CN113121124A - 一种铈掺杂硫化铋/三氧化二铁纳米异质结的制备方法 - Google Patents

一种铈掺杂硫化铋/三氧化二铁纳米异质结的制备方法 Download PDF

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CN113121124A
CN113121124A CN202110329970.6A CN202110329970A CN113121124A CN 113121124 A CN113121124 A CN 113121124A CN 202110329970 A CN202110329970 A CN 202110329970A CN 113121124 A CN113121124 A CN 113121124A
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周威
钟福新
劳昌玲
王家钰
黎燕
莫德清
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Guilin University of Technology
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Abstract

本发明公开了一种铈掺杂硫化铋/三氧化二铁纳米异质结的制备方法。(1)将Fe(NO3)3·9H2O和Na2C2O4的混合溶液倒入反应釜,插入FTO后于烘箱中反应,冷却,去离子水冲洗三遍后烘干,得到Fe2O3/FTO。(2)将Bi(NO3)3·5H2O冰醋酸溶液旋涂于Fe2O3/FTO上,重复1~5次,放入含硫脲与Ce(NO3)3·6H2O的1mol/L氨水溶液的反应釜中,于烘箱里反应,即在Fe2O3/FTO上得到Ce‑Bi2S3/Fe2O3纳米异质结,其光压值为0.1466 V~0.3468 V。本发明对原料及仪器要求不高、工艺简单、周期较短,产品的光电性能稳定。

Description

一种铈掺杂硫化铋/三氧化二铁纳米异质结的制备方法
技术领域
本发明涉及一种铈掺杂硫化铋/三氧化二铁纳米异质结的制备方法,即一种Ce掺杂Bi2S3/Fe2O3纳米异质结的制备方法。
背景技术
硫化铋(Bi2S3)是一种禁带宽度为1.3eV~1.7eV的直接带隙n型半导体,在太阳光范围内具有105cm-1的高吸收系数,可吸收800nm内大部分可见光并转移电子,可以直接对太阳光进行利用,在太阳能材料、光电转换材料、光催化降解材料和光裂解制氢等领域具有重要的发展前景。Bi2S3因空穴与电子容易复合和载流子寿命较低导致光电转换效率和量子转化效率较低,使其应用受到很大程度的制约。Fe2O3为铁的三价氧化物,有多种晶形,其中α-Fe2O3是一种禁带宽度为2.0~2.2eV的间接带隙n型半导体,对紫外光和可见光均表现出较好的光电响应,具有太阳光利用效率和理论光电流密度高、来源丰富、成本低廉、无毒环保等特性,是一种极具应用潜力的材料,在光催化、太阳能电池、传感器、锂离子电池、超级电容器等领域都有较广泛的应用。但α-Fe2O3存在光生电子和空穴容易复合、导电率较低、表面电子迁移率低、孔扩散长度短等缺陷,使其应用也受到一定限制。
对制备方法进行优化、元素掺杂和形成异质结等措施是克服Bi2S3和Fe2O3的上述缺陷的有效方法。本发明采用水热法制备Fe2O3薄膜,再在Fe2O3表面采用旋涂法-水热法沉积Ce掺杂Bi2S3(Ce-Bi2S3)纳米薄膜,获得Ce-Bi2S3/Fe2O3纳米异质结,其光电压值可达0.3468V。该制备工艺具有反应条件温和,设备简单、条件稳定,制备周期较短等特点,有望在光电转换领域得到应用。
发明内容
本发明的目的是提供一种采用水热法制备Fe2O3薄膜,再在Fe2O3表面采用旋涂法-水热法沉积Ce掺杂Bi2S3纳米薄膜,得到Ce掺杂Bi2S3/Fe2O3纳米异质结(记为Ce-Bi2S3/Fe2O3)。
具体步骤为:
(1)将15mL含有浓度为0.015~0.035mol/L的Fe(NO3)3·9H2O和浓度为0.045~0.105mol/L的Na2C2O4的混合溶液倒入聚四氟乙烯反应釜,把洁净的FTO斜靠釜内,盖紧釜盖;然后将其置于170℃的烘箱中反应8小时;冷却后取出FTO,使用去离子水冲洗三遍后烘干,即在FTO上制得Fe2O3薄膜(Fe2O3/FTO)。
(2)用移液枪取200μL浓度为0.2~0.6mol/L的Bi(NO3)3·5H2O冰醋酸溶液于Fe2O3/FTO上,以1200r/min的转速旋涂10秒,重复1~5次;然后将其放入盛有15mL由1mol/L氨水溶液配制而成、内含浓度为0.075~0.175mol/L的硫脲与浓度为0.000~0.008mol/L的Ce(NO3)3·6H2O混合液的反应釜中,把釜置于150℃的烘箱里反应6小时,冷却后取出,使用去离子水清洗三次后烘干,即在Fe2O3/FTO上得到Ce掺杂Bi2S3/Fe2O3纳米异质结(Ce-Bi2S3/Fe2O3),其光电压值为0.1466V~0.3468V。
本发明与其他相关技术相比,最显著的特点是先用水热法在FTO上制备Fe2O3纳米薄膜,再在Fe2O3薄膜上旋涂Bi(NO3)3溶液,让后续Ce元素掺杂的Bi2S3(Ce-Bi2S3)在Fe2O3表面原位生成,这一方面使异质结界面接触良好,进而促进载流子在结界面的传输,减小样品电子-空穴对的复合;另一方面Ce3+进入Bi2S3晶体中改变Bi2S3带隙宽度并与Fe2O3产生能带结构的协同效应,从而有效提高样品的光电性能。此方法对原料及仪器要求不高、工艺简单、周期较短,产品的光电性能稳定。
具体实施方式
实施例1:
(1)将15mL含有浓度为0.015mol/L的Fe(NO3)3·9H2O和浓度为0.045mol/L的Na2C2O4的混合溶液倒入聚四氟乙烯反应釜内,把洁净的FTO斜靠釜内,盖紧釜盖。然后将其置于170℃的烘箱中反应小时;冷却后取出FTO,使用去离子水冲洗三遍后烘干,即在FTO上制得Fe2O3薄膜(Fe2O3/FTO)。
(2)用移液枪取200μL浓度为0.2mol/L的Bi(NO3)3·5H2O冰醋酸溶液于Fe2O3/FTO上,以1200r/min的转速旋涂10秒,重复1次。然后将其放入盛有15mL由浓度为1mol/L氨水溶液配制而成、内含浓度为0.075mol/L硫脲混合液的反应釜中,把釜置于150℃的烘箱里反应6小时,冷却后取出,使用去离子水清洗三次后烘干,即在Fe2O3/FTO上得到Bi2S3/Fe2O3纳米异质结,其光电压值为0.2399V。
实施例2:
(1)将15mL含有浓度为0.020mol/L的Fe(NO3)3·9H2O和浓度为0.060mol/L的Na2C2O4的混合溶液倒入聚四氟乙烯反应釜内,FTO斜靠釜内,把洁净的FTO斜靠釜内,盖紧釜盖。然后将其置于170℃的烘箱中反应8小时;冷却后取出FTO,使用去离子水冲洗三遍后烘干,即在FTO上制得Fe2O3薄膜(Fe2O3/FTO)。
(2)用移液枪取200μL浓度为0.3mol/L的Bi(NO3)3·5H2O冰醋酸溶液于Fe2O3/FTO上,以1200r/min的转速旋涂10秒,重复2次。然后将其放入盛有15mL由浓度为1mol/L氨水溶液配制而成、内含浓度为0.100mol/L硫脲混合液的反应釜中,把釜置于150℃的烘箱里反应6小时,冷却后取出,使用去离子水清洗三次后烘干,即在Fe2O3/FTO上得到Bi2S3/Fe2O3纳米异质结,其光电压值为0.2790V。
实施例3:
(1)将15mL含有浓度为0.035mol/L的Fe(NO3)3·9H2O和浓度为0.105mol/L的Na2C2O4的混合溶液取,倒入聚四氟乙烯反应釜内,把洁净的FTO斜靠釜内,盖紧釜盖。然后将其置于170℃的烘箱中反应8小时;冷却后取出FTO,使用去离子水冲洗三遍后烘干,即在FTO上制得Fe2O3薄膜(Fe2O3/FTO)。
(2)用移液枪取200μL浓度为0.6mol/L的Bi(NO3)3·5H2O冰醋酸溶液于Fe2O3/FTO上,以1200r/min的转速旋涂10秒,重复5次。然后将其放入盛有15mL由浓度为1mol/L氨水溶液配制而成、内含浓度为0.175mol/L硫脲混合液的反应釜中,把釜置于150℃的烘箱里反应6小时,冷却后取出,使用去离子水清洗三次后烘干,即在Fe2O3/FTO上得到Bi2S3/Fe2O3纳米异质结,其光电压值为0.1466V
实施例4:
(1)将15mL含有浓度为0.030mol/L的Fe(NO3)3·9H2O和浓度为0.090mol/L的Na2C2O4的混合溶液倒入聚四氟乙烯反应釜内,把洁净的FTO斜靠釜内,盖紧釜盖。然后将其置于170℃的烘箱中反应8小时;冷却后取出FTO,使用去离子水冲洗三遍后烘干,即在FTO上制得Fe2O3薄膜(Fe2O3/FTO)。
(2)用移液枪取200μL浓度为0.5mol/L的Bi(NO3)3·5H2O冰醋酸溶液于Fe2O3/FTO上,以1200r/min的转速旋涂10秒,重复4次。然后将其放入盛有15mL由浓度为1mol/L氨水溶液配制而成、内含浓度为0.150mol/L硫脲混合液的反应釜中,把釜置于150℃的烘箱里反应6小时,冷却后取出,使用去离子水清洗三次后烘干,即在Fe2O3/FTO上得到Bi2S3/Fe2O3纳米异质结,其光电压值为0.2543V。
实施例5:
(1)将15mL含有浓度为0.025mol/L的Fe(NO3)3·9H2O和浓度为0.075mol/L的Na2C2O4的混合溶液倒入聚四氟乙烯反应釜内,把洁净的FTO斜靠釜内,盖紧釜盖。然后将其置于170℃的烘箱中反应8小时;冷却后取出FTO,使用去离子水冲洗三遍后烘干,即在FTO上制得Fe2O3薄膜(Fe2O3/FTO)。
(2)用移液枪取200μL浓度为0.4mol/L的Bi(NO3)3·5H2O冰醋酸溶液于Fe2O3/FTO上,以1200r/min的转速旋涂10秒,重复3次。然后将其放入盛有15mL由浓度为1mol/L氨水溶液配制而成、内含0.125mol/L硫脲混合液的反应釜中,把釜置于150℃的烘箱里反应6小时,冷却后取出,使用去离子水清洗三次后烘干,即在Fe2O3/FTO上得到Bi2S3/Fe2O3纳米异质结,其光电压值为0.2893V。
实施例6:
(1)将15mL含有浓度为0.025mol/L的Fe(NO3)3·9H2O和浓度为0.075mol/L的Na2C2O4的混合溶液倒入聚四氟乙烯反应釜内把洁净的FTO斜靠釜内,盖紧釜盖。然后将其置于170℃的烘箱中反应8小时;冷却后取出FTO,使用去离子水冲洗三遍后烘干,即在FTO上制得Fe2O3薄膜(Fe2O3/FTO)。
(2)用移液枪取200μL浓度为0.4mol/L的Bi(NO3)3·5H2O冰醋酸溶液于Fe2O3/FTO上,以1200r/min的转速旋涂10秒,重复3次。然后将其放入盛有15mL由浓度为1mol/L氨水溶液配制而成、内含0.125mol/L硫脲与0.001mol/L Ce(NO3)3·6H2O的混合液的反应釜中,把釜置于150℃的烘箱里反应6小时,冷却后取出,使用去离子水清洗三次后烘干,即在Fe2O3/FTO上得到Ce掺杂Bi2S3/Fe2O3纳米异质结(Ce-Bi2S3/Fe2O3),其光电压值为0.3056V。
实施例7:
参照实施例6,保持其他条件不变,只需改变Ce(NO3)3·6H2O的掺杂浓度为0.008mol/L,即可获得光电压值为0.2871V的Ce-Bi2S3/Fe2O3纳米薄膜异质结。
实施例8:
参照实施例6,保持其他条件不变,只需改变Ce(NO3)3·6H2O的掺杂浓度为0.002mol/L,即可获得光电压值为0.3448V的Ce-Bi2S3/Fe2O3纳米薄膜异质结。
实施例9:
参照实施例6,保持其他条件不变,只需改变Ce(NO3)3·6H2O的掺杂浓度为0.004mol/L,即可获得光电压值为0.3468V的Ce-Bi2S3/Fe2O3纳米薄膜异质结。

Claims (1)

1.一种铈掺杂硫化铋/三氧化二铁纳米异质结的制备方法,其特征在于具体步骤为:
(1)将15 mL含有浓度为0.015~0.035 mol/L的Fe(NO3)3·9H2O和浓度为0.045 ~ 0.105mol/L的Na2C2O4的混合溶液倒入聚四氟乙烯反应釜,把洁净的FTO斜靠釜内,盖紧釜盖;然后将其置于170 ℃的烘箱中反应8 小时;冷却后取出FTO,使用去离子水冲洗三遍后烘干,即在FTO上制得Fe2O3薄膜即Fe2O3/FTO;
(2)用移液枪取200 μL 浓度为0.2 ~ 0.6 mol/L的Bi(NO3)3·5H2O冰醋酸溶液于Fe2O3/FTO上,以1200 r/min的转速旋涂10 秒,重复1 ~ 5次;然后将其放入盛有15mL由1mol/L氨水溶液配制而成、内含浓度为0.075 ~ 0.175 mol/L的硫脲与浓度为0.000 ~ 0.008 mol/L的Ce(NO3)3·6H2O混合液的反应釜中,把釜置于150 ℃的烘箱里反应6小时,冷却后取出,使用去离子水清洗三次后烘干,在Fe2O3/FTO上得到铈掺杂硫化铋/三氧化二铁纳米异质结即Ce-Bi2S3/Fe2O3,其光电压值为0.1466 V ~0.3468 V。
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