CN112973686A - 一种热释电效应增强异质结构复合材料光催化性能的方法及应用 - Google Patents
一种热释电效应增强异质结构复合材料光催化性能的方法及应用 Download PDFInfo
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Abstract
本发明公开的一种热释电效应增强异质结构复合材料光催化性能的方法及应用。以Ba(CH3COO)2、Sr(CH3COO)2和钛酸四丁酯为原料，按照Ba1‑xSrxTiO3(0≤x≤1)的化学计量比，经过水解、缩聚过程形成稳定的溶胶再逐渐转变为湿凝胶，并通过静电纺丝和煅烧法将其制备成中空的Ba1‑xSrxTiO3纳米管，并通过离子吸附法将银纳米粒子和氧化银颗粒附着在Ba1‑xSrxTiO3纳米管上，经过离心、干燥、热处理后得到S型或Z型异质结构复合材料Ba1‑xSrxTiO3/Ag/Ag2O。该制备方法工艺和流程简单，参数可调范围宽，可重复性强，是一种具有商业前景的制备方法。利用Ba1‑ xSrxTiO3产生的热释电效应增强所制备的异质结构复合材料的光催化效率，并在光催化杀菌、降解多糖、有机污染物降解和重金属离子还原等领域有重要的应用价值。
Description
技术领域
本发明属于光催化领域，是一种借助于太阳能来达到催化氧化和还原，利用热释电效应达到增强光催化的效果。
背景技术
光催化作为一种低能耗、高效、无二次污染的技术,因其反应条件温和、能直接利用太阳能转化为化学能的优势而备受关注，已被广泛应用于降解污染物、分解水制氢和二氧化碳还原等领域。但是传统的催化剂目前存在着三点问题:(1)电子/空穴复合速度快，导致材料性能下降；(2)可见光吸附量低，从技术利用和资源上制约了其应用；(3)光催化剂表面覆盖度低，导致有机污染物降解速率低。
目前，通过掺杂离子(包括阳离子或阴离子)或与其他半导体光催化剂偶联来扩大光谱可见区域的光吸收，可以提高光催化性能。利用太阳能进行实际应用，增强其光催化活性的研究很多,如CuO/Ag2O、Ag2O/ZnO、Ag2O/Ag2S等。但是由于单一的只依赖于太阳能的作用，并且只能对太阳光中的紫外和可见部分响应，在催化效率方面仍存在着明显的不足。
发明内容
本发明目的是提供一种热释电效应增强光催化性能的方法，将该方法用于增强异质结构复合材料的光催化性能，并进行光催化氧化与还原等应用。
本发明利用Ba1-xSrxTiO3热释电效应增强异质结构复合材料的光催化性能，异质结构复合材料为：Ba1-xSrxTiO3/Ag/Ag2O(0≤x≤1)。
本发明完整的技术方案为：一种热释电效应增强异质结构复合材料光催化性能的方法，其步骤如下：
a.按照Ba1-xSrxTiO3(0≤x≤1)的化学计量比，将乙酸钡和乙酸锶溶于溶剂中，得到溶液A；再将钛酸四丁酯加入溶液A中，得到溶液B，经过水解、缩合反应得到Ba1-xSrxTiO3湿凝胶；再经煅烧得到Ba1-xSrxTiO3干凝胶；
b.将上述a得到的Ba1-xSrxTiO3干凝胶研磨成粉体，加入溶剂配置前驱体溶液，通过静电纺丝法纺成Ba1-xSrxTiO3纳米纤维，再放入马弗炉中煅烧，得到Ba1-xSrxTiO3纳米管；
c.将上述b得到的Ba1-xSrxTiO3纳米管称取1mmol，放入一定量浓度的AgNO3溶液中，用0.2mol/L的氢氧化钠溶液调节pH值，将Ag2O附着到Ba1-xSrxTiO3纳米管，得到Ba1-xSrxTiO3/Ag2O复合异质结构；
d.将上述c得到的Ba1-xSrxTiO3/Ag2O悬浊液置于紫外灯下照射一段时间，得到Ba1- xSrxTiO3/Ag/Ag2O悬浊液，去除上清液，将沉淀用去离子水和酒精分别洗涤3次，最后离心，在60℃烘箱中干燥24小时，得到Ba1-xSrxTiO3/Ag/Ag2O异质结构复合材料催化剂。
步骤a中所述的溶剂为去离子水，加入的体积为10mL-30mL。
步骤a中马弗炉煅烧的温度为300℃-800℃。
步骤b中的通过静电纺丝法配置前驱体溶液时所用到的溶剂包括聚乙烯吡咯烷酮(PVP)和二甲基酰胺(DMF)。
步骤b中的煅烧温度为500℃-800℃。
步骤c中AgNO3的浓度为0.1mol/L-1mol/L
步骤c中的调节的pH值范围为11-13.
步骤d中紫外灯照射的时间为10min-60min，照射距离为5cm-10cm。
步骤d中的Ba1-xSrxTiO3/Ag/Ag2O异质结构复合材料催化剂，其中Ba1-xSrxTiO3具有热释电效应，能够增强光催化性能。
步骤d中的Ba1-xSrxTiO3/Ag/Ag2O构成S型或Z型异质结构。
本发明与现有技术相比，具有以下优异特点：
(1)利用热释电效应的优势，来增强异质结构复合材料的光催化性能，实现了了良好的光催化性能增强。
(2)异质复合结构催化剂比表面积大大提高，由Ba1-xSrxTiO3制成的中空纳米管搭载Ag2O纳米颗粒使得对污染物等有着高效的接触。
(3)构建了新型的S型或Z型Ba1-xSrxTiO3异质复合结构，大大减少了电子空穴对的复合，拓宽光谱响应范围至近红外光区，提高了光催化效率。
(4)工艺和流程简单，反应时间短，参数可调，范围宽，可重复性强，便于实现工业化生产。
(5)与传统的光催化剂相比，其引入热释电效应来增强内部电子的转移，大大提高了单一依靠太阳能实现光催化的效率。在20min内对活性艳红的催化效率达到了100％。
附图说明
图1本发明实施例1制备的异质结构复合材料催化剂的SEM图像。
图2本发明实施例1制备的异质结构复合材料催化剂的TEM图像。
图3本发明实施例1制备的异质结构复合材料催化剂的XPS图谱。
图4本发明实施例2制备的异质结构复合材料热释电催化降解效率图。
图5本发明实施例2制备的异质结构复合材料光催化降解效率图。
图6本发明实施例2制备的异质结构复合材料热释电光催化协同催化降解效率图。
图7本发明实施例1制备的异质结构复合材料催化剂的比表面积(BSA)图。
具体实施方式
本发明利用Ba(CH3COO)2、Sr(CH3COO)2和钛酸四丁酯为原料，按照Ba1-xSrxTiO3(0≤x≤1)的化学计量比，经过水解、缩聚过程形成稳定的溶胶再逐渐转变为湿凝胶，并通过静电纺丝和煅烧法将其制备成中空的纳米管，并通过离子吸附法将银纳米粒子和氧化银颗粒附着在纳米管上，经过离心、干燥、热处理后得到形成异质结构材料Ba1-xSrxTiO3/Ag/Ag2O。利用Ba1-xSrxTiO3产生的热释电效应来增强异质结构复合材料的光催化性能，并应用于光催化杀菌、降解多糖等。
具体工艺流程：
(1)采用溶胶-凝胶法制备Ba0.6Sr0.4TiO3前驱体溶液，将Ba(CH3COO)2、Sr(CH3COO)2和钛酸四丁酯分别溶解后，经过水解，缩聚等过程形成稳定的溶胶，再逐渐转变为湿凝胶，然后采用静电纺丝法制成Ba0.6Sr0.4TiO3纳米纤维，制成后将其在800°的马弗炉中煅烧3h，得到Ba0.6Sr0.4TiO3中空纳米管。
(2)称取1mmol的Ba0.6Sr0.4TiO3纳米管，加入10ml的去离子水并充分搅拌，分别称取0.1mol/L、0.2mol/L、0.3mol/L的硝酸银溶液。搅拌至其充分溶解，将其分别滴入含有1mmol的Ba0.6Sr0.4TiO3的烧杯中，用0.2mol/L的氢氧化钠溶液调节pH值到12.64，在磁力搅拌器上搅拌60分钟，在将其移到紫外光下照射20min后，去除上清液，将沉淀用去离子水和酒精分别洗涤3次，最后在60℃烘箱中干燥24小时，分别得到Ba0.6Sr0.4TiO3:Ag2O为1:0.5、1:1、1:2的复合材料，将其命名为BST/Ag/Ag2O-0.5、BST/Ag/Ag2O-1、BST/Ag/Ag2O-1.5。
实施例1：
(1)将1.53g的Ba(CH3COO)2和0.584g的Sr(CH3COO)2和5ml的钛酸四丁酯溶解在20ml的去离子水中，经过水解、缩合生成湿凝胶。然后采用静电纺丝法制成Ba0.6Sr0.4TiO3纳米纤维，制成后将其在800°的马弗炉中煅烧3h，得到Ba0.6Sr0.4TiO3中空纳米管。
(2)取1mmol的Ba0.6Sr0.4TiO3纳米管置于0.2mol/L的硝酸银溶液中均匀搅拌20分钟，随后用0.2mol/L的NaOH溶液调节pH值至12.64，得到Ba0.6Sr0.4TiO3/Ag2O复合材料，随后将其移至紫外灯下照射20分钟得到Ba0.6Sr0.4TiO3/Ag/Ag2O催化剂。将此催化剂用于灭杀大肠杆菌，细胞内的辅酶A被氧化成二聚体辅酶A，使细胞呼吸衰退导致死亡。
如图1和2所示，根据异质结构复合材料催化剂SEM图像以及TEM图像，表明在Ba0.6Sr0.4TiO3纳米管上成功地附着了Ag纳米粒子和Ag2O颗粒。图3显示了用XPS测试的Ba0.6Sr0.4TiO3/Ag/Ag2O复合材料中的化学元素和化学环境。图3(a)中给出的完整XPS光谱清楚地显示了样品中Ba、Sr、Ti、Ag和O元素的存在。在图3(e)中，Ag-3d的峰值包括Ag0和Ag+，说明Ag表现出Ag+氧化态和元素银。如图7所示，上述实施方式制得的异质复合结构催化剂比表面积大大提高。
实施列2：
(1)将1.53g的Ba(CH3COO)2和0.584g的Sr(CH3COO)2和5ml的钛酸四丁酯溶解在20ml的去离子水中，经过水解、缩合生成湿凝胶，然后采用静电纺丝法制成Ba0.6Sr0.4TiO3纳米纤维，制成后将其在800°的马弗炉中煅烧3h，得到Ba0.6Sr0.4TiO3中空纳米管。
(2)取1mmol的Ba0.6Sr0.4TiO3纳米管置于0.3mol/L的硝酸银溶液中均匀搅拌20分钟，随后用0.2mol/L的NaOH溶液调节pH值至12.64，得到Ba0.6Sr0.4TiO3/Ag2O，随后将其移至紫外灯下照射20分钟得到Ba0.6Sr0.4TiO3/Ag/Ag2O催化剂。
将得到的异质结构复合材料催化剂用于降解有机污染物活性艳红-xb(Rbr-xb)。光催化降解由三个实验来完成。第一个实验为热释电催化，如图4所示，在无光照的情况下，将0.05g催化剂加入100mL 5mg/L的Rbr-xb溶液中，充分搅拌1h使其达到吸附平衡，通过加热水浴的磁力搅拌器使冷热循环水在25℃-60℃之间变化。每隔5个循环取出3ml的Rbr-xb溶液，离心之后抽取上清液在可见分光光度计下测其在510nm处的吸光度。第二个实验为光催化，如图5所示，不通入冷热循环水，只在可见光照射下，其余条件保持不变，每间隔10分钟取出3mL溶液离心处理，然后测其510nm处的吸光度。最后为热释电光催化协同催化实验，如图6所示，在光照和冷热循环水也同时加入的情况下，和上述相同的时间取出3mL溶液，进行测量其在510nm处的吸光度。根据公式η＝(C0-Ct)/C0×100％，可计算出Rbr-xb降解速率，其中C0为初始浓度，Ct为取出样的浓度。
通过三组实验对比得出，在只通过冷却循环水即仅有热释电催化时，经过42个冷热循环后Rbr-xb的降解效率为77％，当仅在可见光照射下，其在50分钟其催化效率为92％，而当热释电光催化协同催化时，即经30min的光照，并在此时间内通过25次冷却循环水，其对Rbr-xb的降解率达到了100％。
以上所述，仅是本发明的较佳实施例，并非对本发明作任何限制，凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效结构变化，均仍属于本发明技术方案的保护范围内。
Claims (10)
1.一种热释电效应增强异质结构复合材料光催化性能的方法，其特征在于，所述异质结构复合材料为Ba1-xSrxTiO3/Ag/Ag2O(0≤x≤1)，其制备步骤如下：
a.按照Ba1-xSrxTiO3(0≤x≤1)的化学计量比，将乙酸钡和乙酸锶溶于溶剂中，得到溶液A；再将钛酸四丁酯加入溶液A中，得到溶液B，经过水解、缩合反应得到Ba1-xSrxTiO3湿凝胶；再经煅烧得到Ba1-xSrxTiO3干凝胶；
b.将上述步骤a得到的Ba1-xSrxTiO3干凝胶研磨成粉体，加入溶剂配置前驱体溶液，通过静电纺丝法纺成Ba1-xSrxTiO3纳米纤维，再放入马弗炉中煅烧，得到Ba1-xSrxTiO3纳米管；
c.将上述步骤b得到的Ba1-xSrxTiO3纳米管称取1mmol，放入一定量浓度的AgNO3溶液中，用0.2mol/L的氢氧化钠溶液调节pH值，将Ag2O附着到Ba1-xSrxTiO3纳米管，得到Ba1-xSrxTiO3/Ag2O复合异质结构悬浊液；
d.将上述步骤c得到的Ba1-xSrxTiO3/Ag2O复合异质结构悬浊液置于紫外灯下照射一段时间，得到Ba1-xSrxTiO3/Ag/Ag2O悬浊液，去除上清液，将沉淀用去离子水和酒精分别洗涤3次，最后离心，在60℃烘箱中干燥24小时，得到Ba1-xSrxTiO3/Ag/Ag2O异质结构复合材料催化剂。
2.根据权利要求1所述的一种热释电效应增强异质结构复合材料光催化性能的方法，其特征在于，步骤a中所述的溶剂为去离子水，加入的体积为10mL-30mL。
3.根据权利要求1所述的一种热释电效应增强异质结构复合材料光催化性能的方法，其特征在于，步骤a中马弗炉煅烧的温度为300℃-800℃。
4.根据权利要求1所述的一种热释电效应增强异质结构复合材料光催化性能的方法，其特征在于，步骤b中的通过静电纺丝法配置前驱体溶液时所用到的溶剂包括聚乙烯吡咯烷酮(PVP)和二甲基酰胺(DMF)。
5.根据权利要求1所述的一种热释电效应增强异质结构复合材料光催化性能的方法，其特征在于，步骤b中的煅烧温度为500℃-800℃。
6.根据权利要求1所述的一种热释电效应增强异质结构复合材料光催化性能的方法，其特征在于，步骤c中AgNO3的浓度为0.1mol/L-1mol/L。
7.根据权利要求1所述的一种热释电效应增强异质结构复合材料光催化性能的方法，其特征在于，步骤c中的调节的pH值范围为11-13。
8.根据权利要求1所述的一种热释电效应增强异质结构复合材料光催化性能的方法，其特征在于，步骤d中紫外灯照射的时间为10min-60min，照射距离为5cm-10cm，优选的，步骤d中的Ba1-xSrxTiO3/Ag/Ag2O异质结构复合材料催化剂，其中Ba1-xSrxTiO3具有热释电效应，能够增强光催化性能，优选的，步骤d中的Ba1-xSrxTiO3/Ag/Ag2O构成S型或Z型异质结构。
9.根据权利要求1-8任一项所述的方法所制备的热释电效应增强异质结构复合材料光催化剂。
10.根据权利要求9所述的热释电效应增强异质结构复合材料光催化剂在杀菌、降解多糖、降解有机污染物、还原重金属离子中的应用。
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| CN114573420A (zh) * | 2022-03-21 | 2022-06-03 | 青岛科技大学 | 一种利用热释电场提高Bi2WO6催化剂光催化转化二氧化碳为甲醇的策略 |
| CN114749169A (zh) * | 2022-04-22 | 2022-07-15 | 陕西科技大学 | 一种热电基光催化剂及其制备方法和应用 |
| CN114749169B (zh) * | 2022-04-22 | 2023-12-22 | 陕西科技大学 | 一种热电基光催化剂及其制备方法和应用 |
| CN116273103A (zh) * | 2023-02-17 | 2023-06-23 | 南京信息工程大学 | 一种氧化锌-MXene复合热释电催化剂的制备方法及其应用 |
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