CN105344342A - 一种基于活性炭的光触媒环境净化材料及其制备方法 - Google Patents
一种基于活性炭的光触媒环境净化材料及其制备方法 Download PDFInfo
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Abstract
本发明属于环境净化材料领域,具体为一种以天然多孔活性炭为载体的光触媒环境净化材料及制备方法。其制备方法包括以原子层淀积技术在活性炭载体上制备特定厚度的光触媒活性材料纳米薄膜(TiO2);然后将包覆有TiO2纳米薄膜的活性炭置于预设好一定加热程序的并有适当气氛的管式炉中热处理,冷却后取出即得到具有高催化活性的活性炭环境净化材料。传统活性炭基环境净化材料单纯依靠高比表面积的活性炭的吸附作用,一旦吸附饱和便失去作用,而本发明制备的环境净化材料可将吸附的有机污染物有效降解以实现循环使用,无吸附饱和。该材料以天然多孔活性炭为载体,无毒无害,机械强度大,耐候性能优异。
Description
技术领域
本发明属于光催化材料技术领域,具体涉及一种基于活性炭的光触媒环境净化材料及其制备方法。
背景技术
伴随室内装修而来的甲醛、苯、氨等挥发性有机物(VOC)已经成为室内环境的主要污染源,成为严重威胁居民身体健康的因素。当前,基于纳米二氧化钛环境净化材料发展前景十分看好。它能有效地将NH3/NOX/SO2以及VOC等有害气体降解为CO2/H2O和相应的无机离子,并具有常温下就能反应,无二次污染的优点。
TiO2(二氧化钛)是一种重要金属氧化物半导体材料,有板钛矿、金红石和锐钛矿三种晶型,其中用于光催化的主要有两种晶型,即锐钛矿型和金红石型。二氧化钛空气净化材料具有化学稳定性好、催化活性强、廉价无毒、耐光腐蚀、对有机污染物选择性小和矿化程度较高等特点,其光催化性能和化学稳定性优于ZnO、WO3和CdS等其他光催化剂。
基于TiO2的环境净化材料目前主要应用于有机污染物的处理和杀菌两大方面。在室内VOC降解方面,TiO2要借助悬浮体系和固定体系两种形式催化降解有机污染物。对于悬浮体系,当前主要是直接将纳米TiO2粉体与有机污染物废液混合,通过机械搅拌或是鼓入环境使粉体分散均匀,提高其光催化效率。这类光催化反应体系结构简单,但纳米TiO2的分离和回收过程复杂,另外,纳米TiO2比普通TiO2价格昂贵得多,且粒径很小,不利于回收,因此这种悬浮体系目前仅用于实验室研究阶段。
所谓固定体系纳米TiO2光催化,是指将有催化活性的纳米TiO2固定在载体上,这是针对悬浮体系中纳米TiO2分离与回收困难而设计的。它是将纳米TiO2催化剂固定于载体上或使用半导体膜的形式,连续处理有机污染物。目前用于负载纳米TiO2催化剂的载体主要有尼龙薄膜、硅胶、玻璃纤维、玻璃或石英砂以及网状纤维等。对于悬浮体系,活性光催化剂主要是借助烧结法、偶联法或是环氧树脂等胶粘剂粘附的方法将TiO2粉末负载到上述具有高比表面积的载体上。
相比于当前负载TiO2光催化剂的主流方法,本发明借助具有超高覆盖性、厚度高度可控的原子层沉积(ALD)技术在天然多孔活性炭材料上负载二氧化钛TiO2光催化剂载体的技术方案优势明显:原子层淀积技术可以以单层原子的超高精度在载体上负载TiO2,可以让少量的TiO2充分发挥其催化作用。此外,本发明所依赖的原子层淀积技术在半导体工业中已经得到广泛应用,现有工业化生产设备就能满足的需要,非常利于廉价、大批量制备。而选取天然多孔活性炭作为载体,除了充分利用其超高的比表面积优势之外,制备的材料还具有相当的耐候性。
发明内容
本发明目的在于提供一种可反复循环使用、耐候性优良的室内环境净化材料及其制备方法。
本发明提供的环境净化材料,是一种以天然多孔活性炭为载体的光触媒环境净化材料。天然多孔活性炭为作为光触媒活性材料二氧化钛的载体,其本身机械性能优异,耐候性良好。作为二氧化钛的载体,其巨大的比表面积大大增强了二氧化钛与有机污染物的接触。而锐钛矿形式的二氧化钛,作为一种n型半导体材料,光催化性能优良。当其受到波长小于或等于387.5nm的光照射后,价带中的电子会获得光子能量而跃迁至导带,形成光电子(e-);而价带中则会形成相应的光生空穴(h+),生成的光电子和光生空穴迁移到二氧化钛颗粒表面的不同位置,共同作用形成一个小型短路光电化学电池;具有强氧化作用的空穴h+则可氧化吸附到二氧化钛表面的有机物质,将其矿化为无机小分子、CO2、H2O等无害物质。
本发明提供的环境净化材料可由下述方法制备得到,其具体制备步骤如下,(其工艺流程见图1):
(1)以天然多孔活性炭为载体(柱状);
(2)采用原子层淀积技术(ALD)在活性炭载体表面包覆光触媒活性材料:
在原子层沉积过程中,以钛源和水(氧源)作为前驱体,控制钛源温度50-150℃,水温度30-60℃,反应温度即基体温度设为120-220℃,在天然多孔活性炭上进行若干个循环的生长,得到包覆在活性炭表面的TiO2纳米薄膜;
(3)借助热退火工艺,改变ALD淀积材料的晶态结构,激活其光催化活性:
将具有TiO2纳米薄膜的活性炭置于氧化铝坩埚中;将氧化铝坩埚放入管式炉中,以0.2-1升/分钟的流速通入气体,以5-20℃/分钟的升温速度升温至200-700℃,灼烧,时间为1-2小时;待自然冷却后取出,即得到具有高催化性能的TiO2纳米薄膜/活性炭环境净化材料。
本发明步骤(1)使用天然多孔活性炭作为载体,其孔容积约为1000-2000m2/g;其单个颗粒(柱)平均直径为1-3mm。
本发明步骤(2)使用的光触媒活性材料为ALD淀积工艺制备的高度均匀的TiO2纳米薄膜,其厚度约为10-100nm。ALD过程的钛源选自:四-二甲氨基钛、四氯化钛或者钛酸四丁酯。
本发明步骤(3)使用管式炉热退火工艺,保护气体为N2或H2的纯气体。热处理后TiO2中锐钛矿和金红石相具备一定的比例,具有很好的光催化降解能力。
附图说明
图1为本发明基于多孔活性炭的光触媒环境净化材料即二氧化钛纳米薄膜/多孔活性炭结构的制备流程示意图。其中,1为天然多孔活性炭;2为原子层淀积系统(ALD)腔体及前驱气体流向示意图;3为ALD包覆二氧化钛的多孔活性炭;4为结构3热处理后得到;5代表管式炉退火工艺;6为活性炭内部微孔;7为ALD技术在活性炭内部微孔上包覆的二氧化钛;8为对样品进行热处理后形成的锐钛矿或金红石结构的二氧化钛。
图2为实例中使用原子层淀积技术包二氧化钛后的多孔活性炭扫描电镜照片。
图3为原始的甲基橙溶液(10mg/L)与加入0.2g纳米二氧化钛薄膜/多孔活性炭样品并使用氙灯照射5小时候的样品颜色对比。
图4为甲基橙溶液在氙灯照射下浓度随光照时间的变化曲线。其中,A线对应加入0.2g普通多孔活性炭后的样品;B线对应加入0.2g使用ALD技术包覆二氧化钛薄层的活性炭(未退火)后的样品;C线对应加入0.2g使用ALD技术包覆二氧化钛薄层并完成热处理后的活性炭的样品。所有样品使用相同的磁力搅拌器、搅拌子和光源,同时容器上遮盖石英玻璃片以控制溶液的蒸发引起浓度的变化。
具体实施方式
以下通过实例进一步对本发明进行描述。
基于天然多孔活性炭的光触媒环境净化材料制备及其表征。
制备:
选取天然活性炭柱状颗粒(φ=1.50mm,l≈2.60mm)置于表面皿中,使用原子层淀积工艺(ALD)包覆二氧化钛,其工艺参数如下:
前驱体1钛源(四-二甲氨基钛)
脉冲时间:400ms
清洗时间:30s
等待时间:2s
前驱体2氧源(水)
脉冲时间:200ms
清洗时间:30s
等待时间:2s
循环次数:200
沉积温度(腔体温度):150℃
为了使沉积的二氧化钛形成具有光催化活性的金红石和锐钛矿结构,需要对材料在氮气氛围下进行管式炉退火处理。其参数为:退火温度500℃,升温时间30min,保温时间60min,氮气流量0.5L/min,冷却时间:自然冷却。
制备后的活性炭形貌如附图2所示。
表征:
为了便于检测有机污染物的浓度,测试样品选择10mg/L的甲基橙溶液,其浓度正好满足朗伯-比尔定律的线性区。即将分解不同阶段的溶液取样放入紫外-可见光谱仪中检测吸收,根据特定波段光吸收的变化可得出甲基橙溶液浓度的变化,进而分析出材料降解能力。
为对比ALD技术修饰活性二氧化钛后的活性碳棒在降解有机物浓度方面的优势,表征实验共设置三组样品如下:
A组采用普通活性碳棒;
B组为包覆二氧化钛(200循环)的活性炭棒;
C组为包覆二氧化钛(200循环)的活性炭棒500℃氮气氛围退火1小时。
其中A、B组为对照组样品。实验时,均取各组样品0.2g置于50mL小烧杯中,各烧杯倒入浓度为10mg/L的甲基橙溶液各15mL;随后每个烧杯放置一个搅拌子,于室温下在磁力搅拌器上低速搅拌。
实验过程采用氙灯光源,为防止溶液蒸发带来的误差,各烧杯口均用可以透紫外光的PE薄膜覆盖;间隔固定时间取样至比色皿,借助光谱仪分析浓度变化。
附图3为A、B、C样品氙灯光照5小时后与初始样品的对比,附图4为氙灯照射过程中不同时间点取样并借助光谱仪分析出的浓度变化。可以看出,基于ALD原子淀积技术制备的活性炭基环境净化材料在吸收降解有机污染物方面相较于单纯的活性炭净化材料优势非常明显,且无明显的吸附饱和现象。
Claims (6)
1.一种基于天然活性炭的光触媒环境净化材料的制备方法,其特征在于具体步骤如下:
(1)以天然多孔活性炭为载体;
(2)采用原子层淀积技术(ALD)在活性炭载体表面包覆光触媒活性材料:
在原子层沉积过程中,以钛源和水作为前驱体,控制钛源温度50-150℃,水温度30-60℃,反应温度即基体温度设为120-220℃,在天然多孔活性炭上进行若干个循环的生长,得到光触媒活性材料层TiO2纳米薄膜;
(3)借助热退火工艺,改变ALD淀积材料的晶态结构,激活其光催化活性:
将具有TiO2纳米薄膜的活性炭置于氧化铝坩埚中;将氧化铝坩埚放入管式炉中,以0.2-1升/分钟的流速通入气体,以5-20℃/分钟的升温速度升温至200-700℃,灼烧,时间为1-2小时;待自然冷却后取出,即得到具有高催化性能的TiO2纳米薄膜/活性炭环境净化材料。
2.根据权利要求1所述的制备方法,其特征在于步骤(1)中,天然多孔活性炭的孔容积为1000-2000m2/g。
3.根据权利要求1所述的制备方法,其特征在于步骤(2)中,所述的钛源选自:四-二甲氨基钛、四氯化钛或者钛酸四丁酯,所述的TiO2纳米薄膜的厚度为10-100nm。
4.根据权利要求1所述的制备方法,其特征在于步骤(3)使用管式炉热退火工艺,保护气体为N2或H2的纯气体。
5.由权利要求1-4之一所述制备方法制备得到的TiO2纳米膜层/多孔活性炭环境净化材料。
6.一种由权利要求1所述制备方法制备得到的基于天然活性炭的光触媒环境净化材料。
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