CN105693750B - 一种环保金属有机骨架材料的快速制备 - Google Patents
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Abstract
一种环保金属有机骨架材料的快速制备，将氨基酸溶解于含有氢氧化钠的去离子水中，加入体积分数为3‑10％的乙胺衍生物为催化剂，搅拌作用下，缓慢滴加0.5mol/L的金属盐溶液，滴加完成后继续反应1‑5h。所得混合物经过滤、水洗、醇洗数次后，于80℃干燥至少24h，得到金属有机骨架材料。所合成的金属有机骨架材料比表面积大，孔隙率高；室温操作，节约能耗；水为溶剂，环境友好。该金属有机骨架材料用于染料废水中，对染料的吸附速率快，吸附效率高；吸附染料后的骨架材料回收简单，可重复利用。
Description
技术领域：
本发明水处理技术领域，涉及用于污水吸附技术的一种环保金属有机骨架材料的快速制备及应用。
背景技术
金属有机骨架材料是最近几年发展起来的一种新型材料，它是由无机金属离子和有机配体通过配位作用而自组装形成的具有无限网络结构的多孔材料，其金属组分主要为过渡金属离子。骨架材料中存在着配位键作用力、氢键作用力及其他的相互作用力。金属离子在骨架材料中作为节点来连接配体，促使络合物形成网状结构。因不同金属离子的配位构型及粒径大小不同导致不同金属离子反应得到的骨架材料空间结构、性质大不相同，使用较多的是Zn2+、Cu2+、Ni2+、Pd2+、Pt2+、Ru2+、Co2+等。
有机配体是合成骨架材料的重要原料，节点间的距离、骨架材料的维数都由其决定，其所包含的官能团、空间结构和配位能力都对骨架材料的结构和性能有较大影响。有机配体至少含有一个多齿型官能团，如-CO2H、-CS2H、-NO2、-SO3H、-PO3H，其中-CO2H最为常用，羧基带有负电荷，负电荷会使羧酸基团与金属离子间的相互作用力增强；羧基的配位方式较多，易形成特殊的拓扑结构，使骨架材料更加稳定；羧基基团越多，越易形成维数较高的骨架材料。有机合成中的溶剂可以改变反应速度，由于有机配体大多呈酸性，溶剂分子可以与有机配体配位，使配体去质子化。溶剂分子的极性越强，与有机配体分子间作用力越强，易得到低维数骨架结构，因此溶剂与配体间的适当的作用力，对提高骨架材料的维数有利。
金属有机骨架材料具有比表面积大、孔道结构均匀、孔隙率大、固体密度小、化学稳定性高的优点，其独特的结构与性质使得该材料在气体吸附与分离、有机催化反应、药物缓释，废水处理等方面都有很好的应用前景。
目前报道较多的金属有机骨架料的合成方法主要有溶剂热法和水热合成法，这两种方法需要在密闭的反应体系中，设置一定的压力，反应温度一般在100-200℃，需要消耗较高的能量。液相扩散法也是较常用的一种方法，该方法是将金属离子和有机配体通过一定的方式混合、接触、静置，最终缓慢沉淀出晶体，这种方法的严重缺点是耗时过长。近年来又发展了离子液体法、微波法、超声波法等，辅助设备的增加使得生产成本增大，制备过程复杂化。因此，如何缩短反应时间，简化操作工艺，节约能源而又能保持金属骨架材料自身的优良性能就变的非常有意义了。
发明内容：
针对骨架材料合成中耗时长、能耗大、成本高、过程复杂的弊端，本发明的目的在于寻找一种可在室温下快速的合成一种无毒环保骨架材料。因此，本发明选择氨基酸为有机配体，在室温条件下，水相中完成与金属离子的配位络合反应。
为达到上述目的，本发明采用的技术方案为：将氨基酸溶解于含有氢氧化钠的去离子水中，加入体积分数为3-10％的乙胺衍生物为催化剂，搅拌作用下，缓慢滴加0.5mol/L的金属盐溶液，滴加完成后继续反应1-5h。所得混合物经过滤、水洗、醇洗数次后，于80℃干燥至少24h，得到金属有机骨架材料。
上述方案中的金属盐为硫酸锌、硫酸铜、硝酸锌、硝酸铜、氯化锌、氯化铜中的一种或两种。
上述方案中的氨基酸为甘氨酸、谷氨酸、胱氨酸、丝氨酸、天冬氨酸中的一种或两种。
上述方案中的乙胺衍生物为乙胺、二乙胺、三乙胺、乙醇胺、二乙醇胺、三乙醇胺中的一种、两种或三种。
将上述合成的金属有机骨架材料放入含有活性染料或酸性染料的模拟染料废水中，静止30-60min，即可完成对染料的吸附过程，离心分离可将材料与废水分离。吸附染料的骨架材料放入含有30％乙醇的醇水溶液中进行超声萃取30min，可以进行材料的再生，重新分离出其中的骨架材料，进行重复利用。
本发明合成的金属有机骨架材料比表面积大，孔隙率大；室温操作，节约能耗；水为溶剂，环境友好；工艺流程简便，可操作性强，生产成本低；材料对染料的吸附速率快，吸附效率高，可重复利用，无二次污染。
下面结合实施例对本发明做进一步详细、完整的说明。
具体实施方式：
实施例1
将0.5mol硫酸铜加入1.0L去离子水中，搅拌使之充分溶解。将1mol NaOH经0.5L去离子水溶解后加入到盛有0.3mol谷氨酸和0.4mol甘氨酸混合和物的烧杯中，氨基酸完全溶解后加入50mL三乙胺。将硫酸铜溶液在磁力搅拌下缓慢滴加到谷氨酸溶液中，30min后溶液中出现固体，继续反应2-3h，反应结束后将所得混合物进行抽滤，固体产物经水洗、醇洗数次后，于60℃下干燥24h得固体铜-氨基酸骨架材料，收率89.8％。
实施例2
将0.5mol硝酸锌加入1.0L去离子水中，搅拌使之充分溶解。将1mol NaOH经0.5L去离子水溶解后加入到盛有0.3mol天冬氨酸和0.2mol谷氨酸的烧杯中，谷氨酸完全溶解后加入35mL二乙醇胺。将硝酸锌溶液在磁力搅拌下缓慢滴加到氨基酸溶液中，50min后溶液中出现固体，继续反应3h，反应结束后将所得混合物进行抽滤，固体产物经水洗、醇洗数次后，于40℃下干燥24h得固体锌-氨基酸骨架材料，收率92.6％。
实施例3
称取实施例1中的骨架材料0.6g加入到0.2L浓度分别为0.1～0.5g/L的酸性蓝黑1、活性红23的染料溶液中，磁力搅拌30min，离心分离后，测定染料溶液的吸光度，染料清除率分别为93-95％和89-93％。
实施例4
将实施例3中离心分离得到的固体骨架材料，放入含有30％乙醇的醇水溶液中，超声处理20-30min，分离其中的固体，经过水洗、醇洗数次后，于80℃干燥至少24h，得到回收金属骨架材料。
将0.6g回收金属骨架材料加入到0.2L浓度分别为0.2g/L的酸性蓝黑1、活性红23的染料溶液中，磁力搅拌30min，离心分离后，测定染料溶液的吸光度，染料清除率分别为90％和86％。
Claims (1)
1.一种环保金属有机骨架材料的快速制备方法，将甘氨酸、谷氨酸、胱氨酸、丝氨酸、天冬氨酸中的一种或两种溶解于含有氢氧化钠的去离子水中，加入体积分数为3-10％的乙胺、二乙胺、三乙胺、乙醇胺、二乙醇胺、三乙醇胺中的一种、两种或三种为催化剂，搅拌作用下，缓慢滴加0.5mol/L的硫酸锌、硫酸铜、硝酸锌、硝酸铜、氯化锌、氯化铜中的一种或两种盐溶液，滴加完成后继续反应1-5h，所得混合物经过滤、水洗、醇洗数次后，于80℃干燥至少24h，得到金属有机骨架材料。
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