CN106831830A - 一种超分子笼配合物及其制备方法和应用 - Google Patents
一种超分子笼配合物及其制备方法和应用 Download PDFInfo
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- CN106831830A CN106831830A CN201710051410.2A CN201710051410A CN106831830A CN 106831830 A CN106831830 A CN 106831830A CN 201710051410 A CN201710051410 A CN 201710051410A CN 106831830 A CN106831830 A CN 106831830A
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- Prior art keywords
- cage complex
- complex
- supramolecular
- electrode
- supramolecular cage
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000862 absorption spectrum Methods 0.000 claims description 17
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- DGGZHROWZDIUAL-UHFFFAOYSA-N 1-[(4-carboxyphenyl)methyl]-2H-pyridine-4-carboxylic acid Chemical compound C(=O)(O)C1=CC=C(CN2CC=C(C(=O)O)C=C2)C=C1 DGGZHROWZDIUAL-UHFFFAOYSA-N 0.000 claims description 13
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- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical class N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 claims description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
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- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
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- 239000011777 magnesium Substances 0.000 claims description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
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- 229910052725 zinc Inorganic materials 0.000 claims description 2
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- 241000534944 Thia Species 0.000 abstract 1
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- 238000012360 testing method Methods 0.000 description 11
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- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical class C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 3
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
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- 125000001624 naphthyl group Chemical group 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- 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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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Immunology (AREA)
- Optics & Photonics (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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Abstract
本发明涉及一种超分子笼配合物及其制备方法和用途,所述超分子笼配合物的结构为:{[M4(μ4‑B)(X)]2Y4}m+Zn‑ m/n。其中M为金属元素;B为H2O(水)或OH;X为硫杂杯[4]芳烃配体;Y为二羧酸配体;Zn‑为阴离子,n为1、2,m为2或4。本发明的超分子笼配合物可以用于检测吡啶氨类化合物。本发明还涉及一种电解水产氧电极及其制备方法和用途,以本发明所述的超分子笼配合物作为催化剂,制备得到的电极应用于电解水析氧反应,过电位可达290mV。经过48h测试,其产氧效果仍保持在99%以上,具有优良的活性和稳定性。
Description
技术领域
本发明属于超分子笼配合物材料领域,涉及一种超分子笼配合物及其制备方法和应用。本发明所述超分子笼配合物可用于检测吡啶氨类化合物或作为催化剂用于电解水析氧反应中。
背景技术
具有特定空腔结构的超分子,可以作为分子容器,通过选择性束缚或包含具有特定大小、构型及官能团的客体分子。这类超分子利用主客体包容作用为所包含的客体分子提供特殊的化学微环境,可应用于封装不稳定的化合物,储存、分离及传输小分子化合物,模板合成单分散的纳米颗粒,以及药物传输等,所以一直以来受到科学研究工作者的广泛关注。
具有高度可控性及金属-配体之间的刚性键合作用的分立配位超分子笼化合物,作为一个重要的研究热点,一直受到国内外许多研究学者的长期关注。这类配位分子笼化合物都具有模板化合成、结构可调控和独特纳米空腔等特征。但是,目前的研究大部分仅停留于分立配位超分子笼化合物对不同客体小分子的结合、包容研究,以及少量的作为反应容器应用于有机催化等。所以,拓展研究配位分子笼的功能化策略,并进一步实现超分子笼材料在传感、能源等领域的应用具有非常重要的意义。
发明内容
本发明的目的是提供一种超分子笼配合物及其制备方法和应用。
本发明的目的通过如下方式实现:
第一方面,本发明提供了一种超分子笼配合物,其结构通式为:
{[M4(μ4-B)(X)]2Y4}m+Zn- m/n;
其中,
M为选自镁、锌、锰、钴、镍、铜、铁、钌的金属元素;
B为H2O(水)或OH;μ4代表4个M与4-配位的O原子形成桥联配位。
X为硫杂杯[4]芳烃配体,其分子结构为:
R1为氢、烷基、芳基;A为S、SO、SO2;
Y为二羧酸配体,其分子结构为:
R2、R3独立的选自氮或碳;
Zn-为阴离子,例如OH-、F-、Cl-、Br-、I-、ClO4 -、PF6 -、SbF6 -、BF4 -、SiF6 2-等,n为1、2,m为2或4。
根据本发明,所述超分子笼配合物阳离子的立体结构如下式(1)所示:
本发明中,所述的烷基是指碳原子数为1-10的直链和支链烷基,优选碳原子4-8的支链烷基,例如,叔丁基、叔戊基、叔辛基等。
所述的芳基是指具有6-20个碳原子的单环、多环芳族基团,代表性的芳基包括:苯基、萘基等。
根据本发明,所述R1优选为叔丁基、叔辛基、苯基;A优选为SO2;B优选为OH。
根据本发明,所述X优选为5,11,17,23-四叔丁基-磺酰基桥连杯[4]芳烃配体,Y优选为1-(4-羧基苄基)异烟酸配体。
具体的,本发明所述的配合物可以为:
{[Zn4(μ4-OH)(TBSC)]2[(DC]4}Br2、{[Ni4(μ4-OH)(TBSC)]2[(DC]4}Br2、{[Co4(μ4-OH)(TBSC)]2[(DC]4}Br2,其中TBSC代表5,11,17,23-四叔丁基-磺酰基桥连杯[4]芳烃配体,DC代表1-(4-羧基苄基)异烟酸配体)。
第二方面,本发明提供了一种制备所述超分子笼配合物的方法,包括如下步骤:将H4X、溴化物H2YBr和M金属盐在有机溶剂中进行自组装反应,得到Zn-为Br-的超分子笼配合物,任选的使用其他阴离子来置换Br-,其中,X、Y、M、Zn-如上所述。
根据本发明,M金属盐优选为硝酸盐或卤代盐。
根据本发明,所述有机溶剂优选为酰胺溶剂,例如N,N'-二甲基甲酰胺(DMF)。
根据本发明,在所述方法中,X:Y:M的摩尔比为0.9~1.1:1.8~4.5:4.0~7.0,优选摩尔比为1:2.2:5。
根据本发明,所述反应在25~140℃温度下进行。优选的,在100~120℃反应温度下,得到超分子笼配合物材料的结晶产物。
第三方面,本发明提供了所述超分子笼配合物在检测吡啶氨类化合物中的应用。所述检测可以通过光谱进行。
根据本发明,超分子笼配合物和待分析的吡啶氨类化合物在溶剂中混合之后,超分子笼配合物和吡啶氨类化合物可形成主客体复合物,它们之间可发生电荷转移,通过检测超分子笼配合物的吸收光谱和/或荧光光谱的最大吸收峰/荧光发射峰的位置变化即可实现对被分析物的检测。
本发明还提供了一种吡啶氨类化合物的检测方法,包括以下步骤:
1)将本发明所述的超分子笼配合物和溶剂混合,检测所得溶液的吸收光谱和/或荧光光谱。所述溶剂优选为二甲基亚砜(DMSO)。所述超分子笼配合物的浓度优选为1×10-6M~1×10-3M,更优选为5×10-6M;
2)将待测物与上述超分子笼配合物溶液混合,检测该溶液的吸收光谱和/或荧光光谱;
3)将步骤2)得到的吸收光谱和/或荧光光谱与步骤1)中得到的超分子笼配合物的吸收光谱和/或荧光光谱进行比较,当最大吸收峰位置或荧光发射峰位置发生蓝移,说明待测物中含有吡啶氨类化合物。
根据本发明,所述待分析物的浓度优选为1×10-4M~1×10-1M,更优选为5×10-4M。
所述混合溶液中待分析物和超分子笼配合物的的摩尔比为0.1~10:1。
本发明对检测光谱强度的设备没有特别限定,优选为紫外光谱仪和荧光光谱仪。
本发明所述超分子笼配合物,可以实现对吡啶氨类化合物的高选择性、高灵敏性和高准确性的传感。其中,优选的吡啶氨类化合物为2-(氨基甲基)吡啶。
第四方面,本发明提供了一种电极,所述电极包含本发明第一方面所述的超分子笼配合物。
本发明还提供一种上述电极的制备方法,包括:将本发明所述的超分子笼配合物和聚偏氟乙烯(PVDF)混合并分散到溶剂(例如N-甲基吡咯烷酮(NMP))中,制备得到催化剂浆料;然后,将得到的催化剂浆料涂到电极(例如泡沫镍)上,干燥,得到电极。
本发明还提供上述电极用于电解水析氧反应。
由于本发明的超分子笼配合物晶体呈片状结构,且具多空腔、大比表面积的优点,使其能更好的和电极表面接触,从而有利于克服电化学产氧过程中的传质、扩散及材料电阻的影响,电解水过电位大大降低,电解水效率得到了极大的提高,具有很好的电催化产氧活性和电化学稳定性,经过48h测试,其产氧效果仍保持在99%以上,具有极高的实际应用价值。
与现有技术相比,本发明具有如下优点:
1)本发明所述超分子笼配合物的制备方法在常温或较低温度(如120℃)条件下即可进行,不仅简单快速而且节能高效,原料和试剂来源广泛并且价格低廉,有利于大规模应用;
2)本发明的超分子笼配合物可应用于光谱传感吡啶氨类化合物,提供的吸收光谱或荧光光谱传感检测方法具有灵敏度高、响应快速、容易与探测仪集成等优点,克服了其他传感技术操作复杂、仪器昂贵、响应速率慢等缺点,使其开发更加灵敏的吡啶氨类化合物探测仪成为可能。
3)本发明的超分子笼配合物作为催化剂应用于电解水析氧反应,具有很好的电催化产氧活性和电化学稳定性,在10mA/cm2下的过电位可达290mV。经过48h测试,其产氧效果仍保持在99%以上,且价格低廉,具有极大的应用前景。
附图说明:
图1为实施例1制得的超分子笼配合物阳离子晶体结构示意图
图2为实施例1制得的超分子笼配合物与不同浓度的2-(氨基甲基)吡啶在二甲基亚砜中的紫外吸收光谱图。
图3为实施例1制得的超分子笼配合物与不同浓度的2-(氨基甲基)吡啶在二甲基亚砜中的荧光发射谱图。
图4为实施例1制得的超分子笼配合物与不同浓度的苄胺在二甲基亚砜中的紫外吸收光谱图。
图5为实施例1制得的超分子笼配合物与不同浓度的苄胺在二甲基亚砜中的荧光发射谱图。
图6为实施例1制得的超分子笼配合物与不同浓度的苯胺在二甲基亚砜中的紫外吸收光谱图。
图7为实施例1制得的超分子笼配合物与不同浓度的苯胺在二甲基亚砜中的荧光发射谱图。
图8为本发明实施例2-3得到的超分子笼配合物制备的电极的电解水产氧线性伏安扫面曲线对比图;
图9为本发明实施例2-3得到的超分子笼配合物制备的电极的电解水产塔菲尔曲线图;
图10为本发明实施例3得到的金属有机配合物纳米片制备的电极的电解水长时间稳定性测试图。
具体实施方式:
为了使本发明的发明目的、技术方案和技术效果更加清晰,以下结合附图和实施例对本发明进行进一步详细说明。应当理解的是,本说明书中描述的实施例只是为了解释本发明,而非限定本发明。所附权利要求概括了本发明的范围,但在本发明的构思引导下,对本发明的各实施例方案所进行的一定改变,都将被本发明的权利要求书的精神和范围所覆盖。
实施例1:制备超分子笼配合物{[Zn4(μ4-OH)(TBSC)]2[(DC]4}Br2(其中TBSC代表5,11,17,23-四叔丁基-磺酰基桥连杯[4]芳烃配体,DC代表1-(4-羧基苄基)异烟酸配体)
Zn(NO3)2·6H2O(148.9mg,0.5mmol),溴化1-(4-羧基苄基)异烟酸(74.4mg,0.22mmol)和H4TBSC(84.9mg,0.1mmol)溶解于2.4mL的N,N'-二甲基甲酰胺(DMF)中,以0.5℃/min的加热速率加热到110℃,温度保持在110℃反应24h后缓慢降温,得到黄色晶体。产率:75%。
对产物进行红外、氢谱、X射线单晶衍射等表征。
具体结果如下:
核磁共振磷谱(d6-DMSO,ppm):9.09-9.16(d,8H),8.26-8.33(d,8H),7.96(s,16H),7.70-7.77(d,8H),7.45-7.55(d,8H),5.91(s,8H),1.14(s,72H).
红外光谱(KBr,cm-1):3051,2960,1655,1635,1610,1569,1492,1418,1385,1363,1287,1260,1134,1081,798,780,765,625,564。
表1.{[Zn4(μ4-OH)(TBSC)]2[(DC]4}Br2的晶体学参数
上述数据表明本实施例得到了目标产物{[Zn4(μ4-OH)(TBSC)]2[(DC]4}Br2(其中TBSC代表5,11,17,23-四叔丁基-磺酰基桥连杯[4]芳烃配体,DC代表1-(4-羧基苄基)异烟酸配体)。
实施例2:制备超分子笼配合物{[Ni4(μ4-OH)(TBSC)]2[(DC]4}Br2(其中TBSC代表5,11,17,23-四叔丁基-磺酰基桥连杯[4]芳烃配体,DC代表1-(4-羧基苄基)异烟酸配体)
Ni(NO3)2·6H2O(145.2mg,0.5mmol),溴化1-(4-羧基苄基)异烟酸(74.4mg,0.22mmol)和H4TBSC(84.9mg,0.1mmol)溶解于2.4mL的N,N'-二甲基甲酰胺(DMF)中,以0.5℃/min的加热速率加热到110℃,温度保持在110℃反应24h后缓慢降温,得到绿色晶体。产率:85%。
对产物进行红外、X射线单晶衍射等表征。
具体结果如下:
红外光谱(KBr,cm-1):3055,2962,1658,1496,1427,1288,1265,1134,1080,802,771,570。
表1.{[Ni4(μ4-OH)(TBSC)]2[(DC]4}Br2的晶体学参数
上述数据表明本实施例得到了目标产物{[Ni4(μ4-OH)(TBSC)]2[(DC]4}Br2(其中TBSC代表5,11,17,23-四叔丁基-磺酰基桥连杯[4]芳烃配体,DC代表1-(4-羧基苄基)异烟酸配体)。
实施例3:制备超分子笼配合物{[Co4(μ4-OH)(TBSC)]2[(DC]4}Br2(其中TBSC代表5,11,17,23-四叔丁基-磺酰基桥连杯[4]芳烃配体,DC代表1-(4-羧基苄基)异烟酸配体)
Co(NO3)2·6H2O(145.5mg,0.5mmol),溴化1-(4-羧基苄基)异烟酸(74.4mg,0.22mmol)和H4TBSC(84.9mg,0.1mmol)溶解于2.4mL的N,N'-二甲基甲酰胺(DMF)中,以0.5℃/min的加热速率加热到110℃,温度保持在110℃反应24h后缓慢降温,得到红色晶体。产率:88%。
对产物进行红外、X射线单晶衍射等表征。
具体结果如下:
红外光谱(KBr,cm-1):2962,1658,1612,1496,1458,1419,1388,1265,1134,1080,802,624,563,486。
表1.{[Co4(μ4-OH)(TBSC)]2[(DC]4}Br2的晶体学参数
上述数据表明本实施例得到了目标产物{[Co4(μ4-OH)(TBSC)]2[(DC]4}Br2(其中TBSC代表5,11,17,23-四叔丁基-磺酰基桥连杯[4]芳烃配体,DC代表1-(4-羧基苄基)异烟酸配体)。
实施例4:
考察实施例1制得的超分子笼配合物与2-(氨基甲基)吡啶在二甲基亚砜(DMSO)溶液中的相互作用。超分子笼配合物的浓度为6×10-6M,2-(氨基甲基)吡啶的浓度为6×10-6M~6×10-5M。检测其紫外吸收强度和荧光发射强度,荧光发射激发波长为340nm,结果如图2和图3所示。图2是本发明实施例1制得的超分子笼配合物与不同浓度的2-(氨基甲基)吡啶在二甲基亚砜中的紫外吸收光谱图。图3是本发明实施例1制得的超分子笼配合物与不同浓度的2-(氨基甲基)吡啶在二甲基亚砜中的荧光发射谱图。
由图2可知,实施例1制得的超分子笼配合物的最大吸收峰位置随着2-(氨基甲基)吡啶浓度的增加而逐渐蓝移。由图3可知,实施例1制得的超分子笼配合物的荧光发射峰位置随着2-(氨基甲基)吡啶浓度的增加而逐渐蓝移,发光颜色从绿色变成蓝色。说明本实施例提供的检测方法,包括紫外吸收光谱和荧光光谱都可以用来传感检测2-(氨基甲基)吡啶化合物。
实施例5:
考察了实施例1制得的超分子笼配合物与苄胺在二甲基亚砜(DMSO)溶液中的相互作用。超分子笼配合物的浓度为6×10-6M,苄胺的浓度为6×10-6M~6×10-5M。检测其紫外吸收强度和荧光发射强度,荧光发射激发波长为340nm,结果如图4和图5所示。图4是本发明实施例1制得的超分子笼配合物与不同浓度的苄胺在二甲基亚砜中的紫外吸收光谱图。图5是本发明实施例1制得的超分子笼配合物与不同浓度的苄胺在二甲基亚砜中的荧光发射谱图。
由图4可知,实施例1制得的超分子笼配合物的最大吸收峰随着苄胺浓度的增加而降低。由图5可知,实施例1制得的超分子笼配合物的荧光发射峰位置随着苄胺浓度的增加而逐渐淬灭,最终被淬灭了约50%。
实施例6:
考察了实施例1制得的超分子笼配合物与苯胺在二甲基亚砜(DMSO)溶液中的相互作用。超分子笼配合物的浓度为6×10-6M,苯胺的浓度为6×10-6M~6×10-5M。检测其紫外吸收强度和荧光发射强度,荧光发射激发波长为340nm,结果如图6和图7所示。图6是本发明实施例1制得的超分子笼配合物与不同浓度的苯胺在二甲基亚砜中的紫外吸收光谱图。图7是本发明实施例1制得的超分子笼配合物与不同浓度的苯胺在二甲基亚砜中的荧光发射谱图。
由图6可知,实施例1制得的超分子笼配合物的吸收峰随着苯胺浓度的变化基本没有改变。由图7可知,实施例1制得的超分子笼配合物的荧光发射峰位置随着苄胺浓度的变化几乎没有任何淬灭。
由上述实施例5和6的实验结果可以看出,本发明所述的超分子笼配合物配合物在对于苄胺、或苯胺的检测中,紫外吸收光谱图或者荧光发射图中均未发生蓝移,说明本发明的配合物对于吡啶氨类化合物的检测具有选择性。
实施例7:实施例2制得的超分子笼配合物应用于电解水析氧的研究
①电极的制备:将实施例2制得的超分子笼配合物和聚偏氟乙烯(PVDF)混合并分散到N-甲基吡咯烷酮(NMP)中,制备得到催化剂浆料;然后,将得到的催化剂浆料滴涂到泡沫镍电极上,干燥,得到电极;
②电解水析氧反应的活性研究
将制备的电极在1M的KOH水溶液中进行线性循环伏安测试,测试结果见图8和图9。
测试结果表明,以实施例2作为催化剂并制备得到的电极表现出了很好的电化学氧析出活性,在10mA/cm2,20mA/cm2和50mA/cm2下的过电位分别为302mV,326mV和372mV。
实施例8:实施例3制得的超分子笼配合物应用于电解水析氧的研究
①电极的制备:将实施例3制得的超分子笼配合物和聚偏氟乙烯(PVDF)混合并分散到N-甲基吡咯烷酮(NMP)中,制备得到催化剂浆料;然后,将得到的催化剂浆料滴涂到泡沫镍电极上,干燥,得到电极;
②电解水析氧反应的活性研究
将制备的电极在1M的KOH水溶液中进行线性循环伏安测试,测试结果见图8和图9。
测试结果表明,以实施例3制得的超分子笼配合物作为催化剂并制备得到电极,由于其独特的结构,由其制得的电极表现出了很好的电化学氧析出活性,在10mA/cm2,20mA/cm2和50mA/cm2下的过电位分别为290mV,313mV和351mV。
③电解水析氧反应的稳定性研究
将制备的电极在1M KOH水溶液中进行恒电位电解水产氧测试(在1.48V条件下电解水),测试结果见图10。结果表明,由实施例3制得的超分子笼配合物制得的电极表现出了非常稳定的氧析出性质。
Claims (10)
1.一种超分子笼配合物,其结构通式为:
{[M4(μ4-B)(X)]2Y4}m+Zn- m/n;
其中,
M为选自镁、锌、锰、钴、镍、铜、铁、钌的金属元素;
B为H2O(水)或OH;μ4代表4个M与4-配位的O原子形成桥联配位。
X为硫杂杯[4]芳烃配体,其分子结构为:
R1为氢、烷基、芳基;A为S、SO、SO2;
Y为二羧酸配体,其分子结构为:
R2、R3独立的选自氮或碳;
Zn-为阴离子,例如OH-、F-、Cl-、Br-、I-、ClO4 -、PF6 -、SbF6 -、BF4 -、SiF6 2-等,n为1、2,m为2或4;
所述的烷基是指碳原子数为1-10的直链和支链烷基,优选碳原子数为4-8的支链烷基,所述的芳基是指具有6-20个碳原子的单环、多环芳族基团。
2.根据权利要求1所述的配合物,超分子笼配合物阳离子的立体结构如下式(1)所示:
3.根据权利要求1或2所述的超分子笼配合物,所述R1优选为叔丁基、叔辛基、苯基;A优选为SO2;B优选为OH。
所述X优选为5,11,17,23-四叔丁基-磺酰基桥连杯[4]芳烃配体,Y优选为1-(4-羧基苄基)异烟酸配体。
具体的,本发明所述的配合物可以为:
{[Zn4(μ4-OH)(TBSC)]2[(DC]4}Br2、{[Ni4(μ4-OH)(TBSC)]2[(DC]4}Br2、{[Co4(μ4-OH)(TBSC)]2[(DC]4}Br2,其中TBSC代表5,11,17,23-四叔丁基-磺酰基桥连杯[4]芳烃配体,DC代表1-(4-羧基苄基)异烟酸配体)。
4.一种权利要求1-3任一项所述的超分子笼配合物的制备方法,包括如下步骤:
将H4X、溴化物H2YBr和M金属盐在有机溶剂中进行自组装反应,得到Zn-为Br-的超分子笼配合物,任选的使用其他阴离子来置换Br-,其中,X、Y、M、Zn-如权利要求1-3中任一项所定义。
所述溶剂优选为N,N'-二甲基甲酰胺(DMF)。
优选的,X:Y:M的摩尔比为1:2.2:5。所述反应的温度在25~140℃下进行。优选的,在100~120℃反应温度下进行。
5.权利要求1-3任一项所述的超分子笼配合物在检测吡啶氨类化合物中的应用。
6.一种吡啶氨类化合物的检测方法,包括以下步骤:
1)将权利要求1-3任一项所述的超分子笼配合物和溶剂混合,检测所得溶液的吸收光谱和/或荧光光谱;
2)将待测物与上述超分子笼配合物溶液混合,检测该溶液的吸收光谱和/或荧光光谱;
3)将步骤2)得到的吸收光谱和/或荧光光谱与步骤1)中得到的超分子笼配合物的吸收光谱和/或荧光光谱进行比较,当最大吸收峰位置或荧光发射峰位置发生蓝移,说明待测物中含有吡啶氨类化合物。
7.权利要求1-3任一项所述的超分子笼配合物作为催化剂用于电解水析氧反应。
8.一种电极,其特征在于,所述电极含有权利要求1-3所述的超分子笼配合物。
9.权利要求8所述电极的制备方法,包括:将超分子笼配合物材料和聚偏氟乙烯(PVDF)混合并分散到溶剂(例如N-甲基吡咯烷酮(NMP))中,制备得到催化剂浆料;然后,将得到的催化剂浆料涂到电极上,得到电极。
10.权利要求8所述的电极用于电解水析氧反应进行产氧。
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