CN105203606A - Preparation method and application of copper metal organic framework complex-based modified gold electrode - Google Patents
Preparation method and application of copper metal organic framework complex-based modified gold electrode Download PDFInfo
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- CN105203606A CN105203606A CN201510707322.4A CN201510707322A CN105203606A CN 105203606 A CN105203606 A CN 105203606A CN 201510707322 A CN201510707322 A CN 201510707322A CN 105203606 A CN105203606 A CN 105203606A
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Abstract
The invention discloses a preparation method and application of a copper metal organic framework complex-based modified gold electrode. The electrode is prepared by using a hydro-thermal method. The preparation method comprises the following steps: 1) preparation of a copper coordination compound {[CuL(H2O)].0.5DMA}; and 2) preparation of the {[CuL(H2O)].0.5DMA} metal organic framework complex-based modified gold electrode. The modified gold electrode is used for separate detection of L-methionine and D-methionine. The invention has the following advantages: the metal organic framework complex {[CuL(H2O)].0.5DMA} is prepared for the first time and undergoes structural characterization; a novel {[CuL(H2O)].0.5DMA} modified electrochemical sensor is prepared and applied to detection of the chiral isomers L-methionine and D-methionine; and the modified gold electrode is simple to prepare and low in price and has substantial technical effects.
Description
Technical field
The present invention relates to the preparation method of a kind of preparation method based on copper metallic organic frame complex and the modified electrode based on this material, and it is in the detection technique of D-Met and METHIONINE chiral isomer.
Background technology
Methionine, also known as methionine, is a kind of sulfur-bearing essential amino acid.In methionine and biosome, the metabolism of various sulfocompound is closely related, and D type must be converted into L-type and could be utilized by body by biosome in vivo.At feed, food, medicine, agricultural and multiple field such as environmental monitoring are all widely used, and can the efficiently and accurately detection identification that realizes methionine chiral isomer be how the problem demanding prompt solutions faced now.
In recent years, metal-organic framework (MOF) is with the porous structure of its uniqueness, various coordination mode, and it obtains region of chemistry in the application in the fields such as the energy, galvanochemistry, catalysis, absorption, energy storage and pays close attention to widely.In electrochemical field, researcher finds by carrying out Electrochemical Detection to many kinds of substance, as the people such as DianaM utilize Pmo at electrode face finish MOF material
12v
2mIL-101 (Cr) porous modified electrode achieves the synchronous detection of dopamine and ascorbic acid; HadiHosseini etc. have researched and developed Au-SH-SiO
2cu-MOF electrochemical sensor is also applied to catalytic oxidation Cys, obtains good effect.Therefore, MOF material has potential application prospect in electrochemical field.But research discovery only has minority MOF material to have electronic conduction function, and this has just limited to the promotion and application of MOF material in electrochemical field.
Summary of the invention
Goal of the invention of the present invention is the difficult problem in order to solve above-mentioned existence, a kind of preparation method of novel metallic organic frame complex is provided, utilize the electrochemical sensor that this metal framework complex preparation is novel, and be applied to the electrochemical recognition of D-Met and METHIONINE.
Technical scheme of the present invention:
Based on a preparation method for copper metallic organic frame complex modified gold electrode, adopt hydro-thermal method preparation, step is as follows:
1) metallic organic frame complex Cu-MOF{ [CuL (H
2o)] the synthesis of 0.5DMA}:
0.2mmol Copper dichloride dihydrate is dissolved in 2mL distilled water and is prepared into storing solution A, by 0.2mmol 2,5-ThiophenedicarboxyliAcid Acid (H
2l) 2mLN is joined, storing solution B is prepared in N-dimethyl acetamide, then storing solution A is mixed with storing solution B, the baking oven being placed in 90 DEG C reacts 48 hours, filter after Temperature fall, the solid distilled water obtained is washed 2-6 time, obtains blue crystalline solid metallic organic frame complex;
2) { [CuL (H
2o)] the preparation of 0.5DMA} complex decorating electrode:
Take 0.25g shitosan, be dissolved in the aqueous acetic acid of 100mL1%, obtain the storing solution C of limpid transparent and homogeneous, take 0.020g{ [CuL (H
2o)] 0.5DMA} complex, adds in above-mentioned C under ultrasound condition, obtains jade-green suspension, gets this suspension point of 10 μ L in clean glassy carbon electrode surface, within 12 hours, naturally dries, obtain { [CuL (H
2o)] 0.5DMA} modified electrode.
Present invention also offers a kind of application based on copper metallic organic frame complex modified gold electrode, namely it is in the detection technique of D-Met and METHIONINE chiral isomer:
Detect D-Met and METHIONINE:
With { [CuL (H
2o)] 0.5DMA} modified electrode is as working electrode, saturated calomel electrode is as contrast electrode, platinum electrode is as auxiliary electrode, composition three-electrode system, access electrochemical workstation, detects D-Met and METHIONINE respectively at phosphate buffer solution (pH=6.8).
Described phosphate buffer solution is mixed with by sodium dihydrogen phosphate (0.2mol/L) aqueous solution and sodium hydrogen phosphate aqueous solution (0.2mol/L).By pH acidometer determination pH value.
Advantage of the present invention is: the present invention has prepared metallic organic frame complex { [CuL (H first
2o)] 0.5DMA}, has carried out structural characterization to it, has prepared { [CuL (H
2o)] 0.5DMA} modifies novel electrochemical sensor, and this modified electrode of the detection preparation being applied to D-Met and METHIONINE is simple, cheap, has significant technique effect.
Accompanying drawing explanation
Fig. 1 is described { [CuL (H
2o)] Advances in crystal X-ray diffraction of 0.5DMA} resolves gained molecular structure.
Fig. 2 is described { [CuL (H
2o)] the powder x-ray diffraction figure of 0.5DMA} and monocrystalline simulated data comparison diagram.
Fig. 3 is described { [CuL (H
2o)] 0.5DMA} modified electrode detects D-Met.
Fig. 4 is described { [CuL (H
2o)] 0.5DMA} modified electrode detects METHIONINE.
Embodiment
The present invention is based on the preparation method of copper metallic organic frame complex modified gold electrode, adopt hydro-thermal method preparation, step is as follows:
1) metallic organic frame complex { [CuL (H
2o)] the synthesis of 0.5DMA}
Take 0.0341gCuCl
22H
2o is dissolved in 2mL distilled water, be prepared into storing solution A, take 0.0344g 2,5-ThiophenedicarboxyliAcid Acid and join 2mLN, storing solution B is prepared in N-dimethyl acetamide, then mixed with storing solution B by storing solution A, be positioned in closed container, the baking oven being placed in 90 DEG C reacts 48 hours, lower the temperature 48 hours, filter the solid that obtains, with distilled water washing 2-6 time, obtain that light green color is crystalline is metallic organic frame complex { [CuL (H
2o)] 0.5DMA};
Described metallic organic frame complex { [CuL (H
2o)] the property representation of 0.5DMA}:
(1) single crystal structure determination
Crystal structure crystal structure determination adopts Supernova type X-ray single crystal diffraction instrument, uses through graphite monochromatised MoK alpha ray
for incident radiation source, with
scan mode collects point diffraction, obtains cell parameter, utilize SHELXL-97 direct method to solve crystal structure from difference Fourier electron-density map through least-squares refinement, and through Lorentz and polarization effect correction.All H atom are synthesized by difference Fourier and are determined through desirable position calculation.Axonometry data are in table 1
The crystallographic data of table 1 compound
Fig. 1 is described compound { [CuL (H
2o)] single crystal diffraction of 0.5DMA} resolves gained minimal structure unit figure, contains copper ion, a dehydrogenation ligand L as seen from the figure in this compound molecule
-, a water of coordination and free solvent molecule DMA.The occupation rate of Cu1 and Cu2 is respectively 0.5.
(2) powder x-ray diffraction measures:
Powder x-ray diffraction data have been collected on RigakuD/Max-2500 diffractometer, and operating voltage is 40kV, and electric current is 100mA, use in test through graphite monochromatised copper target X-ray be incident radiation source.Density data collects use 2 θ/θ scan pattern, and within the scope of 3 ° to 60 °, carry out continuous sweep, sweep velocity is 8 °s/sec, and span is 0.02 °/time.Fitting experimental data uses Cerius2 program, and mono-crystalline structures powder x-ray diffraction spectrum analog transforms and uses software Mercury1.42.
Fig. 2 is described { [CuL (H
2o)] 0.5DMA} complex powder x-ray diffraction figure with simulate comparison diagram according to single crystal data.
2) { [CuL (H
2o)] the preparation of 0.5DMA} complex decorating electrode:
Take 0.25g shitosan, be dissolved in the aqueous acetic acid of 100mL1%, obtain the storing solution C of limpid transparent and homogeneous.Take 0.020g{ [CuL (H
2o)] 0.5DMA} complex, adds in above-mentioned C under ultrasound condition, obtains jade-green suspension.Get this suspension point of 10 μ L in clean glassy carbon electrode surface, within 12 hours, naturally dry, obtain { [CuL (H
2o)] 0.5DMA} modified electrode.
Gained of the present invention [CuL (H2O)] 0.5DMA} complex decorating gold electrode, can be used for the detection of METHIONINE and D-Met, detection method is as follows:
(1) { [CuL (H
2o)] the detection of 0.5DMA} complex decorating electrode pair METHIONINE:
By obtained metallic organic frame complex { [CuL (H
2o)] 0.5DMA} modified electrode is as working electrode, saturated calomel electrode is as contrast electrode, and platinum electrode, as auxiliary electrode, forms three-electrode system, access electrochemical workstation, detects METHIONINE at phosphate buffer solution (pH=6.8).This modified electrode has good response to METHIONINE, sees Fig. 3.
(2) { [CuL (H
2o)] the detection of 0.5DMA} complex decorating electrode pair D-Met:
By obtained metallic organic frame complex { [CuL (H
2o)] 0.5DMA} modified electrode is as working electrode, saturated calomel electrode is as contrast electrode, and platinum electrode, as auxiliary electrode, forms three-electrode system, access electrochemical workstation, detects D-Met at phosphate buffer solution (pH=6.8).This modified electrode has good response to D-Met, sees Fig. 4.
Claims (7)
1., based on a preparation method for copper metallic organic frame complex modified gold electrode, it is characterized in that step is as follows:
1) metallic organic frame complex Cu-MOF{ [CuL (H
2o)] the synthesis of 0.5DMA}:
Copper dichloride dihydrate is dissolved in distilled water and is prepared into storing solution A, by thiophene-2,5-dicarboxylic acid joins N, storing solution B is prepared in N-dimethyl acetamide, then mixed with storing solution B by storing solution A, the baking oven being placed in 90 DEG C reacts 48 hours, filters after Temperature fall, the solid distilled water obtained is washed 2-6 time, obtains blue crystalline solid metallic organic frame complex;
2) { [CuL (H
2o)] the preparation of 0.5DMA} complex decorating electrode:
Take 0.25g shitosan, be dissolved in the aqueous acetic acid of 100mL1%, obtain the storing solution C of limpid transparent and homogeneous, take 0.020g{ [CuL (H
2o)] 0.5DMA} complex, adds in above-mentioned C under ultrasound condition, obtains jade-green suspension, gets this suspension point of 10 μ L in clean glassy carbon electrode surface, within 12 hours, naturally dries, obtain { [CuL (H
2o)] 0.5DMA} modified electrode.
2., according to claim 1 based on the preparation method of copper metallic organic frame complex modified gold electrode, it is characterized in that: step 1) described in copper chloride dihydrate, 2,5-ThiophenedicarboxyliAcid Acid mol ratio be 1:1; The volume ratio of distilled water and DMA is 1:1.
3. according to claim 1 or 2 based on the preparation method of copper metallic organic frame complex modified gold electrode, it is characterized in that: step 1) described in Copper dichloride dihydrate be 0.2mmol, described distilled water is 2mL, described thiophene-2,5-dicarboxylic acid is 0.2mmol, described DMA is 2mL.
4. based on an application for copper metallic organic frame complex modified gold electrode, it is characterized in that: in phosphate buffer solution, complete and D-Met or METHIONINE are detected.
5. the application based on copper metallic organic frame complex modified gold electrode according to claim 3, is characterized in that: as follows to the detecting step of METHIONINE:
By obtained metallic organic frame complex { [CuL (H
2o)] 0.5DMA} modified electrode is as working electrode, and saturated calomel electrode is as contrast electrode, and platinum electrode is as auxiliary electrode, and composition three-electrode system, access electrochemical workstation, detects METHIONINE at phosphate buffer solution.
6. the application based on copper metallic organic frame complex modified gold electrode according to claim 3, is characterized in that: as follows to the detecting step of D-Met:
By obtained metallic organic frame complex { [CuL (H
2o)] 0.5DMA} modified electrode is as working electrode, and saturated calomel electrode is as contrast electrode, and platinum electrode is as auxiliary electrode, and composition three-electrode system, access electrochemical workstation, detects D-Met at phosphate buffer solution.
7. the application based on copper metallic organic frame complex modified gold electrode according to claim 4 or 5, is characterized in that: phosphate buffer solution pH=6.8.
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| CN105977467A (en) * | 2016-07-01 | 2016-09-28 | 北京工业大学 | Preparation method for preparing Co3O4@CoP composite electrode based on MOF template |
| CN106198701A (en) * | 2016-08-18 | 2016-12-07 | 济南大学 | A kind of metal-organic framework material area load molecular imprinted polymer membrane is for the electrochemical detection method of orthene |
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| CN106248749A (en) * | 2016-09-12 | 2016-12-21 | 济南大学 | A kind of chiral metal organic nanocrystalline sensor and its preparation method and application |
| CN106442686A (en) * | 2016-09-12 | 2017-02-22 | 济南大学 | Chiral metal organic framework polymer sensor as well as preparation and application thereof |
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| CN112649413A (en) * | 2020-11-03 | 2021-04-13 | 中山大学 | Nano-gold-MOF composite flexible SERS film substrate and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005023856A1 (en) * | 2005-05-24 | 2006-11-30 | Basf Ag | Process for the preparation of porous metal-organic frameworks |
| CN101384537A (en) * | 2006-02-10 | 2009-03-11 | 巴斯夫欧洲公司 | Process for preparing porous metal-organic framework materials |
| CN104370943A (en) * | 2014-11-03 | 2015-02-25 | 南开大学 | Preparation method and application of [Cu2(HL)2(Mu2-OH)2(H2O)5] |
| KR101655245B1 (en) * | 2010-03-23 | 2016-09-07 | 삼성전자 주식회사 | Electrochromic material and electrochromic device including the same |
-
2015
- 2015-10-27 CN CN201510707322.4A patent/CN105203606B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005023856A1 (en) * | 2005-05-24 | 2006-11-30 | Basf Ag | Process for the preparation of porous metal-organic frameworks |
| CN101384537A (en) * | 2006-02-10 | 2009-03-11 | 巴斯夫欧洲公司 | Process for preparing porous metal-organic framework materials |
| KR101655245B1 (en) * | 2010-03-23 | 2016-09-07 | 삼성전자 주식회사 | Electrochromic material and electrochromic device including the same |
| CN104370943A (en) * | 2014-11-03 | 2015-02-25 | 南开大学 | Preparation method and application of [Cu2(HL)2(Mu2-OH)2(H2O)5] |
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| CN105977467A (en) * | 2016-07-01 | 2016-09-28 | 北京工业大学 | Preparation method for preparing Co3O4@CoP composite electrode based on MOF template |
| CN106198701A (en) * | 2016-08-18 | 2016-12-07 | 济南大学 | A kind of metal-organic framework material area load molecular imprinted polymer membrane is for the electrochemical detection method of orthene |
| CN106226375B (en) * | 2016-09-12 | 2019-01-15 | 济南大学 | A kind of organometallic polymer dopen Nano silver composite material sensor and its preparation method and application |
| CN106442686A (en) * | 2016-09-12 | 2017-02-22 | 济南大学 | Chiral metal organic framework polymer sensor as well as preparation and application thereof |
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| CN106226375A (en) * | 2016-09-12 | 2016-12-14 | 济南大学 | A kind of organometallic polymer dopen Nano silver composite material sensor and its preparation method and application |
| CN107490610B (en) * | 2017-09-05 | 2019-09-27 | 济南大学 | A kind of chirality MOF- graphene hybrid material and its preparation method and application |
| CN107490610A (en) * | 2017-09-05 | 2017-12-19 | 济南大学 | A kind of chiral MOF graphene hybrid materials and its preparation method and application |
| CN108444500A (en) * | 2018-03-12 | 2018-08-24 | 天津大学 | Flexible sensing device based on metal-organic framework material and preparation method thereof |
| CN108562627B (en) * | 2018-04-09 | 2019-11-26 | 江南大学 | A kind of electrochemical sensor based on chiral covalent organic framework compound |
| CN108562627A (en) * | 2018-04-09 | 2018-09-21 | 江南大学 | A kind of electrochemical sensor based on chiral covalent organic framework compound |
| CN110095520A (en) * | 2019-05-08 | 2019-08-06 | 哈尔滨理工大学 | One kind being based on Cs/Ce-MOF electrochemical sensor working electrode |
| CN110095520B (en) * | 2019-05-08 | 2021-10-12 | 哈尔滨理工大学 | Working electrode for electrochemical sensor based on Cs/Ce-MOF |
| CN112649413A (en) * | 2020-11-03 | 2021-04-13 | 中山大学 | Nano-gold-MOF composite flexible SERS film substrate and preparation method and application thereof |
| WO2023138283A1 (en) * | 2022-01-24 | 2023-07-27 | 中国科学院深圳先进技术研究院 | Environmentally friendly and rapid preparation method for metal-organic framework compound thin film plating |
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