CN109529807A - 增强光催化降解反应的压电-光催化剂及其制法和应用 - Google Patents
增强光催化降解反应的压电-光催化剂及其制法和应用 Download PDFInfo
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Abstract
本发明涉及一种增强光催化降解反应的压电‑光催化剂及其制备方法和应用，该材料通过制备压电材料锆钛酸铅粉末，制备氧化钛纳米包裹颗粒前驱体：光催化剂氧化钛纳米颗粒包裹锆钛酸铅压电粉末三个步骤制得；应用在紫外光光功率密度为1‑20mW·cm‑2、磁力搅拌的转速为200‑1200rpm的罗丹明B染料、双酚A、对氯苯酚和苯酚液相催化降解反应体系。与现有技术相比，本发明仅仅需要通过流体机械能诱导适当的压电场，不需要引入其他元素掺杂或者异质结结构，提升光催化反应效果明显。且核壳结构的复合型催化剂机械性能、化学性质稳定，在环境治理的同时对环境无副作用。
Description
技术领域
本发明涉及催化剂领域，具体涉及一种利用压电材料捕获的流体机械能诱导压电场增强光催化降解性能的压电-光催化剂及其制备方法和应用。
背景技术
半导体光催化是一种很有前景的解决环境污染和能源短缺的技术。然而该技术的发展和实际应用严重受限于光生电子-空穴的严重复合所致的催化效率和光量子效率低下等问题。传统的提升光催化反应的方法有提升半导体的结晶度、比表面积或暴露晶面、电子结构以及光电催化复合、半导体异质结复合。实验数据表明，通过高频超声波诱导压电晶体产生压电场可以有效促进广生电子-空穴的分离、提升光催化反应表现。然而额外的超声波引入很大程度上限制了工业范围上的潜在应用。因此，设计一种能够主动捕获诸如流体机械能等离散能量来形成压电场的复合型催化剂具有明显的实用意义。
201810681760.1公开了一种光催化系统，包括依次设置：非易失性极化场层、导电层与光催化剂层；所述非易失性极化场层由铁电材料在外加电场极化作用后得到；所述铁电材料选自铌镁酸铅系铁电材料、钛酸铋或锆钛酸铅；所述导电层选自Au、Ag、Cu与In中的一种或多种，贵金属加大催化剂成本且金属易造成二次污染；所述光催化剂层选自CdS和/或TiO2，而CdS不稳定易发生光腐蚀。
201711166206.1公开了一种掺杂改性锆钛酸铅压电陶瓷及其制备方法，将Pb3O4、TiO2、ZrO2、Nb2O5、Mg(OH)2·4MgCO3·6H2O、Ni(CH3COO)2·4H2O、ZnO、SrCO3和Q的混合物进行预烧，以得到预烧粉料，加入造粒剂进行造粒，并制备成设定形状的粗坯，将所述粗坯进行排胶处理，将排胶处理后的所述粗坯进行烧结，以得到陶瓷元件；极化：将陶瓷元件进行极化，以得到掺杂改性锆钛酸铅压电陶瓷。所述方法较为繁杂，且需在高温下长时间煅烧，既耗能又耗时。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种增强光催化降解反应的压电-光催化剂，该催化剂利用压电材料捕获的流体机械能诱导压电场来增强光催化降解性能。
本发明的目的可以通过以下技术方案来实现：
一种增强光催化降解反应的压电-光催化剂，该催化剂为压电材料表面包裹光催化材料组成，其中压电材料为锆钛酸铅压电粉末，所述的光催化材料为光催化剂氧化钛纳米颗粒，所述的压电材料与光催化材料的质量比为1:(2.34-9.35)：
进一步地，所述的锆钛酸铅压电粉末中铅元素、锆元素、钛元素摩尔比为100:(90-98):(2-5)。
一种增强光催化降解反应的压电-光催化剂的制备方法，包括以下步骤：
(1)制备压电材料锆钛酸铅粉末：将氧化锆、氧化钛、氧化铅混合粉末球磨后，进行煅烧和粉碎，即可得到具有球形结构的锆钛酸铅粉末；
(2)制备氧化钛纳米包裹颗粒前驱体：将所述的锆钛酸铅粉末超声分散在无水乙醇中，然后加入浓氨水，最后逐滴加入钛酸四丁酯，即得到前驱体溶液；
(3)制备压电-光催化剂；将所述的前驱体溶液转移至水热釜中，在磁力搅拌的情况下加热后，经过多次洗涤、烘干，最后在马弗炉中煅烧后进行研磨，即可得到压电-光催化剂。
进一步地，步骤(1)中所述的球磨的时间为4-12h，所述的煅烧分别在800℃和1200℃进行1-5h。
进一步地，步骤(2)中每120ml的无水乙醇中所述的锆钛酸铅粉末加入量为0.2-0.4g，浓氨水加入量为1-2mL，钛酸四丁酯滴加量为1.0-2.0mL，所述超声的时间为10-20min
进一步地，步骤(3)中所述的磁力搅拌温度为100-120℃，加热时间为18-36h，煅烧温度为480-520℃，时间为1-3h。
一种增强光催化降解反应的压电-光催化剂的应用，所述的压电-光催化剂应用在罗丹明B染料、双酚A、对氯苯酚和苯酚的降解中。
进一步地，将所述的压电-光催化剂加入所述降解过程的液相反应体系中，进行搅拌反应降解，所述压电-光催化剂在液相反应体系的紫外光光功率密度为1-20mW·cm-2、搅拌速率为200-1200rpm。利用带有数显装置的磁力搅拌器施加于溶液体系不同的搅拌速率，以此使得溶液机械能在复合型催化剂表面施加不能程度的压应力，以此诱导不同强度的压电场。
与现有技术相比，本发明具有以下优点：
(1)利用非中心对称结构的晶体具有压电性，其所产生压电势或者压电场能够自发的调制载流子的传输行为。将压电晶体受应力所诱导的压电场引入到光催化反应中，可以通过促进光生电子空穴对的分离效率及载流子的迁移，提升光催化反应效率。通过捕获使用压电材料捕获流体机械能或者反应体系内离散的水流能量，所诱导的压电场可以使得光催化速率得以可控的提升，因此不需要引入其他元素掺杂或者异质结结构，提升光催化反应效果明显。
(2)核壳结构的复合型催化剂机械性能、化学性质稳定，在环境治理的同时对环境无副作用。通过磁力搅拌转速的提升，光催化降解染料和苯系有机物速率和矿化程度得以明显的提升。这种利用流体机械能诱导压电场增强光催化降解性能的方法在光催化环境治理方面有着潜在的应用价值。
附图说明
图1为所制得的压电-光催化剂样品的TEM图；
图2为压电-光催化剂与直接物理混合性催化剂降解罗丹明B活性对比；
图3为不同转速下压电-光催化剂光催化降解罗丹明B的活性示意图；
图4为不同转速下压电-光催化剂光催化降解对氯苯酚的活性示意图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
一种增强光催化降解反应的压电-光催化剂的制备方法，包括以下步骤：
(1)制备压电材料锆钛酸铅粉末：将氧化锆、氧化钛、氧化铅混合粉末按照铅元素、锆元素、钛元素摩尔比为100:95:5球磨混合6h，分别800℃、1200℃煅烧2h。经过粉碎后即可得到具有球形结构的锆钛酸铅粉末，即可得到具有球形结构的锆钛酸铅粉末；
(2)将0.4g锆钛酸铅粉末分散在120mL无水乙醇中，在超声浴中分散15min，然后加入2mL浓氨水，后逐滴加入2.0mL钛酸四丁酯，将以上混合液体转移至200mL不锈钢密封的水热釜中，放置于110℃的油浴中在磁力搅拌的情况下加热24h。经过多次洗涤、烘干后，在500℃的马弗炉中煅烧2h后研磨成粉，制得压电-光催化剂。
如图1，所得到压电-光催化剂的TEM图，可以从不同的衬度对比中看出氧化钛纳米颗粒成功包裹在锆钛酸铅压电颗粒表面。
如图2，将本实施例得到的压电-光催化剂制备成2g/L的分散液与现有的直接的物理混合性催化剂在1.2mW·cm-2的紫外光辐照下光催化降解10mg/L罗丹明B染料的活性示意图，表明该催化剂更有利于光催化反应。
实施例2
将实施例1得到的压电-光催化剂分散在10mg/L罗丹明B染料溶液中，使其质量分数为2g/L。
如图3，给出了在15mW·cm-2的紫外光辐照下，200、400、600和800rpm的搅拌速率下光催化降解罗丹明B的测试结果，表明更高搅拌速率诱导的更强的压电场更能促进光催化反应。
实施例3
重复实施例2的操作步骤，不同之处在于检测目标为溶液中的总有机碳含量，结果和实施例1类似，总有机碳含量随着搅拌强度增大得以明显的降低。
实施例4
重复实施例2的操作步骤，不同之处在于该实例为循环套用测试，且搅拌转速固定为800rpm，循环测试8次。实验数据表明，光催化降解罗丹明B的效率不随着循环次数增多而降低。
实施例5
重复实施例2的操作步骤，不同之处在于光催化降解对象为10ppm双酚A，结果和实施例1类似，溶液中双酚A的残余浓度在相同时间内随着搅拌速度从200rpm到800rpm的提升，浓度降低速率明显增大。
实施例6
重复实施例5的操作步骤，不同之处在于检测目标为双酚A溶液中的总有机碳含量，结果和实施例3类似，溶液中总有机碳含量随着搅拌强度增大得以明显的降低。
实施例7
重复实施例2的操作步骤，不同之处在于光催化降解对象为60ppm对氯苯酚。
如图4，和实施例2类似，溶液中对氯苯酚的浓度减小速率随着搅拌强度增大而明显增加。
实施例8
重复实施例2的操作步骤，不同之处在于光催化降解对象为10ppm苯酚，结果和实施例2类似，光催化降解苯酚的速率随着搅拌强度增大得以明显的提升。
实施例9
(1)制备压电材料锆钛酸铅粉末：将氧化锆、氧化钛、氧化铅混合粉末按照铅元素、锆元素、钛元素摩尔比为100:90:2。球磨混合4h，分别800℃、1200℃煅烧2h。经过粉碎后即可得到具有球形结构的锆钛酸铅粉末，即可得到具有球形结构的锆钛酸铅粉末；
(2)将0.2g锆钛酸铅粉末分散在120mL无水乙醇中，在超声浴中分散10min，然后加入1mL浓氨水，后逐滴加入1.0mL钛酸四丁酯，将以上混合液体转移至200mL不锈钢密封的水热釜中，放置于100℃的油浴中在磁力搅拌的情况下加热18h。经过多次洗涤、烘干后，在480℃的马弗炉中煅烧1h后研磨成粉，制得压电-光催化剂。
实施例10
(1)制备压电材料锆钛酸铅粉末：将氧化锆、氧化钛、氧化铅混合粉末按照铅元素、锆元素、钛元素摩尔比为100:98:5。球磨混合12h，分别800℃、1200℃煅烧2h。经过粉碎后即可得到具有球形结构的锆钛酸铅粉末，即可得到具有球形结构的锆钛酸铅粉末；
(2)将0.4g锆钛酸铅粉末分散在120mL无水乙醇中，在超声浴中分散20min，然后加入2mL浓氨水，后逐滴加入2.0mL钛酸四丁酯，将以上混合液体转移至200mL不锈钢密封的水热釜中，放置于120℃的油浴中在磁力搅拌的情况下加热36h。经过多次洗涤、烘干后，在520℃的马弗炉中煅烧3h后研磨成粉，制得压电-光催化剂。
上述各实施例所得催化剂性能如下表所示：
Claims (8)
1.一种增强光催化降解反应的压电-光催化剂，其特征在于，该催化剂为压电材料表面包裹光催化材料组成，其中压电材料为锆钛酸铅压电粉末，所述的光催化材料为光催化剂氧化钛纳米颗粒，所述的压电材料与光催化材料的质量比为1:(2.33-9.36)。
2.根据权利要求1所述的一种增强光催化降解反应的压电-光催化剂，其特征在于，所述的锆钛酸铅压电粉末中铅元素、锆元素、钛元素摩尔比为100:(90-98):(2-5)。
3.一种如权利要求1-2所述增强光催化降解反应的压电-光催化剂的制备方法，其特征在于，包括以下步骤：
(1)制备压电材料锆钛酸铅粉末：将氧化锆、氧化钛、氧化铅混合粉末球磨后，进行煅烧和粉碎，即可得到具有球形结构的锆钛酸铅粉末；
(2)制备氧化钛纳米包裹颗粒前驱体：将所述的锆钛酸铅粉末超声分散在无水乙醇中，然后加入浓氨水，最后逐滴加入钛酸四丁酯，即得到前驱体溶液；
(3)制备压电-光催化剂；将所述的前驱体溶液转移至水热釜中，在磁力搅拌的情况下加热后，经过多次洗涤、烘干，最后在马弗炉中煅烧后进行研磨，即可得到压电-光催化剂。
4.根据权利要求1-2所述的一种增强光催化降解反应的压电-光催化剂的制备方法，其特征在于，步骤(1)中所述的球磨的时间为4-12h，所述的煅烧分别在800℃和1200℃进行1-5h。
5.根据权利要求1-2所述的一种增强光催化降解反应的压电-光催化剂的制备方法，其特征在于，步骤(2)中每120ml的无水乙醇中所述的锆钛酸铅粉末加入量为0.2-0.4g，浓氨水加入量为1-2mL，钛酸四丁酯滴加量为1.0-2.0mL，所述超声的时间为10-20min。
6.根据权利要求1-2所述的一种增强光催化降解反应的压电-光催化剂的制备方法，其特征在于，步骤(3)中所述的磁力搅拌温度为100-120℃，加热时间为18-36h，煅烧温度为480-520℃，时间为1-3h。
7.一种如权利要求1-2任一项所述的增强光催化降解反应的压电-光催化剂的应用，其特征在于，所述的压电-光催化剂应用在罗丹明B染料、双酚A、对氯苯酚和苯酚的降解中。
8.根据权利要求7所述增强光催化降解反应的压电-光催化剂的应用，其特征在于，将所述的压电-光催化剂加入所述降解过程的液相反应体系中，进行搅拌反应降解，所述压电-光催化剂在液相反应体系的紫外光光功率密度为1-20mW·cm-2、搅拌速率为200-1200rpm。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112371177A (zh) * | 2020-11-13 | 2021-02-19 | 南京晓庄学院 | 一种掺杂压电催化材料的柔性多孔复合材料及其制备 |
| CN113385169A (zh) * | 2021-06-21 | 2021-09-14 | 大连理工大学 | 一种高效降解有机污染物的新型压电光催化剂、制备方法及应用 |
| CN113546615A (zh) * | 2021-07-29 | 2021-10-26 | 常州大学 | Bi2WO6/Black-TiO2复合催化剂及其制备方法和应用 |
| CN115121257A (zh) * | 2022-07-06 | 2022-09-30 | 苏州大学 | 一种铜掺杂氧化锌纳米棒、制备方法及其在压电-光催化去除有机污染物中的应用 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887562A (zh) * | 2012-11-01 | 2013-01-23 | 浙江师范大学 | 一种采用纳米压电材料超声降解染料废水的方法 |
| CN108772063A (zh) * | 2018-07-05 | 2018-11-09 | 天津城建大学 | 一种Ag2O/Bi4Ti3O12压电光催化剂及其合成方法、光催化降解率检测方法 |
| CN108906027A (zh) * | 2018-06-04 | 2018-11-30 | 上海师范大学 | 一种钛酸铅光催化剂用于增强光催化反应的方法 |
-
2018
- 2018-12-23 CN CN201811576864.2A patent/CN109529807A/zh active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887562A (zh) * | 2012-11-01 | 2013-01-23 | 浙江师范大学 | 一种采用纳米压电材料超声降解染料废水的方法 |
| CN108906027A (zh) * | 2018-06-04 | 2018-11-30 | 上海师范大学 | 一种钛酸铅光催化剂用于增强光催化反应的方法 |
| CN108772063A (zh) * | 2018-07-05 | 2018-11-09 | 天津城建大学 | 一种Ag2O/Bi4Ti3O12压电光催化剂及其合成方法、光催化降解率检测方法 |
Non-Patent Citations (2)
| Title |
|---|
| 冯亚伟: ""极化电场调制催化及增强光催化反应的研究和应用"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 姚曼: ""TiO2/BaTiO3复合光催化剂的制备及其光催化性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112371177A (zh) * | 2020-11-13 | 2021-02-19 | 南京晓庄学院 | 一种掺杂压电催化材料的柔性多孔复合材料及其制备 |
| CN112371177B (zh) * | 2020-11-13 | 2023-03-21 | 南京晓庄学院 | 一种掺杂压电催化材料的柔性多孔复合材料及其制备 |
| CN113385169A (zh) * | 2021-06-21 | 2021-09-14 | 大连理工大学 | 一种高效降解有机污染物的新型压电光催化剂、制备方法及应用 |
| CN113546615A (zh) * | 2021-07-29 | 2021-10-26 | 常州大学 | Bi2WO6/Black-TiO2复合催化剂及其制备方法和应用 |
| CN115121257A (zh) * | 2022-07-06 | 2022-09-30 | 苏州大学 | 一种铜掺杂氧化锌纳米棒、制备方法及其在压电-光催化去除有机污染物中的应用 |
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