CN110339816B - 一种锆基金属有机骨架材料的制备方法及其应用 - Google Patents
一种锆基金属有机骨架材料的制备方法及其应用 Download PDFInfo
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- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C07D213/80—Acids; Esters in position 3
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
本发明提供了一种锆基金属有机骨架材料的制备方法及其应用，属于烟酰胺和烟酸吸附分离技术领域，解决现有的常规分离方法不易将烟酰胺和烟酸吸附分离的技术问题。本发明公开的锆基金属有机骨架材料DUT‑67，利用溶剂热法进行合成，锆基金属有机骨架DUT‑67的化学式为Zr6O6(OH)2(tdc)4·3.1H2O·0.6DMF，具有一定的孔道结构和独特的结合位点，能够快速选择性吸附分离烟酰胺和烟酸，分离效果明显，操作过程简单，可有效提高烟酰胺和烟酸的利用率，改善经济效益。
Description
技术领域
本发明属于烟酰胺和烟酸吸附分离技术领域，涉及一种锆基金属有机骨架材料高效选择性吸附分离烟酰胺和烟酸，具体涉及的是一种锆基金属有机骨架材料的制备方法及其应用。
背景技术
金属有机骨架材料（Metal-OrganicFrameworks,MOFs）作为一种多孔型材料，是由金属中心通过有机配体桥联而成，具有规整孔结构的晶体材料。与其它多孔材料相比较，金属有机骨架材料具有大的比表面积、可调控的孔道结构、丰富的结合位点、良好的热稳定性等优良特征，使其在吸附分离、药物传递、生物传感和成像、催化等研究领域具有重要的应用价值。尤其在吸附分离方面，金属有机骨架可调控的孔结构和作用位点，使其能够分离尺寸相近、物理性质相似的分子。
烟酸和烟酰胺，广泛的应用于食品工业、制药生产、聚合物的稳定试剂和抗氧化试剂等。适量烟酸和烟酰胺的摄入有益于维持人体健康。二十世纪五十年代，人们尝试人工法合成烟酸和烟酰胺，所用方法主要有液相氧化、电解氧化、氨氧化等，然而，经这些技术生产的产品中，烟酸和烟酰胺通常混杂在一起，产品需进一步提纯。因此从液相中选择性分离烟酸和烟酰胺能够有效提高经济效益。由于烟酸和烟酰胺的物理性质非常相似，比如溶解度、分子尺寸、分子质量等，导致二者的分离比较困难。目前的分离技术包括分子印迹方法、再结晶、萃取等，然而这些方法面临很大的挑战。例如，传统的分子印迹聚合物具有较高程度的交联，可能会导致不同的模板分子的洗脱，同时，对目标分子的吸附速率和吸附能力降低，这限制了分子印迹方法在同系物或同分异构体分离方面的应用。
作为一种多孔型吸附剂，金属有机骨架材料用于液相分离领域具有成本低、结合位点多、可调控性等优点，在同系物或者同分异构体等复杂体系分离方面，具有良好的潜能。
发明内容
本发明的目的在于克服现有技术的不足，提供基于锆基金属有机骨架材料的烟酸和烟酰胺的吸附分离方法，利用制备的具有独特结构的金属有机骨架材料作为吸附剂，实现了高选择性、快速的分离烟酸和烟酰胺，节省了人力物力，提高了烟酸和烟酰胺的利用率，改善了经济效益。
为了实现上述发明目的，本发明通过以下技术方案予以实现。
一种锆基金属有机骨架材料在吸附分离烟酸和烟酰胺中的应用。
进一步地，所述锆基金属有机骨架材料为DUT-67。
进一步地，锆基金属有机骨架材料用于将溶解有烟酰胺与烟酸的溶液中吸附分离烟酸，吸附分离步骤如下：称取DUT-67样品5mg添加到10mL浓度均为5-500mg/g的烟酰胺和烟酸的混合液中，在30℃下搅拌12小时，过滤后收集滤液，获得吸附分离后的烟酰胺与烟酸的混合溶液，其中DUT-67对烟酸的吸附量为110.2mg/g，DUT-67对烟酰胺的吸附量为11.2mg/g。
进一步地，所述溶解有烟酰胺和烟酸的原始混合液中，烟酰胺和烟酸的质量比为2:8，或者为5:5，或者为8:2。
进一步地，所述溶解有烟酰胺和烟酸的原始混合液中，烟酸的比例越低，烟酸相对于烟酰胺的分离选择性越高。
一种实施锆基金属有机骨架材料吸附分离烟酸和烟酰胺的应用中锆基金属有机骨架材料的制备方法，包括以下步骤：
S1、将二甲基甲酰胺和N-甲基-2-吡咯烷酮按照体积比1：1的混合，得到150mL混合溶液A；称取物质的量为6mmol的氯化锆1.38g和物质的量为4mmol的噻吩二羧酸0.66g，将称取的氯化锆和噻吩二羧酸一起加入配置好的混合溶液A中，再向混合溶液中加入甲酸溶液26.8mL，得到混合溶液B；
S2、将步骤S1制得的混合溶液B搅拌2分钟，然后转移到100mL聚四氟乙烯内衬的不锈钢高压釜中，在120℃温度条件下加热48小时；反应结束后，收集白色固体，并用二甲基甲酰胺和甲醇清洗，然后将得到的固体在100℃下干燥，制得锆基金属有机骨架材料，锆基金属有机骨架材料的化学式为Zr6O6(OH)2(tdc)4·3.1H2O·0.6DMF，其中H2tdc为2,5-噻吩二羧酸，DMF为二甲基甲酰胺。
进一步地，所述步骤S2制得的锆基金属有机骨架材料由十四面体孔和八面体孔组成，其BET比表面积为967.2m2/g。
与现有技术相比，本发明的有益效果为：本发明公开的锆基金属有机骨架材料具有独特的结合位点，如丰富的μ-OH位点、丰富的带电表面等特点，这使其与以及骨架良好的稳定性使其在吸附分离方面具有独特的应用价值。不同于目前烟酸和烟酰胺的分离方法，本发明利用两种维生素在水中电离能力的差异，选择带有强正电荷的多孔材料对阴离子性质的烟酸进行选择性吸附，实现二者的高效分离。
附图说明
图1是锆基金属有机骨架DUT-67的形貌图。
图2是锆基金属有机骨架DUT-67的X射线衍射图谱。
图3是锆基金属有机骨架DUT-67在77K下的氮气吸附脱附曲线图。
图4是锆基金属有机骨架DUT-67对于烟酰胺和烟酸混合溶液的吸附分离结果图。
图5是锆基金属有机骨架DUT-67对烟酰胺和烟酸吸附量随吸附时间的变化关系图。
图6是无机盐对锆基金属有机骨架DUT-67吸附分离烟酰胺和烟酸的影响图。
图7是常见的吸附剂吸附分离烟酰胺和烟酸的效果图。
图8是不同烟酰胺和烟酸比例对锆基金属-有机骨架DUT-67吸附分离性能的影响图。
图9是锆基金属-有机骨架DUT-67的zeta电位图。
图10是DUT-67与烟酰胺结合的DFT计算结果图。
图11是DUT-67与烟酸结合的DFT计算结果图。
具体实施方式
下面结合附图和实施例对本发明作进一步的详细描述。
下述实施例所使用的化学试剂为二甲基甲酰胺、N-甲基-2-吡咯烷酮、氯化锆、噻吩二羧酸、甲酸、甲醇、烟酰胺和烟酸等，均购于北京市华威锐科化工有限公司。
另外需要加以说明的是：粉末X射线衍射测试条件：Cu-Kα辐射，D8AdvanceX衍射计，室温，2θ的范围是3°~30°，步长为0.02°；氮气吸附脱附测试：Autosorb-iQ-MP表面面积分析仪，77K；金属有机骨架材料形貌和元素图运用带有能量散射X射线系统的HitachiS-4700场激发扫描电子显微镜；傅里叶变换红外光谱使用NicoletiS50傅里叶变换分光光度计，4000到400cm-1，分辨率为4cm-1；zeta电势测量使用ZetasizerNanoZS电势分析仪；烟酰胺和烟酸的浓度测量：超高液相色谱仪，流动相为86%水和14%乙醇，柱子温度为25℃，波长为254nm，样品进样体积为10μL。
实施例1锆基金属有机骨架材料DUT-67的合成
一种锆基金属有机骨架材料（DUT-67）的制备方法，包括以下步骤：
S1、将二甲基甲酰胺和N-甲基-2-吡咯烷酮按体积比1：1混合，得到150mL混合溶液A；称取物质的量为6mmol的氯化锆1.38g和物质的量为4mmol的噻吩二羧酸0.66g，将称取的氯化锆和噻吩二羧酸一起加入配置好的混合溶液A中，再向混合溶液中加入甲酸溶液26.8mL，得到混合溶液B；
S2、将步骤S1制得的混合溶液B搅拌5分钟，然后转移到100mL聚四氟乙烯内衬的不锈钢高压釜中，在120℃温度条件下加热48小时；反应结束后，收集白色固体，并用二甲基甲酰胺和甲醇清洗，然后将得到的固体在100℃下干燥，制得锆基金属-有机骨架材料，锆基金属-有机骨架材料的化学式为Zr6O6(OH)2(tdc)4·3.1H2O·0.6DMF，其中H2tdc为2,5噻吩二羧酸，DMF为二甲基甲酰胺。
进一步地，制得的锆基金属-有机骨架材料由十四面体孔和八面体孔组成，其BET比表面积为967.2m2/g。
对制备的锆基金属-有机骨架材料DUT-67进行测定，如图1所示，在显微镜下观察DUT-67的形貌为十面体晶型，利用粉末X射线衍射仪测试DUT-67晶体的衍射图谱，如图2所示，与模拟的X射线衍射图谱相吻合。利用Autosorb-iQ-MP表面面积分析仪测定77K下氮气吸附脱附曲线，如图3所示，计算得到DUT-67的BET比表面积为967.2m2g-1。
实施例2锆基金属-有机骨架材料DUT-67用于烟酰胺和烟酸的混合溶液中吸附分离烟酸
以实施例1中制备的锆基金属有机骨架材料DUT-67在pH值为4.26和303K下对烟酰胺和烟酸进行吸附，具体方法为：
称取5mg样品DUT-67添加到10mL初始浓度均为5-500mg/g的烟酰胺和烟酸的混合溶液中，超声10秒后，将该混合体系转入恒温摇床中在303K下吸附12h，摇床转速设定为155rpm。吸附分离结束后，使用孔径为0.22μm的微孔滤膜进行过滤，收集清澈的滤液并使用超高效液相色谱测定烟酸和烟酰胺的含量。吸附量计算使用方程：
，其中Q(mg/g)表示锆基金属-有机骨架材料DUT-67对烟酸和烟酰胺的吸附量，C 0 (mg/L)表示烟酸和烟酰胺混合液的初始浓度，C e (mg/L) 表示烟酸和烟酰胺混合液的最终浓度，m (g)为吸附质量，V (L)是水溶液的体积。吸附选择性计算使用方程：。
如图4所示，最终对烟酰胺和烟酸的吸附量分别为110.2mg/g-1和11.2mg/g。以初始浓度100mg/L为例，如图5所示，在30分钟内，DUT-67对烟酸的吸附快速达到62mg/g，之后缓慢达到吸附平衡；对烟酰胺的吸附则是随着时间缓慢进行，240分钟时，吸附量为8mg/g。
对实施例2中实际应用情况进行分析，具体包括：
溶液中共存离子的影响。如附图6所示，一方面，一价盐NaCl，NaNO3，KNO3对于烟酸和烟酰胺的吸附有较弱的影响，而二价盐Na2SO4则能较明显地削弱DUT-67对烟酸和烟酰胺的吸附性能；另一方面，共存离子的存在对于分离性能没有明显的影响；
另外，如图7所示，相比于常见的吸附剂如Al2O3、沸石、活性炭等，DUT-67在烟酰胺和烟酸的分离选择性方面，均具有明显的优势；
如图8所示，在烟酰胺和烟酸的混合溶液中，烟酸的比例越低，烟酸相对于烟酰胺的分离选择性α越高。
本发明提供的技术方案在当前两种维生素的分离机理方面，也具有一定创新性：
一方面，如图9所示，在pH值为4~8时，DUT-67表面带正电荷。在pH值为4~8时，烟酸比较容易释放氢离子形成烟酸负离子，通过静电引力与DUT-67结合，而烟酰胺比较容易得到氢离子形成烟酰胺烟酰胺正离子，基于静电斥力作用，不易与DUT-67相结合。
另一方面，如图10和图11所示，通过密度泛函理论计算，DUT-67中氧原子与烟酸中氢原子的键长为1.937Å，与烟酰胺中氢原子的键长为2.440Å。DUT-67和烟酸的结合能为-219.90kJ/mol，高于和烟酰胺的结合能-178.98kJ/mol。说明DUT-67与烟酸之间的氢键作用也要强于烟酰胺。
以上两方面原因导致了DUT-67更容易吸附烟酸，从而实现了烟酸和烟酰胺的分离。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (4)
1.一种锆基金属有机骨架材料在吸附分离烟酸和烟酰胺中的应用，其特征在于：锆基金属有机骨架材料用于在溶解有烟酰胺与烟酸的溶液中吸附分离烟酸，所述锆基金属有机骨架材料为DUT-67，吸附分离步骤如下：称取DUT-67样品5mg添加到10mL浓度均为5-500mg/g的烟酰胺和烟酸的混合液中，在30℃下搅拌12小时，过滤后收集滤液，获得吸附分离后的烟酰胺与烟酸的混合溶液，其中DUT-67对烟酸的吸附量为110.2mg/g，DUT-67对烟酰胺的吸附量为11.2mg/g。
2.根据权利要求1所述的应用，其特征在于：所述溶解有烟酰胺和烟酸的原始混合液中，烟酰胺和烟酸的质量比为2:8，或者为5:5，或者为8:2。
3.根据权利要求1所述的一种锆基金属有机骨架材料在吸附分离烟酸和烟酰胺中的应用，其特征在于：所述锆基金属有机骨架材料的制备方法包括以下步骤：
S1、将二甲基甲酰胺和N-甲基-2-吡咯烷酮按照体积比1：1混合，得到150mL混合溶液A；称取物质的量为6mmol的氯化锆1.38g和物质的量为4mmol的2,5-噻吩二羧酸0.66g，将称取的氯化锆和2,5-噻吩二羧酸一起加入配置好的混合溶液A中，再向混合溶液中加入甲酸溶液26.8mL，得到混合溶液B；
S2、将步骤S1制得的混合溶液B搅拌2分钟，然后转移到100mL聚四氟乙烯内衬的不锈钢高压釜中，在120℃温度条件下加热48小时；反应结束后，收集白色固体，并用二甲基甲酰胺和甲醇清洗，然后将得到的固体在100℃下干燥，制得锆基金属有机骨架材料，锆基金属有机骨架材料的化学式为Zr6O6(OH)2(tdc)4·3.1H2O·0.6DMF，H2tdc为2,5-噻吩二羧酸，DMF为二甲基甲酰胺。
4.根据权利要求3所述的一种锆基金属有机骨架材料在吸附分离烟酸和烟酰胺中的应用，其特征在于：所述步骤S2制得的锆基金属有机骨架材料由十四面体孔和八面体孔组成，其BET比表面积为967.2m2/g。
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