CN107328825A - 一种n‑p异质型介孔球状气敏材料的制备方法 - Google Patents
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Abstract
一种n‑p异质型介孔球状气敏材料的制备方法,它涉及一种n型SnO2负载p型介孔球状金属氧化物NiO气敏材料的制备方法,包括步骤:以有序介孔二氧化硅FDU‑12为模板,利用纳米复制法合成介孔球状NiO前驱体,再利用改性浸渍法在NiO表面负载SnO2,得到n‑p异质型介孔球状SnO2/NiO气敏材料。本发明方法一方面通过介孔结构增加表面积以提高气敏性,另一方面通过调控n‑p异质型界面电子传输以提高气敏材料针对特定气体的灵敏度和选择性。本发明所采用的方法原料来源广泛,价格低廉,而且化学制备手段简单,得到的n‑p异质型介孔气敏材料灵敏度高,选择性强。
Description
技术领域
本发明涉及气敏材料领域,具体涉及一种n-p异质型介孔球状SnO2/NiO气敏材料的制备方法。
背景技术
近年来,随着我国汽车保有量的快速增长,汽车尾气中产生大量的NOx(主要是NO2和NO),将会严重影响空气质量,导致PM2.5飙升。针对日益突出大气环境污染问题,2016年1月1日国家正式施行《中华人民共和国大气污染防治法》。所以,防治大气污染,监控气体污染源具有高度紧迫性。目前,面向大气检测的商业化NO2传感器主要是基于电化学原理,其结构复杂,价格昂贵,响应速度较慢。因此,发展针对NO2等有毒有害气体的快速、高灵敏度、低浓度(ppb量级)检测技术具有重要意义。
NiO是一种直接带隙宽禁带P型半导体纳米材料,室温下的禁带宽度为3.6eV-4.0eV之间,气敏传导机制为表面控制型。通常,提高NiO半导体材料的气敏性能一般是调控材料的形貌、尺寸结构,如Lin等比较了纳米线、纳米棒、纳米片和纳米球四种纳米结构对提高乙醇气体气敏性能的影响(Mater. Res. Bull. 2013, 48, 449-454.);同时,通过将不同的金属氧化物进行复合,可以改善材料的能带结构,调节材料表面或界面的电子耗尽层(n型)或者空穴聚集层(p型),从而提高材料的气敏性能。如Hur等用溶液法制备n-p型ZnO-CuO气敏材料(Physica Status Solidi (a) 2013, 210 (6), 1213-1216.);中国专利CN103115946 B 发明了一种n-p结型铁铜基氧化物气敏元件的制备方法及应用。由此可见,将n型和p型氧化物通过一定的技术组装构建异质型复合结构,为开发灵敏度高、选择性强的气敏材料提供了可能。介孔结构金属氧化物利用介孔结构比表面积大,对气体吸附能力强,增加化学反应的活性点这一特性,可以提高金属氧化物气敏材料对气体的敏感性。因此,在保证良好的介孔球状结构的基础上,对p型半导体NiO气敏材料进行n型负载可以进一步提高材料的灵敏度以及选择性。
发明内容
本发明针对目前纯的p型NiO气敏材料在灵敏度以及选择性方面的不足,提供一种n-p异质型介孔球状气敏材料的制备方法,该发明方法一方面通过介孔结构增加表面积以提高气敏性,另一方面通过调控n-p异质型界面电子传输以提高气敏材料针对特定气体的灵敏度以及选择性。
为了实现上述目的,本发明提供一种n-p异质型介孔球状气敏材料的制备方法,其特征在于,具体包括以下步骤:一、以介孔FDU-12为模板,将一定量的FDU-12和Ni(NO3)2·6H2O放入聚四氟乙烯杯中,加酒精和正己烷搅拌至粉末;二、将所得粉末放入马弗炉中200~250℃煅烧2~6 h,在球道内得到氧化物前驱体。三、待样品冷却,用去离子水洗去模板外表面的Ni(NO3)2·6 H2O;四、把步骤三得到的样品放入聚四氟乙烯杯中,加入一定量的十二烷基磺酸钠、蒸馏水和正己烷搅拌2 h,再加入一定量的SnCl4·5H2O并搅拌至粉末,然后放入马弗炉中500~700℃煅烧4~8h,待样品冷却,用4mol/L的NaOH除掉FDU-12模板,并用蒸馏水和乙醇离心洗涤至中性,80℃真空干燥得到n-p异质型介孔球状SnO2/NiO气敏材料。
本发明优点:本发明所采用的方法原料来源广泛,价格低廉,而且化学制备手段简单;所获得的的n-p异质型介孔球状SnO2/NiO气敏材料灵敏度高,选择性强。
本发明采用X射线衍射技术(XRD)分析本发明制备的介孔SnO2/NiO气敏材料的物相,采用透射电子显微镜(TEM)表征本发明制备的介孔球状SnO2/NiO气敏材料的微观结构,采用气敏测试仪来测试本发明制备的SnO2/NiO气敏材料的气敏性能,可知本发明成功制备出了具有灵敏度高,选择性强的n-p异质型介孔球状SnO2/NiO气敏材料。
附图说明
图1是实施方式一制备的SnO2/NiO气敏材料的XRD曲线图,证实制备的SnO2/NiO气敏材料含有SnO2物相和NiO物相。
图2是实施方式一制备的SnO2/NiO气敏材料的TEM图,通过图2可知本发明制备的SnO2/NiO气敏材料具有介孔球状结构。
图3是实施方式一制备的SnO2/NiO气敏材料在300℃工作温度下对5 ppm的NO及NO2的气敏度图,从图中可以看出SnO2/NiO气敏材料在300℃下对5 ppm的NO的灵敏度为11.5,恢复时间为15s;对5 ppm的NO2的灵敏度为13.7,恢复时间为10s。
具体实施方式
下面是结合具体实施例,进一步阐述本发明。这些实施例仅用于说明本发明,但不用来限制本发明的范围。
具体实施方式一:一种n-p异质型介孔球状气敏材料的制备方法,具体是按以下步骤完成的:一、将1 g的FDU-12和4.85 g的Ni(NO3)2·6 H2O放入聚四氟乙烯杯中,加20 ml酒精和20 ml正己烷搅拌至粉末;二、将所得粉末放入马弗炉中200℃煅烧6 h,在球道内得到氧化物前驱体。三、待样品冷却,用去离子水洗去模板外表面的Ni(NO3)2·6 H2O;四、把步骤三得到的样品放入聚四氟乙烯杯中,加入一定量的十二烷基磺酸钠、蒸馏水和正己烷搅拌2h,再加入5.84g的SnCl4·5H2O并搅拌至粉末,然后放入马弗炉中500℃煅烧8h,待样品冷却,用4mol/L的NaOH除掉FDU-12模板,并用蒸馏水和乙醇离心洗涤至中性,80℃真空干燥得到n-p异质型介孔球状SnO2/NiO气敏材料。
具体实施方式二:一种n-p异质型介孔球状气敏材料的制备方法,具体是按以下步骤完成的:一、将2 g的FDU-12和4.85 g的Ni(NO3)2·6 H2O放入聚四氟乙烯杯中,加20 ml酒精和20 ml正己烷搅拌至粉末;二、将所得粉末放入马弗炉中250℃煅烧2 h,在球道内得到氧化物前驱体。三、待样品冷却,用去离子水洗去模板外表面的Ni(NO3)2·6 H2O;四、把步骤三得到的样品放入聚四氟乙烯杯中,加入一定量的十二烷基磺酸钠、蒸馏水和正己烷搅拌2h,再加入1.46g的SnCl4·5H2O并搅拌至粉末,然后放入马弗炉中700℃煅烧4h,待样品冷却,用4mol/L的NaOH除掉FDU-12模板,并用蒸馏水和乙醇离心洗涤至中性,80℃真空干燥得到n-p异质型介孔球状SnO2/NiO气敏材料。
具体实施方式三:一种n-p异质型介孔球状气敏材料的制备方法,具体是按以下步骤完成的:一、将4 g的FDU-12和4.85 g的Ni(NO3)2·6 H2O放入聚四氟乙烯杯中,加20 ml酒精和20 ml正己烷搅拌至粉末;二、将所得粉末放入马弗炉中220℃煅烧4 h,在球道内得到氧化物前驱体。三、待样品冷却,用去离子水洗去模板外表面的Ni(NO3)2·6 H2O;四、把步骤三得到的样品放入聚四氟乙烯杯中,加入一定量的十二烷基磺酸钠、蒸馏水和正己烷搅拌2h,再加入2.92g的SnCl4·5H2O并搅拌至粉末,然后放入马弗炉中600℃煅烧6h,待样品冷却,用4mol/L的NaOH除掉FDU-12模板,并用蒸馏水和乙醇离心洗涤至中性,80℃真空干燥得到n-p异质型介孔球状SnO2/NiO气敏材料。
具体实施方式四:一种n-p异质型介孔球状气敏材料的制备方法,具体是按以下步骤完成的:一、将1 g的FDU-12和4.85 g的Ni(NO3)2·6 H2O放入聚四氟乙烯杯中,加20 ml酒精和20 ml正己烷搅拌至粉末;二、将所得粉末放入马弗炉中250℃煅烧6 h,在球道内得到氧化物前驱体。三、待样品冷却,用去离子水洗去模板外表面的Ni(NO3)2·6 H2O;四、把步骤三得到的样品放入聚四氟乙烯杯中,加入一定量的十二烷基磺酸钠、蒸馏水和正己烷搅拌2h,再加入4.38g的SnCl4·5H2O并搅拌至粉末,然后放入马弗炉中700℃煅烧8h,待样品冷却,用4mol/L的NaOH除掉FDU-12模板,并用蒸馏水和乙醇离心洗涤至中性,80℃真空干燥得到n-p异质型介孔球状SnO2/NiO气敏材料。
Claims (2)
1.一种n-p异质型介孔球状气敏材料的制备方法,其特征在于,由以下步骤组成:一、以介孔FDU-12为模板,将一定量的FDU-12和Ni(NO3)2·6 H2O放入聚四氟乙烯杯中,加酒精和正己烷搅拌至粉末;二、将所得粉末放入马弗炉中200~250℃煅烧2~6 h,在球道内得到氧化物前驱体;三、待样品冷却,用去离子水洗去模板外表面的Ni(NO3)2·6 H2O;四、把步骤三得到的样品放入聚四氟乙烯杯中,加入一定量的十二烷基磺酸钠、蒸馏水和正己烷搅拌2 h,再加入一定量的SnCl4·5H2O并搅拌至粉末,然后放入马弗炉中500~700℃煅烧4~8h,待样品冷却,用4mol/L的NaOH除掉FDU-12模板,并用蒸馏水和乙醇离心洗涤至中性,80℃真空干燥得到n-p异质型介孔球状SnO2/NiO气敏材料。
2.在根据权利要求1所述的制备方法,其特征在于,所述的FDU-12和Ni(NO3)2·6 H2O的物质的量比为1:1~4:1;所述的Ni(NO3)2·6 H2O和SnCl4·5H2O的物质的量比为1:1~4:1。
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CN109085209A (zh) * | 2018-07-24 | 2018-12-25 | 徐靖才 | 一种n-p异质型多孔球状气敏材料及制备方法 |
CN109085208A (zh) * | 2018-07-24 | 2018-12-25 | 徐靖才 | 一种n-p异质型气敏材料及制备方法 |
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CN109085209A (zh) * | 2018-07-24 | 2018-12-25 | 徐靖才 | 一种n-p异质型多孔球状气敏材料及制备方法 |
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CN114839232A (zh) * | 2022-05-11 | 2022-08-02 | 兰州大学 | 一种气敏材料、气敏传感器及其制备方法和应用 |
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