CN106847666B - 一种TiO2/BaTiO3/RGO三元复合光电薄膜、其快速原位制备方法及应用 - Google Patents
一种TiO2/BaTiO3/RGO三元复合光电薄膜、其快速原位制备方法及应用 Download PDFInfo
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Abstract
本发明提供一种TiO2/BaTiO3/RGO三元复合光电薄膜、其快速原位制备方法及应用,属于材料合成领域。本发明以钛箔经阳极氧化得到的TiO2有序纳米管阵列模板,以水热法为基础,采用微波为能量源,TiO2有序纳米管阵列模板在Ba(OH)2和GO的前驱体混合溶液中反应,通过控制反应参数,使部分TiO2有序纳米管阵列模板原位反应生成BaTiO3的同时,将分散性好的RO原位还原,一步制备出高性能的TiO2/BaTiO3/RGO三元复合光电薄膜,有效解决了石墨烯分散性不良、TiO2光电性能欠佳及水热合成时间较长等问题,促进TiO2复合材料在光生阴极保护领域的应用。
Description
技术领域
本发明涉及一种TiO2/BaTiO3/RGO三元复合光电薄膜、其快速原位制备方法及应用,该薄膜可作为海洋工程装备的光生阴极保护材料,属于材料合成领域。
背景技术
对于常年处于海洋及大气环境中的工程装备来说,腐蚀一直是其面临的关键问题,而光生阴极保护是利用太阳光作为能源实现金属材料阴极保护的一种前沿技术。
在众多半导体材料中,TiO2是一种价廉、使用寿命长、环境友好的光生阴极保护材料。但由于TiO2带隙较宽,仅能吸收太阳光中少量的紫外线,并且产生的光生电子迁移速度较慢,使光生电子和空穴容易复合,导致光量子效率较低。因此,国内外学者对其进行了离子掺杂、半导体复合、贵金属负载等改性研究。近年来,由于石墨烯(graphene)具有较大的比表面积(2630 m2•g-1)、良好的导电性和更高的化学稳定性,利用石墨烯的优异特性对TiO2改性成为当前的研究热点。
柳伟等[郭祥芹,石墨烯/TiO2复合薄膜的制备及其光生阴极保护性能研究,D,青岛:中国海洋大学,2013]通过溶胶-凝胶结合热处理技术,以制备的石墨烯和TiO2溶胶为前驱体,采用旋涂的方法在304不锈钢表面成功制备了石墨烯/TiO2复合薄膜。研究发现,当涂覆于试样的涂层的复合方式为一层石墨烯/TiO2复合薄膜覆盖一层TiO2薄膜时,试样的开路电位负移最大,约为-600mV,光生电流密度约为100mA/cm2。
Ji Hoon Park等[Surface and Coating Technology, 2014, 258, 62-71]以石墨烯和TiO2溶液为前驱体,通过电泳沉积的方法在304不锈钢表面成功制备了石墨烯/TiO2复合薄膜。研究发现,在紫外灯照射下,涂覆有复合薄膜的试样的开路电位在-400mV--700mV之间。
由于三元材料体系的复杂性,合成过程中石墨烯的反应机制及其光电作用机理有待探讨,因此,国内外学者目前大部分选择石墨烯/TiO2二元材料体系为研究对象,但该体系对基体材料的光生阴极保护效果有待提高。另外,研究者多直接将石墨烯作为前驱体进行复合,但由于石墨烯具有不亲水特性,并且范德华力容易使其发生团聚,往往会导致石墨烯在产物中分散不均匀,进而影响到制备材料的光电转换性能。
BaTiO3作为一种n型半导体,其导带电位与TiO2导带电位接近,两者复合后可在其结合面形成势垒和能谷,有效的促进光生电子和空穴分离。氧化石墨烯边缘含有大量的含氧官能团,具有良好的亲水性,并且价格低廉。因此,在合成过程中,可调控部分TiO2前驱体通过原位反应生成BaTiO3,同时,将分散性良好的氧化石墨烯前驱体原位还原,一步制备出高性能TiO2/BaTiO3/RGO三元复合光电薄膜。目前尚未有该研究的相关报道。
TiO2复合薄膜的制备方法主要有溶胶-凝胶法、水热法、电泳沉积法、物理气相沉积法等。这些方法或工序复杂,无法实现一步制备,或制备所需时间较长,或无法对产物进行形貌控制。而一维有序结构正具有一维电子传输特性,可大大促进电子-空穴分离,提高材料光电转换性能。因此,以水热法为基础,以钛箔经阳极氧化得到的TiO2有序纳米管阵列模板,采用微波为能量源,通过反应物分子自身之间的摩擦、振动转化成热能来进行材料的原位合成,既可以控制产物的形貌,又可以将反应时间缩短至分钟甚至秒,同时,所需的合成温度更低,产物形貌更均一,产率也有所提高。目前微波水热快速合成TiO2/BaTiO3/RGO有序纳米管阵列的研究也尚未见报道。
发明内容
本发明的技术任务是解决现有技术的不足,提供一种TiO2/BaTiO3/RGO三元复合光电薄膜、其快速原位制备方法及应用。
本发明解决其技术问题所采用的技术方案是:
BaTiO3作为一种n型半导体,其导带电位与TiO2导带电位具有良好的匹配性。氧化石墨烯在水溶液中具有良好的分散性,还原后具有优异的导电性。微波加热利用反应物分子间的摩擦振动,可实现快速加热。因此,可采用微波水热快速制备方法,通过控制反应参数,使部分TiO2有序纳米管阵列前驱体原位反应生成BaTiO3的同时,将分散性良好的氧化石墨烯原位还原,一步制备出高性能TiO2/BaTiO3/RGO三元复合光电薄膜,以解决石墨烯分散性不良、TiO2光电性能欠佳及水热合成时间较长等问题,促进TiO2复合材料在光生阴极保护领域的应用。
1、本发明提供一种TiO2/BaTiO3/RGO三元复合光电薄膜,包括如下组分:TiO2、BaTiO3和RGO,其中,BaTiO3在TiO2表面通过原位反应生成TiO2/BaTiO3有序纳米管阵列,RGO则分布在TiO2/BaTiO3有序纳米管阵列的表面及管内,具有快速传到光生电子的功能。
进一步地,TiO2/BaTiO3/RGO三元复合光电薄膜以钛箔经阳极氧化得到的TiO2有序纳米管阵列模板,以水热法为基础,采用微波为能量源,TiO2有序纳米管阵列模板在Ba(OH)2和GO的前驱体混合溶液中反应,使部分TiO2有序纳米管阵列模板原位反应生成BaTiO3的同时,将分散性好的RO原位还原,一步制备出高性能的TiO2/BaTiO3/RGO三元复合光电薄膜。
2、本发明另提供一种TiO2/BaTiO3/RGO三元复合光电薄膜的快速原位制备方法,包括如下步骤:
1)钛基表面TiO2纳米管的制备:将钛箔超声清洗、化学抛光,然后以铂片为阴极,钛箔为阳极,在NH4F和H2O的甘油溶液中阳极氧化,阳极氧化后钛基表面TiO2纳米管的平均直径为100 nm-160 nm;
2)前驱体混合溶液的制备:在搅拌条件下,将Ba(OH)2溶解于水中,形成Ba(OH)2的澄清溶液,称为A液;将氧化石墨烯GO溶解于水中,分散均匀后制得GO的水溶液,称为B液;在搅拌条件下,将A液缓慢滴加到B液中,形成前驱体混合溶液,称为C液,其中C液中Ba2+含量在0.005 mol/L–0.02 mol/L,GO含量在0.25 g/L-0.80 g/L;
3)TiO2/BaTiO3/RGO三元复合光电薄膜的制备:将步骤1)制备的TiO2纳米管试样与步骤2)制备的C液转移到聚四氟乙烯反应容器中,保持填充率为40%,设定微波水热反应仪的升温速率为5-20℃/min,反应温度为120-150℃,保温时间为5-30min,进行微波水热合成反应;
4)待反应完成,再经煅烧处理、随炉冷却至室温后,即得TiO2/BaTiO3/RGO三元复合光电薄膜。
进一步地,步骤1)中,将钛箔依次用丙酮、乙醇和去离子水超声清洗、化学抛光。
进一步地,步骤2)中,将Ba(OH)2溶解于去CO2的离子水中,电磁搅拌20-30 min,得到Ba(OH)2的澄清溶液,称为A液;将氧化石墨烯GO溶解于去离子水中,超声40-60 min,电磁搅拌20-30 min,制得GO的水溶液,称为B液;将A液缓慢滴加到B液中,继续电磁搅拌5-10min,形成前驱体混合溶液,称为C液,其中C液中Ba2+含量在0.005 mol/L–0.02 mol/L,GO含量在0.25 g/L-0.80 g/L。
进一步地,步骤4)中,待反应完成,冷却到室温后取出试样,并将试样依次用盐酸和去离子水冲洗,干燥,最后在350-400℃马弗炉中保温1-2.5 h,随炉冷却至室温后取出。
3、本发明还一种TiO2/BaTiO3/RGO三元复合光电薄膜的应用,将所制备的TiO2/BaTiO3/RGO三元复合光电薄膜用作光生阴极保护材料。
本发明的一种TiO2/BaTiO3/RGO三元复合光电薄膜、其快速原位制备方法及应用,与现有技术相比所产生的有益效果是:
1、反应速度快,所需时间短,往往仅需要5-30 min,相比于其他合成方法,时间大大缩短;
2、合成步骤简单,反应过程中同时进行BaTiO3的原位合成和氧化石墨烯的还原反应;
3、利用氧化石墨烯作为反应原料,在水热过程中原位还原成石墨烯,不仅节省成本,而且具有更好的界面相容性,解决了石墨烯在产物中的分散均匀性问题;
4、TiO2/BaTiO3/RGO三元复合光电薄膜可加速光生电子-空穴分离,具有较高的光电性能,是一种新型的优异的光生阴极保护材料。
附图说明
附图1是本发明实施例一所制备试样的微观形貌图;
附图2是本发明实施例二所制备试样的微观形貌图;
附图3是本发明实施例三所制备试样的微观形貌图;
附图4是本发明实施例一、实施例二所制备试样的开路电位曲线图。
具体实施方式
下面结合附图1-4,对本发明的一种TiO2/BaTiO3/RGO三元复合光电薄膜、其快速原位制备方法及应用作以下详细说明。
本发明提供一种TiO2/BaTiO3/RGO三元复合光电薄膜,包括如下组分:TiO2、BaTiO3和RGO,其中,BaTiO3在TiO2表面通过原位反应生成TiO2/BaTiO3有序纳米管阵列,RGO则分布在TiO2/BaTiO3有序纳米管阵列的表面及管内,具有快速传到光生电子的功能。具体的:
TiO2/BaTiO3/RGO三元复合光电薄膜以钛箔经阳极氧化得到的TiO2有序纳米管阵列模板,以水热法为基础,采用微波为能量源,TiO2有序纳米管阵列模板在Ba(OH)2和GO的前驱体混合溶液中反应,使部分TiO2有序纳米管阵列模板原位反应生成BaTiO3的同时,将分散性好的RO原位还原,一步制备出高性能的TiO2/BaTiO3/RGO三元复合光电薄膜。
实施例一
本发明的一种TiO2/BaTiO3/RGO三元复合光电薄膜的快速原位制备方法,包括如下步骤:
1)钛基表面TiO2纳米管的制备
将钛箔依次用丙酮、乙醇和去离子水超声清洗、化学抛光,然后以铂片为阴极,钛箔为阳极,在15V电压下阳极氧化1h,两电极之间距离2cm,温度为室温,电解液为0.5 wt%NH4F和40 wt% H2O的甘油溶液,阳极氧化后钛基表面TiO2纳米管的平均直径为100 nm;
2)前驱体混合溶液的制备
将0.1260 g Ba(OH)2·8H2O溶解于25 mL去CO2的离子水中,电磁搅拌20 min,形成Ba(OH)2的澄清溶液,称为A液;将0.0120 g氧化石墨烯GO溶解于15 mL去离子水中,超声40min,电磁搅拌30 min,制得GO的水溶液,称为B液;将A液用滴管缓慢滴加到B液中,继续电磁搅拌8 min,形成前驱体混合溶液,称为C液;
3)TiO2/BaTiO3/RGO三元复合光电薄膜的制备
将步骤1)制备的TiO2纳米管试样与步骤2)制备的C液转移到100 mL聚四氟乙烯反应容器中,保持填充率为40%,设定微波水热反应仪的升温速率为5℃/min,反应温度为130℃,保温时间为30 min,进行微波水热合成反应;
4)待反应完成,进一步地,步骤4)中,待反应完成,冷却到室温后取出试样,并将试样依次用盐酸和去离子水冲洗,干燥,最后在350℃马弗炉中保温1 h,随炉冷却至室温后取出。
制备试样的微观形貌图如图1,与之偶接后的304不锈钢的开路电位如图4(a)所示。
实施例二
本发明的一种TiO2/BaTiO3/RGO三元复合光电薄膜的快速原位制备方法,包括如下步骤:
1)钛基表面TiO2纳米管的制备
将钛箔依次用丙酮、乙醇和去离子水超声清洗、化学抛光,然后以铂片为阴极,钛箔为阳极,在20V电压下阳极氧化1h,两电极之间距离2cm,温度为室温,电解液为0.5 wt%NH4F和40 wt% H2O的甘油溶液,阳极氧化后钛基表面TiO2纳米管的平均直径为140 nm;
2)前驱体混合溶液的制备
将0.0630 g Ba(OH)2·8H2O溶解于25 mL去CO2的离子水中,电磁搅拌15 min,形成Ba(OH)2的澄清溶液,称为A液;将0.010 g氧化石墨烯GO溶解于25 mL去离子水中,超声60min,电磁搅拌20 min,制得GO的水溶液,称为B液;将A液用滴管缓慢滴加到B液中,继续电磁搅拌10 min,形成前驱体混合溶液,称为C液;
3)TiO2/BaTiO3/RGO三元复合光电薄膜的制备
将步骤1)制备的TiO2纳米管试样与步骤2)制备的C液转移到100 mL聚四氟乙烯反应容器中,保持填充率为40%,设定微波水热反应仪的升温速率为20℃/min,反应温度为120℃,保温时间为20 min,进行微波水热合成反应;
4)待反应完成,进一步地,步骤4)中,待反应完成,冷却到室温后取出试样,并将试样依次用盐酸和去离子水冲洗,干燥,最后在370℃马弗炉中保温2 h,随炉冷却至室温后取出。
制备试样的微观形貌如图2,与之偶接后的304不锈钢的开路电位如图4(b)所示。
实施例三
本发明的一种TiO2/BaTiO3/RGO三元复合光电薄膜的快速原位制备方法,包括如下步骤:
1)钛基表面TiO2纳米管的制备
将钛箔依次用丙酮、乙醇和去离子水超声清洗、化学抛光,然后以铂片为阴极,钛箔为阳极,在25V电压下阳极氧化1h,两电极之间距离2cm,温度为室温,电解液为0.5 wt%NH4F和40 wt% H2O的甘油溶液,阳极氧化后钛基表面TiO2纳米管的平均直径为160 nm;
2)前驱体混合溶液的制备
将0.2520 g Ba(OH)2·8H2O溶解于20 mL去CO2的离子水中,电磁搅拌30 min,形成Ba(OH)2的澄清溶液,称为A液;将0.0320 g氧化石墨烯GO溶解于20 mL去离子水中,超声45min,电磁搅拌25 min,制得GO的水溶液,称为B液;将A液用滴管缓慢滴加到B液中,继续电磁搅拌5 min,形成前驱体混合溶液,称为C液;
3)TiO2/BaTiO3/RGO三元复合光电薄膜的制备
将步骤1)制备的TiO2纳米管试样与步骤2)制备的C液转移到100 mL聚四氟乙烯反应容器中,保持填充率为40%,设定微波水热反应仪的升温速率为10℃/min,反应温度为150℃,保温时间为5 min,进行微波水热合成反应;
4)待反应完成,进一步地,步骤4)中,待反应完成,冷却到室温后取出试样,并将试样依次用盐酸和去离子水冲洗,干燥,最后在400℃马弗炉中保温2.5 h,随炉冷却至室温后取出。
制备试样的微观形貌如图3。
上述本发明所述的高性能TiO2/BaTiO3/RGO三元复合光电薄膜不仅可以抑制金属的腐蚀,具有优良的光电转换效应,作为光阳极对304不锈钢能起到良好的光生阴极保护效应。而且高性能TiO2/BaTiO3/RGO三元复合光电薄膜本身的稳定性良好,暗态下也能维持良好的光生阴极保护效应。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (4)
1.一种TiO2/BaTiO3/RGO三元复合光电薄膜的快速原位制备方法,其特征在于,
该TiO2/BaTiO3/RGO三元复合光电薄膜,包括如下组分:TiO2、BaTiO3和RGO,其中,BaTiO3在TiO2表面通过原位反应生成TiO2/BaTiO3有序纳米管阵列,RGO则分布在TiO2/BaTiO3有序纳米管阵列的表面及管内;
TiO2/BaTiO3/RGO三元复合光电薄膜以钛箔经阳极氧化得到的TiO2有序纳米管阵列模板,以水热法为基础,采用微波为能量源,TiO2有序纳米管阵列模板在Ba(OH)2和GO的前驱体混合溶液中反应,使部分TiO2有序纳米管阵列模板原位反应生成BaTiO3的同时,将分散性好的RO原位还原,一步制备出的TiO2/BaTiO3/RGO三元复合光电薄膜;
具体包括如下步骤:
1)钛基表面TiO2纳米管的制备:将钛箔超声清洗、化学抛光,然后以铂片为阴极,钛箔为阳极,在NH4F和H2O的甘油溶液中阳极氧化,阳极氧化后钛基表面TiO2纳米管的直径为100nm-160 nm;
2)前驱体混合溶液的制备:在搅拌条件下,将Ba(OH)2溶解于水中,形成Ba(OH)2的澄清溶液,称为A液;将氧化石墨烯GO溶解于水中,分散均匀后制得GO的水溶液,称为B液;在搅拌条件下,将A液缓慢滴加到B液中,形成前驱体混合溶液,称为C液,其中C液中Ba2+含量在0.005 mol/L–0.02 mol/L,GO含量在0.25 g/L-0.80 g/L;
3)TiO2/BaTiO3/RGO三元复合光电薄膜的制备:将步骤1)制备的TiO2纳米管试样与步骤2)制备的C液转移到聚四氟乙烯反应容器中,保持填充率为40%,设定微波水热反应仪的升温速率为5-20℃/min,反应温度为120-150℃,保温时间为5-30min,进行微波水热合成反应;
4)待反应完成,再经煅烧处理、随炉冷却至室温后,即得TiO2/BaTiO3/RGO三元复合光电薄膜。
2.根据权利要求1所述的TiO2/BaTiO3/RGO三元复合光电薄膜的快速原位制备方法,其特征在于,步骤1)中,将钛箔依次用丙酮、乙醇和去离子水超声清洗、化学抛光。
3.根据权利要求1或2所述的TiO2/BaTiO3/RGO三元复合光电薄膜的快速原位制备方法,其特征在于,步骤2)中,将Ba(OH)2溶解于去CO2的离子水中,电磁搅拌20-30 min,得到Ba(OH)2的澄清溶液,称为A液;将氧化石墨烯GO溶解于去离子水中,超声40-60 min,电磁搅拌20-30 min,制得GO的水溶液,称为B液;将A液缓慢滴加到B液中,继续电磁搅拌5-10 min,形成前驱体混合溶液,称为C液,其中C液中Ba2+含量在0.005 mol/L–0.02 mol/L,GO含量在0.25 g/L-0.80 g/L。
4.根据权利要求1或2所述的TiO2/BaTiO3/RGO三元复合光电薄膜的快速原位制备方法,其特征在于,步骤4)中,待反应完成,冷却到室温后取出试样,并将试样依次用盐酸和去离子水冲洗,干燥,最后在350-400℃马弗炉中保温1-2.5 h,随炉冷却至室温后取出。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101475161A (zh) * | 2009-01-13 | 2009-07-08 | 东华大学 | 一种钛酸钡(BaTiO3)/多壁碳纳米管(MWCNTs)纳米复合材料的制备方法 |
CN102122579A (zh) * | 2010-12-08 | 2011-07-13 | 天津理工大学 | 一种碳纳米管阵列光阴极材料及其制备方法和应用 |
CN103361689A (zh) * | 2013-05-28 | 2013-10-23 | 青岛农业大学 | 二氧化钛纳米管阵列光电极的制备方法 |
CN103936065A (zh) * | 2014-03-27 | 2014-07-23 | 南京邮电大学 | 二氧化钛与石墨烯复合纳米材料的制备方法 |
CN104577139A (zh) * | 2015-01-21 | 2015-04-29 | 苏州大学 | 光响应的二氧化钛纳米管负载催化剂电极及其制备方法 |
CN104962232A (zh) * | 2015-06-24 | 2015-10-07 | 南京理工大学 | 一种Fe3O4@BaTiO3/RGO三元复合吸波材料及其制备方法 |
-
2016
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101475161A (zh) * | 2009-01-13 | 2009-07-08 | 东华大学 | 一种钛酸钡(BaTiO3)/多壁碳纳米管(MWCNTs)纳米复合材料的制备方法 |
CN102122579A (zh) * | 2010-12-08 | 2011-07-13 | 天津理工大学 | 一种碳纳米管阵列光阴极材料及其制备方法和应用 |
CN103361689A (zh) * | 2013-05-28 | 2013-10-23 | 青岛农业大学 | 二氧化钛纳米管阵列光电极的制备方法 |
CN103936065A (zh) * | 2014-03-27 | 2014-07-23 | 南京邮电大学 | 二氧化钛与石墨烯复合纳米材料的制备方法 |
CN104577139A (zh) * | 2015-01-21 | 2015-04-29 | 苏州大学 | 光响应的二氧化钛纳米管负载催化剂电极及其制备方法 |
CN104962232A (zh) * | 2015-06-24 | 2015-10-07 | 南京理工大学 | 一种Fe3O4@BaTiO3/RGO三元复合吸波材料及其制备方法 |
Non-Patent Citations (1)
Title |
---|
2016年全国腐蚀电化学及测试方法学术交流会;母事理等;《异质结构BaTiO3/ TiO2纳米管复合薄膜的原位制备及其对不锈钢的光生阴极保护性能研究》;20160713;第1-2段及附图1 * |
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