CN107376912B - 一种多层TiO2纳米管基光催化剂及其制备方法与应用 - Google Patents
一种多层TiO2纳米管基光催化剂及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种多层TiO2纳米管基光催化剂及其制备方法与应用。光催化剂为TN@SrTiO3@Ag@Bi2O3@Ag,每层Ag的质量分数0.5%,SrTiO3为1%,Bi2O3为1%。制备方法如下:1)将TiO2纳米管放于马弗炉中煅烧得到锐钛矿型TN;2)通过搅拌将TN均匀分散于Sr(OH)2溶液中,再水热处理得到TN@SrTiO3;3)通过搅拌将TN@SrTiO3均匀分散于AgNO3溶液中,再经过微波水热处理得到TN@SrTiO3@Ag;4)通过搅拌将TN@SrTiO3@Ag均匀分散于Bi(NO3)3溶液中,随后微波水热处理,洗涤、干燥、煅烧处理;5)按照3)中方法将TN@SrTiO3@Ag@Bi2O3与AgNO3溶液水热反应得到。本发明的光催化剂将贵金属沉积在两层之间,通过Ag的界面调控,加快电子迁移速率,降低光生载流子的复合。同时所形成的异质结不仅拓宽了光响应范围,且增强了光吸收能力,表现出优异的光催化性能。
Description
技术领域
本发明涉及一种用于光催化反应的多层TiO2纳米管基材料及其制备方法,属于光催化材料和环境保护技术领域。
背景技术
随着工业的发展,环境污染问题日趋严重,室外废气的排放量越来越大,同时室内的空气污染问题也不容忽视,怎样更好地处理这些废气成为亟待解决的问题。光催化降解技术因反应过程快速高效、能耗低、无二次污染等优点,成为最有前景的技术之一。但仍存在一些缺陷,传统光催化剂如TiO2的禁带宽,只对紫外光响应,且电子和空穴易复合,导致光催化活性和效率降低。因此构筑高效TiO2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。 TN@SrTiO3@Ag@Bi2O3@Ag是在TiO2纳米管的基础上依次沉积 SrTiO3、Ag、Bi2O3、Ag而形成的。一维纳米管结构能促进对光子的捕获能力,有利于加快电荷的迁移和分离。SrTiO3能充当空穴传输层,有效抑制TN光生载流子的复合。同时将贵金属沉积在两层之间,通过Ag的界面调控,加快电子迁移速率,降低光生载流子的复合,从而提高光催化效率。Shuang Shuang等人(Sci Rep.2016;6:26670.) 提出一种TiO2纳米阵列管的设计。用Au和Pt纳米粒子通过连续离子层吸附和反应在室温下直接合成。显著提高了TiO2的光生电荷分离,进而提高光催化效率。Sunita Khanchandani等人(J.Phys.Chem. C 2013,117,5558-5567)制备了ZnO/In2S3II型核壳的纳米阵列。核 /壳光催化剂能够在可见光照射下明显的光催化降解RhB,效率高于 In2S3/ZnO纳米棒。催化活性的提高是由于两半导体异质结的形成促使光生电子-空穴的有效分离。但这些复合材料的合成方法,一是贵金属中Au、Pt价格较为昂贵,二是复合材料组分较为单一很难充分交织形成利于电子和空穴分离的相界面。
发明内容
针对上述光催化领域,特别是TiO2纳米管基光催化剂所面临的问题,本发明提供了一种多层TiO2纳米管基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:
一种多层TiO2纳米管基光催化剂,所述光催化剂是由TiO2纳米管做基底,依次沉积SrTiO3、Ag、Bi2O3、Ag组成,以催化剂的重量为100%计,每层Ag的质量分数0.5%,SrTiO3的质量分数为1%, Bi2O3的质量分数为1%,余量为TiO2纳米管。
上述多层TiO2纳米管基光催化剂的制备方法,包括以下步骤:
(1)将TiO2纳米管放于马弗炉中煅烧得到处理好的TiO2纳米管;
(2)将TiO2纳米管溶解于乙醇中,磁力搅拌;取Sr(OH)2溶于纯水中,超声使其均匀;再将其滴加到TiO2纳米管溶液中,磁力搅拌;后水热,离心洗涤干燥得到TN@SrTiO3;
(3)将TN@SrTiO3溶于乙醇与水体积比1:1的溶液中,磁力搅拌;取AgNO3溶于乙醇与水体积比1:1的溶液中,超声使其均匀;再将其滴加到TN@SrTiO3溶液中磁力搅拌;后微波水热,离心洗涤干燥得到TN@SrTiO3@Ag;
(4)将TN@SrTiO3@Ag溶于乙醇中,磁力搅拌;取Bi(NO3)3溶于乙二醇和乙醇混合溶液中,超声使其均匀;再将其滴加到 TN@SrTiO3@Ag溶液中磁力搅拌;后微波水热,离心洗涤干燥,再煅烧得到TN@SrTiO3@Ag@Bi2O3;
(5)按照步骤(3)中方法在TN@SrTiO3@Ag@Bi2O3上再沉积一层Ag即得到TN@SrTiO3@Ag@Bi2O3@Ag。
其中步骤(1)中所述煅烧过程,是指在350~500℃条件下煅烧 2~4h。
步骤(2)中所述磁力搅拌时间均为30~60min,水热条件为 180~240℃水热18~30h,洗涤过程是指用0.05~0.2M醋酸洗涤几次,再用纯水和无水乙醇洗涤几次。干燥过程是指在60~80℃的空气氛围内恒温干燥6~24h。
步骤(3)中所述磁力搅拌时间均为30~60min,微波水热参数:温度为120~180℃,时间为1~3h,功率为300~500W。洗涤过程是指用纯水和无水乙醇洗涤几次。干燥过程是指在60~80℃的空气氛围内恒温干燥6~24h。
步骤(4)中所述磁力搅拌时间均为30~60min,微波水热参数:温度为120~180℃,时间为1~3h,功率为300~500W。洗涤过程是指用纯水和无水乙醇洗涤几次。干燥过程是指在60~80℃的空气氛围内恒温干燥6~24h。煅烧过程是指在马弗炉中400~600℃煅烧3~5h。
本发明的再一个目的是提供上述多层TiO2纳米管基光催化剂的应用。
本发明所提供的多层TiO2纳米管基光催化剂的应用是其在室温可见光催化领域中的应用。所述可见光催化剂对单体小分子有机物都具有一定的催化效果,可用于降解空气中有机污染物,如甲醛、甲苯等。
与现有技术相比,本发明具有如下有益效果:
本发明采用的多层TiO2纳米管基光催化剂的制备方法为微波水热法,一维纳米管结构能促进对光子的捕获能力,有利于加快电荷的迁移和分离。SrTiO3能充当空穴传输层,有效抑制TN光生载流子的复合。此外Ag作为一种贵金属均匀沉积在两层之间,通过Ag的界面调控,加快电子迁移速率,降低光生载流子的复合。同时还沉积有 Bi2O3作为复合相组分,形成多相异质结,促进光生电子-空穴的分离,从而提高光催化反应效率。用于低浓度甲苯、甲醛等有机气体的可见光催化反应时,可以在室温条件下将体系中甲苯、甲醛几乎完全氧化为二氧化碳和水。多层TiO2纳米管基光催化剂的制备方法条件温和,催化效率高,操作方便,便于工业放大生产。
附图说明
图 1为各实施例中制备的样品 TN@SrTiO3@Ag@Bi2O3@Ag(TSABA), TN@Ag@SrTiO3@Ag(TASA),TN@SrTiO3@Bi2O3@Ag(TSBA), TN@SrTiO3@Bi2O3(TSB)和TN@Ag(TA)的紫外可见光谱对比图。
具体实施方式
为更好地说明本发明,便于理解本发明的技术方案,本发明的典型但非限制性的实施例如下:
实施例1
一种多层TiO2纳米管基光催化剂的制备方法:(1)将购买的TiO2纳米管放于马弗炉中400℃煅烧2h得到处理好的TiO2纳米管;(2) 将0.30g TiO2纳米管溶于20mL乙醇中,磁力搅拌30min。将0.0044 g Sr(OH)2溶于纯水中,并加入TiO2纳米管溶液中,再磁力搅拌30min后,倒入高压反应釜中200℃水热24h,自然冷却到室温后,离心分离得到固体,并用0.1M醋酸溶液洗涤2次,纯水和无水乙醇各洗3 次,放入60℃烘箱恒温干燥10h得到TN@SrTiO3;(3)将0.30g TN@SrTiO3溶于20mL乙醇与水体积比1:1的溶液中,磁力搅拌30 min。将0.0024gAgNO3溶于20mL乙醇与水体积比1:1的溶液中,并加入TN@SrTiO3溶液中,磁力搅拌30min。150℃水热2h后,用纯水和无水乙醇各洗涤3次,放入60℃烘箱恒温干燥10h得到 TN@SrTiO3@Ag;(4)将0.30g TN@SrTiO3@Ag溶于20mL乙醇中。将0.0031g Bi(NO3)3溶于20mL乙二醇和20mL乙醇混合溶液中,并加入TN@SrTiO3@Ag溶液中,磁力搅拌30min,150℃水热2h后,用纯水和无水乙醇各洗涤3次,放入60℃烘箱恒温干燥10h后, 450℃煅烧3h得到TN@SrTiO3@Ag@Bi2O3;(5)按照(3)中方法在TN@SrTiO3@Ag@Bi2O3上再沉积一层Ag得到最终产品。
对比例1
对比一种多层TiO2纳米管基光催化剂的制备方法:(1)将购买的TiO2纳米管放于马弗炉中400℃煅烧2h得到处理好的TiO2纳米管;(2)将0.30g TiO2纳米管溶于20mL乙醇中,磁力搅拌30min。将0.0044g Sr(OH)2溶于纯水中,并加入TiO2纳米管溶液中,再磁力搅拌30min后,倒入高压反应釜中200℃水热24h,自然冷却到室温后,离心分离得到固体,并用0.1M醋酸溶液洗涤2次,纯水和无水乙醇各洗3次,放入60℃烘箱恒温干燥10h得到TN@SrTiO3;(3)将0.30g TN@SrTiO3溶于20mL乙醇与水体积比1:1的溶液中,磁力搅拌30min。将0.0024gAgNO3溶于20mL乙醇与水体积比1:1的溶液中,并加入TN@SrTiO3溶液中,磁力搅拌30min。150℃水热2h 后,用纯水和无水乙醇各洗涤3次,放入60℃烘箱恒温干燥10h 得到TN@SrTiO3@Ag;(4)将0.30g TN@SrTiO3@Ag溶于20mL 乙醇中。将0.0031g Bi(NO3)3溶于20mL乙二醇和20mL乙醇混合溶液中,并加入TN@SrTiO3@Ag溶液中,磁力搅拌30min,150℃水热 2h后,用纯水和无水乙醇各洗涤3次,放入60℃烘箱恒温干燥10h 后,450℃煅烧3h得到最终产品。
实施例2
一种多层TiO2纳米管基光催化剂的制备方法:(1)将购买的TiO2纳米管放于马弗炉中400℃煅烧2h得到处理好的TiO2纳米管;(2) 将0.30g TN溶于20mL乙醇与水体积比1:1的溶液中,磁力搅拌30 min。将0.0024g AgNO3溶于20mL乙醇与水体积比1:1的溶液中,并加入TN溶液中,磁力搅拌30min。150℃水热2h后,用纯水和无水乙醇各洗涤3次,放入60℃烘箱恒温干燥10h得到TN@Ag; (3)通过搅拌将TN@Ag溶液和Sr(OH)2溶液混合,再通过水热得到TN@Ag@SrTiO3将0.30g TN@Ag溶于20mL乙醇中,磁力搅拌 30min。将0.0044g Sr(OH)2溶于纯水中,并加入TN@Ag溶液中,再磁力搅拌30min后,倒入高压反应釜中200℃水热24h,自然冷却到室温后,离心分离得到固体,并用0.1M醋酸溶液洗涤2次,纯水和无水乙醇各洗3次,放入60℃烘箱恒温干燥10h得到 TN@Ag@SrTiO3;(4)按照(2)中方法在TN@Ag@SrTiO3上再沉积一层Ag得到最终产品。
实施例3
一种多层TiO2纳米管基光催化剂的制备方法:(1)将购买的TiO2纳米管放于马弗炉中400℃煅烧2h得到处理好的TiO2纳米管;(2) 将0.30g TiO2纳米管溶于20mL乙醇中,磁力搅拌30min。将0.0044 g Sr(OH)2溶于纯水中,并加入TiO2纳米管溶液中,再磁力搅拌30min后,倒入高压反应釜中200℃水热24h,自然冷却到室温后,离心分离得到固体,并用0.1M醋酸溶液洗涤2次,纯水和无水乙醇各洗3 次,放入60℃烘箱恒温干燥10h得到TN@SrTiO3;(3)将0.30g TN@SrTiO3溶于20mL乙醇中。将0.0031g Bi(NO3)3溶于20mL乙二醇和20mL乙醇混合溶液中,并加入TN@SrTiO3溶液中,磁力搅拌 30min,150℃水热2h后,用纯水和无水乙醇各洗涤3次,放入60℃烘箱恒温干燥10h后,450℃煅烧3h得到TN@SrTiO3@Bi2O3;(4) 将0.30gTN@SrTiO3@Bi2O3溶于20mL乙醇与水体积比1:1的溶液中,磁力搅拌30min。将0.0024g AgNO3溶于20mL乙醇与水体积比1:1的溶液中,并加入TN@SrTiO3@Bi2O3溶液中,磁力搅拌30min。150℃水热2h后,用纯水和无水乙醇各洗涤3次,放入60℃烘箱恒温干燥10h得到最终产品。
实施例4
一种多层TiO2纳米管基光催化剂的制备方法:(1)将购买的TiO2纳米管放于马弗炉中400℃煅烧2h得到处理好的TiO2纳米管;(2) 将0.30g TiO2纳米管溶于20mL乙醇中,磁力搅拌30min。将0.0044 g Sr(OH)2溶于纯水中,并加入TiO2纳米管溶液中,再磁力搅拌30min后,倒入高压反应釜中200℃水热24h,自然冷却到室温后,离心分离得到固体,并用0.1M醋酸溶液洗涤2次,纯水和无水乙醇各洗3 次,放入60℃烘箱恒温干燥10h得到TN@SrTiO3;(3)将0.30g TN@SrTiO3溶于20mL乙醇中。将0.0031g Bi(NO3)3溶于20mL乙二醇和20mL乙醇混合溶液中,并加入TN@SrTiO3溶液中,磁力搅拌 30min,150℃水热2h后,用纯水和无水乙醇各洗涤3次,放入60℃烘箱恒温干燥10h后,450℃煅烧3h得到最终产品。
实施例5
一种多层TiO2纳米管基光催化剂的制备方法:(1)将购买的TiO2纳米管放于马弗炉中400℃煅烧2h得到处理好的TiO2纳米管;(2) 将0.30g TN溶于20mL乙醇与水体积比1:1的溶液中,磁力搅拌30 min。将0.0024g AgNO3溶于20mL乙醇与水体积比1:1的溶液中,并加入TN溶液中,磁力搅拌30min。150℃水热2h后,用纯水和无水乙醇各洗涤3次,放入60℃烘箱恒温干燥10h得到最终产品。
实施例6
分别取0.2g实施例1-5所述催化剂,以纯水作溶剂,均匀涂抹在7.0cm2的表面皿内并烘干,置于反应釜底部,用混合气(O2:N2=1:3)吹扫20min除去反应釜内CO2。甲苯可见光催化反应实验条件为:纯甲苯液体通过鼓泡,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~400ppm,相对湿度为~18%,光照前反应釜在室温下避光处理20min,使甲苯在催化剂表面达到吸附-脱附平衡。装上全反射片和滤掉紫外的反射片,使用200w的氙灯作为模拟可见光源(λ=420~780nm,光强为150mw·cm-2),反应5h,每隔30min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:其中为甲苯初始物质的量(mol),为某时刻CO2的物质的量(mol)。
表1多层TiO2纳米管基光催化剂TN@SrTiO3@Ag@Bi2O3@Ag的活性评价结果
Claims (6)
1.一种多层TiO2纳米管基光催化剂的制备方法,其特征在于:所述光催化剂是由TiO2纳米管做基底,依次沉积SrTiO3、Ag、Bi2O3、Ag组成,以催化剂的重量为100%计,每层Ag的质量分数0.5%,SrTiO3的质量分数为1%,Bi2O3的质量分数为1%,余量为TiO2纳米管;
制备方法包括以下步骤:
(1)将TiO2纳米管放于马弗炉中煅烧得到处理好的TiO2纳米管;
(2)将TiO2纳米管溶解于乙醇中,磁力搅拌;取Sr(OH)2溶于纯水中,超声使其均匀;再将其滴加到TiO2纳米管溶液中,磁力搅拌;后水热,离心洗涤干燥得到TN@SrTiO3;
(3)将TN@SrTiO3溶于乙醇与水体积比1:1的溶液中,磁力搅拌;取AgNO3溶于乙醇与水体积比1:1的溶液中,超声使其均匀;再将其滴加到TN@SrTiO3溶液中磁力搅拌;后微波水热,离心洗涤干燥得到TN@SrTiO3@Ag;
(4)将TN@SrTiO3@Ag溶于乙醇中,磁力搅拌;取Bi(NO3)3溶于乙二醇和乙醇混合溶液中,超声使其均匀;再将其滴加到TN@SrTiO3@Ag溶液中磁力搅拌;后微波水热,离心洗涤干燥,再煅烧得到TN@SrTiO3@Ag@Bi2O3;
(5)按照步骤(3)中方法在TN@SrTiO3@Ag@Bi2O3上再沉积一层Ag即得到TN@SrTiO3@Ag@Bi2O3@Ag。
2.根据权利要求1所述的制备方法,其特征在于:步骤(1)中所述煅烧过程,是指在350~500 ℃条件下煅烧2~4 h。
3.根据权利要求1所述的制备方法,其特征在于:步骤(2)中所述磁力搅拌时间均为30~60 min,水热条件为180~240 ℃水热18~30 h,洗涤过程是指用0.05~0.2 M 醋酸洗涤几次,再用纯水和无水乙醇洗涤几次;干燥过程是指在60~80 ℃的空气氛围内恒温干燥6~24 h。
4.根据权利要求1所述的制备方法,其特征在于:步骤(3)中所述磁力搅拌时间均为30~60 min,微波水热参数:温度为120~180 ℃,时间为1~3 h,功率为300~500 W;洗涤过程是指用纯水和无水乙醇洗涤几次;干燥过程是指在60~80 ℃的空气氛围内恒温干燥6~24 h。
5.根据权利要求1所述的制备方法,其特征在于:步骤(4)中所述磁力搅拌时间均为30~60 min,微波水热参数:温度为120~180 ℃,时间为1~3 h,功率为300~500 W;洗涤过程是指用纯水和无水乙醇洗涤几次;干燥过程是指在60~80 ℃的空气氛围内恒温干燥6~24 h;煅烧过程是指在马弗炉中400~600 ℃煅烧3~5 h。
6.权利要求1~5任一项所述制备方法所得到的多层TiO2纳米管基光催化剂在作为可见光催化剂中的应用。
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