem, Zn is added0.8Cd0.2S is loaded on a magnetic material, magnetic separation is carried out by utilizing the action of an external magnetic field, the recovery efficiency is greatly improved, and the original catalytic activity can be further enhanced by an effective compound mode.
Manganese zinc ferrite (Mn)xZn1-xFe2O4) With conventional soft magnetic materials (e.g. Fe)3O4、MFe2O4) Compared with the prior art, the magnetic material has the characteristics of high saturation magnetization (Ms), high magnetic conductivity and the like, and has the advantages of high production efficiency, low cost, stable product performance and the like. Therefore, the composite magnetic photocatalyst prepared by taking the manganese-zinc ferrite as the magnetic matrix has strong magnetism and is more convenient to separate and recycle.
At present, Zn is treated0.8Cd0.2S modification is mainly focused on complex heterojunctions (TiO)2、NiO、g-C3N4) And the like, such as "environ. Sci. technol." 2011 volume 45 "Novel pro to enhanced photoactive definition of Rhodamine B under visible light irradiation byte ZnxCd1-xS/TiO2nanocomposites "(reference 1), a composite nanophotocatalyst Zn prepared by a hydrothermal methodxCd1-xS/TiO2. The method has the following disadvantages: (1) the process conditions are complex, thiourea is used as a sulfur source, polyethylene glycol (PEG) is used as a dispersing agent, and odor pollution is generated in the hydrothermal reaction process; hydrothermal reaction is carried out for 24 hours at 200 ℃, and energy consumption is high; cadmium acetate and zinc acetate which are used as raw materials are dissolved by ethanol, so that the danger of the hydrothermal reaction process is increased, and high-concentration organic wastewater can be generated; (2) znxCd1-xThe sample has the best photocatalytic activity when Cd/Zn is 3:1 in S, namely the cadmium zinc sulfide in the sample consists of Zn0.25Cd0.75S, the molar ratio of cadmium with stronger toxicity or pollution is higher; (3) the photocatalyst is difficult to recycle, the operation cost is high, and secondary pollution is possibly caused.
Disclosure of Invention
The invention aims to provide a magnetic zinc cadmium sulfide composite photocatalyst (Mn) aiming at the problems of complex preparation process and difficult recovery of zinc cadmium sulfidexZn1-xFe2O4/C/Zn0.8Cd0.2S), the preparation method is simple and low in cost. Prepared magnetic composite photocatalyst MnxZn1-xFe2O4/C/Zn0.8Cd0.2S has higher photocatalytic activity under the irradiation of simulated sunlight, and is convenient to separate and recycle from a liquid phase system through an external magnetic field, and the recycled catalyst still has higher photocatalytic activity. The method not only realizes resource recycling simply and efficiently, but also avoids secondary pollution possibly caused by incomplete catalyst recovery.
The invention relates to a magnetic zinc cadmium sulfide composite photocatalyst MnxZn1-xFe2O4/C/Zn0.8Cd0.2The preparation method of S comprises the following steps:
(1)MnxZn1-xFe2O4preparation of/C
According to the molar ratio of n (MnO) n (ZnO) n (Fe)2O3) Weighing certain amount of MnSO (respectively) 32.8:13.3:53.94·H2O、ZnSO4·7H2O and Fe2(SO4)3Adding a certain amount of deionized water, and fully stirring to obtain a uniform mixed solution; weighing a certain amount of NaOH as a precipitator to prepare NaOH solution with the concentration of 2 mol/L; slowly dripping NaOH solution into the mixed solution under magnetic stirring, quickly dripping NaOH solution when brown flocculent precipitate is generated in the solution, adjusting the pH value to 13, and continuously stirring for 20 min; transferring the stirred solution into a 100mL reaction kettle, and heating and reacting for 5h in an oven at 200 ℃; after the hydrothermal reaction is finished, taking out the sample, placing the sample for cooling to room temperature, repeatedly cleaning the sample by using distilled water and absolute ethyl alcohol under the action of an additional magnet, placing the sample in an oven for drying for 12 hours at the temperature of 60 ℃, and finally grinding the sample to obtain powdery MnxZn1-xFe2O4And (3) sampling.
3g of glucose was weighed and dissolved in 30mL of deionized water by ultrasonic to obtain a concentration of 0.5mol/L glucose solution; 0.2g of Mn prepared was weighedxZn1-xFe2O4Adding the powder into the solution and stirring vigorously for 1 h; then transferring the solution into a 50mL reaction kettle, and heating the solution in an oven at 180 ℃ for 5 hours; cooling to room temperature, washing with distilled water and anhydrous ethanol repeatedly by using an additional magnet, drying in an oven at 60 deg.C for 12 hr, and grinding to obtain powdered MnxZn1-xFe2O4And C, sampling.
(2) Magnetic composite photocatalyst MnxZn1-xFe2O4/C/Zn0.8Cd0.2Preparation of S
According to the molar ratio n (Zn)2+):n(Cd2+):n(S2-) Weighing appropriate amount of Zn (Ac) 0.8:0.2:1.252·2H2O and Cd (Ac)2·2H2Dissolving O, ultrasonic into 40mL deionized water, adding Zn generated theoretically0.8Cd0.2Mn with an S mass ratio of 5-25: 100xZn1-xFe2O4Performing mechanical stirring for 30min to obtain suspension A; 0.9g of Na was weighed2S·9H2Dissolving O in 40mL of deionized water by ultrasonic wave to obtain a solution B; under the condition of continuous stirring, dropwise adding the solution B into the suspension A at a certain speed by using a rubber head dropper, continuously stirring for a period of time, and standing for 24 hours; centrifuging at 4000rpm with a centrifuge, washing the solid with distilled water and anhydrous ethanol for 3 times, drying in a drying oven at 60 deg.C for 12 hr, and grinding to obtain powdered magnetic composite photocatalyst MnxZn1-xFe2O4/C/Zn0.8Cd0.2S。
By adopting the technical scheme, the invention mainly has the following effects:
(1) the magnetic composite photocatalyst Mn prepared by the methodxZn1-xFe2O4/C/Zn0.8Cd0.2S has higher photocatalytic activity, and 0.1g of prepared magnetic Mn is irradiated by a simulated sunlight xenon lampxZn1-xFe2O4the/C/CdS composite photocatalyst is dispersed in 100mL of rhodamine B solution with the concentration of 10mg/L,the degradation rate of rhodamine B after illumination for 90min reaches 92.6 percent.
(2) The magnetic composite photocatalyst Mn prepared by the methodxZn1-xFe2O4/C/Zn0.8Cd0.2The degradation rate of S after 5 times of repeated use still reaches 86.9 percent after the S is recovered under the action of an external magnetic field.
(3) The magnetic composite photocatalyst Mn prepared by the methodxZn1-xFe2O4/C/Zn0.8Cd0.2S, the preparation operation method is simple, the required equipment is few, and the energy consumption is low.
Drawings
FIG. 1 shows MnxZn1-xFe2O4/C、Zn0.8Cd0.2S and MnxZn1-xFe2O4/C/Zn0.8Cd0.2X-ray diffraction pattern of S.
FIG. 2 shows MnxZn1-xFe2O4、MnxZn1-xFe2O4/C、Zn0.8Cd0.2S and MnxZn1-xFe2O4/C/Zn0.8Cd0.2Scanning electron microscopy image of S.
FIG. 3 shows MnxZn1-xFe2O4、MnxZn1-xFe2O4C and MnxZn1-xFe2O4/C/Zn0.8Cd0.2Magnetic hysteresis curve of S.
Detailed Description
The present invention will be further described with reference to the following specific embodiments.
Example 1
Magnetic zinc cadmium sulfide composite photocatalyst (Mn)xZn1-xFe2O4/C/Zn0.8Cd0.2S) the preparation method comprises the following specific steps:
(1)MnxZn1-xFe2O4preparation of/C
According to the molar ratio of n (MnO) to n (Zn)O):n(Fe2O3) Weighing certain amount of MnSO (respectively) 32.8:13.3:53.94·H2O、ZnSO4·7H2O and Fe2(SO4)3Adding a certain amount of deionized water, and fully stirring to obtain a uniform mixed solution; weighing a certain amount of NaOH as a precipitator to prepare NaOH solution with the concentration of 2 mol/L; slowly dripping NaOH solution into the mixed solution under magnetic stirring, quickly dripping NaOH solution when brown flocculent precipitate is generated in the solution, adjusting the pH value to 13, and continuously stirring for 20 min; transferring the stirred solution into a 100mL reaction kettle, and heating and reacting for 5h in an oven at 200 ℃; after the hydrothermal reaction is finished, taking out the sample, placing the sample for cooling to room temperature, repeatedly cleaning the sample by using distilled water and absolute ethyl alcohol under the action of an additional magnet, placing the sample in an oven for drying for 12 hours at the temperature of 60 ℃, and finally grinding the sample to obtain powdery MnxZn1-xFe2O4A sample;
weighing 3g of glucose, and ultrasonically dissolving the glucose into 30mL of deionized water to obtain a glucose solution with the concentration of 0.5 mol/L; 0.2g of Mn prepared was weighedxZn1-xFe2O4Adding the powder into the solution and stirring vigorously for 1 h; then transferring the solution into a 50mL reaction kettle, and heating the solution in an oven at 180 ℃ for 5 hours; cooling to room temperature, washing with distilled water and anhydrous ethanol repeatedly by using an additional magnet, drying in an oven at 60 deg.C for 12 hr, and grinding to obtain powdered MnxZn1-xFe2O4a/C sample;
(2) magnetic composite photocatalyst MnxZn1-xFe2O4/C/Zn0.8Cd0.2Preparation of S
According to the molar ratio n (Zn)2+):n(Cd2+):n(S2-) Weighing appropriate amount of Zn (Ac) 0.8:0.2:1.252·2H2O and Cd (Ac)2·2H2Dissolving O, ultrasonic into 40mL deionized water, adding Zn generated theoretically0.8Cd0.2Mn with S mass ratio of 5:100xZn1-xFe2O4Performing mechanical stirring for 30min to obtain suspension A; 0.9g of Na was weighed2S·9H2Dissolving O in 40mL of deionized water by ultrasonic wave to obtain a solution B; under the condition of continuous stirring, dropwise adding the solution B into the suspension A at a certain speed by using a rubber head dropper, continuously stirring for a period of time, and standing for 24 hours; centrifuging at 4000rpm with a centrifuge, washing the solid with distilled water and anhydrous ethanol for 3 times, drying in a drying oven at 60 deg.C for 12 hr, and grinding to obtain powdered magnetic composite photocatalyst MnxZn1- xFe2O4/C/Zn0.8Cd0.2S。
Example 2
Magnetic zinc cadmium sulfide composite photocatalyst (Mn)xZn1-xFe2O4/C/Zn0.8Cd0.2S) the preparation method comprises the following specific steps:
(1)MnxZn1-xFe2O4preparation of/C
The same as in (1) in example 1.
(2) Magnetic composite photocatalyst MnxZn1-xFe2O4/C/Zn0.8Cd0.2Preparation of S
According to the molar ratio n (Zn)2+):n(Cd2+):n(S2-) Weighing appropriate amount of Zn (Ac) 0.8:0.2:1.252·2H2O and Cd (Ac)2·2H2Dissolving O, ultrasonic into 40mL deionized water, adding Zn generated theoretically0.8Cd0.2Mn with S mass ratio of 10:100xZn1-xFe2O4Performing mechanical stirring for 30min to obtain suspension A; 0.9g of Na was weighed2S·9H2Dissolving O in 40mL of deionized water by ultrasonic wave to obtain a solution B; under the condition of continuous stirring, dropwise adding the solution B into the suspension A at a certain speed by using a rubber head dropper, continuously stirring for a period of time, and standing for 24 hours; centrifuging at 4000rpm with a centrifuge, washing the solid with distilled water and anhydrous ethanol for 3 times, drying in a drying oven at 60 deg.C for 12 hr, and grinding to obtain powdered magnetic composite photocatalyst MnxZn1- xFe2O4/C/Zn0.8Cd0.2S。
Example 3
Magnetic zinc cadmium sulfide composite photocatalyst (Mn)xZn1-xFe2O4/C/Zn0.8Cd0.2S) the preparation method comprises the following specific steps:
(1)MnxZn1-xFe2O4preparation of/C
The same as in (1) in example 1.
(2) Magnetic composite photocatalyst MnxZn1-xFe2O4/C/Zn0.8Cd0.2Preparation of S
According to the molar ratio n (Zn)2+):n(Cd2+):n(S2-) Weighing appropriate amount of Zn (Ac) 0.8:0.2:1.252·2H2O and Cd (Ac)2·2H2Dissolving O, ultrasonic into 40mL deionized water, adding Zn generated theoretically0.8Cd0.2Mn with S mass ratio of 15:100xZn1-xFe2O4Performing mechanical stirring for 30min to obtain suspension A; 0.9g of Na was weighed2S·9H2Dissolving O in 40mL of deionized water by ultrasonic wave to obtain a solution B; under the condition of continuous stirring, dropwise adding the solution B into the suspension A at a certain speed by using a rubber head dropper, continuously stirring for a period of time, and standing for 24 hours; centrifuging at 4000rpm with a centrifuge, washing the solid with distilled water and anhydrous ethanol for 3 times, drying in a drying oven at 60 deg.C for 12 hr, and grinding to obtain powdered magnetic composite photocatalyst MnxZn1- xFe2O4/C/Zn0.8Cd0.2S。
Example 4
Magnetic zinc cadmium sulfide composite photocatalyst (Mn)xZn1-xFe2O4/C/Zn0.8Cd0.2S) the preparation method comprises the following specific steps:
(1)MnxZn1-xFe2O4preparation of/C
The same as in (1) in example 1.
(2) Magnetic composite photocatalyst MnxZn1-xFe2O4/C/Zn0.8Cd0.2Preparation of S
According to the molar ratio n (Zn)2+):n(Cd2+):n(S2-) Weighing appropriate amount of Zn (Ac) 0.8:0.2:1.252·2H2O and Cd (Ac)2·2H2Dissolving O, ultrasonic into 40mL deionized water, adding Zn generated theoretically0.8Cd0.2Mn with S mass ratio of 20:100xZn1-xFe2O4Performing mechanical stirring for 30min to obtain suspension A; 0.9g of Na was weighed2S·9H2Dissolving O in 40mL of deionized water by ultrasonic wave to obtain a solution B; under the condition of continuous stirring, dropwise adding the solution B into the suspension A at a certain speed by using a rubber head dropper, continuously stirring for a period of time, and standing for 24 hours; centrifuging at 4000rpm with a centrifuge, washing the solid with distilled water and anhydrous ethanol for 3 times, drying in a drying oven at 60 deg.C for 12 hr, and grinding to obtain powdered magnetic composite photocatalyst MnxZn1- xFe2O4/C/Zn0.8Cd0.2S。
Example 5
Magnetic zinc cadmium sulfide composite photocatalyst (Mn)xZn1-xFe2O4/C/Zn0.8Cd0.2S) the preparation method comprises the following specific steps:
(1)MnxZn1-xFe2O4preparation of/C
The same as in (1) in example 1.
(2) Magnetic composite photocatalyst MnxZn1-xFe2O4/C/Zn0.8Cd0.2Preparation of S
According to the molar ratio n (Zn)2+):n(Cd2+):n(S2-) Weighing appropriate amount of Zn (Ac) 0.8:0.2:1.252·2H2O and Cd (Ac)2·2H2Dissolving O, ultrasonic into 40mL deionized water, adding Zn generated theoretically0.8Cd0.2Mn with S mass ratio of 25:100xZn1-xFe2O4Performing mechanical stirring for 30min to obtain suspension A; 0.9g of Na was weighed2S·9H2Dissolving O in 40mL of deionized water by ultrasonic,obtaining a solution B; under the condition of continuous stirring, dropwise adding the solution B into the suspension A at a certain speed by using a rubber head dropper, continuously stirring for a period of time, and standing for 24 hours; centrifuging at 4000rpm with a centrifuge, washing the solid with distilled water and anhydrous ethanol for 3 times, drying in a drying oven at 60 deg.C for 12 hr, and grinding to obtain powdered magnetic composite photocatalyst MnxZn1- xFe2O4/C/Zn0.8Cd0.2S。
Results of the experiment
Magnetic composite photocatalyst Mn prepared in example 4xZn1-xFe2O4/C/Zn0.8Cd0.2The catalytic degradation activity of S is optimal. For convenience of comparison, Zn was prepared0.8Cd0.2And (5) sampling S. Zn0.8Cd0.2S preparation method is that Mn is not added in the step (2) of example 4xZn1-xFe2O4/C。
Zn0.8Cd0.2As shown in fig. 1(b), the X-ray diffraction pattern of S has diffraction peaks at 26.57 °, 44.67 °, and 54.61 ° respectively, and the diffraction peaks are gradually shifted from the diffraction peak of CdS having a face-centered cubic structure to a high angle, and correspond to the (111), (220), and (311) crystal planes respectively.
MnxZn1-xFe2O4The X-ray diffraction pattern of/C is shown in FIG. 1(C), and the diffraction peak position, intensity and Mn thereofxZn1-xFe2O4The basic agreement shows that the coating carbon layer does not affect MnxZn1-xFe2O4A crystal structure.
MnxZn1-xFe2O4/C/Zn0.8Cd0.2The X-ray diffraction pattern of S is shown in FIG. 1(a), and three strong diffraction peaks correspond to Zn0.8Cd0.2The crystal planes (111), (220) and (311) of S simultaneously have a smaller diffraction peak at the position of 35.2 degrees 2 theta, and can be matched with MnxZn1-xFe2O4The (311) crystal face corresponding to the highest peak of/C is matched. Indicates MnxZn1-xFe2O4C and Zn0.8Cd0.2S is successfully compounded, diffraction peaks can be matched with respective diffraction peaks, and the diffraction peaks are not mutually influenced, so that the active ingredients of the photocatalyst are effectively ensured.
Zn0.8Cd0.2The SEM scan of S is shown in FIG. 2(a), which is formed by aggregating small particles with a much smaller particle size than MnxZn1-xFe2O4Particle size of/C. MnxZn1-xFe2O4And MnxZn1-xFe2O4SEM scans of/C are shown in FIG. 2(b) and FIG. 2(C), respectively, both of which are formed by irregular particle agglomeration, and MnxZn1-xFe2O4the/C surface is significantly altered by coating with a carbon layer, indicating MnxZn1-xFe2O4Successful preparation of/C.
MnxZn1-xFe2O4/C Zn0.8Cd0.2The SEM scan of (B) is shown in FIG. 2(d), and it can be seen that Mn is presentxZn1-xFe2O4Zn with small particles distributed on the surface of/C large particles0.8Cd0.2And (3) S solid solution. The result of analysis from SEM image showed MnxZn1- xFe2O4/C/Zn0.8Cd0.2S forms MnxZn1-xFe2O4C and Zn0.8Cd0.2S layer structure, Zn0.8Cd0.2S successfully loaded to MnxZn1-xFe2O4The surface of/C.
MnxZn1-xFe2O4、MnxZn1-xFe2O4C and MnxZn1-xFe2O4/C/Zn0.8Cd0.2The hysteresis loops of S are shown in FIG. 3, their saturation magnetizations (Ms) are 66.10, 30.82 and 4.19emu/g, respectively, and the magnitude of the saturation magnetization is mainly related to the magnetic material MnxZn1-xFe2O4The content of (A) is related to; mnxZn1-xFe2O4/C/Zn0.8Cd0.2The saturation magnetization of S meets the requirement of the composite magnetic photocatalyst on magnetic recovery, and Mn dispersed in the aqueous solutionxZn1-xFe2O4/C/Zn0.8Cd0.2S can be quickly adsorbed and recovered by a magnet, which shows that the composite magnetic photocatalyst MnxZn1-xFe2O4/C/Zn0.8Cd0.2S has good magnetic property, is favorable for recycling and avoids secondary pollution.
The photocatalysis result shows that under the irradiation of a simulated sunlight xenon lamp, 0.1g of the prepared magnetic composite photocatalyst degrades 100mL of rhodamine B solution with the concentration of 10mg/L, the degradation rate of 90min reaches 92.6%, the magnetic recovery of the photocatalyst is repeatedly used under an external magnetic field, and the degradation rate is 86.9% after 5 times, which indicates that the magnetic composite photocatalyst Mn prepared by the invention is degraded by adopting the methodxZn1-xFe2O4/C/Zn0.8Cd0.2S has higher photocatalytic activity and stable magnetic recovery performance.

Claims (2)

1. Magnetic zinc-cadmium sulfide composite photocatalyst MnxZn1-xFe2O4/C/Zn0.8Cd0.2The preparation method of S comprises the following specific steps:
(1)MnxZn1-xFe2O4preparation of/C
According to the mol ratio of MnO to ZnO to Fe2O3Weighing certain amount of MnSO (respectively) 32.8:13.3:53.94·H2O、ZnSO4·7H2O and Fe2(SO4)3Adding a certain amount of deionized water, and fully stirring to obtain a uniform mixed solution; weighing a certain amount of NaOH as a precipitator to prepare NaOH solution with the concentration of 2 mol/L; slowly dripping NaOH solution into the mixed solution under magnetic stirring, quickly dripping NaOH solution when brown flocculent precipitate is generated in the solution, adjusting the pH value to 13, and continuously stirring for 20 min; transferring the stirred solution into a 100mL reaction kettle, and heating and reacting for 5h in an oven at 200 ℃; after the hydrothermal reaction is finished, taking out the mixture, standing the mixture, cooling the mixture to room temperature, and externally applying magnetismRepeatedly cleaning the sample with distilled water and anhydrous ethanol under the action of iron, drying in an oven at 60 deg.C for 12 hr, and grinding to obtain powdered MnxZn1-xFe2O4A sample;
weighing 3g of glucose, and ultrasonically dissolving the glucose into 30mL of deionized water to obtain a glucose solution with the concentration of 0.5 mol/L; 0.2g of Mn prepared was weighedxZn1-xFe2O4Adding the powder into the solution and stirring vigorously for 1 h; then transferring the solution into a 50mL reaction kettle, and heating the solution in an oven at 180 ℃ for 5 hours; cooling to room temperature, washing with distilled water and anhydrous ethanol repeatedly by using an additional magnet, drying in an oven at 60 deg.C for 12 hr, and grinding to obtain powdered MnxZn1-xFe2O4a/C sample;
(2) magnetic composite photocatalyst MnxZn1-xFe2O4/C/Zn0.8Cd0.2Preparation of S
According to the molar ratio Zn2+:Cd2+:S2-Weighing appropriate amount of Zn (Ac) 0.8:0.2:1.252·2H2O and Cd (Ac)2·2H2Dissolving O, ultrasonic into 40mL deionized water, adding Zn generated theoretically0.8Cd0.2Mn with an S mass ratio of 5-25: 100xZn1- xFe2O4Performing mechanical stirring for 30min to obtain suspension A; 0.9g of Na was weighed2S·9H2Dissolving O in 40mL of deionized water by ultrasonic wave to obtain a solution B; under the condition of continuous stirring, dropwise adding the solution B into the suspension A at a certain speed by using a rubber head dropper, continuously stirring for a period of time, and standing for 24 hours; centrifuging at 4000rpm with a centrifuge, washing the solid with distilled water and anhydrous ethanol for 3 times, drying in a drying oven at 60 deg.C for 12 hr, and grinding to obtain powdered magnetic composite photocatalyst MnxZn1-xFe2O4/C/Zn0.8Cd0.2S。
2. The preparation method of the magnetic zinc-cadmium sulfide composite photocatalyst according to claim 1, characterized in that the preparation is carried out by a dip precipitation method, so that effective compounding of the magnetic matrix carbon-coated manganese-zinc ferrite and the active component zinc-cadmium sulfide is realized.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114082437A (en) * 2021-12-10 2022-02-25 郑州大学 Preparation method of composite catalyst for hydrogen production by photolysis of water

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101940933A (en) * 2010-07-30 2011-01-12 武汉理工大学 Preparation method for visible light photocatalyst prepared by CdS quantum dot sensitization Zn1-xCdxs and photodecomposition of water into hydrogen
CN102350365A (en) * 2011-08-16 2012-02-15 淮阴师范学院 Synthesis method of CdS-attapulgite photoelectric composite material
CN103464173A (en) * 2013-09-25 2013-12-25 聊城大学 Preparation method of cadmium sulfide/ferroferric oxide composite material
CN103785476A (en) * 2014-01-15 2014-05-14 江苏大学 Preparation method of surface imprinting CdS compound photocatalyst based on magnetic carbon material
CN104275196A (en) * 2014-10-24 2015-01-14 浙江师范大学 Ferroferric oxide/carbon/cadmium sulfide composite nano material and preparation method thereof
CN106111211A (en) * 2016-06-25 2016-11-16 董晓 A kind of modified core shell structure Fe3o4/ C/TiO2the preparation method of composite
CN107790160A (en) * 2017-10-30 2018-03-13 中国科学院理化技术研究所 A kind of method of phosphorus doping zinc-cadmium sulfide solid solution catalyst, photocatalytic system and hydrogen production by water decomposition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101940933A (en) * 2010-07-30 2011-01-12 武汉理工大学 Preparation method for visible light photocatalyst prepared by CdS quantum dot sensitization Zn1-xCdxs and photodecomposition of water into hydrogen
CN102350365A (en) * 2011-08-16 2012-02-15 淮阴师范学院 Synthesis method of CdS-attapulgite photoelectric composite material
CN103464173A (en) * 2013-09-25 2013-12-25 聊城大学 Preparation method of cadmium sulfide/ferroferric oxide composite material
CN103785476A (en) * 2014-01-15 2014-05-14 江苏大学 Preparation method of surface imprinting CdS compound photocatalyst based on magnetic carbon material
CN104275196A (en) * 2014-10-24 2015-01-14 浙江师范大学 Ferroferric oxide/carbon/cadmium sulfide composite nano material and preparation method thereof
CN106111211A (en) * 2016-06-25 2016-11-16 董晓 A kind of modified core shell structure Fe3o4/ C/TiO2the preparation method of composite
CN107790160A (en) * 2017-10-30 2018-03-13 中国科学院理化技术研究所 A kind of method of phosphorus doping zinc-cadmium sulfide solid solution catalyst, photocatalytic system and hydrogen production by water decomposition

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHIH-CHIEH CHAN ET AL.: ""Efficient and stable photocatalytic hydrogen production from water splitting over ZnxCd1-xS solid solutions under visible light irradiation"", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 *
黄华等: ""新型磁性Mn0.6Zn0.4Fe2O4@CdS纳米复合光催化剂的制备及其吸附和光催化特性"", 《环境科学学报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114082437A (en) * 2021-12-10 2022-02-25 郑州大学 Preparation method of composite catalyst for hydrogen production by photolysis of water

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