CN106311356A - 一种卤化银/硅钛气凝胶三元复合光催化剂及其制备方法 - Google Patents
一种卤化银/硅钛气凝胶三元复合光催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种卤化银/硅钛气凝胶三元复合光催化剂及其制备方法。本发明首先通过溶胶‑凝胶法结合超临界干燥方法制备出TiO2/SiO2气凝胶块体材料,再然后在气凝胶介孔中沉积Ag纳米颗粒,并利用Ag与FeX3之间的氧化还原反应制备AgX颗粒,制备出AgX/TiO2/SiO2复合光催化剂。本发明利用硅钛气凝胶块体材料作为AgX纳米颗粒的载体,并充分发挥AgX、TiO2和SiO2三者的协同光催化作用,制备一种兼有催化活性高、催化时效长及易回收功能的三元复合光催化剂。
Description
技术领域
本发明属于光催化技术领域,特别是涉及一种气凝胶三元复合光催化剂及其制备方法。
背景技术
自从1972年Fujishima和Honda教授报道在n型TiO2电极上发现水的光电催化分解产生氢气和氧气后,光催化剂在解决能源和环境问题方面的应用已经引起研究者越来越多的关注,各种新型高效的光催化剂被研发出来,光催化机理也被深入探讨。
截止目前,TiO2是唯一真正实现实际应用的光催化剂,在空气净化、有机污染物降解及重金属还原等领域得到了广泛应用。然而,由于自身缺陷,TiO2光催化剂在应用过程中存在以下两大问题:(1)TiO2在液体环境中一般是以悬浮的颗粒状态存在,存在不宜回收的问题,容易造成体系的二次污染。(2)TiO2的催化反应需要紫外光来激发,在可见光波长范围内光催化效率很低。近年来,研究者为克服TiO2的上述缺陷,做了大量的研究工作。
针对TiO2光催化剂不易回收的缺点,研究者采取的主要措施是将其构筑为气凝胶块体材料,使其易于实现与液体的分离。气凝胶是一种由胶体粒子聚结而成的轻质纳米多孔材料,其孔洞尺寸在介孔范围内,在具备纳米粒子高比表面积性质的同时,还兼具块体材料的宏观物理性质。TiO2气凝胶作为光催化材料具备天然的优势:高比表面积和高孔容意味着其具有很强的吸附能力,即反应物能够在TiO2颗粒表面富集;而纳米粒子的尺寸效应可增加催化活性位点,改善光催化反应的动力学条件,还可缩短电子/空穴对由催化剂内部迁移到表面的时间,降低它们复合的几率,这都有助于光催化活性的提高。然而,TiO2气凝胶存在易碎、易烧结的缺陷,在高温下介孔会逐渐锁闭,这大大限制了TiO2气凝胶的实际应用。目前,研究者一般将TiO2气凝胶与SiO2或其它金属氧化物气凝胶进行复合,以提高其机械强度和高温下的稳定性。
AgX是一种优良的表面等离子体光催化剂,它结合了贵金属的表面等离子体共振效应、金属半导体接触和半导体光催化材料的特性,具有更强的可见光吸收效率,能够降低半导体光催化材料和目标分子之间的接触能,并且光生电子和空穴能够更有效地分离,从而大大提高了体系的光催化性能。当然,AgX作为光催化剂也有其固有的缺陷,即AgX在可见光照射下很容易发生分解形单质Ag和卤素,光催化活性逐渐减弱,即AgX的催化时效很低,这就大大限制了AgX作为光催化剂的实际应用。
发明内容
本发明提供了一种三元复合光催化剂材料的设计的新思路,即在TiO2/SiO2气凝胶介孔中沉积制备AgX纳米颗粒,制备一种兼有催化活性高、催化时效长及易回收功能的AgX/TiO2/SiO2三元复合光催化剂。
本发明的技术方案是:一种卤化银/硅钛气凝胶三元复合光催化剂,其特征是,它是在TiO2/SiO2气凝胶介孔中沉积AgX纳米颗粒,得到的AgX/TiO2/SiO2三元复合光催化剂。其中X=Cl、Br、I中的任意一种或几种。
上述复合光催化剂的制备方法为:通过溶胶-凝胶法结合超临界干燥方法制备出TiO2/SiO2气凝胶块体材料,再然后在气凝胶介孔中沉积Ag纳米颗粒,并利用Ag与FeX3之间的氧化还原反应制备AgX颗粒,合成出AgX/TiO2/SiO2复合光催化剂。
具体包括以下步骤:
(1)将有机硅烷和无水乙醇按体积比1:2~1:0.5均匀混合,用酸调节溶液pH值为0.5~1.0,室温静置继续水解,制得SiO2溶胶;
(2)将有机酞酸酯和无水乙醇按体积比1:2~1:0.5均匀混合,用酸调节pH值为0.5~1.0,得到溶液1;由无水乙醇和去离子水按体积比1:1~5:1均匀混合,用酸调节pH值为0.6~1.0,得溶液2;溶液1与溶液2按体积比5:1~1:1混合,制得TiO2溶胶;
(3)在强搅拌下将SiO2溶胶用滴管缓慢滴加到TiO2溶胶中(SiO2溶胶和TiO2溶胶的体积比为0.5:1~5:1),并加入胺类碱至调pH值为3~7,室温下静置直至凝结,得到复合醇凝胶;醇凝胶陈化12~48h,再用无水乙醇浸泡2~5天,其间更换无水乙醇4~8次,然后采用超临界干燥方法制备出硅钛气凝胶块体材料;
(4)将硅钛气凝胶块体材料在硝酸银的乙醇溶液中浸泡,硝酸银的质量百分比浓度为1~10%,在气凝胶介孔中沉积Ag纳米颗粒;
(5)将Ag/硅钛复合气凝胶在FeX3水溶液中浸泡,FeX3的质量百分比浓度为5~20%,利用Ag与FeX3之间的氧化还原反应制备AgX颗粒,制备了AgX/TiO2/SiO2块体复合光催化剂。
所述的有机硅烷为正硅酸乙酯、正硅酸甲酯、异丁基三乙氧基硅、乙烯基三乙氧基硅烷、丙基三甲氧基硅烷。
所述的有机酞酸酯为钛酸四丁酯、钛酸四异丙酯、三异硬脂酸钛酸异丙酯。
所述的调节pH值的酸为盐酸、硫酸、盐酸、甲酸、乙酸、草酸、柠檬酸或它们的任意混合物。
所述的胺类碱为氨水、甲酰胺、三甲基氨、乙醇胺、三乙醇胺或它们的任意混合物。
本发明的创新点为:将表面等离子体增强光催化剂AgX与硅钛气凝胶光催化剂相结合,既具备AgX在可见光下催化效率高的优点,又具备硅钛气凝胶比表面积大、易回收的特点,而且AgX与硅钛气凝胶复合后,由于气凝胶孔隙的限制作用,卤素被控制在孔隙中,使得AgX的光化学稳定性显著提高,这就使得三元复合光催化剂具备催化活性高、催化时效长及易回收的优良性能,易于有机废水降解中应用。
本发明的益效果是:利用硅钛(TiO2/SiO2)气凝胶块体材料作为AgX纳米颗粒的载体,并充分发挥AgX、TiO2和SiO2三者的协同光催化作用,制备一种兼有催化活性高、催化时效长及易回收功能的三元复合光催化剂。
附图说明
图1.本发明实施例1样品SEM图像,可以看到TiO2和SiO2形成了网状结构,并且AgCl颗粒在孔隙中较均匀的分布;
图2.本发明实施例1样品与AgCl、TiO2/SiO2气凝胶在可见光范围内光催化性能对比图;
图3.本发明实施例1样品与AgCl、TiO2/SiO2气凝胶在可见光范围内光催化性能随时间变化的对比图;
图4.本发明实施例3样品SEM图像,相较于图1,TiO2和SiO2粒径较大,形成了网状结构,并且AgI颗粒在孔隙中较均匀的分布;
图5.本发明实施例3样品与AgI、TiO2/SiO2气凝胶在可见光范围内光催化性能对比图;
图6.本发明实施例3样品与AgI、TiO2/SiO2气凝胶在可见光范围内光催化性能随时间变化的对比图。
具体实施方式
实施例1
(1)将正硅酸乙酯、无水乙醇按体积比1:2均匀混合,用酸调节溶液pH值为0.6,室温静置继续水解,制得SiO2溶胶;
(2)将钛酸四丁酯和无水乙醇按1:2体积比均匀混合,用酸调节pH值为1,得到溶液1;由无水乙醇和去离子水按1:1体积比均匀混合,用酸调节pH值为0.6,得溶液2;溶液1与溶液2按体积比4.8:1混合,制得TiO2溶胶;
(3)在强搅拌下将SiO2溶胶用滴管缓慢滴加到TiO2溶胶(SiO2溶胶和TiO2溶胶的体积比为2:1)中,并加入氨水调pH值为5,室温下静置直至凝结,得到复合醇凝胶;醇凝胶陈化12h,再用无水乙醇浸泡2天,其间更换无水乙醇4次,然后采用超临界干燥方法制备出硅钛气凝胶块体材料;
(4)将硅钛气凝胶在硝酸银的乙醇溶液中浸泡,硝酸银的质量百分比浓度为5%,在气凝胶介孔中沉积Ag纳米颗粒;
(5)将Ag/硅钛复合气凝胶在FeCl3水溶液中浸泡,FeCl3的质量百分比浓度为5%,利用Ag与FeCl3之间的氧化还原反应制备AgCl颗粒,制备了AgCl/TiO2/SiO2复合光催化剂。产品的SEM图像如图1所示,从图1可以看出:TiO2和SiO2形成了网状结构,并且AgCl颗粒在孔隙中较均匀的分布。
(6)将AgCl、TiO2/SiO2气凝胶、AgCl/TiO2/SiO2分别投入甲基橙溶液中,经过可见光照射进行光催化反应,利用紫外分光光度计表征染料的降解率,评价AgCl、TiO2/SiO2气凝胶、AgCl/TiO2/SiO2三者的光催化性能,结果如图2-3所示。从图2可以看出:AgCl/TiO2/SiO2气凝胶的染料降解率相比TiO2/SiO2气凝胶具有大幅度的提高。从图3可以看出:AgCl/TiO2/SiO2气凝胶催化时效为:6天后,催化活性下降不足10%,染料降解率仍然大于90%;而TiO2/SiO2气凝胶在1天后,催化活性下降50%以上,2天后染料降解率不足20%。而AgCl由于容易分解,其染料降解率不足5%。
实施例2
(1)将丙基三甲氧基硅烷、无水乙醇按体积比1:1均匀混合,用酸调节溶液pH值为0.7,室温静置继续水解,制得SiO2溶胶;
(2)将钛酸四异丙酯和无水乙醇按1:0.5体积比均匀混合,用酸调节pH值为0.7,得到溶液1;由无水乙醇和去离子水按4:1体积比均匀混合,用酸调节pH值为0.6,得溶液2;溶液1与溶液2按体积比3:1混合,制得TiO2溶胶;
(3)在强搅拌下将SiO2溶胶用滴管缓慢滴加到TiO2溶胶中(SiO2溶胶和TiO2溶胶的体积比为1:1)中,并加入氨水调pH值为6;室温下静置直至凝结,得到复合醇凝胶;醇凝胶陈化24h,再用无水乙醇浸泡2天,其间更换无水乙醇6次,然后采用超临界干燥方法制备出硅钛气凝胶块体材料;
(4)将硅钛气凝胶在硝酸银的乙醇溶液中浸泡,硝酸银的质量百分比浓度为10%,在气凝胶介孔中沉积Ag纳米颗粒;
(5)将Ag/硅钛复合气凝胶在FeBr3水溶液中浸泡,FeBr3的质量百分比浓度为20%,利用Ag与FeBr3之间的氧化还原反应制备AgBr颗粒,制备了AgBr/TiO2/SiO2复合光催化剂;
(6)将AgBr、TiO2/SiO2气凝胶、AgBr/TiO2/SiO2分别投入甲基橙溶液中,经过可见光照射进行光催化反应,利用紫外分光光度计表征染料的降解率,评价AgBr、TiO2/SiO2气凝胶、AgBr/TiO2/SiO2三者的光催化性能。
实施例3
(1)将异丁基三乙氧基硅、无水乙醇按体积比1:2均匀混合,用酸调节溶液pH值为0.6,室温静置继续水解,制得SiO2溶胶;
(2)将三异硬脂酸钛酸异丙酯和无水乙醇按1:2体积比均匀混合,用酸调节pH值为0.5,得到溶液1;由无水乙醇和去离子水按5:1体积比均匀混合,用酸调节pH值为1,得溶液2;溶液1与溶液2按体积比5:1混合,制得TiO2溶胶;
(3)在强搅拌下将SiO2溶胶用滴管缓慢滴加到TiO2溶胶中(SiO2溶胶和TiO2溶胶的体积比为2:1)中,并加入氨水调pH值为5,室温下静置直至凝结,得到复合醇凝胶;醇凝胶陈化36h,再用无水乙醇浸泡4天,其间更换无水乙醇8次,之后常温下自然干燥5天,制备出硅钛气凝胶块体材料;
(4)将硅钛气凝胶在硝酸银的乙醇溶液中浸泡,硝酸银的质量百分比浓度为1%,在气凝胶介孔中沉积Ag纳米颗粒;
(5)将Ag/硅钛复合气凝胶在并FeI3水溶液中浸泡,FeI3的质量百分比浓度为5%,利用Ag与FeI3之间的氧化还原反应制备AgI颗粒,制备了AgI/TiO2/SiO2复合光催化剂,SEM图像如图3所示。从图3可以看出:相较于图1,TiO2和SiO2粒径较大,形成了网状结构,并且AgI颗粒在孔隙中较均匀的分布。
(6)将AgI、TiO2/SiO2气凝胶、AgI/TiO2/SiO2分别投入甲基橙溶液中,经过可见光照射进行光催化反应,利用紫外分光光度计表征染料的降解率,评价AgI、TiO2/SiO2气凝胶、AgI/TiO2/SiO2三者的光催化性能,结果如图5-6所示。从图5可以看出:AgI/TiO2/SiO2气凝胶的染料降解率相比TiO2/SiO2气凝胶具有大幅度的提高。从图6可以看出:AgI/TiO2/SiO2气凝胶催化时效为:6天后,催化活性下降不足10%,染料降解率仍然大于90%;而TiO2/SiO2气凝胶在1天后,催化活性下降65%以上,2天后染料降解率不足10%。而AgI由于容易分解,其染料降解率不足5%。
Claims (9)
1.一种卤化银/硅钛气凝胶三元复合光催化剂,其特征是,它是在TiO2/SiO2气凝胶介孔中沉积AgX纳米颗粒,得到的AgX/TiO2/SiO2三元复合光催化剂;其中X=Cl、Br、I中的任意一种或几种。
2.权利要求1所述的三元复合光催化剂的制备方法,其特征是,通过溶胶-凝胶法结合超临界干燥方法制备出TiO2/SiO2气凝胶块体材料,再然后在气凝胶介孔中沉积Ag纳米颗粒,并利用Ag与FeX3之间的氧化还原反应制备AgX颗粒,制备出AgX/TiO2/SiO2三元复合光催化剂。
3.如权利要求2所述的三元复合光催化剂的制备方法,其特征是,包括以下步骤:
(1)将有机硅烷和无水乙醇按体积比1:2~1:0.5均匀混合,用酸调节溶液pH值为0.5~1.0,室温静置继续水解,制得SiO2溶胶;
(2)将有机酞酸酯和无水乙醇按体积比1:2~1:0.5均匀混合,用酸调节pH值为0.5~1.0,得到溶液1;由无水乙醇和去离子水按体积比1:1~5:1均匀混合,用酸调节pH值为0.6~1.0,得溶液2;溶液1与溶液2按体积比5:1~1:1混合,制得TiO2溶胶;
(3)在强搅拌下将SiO2溶胶滴加到TiO2溶胶中,并加入胺类碱调节pH值为3~7,室温下静置直至凝结,得到复合醇凝胶;复合醇凝胶陈化12~48h,再用无水乙醇浸泡2~5天,然后采用超临界干燥方法制备出硅钛气凝胶块体材料;
(4)将硅钛气凝胶块体材料在硝酸银的乙醇溶液中浸泡,硝酸银的质量百分比浓度为1~10%,在气凝胶介孔中沉积Ag纳米颗粒;
(5)将Ag/硅钛复合气凝胶在FeX3水溶液中浸泡,FeX3的质量百分比浓度为5~20%,利用Ag与FeX3之间的氧化还原反应制备AgX颗粒,制备了AgX/TiO2/SiO2三元复合光催化剂。
4.如权利要求3所述的三元复合光催化剂的制备方法,其特征是,所述的有机硅烷为正硅酸乙酯、正硅酸甲酯、异丁基三乙氧基硅、乙烯基三乙氧基硅烷或丙基三甲氧基硅烷。
5.如权利要求3所述的三元复合光催化剂的制备方法,其特征是,所述的有机酞酸酯为钛酸四丁酯、钛酸四异丙酯或三异硬脂酸钛酸异丙酯。
6.如权利要求3所述的三元复合光催化剂的制备方法,其特征是,所述的调节pH值的酸为盐酸、硫酸、盐酸、甲酸、乙酸、草酸、柠檬酸或它们的任意混合物。
7.如权利要求3所述的三元复合光催化剂的制备方法,其特征是,所述的胺类碱为氨水、甲酰胺、三甲基氨、乙醇胺、三乙醇胺或它们的任意混合物。
8.如权利要求3-7中任意一项所述的三元复合光催化剂的制备方法,其特征是,所述步骤(3)无水乙醇浸泡过程中,其间更换无水乙醇4~8次。
9.如权利要求3-7中任意一项所述的三元复合光催化剂的制备方法,其特征是,所述步骤(3)SiO2溶胶和TiO2溶胶的体积比为0.5:1~5:1。
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Effective date of registration: 20230626 Address after: 203-K, Shanke Maker Space, No. 19, Keyuan Road, Lixia District, Jinan City, Shandong Province, 250000 Patentee after: Shandong Ke Ning Thermal Insulation New Material Technology Co.,Ltd. Address before: 250014 No. 19, ASTRI Road, Lixia District, Shandong, Ji'nan Patentee before: NEW MATERIAL INSTITUTE OF SHANDONG ACADEMY OF SCIENCES |
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