CN106311308A - 隧道沥青路面用氮‑钒共掺杂二氧化钛光催化剂制备方法 - Google Patents
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Abstract
本发明是一种隧道沥青路面用氮‑钒共掺杂二氧化钛光催化剂制备方法,属于隧道沥青路面技术领域,解决目前沥青路面所添加的常规二氧化钛只能吸收紫外光、难以利用可见光、降解效率低、在隧道照明条件下降解尾气效果差的问题。本发明首先采用溶胶‑凝胶法制备氮‑钒共掺杂二氧化钛溶胶,在室温陈化12小时制得凝胶,在125℃干燥2小时;在450℃煅烧2小时,充分研磨后制得纳米氮‑钒共掺杂纳米二氧化钛;最后成型添加氮‑钒共掺杂二氧化钛的沥青混合料车辙板试件,模拟隧道光照下测试其对汽车尾气的实际降解效果,确定氮、钒的最佳掺杂量。本发明制备的氮‑钒共掺杂二氧化钛用于量大面广的隧道沥青路面,对降解隧道内汽车尾气,改善行车环境具有重要现实意义。
Description
技术领域
本发明是一种隧道沥青路面用氮-钒共掺杂二氧化钛光催化剂制备方法,属于隧道沥青路面技术领域。
背景技术
随着中国经济的快速发展,公路隧道建设进入了一个高速发展的时期,特长和长大隧道以及大规模隧道群不断涌现,然而隧道是个相对封闭的空间,车辆行驶时排出的废气、烟尘、有机物等污染物难以排出,导致隧道内的汽车尾气浓度明显高于隧道外,有毒有害物质含量高,导致严重空气污染,危害司乘人员的健康。因此,在整个隧道的使用过程中,通风方案的优劣及通风运营效果的好坏,将直接关系到隧道的工程造价、运营环境、救灾功能及运营效益,特别是许多长大或特长公路隧道的建设和规划,通风已经成为影响和制约长大公路隧道建设的关键。从环境角度讲,通风设备仅仅是向隧道内注入新鲜空气,稀释洞内由汽车排出的废气CO、CO2、NOx、HC和烟雾,使得隧道内的空气质量和烟雾透过率能保证司乘人员的身体健康和行车安全,但是从隧道中排出的污染物仍然会对隧道口周围环境造成严重危害,不能从根本上解决空气污染问题。
在汽车尾气处理方面除了使用清洁能源、改善发动机性能、采用机外净化技术之外,近年来具有光催化分解有害气体效果的纳米二氧化钛也逐渐被应用于隧道工程建设之中,已取得一定成果。但是,由于二氧化钛禁带宽度的限制(3.2eV),使其只能响应紫外光(小于387nm),如果在隧道内安放紫外光灯,隧道内设施长时间接受紫外光的照射会加速老化,同时引起司乘人员的健康问题,因此隧道内多选取紫外线较低的灯具。同时二氧化钛受光激发所产生的光生电子-空穴复合率高,导致光量子效率低,光催化性能不突出。因此,如何提高其对可见光的利用效率,使二氧化钛在隧道照明条件下具有较高的汽车尾气降解效果是现在研究的重点问题,目前研究者采用金属离子掺杂、非金属离子掺杂和金属-非金属离子共掺杂等方式对二氧化钛改性,以期改善其光催化性能。
金属-非金属共掺杂的方法是近年来研究的热点,利用双元素来掺杂改性二氧化钛,其目的是利用共掺杂离子间以不同机制协同作用来提高二氧化钛的光催化活性,由于离子的相互协同作用,不仅提高了光催化活性,也使二氧化钛吸收光谱扩展到可见光区,提高了其在可见光下的光催化能力,使催化效果更加明显。主要表现在:①共掺杂的杂质离子在库伦力的作用下,有团聚成键的作用,有利于提高杂质缺陷的溶解度;②金属和非金属的掺杂可以改变二氧化钛在费米能级附近的电子结构;③共掺杂会使二氧化钛的导带上存在金属离子提供的3p杂质能带和非金属离子提供的2p杂质能带。
沥青路面因其抗滑性能好、行车舒适、噪音小、施工期短、维修养护方便等优点越来越受到重视,为了提高行车舒适性,沥青路面已成为长大隧道主要路面铺装形式之一,这也为采用沥青路面负载氮-钒共掺杂二氧化钛光催化剂降解汽车尾气提供了有利条件。本发明把制备的氮-钒共掺杂二氧化钛光催化剂粉末作为原材料添加到沥青路面中,利用隧道照明条件,提高可见光吸收率,改善二氧化钛光催化效率,从而降解汽车尾气,改善隧道内空气质量。
发明内容
(1)技术问题
本发明目的是提供一种隧道沥青路面用氮-钒共掺杂二氧化钛光催化剂制备方法,解决目前沥青路面所添加的常规二氧化钛只能吸收紫外光、难以利用可见光、降解效率低、在隧道照明条件下降解尾气效果差的问题。
(2)技术方案
鉴于目前沥青路面所添加的常规方法制备的二氧化钛光催化剂带隙宽度大,对可见光能利用率低,反应过程中光生电子-空穴的复合率高,汽车尾气降解效果差等问题。本发明在二氧化钛光催化机理和二氧化钛微观结构的基础上,选取金属钒离子和非金属氮离子共同作为掺杂剂,在隧道特殊环境下,提高二氧化钛光催化剂对汽车尾气的降解效果,提供一种隧道沥青路面用氮-钒共掺杂二氧化钛光催化剂制备方法。本发明技术方案如下:采用溶胶-凝胶法制得氮掺杂二氧化钛溶胶,经陈化制得凝胶,再研磨和煅烧制备纳米氮掺杂二氧化钛光催化剂,然后利用X射线衍射、透射电子显微镜、紫外-可见光漫反射光谱、X射线光电子能谱等表征手段分析氮、钒离子对二氧化钛的微观结构的影响,最后在模拟隧道环境下,对氮-钒掺杂二氧化钛进行汽车尾气的实际降解效果测试,以分别确定氮、钒的最佳掺杂量。
(3)有益效果
随着我国汽车保有量的不断增加,汽车尾气污染已经成为空气污染的主要来源之一,是大气环境质量改善的瓶颈之一。同时,近几年我国公共交通事业迅速发展,大量的长大型隧道相继建成投入使用,公路隧道由于环境相对密封,大量的汽车尾气无法及时排除,特别是在交通繁忙的长大型隧道中,汽车尾气更容易积聚,在影响司乘人员健康的同时还污染了隧道内的设施。传统的隧道内空气净化方式主要为机械通风,这仅仅是稀释污染物,不能达到彻底的环保目的,而且机械通风设备运营费用较高。本发明提供一种隧道沥青路面用氮-钒共掺杂二氧化钛光催化剂制备方法,充分发挥非金属和金属离子共掺杂相互协同作用,利用隧道沥青路面量大面广的优势,提高二氧化钛在可见光下的光催化能力,改善对汽车尾气的降解效果和隧道内行车环境。
具体实施方式
本发明提供一种隧道沥青路面用氮-钒共掺杂二氧化钛光催化剂制备方法,具体实施步骤如下:
(1)按照钛酸丁酯/水/无水乙醇/硝酸的摩尔比为1/30/20/0.1依次称取钛酸丁酯、水、无水乙醇、硝酸放在四个烧杯中;
(2)以三乙胺作为二氧化钛的氮掺杂源,先把一定量的三乙胺与钛酸丁酯、无水乙醇充分混合,再加入水和硝酸,制得溶液A;
(3)以偏钒酸铵作为二氧化钛的钒掺杂源,先把一定量的偏钒酸铵溶解于水中,再加入钛酸丁酯中,充分混合,制得溶液B;
(4)把溶液B逐滴加入溶液A中,充分混合2小时,制得溶胶,在室温陈化12小时制得凝胶,用乙醇清洗三次,在125℃干燥2小时;
(5)在450℃煅烧2小时,采用球磨机以500转/分钟转速研磨6小时,每研磨1小时冷却1小时,再继续研磨,制得纳米氮-钒共掺杂纳米二氧化钛;
(6)成型添加氮-钒共掺杂二氧化钛的沥青混合料车辙板试件,利用光催化剂降解汽车尾气测试装置,模拟隧道照明条件测试氮-钒共掺杂二氧化钛对汽车尾气各成分的实际光催化降解效果,经反复试验确定氮、钒的最佳掺杂量,使氮-钒共掺杂二氧化钛在隧道照明条件下,发挥更好的降解效果。
Claims (1)
1.一种隧道沥青路面用氮-钒共掺杂二氧化钛光催化剂制备方法,其特征在于该方法的具体步骤如下:
(1)按照钛酸丁酯/水/无水乙醇/硝酸的摩尔比为1/30/20/0.1依次称取钛酸丁酯、水、无水乙醇、硝酸放在四个烧杯中;
(2)以三乙胺作为二氧化钛的氮掺杂源,先把一定量的三乙胺与钛酸丁酯、无水乙醇充分混合,再加入水和硝酸,制得溶液A;
(3)以偏钒酸铵作为二氧化钛的钒掺杂源,先把一定量的偏钒酸铵溶解于水中,再加入钛酸丁酯中,充分混合,制得溶液B;
(4)把溶液B逐滴加入溶液A中,充分混合2小时,制得溶胶,在室温陈化12小时制得凝胶,用乙醇清洗三次,在125℃干燥2小时;
(5)在450℃煅烧2小时,采用球磨机以500转/分钟转速研磨6小时,每研磨1小时冷却1小时,再继续研磨,制得纳米氮-钒共掺杂纳米二氧化钛;
(6)成型添加氮-钒共掺杂二氧化钛的沥青混合料车辙板试件,利用光催化剂降解汽车尾气测试装置,模拟隧道照明条件测试氮-钒共掺杂二氧化钛对汽车尾气各成分的实际光催化降解效果,经反复试验确定氮、钒的最佳掺杂量,使氮-钒共掺杂二氧化钛在隧道照明条件下,发挥更好的降解效果。
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