CN102617651A - Manganese-rhenium metal-organic compound, synthesis thereof and application of metal-organic compound in electrochemistry - Google Patents
Manganese-rhenium metal-organic compound, synthesis thereof and application of metal-organic compound in electrochemistry Download PDFInfo
- Publication number
- CN102617651A CN102617651A CN2012100570345A CN201210057034A CN102617651A CN 102617651 A CN102617651 A CN 102617651A CN 2012100570345 A CN2012100570345 A CN 2012100570345A CN 201210057034 A CN201210057034 A CN 201210057034A CN 102617651 A CN102617651 A CN 102617651A
- Authority
- CN
- China
- Prior art keywords
- rhenium
- manganese
- double
- core
- organometallics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a manganese-rhenium double-core metal-organic compound containing a bisulfur ligand, a synthesis thereof, and an application of the compound to reaction for producing hydrogen by electrochemical catalysis of proton. Compared with the traditional nonferrous catalysts, the catalyst has the advantages that the catalyst can catalyze proton in acetic acid to be subjected to electrolytic reduction into hydrogen gas, the electrolytic potential is low and the synthesis conditions are mild, so that the manganese-rhenium metal-organic compound containing the bisulfur ligand becomes an excellent hydrogen-producing catalyst.
Description
Technical field
The present invention relates to stand-in field, hydrogenase active site, particularly a kind of manganese rhenium double-core organometallics that contains two sulphur parts and synthetic, and this compounds is applied to the electrochemical catalysis reaction.
Background technology
Hydrogenase is one type of existence and the intravital enzyme of mikrobe, and the oxidizing reaction that it both can catalysis hydrogen also can produce hydrogen by the catalytic reduction proton.Because hydrogen the time gives off energy and produces the water of non-environmental-pollution in oxidation or burning, thereby is considered to a kind of eco-friendly energy carrier.Therefore, the exploitation hydrogen energy source substitutes existing fossil oil, thereby reduces environmental pollution, and alleviating energy crisis has become countries in the world and solved one of important directions of energy problem.The research that is directed against the stand-in in hydrogenase active site at present mainly concentrates on the 8th family's metal, and very few as the research report of the stand-in in hydrogenase active site about non-the 8th family's metal, Thomas B.Rauchfuss has synthesized one type of hydrogenase stand-in (Journal of the American Chemical Society that the active site is a metal Ru; 2004,13214-13215), but it is not carried out electrolytic trial; And ruthenium is as noble metal catalyst; Cost is higher, and in a word, present non-iron is that the hydrogenase stand-in exist the reduction potential height; Reaction cost is higher, deficiencies such as experiment condition strictness.
Summary of the invention
The object of the invention has just provided a kind of manganese rhenium double-core organometallics that contains two sulphur parts, and this compounds is applied to the electrochemical catalysis reaction.
Among the present invention, we provide catalyzer as follows:
Wherein, part is pyridine or triphenylphosphine.
The said manganese rhenium double-core organometallics that contains two sulphur parts, its Mn (CO)
3And Re (CO)
3Through bridge SBu
nWith bridge SC (H) PCy
3Bridging together, part links to each other with rhenium metal, SC (H) PCy
3Bridge adopts η
1(S) key of coordination mode has been linked on the rhenium, η
2(C, S) the coordination mode key has been linked on the manganese.
The said manganese rhenium double-core organometallics that contains two sulphur parts is with MnRe (CO)
6(μ-S
2CPCy
3) be feedstock production.Concrete preparation method is following:
Step (1) is with MnRe (CO)
6(μ-S
2CPCy
3) being dissolved in organic solvent, this organic solvent is the anhydrous and oxygen-free THF.
Step (2) is added dropwise to n-Butyl Lithium in above-mentioned solution under-78 ℃.
Step (3) adds NH in above-mentioned solution
4PF
6, at room temperature reacted 1 hour, add part again and continue reaction 1 hour, can obtain the manganese rhenium double-core organometallics that contains two sulphur parts of the present invention.
With the said manganese rhenium double-core organometallics that contains two sulphur parts as catalyst applications in electrochemical reaction, concrete electrolytic experiment method is following:
Step (1) electrolytic experiment carries out in H pipe, and catalyzer and supporting electrolyte are dissolved in acetonitrile, and catalyst concn is 1mM, and supporting electrolyte concentration is 0.1M.
Step (2) used for electrolyte nitrogen thread bubbling 10 minutes, electrolysis under-2V voltage.
Step (3) vigorous stirring solution begins test, and the hydrogen of generation is collected in the H pipe, after strength of current is stable, stops test.
The proton electrolytic reduction of this catalyzer in can catalysis acetic acid becomes hydrogen; Electrolytic potential is low; And use non-Ferrious material, and electrolytic efficiency reaches 99%, and the manganese rhenium organometallics that above-mentioned advantage makes this kind contain two sulphur parts becomes a kind of good product hydrogen catalyst.
Embodiment
The compound method of catalyzer is following:
At 0.076g (0.1mmol) [(MnRe) (CO)
6(μ-S
2CPCy
3)] be dissolved among 30 milliliters of THF, under-78 ℃, add nBuLi 0.2ml (2.5M), react after 20 minutes adding excessive N H in reaction solution
4PF
6(0.059g, 0.36mmol).Stir after 15 minutes, remove low-temperature receiver and heat up naturally, be heated to 30 ℃ of reactions 1 hour with water-bath again.Add excessive pyridine then, keep temperature of reaction about 30 ℃, react half a hour again.Vacuum is drained solvent, with sherwood oil/methylene dichloride column chromatography (v/v, 1: 1, Al
2O
3, activity III), collect yellow colour band solution, vacuum is drained solvent, gets deep yellow liquid, passes through CH then
2Cl
2/ sherwood oil (v/v 1: 20 ,-20 ℃) recrystallization obtains yellow solid 29mg, yield 32.1%.
1H?NMR(CDCl
3，ppm)：
δ3.12[s，1H，SC(H)P]，0.85-2.85[m，42H，Cy?and?Bu]，7.51-8.97[m，5H，C5H5N]。
31P?NMR(CDCl
3，ppm)：
δ40.24[s，PCy
3]。
The electrolytic experiment method is following:
The electrolytic trial working electrode is a glass-carbon electrode, and counter electrode is a platinum wire electrode, and reference electrode is Ag/Ag
+Electrode.Test is carried out in H pipe, wherein between with G3 sand burning plate separate with reduce two survey solution exchange, when carrying out electrolysis, the 25mL acetonitrile is injected in both sides, before the electrolysis, N is all used on the H pipe both sides
2Bubbling was removed oxygen in 5 minutes.[(MnRe) (CO) that adds 50mM acetic acid, 1mM in H pipe one side
6(μ-SBu
n) (μ-SC (H) PCy
3) (PPh
3)] and the supporting electrolyte solution of 0.1M.Electrolytic experiment carries out under the ydrodynamics condition at-2V voltage, and vigorous stirring solution is to increase velocity of diffusion.After strength of current is stable, stop test, the hydrogen that produces in the H pipe is collected (the water gaging method records) in the 305mL round-bottomed flask that vacuumizes in advance with needle tubing, after collection hydrogen is accomplished, with the normal atmosphere of the air pressure balance to 1 in the round-bottomed flask.Standard gas is the mixed gas of hydrogen and nitrogen, and with the volume(tric)fraction sign hydrogen content of hydrogen, concentration is 496ppm, corresponding integral area 18000.From flask and standard gas, extract 2.5mL gas respectively and carry out gas chromatographic detection.The integral area of collecting hydrogen is 283722, and the concentration that draws hydrogen is 7818ppm, calculates to such an extent that the amounts of hydrogen of collecting is 2.38mL, and actual theoretical hydrogen tolerance is 2.41mL through 20.75 coulombs of electric weight, and electrolytic efficiency is 99%.
Claims (5)
1. manganese rhenium double-core organometallics that contains two sulphur parts, its structure is following:
2. the manganese rhenium double-core organometallics that contains two sulphur parts according to claim 1 is characterized in that Mn (CO)
3And Re (CO)
3Through bridge SBu
nWith bridge SC (H) PCy
3Bridging together, part links to each other with rhenium metal, SC (H) PCy
3Bridge adopts η
1(S) key of coordination mode has been linked on the rhenium, η
2(C, S) the coordination mode key has been linked on the manganese.
3. the manganese rhenium double-core organometallics that contains two sulphur parts according to claim 1 is characterized in that part is pyridine or triphenylphosphine.
4. prepare the described metal-organic method of manganese rhenium double-core that contains two sulphur parts of claim 1:
Step (1) is with MnRe (CO)
6(μ-S
2CPCy
3) be dissolved in organic solvent, it is characterized in that this organic solvent is the anhydrous and oxygen-free THF;
Step (2) is added dropwise to n-Butyl Lithium in above-mentioned solution, the reaction half a hour after, in above-mentioned solution, add NH
4PF
6, add part again and continue reaction 1 hour, can obtain the manganese rhenium double-core organometallics that contains two sulphur parts of the present invention, it is characterized in that temperature of reaction is-78～30 ℃.
5. the manganese rhenium double-core organometallics that contains two sulphur parts as claimed in claim 1 is characterized in that, can be used for the electrocatalysis proton and produces hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100570345A CN102617651A (en) | 2012-03-07 | 2012-03-07 | Manganese-rhenium metal-organic compound, synthesis thereof and application of metal-organic compound in electrochemistry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100570345A CN102617651A (en) | 2012-03-07 | 2012-03-07 | Manganese-rhenium metal-organic compound, synthesis thereof and application of metal-organic compound in electrochemistry |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102617651A true CN102617651A (en) | 2012-08-01 |
Family
ID=46557903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100570345A Pending CN102617651A (en) | 2012-03-07 | 2012-03-07 | Manganese-rhenium metal-organic compound, synthesis thereof and application of metal-organic compound in electrochemistry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102617651A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109750317A (en) * | 2018-12-26 | 2019-05-14 | 浙江工业大学 | A kind of preparation method of the compound hydrogen-precipitating electrode of porous Ni-base copper rhenium |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5637739A (en) * | 1990-03-21 | 1997-06-10 | Research Corporation Technologies, Inc. | Chiral catalysts and catalytic epoxidation catalyzed thereby |
| EP1329455A1 (en) * | 2002-01-22 | 2003-07-23 | Universiteit Gent | Metal carbene complexes, methods and intermediates for making them and their use in metathesis reactions |
| CN100999533A (en) * | 2007-01-12 | 2007-07-18 | 中国科学院上海光学精密机械研究所 | Bridge linking binuclear metallic hydrazone kind compound and its synthesizing process |
| CN101972648A (en) * | 2010-09-10 | 2011-02-16 | 常州大学 | Modified Mn-Zr catalyst as well as preparation method and application thereof to preparing dimethyl ether |
| CN102219743A (en) * | 2004-02-12 | 2011-10-19 | 分子制药洞察公司 | Technetium- and rhenium-bis(heteroaryl) complexes, and methods of use thereof |
-
2012
- 2012-03-07 CN CN2012100570345A patent/CN102617651A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5637739A (en) * | 1990-03-21 | 1997-06-10 | Research Corporation Technologies, Inc. | Chiral catalysts and catalytic epoxidation catalyzed thereby |
| EP1329455A1 (en) * | 2002-01-22 | 2003-07-23 | Universiteit Gent | Metal carbene complexes, methods and intermediates for making them and their use in metathesis reactions |
| CN102219743A (en) * | 2004-02-12 | 2011-10-19 | 分子制药洞察公司 | Technetium- and rhenium-bis(heteroaryl) complexes, and methods of use thereof |
| CN100999533A (en) * | 2007-01-12 | 2007-07-18 | 中国科学院上海光学精密机械研究所 | Bridge linking binuclear metallic hydrazone kind compound and its synthesizing process |
| CN101972648A (en) * | 2010-09-10 | 2011-02-16 | 常州大学 | Modified Mn-Zr catalyst as well as preparation method and application thereof to preparing dimethyl ether |
Non-Patent Citations (6)
| Title |
|---|
| DANIEL MIGUEL: "Migrations of the Carbon Atom of the SC(H)PR3 Ligand in the Reduction/Protonation Processes of Heterodinuclear Mn-Re Complexes", 《ORGANOMETALLICS》, vol. 20, no. 14, 15 June 2001 (2001-06-15), pages 3063 - 3069 * |
| TIANBIAO LIU，等: "Synthesis, Structures and Electrochemical Properties of Nitro- and Amino-Functionalized Diiron Azadithiolates as Active Site Models of Fe-Only Hydrogenases", 《CHEMISTRY：A EUROPEAN JOURNAL》, vol. 10, no. 18, 8 July 2004 (2004-07-08), pages 4474 - 4479 * |
| YONG QIANG MA等: "Synthesis and Reaction of [MnRe(CO)6(μ-SH)(μ-SC(H)PPri3)(PPh3)]", 《CHINESE CHEMICAL LETTERS》, vol. 14, no. 4, 30 April 2003 (2003-04-30), pages 413 - 416 * |
| 佟欣: "《STN检索报告》", 19 February 2014, article "2012100570345" * |
| 柏志峰: "MnM(M=Mn，Re)双核化合物的唯铁氢化酶活性中心模拟化学研究", 《南开大学硕士学位论文》, 24 November 2010 (2010-11-24) * |
| 马永强: "一些含有SCPR配体及其衍生物的双核化合物的合成与反应研究", 《南开大学博士学位论文》, 31 December 2010 (2010-12-31) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109750317A (en) * | 2018-12-26 | 2019-05-14 | 浙江工业大学 | A kind of preparation method of the compound hydrogen-precipitating electrode of porous Ni-base copper rhenium |
| CN109750317B (en) * | 2018-12-26 | 2020-06-30 | 浙江工业大学 | Preparation method of porous nickel-based copper-rhenium composite hydrogen evolution electrode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Collin et al. | Electrocatalytic properties of (tetraazacyclotetradecane) nickel (2+) and Ni2 (biscyclam) 4+ with respect to carbon dioxide and water reduction | |
| Liu et al. | Synthesis, Structures and Electrochemical Properties of Nitro‐and Amino‐Functionalized Diiron Azadithiolates as Active Site Models of Fe‐Only Hydrogenases | |
| Jiang et al. | Chemical and photocatalytic water oxidation by mononuclear Ru catalysts | |
| Canaguier et al. | Cyclopentadienyl ruthenium–nickel catalysts for biomimetic hydrogen evolution: electrocatalytic properties and mechanistic DFT studies | |
| Durgaprasad et al. | Synthesis, structural characterization and electrochemical studies of [Fe2 (μ-L)(CO) 6] and [Fe2 (μ-L)(CO) 5 (PPh3)](L= pyrazine-2, 3-dithiolate, quinoxaline-2, 3-dithiolate and pyrido [2, 3-b] pyrazine-2, 3-dithiolate): Towards modeling the active site of [FeFe]–Hydrogenase | |
| Dolganov et al. | Iron vs. cobalt clathrochelate electrocatalysts of HER: the first example on a cage iron complex | |
| Fogeron et al. | Nickel complexes based on molybdopterin-like dithiolenes: catalysts for CO2 electroreduction | |
| Darmon et al. | Increasing the rate of hydrogen oxidation without increasing the overpotential: a bio-inspired iron molecular electrocatalyst with an outer coordination sphere proton relay | |
| Ostericher et al. | Utilization of Thermodynamic Scaling Relationships in Hydricity To Develop Nickel Hydrogen Evolution Reaction Electrocatalysts with Weak Acids and Low Overpotentials | |
| Fang et al. | A new copper (I)–triazenido electro-catalyst for catalyzing hydrogen evolution from acetic acid and water | |
| Chu et al. | Synthesis and electro-catalytic properties of a dinuclear palladium (I) 1, 3-bis [(2-chloro) benzene] triazenide complex | |
| Zhang et al. | A trinuclear ruthenium complex as a highly efficient molecular catalyst for water oxidation | |
| Liu et al. | Designed Nanomaterials for Electrocatalytic Organic Hydrogenation Using Water as the Hydrogen Source | |
| CN115216024B (en) | Metal organic coordination supermolecule ball and preparation method thereof | |
| CN102558230A (en) | Quaternary phosphor salt acidic ionic liquid and application thereof in synthesizing benzyltoluene | |
| Cao et al. | A molybdenum–Schiff base complex, a new molecular electro-catalyst for generating hydrogen from acetic acid or water | |
| Li et al. | Phenyl-functionalized Diiron Propanedithiolate Complexes with 1, 3-Bis (diphenylphosphine) propane Ligand: Chelated and Bridged Isomers as Proton-reduction Catalysts | |
| CN105884745B (en) | Nickel-Cabbeen binuclear complex and its preparation method and application | |
| Zaltariov et al. | A Bis (µ‐chlorido)‐Bridged Cobalt (II) Complex with Silyl‐Containing Schiff Base as a Catalyst Precursor in the Solvent‐Free Oxidation of Cyclohexane | |
| CN102617651A (en) | Manganese-rhenium metal-organic compound, synthesis thereof and application of metal-organic compound in electrochemistry | |
| CN115449082B (en) | Metal organic coordination supermolecule sphere, preparation method and application thereof | |
| US20230014161A1 (en) | Metal-metal bonded ammonia oxidation catalysts | |
| Dai et al. | Fe-quaterpyridine complex: a comprehensive DFT study on the mechanism of CO 2-to-CO conversion | |
| Yang et al. | Structural evolution of the Ru-bms complex to the real water oxidation catalyst of Ru-bda: the bite angle matters | |
| JPH10249208A (en) | Binucleic iron complex catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120801 |