CN111097401A - 旋涂制备ZnO/TiO2异质结薄膜材料的方法 - Google Patents
旋涂制备ZnO/TiO2异质结薄膜材料的方法 Download PDFInfo
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Abstract
一种旋涂制备ZnO/TiO2异质结薄膜材料的方法,通过在TiO2纳米棒薄膜表面,控制旋涂醋酸锌‑乙醇溶液旋涂转速和旋涂次数,以控制ZnO晶种形成的均匀分布程度和密度,然后在水热条件下在ZnO晶种上生长ZnO纳米线,制备得到ZnO/TiO2异质材料具有鸟巢状结构。本发明得到的ZnO/TiO2薄膜,比表面积大,具有更高的光吸收性能、高的光电效率和电荷传输效率,可以广泛应用于光电催化产氢和光电催化降解有机物等领域。
Description
技术领域
本发明涉及的是一种光电催化领域的技术,具体是一种旋涂制备ZnO/TiO2异质结薄膜材料的方法。
背景技术
二氧化钛(TiO2)作为光电催化光阳极,具有合适的导带/价带位置、储量丰富、低价、无毒、稳定性好等优点。但TiO2较宽的带隙能(锐钛矿~3.2eV,金红石~3.0eV),使其只能吸收紫外光,且载流子分离和传输动力学过程非常缓慢。现有技术有采用氧化锌(ZnO)修饰TiO2的ZnO/TiO2异质结薄膜作为改进光电极,由于其具有基于ZnO较高的电子迁移率(ZnO纳米线:1000cm2 V s-1)和基于二者之间良好的能级匹配关系而具有优异光生电荷分离效率的潜力。
现有的ZnO/TiO2薄膜的制备方法,是通过在TiO2薄膜表面生长ZnO来进行制备的。但是现有方法无法在TiO2薄膜表面生长出有序的ZnO纳米结构,因而难以获得高比表面积的ZnO薄膜层,导致ZnO/TiO2薄膜载流子分离效率和传输性能差,光电催化活性和稳定性差。如Int.J.hydrogen Energy 42(2017)3938-3946将醋酸锌直接滴加到TiO2薄膜上,浸润之后,烧结后形成ZnO/TiO2异质结薄膜,由于该方法也没有采用ZnO晶种诱导ZnO生长,获得的ZnO/TiO2薄膜,ZnO薄膜层为核壳结构,这种核壳结构的ZnO层比表面积小,光吸收差。中国发明专利CN101760739A中,则直接在TiO2薄膜表面水热生长ZnO纳米棒,获得ZnO/TiO2薄膜,该方法在TiO2薄膜表面制备ZnO时,没有使用ZnO晶种,但所获得的ZnO纳米棒短,比表面积小,光吸收差。J.Nanopart.Res,2017,19(9):297通过在TiO2薄膜表面上先引入ZnO晶种,通过在TiO2薄膜表面浸渍醋酸锌-乙醇溶液,烧结形成ZnO晶种,然后放入水热体系,在ZnO晶种上生长ZnO,形成了表面包含有粗短ZnO纳米棒(长~200nm)的ZnO/TiO2异质结薄膜。该方法尽管改善了ZnO的表面结构,但是由于浸渍醋酸锌-乙醇溶液,无法在TiO2薄膜表面均匀地分散,导致ZnO晶种局部堆积在TiO2薄膜表面而无法均匀分散,最终ZnO在TiO2薄膜表面生长了较厚的核壳结构ZnO/TiO2,这种堆积结构的ZnO层比表面积依然较小,光吸收差,光电催化活性和稳定性差。
发明内容
本发明针对现有技术存在的上述不足,提出一种旋涂制备ZnO/TiO2异质结薄膜材料的方法,得到的ZnO/TiO2薄膜具有鸟巢状有序结构,比表面积大,光吸收性能强、光电效率和电荷传输效率高,可以广泛应用于光电催化产氢和光电催化降解有机物等领域。
本发明是通过以下技术方案实现的:
本发明涉及一种旋涂制备ZnO/TiO2异质结薄膜材料的方法,通过在TiO2纳米棒薄膜表面,控制旋涂醋酸锌-乙醇溶液旋涂转速和旋涂次数,以控制ZnO晶种形成的均匀分布程度和密度,然后在水热条件下在ZnO晶种上生长ZnO纳米线,制备得到具有鸟巢状有序结构的ZnO/TiO2异质材料。
所述的TiO2纳米棒薄膜其制备方法是:在30mL的1:1浓盐酸-水溶液中加入0.6mL钛酸四丁酯,快速搅拌2h,得透明溶液;将导电玻璃置于装有上述钛酸四丁酯溶液的水热釜中,150℃反应12h,冷却后,经水洗、烘干后,在马弗炉中以1℃/min的速度加热到450℃,保温1h,即得TiO2纳米棒薄膜。
所述的控制旋涂,具体是指:在制备好的TiO2纳米棒薄膜上旋涂10mM的醋酸锌-乙醇溶液,旋涂转速为2000~4000rpm,旋涂次数为6~10次,每次旋涂完毕后,将其置于150℃的热盘上加热2min后取下并冷却至室温,然后再进行下一次旋涂。
所述的ZnO晶种形成,具体是指:全部旋涂步骤完成后,将TiO2纳米棒薄膜置于450℃的热盘上1h,在TiO2纳米棒薄膜表面生长ZnO晶种。
所述的生长ZnO纳米线,具体是指:将表面具有ZnO晶种的TiO2纳米棒薄膜置于5~20mM硝酸锌和六次甲基四胺的混合溶液中,于烘箱90℃下加热4h生长ZnO纳米线。
本发明涉及上述方法制备得到的ZnO/TiO2异质结薄膜材料,表面具有鸟巢状有序结构,与传统的ZnO/TiO2异质结薄膜相比,具有更大的比表面积,更好的光吸收和更高的载流子分离和传输性能,以及更好的光电催化性能。
本发明涉及一种旋涂制备ZnO/TiO2异质结薄膜电极在光电催化制氢和光电催化降解有机污染物等领域中的应用。
技术效果
与现有技术相比,本发明整体解决了ZnO/TiO2异质结中ZnO层比表面积小、光吸收性能差、载流子动力学缓慢的问题,由此产生的技术效果包括:
1)ZnO/TiO2异质结是在TiO2纳米棒表面,由均匀分散的ZnO晶种生长的ZnO长纳米线结合而成,ZnO长纳米线相互交错,构成具有更高比表面积的鸟巢庄有序结构,当其与电解液界面接触时,具有更大的接触面积,有利于光的吸收和载流子的传输和界面反应;
2)TiO2与ZnO之间存在着能级匹配关系,见图1,这种能级匹配关系能够满足电子与空穴的分离与传输,有利于克服TiO2中光生电子-空穴对复合严重的问题;
3)相比传统结构的ZnO/TiO2薄膜,本发明是一种开放的具有高比表面积的鸟巢状结构,光线可以直接照射到TiO2纳米棒上,有效减弱了ZnO的光腐蚀,提高了其稳定性。
附图说明
图1为TiO2与ZnO的能级结构示意图;
图2为本发明的制备工艺示意图;
图3为实施例1中TiO2纳米棒薄膜(a)和本发明鸟巢状结构的ZnO/TiO2薄膜(b)的扫面电镜照片;
图4为实施例1中TiO2纳米棒薄膜、传统的核壳结构的ZnO/TiO2薄膜和本发明鸟巢状结构的ZnO/TiO2薄膜的紫外可见吸收光谱图;
图5为实施例1中TiO2纳米棒薄膜、传统的核壳结构的ZnO/TiO2薄膜和本发明鸟巢状结构的ZnO/TiO2薄膜在0.2M Na2SO4电解液中、100mW cm-2光照强度下测得的线性扫描伏安曲线示意图;
图6为实施例1中TiO2纳米棒薄膜、传统的核壳结构的ZnO/TiO2薄膜和本发明鸟巢状结构的ZnO/TiO2薄膜在0.2M Na2SO4电解液中、100mW cm-2光照强度和1.23V(vs.RHE)偏压下测得的光电转化效率曲线示意图;
图7为实施例1中TiO2纳米棒薄膜、传统的核壳结构的ZnO/TiO2薄膜和本发明鸟巢状结构的ZnO/TiO2薄膜的交流阻抗曲线示意图;
图8为实施例1中TiO2纳米棒薄膜、传统的核壳结构的ZnO/TiO2薄膜和本发明鸟巢状结构的ZnO/TiO2薄膜在不同光照强度下的电子传输时间和电子寿命示意图;
图9为实施例1中TiO2纳米棒薄膜、传统的核壳结构的ZnO/TiO2薄膜和本发明鸟巢状结构的ZnO/TiO2薄膜在0.2M Na2SO4电解液中、100mW cm-2光照强度和1.23V(vs.RHE)偏压下测得的光电流-时间曲线示意图。
具体实施方式
实施例1
本实施例具体包括以下步骤:
①采用水热法制备TiO2纳米棒薄膜:在30mL的1:1浓盐酸的水溶液中加入0.6mL钛酸四丁酯,快速搅拌2h,得透明溶液;将导电玻璃置于装有上述钛酸四丁酯溶液的水热釜中,150℃反应12h,冷却后,经水洗、烘干后,在马弗炉中以1℃/min的速度加热到450℃,保温1h,即得TiO2纳米棒薄膜。
②在制备好的TiO2纳米棒薄膜上旋涂10mM的醋酸锌-乙醇溶液,制备ZnO晶种;旋涂速度为3000rpm,旋涂次数为8次,每次旋涂完毕后,将其置于150℃的热盘上加热2min,然后取下,冷却至室温,进行下一次旋涂。
③旋涂完成后,将其置于450℃的热盘上加热1h,在TiO2纳米棒薄膜表面生长ZnO晶种层;随后,将具有ZnO晶种层的TiO2薄膜置于10mM的硝酸锌和六次甲基四胺的混合溶液中,于烘箱90℃下加热4h生长ZnO纳米线后,取出并用去离子水冲洗数次,然后在50℃下干燥1h,即得表面具有鸟巢状结构的ZnO/TiO2异质结薄膜电极。
将本实施例制备得到的鸟巢状结构的ZnO/TiO2薄膜光阳极在0.2M Na2SO4电解质溶液中、100mW cm-2光照强度下测得的伏安曲线表明,其光电流密度在1.23V(vs RHE)偏压下为2.72mA/cm-2,经过8h稳定性测试光电流只下降了不到4%,光电转换效率达到88.4%。该薄膜材料可以作为光电催化电极用于光电催化制氢和光电催化降解有机污染物中。
以下以1个对照例来说明实施例1的效果。
对照例1
步骤1)先采用水热法制备TiO2纳米棒薄膜:在30mL的1:1浓盐酸的水溶液中加入0.6mL钛酸四丁酯,快速搅拌2h,得透明溶液;将导电玻璃置于装有上述钛酸四丁酯溶液的水热釜中,150℃反应12h,冷却后,经水洗、烘干后,在马弗炉中以1℃/min的速度加热到450℃,保温1h,即得TiO2纳米棒薄膜。
步骤2)按照文献Int.J.hydrogen Energy 42(2017)3938-3946的方法制备传统的核壳结构的ZnO/TiO2薄膜:首先配置5mM的醋酸锌溶液,将制备好的TiO2纳米棒薄膜置于100℃的热盘上,取1mL该溶液滴在TiO2纳米棒薄膜上,待所滴醋酸锌溶液干燥后,再进行下一次滴加,重复几次。然后,将其置于马弗炉中,加热到400℃,保温30min,冷却后,即得传统的具有核壳结构的ZnO/TiO2异质结薄膜电极。
如图3所示,为TiO2纳米棒薄膜(图3a)和本发明鸟巢状结构的ZnO/TiO2薄膜(图3b)的SEM照片,传统的核壳结构的SEM照片参见文献Int.J.hydrogen Energy 42(2017)3938-3946的3940页的图1d。在传统的核壳结构的ZnO/TiO2薄膜中,TiO2纳米棒被厚的ZnO包裹着。而在本发明鸟巢状结构的ZnO/TiO2薄膜中,TiO2纳米棒上长了很多相互交错的、疏密有致的ZnO纳米线,ZnO纳米线长度高达6μm,具有更高的比表面积。
如图4所示,为TiO2纳米棒薄膜、传统的核壳结构的ZnO/TiO2薄膜、本发明鸟巢状结构的ZnO/TiO2薄膜的紫外可见吸收光谱。传统的核壳结构ZnO/TiO2薄膜表现出较差的吸光性能。
如图5所示,为TiO2纳米棒薄膜、传统的核壳结构的ZnO/TiO2薄膜、本发明鸟巢状结构的ZnO/TiO2薄膜在0.2M Na2SO4电解质溶液中、100mW cm-2光照强度下测得的伏安曲线。所述的TiO2薄膜和核壳结构的ZnO/TiO2薄膜的光电流密度在1.23V(vs RHE)偏压下分别为1.25mA/cm-2和1.74mA/cm-2,远低于实施例1中本发明具有鸟巢状结构的ZnO/TiO2薄膜的光电流密度(2.72mA/cm-2)。
如图6所示,为TiO2纳米棒薄膜、传统的核壳结构的ZnO/TiO2薄膜、本发明鸟巢状结构的ZnO/TiO2薄膜的光电转化效率。所述的TiO2薄膜和传统核壳结构的ZnO/TiO2薄膜在380nm波长的光电转化效率分别为38.9%和58.5%,远低于实施例1中本发明具有鸟巢状结构的ZnO/TiO2薄膜的光电转化效率(88.4%)。
如图7所示,为TiO2纳米棒薄膜、传统的核壳结构的ZnO/TiO2薄膜、本发明鸟巢状结构的ZnO/TiO2薄膜的电化学阻抗谱。所述的TiO2薄膜和传统核壳结构的ZnO/TiO2薄膜的阻抗明显大于本发明具有鸟巢结构的ZnO/TiO2薄膜,说明实施例1中鸟巢状结构的ZnO/TiO2薄膜的载流子分离和传输效率得到大幅度提高。
如图8所示,为TiO2纳米棒薄膜、传统的核壳结构的ZnO/TiO2薄膜、本发明鸟巢状结构的ZnO/TiO2薄膜随光照强度变化的电子传输时间(图8a)和电子寿命(图8b)。电子传输时间为光阳极薄膜中多数载流子(电子)到达导电基底的平均迁移时间,电子寿命为光阳极薄膜中多数载流子(电子)的平均寿命。结果表明通过本发明得到的鸟巢状结构的ZnO/TiO2薄膜中的光生载流子的迁移速率和寿命均要远高于所述的TiO2薄膜和传统核壳结构的ZnO/TiO2薄膜中光生载流子的迁移速率和寿命。
如图9所示,为TiO2纳米棒薄膜、传统的核壳结构的ZnO/TiO2薄膜、本发明鸟巢状结构的ZnO/TiO2薄膜的稳定性测试。TiO2是一种非常稳定的光阳极材料,所述的TiO2薄膜经过8h稳定性测试后光电流没有发生衰减。所述的传统核壳结构的ZnO/TiO2薄膜在相同测试条件下光电流衰减了~28%,而实施例1中本发明具有鸟巢状结构的ZnO/TiO2薄膜的光电流仅衰减了不到4%,表现出非常好的稳定性。
对照例2
根据文献J.Nanopart.Res,2017,19(9):297制备表面具有粗短的ZnO棒的核壳结构的ZnO/TiO2薄膜。
步骤1)先采用水热法制备TiO2纳米棒薄膜:在20mL浓盐酸、4mL醋酸和24mL水的混合溶液中加入0.8mL钛酸四丁酯,快速搅拌至溶液透明后,将导电玻璃置于装有上述钛酸四丁酯溶液的水热釜中,150℃反应20h,冷却后,经水洗、烘干后,在马弗炉中以1℃/min的速度加热到450℃,保温0.5h,即得TiO2纳米棒薄膜。
步骤2)将1.01g醋酸锌和0.5mL二乙基胺加入到50mL的乙醇溶液中,搅拌至均匀,得到ZnO晶种溶液。将TiO2纳米棒薄膜浸渍在该溶液中,一段时间后取出,干燥后,在空气气氛中,400℃下热解0.5h,即得到表面覆盖一层ZnO晶种的TiO2纳米棒薄膜。
步骤3)随后,将具有ZnO晶种层的TiO2薄膜置于10mM的硝酸锌和六次甲基四胺的混合溶液中,于烘箱90℃下加热3h后,取出并用去离子水冲洗数次,然后在50℃下干燥1h;然后将其置于马弗炉中,于450℃下热解0.5h,即得表面具有粗短的ZnO棒的核壳结构的ZnO/TiO2异质结薄膜电极。
所述的核壳结构的ZnO/TiO2薄膜的扫描电镜照片、伏安曲线和光电转化效率曲线分别见文献J.Nanopart.Res,2017,19(9):297第四页图2c,第六页图5a和第七页图6b。从扫描电镜照片中可以清晰地看到,TiO2纳米棒被厚厚的ZnO包裹着,形成核壳结构,同时在表面生长了许多粗短的ZnO纳米棒(长~200nm)。其光电流密度在1.23V(vs RHE)偏压下分别为1.12mA/cm-2,最大光电转化效率为35%,远低于实施例1中鸟巢状结构的ZnO/TiO2薄膜的光电流密度(2.72mA/cm-2)和光电转化效率(88.4%)。
实施例2
按照实施例1制备TiO2纳米棒薄膜,在制备好的TiO2纳米棒薄膜上旋涂10mM的醋酸锌-乙醇溶液,制备ZnO晶种;旋涂速度为2000rpm,旋涂次数为6次,每次旋涂完毕后,将其置于150℃的热盘上加热2min,然后取下,冷却至室温,进行下一次旋涂直至旋涂完成后,置于450℃的热盘上加热1h,在TiO2纳米棒薄膜表面生长ZnO纳米线;随后,将具有ZnO晶种层的TiO2薄膜置于20mM的硝酸锌和六次甲基四胺的混合溶液中,于烘箱90℃下加热4h生长ZnO纳米线后,取出并用去离子水冲洗数次,然后在50℃下干燥1h,即得鸟巢状结构的ZnO/TiO2异质结薄膜电极。
本实施例制备得到的鸟巢状结构的ZnO/TiO2薄膜在0.2M Na2SO4电解质溶液中、100mW cm-2光照强度下测得的伏安曲线表明,其光电流密度在1.23V(vs RHE)偏压下为2.42mA/cm-2,经过8h稳定性测试光电流只下降了不到8%,光电转换效率达到83.1%。该薄膜材料可以作为光电催化电极用于光电催化制氢和光电催化降解有机污染物中。
实施例3
按照实施例1制备TiO2纳米棒薄膜,在制备好的TiO2纳米棒薄膜上旋涂10mM的醋酸锌-乙醇溶液,制备ZnO晶种;旋涂速度为4000rpm,旋涂次数为10次,每次旋涂完毕后,将其置于150℃的热盘上加热2min,然后取下,冷却至室温,进行下一次旋涂直至旋涂完成后,将其置于450℃的热盘上加热1h,在TiO2纳米棒薄膜表面生长ZnO纳米线;随后,将具有ZnO晶种层的TiO2薄膜置于5mM的硝酸锌和六次甲基四胺的混合溶液中,于烘箱90℃下加热4h生长ZnO纳米线后,取出并用去离子水冲洗数次,然后在50℃下干燥1h,即得表面具有鸟巢状结构的ZnO/TiO2异质结薄膜电极。
本实施例制备得到的鸟巢状结构的ZnO/TiO2薄膜在0.2M Na2SO4电解质溶液中、100mW cm-2光照强度下测得的伏安曲线表明,其光电流密度在1.23V(vs RHE)偏压下为2.50mA/cm-2,经过8h稳定性测试光电流只下降了不到6%,光电转换效率达到84.4%。该薄膜材料可以作为光电催化电极用于光电催化制氢和光电催化降解有机污染物中。
本发明通过控制旋涂醋酸锌-乙醇溶液的转速和旋涂次数,实现ZnO晶种在/TiO2薄膜表面的均匀分布,最终控制水热条件得到具有鸟巢状结构的ZnO/TiO2异质薄膜,该薄膜ZnO层具有更高的比表面积。
经过具体实际实验,在室温的具体环境设置下,以0.2M Na2SO4电解质溶液中、100mW cm-2光照强度,能够得到的实验数据是:光电流、光电转化效率以及稳定性。
与现有技术相比,本发明的鸟巢状结构的ZnO/TiO2具有更高的光电催化活性和稳定性,在光电催化制氢和光电催化降解有机污染物中具有广泛的前途。
上述具体实施可由本领域技术人员在不背离本发明原理和宗旨的前提下以不同的方式对其进行局部调整,本发明的保护范围以权利要求书为准且不由上述具体实施所限,在其范围内的各个实现方案均受本发明之约束。
Claims (6)
1.一种旋涂制备ZnO/TiO2异质结薄膜材料的方法,通过在TiO2纳米棒薄膜表面,控制旋涂醋酸锌-乙醇溶液的旋涂转速和旋涂次数,以控制ZnO晶种形成的分布程度和密度,然后在水热条件下在ZnO晶种上生长ZnO纳米线,制备具有鸟巢状结构的ZnO/TiO2异质材料;
所述的旋涂转速为2000~4000rpm,旋涂次数为6~10次,水热反应液为5~20Mm硝酸锌和六次甲基四胺的混合溶液。
2.根据权利要求1所述的制备方法,其特征是,所述的TiO2纳米棒薄膜的制备方法:在30mL的1:1浓盐酸-水溶液中加入0.6mL钛酸四丁酯,快速搅拌2h,得透明溶液;将导电玻璃置于装有上述钛酸四丁酯溶液的水热釜中,150℃反应12h,冷却后,经水洗、烘干后,在马弗炉中以1℃/min的速度加热到450℃,保温1h,即得TiO2纳米棒薄膜。
3.根据权利要求1所述的制备方法,其特征是,所述的控制旋涂,具体是指:在制备好的TiO2纳米棒薄膜上旋涂10mM的醋酸锌-乙醇溶液;每次旋涂完毕后,将其置于150℃的热盘上加热2min后取下并冷却至室温,然后再进行下一次旋涂。
4.根据权利要求1所述的制备方法,其特征是,所述的ZnO晶种形成,具体是指:全部旋涂步骤完成后,将TiO2纳米棒薄膜置于450℃的热盘上1h,在TiO2纳米棒薄膜表面生长ZnO晶种。
5.根据权利要求1所述的制备方法,其特征是,所述的生长ZnO纳米线,具体是指:将表面具有ZnO晶种的TiO2纳米棒薄膜置于水热反应液硝酸锌和六次甲基四胺混合溶液中,于烘箱90℃下加热4h生长ZnO纳米线。
6.一种根据上述任一权利要求所述方法制备得到的ZnO/TiO2异质结薄膜电极的应用,其特征在于,用于光电催化制氢和光电催化降解有机污染物的电极材料。
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