CN115159627B - 一种流水驱动的二硫化钼/碳毡柔性压电材料及其制备方法和对抗生素的降解应用 - Google Patents
一种流水驱动的二硫化钼/碳毡柔性压电材料及其制备方法和对抗生素的降解应用 Download PDFInfo
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Abstract
本发明公开了一种流水驱动的二硫化钼/碳毡柔性压电材料及其制备方法和对抗生素的降解应用,属于压电催化降解领域。本发明旨在解决传统压电催化材料不可回收、耗能高的问题。本发明将钼酸钠和硫脲溶于去离子水中,得到溶液A;对碳毡亲水化处理后完全浸没在溶液A中,然后在密封下进行水热处理;反应完毕后取出,依次用去离子水和无水乙醇清洗,密闭条件下干燥得到所述的二硫化钼/碳毡。获得二硫化钼微观形貌为纳米花状,特殊的结构对外界机械力响应极强,在同等强度机械力作用下能够产生更强的压电效应,具有优异的污染物降解效率。本发明在医疗废水处理、废水循环再利用、饮用水净化、土壤及地下水环境净化等领域,具有十分广泛的应用前景。
Description
技术领域
本发明属于压电催化降解技术领域,具体地说,涉及一种流水驱动的二硫化钼/碳毡柔性压电材料,及一种流水驱动的二硫化钼/碳毡柔性压电材料的制备方法;以及所述二硫化钼/碳毡柔性压电材料降解抗生素的应用。
背景技术
抗生素作为一类抑菌杀菌的典型药物,广泛应用于人兽传染病防治以及水产养殖等方面。然而,在药品生产以及使用过程中,会产生大量含有抗生素的废水。抗生素具有化学稳定性,因而很难被自然微生物降解。目前世界各地在土壤、地表水、地下水、沉积物甚至饮用水中都检测到了抗生素残余。环境中残留的抗生素可能会导致耐药细菌的产生以及抗生素在食物链中的富集,从而对生态系统和人类健康构成严重威胁。因此,有效去除抗生素类污染物已成为水处理领域的研究热点。
目前,去除抗生素的方法主要有吸附法、生物降解法和高级氧化法。高级氧化法包含Fenton法、臭氧氧化法、电化学氧化法和光催化氧化法。物理方法可以转移抗生素,但不能完全将其从环境中移除。而生物降解法由于抗生素分子量大、结构复杂、抗菌谱广,使用受到很大限制。高级氧化过程会产生羟基自由基,该自由基具有相当高的氧化活性,可以有效地将有机分子分解成几个无毒的小分子,是当下的研究热点。
在高级氧化法中,Fenton法实质是二价铁离子和双氧水之间的链反应催化生成羟基自由基,虽然效率较高,但反应过程需要铁离子参与,可能造成二次污染。而臭氧氧化及电化学氧化成本较高,反应所需的条件及原料的获取有一定难度,因此其大规模商业化应用受到一定限制。光催化反应的机理是材料接受光照致使电子与空穴分离,并与液体环境中的污染物在材料表面反应以达到降解目的,其实际应用受到环境中光强的影响,难以长时间高效降解。
近年来,由于在黑暗环境中具有超高降解效率,压电催化得到了很好的发展。在机械力导致的机械应变下,压电材料可以产生内电场并诱发化学反应,形成羟基自由基用于降解有机污染物,具有性能稳定,绿色环保,操作简单等优势。但现有的压电降解材料主要有两点不足:首先,材料多为粉体,使用后难以回收,会混在水体中造成二次污染;其次,现有材料多由超声作为机械力来源驱动压电反应,对能源需求较高。
发明内容
本发明旨在解决传统粉体式压电催化剂所造成的二次污染,原材料不可回收及反应所需能量较高等一系列问题,提供了一种流水驱动的二硫化钼/碳毡柔性压电材料及其制备方法和对抗生素的降解应用;本发明的压电降解材料具有可持续、可再生、低耗能、绿色环保的优点。
本发明提供一种二硫化钼/碳毡柔性压电材料及制备方法,获得的二硫化钼/碳毡柔性压电材料用于压电催化降解抗生素类污染物,特别是在高浓度环丙沙星抗生素中的应用,以解决传统压电催化材料不可回收,耗能高的技术问题。为了解决上述技术问题,本发明采取了以下的技术方案:
本发明中的一种流水驱动的二硫化钼/碳毡柔性压电材料的制备方法是按下述步骤进行的:
步骤一、将钼酸钠和硫脲溶于去离子水中,得到溶液A;
步骤二、对碳毡亲水化处理,然后完全浸没在溶液A中,然后在密封下进行水热处理,反应完毕后冷却至室温,取出,依次用去离子水和无水乙醇清洗,然后密闭下干燥;得到所述的二硫化钼/碳毡柔性压电材料,获得二硫化钼/碳毡柔性压电材料中的二硫化钼微观形貌为纳米花状。
进一步地限定,步骤一中将2.0g~3.0g钼酸钠和4.0g~5.0g硫脲溶于60mL~70mL去离子水中。
进一步地限定,步骤二中采用电化学法对碳毡亲水化处理,具体是通过下述步骤实现的:将将2片碳毡分别固定于外接电源两极上,然后浸泡于浓度为0.1mol/L的硫酸铵溶液中,调整电源电压为10V,通电1分钟,取阳极碳毡。
进一步地限定,步骤二中水热处理温度为180~200℃,水热处理时间为20h~24h。
进一步地限定,步骤二中水热处理是在聚四氟乙烯内衬的不锈钢高压釜内进行的。
进一步地限定,步骤二中干燥温度为60℃~80℃,干燥时间为6h~8h。
本发明还保护上述方法制备的二硫化钼/碳毡柔性压电材料。
上述方法制备的二硫化钼/碳毡柔性压电材料在抗生素废水的压电催化降解应用。
另外,本发明保护一种抗生素废水的压电催化降解方法,其是按下述步骤进行的:将上述方法制备的二硫化钼/碳毡柔性压电材料置于降解装置中;向降解装置中通入抗生素废水,进行降解处理。可每隔30s~1min取2~3mL溶液,并用紫外-可见吸收光谱仪测试其吸光度,检测处理效果。
进一步地限定,所述抗生素废水为环丙沙星等抗生素废水。
本发明采用水热法的方式在碳毡表面生长二硫化钼纳米花,从而制备出一种多孔、压电性能优异的复合压电体系。改进点在于将二硫化钼生长于碳毡上,同时通过特定条件合成了纳米花结构的二硫化钼,创造了一种由自然力驱动的压电降解抗生素体系。
本发明提出了以二硫化钼/碳毡柔性压电材料降解抗生素的方案,最终产品性能优异,使用方便简单,且产品可塑形性强,泛用性广,为日后降解抗生素研究提供了新的思路与方向。
与现有技术相比,本发明具备以下实验原理和有益技术效果:
从制备工艺上来看,该种二硫化钼/碳毡柔性压电材料在合成过程中对作为基底的碳毡预先进行了电化学亲水处理,在碳毡表面枝接了许多诸如羟基、氨基等一系列亲水基团,使得作为活性物质的二硫化钼更容易在碳纤维表面形成化学键,以键合力而非物理吸附力紧密结合在其上,避免了在使用过程中受到外界机械力作用时活性物质脱落,有效阻止了材料失活以及水体二次污染。
从产品组分上来看,本发明选用了碳毡这一柔性多孔材料作为基底,使得材料具有良好的耐冲击性和可变形性,能够充分满足多种不同尺寸、形状排水系统的需要,同时又对水流具有良好的透过性,能够充分满足排水系统对排水效率的需求。与此同时,通过对反应物配比、加热时间、加热温度以及反应过程压强的精准控制,本发明制备得到了形如花朵的团簇状二硫化钼纳米花。这种特殊的结构对外界机械力响应极强,极易形变,这就确保了本发明中的活性物质与普通二硫化钼粉体相比,在同等强度机械力作用下能够产生更强的压电效应,进而确保了本发明优异的污染物降解效率。
从作用机制上来看,与以往的技术不同,本发明的高效降解,依赖于其独特的“流水线”组分协同机制。本发明是一种二硫化钼碳毡复合压电降解体系,其中碳毡作为基底构成了支撑骨架承受机械力,而纳米花状的二硫化钼均匀包覆在每一根碳纤维表面作为活性物质。在进行压电反应降解有机污染物时,外来流水不仅提供了激发二硫化钼压电效应所必需的机械力,更是有如一条“流水线”,源源不断的向二硫化钼/碳毡柔性压电材料压电降解体系输送反应原材料:有机污染物。对于常规粉体状二硫化钼,在受到外界机械力后会发生压电效应,与水反应后在其表面生成羟基自由基,然而羟基自由基化学性质活泼,寿命极短,难以在溶液中长距离扩散,因此久而久之,羟基会充分降解粉体颗粒周围污染物而难以降解距离较远污染物,使得粉体颗粒周围形成“真空层”,从宏观上降低分解效率。对于本发明,机械力来源为自然流水,提供压电效应前置的条件同时具备传质功能。碳毡是多孔材料,水流进入碳毡后,进行分流,将污染物带入碳毡内部不同的孔洞中,孔洞中充满二硫化钼纳米花,产生压电效应分解污染物,犹如流水线上的一座小型加工厂,此后水流将继续携带未降解充分的污染物进入“流水线”上的下一个“小型加工厂”,历经层层降解,污染物会彻底分解为无机物流出压电降解体系。正是这种独特的“流水线”组分协同机制保证了本发明优异的降解效率。
本发明在医疗废水处理、废水循环再利用、饮用水净化、土壤及地下水环境净化等领域,具有十分广泛的应用前景。
为了能够更进一步了解本发明的特征及技术内容,请参阅以下有关本发明详细说明与附图,然而所附的附图仅提供参考和说明之用,并非用来对本发明加以限制。
附图说明
图1为流水降解有机污染物装置示意图;
图2为实施例1制备得到的二硫化钼/碳毡柔性压电材料X射线衍射图;
图3为实施例1制备得到的二硫化钼/碳毡柔性压电材料傅里叶红外光谱测试图;
图4为实施例1制备得到的二硫化钼/碳毡柔性压电材料扫描电镜图;
图5为实施例2制备得到的二硫化钼/碳毡柔性压电材料压电降解环丙沙星浓度随时间的变化曲线
图6为实施例3制备得到的二硫化钼/碳毡柔性压电材料压电降解罗丹明B浓度随时间的变化曲线。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。
实施例1:本实施例中的一种流水驱动的二硫化钼/碳毡柔性压电材料的制备方法是按下述步骤进行的:
步骤一、碳毡亲水化处理:采用电化学法,裁取2片面积为100cm2正方形碳毡,先将碳毡固定于外接电源两极上,而后将固定好的碳毡浸泡于1L浓度为0.1mol/L的硫酸铵溶液中。调整电源电压为10V,通电1分钟,取阳极碳毡。
步骤二、配置溶液:将2.470g钼酸钠和4.568g硫脲溶于70mL去离子水中;
步骤三、将步骤二配置的溶液转入聚四氟乙烯内衬下的不锈钢高压釜,将经过亲水化处理的碳毡完全浸没在步骤二配置的溶液中,并将水热釜置于200℃密封环境下保温24h;
步骤四、待反应釜冷却至室温后将二硫化钼/碳毡柔性压电材料从其中取出,依次用去离子水和无水乙醇清洗后,置于80℃密闭环境干燥6h,得到所述的二硫化钼/碳毡柔性压电材料。
经测试,本实施例获得二硫化钼/碳毡柔性压电材料的X射线衍射图、傅里叶红外光谱测试图及扫描电镜分别如图2-图4所示。从图可知,碳毡的孔洞中充满二硫化钼纳米花。当水流进入碳毡后,进行分流,将污染物带入碳毡内部不同的孔洞中,孔洞中充满二硫化钼纳米花,产生压电效应分解污染物,犹如流水线上的一座小型加工厂,此后水流将继续携带未降解充分的污染物进入“流水线”上的下一个“小型加工厂”,历经层层降解,污染物会彻底分解为无机物流出压电降解体系。
实施例2:本实施例中的抗生素废水的压电催化降解方法是按下述步骤进行的:
步骤1)配制浓度为10mg/L的环丙沙星水溶液,裁取1cm2的二硫化钼/碳毡柔性压电材料,将其置于降解装置中;
步骤2)向降解装置中加入10mL、10mg/L环丙沙星水溶液;
步骤3)每隔30s取2.5mL溶液,并用紫外-可见吸收光谱仪测试其吸光度,以检测环丙沙星浓度随时间变化。
本实施例降解装置如图1所示,由循环泵及装载有二硫化钼/碳毡柔性压电材料的管道组成,通过液体在装置中的循环来模拟自然界中的水流,流速为20mL/min。
实施例3:本实施例中的罗丹明B水溶液的压电催化降解方法是按下述步骤进行的:
步骤1、配制浓度为10mg/L的罗丹明B水溶液,裁取1cm2的二硫化钼/碳毡柔性压电材料,将其置于降解装置(采用图1的装置)中;
步骤2、向降解装置中加入10mL罗丹明B水溶液;
步骤3、每隔30s取2.5mL溶液,并用紫外-可见吸收光谱仪测试其吸光度,以检测罗丹明B浓度随时间变化。
本实施例降解装置如图1所示,由循环泵及装载有二硫化钼/碳毡柔性压电材料的管道组成,通过液体在装置中的循环来模拟自然界中的水流,流速为20mL/min。
通过实施例1制备的二硫化钼/碳毡柔性压电材料压电催化材料,压电催化降解环丙沙星、罗丹明B有机污染物溶液的浓度随时间变化分别如图5、图6所示,从图中可见所制备的二硫化钼/碳毡柔性压电材料压电催化材料具有良好的催化降解环丙沙星和罗丹明B的性能。当降解10mg/L环丙沙星时,降解率达到百分之九十五以上;当降解10mg/L罗丹明B时,降解率达到百分之九十五以上。因此,本发明制备的二硫化钼/碳毡柔性压电材料压电催化剂对环丙沙星抗生素废水和罗丹明B有机污染物有良好的压电催化降解效果。
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。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (5)
1.一种抗生素废水的压电催化降解方法,其特征在于,所述方法是按下述步骤进行的:
将下述方法制备的流水驱动的二硫化钼/碳毡柔性压电材料置于降解装置中;向降解装置中通入抗生素废水,进行降解处理;
其中,所述流水驱动的二硫化钼/碳毡柔性压电材料的制备方法是按下述步骤进行的:
步骤一、将钼酸钠和硫脲溶于去离子水中,得到溶液A;
步骤二、对碳毡亲水化处理,然后完全浸没在溶液A中,然后在密封下进行水热处理,反应完毕后冷却至室温,取出,依次用去离子水和无水乙醇清洗,然后密闭下干燥;得到所述的二硫化钼/碳毡柔性压电材料,所述柔性压电材料中的二硫化钼微观形貌为纳米花状;
其中,步骤二中采用电化学法对碳毡亲水化处理,具体是通过下述步骤实现的:将碳毡固定于外接电源两极上,然后浸泡于浓度为0.1mol/L的硫酸铵溶液中,调整电源电压为10V,通电1分钟,取阳极碳毡;步骤二中水热处理温度为180~200℃,水热处理时间为20h~24h。
2.根据权利要求1所述方法,其特征在于,步骤一中将2.0g~3.0g钼酸钠和4.0g~5.0g硫脲溶于60mL~70mL去离子水中。
3.根据权利要求1所述方法,其特征在于,步骤二中水热处理是在聚四氟乙烯内衬的不锈钢高压釜内进行的。
4.根据权利要求1所述方法,其特征在于,步骤二中干燥温度为60℃~80℃,干燥时间为6h~8h。
5.根据权利要求1所述方法,其特征在于,抗生素废水为环丙沙星抗生素废水。
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