CN110817893B - 铁掺杂的凹凸棒石光电材料的制备方法 - Google Patents

铁掺杂的凹凸棒石光电材料的制备方法 Download PDF

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CN110817893B
CN110817893B CN201911112948.5A CN201911112948A CN110817893B CN 110817893 B CN110817893 B CN 110817893B CN 201911112948 A CN201911112948 A CN 201911112948A CN 110817893 B CN110817893 B CN 110817893B
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张立静
杨春雷
杨烨
张玉婷
闾蓉蓉
徐孙悦
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Abstract

本发明涉及纳米复合光电材料的制备技术领域，公开了一种铁掺杂凹凸棒石光电材料的制备方法，将高纯度的纳米凹凸棒石均匀分散到三氯化铁的酸性溶液中,然后将上述混合溶液放在反应釜中，100‑180ºC水热条件下反应24h‑150h，然后将所得到的产品离心、清洗、干燥，得到铁掺杂的凹凸棒石光电材料；其中，所述纳米凹凸棒石与所述六水合三氯化铁的质量比为100：1‑5。本发明通过水热法将Fe离子引入到凹凸棒石中，制成的光电材料具有较好的光电响应，成本低，操作简单，对环境污染小。

Description

铁掺杂的凹凸棒石光电材料的制备方法
技术领域
本发明涉及纳米复合光电材料的制备技术领域，特别涉及一种铁掺杂的凹土棒石光电材料的制备方法。
背景技术
凹凸棒石是一种稀有的非金属矿产资源，在农牧业，建材，药物，石油，食品等领域有着广泛地应用。凹凸棒石是一种具有层链状结构的含水富镁铝硅酸盐，本身是一种绝缘体，硅酸盐半导体很少见。有文献报道，理论计算表明凹凸棒石中引入铁离子可以将凹凸棒石由绝缘体变成半导体（张键，天然接铁桂黢盐可见光催化分解水制氢研究[D]，南京理工大学，2014）。但是人工合成铁离子掺杂凹凸棒石，铁很容易水解胶团化，因此很多时候只会在凹凸棒石表面引入氧化铁，或者形成单独的氧化铁颗粒，Fe离子很难进入到凹凸棒石的内部。
发明内容
发明目的：针对现有技术中存在的问题，本发明提供一种铁掺杂的凹凸棒石光电材料的制备方法，通过水热法将Fe离子引入到凹凸棒石中，制成的光电材料具有较好的光电响应，制作方法简单，成本低，环境友好。
技术方案： 本发明还提供了一种铁掺杂凹凸棒石光电材料的制备方法，将纳米凹凸棒石均匀分散到三氯化铁的酸性溶液中, 然后将上述混合溶液放在反应釜中，100-180ºC水热条件下反应24h-150h，然后将所得到的产品离心、清洗、干燥，得到铁掺杂的凹凸棒石光电材料；
其中，所述纳米凹凸棒石与所述六水三氯化铁的质量比为：100：1-5；优选100：4.8。
优选地，所述三氯化铁的酸性溶液是通过将六水合三氯化铁分散到pH=2的硫酸溶液中制得。
优选地，所述清洗的方法为用水洗三次后，再用乙醇清洗一次。
有益效果：本发明通过简单的水热法将Fe离子引入到凹凸棒石中，将六水合三氯化铁溶解于pH=2的硫酸溶液中，其目的是防止三价铁离子水解，阻止大块铁胶团的形成，然后通过水热方法，在反应釜中形成的高温高压的状态，使得铁离子与凹凸棒石进行离子交换，从而形成Fe离子掺杂的凹凸棒石，使得凹凸棒石成为具有较好的光电响应的半导体材料，制备成的铁掺杂的凹凸棒石光电材料具有较好的光电响应。该方法合成步骤简单，无污染，无毒，环境友好，便于工业化。
附图说明
图1为凹凸棒石（ATP）及150ºC下水热反应24 h、72h、150 h的铁掺杂凹凸棒石的XRD图；
图2为不同水热温度和时间的SEM图，其中，(1)为 150ºC下水热反应24 h的Fe-凹凸棒石的复合样品；(2) 为150ºC下水热反应72 h的Fe-凹凸棒石的复合样品；(3) 为150ºC下水热反应150 h的Fe-凹凸棒石的复合样品的SEM图；
图3为150ºC不同反应时间的I-V曲线图。(1) 凹凸棒石（ATP）的I-V曲线图；(2)150ºC下水热反应72 h的Fe-凹土棒石的复合样品的I-V曲线图；
图4为凹凸棒石及150ºC水热反应24 h、72 h及150 h的Fe掺杂凹土棒石的阻抗谱图，测试电压为0.33 V vs.SCE。
具体实施方式
下面结合附图对本发明进行详细的介绍。
实施方式1：
将凹凸棒石0.1g溶于pH=1的六水合三氯化铁的硫酸溶液40 mL中，磁力搅拌10min，超声10min；
将上述溶液转移到反应釜中，150℃水热反应24h；
将所得到的沉淀用去离子水清洗三次，乙醇清洗1次，去除多余的离子，然后干燥，得铁掺杂的凹凸棒石光电材料。
实施方式2：
将凹凸棒石0.1g溶于pH=2的六水合三氯化铁的硫酸溶液40 mL中，磁力搅拌10min，超声10min；
将上述溶液转移到反应釜中，150℃水热反应72h；
将所得到的沉淀用去离子水清洗三次，乙醇清洗1次，去除多余的离子，然后干燥，得铁掺杂的凹凸棒石光电材料。
实施方式3：
将凹凸棒石0.1g溶于pH=2.1的六水合三氯化铁的硫酸溶液中40 mL，磁力搅拌10min，超声10min；
将上述溶液转移到反应釜中，150℃水热反应150 h；
将所得到的沉淀用去离子水清洗三次，乙醇清洗1次，去除多余的离子，然后干燥，得铁掺杂的凹凸棒石光电材料。
对上述实施方式1至3中所得的Fe掺杂凹凸棒石的性能进行分析如下：
图1是Fe掺杂凹凸棒石在150ºC下反应24，72，150h的XRD图，随着反应时间的延长，凹凸棒石的的衍射峰变弱，说明随着反应时间的延长，凹凸棒石的结晶度变弱，但是并未出现氧化铁的衍射峰，说明在反应体系中并没有铁的氧化物的生成。
图2表明反应温度不变，反应时间延长，样品的形貌没有发生明显的变化，所有的样品都表现为棒状结构。
图3表明Fe掺杂凹凸棒石无论暗态电流密度还是光照下的电流密度都较凹凸棒石明显提高，说明Fe的掺杂明显提高了凹凸棒石的光电响应。
图4表明，Fe掺杂凹凸棒石在150ºC下反应72 h的阻抗半圆最小，说明铁掺杂凹土后，电子的转移电阻变小，进一步说明Fe的掺杂使得凹凸棒石由绝缘体变成半导体。
表1 实施方式1至3所得的Fe掺杂凹凸棒石中的元素含量表（EDX测试）
Figure 170162DEST_PATH_IMAGE002
表1 表明随着反应时间的延长，Fe的质量分数增加，Mg的质量分数减少，说明Fe置换了凹凸棒石中的Mg元素。
上述实施方式只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所做的等效变换或修饰，都应涵盖在本发明的保护范围之内。

Claims (2)

1.一种铁掺杂凹凸棒石光电材料的制备方法，其特征在于，将纳米凹凸棒石均匀分散到六水合三氯化铁的酸性溶液中, 然后将混合溶液放在反应釜中，100-180ºC水热条件下反应24h-150h，然后将所得到的产品离心、清洗、干燥，得到铁掺杂的凹凸棒石光电材料；
其中，纳米凹凸棒石与六水合三氯化铁的质量比为100：1-5；
六水合三氯化铁的酸性溶液是通过将六水合三氯化铁分散到pH=2的硫酸溶液中制得。
2.根据权利要求1所述的铁掺杂凹凸棒石光电材料的制备方法，其特征在于，所述清洗的方法为用水洗三次后，再用乙醇清洗一次。
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