CN107285376B - 一种二维TiO2超薄纳米片及其制备方法 - Google Patents
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Abstract
本发明公开了一种二维TiO2超薄纳米片及其制备方法。该方法是以钛酸四正丁酯以及氢氟酸作为主要原料，乙二醇作为修饰剂，通过调配各项原料物质的量，并采用高温高压下的水热法实现对超薄TiO2纳米片的合成。此种制备方法获得的TiO2纳米片分散性好，可实现片厚度约为2nm‑20nm的调控，横向尺寸约为200nm，且具有优良的光催化产氢性能，在众多领域具有潜在应用。
Description
技术领域
本发明属于无机非金属及光催化材料制备领域，涉及一种二维TiO2超薄纳米片及其制备方法。
背景技术
TiO2作为最重要的氧化物半导体之一，已经被广泛的研究并且在能源和环境领域得到了很多应用。其中，光降解有机染料、光分解水制氢等光催化性能与TiO2的暴露晶面密切相关。其中锐钛矿TiO2中(001)和(101)晶面在选择性分离光生载流子中起到了重要作用，这对光催化的影响是很大的。现阶段为了制备高(001) 晶面暴露率的TiO2所面临的问题可分为两个方面：一是不规则形貌问题，另一个是纳米片聚集问题。在本发明的制备方法中引入乙二醇作为修饰剂，期望通过 HF和乙二醇的协同作用，使得(001)晶面的暴露率提高的同时，增强其分散性，从而提高其光催化性能。
发明内容
本发明的目的在于针对现有技术的不足，提供一种二维TiO2超薄纳米片及其制备方法，该方法采用水热法实现二维TiO2超薄纳米片的合成，获得的TiO2纳米片厚度范围约为2～20nm，横向尺寸约为200nm，(001)面暴露率约为97％，分散性好，产氢速率最高达到19.24mmolh-1g-1，根据现有资料及文献分析，该数据超过了现阶段所有TiO2及TiO2基光催化剂的光催化产氢速率。并且可以通过对乙二醇及HF用量比例的调节来达到对纳米片厚度的调控。
本发明提供一种二维TiO2超薄纳米片的制备方法，制备方法包括以下步骤：
将TBOT(钛酸四正丁酯)和HF混合，加入乙二醇，室温搅拌混合均匀；在 180℃的条件下水热反应16h；所得产物用去离子水和无水乙醇清洗后，置于烘箱中烘干，获得二维TiO2超薄纳米片。
上述技术方案中，优选的，所述的TBOT和HF的摩尔比为1:8。
优选的，所述的乙二醇和HF的摩尔比为1:1。
所用的原料钛酸四正丁酯、氢氟酸以及乙二醇的纯度均不低于化学纯。
所述的搅拌过程在室温下进行，且搅拌时长以60min为最佳。
采用本发明方法制备获得的TiO2纳米片为具有规则的矩形形貌，横向尺寸约为200nm，厚度范围约为2～20nm，且薄片具有良好的光催化产氢效率。且本发明通过大量研究发现，乙二醇与F-之间存在协同作用，通过调控乙二醇与HF的用量比例，可以实现对产物厚度及(001)面暴露率的调控，从而实现对光催化产氢效率的调节。
附图说明
图1是实例1制备的二维TiO2超薄纳米片的X射线衍射(XRD)图谱；
图2是实例1制备的二维TiO2超薄纳米片的扫描电子显微镜(SEM)照片；
图3是实例1，2制备的二维TiO2超薄纳米片的透射电子显微镜(TEM)照片下的厚度统计图；
图4是实例3制备的二维TiO2超薄纳米片的扫描电子显微镜(SEM)照片；
图5是实例1制备的二维TiO2超薄纳米片的光催化产氢速率图。
具体实施方式
以下结合实例进一步说明本发明。
实施例1
1)分别称取钛酸四正丁酯10g和氢氟酸4.5ml置于反应釜中，2)称量15ml 乙二醇溶液，与步骤1)所得溶液混合，磁力搅拌60min；
3)将反应釜拧紧，置于马弗炉中加热180℃保温16h；
4)将步骤3)所得溶液的沉淀物分别用去离子水以及无水乙醇清洗3次，最终得到的沉淀物置于马弗炉加热至70℃保温6h烘干，即可得最终产物。所合成的材料XRD分析图如图1，SEM照片如图2，纳米片的TEM图如图3(a)，光催化产氢速率图如图5。
可以看出：该水热反应产物为锐钛矿TiO2，纳米片厚度约为2～3nm，横向尺寸约为200nm，其光催化产氢效率可达到19.24mmolh-1g-1。
实施例2
1)分别称取钛酸四正丁酯10g和氢氟酸4.5ml置于反应釜中；
2)称量10ml乙二醇溶液，与步骤1)所得溶液混合，磁力搅拌60min；
3)将反应釜拧紧，置于马弗炉中加热180℃保温16h；
4)将步骤3)所得溶液的沉淀物分别用去离子水以及无水乙醇清洗3次，最终得到的沉淀物置于马弗炉加热至70℃保温6h烘干，即可得最终产物。其纳米片的TEM图如图3(b)，可以看出：产物呈纳米片状，厚度约为20nm，横向尺寸约为50nm。
实施例3
1)分别称取钛酸四正丁酯10g和氢氟酸4.5ml置于反应釜中；
2)称量20ml乙二醇溶液，与步骤1)所得溶液混合，磁力搅拌60min；
3)将反应釜拧紧，置于马弗炉中加热180℃保温16h；
4)将步骤3)所得溶液的沉淀物分别用去离子水以及无水乙醇清洗3次，最终得到的沉淀物置于马弗炉加热至70℃保温6h烘干，即可得最终产物。其纳米片的SEM图如图4，可以看出：产物已难以维持片状形貌。
研究表明，乙二醇的用量对最终产物的形貌及性能起到至关重要的作用，以上述实施例为例，其余条件不变，当乙二醇的用量低于5mL或高于20mL时，获得的TiO2将难以维持规则矩形片状，其(001)面暴露率也相应急剧减小。其原因可能为乙二醇与F-之间存在协同作用，乙二醇分子在(001)面上与F-之间的结合使得光催化过程中氧化还原的位点增加，并且增强了(001)面的稳定性，故 (001)面暴露率增大，从而提高了光催化产氢反应效率。
Claims (2)
1.二维TiO2超薄纳米片的制备方法，其特征是，包括以下步骤：
将TBOT和HF混合，加入乙二醇，室温搅拌混合均匀；在180℃的条件下水热反应16h；所得产物用去离子水和无水乙醇清洗后，置于烘箱中烘干，获得二维TiO2超薄纳米片，所述的乙二醇和HF的摩尔比为1:1。
2.根据权利要求1所述的二维TiO2超薄纳米片的制备方法，其特征是，所述的TBOT和HF的摩尔比为1:8。
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| CN108190949A (zh) * | 2018-02-13 | 2018-06-22 | 武汉理工大学 | 一种快速制备小粒径锐钛矿型纳米二氧化钛的方法 |
| CN108597882A (zh) * | 2018-03-30 | 2018-09-28 | 梧州井儿铺贸易有限公司 | 一种改进光阳极的染料太阳能电池 |
| CN109603793A (zh) * | 2018-12-28 | 2019-04-12 | 上海理工大学 | 单斜相二氧化钛可见光催化剂的制备方法及用途 |
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| CN110227433B (zh) * | 2019-06-26 | 2020-10-23 | 浙江大学 | 一种锐钛矿型TiO2晶面异质结的制备方法 |
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