CN114935594B - 一种基于Fe@Pt/C核壳纳米催化材料的气体传感器敏感膜及气体传感器 - Google Patents
一种基于Fe@Pt/C核壳纳米催化材料的气体传感器敏感膜及气体传感器 Download PDFInfo
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Abstract
本发明涉及传感器技术领域，公开了一种基于Fe@Pt/C核壳纳米催化材料的气体传感器敏感膜及气体传感器，所述敏感膜的制备方法为：首先制备铁纳米粒子悬浮液，然后加入导电炭黑制备Fe/C悬浮液，向Fe/C悬浮液中加入氯亚铂酸钾溶液，制备Fe@Pt/C核壳纳米粒子悬浊液；离心洗涤后干燥、研磨，得到Fe@Pt/C核壳纳米催化材料，最后制备成敏感膜。本发明制备的Fe@Pt/C核壳纳米催化材料具有良好的催化性能，以其制备的电极膜(20wt.％Fe@Pt)组装的H2S传感器对H2S进行电化学检测，检测灵敏度高，灵敏度可达3.49μA/ppm，同时检测范围大，重复性好，H2S浓度范围在5‑50ppm内有良好的线性关系，重复检测效果稳定。
Description
技术领域
本发明涉及传感器技术领域，具体涉及一种基于Fe@Pt/C核壳纳米催化材料的气体传感器敏感膜及气体传感器。
背景技术
H2S是一种无色、易燃、有臭鸡蛋味的气体，作为一种剧毒性物质，对人体具有很大的危害性，因此监测H2S的浓度对人体健康有着重要意义。目前使用较为广泛的电化学气体敏感元件主要依赖进口，价格昂贵。
颗粒均匀的纳米级贵金属催化剂，是保证电化学气体敏感元件催化电极活性的核心物质。铂黑纳米催化剂由于其优异的催化活性和稳定性，被广泛应用于H2S、CO等气体传感器。由于铂黑属于贵金属催化剂，价格昂贵，生产成本高，故大多将其负载于炭黑上，制成铂碳催化剂。铂含量低的铂碳催化剂与纯铂黑相比，相同质量下催化活性大大降低，达不到检测标准，为达到检测标准，须提高铂碳催化剂中铂的含量，增加成本。
Pt@M(M为Fe，Co，Ni等)核壳结构纳米复合材料在燃料电池、生物传感器等领域有所应用，但在气体传感器特别是硫化氢气体传感器领域未见报道。本发明制备的基于Fe@Pt/C核壳纳米催化材料的气体传感器可用于检测硫化氢气体，且传感器性能优异，具有极高的应用价值。
发明内容
本发明的目的在于克服现有技术存在的缺点，提供一种基于Fe@Pt/C核壳纳米催化材料的气体传感器敏感膜及气体传感器。
为了实现上述目的，本发明的技术方案之一是：一种基于Fe@Pt/C核壳纳米催化材料的气体传感器敏感膜，其特征在于：所述敏感膜的制备方法为：
1)取七水合硫酸亚铁和分散剂，溶于去离子水中，并在N2环境下机械搅拌30min，充分溶解成6mg/mL的前驱体溶液，所述七水合硫酸亚铁与分散剂的质量比为19:5；
2)取硼氢化钠溶于去离子水中制备成2.8mg/mL的硼氢化钠溶液，在N2环境下将硼氢化钠溶液逐滴加入前驱体溶液中，所述硼氢化钠与七水合硫酸亚铁的质量比为1:5，滴加结束后500r/min持续搅拌1h，反应完全后，在700r/min下加入去离子水，持续搅拌1h，除去残余的硼氢化钠，得到含有铁纳米粒子的黑色悬浮液；
3)将铁纳米粒子悬浮液进行密封超声分散20min，超声分散后在N2环境下加入导电炭黑，持续搅拌1h得黑色悬浮液，所述导电炭黑与七水合硫酸亚铁的质量比为23:2；
4)称取氯亚铂酸钾并溶于去离子水中制备成6.2mg/mL的氯亚铂酸钾溶液，所述七水合硫酸亚铁中的Fe与氯亚铂酸钾中的Pt的摩尔比为33:10，将氯亚铂酸钾溶液逐滴加入到步骤3)制备的黑色悬浮液中，反应3h，放置过夜，得到Fe@Pt/C核壳纳米粒子悬浊液；
5)分别用水、乙醇离心洗涤步骤4)制得的Fe@Pt/C核壳纳米粒子悬浊液，将得到的黑色粉末在40℃下真空干燥过夜，干燥完成后进行研磨，得到粒度均匀的Fe@Pt/C核壳纳米催化材料；
6)将步骤5)制得的Fe@Pt/C核壳纳米催化材料与连结剂、分散剂、流平剂、消泡剂和PTFE乳液混合制得电极浆料，所述Fe@Pt/C核壳纳米催化材料、连结剂、分散剂、流平剂、消泡剂与PTFE的质量比为65:8:12:5:5:5，将电极浆料通过丝网印刷技术印刷在PTFE膜上，经干燥、洗涤、200℃的条件下烧结制成敏感膜。
进一步地；步骤1)中所述分散剂为PVP。
进一步地；步骤5)中所述Fe@Pt/C核壳纳米催化材料的粒径约为50nm。
进一步地；步骤6)所述连结剂为羟乙基纤维素，分散剂为聚乙二醇辛基苯基醚，流平剂为BYK-333，消泡剂为BYK-094。
本发明另一技术方案是：一种气体传感器，其特征在于：所述气体传感器为三电极体系，包括工作电极、对电极和参比电极，以细铂丝为导线，5mol/L硫酸为电解质溶液，所述工作电极、对电极和参比电极均是由权利要求1制备的敏感膜构成的电极。
进一步地；所述气体传感器为硫化氢传感器。
本发明的有益效果：本发明制备的Fe@Pt/C核壳纳米催化材料具有良好的催化性能，以其制备的电极膜组装的H2S传感器对H2S进行电化学检测，检测灵敏度高，灵敏度可达3.49μA/ppm，同时检测范围大，重复性好，H2S浓度范围在5-50ppm内有良好的线性关系，重复检测效果稳定，检测水平高于同用量铂的采用市场购买的Pt/C纳米催化剂制备的电极膜组装的H2S传感器。
本发明基于Fe@Pt/C核壳纳米催化材料的气体传感器敏感膜制备过程简便、易操作、成本较低。
附图说明
图1为实施例1制备的Fe@Pt/C核壳纳米粒子的SEM图像；
图2为实施例1制备的Fe@Pt/C核壳纳米粒子的TEM图像；
图3为实施例1制备的Fe@Pt/C核壳纳米粒子的Mapping图像；
图4为实施例2组装的H2S传感器进行的时间-电流测试图像；
图5为实施例2组装的H2S传感器进行的H2S浓度-响应电流值测试柱状图；
图6为图5的拟合直线图；
图7为对比例1组装的H2S传感器进行的时间-电流测试图像；
图8为实施例2组装的H2S传感器进行的稳定性测试的响应电流变化柱状图。
具体实施方式
以下实施例进一步说明本发明的内容，但不应理解为对本发明的限制。在不背离本发明精神和实质的情况下，对本发明方法、步骤或条件所作的修改和替换，均属于本发明的范围。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。
实施例1：
一种基于Fe@Pt/C核壳纳米催化材料的气体传感器敏感膜，所述敏感膜的制备方法为：
1)称取0.139g七水合硫酸亚铁和0.0367gPVP(聚乙烯吡咯烷酮)，将两者溶于30mL去离子水中，并在N2环境下500r/min机械搅拌30min，充分溶解制成前驱体溶液；
2)称取0.0284g硼氢化钠，溶于10mL去离子水中制成硼氢化钠溶液，在N2环境下将硼氢化钠溶液逐滴加入前驱体溶液中，溶液由无色变为黑色，滴加结束后500r/min持续搅拌1h，反应完全后，在500r/min下加入10mL去离子水，持续搅拌1h，除去残余的硼氢化钠，得到铁纳米粒子悬浮液；
3)将铁纳米粒子悬浮液进行密封超声分散20min，超声分散后在N2环境下加入0.16g导电炭黑，500r/min下持续搅拌1h得黑色悬浮液；
4)称取0.062g氯化亚铂酸钾，溶于10mL去离子水中制成氯化亚铂酸钾溶液，将氯化亚铂酸钾溶液逐滴加入到步骤3)制备的黑色悬浮液中，反应3h，放置过夜，得到Fe@Pt/C核壳纳米粒子悬浊液；
5)分别用水、乙醇离心洗涤步骤4)制得的Fe@Pt/C核壳纳米粒子悬浊液，将得到的黑色粉末在40℃下真空干燥过夜，干燥完成后进行研磨，得到均匀的粒径约为50nm的Fe@Pt/C核壳纳米催化材料；Fe@Pt/C核壳纳米粒子的SEM图像如图1所示，Fe@Pt/C核壳纳米粒子的TEM图像如图2所示，Fe@Pt/C核壳纳米粒子的Mapping图像如图3所示；由图1和图2所示，制备的Fe@Pt/C核壳纳米粒子呈纳米球的形状，平均粒径50nm左右，分散均匀；由图3Mapping分析图可以看出，Fe@Pt核壳纳米粒子被成功合成；
6)称取0.1g步骤5)制备的Fe@Pt/C核壳纳米催化材料，与0.6mL羟乙基纤维素溶液(2wt.％)、0.2mL聚乙二醇辛基苯基醚溶液(10wt.％)、0.1mLPTFE乳液(10wt.％)、0.1mLBYK-333(10wt.％)、0.1mLBYK-094(10wt.％)混合制成电极浆料，将电极浆料通过丝网印刷技术印刷在PTFE膜上，60℃干燥过夜，用去离子水洗涤后，在真空干燥箱中200℃烧结制成敏感膜。
实施例2：
一种H2S传感器，所述H2S传感器为三电极体系，包括工作电极、对电极和参比电极，以细铂丝为导线，5mol/L硫酸为电解质溶液，所述工作电极、对电极和参比电极均是由实施例1制备的敏感膜构成的电极，采用现有公知方法组装H2S传感器。
对比例1：
本对比例中所用Pt/C纳米催化剂为市场购买。
一种敏感膜，制备方法为：称取0.1g Pt/C纳米催化剂(10wt.％Pt)，与0.6mL羟乙基纤维素溶液(2wt.％)、0.2mL聚乙二醇辛基苯基醚溶液(10wt.％)、0.1mL PTFE乳液(10wt.％)、0.1mLBYK-333流平剂(10wt.％)、0.1mL BYK-094消泡剂(10wt.％)混合制成电极浆料，将电极浆料通过丝网印刷技术印刷在PTFE膜上，60℃干燥过夜，用去离子水洗涤后，在真空干燥箱中200℃烧结制成敏感膜。
一种H2S传感器，所述H2S传感器为三电极体系，包括工作电极、对电极和参比电极，以细铂丝为导线，5mol/L硫酸为电解质溶液，所述工作电极、对电极和参比电极均是由本对比例1制备的敏感膜构成的电极，采用现有公知方法组装H2S传感器。
测试实验：
采用实施例2组装的H2S传感器进行时间-电流测试试验，使用电化学工作站(CHI660E)控制电压恒定为0.3V，测试结果如图4所示。
采用实施例2组装的H2S传感器进行H2S浓度-响应电流值测试试验，使用电化学工作站(CHI660E)控制电压恒定为0.3V，测试结果如图5、6所示。
采用实施例2组装的H2S传感器进行稳定性测试，测试时间为期一周，用于测试的H2S气体浓度为20ppm，定义第一日测得的响应电流值为100％，其后每日响应电流值相较于第一日响应电流值折算为对应的百分比，测试结果如图8所示。
采用对比例1组装的H2S传感器进行时间-电流测试试验，测试结果如图7所示。
如图4所示，实施例2组装的H2S传感器对H2S具有很好的电流信号响应，响应时间(T90％)在15s左右，恢复时间(T90％)略长，在40s左右。如图5、6所示，在测试范围内(5-50ppm)响应电流值与H2S的浓度具有良好的线性关系，线性相关系数(r)为0.99941，灵敏度达到了3.49μA/ppm。
如图7所示，对比例1组装的H2S传感器相比实施例2组装的H2S传感器的灵敏度低得多，经过计算仅为1.68μA/ppm。这是因为相同的铂用量下，Fe@Pt纳米粒子的数量要比单纯的Pt纳米粒子多得多，催化能力得到增强。而且在催化过程中，只有粒子表面薄薄的一层铂原子参与反应，内层的铂原子不参与反应。本发明通过在铁纳米粒子表面刻蚀铂原子层，在大大降低成本的同时，灵敏度也大大提高。
如图8所示，通过为期一周的重复性测试，相对于第一天，响应电流值相应变化在-2.1％～2.3％的范围内，这表明本发明实施例2组装的H2S气体传感器具有良好的稳定性。
Claims (6)
1.一种基于Fe@Pt/C核壳纳米催化材料的气体传感器敏感膜，其特征在于：所述敏感膜的制备方法为：
1）取七水合硫酸亚铁和分散剂，溶于去离子水中，并在N2环境下机械搅拌30 min，充分溶解成6 mg/mL的前驱体溶液，所述七水合硫酸亚铁与分散剂的质量比为19:5；
2）取硼氢化钠溶于去离子水中制备成2.8 mg/mL的硼氢化钠溶液，在N2环境下将硼氢化钠溶液逐滴加入前驱体溶液中，所述硼氢化钠与七水合硫酸亚铁的质量比为1:5，滴加结束后500 r/min持续搅拌1 h，反应完全后，在700 r/min下加入去离子水，持续搅拌1 h，除去残余的硼氢化钠，得到含有铁纳米粒子的黑色悬浮液；
3）将铁纳米粒子悬浮液进行密封超声分散20 min，超声分散后在N2环境下加入导电炭黑，持续搅拌1 h得黑色悬浮液，所述导电炭黑与七水合硫酸亚铁的质量比为23:2；
4）称取氯亚铂酸钾并溶于去离子水中制备成6.2 mg/mL的氯亚铂酸钾溶液，所述七水合硫酸亚铁中的Fe与氯亚铂酸钾中的Pt的摩尔比为33:10，将氯亚铂酸钾溶液逐滴加入到步骤3）制备的黑色悬浮液中，反应3 h，放置过夜，得到Fe@Pt/C核壳纳米粒子悬浊液；
5）分别用水、乙醇离心洗涤步骤4）制得的Fe@Pt/C核壳纳米粒子悬浊液，将得到的黑色粉末在40℃下真空干燥过夜，干燥完成后进行研磨，得到粒度均匀的Fe@Pt/C核壳纳米催化材料；
6）将步骤5）制得的Fe@Pt/C核壳纳米催化材料与连结剂、分散剂、流平剂、消泡剂和PTFE乳液混合制得电极浆料，所述Fe@Pt/C核壳纳米催化材料、连结剂、分散剂、流平剂、消泡剂与PTFE的质量比为65:8:12:5:5:5，将电极浆料通过丝网印刷技术印刷在PTFE膜上，经干燥、洗涤、200℃的条件下烧结制成敏感膜。
2.根据权利要求1所述的基于Fe@Pt/C核壳纳米催化材料的气体传感器敏感膜，其特征在于：步骤1）中所述分散剂为PVP。
3.根据权利要求1所述的基于Fe@Pt/C核壳纳米催化材料的气体传感器敏感膜，其特征在于：步骤5）中所述Fe@Pt/C核壳纳米催化材料的粒径约为50 nm。
4.根据权利要求1所述的基于Fe@Pt/C核壳纳米催化材料的气体传感器敏感膜，其特征在于：步骤6）中所述连结剂为羟乙基纤维素，分散剂为聚乙二醇辛基苯基醚，流平剂为BYK-333，消泡剂为BYK-094。
5.一种气体传感器，其特征在于：所述气体传感器为三电极体系，包括工作电极、对电极和参比电极，以细铂丝为导线，5 mol/L 硫酸为电解质溶液，所述工作电极、对电极和参比电极均是由权利要求1所述的敏感膜构成的电极。
6.根据权利要求5所述的气体传感器，其特征在于：所述气体传感器为硫化氢传感器。
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| US4001757A (en) * | 1973-08-14 | 1977-01-04 | Matsushita Electric Industrial Co., Ltd. | Method for detecting a reducing material in a gas phase |
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