CN106914261B - 一种碳酸银纳米球修饰的氧化石墨烯复合材料及其制备方法及应用 - Google Patents
一种碳酸银纳米球修饰的氧化石墨烯复合材料及其制备方法及应用 Download PDFInfo
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Abstract
一种碳酸银纳米球修饰的氧化石墨烯复合材料及其制备方法及应用,属于光催化纳米材料技术领域。棒状纳米碳酸银修饰到氧化石墨烯表面后转变为纳米球,粒径为50~100nm,制备方法为:避光条件下,将表面活性剂加入硝酸银溶液中,再逐滴加入碳酸钠溶液,磁力搅拌混匀后进行水热反应、洗涤、烘干后得到棒状纳米碳酸银,将氧化石墨烯和得到的棒状纳米碳酸银混合反应、产物离心洗涤、烘干后得到最终产物。该复合材料解决了单独的纳米碳酸银作为光催化材料在可见光条件下会表现出不稳定性,可重复利用性差,催化活性低的问题,可以在可见光下高效光催化降解苯酚,从而提供一种可应用于废水处理系统中有机污染物降解的光催化材料。
Description
技术领域
本发明属于光催化纳米材料技术领域,具体为一种碳酸银纳米球修饰的氧化石墨烯复合材料及其制备方法及应用。
背景技术
光催化降解是近年来发展起来的水污染控制领域的一项重要技术,指有机物在光照和光催化剂的双重作用下,经过一系列反应产生具有强氧化能力的羟基自由基和超级氧离子,来降解分解有机污染物,有机物逐步氧化成低分子中间产物,并最终生成二氧化碳、水及其它离子如硝酸根、磷酸根、氯离子等,从而实现有机污染物的降解去除。光催化剂在有机物光降解中的作用不容小觑,半导体光催化剂具有很多优异的光学性能,近几十年来在能源和环境中的诸多应用使其受到光降解污染物研究领域的广泛关注。
作为一种半导体光催化材料,碳酸银在可见光下具有高效的光催化降解有机物的性能。然而,用单独的纳米碳酸银作为光催化材料在光照下会表现出不稳定性,主要由于金属银元素易于促进光生电子和空穴的复合,导致材料产生光学腐蚀,从而使得光催化降解性能有所降低。为解决上述问题,在碳酸银中引入一种新型纳米材料氧化石墨烯,氧化石墨烯是石墨烯氧化的产物,表面含有大量羟基和羧基官能团,通过共价作用可以与光催化材料结合形成复合材料。更重要的是,氧化石墨烯有利于拓宽纳米碳酸银对太阳光谱的吸收范围,从而促进更多电子空穴对的产生;同时,氧化石墨烯能加速电子传递,通过对光生电子的转移有效抑制碳酸银的光生电子和空穴的复合。
随着纳米技术的发展,纳米结构半导体材料的制备已经不是难题。鉴于光催化剂的反应活性点位越多越有利于增强其光催化性能,将碳酸银制备成纳米级能增加材料比表面积,从而提高其对污染物的光催化降解效率。本申请实现纳米级碳酸银的一步制备,并将其修饰到氧化石墨烯表面,碳酸银的纳米形态进一步优化,得到一种碳酸银纳米球修饰的氧化石墨烯复合材料,这种复合光催化材料在光催化活性和材料稳定性方面都将有显著提高。
发明内容
解决的技术问题:针对单独的纳米碳酸银作为光催化材料在光照条件下会表现出不稳定性,催化活性低的问题,本发明提供一种碳酸银纳米球修饰的氧化石墨烯复合材料及其制备方法及应用,可以在可见光下高效光催化降解苯酚,从而提供一种可应用于废水处理系统中有机污染物降解的光催化材料。
技术方案:一种碳酸银纳米球修饰的氧化石墨烯复合材料,棒状纳米碳酸银通过静电自组装修饰到氧化石墨烯表面后转变为纳米球,粒径为50~100nm。
一种上述碳酸银纳米球修饰的氧化石墨烯复合材料的制备方法,包括以下步骤:
步骤一、避光条件下,将表面活性剂十六烷基三甲基溴化铵溶液加入硝酸银溶液,再逐滴加入碳酸钠溶液,经磁力搅拌充分混匀后转移至高压反应釜中进行水热反应,待产物自然冷却至室温后用乙醇离心洗涤,烘干得到表面带正电性的棒状纳米碳酸银;
步骤二、避光条件下,将呈现负电性的氧化石墨烯超声分散在乙二醇中,再将步骤一所得的纳米碳酸银超声分散在蒸馏水中,混合并磁力搅拌,发生静电作用促进材料间的自组装反应,产物用蒸馏水离心洗涤,烘干得到碳酸银纳米球修饰的氧化石墨烯复合材料。
作为优选,所述步骤一中硝酸银溶液、十六烷基三甲基溴化铵溶液与碳酸钠溶液的浓度分别为0.1mol/L、3.5mmol/L、0.1mol/L,其溶液体积比例为1:1:0.5,体积范围为20~40mL:20~40mL:10~20mL,磁力搅拌充分混匀时间为0.5-1.5小时。
作为优选,所述步骤一中硝酸银溶液、十六烷基三甲基溴化铵溶液与碳酸钠溶液的比例优选为30mL:30mL:15mL,磁力搅拌充分混匀时间为1小时。
作为优选,所述步骤一中水热反应的温度为60~80℃,反应1~3小时。
作为优选,所述步骤一中水热反应的温度优选为70℃,反应2小时。
作为优选,所述步骤二中碳酸银与氧化石墨烯的质量比为50~150:1,磁力搅拌充分混匀时间为1~3小时。
作为优选,所述步骤二中碳酸银与氧化石墨烯的质量比优选为100:1,磁力搅拌充分混匀时间为2小时。
一种碳酸银纳米球修饰的氧化石墨烯复合材料在光催化降解废水中有机污染物上的应用。
作为优选,所述有机污染物为酚类。
有益效果:1、纳米碳酸银的水热合成过程中,添加表面活性剂十六烷基三甲基溴化铵溶液以控制碳酸银纳米形态的生长,残留的表面活性剂用乙醇离心洗涤去除;
2、碳酸银纳米球修饰的氧化石墨烯复合材料的制备中,发生静电自组装反应,所述静电自组装反应能够使棒状纳米碳酸银的正电荷银离子部分与带负电的氧化石墨烯通过静电吸附作用而均匀稳固地结合;
3、碳酸银修饰到氧化石墨烯表面后,由原来的纳米棒状转变为粒径50~100nm的纳米球,纳米碳酸银尺寸的优化使复合材料的比表面积显著增大,有利于光催化性能的提高。
附图说明
图1为实施例3中纳米碳酸银和碳酸银纳米球修饰的氧化石墨烯复合材料的扫描电镜图;
图2为实施例3中氧化石墨烯、纳米碳酸银和碳酸银纳米球修饰的氧化石墨烯复合材料的红外光谱图;
图3为实施例4中可见光下苯酚的光催化降解图。
具体实施方式
下面结合附图及具体实施方式对本发明做进一步详细说明。
实施例1
一种碳酸银纳米球修饰的氧化石墨烯复合材料,棒状纳米碳酸银通过静电自组装修饰到氧化石墨烯表面后转变为纳米球,平均粒径约为50nm。
一种碳酸银纳米球修饰的氧化石墨烯复合材料的制备方法,步骤如下:
步骤一、在避光条件下,将20ml 3.5mmol/L表面活性剂十六烷基三甲基溴化铵溶液加入20ml 0.1m/L的硝酸银水溶液,再向混合物中逐滴加入10ml 0.1m/L的碳酸钠水溶液,经磁力搅拌充分混匀1小时后转移到高压反应釜中,
在70℃下水热反应2小时,待产物自然冷却至室温后用乙醇离心洗涤3次,最后烘干得到棒状纳米碳酸银;
步骤二、在避光条件下,将1.0mg氧化石墨烯超声分散在乙二醇中,步骤一所得的纳米碳酸银取0.1g超声分散在蒸馏水中,混合并磁力搅,使之发生静电自组装反应,反应2小时后用蒸馏水离心洗涤3次,最后烘干得到碳酸银纳米球修饰的氧化石墨烯复合材料。
实施例2
一种碳酸银纳米球修饰的氧化石墨烯复合材料,棒状纳米碳酸银修饰到氧化石墨烯表面后转变为纳米球,平均粒径约为100nm。
一种碳酸银纳米球修饰的氧化石墨烯复合材料的制备方法,步骤如下:
步骤一、在避光条件下,将40ml 3.5mmol/L表面活性剂十六烷基三甲基溴化铵溶液加入40ml 0.1m/L的硝酸银水溶液,再向混合物中逐滴加入20ml 0.1m/L的碳酸钠水溶液,经磁力搅拌充分混匀1小时后转移到高压反应釜中,在70℃下水热反应2小时,待产物自然冷却至室温后用乙醇离心洗涤3次,最后烘干得到棒状纳米碳酸银;
步骤二、在避光条件下,将3.0mg氧化石墨烯超声分散在乙二醇中,步骤一所得的纳米碳酸银取0.3g超声分散在蒸馏水中,混合并磁力搅拌,使之发生静电自组装反应,反应2小时后用蒸馏水离心洗涤3次,最后烘干得到碳酸银纳米球修饰的氧化石墨烯复合材料。
实施例3
一种碳酸银纳米球修饰的氧化石墨烯复合材料,棒状纳米碳酸银修饰到氧化石墨烯表面后转变为纳米球,平均粒径约为70nm。
一种碳酸银纳米球修饰的氧化石墨烯复合材料的制备方法,步骤如下:
步骤一、在避光条件下,将30ml 3.5mmol/L表面活性剂十六烷基三甲基溴化铵溶液加入30ml 0.1m/L的硝酸银水溶液,再向混合物中逐滴加入15ml 0.1m/L的碳酸钠水溶液,经磁力搅拌充分混匀1小时后转移到高压反应釜中,在70℃下水热反应2小时,待产物自然冷却至室温后用乙醇离心洗涤3次,最后烘干得到棒状纳米碳酸银;
步骤二、在避光条件下,将2.0mg氧化石墨烯超声分散在乙二醇中,步骤一所得的纳米碳酸银取0.2g超声分散在蒸馏水中,混合并磁力搅拌,使之发生静电自组装反应,反应2小时后用蒸馏水离心洗涤3次,最后烘干得到碳酸银纳米球修饰的氧化石墨烯复合材料。
实施例4
实施例3制得的碳酸银纳米球修饰的氧化石墨烯复合材料对苯酚的光催化降解应用:
取50mg实施例3制得的碳酸银纳米球修饰的氧化石墨烯复合材料,加入50mL10mg/L的苯酚溶液,在避光条件下,超声30分钟以保证纳米复合材料光催化剂完全分散于溶液中,继续将分散液置于磁力搅拌下充分混匀1小时以达到吸附-解吸平衡,然后转移到可见光下发生光催化降解反应,反应后所得混合物用薄膜过滤器过滤,使用高效液相色谱测定光催化降解前后苯酚的浓度变化。
为了进一步证明纳米碳酸银的性能优越,用普通沉淀法制备得到碳酸银,并通过与步骤二相同的方法制备碳酸银-氧化石墨烯材料。控制其他条件相同,在没有催化剂(nocatalyst)、仅有氧化石墨烯(GO)、仅有纳米碳酸银(Ag2CO3,HT)、仅有沉淀法制备的碳酸银(Ag2CO3)和沉淀法制备的碳酸银-氧化石墨烯(GO/Ag2CO3)材料的情况下,作为五组对照实验,与实施例3制备的纳米碳酸银-氧化石墨烯(GO/Ag2CO3,HT)材料一起对苯酚进行光催化降解。如图3所示,在没有催化剂和仅有氧化石墨烯的情况下,苯酚几乎未发生降解;对比两种制备方法得到的碳酸银对苯酚的降解曲线,发现水热法制备的纳米碳酸银对苯酚的降解率明显更高;水热法制备的纳米碳酸银及其复合材料对苯酚的吸收及光催化降解结果如表1。
表1 水热法制备的碳酸银对苯酚的吸收及光催化降解结果
在碳酸银纳米球修饰的氧化石墨烯复合材料的催化作用下,苯酚的浓度降低最为显著。这说明了碳酸银纳米球修饰的氧化石墨烯复合材料在可见光下光催化降解苯酚的应用具有显著的优越性。
以上所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径获得。此外,以上实施例中所使用的硝酸银、十六烷基三甲基溴化铵、碳酸钠、乙醇和乙二醇购自国药集团化学试剂有限公司,氧化石墨烯购自先锋纳米材料科技有限公司;实施例中所使用的高效液相色谱以甲醇为流动相。
Claims (7)
1.一种碳酸银纳米球修饰的氧化石墨烯复合材料的制备方法,其特征在于,包括以下步骤:
步骤一、避光条件下,将表面活性剂十六烷基三甲基溴化铵溶液加入硝酸银溶液,再逐滴加入碳酸钠溶液,经磁力搅拌充分混匀后转移至高压反应釜中进行水热反应,待产物自然冷却至室温后用乙醇离心洗涤,烘干得到表面带正电性的纳米碳酸银;
步骤二、避光条件下,将呈现负电性的氧化石墨烯超声分散在乙二醇中,再将步骤一所得的纳米碳酸银超声分散在蒸馏水中,混合并磁力搅拌,发生静电作用促进材料间的自组装反应,产物用蒸馏水离心洗涤,烘干得到碳酸银纳米球修饰的氧化石墨烯复合材料,棒状纳米碳酸银通过静电自组装修饰到氧化石墨烯表面后形成纳米球,粒径为50-100nm。
2.根据权利要求1所述的一种碳酸银纳米球修饰的氧化石墨烯复合材料的制备方法,其特征在于,所述步骤一中硝酸银溶液、十六烷基三甲基溴化铵溶液与碳酸钠溶液的浓度分别为0.1mol/L、3.5mmol/L、0.1mol/L,其溶液体积比例为1:1:0.5,体积范围为20~40mL:20~40mL:10~20mL,磁力搅拌充分混匀时间为0.5-1.5小时。
3.根据权利要求1所述的一种碳酸银纳米球修饰的氧化石墨烯复合材料的制备方法,其特征在于,所述步骤一中硝酸银溶液、十六烷基三甲基溴化铵溶液与碳酸钠溶液的比例为30mL:30mL:15mL,磁力搅拌充分混匀时间为1小时。
4.根据权利要求1所述的一种碳酸银纳米球修饰的氧化石墨烯复合材料的制备方法,其特征在于,所述步骤一中水热反应的温度为60~80℃,反应1~3小时。
5.根据权利要求1所述的一种碳酸银纳米球修饰的氧化石墨烯复合材料的制备方法,其特征在于,所述步骤一中水热反应的温度为70℃,反应2小时。
6.根据权利要求1所述的一种碳酸银纳米球修饰的氧化石墨烯复合材料的制备方法,其特征在于,所述步骤二中碳酸银与氧化石墨烯的质量比为50~150:1,磁力搅拌充分混匀时间为1~3小时。
7.根据权利要求1所述的一种碳酸银纳米球修饰的氧化石墨烯复合材料的制备方法,其特征在于,所述步骤二中碳酸银与氧化石墨烯的质量比为100:1,磁力搅拌充分混匀时间为2小时。
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