CN108250808A - 硅藻土负载的氮掺杂二氧化钛/二氧化硅光催化涂料 - Google Patents
硅藻土负载的氮掺杂二氧化钛/二氧化硅光催化涂料 Download PDFInfo
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Abstract
本发明公开了一种硅藻土负载的氮掺杂二氧化钛/二氧化硅光催化涂料,属于化工涂料领域。所述涂料包括以下成分:水、硅藻土负载N‑TiO2/SiO2、硅灰石粉、Ca(OH)2、胶粉、膨润土、分散剂、固化剂和消泡剂。本发明通过制备N‑TiO2/SiO2复合材料并负载于硅藻土中,将TiO2光响应范围由掺杂前的紫外光区扩展到了可见光区,保护了TiO2光催化活性,还改善了纯纳米TiO2易团聚、光生电子‑空穴对易发生再次复合、大比表面积的粒径小而在涂料中易脱落的缺点;而且改善了N‑TiO2/SiO2在涂料中的分散性,抑制了TiO2光催化性能的失活,延长其在涂料中的使用寿命,且提高了负载率,具有很好的应用前景。
Description
技术领域
本发明属于化工涂料领域,具体涉及一种硅藻土负载的氮掺杂二氧化钛/二氧化硅光催化涂料。
背景技术
室内污染是人类在经历煤烟型污染、光化学烟雾污染之后的第三代污染。在我国新装修的房子中,空气质量合格率不足20%,而其主要原因是墙体材料、建筑装饰材料、各种家具地板等有害污染物的严重超标,这些有害物质主要有氡、氨、苯、甲醛和其它挥发性有机物(VOCs) ,而其中又以甲醛含量最多、危害最大。因此近年来,墙体建筑材料产业结构调整的重点方向是鼓励环境友好型、资源节约型材料的生产,特别是空气净化功能建材的发展更是备受关注,其中光催化涂料就是其发展的主流方向之一。
纳米级二氧化钛广泛用作光催化剂,由于其优良的气敏性能和介电性能,能够将这些有害物质分解成CO2和水,并且不会造成二次污染。由于TiO2只在紫外光区有响应,即其光催化活动只在紫外光照射下才能进行,并且纯TiO2的光生电子-空穴对很容易发生再次复合,因此需对纯纳米TiO2进行改性,使其在太阳光和室内光照射下也能进行光催化活动。SiO2因其良好的防粘结性、消光、增稠和补强性等特性使得其在涂料方面常常用作消光剂和增稠剂。将TiO2与SiO2结合,通过SiO2所提供的高浓度环境来提高TiO2 光催化降解有机及无机污染物的速率具有良好的效果,而且SiO2的存在还可改善TiO2 分离性能,抑制了TiO2 失活,提高了使用寿命;抑制TiO2 晶粒生长,提高相转变温度。因此SiO2/TiO2 复合材料具有化学稳定性好、超低热膨胀性和高折射指数等性能而能够应用于光电器件中。
硅藻土是一种由古生物硅藻的尸骸沉积多年而形成的天然矿物材料,一般呈灰色或白色,我国硅藻土资源丰富,储量仅次于美国。硅藻土的硅藻表面有很多微孔结构和丰富且突出的分子筛结构,是优异的催化剂载体材料,且其具有很高的物理吸附性能和优越的离子交换性能,因此硅藻土涂料被称为“会呼吸的涂料”。
发明内容
针对现有二氧化钛光催化涂料难以在可见光照射下进行光催化活动,其光生电子-空穴对很容易发生再次复合且二氧化钛在涂料中易团聚而分散性差,导致其分解室内有害气体效率低的问题,提供一种硅藻土负载N-TiO2/SiO2光催化涂料及其制备方法。该硅藻土涂料能在可见光范围内分解甲醛,分解效率也高,并且二氧化钛在硅藻土涂料中分散性好。
为达到上述目的,本发明是通过以下技术方案实现的:
一种硅藻土负载N-TiO2/SiO2光催化涂料,按重量份数计,其原料组成为:水25~35份,硅藻土负载N-TiO2/SiO2 15~20份,Ca(OH)2 2~2.5份,硅灰石粉7~7.5份,胶粉2~3份,膨润土2~2.5份,固化剂1~1.5份,消泡剂0.8~1份,分散剂1.5~2.5份。
所述固化剂为聚酰胺类固化剂、消泡剂为有机硅类消泡剂、分散剂为羧酸共聚物盐类分散剂。
所述硅藻土负载N-TiO2/SiO2的制备方法具体包括以下步骤:
(1)以异丙醇钛为钛源,正硅酸乙酯为硅源,并加入氮源,采用高温水解法制备N-TiO2/SiO2,备用;
(2)以酸浸法和高温煅烧法对硅藻土进行提纯处理,备用;
(3)LBL法在硅藻土中负载N-TiO2/SiO2:将步骤(2)所得的硅藻土浸渍于步骤(1)所得的胶状N-TiO2/SiO2中1~5min,然后过滤并用蒸馏水冲洗,再浸入40mM植酸水溶液中1~5min,过滤并用蒸馏水冲洗;重复硅藻土浸渍、过滤清洗、浸渍植酸水、过滤清洗这一过程,逐层形成N-TiO2/SiO2植酸盐涂层;再将所得N-TiO2/SiO2植酸盐涂层进行煅烧以除去植酸,制得所述硅藻土负载N-TiO2/SiO2。
进一步的,步骤(1)中采用高温水解法制备N-TiO2/SiO2的具体步骤为:将异丙醇钛溶于一定量的乙二醇中磁力搅拌4h,得溶液A;将十六烷基三甲基溴化铵、硝酸、氮源、正硅酸乙酯溶于乙醇中,磁力搅拌30min得溶液B;将溶液A滴入溶液B中混合均匀后移入带有聚四氟乙烯内衬的不锈钢水热合成反应釜中进行水热反应;冷却至室温后再离心、洗涤。
进一步的,所述乙二醇与异丙醇钛的体积比为6~10;异丙醇钛与正硅酸乙酯的体积比为1~1.2;所述氮源为氨水、尿素中的一种;所述水热反应的工艺参数为:水热温度为130℃~170℃,水热时间为10h。
进一步的,所述步骤(2)的具体步骤为:将硅藻土于2mol·L-1的酸中浸渍12h,离心、洗涤至中性后在550℃下煅烧6小时。
进一步的,酸浸法用的酸为硝酸、硫酸中的一种或两种。
进一步的,步骤(3)中的N-TiO2/SiO2与硅藻土的质量比为0.25~0.35;步骤(3)中所述煅烧的工艺参数为:煅烧温度为400℃,煅烧时间为6h。
一种制备如上所述的硅藻土负载N-TiO2/SiO2光催化涂料方法:将水、硅灰石粉、Ca(OH)2、胶粉、膨润土、分散剂、固化剂、消泡剂混合均匀后,加入硅藻土负载的N-TiO2/SiO2,利用机械搅拌作用混合均匀。
本发明通过对传统配方的改进,将氮掺杂进TiO2并与SiO2复合后负载到硅藻土中。在TiO2中掺杂氮后,不仅获得了更大的比表面积和更细小的晶粒尺寸,还使得其价带和导带之间形成了新的能量级,将TiO2光响应范围由掺杂前的紫外光区扩展到了可见光区。并且与SiO2复合后,不仅起到保护TiO2光催化活性,改善了纯纳米TiO2易团聚、大比表面积的粒径小在涂料中易脱落的缺点。通过LBL层状法负载到硅藻土,进一步改善了N-TiO2/SiO2在涂料中的分散性,抑制了TiO2光催化性能的失活,延长了其在涂料中的使用寿命,并且提高了其负载率,负载工艺也安全简单、价格低廉。
本发明的有益效果在于:
(1)本发明制备的光催化涂料,通过氮掺杂将TiO2光响应范围扩展到可见光区,使得涂料在可见光下光催化除甲醛速度快、清除率高,且降解过程不可逆,过程中不产生二次污染,与SiO2复合负载在硅藻土中不会脱落,在涂料中分散均匀;
(2)本发明不同于一般的物理混合,而是通过与SiO2复合,通过LBL层状法在硅藻土上负载氮掺杂TiO2,不仅能够避免纯TiO2的光生电子-空穴对易发生再次复合,还能避免TiO2在涂料中容易团聚,起到固定TiO2使其不会脱落,并且能够起到保护TiO2光催化活性的效果,抑制TiO2光催化性能失活,使得TiO2的分散性提高、比表面积增大、光催化活性增强,因而降解甲醛效率提高,降解率更加快速持久;
(3)通过降解甲醛进行测试,与掺杂较好的纯纳米二氧化钛涂料相比,十天内对甲醛的最大清除率为60.4%,本光催化涂料在与SiO2复合并且通过LBL法负载至硅藻土上的共同作用下的最大甲醛清除率可达92.5%,大大提高了清除甲醛的效果。
附图说明
图1:降解甲醛效果测试;
图2:硅藻土负载N-TiO2/SiO2(a)、N-TiO2/SiO2 (b)的SEM图;
图3:TiO2、N-TiO2/SiO2 XRD图谱;
图4:N-TiO2/SiO2的N1s XPS图谱。
具体实施方式
以下结合具体实施例对本发明做进一步说明,但本发明不仅仅限于这些实施例。
实施例1
一种硅藻土负载N-TiO2/SiO2光催化涂料,按重量份数计,其原料组成为:水25份,硅藻土负载N-TiO2/SiO2 18份,Ca(OH)2 2.5份,硅灰石粉7.5份,可再分散性胶粉2.5份,膨润土2.5份,分散剂1.5份,固化剂1份,消泡剂0.8份。
所述硅藻土负载N-TiO2/SiO2的制备:
(1)将3ml异丙醇钛溶于21ml乙二醇中磁力搅拌4h,得溶液A;将0.5g十六烷基三甲基溴化铵、0.25g尿素、15ml 5mol/L硝酸溶液、2.5ml正硅酸乙酯溶于乙醇中,磁力搅拌30min得溶液B;将溶液A滴入溶液B中混合均匀后移入带有聚四氟乙烯内衬的不锈钢水热合成反应釜中150℃反应10h;冷却至室温后再离心、乙醇、去离子水分别洗涤至溶液pH为7,备用;
(2)将硅藻土于2mol·L-1的硫酸中浸渍12h,离心、洗涤至溶液pH为7在550℃下煅烧6小时,备用;
(3)LBL法在硅藻土中负载N-TiO2/SiO2:将步骤(2)所得的6g硅藻土浸渍于步骤(1)所得的胶状N-TiO2/SiO2中1分钟,然后过滤并用蒸馏水冲洗,再浸入40mM植酸水溶液中1分钟,过滤并用蒸馏水冲洗;重复硅藻土浸渍、过滤清洗、浸渍植酸水、过滤清洗这一过程,逐层形成N-TiO2/SiO2植酸盐涂层;再将所得N-TiO2/SiO2植酸盐涂层进行在400℃下煅烧6h以除去植酸。
一种制备如上所述的硅藻土负载N-TiO2/SiO2光催化涂料的方法:将水、可再分散性胶粉、硅藻土负载N-TiO2/SiO2、Ca(OH)2、硅灰石粉、膨润土、分散剂、固化剂和消泡剂按比例机械搅拌混合均匀。
实施例2
一种硅藻土负载N-TiO2/SiO2光催化涂料,按重量份数计,其原料组成为:水30份,硅藻土负载N-TiO2/SiO2 16份,Ca(OH)2 2.5份,可再分散性胶粉2.5份,硅灰石粉7.5份,膨润土2.5份,分散剂1份,固化剂1份,消泡剂0.8份。
所述硅藻土负载N-TiO2/SiO2的制备:
(1)将3ml异丙醇钛溶于21ml乙二醇中磁力搅拌4h,得溶液A;将0.5g十六烷基三甲基溴化铵、0.25g尿素、15ml 5mol/L硝酸溶液、2.5ml正硅酸乙酯溶于乙醇中,磁力搅拌30min得溶液B;将溶液A滴入溶液B中混合均匀后移入带有聚四氟乙烯内衬的不锈钢水热合成反应釜中130℃反应10h;冷却至室温后再离心、乙醇、去离子水分别洗涤至溶液pH为7,备用;
(2)将硅藻土于2mol·L-1的硝酸中浸渍12h,离心、洗涤至溶液pH为7在550℃下煅烧6小时,备用;
(3)LBL法在硅藻土中负载N-TiO2/SiO2:将步骤(2)所得的6g硅藻土浸渍于步骤(1)所得的胶状N-TiO2/SiO2中5分钟,然后过滤并用蒸馏水冲洗,再浸入40mM植酸水溶液中5分钟,过滤并用蒸馏水冲洗;重复硅藻土浸渍、过滤清洗、浸渍植酸水、过滤清洗这一过程,逐层形成N-TiO2/SiO2植酸盐涂层;再将所得N-TiO2/SiO2植酸盐涂层进行在400℃下煅烧6h以除去植酸。
一种制备如上所述的硅藻土负载N-TiO2/SiO2光催化涂料的方法:将水、可再分散性胶粉、硅藻土负载N-TiO2/SiO2、Ca(OH)2、硅灰石粉、膨润土、分散剂、固化剂和消泡剂按比例机械搅拌混合均匀。
实施例3
一种硅藻土负载N-TiO2/SiO2光催化涂料,按重量份数计,其原料组成为:水25份,硅藻土负载N-TiO2/SiO2 20份,硅灰石粉7.5份,Ca(OH)2 2.5份,可再分散性胶粉2份,膨润土2.5份,分散剂1.5份,固化剂1份,消泡剂0.8份。
所述硅藻土负载N-TiO2/SiO2的制备:
(1)将3ml异丙醇钛溶于21ml乙二醇中磁力搅拌4h,得溶液A;将0.5g十六烷基三甲基溴化铵、0.8ml氨水、15ml 5mol/L硝酸溶液、3ml正硅酸乙酯溶于乙醇中,磁力搅拌30min得溶液B;将溶液A滴入溶液B中混合均匀后移入带有聚四氟乙烯内衬的不锈钢水热合成反应釜中170℃反应10h;冷却至室温后再离心、乙醇、去离子水分别洗涤至溶液pH为7,备用;
(2)将硅藻土分别于2mol·L-1的硝酸和硫酸中浸渍12h,离心、洗涤至溶液pH为7在550℃下煅烧6小时,备用;
(3)LBL法在硅藻土中负载N-TiO2/SiO2:将步骤(2)所得的6g硅藻土浸渍于步骤(1)所得的胶状N-TiO2/SiO2中3分钟,然后过滤并用蒸馏水冲洗,再浸入40mM植酸水溶液中3分钟,过滤并用蒸馏水冲洗;重复硅藻土浸渍、过滤清洗、浸渍植酸水、过滤清洗这一过程,逐层形成N-TiO2/SiO2植酸盐涂层;再将所得N-TiO2/SiO2植酸盐涂层在400℃下煅烧6h以除去植酸。
一种制备如上所述的硅藻土负载N-TiO2/SiO2光催化涂料的方法:将水、可再分散性胶粉、硅藻土负载N-TiO2/SiO2、Ca(OH)2、硅灰石粉、膨润土、分散剂、固化剂和消泡剂按比例机械搅拌混合均匀。
对比例1
普通纳米二氧化钛硅藻土光催化涂料,按重量份数计,其原料组成为:水25份,硅藻土12.5份,二氧化硅5份,Ca(OH)22.5份,可再分散性胶粉2.5份,硅灰石粉7.5份,膨润土2.5份,分散剂1.5份、固化剂1份、消泡剂0.8份。
将水、硅藻土、二氧化硅、Ca(OH)2、可再分散性胶粉、硅灰石粉、膨润土、分散剂、固化剂和消泡剂按比例混合均匀后,往里加入纳米二氧化钛,然后利用机械搅拌混合均匀便可得普通纳米二氧化钛硅藻土光催化涂料。
性能测试
降解甲醛效果测试
图1为上述实施实例及对比例所得涂料的降解甲醛曲线。所有试样的甲醛降解曲线均为环境模拟实验箱测得,箱体温度均为20℃,湿度均为50%,箱体内光照亮度均为600Lx,箱体体积为1m3,涂覆面积为3m2。每次放入甲醛量为0.5ml,每隔12h采集一次数据。从图1中我们可以清楚地看见对于甲醛的降解情况,240h也就是十天后,实施例1、2、3中的甲醛浓度分别为0.04mg/m3、0.06mg/m3和0.05mg/m3,,甲醛降解率达92.5%、88.7%和90.6%,均已符合人居环境健康要求,与普通纳米二氧化钛硅藻土光催化涂料的降解率60.4%相比,降解速率更大,降解效果也更加显著。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (10)
1.一种硅藻土负载N-TiO2/SiO2光催化涂料,其特征在于:所述光催化涂料的原料组成按重量份数计为:水25~35份,硅藻土负载N-TiO2/SiO2 15~20份,硅灰石粉7~7.5份,Ca(OH)2 2~2.5份,胶粉2~3份,膨润土2~2.5份,分散剂1.5~2.5份,固化剂1~1.5份,消泡剂0.8~1份;所述的硅藻土负载N-TiO2/SiO2的制备方法为:
(1)以异丙醇钛为钛源,正硅酸乙酯为硅源,并加入氮源,采用高温水解法制备N-TiO2/SiO2,备用;
(2)以酸浸法和高温煅烧法对硅藻土进行提纯处理,备用;
(3)LBL法在硅藻土中负载N-TiO2/SiO2:将步骤(2)所得的硅藻土浸渍于步骤(1)得到的N-TiO2/SiO2中1~5min,然后过滤并用蒸馏水冲洗,再浸入40mM植酸水溶液中1~5min,过滤并用蒸馏水冲洗;重复硅藻土浸渍、过滤清洗、浸渍植酸水、过滤清洗这一过程,逐层形成N-TiO2/SiO2植酸盐涂层;再将所得N-TiO2/SiO2植酸盐涂层进行煅烧制得所述硅藻土负载N-TiO2/SiO2。
2.根据权利要求1所述的硅藻土负载N-TiO2/SiO2光催化涂料,其特征在于:步骤(1)中所述的N-TiO2/SiO2的制备方法具体步骤为:将异丙醇钛溶于乙二醇中,磁力搅拌4h,得溶液A;将十六烷基三甲基溴化铵、硝酸、氮源和正硅酸乙酯溶于乙醇中,磁力搅拌30min得溶液B;将溶液A滴入溶液B中混合均匀后进行水热反应,冷却至室温后再离心和洗涤,备用。
3.根据权利要求2所述的硅藻土负载N-TiO2/SiO2光催化涂料,其特征在于:所述异丙醇钛和正硅酸乙酯的体积比为1~1.2。
4.根据权利要求1或2所述的硅藻土负载N-TiO2/SiO2光催化涂料,其特征在于:所述氮源为氨水、尿素中的一种。
5.根据权利要求2所述的硅藻土负载N-TiO2/SiO2光催化涂料,其特征在于:所述水热反应的工艺参数为:水热温度为130℃~170℃,水热时间为10h。
6.根据权利要求1所述的硅藻土负载N-TiO2/SiO2光催化涂料,其特征在于:所述步骤(2)的具体步骤为:将硅藻土于2mol·L-1的酸中浸渍12h,离心、洗涤至中性后在550℃下煅烧6小时。
7.根据权利要求1或6所述的硅藻土负载N-TiO2/SiO2光催化涂料,其特征在于:酸浸法用的酸为硝酸、硫酸中的一种或两种。
8.根据权利要求1所述的硅藻土负载N-TiO2/SiO2光催化涂料,其特征在于:步骤(3)中的N-TiO2/SiO2与硅藻土的质量比为0.25~0.35。
9.根据权利要求1所述的硅藻土负载N-TiO2/SiO2光催化涂料,其特征在于:步骤(3)中所述煅烧的工艺参数为:煅烧温度为400℃,煅烧时间为6h。
10.一种制备如权利要求1-9中任一项所述的硅藻土负载N-TiO2/SiO2光催化涂料的方法,其特征在于:将水、硅灰石粉、Ca(OH)2、胶粉、膨润土、分散剂、固化剂和消泡剂混合均匀后,加入硅藻土负载的N-TiO2/SiO2,利用机械搅拌作用混合均匀。
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