CN106220686A - 具有氢气吸附性质的蒽环双三唑间苯二甲酸钴配合物单晶与应用 - Google Patents
具有氢气吸附性质的蒽环双三唑间苯二甲酸钴配合物单晶与应用 Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 31
- 239000001257 hydrogen Substances 0.000 title claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 150000001454 anthracenes Chemical class 0.000 title claims abstract description 18
- -1 triazole M-phthalic acid cobalt complex Chemical class 0.000 title claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 title abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 17
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- ABMDIECEEGFXNC-UHFFFAOYSA-N n-ethylpropanamide Chemical compound CCNC(=O)CC ABMDIECEEGFXNC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000011232 storage material Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000005260 alpha ray Effects 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 abstract description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 abstract 2
- 238000003860 storage Methods 0.000 description 9
- 239000012621 metal-organic framework Substances 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
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- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
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Abstract
本发明公开了具有氢气吸附性质的蒽环双三唑间苯二甲酸钴配合物单晶与应用,其结构:[Co(L)(ipa)]·0.5DEMC,其中,L=1‑[9‑(1H‑1,2,4‑三氮唑‑1‑基)蒽‑10‑基]‑1H‑1,2,4‑三氮唑,ipa=间苯二甲酸;DEMC=N,N'‑二乙基甲酰胺。同时还公开了单晶的制备方法。它是采用“常温挥发法”,即Co(NO3)2·6H2O、ipa和L在水和DEMC的混合溶剂中搅拌半小时后过滤,滤液常温挥发一周后得到适合X‑射线单晶衍射的红褐色块状晶体。其中Co(NO3)2·6H2O、ipa和L的摩尔比为1:1:1。本发明进一步公开了蒽环双三唑间苯二甲酸钴配合物单晶作为储氢材料吸附氢气方面的应用。
Description
本发明得到天津市教委创新团队(TD12-5037)的资助。
技术领域
本发明涉及三唑有机酸钴配合物储氢材料的制备方法及其应用,更具体的说是一种蒽环双三唑间苯二甲酸钴配合物单晶与应用。
背景技术
金属-有机框架(MOFs)的合成与性质研究是二十世纪九十年代后期发展起来的无机化学和材料化学中重要的研究领域之一。由于开放的金属-有机配位聚合物密度小,仅是传统金属氢化物的三分之一,采用MOFs作为储氢介质可大大降低储氢器的重量。这一特点尤其符合氢燃料电池汽车的供氢系统要求。此外该类材料还具有比表面积大、孔洞体积大的特点,因此是一种新型高容量轻质储氢材料,近年来已成为一种新型简便的储氢方法应运而生。一般说来,储氢机理可分为化学吸附和物理吸附,而配合物的储氢机制大多为物理吸附。1997年日本的Kitagawa等报道了4,4’-联吡啶构筑的金属-有机框架具有吸附气体小分子的性质之后[S. Kitagawa等, Angew.Chem.Int.Ed.1997,36, 1725],相关研究引起了世界各国的广泛重视。2003年美国科学家Yaghi等报道了微孔金属-有机框架MOF-5具有良好的储氢性能后[O. M. Yaghi等, Science2003, 300, 1127],金属-有机框架储氢技术逐渐成为二十一世纪国际新兴的前沿研究领域。
发明内容
本发明即是选用Co(NO3)2·6H2O、ipa和L在水和DEMC的混合溶剂中搅拌半小时后过滤,滤液常温挥发一周后得到适合X-射线单晶衍射的红褐色块状晶体[Co(L)(ipa)]·0.5DEMC (1) (L = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑;ipa =间苯二甲酸;DEMC = N,N'-二乙基甲酰胺)。该配合物单晶作为储氢材料可以对氢气进行吸附。
为此本发明人提供了如下的技术方案:
一种蒽环双三唑间苯二甲酸钴配合物单晶,其特征在于该单晶结构采用APEX II CCD单晶衍射仪,使用经过石墨单色化的Mokα射线,λ = 0.71073 Å为入射辐射,以ω-2θ扫描方式收集衍射点,经过最小二乘法修正得到晶胞参数,从差值傅立叶电子密度图利用SHELXL-97直接法解得单晶数据:
其化学结构如下:
[Co(L)(ipa)]·0.5DEMC,其中
L = 1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑;
ipa = 间苯二甲酸;
DEMC = N,N'-二乙基甲酰胺。
本发明进一步公开了蒽环双三唑间苯二甲酸钴配合物单晶的制备方法,其特征在于它是采用“常温挥发法”,即Co(NO3)2·6H2O、ipa和L在水和DEMC的混合溶剂中搅拌半小时后过滤,滤液常温挥发一周后得到适合X-射线单晶衍射的红褐色块状晶体;其中L、ipa和Co(NO3)2·6H2O的摩尔比为1:1:1;
蒽环双三唑间苯二甲酸钴配合物单晶的结构为[Co(L)(ipa)]·0.5DEMC;其中L = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑;ipa = 间苯二甲酸;DEMC = N,N'-二乙基甲酰胺;
L ipa。
本发明更进一步公开了蒽环双三唑间苯二甲酸钴配合物单晶作为储氢材料在制备对氢气吸附方面的应用,实验结果显示:蒽环双三唑间苯二甲酸钴二维配位框架配合物单晶在大约3.4 MPa下,298和77 K时,该储氢孔材料的氢气吸附量分别达到了0.87 和1.38wt%。
本发明公开的一种蒽环双三唑间苯二甲酸钴配合物单晶所具有的优点和特点在于:
(1) 反应操作简便易行。
(2) 反应收率高,所得产品的纯度高。
(3) 本发明所制备的蒽环双三唑间苯二甲酸钴配合物单晶,生产成本低,方法简便,适合大规模生产。蒽环双三唑间苯二甲酸钴配合物单晶作为储氢材料在储存氢气方面具有良好的应用效果。
附图说明
图1:配合物单晶的晶体结构图;
图2:配合物单晶的二维结构图;
图3:吸氢曲线。
具体实施方式
下面结合实施例对本发明做进一步的说明,实施例仅为解释性的,决不意味着它以任何方式限制本发明的范围。所有的原料例如:蒽环等都是从国内外的化学试剂公司进行购买,没有经过继续提纯而是直接使用的。所用原料9,10-二溴蒽、1H-1,2,4-三氮唑、碳酸钾、氧化铜、间苯二甲酸和硝酸钴等均有市售。
实施例1
9,10-二溴蒽:1H-1,2,4-三唑:碳酸钾:氧化铜的摩尔比为2:10-15:30:1
在装有磁子、回流冷凝器和温度计的50 mL三口圆底烧瓶内分别加入CuO (0.0398 mg,0.5 mmol),碳酸钾(2.0731 g,15 mmol),三唑(0.345 mg,5 mmol),9,10-二溴蒽(0.3360g,1 mmol),20 mL DMF。开动搅拌在100 oC,反应24小时。反应结束后,将反应液降至室温,过滤,滤液加入100 mL水,析出大量沉淀,抽滤,收集滤饼,收率60%。
实施例2
1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑 (0.1 mmol)、间苯二甲酸(0.1 mmol)和Co(NO3)2·6H2O (0.1 mmo)在10 mL水和2 mL N,N'-二乙基甲酰胺的混合溶剂中搅拌半小时后过滤,滤液呈红褐色。常温挥发一周后有适合X-射线单晶衍射的红褐色块状晶体。产率:35%。元素分析(C28.5H21.5CoN6.5O4.5) 理论值(%):C,58.42;H,3.70;N,15.54。实测值:C,58.47;H,3.72;N,15.29。
实施例3
晶体结构测定采用APEX II CCD单晶衍射仪,使用经过石墨单色化的Mokα射线,λ =0.71073 Å为入射辐射,以ω-2θ扫描方式收集衍射点,经过最小二乘法修正得到晶胞参数,从差值傅立叶电子密度图利用软件解出晶体结构,并经洛仑兹和极化效应修正。所有的H原子由差值傅立叶合成并经理想位置计算确定。详细的晶体测定数据:
实施例4
该金属-有机框架储氢孔材料的吸氢曲线如图3所示。在298和77 K下进行的氢气吸附实验是一个很快的吸附过程,在几秒钟之内达到了热力学平衡,我们认为这是物理吸附过程。该吸附过程属于第一类气体吸附类型,这也是MOFs微孔材料吸附气体分子最典型的一种。氢气位于在孔道内,而孔道的大小限制了吸附量为一层或者几层氢气分子。在大约3.4MPa和77 K时,氢气的吸附量达到了1.38 wt%。
在详细说明的较佳实施例之后,熟悉该项技术人士可清楚地了解,在不脱离上述申请专利范围与精神下可进行各种变化与修改,凡依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均属于本发明技术方案的范围。且本发明亦不受说明书中所举实例实施方式的限制。
Claims (3)
1.一种蒽环双三唑间苯二甲酸钴配合物的单晶,其特征在于该单晶结构采用APEX IICCD单晶衍射仪,使用经过石墨单色化的Mokα射线,λ = 0.71073 Å为入射辐射,以ω-2θ扫描方式收集衍射点,经过最小二乘法修正得到晶胞参数,从差值傅立叶电子密度图利用软件解出单晶数据:
其化学结构如下:
[Co(L)(ipa)]·0.5DEMC,其中
L = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑;
ipa = 间苯二甲酸;
DEMC = N,N'-二乙基甲酰胺。
2.权利要求1所述蒽环双三唑间苯二甲酸钴配合物单晶的制备方法,其特征在于它是采用“常温挥发法”,即,即Co(NO3)2·6H2O、ipa和L在水和DEMC的混合溶剂中搅拌半小时后过滤,滤液常温挥发一周后得到适合X-射线单晶衍射的红褐色块状晶体;其中,Co(NO3)2·6H2O、ipa和L的摩尔比为1:1:1;
蒽环双三唑间苯二甲酸钴配合物单晶的结构为[Co(L)(ipa)]·0.5DEMC;其中L = 1-[9-(1H-1,2,4-三氮唑-1-基)蒽-10-基]-1H-1,2,4-三氮唑;ipa = 间苯二甲酸;DEMC = N,N'-二乙基甲酰胺;
L ipa。
3.权利要求1所述蒽环双三唑间苯二甲酸钴配合物单晶作为储氢材料在制备对氢气吸附方面的应用。
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