CN112028168B - 二硫化锡/碳纳米纤维复合材料在降解有机污染物中的应用 - Google Patents
二硫化锡/碳纳米纤维复合材料在降解有机污染物中的应用 Download PDFInfo
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Abstract
本发明公开了二硫化锡/碳纳米纤维复合材料在降解有机污染物中的应用,将碳纳米纤维膜置于含有锡源与硫源的前驱体溶液中,反应后干燥,得到二硫化锡/碳纳米纤维复合材料,将二硫化锡/碳纳米纤维复合材料置入含有有机污染物的水中,然后超声处理,完成水中有机污染物的去除。本发明通过利用不同的技术思路,实现单纯SnS2的催化降解有机污染物双酚A的目的,在催化过程,SnS2在超声波刺激下可高效去除有机污染物。
Description
技术领域
本发明涉及纳米复合材料及压电催化技术领域,具体涉及一种一维碳纳米纤维与二维二硫化锡纳米片复合材料的制备方法及其在压电催化去除水体污染物中的应用。
背景技术
全球工业化迅速发展的同时带来严峻的环境污染和资源短缺问题。特别是一些有毒的有机化合物的积累,导致水、空气和土壤的质量下降,这些有毒化合物的危险特性已经严重影响了生态系统,危害到人类健康。太阳能的存储和利用被认为是缓解当前环境污染和资源短缺的有效策略。半导体光催化通常包括三个基本步骤:(1)吸收光子并在半导体中生成电子-空穴对,(2)电荷分离并迁移到催化剂表面,(3)表面氧化还原反应。半导体光催化剂的性能基本上取决于电荷分离和转移动力学。然而,目前大多数光催化剂面临光生电子-空穴快速复合的问题,因此极大地限制了光催化的活性。
发明内容
本发明提供一种一维碳纳米纤维与二维二硫化锡(SnS2)纳米片的复合材料(SnS2/CNFs)及其制备方法,在无需光照的条件下,通过超声处理,实现了催化降解水体污染物的目的。
为了达到上述目的,本发明采用如下具体技术方案:
二硫化锡/碳纳米纤维复合材料在降解有机污染物中的应用。
二硫化锡/碳纳米纤维复合材料去除水中有机污染物的方法,包括以下步骤:将二硫化锡/碳纳米纤维复合材料置入含有有机污染物的水中,然后超声处理,完成水中有机污染物的去除。
本发明所述二硫化锡/碳纳米纤维复合材料(SnS2/CNFs)的制备方法,包括以下步骤:将碳纳米纤维膜置于含有锡源与硫源的前驱体溶液中,反应后干燥,得到二硫化锡/碳纳米纤维复合材料。
本发明中,通过静电纺丝的方法得到聚丙烯腈(PAN)纳米纤维膜;然后通过高温煅烧处理,使得PAN纳米纤维膜碳化得到碳纳米纤维膜(CNFs);再通过溶剂热法在碳纳米纤维膜表面负载一层SnS2纳米片,得到所述纳米复合材料(SnS2/CNFs)。
本发明中,静电纺丝方法中,配制质量分数为8%~12%的聚丙烯腈(PAN)溶液,溶剂为DMF,使用注射器进行静电纺丝。静电纺丝的条件是:滚筒接收器施加负压-8~-2KV,注射器针头施加正压+12~+18KV;针头与接收器之间的距离为15~20 cm;注射器推注速率为0.1~0.3 mm/min;滚筒接收器转速为50~100r/min。优选的,静电纺丝的条件如下:PAN溶液的质量分数为10%,滚筒接收器施加负压-5KV,注射器针头施加正压+15KV;针头与接收器距离为20 cm;纺丝速率为0.2 mm/min;滚筒接收器转速为70 r/min。
本发明中,静电纺丝后得到PAN纳米纤维膜,随后将其在氩气气氛下以2oC/min的速率从室温升温至500oC再保持2~5小时。优选的,在500oC下保持4小时后得到碳纳米纤维膜(CNFs)。
本发明中,为得到SnS2/CNFs纳米复合材料,将一片碳纳米纤维膜(比如2×4cm2)置于含有锡源与硫源的前驱体溶液中,然后溶剂热反应,之后用去离子水和乙醇分别洗涤三次,60oC下鼓风干燥12小时,得到SnS2/CNFs纳米复合材料。
进一步的,使用五水合四氯化锡(SnCl4·5H2O)作为锡源,使用硫代乙酰胺(CH3CSNH2)作为硫源,溶解于无水乙醇得到含有锡源与硫源的前驱体溶液;SnCl4·5H2O与CH3CSNH2的摩尔比为1~3:8,优选的,SnCl4·5H2O与CH3CSNH2的摩尔比为2:8;溶剂热反应在反应釜中120~160oC下反应6~24小时,优选的条件为120oC下12小时。
本发明中,水体中的有机污染物为双酚A;超声处理的功率为300 W。进一步的,超声处理前避光处理;超声处理时不进行光照,可以理解的,所述光照为本领域常识,为了实现光催化而进行的光照,而非常规环境下的照明,不过本发明的超声处理可以在完全避光下进行。
本发明将上述SnS2/CNFs纳米复合材料(2×4 cm2,SnS2的质量为8 mg)放入双酚A水溶液中,黑暗条件下吸附1小时后提供超声波振动开始降解,实现水体中有机污染物的去除。
本发明与现有技术不同之处在于催化降解的目标污染物不同,而且催化过程提供的条件以及机理不同。SnS2作为过渡金属二硫化物,其导带位置较负,现有技术在催化领域通常用于分解水产氢、CO2还原以及还原Cr(VI),未见到用于光催化降解有机污染物方面的文献报道,更没有利用单纯的SnS2可实现光催化去除有机污染物,若要通过能带调控或贵金属等的修饰,不仅制备过程繁琐,而且成本增加。本发明通过利用不同的技术思路,实现单纯SnS2的催化降解有机污染物双酚A的目的,在催化过程,SnS2在超声波刺激下可高效去除有机污染物。
本发明的优点
(1) 本发明采用静电纺丝的方法得到碳纳米纤维膜作为粉末催化剂的载体,便于催化剂的回收利用,不易造成二次污染。在制备方法上简单方便,同时得到的纳米纤维膜具有一级孔道,较大的比表面积利于粉末催化剂的分散,也提高纳米复合材料对有机污染物的吸附能力,实现吸附—降解一体化。
(2) 本发明采用溶剂热法制备的二维二硫化锡纳米片具有丰富的活性边缘,均匀分散在碳纳米纤维的表面进一步增大比表面积,不仅提高材料的吸附性,还可以提供更多的活性位点进而提高催化活性。
(3) 本发明首次将二硫化锡应用于催化降解有机污染物体系中,在无需光照的条件下,通过提供超声振动,促使SnS2弯曲变形,提高催化活性。
附图说明
图1为碳纳米纤维(CNFs)的扫描电镜图;
图2为碳纳米纤维负载二硫化锡纳米片(SnS2/CNFs)的扫描电镜图;
图3为碳纳米纤维负载二硫化锡纳米片(SnS2/CNFs)的透射电镜图;
图4为碳纳米纤维负载二硫化锡纳米片(SnS2/CNFs)降解双酚A的效果图。
具体实施方式
本发明通过简便的静电纺丝的方法得到一维碳纳米纤维,然后采用简单的溶剂热的方法在碳纳米纤维表面负载二维SnS2纳米片,在无需光照的条件下,实现降解水体污染物的目的。
实施例一
碳纳米纤维的制备,具体步骤如下:
1.0 g PAN溶解于10 mL DMF中,搅拌12小时得到透明溶液。转移至5 mL 注射器中进行静电纺丝。静电纺丝的条件设置为滚筒接收器施加负压-5KV,注射器针头施加正压+15KV;针头与接收器距离为20 cm;纺丝速率为0.2 mm/min;滚筒接收器转速为50 r/min。得到的PAN纳米纤维膜在管式炉中氩气气氛下500oC碳化4小时得到碳纳米纤维膜(CNFs),升温速率为2oC/min(室温至500oC)。得到的碳纳米纤维用于实施例二到例六。
附图1为上述碳纳米纤维(CNFs)的扫描电镜图。从图中可以看到纤维的直径均匀分布(大约500nm)。
实施例二
SnS2/CNFs纳米复合材料(0.25-SnS2/CNFs)的制备,具体步骤如下:
称取87.7 mg(0.25 mol)SnCl4·5H2O溶解于20 mL无水乙醇中,记为A溶液。称取150 mg(2 mol)CH3CSNH2溶解于20 mL无水乙醇中,记为B溶液。将A和B两种溶液混合均匀之后,倒入体积为50mL反应釜内胆中,将一片碳纳米纤维膜(2×4cm2)倾斜浸入其中,在120oC下反应12小时,得到的产物依次用去离子水和乙醇洗涤三次,最后在60oC下干燥12小时得到0.25-SnS2/CNFs纳米复合材料。
实施例三
SnS2/CNFs纳米复合材料(0. 5-SnS2/CNFs)的制备,具体步骤如下:
称取175.3 mg(0.5mol)SnCl4·5H2O溶解于20 mL无水乙醇中,记为A溶液。称取150mg(2 mol)CH3CSNH2溶解于20 mL无水乙醇中,记为B溶液。将A和B两种溶液混合均匀之后,倒入体积为50 mL反应釜内胆中,将一片碳纳米纤维膜(2×4cm2)倾斜浸入其中,在120oC下反应12小时,得到的产物依次用去离子水和乙醇洗涤三次,最后在60oC下干燥12小时得到0.5-SnS2/CNFs纳米复合材料,SnS2的负载质量为8 mg。附图2为上述0.5-SnS2/CNFs纳米复合材料的扫描电镜图,附图3为上述0.5-SnS2/CNFs纳米复合材料的透射电镜照片;从图中可以看到,SnS2纳米片均匀地负载在碳纳米纤维表面。
实施例四
SnS2/CNFs纳米复合材料(0.75-SnS2/CNFs)的制备,具体步骤如下:
称取263.0 mg(0.75mol)SnCl4·5H2O溶解于20mL无水乙醇中,记为A溶液。称取150mg(2 mol)CH3CSNH2溶解于20 mL无水乙醇中,记为B溶液。将A和B两种溶液混合均匀之后,倒入体积为50mL反应釜内胆中,将一片碳纳米纤维膜(2×4cm2)倾斜浸入其中,在120oC下反应12小时,得到的产物依次用去离子水和乙醇洗涤三次,最后在60oC下干燥12小时得到0.75-SnS2/CNFs纳米复合材料。
实施例五
0.5-SnS2/CNFs对双酚A的光降解实验:取一片根据实施例三方法制备的0.5-SnS2/CNFs(2×4cm2)复合材料置于含10 mL浓度为10 mg/L的双酚A水溶液小烧杯中,避光吸附1小时达到吸附平衡,期间每30 分钟取样800 μL,经滤头(0.22 μm)过滤后注入高效液相样品瓶中。吸附平衡之后,用300 W的氙灯照射催化剂(不进行超声、搅拌等处理),每20 分钟取样800 μL,经滤头(0.22 μm)过滤除去催化剂后注入高效液相样品瓶中,使用高效液相色谱仪在去离子水:甲醇= 30:70 的流动相中测试样品在290 nm 紫外波长下的吸收曲线,记录在6 分钟 左右的双酚A 出峰面积,并把初始双酚A 的浓度记为100 %,得到双酚A 的光降解曲线。
实施例六
0.5-SnS2/CNFs对双酚A的压电催化降解实验:取一片根据实施例三方法制备的0.5-SnS2/CNFs(2×4 cm2)复合材料置于含10 mL浓度为10 mg/L的双酚A水溶液小烧杯中,避光吸附1小时,期间每30 分钟取样800 μL,经滤头(0.22 μm)过滤后注入高效液相样品瓶中。吸附平衡之后,将样品转移至玻璃试管中,将试管斜置于超声清洁器中,避光下打开超声,功率调至300 W,每20 分钟取样800 μL,经滤头(0.22 μm)过滤除去催化剂后注入高效液相样品瓶中,使用高效液相色谱仪在去离子水:甲醇= 30:70 的流动相中测试样品在290nm 紫外波长下的吸收曲线,记录在6 分钟 左右的双酚A 出峰面积,并把初始双酚A 的浓度记为100 %,得到双酚A 的压电催化降解曲线。
附图4是碳纳米纤维负载二硫化锡纳米片(0.5-SnS2/CNFs)降解双酚A的效果图。从图中可以看到,在光照条件下,0.5-SnS2/CNFs对双酚A无降解能力,但在超声条件下,0.5-SnS2/CNFs对双酚A的降解率为100%。
采用上述同样的测试方法(避光超声),测试0.25-SnS2/CNFs纳米复合材料、0.75-SnS2/CNFs纳米阵列复合材料对含10 mL浓度为10 mg/L的双酚A 水溶液的降解效果,降解120 分钟时,双酚A 的残留率分别为5.38%和0%。
称取175.3 mg(0.5 mol)SnCl4·5H2O溶解于20 mL无水乙醇中,记为A溶液。称取150 mg(2 mol)CH3CSNH2溶解于20 mL无水乙醇中,记为B溶液。将A和B两种溶液混合均匀之后,倒入体积为50mL反应釜内胆中,在120oC下反应12小时,得到的产物依次用去离子水和乙醇洗涤三次,最后在60oC下干燥12小时得到SnS2纳米花。采用实施例六同样的测试方法(硫化锡用量为8mg),降解120分钟后,双酚A的残留率为88.5%,去除率很低。
将实施例一的碳纳米纤维(2×4cm2)采用实施例六同样的测试方法,对双酚A无降解能力。将实施例六中超声更换为磁力搅拌(200rpm),其余不变,降解120分钟后,双酚A的残留率为75.1%;如果超声更换为磁力搅拌(200rpm)加上300 W的氙灯照射,降解120分钟后,双酚A的残留率为73.92%。
根据实施例三制备的0.5-SnS2/CNFs(2×4 cm2)复合材料置于管式炉中,400℃煅烧15分钟,得到复合催化剂,采用实施例五的测试方法,降解120 分钟后,双酚A的残留率为64.7%;采用实施例六的测试方法,降解120 分钟后,双酚A的残留率为68.5%。
本发明公开了一种无需光照、利用机械能刺激进行水体有机污染物降解的纳米复合材料的制备方法,实现了催化双酚A的有效降解。首先通过静电纺丝得到聚丙烯腈纳米纤维,然后在氩气气氛下高温碳化转化为碳纳米纤维,最后通过简单的溶剂热法在碳纳米纤维表面负载一层二硫化锡纳米片。二硫化锡由于其合适的带隙(2.08~2.44eV)和对可见光较大范围的吸收而作为常见的光催化剂,但其通常用作还原重金属离子Cr(VI)、还原二氧化碳等,很少用于有机污染物的去除。本发明首次将其应用到水体有机污染物的催化降解体系中,降解过程提供的超声波实现有效去除有机污染物的目的,另外,将其分散负载于碳纳米纤维表面,有利于回收利用,减少造成二次污染的可能。
Claims (2)
1.二硫化锡/碳纳米纤维复合材料去除水中有机污染物的方法,包括以下步骤:将二硫化锡/碳纳米纤维复合材料置入含有有机污染物的水中,然后超声处理,完成水中有机污染物的去除;有机污染物为双酚A;超声处理时不进行光照,超声处理的功率为200~500 W;所述二硫化锡/碳纳米纤维复合材料的制备方法为,将碳纳米纤维膜置于含有锡源与硫源的前驱体溶液中,反应后干燥,得到二硫化锡/碳纳米纤维复合材料;锡源与硫源的摩尔比为1~3∶8。
2.根据权利要求1所述二硫化锡/碳纳米纤维复合材料去除水中有机污染物的方法,其特征在于,二硫化锡负载于碳纳米纤维表面。
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