CN114950492B - 一种用于光电催化杀灭细菌的1,2-二氨基蒽醌-二硫化钼复合抗菌材料 - Google Patents
一种用于光电催化杀灭细菌的1,2-二氨基蒽醌-二硫化钼复合抗菌材料 Download PDFInfo
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- -1 1, 2-diaminoanthraquinone-molybdenum disulfide Chemical compound 0.000 title claims abstract description 19
- 241000894006 Bacteria Species 0.000 title claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 17
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 14
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- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
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- ZGHDMISTQPRNRG-UHFFFAOYSA-N dimolybdenum Chemical compound [Mo]#[Mo] ZGHDMISTQPRNRG-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种用于光电催化杀灭细菌的1,2‑二氨基蒽醌‑二硫化钼复合抗菌材料,是将羧基功能化的二硫化钼在EDC·HCl条件下与1,2‑二氨基蒽醌脱水缩合得到,将其负载到ITO导电玻璃上可获得光阳极。本发明的复合抗菌材料具有高效杀菌效果,且多次回收利用仍可保持高效抗菌,相较于光催化抗菌更具有经济和环保效益。
Description
技术领域
本发明涉及一种用于光电催化杀灭细菌的1,2-二氨基蒽醌-二硫化钼复合光阳极的制备方法,属于光电杀菌领域。
背景技术
近些年,光催化抗菌凭借着无明显耐药性、副作用少等优势引起大家的广泛关注。但是,光催化杀菌的材料多为粉末,面临着回收难、污染水源等问题。为了解决这些弊端,研究人员致力于探索是否存在改良的合成方法或材料既可以保持材料的抗菌性能又能解决材料回收难的问题。
光电催化氧化法(PEC)作为一种反应可控、氧化速度快、无需化学添加剂的绿色高效技术,集光催化法和电化学法的优点于一身,被认为是一种高效的灭菌处理方法。例如,阳极光照下产生的电子会在外部电路驱动下向阴极移动,降低电子和空穴的高复合率问题。同样因为光敏剂固定在基底上,不需要在反应结束后从悬浮液中回收光催化剂,最令人担忧的回收问题也得以迎刃而解。PEC技术将催化剂固定在载体表面作为光敏阳极,是电化学抗菌***的关键。1,2-二氨基蒽醌是一种吸收大范围可见光、易于与半导体相互作用的光敏剂,已证明1,2-二氨基蒽醌与MoS2物理复合具有较好的抗菌效果,但是从最终结果来看仍然是低于理想的。有研究发现,相同原料之间不同的联接方式会大大影响材料的结构以及性能,如MoS2与BCN共价联接方式被证明比物理共混方式具有更高的HER活性。
发明内容
本发明的目的在于提供一种用于光电催化杀灭细菌的1,2-二氨基蒽醌-二硫化钼复合抗菌材料,并将其负载于ITO导电玻璃上构成光阳极,实现材料的可回收和抗菌效率的提高。
为了实现上述目的,本发明采用如下技术方案:
本发明首先公开了一种用于光电催化杀灭细菌的1,2-二氨基蒽醌-二硫化钼复合抗菌材料,其制备方法为:首先通过超声作用将巯基乙酸嵌入二硫化钼,获得羧基功能化的二硫化钼;然后将所述羧基功能化的二硫化钼在EDC·HCl条件下与1,2-二氨基蒽醌脱水缩合得到共价接枝的1,2-二氨基蒽醌-二硫化钼复合抗菌材料。具体包括如下步骤:
步骤1、制备羧基功能化的二硫化钼
取50-150mg MoS2粉末加入50-100mL超纯水中,超声2-4h以分散均匀,再加入200-600μL巯基乙酸并在冰冷却下超声15-24h;将所得混合物用超纯水透析2-3天,冻干收集固体,即为羧基功能化的二硫化钼,记为MoS2-COOH;
步骤2、接枝1,2-二氨基蒽醌
将10-60mg的MoS2-COOH、10-60mg的1,2-二氨基蒽醌和3-6mL干燥的DMF依次加入三口烧瓶中,超声2-4h,再在氮气氛围下加入10-60mg EDC·HCl、10-60mg HOBt和300-600μL DIPEA;在室温下搅拌48-72h后,离心收集固体产物,依次用DMF、水、乙醇洗涤,60℃干燥得到目标产物1,2-二氨基蒽醌-二硫化钼复合抗菌材料,记为1,2-DAQ-MoS2。
本发明还公开了一种用于光电催化杀灭细菌的光阳极,所述光阳极是在ITO导电玻璃上通过电泳技术负载有上述的1,2-二氨基蒽醌-二硫化钼复合抗菌材料,具体制备方法为:将20-50mg的1,2-DAQ-MoS2超声分散在乙醇与水的混合溶液中,以Pt片为阳极、以ITO导电玻璃作为阴极,在40-60V的电压下反应,使1,2-DAQ-MoS2负载在ITO上,即获得用于光电催化杀灭细菌的光阳极。
作为优选,所述反应的时间为30-60min。
作为优选,所述乙醇与水的混合溶液是由乙醇和水按体积比1~2:1混合而成。
利用本发明的光阳极,结合光源和电源可以构建一个抗菌体系,该体系对细菌具有高效灭活作用。
本发明的有益效果体现在:
1、本发明利用简单的脱水缩合法,在常温下将1,2-二氨基蒽醌与羧基功能化的二硫化钼共价接枝,获得1,2-二氨基蒽醌-二硫化钼复合抗菌材料,再利用电泳技术将其负载于ITO导电玻璃上构成光阳极,方法简单、制作成本低。
2、本发明1,2-二氨基蒽醌-二硫化钼是通过共价接枝获得,相较于物理方式制备的1,2-二氨基蒽醌/二硫化钼复合材料结晶性得到提高,抗菌性能得到优化。
3、本发明的光阳极对大肠杆菌和金黄色葡萄球菌具有高效杀菌效果,电偏压的存在促进载流子有效分离,相较于光催化杀菌在抗菌效果上实现了显著突破;同时该材料可以多次回收利用仍保持高效抗菌,具有经济和环保效益。
4、本发明通过筛选最优的原料配比以及反应条件,使所得材料具有最优的抗菌性能。
附图说明
图1为对比例1所得1,2-DAQ/MoS2(图1a)和实施例1所得1,2-DAQ-MoS2(图1b)的SEM图。
图2为对比例1所得1,2-DAQ/MoS2和实施例1所得1,2-DAQ-MoS2的XRD图。
图3为对比例1所得1,2-DAQ/MoS2和实施例1所得1,2-DAQ-MoS2对大肠杆菌的抗菌平板涂布图。
图4为实施例1所得1,2-DAQ-MoS2的XPS谱图,其中图4a为全谱图、图4b为C1s图、图4c为N1s图。
图5为实施例1所得1,2-DAQ-MoS2/ITO的XPS谱图。
图6为实施例1所得1,2-DAQ-MoS2/ITO的SEM图。
图7为实施例1所得1,2-DAQ-MoS2/ITO对大肠杆菌的抗菌平板涂布图,图中L代表光反应组、PEC代表光电反应组。
图8为实施例1所得1,2-DAQ-MoS2/ITO对金黄色葡萄球菌的抗菌平板涂布图,图中L代表光反应组、PEC代表光电反应组。
图9为本发明实施例1所得1,2-DAQ-MoS2/ITO的抗菌循环稳定性图。
具体实施方式
下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
对比例1
将150mg片层状二硫化钼加入到5mL水中并超声30min,再加入10mg 1,2-氨基蒽醌并超声30min,常温搅拌12h,然后离心收集产物,冻干,即获得1,2-氨基蒽醌敏化二硫化钼复合光催化抗菌材料,记为1,2-DAQ/MoS2。
实施例1
本实施例按如下步骤制备1,2-二氨基蒽醌-二硫化钼复合抗菌材料:
步骤1、制备羧基功能化的二硫化钼
取50mg MoS2粉末加入50mL超纯水中,超声2h以分散均匀,再加入200μL巯基乙酸并在冰冷却下超声15h;将所得混合物用超纯水透析2天,冻干收集固体,即为羧基功能化的二硫化钼,记为MoS2-COOH。
步骤2、接枝1,2-二氨基蒽醌
将20mg的MoS2-COOH、20mg的1,2-二氨基蒽醌和3mL干燥的DMF依次加入三口烧瓶中,超声2h,再在氮气氛围下加入20mg EDC·HCl、20mg HOBt和300μLDIPEA;在室温下搅拌48h后,离心收集固体产物,依次用DMF、水、乙醇洗涤,60℃干燥得到目标产物1,2-二氨基蒽醌-二硫化钼复合抗菌材料,记为1,2-DAQ-MoS2。
步骤3、负载于ITO导电玻璃
将20mg的1,2-DAQ-MoS2超声分散在乙醇与水的混合溶液中,以Pt片为阳极、以ITO导电玻璃作为阴极,在60V的电压下反应40min,使1,2-DAQ-MoS2负载在ITO上,即用于光电催化杀灭细菌的光阳极,记为1,2-DAQ-MoS2/ITO。
图1为对比例1所得1,2-DAQ/MoS2(图1a)和实施例1所得1,2-DAQ-MoS2(图1b)的SEM图,从图中可以看出:1,2-DAQ/MoS2和1,2-DAQ-MoS2都是片层结构,但是1,2-DAQ-MoS2表面更粗糙、结晶更明显。
图2为对比例1所得1,2-DAQ/MoS2和实施例1所得1,2-DAQ-MoS2的XRD图,从图中可以看出1,2-DAQ/MoS2和1,2-DAQ-MoS2的峰位置相一致,但是1,2-DAQ-MoS2峰强度更大,这意味着其结晶性更好。
图3为对比例1所得1,2-DAQ/MoS2和实施例1所得1,2-DAQ-MoS2对大肠杆菌的抗菌平板涂布图,其光催化杀菌的具体测试方法为:取50μL的大肠杆菌稀释液(菌液浓度为105CFU/mL)与1mL 0.1mg/mL的抗菌材料的水溶液混合加入50mL PBS缓冲液中,设置光反应组和暗反应组。将反应开始前的平板涂布作为对照组,反应80min后,分别从光反应组和暗反应组取30μL混合均匀的PBS溶液涂布在平板上。平板倒置培养在生物培养箱中18h,通过计数法统计平板涂布前后的菌落数定性评估1,2-DAQ/MoS2和1,2-DAQ-MoS2的抗菌性能。从图中可以看出:1,2-DAQ-MoS2在光照条件下具有更好的抗菌性能,具体体现在其光照80min有效灭活体系内的细菌。
图4为实施例1所得1,2-DAQ-MoS2的XPS谱图。从图4a中可以看出复合材料存在Mo、S、C、N、O元素。图4b是1,2-DAQ-MoS2的C1s图,可以看出286.2eV存在C=O键。图4c是1,2-DAQ-MoS2的N1s图,可以看出399.35eV存在N-H键。
图5为实施例1所得1,2-DAQ-MoS2/ITO的XPS谱图,从图中可以看出其既存在1,2-DAQ-MoS2的Mo、S、C、N、O元素,又存在ITO导电玻璃的In、Sn元素。
图6为实施例1所得1,2-DAQ-MoS2/ITO的SEM图,可以看出片层结构的1,2-二氨基蒽醌-二硫化钼生长在ITO导电玻璃面。
本实施例的1,2-二氨基蒽醌-二硫化钼复合抗菌材料负载于ITO导电玻璃构建了光电杀菌体系,可应用于水环境中有害微生物的杀灭,以大肠杆菌为例,其光电催化杀菌的具体测试方法为:取50μL的大肠杆菌稀释液(菌液浓度为105CFU/mL)加入50mL PBS缓冲液中作为菌体环境,以1,2-DAQ-MoS2/ITO为光阳极、以Pt片为光阴极,设置光反应组和光电反应组。将反应开始前的平板涂布作为对照组,反应10min后,分别从光反应组和光电反应组取30μL混合均匀的PBS溶液涂布在平板上。平板倒置培养在生物培养箱中18h,通过计数法统计平板涂布前后的菌落数定性评估1,2-DAQ-MoS2/ITO的抗菌性能。
图7为实施例1中1,2-DAQ-MoS2/ITO对大肠杆菌的抗菌平板涂布图。可以看出,5分钟后,1,2-DAQ-MoS2/ITO光电组(PEC)的细菌全部死亡。
图8为实施例1中1,2-DAQ-MoS2/ITO对金黄色葡萄球菌的抗菌平板涂布图,其测试方法与大肠杆菌相同。可以看出,10分钟后,1,2-DAQ-MoS2/ITO光电组(PEC)的细菌全部死亡。
1,2-DAQ-MoS2/ITO在首次抗菌操作完成后(即光照组和光电组反应5min后),通过离心收集固体,进行第两次及以上的抗菌操作。图9为1,2-DAQ-MoS2/ITO的抗菌循环稳定性图,图中抗菌率的计算方法为(反应开始前的大肠杆菌个数-反应5min结束后的大肠杆菌个数)/反应开始前的大肠杆菌个数。从图中可以发现三次循环后,材料的抗菌性能未发生改变。1,2-DAQ-MoS2/ITO具有十分优秀的抗菌稳定性。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型,仍属于本发明技术方案的保护范围。
Claims (3)
1.一种用于光电催化杀灭细菌的光阳极,其特征在于:所述光阳极是在ITO导电玻璃上负载有1,2-二氨基蒽醌-二硫化钼复合抗菌材料;
所述1,2-二氨基蒽醌-二硫化钼复合抗菌材料的制备方法包括如下步骤:
步骤1、通过超声作用将巯基乙酸嵌入二硫化钼,获得羧基功能化的二硫化钼:
取50-150 mg MoS2粉末加入50-100 mL超纯水中,超声2-4 h以分散均匀,再加入200-600 μL巯基乙酸并在冰冷却下超声15-24 h;将所得混合物用超纯水透析2-3天,冻干收集固体,即为羧基功能化的二硫化钼,记为MoS2-COOH;
步骤2、将所述羧基功能化的二硫化钼在EDC·HCl条件下与1,2-二氨基蒽醌脱水缩合得到共价接枝的1,2-二氨基蒽醌-二硫化钼复合抗菌材料:
将10-60 mg的MoS2-COOH、10-60 mg的1,2-二氨基蒽醌和3-6 mL干燥的DMF依次加入三口烧瓶中,超声2-4 h,再在氮气氛围下加入10-60 mg EDC·HCl、10-60 mg HOBt和300-600μL DIPEA;在室温下搅拌48-72 h后,离心收集固体产物,依次用DMF、水、乙醇洗涤,60 ℃干燥得到目标产物1,2-二氨基蒽醌-二硫化钼复合抗菌材料,记为1,2-DAQ-MoS2;
所述光阳极是通过电泳技术将1,2-二氨基蒽醌-二硫化钼复合抗菌材料负载到ITO导电玻璃上,从而获得,具体步骤为:将20-50 mg的1,2-DAQ-MoS2超声分散在乙醇与水的混合溶液中,以Pt片为阳极、以ITO导电玻璃作为阴极,在40-60 V的电压下反应,使1,2-DAQ-MoS2负载在ITO上,即获得用于光电催化杀灭细菌的光阳极。
2.根据权利要求1述的用于光电催化杀灭细菌的光阳极,其特征在于:所述反应的时间为30-60 min。
3.根据权利要求1述的用于光电催化杀灭细菌的光阳极,其特征在于:所述乙醇与水的混合溶液是由乙醇和水按体积比1~2:1混合而成。
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