CN108654651A - 一种二氧化钛/二氟氧钛复合气相光催化剂的制备方法 - Google Patents
一种二氧化钛/二氟氧钛复合气相光催化剂的制备方法 Download PDFInfo
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Abstract
本发明涉及一种二氧化钛/二氟氧钛复合气相光催化剂的制备方法。包含如下步骤:步骤一、将氢氟酸和甲苯按照1:(0.4‑2.5)的体积比搅拌混合均匀;步骤二、向步骤一获得的溶液中加入钛源搅拌混合均匀,所述钛源和氢氟酸的比例为25g:(1‑4)mL;步骤三、将步骤二所得反应液置于180℃‑200℃条件下反应1‑24h;步骤四、将步骤三所得产物后处理即得到所述的二氧化钛/二氟氧钛复合气相光催化剂材料。本发明提供的二氧化钛/二氟氧钛复合光催化剂的微观形貌为纳米片组成的多孔分级结构微球,为锐钛矿二氧化钛/二氟氧钛复合相结构,具有优异的气相光催化性能,且催化剂可循环使用,在去除VOC(挥发性有机化合物)方面具有重要的应用价值。
Description
技术领域
本发明涉及光催化材料合成技术领域,具体涉及一种二氧化钛/二氟氧钛复合气相光催化剂的制备方法。
背景技术
二氧化钛是一种重要的半导体材料,有着其独特的物理和化学性能,因而在光催化,太阳能电池,锂离子电池等领域都有着广泛的应用前景,引起了人们广泛的关注。研究表明,二氧化钛作为光催化剂,在被用来净化空气,降解挥发性有机化合物,治理水污染及大气污染等方面,有着很好的作用。
但反应过程中,电子-空穴对的复合严重降低了二氧化钛光催化的效率,因此如何提高电子-空穴分离效率成为亟待解决的问题。而通过增加电子-空穴分离效率来提高其光催化性,主要有三种途径:一是负载贵金属纳米粒子,这一途径主要以负载Pt纳米颗粒应用最为广泛;二是进行元素掺杂,这个方法成本较高;三是通过制备异质结结构,其中以Degussa公司生产的P25型商业二氧化钛粉应用最为广泛,其为锐钛矿相二氧化钛/金红石相二氧化钛(71:29)复合的混合相。
但是目前的二氧化钛气相光催化材性能有待提高,制备方法也较为复杂,已经不能满足现有行业的需要。因此亟需一种的具有高气相催化活性的二氧化钛气相光催化材料。
发明内容
基于以上现有技术的不足,本发明所解决的技术问题在于一种新型的二氧化钛/二氟氧钛复合气相光催化剂的制备方法及二氧化钛/二氟氧钛复合气相光催化剂。该制备方法工艺简单,能大规模合成具有高气相催化活性的二氧化钛/二氟氧钛复合气相光催化剂。
为了解决上述技术问题,本发明采用的技术方案如下:
提供一种二氧化钛/二氟氧钛复合气相光催化剂的制备方法,包含如下步骤:
步骤一、将氢氟酸和甲苯按照1:(0.4-2.5)的体积比例搅拌混合均匀;
步骤二、向步骤一获得的溶液中加入钛源搅拌混合均匀,所述钛源和氢氟酸的比例为25g:(1-4)mL;
步骤三、将步骤二所得反应液置于180℃-200℃条件下反应;
步骤四、将步骤三所得产物后处理即得到所述的二氧化钛/二氟氧钛复合气相光催化剂材料。
按上述方案,步骤一中的匀速搅拌时间为10-15min。
按上述方案,步骤二中的匀速搅拌时间为5-30min。
按上述方案,所述钛源为钛酸四丁酯。
按上述方案,所述搅拌转速为500-1500r/min。
按上述方案,步骤三中的水热反应时间为1-24h。
按上述方案,所述的后处理为:过滤取滤渣,用无水乙醇清洗并离心分离,重复清洗、离心过程至少三遍,然后在40-70℃条件烘干。
提供一种二氧化钛/二氟氧钛复合气相光催化剂材料,其为由3-30nm厚,长50-200nm的纳米片组成的直径为6-10μm的微球,纳米片之间有堆积孔,具有锐钛矿二氧化钛/二氟氧钛复合相结构,其中二氟氧钛占比为7-25wt%。
按上述方案,本发明提供的二氧化钛/二氟氧钛复合气相光催化剂比表面积为52-82m2/g,纳米片之间堆积孔的孔径大小为40-70nm。
锐钛矿二氧化钛的理论导带位置及价带位置分别约为(-0.3eV、2.8eV),二氟氧钛的理论导带位置及价带位置分别约为(1.3eV、4.3eV),本发明提供的二氧化钛/二氟氧钛复合气相光催化剂材料二氧化钛/二氟氧钛两相复合时会形成异质结结构,光照激发产生的电子会从锐钛矿二氧化钛的导带向二氟氧钛的导带迁移,空穴则由二氟氧钛的价带向二氧化钛的价带迁移,降低电子-空穴复合机率,有效的提升光生载流子的寿命,从而提升材料的光催化性能。同时本发明的纳米片球结构也可有效的阻止催化过程中的纳米片团聚,其特殊的球形结构使其在气相催化上具有很好的应用前景。
本发明采用水热法合成纳米片球结构的二氧化钛/二氟氧钛复合气相光催化材料,具体地,反应开始前,甲苯与氢氟酸混合,两相不相容形成甲苯包覆的氢氟酸微球,加入钛源后,钛源与氢氟酸中的水反应,氟离子的存在抑制了晶粒沿001方向的生长,形成纳米片结构,两相分离导致微球结构的出现,同时过量的氟促使二氟氧钛的生成,由此可原位获得本发明所述的具有纳米片球结构的二氧化钛/二氟氧钛复合气相光催化剂材料。
与现有技术相比,本发明有如下有益效果:
(1)本发明提供的二氧化钛/二氟氧钛复合光催化剂的微观形貌为纳米片组成的多孔分级结构微球,为锐钛矿二氧化钛/二氟氧钛复合相结构,具有较高的比表面积和丰富的孔道结构,有优异的气相光催化性能,且催化剂可循环使用,气相降解丙酮的速率最高可达到商业二氧化钛材料P25的6倍,在去除VOC(挥发性有机化合物)方面具有重要的应用价值。
(2)合成方法简单,成本低,可以大量合成,重复性高,适用于工业生产。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,而可依照说明书的内容予以实施,并且为了让本发明的上述和其他目的、特征和优点能够更明显易懂,以下结合优选实施例,详细说明如下。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例的附图作简单地介绍。
图1为实施例1的二氧化钛/二氟氧钛复合气相光催化剂的高分辨SEM图;
图2是实施例1的二氧化钛/二氟氧钛复合气相光催化剂的XRD图;
图3(a)是实施例1的二氧化钛/二氟氧钛复合气相光催化剂的氮气吸附-脱附曲线图;
图3(b)是实施例1的二氧化钛/二氟氧钛复合气相光催化剂的孔径分布图;
图4是实施例1的二氧化钛/二氟氧钛复合气相光催化剂与P25的气相催化降解丙酮性能对比图。
具体实施方式
下面详细说明本发明的具体实施方式,其作为本说明书的一部分,通过实施例来说明本发明的原理,本发明的其他方面、特征及其优点通过该详细说明将会变得一目了然。
实施例1
(1)取4mL的甲苯倒入聚四氟乙烯反应釜中,往里面加入2mL氢氟酸,匀速1500r/min搅拌10min。
(2)10min后,往(1)中所获得溶液中加入25mL钛酸四丁酯,均匀1500r/min搅拌20min。
(3)搅拌完成后,将反应釜中的磁子取出,封装好反应釜,放入鼓风干燥箱中,温度设定为180℃,保温反应24h。
(4)从鼓风干燥箱中取出反应釜,离心去除液体,得到蓝色固体产物,无水乙醇清洗产物,8000r/min的速度离心分离10min,重复此步骤清洗产物三遍,清洗后将产物放入40℃烘箱中烘干,即得到所述的二氧化钛/二氟氧钛复合气相光催化剂。
(5)将10mg上述产物分散于2mL乙醇溶液中,超声分散15min,所得溶液置于玻璃培养皿中,40℃干燥12h,制得气相测试样品。
(6)将(5)中样品置于密封反应器内,用注射器注入2μL丙酮溶液,300W的氙灯光照(320-780nm),使用气相色谱FID检测器,检测VOC气体丙酮浓度变化。
图1为本实施例1所制备的二氧化钛/二氟氧钛复合气相光催化剂的低倍扫描图(左图)和高分辨SEM图(右图);图2是二氧化钛/二氟氧钛复合气相光催化剂的XRD图;图3(a)是二氧化钛/二氟氧钛复合气相光催化剂的氮气吸附-脱附曲线图;图3(b)是二氧化钛/二氟氧钛复合气相光催化剂的孔径分布图;图4是二氧化钛/二氟氧钛复合气相光催化剂与P25的气相催化降解丙酮性能对比图。
从图1中可以看出制备出的二氧化钛/二氟氧钛复合气相光催化剂为8-10μm的微球,由3-6nm厚,长100-200nm的纳米片组装得到。图2为XRD图,分析结果表明:制备出的复合材料为锐钛矿晶型二氧化钛与二氟氧钛复合晶型,二氟氧钛占比20wt%。
图3为二氧化钛/二氟氧钛复合气相光催化剂的氮气吸附曲线图及孔径分布图,其中左图中为吸附-脱附曲线,右图为孔径分布图。由测试结果可知制备出的多孔分级结构二氧化钛微球材料的比表面积为52m2/g,平均孔径大小为46nm。图4为实施例1所制备的二氧化钛/二氟氧钛复合气相光催化剂与P25的气相催化降解丙酮性能对比图,由公式ln(C0/C)=kt计算所得kP25=0.008min-1,k TiO2/TiOF2=0.046min-1。我们所制材料的气相催化降解丙酮反应速率常数约为P25的6倍。
实施例2
(1)取4mL的甲苯倒入聚四氟乙烯反应釜中,往里面加入2mL氢氟酸,匀速1500r/min搅拌10min。
(2)10min后,往(1)中所获得溶液中加入25mL钛酸四丁酯,均匀1000r/min搅拌20min。
(3)搅拌完成后,将反应釜中的磁子取出,封装好反应釜,放入鼓风干燥箱中,温度设定为200℃,保温反应6h。
(4)从鼓风干燥箱中取出反应釜,离心去除液体,得到蓝色固体产物,无水乙醇清洗产物,8000r/min的速度离心分离10min,重复此步骤清洗产物三遍,清洗后将产物放入40℃烘箱中烘干,即得到所述的二氧化钛/二氟氧钛复合气相光催化剂。
(5)将10mg上述产物分散于2mL乙醇溶液中,超声分散15min,所得溶液置于玻璃培养皿中,40℃干燥12h,制得气相测试样品。
(6)将(5)中样品置于密封反应器内,用注射器注入2μL丙酮溶液,300W的氙灯光照(320-780nm),使用气相色谱FID检测器,检测VOC气体丙酮浓度变化。
经SEM、XRD分析表明:制备出的复合材料为8-10μm的微球,由10-30nm厚,长50-200nm的纳米片组装得到,为锐钛矿晶型二氧化钛与二氟氧钛复合晶型,二氟氧钛占比25wt%,用于气相催化降解丙酮k TiO2/TiOF2=0.014min-1。
随着氢氟酸用量的增加材料表面的片状结构不断增大,且能更快的形成片状结构,获得的材料中二氟氧钛占比可从7%增加到25%。当二氟氧钛含量占比约为20%,材料具有最优的气相催化性能,其性能可达到商业用二氧化钛性能的6倍。
对比例1
(1)取4mL的甲苯倒入聚四氟乙烯反应釜中,往里面加入10mL氢氟酸,匀速500r/min搅拌10min。
(2)10min后,往(1)中所获得溶液中加入25mL钛酸四丁酯,均匀500r/min搅拌20min。
(3)搅拌完成后,将反应釜中的磁子取出,封装好反应釜,放入鼓风干燥箱中,温度设定为180℃,保温反应24h。
(4)从鼓风干燥箱中取出反应釜,离心去除液体,得到蓝色固体产物,无水乙醇清洗产物,8000r/min的速度离心分离10min,重复此步骤清洗产物三遍,清洗后将产物放入40℃烘箱中烘干,即得到所述的二氧化钛/二氟氧钛复合气相光催化剂。
(5)将10mg上述产物分散于2mL乙醇溶液中,超声分散15min,所得溶液置于玻璃培养皿中,40℃干燥12h,制得气相测试样品。
(6)将(5)中样品置于密封反应器内,用注射器注入2μL丙酮溶液,300W的氙灯光照(320-780nm),使用气相色谱FID检测器,检测VOC气体丙酮浓度变化。
经SEM、XRD分析表明:制备出的复合材料为3-4μm花状结构,由400-800nm长,10-50nm厚的纳米片组成,为锐钛矿晶型二氧化钛与二氟氧钛复合晶型,二氟氧钛占比90wt%,用于气相催化降解丙酮kTiO2/TiOF2=0.001min-1。
本发明所列举的各原料,以及本发明各原料的上下限、区间取值,以及工艺参数(如温度、时间等)的上下限、区间取值都能实现本发明,在此不一一列举实施例。
以上所述是本发明的优选实施方式而已,当然不能以此来限定本发明之权利范围,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和变动,这些改进和变动也视为本发明的保护范围。
Claims (9)
1.一种二氧化钛/二氟氧钛复合气相光催化剂的制备方法,其特征在于:包含如下步骤:
步骤一、将氢氟酸和甲苯按照1:(0.4-2.5)的体积比例搅拌混合均匀;
步骤二、向步骤一获得的溶液中加入钛源搅拌混合均匀,所述钛源和氢氟酸的比例为25g:(1-4)mL;
步骤三、将步骤二所得反应液置于180℃-200℃条件下反应;
步骤四、将步骤三所得产物后处理即得到所述的二氧化钛/二氟氧钛复合气相光催化剂材料。
2.根据权利要求1所述的制备方法,其特征在于:步骤一中的匀速搅拌时间为10-15min。
3.根据权利要求1所述的制备方法,其特征在于:步骤二中的匀速搅拌时间为5-30min。
4.根据权利要求1所述的制备方法,其特征在于:所述钛源为钛酸四丁酯。
5.根据权利要求1所述的制备方法,其特征在于:所述搅拌转速为500-1500r/min。
6.根据权利要求1所述的制备方法,其特征在于:步骤三中的水热反应时间为1-24h。
7.根据权利要求1所述的制备方法,其特征在于:所述的后处理为:过滤取滤渣,用无水乙醇清洗并离心分离,重复清洗、离心过程至少三遍,然后在40-70℃条件烘干。
8.一种二氧化钛/二氟氧钛复合气相光催化剂材料,其特征在于:为由3-6nm厚,长100-200nm的纳米片组成的直径为6-10μm的微球,纳米片之间有堆积孔,具有锐钛矿二氧化钛/二氟氧钛复合相结构,其中二氟氧钛占比为13-90wt%。
9.根据权利要求8所述的光催化剂材料,其特征在于:比表面积为52-82m2/g,纳米片之间堆积孔的孔径大小为40-70nm。
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