CN108654602A - 室温消除甲醛的高比表面积铂修饰多孔碳基二氧化钛催化剂的制备方法 - Google Patents
室温消除甲醛的高比表面积铂修饰多孔碳基二氧化钛催化剂的制备方法 Download PDFInfo
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Abstract
本发明涉及环保技术领域,具体涉及一种室温消除甲醛的高比表面积铂修饰多孔碳基二氧化钛催化剂的制备方法,包括如下步骤:以钛基金属有机框架化合物为前驱体,先通过高温碳化制备含钛碳基复合材料,经过氯铂酸溶液浸渍后,再与氯化锌混合,最后通过高温活化、水洗、烘干,得到铂修饰多孔碳基二氧化钛催化剂。本发明制备方法简单、实用,还可以通过改变钛基金属有机框架化合物的种类、活化温度对催化剂的性能进行调节,所获得的铂修饰多孔碳基二氧化钛催化剂具有多孔性好、孔的形状可调控、比表面积高、室温氧化分解甲醛性能好等优点,可广泛应用在空调设备、通风管道、空气净化器等设备上。
Description
技术领域
本发明涉及环保技术领域,具体涉及一种室温消除甲醛的高比表面积铂修饰多孔碳基二氧化钛催化剂的制备方法。
背景技术
甲醛是一种常见的室内空气污染物,会刺激人的眼、鼻、喉器官,导致皮疹等严重过敏症状,同时也被认为是一种潜在的致癌物质。根据中华人民共和国国家标准《居室空气中甲醛的卫生标准》规定:居室空气中甲醛的最高容许浓度为0.08mg/m3,但是日常生活中新装住宅平均浓度大于0.2mg/m3。近几年,利用空气净化器处理室内甲醛污染已经成为比较普遍的家用空气净化手段,在其净化空气过程中,主要采用的是物理吸附法、化学吸附法、光催化法和催化氧化法。
物理吸附如活性炭类、硅藻土类材料,吸附量有限,需要经常更换,而且随着温度和湿度的变化,还会形成新的释放;化学吸附能够处理的甲醛量较大,但是多数为含有一定毒性的化合物,会引起新种类的污染。使用光催化剂材料可以实现在光的作用下,利用其分解经过催化剂表面的甲醛分子。目前的光催化剂材料主要是二氧化钛,其优点是二氧化钛廉价无毒,用作催化剂时催化活性高,选择性好,反应条件温和,而且二次污染小,制各工艺简单。但二氧化钛用作催化剂时降解甲醛的光催化效率较低,因为其本身对有机物的吸附能力较差。此外,二氧化钛催化剂一般比表面积大、表面能高,极易发生团聚,在降解甲醛时分散不均匀、失活快,使其应用受到了限制。而且二氧化钛基催化剂要求有较大的紫外光通量,这样限制了二氧化钛基催化剂材料的厚度,限制了其机械体积催化效率。相对来说,催化氧化法,利用空气中的氧气,将甲醛转化为无污染的二氧化碳和水,是一种更清洁,方便的消除甲醛污染的方法。目前,常见的甲醛催化氧化催化剂都需要加热才能实现甲醛的完全转化,在室温下能够实现高浓度甲醛的完全氧化的催化剂较少。室温催化氧化法相对于其它方式具有独特的优势,它能在常温常压下进行,具有甲醛脱除效率高、设备简单、寿命长等优点,是最具应用潜力的甲醛脱除技术。但是,目前采用氯化锌活化法制备室温消除甲醛的高比表面积铂修饰多孔碳基二氧化钛催化剂的研究报道还极为缺乏。
本发明采用具有不同孔道结构和化学特性的金属有机框架化合物前驱体,通过氯化锌活化法来制备室温消除甲醛的铂修饰多孔碳基二氧化钛催化剂,所获得的催化剂具有多孔性好、孔的形状可调控、比表面积高、室温氧化分解甲醛性能好等优点,是一条可行的途径。
发明内容
本发明所要解决的技术问题是针对上述现有技术提供一种多孔性好、孔的形状可调控、比表面积高、室温氧化分解甲醛性能好的铂修饰多孔碳基二氧化钛催化剂的制备方法。
本发明解决上述技术问题所采用的技术方案为:一种室温消除甲醛的高比表面积铂修饰多孔碳基二氧化钛催化剂的制备方法,其特征在于包括以下步骤:a,称取一定量的钛基金属有机框架化合物放入管式炉,在氩气气流下,升温至400℃高温碳化5h,制得含钛碳基复合材料;b,将得到的含钛碳基复合材料加入氯铂酸溶液,于20℃浸渍24h;c,将沉淀取出,真空烘干,再将所得产物和分析纯的氯化锌固体按质量比1∶2混合均匀;d,将所得混合物放入管式炉中,在氩气气流下,升温至一定的温度活化3h;e,将活化后的产物用去离子水洗涤至滤液的pH为6~7,真空烘干后,得到铂修饰多孔碳基二氧化钛催化剂。
作为优选,步骤a所述钛基金属有机框架化合物为ZTOF-1、MIL-125、NH2-MIL-125之一种或几种。
作为优选,步骤d所述混合物的活化温度为750~950℃。
与现有技术相比,本发明的优点在于:制备方法简单、实用,还可以通过改变钛基金属有机框架化合物前驱体的种类、活化温度对催化剂的性能进行调节,所获得的铂修饰多孔碳基二氧化钛催化剂具有多孔性好、孔的形状可调控、比表面积高、室温氧化分解甲醛性能好等优点,本发明可用于环保技术领域,特别是用于室温消除甲醛的高比表面积铂修饰多孔碳基二氧化钛催化剂的制备中。
具体实施方式
以下结合实施例对本发明作进一步详细描述。
实施例1:
称取0.4g的ZTOF-1放入管式炉,在氩气气流下以10℃/min的速率升温至400℃,并保温5h,制得0.19g含钛碳基复合材料。按照铂与含钛碳基复合材料质量比为2%的比例将得到的含钛碳基复合材料加入到浓度为4g/L的氯铂酸溶液中,于20℃浸渍24h后,将沉淀取出,在80℃下真空烘24h,再将所得产物和分析纯的氯化锌固体按质量比1∶2混合均匀,放入管式炉,在氩气气流下以10℃/min的速率升温至950℃,活化2h,将活化后的产物用去离子水洗涤至滤液的pH为6~7,真空烘干后,得到0.16g铂修饰多孔碳基二氧化钛催化剂,其比表面积为3003m2/g,记为1#催化剂。
1#催化剂的室温降解甲醛性能测试过程如下:将含有所制备的1#催化剂0.1g的密封培养皿,置于容积为5L的密闭反应器中,然后注入一定量的浓甲醛溶液,当甲醛挥发至浓度平衡后,打开培养皿的盖子,进行室温甲醛催化降解反应,同时通过仪器在线检测甲醛浓度的变化,经过1h催化降解后,甲醛降解率达到93.9%。
实施例2:
其他同1#催化剂,铂修饰多孔碳基二氧化钛催化剂制备时活化温度为850℃,得到0.17g铂修饰多孔碳基二氧化钛催化剂,其比表面积为3136m2/g,记为2#催化剂,其它与实施例1是类似的。2#催化剂的室温降解甲醛性能测试过程与实施例1也是类似的。经过1h催化降解后,甲醛降解率达到96.8%。
实施例3:
其他同1#催化剂,铂修饰多孔碳基二氧化钛催化剂制备时活化温度为750℃,得到0.21g铂修饰多孔碳基二氧化钛催化剂,其比表面积为2767m2/g,记为3#催化剂,其它与实施例1是类似的。3#催化剂的室温降解甲醛性能测试过程与实施例1也是类似的。经过1h催化降解后,甲醛降解率达到91.1%。
实施例4:
其他同1#催化剂,钛基金属有机框架化合物为MIL-125,得到0.22g铂修饰多孔碳基二氧化钛催化剂,其比表面积为2673m2/g,记为4#催化剂,其它与实施例2是类似的。4#催化剂的室温降解甲醛性能测试过程与实施例1也是类似的。经过1h催化降解后,甲醛降解率达到90.2%。
实施例5:
其他同1#催化剂,钛基金属有机框架化合物为NH2-MIL-125,得到0.23g铂修饰多孔碳基二氧化钛催化剂,其比表面积为2588m2/g,记为5#催化剂,其它与实施例2是类似的。5#催化剂的室温降解甲醛性能测试过程与实施例1也是类似的。经过1h催化降解后,甲醛降解率达到88.7%。
Claims (3)
1.一种室温消除甲醛的高比表面积铂修饰多孔碳基二氧化钛催化剂的制备方法,其特征在于包括以下步骤:a,称取一定量的钛基金属有机框架化合物放入管式炉,在氩气气流下,升温至400℃高温碳化5h,制得含钛碳基复合材料;b,将得到的含钛碳基复合材料加入氯铂酸溶液,于20℃浸渍24h;c,将沉淀取出,真空烘干,再将所得产物和分析纯的氯化锌固体按质量比1∶2混合均匀;d,将所得混合物放入管式炉中,在氩气气流下,升温至一定的温度活化3h;e,将活化后的产物用去离子水洗涤至滤液的pH为6~7,真空烘干后,得到铂修饰多孔碳基二氧化钛催化剂。
2.根据权利要求1所述的制备方法,其特征在于:步骤a的钛基金属有机框架化合物为ZTOF-1、MIL-125、NH2-MIL-125之一种或几种。
3.根据权利要求1所述的制备方法,其特征在于:在步骤d中,混合物的活化温度为750~950℃。
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CN109174088A (zh) * | 2018-10-25 | 2019-01-11 | 浙江工业大学 | 一种用于炔类化合物选择性加氢反应的多相催化剂及其应用 |
CN109873172A (zh) * | 2019-03-07 | 2019-06-11 | 肇庆市华师大光电产业研究院 | 一种甲醇燃料电池催化剂的制备方法 |
CN111686760A (zh) * | 2020-07-01 | 2020-09-22 | 广东能创科技有限公司 | 一种钛基甲烷化催化剂的制备方法 |
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CN109174088A (zh) * | 2018-10-25 | 2019-01-11 | 浙江工业大学 | 一种用于炔类化合物选择性加氢反应的多相催化剂及其应用 |
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CN109873172A (zh) * | 2019-03-07 | 2019-06-11 | 肇庆市华师大光电产业研究院 | 一种甲醇燃料电池催化剂的制备方法 |
CN109873172B (zh) * | 2019-03-07 | 2020-12-11 | 肇庆市华师大光电产业研究院 | 一种甲醇燃料电池催化剂的制备方法 |
CN111686760A (zh) * | 2020-07-01 | 2020-09-22 | 广东能创科技有限公司 | 一种钛基甲烷化催化剂的制备方法 |
CN111686760B (zh) * | 2020-07-01 | 2023-03-21 | 广东能创科技有限公司 | 一种钛基甲烷化催化剂的制备方法 |
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