CN113244962B - 一种产生单线态氧的锆卟啉基mof-石墨烯复合光催化剂的制备方法及应用 - Google Patents
一种产生单线态氧的锆卟啉基mof-石墨烯复合光催化剂的制备方法及应用 Download PDFInfo
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Abstract
本发明属于催化剂技术领域，具体涉及一种产生单线态氧的锆卟啉基MOF‑石墨烯复合光催化剂的制备方法及应用。制备方法包括如下步骤：首先利用溶剂热法制备锆卟啉基MOF纳米颗粒，其次，将氧化石墨烯和锆卟啉基MOF纳米颗粒在超声波细胞破碎仪作用下均匀分散在乙醇溶液中，利用π‑π键的相互作用进行复合，制得锆卟啉基MOF‑石墨烯复合光催化剂。本发明提供的锆卟啉基MOF‑石墨烯复合光催化剂在模拟太阳光照射下能够产生活性氧物种单线态氧，对水体系中典型的喹诺酮类抗生素光能够有效降解，在消除抗生素污染物方面具有良好的应用前景。
Description
技术领域
本发明属于催化剂技术领域，具体涉及一种产生单线态氧的锆卟啉基MOF-石墨烯复合光催化剂的制备方法及应用。
背景技术
随着现代环境分析技术的进步，抗生素残留在各种水环境介质中被频繁地检出，如河水、废水处理厂出水、地下水和饮用水。长期接触这些抗生素残留物可以使生物对其产生耐药性并影响新陈代谢，由于其具有较强的生物活性、生物累积性和不易被生物降解性，使得该类污染物的残留势必对饮用水体、生态环境和人类健康产生长期潜在的威胁。其中，喹诺酮类抗生素是使用较为广泛的一类抗生素，主要包括诺氟沙星、氧氟沙星、环丙沙星等药物，广泛用于泌尿生殖系统疾病、胃肠疾病，以及呼吸道、皮肤组织细菌感染的治疗。对于水环境中抗生素的去除已经成为了环境领域的研究热点之一，光催化是处理抗生素残留最有前景的技术之一，它可以利用太阳能，产生具有氧化或还原作用的活性物种，将抗生素有机物分子降解为水、二氧化碳等无机小分子，具有高效节能、操作便捷、清洁无毒、无二次污染等优点。
目前用于处理抗生素的光催化剂主要集中于无机氧化物、卤氧化物、氮化碳半导体。金属有机框架材料(MOF)是通过金属离子或金属簇与有机配体自组装形成的一种多孔有机-无机杂化材料。由于具有可控性好、孔隙率高、设计性强和结构稳定等特点，使其在催化中具有良好的应用前景。开发MOF基光催化剂，丰富光催化剂体系，对于推进MOF材料在光催化领域中的应用具有重要的意义。
卟啉是一类光敏性物质，将卟啉作为有机配体与金属簇配位构建成卟啉基MOF，可以把两者的功能和结构特点有效地结合起来。锆卟啉基MOF是由锆氧簇和有机卟啉配体(TCPP)构成，具有优异的光响应性、生物相容性和稳定性。由于卟啉的存在，锆卟啉基MOF可以在光照下产生单线态氧作为活性氧物种，具有降解有机污染物的能力。然而，单一的锆卟啉基MOF纳米颗粒作为光催化剂时，由于纳米粒子的团聚，造成反应活性位暴露不充分。
发明内容
本发明的目的在于提供一种锆卟啉基MOF-石墨烯复合光催化剂，制得的光催化剂充分暴露反应活性位，在光照下快速产生活性氧物种单线态氧，在模拟太阳光下可以有效降解喹诺酮类抗生素，具有广泛的应用前景。
本发明产生单线态氧的锆卟啉基MOF-石墨烯复合光催化剂的制备方法，具体按以下步骤进行：
(1)制备锆卟啉基MOF纳米颗粒
将前驱体5,10,15,20-四羧基苯基卟啉(H2TCPP)、ZrOCl2·8H2O和苯甲酸溶解于DMF溶剂中得到混合溶液，上述溶液移入高压反应釜中，在120℃下进行溶剂热反应5h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF纳米颗粒。
其中，H2TCPP在DMF溶剂中的浓度为1mg/mL，H2TCPP、ZrOCl2·8H2O和苯甲酸的质量比为1:3:(22-30)；
(2)制备锆卟啉基MOF-石墨烯复合光催化剂
将氧化石墨烯和步骤(1)得到的锆卟啉基MOF纳米颗粒在超声细胞破碎仪作用下均匀分散到乙醇中，将上述分散液移入高压反应釜，在120℃下进行复合反应，反应时间为3h-5h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF-RGO复合光催化剂。
其中，超声细胞破碎仪功率为60W，超声时间为10-15min，氧化石墨烯为锆卟啉基MOF质量的5％-20％。
本发明的技术效果是：
(1)本发明提供的锆卟啉基MOF在紫外-可见光区都具有响应，解决了传统光催化剂对可见光利用不足的问题，且在光照下通过能量转移过程快速产生活性氧物种单线态氧，具有降解抗生素的能力。
(2)本发明利用π-π相互作用将锆卟啉基MOF纳米颗粒与石墨烯进行复合，将石墨烯作为MOF纳米颗粒的载体，解决了单一锆卟啉基MOF纳米颗粒作为光催化剂容易团聚的问题，充分暴露光催化反应的活性位。研究表明，锆卟啉基MOF-RGO复合光催化剂在降解抗生素污染物时，具有比单独的锆卟啉基MOF纳米颗粒更好的活性，在模拟太阳光照射下，对喹诺酮类抗生素的降解率达96％以上，推广应用具有很大的优势。
附图说明
图1为本发明实施例1制备的锆卟啉基MOF纳米颗粒的紫外-可见漫反射光谱图(UV-vis DRS)。
图2为本发明实施例2制备的锆卟啉基MOF-石墨烯复合光催化剂在模拟太阳光照射10min后产生单线态氧的电子顺磁光谱图(ESR)。
图3为本发明实施例3制备的锆卟啉基MOF-石墨烯复合光催化剂与锆卟啉基MOF光催化降解喹诺酮类抗生素环丙沙星的活性对比图。
具体实施方式
实施例1
(1)制备锆卟啉基MOF纳米颗粒
将前驱体H2TCPP、ZrOCl2·8H2O和苯甲酸溶解于DMF溶剂中，H2TCPP在DMF溶剂中的浓度为1mg/mL，H2TCPP、ZrOCl2·8H2O和苯甲酸的质量比为1:3:22；上述溶液移入高压反应釜中，在120℃下进行溶剂热反应5h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF纳米颗粒。
本实施例制得的锆卟啉基MOF纳米颗粒的紫外-可见漫反射光谱图(UV-vis DRS)见图1。
从图1可见，锆卟啉基MOF纳米颗粒在整个紫外-可见光区均有光响应，具体表现为在420nm处有强的Soret带吸收峰，在500-700nm有Q带吸收峰。
(2)制备锆卟啉基MOF-石墨烯复合光催化剂
将氧化石墨烯和步骤(1)得到的锆卟啉基MOF纳米颗粒在超声细胞破碎仪(超声细胞破碎仪功率为60W)作用下均匀分散到乙醇中，超声时间为10min，氧化石墨烯占锆卟啉基MOF质量的15％；将上述分散液移入高压反应釜，在120℃下进行复合反应，反应时间为5h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF-RGO复合光催化剂。
(3)光催化降解反应
使用300W氙灯来模拟太阳光照射。将10mg上述制备的锆卟啉基MOF纳米颗粒、锆卟啉基MOF-石墨烯复合光催化剂分散在喹诺酮类抗生素环丙沙星水溶液(50mL，10ppm)中。先进行暗反应，反应液在无光照情况下搅拌1h以达到吸附/解吸平衡状态。其次，用上述氙灯光照反应液，每隔30分钟取出3mL溶液，使用液相色谱进行抗生素降解率分析。测得锆卟啉基MOF纳米颗粒、锆卟啉基MOF-石墨烯复合光催化剂对抗生素的降解率在180min内分别达到82.4％和96.7％，说明锆卟啉基MOF-石墨烯复合光催化剂对喹诺酮类抗生素具有强的光催化降解活性。
实施例2
(1)制备锆卟啉基MOF纳米颗粒
将前驱体H2TCPP、ZrOCl2·8H2O和苯甲酸溶解于DMF溶剂中，H2TCPP在DMF溶剂中的浓度为1mg/mL，H2TCPP、ZrOCl2·8H2O和苯甲酸的质量比为1:3:30；上述溶液移入高压反应釜中，在120℃下进行溶剂热反应5h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF纳米颗粒。
(2)制备锆卟啉基MOF-石墨烯复合光催化剂
将氧化石墨烯和步骤(1)得到的锆卟啉基MOF纳米颗粒在超声细胞破碎仪作用下均匀分散到乙醇中，超声时间为15min，氧化石墨烯占锆卟啉基MOF质量的5％；将上述分散液移入高压反应釜，在120℃下进行复合反应，反应时间为4h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF-RGO复合光催化剂。
本实例中制得的锆卟啉基MOF-石墨烯复合光催化剂在模拟太阳光照射10min后产生单线态氧的电子顺磁光谱图(ESR)见图2。
从图2可见，以TMPO作为捕获剂，使用电子顺磁光谱(ESR)测出较强的单线态氧(1O2)的信号，表明制得的光催化剂在模拟太阳光照射可以有效快速地产生活性氧物种单线态氧。
(3)光催化降解反应
使用300W氙灯来模拟太阳光照射。将10mg上述制备的锆卟啉基MOF纳米颗粒或锆卟啉基MOF-石墨烯复合光催化剂分散在喹诺酮类抗生素氧氟沙星水溶液(50mL，10ppm)中。先进行暗反应，反应液在无光照情况下搅拌1h以达到吸附/解吸平衡状态。其次，用上述氙灯光照反应液，每隔30分钟取出3mL溶液，使用液相色谱进行抗生素降解率分析。测得锆卟啉基MOF纳米颗粒、锆卟啉基MOF-石墨烯复合光催化剂对抗生素的降解率在180min内分别达到75.5％和89.2％，说明锆卟啉基MOF-石墨烯复合光催化剂对喹诺酮类抗生素具有强的光催化降解活性。
实施例3
(1)制备锆卟啉基MOF纳米颗粒
将前驱体H2TCPP、ZrOCl2·8H2O和苯甲酸溶解于DMF溶剂中，H2TCPP在DMF溶剂中的浓度为1mg/mL，H2TCPP、ZrOCl2·8H2O和苯甲酸的质量比为1:3:28；上述溶液移入高压反应釜中，在120℃下进行溶剂热反应5h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF纳米颗粒。
(2)制备锆卟啉基MOF-石墨烯复合光催化剂
将氧化石墨烯和步骤(1)得到的锆卟啉基MOF纳米颗粒在超声细胞破碎仪作用下均匀分散到乙醇中，超声时间为12min，氧化石墨烯占锆卟啉基MOF质量的10％；将上述分散液移入高压反应釜，在120℃下进行复合反应，反应时间为3h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF-RGO复合光催化剂。
(3)光催化降解反应
使用300W氙灯来模拟太阳光照射。将10mg上述制备的锆卟啉基MOF纳米颗粒或锆卟啉基MOF-石墨烯复合光催化剂分散在喹诺酮类抗生素诺氟沙星水溶液(50mL，10ppm)中。先进行暗反应，反应液在无光照情况下搅拌1h以达到吸附/解吸平衡状态。其次，用上述氙灯光照反应液，每隔30分钟取出3mL溶液，使用液相色谱进行抗生素降解率分析。测得锆卟啉基MOF纳米颗粒、锆卟啉基MOF-石墨烯复合光催化剂对抗生素的降解率在180min内分别达到83.3％和91.1％，说明锆卟啉基MOF-石墨烯复合光催化剂对喹诺酮类抗生素具有强的光催化降解活性。
本实施例制备的锆卟啉基MOF-石墨烯复合光催化剂与锆卟啉基MOF光催化降解喹诺酮类抗生素环丙沙星的光催化活性对比图见图3。
从图3可见，锆卟啉基MOF-RGO复合光催化剂在降解抗生素污染物时，具有比单独的锆卟啉基MOF纳米颗粒更好的活性。
实施例4
(1)制备锆卟啉基MOF纳米颗粒
将前驱体H2TCPP、ZrOCl2·8H2O和苯甲酸溶解于DMF溶剂中，H2TCPP在DMF溶剂中的浓度为1mg/mL，H2TCPP、ZrOCl2·8H2O和苯甲酸的质量比为1:3:26；上述溶液移入高压反应釜中，在120℃下进行溶剂热反应5h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF纳米颗粒。
(2)制备锆卟啉基MOF-石墨烯复合光催化剂
将氧化石墨烯和步骤(1)得到的锆卟啉基MOF纳米颗粒在超声细胞破碎仪作用下均匀分散到乙醇中，超声时间为15min，氧化石墨烯：锆卟啉基MOF的质量百分数为15％；将上述分散液移入高压反应釜，在120℃下进行复合反应，反应时间为5h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF-RGO复合光催化剂。
(3)光催化降解反应
使用300W氙灯来模拟太阳光照射。将10mg上述制备的锆卟啉基MOF纳米颗粒或锆卟啉基MOF-石墨烯复合光催化剂分散在喹诺酮类抗生素环丙沙星水溶液(50mL，10ppm)中。先进行暗反应，反应液在无光照情况下搅拌1h以达到吸附/解吸平衡状态。其次，用上述氙灯光照反应液，每隔30分钟取出3mL溶液，使用液相色谱进行抗生素降解率分析。测得锆卟啉基MOF纳米颗粒、锆卟啉基MOF-石墨烯复合光催化剂对抗生素的降解率在180min内分别达到85.2％和97.5％，说明锆卟啉基MOF-石墨烯复合光催化剂对喹诺酮类抗生素具有强的光催化降解活性。
实施例5
(1)制备锆卟啉基MOF纳米颗粒
将前驱体H2TCPP、ZrOCl2·8H2O和苯甲酸溶解于DMF溶剂中，H2TCPP在DMF溶剂中的浓度为1mg/mL，H2TCPP、ZrOCl2·8H2O和苯甲酸的质量比为1:3:22；上述溶液移入高压反应釜中，在120℃下进行溶剂热反应5h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF纳米颗粒。
(2)制备锆卟啉基MOF-石墨烯复合光催化剂
将氧化石墨烯和步骤(1)得到的锆卟啉基MOF纳米颗粒在超声细胞破碎仪作用下均匀分散到乙醇中，超声时间为10min，氧化石墨烯：锆卟啉基MOF的质量百分数为10％；将上述分散液移入高压反应釜，在120℃下进行复合反应，反应时间为5h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF-RGO复合光催化剂。
(3)光催化降解反应
使用300W氙灯来模拟太阳光照射。将10mg上述制备的锆卟啉基MOF纳米颗粒或锆卟啉基MOF-石墨烯复合光催化剂分散在喹诺酮类抗生素诺氟沙星水溶液(50mL，10ppm)中。先进行暗反应，反应液在无光照情况下搅拌1h以达到吸附/解吸平衡状态。其次，用上述氙灯光照反应液，每隔30分钟取出3mL溶液，使用液相色谱进行抗生素降解率分析。测得锆卟啉基MOF纳米颗粒、锆卟啉基MOF-石墨烯复合光催化剂对抗生素的降解率在180min内分别达到79.5％和91.0％，说明锆卟啉基MOF-石墨烯复合光催化剂对喹诺酮类抗生素具有强的光催化降解活性。
实施例6
(1)制备锆卟啉基MOF纳米颗粒
将前驱体H2TCPP、ZrOCl2·8H2O和苯甲酸溶解于在DMF溶剂中，H2TCPP在DMF溶剂中的浓度为1mg/mL，H2TCPP、ZrOCl2·8H2O和苯甲酸的质量比为1:3:22；上述溶液移入高压反应釜中，在120℃下进行溶剂热反应5h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF纳米颗粒。
(2)制备锆卟啉基MOF-石墨烯复合光催化剂
将氧化石墨烯和步骤(1)得到的锆卟啉基MOF纳米颗粒在超声细胞破碎仪作用下均匀分散到乙醇中，超声时间为10min，氧化石墨烯：锆卟啉基MOF的质量百分数为20％；将上述分散液移入高压反应釜，在120℃下进行复合反应，反应时间为5h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF-RGO复合光催化剂。
(3)光催化降解反应
使用300W氙灯来模拟太阳光照射。将10mg上述制备的锆卟啉基MOF纳米颗粒或锆卟啉基MOF-石墨烯复合光催化剂分散在喹诺酮类抗生素诺氟沙星水溶液(50mL，10ppm)中。先进行暗反应，反应液在无光照情况下搅拌1h以达到吸附/解吸平衡状态。其次，用上述氙灯光照反应液，每隔30分钟取出3mL溶液，使用液相色谱进行抗生素降解率分析。测得锆卟啉基MOF纳米颗粒、锆卟啉基MOF-石墨烯复合光催化剂对抗生素的降解率在180min内分别达到80.2％和92.1％，说明锆卟啉基MOF-石墨烯复合光催化剂对喹诺酮类抗生素具有强的光催化降解活性。
Claims (4)
1.一种产生单线态氧的锆卟啉基MOF-石墨烯复合光催化剂的应用，其特征在于，所述光催化剂应用于模拟太阳光照射下降解喹诺酮类抗生素；
所述复合光催化剂的制备方法步骤如下：
（1）制备锆卟啉基MOF纳米颗粒
将前驱体5,10,15,20- 四羧基苯基卟啉H2TCPP、ZrOCl2·8H2O和苯甲酸溶解于DMF溶剂中；上述溶液移入高压反应釜中，在120℃下进行溶剂热反应5 h；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF纳米颗粒；
所述H2TCPP、ZrOCl2·8H2O和苯甲酸的质量比为1:3:22-30；
（2）制备锆卟啉基MOF-石墨烯复合光催化剂
将氧化石墨烯和步骤（1）得到的锆卟啉基MOF纳米颗粒在超声细胞破碎仪作用下均匀分散到乙醇中；将上述分散液移入高压反应釜，在120℃下进行复合反应；反应结束后，通过离心、洗涤、干燥，得到锆卟啉基MOF-RGO复合光催化剂。
2.根据权利要求1所述的产生单线态氧的锆卟啉基MOF-石墨烯复合光催化剂的应用，其特征在于，步骤（1）中，所述前驱体H2TCPP在DMF溶剂中的浓度为1 mg/mL。
3.根据权利要求1所述的产生单线态氧的锆卟啉基MOF-石墨烯复合光催化剂的应用，其特征在于，步骤（2）中，所述的氧化石墨烯用量为锆卟啉基MOF质量的5%-20%。
4.根据权利要求1所述的产生单线态氧的锆卟啉基MOF-石墨烯复合光催化剂的应用，其特征在于，步骤（2）中，所述超声细胞破碎仪功率为60 W，超声时间为10 min-15 min，复合反应的时间为3 h-5 h。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597828A (zh) * | 2015-12-28 | 2016-05-25 | 上海应用技术学院 | 一种氧化石墨烯/卟啉复合物光催化剂的制备方法 |
| CN106927535A (zh) * | 2017-03-16 | 2017-07-07 | 南京师范大学 | 基于稳定卟啉金属有机骨架材料的光催化降解酚类污染物的方法 |
| CN107433206A (zh) * | 2017-09-09 | 2017-12-05 | 中国科学院福建物质结构研究所 | 一种多元锆基多孔材料、制备方法、光催化脱铬中的应用 |
| CN107694605A (zh) * | 2017-11-01 | 2018-02-16 | 中国科学院福建物质结构研究所 | 碳量子点@卟啉基金属有机骨架催化剂及制备方法和应用 |
| CN110743503A (zh) * | 2019-10-25 | 2020-02-04 | 哈尔滨工程大学 | Pcn金属有机骨架与氧化石墨烯复合吸附材料及制备方法 |
| CN111056530A (zh) * | 2019-12-27 | 2020-04-24 | 武汉大学 | 一种光催化含氮杂环化合物产氢的方法 |
-
2021
- 2021-05-24 CN CN202110563507.8A patent/CN113244962B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105597828A (zh) * | 2015-12-28 | 2016-05-25 | 上海应用技术学院 | 一种氧化石墨烯/卟啉复合物光催化剂的制备方法 |
| CN106927535A (zh) * | 2017-03-16 | 2017-07-07 | 南京师范大学 | 基于稳定卟啉金属有机骨架材料的光催化降解酚类污染物的方法 |
| CN107433206A (zh) * | 2017-09-09 | 2017-12-05 | 中国科学院福建物质结构研究所 | 一种多元锆基多孔材料、制备方法、光催化脱铬中的应用 |
| CN107694605A (zh) * | 2017-11-01 | 2018-02-16 | 中国科学院福建物质结构研究所 | 碳量子点@卟啉基金属有机骨架催化剂及制备方法和应用 |
| CN110743503A (zh) * | 2019-10-25 | 2020-02-04 | 哈尔滨工程大学 | Pcn金属有机骨架与氧化石墨烯复合吸附材料及制备方法 |
| CN111056530A (zh) * | 2019-12-27 | 2020-04-24 | 武汉大学 | 一种光催化含氮杂环化合物产氢的方法 |
Non-Patent Citations (3)
| Title |
|---|
| "PCN-224/rGO nanocomposite based photoelectrochemical sensor with intrinsic recognition ability for efficient p-arsanilic acid detection";Miao Peng et al.;《Environmental Science Nano》;20181115;第6卷;第207-215页 * |
| "Ultrahigh adsorption and singletoxygen mediated degradation for efficient synergetic removal of bisphenol A by a stable zirconiumporphyrin metal-organic framework";Ai-Na Meng et al.;《Scientific Reports》;20170724;第7卷;摘要和第6-7页 * |
| "紫外可见光谱协助快速纯化卟啉及金属卟啉的光催化取代基效应";赵新筠等;《中南民族大学学报( 自然科学版)》;20210228;第40卷(第1期);第1-8页 * |
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