CN105749897A - 一种具有多通道载流子分离功能的异质光催化剂及其制备方法与应用 - Google Patents
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Abstract
本发明公开了一种具有多通道载流子分离功能的异质光催化剂及其制备方法与应用。所述异质光催化剂是由ZnO和混合相二氧化钛P25组成,以催化剂的重量为100%计,ZnO的质量分数为0.1%~10.0%,余量为二氧化钛P25。ZnO作为复合相组分,均匀分散在催化剂中,两相之间充分交织在一起,能有效分离P25受紫外光激发产生的电子?空穴,ZnO/P25异质光催化剂表现出比纯相P25更优异的光催化性能。用于低浓度甲苯有机气体的紫外光催化反应时,可以在室温条件下将体系中甲苯完全氧化为二氧化碳和水。本发明的制备方法简单,制备条件温和,操作方便,便于工业放大生产。
Description
技术领域
本发明涉及光催化材料技术领域,具体地说,涉及一种具有多通道载流子分离功能的异质光催化剂及其制备方法与应用。
背景技术
在消除环境污染物方面,光催化降解反应能耗低,净化效率高,是最有应用前景的技术之一。但目前光催化技术也还存在一些亟待解决的技术问题,比如传统光催化剂如TiO2的光生电子-空穴对快速复合导致光催化剂的量子产率低。因此,以促进光生电子-空穴对分离为目的异质结光催化剂的研发和利用一直是光催化领域内的重点研究对象。
对传统TiO2进行贵金属沉积、石墨稀复合、其它半导体复合,构筑新的异质结,提高光生载流子分离效率,从而提升其光催化活性,是目前常用的设计手段。由于ZnO的低成本、无毒和高光催化活性,在锐钛矿TiO2上负载ZnO引起了广泛关注。Kim等人(Int.J.Hydrogen Energ.,2007,32,3137-3140)通过溶胶-凝胶旋转喷涂法制备ZnO-TiO2纳米多孔膜,报道指出TiO2膜负载ZnO后其光催化活性提高了,但随着ZnO膜厚度的增加,其光电流和光催化苯酚的活性都有所降低。Lei等人(J.Phys.Chem.C,2009,113,19067-19076)通过多步水热法在TiO2纳米管上嫁接ZnO纳米棒,不仅扩大了光响应范围,还有效降低了载流子的复合率,另外由于ZnO提供了有效通道转移TiO2的光生空穴,其光腐蚀性得到了抑制,并且提高了ZnO/TiO2的稳定性。但这些通过多步法将两类相关性不大的材料复合而成,一是制备流程复杂,二是复合材料各组分之间很难充分交织形成利于电子和空穴分离的相界面,三是大多数报道的ZnO/TiO2光催化活性仍比由锐钛矿和金红石相(4/1,W/W)组成的商业P25颗粒的活性低,性能仍需进一步提高以满足其在光催化领域中的应用。
发明内容
针对上述光催化领域所面临的问题,本发明提供了一种具有多通道载流子分离功能和性能稳定的异质光催化剂及其制备方法,并用于光催化降解有机废气。
为了实现上述目的,本发明采用如下技术方案:
一种具有多通道载流子分离功能的异质光催化剂,所述异质光催化剂是由ZnO和混合相二氧化钛P25组成,以催化剂的重量为100%计,ZnO的质量分数为0.1%~10.0%,余量为二氧化钛P25。
上述异质光催化剂的制备方法,包括以下步骤:
(1)配置锌盐水溶液;
(2)将P25粉末分散在溶液中;
(3)干燥、煅烧得到ZnO/P25异质光催化剂。
作为优选的,在上述制备方法中,步骤(1)中所述锌盐为醋酸锌或者硝酸锌中的一种,锌盐在溶液中的质量分数为0.1%~30%
作为优选的,在上述制备方法中,步骤(3)中所述干燥过程,是指在80~120℃的空气氛围内恒温干燥6~24h;所述煅烧过程,是指在煅烧温度为300~900℃的空气气氛中煅烧3~12h。
上述异质光催化剂在光催化降解空气中有机污染物中的应用。指的是其在室温下,作为紫外光催化剂的应用。所述紫外光催化剂对单体小分子有机物都具有一定的催化效能,可用于降解空气中有机污染物物,如甲醛、甲苯等。
与现有技术相比,本发明具有如下有益效果:
本发明的具有多通道载流子分离功能的ZnO/P25异质光催化剂的制备方法为一步浸渍法,ZnO作为复合相组分,均匀分散在催化剂中,两相之间充分交织在一起,能有效分离P25受紫外光激发产生的电子-空穴,ZnO/P25异质光催化剂表现出比纯相P25更优异的光催化性能。此外,由于P25本身具有锐钛矿/金红石异质结,与ZnO复合,形成三相异质结(见图1),提供多通道分离载流子(见图2),促进光催化反应。用于低浓度甲苯有机气体的紫外光催化反应时,可以在室温条件下将体系中甲苯完全氧化为二氧化碳和水。本发明的制备方法简单,制备条件温和,操作方便,便于工业放大生产。
附图说明
图1为实施例1的HRTEM图;
图2为ZnO/P25异质结中多通道分离载流子机理图。
具体实施方式
实施例1:
一种具有多通道载流子分离功能的ZnO/P25异质光催化剂的制备方法:(1)在室温条件下,将醋酸锌溶解于纯水中,配置成重量百分数0.5%浓度的醋酸锌水溶液。(2)将P25粉末倒入并充分分散在此溶液中。(3)将步骤(2)中的溶液在120℃恒温干燥10h,随后500℃煅烧6h得到最终产品。通过TiO2两相最强特征峰强度对两相含量做半定量分析,结果显示,锐钛矿与金红石含量比约为3.83/1。图1为实施例1的HRTEM图;图2为ZnO/P25异质结中多通道分离载流子机理图。
对比例1:
对比一种P25异质光催化剂的制备方法:P25粉末在500℃煅烧6h得到最终产品。锐钛矿与金红石含量比约为3.93/1。
实施例2:
一种具有多通道载流子分离功能的ZnO/P25异质光催化剂的制备方法:(1)在室温条件下,将硝酸锌水合物溶解于纯水中,配置成重量百分数0.1%浓度的硝酸锌水溶液。(2)将P25粉末倒入并充分分散在此溶液中。(3)将步骤(2)中的溶液在120℃恒温干燥10h,随后600℃煅烧6h得到最终产品。锐钛矿与金红石含量比约为3.90/1。
实施例3:
分别取0.2g实施例1-2和对比例所述催化剂,均匀涂膜在7.0cm2的表面皿上,并置于反应釜底部,用混合气(O2:N2=1:3)吹扫1h除去反应釜内CO2。甲苯可见光催化反应实验条件:甲苯气体通过鼓泡,由混合气(O2:N2=1:3)吹入反应釜,控制反应釜内甲苯初始浓度为~200ppm,相对湿度为~16%,光照前反应釜在室温下避光处理2h,使甲苯在催化剂表面达到吸附-脱附平衡。装上UV反射片的200w的氙灯作为模拟紫外光源(λ=300~400nm,光强为200mw·cm-2),反应120min,每隔10min取一次样,通过气相色谱(GC7900,FID)检测甲苯浓度和GC2060,FID)检测CO2产量。并用以下公式算出转化率:其中nTol,0为甲苯初始物质的量(mol),为某时刻的CO2的产量(mol)。
表1.ZnO/P25异质光催化剂的活性评价结果
Claims (5)
1.一种具有多通道载流子分离功能的异质光催化剂,其特征在于:所述异质光催化剂是由ZnO和混合相二氧化钛P25组成,以催化剂的重量为100%计,ZnO的质量分数为0.1%~10.0%,余量为二氧化钛P25。
2.权利要求1所述异质光催化剂的制备方法,其特征在于包括以下步骤:
(1)配置锌盐水溶液;
(2)将P25粉末分散在溶液中;
(3)干燥、煅烧得到ZnO/P25异质光催化剂。
3.根据权利要求2所述的制备方法,其特征在于:步骤(1)中所述锌盐为醋酸锌或者硝酸锌中的一种,锌盐在溶液中的质量分数为0.1%~30%。
4.根据权利要求2所述的制备方法,其特征在于:步骤(3)中所述干燥过程,是指在80~120℃的空气氛围内恒温干燥6~24 h;所述煅烧过程,是指在煅烧温度为300~900℃的空气气氛中煅烧3~12 h。
5.权利要求1所述异质光催化剂在光催化降解空气中有机污染物中的应用。
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Cited By (5)
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CN106881093A (zh) * | 2017-02-22 | 2017-06-23 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种高效除甲醛喷剂及其制备方法和应用 |
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CN110026173A (zh) * | 2019-04-28 | 2019-07-19 | 苏州科技大学 | 纳米ZnO/TiO2复合光催化剂及其制备方法和应用 |
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CN114452826A (zh) * | 2021-12-14 | 2022-05-10 | 长安大学 | 一种光驱动自清洁的Ti3C2@TiO2-C3N4异质结分离膜的制备方法 |
CN114452826B (zh) * | 2021-12-14 | 2022-11-08 | 长安大学 | 一种光驱动自清洁的Ti3C2@TiO2-C3N4异质结分离膜的制备方法 |
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