CN106279221B - 一种高质子导电金属有机骨架材料的合成方法 - Google Patents
一种高质子导电金属有机骨架材料的合成方法 Download PDFInfo
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 48
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- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 claims description 4
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- QHNXEVRKFKHMRL-UHFFFAOYSA-N dimethylazanium;acetate Chemical compound CNC.CC(O)=O QHNXEVRKFKHMRL-UHFFFAOYSA-N 0.000 claims description 2
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- KTAFYYQZWVSKCK-UHFFFAOYSA-N n-methylmethanamine;nitric acid Chemical compound CNC.O[N+]([O-])=O KTAFYYQZWVSKCK-UHFFFAOYSA-N 0.000 claims description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种高质子导电金属有机骨架材料的合成方法,其具体步骤为:向含有草酸和一价有机胺盐的水溶液中,滴加三价金属盐和一价有机胺盐的水溶液,搅拌反应10‑60分钟;或者是将三价金属氧化物、酸和水混合,待溶液澄清后,用有机胺调节溶液pH=2~4,再将其加入含有草酸和一价有机胺盐的水溶液中,搅拌反应10‑60分钟;然后抽滤,沉淀,洗涤,干燥,得目标产物;所合成材料结构通式为:(HA)[Ln(C2O4)2(H2O)]·3H2O。所合成的化合物属于微孔MOF材料,具有很高的热稳定性(大于330℃)和优异的质子导电性能。本方法所采用的反应原料廉价易得,反应条件温和,工艺简单,产率高,成本低,不使用任何有机溶剂,属于绿色合成,非常适合大规模工业化生产。
Description
技术领域
本发明涉及一种高质子导电金属有机骨架材料的合成方法
背景技术
金属有机骨架(Metal-Organic Frameworks,MOFs)是由金属离子或离子簇与有机配体通过自组装形成的具有周期性骨架结构的晶体多孔材料。与传统的沸石分子筛相比,MOFs材料拥有大孔容、高比表面、孔道尺寸可调且容易功能化等优势,使其在气体储存、吸附与分离、催化等领域有广泛的应用前景。同时MOFs还具有独特的光、电、磁等多种功能,被认为是一种新兴的多孔材料。在过去二十年中已经成为化学和材料领域增长最快的研究热点之一(参见:Yaghi O.M.等,Science,2013,341,974)。
近年来,随着全球能源需求的急剧增加和化石燃料的不断消耗,寻找可替代的能源已成为新的研究目标。而能将化学能直接转变为电能的燃料电池技术正受到日益重视,其中质子交换膜燃料电池(PEMFC)被认为最有应用前景。质子交换膜燃料电池的关键部件是质子交换膜,目前常用的是Nafion膜,但Nafion膜价格昂贵,生产过程不环保,严重阻碍了其大规模工业化应用。因此开发新的质子交换膜是当今燃料电池领域的研究热点。由于MOFs具有规整的结构和易于功能化的孔道,将其开发为新的质子导电材料引起了科学家的极大的兴趣(参见:Shimizu G.K.H.等,Science,2013,341,354)。但目前大多数质子导电性好的MOFs材料都存在水稳定性差、生产成本高、难以工业化合成等问题,所以如何获得具有高质子导电性能、水稳定性高、原料廉价且易大量制备的MOFs材料仍是一个巨大的挑战(参见:Ghosh S.K.等,Angew.Chem.Int.Ed.,2014,53,2638;Hong C.S.等,Angew.Chem.Int.Ed.,2015,54,5142)。
另外,本专利实施例四中的MOF材料[(CH3)2NH2][Eu(C2O4)2(H2O)]·3H2O(4)的晶体结构已有报道(参见:Ng S.W.等,Acta Cryst.,2005,E61,m1912),但该文献仅报道了MOF 4晶体的高温水热合成,并没有注明产率,也没有对其进行任何光谱表征和质子导电性质方面的研究。
发明内容
本发明的目的是针对上述技术现状,为了改进现有技术的不足而提供一种高质子导电金属有机骨架材料的合成方法。
本发明的技术方案为:一种高质子导电金属有机骨架材料的合成方法,其具体步骤为:
A.向含有草酸和一价有机胺盐的水溶液中,滴加三价金属盐和一价有机胺盐的水溶液,搅拌反应10-60分钟后;抽滤,分离沉淀,用水洗涤,空气中干燥,得目标产物高质子导电金属有机骨架材料;
或者为A1.将三价金属氧化物、酸和水按一定摩尔比混合,待溶液澄清后,用有机胺调节溶液pH=2~4;然后将其加入含有草酸和一价有机胺盐的水溶液中,搅拌反应10-60分钟后;抽滤,分离沉淀,用水洗涤,空气中干燥,得目标产物高质子导电金属有机骨架材料;
上述所合成的高质子导电金属有机骨架材料的结构通式为:(HA)[Ln(C2O4)2(H2O)]·3H2O,其中A为二甲胺(CH3)2NH或咪唑(Im);Ln为Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb或Lu。
优选步骤A中所述的三价金属盐为LnCl3、Ln(NO3)3或Ln(OAc)3;步骤A或A1中所述的一价有机胺盐为二甲胺盐酸盐、二甲胺硝酸盐、二甲胺醋酸盐、咪唑盐酸盐、咪唑硝酸盐或咪唑醋酸盐;步骤A1中所述的三价金属氧化物为Ln2O3;步骤A1中所述的酸为盐酸、硝酸或醋酸;步骤A1中所述的有机胺为二甲胺或咪唑。
优选步骤A中一价有机胺盐、三价金属盐和草酸的摩尔比为(5~30):1:(2~2.5)。
优选步骤A1中一价有机胺盐(是指加入的一价有机胺盐和由有机胺和酸生成的一价有机胺盐的总摩尔量)、三价金属氧化物、酸和草酸的摩尔比为(15~60):1:(10~30):(4~5)。
本发明所制备的材料可作为高质子导电材料的应用。
有益效果:
1、制备的MOF材料有高的质子导电性质(在55℃和95%的相对湿度下电导率为2.58~2.73×10-3S/cm),可用作燃料电池的质子交换膜,为燃料电池的实用化奠定良好的基础,对国家的“节能减排”有重要的贡献。
2、制备的MOF材料在空气、水中稳定,不与普通的酸及有机溶剂反应,具有很高的热稳定性(大于330℃),能满足实际应用的要求。
3、制备MOF材料时采用水作为溶剂,绿色环保。
4、制备MOF材料的原料易得,且价格便宜。
5、MOF材料的生产工艺简单,反应条件温和,产率高,生产效率高,易于工业化生产。
附图说明
图1为实施例一中MOF 1材料单晶的不对称单元结构图;
图2为实施例一至六中MOFs 1-6材料的粉末X-射线衍射(PXRD)图;
图3为实施例四中的MOF 4材料的三维孔道结构图;
图4为实施例四中的MOF 4材料红外光谱(FT-IR)图;
图5为实施例四中的MOF 4材料在95%相对湿度下的变温交流阻抗谱;
图6为实施例四中的MOF 4材料简化的三维孔道结构图。
具体实施方式
下面通过实例对本发明作进一步说明,但不限制本发明的保护范围。
实施例一:[(CH3)2NH2][Y(C2O4)2(H2O)]·3H2O(1)的制备
将Y(NO3)3·6H2O(3.83g,0.01mol)和二甲胺盐酸盐(2.04g,0.025mol)溶于50mL水中,在搅拌下,将其滴加到草酸(2.52g,0.02mol)和二甲胺盐酸盐(2.04g,0.025mol)的50mL水溶液中,搅拌10分钟反应结束。抽滤,白色沉淀用水洗涤,常温干燥,得3.68g,产率96%。
FT-IR(KBr,cm-1):3455(b,m),3103(m),2827(w),1629(vs),1321(m),1023(w),795(m)。元素分析:C6H16NO12Y,计算值(%):C 18.81,H 4.21,N 3.66;实验值(%):C 18.77,H4.10,N 3.78。MOF 1属于单斜晶系,P21/n空间群,晶胞参数分别为:β=99.083(3)°。MOF 1单晶的不对称单元结构图见图1。MOF 1材料的粉末X-射线衍射图见图2。MOF 1材料在55℃和95%的相对湿度下电导率为2.65×10-3S/cm。
实施例二:[(CH3)2NH2][La(C2O4)2(H2O)]·3H2O(2)的制备
将LaCl3·7H2O(3.71g,0.01mol)和二甲胺盐酸盐(4.08g,0.05mol)溶于50mL水中,在搅拌下,将其滴加到草酸(3.15g,0.025mol)和二甲胺盐酸盐(2.04g,0.025mol)的50mL水溶液中,搅拌25分钟反应结束。抽滤,白色沉淀用水洗涤,常温干燥,得4.11g,产率95%。
FT-IR(KBr,cm-1):3454(b,m),3112(m),2822(w),1617(vs),1314(m),1022(w),792(m)。元素分析:C6H16NO12La,计算值(%):C 16.64,H 3.72,N 3.23;实验值(%):C 16.81,H3.59,N 3.12。MOF 2属于单斜晶系,P21/n空间群,晶胞参数分别为:β=99.747(2)°。MOF 2材料的粉末X-射线衍射图见图2。MOF 2材料在55℃和95%的相对湿度下电导率为2.70×10-3S/cm。
实施例三:[(CH3)2NH2][Ce(C2O4)2(H2O)]·3H2O(3)的制备
将Ce(OAc)3·5H2O(4.07g,0.01mol)和二甲胺盐酸盐(12.24g,0.15mol)溶于75mL水中,在搅拌下,将其滴加到草酸(3.15g,0.025mol)和二甲胺盐酸盐(12.24g,0.15mol)的75mL水溶液中,搅拌30分钟反应结束。抽滤,白色沉淀用水洗涤,常温干燥,得4.21g,产率97%。
FT-IR(KBr,cm-1):3456(b,m),3112(m),2822(w),1616(vs),1312(m),1022(w),791(m)。元素分析:C6H16NO12Ce,计算值(%):C 16.59,H 3.71,N 3.23;实验值(%):C 16.71,H3.60,N 3.10。MOF 3材料的粉末X-射线衍射图见图2。MOF 3材料在55℃和95%的相对湿度下电导率为2.61×10-3S/cm。
实施例四:[(CH3)2NH2][Eu(C2O4)2(H2O)]·3H2O(4)的制备
将Eu2O3(1.76g,0.005mol),37%盐酸(8.3mL,0.05mol)和30mL水混合,搅拌至澄清后,用二甲胺调节溶液pH=4,然后将其滴加到草酸(3.15g,0.025mol)和二甲胺盐酸盐(2.04g,0.025mol)的60mL水溶液中,搅拌15分钟反应结束。抽滤,白色沉淀用水洗涤,常温干燥,得4.19g,产率94%。
FT-IR(KBr,cm-1):3455(b,m),3109(m),2826(w),1629(vs),1321(m),1023(w),796(m)。元素分析:C6H16NO12Eu,计算值(%):C 16.15,H 3.61,N 3.14;实验值(%):C 16.31,H3.80,N 3.27。MOF 4属于单斜晶系,P21/n空间群,晶胞参数分别为:β=99.2690(10)°。MOF 4材料的粉末X-射线衍射图见图2,三维孔道结构图见图3,简化的三维孔道结构图见图6;红外光谱见图4。MOF 4材料在95%相对湿度下的变温交流阻抗谱见图5。MOF 4材料在55℃和95%的相对湿度下电导率为2.73×10-3S/cm。
实施例五:[(CH3)2NH2][Gd(C2O4)2(H2O)]·3H2O(5)的制备
将Gd2O3(1.81g,0.005mol),68%硝酸(10mL,0.15mol)和50mL水混合,搅拌至澄清后,用二甲胺调节溶液pH=2,然后将其滴加到草酸(2.52g,0.02mol)和二甲胺盐酸盐(12.04g,0.15mol)的60mL水溶液中,搅拌50分钟反应结束。抽滤,白色沉淀用水洗涤,常温干燥,得4.29g,产率95%。
FT-IR(KBr,cm-1):3454(b,m),3115(m),2825(w),1623(vs),1316(m),1022(w),795(m)。元素分析:C6H16NO12Gd,计算值(%):C 15.96,H 3.57,N 3.10;实验值(%):C 15.87,H3.35,N 3.26。MOF 5属于单斜晶系,P21/n空间群,晶胞参数分别为:β=99.312(14)°。MOF 5材料的粉末X-射线衍射图见图2。MOF 5材料在55℃和95%的相对湿度下电导率为2.68×10-3S/cm。
实施例六:[HIm][Eu(C2O4)2(H2O)]·3H2O(6)的制备
将Eu(NO3)3·6H2O(2.23g,0.005mol)和咪唑盐酸盐(2.61g,0.025mol)溶于50mL水,在搅拌下,将其滴加到草酸(1.26g,0.01mol)和咪唑盐酸盐(2.61g,0.025mol)的50mL水溶液中,搅拌60分钟反应结束。抽滤,白色沉淀用水洗涤,常温干燥,得2.23g,产率95%。
FT-IR(KBr,cm-1):3448(b,s),3171(m),1636(vs),1400(m),1319(m),799(m)。元素分析:C7H13N2O12Eu,计算值(%):C 17.92,H 2.79,N 5.97;实验值(%):C 18.04,H 2.94,N5.82。MOF 6材料的粉末X-射线衍射图见图2。MOF 6材料在55℃和95%的相对湿度下电导率为2.58×10-3S/cm。
Claims (6)
1.一种高质子导电金属有机骨架材料的合成方法,其具体步骤为:
A.向含有草酸和一价有机胺盐的水溶液中,滴加三价金属盐和一价有机胺盐的水溶液,搅拌反应10-60分钟后;抽滤,分离沉淀,用水洗涤,空气中干燥,得目标产物高质子导电金属有机骨架材料;其中一价有机胺盐、三价金属盐和草酸的摩尔比为(5~30):1:(2~2.5);
或者为A1.将三价金属氧化物、酸和水按一定摩尔比混合,待溶液澄清后,用有机胺调节溶液pH=2~4;然后将其加入含有草酸和一价有机胺盐的水溶液中,搅拌反应10-60分钟后;抽滤,分离沉淀,用水洗涤,空气中干燥,得目标产物高质子导电金属有机骨架材料;其中一价有机胺盐、三价金属氧化物、酸和草酸的摩尔比为(15~60):1:(10~30):(4~5);
上述所合成的高质子导电金属有机骨架材料的结构通式为:(HA)[Ln(C2O4)2(H2O)]·3H2O,其中A为二甲胺(CH3)2NH或咪唑(Im);Ln为Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb或Lu。
2.根据权利要求1所述的合成方法,其特征是步骤A中所述的三价金属盐为LnCl3、Ln(NO3)3或Ln(OAc)3。
3.根据权利要求1所述的合成方法,其特征是步骤A或A1中所述的一价有机胺盐为二甲胺盐酸盐、二甲胺硝酸盐、二甲胺醋酸盐、咪唑盐酸盐、咪唑硝酸盐或咪唑醋酸盐。
4.根据权利要求1所述的合成方法,其特征是步骤A1中所述的三价金属氧化物为Ln2O3。
5.根据权利要求1所述的合成方法,其特征是步骤A1中所述的酸为盐酸、硝酸或醋酸。
6.根据权利要求1所述的合成方法,其特征是步骤A1中所述的有机胺为二甲胺或咪唑。
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Non-Patent Citations (3)
Title |
---|
Poly[dimethylammonium [aquadi-μ2-oxalato-dysprosate(III)] trihydrate];Su-Fang Ye等;《ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE》;20100831;第66卷;第m901-m902页,supporting information * |
Poly[dimethylammonium [aquadi-μ2-oxalato-yttriate(III)] trihydrate];Yao-Kang Lv等;《ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE》;20110630;第67卷;第m837-m838页,supporting information * |
Poly[dimethylammonium aquadi-μ-oxalato-europate(III) trihydrate];Yang-Yi Yang等;《ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE》;20050907;第61卷;第m1912-m1914页,supporting information * |
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