CN106866181A - 一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法 - Google Patents
一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法 Download PDFInfo
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Abstract
本发明涉及一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法，属于纳米传感器的制备技术领域。本发明的方法，包括以下步骤：（1）将陶瓷管置于氯化铁和硫酸钠的混合溶液中，进行水热反应；（2）水热反应完成后，将陶瓷管在马弗炉中进行退火处理。本发明制备出海胆状Fe2O3纳米针的关键在于水热反应温度和水热反应时间的控制。首次公开了在氧化铝陶瓷管上原位生长海胆状氧化铁纳米针的方法。本发明的方法，无需事先制备出涂覆法所需粉末，无需手工涂覆；而是在氧化铝陶瓷管上直接生长出海胆状氧化铁纳米针。海胆状氧化铁纳米针的制备过程也是气敏陶瓷管的制备过程；步骤简单、耗时短；简化了传统气敏陶瓷管的制备工艺，省时省力，节约成本。
Description
技术领域
本发明涉及一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法，属于纳米传感器的制备技术领域。
背景技术
随着人类科技和工业社会的发展，各种易燃、有毒有害气体的应用越来越广泛。由于我们人类自身感知范围的局限性，对这些有毒有害气体的种类及浓度定量没有判断能力。因此，如何对这些气体作出快速而准确地检测变得尤为重要。
Fe2O3材料是一种n型半导体材料，它的禁带宽度较窄（Eg=2.2 eV），并且具有良好的稳定性，因此可以作为气敏材料。当前，人们已经掌握了采用不同物理、化学方法制备出不同形貌的Fe2O3纳米材料，例如：粒状、棒状、环状、针状、核壳状、空心球状、雪花状、海胆状、螺旋状等。而氧化铁材料的气敏机理为表面电阻型，与气体的响应过程主要是发生在材料的表面。即所制备的氧化铁材料的比表面积越大，其气敏性能越出色。与传统的氧化铁平面薄膜材料相比较，具有良好一维形貌的Fe2O3纳米针材料无疑具有更大的比表面积，所以在气敏传感器领域更加具有应用价值。
目前，以氧化铝陶瓷管为衬底的气敏元件的制备方法包括以下几种：粉末涂覆法和籽晶层辅助生长法；其中较为先进的方法是：首先在氧化铝陶瓷管的表面形成籽晶层，然后在籽晶层的辅助下在籽晶层表面生长纳米材料。但是这种先形成籽晶层再生长纳米材料的方法仍然存在以下有待改进的地方：1）籽晶层溶液的配制需要较繁琐的步骤，且一般还需静置12 h以上；2）籽晶层覆盖到氧化铝陶瓷管表面上后，还需在空气中自然晾干12 h以上。
发明内容
本发明的目的在于提供一种直接生长于陶瓷管的海胆状氧化铁纳米针的新的制备方法。
技术方案
一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法，包括以下步骤：
（1）将陶瓷管置于氯化铁和硫酸钠的混合溶液中，进行水热反应；所述氯化铁和硫酸钠的混合溶液，氯化铁和硫酸钠的浓度均为0.05mol/L；水热反应温度为140℃，水热反应时间为6-8h；
（2）水热反应完成后，将陶瓷管在马弗炉中进行退火处理；退火条件为：以3-4℃/min的速率升温至600-700℃，保温1.5-2.5h，然后自然冷却至室温。
本发明的方法：
首先，与“先在氧化铝陶瓷管的表面形成籽晶层，然后再在籽晶层表面生长纳米材料”的现有方法相比，本发明是直接在氧化铝陶瓷管表面上生长出氧化铁纳米针，并不需要“在氧化铝陶瓷管的表面形成籽晶层”的步骤；更加简单。
其次，本发明实现在陶瓷管上原位生长Fe2O3纳米针的关键之处在于，采用0.05mol/L的硫酸钠溶液和0.05 mol/L的氯化铁溶液作为反应原料，及水热反应条件的控制。本发明通过实验研究发现，采用相同浓度的氯化亚铁或硝酸铁溶液代替氯化铁溶液，均无法获得本发明的“纳米针”形貌。由此可见，虽然氯化铁、氯化亚铁和硝酸铁均为常见铁源，而且在水热反应中通常可以相互替换，但是，在本发明中却超出了预期、产生了完全不同的技术效果。而采用本发明水热条件以外的温度、时间条件，或者无法获得本发明的“纳米针”形貌，或者会导致电极丝发生脱落。例如，当水热温度为155℃时，电极丝发生脱落；而在通常情况下，155℃的温度不会导致电极丝脱落。因此，低于155℃的温度条件同样在本发明中超出本领域技术人员的预期、产生防止电极丝脱落的技术效果。
再次，本发明制备出海胆状Fe2O3纳米针的关键在于水热反应温度和水热反应时间的控制；虽然在“水热反应温度为125-155℃，不包含155℃，水热反应时间为6-18h”的条件下，均能制备出Fe2O3纳米针；但是，只有在“水热反应温度为140℃，水热反应时间为6-8h”的条件下才能获得海胆状Fe2O3纳米针；水热反应温度过高或过低、反应时间过长，均无法获得海胆状Fe2O3纳米针。
上述方法，为了在氧化铝陶瓷管上获得生长形貌良好的氧化铁，优选的，陶瓷管在使用之前用丙酮、乙醇分别超声30 min。
本发明还提供了一种采用上述方法制备的表面生长有Fe2O3纳米针的氧化铝陶瓷管。其中，氧化铝陶瓷管的尺寸，可以根据具体生产需要进行确定；例如，长度为4 mm，内径1mm，外径1.4 mm。
本发明还提供了一种氧化铁/氧化锡纳米针异质结陶瓷管，是利用脉冲激光沉积技术，在上述氧化铝陶瓷管的Fe2O3纳米针表面沉积n型半导体材料氧化锡而成。
本发明还提供了一种三元复合陶瓷管，是利用脉冲激光沉积技术和物理气相沉积技术，在上述的氧化锡/氧化铁纳米针异质结陶瓷管的异质结表面溅射金颗粒而成。
本发明还提供了一种采用上述陶瓷管制备的气敏传感器。该气敏传感器可应用于有机气体的检测，包括乙醇、异丙醇、丙酮、笨、对二甲苯、三乙胺等有机气体。该气敏传感器，其氧化铝陶瓷管两端集成金电极，金电极之间相距2 mm，金电极上集成四根铂导线。
有益效果
首次公开了在氧化铝陶瓷管上原位生长海胆状氧化铁纳米针的方法。本发明的方法，无需事先制备出涂覆法所需粉末，无需手工涂覆；而是在氧化铝陶瓷管上直接生长出海胆状氧化铁纳米针。海胆状氧化铁纳米针的制备过程也是气敏陶瓷管的制备过程；步骤简单、耗时短；简化了传统气敏陶瓷管的制备工艺，省时省力，节约成本。
本发明所制备的原位生长于氧化铝陶瓷管的海胆状氧化铁纳米针形貌可控、纳米针结晶良好、分布均匀，纳米针长度约为100 nm，彼此相互连接形成网络。
本发明的氧化铁/氧化锡纳米针异质结传感器，能改善氧化铁纳米针的气敏性能；对三乙胺表现出较好的选择性，且对三乙胺的响应有所提高。
附图说明
图1为实施例1制备的原位生长于氧化铝陶瓷管的氧化铁纳米针的X射线衍射图谱；
图2为实施例1制备的原位生长于氧化铝陶瓷管的氧化铁纳米针的场发射扫描电镜图及EDS能量色散谱图；
图3为实施例1制备的气敏传感器的气敏性能图谱；
图4为实施例2的原位生长于氧化铝陶瓷管的氧化铁/氧化锡异质结扫描电镜图片；
图5为实施例2制备的原位生长于氧化铝陶瓷管的氧化铁/氧化锡/金三元复合纳米结构的扫描电镜图片；
图6为本发明制备的氧化铁/氧化锡异质结气敏传感器及氧化铁/氧化锡/金三元复合气敏传感器的气敏性能图；
图7为实施例3制备的氧化铁纳米针的场发射扫描电镜图片；
图8为对比例1制备的原位生长于氧化铝陶瓷管的纳米氧化铁的场发射扫描电镜图片；
图9为对比例2制备的原位生长于氧化铝陶瓷管的纳米氧化铁的场发射扫描电镜图片。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述。
实施例 1
将氧化铝陶瓷管用丙酮、乙醇、去离子水分别超声30 min清洗干净，并烘干备用。将清洗干净的陶瓷管置入装有氯化铁和硫酸钠的混合溶液（混合溶液中，氯化铁和硫酸钠的浓度均为0.05 mol/L）高压反应釜中，于140℃下水热生长6 h，将生长过后的陶瓷管在马弗炉中进行以3℃ /min的速率升温至600℃并保温2 h退火处理，然后自然冷却至室温；即得原位生长于氧化铝陶瓷管的海胆状氧化铁纳米针。该氧化铁纳米针的X射线衍射图谱如图1所示；从图1可以看出，氧化铁纳米针结晶良好，无其它杂质存在。该氧化铁纳米针的扫描电镜如图2所示；从图2 可以看出，Fe2O3纳米针尺寸均一，纳米针结晶良好，呈海胆状。将表面生长有Fe2O3纳米针的氧化铝陶瓷管焊接成气敏传感器测试其气敏性能，如图3所示；从图3中可以看出，在最佳工作温度下，纯相Fe2O3纳米针对三乙胺的灵敏度可以达到27，且对三乙胺表现出较好的选择性。
实施例2
利用脉冲激光沉积技术在实施例1所制备的原位生长有氧化铁纳米针的陶瓷管的针状结构纳米氧化铁表面沉积n型半导体材料氧化锡，得氧化铁/氧化锡异质结陶瓷管；扫描电镜如图4。从图4可以看出氧化铁/氧化锡异质结的Fe2O3纳米针结构仍为海胆状，在其上明显存在SnO2颗粒。结合真空离子镀金镀碳仪在上述制备的氧化铁/氧化锡异质结陶瓷管的异质结表面溅射Au纳米颗粒，构筑氧化铁/氧化锡/Au三元复合气敏材料，其扫描电镜如图5所示。从图5可以看出Fe2O3纳米针结构仍为海胆状。分别将氧化铁/氧化锡异质结陶瓷管、氧化铁/氧化锡/Au三元复合陶瓷管焊接成气敏传感器测试其气敏性能，如图6所示。从图6中可以看出，氧化铁/氧化锡气敏元件及氧化铁/氧化锡/金三元复合气敏元件的的气敏性能逐次提升，三元复合气敏元件对三乙胺响应值达到38，且都对三乙胺表现出最好的选择性。
实施例3
将氧化铝陶瓷管用丙酮、乙醇、去离子水分别超声30 min清洗干净，并烘干备用。将清洗干净的陶瓷管置入装有氯化铁和硫酸钠的混合溶液（混合溶液中，氯化铁和硫酸钠的浓度均为0.05 mol/L）高压反应釜中，于140℃下水热生长9 h，然后将生长过后的陶瓷管在马弗炉中进行以3℃ /min的速率升温至600℃保温2 h的退火处理，然后自然冷却至室温；即得到原位生长于氧化铝陶瓷管的氧化铁纳米针。扫描电镜如图7所示。
实施例4-7
采用实施例1的方法步骤，采用下表中的参数，其他参数同实施例1；
表中，参数A：水热生长温度；
参数B：水热生长时间；
实施例4、5、6所制备的原位生长于氧化铝陶瓷管的纳米氧化铁的场发射扫描电镜图片如图7所示；
实施例7所制备的原位生长于氧化铝陶瓷管的纳米氧化铁的电极丝发生脱落。
对比例1
将氧化铝陶瓷管用丙酮、乙醇、去离子水分别超声30 min清洗干净，并烘干备用。将清洗干净的陶瓷管置入装有氯化亚铁和硫酸钠的混合溶液（混合溶液中，氯化亚铁和硫酸钠的浓度均为0.05 mol/L）高压反应釜中，于140℃下水热生长12 h，然后将生长过后的陶瓷管在马弗炉中进行以3℃ /min的速率升温至600℃保温2 h的退火处理，然后自然冷却至室温；即得到原位生长于氧化铝陶瓷管的纳米氧化铁。该纳米氧化铁的扫描电镜如图8所示；从图8 可以看出，以氯化亚铁为铁源制备的样品，表面没有特定的纳米材料形貌，更没有海胆状纳米针结构。
对比例2
将氧化铝陶瓷管用丙酮、乙醇、去离子水分别超声30 min清洗干净，并烘干备用。将清洗干净的陶瓷管置入装有硝酸铁和硫酸钠的混合溶液（混合溶液中，硝酸铁和硫酸钠的浓度均为0.05 mol/L）高压反应釜中，于140℃下水热生长12 h，然后将生长过后的陶瓷管在马弗炉中进行以3℃/min的速率升温至600℃保温2 h的退火处理，然后自然冷却至室温；即得到原位生长于氧化铝陶瓷管的纳米氧化铁。该纳米氧化铁的扫描电镜如图9所示；从图9可以看出陶瓷管上生长着一层厚厚的类似纺锤体纳米结构，但这些纺锤体结构在衬底上堆积倒伏，分布不均，且取向杂乱。
对比例3
将玻璃基片用丙酮、乙醇、去离子水分别超声30 min清洗干净，并烘干备用。将清洗干净的玻璃基片置入装有氯化铁和硫酸钠的混合溶液（混合溶液中，氯化铁和硫酸钠的浓度均为0.05 mol/L）高压反应釜中，于140℃下水热生长12 h，然后将生长过后的玻璃基片在马弗炉中进行以3℃ /min的速率升温至600℃保温2 h的退火处理，然后自然冷却至室温。发现在玻璃基片上，很难生长出氧化铁纳米针结构。
Claims (6)
1.一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法，其特征在于，包括以下步骤：
（1）将陶瓷管置于氯化铁和硫酸钠的混合溶液中，进行水热反应；所述氯化铁和硫酸钠的混合溶液，氯化铁和硫酸钠的浓度均为0.05mol/L；水热反应温度为140℃，水热反应时间为6-8h；
（2）水热反应完成后，将陶瓷管在马弗炉中进行退火处理；退火条件为：以3-4℃/min的速率升温至600-700℃，保温1.5-2.5h，然后自然冷却至室温。
2.根据权利要求1所述方法，其特征在于，陶瓷管在使用之前用丙酮、乙醇分别超声30min。
3.一种采用权利要求1或2所述方法制备的表面生长有Fe2O3纳米针的氧化铝陶瓷管。
4.一种氧化铁/氧化锡纳米针异质结陶瓷管，其特征在于，是利用脉冲激光沉积技术，在权利要求3所述氧化铝陶瓷管的Fe2O3纳米针表面沉积n型半导体材料氧化锡而成。
5.一种三元复合陶瓷管，其特征在于，是利用脉冲激光沉积技术和物理气相沉积技术，在权利要求4所述的氧化锡/氧化铁纳米针异质结陶瓷管的异质结表面溅射金颗粒而成。
6.一种采用权利要求3、4或5所述陶瓷管制备的气敏传感器。
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