CN111659323B - 一种复合型气凝胶功能材料及其制备方法和应用 - Google Patents
一种复合型气凝胶功能材料及其制备方法和应用 Download PDFInfo
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Abstract
一种复合型气凝胶功能材料及其制备方法和应用。步骤如下:首先制备硅、钛混合溶胶,并将一定比例的MnO2前驱体溶液通过共凝胶方式掺杂,对醇凝胶进行老化、置换、常温常压干燥、焙烧等后续工艺调整,获得MnOx‑TiO2‑SiO2复合气凝胶催化剂。本发明制备的三维网状气凝胶材料通过共凝胶方式改善MnOx粒子团聚,利于臭氧接触催化氧化。通过254nm紫外光引入,在光激发作用下,促进电子产生和转移,实现臭氧光解、臭氧氧化、光催化协同作用,大大提高臭氧、紫外光利用率和VOCs降解效率,延长催化剂的使用寿命。
Description
技术领域
本发明涉及催化降解VOCs领域,具体涉及一种复合型气凝胶功能材料及其制备方法和应用。
背景技术
工业水平带动了社会经济水平不断提高,人们生活质量也得到改善,但是人们不断地追求过高的GDP,造成了环境的加速恶化,其中包括大气污染、水体污染、土壤污染等。挥发性有机物(VOCs)是工业废气中的主要成分,具有疏水、易挥发等性质,其致畸、致癌、致突变性对人类生存造成极大的威胁,随着我国各项政策的出台,VOCs治理已成为大气污染控制方面的重中之重的工作。紫外耦合臭氧氧化法是一种高级氧化技术,通过有机废气与臭氧、紫外光相互作用,逐步将其分解为小分子物质,并最终分解为CO2和H2O。与其他处理方法相比,此常温催化法具有低耗能、高催化效率等优势,但也存在对光、臭氧利用效率低等缺陷。随着对紫外耦合臭氧氧化法研究的不断深入,锰、钴等非贵金属催化剂在此反应体系中展现出了优异的性能,不仅表现出了一定的吸附性,而且大大提高了对光、臭氧的利用效率,因此对催化剂的研究已成为紫外耦合臭氧降解有机废气的主要热点。
目前研究的催化剂针对处理大风量低浓度有机废气,仍存在吸附性较差、对光和臭氧利用效率较低、催化剂寿命短等问题。
发明内容
解决的技术问题:本发明为了提高催化体系对臭氧的利用效率,增强催化剂的光响应和催化活性以及对VOCs的吸附性等问题。提供一种复合型气凝胶功能材料及其制备方法和应用,首先选择254 nm紫外灯作为光源,充分利用其光解臭氧的能力。与此同时,选择TiO2-SiO2复合气凝胶作为支撑体,充分发挥其高孔隙率、大比表面积、强导电性以及其良好的表面酸性等优势,增强了对底物和臭氧的吸附性能和光催化性能。以共凝胶方式掺杂MnOx,则可以使活性组分更好的分散于支撑体表面,保持对臭氧良好利用率的同时,增强了对光响应性能,通过产生更多的活性物质,达到对有机物充分降解的效果。
技术方案:一种复合型气凝胶功能材料的制备方法,制备步骤为:(1)配制正硅酸四乙酯、无水乙醇、去离子水和HCl的混合溶液,其中摩尔比n(TEOs): n(EtOH): n(H2O): n(HCl)=1:(4~6):(4~6):2.4×10-3,并将其置于55 ℃搅拌水解2~4 h,获得SiO2溶胶,记为溶胶A;(2)将钛酸四丁酯溶解于无水乙醇中,并向其滴加冰醋酸,经快速搅拌后得到溶液B,溶液B中钛酸四丁酯、无水乙醇和冰醋酸的摩尔配比为1:(10~15):(1~1.5);配制无水乙醇、冰醋酸和去离子水混合溶液C,三者摩尔配比为(1~3):(0~0.3):1;将溶液C滴加到溶液B中,制得TiO2溶胶,记为溶胶D,其中溶液C与溶液B质量比1:(1~2);(3)根据硅钛摩尔比1:(1~5),将溶胶A加入溶胶D中,搅拌下得到SiO2-TiO2复合溶胶,随后按照1 wt.%~15wt.% MnOx负载量向复合溶胶中滴加预先配制的10 wt.%乙酸锰水溶液,并在搅拌状态下,加入与复合溶胶体积比为1:(80~120)的甲酰胺试剂,之后将置于35 ℃水浴锅中得醇凝胶;(4)向得到的醇凝胶中加入正硅酸四乙酯:无水乙醇体积比为1:(3~5)的混合溶液,使凝胶完全浸入,并置于50 ℃水浴锅中,老化12 h,倾倒上清液,再于40 ℃下,用正己烷对其进行至少3次置换;(5)将去上清液的凝胶放置于鼓风干燥箱中,进行梯度烘干;最后通过马弗炉焙烧后,即得MnOx-TiO2-SiO2复合气凝胶。
优选的,上述步骤(1)所述溶胶A中TEOs、EtOH、H2O和HCl的摩尔配比为1:4.95:4.95:2.4×10-3,所述搅拌下水解时间为3 h。
优选的,上述步骤(2)所述溶液B中钛酸四丁酯、无水乙醇和冰醋酸的摩尔配比为1:13.6:1.1,所述溶液C中无水乙醇、冰醋酸和去离子水的摩尔配比为1.7:0.1:1,所述溶液C与溶液B的质量比1:1.72。
优选的,上述步骤(3)所述硅钛摩尔比为1:3,所述MnOx的负载量为5 wt.%,所述复合溶胶与甲酰胺的体积比1:110。
优选的,上述步骤(4)所述正硅酸四乙酯、无水乙醇混合溶液的体积比为1:4,所述正己烷置换次数不少于3次,置换时间不少于3 h。
优选的,上述步骤(5)所述梯度烘干温度分别为60 ℃、80 ℃、100 ℃、120 ℃、150℃,每个温度点保温2 h,所述焙烧温度为550 ℃,5 h。
上述制备方法制得的复合型气凝胶功能材料。
上述复合型气凝胶功能材料在VOCs处理中的应用。
有益效果:1、本发明以254 nm紫外灯作为光源,有利于更多的光能应用于臭氧的光解,增加臭氧的利用效率,同时紫外光波可作用于底物和催化剂,并引起光催化效应。2、本发明以TiO2-SiO2复合气凝胶作为支撑体,可充分发挥气凝胶所共有的高吸附、强导电等性能,而且其表面酸性有利于对VOCs和臭氧的吸附与分解。与此同时,TiO2-SiO2复合气凝胶作为一种光催化材料,促进臭氧光解与光催化效应协同发生。3、本发明通过共凝胶方式掺杂活性组分,减少MnOx粒子团聚现象,增加了臭氧的接触范围,提高臭氧利用率。4、本发明的制备过程易控制,而且可通过凝胶条件改变催化剂形状,在保持对VOCs良好的降解效果的同时,增加催化材料的兼容性。
附图说明
图1为实施例1、2、3制备的复合气凝胶功能材料在紫外耦合臭氧氧化体系对甲苯的去除率示意图;
图2为实施例2、4、5制备的复合气凝胶功能材料在紫外耦合臭氧氧化体系对甲苯的去除率示意图;
图3为两种反应体系O3催化、紫外耦合O3氧化对甲苯去除效率示意图,其中催化剂为实施例2所制备。
具体实施方式
以下通过结合具体实施例进一步对本发明进行详述,但本发明并不限于此。
实施例1
(1)分别称取6.62 g无水乙醇、6.03 g正硅酸四乙酯、2.58 g去离子水,按照先后顺序加入烧杯搅拌,搅拌均匀后加入0.7 mL HCl溶液(0.1 mol/L),将烧杯置于55 ℃下,搅拌水解3 h,获得SiO2溶胶记为溶胶A;
(2)将9.86 g钛酸四丁酯溶解于18.15 g无水乙醇中,并向混合溶液中滴加2 g冰醋酸,经搅拌后得到溶液B,与此同时,称取13.41 g无水乙醇、1 g冰醋酸、3.06 g去离子水配制溶液C,随后将C溶液滴加到B溶液中,制备TiO2溶胶,记为溶胶D;
(3)将溶胶A加入溶胶D中,搅拌下,得到SiO2-TiO2复合溶胶,按照5 wt.% MnOx最优负载量,称取4.3 g 10 wt.%乙酸锰水溶液滴加于复合溶胶,最后加入670 μL甲酰胺搅拌均匀后,将烧杯置于35 ℃水浴锅中待凝胶;
(4)凝胶后,向其加入5 mL正硅酸四乙酯、20 mL无水乙醇混合溶液,并将烧杯放置于50 ℃水浴12 h,老化结束后,于40 ℃下,用正己烷对凝胶置换3次,每次3 h;
(5)对置换结束后的凝胶,分别置于60 ℃、80 ℃、100 ℃、120 ℃、150 ℃进行梯度烘干,每个温度点保温2 h,将干燥后的样品,在550 ℃下焙烧5 h后,得到复合功能型气凝胶:MnOx-TiO2-SiO2。
实施例2
(1)分别称取6.62 g无水乙醇、6.03 g正硅酸四乙酯、2.58 g去离子水,按照先后顺序加入烧杯搅拌,搅拌均匀后加入0.7 mL HCl溶液(0.1 mol/L),将烧杯置于55 ℃下,搅拌水解3 h,获得SiO2溶胶记为溶胶A;
(2)将9.86 g钛酸四丁酯溶解于18.15 g无水乙醇中,并向混合溶液中滴加2 g冰醋酸,经搅拌后得到溶液B,与此同时,称取13.41 g无水乙醇、1 g冰醋酸、3.06 g去离子水配制溶液C,随后将C溶液滴加到B溶液中,制备TiO2溶胶,记为溶胶D;
(3)取1/3溶胶A加入溶胶D中,搅拌下,得到SiO2-TiO2复合溶胶,按照5 wt.% MnOx最优负载量,称取3.1 g 10 wt.%乙酸锰水溶液滴加于复合溶胶,最后加入560 μL甲酰胺搅拌均匀后,将烧杯置于35 ℃水浴锅中待凝胶;
(4)凝胶后,向其加入5 mL正硅酸四乙酯、20 mL无水乙醇混合溶液,并将烧杯放置于50 ℃水浴12 h,老化结束后,于40 ℃下,用正己烷对凝胶置换3次,每次3 h;
(5)对置换结束后的凝胶,分别置于60 ℃、80 ℃、100 ℃、120 ℃、150 ℃进行梯度烘干,每个温度点保温2 h,将干燥后的样品,在550 ℃下焙烧5 h后,得到复合功能型气凝胶:MnOx-TiO2-SiO2。
实施例3
(1)分别称取6.62 g无水乙醇、6.03 g正硅酸四乙酯、2.58 g去离子水,按照先后顺序加入烧杯搅拌,搅拌均匀后加入0.7 mL HCl溶液(0.1 mol/L),将烧杯置于55 ℃下,搅拌水解3 h,获得SiO2溶胶记为溶胶A;
(2)将9.86 g钛酸四丁酯溶解于18.15 g无水乙醇中,并向混合溶液中滴加2 g冰醋酸,经搅拌后得到溶液B,与此同时,称取13.41 g无水乙醇、1 g冰醋酸、3.06 g去离子水配制溶液C,随后将C溶液滴加到B溶液中,制备TiO2溶胶,记为溶胶D;
(3)取1/5溶胶A加入溶胶D中,搅拌下,得到SiO2-TiO2复合溶胶,按照5 wt.% MnOx最优负载量,称取2.8 g 10 wt.%乙酸锰水溶液滴加于复合溶胶,最后加入560 μL甲酰胺搅拌均匀后,将烧杯置于35 ℃水浴锅中待凝胶;
(4)凝胶后,向其加入5 mL正硅酸四乙酯、20 mL无水乙醇混合溶液,并将烧杯放置于50 ℃水浴12 h,老化结束后,于40 ℃下,用正己烷对凝胶置换3次,每次3 h;
(5)对置换结束后的凝胶,分别置于60 ℃、80 ℃、100 ℃、120 ℃、150 ℃进行梯度烘干,每个温度点保温2 h,将干燥后的样品,在550 ℃下焙烧5 h后,得到复合功能型气凝胶:MnOx-TiO2-SiO2。
实施例4
(1)分别称取6.62 g无水乙醇、6.03 g正硅酸四乙酯、2.58 g去离子水,按照先后顺序加入烧杯搅拌,搅拌均匀后加入0.7 mL HCl溶液(0.1 mol/L),将烧杯置于55 ℃下,搅拌水解3 h,获得SiO2溶胶记为溶胶A;
(2)将9.86 g钛酸四丁酯溶解于18.15 g无水乙醇中,并向混合溶液中滴加2 g冰醋酸,经搅拌后得到溶液B,与此同时,称取13.41 g无水乙醇、1 g冰醋酸、3.06 g去离子水配制溶液C,随后将C溶液滴加到B溶液中,制备TiO2溶胶,记为溶胶D;
(3)取1/3溶胶A加入溶胶D中,搅拌下,得到SiO2-TiO2复合溶胶,按照1 wt.% MnOx最优负载量,称取0.6 g 10 wt.%乙酸锰水溶液滴加于复合溶胶,最后加入560 μL甲酰胺搅拌均匀后,将烧杯置于35 ℃水浴锅中待凝胶;
(4)凝胶后,向其加入5 mL正硅酸四乙酯、20 mL无水乙醇混合溶液,并将烧杯放置于50 ℃水浴12 h,老化结束后,于40 ℃下,用正己烷对凝胶置换3次,每次3 h;
(5)对置换结束后的凝胶,分别置于60 ℃、80 ℃、100 ℃、120 ℃、150 ℃进行梯度烘干,每个温度点保温2 h,将干燥后的样品,在550 ℃下焙烧5 h后,得到复合功能型气凝胶:MnOx-TiO2-SiO2。
实施例5
(1)分别称取6.62 g无水乙醇、6.03 g正硅酸四乙酯、2.58 g去离子水,按照先后顺序加入烧杯搅拌,搅拌均匀后加入0.7 mL HCl溶液(0.1 mol/L),将烧杯置于55 ℃下,搅拌水解3 h,获得SiO2溶胶记为溶胶A;
(2)将9.86 g钛酸四丁酯溶解于18.15 g无水乙醇中,并向混合溶液中滴加2 g冰醋酸,经搅拌后得到溶液B,与此同时,称取13.41 g无水乙醇、1 g冰醋酸、3.06 g去离子水配制溶液C,随后将C溶液滴加到B溶液中,制备TiO2溶胶,记为溶胶D;
(3)取1/3溶胶A加入溶胶D中,搅拌下,得到SiO2-TiO2复合溶胶,按照10 wt.% MnOx最优负载量,称取6.2 g 10 wt.%乙酸锰水溶液滴加于复合溶胶,最后加入560 μL甲酰胺搅拌均匀后,将烧杯置于35 ℃水浴锅中待凝胶;
(4)凝胶后,向其加入5 mL正硅酸四乙酯、20 mL无水乙醇混合溶液,并将烧杯放置于50 ℃水浴12 h,老化结束后,于40 ℃下,用正己烷对凝胶置换3次,每次3 h;
(5)对置换结束后的凝胶,分别置于60 ℃、80 ℃、100 ℃、120 ℃、150 ℃进行梯度烘干,每个温度点保温2 h,将干燥后的样品,在550 ℃下焙烧5 h后,得到复合功能型气凝胶:MnOx-TiO2-SiO2。
性能测试:以上所有实施例制备的复合型气凝胶作为测试对象
所有实施例制备的复合型气凝胶MnOx-TiO2-SiO2于紫外辅助臭氧催化体系催化降解甲苯,利用固定床反应器,构建紫外耦合臭氧氧化VOCs测试***,其中内置紫外灯为25 W(波长为254 nm);并以甲苯作为探究对象,向反应器中通入流速为1500 mL/min的120 ppm甲苯气体,向反应体系加入2 g催化剂,通过气相色谱(FID检测器)进行检测分析,计算甲苯的去除率。通过附图1、2可以得出,活性组分与钛硅比过多或过少均会对整体催化剂活性产生重要影响。从附图3可以看出,254 nm紫外光的引入,可有效提高臭氧的利用效率,产生更多的活性物质应用于底物降解,延长了催化剂的使用寿命。
通过O3催化、紫外耦合O3氧化两种反应体系对实施例2制备的复合型气凝胶进行测试,得到数据如附图3所示。
以上实施例的只是用于分析理解本发明的制备方法及应用范围,但本发明不限于以上实例。如果本领域的普通技术人员受其启示,对本发明直接进行改变、替代、修饰等,均应属于本专利的保护范围。
Claims (8)
1.一种复合型气凝胶功能材料的制备方法,其特征在于制备步骤为:(1)配制正硅酸四乙酯、无水乙醇、去离子水和HCl的混合溶液,其中摩尔比n(TEOS ): n(EtOH): n(H2O): n(HCl)=1:(4~6):(4~6):2.4×10-3,并将其置于55 ℃搅拌水解2~4 h,获得SiO2溶胶,记为溶胶A;(2)将钛酸四丁酯溶解于无水乙醇中,并向其滴加冰醋酸,经快速搅拌后得到溶液B,溶液B中钛酸四丁酯、无水乙醇和冰醋酸的摩尔配比为1:(10~15):(1~1.5);配制无水乙醇、冰醋酸和去离子水混合溶液C,三者摩尔配比为(1~3):(0~0.3):1;将溶液C滴加到溶液B中,制得TiO2溶胶,记为溶胶D,其中溶液C与溶液B质量比1:(1~2);(3)根据硅钛摩尔比1:(1~5),将溶胶A加入溶胶D中,搅拌下得到SiO2-TiO2复合溶胶,随后按照1 wt.%~15wt.% MnOx负载量向复合溶胶中滴加预先配制的10 wt.%乙酸锰水溶液,并在搅拌状态下,加入与复合溶胶体积比为1:(80~120)的甲酰胺试剂,之后将置于35 ℃水浴锅中得醇凝胶;(4)向得到的醇凝胶中加入正硅酸四乙酯:无水乙醇体积比为1:(3~5)的混合溶液,使凝胶完全浸入,并置于50 ℃水浴锅中,老化12 h,倾倒上清液,再于40 ℃下,用正己烷对其进行至少3次置换;(5)将去上清液的凝胶放置于鼓风干燥箱中,进行梯度烘干;最后通过马弗炉焙烧后,即得MnOx-TiO2-SiO2复合气凝胶。
2.根据权利要求1所述复合型气凝胶功能材料的制备方法,其特征在于:步骤(1)所述溶胶A中TEOS 、EtOH、H2O和HCl的摩尔配比为1:4.95:4.95:2.4×10-3,所述搅拌水解时间为3 h。
3.根据权利要求1所述复合型气凝胶功能材料的制备方法,其特征在于:步骤(2)所述溶液B中钛酸四丁酯、无水乙醇和冰醋酸的摩尔配比为1:13.6:1.1,所述溶液C中无水乙醇、冰醋酸和去离子水的摩尔配比为1.7:0.1:1,所述溶液C与溶液B的质量比1:1.72。
4.根据权利要求1所述复合型气凝胶功能材料的制备方法,其特征在于:步骤(3)所述硅钛摩尔比为1:3,所述MnOx的负载量为5 wt.%,所述复合溶胶与甲酰胺的体积比1:110。
5.根据权利要求1所述复合型气凝胶功能材料的制备方法,其特征在于:步骤(4)所述正硅酸四乙酯、无水乙醇混合溶液的体积比为1:4,所述正己烷置换次数不少于3次,置换时间不少于3 h。
6.根据权利要求1所述复合型气凝胶功能材料的制备方法,其特征在于:步骤(5)所述梯度烘干温度分别为60 ℃、80 ℃、100 ℃、120 ℃、150 ℃,每个温度点保温2 h,所述焙烧温度为550 ℃,焙烧时间为5 h。
7.权利要求1~6任一所述制备方法制得的复合型气凝胶功能材料。
8.权利要求7所述复合型气凝胶功能材料在VOCs处理中的应用。
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