CN108940207A - Mof-5材料及其制备方法和用途 - Google Patents
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Abstract
本发明涉及一种MOF‑5材料及其制备方法和用途，主要解决现有技术中吸附甲醛材料比表面积小、甲醛去除率较低的问题。本发明通过采用一种MOF‑5材料，该材料还含有纳米二氧化钛，纳米二氧化钛质量占有机骨架结构质量的1～10％，所述MOF‑5材料的孔径为0.60‑0.90nm，比表面为2000‑4000m2/g及其制备方法和用途的技术方案较好地解决了上述问题，可用于吸附分解室内甲醛中。
Description
技术领域
本发明涉及一种MOF-5材料及其制备方法和用途。
背景技术
当今社会，室内空气污染比室外高5～10倍，室内空气污染物多达500多种，已成为多种疾病的诱因。甲醛作为室内主要污染物之一，位居我国有毒化学品优先控制名单第二位，严重威胁人体健康。甲醛有刺激性气味，低浓度即可嗅到，人对甲醛的嗅觉阈通常是0.06～0.07mg/m3。长期、低浓度接触甲醛会引起头痛、头晕、乏力、感觉障碍、免疫力降低，并可出现瞌睡、记忆力减退或神经衰弱、精神抑郁；慢性中毒对呼吸系统的危害也是巨大的，长期接触甲醛可引发呼吸功能障碍和肝中毒性病变，表现为肝细胞损伤、肝辐射能异常等。长期接触甲醛增大了患上霍奇金淋巴瘤、多发性骨髓瘤、骨髓性白血病等特殊癌症的几率。
针对室内甲醛污染具有释放周期长、来源广、危害大等特点，吸附技术已成为净化室内空气的比较常用手段。吸附材料的性能在吸附过程中非常关键，是整个吸附技术的核心。多孔材料是最常使用的脱除甲醛的吸附剂，常见的吸附剂有活性炭、活性炭纤维、分子筛、硅藻土等。目前专利中关于吸附甲醛材料的研究主要集中于对活性炭等材料进行高锰酸钾、硝酸或氢氧化钾改性，改性后的材料虽然提高了其对甲醛的吸附容量，但并不能从根本上彻底消除甲醛。另外，难以确定材料何时达到吸附饱和，影响及时更换材料，室内残留甲醛仍然会危及人体健康。
而金属有机骨架材料(Metal-Organic Frameworks，MOFs)是一种新型的多孔骨架材料，它是由有机配体与金属离子通过自组装过程形成的具有周期性的三维网络骨架的晶体材料。MOFs材料作为一种新型功能性分子材料，与活性炭、沸石材料相比，具有以下优势：比表面积巨大、孔径可调节、微孔结构有序、孔尺寸和骨架结构的多样、孔表面官能团可修饰、具有不饱和的金属配位点等。MOFs材料具有巨大的比表面积和孔容，使得它们在常温常压下对许多有毒气体具有超高的吸附容量，在甲醛吸附方面具有极大的竞争优势；另外，不饱和的金属配位点增强了材料与甲醛之间的相互作用力，使甲醛更牢固的束缚在材料中。二氧化钛(TiO2)纳米材料活性高、热稳定性好、价格便宜，无毒，具有催化分解甲醛的功能，已经被广泛使用在不同材料(包括涂料)中分解甲醛。
因此，开发一种室内吸附并分解甲醛的材料，用于吸附、催化分解室内甲醛是十分有必要的，也是目前现有技术需要解决的问题。
发明内容
本发明所要解决的技术问题之一是现有技术中吸附甲醛材料比表面积小、甲醛去除率较低的问题，提供一种新的MOF-5材料，该材料具有吸附甲醛材料比表面积大、甲醛去除率较高的优点。本发明所要解决的技术问题之二是提供一种与解决的技术问题之一相对应的MOF-5材料的制备方法。本发明所要解决的技术问题之三是提供一种与解决的技术问题之一相对应的MOF-5材料的用途。
为解决上述问题之一，本发明采用的技术方案如下：一种MOF-5材料，该材料还含有纳米二氧化钛，纳米二氧化钛质量占有机骨架结构质量的1～10％，所述MOF-5材料的孔径为0.60-0.90nm，比表面为2000-4000m2/g。
上述技术方案中，优选地，所述MOF-5材料的孔径为0.70-0.85nm，比表面为2500-3100m2/g。
为解决上述问题之二，本发明采用的技术方案如下：一种MOF-5材料料的制备方法，包括如下步骤：(1)将所需比例的金属盐、有机配体添加至反应溶剂中，搅拌均匀；(2)将混合均匀的反应液移至反应容器中，在反应温度60-150℃下，反应2-12h；(3)冷却至室温，将反应体系中母液导出，剩余固体用溶剂洗涤，低沸点溶剂浸泡过夜；(4)溶剂倒出，将固体于真空度0.07～0.1MPa下加热至80-150℃，活化2-48h后烘干即得MOF-5材料；(5)采用超声振动将制备的MOF-5材料与所需量的纳米二氧化钛混合均匀即为负载纳米二氧化钛的MOF-5材料。
上述技术方案中，优选地，步骤(1)中，所述金属盐包括六水合硝酸锌、氯化锌，有机配体包括对苯二甲酸、对苯二甲酸甲酯，金属盐与有机配体摩尔比为1:1～4:1，反应溶剂为N,N-二甲基甲酰胺(DMF)、N,N-二乙基甲酰胺(DEF)。
上述技术方案中，更优选地，所述金属盐为六水合硝酸锌，有机配体为对苯二甲酸；金属盐与有机配体摩尔比为2:1～3:1，反应溶剂为N,N-二甲基甲酰胺(DMF)。
上述技术方案中，优选地，步骤(2)中，反应温度为120-150℃；反应时间为4-8h。
上述技术方案中，优选地，步骤(3)中，洗涤溶剂包括N,N-二甲基甲酰胺(DMF)、N,N-二乙基甲酰胺(DEF)；低沸点溶剂为二氯甲烷、三氯甲烷。
上述技术方案中，更优选地，洗涤溶剂为N,N-二甲基甲酰胺(DMF)，低沸点溶剂为二氯甲烷。
上述技术方案中，优选地，步骤(4)中，将固体于真空度0.08～0.1MPa下加热至120-150℃，活化12-24h后烘干即得MOF-5材料。
为解决上述问题之三，本发明采用的技术方案如下：所述MOF-5材料应用于吸附分解室内甲醛。
目前室内甲醛吸附材料主要有活性炭等，其较小的比表面积(200-1000m2/g)限制了对甲醛的吸附容量；另一方面，活性炭及改性活性炭对甲醛的吸附主要是简单的物理吸附，并不能从根本上消除甲醛。为解决该技术问题，本发明提出一种吸附并分解室内甲醛的材料，该材料是由比表面积巨大(2000-4000m2/g)的金属有机骨架材料MOF-5与具有甲醛催化分解性能的TiO2纳米材料复合而来，制备得到的室内甲醛清除材料具有优异的甲醛吸附和催化分解能力，净化效率高，且无污染。取得了较好的技术效果。
下面通过实施例对本发明作进一步的阐述，但不仅限于本实施例。
具体实施方式
下面将结合具体实施方式，对本发明的技术方案进行详细说明，但如下实施例仅是用以理解本发明，各实施例种物料成分和用量进行的各种改变或改动也属于本发明的保护范围。
实施例1
将锌盐Zn(NO3)2·6H2O(6.0mmol，1.78g)、有机配体对苯二甲酸(2.0mmol，332mg)，加入到盛有20mL N,N-二甲基甲酰胺的反应瓶中，搅拌均匀。将混合均匀的反应液移至厚壁耐压反应瓶中，于120℃下加热反应4h。冷却至室温，将反应体系中母液导出，剩余固体分别用DMF、二氯甲烷洗涤，并用二氯甲烷溶剂浸泡24h。将固体在真空度0.07MPa、120℃温度下，加热干燥12h即得最终产品MOF-5，测得其Langmuir比表面积为3020m2/g，孔径为0.85nm。
将MOF-5材料用于吸附室内甲醛。对本实施例获得的甲醛吸附剂性能进行评价，在干燥器中放入盛有20mL甲醛溶液(37％)的烧杯。室温下挥发8h后，取出烧杯放入含有1g甲醛吸附剂产品的培养皿和盛有10mL去离子水的培养皿。12h后，用乙酰丙酮分光光度计法测定去离子水中甲醛浓度，并计算去除率，经计算本实施例获得的甲醛吸附剂的甲醛去除率为92.3％。
实施例2
将锌盐Zn(NO3)2·6H2O(4.0mmol，1.19g)、有机配体对苯二甲酸(2.0mmol，332mg)，加入到盛有20mL N,N-二甲基甲酰胺的反应瓶中，搅拌均匀。将混合均匀的反应液移至厚壁耐压反应瓶中，于120℃下加热反应6h。冷却至室温，将反应体系中母液导出，剩余固体用DMF洗涤，并用二氯甲烷溶剂浸泡24h。将固体在真空度0.08MPa、150℃温度下，加热干燥12h即得MOF-5产品。采用超声振动将上述制备的金属有机骨架材料与纳米二氧化钛(3wt％)混合均匀即为负载纳米二氧化钛的金属有机骨架材料，测得其Langmuir比表面积为2908m2/g，孔径为0.81nm。
将MOF-5材料用于吸附室内甲醛。对本实施例获得的甲醛吸附剂性能进行评价，在干燥器中放入盛有20mL甲醛溶液(37％)的烧杯。室温下挥发8h后，取出烧杯放入含有1g甲醛吸附剂产品的培养皿和盛有10mL去离子水的培养皿。12h后，用乙酰丙酮分光光度计法测定去离子水中甲醛浓度，并计算去除率，经计算本实施例获得的甲醛吸附剂的甲醛去除率为94.6％。
实施例3
将锌盐Zn(NO3)2·6H2O(6.0mmol，1.78g)、有机配体对苯二甲酸(2.0mmol，332mg)，加入到盛有20mL N,N-二甲基甲酰胺的反应瓶中，搅拌均匀。将混合均匀的反应液移至厚壁耐压反应瓶中，于120℃下加热反应4h。冷却至室温，将反应体系中母液导出，剩余固体用DMF洗涤，并用二氯甲烷溶剂浸泡12h。将固体在真空度0.09MPa、150℃温度下，加热干燥12h即得MOF-5产品。采用超声振动将上述制备的金属有机骨架材料与纳米二氧化钛(6wt％)混合均匀即为负载纳米二氧化钛的金属有机骨架材料，测得其Langmuir比表面积为2776m2/g，孔径为0.79nm。
将MOF-5材料用于吸附室内甲醛。对本实施例获得的甲醛吸附剂性能进行评价，在干燥器中放入盛有20mL甲醛溶液(37％)的烧杯。室温下挥发8h后，取出烧杯后放入含有1g甲醛吸附剂产品的培养皿和盛有10mL去离子水的培养皿。12h后，用乙酰丙酮分光光度计法测定去离子水中甲醛浓度，并计算去除率，经计算本实施例获得的甲醛吸附剂的甲醛去除率为96.8％。
实施例4
将锌盐Zn(NO3)2·6H2O(5.0mmol，1.48g)、有机配体对苯二甲酸(2.0mmol，332mg)，加入到盛有20mL N,N-二乙基甲酰胺的反应瓶中(DEF)，搅拌均匀。将混合均匀的反应液移至厚壁耐压反应瓶中，于150℃下加热反应4h。冷却至室温，将反应体系中母液导出，剩余固体用DMF洗涤，并用二氯甲烷溶剂浸泡12h。将固体在真空度0.1MPa、150℃温度下，加热干燥12h即得MOF-5产品。采用超声振动将上述制备的金属有机骨架材料与纳米二氧化钛(9wt％)混合均匀即为负载纳米二氧化钛的金属有机骨架材料，测得其Langmuir比表面积为2537m2/g，孔径为0.72nm。
将MOF-5材料用于吸附室内甲醛。对本实施例获得的甲醛吸附剂性能进行评价，在干燥器中放入盛有20mL甲醛溶液(37％)的烧杯。室温下挥发8h后，取出烧杯后放入含有1g甲醛吸附剂产品的培养皿和盛有10mL去离子水的培养皿。12h后，用乙酰丙酮分光光度计法测定去离子水中甲醛浓度，并计算去除率，经计算本实施例获得的甲醛吸附剂的甲醛去除率为98.3％。
实施例1-4的结果汇总于表1中。
表1各实施例合成甲醛吸附剂的比表面积和甲醛净化性能
Claims (10)
1.一种MOF-5材料，该材料具有MOF-5有机骨架结构，该材料还含有纳米二氧化钛，纳米二氧化钛质量占有机骨架结构质量的1～10％，所述MOF-5材料的孔径为0.60-0.90nm，比表面为2000-4000m2/g。
2.根据权利要求1所述MOF-5材料，其特征在于所述MOF-5材料的孔径为0.70-0.85nm，比表面为2500-3100m2/g。
3.权利要求1所述MOF-5材料的制备方法，包括如下步骤：(1)将所需比例的金属盐、有机配体添加至反应溶剂中，搅拌均匀；(2)将混合均匀的反应液移至反应容器中，在反应温度60-150℃下，反应2-12h；(3)冷却至室温，将反应体系中母液导出，剩余固体用溶剂洗涤，低沸点溶剂浸泡过夜；(4)溶剂倒出，将固体于真空度0.07～0.1MPa下加热至80-150℃，活化2-48h后烘干即得MOF-5材料；(5)采用超声振动将制备的MOF-5材料与所需量的纳米二氧化钛混合均匀即为负载纳米二氧化钛的MOF-5材料。
4.根据权利要求3所述MOF-5材料的制备方法，其特征在于步骤(1)中，所述金属盐包括六水合硝酸锌、氯化锌，有机配体包括对苯二甲酸、对苯二甲酸甲酯，金属盐与有机配体摩尔比为1:1～4:1，反应溶剂为N,N-二甲基甲酰胺(DMF)、N,N-二乙基甲酰胺(DEF)。
5.根据权利要求4所述吸附分解室内甲醛的材料的制备方法，其特征在于所述金属盐为六水合硝酸锌，有机配体为对苯二甲酸；金属盐与有机配体摩尔比为2:1～3:1，反应溶剂为N,N-二甲基甲酰胺(DMF)。
6.根据权利要求3所述MOF-5材料的制备方法，其特征在于步骤(2)中，反应温度为120-150℃；反应时间为4-8h。
7.根据权利要求3所述MOF-5材料的制备方法，其特征在于步骤(3)中，洗涤溶剂包括N,N-二甲基甲酰胺(DMF)、N,N-二乙基甲酰胺(DEF)；低沸点溶剂为二氯甲烷、三氯甲烷。
8.根据权利要求7所述MOF-5材料的制备方法，其特征在于洗涤溶剂为N,N-二甲基甲酰胺(DMF)，低沸点溶剂为二氯甲烷。
9.根据权利要求3所述MOF-5材料的制备方法，其特征在于步骤(4)中，将固体于真空度0.08～0.1MPa下加热至120-150℃，活化12-24h后烘干即得MOF-5材料。
10.权利要求1所述MOF-5材料，应用于吸附分解室内甲醛。
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