CN104399528A - Azoic copper complex water oxidizing catalyst - Google Patents
Azoic copper complex water oxidizing catalyst Download PDFInfo
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- CN104399528A CN104399528A CN201410545691.3A CN201410545691A CN104399528A CN 104399528 A CN104399528 A CN 104399528A CN 201410545691 A CN201410545691 A CN 201410545691A CN 104399528 A CN104399528 A CN 104399528A
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Abstract
The invention discloses an azoic copper complex water oxidizing catalyst and belongs to the technical field of chemical catalysts. The water oxidizing catalyst is a 1-(2-pyridineazo)-2-naphthol (PAN) copper (II) complex which is a penta-coordinative compound formed by 1-(2-pyridineazo)-2-naphthol and Cu<2+> in a coordination manner. The complex contains trifluoromethane sulfonate coordination and is 477.97 in molecular weight. The 1-(2-pyridineazo)-2-naphthol (PAN) copper (II) complex water oxidizing catalyst is stable in structure, is low in cost, is excellent in effect on reaction of preparing oxygen from water through catalytic oxidization, and has excellent catalytic effects in various solvent systems.
Description
Technical field
The invention belongs to chemical catalyst technical field, be specifically related to a kind of azo copper complex Water oxidize catalyst.
Background technology
Along with development and the progress of society, the consumption of the energy increases year by year, and energy crisis is day by day aggravated.Due to rapid exhaustion and the environmental pollution of the fossil energies such as coal, oil, natural gas, find the concern that a kind of continuable clean energy resource causes global scientist day by day.Solar energy is a kind of continuable clean energy resource, and sun transformation of energy and utilization have become the essential condition that energy resource structure makes the transition, social economy ensures, Environmental Health develops, have become the focus that the whole world is common.
Solar energy is converted into chemical energy by photosynthesis by plant effectively, is the medium of earth carbon cycle.It provides energy and oxygen for biology, is the basis that living nature is depended on for existence.In photosynthesis, optical drive decomposition water produces oxygen and proton, the a series of electro transfer of simultaneous and energy trasfer, luminous energy being transformed in ATP active chemical energy and being transformed into stable chemical energy in organic matter again, is carbohydrate by carbon dioxide conversion.
In order to utilize solar energy better, there has been proposed the photosynthetic concept of manual simulation, namely manually setting up and a set ofly can absorb the system that solar energy is converted into chemical energy.Artificial photosynthesis's system, all the same with the photosynthesis of plant, have that light catches, separation of charge and transfer, catalytic reaction three processes.
Water oxidize is an important step in artificial photosynthesis's system, is the source of proton and electronics.But because this reaction needed shifts 4 electronics and 4 protons, be thermodynamically difficult to occur.Therefore Water oxidize process has become the bottleneck of artificial photosynthesis's system, so exploitation High-efficient Water oxidation catalyst has become the main direction of studying of artificial photosynthesis's system.
Water oxidize catalyst was becoming study hotspot in recent years, in homogeneous phase and heterogeneous catalysis, all achieve good achievement.Heterogeneous catalysis and heterogeneous catalysis, be that catalyst is modified at electrode surface, study its catalytic performance by electro-catalysis, its feature is good stability, and the life-span is long.The research of heterogeneous catalysis makes great progress, homogeneous catalyst due to its outstanding catalytic effect, the concern also increased gradually in recent years.Homogeneous phase Water oxidize catalyst reported in recent years is all metal organic complex form, and this is similar to the structure of photosynthesis of plant oxygen-evolving center, because the synergy of organic ligand and metallic atom, realizes oxidize water molecule.Except catalytic effect is outstanding, homogeneous phase Water oxidize catalyst also has the advantage being easy to modification from structure, and people can by changing ligand structure and regulating the structures and characteristics of catalyst for character etc. such as inhaling electricity.And homogeneous phase Water oxidize catalyst is soluble in water, be convenient to study its Water oxidize catalytic mechanism by spectrum means.These factors comprehensive, the development of homogeneous phase Water oxidize catalyst is very rapid.
Think that desirable Water oxidize catalyst should possess following features under normal circumstances: 1, catalytic efficiency is high, and catalytic cycle speed is high; 2, catalytic capability is lasting, and catalytic cycle number is high; 3, structure is simple, and be easy to synthesis, cost is low.In order to meet above requirement, during design ideal Water oxidize catalyst, needing to understand catalytic mechanism in depth, being familiar with the relation of catalyst structure and character.So, at present the research of Water oxidize catalyst is mainly set about from the several aspect of catalyst structure, catalyst property, catalytic effect and catalytic mechanism.
Copper is the element that occurring in nature extensively exists, and its reserves is large, price is low, has superior character, be all widely used always and study in electricity, optics, microorganism, catalysis etc.
Azo compound is commonly used for dyestuff, is widely used all the time.Research shows, azo compound has excellent electronic property.1-(2-pyridylazo)-beta naphthal (PAN) is a kind of azo part, has excellent electronic property.
The Appropriate application of energy crisis and water resource be the world today faced by common issue, attracted increasing experts and scholars to go to explore and research.1-(2-pyridylazo)-beta naphthal (PAN) copper complex relies on its excellent electronic property, stable structure, cheap price, is expected to the catalyst as Water oxidize.
Summary of the invention
The object of the present invention is to provide a kind of azo copper complex that can be used as Water oxidize catalyst and preparation method thereof.
The invention provides a kind of azo copper complex---1-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex, it is 1-(2-pyridylazo)-beta naphthal and Cu
2+the pentacoordinate compound that coordination is formed, molecular weight is 477.97, and containing the coordination of a trifluoromethane sulfonic acid root, its structure is as follows:
Above-mentioned azo copper complex can be applied in the reaction of Water oxidize Preparation of oxygen as catalyst.
The synthetic route of 1-provided by the invention (2-pyridylazo)-beta naphthal (PAN) copper (II) complex is as follows:
Above-mentioned azo copper complex can be synthesized by traditional preparation method, comprising:
1, heating: (1) is dissolved agitation and filtration copper chloride and silver triflate and obtained copper triflate in methanol solvate; (2) add 1-(2-pyridylazo)-beta naphthal part, heating is stirred to 60 DEG C and obtains 1-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex.
2, the methyl alcohol method of fractional steps: (1) is dissolved agitation and filtration copper chloride and silver triflate and obtained copper triflate in methanol solvate; (2) add 1-(2-pyridylazo)-beta naphthal part, add 2 triethylamines, stir under normal temperature and obtain product.
3, the carrene method of fractional steps: (1) is dissolved agitation and filtration copper chloride and silver triflate and obtained copper triflate in dichloromethane solvent; (2) add 1-(2-pyridylazo)-beta naphthal part, add 2 triethylamines, stir under normal temperature and obtain product.
4, methyl alcohol one kettle way: (1) dissolves stirring copper chloride and silver triflate in methanol solvate; (2) directly add 1-(2-pyridylazo)-beta naphthal (PAN) part continuation stirring and obtain product.
5, carrene one kettle way: (1) dissolves stirring copper chloride and silver triflate in dichloromethane solvent; (2) directly add 1-(2-pyridylazo)-beta naphthal (PAN) part continuation stirring and obtain product.
6, one pot of heating: (1) dissolves stirring copper chloride and silver triflate in methanol solvate; (2) directly add 1-(2-pyridylazo)-beta naphthal (PAN) part at 60 DEG C, to continue stirring obtain product.
7, Laue method: (1) prepares the methanol solution of 1-(2-pyridylazo)-beta naphthal part and copper triflate respectively; (2) get the methanol solution of copper triflate, 1-(2-pyridylazo)-beta naphthal methanol solution in 10mL vial, obtain 1-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex monocrystal as in 60 DEG C of baking ovens 6 hours.
The principles of science of the present invention:
1, utilize transition metal Cu atom to tend to four-coordination, thus define the rock-steady structure (18 electron Rule) that outermost electron number reaches 18;
2, utilize part to contain N and O two kinds of electron donors, thus be easy to and central metal atom coordination, generate stable complex;
3, azo copper complex and Inorganic Copper Compound Phase are than the utilization rate that can improve copper, the electronic property of compound can be optimized compared with pure organic compound, the stability of compound can also be strengthened simultaneously, can as a kind of efficient, stable Water oxidize catalyst.
Compared with prior art, the present invention has following technique effect:
1,1-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex of the present invention's synthesis is a kind of novel Water oxidize catalyst and Stability Analysis of Structures, cheap;
2, this catalyst is respond well in catalytic water oxidation reaction; And in different solvents system, this catalyst also has good catalytic effect.
Detailed description of the invention
Below by specific embodiment, the invention will be further described.
One, the preparation of azo copper complex Water oxidize catalyst of the present invention
1, heating:
(1) accurately take copper chloride 8.5mg, silver triflate 30mg in eggplant shaped reaction bottle, add 5mL methyl alcohol as solvent, under normal temperature and pressure, stirring 3 is little of reacting completely;
(2) above-mentioned solution is filtered the methanol solution obtaining copper triflate;
(3) accurately take 12.5mg 1-(2-pyridylazo)-beta naphthal part, add in the methanol solution of copper triflate, at 60 DEG C, stirring 5 is little of reacting completely;
(4) concentrated solution is to about 0.5mL, and slowly drip ether and separate out to a large amount of solid, centrifugal suspension, obtains violet solid 1-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex.
2, the methyl alcohol method of fractional steps:
(1) accurately take copper chloride 8.5mg, silver triflate 30mg in reaction bulb, add 5mL methyl alcohol as solvent, under normal temperature and pressure, stirring 3 is little of reacting completely;
(2) above-mentioned solution is filtered the methanol solution obtaining copper triflate;
(3) accurately take 12.5mg 1-(2-pyridylazo)-beta naphthal part, add in the methanol solution of copper triflate, and drip 3 triethylamines, under normal temperature and pressure, stirring 5 is little of reacting completely;
(4) concentrated solution is to about 0.5mL, and slowly drip ether and separate out to a large amount of solid, centrifugal suspension, obtains violet solid 1-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex.
3, the carrene method of fractional steps:
(1) accurately take copper chloride 8.5mg, silver triflate 30mg in reaction bulb, add 5mL carrene as solvent, under normal temperature and pressure, stirring 3 is little of reacting completely;
(2) above-mentioned solution is filtered the dichloromethane solution obtaining copper triflate;
(3) accurately take 12.5mg 1-(2-pyridylazo)-beta naphthal part, add in the dichloromethane solution of copper triflate, and drip 3 triethylamines, under normal temperature and pressure, stirring 5 is little of reacting completely;
(4) concentrated solution is to about 0.5mL, and slowly drip ether and separate out to a large amount of solid, centrifugal suspension, obtains violet solid 1-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex.
4, methyl alcohol one kettle way:
(1) accurately take copper chloride 8.5mg, silver triflate 30mg in reaction bulb, add 5mL methyl alcohol as solvent, under normal temperature and pressure, stirring 3 is little of reacting completely;
(2) above-mentioned solution is filtered the methanol solution obtaining copper triflate;
(3) accurately take 12.5mg 1-(2-pyridylazo)-beta naphthal part, directly add in above-mentioned methanol solution, and drip 3 triethylamines, under normal temperature and pressure, stirring 5 is little of reacting completely;
(4) concentrated solution is to about 0.5mL, and slowly drip ether and separate out to a large amount of solid, centrifugal suspension, obtains violet solid 1-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex.
5, carrene one kettle way:
(1) accurately take copper chloride 8.5mg, silver triflate 30mg in reaction bulb, add 5mL carrene as solvent, under normal temperature and pressure, stirring 3 is little of reacting completely;
(2) above-mentioned solution is filtered the dichloromethane solution obtaining copper triflate;
(3) accurately take 12.5mg 1-(2-pyridylazo)-beta naphthal part, directly add in above-mentioned dichloromethane solution, and drip 3 triethylamines, under normal temperature and pressure, stirring 5 is little of reacting completely;
(4) concentrated solution is to about 0.5mL, and slowly drip ether and separate out to a large amount of solid, centrifugal suspension, obtains violet solid 1-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex.
6, one pot of heating:
(1) accurately take copper chloride 8.5mg, silver triflate 30mg in reaction bulb, add 5mL methyl alcohol as solvent, under normal temperature and pressure, stirring 3 is little of reacting completely;
(2) above-mentioned solution is filtered the methanol solution obtaining copper triflate;
(3) accurately take 12.5mg 1-(2-pyridylazo)-beta naphthal part, directly add in above-mentioned methanol solution, at 60 DEG C, stirring 5 is little of reacting completely;
(4) concentrated solution is to about 0.5mL, and slowly drip ether and separate out to a large amount of solid, centrifugal suspension, obtains violet solid 1-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex.
7, Laue method:
(1) accurately take copper chloride 102mg, silver triflate 360mg in reaction bulb, add 21.5mL methyl alcohol as solvent, under normal temperature and pressure, stirring 3 is little of reacting completely;
(2) above-mentioned solution is filtered the methanol solution obtaining copper triflate;
(3) accurately take 60mg 1-(2-pyridylazo)-beta naphthal part, add in 12mg methyl alcohol, be stirred to and dissolve completely, make 1-(2-the pyridylazo)-beta naphthal methanol solution of 5mg/mL;
(4) get the methanol solution of 0.5mL copper triflate, 0.5mL1-(2-pyridylazo)-beta naphthal methanol solution in 10mL vial, mixing shook up, as in 60 DEG C of baking ovens 6 hours;
(5) cool, having purple crystals to separate out as seen, is 1-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex monocrystal.
Two, the catalytic effect evaluation of azo copper complex Water oxidize catalyst of the present invention
(1) pH=11.0 is measured, concentration c=0.1molL
-1pBS 30mL in the vial of 50mL, accurately measure 1 × 10
-3molL
-11-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex methyl alcohol or acetonitrile solution 10uL add, and take oxidant ammonium ceric nitrate 0.6g and add, and start reaction;
(2) instantaneous pressure recorder (INSTRUMENT MODEL: OM-CP-PRTRANS-1-30A is connected; Manufacturer: the U.S., OMEGA), sealing, stirs and starts reaction; Open software records pressure;
(3) preserve, analyze data;
(4) catalytic effect:
A) when 1-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex is dissolved in methyl alcohol, catalytic efficiency is: 1.4kPa/h;
B) when 1-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex is dissolved in acetonitrile, catalytic efficiency is: 1.2kPa/h;
C) when 1-(2-pyridylazo)-beta naphthal (PAN) copper (II) complex is dissolved in water, catalytic efficiency is: 0.8kPa/h.
Claims (1)
1. an azo copper complex Water oxidize catalyst, is characterized in that, this catalyst molecule amount is 477.97, is 1-(2-pyridylazo)-beta naphthal and Cu
2+the pentacoordinate compound that coordination is formed, containing the coordination of a trifluoromethane sulfonic acid root, its structural formula is as follows:
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111359662A (en) * | 2018-12-26 | 2020-07-03 | 万华化学集团股份有限公司 | Copper ligand catalyst, preparation method thereof and application thereof in mandelic acid oxidation reaction |
Citations (4)
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| CN1093095A (en) * | 1993-03-12 | 1994-10-05 | 赫彻斯特股份公司 | Water soluble coppercomplexmonoazocompoundcarbonacid compoundcarbonacid, its method for making and application |
| JP2000103797A (en) * | 1998-09-29 | 2000-04-11 | Mitsubishi Chemicals Corp | Rhodium-(bidentate chelate ligand) binuclear complex |
| CN102069014A (en) * | 2010-09-15 | 2011-05-25 | 罗梅 | Chiral zinc complex and copper complexes of alpha-phenylethylamine |
| WO2012017966A1 (en) * | 2010-08-02 | 2012-02-09 | 国立大学法人岡山大学 | Metal complex compound and amide production method that utilizes said metal complex compound |
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2014
- 2014-10-15 CN CN201410545691.3A patent/CN104399528B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093095A (en) * | 1993-03-12 | 1994-10-05 | 赫彻斯特股份公司 | Water soluble coppercomplexmonoazocompoundcarbonacid compoundcarbonacid, its method for making and application |
| JP2000103797A (en) * | 1998-09-29 | 2000-04-11 | Mitsubishi Chemicals Corp | Rhodium-(bidentate chelate ligand) binuclear complex |
| WO2012017966A1 (en) * | 2010-08-02 | 2012-02-09 | 国立大学法人岡山大学 | Metal complex compound and amide production method that utilizes said metal complex compound |
| CN102069014A (en) * | 2010-09-15 | 2011-05-25 | 罗梅 | Chiral zinc complex and copper complexes of alpha-phenylethylamine |
Non-Patent Citations (1)
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| WEI-BIN YU等: "Water oxidation catalysts and pH sensors based on azo-conjugated iridium/rhodium motifs", 《DALTON TRANSACTIONS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111359662A (en) * | 2018-12-26 | 2020-07-03 | 万华化学集团股份有限公司 | Copper ligand catalyst, preparation method thereof and application thereof in mandelic acid oxidation reaction |
| CN111359662B (en) * | 2018-12-26 | 2023-01-13 | 万华化学集团股份有限公司 | Copper ligand catalyst, preparation method thereof and application thereof in mandelic acid oxidation reaction |
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