CN108677211A - Carbon nano-tube/poly closes ionic liquid/copper complex complex light anode catalyst system and catalyzing and its application - Google Patents
Carbon nano-tube/poly closes ionic liquid/copper complex complex light anode catalyst system and catalyzing and its application Download PDFInfo
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Abstract
The present invention discloses carbon nano-tube/poly and closes ionic liquid/copper complex complex light anode catalyst system and catalyzing and its application.Using the surface of polymeric ionic liquid non-covalent modification carbon nanotube, with copper complex [NMe4]2[CuL1] and [NMe4]2[CuL2] it is catalyst, anion exchange is carried out by catalyst and polymeric ionic liquid, constitutes CNTs/PIL/CuL1And CNTs/PIL/CuL2Complex light anode catalyst system and catalyzing, because the integrality of complex is maintained there was only limited pH ranges, the copper complex catalyst resolves into corresponding water/hydroxo complex and free ligand in acid condition, polymeric ionic liquid, which is effectively prevented, is fixed on catalyst on glass-carbon electrode by nafion, the composite anode of the present invention not only substantially increases the catalytic activity of catalyst, but also realizes the catalytic water oxidation under applied voltage driving of the composite anode of heterogeneous catalysis and generate oxygen.
Description
Technical field
The invention belongs to electrochemical catalysis fields, are specifically related to a kind of using polymeric ionic liquid π-π non-covalent modifications
The surface of carbon nanotube, with the molecular level copper complex [NMe with rock-steady structure4]2[CuL1] and [NMe4]2[CuL2] it is to urge
Agent constitutes CNTs/Poly/CuL by the way that catalyst and poly ion liquid are carried out anion exchange1And CNTs/Poly/CuL2
Complex light anode catalyst system and catalyzing, composite anode prepared by the present invention not only substantially increase the catalytic activity of catalyst, Er Qieshi
Show the catalytic water oxidation under applied voltage driving of the composite anode of heterogeneous catalysis and generates oxygen.
Background technology
With the rapid development of social economy, demand of the mankind to the energy is growing day by day, the influence and pollution of natural environment
Also gradually increase, energy crisis and environmental pollution have become the huge challenge of human survival and development.Fossil fuel is support
The basis of development of all countries economy and power, for a long time, people, which excessively develop fossil fuel, makes it face exhausted circumstances.Face
To this problem existing for the energy, a kind of novel and clean energy of exploitation becomes a urgent challenge.Novel energy is divided into
Reproducible primary energy and reproducible secondary energy sources, and reproducible secondary energy sources such as Hydrogen Energy, it is abundant with reserves, it is green
Color is pollution-free, the advantages such as is widely used, becomes one of most advantageous and most promising energy.High heating value is obtained by electrolysis water
With reproducible Hydrogen Energy, it is considered to be one of optimal hydrogen manufacturing approach.
Related water electrolysis hydrogen production mainly has following three kinds of approach at present：One, electrolyzed alkaline water hydrogen manufacturing.Alkali electrochemical decomposes
Water is considered as the most universal hydrogen manufacturing mode, and main device is the electrolytic cell as diaphragm, anode, cathode and electricity by asbestos
Source is constituted.Two, solid polymer electrolytic water hydrogen manufacturing.Solid polymer electrolytic water hydrogen manufacturing mainly passes through electrolytic cell, anode and cathode, electricity
Source and proton exchange membrane composition costly because of electrode material are difficult to realize industrialized development.Three, solid high-temperature oxide electricity
Solve water hydrogen manufacturing.The method is that efficiency is highest in three kinds of electrolysis waters, but electrolytic process is due to the influence of high temperature and corrosion, electrolysis
The reduced performance of slot material is very fast, and consumption is very fast, causes to substantially increase production cost.
The research of early stage, mainly with Ru, the precious metal simple substances such as Ir and corresponding oxide, complex is Journal of Molecular Catalysis
The oxygenolysis of water is realized in agent in homogeneous system.By the research of last decade, water oxygen from initial chemical catalysis system by
Gradually develop to electro-catalysis system, a variety of reaction systems such as photoelectrochemical cell.With traditional metal oxide heterogeneous catalyst phase
Than the water oxidation catalyst of many molecular levels has a clear superiority in catalytic activity and adjustability of structure.
Invention content
This invention address that the research of catalytic water oxidation, designs and constructs carbon nano-tube/poly conjunction ionic liquid/molecule and urge
The glass-carbon electrode anode of agent modification has a very important significance structure novel electrochemical cells.Electro-catalysis the results show that
Utilize mode of loading of the present invention, when applying bias is 1.05V (vs NHE), NEW TYPE OF COMPOSITE light anode CNTs/PIL/
CuL1The density of photocurrent of electrode is 1.4mA/cm2, CNTs/PIL/CuL2Density of photocurrent be 1.55mA/cm2, it is approximately CNTs
10 times of electrode, catalytic activity are much better than the glass-carbon electrode of copper complex modification.
The technical solution adopted by the present invention is：Carbon nano-tube/poly closes ionic liquid/copper complex complex light anode catalytic body
System, first by polymeric ionic liquid PIL with the surface of π-π non-covalent modification carbon nanotubes CNTs, then with copper complex [NMe4]2
[CuL1] or [NMe4]2[CuL2] it is catalyst, by the way that catalyst and poly ion liquid PIL are carried out anion exchange, constitute
CNTs/PIL/CuL1Complex light anode catalyst system and catalyzing or CNTs/PIL/CuL2Complex light anode catalyst system and catalyzing.
Above-mentioned carbon nano-tube/poly closes ionic liquid/copper complex complex light anode catalyst system and catalyzing, the copper complex
[NMe4]2[CuL1] there is the structural formula as shown in (I)；Copper complex [the NMe4]2[CuL2] have as shown in (II)
Structural formula：
Carbon nano-tube/poly closes ionic liquid/copper complex modified electrode, above-mentioned in glass-carbon electrode GC area loads
CNTs/PIL/CuL1Complex light anode catalyst system and catalyzing or CNTs/PIL/CuL2Complex light anode catalyst system and catalyzing prepares CNTs/PIL/
CuL1/ GC modified electrodes or CNTs/PIL/CuL2/ GC modified electrodes.
Carbon nano-tube/poly closes the preparation method of ionic liquid/copper complex modified electrode, includes the following steps：
1) preparation of ionic liquid monomer 1- vinyl -3- ethyl imidazol(e)s bromide (ViEtImBr)：Bromoethane is added dropwise
Into 1- vinyl imidazoles, back flow reaction 16 hours at 40-90 DEG C, filtering obtained solid is washed with ethyl acetate, and vacuum is dry
It is dry, obtain ionic liquid monomer ViEtlmBr.
2) preparation of polymeric ionic liquid PIL：Under a nitrogen, ionic liquid monomer ViEtlmBr is diluted with chloroform, so
After azodiisobutyronitrile is added, heated 3 hours at 70 DEG C, obtained solid chloroform, be dried in vacuo, obtain polymerization plasma liquid
Body PIL.
3) preparation of CNTs/PIL：At room temperature, polymeric ionic liquid PIL is dissolved in deionized water, CNTs is then added
It with the mixed solution of isopropanol, stirs 12 hours, centrifuges, vacuum drying obtains CNTs/PIL.
Preferably, the preparation method of the mixed solution of the CNTs and isopropanol is that CNTs is dispersed in isopropanol,
It is ultrasonically treated 10 minutes.
4) CNTs/PIL is dispersed in isopropanol, copper complex [NMe4]2[CuL1] or copper complex [NMe4]2[CuL2]
In deionized water, then, the aqueous isopropanol and [NMe of CNTs/PIL is added dropwise in dissolving successively4]2[CuL1] or [NMe4]2
[CuL2] aqueous solution to glass-carbon electrode GC on, drying, obtain CNTs/PIL/CuL1/ GC modified electrodes or CNTs/PIL/CuL2/GC
Modified electrode.
Preferably, described that CNTs/PIL is dispersed in isopropanol, it is that CNTs/PIL is added dropwise in isopropanol.
Preferably, the copper complex [NMe4]2[CuL1] preparation method, include the following steps：
1) the double oxamides (H of ligand N, N'- adjacent phenylene2L1) preparation：By THF, o-phenylenediamine and ethanedioly chloride, mixing
Uniformly, at 60 DEG C, heating reflux reaction 1-2 hours, filtering adds deionized water to generate white powder, mistake after filtrate concentration
Filter is washed, and vacuum drying obtains ligand H2L1。
2) copper complex [NMe4]2[CuL1] preparation：By H2L1It is dissolved in methanol, is added containing tetramethylammonium hydroxide
Methanol solution heats the mixture to 60 DEG C, and back flow reaction is added cupric perchlorate hexahydrate, continues back at 60 DEG C after 1 hour
Stream reaction 1 hour is added ether, filters again, sediment acetone, ether wash, very after filtering gained filtrate is concentrated by evaporation
Sky is dry, obtains [NMe4]2[CuL1].Preferably, in molar ratio, H2L1:Cupric perchlorate hexahydrate=1:1.
Preferably, the copper complex [NMe4]2[CuL2] preparation method, include the following steps：
1) the double oxamides (H of ligand N, N'- adjacent phenylene2L1) preparation：By THF, o-phenylenediamine and ethanedioly chloride, mixing
Uniformly, at 60 DEG C, heating reflux reaction 1-2 hours, filtering adds deionized water to generate white powder, mistake after filtrate concentration
Filter is washed, and vacuum drying obtains ligand H2L1。
2) the double methyl nitrosourea (H of ligand N, N'- adjacent phenylene2L2) preparation：By H2L1It is dissolved in methanol, methylamine is added
Aqueous solution, at 70 DEG C, heating reflux reaction 1-2 hours filters, and precipitation is washed with methanol, is dried in vacuo, obtains ligand H2L2。
3) copper complex [NMe4]2[CuL2] preparation：By H2L2It is dissolved in methanol, is added containing tetramethylammonium hydroxide
Methanol solution heats the mixture to 70 DEG C, after forming clear solution, cupric perchlorate hexahydrate is added, continues at 70 DEG C
Reaction 1 hour is added ether, filters again, sediment acetone, ether wash, vacuum after filtering gained filtrate is concentrated by evaporation
It is dry, obtain [NMe4]2[CuL2].Preferably, in molar ratio, H2L2：Cupric perchlorate hexahydrate=1:1.
Above-mentioned carbon nano-tube/poly closes ionic liquid/copper complex modified electrode answering in electrocatalytic decomposition water hydrogen manufacturing
With.Method is as follows：With CNTs/PIL/CuL1/ GC modified electrodes or CNTs/PIL/CuL2/ GC modified electrodes are working electrode, platinum
Silk or platinum guaze are to electrode, and Ag/AgCl is reference electrode, and water hydrogen manufacturing is catalytically decomposed.
The present invention uses the surface of polymeric ionic liquid π-π non-covalent modification carbon nanotubes, with point with rock-steady structure
Horizontal copper complex [the NMe of son4]2[CuL1] or [NMe4]2[CuL2] it is catalyst, by the way that catalyst and poly ion liquid are carried out
Anion exchange constitutes carbon nano-tube/poly ionic liquid/molecular catalyst (CNTs/PIL/CuL1And CNTs/PIL/CuL2) multiple
The anode-catalyzed system of closing light, because the integrality of complex is maintained there was only limited pH ranges, the copper complex catalyst is in acid
Corresponding water/hydroxo complex and free ligand are resolved under the conditions of property, polymeric ionic liquid, which effectively prevents, passes through nafion
Catalyst is fixed on glass-carbon electrode, because the aobvious acidity of nafion, can change copper complex structure, composite anode of the invention
The catalytic activity for not only substantially increasing catalyst, improves stability, to realize the composite anode of heterogeneous catalysis
Catalytic water oxidation generates oxygen under applied voltage driving.
The invention has the advantages that：
1) of the invention, design has synthesized copper complex catalyst, is bridge joint with polymeric ionic liquid, passes through ion-exchange absorption
Copper complex catalyst is loaded to the surfaces CNTs by attached mode, is prepared for carbon nano-tube/poly and is closed ionic liquid/molecular catalyst
Compound anode.
2) of the invention, replace noble ruthenium, iridium equimolecular catalyst with a large amount of existing base metal copper molecule catalyst；
With polymeric ionic liquid by π-π covalent modification carbon nanotubes, copper complex catalyst is attached to CNTs by ion-exchange absorption
Surface substitutes common acid adhesive nafion, PMAA etc., realizes that catalyst structure is stablized, the two is combined, prepare
It can efficient under the conditions of alkalinity, low potential, stabilization electrolysis aquatic products oxygen composite anode；Such anode has not been reported.It is preliminary real
The device of the electrolysis water of molecular catalyst is showed, new approach is opened for the application of water oxygen chemoattractant molecule catalyst.
3) of the invention, using the ion exchange property of ionic liquid, it is each to prepare functionalization using the adjustability of anion
Different polymeric ionic liquid.First by the surface of polymeric ionic liquid π-π covalent modification carbon nanotubes, ionic liquid is further utilized
Anion exchange, build novel composite anode catalyst system and catalyzing, in environmental protection, tap a new source of energy, solar energy and fuel cell
There is boundless application prospect in equal fields.
Description of the drawings
Fig. 1 is ligand H2L1's1H NMR。
Fig. 2 is ligand H2L2's1H NMR。
Fig. 3 is ionic liquid monomer ViEtlmBr1H NMR。
Fig. 4 is polymeric ionic liquid PIL1H NMR。
Fig. 5 is the scanning electron microscope diagram (SEM figures) of CNTs and relevant modifications electrode；
Wherein, A：CNTs；B：CNTs/PIL/CuL1；C：CNTs/PIL/CuL2。
Fig. 6 a are CNTs, [NMe4]2[CuL1]、CNTs/PIL/CuL1Raman spectrum.
Fig. 6 b are CNTs, [NMe4]2[CuL1]、CNTs/PIL/CuL2Raman spectrum.
Fig. 7 is [NMe4]2[CuL1] and [NMe4]2[CuL2] in the acetonitrile solution containing 0.1M hexafluorophosphates
Cyclic voltammetry curve.GC is working electrode, and Ag/AgCl is used as reference electrode, Pt electrodes to electrode, and sweep speed is
100mV/s。
Fig. 8 is the CV in phosphate buffer of the different samples at pH 11.5 (0.1M ionic strengths).GC is work electricity
Pole, Ag/AgCl is as reference electrode, and Pt electrodes are as counterelectrode, sweep speed 100mV/s.
Fig. 9 is the CV in phosphate buffer of the different samples at pH 11.5 (0.1M ionic strengths).GC is work electricity
Pole, Ag/AgCl is as reference electrode, and Pt electrodes are as counterelectrode, sweep speed 100mV/s.
Specific implementation mode
Embodiment 1CNTs/PIL/CuL1/ GC modified electrodes
1、[NMe4]2[CuL1] synthesis
1.1) synthetic ligands H2L1
120mL THF are added in round-bottomed flask, then o-phenylenediamine (2.2g, 0.02mol) and 7mL are added into solution
(6.16g, 0.044mol) ethanedioly chloride is uniformly mixed, at 60 DEG C, heating reflux reaction 1 hour, and filtering.After filtrate concentration,
Add deionized water to generate white polycrystal powder, white polycrystal powder be collected by filtration, is washed with water, and is dried under vacuum,
Obtain ligand H2L1.Yield 5.7g (93%).
1H NMR (600MHz, DMSO) δ 10.41 (s, 1H), 7.59 (dd, J=6.0,3.5Hz, 1H), 7.30 (dd, J=
6.0,3.5Hz, 1H), 4.32 (d, J=7.1Hz, 2H), 1.32 (t, J=7.1Hz, 3H).
The proof of catalyst molecule level, is shown in Fig. 1, through nucleus magnetic hydrogen spectrum test chart, it was demonstrated that successfully synthesize H2L1。
1.2) [NMe is synthesized4]2[CuL1]
By H2L1(0.770g, 2.50mmol) is dissolved in 50mL methanol, and 5mL is added and contains tetramethylammonium hydroxide
The methanol solution of (25wt%, 12.5mmol) heats the mixture to 60 DEG C, and cupric perchlorate six is added after 1 hour in back flow reaction
Hydrate (0.925g, 2.50mmol), continues back flow reaction at 60 DEG C 1 hour, is filtered to remove solid formation, and filtrate evaporation is dense
It is reduced to about residue 10mL solution.Ether is added and handles surplus solution, obtains violet solid precipitation, filters again, sediment is with third
Ketone, ether washing, vacuum drying obtain [NMe4]2[CuL1].Yield：0.822g (85%).
2, the preparation of ionic liquid monomer ViEtlmBr (1- vinyl -3- ethyl imidazol(e)s bromide)
In round-bottomed flask, 1- vinyl imidazoles that bromoethane (4.07g, 0.367mol) is added drop-wise to (2.10g,
In 0.213mol), back flow reaction 16 hours at 40 DEG C.The white-yellowish solid of filtering gained is washed for several times with ethyl acetate, and
It is dry in vacuum drying oven, obtain ionic liquid monomer ViEtlmBr.Yield：3.27g (76%).
1H NMR(600MHz,D2O) δ 9.13 (s, 1H), 7.83 (s, 1H), 7.66 (s, 1H), 7.20 (dd, J=15.6,
8.7Hz, 1H), 5.85 (dd, J=15.6,2.8Hz, 1H), 5.46 (dd, J=8.7,2.7Hz, 1H), 4.33 (q, J=7.4Hz,
1H), 1.57 (t, J=7.4Hz, 1H).
As shown in Figure 3, through nucleus magnetic hydrogen spectrum test chart, it was demonstrated that successfully synthesize ionic liquid monomer ViEtlmBr.
3, the preparation of polymeric ionic liquid PIL
Under a nitrogen, ViEtlmBr (2.03g, 0.01mol) is diluted in Schlenk round-bottomed flasks with 30mL chloroforms.
Then, be added 0.04g azodiisobutyronitriles, heated 3 hours at 70 DEG C, gained white-yellowish solid with chloroform for several times, true
It is dry in empty baking oven, obtain polymeric ionic liquid PIL.Yield：1.984g (99%).
As shown in figure 4, through nucleus magnetic hydrogen spectrum test chart, it was demonstrated that successfully synthesize polymeric ionic liquid PIL.
4, the preparation of CNTs/PIL
At room temperature, 30mg polymeric ionic liquids PIL is dissolved in the deionized water of 20mL, obtains mixed liquor A.By 10mg's
CNTs is dispersed in the isopropanol of 10mL, is ultrasonically treated 10 minutes, is obtained mixed liquid B.Mixed liquor A and mixed liquid B are mixed
It 12 hours, centrifuges, vacuum drying obtains CNTs/PIL.
5、CNTs/PIL/CuL1/ GC modified electrodes
Before anion exchange, GC electrodes are polished with 2.0 μm of alumina powders, then use deionized water and acetone
Ultrasonic cleaning is carried out, and is dried in air.
CNTs/PIL is added dropwise in the isopropanol of 10mL, ultrasonic disperse so that a concentration of 1mg/mL of CNTs.It will
[the NMe of 0.0038g4]2[CuL1] be dissolved in 10mL deionized waters so that [NMe4]2[CuL1] a concentration of 1mM.By CNTs/
The aqueous isopropanol and [NMe of PIL4]2[CuL1] aqueous solution respectively take 5 μ L to drip to successively on glass-carbon electrode GC, make [NMe4]2
[CuL1] and poly ion liquid progress ion exchange, GC is dried 3 hours in an oven later, obtains CNTs/PIL/CuL1/ GC is repaiied
Adorn electrode.
Embodiment 2CNTs/PIL/CuL2/ GC modified electrodes
1、[NMe4]2[CuL2] synthesis
1.1) synthetic ligands H2L2
By H2L1(0.86g, 0.46mmol) is dissolved in 30mL methanol, and the aqueous solution of the 40wt% methylamines of 1.00mL is added,
At 70 DEG C, heating reflux reaction 1 hour filters, and precipitation is washed with methanol, is dried in vacuo, obtains ligand H2L2.Yield：0.87g
(87%).
1H NMR (600MHz, DMSO) δ 10.50 (s, 1H), 8.98 (dd, J=9.3,4.5Hz, 1H), 7.60 (dd, J=
6.0,3.6Hz, 1H), 7.28 (dd, J=6.0,3.5Hz, 1H), 2.73 (d, J=4.9Hz, 3H).
1.2) [NMe is synthesized4]2[CuL2]
By H2L2(0.696g, 2.50mmol) is dissolved in 30mL methanol, and 5.3mL is added and contains tetramethylammonium hydroxide
The methanol solution of (25wt%, 12.5mmol) heats the mixture to 70 DEG C, after stirring is until form clear solution, is added high
Copper chlorate hexahydrate (0.925g, 2.50mmol), the reaction was continued at 70 DEG C 1 hour, is filtered to remove solid formation, gained
Filtrate is concentrated by evaporation to residue about 10mL solution, and ether is added, and obtains brown solid precipitation, filters again, precipitation acetone,
Ether washs, and vacuum drying obtains [NMe4]2[CuL2].Yield：0.167g (80%).
The proof of catalyst molecule level, as shown in Fig. 2, through nucleus magnetic hydrogen spectrum test chart, it was demonstrated that successfully synthesize H2L2。
2, the preparation of ionic liquid monomer ViEtlmBr：With embodiment 1
3, the preparation of polymeric ionic liquid PIL：With embodiment 1
4, the preparation of CNTs/PIL：With embodiment 1
5、CNTs/PIL/CuL2/ GC modified electrodes
Before anion exchange, GC electrodes are polished with 2.0 μm of alumina powders, then use deionized water and acetone
Ultrasonic cleaning is carried out, and is dried in air.
CNTs/PIL is added dropwise in the isopropanol of 10mL, ultrasonic disperse so that a concentration of 1mg/mL of CNTs.It will
[the NMe of 0.0038g4]2[CuL2] be dissolved in 10mL deionized waters so that [NMe4]2[CuL2] a concentration of 1mM.By CNTs/
The aqueous isopropanol and [NMe of PIL4]2[CuL2] aqueous solution respectively take 5 μ L to drip to successively on glass-carbon electrode GC, make [NMe4]2
[CuL2] and poly ion liquid progress ion exchange, GC is dried 3 hours in an oven later, obtains CNTs/PIL/CuL2/ GC is repaiied
Adorn electrode.
3 carbon nano-tube/poly of embodiment closes ionic liquid/copper complex modified electrode answering in electrocatalytic decomposition water hydrogen manufacturing
With
1, the electron scanning micrograph (SEM) of related electrode, is shown in Fig. 5.
Such as Fig. 5, the present invention tests the scanning electron microscope (SEM) photograph (a in Fig. 5) of business CNTs, it can be seen from the figure that CNTs tables
Face is that unordered tubulose is overlapped mutually, and has prodigious specific surface area, and guarantee is provided for poly ion liquid adsorbance.Fig. 5
In (b) be CNTs/PIL/CuL1Scanning electron microscope (SEM) photograph, (c) is CNTs/PIL/CuL in Fig. 52Scanning electron microscope (SEM) photograph, from pattern
From the point of view of, compared with (a) in Fig. 5, it is evident that find out catalyst block structure well load on the carbon nanotubes, catalyst
[NMe4]2[CuL1] and [NMe4]2[CuL2] it is by having carried out ion exchange on the carbon nanotubes with ionic liquid.
2, the Raman spectrum of catalyst and different composite electrode is shown in Fig. 6 a and Fig. 6 b.
In order to further prove that copper complex Catalyst Adsorption has arrived the surface of CNTs, Raman spectrum test is carried out, such as
Fig. 6 a and Fig. 6 b, prepared original [NMe4]2[CuL1] and [NMe4]2[CuL2] catalyst peak value in 1300-1800nm models
Enclose lower and CNTs/PIL/CuL1With CNTs/PIL/CuL2Anode is consistent, and the peak at 1350nm is the peak of catalyst, and CNTs exists
1350nm not appearances.
3, the electrochemical property test of composite anode
Electro-chemical test is shown in Fig. 7, Fig. 8, Fig. 9.All tests of this experiment are all made of the CHI660E electricity of Shanghai Chen Hua company
Chem workstation, is done with platinum filament to electrode, and reference electrode, CNTs/PIL/ are with Ag/AgCl (2.5M saturated potassium chloride solutions)
CuL1/ GC modified electrodes or CNTs/PIL/CuL2/ GC modified electrodes are working electrode.Using three-electrode system, catalyst follows
Ring volt-ampere (CV) test carries out in acetonitrile and aqueous solution.
The present invention uses the mode of loading of dripping method, increases electric conductivity with CNTs, polymeric ionic liquid is bridge joint, [NMe4]2
[CuL1] or [NMe4]2[CuL2] it is catalyst, under the environment of alkaline pH=11.5, investigate the change of system water oxygen galvanic current potential
The performance of change.
Using contain 0.1M hexafluorophosphate acetonitrile solution as electrolyte solution, by [NMe4]2[CuL1] or
[NMe4]2[CuL2] be dissolved in electrolyte solution, make a concentration of 1mM, GC be working electrode, Ag/AgCl as reference electrode,
Pt electrodes are used as to electrode, sweep speed 100mV/s, carry out electro-chemical test.From figure 7 it can be seen that [NMe4]2[CuL1]
Without reversed reduction peak, this is because fast chemical reaction is combined with electrochemical process, it is attributed to Oxamide Ligands (L1) copper
(III) catalyzing hydrolysis decomposes, and obtains corresponding Oxalate Complexes.[NMe4]2[CuL2] hydrolysis pass through H2OH in O or alkaline medium-
Nucleophillic attack on amide groups carbon atom carries out, and copper (III) substitution copper (II) can increase the positive charge density on amide carbon, to
Increase nucleophillic attack, i.e. [NMe4]2[CuL2] there are redox peaks.That is copper complex catalyst of the present invention needs
Electro-chemical test is carried out under conditions of alkalinity, can form free ligand in acid condition, and common adhesive is aobvious sour
Property, catalyst cannot be supported on glass-carbon electrode, so the present invention is existed catalyst by ion exchange by polymerization plasma
On CNTs.
With pH=11.5, ionic strength is 0.1M phosphate buffer solutions as electrolyte solution, when to CNTs/PIL/
CuL1/ GC modified electrodes and CNTs/PIL/CuL2When/GC modified electrodes are tested, which shows good urge
Change activity.As shown in Figure 8 and Figure 9, when testing CV to blank glass-carbon electrode, in applied voltage 1.05V vs Ag/AgCl,
Electric current is only 0.03mA/cm2, CNTs, CNTs/PIL or PIL/CuL are added dropwise on glass-carbon electrode1(PIL/CuL2) and [NMe4]2
[CuL1] or [NMe4]2[CuL2], in applied voltage 1.05V vs Ag/AgCl, improved by a small margin although current density has,
It is still unobvious.And after by ion exchange, there is catalyst CNTs/PIL/CuL on glass-carbon electrode1And CNTs/PIL/CuL2It is multiple
When the anode-catalyzed system of closing light, water oxygen occurs in 0.8V vs Ag/AgCl or so.By Fig. 8 and Fig. 9 as it can be seen that when comparing
Under specific voltage when the current density of combination electrode, in 1.05V vs Ag/AgCl, there is CNTs/PIL/CuL on glass-carbon electrode1
And CNTs/PIL/CuL2Complex light anode catalyst system and catalyzing shows better catalytic performance：In 1.05V vs Ag/AgCl
When, the density of photocurrent of CNTs electrodes is 0.15mA/cm2, the density of photocurrent of CNTs/PIL electrodes is 0.30mA/cm2, and
CNTs/PIL/CuL1The density of photocurrent of electrode is 1.4mA/cm2, CNTs/PIL/CuL2Density of photocurrent be 1.55mA/
cm2, it is approximately 10 times of CNTs electrodes.It can be seen that in 1.05V vs Ag/AgCl by Fig. 8 and Fig. 9, CNTs/PIL/CuL1
And CNTs/PIL/CuL2Than [NMe4]2[CuL1] and [NMe4]2[CuL2], current density improves 4 times or so, i.e., CNTs is increased
Electric conductivity, and copper complex catalyst can form free ligand in acid condition, so being loaded by polymerization plasma
On CNTs.
Claims (10)
1. carbon nano-tube/poly close ionic liquid/copper complex complex light anode catalyst system and catalyzing, which is characterized in that will first polymerize from
Sub- liquid PIL is with the surface of π-π non-covalent modification carbon nanotubes CNTs, then with copper complex [NMe4]2[CuL1] or [NMe4]2
[CuL2] it is catalyst, by the way that catalyst and poly ion liquid PIL are carried out anion exchange, constitute CNTs/PIL/CuL1It is compound
Light anode catalyst system and catalyzing or CNTs/PIL/CuL2Complex light anode catalyst system and catalyzing.
2. carbon nano-tube/poly according to claim 1 closes ionic liquid/copper complex complex light anode catalyst system and catalyzing,
It is characterized in that, the copper complex [NMe4]2[CuL1] there is the structural formula as shown in (I)；Copper complex [the NMe4]2
[CuL2] there is the structural formula as shown in (II)：
3. carbon nano-tube/poly closes ionic liquid/copper complex modified electrode, which is characterized in that in glass-carbon electrode GC area loads
CNTs/PIL/CuL as claimed in claim 1 or 21Complex light anode catalyst system and catalyzing or CNTs/PIL/CuL2Complex light anode is catalyzed
System prepares CNTs/PIL/CuL1/ GC modified electrodes or CNTs/PIL/CuL2/ GC modified electrodes.
4. carbon nano-tube/poly closes the preparation method of ionic liquid/copper complex modified electrode, which is characterized in that including walking as follows
Suddenly：
1) preparation of ionic liquid monomer 1- vinyl -3- ethyl imidazol(e)s bromide (ViEtImBr)：Bromoethane is added drop-wise to 1-
In vinyl imidazole, back flow reaction 16 hours at 40-90 DEG C, filtering obtained solid is washed with ethyl acetate, is dried in vacuo, is obtained
Ionic liquid monomer ViEtlmBr；
2) preparation of polymeric ionic liquid PIL：Under a nitrogen, ionic liquid monomer ViEtlmBr is diluted with chloroform, is then added
Enter azodiisobutyronitrile, heated 3 hours at 70 DEG C, obtained solid chloroform, is dried in vacuo, obtains polymeric ionic liquid
PIL；
3) preparation of CNTs/PIL：At room temperature, polymeric ionic liquid PIL is dissolved in deionized water, CNTs and different is then added
The mixed solution of propyl alcohol stirs 12 hours, centrifuges, and vacuum drying obtains CNTs/PIL；
4) CNTs/PIL is dispersed in isopropanol, copper complex [NMe4]2[CuL1] or copper complex [NMe4]2[CuL2] dissolving
In deionized water, then, the aqueous isopropanol and [NMe of CNTs/PIL are added dropwise successively4]2[CuL1] or [NMe4]2[CuL2]
On aqueous solution to glass-carbon electrode GC, drying obtains CNTs/PIL/CuL1/ GC modified electrodes or CNTs/PIL/CuL2/ GC modification electricity
Pole.
5. preparation method according to claim 4, which is characterized in that step 3), the mixing of the CNTs and isopropanol
The preparation method of solution is that CNTs is dispersed in isopropanol, is ultrasonically treated 10 minutes；Step 4), it is described by CNTs/PIL
It is dispersed in isopropanol, is that CNTs/PIL is added dropwise in isopropanol.
6. preparation method according to claim 4, which is characterized in that the copper complex [NMe4]2[CuL1] preparation
Method includes the following steps：
1) the double oxamides (H of ligand N, N'- adjacent phenylene2L1) preparation：By THF, o-phenylenediamine and ethanedioly chloride, it is uniformly mixed,
At 60 DEG C, heating reflux reaction 1-2 hours, filtering after filtrate concentration, adds deionized water to generate white powder, and filtering is washed
It washs, is dried in vacuo, obtains ligand H2L1；
2) copper complex [NMe4]2[CuL1] preparation：By H2L1It is dissolved in methanol, the methanol containing tetramethylammonium hydroxide is added
Solution heats the mixture to 60 DEG C, and back flow reaction is added cupric perchlorate hexahydrate, it is anti-to continue reflux at 60 DEG C after 1 hour
It answers 1 hour, after filtering gained filtrate is concentrated by evaporation, ether is added, filters again, sediment acetone, ether wash, and vacuum is dry
It is dry, obtain [NMe4]2[CuL1]。
7. preparation method according to claim 4, which is characterized in that the copper complex [NMe4]2[CuL2] preparation
Method includes the following steps：
1) the double oxamides (H of ligand N, N'- adjacent phenylene2L1) preparation：By THF, o-phenylenediamine and ethanedioly chloride, it is uniformly mixed,
At 60 DEG C, heating reflux reaction 1-2 hours, filtering after filtrate concentration, adds deionized water to generate white powder, and filtering is washed
It washs, is dried in vacuo, obtains ligand H2L1；
2) the double methyl nitrosourea (H of ligand N, N'- adjacent phenylene2L2) preparation：By H2L1It is dissolved in methanol, it is water-soluble that methylamine is added
Liquid, at 70 DEG C, heating reflux reaction 1-2 hours filters, and precipitation is washed with methanol, is dried in vacuo, obtains ligand H2L2；
3) copper complex [NMe4]2[CuL2] preparation：By H2L2It is dissolved in methanol, the methanol containing tetramethylammonium hydroxide is added
Solution heats the mixture to 70 DEG C, after forming clear solution, cupric perchlorate hexahydrate is added, continues to flow back at 70 DEG C
Reaction 1 hour is added ether, filters again, sediment acetone, ether wash, vacuum after filtering gained filtrate is concentrated by evaporation
It is dry, obtain [NMe4]2[CuL2]。
8. the preparation method described according to claim 6 or 7, which is characterized in that in molar ratio, H2L1:Cupric perchlorate hexahydrate
=1:1；H2L2：Cupric perchlorate hexahydrate=1:1.
9. the carbon nano-tube/poly described in claim 3 closes ionic liquid/copper complex modified electrode in electrocatalytic decomposition water hydrogen manufacturing
In application.
10. application according to claim 9, which is characterized in that with CNTs/PIL/CuL1/ GC modified electrodes or CNTs/
PIL/CuL2/ GC modified electrodes are working electrode, and platinum filament or platinum guaze are to electrode, and Ag/AgCl is reference electrode, and water is catalytically decomposed
Hydrogen manufacturing.
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