CN112876689B - 一种金属-有机框架材料及其制备方法与应用 - Google Patents
一种金属-有机框架材料及其制备方法与应用 Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- LFXNSEDBSIKYAU-UHFFFAOYSA-N 4-(3,5-dimethyl-1H-pyrazol-4-yl)-1,2,4-triazole Chemical group CC1=NNC(C)=C1N1C=NN=C1 LFXNSEDBSIKYAU-UHFFFAOYSA-N 0.000 claims abstract description 24
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- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical group O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 5
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- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
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Abstract
本发明公开了一种金属‑有机框架材料及其制备方法与应用,该金属‑有机框架材料化学式为[Cu(btr)2(hpztr)2·(pztr‑1)2·(NO3 ‑)3]n,其中,Hpztr为4‑(3,5‑二甲基吡唑‑4‑基)‑1,2,4‑三唑,btr为4,4’‑双‑1,2,4‑三氮唑;该材料的制备方法包括以下步骤:(1)合成Hpztr;(2)合成btr;(3)利用混合溶剂将铜盐和Hpztr、btr进行溶解,得到混合溶液;(4)将混合溶液置于90~100℃恒温干燥箱当中反应,冷却至室温,过滤、洗涤、干燥,即得到金属‑有机框架材料;该材料能够应用在去除水中离子中。该材料具有较高的热稳定性和化学稳定性;能够在常温常压下有效吸附富集水中阴离子,尤其是吸附速率高和吸附量大;能够作为一种高效的净水吸附剂用于去除水中的
Description
技术领域
本发明涉及一种材料及其制备方法与应用,更具体地,涉及一种金属-有机框架材料及其制备方法与应用。
背景技术
水作为地球上最为宝贵的自然资源之一,对人类及动植物等的生存和发展具有不可取代的重要意义。然而,随着人类活动范围的扩张和现代工业的飞速发展,水污染日益严峻,现已成为全世界共同面临的严重问题。工业废渣丢弃、化学废水排放、核废料泄漏和农药超标使用等在水体中引入了各种各样不同的有害物质。废水中常见的重金属离子主要包括砷、铜、铬、铅、汞、镍和锌离子等。这些离子含量超标将对人类和其他生物的生存构成了巨大的威胁。要去除水中的这些重金属离子通常借助多孔材料的吸附或离子交换来实现。目前,用于水中重金属离子污染物去除的常用多孔材料主要包括沸石、活性炭、粘土和铝磷酸盐等几类。这些多孔材料大多容易获得,成本较低。然而,这类材料比表面积低、表面修饰存在一定困难,因而污染物的去除速率和吸附量都较差,材料性能不够理想。
发明内容
发明目的:本发明的目的是提供一种能够吸附水中重金属离子、吸附速度快、稳定性好的金属-有机框架材料,本发明的另一目的是提供该金属-有机框架材料的制备方法,本发明的另一目的是提供该金属-有机框架材料的应用。
技术方案:本发明所述的金属-有机框架材料,金属-有机框架材料的化学式为[Cu(btr)2(hpztr)2·(pztr-1)2·(NO3 -)3]n,其中,Hpztr为4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑,btr为4,4’-双-1,2,4-三氮唑。
本发明所述的金属-有机框架材料的制备方法,包括以下步骤:
(1)合成有机配体4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑;
(2)合成有机配体4,4’-双-1,2,4-三氮唑;
(3)利用混合溶剂将铜盐和有机配体4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑、4,4’-双-1,2,4-三氮唑进行溶解,得到混合溶液;
(4)将混合溶液置于90~100℃恒温干燥箱当中反应,冷却至室温,过滤、洗涤、干燥,即得到金属-有机框架材料。
其中,步骤1包括以下步骤:
(11)将4-硝基-3,5-二甲基吡唑和KOH溶解于去离子水中,加热至90-100℃,加入SnCl2·2H2O,保持温度不变,继续反应,反应完全后冷却至室温,过滤固体产物洗涤、干燥;得4-氨基-3,5-二甲基吡唑中间体;
(12)将4-氨基-3,5-二甲基吡唑配体中间体、N,N'-双(二甲基氨基亚甲基)肼和对甲苯磺酸溶于邻二甲苯中,搅拌回流反应,反应完成后,冷却至室温,过滤、用二甲苯和乙醇洗涤,即得有机配体4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑。
其中,步骤11中4-硝基-3,5-二甲基吡唑、KOH和SnCl2·2H2O质量比为1:8~10:5~6;所述步骤12中4-氨基-3,5-二甲基吡唑、N,N'-双(二甲基氨基亚甲基)肼、对甲苯磺酸质量比为1:1~2:0.05~0.1,4-氨基-3,5-二甲基吡唑与邻二甲苯使用量为1g:7~10mL。
其中,步骤2包括以下步骤:
(21)将N,N'-双(二甲基氨基亚甲基)肼盐酸盐和4-氨基-1,2,4-三唑溶于甲苯中;
(22)加热回流反应后,过滤所得沉淀物,用冷甲醇洗涤,干燥即得到4,4’-双-1,2,4-三氮唑。
其中,步骤21中4-氨基-1,2,4-三唑和N,N'-双(二甲基氨基亚甲基)肼盐酸盐质量比为1:1~3,4-氨基-1,2,4-三唑与甲苯使用量为1~2g:20mL。
其中,步骤3中混合溶剂为体积比为3~2:1的去离子水和甲醇,铜盐为三水合硝酸铜,铜盐和有机配体4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑、4,4’-双-1,2,4-三氮唑的摩尔比为1~2:1:1。
工作原理:4,4’-双-1,2,4-三氮唑为中性配体,利用该分子与带正电的金属阳离子配位,能够最大程度上保证制备所得MOFs的主体骨架呈阳性。根据软硬酸碱理论,Cu+离子的选用能进一步确保体系中的抗衡离子(NO3 -)不参与配位。以上两点从根本上赋予了材料通过离子交换方式吸附有毒阴离子的能力。此外,4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑与4,4’-双-1,2,4-三氮唑两类分子中丰富的N位点为主体骨架与形成氢键,进而提高吸附量和选择性提供了保障。
附图说明
图1是金属-有机框架材料的配位环境图;
图2是金属-有机框架材料的三维结构图;
图3是金属-有机框架材料实际测试和模拟XRD对比图;
图4是金属-有机框架材料在不同pH值水溶液中浸泡后测得的XRD图;
图5是金属-有机框架材料在有机溶剂中浸泡后测得的XRD图;
图6是金属-有机框架材料热重谱图;
具体实施方式
实施例1
(1)合成有机配体4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑Hpztr:
合成4-氨基-3,5-二甲基吡唑配体中间体:将5.07g,36mmol的4-硝基-3,5-二甲基吡唑和40.0g KOH溶解于100mL去离子水中,将其在油浴锅中加热至90℃,称取27.57g,122mmol的SnCl2·2H2O,分三次加入上述体系中,加料间隔为1小时,保持温度不变,继续反应6小时后,冷却至室温,过滤固体产物、用3mL冰水洗涤,干燥,得4-氨基-3,5-二甲基吡唑配体中间体2.60g,产率约为65%;
合成4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑Hpztr配体:将3.33g,30mmol的4-氨基-3,5-二甲基吡唑、4.69g,33mmol的N,N'-双(二甲基氨基亚甲基)肼和0.24g,1.3mmol的对甲苯磺酸溶于25mL邻二甲苯中,搅拌回流24h,反应完成后,将体系冷却至室温,过滤,用二甲苯和乙醇洗涤,得到4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑Hpztr配体3.28g,产率约为67%,结构式如下:
(2)合成有机配体4,4’-双-1,2,4-三氮唑btr:
将3.30g,15.4mmol的N,N'-双(二甲基氨基亚甲基)肼盐酸盐和1.55g,18.4mmol的4-氨基-1,2,4-三唑溶于20mL甲苯中,加热至110℃,回流12h后,过滤所得沉淀物,用冷甲醇洗涤,在真空中干燥,得到1.77g合成有机配体4,4’-双-1,2,4-三氮唑btr白色粉末,产率为86.4%,结构式如下:
(3)称取0.20mmol三水合硝酸铜、0.10mmol的有机配体4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑Hpztr和0.10mmol的有机配体4,4’-双-1,2,4-三氮唑btr,加入到20mL耐高温玻璃瓶中,再向其中加入总体积为8mL的混合溶剂,混合溶剂中为体积比为3:1的甲醇和去离子水;
(4)将玻璃瓶封口后放入恒温干燥箱中,在90℃条件下反应2天,缓慢冷却至室温后,过滤得到65mg无色透明块状晶体,即为金属有机骨架材料[Cu(btr)2(hpztr)2·(pztr-1)2·(NO3 -)3]n,产率约为67%,
[Cu(btr)2(hpztr)2·(pztr-1)2·(NO3 -)3]n实际XRD图谱和模拟XRD图谱如图3所示,两图谱中XRD衍射峰可以很好的吻合,这意味着所得材料的分子结构与通过单晶衍射获得的结果一致,且材料具有很高的相纯度。为检验所得MOF材料的化学稳定性,将[Cu(btr)2(hpztr)2·(pztr-1)2·(NO3 -)3]n分别泡在pH=1、pH=3、pH=7、pH=13的水溶液中,12h后测试样品的XRD。如图4所示,在近中性或酸性条件下,该MOF材料的XRD无明显变化。这意味着骨架在相应条件下可保持完整。但在pH=13的碱性水溶液中浸泡后的样品无尖锐的衍射峰,该条件下骨架坍塌。将[Cu(btr)2(hpztr)2·(pztr-1)2·(NO3 -)3]n分别泡在DMF、乙醇、乙腈、去离子水和K2Cr2O7水溶液中,12h测试浸泡后样品的XRD。图谱如图5所示,浸泡后样品的衍射峰能与新制备样品的峰较好对应,这意味着在上述溶液或溶剂中浸泡,12h内不会对MOF的骨架造成明显的破坏。对[Cu(btr)2(hpztr)2·(pztr-1)2·(NO3 -)3]n进行热重测试,测试条件:在氮气保护下进行,升温区间从室温到800℃,升温速率为10℃·min-1,图谱如图6所示,曲线存在三个较为明显的失重过程。第一个失重过程发生在60℃附近,应为骨架中甲醇、水等溶剂的脱出过程。200℃以后的两个失重过程应对应骨架的破坏及有机组分的分解。
将0.05mmol的[Cu(btr)2(hpztr)2·(pztr-1)2·(NO3 -)3]n浸泡在20mL浓度为0.0025mol·L-1的K2Cr2O7水溶液中,其中,[Cu(btr)2(hpztr)2·(pztr-1)2·(NO3 -)3]n与摩尔比为1:1,室温下磁力搅拌48h,利用紫外-可见光谱对的吸附过程进行监测,在不同时刻移取0.2mL上清液,测定UV-Vis吸附强度,其测试图如图8所示,随实验时间的不断延长,吸收峰的强度逐渐减弱,这意味着上清液中的含量在逐渐减少,MOF可有效将其吸附去除。通过测定K2Cr2O7水溶液的脱色率,用以下公式计算评价[Cu(btr)2(hpztr)2·(pztr-1)2·(NO3 -)3]n的吸附能力:
其中D为吸附容量,C0,A0和C1,A1分别为阴离子交换前后吸附平衡峰257nm处K2Cr2O7水溶液的浓度和吸光度。经48h连续吸附,约有39%的Cr2O7 2-被富集到金属有机骨架中。此后,将溶液中的晶体滤出,用去离子水冲洗,在空气中干燥,对这些样品进行XRD和IR测试;金属-有机框架材料吸附前、后IR对比谱图。如图7所示,吸附测试后样品中NO3 -对应的特征峰明显减弱,而的特征峰增强。测试结果证实吸附过程不会对MOF材料整体骨架的完整性造成破坏,骨架中原有的NO3 -被部分交换为。
实施例2
(1)合成有机配体4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑Hpztr:
合成4-氨基-3,5-二甲基吡唑配体中间体:将5.07g,36mmol的4-硝基-3,5-二甲基吡唑和51.0g KOH溶解于100mL去离子水中,将其在油浴锅中加热至90℃,称取27.0g的SnCl2·2H2O,分三次加入上述体系中,加料间隔为1小时,保持温度不变,继续反应6小时后,冷却至室温,过滤固体产物、用3mL冰水洗涤,干燥,得4-氨基-3,5-二甲基吡唑配体中间体2.10g,产率约为52%;
合成4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑Hpztr配体:将3.33g,30mmol的4-氨基-3,5-二甲基吡唑、3.50g的N,N'-双(二甲基氨基亚甲基)肼和0.16g的对甲苯磺酸溶于25mL邻二甲苯中,搅拌回流24h,反应完成后,将体系冷却至室温,过滤,用二甲苯和乙醇洗涤,得到4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑Hpztr配体2.8g,产率约为56%;
(2)合成有机配体4,4’-双-1,2,4-三氮唑btr:
将2g的N,N'-双(二甲基氨基亚甲基)肼盐酸盐和1.55g的4-氨基-1,2,4-三唑溶于20mL甲苯中,加热至110℃回流12h后,过滤所得沉淀物,用冷甲醇洗涤,在真空中干燥,得到0.95g合成有机配体4,4’-双-1,2,4-三氮唑btr白色粉末,产率约为60.4%;
(3)称取0.10mmol三水合硝酸铜、0.10mmol的有机配体4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑Hpztr和0.10mmol的有机配体4,4’-双-1,2,4-三氮唑btr,加入到20mL耐高温玻璃瓶中,再向其中加入总体积为4mL的混合溶剂,混合溶剂中为体积比为3:1的甲醇和去离子水;
(4)将玻璃瓶封口后放入恒温干燥箱中,在90℃条件下反应2天,缓慢冷却至室温后,过滤得到30mg无色透明块状晶体,即为金属有机骨架材料[Cu(btr)2(hpztr)2·(pztr-1)2·(NO3 -)3]n,产率为35%,
将0.1mmol的[Cu(btr)2(hpztr)2·(pztr-1)2·(NO3 -)3]n浸泡在20mL浓度为0.0025mol·L-1的K2Cr2O7水溶液中,其中,[Cu(btr)2(hpztr)2·(pztr-1)2·(NO3 -)3]n与摩尔比为2:1,室温下磁力搅拌48h,利用紫外-可见光谱对的吸附过程进行监测,在不同时刻移取0.2mL上清液,测定UV-Vis吸附强度,其测试图如图9所示,随实验时间的延长,吸光强度逐渐降低,经48h连续吸附,约有77%的Cr2O7 2-被富集到金属有机骨架中。
实施例3
(1)合成有机配体4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑Hpztr:
合成4-氨基-3,5-二甲基吡唑配体中间体:将5.07g,36mmol的4-硝基-3,5-二甲基吡唑和40.0g KOH溶解于100mL去离子水中,将其在油浴锅中加热至90℃,称取27.57g,122mmol的SnCl2·2H2O,分三次加入上述体系中,加料间隔为1小时,保持温度不变,继续反应6小时后,冷却至室温,过滤固体产物、用3mL冰水洗涤,干燥,得4-氨基-3,5-二甲基吡唑配体中间体2.60g,产率约为65%;
合成4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑Hpztr配体:将3.33g,30mmol的4-氨基-3,5-二甲基吡唑、4.69g 33mmol的N,N'-双(二甲基氨基亚甲基)肼和0.24g,1.3mmol的对甲苯磺酸溶于25mL邻二甲苯中,搅拌回流24h,反应完成后,将体系冷却至室温,过滤,用二甲苯和乙醇洗涤,得到4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑Hpztr配体3.28g,产率约为67%:
(2)合成有机配体4,4’-双-1,2,4-三氮唑btr:
将3.30g,15.4mmol的N,N'-双(二甲基氨基亚甲基)肼盐酸盐和1.55g,18.4mmol的4-氨基-1,2,4-三唑溶于20mL甲苯中,加热至110℃回流12h后,过滤所得沉淀物,用冷甲醇洗涤,在真空中干燥,得到1.77g合成有机配体4,4’-双-1,2,4-三氮唑btr白色粉末,产率为86.4%:
(3)称取0.10mmol三水合硝酸铜、0.10mmol的有机配体4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑Hpztr和0.10mmol的有机配体4,4’-双-1,2,4-三氮唑btr,加入到20mL耐高温玻璃瓶中,再向其中加入总体积为8mL的混合溶剂,混合溶剂中为体积比为3:1的甲醇和去离子水;
(4)将玻璃瓶封口后放入恒温干燥箱中,在90℃条件下反应2天,缓慢冷却至室温后,过滤得到65mg无色透明块状晶体,即为金属有机骨架材料[Cu(btr)2(hpztr)2·(pztr-1)2·(NO3 -)3]n,产率为67%。
Claims (9)
2.一种权利要求1所述的金属-有机框架材料的制备方法,其特征在于,包括以下步骤:
(1)合成有机配体4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑;
(2)合成有机配体4,4’-双-1,2,4-三氮唑;
(3)利用混合溶剂将铜盐和有机配体4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑、4,4’-双-1,2,4-三氮唑进行溶解,得到混合溶液;
(4)将混合溶液置于90~100℃恒温干燥箱当中反应,冷却至室温,过滤、洗涤、干燥,即得到金属-有机框架材料。
3.根据权利要求2所述的金属-有机框架材料的制备方法,其特征在于,所述步骤1包括以下步骤:
(11)将4-硝基-3,5-二甲基吡唑和KOH溶解于去离子水中,加热至90-100℃,加入SnCl2·2H2O,保持温度不变,继续反应,反应完全后冷却至室温,过滤固体产物洗涤、干燥;得4-氨基-3,5-二甲基吡唑中间体;
(12)将4-氨基-3,5-二甲基吡唑配体中间体、N,N'-双(二甲基氨基亚甲基)肼和对甲苯磺酸溶于邻二甲苯中,搅拌回流反应,反应完成后,冷却至室温,过滤、用二甲苯和乙醇洗涤,即得有机配体4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑。
4.根据权利要求3所述的金属-有机框架材料的制备方法,其特征在于,所述步骤11中4-硝基-3,5-二甲基吡唑、KOH和SnCl2·2H2O质量比为1:8~10:5~6;所述步骤12中4-氨基-3,5-二甲基吡唑、N,N'-双(二甲基氨基亚甲基)肼、对甲苯磺酸质量比为1:1~2:0.05~0.1,4-氨基-3,5-二甲基吡唑与邻二甲苯使用量为1g:7~10mL。
5.根据权利要求2所述的金属-有机框架材料的制备方法,其特征在于,所述步骤2包括以下步骤:
(21)将N,N'-双(二甲基氨基亚甲基)肼盐酸盐和4-氨基-1,2,4-三唑溶于甲苯中;
(22)加热回流反应后,过滤所得沉淀物,用冷甲醇洗涤,干燥即得到4,4’-双-1,2,4-三氮唑。
6.根据权利要求5所述的金属-有机框架材料的制备方法,其特征在于,所述步骤21中4-氨基-1,2,4-三唑和N,N'-双(二甲基氨基亚甲基)肼盐酸盐质量比为1:1~3,4-氨基-1,2,4-三唑与甲苯使用量为1~2g:20mL。
7.根据权利要求2所述的金属-有机框架材料的制备方法,其特征在于,所述步骤3中混合溶剂为体积比为3~2:1的去离子水和甲醇,铜盐为三水合硝酸铜,铜盐和有机配体4-(3,5-二甲基吡唑-4-基)-1,2,4-三唑、4,4’-双-1,2,4-三氮唑的摩尔比为1~2:1:1。
8.一种权利要求1所述的金属-有机框架材料在去除水中阴离子中的应用。
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