CN113926398A - 一种金属有机凝胶,及其制备方法和应用 - Google Patents
一种金属有机凝胶,及其制备方法和应用 Download PDFInfo
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- 229940012189 methyl orange Drugs 0.000 claims abstract description 36
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Abstract
本发明属于工业污水处理技术领域,尤其涉及一种金属有机凝胶,及其制备方法和应用。本发明通过将叶酸、氢氧化钠以及氯化钙在水中按特定比例搅拌混合的方式,制得钙离子‑叶酸‑金属有机凝胶,以用于在甲基橙水溶液中进行甲基橙的吸附去除操作。本发明具有以下优点:第一、叶酸分子的具有配位点相对较多的优点,最终使得Ca‑MOG呈现多孔结构,有利于染料分子的吸附;第二、Ca‑MOG的BET比表面积和孔体积都相对较大,进一步验证具有高效的染料分子吸附功能;第三、Ca‑MOG在常温常压下制备合成,生产方法简单经济;第四、Ca‑MOG对甲基橙溶液中甲基橙染料的吸附去除能力显著,在纺织污水中具有较大的应用前景。
Description
技术领域
本发明属于工业污水处理技术领域,尤其涉及一种金属有机凝胶,及其制备方法和应用。
背景技术
纺织工业污水中,包含大量的染料,而常见的污水处理方法,例如吸附法、化学混凝法、 化学氧化法、膜分离法以及电化学法,对染料的去除效果都十分有限,这主要是由于染料自 身具有强大的化学稳定性、光解性和微生物稳定性。
因此,现在也出现了一些相对新兴的染料污水处理方法,其中就包括金属有机凝胶法。 金属有机凝胶(MOG)本质上是一种新型超分子软材料,其中的金属离子和有机配体分子之间 通过配位键形成骨架网络,溶剂分子和尚未参与配位的有机配体分子的活性官能团之间,则 通过氢键、π-π堆积作用和范德华力等弱分子间作用力附着在上述骨架网络上。此外,MOG 还具有可以在室温下合成,合成条件温和,以及便于规模化生产的优点。
但是另一方面,现有的MOG,例如Pb-MOG,其在用于处理染料污水时,存在的不足之处 就是开孔率不足、开孔孔径较小,因此吸附染料的效率就一般。
所以综上所述,现在急需一种具有优异多孔结构的新型MOG,以用于在纺织工业污水中 吸附、去除染料。
专利公开号为CN 103240060A,公开日为2013.08.14的中国发明专利公开了一种金属有 机凝胶及其制备和在处理染料废水中的应用,其中的金属有机凝胶,是由苯并咪唑羧酸衍生 物和金属铅离子形成配合物而束缚住溶剂小分子形成的凝胶,经SEM结果表明,该金属有机 凝胶呈现交织的三维网状结构,以用于吸附甲基橙染料分子。
但是该发明专利中的金属有机凝胶,其三维网状结构的比表面积和孔体积这两项参数都 相对较小,因此吸附甲基橙染料分子的能力始终是相对较差的,不能满足现在的纺织污水治 理要求。
发明内容
本发明提供一种金属有机凝胶,及其制备方法和应用,其能通过将叶酸、氢氧化钠以及 氯化钙在水中按特定比例搅拌混合的方式,制得钙离子-叶酸-金属有机凝胶,以用于在甲基 橙水溶液中进行甲基橙的吸附去除操作。
本发明解决上述问题采用的技术方案是:一种金属有机凝胶,所述金属有机凝胶为钙离 子-叶酸-金属有机凝胶,记为Ca-MOG。
进一步优选的技术方案在于:所述Ca-MOG的分子结构为
进一步优选的技术方案在于:所述Ca-MOG的BET比表面积为6.2-6.5m2g-1,所述Ca-MOG 的BET孔体积为0.010-0.014cm3g-1。
进一步优选的技术方案在于:所述Ca-MOG的微孔的孔径分布范围为0.5-2.0nm。
进一步优选的技术方案在于:所述Ca-MOG的颜色为棕黄色。
一种金属有机凝胶的制备方法,依次包括以下步骤:
S1、在去离子水中加入叶酸和氢氧化钠,搅拌后得到溶液A;
S2、在另一份去离子水中加入氯化钙,搅拌后得到溶液B;
S3、将所述溶液B倒入所述溶液A,搅拌静置后得到所述Ca-MOG。
进一步优选的技术方案在于:S1、S2中,叶酸、氢氧化钠以及氯化钙之间的摩尔比为1∶ 2∶2。
进一步优选的技术方案在于:S1中,每1.0ml的去离子水中,添加0.1-0.3mmol的叶酸。
进一步优选的技术方案在于:S2中,每1.0ml的去离子水中,添加0.1-0.4mmol的氯化 钙。
一种金属有机凝胶的应用,所述Ca-MOG用于吸附甲基橙染料。
本发明具有以下优点:第一、叶酸分子的具有配位点相对较多的优点,最终使得Ca-MOG 呈现多孔结构,有利于染料分子的吸附;第二、Ca-MOG的BET比表面积和孔体积都相对较大, 进一步验证具有高效的染料分子吸附功能;第三、Ca-MOG在常温常压下制备合成,生产方法 简单经济;第四、Ca-MOG对甲基橙溶液中甲基橙染料的吸附去除能力显著,在纺织污水中具 有较大的应用前景。
附图说明
图1为本发明实施例中Ca-MOG的扫描电镜表征。
图2为本发明实施例中Ca-MOG的红外图谱。
图3为本发明实施例中Ca-MOG的孔径分布图。
图4为本发明实施例中Ca-MOG对甲基橙溶液的吸附平衡时间示意图。
图5为本发明实施例中Ca-MOG对不同初始浓度的甲基橙溶液的吸附量变化示意图。
图6为本发明实施例中Ca-MOG对不同氯化钠浓度的甲基橙溶液的吸附量变化示意图。
图7为本发明实施例中Ca-MOG对不同温度条件下的甲基橙溶 液的吸附量变化示意图。
图8为本发明实施例中甲基橙的标准曲线。
说明:
图1中,Ca-MOG呈现多孔结构,这主要是因为叶酸分子的多配位点导致的,多孔微观结 构十分有利于染料分子的吸附。
图2中,叶酸分子与Ca-MOG的红外图谱,红外光谱表明,1700cm-1的峰归属于叶酸分子 上的羧酸根在形成凝胶后,位移到1600cm-1,表明羧酸根与钙离子参与了配位,而胺基等其 他含N杂原子官能团没有发生位移,表明未参与配位反应。
图3中,Ca-MOG的孔径分布图,结果清楚地表明,Ca-MOG在0.5-2nm之间都具有大量的微孔,这有利于增加吸收染料的活性位点数量。
具体实施方式
以下所述仅为本发明的较佳实施例,并非对本发明的范围进行限定。
实施例:如附图1-8所示,一种金属有机凝胶,所述金属有机凝 胶为钙离子-叶酸-金属有机凝胶,记为Ca-MOG。
所述Ca-MOG的分子结构为
在本实施例中,叶酸分子中的两个羧酸根官能团与钙离子配位,胺基等其他含N杂原子 官能团与溶剂分子形成弱作用力,最终构成金属有机凝胶。
所述Ca-MOG的制备方法,依次包括以下步骤:
S1、在1.0ml的去离子水中加入0.1mmol的叶酸和0.2mmol的氢氧化钠,搅拌10min后, 得到溶液A;
S2、在另一份1.0ml的去离子水中加入0.2mmol的氯化钙,搅拌10min后,得到溶液B;
S3、将所述溶液B倒入所述溶液A,搅拌10min后静置,得到最终的棕黄色的所述Ca-MOG 产品。
接着,对所述Ca-MOG进行检测,得到的数据为:所述Ca-MOG的BET比表面积为6.4m2g-1, 所述Ca-MOG的BET孔体积为0.012cm3g-1,所述Ca-MOG的微孔的孔径分布范围为0.5-2.0nm。
再是,将所述Ca-MOG用于甲基橙水溶液中,以用于吸附去除甲基橙染料。
此外,整个制备和检测方法中所用到的仪器有:高功率数控超声波清洗器(昆山市超声 仪器有限公司,KQ-200KDE),恒温磁力搅拌器(78HW-1),电动离心沉淀机(湖南湘仪实验仪 器开发有限公司,LXJ-II),循环水式多用真空泵(南京文尔仪器设备有限公司,SHB-IIA), 旋转蒸发仪(上海亚荣生化仪器厂,RE-5220D),电热恒温鼓风干燥箱(精宏设备有限公司, DHG-9036A),核磁共振仪(1H NMR Bruker,Avance-300),紫外可见分光光度计(UV-Vis-3010, 日本日立公司Hitachi),场发射扫描电子显微镜(SEM,S-4800,日本日立公司),红外光谱 仪(FT-IR VECTOR22,日本日立公司Hitachi,KBr压片制样),电热恒温培养箱(DHG-9036A), X-射线粉末衍射仪(XRD-6000,Shimadzu,Cu靶,日本日立公司)。
所有的化学试剂均为分析纯,使用前未做进一步处理,实验用水为二次蒸馏水,氯化钙 (A.R,天津阿法埃莎试剂公司),叶酸(A.R,天津阿法埃莎试剂公司),氢氧化钠(A.R,天 津阿法埃莎试剂公司),无水乙醇(A.R,国药集团化学试剂有限公司),N、N-二甲基甲酰胺 (A.R,国药集团化学试剂有限公司),二甲亚砜(A.R,上海凌风化学试剂有限公司),乙腈(A.R,上海凌风化学试剂有限公司),丙酮(A.R,上海凌风化学试剂有限公司),甲醇(A.R,国药集团化学试剂有限公司),甲基橙(A.R,国药集团化学试剂有限公司)。
在本实施例中,就最终得到的确定重量的所述Ca-MOG产品,针对其应用,即对甲基橙染 料的吸附,再做如下试验。
1、甲基橙的标准曲线的测定
分别配制0.1、0.5、1.0、2.0、3.0、5.0、7.0、9.0、10.0mg/L的甲基橙溶液各10mL,以蒸馏水为参比。甲基橙的紫外最大吸收波长为540-545nm,选择545nm并在此波长下绘 制浓度-吸光度标准曲线,见附图8。
经线性拟合,得到吸光度与甲基橙浓度的线性为:A=0.0668C-0.00574。
2、Ca-MOG吸附甲基橙的最优化条件选择
本试验从吸附平衡时间、甲基橙溶液浓度、离子强度以及温度这4个方面做了最优条件 的探究,即对应附图4-7。
2.1、吸附平衡时间
吸附平衡时间的探究见附图4。为了确定吸附时间是如何影响Ca-MOG对甲基橙的吸附效 果的,以及达到最大吸附量所用的时间,在0-180min内,每隔20min测试一次吸光度,由所 得的实验数据作图可以看出,在0-120min内吸附较快,吸附速率迅速增长,120-180min 内吸附速率减慢,但仍在增长,180min后吸附量基本不变,吸附基本达到平衡,即达到了最 大吸附。
2.2、甲基橙溶液浓度
甲基橙的初始浓度对吸附的影响见附图5。甲基橙的初始浓度也有可能影响Ca-MOG对其 的吸附量,为了确定是否有影响以及如何影响,进行了如下实验。
控制温度、吸附剂的用量、离子强度等条件不变,对初始浓度分别为150mg/L、200mg/L、 250mg/L、300mg/L、350mg/L、400mg/L、450mg/L、500mg/L的甲基橙进行吸附实验。
实验结果表明,随着甲基橙初始浓度的增加,残余的甲基橙分子浓度降低,吸附容量随 之增加,但当甲基橙溶液初始浓度达到400mg/L以上时,吸附速度减慢,同时吸附容量趋于 稳定。这可能是随着甲基橙溶液浓度的增加,吸附容量逐渐达到饱和,增加趋势趋于平缓, 因为对于本实施例中确定重量的Ca-MOG而言,其功能基团含量有限,即对甲基橙分子吸附的 有用的基团的量一定,故其饱和吸附容量也有限,当达到这个饱和吸附量以后,即使甲基橙 分子再多也不再对吸附容量有贡献。
2.3、离子强度
溶液离子强度对Ca-MOG吸附容量的影响见附图6。溶液的离子强度是控制吸附剂表面和 染料的一种静电和非静电的相互作用的因素之一,为了确定所进行的吸附过程是否被离子强 度影响,Ca-MOG对甲基橙的吸附是在甲基橙初始浓度为10mg/L,氯化钠浓度分别为0moL/L、 0.25moL/L、0.5moL/L的溶液中进行的,且吸附剂Ca-MOG的用量均为0.5g,吸附时间均为 30min。
实验结果表明,随着离子强度的增大,Ca-MOG的吸附量是在减小的,即Ca-MOG的吸附 容量和甲基橙溶液的离子强度是成反比的。
2.4、温度
温度对Ca-MOG吸附容量的影响见附图7。温度也是影响Ca-MOG的吸附容量的重要因素。 为了确定所进行的吸附过程本质上是吸热的还是放热的,Ca-MOG对甲基橙的吸附是在最初甲 基橙浓度为10mg/L、吸附剂Ca-MOG的用量为0.5g/L,进行温度分别为303K、323K、343K的 三组实验,且每组实验的吸附时间均为24h。根据所得的实验数据作图可以看出,温度对 Ca-MOG的吸附量影响不大。
3、结论
因此,由本实验可得,Ca-MOG对甲基橙的吸附量受时间、甲基橙的初始浓度以及离子强 度三者的影响。
综上所述,本实施例中的Ca-MOG,对甲基橙溶液中的甲基橙染料,具有相对高效的吸附 效果。
上面结合附图对本发明的实施方式作了详细说明,但是本发明不限于上述实施方式,在 所述技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下做出 各种修改。这些都是不具有创造性的修改,只要在本发明的权利要求范围内都受到专利法的 保护。
Claims (10)
1.一种金属有机凝胶,其特征在于:所述金属有机凝胶为钙离子-叶酸-金属有机凝胶,记为Ca-MOG。
3.根据权利要求1所述的一种金属有机凝胶,其特征在于:所述Ca-MOG的BET比表面积为6.2-6.5m2g-1,所述Ca-MOG的BET孔体积为0.010-0.014cm3g-1。
4.根据权利要求1所述的一种金属有机凝胶,其特征在于:所述Ca-MOG的微孔的孔径分布范围为0.5-2.0nm。
5.根据权利要求1所述的一种金属有机凝胶,其特征在于:所述Ca-MOG的颜色为棕黄色。
6.一种如权利要求1所述的金属有机凝胶的制备方法,其特征在于依次包括以下步骤:
S1、在去离子水中加入叶酸和氢氧化钠,搅拌后得到溶液A;
S2、在另一份去离子水中加入氯化钙,搅拌后得到溶液B;
S3、将所述溶液B倒入所述溶液A,搅拌静置后得到所述Ca-MOG。
7.根据权利要求6所述的一种金属有机凝胶的制备方法,其特征在于:S1、S2中,叶酸、氢氧化钠以及氯化钙之间的摩尔比为1∶2∶2。
8.根据权利要求6所述的一种金属有机凝胶的制备方法,其特征在于:S1中,每1.0ml的去离子水中,添加0.1-0.3mmol的叶酸。
9.根据权利要求6所述的一种金属有机凝胶的制备方法,其特征在于:S2中,每1.0ml的去离子水中,添加0.1-0.4mmol的氯化钙。
10.一种如权利要求1所述的金属有机凝胶的应用,其特征在于:所述Ca-MOG用于吸附甲基橙染料。
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