技术领域technical field
本发明属于光催化、环境保护技术领域，具体涉及到一种磁性Fe3O4/ZnO/g-C3N4复合纳米粒光催化剂的制备方法。The invention belongs to the technical fields of photocatalysis and environmental protection, and in particular relates to a method for preparing a magneticFe3O4/ ZnO/gC3N4 composite nanoparticle photocatalyst.
背景技术Background technique
近年来，很多工业(如纺织、印染等)有机废水严重地影响了生态环境以及人们的身体健康。应用半导体光催化技术，在太阳光或紫外光源的照射下，可以有效的将有机废水中的有害物质转化成CO2、水等无害物质，从而达到治理废水的目的。因此，应用半导体光催化技术净化废水越来越多的引起人们的关注。In recent years, many industrial (such as textile, printing and dyeing, etc.) organic wastewater has seriously affected the ecological environment and people's health. Applying semiconductor photocatalysis technology, under the irradiation of sunlight or ultraviolet light source, can effectively convert harmful substances in organic wastewater into CO2 , water and other harmless substances, so as to achieve the purpose of treating wastewater. Therefore, the application of semiconductor photocatalytic technology to purify wastewater has attracted more and more attention.
ZnO是一种应用十分广泛的半导体材料。ZnO亦是一种重要半导体光催化剂，其室温下禁带宽度为3.37eV。ZnO在紫外光照射下，产生高活性的空穴能将有机污染物分解成无二次污染的产物(如CO2、H2O)，从而达到除污目的。然而，ZnO只在紫外光区域被光子激发，这就限制了ZnO在的实际应用。与氧化锌相比，g-C3N4具有较窄的禁带宽度(2.2e V)，对可见光区域响应，具有原料低廉、热稳定性好以及易制备等特点。将ZnO与g-C3N4复合，由于g-C3N4与ZnO能带匹配，有利于提高载流子的分离效率，能够有效提高了有机污染物的降解效率。并且扩大了光响应范围，提高了对太阳光的利用率。ZnO is a widely used semiconductor material. ZnO is also an important semiconductor photocatalyst with a band gap of 3.37eV at room temperature. Under the irradiation of ultraviolet light, ZnO generates highly active holes, which can decompose organic pollutants into non-secondary pollution products (such as CO2 , H2 O), so as to achieve the purpose of decontamination. However, ZnO is only excited by photons in the ultraviolet region, which limits the practical application of ZnO. Compared with zinc oxide, gC3 N4 has a narrower band gap (2.2e V), responds to visible light region, has the characteristics of low raw material, good thermal stability and easy preparation. Combining ZnO with gC3 N4 , because the energy bands of gC3 N4 and ZnO match, is conducive to improving the separation efficiency of carriers, and can effectively improve the degradation efficiency of organic pollutants. Moreover, the light response range is expanded, and the utilization rate of sunlight is improved.
用于有机废水处理光催化剂主要是粉末产品。粉末状的光催化剂在使用后存在难以与溶液分离以及难以循环使用等问题，这些缺点在一定程度上限制了它的实际应用。因此，将g-C3N4、ZnO与磁性g-C3N4复合，复合后的光催化剂可在外加磁场的作用下进行快速回收，防止光催化剂在实际应用中对水体造成二次污染。目前，制备Fe3O4/ZnO/g-C3N4复合的方法主要先采用热解法制备g-C3N4，再利用超声分散、水热法、回流法、固相法等方法制备Fe3O4/ZnO/g-C3N4复合材料。这些制备方法存在成本高，形貌尺寸难以控制等缺点，更重要的是难以大规模制备。实践证明，光催化剂的微观形态结构对其性能起着至关重要的作用。因此，发展一种工艺简单，适合大规模生产、且形貌可控的制备Fe3O4/ZnO/g-C3N4方法在光催化领域的应用具有重要意义。Photocatalysts used for organic wastewater treatment are mainly powder products. Powdered photocatalysts are difficult to separate from the solution and difficult to recycle after use, and these shortcomings limit its practical application to a certain extent. Therefore, gC3 N4 , ZnO and magnetic gC3 N4 are compounded, and the compounded photocatalyst can be quickly recovered under the action of an external magnetic field, preventing the photocatalyst from causing secondary pollution to water in practical applications. At present, the method of preparing Fe3 O4 /ZnO/gC3 N4 composite mainly adopts pyrolysis method to prepare gC3 N4 , and then uses methods such as ultrasonic dispersion, hydrothermal method, reflux method, and solid phase method to prepare Fe3 O4 /ZnO/gC3 N4 composites. These preparation methods have the disadvantages of high cost, difficulty in controlling the shape and size, and more importantly, it is difficult to prepare on a large scale. Practice has proved that the micro-morphological structure of photocatalysts plays a crucial role in its performance. Therefore, it is of great significance to develop a method for preparing Fe3 O4 /ZnO/gC3 N4 with simple process, suitable for large-scale production, and controllable morphology in the field of photocatalysis.
发明内容Contents of the invention
本发明针对现有制备技术的缺点，提供一种磁性Fe3O4/ZnO/g-C3N4复合纳米粒光催化剂的制备方法。该方法所用的化学试剂廉价，合成条件温和，制备工艺简单；采用化学沉淀法，在Fe3O4和ZnO纳米粒子存在下，一步合成了磁性Fe3O4/ZnO/g-C3N4复合光催化剂；制备的磁性Fe3O4/ZnO/g-C3N4复合物不会引入杂质、纯度高，使用方便，且利于回收及重复使用。Aiming at the shortcomings of the existing preparation technology, the invention provides a preparation method of magnetic Fe3 O4 /ZnO/gC3 N4 composite nanoparticle photocatalyst. The chemical reagents used in this method are cheap, the synthesis conditions are mild, and the preparation process is simple; the magnetic Fe3 O4 /ZnO/gC3 N4 composite optical fiber was synthesized in one step by chemical precipitation method in the presence of Fe3 O4 and ZnO nanoparticles. Catalyst; the prepared magnetic Fe3 O4 /ZnO/gC3 N4 composite does not introduce impurities, has high purity, is convenient to use, and is beneficial to recovery and repeated use.
本发明提供了一种磁性Fe3O4/ZnO/g-C3N4复合纳米颗粒光催化剂的制备方法，具体步骤如下：The invention provides a method for preparing a magnetic Fe3 O4 /ZnO/gC3 N4 composite nanoparticle photocatalyst, the specific steps are as follows:
1)称取10g CO(NH2)2置于坩埚中，将其在管式电炉中以5度/分钟的升温速率升温到550度，保温2小时，冷却后制备出g-C3N4纳米片。1) Weigh 10g CO(NH2 )2 and place it in a crucible, heat it up to 550°C at a heating rate of 5°C/min in a tube electric furnace, keep it warm for 2 hours, and prepare gC3 N4 nanosheets after cooling .
2)称取3mmol Zn(NO3)2·6H2O溶解于30mL去离子水中,称取6mmol NH4HCO3溶解于60mL去离子水中，将NH4HCO3溶液加入Zn(NO3)2·6H2O溶液中磁力搅拌15min，离心洗涤干燥后，在管式电炉中以400℃温度煅烧2小时。制备出ZnO纳米片。2) Weigh 3mmol Zn(NO3 )2 ·6H2 O and dissolve in 30mL deionized water, weigh 6mmol NH4 HCO3 and dissolve in 60mL deionized water, add the NH4 HCO3 solution to Zn(NO3 )2 · Magnetically stirred in 6H2 O solution for 15 minutes, washed and dried by centrifugation, and calcined in a tube electric furnace at 400°C for 2 hours. ZnO nanosheets were prepared.
4)称取10mmol FeCl3·6H2O和5mmol FeCl2·4H2O溶解于150mL去离子水中，在55℃温度下搅拌40min。加入100mL NH3·H2O滴至溶液中。搅拌1小时后，制得红褐色悬浮液。经磁力分离，洗涤，干燥后制备出Fe3O4纳米球。4) Dissolve 10 mmol FeCl3 ·6H2 O and 5 mmol FeCl2 ·4H2 O in 150 mL deionized water, and stir at 55° C. for 40 min. Add 100 mL of NH3 ·H2 O dropwise into the solution. After stirring for 1 hour, a red-brown suspension was obtained. After magnetic separation, washing and drying, Fe3 O4 nanospheres were prepared.
5)分别称取0.5g Fe3O4和0.5g ZnO以及0.03～0.09g(优选0.07g)g-C3N4，将Fe3O4和ZnO加入浓度分别为0.6～1.8mg/mL的50mL g-C3N4甲醇溶液；混合后进行搅拌，收集搅拌后的样品。样品在真空中干燥。制备出Fe3O4/ZnO/g-C3N4复合纳米粒。5) Weigh 0.5g Fe3 O4 and 0.5g ZnO and 0.03-0.09g (preferably 0.07g) gC3 N4 respectively, add Fe3 O4 and ZnO to 50mL gC with concentrations of 0.6-1.8mg/mL3 N4 methanol solution; mix and stir, collect stirred sample. The samples were dried in vacuo. Fe3 O4 /ZnO/gC3 N4 composite nanoparticles were prepared.
本发明的有益效果：Beneficial effects of the present invention:
1、本发明采用化学沉淀法，在Fe3O4和ZnO纳米粒子存在下，一步合成了磁性Fe3O4/ZnO/g-C3N4复合纳米颗粒光催化剂。制备工艺简单，尺寸均匀，所用试剂低廉。1. The present invention uses a chemical precipitation method to synthesize a magnetic Fe3 O4 /ZnO/gC3 N4 composite nanoparticle photocatalyst in one step in the presence of Fe3 O4 and ZnO nanoparticles. The preparation process is simple, the size is uniform, and the reagents used are cheap.
2、磁性Fe3O4/ZnO/g-C3N4复合纳米粒的异质结，不但抑制了光生载流子的复合，也扩大了光催化剂的光响应范围，很大程度提高了可见光的利用率。2. The heterojunction of magnetic Fe3 O4 /ZnO/gC3 N4 composite nanoparticles not only inhibits the recombination of photogenerated carriers, but also expands the photoresponse range of photocatalysts, greatly improving the utilization of visible light Rate.
3、本发明所得磁性Fe3O4/ZnO/g-C3N4复合纳米粒光催化剂在可见光下具有较高的活性，在光催化降解有机染料时具有使用方便、利于回收、可重复使用等优点，120min罗丹明-B降解效率可达到97.3％以上。3. The magnetic Fe3 O4 /ZnO/gC3 N4 composite nanoparticle photocatalyst obtained in the present invention has high activity under visible light, and has the advantages of convenient use, favorable recovery, and reusability when photocatalytically degrading organic dyes. , 120min rhodamine-B degradation efficiency can reach more than 97.3%.
附图说明Description of drawings
图1为本发明实施例1～4所得产物的X射线衍射(XRD)谱图。Fig. 1 is the X-ray diffraction (XRD) spectrogram of the product obtained in Examples 1-4 of the present invention.
图2为本发明实施例1～4所得产物的X射线衍射(XRD)谱图。Fig. 2 is the X-ray diffraction (XRD) spectrogram of the products obtained in Examples 1-4 of the present invention.
图3为本发明实施例1～4所得产物的红外光谱分析(FT-IR)谱图。Fig. 3 is the infrared spectroscopic analysis (FT-IR) spectrogram of the products obtained in Examples 1-4 of the present invention.
图4为本发明实施例1所得产物的透射电镜(TEM)照片。Fig. 4 is a transmission electron microscope (TEM) photograph of the product obtained in Example 1 of the present invention.
图5为本发明实施例1～4所得产物随反应时间变化的RhB浓度曲线。Fig. 5 is the RhB concentration curve of the products obtained in Examples 1-4 of the present invention as a function of reaction time.
具体实施方式Detailed ways
实施例1Example 1
1)称取10g CO(NH2)2置于坩埚中，将其在管式电炉中以5度/分钟的升温速率升温到550度，保温2小时，冷却后制备出g-C3N4纳米片。1) Weigh 10g CO(NH2 )2 and place it in a crucible, heat it up to 550°C at a heating rate of 5°C/min in a tube electric furnace, keep it warm for 2 hours, and prepare gC3 N4 nanosheets after cooling .
2)称取3mmol Zn(NO3)2·6H2O溶解于30mL去离子水中,称取6mmol NH4HCO3溶解于60mL去离子水中，将NH4HCO3溶液加入Zn(NO3)2·6H2O溶液中磁力搅拌15min，离心洗涤干燥后，在管式电炉中以400℃温度煅烧2小时。制备出ZnO纳米片。2) Weigh 3mmol Zn(NO3 )2 ·6H2 O and dissolve in 30mL deionized water, weigh 6mmol NH4 HCO3 and dissolve in 60mL deionized water, add the NH4 HCO3 solution to Zn(NO3 )2 · Magnetically stirred in 6H2 O solution for 15 minutes, washed and dried by centrifugation, and calcined in a tube electric furnace at 400°C for 2 hours. ZnO nanosheets were prepared.
4)称取10mmol FeCl3·6H2O和5mmol FeCl2·4H2O溶解于150mL去离子水中，在55℃温度下搅拌40min。加入100mL NH3·H2O滴至溶液中。搅拌1小时后，制得红褐色悬浮液。经磁力分离，洗涤，干燥后制备出Fe3O4纳米球。4) Dissolve 10 mmol FeCl3 ·6H2 O and 5 mmol FeCl2 ·4H2 O in 150 mL deionized water, and stir at 55° C. for 40 min. Add 100 mL of NH3 ·H2 O dropwise into the solution. After stirring for 1 hour, a red-brown suspension was obtained. After magnetic separation, washing and drying, Fe3 O4 nanospheres were prepared.
5)分别称取0.5g Fe3O4和ZnO以及0.07g g-C3N4，将Fe3O4和ZnO加入50mLg-C3N4甲醇溶液中。混合后进行搅拌，收集搅拌后的样品。样品在真空中干燥。制备出Fe3O4/ZnO/g-C3N4复合纳米粒。5) Weigh 0.5g Fe3 O4 and ZnO and 0.07g gC3 N4 respectively, and add Fe3 O4 and ZnO into 50mL g-C3 N4 methanol solution. Stirring is performed after mixing, and samples after stirring are collected. The samples were dried in vacuo. Fe3 O4 /ZnO/gC3 N4 composite nanoparticles were prepared.
实施例2Example 2
1)称取10g CO(NH2)2置于坩埚中，将其在管式电炉中以5度/分钟的升温速率升温到550度，保温2小时，冷却后制备出g-C3N4纳米片。1) Weigh 10g CO(NH2 )2 and place it in a crucible, heat it up to 550°C at a heating rate of 5°C/min in a tube electric furnace, keep it warm for 2 hours, and prepare gC3 N4 nanosheets after cooling .
2)称取3mmol Zn(NO3)2·6H2O溶解于30mL去离子水中,称取6mmol NH4HCO3溶解于60mL去离子水中，将NH4HCO3溶液加入Zn(NO3)2·6H2O溶液中磁力搅拌15min，离心洗涤干燥后，在管式电炉中以400℃温度煅烧2小时。制备出ZnO纳米片。2) Weigh 3mmol Zn(NO3 )2 ·6H2 O and dissolve in 30mL deionized water, weigh 6mmol NH4 HCO3 and dissolve in 60mL deionized water, add the NH4 HCO3 solution to Zn(NO3 )2 · Magnetically stirred in 6H2 O solution for 15 minutes, washed and dried by centrifugation, and calcined in a tube electric furnace at 400°C for 2 hours. ZnO nanosheets were prepared.
4)称取10mmol FeCl3·6H2O和5mmol FeCl2·4H2O溶解于150mL去离子水中，在55℃温度下搅拌40min。加入100mL NH3·H2O滴至溶液中。搅拌1小时后，制得红褐色悬浮液。经磁力分离，洗涤，干燥后制备出Fe3O4纳米球。4) Dissolve 10 mmol FeCl3 ·6H2 O and 5 mmol FeCl2 ·4H2 O in 150 mL deionized water, and stir at 55° C. for 40 min. Add 100 mL of NH3 ·H2 O dropwise into the solution. After stirring for 1 hour, a red-brown suspension was obtained. After magnetic separation, washing and drying, Fe3 O4 nanospheres were prepared.
5)分别称取0.5g Fe3O4和ZnO以及0.03g g-C3N4，将Fe3O4和ZnO加入50mL g-C3N4甲醇溶液中。混合后进行搅拌，收集搅拌后的样品。样品在真空中干燥。制备出Fe3O4/ZnO/g-C3N4复合纳米粒。5) Weigh 0.5g Fe3 O4 and ZnO and 0.03g gC3 N4 respectively, and add Fe3 O4 and ZnO into 50mL gC3 N4 methanol solution. Stirring is performed after mixing, and samples after stirring are collected. The samples were dried in vacuo. Fe3 O4 /ZnO/gC3 N4 composite nanoparticles were prepared.
实施例3Example 3
1)称取10g CO(NH2)2置于坩埚中，将其在管式电炉中以5度/分钟的升温速率升温到550度，保温2小时，冷却后制备出g-C3N4纳米片。1) Weigh 10g CO(NH2 )2 and place it in a crucible, heat it up to 550°C at a heating rate of 5°C/min in a tube electric furnace, keep it warm for 2 hours, and prepare gC3 N4 nanosheets after cooling .
2)称取3mmol Zn(NO3)2·6H2O溶解于30mL去离子水中,称取6mmol NH4HCO3溶解于60mL去离子水中，将NH4HCO3溶液加入Zn(NO3)2·6H2O溶液中磁力搅拌15min，离心洗涤干燥后，在管式电炉中以400℃温度煅烧2小时。制备出ZnO纳米片。2) Weigh 3mmol Zn(NO3 )2 ·6H2 O and dissolve in 30mL deionized water, weigh 6mmol NH4 HCO3 and dissolve in 60mL deionized water, add the NH4 HCO3 solution to Zn(NO3 )2 · Magnetically stirred in 6H2 O solution for 15 minutes, washed and dried by centrifugation, and calcined in a tube electric furnace at 400°C for 2 hours. ZnO nanosheets were prepared.
4)称取10mmol FeCl3·6H2O和5mmol FeCl2·4H2O溶解于150mL去离子水中，在55℃温度下搅拌40min。加入100mL NH3·H2O滴至溶液中。搅拌1小时后，制得红褐色悬浮液。经磁力分离，洗涤，干燥后制备出Fe3O4纳米球。4) Dissolve 10 mmol FeCl3 ·6H2 O and 5 mmol FeCl2 ·4H2 O in 150 mL deionized water, and stir at 55° C. for 40 min. Add 100 mL of NH3 ·H2 O dropwise into the solution. After stirring for 1 hour, a red-brown suspension was obtained. After magnetic separation, washing and drying, Fe3 O4 nanospheres were prepared.
5)分别称取0.5g Fe3O4和ZnO以及0.05g g-C3N4，将Fe3O4和ZnO加入50mL g-C3N4甲醇溶液中。混合后进行搅拌，收集搅拌后的样品。样品在真空中干燥。制备出Fe3O4/ZnO/g-C3N4复合纳米粒。5) Weigh 0.5g Fe3 O4 and ZnO and 0.05g gC3 N4 respectively, and add Fe3 O4 and ZnO into 50mL gC3 N4 methanol solution. Stirring is performed after mixing, and samples after stirring are collected. The samples were dried in vacuo. Fe3 O4 /ZnO/gC3 N4 composite nanoparticles were prepared.
实施例4Example 4
1)称取10g CO(NH2)2置于坩埚中，将其在管式电炉中以5度/分钟的升温速率升温到550度，保温2小时，冷却后制备出g-C3N4纳米片。1) Weigh 10g CO(NH2 )2 and place it in a crucible, heat it up to 550°C at a heating rate of 5°C/min in a tube electric furnace, keep it warm for 2 hours, and prepare gC3 N4 nanosheets after cooling .
2)称取3mmol Zn(NO3)2·6H2O溶解于30mL去离子水中,称取6mmol NH4HCO3溶解于60mL去离子水中，将NH4HCO3溶液加入Zn(NO3)2·6H2O溶液中磁力搅拌15min，离心洗涤干燥后，在管式电炉中以400℃温度煅烧2小时。制备出ZnO纳米片。2) Weigh 3mmol Zn(NO3 )2 ·6H2 O and dissolve in 30mL deionized water, weigh 6mmol NH4 HCO3 and dissolve in 60mL deionized water, add the NH4 HCO3 solution to Zn(NO3 )2 · Magnetically stirred in 6H2 O solution for 15 minutes, washed and dried by centrifugation, and calcined in a tube electric furnace at 400°C for 2 hours. ZnO nanosheets were prepared.
4)称取10mmol FeCl3·6H2O和5mmol FeCl2·4H2O溶解于150mL去离子水中，在55℃温度下搅拌40min。加入100mL NH3·H2O滴至溶液中。搅拌1小时后，制得红褐色悬浮液。经磁力分离，洗涤，干燥后制备出Fe3O4纳米球。4) Dissolve 10 mmol FeCl3 ·6H2 O and 5 mmol FeCl2 ·4H2 O in 150 mL deionized water, and stir at 55° C. for 40 min. Add 100 mL of NH3 ·H2 O dropwise into the solution. After stirring for 1 hour, a red-brown suspension was obtained. After magnetic separation, washing and drying, Fe3 O4 nanospheres were prepared.
5)分别称取0.5g Fe3O4和ZnO以及0.09g g-C3N4，将Fe3O4和ZnO加入50mL g-C3N4甲醇溶液中。混合后进行搅拌，收集搅拌后的样品。样品在真空中干燥。制备出Fe3O4/ZnO/g-C3N4复合纳米粒。5) Weigh 0.5g Fe3 O4 and ZnO and 0.09g gC3 N4 respectively, and add Fe3 O4 and ZnO into 50mL gC3 N4 methanol solution. Stirring is performed after mixing, and samples after stirring are collected. The samples were dried in vacuo. Fe3 O4 /ZnO/gC3 N4 composite nanoparticles were prepared.
由图1和图2所示：实施例1-4所得产物ZnO和Fe3O4的XRD谱图与标准卡片(JCPDS36-1451)和(JCPDS 65-3107)的衍射峰位相吻合。g-C3N4的衍射峰的峰位也与其特征峰吻合。实施例1-4所得Fe3O4/ZnO/g-C3N4复合纳米粒的XRD谱图中未发现其他衍射峰，这说明Fe3O4和g-C3N4的引入没有改变ZnO的晶形。没有明显g-C3N4衍射峰，可能是由于其分散性较好或者是结晶度低所致。As shown in Figure 1 and Figure 2: the XRD spectra of the products ZnO and Fe3 O4 obtained in Examples 1-4 are consistent with the diffraction peaks of the standard cards (JCPDS36-1451) and (JCPDS 65-3107). The peak position of the diffraction peak of gC3 N4 is also consistent with its characteristic peak. No other diffraction peaks were found in the XRD spectrum of Fe3 O4 /ZnO/gC3 N4 composite nanoparticles obtained in Examples 1-4, which indicated that the introduction of Fe3 O4 and gC3 N4 did not change the crystal form of ZnO. There is no obvious gC3 N4 diffraction peak, which may be due to its good dispersion or low crystallinity.
为了进一步确认g-C3N4在复合材料中的存在，对实施例1-4所得产物进行了红外光谱分析谱图。如图3所示：位于3435cm-1的吸收峰是由O-H拉伸引起的。这可能是由于水吸附在样品表面造成的。位于1232cm-1、1326cm-1、1406cm-1、1575cm-1和1645cm-1的吸收峰对应g-C3N4的C-N杂环的拉伸模式。位于810cm-1的吸收峰是由g-C3N4的s-三嗪单元的典型弯曲振动引起的。位于500cm-1和599cm-1，这是由于Zn-O和Fe-O的振动引起的。说明所制备的样品是Fe3O4/ZnO/g-C3N4复合材料。In order to further confirm the existence of gC3 N4 in the composite material, infrared spectroscopic analysis was carried out on the spectrograms of the products obtained in Examples 1-4. As shown in Figure 3: the absorption peak located at 3435cm-1 is caused by OH stretching. This may be due to water adsorption on the sample surface. The absorption peaks at 1232cm-1 , 1326cm-1 , 1406cm-1 , 1575cm-1 and 1645cm-1 correspond to the stretching mode of the CN heterocycle of gC3 N4 .The absorption peak located at 810 cm is caused by the typical bending vibration of the s- triazine unit ofgC3N4 . Located at 500cm-1 and 599cm-1 , this is due to the vibration of Zn-O and Fe-O. It shows that the prepared sample is Fe3 O4 /ZnO/gC3 N4 composite material.
为了进一步验证Fe3O4/ZnO/g-C3N4复合光催化剂的结构，对本发明实施例1所得产物进行了透射电镜(TEM)表征。如图4所示：片状的g-C3N4由方片形ZnO和球形Fe3O4支撑，复合材料中ZnO和Fe3O4粒子的半径尺寸分别为18-20nm和10-15nm。这种结构表明了ZnO/g-C3N4异质结的形成,有利于提高载流子的分离效率，能够有效提高了有机污染物的降解效率。Fe3O4纳米粒子均匀的分布在复合材料中，对光催化剂的磁力快速回收起到了至关重要的作用。In order to further verify the structure of the Fe3 O4 /ZnO/gC3 N4 composite photocatalyst, the product obtained in Example 1 of the present invention was characterized by a transmission electron microscope (TEM). As shown in Figure 4: the flaky gC3 N4 is supported by square plate-shaped ZnO and spherical Fe3 O4 , and the radius sizes of ZnO and Fe3 O4 particles in the composite material are 18-20nm and 10-15nm, respectively. This structure shows that the formation of ZnO/gC3 N4 heterojunction is conducive to improving the separation efficiency of carriers and can effectively improve the degradation efficiency of organic pollutants. The uniform distribution of Fe3 O4 nanoparticles in the composite plays a vital role in the rapid magnetic recovery of the photocatalyst.
图5为本发明实施例1-4所得产物随反应时间变化的RhB浓度曲线。如图所示：罗丹明-B溶液浓度：5mg/L；可见光光源为250W的氙灯(波长λ≥400nm)反应时间为120min时，罗丹明-B的浓度仅为初始时的3.7％。Fig. 5 is the RhB concentration curve of the product obtained in Examples 1-4 of the present invention as a function of reaction time. As shown in the figure: Rhodamine-B solution concentration: 5mg/L; when the visible light source is a 250W xenon lamp (wavelength λ≥400nm) and the reaction time is 120min, the concentration of Rhodamine-B is only 3.7% of the initial value.
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