CN106423275A - 一种用于可见光降解水中抗生素的磁性复合材料 - Google Patents
一种用于可见光降解水中抗生素的磁性复合材料 Download PDFInfo
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
一种用于可见光降解水中抗生素的磁性复合材料及其制备方法与应用,其是将巯基乙酸改性的Fe3O4磁性纳米粒子添加到碱性MIL‑101(Cr)前驱体溶液中,得到磁性Fe3O4@MIL‑101(Cr)后,利用共沉淀法将AgBr‑Ag3PO4负载于所制备的Fe3O4@MIL‑101(Cr)上,得到目标产物Fe3O4@MIL‑101(Cr)@AgBr‑Ag3PO4。所得复合材料兼具磁性纳米粒子的磁特性及优异的可见光催化降解污染物的能力,可作为光催化材料应用于水相中抗生素的光降解去除,并可采用外加磁场实现材料的回收再利用。
Description
技术领域
本发明属于水处理领域,具体涉及一种用于可见光降解水中抗生素的磁性复合材料及其制备方法与应用。
背景技术
抗生素是由生物(包括微生物和高等动植物)在生活过程中所生产的具有抗病原体或其它活性的一类次级代谢产物,是能干扰其他生活细胞发育功能的有机物质。抗生素因被人类发现了其巨大功能,如抑制和杀灭细菌、霉菌、支原体等其他致病微生物,而开始被广泛地研究和应用。目前,抗生素不仅被用来治疗人类临床的各种疾病,如杀菌、消炎;而且也在畜牧业医疗救治中发挥了巨大的作用,如作为动物饲料添加剂和动物生长促进剂。但是,由于抗生素类药物具有稳定性、持久性等特点,以及其本身对细菌有较强的抑制作用,难于通过自然生物降解去除,容易产生积累,排放到环境中的抗生素有的会随着水进入土壤和沉积物中。抗生素过量积累会导致微生物抗药基因的产生,即使是在微量水平上的抗生素长期暴露,也会对生态环境和人体健康造成危害,与此同时,含抗生素的废水大量排放,会导致水体环境受到严重危害。
在各种环境净化方法中,光催化技术具有可以直接利用太阳光、在常温下反应、无二次污染等优点备受关注。近年来,AgBr分散在于Ag3PO4表面形成复合物AgBr-Ag3PO4光催化材料引起了大家的广泛关注,Ag3PO4的导带和价带电势低于AgBr导带和价带的电势,有利于光生电子和空穴对的有效分离,使得该类光催化材料对可见光具有很好的响应。
为了实现光催化材料的回收利用,研究人员将光催化材料与磁性纳米粒子(磁基体)结合制备磁性光催化材料,使其在保持较高的催化活性下,又具有一定的磁性,实现在外加磁场作用下的简单分离。而对于磁性光催化材料的研究通常是将具有光催化活性的组分分散于Fe3O4、Fe2O3及各种铁氧体(MFe2O4,其中M=Zn、Co、Ni、Ba、Sr等)上,但是这些磁基体的比表面积较小,因而所能结合的活性组分的量受到限制,磁基体表面的光催化活性组分也较易发生团聚,同时由于这些磁基体对水中的有机污染物的亲和力较弱,使得当有机污染物浓度较低时,活性组分与有机污染物的碰撞频率较低,限制了光催化反应的速率。因此,需要寻求一种更优异的磁基体用于制备磁性光催化材料,该类磁基体必须拥有发达的孔隙及较大的比表面积。
MIL-101(Cr)是由铬金属离子和有机配体对苯二甲酸组装而成的一种金属有机骨架材料,其不仅拥有较大的比表面积、孔径尺寸和孔体积,同时也对可见光具有一定的响应,并且该材料在水相中具有非比寻常的稳定性,使得其在水相中的应用及发展拥有巨大的潜力。因此若能获得磁性Fe3O4@MIL-101(Cr)材料,便可以满足上述对磁基体的要求。然而磁性Fe3O4@MIL-101(Cr)材料的制备面临着巨大的挑战,这主要是由于传统的MIL-101(Cr)是以氢氟酸作为矿化剂,在220℃、pH<2条件下合成的,而HF具有强的腐蚀性,将会对添加的Fe3O4形成破坏。
发明内容
为了解决上述存在的难题,本发明的目的在于提供一种用于可见光降解水中抗生素的磁性复合材料及其制备方法与应用。本发明制备方法简单,所得磁性复合材料兼具磁性纳米粒子的磁特性及优异的可见光催化降解污染物的能力,可作为光催化材料应用于水相中抗生素的光降解去除,并可采用外加磁场实现光催化材料的简单回收再利用。
为实现上述目的,本发明采用如下技术方案:
一种用于可见光降解水中抗生素的磁性复合材料,其为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4。
所述磁性复合材料是先采用巯基乙酸对Fe3O4磁性纳米粒子进行改性,然后将改性的Fe3O4磁性纳米粒子加入到MIL-101(Cr)前驱体溶液中,得到磁性Fe3O4@MIL-101(Cr),再在避光条件下,将所得磁性Fe3O4@MIL-101(Cr)与硝酸银、磷酸二氢钾、十六烷基三甲基溴化铵进行共沉淀反应,使AgBr、Ag3PO4共同负载在磁性Fe3O4@MIL-101(Cr)上制备而成;其制备具体步骤如下:
(1)改性Fe3O4磁性纳米粒子的制备
将2.5 mmol氯化铁溶解于40 mL乙二醇中形成清液,然后加入1.8 g无水乙酸钠、0.5 g聚乙二醇,搅拌溶解后转移至高压反应釜中,于200℃下反应8 h,利用磁铁分离反应产物并用无水乙醇和去离子水交替洗涤3~6次,60℃下真空干燥6~8 h,制得Fe3O4磁性纳米粒子;将1.25 g所得Fe3O4磁性纳米粒子加入到250 mL浓度为0.29 mmol/L的巯基乙酸乙醇溶液中搅拌24 h,产物采用磁铁分离并用去离子水和无水乙醇交替洗涤3~6次,60℃下真空干燥8~10h,即得到巯基乙酸改性的Fe3O4磁性纳米粒子;
(2)磁性Fe3O4@MIL-101(Cr)的制备
将5 mmol硝酸铬、5 mmol对苯二甲酸溶于25 mL去离子水中,然后加入1.29 mmol四甲基氢氧化铵,搅拌溶解20 min,再加入0.12~1.2 g步骤(1)得到的巯基乙酸改性的Fe3O4磁性纳米粒子进行超声混合,将混合物移入高压反应釜中,在180℃下反应18~24 h,产物利用磁铁进行分离,然后依次用N,N-二甲基甲酰胺、无水乙醇和去离子水分别于110℃、60℃、80℃回流纯化产物,再于100℃下真空干燥18~24 h,即获得磁性Fe3O4@MIL-101(Cr);
(3)Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4磁性复合材料的制备
将0.4 g步骤(2)所得磁性Fe3O4@MIL-101(Cr)溶于蒸馏水中并通过超声使其分散均匀,加入1.85~5.55 mmol硝酸银,在避光条件下搅拌1 h,然后逐滴加入0.46~1.39 mmol磷酸二氢钾,于避光条件下继续混合搅拌3 h,最后逐滴加入十六烷基三甲基溴化铵0.27~0.84 mmol,于避光条件下继续搅拌3 h,反应产物分别用去离子水、无水乙醇交替洗涤3~6次,经磁铁分离后于60℃下干燥12 h,即获得Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4磁性复合材料。
所述磁性复合材料兼具磁性纳米粒子的磁特性及优异的可见光催化降解污染物的能力,可用于可见光催化降解水中抗生素。
本发明的优点及技术效果在于:
本发明首先采用溶剂热法合成Fe3O4纳米粒子并利用巯基乙酸对其表面进行改性,然后将改性的Fe3O4磁性纳米粒子添加到碱性MIL-101(Cr)前驱体溶液中,通过简单的水热法原位制备磁性金属有机骨架材料Fe3O4@MIL-101(Cr),再采用共沉淀法将AgBr-Ag3PO4分散于Fe3O4@MIL-101(Cr)上,得到具有可见光响应的磁性光催化复合材料Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4。该复合材料兼具磁性纳米粒子的磁特性及优异的可见光催化降解污染物的能力,在降解水中抗生素后可采用外加磁场实现光催化材料的简单回收再利用。
附图说明
图1为Fe3O4、MIL-101(Cr)、Fe3O4@MIL-101(Cr)和Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4和AgBr-Ag3PO4的XRD图。
图2为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4的XPS图。
图3为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4的TEM图。
图4为Fe3O4、AgBr-Ag3PO4和Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4的UV-Vis DRS图。
图5为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4的磁滞回曲线图(A)和磁分离效果图(B)。
图6为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4在不同pH下对土霉素的降解效果图。
图7为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4在不同pH下对氧氟沙星的降解效果图。
图8为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4对土霉素降解效果的高效液相色谱图。
图9为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4对氧氟沙星降解效果的高效液相色谱图。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1:磁性复合材料Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4的制备,包括如下步骤:
(1)改性Fe3O4磁性纳米粒子的制备
将0.675 g氯化铁(Fe3Cl3·6H2O)溶解于40 mL乙二醇中形成清液,然后加入1.8 g无水乙酸钠、0.5 g聚乙二醇,搅拌溶解后转移至高压反应釜中,于200℃下反应8 h,利用磁铁分离反应产物并用无水乙醇和去离子水交替洗涤5次,60℃下真空干燥8 h,制得Fe3O4磁性纳米粒子;将1.25 g Fe3O4磁性纳米粒子加入到250 mL浓度为0.29 mmol/L的巯基乙酸乙醇溶液中搅拌24h,产物采用磁铁分离并用去离子水和无水乙醇交替洗涤3次,60℃下真空干燥8h,即得到巯基乙酸改性的Fe3O4磁性纳米粒子;
(2)磁性Fe3O4@MIL-101(Cr)的制备
将2.0 g硝酸铬(Cr(NO3)3·9H2O)、0.832 g对苯二甲酸(H2BDC)溶于25 mL去离子水中,然后加入1.29 mmol四甲基氢氧化铵(TMAOH),搅拌溶解20 min,再加入0.232 g步骤(1)得到的巯基乙酸改性的Fe3O4磁性纳米粒子进行超声混合,将混合物移入高压反应釜中,在180℃下反应24 h,产物利用磁铁进行分离,然后依次用N,N-二甲基甲酰胺、无水乙醇和去离子水分别于110℃、60℃、80℃回流纯化产物,再于100℃下真空干燥24 h,即获得磁性Fe3O4@MIL-101(Cr);
(3)Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4 磁性复合材料的制备
将0.4 g步骤(2)所得磁性Fe3O4@MIL-101(Cr)溶于20 mL蒸馏水中并通过超声使其分散均匀,加入0.6296 g硝酸银(AgNO3),在避光条件下搅拌1 h,然后逐滴加入25 mL浓度为37 mmoL/L磷酸二氢钾溶液,于避光条件下继续混合搅拌3 h,最后逐滴加入40 mL浓度为13.875 mmoL/L的十六烷基三甲基溴化铵(CTAB)溶液,于避光条件下继续搅拌3 h,反应产物分别用去离子水、无水乙醇交替洗涤6次,经磁铁分离后于60℃下干燥12 h,即获得Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4磁性复合材料。
实施例2:MIL-101(Cr)材料的制备
其制备方法同实施例1步骤(2)所述,但不加入Fe3O4磁性纳米粒子。
图1为Fe3O4、MIL-101(Cr)、Fe3O4@MIL-101(Cr)和Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4和AgBr-Ag3PO4的XRD图。由图1可知,所制备的Fe3O4@MIL-101(Cr)的XRD图谱上兼具Fe3O4和MIL-101(Cr)的特征峰,说明在碱性条件下成功合成了Fe3O4@MIL-101(Cr)材料,水热过程不会造成Fe3O4晶体的破坏;而Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4的XRD图谱上具有Fe3O4、MIL-101(Cr)和AgBr-Ag3PO4三种成分的特征峰,说明Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4复合材料由这三种材料组成,AgBr-Ag3PO4的负载过程并未引起金属有机骨架结构的变化。
图2为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4的XPS图。由图2可以看出,所制备的Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4的X射线光电子能谱(XPS)能检测到Fe、Cr、O、Ag、C、P和Br等元素。
图3为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4的TEM图。由图3可以看出,尺寸为300 nm左右的Fe3O4磁性粒子包裹在材料中心,MIL-101(Cr)均匀的生长在其外,AgBr-Ag3PO4分散负载于MIL-101(Cr)上。
图4为Fe3O4、AgBr-Ag3PO4和Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4的UV-Vis DRS图。由图4可以看出,所制备的Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4的可见光响应范围明显得到拓宽。
图5为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4的磁滞回曲线图(A)和磁分离效果图(B)。由图5(A)可以看出,所制备的Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4显示了明显的磁滞回特性;由图5(B)可以看出,所制备的Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4可均匀分散于水相中,而通过外加磁铁处理可实现其与水相的分离。
实施例3:不同pH对磁性复合材料催化降解土霉素效果的影响
(1)取100 mL浓度为30 mg/L的土霉素溶液置于烧杯中,分别用0.1 mol/L的NaOH和HCl调节土霉素溶液的pH,使其pH值分别为3、5、7和9。加入100 mg实施例1中制备的磁性复合材料,在黑暗条件下搅拌反应12 h,使其达到吸附平衡,然后将溶液置于氙灯下,打开氙灯(300 W,滤光片波长大于400 nm),在室温下照射反应30 min,每隔一定时间取样3 mL,样品经离心后取上清液经0.45 μm滤膜过滤后于液相色谱仪中分析测定其浓度。
(2)测定条件:色谱柱:Agilent C18反向色谱柱(250 mm×4.5 mm I.d.,5 μm)。检测波长355 nm,柱温为30℃。流动相为乙腈:水=80:20(其中水的pH=2)。流动相流速为1.0mL/min,进样量为20 μL,保留时间为10 min。
图6为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4在不同pH下对土霉素的降解效果图。由图6可知,在酸性条件下(pH=3、5),土霉素的降解效率得到抑制,而在中性和碱性的环境中,Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4对土霉素能够发挥最好的降解效率。
实施例4:不同pH对磁性复合材料催化降解氧氟沙星效果的影响
(1)取100 mL浓度为30 mg/L的氧氟沙星溶液置于烧杯中,分别用0.1 mol/L的NaOH和HCl调节氧氟沙星溶液的pH,使其pH值分别为3、5、7和9。加入100 mg实施例1中制备的磁性复合材料,在黑暗条件下搅拌反应12 h,使其达到吸附平衡,然后将溶液置于氙灯下,打开氙灯(300 W,滤光片波长大于400 nm),在室温下照射反应30 min,每隔一定时间取样3 mL,样品经离心后取上清液经0.45 μm滤膜过滤后于液相色谱仪中分析测定其浓度。
(2)测定条件:色谱柱:Agilent C18反向色谱柱(250 mm×4.5 mm I.d.,5 μm)。检测波长290 nm,柱温为25℃。流动相为乙腈:水=15:85(其中磷酸的体积为水的1%)。流动相流速为1.5 mL/min,进样量为20 μL,保留时间为6 min。
图7为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4在不同pH下对氧氟沙星的降解效果图。由图7可知,在酸性条件下(pH=3、5),氧氟沙星的降解效率得到抑制,而在中性和碱性的环境中,e3O4@MIL-101(Cr)@AgBr-Ag3PO4对氧氟沙星能够发挥最好的降解效率。
实施例5:Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4对土霉素的降解试验
(1)取100 mL浓度为30 mg/L的土霉素溶液置于烧杯中,将其pH调节至7~9,然后加入100 mg实施例1中制备的磁性复合材料,在黑暗条件下搅拌反应12 h,使其达到吸附平衡,然后将溶液置于氙灯下,打开氙灯(300 W,滤光片波长大于400 nm),在室温下照射反应30min,每隔一定时间取样3 mL,样品经离心后取上清液经0.45 μm滤膜过滤后于液相色谱仪中分析测定其浓度。
(2)测定条件:色谱柱:Agilent C18反向色谱柱(250 mm×4.5 mm I.d.,5 μm)。检测波长355 nm,柱温为30℃。流动相为乙腈:水=80:20(其中水的pH=2)。流动相流速为1.0mL/min,进样量为20 μL,保留时间为10 min。
图8为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4降解土霉素效果的高效液相色谱图。由图8可以看出,经过30 min分钟的可见光降解,在出峰时间t=2.5 min的特征峰已经非常小,说明土霉素几乎完全降解,降解率高达97.0%。
实施例6:Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4对氧氟沙星的降解试验
(1)取100 mL浓度为20 mg/L的氧氟沙星溶液置于烧杯中,将其pH调节至7~9,然后加入100 mg实施例1中制备的磁性复合材料,在黑暗条件下搅拌反应12 h,使其达到吸附平衡,然后将溶液置于氙灯下,打开氙灯(300 W,滤光片波长大于400 nm),在室温下照射反应40min,每隔一定时间取样3 mL,样品经离心后取上清液再经0.45 μm滤膜过滤后于液相色谱仪中分析测定其浓度。
(2)测定条件:色谱柱:Agilent C18反向色谱柱(250 mm×4.5 mm I.d.,5 μm)。检测波长290 nm,柱温为25℃。流动相为乙腈:水=15:85(其中磷酸的体积为水的1%)。流动相流速为1.5 mL/min,进样量为20 μL,保留时间为6 min。
图9为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4对氧氟沙星降解效果的高效液相色谱图。由图9可以看出,经过40 min分钟的可见光降解,在出峰时间t=4.1 min的特征峰已经非常小,说明氧氟沙星几乎完全降解,降解率高达98.1%。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (4)
1.一种用于可见光降解水中抗生素的磁性复合材料,其特征在于:所述复合材料为Fe3O4@MIL-101(Cr)@AgBr-Ag3PO4。
2.根据权利要求1所述用于可见光降解水中抗生素的磁性复合材料,其特征在于:先采用巯基乙酸对Fe3O4磁性纳米粒子进行改性,然后将改性的Fe3O4磁性纳米粒子加入到MIL-101(Cr)前驱体溶液中,得到磁性Fe3O4@MIL-101(Cr),再在避光条件下,将所得磁性Fe3O4@MIL-101(Cr)与硝酸银、磷酸二氢钾、十六烷基三甲基溴化铵进行共沉淀反应,使AgBr、Ag3PO4共同负载在磁性Fe3O4@MIL-101(Cr)上,制得所述磁性复合材料。
3. 根据权利要求2所述用于可见光降解水中抗生素的磁性复合材料,其特征在于:所述共沉淀反应的具体操作为:将0.4 g磁性Fe3O4@MIL-101(Cr)溶于蒸馏水中并通过超声使其分散均匀,加入1.85~5.55 mmol硝酸银,在避光条件下搅拌1 h,然后逐滴加入0.46~1.39mmol磷酸二氢钾,于避光条件下继续混合搅拌3 h,最后逐滴加入十六烷基三甲基溴化铵0.27~0.84 mmol,于避光条件下继续搅拌3 h,反应产物分别用去离子水、无水乙醇交替洗涤3~6次,经磁铁分离后于60℃下干燥12 h。
4.一种如权利要求1所述磁性复合材料在可见光催化降解水中抗生素的应用。
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107117683A (zh) * | 2017-06-21 | 2017-09-01 | 湖南工程学院 | 一种含In‑Co MOFs在可见光下催化降解水体中低浓度抗生素的方法 |
CN108579776A (zh) * | 2017-12-29 | 2018-09-28 | 南京农业大学 | 多层半导体可见光催化剂及其制备方法与应用 |
CN109174198A (zh) * | 2018-09-25 | 2019-01-11 | 吉林化工学院 | 一种磁性金属有机凝胶负载磷酸银复合光催化剂及其制备方法和应用 |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105728051A (zh) * | 2016-01-29 | 2016-07-06 | 福州大学 | 一种可见光响应的磁性复合光催化材料及其制备方法 |
CN105944741A (zh) * | 2016-05-19 | 2016-09-21 | 南京理工大学 | 一种GO/Ag3PO4/AgBr三元复合光催化剂及其制备方法 |
-
2016
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105728051A (zh) * | 2016-01-29 | 2016-07-06 | 福州大学 | 一种可见光响应的磁性复合光催化材料及其制备方法 |
CN105944741A (zh) * | 2016-05-19 | 2016-09-21 | 南京理工大学 | 一种GO/Ag3PO4/AgBr三元复合光催化剂及其制备方法 |
Non-Patent Citations (1)
Title |
---|
SHAOMANG WANG等: ""Highly efficient photocatalytic treatment of dye wastewater via visible-light-driven AgBr–Ag3PO4/MWCNTs"", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
Cited By (8)
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CN107117683A (zh) * | 2017-06-21 | 2017-09-01 | 湖南工程学院 | 一种含In‑Co MOFs在可见光下催化降解水体中低浓度抗生素的方法 |
CN107117683B (zh) * | 2017-06-21 | 2020-08-11 | 湖南工程学院 | 一种含In-Co MOFs在可见光下催化降解水体中低浓度抗生素的方法 |
CN108579776A (zh) * | 2017-12-29 | 2018-09-28 | 南京农业大学 | 多层半导体可见光催化剂及其制备方法与应用 |
CN108579776B (zh) * | 2017-12-29 | 2021-03-23 | 南京农业大学 | 多层半导体可见光催化剂及其制备方法与应用 |
CN109174198A (zh) * | 2018-09-25 | 2019-01-11 | 吉林化工学院 | 一种磁性金属有机凝胶负载磷酸银复合光催化剂及其制备方法和应用 |
CN114181402A (zh) * | 2021-12-21 | 2022-03-15 | 吉林化工学院 | 一种可磁回收的金属有机框架材料及其制备方法和用途 |
CN115445642A (zh) * | 2022-09-19 | 2022-12-09 | 佛山科学技术学院 | 一种包覆型双功能催化剂及其制备方法和应用 |
CN115445642B (zh) * | 2022-09-19 | 2023-10-03 | 佛山科学技术学院 | 一种包覆型双功能催化剂及其制备方法和应用 |
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