CN113457650A - 一种催化氧化甲醛和长效荧光光催化复合材料及制备方法 - Google Patents
一种催化氧化甲醛和长效荧光光催化复合材料及制备方法 Download PDFInfo
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Abstract
本发明公开了一种催化氧化甲醛和长效荧光光催化复合材料及制备方法,其催化氧化甲醛复合材料的制备:将钛酸四丁酯和卤酸盐加入到水、醇溶液中,搅拌后加入金属离子溶液,加热至沸腾后滴入还原剂,待冷却至室温后经干燥、研磨、烧结,得到卤素掺杂TiO2/纳米金属复合材料;其长效荧光光催化复合材料的制备,即将钛酸四丁酯、长余辉发光材料和卤酸盐加入到水、醇溶液中,搅拌后加入金属离子溶液,加热至沸腾后滴入还原剂,待冷却至室温后经干燥、研磨、烧结,得到长余辉发光粉/卤素掺杂TiO2/纳米金属复合材料;本发明制得的复合材料具有在可见光下提升降解甲醛和灭菌效率及在无光环境下对甲醛有效降解的作用,实现全天候24小时催化净化的应用目标。
Description
技术领域
本发明涉及环境净化领域,具体涉及一种具有催化氧化甲醛和灭菌功能的长效光催化净化复合材料及其制备方法。
背景技术
随着社会与科技水平的不断进步与发展,人们对于更加适宜的生存环境越来越注重。但同时,空气污染、水质污染、细菌等的抗药性提高等问题也日益严重。因此,人们对于自己周围生存环境的净化也更加重视。特别是2020年,在新冠病毒对全世界产生侵害的关键时刻,日常生活中的良性消毒防范措施成为重要的防疫手段。
近年来,为了良好的生活环境,国家尤其重视雾霾、易挥发的有机物质(VOC)、烟气等的排放管理和治理。在各种室内环境治理技术中,光催化氧化技术是一种具有高性价比并且有效的技术,因此推出了众多产品,包括光触媒涂料、光催化净化器等等。现有技术中多采用纳米二氧化钛,其物理化学性质稳定、成本低、无毒等优点,成为光催化氧化技术中主要的光催化剂。但是,二氧化钛带隙较宽,只有在紫外光的照射下才能激发出光生电子-空穴对,且光生电子空穴对易复合,导致净化效率低等问题。CN108355633A提出了一种通过添加前驱体和高温烧结获得二氧化钛掺杂氮的工艺,并提高其可见光催化性能,但是,该技术是在惰性气体条件下烧结而成,氧缺陷低,导致产物光催化性能有限。另外,氮元素掺杂的二氧化钛可以将光吸收移到420-460nm左右,在室内很难实现高效率使用。CN104138764A提出用放电等离子发生装置对二氧化钛实现碳与氟的共掺杂来提高可见光下的催化活性,但是碳本身是吸光物质,不利于净化效率的提高。在实际应用中,除了VOC的去除外,室内空气净化很关键的一部分是杀菌、消毒,菌群和病毒可附着在材料表面,影响材料的净化功能。现有的杀菌消毒多为臭氧、含氯消毒剂等技术,对人体有一定的危害性。
光催化氧化技术对于有机污染物及细菌的降解杀毒作用主要包括光催化剂的光激发、光生载流子的产生及迁移、氧化还原基团的形成和污染物质的分解。在以上步骤中,光催化剂的光激发是必不可少的。但是,在无光源或弱光环境下,光催化反应也会停止,降低了光催化反应效率,限制了光催化氧化技术的应用。
发明内容
本发明的目的在于针对所要解决的技术问题,提供一种在可见光、弱光或无光条件下长效降解各种有机挥发性气体,同时兼具高效杀菌消毒能力的复合材料,所述材料结构、性能稳定,不会产生次级污染。
实现本发明目的的具体技术方案是:
一种催化氧化甲醛的复合材料的制备方法,该方法包括以下具体步骤:
步骤1:将钛酸四丁酯逐滴加入到无水乙醇中,形成溶液A;
步骤2:将含有卤素元素的盐或酸溶解在无水乙醇中,而后加入去离子水,形成溶液B,分别加入体积比为1:10的盐酸(分析纯,含量36~38%)和冰醋酸(优级纯,含量≥99.8%),使溶液的pH=4-7;
步骤3:将溶液B逐滴滴加到溶液A中,静置陈化放置,形成溶液C,溶液C中酯、醇、水的总的摩尔比为0.01~0.06:1:0.1~8.2;取质量分数为1%的金属离子溶液,加入到溶液C中,于100-160℃加热10-30分钟至沸腾后迅速滴加质量分数为1%的还原剂;边搅拌边加热,反应完全后冷却至室温;
步骤4:将反应后的溶液在80-100℃干燥12-24h,经研磨后,在400-500℃烧结1-2h后,得到卤素掺杂TiO2/纳米金属复合材料即所述催化氧化甲醛的复合材料;其中:
所述含有卤素元素的盐或酸为氟化铵或碘酸中的一种;所述金属离子溶液为氯金酸或硝酸银溶液;所述还原剂为柠檬酸三钠或聚乙烯吡咯烷酮(PVP)溶液;所述卤素元素与钛元素质量比为0.05~0.4:1;所述金属离子溶液与钛酸四丁酯的体积比为1:5~7;所述金属离子溶液与还原剂的质量比为1:3~8。
一种上述方法制得的具有催化氧化甲醛的复合材料。
一种长效荧光光催化的复合材料的制备方法,该方法包括以下具体步骤:
步骤1:将含有卤素元素的盐或酸溶解在的去离子水中;
步骤2:在去离子水中加入长余辉荧光材料,逐滴加入钛酸四丁酯,所述酯、水摩尔比为1:8~190;
步骤3:取质量分数为1%的金属离子溶液加入到步骤2溶液中,100-160℃加热10-30分钟至沸腾后迅速滴加质量分数为1%的还原剂;边搅拌边加热,反应完全后冷却至室温;
步骤4:将反应后的溶液在80-100℃干燥12-24h,经研磨后,在400-500℃烧结1-2h后,得到长余辉荧光粉/卤素掺杂TiO2/纳米金属的复合材料,即所述长效荧光光催化的复合材料;其中:
所述含有卤素元素的盐或酸为氟化铵或碘酸中的一种,所述金属离子溶液为氯金酸或硝酸银溶液;所述长余辉荧光材料为Sr4Al14O25:Eu,Dy或SrAl2O4:Eu,Dy;所述还原剂为柠檬酸三钠或聚乙烯吡咯烷酮(PVP)溶液;所述卤素元素与钛元素质量比为0.05~0.4:1;所述长余辉荧光材料与钛酸四丁酯质量比为0.01~0.5:1;所述金属离子溶液与钛酸四丁酯的体积比为1:5~7;所述金属离子溶液与还原剂的质量比为1:3~8。
一种上述方法制得的长效荧光光催化的复合材料,该复合材料中纳米金属质量含量为1-30%,卤素掺杂二氧化钛质量含量为60-90%,长余辉荧光粉含量为10-40%。
本发明提出了一种具有环境净化兼具杀菌消毒能力的二氧化钛体系材料及其制备方法,与现有的技术相比,本发明具有如下技术效果:
1、本发明制备的卤素元素掺杂二氧化钛及其与纳米金属复合材料,性能优异,可以广泛地应用于环境净化等方面;
2、通过卤素元素掺杂二氧化钛与纳米金属复合,大大提高了复合材料在可见光下对有机污染物的降解效率;
3、通过卤素元素掺杂二氧化钛与纳米金属复合,使复合材料在阴暗潮湿的环境中也具有高效的杀菌消毒功能;
4、通过卤素元素掺杂二氧化钛与长余辉荧光粉复合,使复合材料在无光源环境下对有机污染物也具有一定的降解效率。
附图说明
图1是长余辉荧光作用下,TiO2降解净化有机污染物的机理图。
具体实施方式
下面结合附图和具体实施例对本发明进行具体说明,但应当注意的是,不应该简单的把本发明理解为仅局限于以下实施例,以下实施例仅用于说明和解释本发明。
参阅图1,根据Matsuzawa的空穴转移模型,在铝酸盐长余辉荧光材料的基质中引入Eu2+、Dy3+后,会产生局部缺陷能级,当受到可见光直接照射时,发光中心Eu2+被激发,发生4f-5d电子跃迁。电子从基态跃迁到激发态,同时,Eu2+捕获部分电子变为Eu+,空穴从基态产生并释放到基质的价带(VB)中,产生空穴-电子对。随后,部分空穴通过价带(VB)迁移到Dy3 +,Dy3+转化为Dy4+,形成陷阱能级。当光激发停止后,由于热激发,空穴会从陷阱能级Dy4+释放到基质的价带(VB)中,随后转移到激发态,Eu+俘获空穴后,转化为Eu2+,同时电子空穴对复合产生长余辉发光。而一部分空穴没有被Dy4+陷阱能级捕获,转移到了TiO2价带(VB)中,参与之后的光催化反应。同时,在无光源或弱光环境中,长余辉荧光材料产生长余辉发光,其产生的可见光可以被TiO2有效吸收。在可见光的照射下,TiO2会产生光生电子-空穴对,光生电子从价带(VB)跃迁到导带(CB),在价带(VB)留下空穴,有些光生电子-空穴对会转移到催化剂的表面,与环境中的O2和H2O发生氧化还原反应,分别产生·O2 -和·OH基团,之后,这些基团将有机污染物降解为CO2和H2O。
实施例1
F-TiO2/纳米金复合颗粒的制备
首先,将7mL钛酸四丁酯溶于30mL无水乙醇中,磁力搅拌30min,命名为溶液I。然后将0.687g NH4F溶于28mL无水乙醇,然后将3mL蒸馏水,10mL冰醋酸,1ml盐酸加入其中,搅拌混匀命名为溶液II。溶液II缓慢滴加到溶液I中,然后将该混合溶液继续搅拌2h后,静置陈化4h,形成溶液III。将溶液III倒入烧瓶后,加入100mL去离子水,固定在铁架台上后放入油浴缸中,将温度调节至120℃,并打开磁力搅拌器进行搅拌。等烧瓶中的混合溶液沸腾后,用滴管吸取1mL的1%氯金酸溶液滴入,再次沸腾后迅速加入2.5mL 1%柠檬酸三钠溶液,当反应进行10分钟后,结束加热和搅拌,取下烧瓶放入冷水中冷却。最后,将获得的溶液100℃干燥后,置于马弗炉中500℃烧结1h即得到F-TiO2/纳米金复合颗粒。
测试:
(1)测试对有机污染物甲醛的去除;
(2)测试细菌消亡率。
所得数据如表1所示。
实施例2
I-TiO2/纳米银复合颗粒的制备
首先,在50mL去离子水中溶解2.64g HIO3,向其中逐滴加入5mL的钛酸四丁酯,并伴随磁力搅拌2h,然后向烧瓶中加入12mg硝酸银,搅拌至溶解;再向此溶液中加入40mg聚乙烯吡咯烷酮(PVP),磁力搅拌20min。逐滴加入6ml硼氢化钠溶液(20mg/ml),溶液变成亮黄色。搅拌1h后,超声15min,然后将该混合溶液置于100℃条件下干燥。最后,将干燥后的粉末研磨均匀,置于马弗炉中420℃退火处理2h即得到I-TiO2/纳米银复合颗粒。
测试方法同实施例1,实验结果如表1所示。
实施例3
I-TiO2/Sr4Al14O25:Eu,Dy/纳米银复合光催化剂的制备
首先,在50mL去离子水中溶解0.3894g的HIO3,向其中逐滴加入5mL的钛酸四丁酯,同时加入质量占比为70%的Sr4Al14O25:Eu,Dy长余辉荧光粉,并伴随磁力搅拌2h。然后向烧瓶中加入12mg硝酸银,搅拌至溶解;再向此溶液中加入40mg聚乙烯吡咯烷酮(PVP),磁力搅拌20min。然后逐滴加入6ml硼氢化钠溶液(20mg/ml)。搅拌1h后,超声15min,然后将该混合溶液置于80℃条件下干燥。最后,将干燥后的粉末研磨均匀,置于马弗炉中400℃退火处理2h即得到I-TiO2/Sr4Al14O25:Eu,Dy/纳米银复合颗粒。
测试方法同实施例1,实验结果如表2所示。
实施例4
F-TiO2/SrAl2O4:Eu,Dy/纳米金复合颗粒的制备
首先,将7mL钛酸四丁酯溶于30mL无水乙醇中,磁力搅拌30min,命名为溶液I。然后将0.0957g NH4F溶于20mL无水乙醇,接着将6mL蒸馏水,10mL冰醋酸加入其中,搅拌混匀命名为溶液II。溶液II缓慢滴加到溶液I中,同时加入质量占比为10%的SrAl2O4:Eu,Dy长余辉荧光粉,磁力搅拌2h。将上述溶液置于三颈烧瓶中并倒入100mL去离子水,固定在铁架台上后放入油浴缸中,将温度调节至120℃,并打开磁力搅拌器进行搅拌。等烧瓶中的混合溶液沸腾后,用滴管吸取1mL的1%氯金酸溶液,再次沸腾后迅速加入2.5mL 1%柠檬酸三钠溶液,当反应进行10分钟后,结束加热和搅拌,取下烧瓶放入冷水中冷却。最后,置于干燥箱中80℃干燥12h。将干燥后的粉末研磨均匀,置于马弗炉中450℃退火处理1h即得到F-TiO2/SrAl2O4:Eu,Dy/纳米金复合颗粒。
测试方法同实施例1,实验结果如表2所示。
表1
表2
性能指标 | 无光源或弱光环境下有机物去除效果 |
实施例4 | 甲醛去除率≥15%(48h) |
实施例5 | 甲醛去除率≥16%(48h) |
Claims (5)
1.一种催化氧化甲醛的复合材料的制备方法,其特征在于,该方法包括以下具体步骤:
步骤1:将钛酸四丁酯逐滴加入到无水乙醇中,形成溶液A;
步骤2:将含有卤素元素的盐或酸溶解在无水乙醇中,而后加入去离子水,形成溶液B,分别加入体积比为1∶10的盐酸和冰醋酸,使溶液的pH=4-7;所述盐酸为分析纯,含量36~38%;冰醋酸为优级纯,含量≥99.8%;
步骤3:将溶液B逐滴滴加到溶液A中,静置陈化放置,形成溶液C,溶液C中酯、醇、水的总的摩尔比为0.01~0.06:1:0.1~8.2;取质量分数为1%的金属离子溶液,加入到溶液C中,于100-160℃加热10-30分钟至沸腾后迅速滴加质量分数为1%的还原剂;边搅拌边加热,反应完全后冷却至室温;
步骤4:将反应后的溶液在80-100℃干燥12-24h,经研磨后,在400-500℃烧结1-2h后,得到卤素掺杂TiO2/纳米金属复合材料即所述催化氧化甲醛的复合材料;其中:
所述含有卤素元素的盐或酸为氟化铵或碘酸中的一种;所述金属离子溶液为氯金酸或硝酸银溶液;所述还原剂为柠檬酸三钠或聚乙烯吡咯烷酮溶液;所述卤素元素与钛元素质量比为0.05~0.4:1;所述金属离子溶液与钛酸四丁酯的体积比为1:5~7;所述金属离子溶液与还原剂的质量比为1:3~8。
2.一种权利要求1所述方法制得的具有催化氧化甲醛的复合材料。
3.一种长效荧光光催化的复合材料的制备方法,其特征在于,该方法包括以下具体步骤:
步骤1:将含有卤素元素的盐或酸溶解在的去离子水中;
步骤2:在去离子水中加入长余辉荧光材料,逐滴加入钛酸四丁酯,所述酯、水摩尔比为1:8~190;
步骤3:取质量分数为1%的金属离子溶液加入到步骤2溶液中,100-160℃加热10-30分钟至沸腾后迅速滴加质量分数为1%的还原剂;边搅拌边加热,反应完全后冷却至室温;
步骤4:将反应后的溶液在80-100℃干燥12-24h,经研磨后,在400-500℃烧结1-2h后,得到长余辉荧光粉/卤素掺杂TiO2/纳米金属的复合材料,即所述长效荧光光催化的复合材料;其中:
所述含有卤素元素的盐或酸为氟化铵或碘酸中的一种,所述金属离子溶液为氯金酸或硝酸银溶液;所述长余辉荧光材料为Sr4Al14O25:Eu,Dy或SrAl2O4:Eu,Dy;所述还原剂为柠檬酸三钠或聚乙烯吡咯烷酮(PVP)溶液;所述卤素元素与钛元素质量比为0.05~0.4:1;所述长余辉荧光材料与钛酸四丁酯质量比为0.01~0.5:1;所述金属离子溶液与钛酸四丁酯的体积比为1:5~7;所述金属离子溶液与还原剂的质量比为1:3~8。
4.一种权利要求3所述方法制得的长效荧光光催化的复合材料。
5.根据权利要求4所述的长效荧光光催化的复合材料,其特征在于,所述复合材料中纳米金属质量含量为1-30%,卤素掺杂二氧化钛质量含量为60-90%,长余辉荧光粉含量为10-40%。
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