CN103467498A - Copper complex having electrocatalytic activity on hydrogen peroxide and preparation method thereof - Google Patents
Copper complex having electrocatalytic activity on hydrogen peroxide and preparation method thereof Download PDFInfo
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- CN103467498A CN103467498A CN2013104201503A CN201310420150A CN103467498A CN 103467498 A CN103467498 A CN 103467498A CN 2013104201503 A CN2013104201503 A CN 2013104201503A CN 201310420150 A CN201310420150 A CN 201310420150A CN 103467498 A CN103467498 A CN 103467498A
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Abstract
The invention discloses a copper complex and a preparation method thereof, and the copper complex is characterized by having good electrocatalytic activity on hydrogen peroxide, the molecular formula of the copper complex is C46H34N6O14Cu2, the crystal system is clinorhomboidal, the space group is P-1, the cell parameters are as follows: alpha is equal to 99.90 degrees, beta is equal to 101.2 degrees and gamma is equal to 93.69 degrees. The copper complex is prepared from a mixing reaction of a copper salt, 5-(di(carboxymethyl) amino)-2-hydroxybenzoic acid and 1,10-phenanthroline according to a certain proportion, the copper complex has a specific spatial structure and an accurate molecular formula, the synthesis steps are simple, and the yield can reach 30-70%. The copper complex prepared in the invention has good electrocatalytic activity, thereby having a broad application prospect of being used as a potential electrocatalytic active material.
Description
Technical field
The present invention relates to the materials chemistry field, relate in particular to a kind of copper complex that hydrogen peroxide is there is to electro catalytic activity and preparation method thereof.
Background technology
Electrocatalysis is a kind of katalysis that makes the charge transfer accelerated reaction on electrode, electrolyte interface.Electrocatalysis is covered with electrode reaction and two aspects of katalysis, so eelctro-catalyst must have this two kinds of functions simultaneously: electronics can be conducted electricity and more freely transmit in (1); (2) can carry out effective catalytic activation effect to substrate.The electrocatalysis that is mainly used in fuel cell, organic sewage is processed; The Electrocatalysis Degradation of chromate waste water; The electrolysis desulfurization of stack gas and feed coal; Electrocatalysis removes NO simultaneously
xand SO
2; The electrolytic reduction of carbonic acid gas; The electrolytic reduction of formaldehyde, hydrogen peroxide etc.
Eelctro-catalyst, as the core of electrocatalysis, is people's study hotspot always.Traditional eelctro-catalyst is platinum metals and alloy catalyst thereof, because there are the problems such as expensive or inadequate resource in this class catalyzer, has limited its application and development.Therefore, the cheap non-noble's metal electric catalyzer of development of new becomes a main direction of studying.At present, the conductor oxidate that nickel borides, wolfram varbide, sodium tungsten bronze, spinel type and tungsten state ore deposit type are arranged that eelctro-catalyst research is more, and transition metal macrocyclic title complex, as porphyrin, phthalocyanine or the four azo annulene isoreactivity catalyzer of iron ion.The stability of conductor oxidate is poor and catalytic activity is lower, still in the research and development stage; Phthalocyanine, the large ring conjugated complex of porphyrin make it have good electro catalytic activity due to itself special large ring conjugated structure, and can there is the adjustable sex change of structure by changing substituting group on its conjugate ring and central metal atom and molecular aggregates mode, given its broad space as the eelctro-catalyst performance development, that platinum group catalyst has one of substitute of application prospect, but the preparation process of catalyzer is too complicated, and by product is more.Transition metal complex can be used as eelctro-catalyst, because the electro catalytic activity of central ion, vacant d track and not paired d electronics are arranged in the atomic structure due to transition metal, by the catalyzer containing transition metal, with the electronics of reactant molecule, contact, the adsorption bond that will form various features on the vacant d track of these catalyzer reaches the purpose of molecule activation, thereby reduced the activation energy of complex reaction, reach the electrocatalysis purpose, part with conjugation group can the active center ion, be conducive to the transmission of electronics, make it there is good electro catalytic activity.
Summary of the invention
Technical problem to be solved by this invention is for prior art, provides a kind of hydrogen peroxide is had to the copper complex of good electro catalytic activity and the preparation method that step is simple, reaction conditions is gentle thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of copper complex, and this compound is a kind of copper complex with good electrical catalytic activity, its molecular formula is C
46h
34n
6o
14cu
2, crystallographic system is three oblique, spacer is P-1, unit cell parameters
α=99.90 °, β=101.2 °, γ=93.69 °.The tetragonal pyramid geometric configuration that cupric ion is pentacoordinate, wherein two nitrogen ligating atoms come from 1,10-phenanthroline, and three nitrogen ligating atoms come from 5-(two (carboxymethyl) amino)-2 hydroxybenzoic acid.Described preparation method is with 5-(two (carboxymethyl) amino)-2 hydroxybenzoic acid and 1, the 10-phenanthroline is as part, by copper metal ion and 5-(two (carboxymethyl) amino)-2 hydroxybenzoic acid and 1, coordination in 10-phenanthroline part between nitrogen-atoms, formation has the copper complex of dual-core architecture, specifically comprises the following steps:
By mantoquita, organic ligand 5-(two (carboxymethyl) amino)-2 hydroxybenzoic acid, 1, the 10-phenanthroline, the ratio of 1:0.1～10:0.1～10 has been mixed in the teflon-lined autoclave in molar ratio, and adding distil water 5～40mL;
This reactor is placed in to 60～90 ℃, heats after 15～60min and take out and be cooled to room temperature;
Regulate mixing solutions to being slightly acidic (pH is 5-7) with dilute alkaline soln;
Room temperature is standing, and slowly solvent flashing, to crystallize out, sucks last solution, and after natural air drying, the gained bulk crystals is copper complex.
Alternatively, the 5-(two (carboxymethyl) amino) of described participation reaction-2 hydroxybenzoic acid, be called for short H
4l, structural formula is:
Preferably, preparation method (the Xu Y.-Q.et al of N-(4-carboxyl phenyl) iminodiethanoic acid in preparation method's reference literature of described 5-(two (carboxymethyl) amino)-2 hydroxybenzoic acid, J.Mol.Struct.2006,789:220-224): KOH solution is added drop-wise in sodium chloroacetate solution and stirs, then 5-aminosalicylic acid solution slowly is added drop-wise in above-mentioned mixed solution, in 85 ℃ of reaction 30h.Reaction is cooled to room temperature after finishing, and with HCl solution, is acidified to and produces precipitation, crosses the leaching filter residue, washed several times with water, and natural air drying, the gained pressed powder is part H
4l.
Alternatively, the mantoquita of described participation reaction is in copper sulfate, cupric chloride, cupric nitrate or neutralized verdigris; The material of described participation reaction is chemical pure.
Compared with prior art, the invention has the advantages that: by 5-(two (carboxymethyl) amino)-2 hydroxybenzoic acid with there is 1 of conjugated structure, 10-phenanthroline and the cupric ion chelating coordination with electrochemical catalysis activity, make novel copper complex, this compound has space structure (Fig. 1) and molecular formula accurately accurately; Prepared material has good electro catalytic activity to hydrogen peroxide, as the electro catalytic activity material, has potential application prospect.
The accompanying drawing explanation
The structural unit figure that Fig. 1 is copper complex of the present invention;
Fig. 2 is that copper complex of the present invention is to H
2o
2the electro catalytic activity response diagram.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Preparation method (the Xu Y.-Q.et al of N-(4-carboxyl phenyl) iminodiethanoic acid in preparation method's reference literature of 5-(two (carboxymethyl) amino)-2 hydroxybenzoic acid, J.Mol.Struct.2006,789:220-224): 20mL KOH solution (12M) is added drop-wise in 20mL sodium chloroacetate solution (6M) and stirs, then by 5-aminosalicylic acid (4.59g, 0.03mol) slowly be added in above-mentioned mixed solution, in 85 ℃ of reaction 30h.Reaction is cooled to room temperature after finishing, and with HCl solution (6mol/L), is acidified to and produces precipitation, crosses the leaching filter residue, washed several times with water, and natural air drying, the gained pressed powder is part H
4l.
Embodiment 1:
Take CuSO
45H
2o(2.497g, 10mmol), H
4l(0.269g, 1.0mmol), 1,10-phenanthroline (0.180g, 1.0mmol) adds in 5.0mL distilled water, is stirred to dissolve; In 60 ℃ of heating 60min, then take out and be cooled to room temperature after reaction unit is sealed; Regulate mixing solutions to being slightly acidic (pH=5) with rare KOH solution afterwards; Room temperature is standing, and slowly solvent flashing is to crystallize out.Remove solution, natural air drying obtains bulk crystals and is copper complex.
Wherein, described part 5-(two (carboxymethyl) amino)-2 hydroxybenzoic acid (H
4l) preparation method: by KOH solution (12M, 20mL) be added drop-wise in sodium chloroacetate (13.978g, the 0.12mol) aqueous solution (20mL) and stir, then by 5-aminosalicylic acid (4.59g, 0.03mmol) slowly be added in above-mentioned mixed solution, in 85 ℃ of reaction 30h.Be cooled to room temperature after reacting end, with HCl solution (6mol/L), be acidified to and produce precipitation, cross the leaching filter residue, use distilled water wash three times, natural air drying, the gained pressed powder is part H
4l.
Embodiment 2:
Take CuCl
22H
2o(0.170g, 1.0mmol), H
4l(2.692g, 10mmol), 1,10-phenanthroline (1.802g, 10mmol) adds in 40mL distilled water, is stirred to dissolve; In 90 ℃ of heating 15min, then take out and be cooled to room temperature after reaction unit is sealed; Regulate mixing solutions to being slightly acidic (pH=7) with rare KOH solution afterwards; Room temperature is standing, and slowly solvent flashing is to crystallize out.Remove solution, natural air drying obtains bulk crystals and is copper complex.
Embodiment 3:
Take Cu (NO
3)
23H
2o(0.483g, 2.0mmol), H
4l(2.692g, 10mmol), 1,10-phenanthroline (1.802g, 10mmol) adds in 15mL distilled water, is stirred to dissolve; In 80 ℃ of heating 30min, then take out and be cooled to room temperature after reaction unit is sealed; Regulate mixing solutions to being slightly acidic (pH=6) with rare KOH solution afterwards; Room temperature is standing, and slowly solvent flashing is to crystallize out.Remove solution, natural air drying obtains bulk crystals and is copper complex.
Embodiment 4:
Take Cu (OAc)
2h
2o(0.399g, 2.0mmol), H
4l(0.269g, 1.0mmol), 1,10-phenanthroline (0.180g, 1.0mmol) adds in 20mL distilled water, is stirred to dissolve; In 70 ℃ of heating 45min, then take out and be cooled to room temperature after reaction unit is sealed; Regulate mixing solutions to being slightly acidic (pH=6.5) with rare KOH solution afterwards; Room temperature is standing, and slowly solvent flashing is to crystallize out.Remove solution, natural air drying obtains bulk crystals and is copper complex.
The copper complex made in above-described embodiment is the deep green bulk crystals, and its molecular formula is C after measured
46h
34n
6o
14cu
2, its structural unit figure as shown in Figure 1.
By prepared cobalt complex C
46h
34n
6o
14cu
2carry out H
2o
2the electrocatalysis characteristic test, as shown in Figure 2, as seen from Figure 2, this compound is to H for its electro catalytic activity response diagram
2o
2show good electrocatalysis characteristic.
5-aminosalicylic acid and derivative thereof, because having carboxyl, hydroxyl activity group concurrently, have good sequestering power, and multiple reaction can occur, and in the title complex of the synthetic different structure of design, are playing the part of important role.The present invention's employing is simple and easy to synthetic 5-aminosalicylic acid derivative and assistant ligand is assembled synthetic copper complex, and hydrogen peroxide is had to good electro catalytic activity, for the development of new eelctro-catalyst provides new approaches, potential application is arranged in the electrocatalysis sensing detection.
Claims (4)
1. the preparation method of a copper complex, is characterized in that, comprises the following steps:
By mantoquita, organic ligand 5-(two (carboxymethyl) amino)-2 hydroxybenzoic acid, 1, the 10-phenanthroline, the ratio of 1:0.1～10:0.1～10 has been mixed in the teflon-lined autoclave in molar ratio, and adding distil water 5～40mL;
This reactor is placed in to 60～90 ℃, heats after 15～60min and take out and be cooled to room temperature;
Regulating mixing solutions with dilute alkaline soln is 5～7 to being pH;
Room temperature is standing, and slowly solvent flashing, to crystallize out, sucks last solution, and after natural air drying, the gained bulk crystals is copper complex.
2. the preparation method of copper complex according to claim 1, is characterized in that, the preparation method of described 5-(two (carboxymethyl) amino)-2 hydroxybenzoic acid comprises the following steps:
Potassium hydroxide solution is added drop-wise in sodium chloroacetate solution and stirs, then 5-aminosalicylic acid slowly is added in above-mentioned mixed solution, in 85 ℃ of reaction 30h; Reaction is cooled to room temperature after finishing, and with hcl acidifying, to producing precipitation, crosses the leaching filter residue, washed several times with water, and natural air drying, the gained pressed powder is 5-(two (carboxymethyl) amino)-2 hydroxybenzoic acid.
3. the preparation method of copper complex according to claim 1, is characterized in that, described mantoquita is in copper sulfate, cupric chloride, cupric nitrate or neutralized verdigris, and the material of described participation reaction is chemical pure.
4. a copper complex, is characterized in that, described copper complex prepares according to the preparation method of the described copper complex of any one in claim 1～3, and this compound is a kind of copper complex with electro catalytic activity, and its molecular formula is C
46h
34n
6o
14cu
2, crystallographic system is three oblique, spacer is P-1, unit cell parameters
α=99.90 °, β=101.2 °, γ=93.69 °, the tetragonal pyramid geometric configuration that cupric ion is pentacoordinate, wherein two nitrogen ligating atoms come from 1,10-phenanthroline, and three nitrogen ligating atoms come from 5-(two (carboxymethyl) amino)-2 hydroxybenzoic acid.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341438A (en) * | 2014-04-15 | 2015-02-11 | 河南理工大学 | Copper coordination compound capable of forming (4,4)-topological structure as well as preparation method and application thereof |
| CN106946798A (en) * | 2017-03-24 | 2017-07-14 | 宁波大学 | It is a kind of that there is cobalt complex of electrochemical response and preparation method thereof to hydrogen peroxide |
| CN107099039A (en) * | 2017-05-18 | 2017-08-29 | 山西大学 | A kind of three core copper coordination polymers and preparation method thereof |
| CN107188907A (en) * | 2017-06-12 | 2017-09-22 | 宁波大学 | It is a kind of that there is nickel compound of electro catalytic activity and preparation method thereof to hydrogen peroxide |
| CN109053772A (en) * | 2018-08-16 | 2018-12-21 | 河南大学 | A kind of couple of H2O2And NaNO2Cu compound with electro catalytic activity and preparation method thereof |
| CN114853789A (en) * | 2022-04-25 | 2022-08-05 | 黄金 | Metal complex, electrocatalyst and preparation method of metal complex |
| CN115779968A (en) * | 2022-12-19 | 2023-03-14 | 浙江工业大学 | Copper-based catalyst for preparing vinyl chloride through acetylene hydrochlorination reaction and preparation method and application thereof |
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| CN102731535A (en) * | 2011-04-11 | 2012-10-17 | 北京化工大学 | Novel inorganic-organic coordination polymer containing transition metal copper. |
| CN102491987A (en) * | 2011-12-13 | 2012-06-13 | 武汉纺织大学 | 1,10-phenanthroline hydrate functionalized N-heterocyclic carbene and tetranuclear copper compound and preparation method for same |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341438B (en) * | 2014-04-15 | 2016-06-22 | 河南理工大学 | Cupric coordination compound with (4,4)-topological structure and preparation method thereof and application can be formed |
| CN104341438A (en) * | 2014-04-15 | 2015-02-11 | 河南理工大学 | Copper coordination compound capable of forming (4,4)-topological structure as well as preparation method and application thereof |
| CN106946798B (en) * | 2017-03-24 | 2019-04-16 | 宁波大学 | A kind of pair of hydrogen peroxide has the cobalt complex and preparation method thereof of electrochemical response |
| CN106946798A (en) * | 2017-03-24 | 2017-07-14 | 宁波大学 | It is a kind of that there is cobalt complex of electrochemical response and preparation method thereof to hydrogen peroxide |
| CN107099039A (en) * | 2017-05-18 | 2017-08-29 | 山西大学 | A kind of three core copper coordination polymers and preparation method thereof |
| CN107099039B (en) * | 2017-05-18 | 2020-06-12 | 山西大学 | Trinuclear copper coordination polymer and preparation method thereof |
| CN107188907A (en) * | 2017-06-12 | 2017-09-22 | 宁波大学 | It is a kind of that there is nickel compound of electro catalytic activity and preparation method thereof to hydrogen peroxide |
| CN109053772A (en) * | 2018-08-16 | 2018-12-21 | 河南大学 | A kind of couple of H2O2And NaNO2Cu compound with electro catalytic activity and preparation method thereof |
| CN109053772B (en) * | 2018-08-16 | 2020-09-15 | 河南大学 | To H2O2And NaNO2Cu compound with electrocatalytic activity and preparation method thereof |
| CN114853789A (en) * | 2022-04-25 | 2022-08-05 | 黄金 | Metal complex, electrocatalyst and preparation method of metal complex |
| CN114853789B (en) * | 2022-04-25 | 2024-02-27 | 黄金 | Metal complex, electrocatalyst and preparation method of metal complex |
| CN115779968A (en) * | 2022-12-19 | 2023-03-14 | 浙江工业大学 | Copper-based catalyst for preparing vinyl chloride through acetylene hydrochlorination reaction and preparation method and application thereof |
| CN115779968B (en) * | 2022-12-19 | 2024-02-13 | 浙江工业大学 | Copper-based catalyst for preparing vinyl chloride by hydrochlorination of acetylene as well as preparation method and application thereof |
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