CN114522741B - 增强去除甲醛效率和寿命的氨基修饰的锰氧化物的制备方法 - Google Patents
增强去除甲醛效率和寿命的氨基修饰的锰氧化物的制备方法 Download PDFInfo
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- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 89
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Abstract
氨基修饰增强锰氧化物去除甲醛效率和寿命的方法,涉及锰氧化物技术领域。首先将MnOx纳米颗粒负载在过滤海绵的表面上,二乙醇胺(DEA)与无水乙醇混合,将负载有MnOx纳米颗粒的过滤海绵浸入溶液,在这个过程中二乙醇胺会与过滤海绵上羟基以氢键的形式结合;最后干燥得到氨基修饰过滤海绵负载锰氧化物催化剂。氨基与中间产物(HCOO‑)反应的性质促进锰氧化物催化甲醛的分解,在除醛的同时还具有杀菌效果。
Description
技术领域
本发明涉及锰氧化物技术领域,尤其涉及增强去除甲醛效率和寿命的氨基修饰的锰氧化物的制备方法。
背景技术
建筑物内的环境空气质量被认为是一个主要的公共卫生问题。在室内空气中可以发现的许多化学物质中,包括干洗溶液、木材固定剂、造纸和纸浆生产,化妆品和纺织工业中的甲醛(HCHO)被认为是毒性最大的挥发性有机化合物(VOC)之一。
长时间暴露在低浓度HCHO即使0.08ppm也可能刺激粘膜,引起鼻炎、气管炎、肺炎等呼吸系统疾病。当暴露在高HCHO浓度下,会引起皮肤和肝脏疾病以及内分泌及免疫系统紊乱,给身体健康带来严重的危害。因此,消除室内HCHO污染,降低公共卫生风险是一项紧迫的任务。
目前可以通过物理吸附、TiO2光催化、等离子体分解、锰氧化物化学催化等方法来去除甲醛。
其中物理吸附主要以多孔活性炭为主,甲醛不会被分解,只是简单的暂时固定在固体多孔材料中,会出现吸附饱和现象,一段时间后还会产生脱附现象,造成二次污染。TiO2光催化降解HCHO只能在有强烈的光照情况下才能实现,不利于室内去除甲醛。等离子体分解会在反应过程中产生有害的副产物。
锰氧化物化学催化法去除甲醛是目前室内去除甲醛方法中最具有潜力的,因为这种方法不需要苛刻的外界条件,且可以利用氧化还原反应分解甲醛,不会像物理吸附那样造成二次污染。而且锰氧化物可以是粉末形态,也可以附载在载体上。
甲醛在锰氧化物催化下完全转化的产物是二氧化碳和水,不完全转化时中间产物多为甲酸盐类(HCOO-)物质,而这些物质会吸附在锰氧化物催化剂的表面,将催化剂包裹减小催化反应的比表面积,进而大幅度降低锰氧化物对甲醛的催化效率,锰氧化物的催化寿命也会明显下降导致催化剂失活。
发明内容
目前解决上述问题的办法是加电,加热,但是这就增加了能耗,缩小了它的使用范围。
本发明用氨基修饰增强锰氧化物去除甲醛效率和寿命的方法,并且还具有抑菌效果,材料制备方法简单,可以被广泛应用到口罩、空气净化器等,适应于大量工业生产。
本发明提供一种氨基修饰增强锰氧化物去除甲醛效率和寿命方法,将利用二乙醇胺中的氨基与中间产物反应的性质,加快中间产物分解促进锰氧化物催化甲醛,提升催化效率,改善催化剂寿命。
一种增强去除甲醛效率和寿命的氨基修饰的锰氧化物的制备方法,其特征在于,包括以下步骤:
(1)首先,用甲醇和超纯水清洗过滤海绵,以去除表面上的残留物;然后在105℃用0.1mol/L的NaOH溶液浸泡,放置至少1.5h形成亲水集团羟基(-OH);将浸泡后的过滤海绵浸入高锰酸钾溶液中,然后添加(NH4)2C2O4溶液,使得高锰酸钾能够反应生成MnOx。
优选每200-600mL(优选500mL)0.05mol/L对应100-150mL(优选120mL)0.3mol/L的(NH4)2C2O4溶液;
反应如下:
将pH调节至7.3后,将混合溶液加热到90℃反应10h;将反应后的产物取出用超纯水洗涤去除残留物,然后干燥,得到负载MnOx纳米颗粒的过滤海绵,MnOx纳米颗粒负载在过滤海绵的表面上。
(2)将二乙醇胺(DEA)与无水乙醇混合,并在室温下搅拌均匀后,将负载有MnOx纳米颗粒的过滤海绵浸入溶液,并在室温下继续搅拌至少6h;在这个过程中二乙醇胺会与过滤海绵上羟基以氢键的形式结合;最后干燥得到氨基修饰过滤海绵负载锰氧化物催化剂。
同时本发明引入氨基后对大肠杆菌有明显的抑菌效果。
本发明的优点:
1.利用二乙醇胺中氨基与中间产物(HCOO-)反应的性质促进锰氧化物催化甲醛的分解。
2.在除醛的同时还具有杀菌效果。
3.材料制备方法简单,且原料低廉,适应于大量工业生产。
4.材料应用较为广泛,可以将其应用到口罩、空气净化器等设备上。
附图说明
图1锰氧化物催化甲醛的机理图
图2锰氧化物催化甲醛失活的机理图
图3过滤海绵负载锰氧化物催化甲醛失活的机理图
图4氨基修饰增强过滤海绵负载锰氧化物去除甲醛机理图
图5过滤海绵负载锰氧化物XRD图
图6氨基修饰过滤海绵负载锰氧化物FTIR图
图7有无氨基修饰的锰氧化物对甲醛催化效率图(左)和有无氨基修饰的锰氧化物的催化寿命(右)图。
图8氨基修饰过滤海绵负载锰氧化物催化甲醛前后对大肠杆菌的抑菌实验图。
具体实施方式
下面结合实施例对本发明做进一步说明,但本发明并不限于以下实施例。
实施例1
1.锰氧化物催化甲醛的机理:
下面解释锰氧化物催化甲醛机理。锰氧化物是一种结构比较复杂的氧化物,其分子式应表示为MnOx,X表示含氧量,数值小于2。由于锰氧化物中氧空位的存在,氧空位留下的电子被邻近金属离子Mn4+捕获形成低价的Mn3+。锰氧化物表面会吸附很多的氧气(O2ads),通常会俘获自由电子成为氧负离子O*(O2-、O2 2-、O-、O2 -等)。甲醛首先会被生成的O*不完全氧化为甲酸盐类(HCOO-)中间产物,接着HCOO-被完全氧化成二氧化碳和水(图1锰氧化物催化甲醛的机理图)。
下面为具体的公式:
Mn4++e→Mn3+
O2(g)→O2(ads)
O2(ads)+Mn3+→O*+Mn4+
HCHO+O*→HCOO-+H+
HCOO-+O*→CO2+H2O
根据锰氧化物催化机理可知,当HCOO-积累较多将锰氧化物覆盖住后,催化剂表面不会产生氧负离子、导致催化效率降低,催化剂稳定变差,催化剂失活(图2锰氧化物催化甲醛失活的机理图)。而本方案主要利用氨基与HCOO-反应,加快中间产物分解使催化剂表面暴露出来。
2.氨基修饰过滤海绵负载锰氧化物催化剂的制备:
(1)首先,用甲醇和超纯水清洗过滤海绵,以去除表面上任何可能的残留物。然后在105℃用0.1mol/L的NaOH溶液浸泡,放置1.5h形成亲水集团羟基(-OH)。将浸泡后的过滤海绵浸入400mL 0.05mol/L高锰酸钾溶液,添加120mL 0.3mol/L(NH4)2C2O4溶液。反应如下:
将pH调节至7.3后,将混合溶液加热到90℃反应10h。将反应后的产物取出用超纯水洗涤3次以去除可能的残留物,然后在105℃下干燥12h将MnOx纳米颗粒沉积在过滤海绵的表面上。
(2)将1ml二乙醇胺(DEA)溶液与30ml无水乙醇混合,并在室温下搅拌30min。溶液混合均匀后,将负载有MnOx纳米颗粒的过滤海绵进入溶液,并在室温下继续搅拌6h。在这个过程中二乙醇胺会与过滤海绵上羟基以氢键的形式结合。最后,在80℃下干燥10h,合成氨基修饰过滤海绵负载锰氧化物催化剂。
3.氨基修饰过滤海绵负载锰氧化物催化剂去除甲醛机理图
当含有甲醛的气体通过催化剂并且反应一段时间后,催化剂被HCOO-覆盖不能产生氧负离子,催化剂失活(图3过滤海绵负载锰氧化物催化剂失活的机理图)。二乙醇胺修饰后氨基可以与覆盖在催化剂表面的HCOO-反应,加快中间产物的分解,使催化剂表面暴露出来促进氧负离子的产生,增强锰氧化物去除甲醛的效率和寿命。并且氨基与HCOO-反应生成的产物为席夫碱(Schiff base),产物具有生理活性有抑菌抗菌作用。下面为具体的公式
RNHx(DEA)+HCOO-→RNCHx(Schiff base)+H2O
4.实际验证以上理论可行
1.已经成功制备氨基修饰过滤海绵负载锰氧化物催化剂,XRD图可以佐证锰氧化物成功制备(如图5)。XRD图谱中2θ为12.5°、25.6°、37.5°和65.6°为锰氧化物的特征衍射。原为红外测试可以佐证氨基修饰成功(如图6),图谱中3271cm-1、2934cm-1和2845cm-1处的特征峰是氨基的特征峰。
2.对于表面有无氨基修饰的锰氧化物进行了静态甲醛催化效率的测试,测试结果表明无氨基修饰的锰氧化物催化甲醛的效率为88.5%。当引入氨基的锰氧化物的催化效率可以达到94.4%(如图7中左图)。在50h催化剂寿命测试中,结果表明无氨基修饰锰氧化物催化剂在10h后催化效率从接近90%降到50%左右。引入氨基后催化效率保持在94%以上(如图7中右图)。很明显引入氨基增强了锰氧化物去除甲醛的效率和寿命。
此外测试了催化剂催化前后对大肠杆菌的抑菌效果,结果表明引入氨基后对大肠杆菌有明显的抑菌效果(如图8)。
Claims (5)
1.一种增强去除甲醛效率和寿命的氨基修饰的锰氧化物的制备方法,其特征在于,包括以下步骤:
(1)首先,用甲醇和超纯水清洗过滤海绵,以去除表面上的残留物;然后在105℃用0.1mol/L的NaOH溶液浸泡,放置至少1.5h形成亲水集团羟基(-OH);将浸泡后的过滤海绵浸入高锰酸钾溶液中,然后添加(NH4)2C2O4溶液,使得高锰酸钾能够反应生成MnOx;
将pH调节至7.3后,将混合溶液加热到90℃反应10h;将反应后的产物取出用超纯水洗涤去除残留物,然后干燥,得到负载MnOx纳米颗粒的过滤海绵,MnOx纳米颗粒负载在过滤海绵的表面上;
(2)将二乙醇胺(DEA)与无水乙醇混合,并在室温下搅拌均匀后,将负载有MnOx纳米颗粒的过滤海绵浸入溶液,并在室温下继续搅拌至少6h;在这个过程中二乙醇胺会与过滤海绵上羟基以氢键的形式结合;最后干燥得到氨基修饰过滤海绵负载锰氧化物催化剂。
2.按照权利要求1所述的方法,其特征在于,步骤(1)每200-600mL、0.05mol/L高锰酸钾对应100-150mL、0.3mol/L的(NH4)2C2O4溶液。
3.按照权利要求1所述的方法,其特征在于,步骤(1)每500mL、0.05mol/L高锰酸钾对应120mL、0.3mol/L的(NH4)2C2O4溶液。
4.按照权利要求1-3任一项所述的方法制备得到的氨基修饰的锰氧化物。
5.按照权利要求1-3任一项所述的方法制备得到的氨基修饰的锰氧化物的应用,应用到口罩、空气净化器设备上去除甲醛,同时抗菌。
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