CN106563442A - 一种超薄二水三氧化钨纳米片的制备方法及其应用 - Google Patents
一种超薄二水三氧化钨纳米片的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种超薄二水三氧化钨纳米片光催化剂的制备方法。采用溶剂热反应制备有机胺插层的有机‑无机杂化物。将10mL1.0mol/L的钨酸钠溶液与90mL3.0mol/L的盐酸溶液混合反应,得到二水三氧化钨块材粉末。取二水三氧化钨粉末与有机胺混合,100~150℃反应2~3天,得到有机胺插层的有机‑无机杂化物,然后用有机酸液相剥离形成二水三氧化钨超薄纳米片。取有机胺插层的二水三氧化钨与有机酸溶液混合,液相超声剥离得到二水三氧化钨超薄纳米片。本发明方法简便,易于操作,所制备的二水三氧化钨超薄纳米片具有较高的光催化活性。
Description
技术领域
本发明所属技术领域为光催化、光电化学材料技术领域,特别涉及三氧化钨超薄纳米片光催化剂的制备方法。
背景技术
三氧化钨为一种宽禁带的n型半导体材料,室温下的禁带宽度为2.63eV,可吸收500nm以下的可见光及紫外光,在电致变色、气敏传感器、光催化与光电转换领域具有重要的应用价值。纳米三氧化钨与传统的半导体材料相比,禁带宽度较窄,在可见光条件下具有良好的光电响应性能,并且价格低廉、性能稳定、无害、无毒,可作为光催化剂,利用太阳光降解水中的有机污染物和空气中的废气,高效节能、清洁、无污染。然而,WO3的性能和实际应用与它的晶相、形态、尺寸、形貌、晶体缺陷以及表面性能紧密相关,而这些又主要取决于WO3的制备方法及制备条件。其中,2D超薄纳米结构是一种厚度在单分子层或少分子层范围的特殊形貌,其平铺尺寸从几十个纳米到微米以上,具有超高的比表面积,表现出高度的各向异性和量子限域效应。当这种特殊的超薄结构材料作为光催化剂时,光生载流子从体内扩散到表面所需要的时间变短,光生电荷分离效率明显提高。因此,2D超薄纳米材料将比其体相材料具有更高的光催化活性。
目前,已经报导的WO3纳米片的合成方法产率过低或需特殊仪器设备,因此,采用插层-剥离的方法制备超薄WO3纳米片,提高光催化性能,用于高效降解有机污染物,以及光电水分解制氢/制氧,对于环境治理、有效提高太阳光利用率和节约能源具有重要的意义。
发明内容
本发明的目的是提供一种二维的超薄二水三氧化钨纳米片的制备方法及其应用,本发明方法简单,易于操作,所制备的超薄二水三氧化钨纳米片具有较高的光电性能以及能够较好地应用于可见光响应光催化领域。
具体步骤为:
(1)采用沉淀法,将10mL1.0mol/L的钨酸钠溶液加入到90mL 3.0mol/L的盐酸溶液中,冰水浴磁力搅拌30分钟,出现黄色产物,用去离子水清洗3次,然后冷冻干燥,得到二水三氧化钨块材粉末;
(2)将0.2g步骤(1)所得二水三氧化钨块材粉末和5~10mL有机胺混合均匀,加入到25mL的聚四氟乙烯反应釜中,在100~150℃条件下反应2~3天,自然冷却至室温后,先后用蒸馏水和乙醇离心洗涤3次,再60℃真空干燥得到有机胺插层的有机-无机杂化物;
(3)取0.1g步骤(2)所得有机胺插层的有机-无机杂化物加入到15mL1.0~3.0mol/L的有机酸溶液中,冰水浴磁力搅拌6~10小时后,用离心机在5000转/分的转速下离心5分钟,然后取上清液,再用离心机在15000转/分的转速下离心收集剥离好的二水三氧化钨超薄纳米片;
所述有机胺为正丙胺、正丁胺、正辛胺和甲酰胺中的一种;
所述有机酸为乙酸、酒石酸、草酸和柠檬酸中的一种;
所述化学试剂纯度均为化学纯以上纯度。
本发明的有益效果是:
本发明所制备的超薄二水三氧化钨纳米片是厚度为2~5nm,面积为1.5~5μm的少层结构,其禁带宽度为2.3~2.7eV之间,紫外区吸收增强,能够吸收可见光。超薄二水三氧化钨纳米片在可见光照射下,能够产生快速的光电流响应,与块体二水三氧化钨相比,催化性能明显增强。因此,超薄二水三氧化钨纳米片作为一种可见光响应的纳米材料,在光催化降解有机污染物,光催化分解水制氢/制氧,太阳能电池等方面有巨大的应用潜力。
附图说明
图1是本发明实施例1制备的二水三氧化钨(WO3·2H2O)块体(a)和超薄二水三氧化钨(WO3·2H2O)纳米片(b)的XRD衍射图谱。
图2是本发明实施例1制备的超薄二水三氧化钨(WO3·2H2O)纳米片的透射电镜(TEM)图,其中(a-d)为不同分辨率倍数的TEM图。
图3是本发明实施例1制备的二水三氧化钨(WO3·2H2O)块体和二水三氧化钨(WO3·2H2O)超薄纳米片的紫外-可见-近红外漫反射光谱图。
图4是本发明实施例1制备的二水三氧化钨(WO3·2H2O)块体和二水三氧化钨(WO3·2H2O)超薄纳米片的电流密度-电位图。
具体实施方式
实施例1:
(1)采用沉淀法,将10mL1.0mol/L的钨酸钠溶液加入到90mL3.0mol/L的盐酸溶液中,冰水浴磁力搅拌30分钟,将所得产物离心,用去离子水清洗3次,然后冷冻干燥,得到二水三氧化钨块材粉末。
(2)将0.2g步骤(1)所得二水三氧化钨块材粉末与5mL正丙胺混合均匀,加入到25mL聚四氯乙烯反应釜中,在100℃反应3天,自然冷却至室温后,将样品离心,先后用蒸馏水和乙醇离心洗涤3次,再60℃真空干燥得到有机胺插层的有机-无机杂化物。
(3)取0.1g步骤(2)所得有机-无机杂化物加入到15mL 3.0mol/L的醋酸溶液中,冰水浴磁力搅拌10小时后,用离心机在5000转/分的转速下离心5分钟,然后取上清液,再用离心机在15000转/分的转速下离心收集剥离好的二水三氧化钨超薄纳米片;
图1显示了实施例1制备的二水三氧化钨块体(a)和二水三氧化钨纳米片(b)的XRD衍射图谱,可见块体二水三氧化钨是单斜相晶体,而二水三氧化钨纳米片是正交相晶体。图2是实施例1制备的超薄二水三氧化钨纳米片的透射电镜(TEM)图,其中(a-d)为不同分辨率倍数的TEM图,几乎透明的片状结构表明成功获得了超薄二水三氧化钨纳米片。图3是实施例1制备的二水三氧化钨块体和二水三氧化钨纳米片的紫外-可见-近红外漫反射光谱图,图3显示二水三氧化钨纳米片的吸收带边明显蓝移,说明存在量子限域效应。
所制备的二水三氧化钨超薄纳米片,通过旋涂法在ITO表面做成光电极,制备电极作为工作电极,辅助电极为铂电极,饱和甘汞电极(SCE)作为参比电极,0.5mol/L Na2SO4为支持电解质溶液,在太阳光模拟器(一个太阳的光强)下测试光电化学性能,外加电压的范围为0.2V~0.8V,测试从低压开始一直扫到高压区,采用光源均为590W的氙灯(NEWPORT-9115X型太阳光模拟器),以光切换的方式来测试。从图4可以看出二水三氧化钨超薄纳米片的光电流远远高于二水三氧化钨块体粉末的光电流。由以上结果可知超薄二水三氧化钨纳米片能作为一种可见光响应的纳米材料应用于光催化领域。
实施例2:
(1)采用沉淀法,将10mL1.0mol/L的钨酸钠溶液加入到90mL3.0mol/L的盐酸溶液中,冰水浴磁力搅拌30分钟,将所得产物离心,用去离子水清洗3次,然后冷冻干燥,得到二水三氧化钨块材粉末。
(2)将0.2g步骤(1)所得二水三氧化钨粉末与10mL正丁胺混合于聚四氯乙烯反应釜内胆中,在120℃反应2天,自然冷却至室温后,将样品离心,先后用蒸馏水和乙醇离心洗涤3次,再60℃真空干燥得到有机胺插层的有机-无机杂化物。
(3)取0.1g步骤(2)所得有机-无机杂化物,加入到15mL1.0mol/L的酒石酸溶液中,冰水浴磁力搅拌6小时后,用离心机在5000转/分的转速下离心5分钟,然后取上清液,再用离心机在15000转/分的转速下离心收集剥离好的二水三氧化钨超薄纳米片。
实施例3:
(1)采用沉淀法,将10mL 1.0mol/L的钨酸钠溶液加入到90mL 3.0mol/L的盐酸溶液中,冰水浴磁力搅拌30分钟,将所得产物离心,用去离子水清洗3次,然后冷冻干燥,得到二水三氧化钨块材粉末。
(2)将0.2g步骤(1)所得块状二水三氧化钨粉末和8mL正辛胺混合均匀,加入聚四氯乙烯反应釜中,在150℃反应2天,自然冷却至室温后,将样品离心,先后用蒸馏水和乙醇离心洗涤3次,再60℃真空干燥得到有机胺插层的有机-无机杂化物。
(3)取0.1g步骤(2)所得有机-无机杂化物,加入到15mL 1.5mol/L的柠檬酸溶液中,冰水浴磁力搅拌8小时后,用离心机在5000转/分的转速下离心5分钟,然后取上清液,再用离心机在15000转/分的转速下离心收集剥离好的二水三氧化钨超薄纳米片。
实施例4:
(1)采用沉淀法,将10mL1.0mol/L的钨酸钠溶液加入到90mL3.0mol/L的盐酸溶液中,冰水浴磁力搅拌30分钟,出现黄色产物,用去离子水清洗2~3次,然后冷冻干燥,得到二水三氧化钨块材粉末;
(2)将0.2g步骤(1)所得二水三氧化钨块材粉末和10mL甲酰胺混合均匀,加入到25mL的聚四氟乙烯反应釜中,在100℃条件下反应3天,自然冷却至室温后,先后用蒸馏水和乙醇离心洗涤3次,再60℃真空干燥得到有机胺插层的有机-无机杂化物;
(3)取0.1g步骤(2)所得有机胺插层的有机-无机杂化物加入到15mL 2.0mol/L的醋酸溶液中,冰水浴磁力搅拌10小时后,用离心机在5000转/分的转速下离心5分钟,然后取上清液,再用离心机在15000转/分的转速下离心收集剥离好的二水三氧化钨超薄纳米片;
以上实施例所述化学试剂纯度均为化学纯以上纯度。
Claims (2)
1.一种超薄二水三氧化钨纳米片的制备方法,其特征在于具体步骤为:
(1)采用沉淀法,将10mL1.0mol/L的钨酸钠溶液加入到90mL 3.0mol/L的盐酸溶液中,冰水浴磁力搅拌30分钟,出现黄色产物,用去离子水清洗3次,然后冷冻干燥,得到二水三氧化钨块材粉末;
(2)将0.2g步骤(1)所得二水三氧化钨块材粉末和5~10mL有机胺混合均匀,加入到25mL的聚四氟乙烯反应釜中,在100~150℃条件下反应2~3天,自然冷却至室温后,先后用蒸馏水和乙醇离心洗涤3次,再60℃真空干燥得到有机胺插层的有机-无机杂化物;
(3)取0.1g步骤(2)所得有机胺插层的有机-无机杂化物加入到15mL1.0~3.0mol/L的有机酸溶液中,冰水浴磁力搅拌6~10小时后,用离心机在5000转/分的转速下离心5分钟,然后取上清液,再用离心机在15000转/分的转速下离心收集剥离好的二水三氧化钨超薄纳米片;
所述有机胺为正丙胺、正丁胺、正辛胺和甲酰胺中的一种;
所述有机酸为乙酸、酒石酸、草酸和柠檬酸中的一种;
所述钨酸钠、盐酸、有机胺、有机酸均为化学纯以上纯度。
2.权利要求1所述的制备方法得到的超薄二水三氧化钨纳米片在可见光响应光催化领域中的应用。
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