CN110372226B - 一种纳米银包覆的草丛状氧化锌光催化薄膜及其制备方法 - Google Patents
一种纳米银包覆的草丛状氧化锌光催化薄膜及其制备方法 Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 132
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 9
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 4
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
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Abstract
本发明涉及一种纳米银包覆的草丛状氧化锌光催化薄膜，其纳米银层均匀地包覆在草丛状氧化锌细棒的表面；其过程为：先制得颗粒度均匀的氧化锌种晶层溶液，再将其旋转涂布到玻璃基板表面，并进行热处理，得到种晶层玻璃基板，然后置于含有六水合硝酸锌、六亚甲基四胺、聚乙烯亚胺和氨水的混合水溶液中进行草丛状氧化锌薄膜的生长；最后，将长有草丛状氧化锌薄膜的基板分别浸入含有氯化亚锡和三氟乙酸的甲醛水溶液和硝酸银水溶液中反应，获得纳米银层包覆的草丛状氧化锌薄膜。本发明制备的原料普通易得，成本低廉，制备过程简单，绿色环保。同时，获得了优良的光催化活性和循环使用性能，在环保领域有潜在的应用价值。
Description
技术领域
本发明属于光催化技术领域，具体涉及一种纳米银包覆的草丛状氧化锌光催化薄膜及其制备方法。
背景技术
随着经济的高速发展，环境污染不断恶化，其中水资源的污染尤为严重。在环境中残留的有机污染物含量不断激增，威胁到人类的生存环境与健康。通过光催化反应，使有机物分解转化为小分子，从而达到净化的目的。
常用的光催化剂主要是一些半导体材料，如TiO2、ZnO、CdS、WO3等。其中，ZnO，Ⅱ-Ⅵ族半导体材料，由于其成本低廉、耐酸碱性好、光电化学稳定性好、对生物无毒性等优点，使其作为光催化剂在环境保护和治理方面有广阔的应用前景。ZnO的带隙较宽，约为3.37eV。在波长小于378nm的紫外光照射下，可以生成光生电子-空穴对，而空穴具有氧化性，因此其光催化性能远大于传统催化剂。但目前报道的纯ZnO的光催化效率较低。Li等人（Li B, LiuT, Wang Y, et al. ZnO/graphene-oxide nanocomposite with remarkably enhancedvisible-light-driven photocatalytic performance[J]. Journal of colloid andinterface science, 2012, 377(1): 114-121）采用商用ZnO在可见光下降解亚甲基蓝（MB）效果不好。Tien H N等人（Tien H N, Khoa N T, Hahn S H, et al. One-potsynthesis of a reduced graphene oxide–zinc oxide sphere composite and its useas a visible light photocatalyst[J]. Chemical engineering journal, 2013, 229:126-133）采用ZnO在可见光照射下90 min降解MB的降解率仅约20 %。通过复合或掺杂等能显著提高其催化效率。贵金属Ag，具有较稳定的物化性质和良好的导电性。采用Ag对ZnO进行改性，会产生SPR效应增强，同时改善ZnO的表面电荷分布，接收光反应过程中光照射后激发所产生的导带电子，阻止光生电子和空穴的再结合，从而有效提高光催化效率。Zhang X等人（Zhang X , Wang Y , Hou F , et al. Effects of Ag loading on structuraland photocatalytic properties of flower-like ZnO microspheres [J]. AppliedSurface Science, 2017, 391:476-483），采用水溶液法成功地制备了花型ZnO/Ag样品，采用MB溶液在可见光照射下降解，对Ag/ZnO样品进行了光催化性能研究，在进行180 min的可见光照射后，降解率达到了80%。但Ag修饰的过程中，如沉积不均匀易导致Ag纳米颗粒的聚集，引起基底比表面积的显著减小，进而导致光催化性能被削弱。
因此，开发一种Ag纳米沉积均匀、可控的贵金属Ag修饰的Ag/ZnO复合材料及其合成方法是一个挑战。本发明通过溶液化学法制备草丛状ZnO，这种新颖的草丛状ZnO薄膜由许多细针状ZnO棒组成，因此具备较大的比表面积，进一步采用简单的浸渍还原法实现Ag在草丛状ZnO表面的可控修饰。应用结果表明纳米银包覆的草丛状氧化锌光催化薄膜具有很好的光催化降解性能。
发明内容
本发明要解决的技术问题，在于提供一种简单且有效的纳米银包覆的草丛状氧化锌光催化薄膜及其制备方法，在草丛状氧化锌基底上均匀生长纳米银，其具有更高效的光催化活性，在紫外波段有优良的响应。
为实现上述目的，本发明采用如下技术方案：
一种纳米银包覆的草丛状氧化锌光催化薄膜的制备方法，包括如下步骤：
(1)配制种晶层溶液：将无水乙醇和醋酸锌混合，得溶液A；同时用无水乙醇溶解氢氧化钠，得溶液B；将A和B溶液相互混合搅拌后，室温下静置陈化，得到均匀的种晶层溶液；
（2）制备草丛状氧化锌基板：利用旋转涂布仪将步骤（1）的种晶层溶液均匀地涂覆在玻璃基板上；然后放入400 ℃电阻烘箱中退火1 h，空冷后得到种晶层基板；
（3）制备草丛状氧化锌基板：将步骤（2）制得的种晶层基板置于含有六水合硝酸锌、六亚甲基四胺、聚乙烯亚胺和适量氨水的水溶液中，然后放入450 ℃电阻烘箱中退火0.5 h，空冷后得到草丛状氧化锌基板；
（4）将步骤（3）制得的草丛状氧化锌基板，先浸入含有氯化亚锡和三氟乙酸的甲醛水溶液，然后固定于旋转涂布仪中央，利用旋转离心作用力将多余的甲醛水溶液液甩除，使甲醛水溶液在草丛状氧化锌的表面更加均匀；再将旋涂完甲醛水溶液的草丛状氧化锌基板浸入硝酸银溶液中；再经清洗、60℃烘干即得到纳米银包覆的草丛状氧化锌光催化薄膜。
进一步地，步骤（2）所述的基板材质为玻璃或不锈钢。
进一步地，步骤（3）中所述聚乙烯亚胺的浓度为3~6 mM。
进一步地，步骤（3）中所述氨水的浓度为0.35~0.78 M。
进一步地，步骤（4）中所述氯化亚锡的浓度为3.85~7.8 mM。
进一步地，：步骤（4）中所述三氟乙酸浓度为8~15.7 mM。
进一步地，步骤（4）中所述旋涂条件为3000 rpm下旋转10~30 s。
进一步地，：步骤（4）中硝酸银溶液的浓度为2~4 mM。
本发明采用水溶液法制备纳米银包覆的草丛状氧化锌光催化薄膜，其光催化性能大大提高；在光催化降解有机污染物方面表现出优良的性能，可用于处理的有机污染物包括：甲基橙、亚甲基蓝、苯酚、罗丹明B等。
本发明具有如下优点：本发明制备所需的原料普通易得，成本低廉，制备过程简便，绿色环保；草丛状氧化锌上众多细针状的ZnO棒提升了其比表面积；简单的浸渍还原法通过反应液浓度和浸渍时间的调控能有效避免Ag在草丛状ZnO表面沉积过程中的团聚发生；同时，获得了优良的光催化活性，在环保领域有潜在的应用价值。
附图说明
图1为本发明的光催化剂SEM图；其中a为Ag/ZnO-1；b为Ag/ZnO-2；c为Ag/ZnO-3；d为 Ag/ZnO-4；
图2为Ag/ZnO-4的EDS mapping图；
图3为Ag/ZnO-4的XRD图；
图4为本发明的光催化剂在紫外光下光催化RhB的降解速率图。
具体实施方式
实施例1
配置种晶层溶液：用25 mL无水乙醇在58 ℃水浴中搅拌0.5 h溶解0.11 g醋酸锌，得溶液A；同时用25 mL无水乙醇室温下0.5 h搅拌溶解0.075 g氢氧化钠，得溶液B。A和B溶液相互混合在70 ℃水浴条件下混合并搅拌2 h，结束后倒入准备好得洁净烧杯，室温下静置陈化4 h，即得到均匀的种晶层溶液。
制备种晶层基板：利用旋转涂布仪将种晶层溶液涂覆在玻璃基板上，最后把基板放在坩埚里并放入400 ℃电阻烘箱中退火1 h，空冷后得到种晶层基板。
制备草丛状氧化锌基底：将种晶层基板置于含有0.05 M六水合硝酸锌，0.05 M六亚甲基四胺，5 mM聚乙烯亚胺和0.35 M氨水的水溶液中，放入83 ℃烘箱2 h，再升高至90℃持续2 h。取出用乙醇、去离子水清洗数次后置于450 ℃电阻烘箱中退火半小时，空冷后得到为草丛状氧化锌基底。
将草丛状氧化锌基底先浸入C液1 s，后固定于旋转涂布仪中央，于3000 rpm下旋转10 s，利用离心作用力将多余的C液甩去，使C液在草丛状氧化锌的表面更加均匀。C液为含有3.85 mM氯化亚锡，15 mL甲醛，15.7 mM三氟乙酸，35 mL去离子水的混合液。同样的把旋涂完的草丛状氧化锌基板浸入D液1 s。D液为4 mM的硝酸银水溶液。最后将基板清洗干净，并置于60 ℃烘箱烘干。将产物分别用乙醇、去离子水各清洗数次得到纳米银包覆的草丛状氧化锌光催化薄膜，称为Ag/ZnO-1。
实施2-4
其他步骤不变，改变氯化亚锡、三氟乙酸和硝酸银的添加量，按下表浓度调整，分别获得样品Ag/ZnO-2、Ag/ZnO-3和Ag/ZnO-4。
表1 实验物料配方表
实施例5
配置10 mg/L的RhB溶液，每次取50 ml作为有机废液，将玻璃样品浸入，降解液全程搅拌。为了达到吸附-解吸平衡，在暗室无氙灯照射30 min后取样。然后在暗室条件下放于氙灯下照射2.5 h，每隔一段时间取5 ml样品用于紫外吸收测试，且每次取样后保持灯源到液面之间的高度为9 cm。从而得到各时间段RhB的浓度。
对上述实施例1~4所得纳米银包覆的草丛状氧化锌光催化薄膜，采用场发射扫描电子显微镜（SEM）、X射线衍射仪（XRD）、紫外分光光度计（Uv-vis）等对产物进行分析。通过实施例5，以RhB溶液为目标染料进行光催化降解实验，通过紫外-可见分光光度计测量吸光度，以评估其光催化活性。具体测试结果如图1~4所示。
图1为样品的SEM图。从图1（a）可以看出，Ag/ZnO-1均匀分布于玻璃基板表面，且草丛状Ag/ZnO-1其针状上点缀Ag纳米粒子而部分包裹着其针尖部。而Ag/ZnO-2（图1（b））明显被Ag包裹，形成棒槌状。ZnO完全厚实覆盖，会影响其光催化性能。图1（c）中，Ag包覆在草丛状Ag/ZnO-3针尖上进而形成一个小球，但是包裹比较稀疏。而图1（d）则是Ag/ZnO-4，能清晰观察到Ag纳米粒子分散于针尖上且量少，可能形成SPR效应大大提升其光催化性能。
图2为Ag/ZnO-4的EDS mapping图，分析样品的元素含量分布。从图中可以看出，Ag/ZnO-4中含有Zn、O、Ag元素，而且Ag元素分布均匀。
图3为样品Ag/ZnO-4的XRD图。可以看到，在32.2°、34.9°、36.8°、48.1°、63.3°分别出现六方铅锌矿ZnO的（100）、（002）、（101）、（102）、（103）晶面（JCPDS NO.75-1526）。在图中没有检测到Ag的特征峰，可能是由于银含量太少的缘故。
图4为样品在紫外光下对RhB的降解速率图。图中a-d分别为Ag/ZnO-2、Ag/ZnO-1、Ag/ZnO-3、Ag/ZnO-4。首先对样品进行30 min的暗吸附，使样品达到吸附解吸平衡，可以看出Ag/ZnO-4在持续150 min紫外光照射后，其性能远远高于其余样品，对RhB的降解率近95%。样品降解率从大到小分别为Ag/ZnO-4、Ag/ZnO-3、Ag/ZnO-1、Ag/ZnO-2。从这个结果发现，随着Ag+浓度和氯化亚锡浓度的增加，得到的复合物样品光催化性能均大大减弱。同时，随着浸泡时长的延长，其Ag+离子浓度也增加，其光催化性能也减弱。表明样品的光催化性能与Ag+离子浓度、浸泡时间和氯化亚锡浓度有关。
虽然以上描述了本发明的具体实施方式，但是熟悉本技术领域的技术人员应当理解，我们所描述的具体的实施例只是说明性的，而不是用于对本发明的范围的限定，熟悉本领域的技术人员在依照本发明的精神所作的等效的修饰以及变化，都应当涵盖在本发明的权利要求所保护的范围内。
Claims (4)
1.一种纳米银包覆的草丛状氧化锌光催化薄膜，其特征在于：其制备方法包括如下步骤：
（1）配制种晶层溶液：将无水乙醇和醋酸锌混合，得溶液A；同时用无水乙醇溶解氢氧化钠，得溶液B；将A和B溶液相互混合搅拌后，室温下静置陈化，得到均匀的种晶层溶液；
（2）制备草丛状氧化锌基板：利用旋转涂布仪将步骤（1）的种晶层溶液均匀地涂覆在基板上；然后放入400 ℃电阻烘箱中退火1 h，空冷后得到种晶层基板；
（3）制备草丛状氧化锌基板：将步骤（2）制得的种晶层基板置于含有六水合硝酸锌、六亚甲基四胺、聚乙烯亚胺和适量氨水的水溶液中，放入83 ℃烘箱2 h，再升高至90 ℃持续2h，然后放入450 ℃电阻烘箱中退火0.5 h，空冷后得到草丛状氧化锌基板；
（4）将步骤（3）制得的草丛状氧化锌基板，先浸入含有氯化亚锡和三氟乙酸的甲醛水溶液，然后固定于旋转涂布仪中央，利用旋转离心作用力将多余的甲醛水溶液甩除，使甲醛水溶液在草丛状氧化锌的表面更加均匀；再将旋涂完甲醛水溶液的草丛状氧化锌基板浸入硝酸银溶液中；再经清洗、60℃烘干即得到纳米银包覆的草丛状氧化锌光催化薄膜；
步骤（4）中所述氯化亚锡的浓度为3.85mM，所述三氟乙酸浓度为15.7 mM，步骤（4）中旋涂条件为3000 rpm下旋转10~30 s，硝酸银溶液的浓度为2 mM。
2.根据权利要求1所述的纳米银包覆的草丛状氧化锌光催化薄膜，其特征在于：步骤（2）所述的基板材质为玻璃或不锈钢。
3.根据权利要求1所述的纳米银包覆的草丛状氧化锌光催化薄膜，其特征在于：步骤（3）中所述聚乙烯亚胺的浓度为3~6 mM。
4.根据权利要求1所述的纳米银包覆的草丛状氧化锌光催化薄膜，其特征在于：步骤（3）中所述氨水的浓度为0.35~0.78 M。
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