CN106362742A - 一种Ag/ZnO纳米复合物及其制备方法和应用 - Google Patents
一种Ag/ZnO纳米复合物及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于ZnO纳米复合材料技术领域,公开了一种Ag/ZnO纳米复合物及其制备方法和应用。该方法包括以下步骤:将二水醋酸锌和硝酸银加入到聚乙二醇中反应,反应结束后将所得反应液冷却至室温后离心分离,将所得的沉淀洗涤干燥得Ag/ZnO纳米复合物。本发明利用聚乙二醇的溶剂化和稳定化作用,以二水醋酸锌和硝酸银为原料,采用一步法制备分散性好的Ag/ZnO纳米复合物。该方法反应条件温和、操作简单、快速且无污染、产率高,原料廉价易得且绿色环保,产物呈固体粉末状,利于保存以及进一步利用,在可见光照射下表现出良好的光催化性能,不同银锌摩尔比下所得Ag/ZnO复合物的光催化活性均优于市售光催化剂P25和纯ZnO。
Description
技术领域
本发明属于ZnO纳米复合材料技术领域,特别涉及一种Ag/ZnO纳米复合物及其制备方法与应用。
背景技术
纳米ZnO是多功能的新型无机材料,随着晶粒尺寸降至纳米级,会产生体积效应、表面效应、量子尺寸效应、宏观量子隧道效应以及晶体结构的变化。近年来人们发现它在光学、电子、化工、陶瓷、医药、生物、纺织等领域有着无与伦比的应用价值。其中在作为光催化剂方面,由于纳米ZnO的小颗粒和大比表面积的特点,其表面活性中心众多,催化活性远高于传统催化剂,另外它不必附着在惰性载体上,可直接放置液相体系中反应,且降解产物多为二氧化碳和水,不会对环境造成二次污染。因此纳米ZnO作为光催化剂被广泛应用于处理废水中的有机污染物。然而纯ZnO对太阳光的利用率只占到3%~5%,并且光生载流子与空位复合的能力较强,这不利于光催化效率的提高。
研究发现,ZnO的复合能改变其杂质能级,提高光量子利用效率,抑制光生电子和空穴的复合,进而有效提高ZnO的光催化活性。其中,具有高导电性的贵金属纳米粒子(如Ag、Au、Pt、Pd)沉积在半导体表面时能作为一个载光生电荷的槽,极大地抑制光生载流子的复合。Ag是最便宜的贵金属,能被大量应用在工业上,所以Ag/ZnO纳米复合物成为进一步研究的首选材料。
目前,已经报道的合成Ag/ZnO纳米复合物的方法有很多。Weiwei Lu等通过简单的一锅水热法得到了Ag/ZnO纳米复合物,他们将Zn(NO3)2·6H2O和AgNO3的水溶液、酪氨酸溶液以及氨水溶液的混合液转移到聚四氟乙烯作内衬的高压锅中,在373K下反应8h得到产物。实验证明,合成的Ag/ZnO纳米复合物在250W的高压汞灯照射下能有效催化降解有机染料,产物还在抑制细菌方面有良好的应用前景。Chungui Tian等以Zn(Ac)2·2H2O为前驱体,乙二醇为媒介在160℃下反应8h后,加入AgNO3继续反应0.5h合成了Ag/ZnO微球。产物在15W的紫外灯照射下降解罗丹明B溶液至完全需要50min。Y.F.Wang等人首先将前处理过的玻璃基片浸入90℃的Zn(Ac)2·2H2O和六亚甲基四胺(C6H12N4)的混合溶液中1h得到ZnO薄膜,再将该薄膜浸入95℃的AgNO3和C6H12N4的混合溶液中一段时间合成出了Ag-ZnO复合薄膜。Dafeng Zhang等人将盛有Zn(NO3)2·6H2O、AgNO3和柠檬酸混合清液的烧杯放在90℃的电热套上蒸发溶剂得到凝胶状物质。然后将烧杯转移到一个家用微波炉(700W)中5min,采用微波燃烧法得到了多孔Ag/ZnO纳米复合物。由于硝酸盐和柠檬酸的氧化还原放热反应会产生气体,随着大量气体的释放,燃烧反应立刻发生,即可得到多孔Ag/ZnO纳米复合物。该课题组还通过改变AgNO3的加入量得到了不同摩尔比的Ag/ZnO复合物(0~2.0at.%)。结果表明,随着Ag浓度的增加,Ag/ZnO纳米复合物的能隙减小同时观察到荧光猝灭现象。在紫外灯照射下Ag/ZnO纳米复合物的光催化活性显著增强,在可见光照射下却得到了相反的结果。Fazhe Sun等人将Zn(NO3)2·6H2O、AgNO3和环六亚甲基四胺[HMT;(CH2)6N4]的混合水溶液置于120W的微波炉中照射10min得到了Ag/ZnO固体沉淀。生成的Ag/ZnO纳米复合物在300W高压汞灯照射下的光催化效果远优于纯ZnO。Kamil Burak Dermenci等以Zn(NO3)2·6H2O、AgNO3和乙醇为原料,采用优化了合成条件的超声雾化热分解法(USP)一步制备出了均匀的球状Ag/ZnO纳米复合物。光催化结果表明,紫外光照射60min时,该球状Ag/ZnO纳米复合物对亚甲基蓝的去除率为40%。J.Wang等则利用光还原法将AgNO3、PEG溶液和提前制备好的ZnO三者的混合液置于一个8W、波长为254nm的紫外灯下,于50℃下搅拌4h后过滤得到Ag/ZnO复合物。
现有制备方法虽能得到形貌较好的Ag/ZnO复合物且产物的光催化效果与纯ZnO相比有显著提高,但仍存在实验操作复杂、反应耗时久、所需温度高、原料众多且不环保等问题,并且所得Ag/ZnO对有机污染物的光催化降解所需时间长、降解不完全、有的只有在紫外光下才能降解。因此,极有必要研究一种简单、快速、温和的制备Ag/ZnO复合物的方法,并要求所得复合物能在可见光下快速降解有机污染物。
发明内容
为了克服上述现有技术的缺点与不足,本发明的首要目的在于提供一种Ag/ZnO纳米复合物的制备方法。该制备方法具有绿色环保、条件温和易控制、用时短、产率高、产物形貌好且稳定、易于工业化生产、低成本等优点。
本发明另一目的在于提供上述方法制备的Ag/ZnO纳米复合物。
本发明再一目的在于提供上述Ag/ZnO纳米复合物在光催化以及抗菌方面的应用。
本发明的目的通过下述方案实现:
一种Ag/ZnO纳米复合物的制备方法,其具体包括以下步骤:将二水醋酸锌和硝酸银加入到聚乙二醇中反应,反应结束后将所得反应液冷却至室温后离心处理,将所得的沉淀洗涤干燥后即得Ag/ZnO纳米复合物。
所述的聚乙二醇优选为聚乙二醇200、聚乙二醇400、聚乙二醇600中的至少一种。
所述的反应是指在160~200℃下反应0.5~2h。
所用的硝酸银与二水醋酸锌的摩尔比为(0~8):100,其中硝酸银的摩尔数不为0。
所用的聚乙二醇用量为每加入10mmol的二水醋酸锌对应使用40mL的聚乙二醇。
所述的洗涤是指先用蒸馏水洗涤2次再用无水乙醇洗涤1次,所述的干燥是指用60~100℃烘箱干燥。
一种由上述方法制备得到的Ag/ZnO纳米复合物,其粒径在20~30nm。
上述的Ag/ZnO纳米复合物在紫外光和可见光照射下均对罗丹明B溶液表现出不错的光催化活性,可应用在光催化领域。同时纳米ZnO和纳米Ag均具有优良的抗菌性能,纳米Ag的复合能有效提高ZnO的抗菌性能,并用于制作抗菌类产品。
本发明的机理为:
Ag/ZnO纳米复合物的制备和应用已经成为科学技术的研究热点之一。但在实际制备中存在反应耗时久、所需温度高、设备复杂、需要加入一些有毒、污染或腐蚀性的化学物质等缺点。本发明利用聚乙二醇的溶剂化和稳定化作用,以二水醋酸锌和硝酸银为原料,采用一步法制备分散性好的Ag/ZnO纳米复合物,并研究产物在可见光照射下的光催化性能。具有反应条件温和、操作简单、快速且无污染、产率高,原料廉价易得且绿色环保等优点,且产物呈固体粉末状,利于保存以及进一步利用,并且在可见光照射下表现出良好的光催化性能。
本发明相对于现有技术,具有如下的优点及有益效果:
(1)本发明采用“一步法”合成出了Ag/ZnO纳米复合物,反应无需提供超声活化、高温、高压等反应条件,具有能量消耗少,操作简单,反应时间短等优点,适于工业化生产。
(2)本发明原料廉价易得且绿色环保,使用清洁无毒的聚乙二醇为溶剂,利用其良好的溶剂化作用和配位效应,且产物易于洗涤分离。
(3)本发明中制备得到的Ag/ZnO纳米复合物具有良好的光催化性能尤其是可见光催化性能,不同银锌摩尔比下所得Ag/ZnO复合物的光催化活性均优于市售光催化剂P25和纯ZnO。
附图说明
图1为不同银锌摩尔比下所得产物的TEM图,其中nAg/nZn(mmol)(a)0%,(b)0.5%,(c)2%,(d)4%,(e)6%,(f)8%。
图2为不同银锌摩尔比下所得产物的XRD谱,其中nAg/nZn(mmol)(a)0%,(b)0.5%,(c)2%,(d)4%,(e)6%,(f)8%。
图3为紫外光照射时P25和不同银锌摩尔比下所得产物对罗丹明B的光催化降解效率。
图4为可见光照射时P25和不同银锌摩尔比下所得产物对罗丹明B的光催化降解效率。
具体实施方式
下面结合实施例和附图对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例中所用试剂如无特殊说明均可从市场常规购得。
实施例1
将10mmol二水醋酸锌和0.2mmol硝酸银加入到180℃的40.00mLPEG-200中磁力搅拌0.5h,得灰色混浊液。自然冷却至室温,将产物离心处理,分离上层溶胶清液及沉淀,将所得沉淀用二次水和无水乙醇洗涤3次,80℃烘箱烘干。然后将产物密封保存以备进一步表征。
实施例2
将10mmol二水醋酸锌和0.2mmol硝酸银加入到180℃的40.00mLPEG-200中磁力搅拌2h,得灰色混浊液。自然冷却至室温,将产物离心处理,分离上层溶胶清液及沉淀,将所得沉淀用二次水和无水乙醇洗涤3次,80℃烘箱烘干。然后将产物密封保存以备进一步表征。
实施例3
将10mmol二水醋酸锌和0.2mmol硝酸银加入到160℃的40.00mLPEG-200中磁力搅拌1h,得灰色混浊液。自然冷却至室温,将产物离心处理,分离上层溶胶清液及沉淀,将所得沉淀用二次水和无水乙醇洗涤3次,80℃烘箱烘干。然后将产物密封保存以备进一步表征。
实施例4
将10mmol二水醋酸锌和0.2mmol硝酸银加入到200℃的40.00mLPEG-200中磁力搅拌1h,得灰色混浊液。自然冷却至室温,将产物离心处理,分离上层溶胶清液及沉淀,将所得沉淀用二次水和无水乙醇洗涤3次,80℃烘箱烘干。然后将产物密封保存以备进一步表征。
实施例5
将10mmol二水醋酸锌和0.2mmol硝酸银加入到180℃的40.00mLPEG-400中磁力搅拌1h,得灰色混浊液。自然冷却至室温,将产物离心处理,分离上层溶胶清液及沉淀,将所得沉淀用二次水和无水乙醇洗涤3次,80℃烘箱烘干。然后将产物密封保存以备进一步表征。
实施例6
将10mmol二水醋酸锌和0.2mmol硝酸银加入到180℃的40.00mLPEG-600中磁力搅拌1h,得灰色混浊液。自然冷却至室温,将产物离心处理,分离上层溶胶清液及沉淀,将所得沉淀用二次水和无水乙醇洗涤3次,80℃烘箱烘干。然后将产物密封保存以备进一步表征。
实施例7
将10mmol二水醋酸锌和0.05mmol硝酸银加入到180℃的40.00mLPEG-200中磁力搅拌1h,得灰色混浊液。自然冷却至室温,将产物离心处理,分离上层溶胶清液及沉淀,将所得沉淀用二次水和无水乙醇洗涤3次,80℃烘箱烘干。然后将产物密封保存以备进一步表征。
实施例8
将10mmol二水醋酸锌和0.2mmol硝酸银加入到180℃的40.00mLPEG-200中磁力搅拌1h,得灰色混浊液。自然冷却至室温,将产物离心处理,分离上层溶胶清液及沉淀,将所得沉淀用二次水和无水乙醇洗涤3次,80℃烘箱烘干。然后将产物密封保存以备进一步表征。
实施例9
将10mmol二水醋酸锌和0.4mmol硝酸银加入到180℃的40.00mLPEG-200中磁力搅拌1h,得灰色混浊液。自然冷却至室温,将产物离心处理,分离上层溶胶清液及沉淀,将所得沉淀用二次水和无水乙醇洗涤3次,80℃烘箱烘干。然后将产物密封保存以备进一步表征。
实施例10
将10mmol二水醋酸锌和0.6mmol硝酸银加入到180℃的40.00mLPEG-200中磁力搅拌1h,得灰色混浊液。自然冷却至室温,将产物离心处理,分离上层溶胶清液及沉淀,将所得沉淀用二次水和无水乙醇洗涤3次,80℃烘箱烘干。然后将产物密封保存以备进一步表征。
实施例11
将10mmol二水醋酸锌和0.8mmol硝酸银加入到180℃的40.00mLPEG-200中磁力搅拌1h,得灰色混浊液。自然冷却至室温,将产物离心处理,分离上层溶胶清液及沉淀,将所得沉淀用二次水和无水乙醇洗涤3次,80℃烘箱烘干。然后将产物密封保存以备进一步表征。
实施例7~11中银锌比分别为0.5%、2%、4%、6%、8%,同时取纯氧化锌作为对比例,纯氧化锌中的银锌比为0%,实施例7~11中得到的产物以及纯氧化锌的TEM图、XRD图分别如图1、图2所示,从图1中可以看出,实施例7~11中的产物均为球形颗粒状团聚物,它们的粒径分布在25~30nm;从图2中可以看出不同银锌摩尔比所得产物中均出现ZnO的所有衍射峰和Ag的三个特征峰,根据谢乐公式计算得到的产物平均晶粒尺寸分布在20~30nm。
从图1和图2中可以测出不同银锌比下得到的产物的平均粒径,结果如下表1所示,从表1中可以看出:与利用谢乐公式计算得到的ZnO晶粒尺寸相比,通过TEM测量得到的粒径略有增大,这可能是由于采用谢乐公式计算过程没有考虑仪器的宽化。
表1不同银锌比下得到的产物的平均粒径
实施例12:Ag/ZnO复合物在紫外光和可见光照射下对罗丹明的光催化降解实验
在一个100mL的烧杯中,将0.05g催化剂(Ag/ZnO)和50mL 1.0×10-5mol/L的罗丹明B水溶液(pH≈6)混合,先于黑暗条件下搅拌30min达到吸附平衡,然后将混合溶液分别置于365nm、12-W的紫外灯和配有420nm紫外截止滤光片的350-W氙灯下不断搅拌照射0,30,60,90,120,150,180min。反应完成后,离心分离得到上层罗丹明B清液,用TU-1901分光光度计测量光催化反应前后罗丹明B水溶液在λ=554nm处的吸光度。作为参照,本实验还测试了市售二氧化钛(P25)和纯氧化锌在相同条件下的光催化活性。
图3和图4分别为Ag/ZnO复合物在紫外光和可见光照射下对罗丹明的光催化降解实验,通过得出的图3和图4可以说明,无论是在紫外光还是可见光照射下,不同银锌摩尔比下所得Ag/ZnO复合物的光催化活性均优于市售光催化剂P25和纯ZnO,其中6%Ag/ZnO复合物的光催化降解效率最高,
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (9)
1.一种Ag/ZnO纳米复合物的制备方法,其特征在于包括以下步骤:将二水醋酸锌和硝酸银加入到聚乙二醇中反应,反应结束后将所得反应液冷却至室温后离心分离,将所得沉淀洗涤干燥即得Ag/ZnO纳米复合物。
2.根据权利要求1所述的Ag/ZnO纳米复合物的制备方法,其特征在于:所述的聚乙二醇为聚乙二醇200、聚乙二醇400、聚乙二醇600中的至少一种。
3.根据权利要求1所述的Ag/ZnO纳米复合物的制备方法,其特征在于:所述的反应是指在160~200℃下反应0.5~2h。
4.根据权利要求1所述的Ag/ZnO纳米复合物的制备方法,其特征在于:所用的硝酸银与二水醋酸银的摩尔比为(0~8):100,其中硝酸银的摩尔数不为0。
5.根据权利要求1所述的Ag/ZnO纳米复合物的制备方法,其特征在于:所用的聚乙二醇的量为每10mmol二水醋酸锌对应使用40.0mL的聚乙二醇。
6.根据权利要求1所述的Ag/ZnO纳米复合物的制备方法,其特征在于:所述的洗涤是指先用蒸馏水洗涤2次再用无水乙醇洗涤1次,所述的干燥是指用60~100℃烘箱干燥。
7.一种根据权利要求1~6任一项所述的方法制备得到的Ag/ZnO纳米复合物。
8.根据权利要求7所述的Ag/ZnO纳米复合物,其特征在于:Ag/ZnO纳米复合物的粒径为20-30mm。
9.根据权利要求6或7所述的Ag/ZnO纳米复合物在光催化以及抗菌方面的应用。
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CN109470683A (zh) * | 2018-10-23 | 2019-03-15 | 江苏大学 | 一种以sers基底结合多元线性回归模型进行2,4-d快速检测的方法 |
CN111018365A (zh) * | 2019-12-30 | 2020-04-17 | 黑龙江省科学院高技术研究院 | 一种原位制备银纳米粒子负载ZnO纳米泡沫的方法 |
CN112675700A (zh) * | 2020-12-29 | 2021-04-20 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种弱光光触媒复合除醛喷剂的制备方法及其产品和应用 |
CN112973687A (zh) * | 2021-03-09 | 2021-06-18 | 西南交通大学 | 一种银/钨酸铋复合光催化材料及其制备方法 |
CN116422326A (zh) * | 2021-12-30 | 2023-07-14 | 宁波晶鑫电子材料有限公司 | 一种半导体光催化材料的掺杂方法 |
CN117467197A (zh) * | 2023-11-06 | 2024-01-30 | 科迈特新材料有限公司 | 一种橡胶用改性纳米氧化锌抗菌剂及其制备方法 |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109470683A (zh) * | 2018-10-23 | 2019-03-15 | 江苏大学 | 一种以sers基底结合多元线性回归模型进行2,4-d快速检测的方法 |
CN111018365A (zh) * | 2019-12-30 | 2020-04-17 | 黑龙江省科学院高技术研究院 | 一种原位制备银纳米粒子负载ZnO纳米泡沫的方法 |
CN112675700A (zh) * | 2020-12-29 | 2021-04-20 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种弱光光触媒复合除醛喷剂的制备方法及其产品和应用 |
CN112973687A (zh) * | 2021-03-09 | 2021-06-18 | 西南交通大学 | 一种银/钨酸铋复合光催化材料及其制备方法 |
CN116422326A (zh) * | 2021-12-30 | 2023-07-14 | 宁波晶鑫电子材料有限公司 | 一种半导体光催化材料的掺杂方法 |
CN117467197A (zh) * | 2023-11-06 | 2024-01-30 | 科迈特新材料有限公司 | 一种橡胶用改性纳米氧化锌抗菌剂及其制备方法 |
CN117467197B (zh) * | 2023-11-06 | 2024-05-10 | 科迈特新材料有限公司 | 一种橡胶用改性纳米氧化锌抗菌剂及其制备方法 |
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