CN105879705A - 一种无支撑固态钛柔性过滤膜的制备方法 - Google Patents
一种无支撑固态钛柔性过滤膜的制备方法 Download PDFInfo
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Abstract
本发明涉及到一种无支撑固态钛柔性过滤膜的制备方法,其特征在于包括如下步骤:(1)钛溶胶的制备:将聚乙烯吡咯烷酮溶解于无水乙醇和乙酸的混合溶液中,搅拌;加入钛酸丁酯,搅拌混合形成溶胶;(2)TiO2纳米颗粒的制备:将上述溶胶进行静电喷涂,收集TiO2粉末;(3)TiO2纳米线的制备;(4)过滤薄的制备:将水热反应的溶液充分过滤水洗至中性,接着酸化后水洗至中性,最后移入乙醇溶液中充分分散后移至一个表面皿内,充分烘干后热处理,得到无支撑固态钛柔性过滤膜。该制备方法简单易操作、水热时间短以及成本低廉,无毒、易回收,还具有优异的光催化活性,负载金属后还具有优良的可见光催化活性,可广泛应用于环境净化等领域。
Description
技术领域
本发明涉及一种无支撑固态钛柔性过滤膜的制备方法,属于光催化技术、空气净化和功能材料领域。
背景技术
室内环境的空气质量对人们的生活和健康十分重要。其中挥发性有机物(VOCs)如乙醛、甲醛、丙酮、苯和甲苯等是室内环境污染主要来源之一。它们会引起机体免疫力水平失调,影响中枢神经功能,还可影响消化系统,严重时可损伤肝脏和造血功能等。因此,消除这些挥发性有机物变得刻不容缓。相比其他环境净化处理技术,异相光催化技术有望可直接利用太阳光来消除污染物,无需消耗额外的能源,是一种绿色的环保技术,引起了科学家极大的兴趣。其中TiO2由于强的氧化还原能力、性能稳定、价格低廉和高的紫外活性,得到人们的广泛关注。然而,TiO2禁带宽度较大(Eg>3.0eV),仅对紫外光有响应,对整个太阳光利用率只有5%。所以怎样有效的利用可见光是TiO2基光催化材料研究的重点。其中掺杂是目前主要的手段之一。
传统TiO2光催化的研究主要以粉末为主,但由于其难以回收利用,重复性较差,且活性难以提高。近年来,随着纳米技术的发展,如纳米棒阵列、纳米管阵列、长纳米纤维、和TiO2纳米晶体薄膜的研究迅速发展。目前,常用的制备薄膜的技术有磁控溅射沉积、化学气相沉积、金属钛阳极氧化、液相沉积以及溶胶凝胶法等。而传统的TiO2薄膜的制备主要是将薄膜生长或沉积到基板上,这种单层二维结构的表面积及厚度有限,严重研制了其光催化性能。因此,如何获得高可见光活性和良好的光催化稳定性的无支撑TiO2薄膜的发展是很有必要的。
发明内容
本发明所要解决的技术问题是针对上述现有技术存在的不足,提供一种无支撑固态钛柔性过滤膜(纳米TiO2过滤薄)的制备方法,所得固态钛柔性过滤膜(纳米TiO2过滤薄)除了解决传统TiO2薄膜必须负载到基片的问题,同时具有高的可见光活性和优良的光催化稳定性。
本发明为解决上述提出的问题所采用的技术方案为:
一种无支撑固态钛柔性过滤膜的制备方法,其特征在于包括如下步骤:
(1)钛溶胶的制备:按聚乙烯吡咯烷酮、无水乙醇、乙酸、钛酸丁酯的用量分别为0.3g、2.5mL、3.8mL和7mL;将无水乙醇和乙酸混合,得到无水乙醇和乙酸的混合溶液;接着将聚乙烯吡咯烷酮(PVP K30)溶解于无水乙醇和乙酸的混合溶液中,搅拌20min,得到混合溶液;最后将钛酸丁酯加入到上述混合溶液中充分搅拌混合形成溶胶;
(2)TiO2纳米颗粒的制备:将上述溶胶进行静电喷涂,待室温下充分干燥后从铝板上刮下并收集TiO2粉末;
(3)TiO2纳米线的制备:将收集的TiO2粉末转移至水热反应釜内,并加入新鲜配置的NaOH溶液,边搅拌边进行水热反应,自然冷却后,收集反应溶液;
(4)过滤薄的制备:将水热反应的溶液充分过滤水洗至中性,接着酸化后水洗至中性,最后移入乙醇溶液中充分分散后移至一个表面皿内,充分烘干后热处理,得到无支撑固态钛柔性过滤膜。
按上述方案,所述步骤(2)中所述静电喷涂,喷涂电压为15kV,喷涂速率为2.5mL/h。
按上述方案,所述步骤(3)中水热反应,使用的NaOH溶液为新鲜配制的,搅拌速率为中速;水热反应的温度为150℃,保温15h。
按上述方案,所述步骤(4)中,热处理温度为400℃,并保温2h。
按上述方案,所述步骤(3)中,TiO2粉末与NaOH溶液的配比为0.2g:30mL。NaOH溶液的浓度为10mol/L。
按上述方案,所述步骤(4)中,将步骤(3)水洗至中性的产物过滤后移至1.0mol/L HCl溶液中进行酸化,且酸化时间为10个小时。
应用(负载金属颗粒):将纸状的TiO2按照热置沉积的方法放置在一定浓度和温度的金属溶液中,一段时间后取出,并用水冲洗数次,热处理后即可将金属负载在纸状的TiO2滤纸上。所述金属溶液分别是氯金酸和氯化铜,并且氯金酸的摩尔浓度为5mM,pH=6;氯化铜的摩尔浓度为1.58mM。溶液的温度分别为70℃和90℃,之后的热处理温度分别为300℃和150℃,保温时间均为2h。
与现有技术相比,本发明的有益效果是:
本发明采用静电喷涂和水热法相结合的方法制备无支撑固态钛柔性过滤膜(纳米TiO2过滤薄),具有高可见光活性和高效的光催化活性的优点,解决了传统TiO2薄膜必须负载到基片,且厚度较薄的缺点;此外,这种无支撑固态钛柔性过滤膜(纳米TiO2过滤薄)还具有优良的光催化稳定性,可回收利用,无污染,且大规模应用于过滤,作为催化剂净化空气和水等功能材料。可应用于空气净化。
附图说明
图1为实施例1、实施例5、实施例6和实施例8制备的TiO2粉末及薄膜的SEM和实物图。((a)静电喷涂制备的TiO2粉末;(b)纯TiO2薄膜实物图;(c)Au5/TiO2薄膜;(b)Cu40/TiO2薄膜;(b)Au5Cu40/TiO2薄膜,其中(a)放大30000倍,(c)放大10000倍,(d)(e)(f)放大50000倍)。
图2为实施例1、实施例4、实施例6和实施例9制备的TiO2粉末及薄膜的X射线衍射图谱。((a)静电喷涂制备的TiO2粉末;(b)纯TiO2薄膜;(c)Au5/TiO2薄膜;(b)Cu40/TiO2薄膜;(b)Au5Cu40/TiO2薄膜)。
图3为实施例1、实施例2、实施例3、实施例4、实施例5、实施例6、实施例7和实施例8制备的TiO2薄膜在可见光照射下降解乙醛(0.9mL)的光催化活性表征图(乙醛的浓度随时间变化曲线图)。
具体实施方式
下面介绍本发明的实施例,以进一步增强对本发明的理解,但本发明绝不局限于实施例。
下述实施例中,基片的清洗方法如下:将FTO玻璃依次用水、无水乙醇、丙酮、水清洗。清洗过程均使用超声机超声清洗20min。最后放入无水乙醇中备用。待用时取出用吹风机吹干即可。
下述实施例中,薄膜的可见光光催化活性检测方法为:将实施例制备的薄膜样品放入密封不漏气的玻璃反应器中,反应器的上底面是透明的石英玻璃视窗,可以透过可见光以及紫外光。在测试之前首先将样品放入反应器内密封,并通入湿度为50%的新鲜空气,10min后停止通气,并将反应器放在光强为200mW/cm2的UV光下照射一晚,之后再通入湿度为50%的新鲜空气10min。光源由大功率的汞灯U-VIX提供并使用420nm截至的长通滤光片,调节光强至100mW/cm2,用来提供可见光光源。反应器的容积为500mL,注入0.9mL乙醛气体,并在暗黑下保持一段时间至反应器内气体浓度达到平衡,用气相色谱仪检测反应器中CO2以及乙醛的浓度变化。
实施例1
一种无支撑固态钛柔性过滤膜的制备方法,包括如下步骤:
(1)钛溶胶的制备:按聚乙烯吡咯烷酮、无水乙醇、乙酸、钛酸丁酯的用量分别为0.3g、2.5mL、3.8mL和7mL;将无水乙醇和乙酸混合,得到无水乙醇和乙酸的混合溶液;接着将聚乙烯吡咯烷酮(PVP K30)溶解于无水乙醇和乙酸的混合溶液中,搅拌20min,得到混合溶液;最后将钛酸丁酯加入到上述混合溶液中充分搅拌混合形成溶胶;
(2)TiO2纳米颗粒的制备:将上述溶胶进行静电喷涂,待室温下充分干燥后从铝板上刮下并收集TiO2粉末,其中实施电压为15kV,喷射速度为2.5mL/min;
(3)TiO2纳米线的制备:将收集的0.2g TiO2粉末转移至容积为50mL的水热反应釜内,并加入30mL 10mol/L NaOH溶液,使用油浴进行边搅拌边水热反应,其中水热反应温度为150℃,反应15h,取出后自然冷却,并收集反应溶液;
(4)纳米TiO2过滤薄(TiO2滤纸)的制备:将水热反应的溶液充分过滤水洗至中性,接着酸化后水洗至中性,最后移入乙醇溶液中充分分散后移至一个表面皿内,充分烘干后热处理,其中热处理温度为400℃,并保温2h,即可得到如纸状的柔性的纳米TiO2过滤薄(或称纸状的TiO2,或称TiO2滤纸,或称无支撑固态钛柔性过滤膜)。
经观察发现,本实施例制备的纳米TiO2过滤薄(纯TiO2薄膜)从图1中可知,样品呈白色,表面存在一些肉眼可见的空洞且表面较为平整。且步骤1制备的TiO2纳米颗粒从图中可知纳米颗粒呈球形,表面较为粗糙,直径约为1μm。
从附图2中可知:实施例1制备的TiO2薄膜具有锐钛矿晶相,但是其衍射峰很弱,主要以NaTi8O13存在。
从附图1中可知:实施例1制备的TiO2薄膜是由许多纳米线相互堆叠在一起形成的,纳米线的表面较为光滑。
从附图3中可知:实施例1制备的薄膜样品纯TiO2在可见光光催化活性检测中,以乙醛为降解对象,测得乙醛的初始浓度为120ppm,在可见光照射5h,乙醛的浓度变化不大,说明实施例1制备的纯TiO2薄膜在可见光下基本不存在活性。
应用实施例1
与实施例1的不同之处在于:步骤(4)之后将纸状的TiO2按照热置沉积的方法放置在摩尔浓度为5mM pH=6温度为70℃的HAuCl4溶液中,30min后取出,300℃热处理2h后即可将金属负载在纸状的TiO2滤纸上。
Au40/TiO2样品呈较为深的紫色,表面存在一些肉眼可见的空洞且表面较为平整。
从附图3中可知:实施例2制备的Au40/TiO2薄膜样品在可见光光催化活性检测中,以乙醛为降解对象,测得乙醛的初始浓度为120ppm,在可见光照射5h,乙醛的浓度有少些降低,说明应用实施例1制备的Au40/TiO2薄膜在可见光下基本存在活性,但是活性较低。
应用实施例2
与实施例1的不同之处在于:将纸状的TiO2放置在摩尔浓度为5mM pH=6温度为70℃的HAuCl4溶液中,10min后取出,300℃热处理2h后即可将金属负载在纸状的TiO2滤纸上。
经观察发现,本实施例制备的Au10/TiO2薄膜样品相比应用实施例1中Au40/TiO2的呈紫色较浅,表面存在一些肉眼可见的空洞且表面较为平整。
从附图3中可知:应用实施例2制备的薄膜样品在可见光光催化活性检测中,以乙醛为降解对象,测得乙醛的初始浓度为120ppm,在可见光照射75min后,乙醛基本完全降解,说明应用实施例2制备的Au10/TiO2薄膜在可见光下基本存在较高的可见光活性。
应用实施例3
与实施例1的不同之处在于:将纸状的TiO2按照热置沉积的方法放置在摩尔浓度为5mMpH=6温度为70℃的HAuCl4溶液中,5min后取出,300℃热处理2h后即可将金属负载在纸状的TiO2滤纸上。
经观察发现,本实施例制备的Au5/TiO2薄膜样品相比应用实施例1中Au10/TiO2的呈紫色较浅,表面存在一些肉眼可见的空洞且表面较为平整。从附图1中可知:纳米线的表面负载大量大小均一的Au纳米颗粒,直径约为10nm。
从附图2中可知:应用实施例3制备的Au40/TiO2薄膜的XRD上能Au的衍射峰较为明显,说明有Au颗粒负载在TiO2薄膜上。
从附图3中可知:应用实施例3制备的Au5/TiO2薄膜样品在可见光光催化活性检测中,以乙醛为降解对象,测得乙醛的初始浓度为120ppm,在可见光照射60min后,乙醛基本完全降解,说明应用实施例3制备的TiO2薄膜在可见光下活性要高于应用实施例2制备的Au10/TiO2。
应用实施例4
与实施例1的不同之处在于:将纸状的Au2/TiO2按照热置沉积的方法放置在摩尔浓度为5mM pH=6温度为70℃的HAuCl4溶液中,2min后取出,300℃热处理2h后即可将金属负载在纸状的TiO2滤纸上。
经观察发现,本实施例制备的Au2/TiO2薄膜样品相比应用实施例3中Au5/TiO2的呈紫色较浅,表面存在一些肉眼可见的空洞且表面较为平整。
从附图3中可知:应用实施例4制备的Au2/TiO2薄膜样品在可见光光催化活性检测中,以乙醛为降解对象,测得乙醛的初始浓度为120ppm,在可见光照射180min后,乙醛基本完全降解,说明应用实施例4制备Au2/TiO2薄膜在可见光下活性要低于应用实施例3制备的Au10/TiO2,但高于应用实施例1制备的Au40/TiO2。
应用实施例5
与实施例1的不同之处在于:将纸状的TiO2按照热置沉积的方法放置在摩尔浓度1.58mM,温度为90℃的CuCl2水溶液中,40min后取出,150℃热处理2h后即可将金属负载在纸状的TiO2滤纸上。
Cu40/TiO2样品,与纯TiO2相比,颜色基本无变化呈白色,表面存在一些肉眼可见的空洞且表面较为平整。
从附图2中可知:应用实施例5制备的Cu40/TiO2薄膜的XRD上没有观察到Cu或者CuOx的衍射峰,说明Cu的量太少。
从附图3中可知:应用实施例5制备的Cu40/TiO2薄膜样品在可见光光催化活性检测中,以乙醛为降解对象,测得乙醛的初始浓度为120ppm,在可见光照射5h后,乙醛降解了78%,说明应用实施例5制备Cu40/TiO2薄膜在可见光下具有活性,但活性略低。
应用实施例6
与应用实施例2的不同之处在于:将纸状的TiO2按照热置沉积的方法放置在摩尔浓度为5mM pH=6温度为70℃的HAuCl4溶液中,10min后取出,300℃热处理2h,之后再讲样品放置在摩尔浓度为1.58mM,温度为90℃的CuCl2水溶液中,40min后取出,150℃热处理2h后取出。
Au10Cu40/TiO2样品呈紫色且偏粉,表面存在一些肉眼可见的空洞且表面较为平整。
从附图3中可知:应用实施例6制备的Au10Cu40/TiO2薄膜样品在可见光光催化活性检测中,以乙醛为降解对象,测得乙醛的初始浓度为120ppm,在可见光照射50min后,乙醛基本完全降解,说明应用实施例6制备Au10Cu40/TiO2薄膜在可见光下具有活性,且强于应用实施例1制备的Au10/TiO2薄膜。
应用实施例7
与应用实施例4的不同之处在于:将纸状的TiO2按照热置沉积的方法放置在摩尔浓度为5mM pH=6温度为70℃的HAuCl4溶液中,5min后取出,300℃热处理2h,之后再讲样品放置在摩尔浓度为1.58mM,温度为90℃的CuCl2水溶液中,40min后取出,150℃热处理2h后取出。
Au5Cu40/TiO2样品呈紫色偏粉且略浅与实施例7制备的Au10Cu40/TiO2薄膜,表面存在一些肉眼可见的空洞且表面较为平整。从附图1中可知:纳米线的表面负载大量大小均一的Au纳米颗粒,直径约为10nm。
从附图2中可知:应用实施例7制备的Au10Cu40/TiO2薄膜的XRD上没有观察到Cu或者CuOx的衍射峰,说明Cu的量太少。
从附图3中可知:应用实施例7制备的Au5Cu40/TiO2薄膜样品在可见光光催化活性检测中,以乙醛为降解对象,测得乙醛的初始浓度为120ppm,在可见光照射45min后,乙醛基本完全降解,说明应用实施例7制备Au5Cu40/TiO2薄膜在可见光下具有活性,且强于实施例8制备的Au10Cu40/TiO2薄膜。
以上所述仅是本发明的优选实施方式,应当指出,对于本领域的普通技术人员来说,在不脱离本发明创造构思的前提下,还可以做出若干改进和变换,这些都属于本发明的保护范围。
Claims (7)
1.一种无支撑固态钛柔性过滤膜的制备方法,其特征在于包括如下步骤:
(1)钛溶胶的制备:按聚乙烯吡咯烷酮、无水乙醇、乙酸、钛酸丁酯的用量分别为0.3 g、2.5 mL、3.8 mL和7 mL;将无水乙醇和乙酸混合,得到无水乙醇和乙酸的混合溶液;接着将聚乙烯吡咯烷酮(PVP K30)溶解于无水乙醇和乙酸的混合溶液中,搅拌20 min,得到混合溶液;最后将钛酸丁酯加入到上述混合溶液中充分搅拌混合形成溶胶;
(2)TiO2纳米颗粒的制备:将上述溶胶进行静电喷涂,待室温下充分干燥后从铝板上刮下并收集TiO2粉末;
(3)TiO2纳米线的制备:将收集的TiO2粉末转移至水热反应釜内,并加入新配置的NaOH溶液,边搅拌边进行水热反应,自然冷却后,收集反应溶液;
(4)过滤薄的制备:将水热反应的溶液充分过滤水洗至中性,接着酸化后水洗至中性,最后移入乙醇溶液中充分分散后移至一个表面皿内,充分烘干后热处理,得到无支撑固态钛柔性过滤膜。
2.根据权利要求1所述的一种无支撑固态钛柔性过滤膜的制备方法,其特征在于,所述步骤(2)中所述静电喷涂,喷涂电压为15 kV ,喷涂速率为2.5 mL/h
。
3.根据权利要求1所述的一种无支撑固态钛柔性过滤膜的制备方法,其特征在于,所述步骤(3)中水热反应的温度为150℃,保温15 h。
4.根据权利要求1所述的一种无支撑固态钛柔性过滤膜的制备方法,其特征在于,所述步骤(4)中,热处理温度为400 ℃,并保温2 h。
5.根据权利要求1所述的一种无支撑固态钛柔性过滤膜的制备方法,其特征在于,所述步骤(3)中NaOH溶液的浓度为10 mol /
L。
6.根据权利要求1所述的一种无支撑固态钛柔性过滤膜的制备方法,其特征在于,所述步骤(3)中,TiO2粉末与NaOH溶液的配比为0.2 g:30 mL。
7.根据权利要求1所述的一种无支撑固态钛柔性过滤膜的制备方法,其特征在于,所述步骤(4)中,使用1.0 mol / L HCl溶液中进行酸化,且酸化时间为10个小时。
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