CN104198561B - A kind of cationic metal phthalocyanine/CNT self-assemble film pole and preparation method thereof - Google Patents
A kind of cationic metal phthalocyanine/CNT self-assemble film pole and preparation method thereof Download PDFInfo
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Abstract
A kind of cationic metal phthalocyanine/CNT self-assemble film pole and preparation method thereof.The invention belongs to electrochemistry/field of biosensors, be specifically related to a kind of positive from metal phthalocyanine/carbon nano-tube self-assemble film pole and preparation method thereof.The present invention is that existing membrane electrode shows to cover complex technical process uneven, that surface coverage is low, electrochemical properties is unstable and preparation method exists, cost is high and pollutes the problems such as environment in order to solve.Product: replace the cationic metal phthalocyanine layer of assembled belt positive charge and electronegative carbon nanotube layer in electronegative substrate, form cationic metal phthalocyanine layer and carbon nanotube layer Multilayer Film Electrode alternately, i.e. obtain cationic metal phthalocyanine/CNT self-assemble film pole.Method: one, the preparation of cationic metal phthalocyanine aqueous solution；Two, the preparation of carbon nano tube dispersion liquid；Three, substrate pretreatment；Four, the preparation of cationic metal phthalocyanine/CNT self-assemble film pole.
Description
Technical field
The invention belongs to electrochemistry/field of biosensors, be specifically related to a kind of positive from metal phthalocyanine/carbon nano-tube self-assembled film
Electrode and preparation method thereof.
Background technology
Conventional method for preparing membrane electrode is divided into drop-coating, absorption method, electrochemical process, doping method and covalent bonding method etc..
Drop-coating is difficult to accurately control due to the consumption of filmogen, and non-uniform film thickness is even, so electrode repeatability is poor, and surface
Coverage rate is relatively big (Yin H.S. etc., Food Chem, 125 (2011) 1097-1103) by the impact on physical properties of decorating liquid.
Membrane electrode stable chemical performance prepared by covalent bonding method, can complete the shape of electrode surface micro structure according to the scheme of being pre-designed
Become.But this method is loaded down with trivial details due to process, the dressing agent molecule coverage rate of final surface bond is low, constrains membrane electrode
Performance (K.Sanusi etc., J.Phys.Chem.C, 118 (2014) 7057-7069).Electrochemical process is generally used for inorganization
Learn material or the electrochemical deposition of complex material.And absorption method can obtain the double-deck list of good stability and high-sequential
Molecular layer thin film.This LBL self-assembly film chemistry is stable, molecules align rule.Because of general only several monolayers
The transmission of thickness, electronics or material is easily carried out on electrode, shows extremely strong electrochemical response.This electrode face finish
The high-sequential of molecules align can produce the effect that other modified electrode does not reaches, in electrochemical sensor, surface electro-catalysis etc.
Aspect is widely used.
Existing phthalocyanine/CNT membrane electrode is all doped with polyelectrolyte, such as polydiene base the third alkyl dimethyl ammonium chloride
(PDDA), polystyrolsulfon acid (PSS), poly-(3,4-rthylene dioxythiophene), Polyetherimide (PEI) etc. (J.B.Han etc.,
J.Mater.Chem, 21 (2011) 2126-2130；R.A.de Sousa Luz etc., Mater Chem.Phys, 130 (2011)
1072–1077；J.R.Siqueira etc., J.Phys.Chem.C, 112 (2008) 9050-9055；J.Pillay etc., Electrochimica
Acta,54(2009)5053–5059).Such preparation method is complicated, additionally, due to the materials such as polyelectrolyte introducing not only
Add preparation cost, and reduce the chemical property of membrane electrode.Though H.Z.Zhao et al. is prepared for phthalocyanine/CNT
Composite membrane, but substrate still needs to first modifying polyethyleneimine, and phthalocyanine and CNT are all dispersed in N, N-dimethyl methyl
In the organic solvents such as amide, organic solvent cost is high and big to human body and environmental hazard, (Environ.Sci.Technol., 46
(2012)5198–5204).Therefore, preparation technology is simple, low cost, uniform sequential, the phthalocyanine/carbon nanometer of good stability
Periosteum electrode is problem demanding prompt solution.
Summary of the invention
The present invention be in order to solve existing membrane electrode show to cover uneven, surface coverage is low, electrochemical properties is unstable,
And preparation method exist complex technical process, cost is high and pollutes the problems such as environment, and provides a kind of cationic metal phthalein
Cyanines/CNT self-assemble film pole and preparation method thereof.
A kind of cationic metal phthalocyanine/CNT self-assemble film pole of the present invention is alternate group in electronegative substrate
Fill positively charged cationic metal phthalocyanine layer and electronegative carbon nanotube layer, form cationic metal phthalocyanine layer and carbon is received
Mitron layer Multilayer Film Electrode alternately.
The preparation method of a kind of cationic metal phthalocyanine/CNT self-assemble film pole of the present invention sequentially includes the following steps:
One, the preparation of cationic metal phthalocyanine aqueous solution: be by the concentration that is configured to soluble in water for cationic metal phthalocyanine
0.5mg/mL～2mg/mL cationic metal phthalocyanine aqueous solution；
Two, the preparation of carbon nano tube dispersion liquid: CNT is joined ultrasonic disperse in deionized water uniform, prepare concentration
Carbon nano tube dispersion liquid for 0.5mg/mL～2mg/mL；
Three, substrate pretreatment: be 1. dissolved in ethanol solution by sodium hydroxide, obtains ethanol alkali liquor；Described ethanol solution
Mass concentration is 40%～60%, and the quality of described sodium hydroxide is 5g:(150～250 with the ratio of the volume of ethanol solution)
mL；2. the substrate cleaned up is put in water heating kettle, be subsequently adding the ethanol alkali liquor 1. obtained, tighten kettle cover, in temperature
Degree is reaction 0.5h～2h at 80～160 DEG C, and after react, taking-up substrate, with distilled water drip washing 1min～2min, so
Dry up with nitrogen afterwards, obtain electronegative substrate, be subsequently placed in strong aqua ammonia and save backup；Described ethanol alkali liquor
Volume is 20mL:(0.9～10 with the ratio of the quality of substrate) g；
Four, the preparation of cationic metal phthalocyanine/CNT self-assemble film pole: 1. step 3 obtained is electronegative
Substrate is immersed in the cationic metal phthalocyanine aqueous solution that concentration is 0.5mg/mL～2mg/mL that step one obtains, and stands
5min～30min, then takes out substrate and with deionized water rinsing 15s～60s, then dries up with nitrogen, and must arrive surface has band just
The substrate of the cationic metal phthalocyanine layer of electric charge；The concentration the most first step 2 obtained is that the carbon of 0.5mg/mL～2mg/mL is received
Mitron dispersion liquid ultrasonic disperse 1h～4h, then has the substrate of positively charged cationic metal phthalocyanine layer by the surface 1. obtained
Immerse in the carbon nano tube dispersion liquid that concentration is 0.5mg/mL～2mg/mL that the step 2 after ultrasonic disperse obtains, stand
5min～30min, then taking out surface has the substrate of positively charged cationic metal phthalocyanine layer and uses deionized water rinsing
15s～60s, then dry up with nitrogen, obtain there is positively charged cation by the surface of electronegative carbon nanotube layer parcel
The substrate of metal phthalocyanine layer；3. 1. circulation repeats～step 4 2.～30 times, forms cationic metal phthalocyanine layer and carbon nanometer
Tube layer Multilayer Film Electrode alternately, i.e. obtains cationic metal phthalocyanine/CNT self-assemble film pole.
Beneficial effects of the present invention:
1. the cationic metal phthalocyanine that the present invention prepares/CNT self-assemble film pole surface molecular arrangement is uniform sequential, with
Equal thickness successively increases.
2. cationic metal phthalocyanine/CNT self-assemble film pole that the present invention prepares has excellent electrocatalysis characteristic, its
Range of linearity width is to 0.1mmol L-1～10mmol L-1, detection limit as little as 10 μm ol L-1, sensitivity is
0.051mA·L·mol-1。
3. cationic metal phthalocyanine/CNT self-assemble film pole that the present invention prepares, due to every layer of monomolecular film all with quiet
Electrical forces attracts each other, so this membrane electrode also has outstanding stability.
4. cationic metal phthalocyanine/CNT self-assemble film pole that the present invention prepares, membrane material is stronger, is difficult to from base
Basal surface comes off, and service life is long, and the life-span is up to more than 2 months.
5. cationic metal phthalocyanine/CNT self-assemble film pole that the present invention prepares does not uses any polyelectrolyte as even
Connect agent, accelerate the transmission of electronics, improve the electro catalytic activity of electrode.
6. the preparation method of the present invention, simple to operate, need not introduce the materials such as polyelectrolyte, reduce preparation in preparation process
The chemical property of membrane electrode is ensure that while cost.
Accompanying drawing explanation
Fig. 1 is the structural representation of the cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole of test one preparation；Wherein
A is glass-carbon electrode, and b is cation cobalt phthalocyanine layer, and c is multi-wall carbon nano-tube tube layer；
Fig. 2 be test one preparation cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole be 1.5mmol L in concentration-1
Cyclic voltammetry curve figure in the phosphate buffer solution (pH=7.0) of sodium nitrite；Wherein dotted line is glass-carbon electrode, solid line
Cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole for test one preparation；
Fig. 3 be test one preparation cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole be 1.0mmol L in concentration-1
Cyclic voltammetry curve figure after scanning 100 is enclosed in the phosphate buffer solution (pH=7.0) of sodium nitrite；Wherein solid line is examination
Test the cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole of a preparation；
Fig. 4 be test one preparation cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole be 0.1mmol L in concentration-1
～10mmol L-1Sodium nitrite phosphate buffer solution (pH=7.0) in cyclic voltammetry curve figure；The most from the bottom to top
The concentration of the phosphate buffer solution being corresponding in turn to sodium nitrite is 0mmol L-1、0.1mmol·L-1、0.2mmol·L-1、0.4
mmol·L-1、0.6mmol·L-1、1.0mmol·L-1、1.4mmol·L-1、1.8mmol·L-1、2.2mmol·L-1、2.6
mmol·L-1、3.0mmol·L-1、3.4mmol·L-1、3.8mmol·L-1、4.2mmol·L-1、5.0mmol·L-1、5.8
mmol·L-1、6.6mmol·L-1、7.4mmol·L-1、8.2mmol·L-1With 10.0mmol L-1；
Fig. 5 is cation cobalt phthalocyanine/its response current of multi-walled carbon nano-tubes self-assemble film pole and the nitrous acid of test one preparation
The linear relationship chart of the relation of the concentration of sodium；
Fig. 6 is the ultraviolet spectrogram of the cation nickel phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole of test two preparation；Wherein
In Fig. 6, curve is corresponding in turn to the 1st of membrane electrode the, 2,3 from bottom to up ... 14 layers.
Detailed description of the invention
Detailed description of the invention one: a kind of cationic metal phthalocyanine/CNT self-assemble film pole of present embodiment is at band
Replace the cationic metal phthalocyanine layer of assembled belt positive charge and electronegative carbon nanotube layer in the substrate of negative charge, form sun
Ionic metal phthalocyanine layer and carbon nanotube layer Multilayer Film Electrode alternately.
1. the cationic metal phthalocyanine that present embodiment prepares/CNT self-assemble film pole surface molecular arrangement uniformly has
Sequence, successively increases with equal thickness.
2. cationic metal phthalocyanine/CNT self-assemble film pole that present embodiment prepares has excellent electrocatalysis
Can, its range of linearity is wide to 0.1～10mmol L-1, detection limit as little as 10 μm ol L-1, sensitivity is 0.051mA L mol-1。
3. cationic metal phthalocyanine/CNT self-assemble film pole that present embodiment prepares, due to every layer of monomolecular film all
Attract each other with electrostatic force, so this membrane electrode also has outstanding stability.
4. cationic metal phthalocyanine/CNT self-assemble film pole that present embodiment prepares, membrane material is stronger, is difficult to
Coming off from substrate surface, service life is long, and the life-span is up to more than 2 months.
5. cationic metal phthalocyanine/CNT self-assemble film pole that present embodiment prepares does not uses any polyelectrolyte to make
For bridging agent, accelerate the transmission of electronics, improve the electro catalytic activity of electrode.
Detailed description of the invention two: present embodiment is unlike detailed description of the invention one: described cationic metal phthalocyanine/
Cationic metal phthalocyanine layer positively charged in CNT self-assemble film pole and the number of plies of electronegative carbon nanotube layer
Identical, it is 4～30 layers.Other steps and parameter are identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment is unlike detailed description of the invention one or two: described positively charged sun
The general structure of ionic metal phthalocyanine layer cationic metal phthalocyanine is as follows:
Wherein M is Co2+、Fe2+、Ni2+、Cu2+、Zn2+、
Pd2+、Pb2+Or Mn2+.Other steps and parameter are identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment is unlike one of detailed description of the invention one to three: described is electronegative
Carbon nanotube layer in CNT be Carboxylation SWCN, Carboxylation multi-walled carbon nano-tubes, hydroxyl single
Pipe or hydroxyl multi-walled carbon nano-tubes.Other steps and parameter are identical with one of detailed description of the invention one to three.
Detailed description of the invention five: present embodiment is unlike one of detailed description of the invention one to four: described is electronegative
Substrate in substrate be glass-carbon electrode, ito glass, FTO glass, piezoid, sheet glass or silicon chip.Other steps
And parameter is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: the preparation of a kind of cationic metal phthalocyanine/CNT self-assemble film pole of present embodiment
Method sequentially includes the following steps:
One, the preparation of cationic metal phthalocyanine aqueous solution: be by the concentration that is configured to soluble in water for cationic metal phthalocyanine
0.5mg/mL～2mg/mL cationic metal phthalocyanine aqueous solution；
Two, the preparation of carbon nano tube dispersion liquid: CNT is joined ultrasonic disperse in deionized water uniform, prepare concentration
Carbon nano tube dispersion liquid for 0.5mg/mL～2mg/mL；
Three, substrate pretreatment: be 1. dissolved in ethanol solution by sodium hydroxide, obtains ethanol alkali liquor；Described ethanol solution
Mass concentration is 40%～60%, and the quality of described sodium hydroxide is 5g:(150～250 with the ratio of the volume of ethanol solution)
mL；2. the substrate cleaned up is put in water heating kettle, be subsequently adding the ethanol alkali liquor 1. obtained, tighten kettle cover, in temperature
Degree is reaction 0.5h～2h at 80～160 DEG C, and after react, taking-up substrate, with distilled water drip washing 1min～2min, so
Dry up with nitrogen afterwards, obtain electronegative substrate, be subsequently placed in strong aqua ammonia and save backup；Described ethanol alkali liquor
Volume is 20mL:(0.9～10 with the ratio of the quality of substrate) g；
Four, the preparation of cationic metal phthalocyanine/CNT self-assemble film pole: 1. step 3 obtained is electronegative
Substrate is immersed in the cationic metal phthalocyanine aqueous solution that concentration is 0.5mg/mL～2mg/mL that step one obtains, and stands
5min～30min, then takes out substrate and with deionized water rinsing 15s～60s, then dries up with nitrogen, and must arrive surface has band
The substrate of the cationic metal phthalocyanine layer of positive charge；The concentration the most first step 2 obtained is 0.5mg/mL's～2mg/mL
Carbon nano tube dispersion liquid ultrasonic disperse 1h～4h, then has positively charged cationic metal phthalocyanine layer by the surface 1. obtained
Substrate immerse the carbon nano tube dispersion liquid that concentration is 0.5mg/mL～2mg/mL that the step 2 after ultrasonic disperse obtains
In, stand 5min～30min, then taking out surface has the substrate of positively charged cationic metal phthalocyanine layer and uses deionization
Water rinses 15s～60s, then dry up with nitrogen, obtain being had positively charged by the surface of electronegative carbon nanotube layer parcel
The substrate of cationic metal phthalocyanine layer；3. 1. circulation repeats～step 4 2.～30 times, forms cationic metal phthalocyanine layer
With carbon nanotube layer Multilayer Film Electrode alternately, i.e. obtain cationic metal phthalocyanine/CNT self-assemble film pole.
1. the preparation method of present embodiment, simple to operate, need not introduce the materials such as polyelectrolyte, reduce in preparation process
The chemical property of membrane electrode is ensure that while preparation cost.
2. the cationic metal phthalocyanine that present embodiment prepares/CNT self-assemble film pole surface molecular arrangement uniformly has
Sequence, successively increases with equal thickness.
3. cationic metal phthalocyanine/CNT self-assemble film pole that present embodiment prepares has excellent electrocatalysis
Can, its range of linearity is wide to 0.1～10mmol L-1, detection limit as little as 10 μm ol L-1, sensitivity is 0.051mA L mol-1。
4. cationic metal phthalocyanine/CNT self-assemble film pole that present embodiment prepares, due to every layer of monomolecular film all
Attract each other with electrostatic force, so this membrane electrode also has outstanding stability.
5. cationic metal phthalocyanine/CNT self-assemble film pole that present embodiment prepares, membrane material is stronger, is difficult to
Coming off from substrate surface, service life is long, and the life-span is up to more than 2 months.
6. cationic metal phthalocyanine/CNT self-assemble film pole that present embodiment prepares does not uses any polyelectrolyte to make
For bridging agent, accelerate the transmission of electronics, improve the electro catalytic activity of electrode.
Detailed description of the invention seven: present embodiment is unlike detailed description of the invention six: the cationic gold described in step one
The general structure belonging to phthalocyanine is as follows:
Wherein M is Co2+、Fe2+、Ni2+、Cu2+、Zn2+、Pd2+、Pb2+Or Mn2+.Other steps and parameter and tool
Body embodiment six is identical.
Detailed description of the invention eight: present embodiment is unlike detailed description of the invention six or seven: the carbon described in step 2 is received
Mitron is Carboxylation SWCN, Carboxylation multi-walled carbon nano-tubes, hydroxyl SWCN or hydroxyl multi-wall carbon nano-tube
Pipe.Other steps and parameter are identical with detailed description of the invention six or seven.
Detailed description of the invention nine: present embodiment is unlike one of detailed description of the invention six to eight: described in step 3
Substrate is after pretreatment and electronegative glass-carbon electrode, ito glass, FTO glass, piezoid, sheet glass or silicon
Sheet.Other steps and parameter are identical with one of detailed description of the invention six to eight.
Detailed description of the invention ten: present embodiment is unlike one of detailed description of the invention six to nine: described in step 3
The quality of sodium hydroxide is 5g:200mL with the ratio of the volume of ethanol solution；The volume of described ethanol alkali liquor and substrate
The ratio of quality is 20mL:9g.Other steps and parameter are identical with one of detailed description of the invention six to nine.
By following verification experimental verification beneficial effects of the present invention:
Test one, the preparation method of a kind of cationic metal phthalocyanine/CNT self-assemble film pole of this test press following step
Suddenly carry out:
One, the preparation of cation cobalt phthalocyanine aqueous solution: be 2mg/mL by the concentration that is configured to soluble in water for cation cobalt phthalocyanine
Cation cobalt phthalocyanine aqueous solution；
Two, the preparation of Carboxylation multi-walled carbon nano-tubes dispersion liquid: Carboxylation multi-walled carbon nano-tubes is joined in deionized water super
Sound is uniformly dispersed, and prepared concentration is the Carboxylation multi-walled carbon nano-tubes dispersion liquid of 1mg/mL；
Three, substrate pretreatment: 1. 5g sodium hydroxide is dissolved in the ethanol solution that 200mL mass concentration is 50%, obtains
Ethanol alkali liquor；2. the glass-carbon electrode cleaned up is put in water heating kettle, is subsequently adding the ethanol alkali liquor that 1. 20mL obtains,
Tighten kettle cover, at temperature is 100 DEG C, reacts 0.5h, after react, taking-up glass-carbon electrode, with distilled water drip washing 1min,
Then dry up with nitrogen, obtain electronegative glass-carbon electrode, be subsequently placed in strong aqua ammonia and save backup；
Four, the preparation of cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole: 1. step 3 obtained is electronegative
Glass-carbon electrode immerse in the cation cobalt phthalocyanine aqueous solution that concentration is 2mg/mL that obtains of step one, stand 10min, so
Rear taking-up glass-carbon electrode also uses deionized water rinsing 30s, then dry up with nitrogen, and must arrive surface has positively charged cation cobalt
The glass-carbon electrode of phthalocyanine layer；The concentration the most first step 2 obtained is that the Carboxylation multi-walled carbon nano-tubes dispersion liquid of 1mg/mL surpasses
Sound dispersion 1h, then has the glass-carbon electrode of positively charged cation cobalt phthalocyanine layer to immerse ultrasonic disperse by the surface 1. obtained
After the Carboxylation multi-walled carbon nano-tubes dispersion liquid that concentration is 1mg/mL that obtains of step 2 in, stand 10min, then take
Go out surface have the glass-carbon electrode of positively charged cation cobalt phthalocyanine layer and use deionized water rinsing 30s, then dry up with nitrogen,
Obtain the glass being had positively charged cation cobalt phthalocyanine layer by the surface of electronegative Carboxylation multi-wall carbon nano-tube tube layer parcel
Carbon electrode；3. 1. circulation repeats～step 20 2. time, and formation cation cobalt phthalocyanine layer and multi-wall carbon nano-tube tube layer replace
Multilayer Film Electrode, i.e. obtains cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole.
Cation cobalt phthalocyanine described in this test procedure one be with reference to existing document (T.T.Tasso etc., Inorg.Chem.,
52 (2013) 9206-9215) disclosed in method synthesis.
Cation cobalt phthalocyanine described in this test procedure one has a below general formula:
Wherein M is Co2+。
The structural representation of cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole that this test obtains is as shown in Figure 1.
(1) by cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole that test one prepares in concentration it is
1.5mmol·L-1Sodium nitrite phosphate buffer solution (pH=7.0) in detect, scanning the 20th circle obtain such as Fig. 2
Shown cyclic voltammetry curve figure.Cation cobalt phthalocyanine/multi-walled carbon nano-tubes that test one prepares as can be seen from Fig. 2 is certainly
Assembling film electrode is to 1.5mmol L-1Sodium nitrite show significantly response at 0.75 volt
Conclusion: cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole that test one prepares can be used for detecting solution
In nitrite.
(2) by cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole that test one prepares in concentration it is
1.0mmol·L-1Sodium nitrite phosphate buffer solution (pH=7.0) in detect, scanning 100 circle after obtain such as Fig. 3
Shown cyclic voltammetry curve figure.Cation cobalt phthalocyanine/multi-walled carbon nano-tubes that test one prepares as can be seen from Fig. 3 is certainly
Assembling film electrode is after scanning 100 circle, and the current-responsive of its 0.75 Fu Chu declines 3%.
Conclusion: cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole that test one prepares has outstanding stablizing
Property, stability is compared and existing is improve 2.1%.
(3) cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole test one prepared is 0.1 in concentration
mmol·L-1～10mmol L-1Sodium nitrite phosphate buffer solution (pH=7.0) in detect, obtain such as Fig. 4 institute
The cyclic voltammetry curve figure shown.Cation cobalt phthalocyanine/multi-walled carbon nano-tubes that test one prepares as can be seen from Fig. 4 is from group
Dress membrane electrode has the electrocatalysis characteristic of excellence for sodium nitrite.
Cation cobalt phthalocyanine/its response current of multi-walled carbon nano-tubes self-assemble film pole prepared is tested at 0.75 Fu Chu
Linear with the concentration of sodium nitrite, its existing graph of a relation is as shown in Figure 5.Linear equation is obtained by Fig. 5:
By Equation for Calculating, Y=3.9778E-5+5.07696E-5*X, can show that its range of linearity is 0.1～10mmol L-1, detection limit low
To 10 μm ol L-1, sensitivity is 0.051mA L mol-1。
Conclusion: cation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole that test one prepares has for sodium nitrite
There is outstanding electrocatalysis characteristic.
Test two, the preparation method of a kind of cationic metal phthalocyanine/CNT self-assemble film pole of this test press following step
Suddenly carry out:
One, the preparation of cation nickel phthalocyanine aqueous solution: be 2mg/mL by the concentration that is configured to soluble in water for cation nickel phthalocyanine
Cation nickel phthalocyanine aqueous solution；
Two, the preparation of Carboxylation multi-walled carbon nano-tubes dispersion liquid: Carboxylation multi-walled carbon nano-tubes is joined in deionized water super
Sound is uniformly dispersed, and prepared concentration is the Carboxylation multi-walled carbon nano-tubes dispersion liquid of 1mg/mL；
Three, substrate pretreatment: 1. 5g sodium hydroxide is dissolved in the ethanol solution that 200mL mass concentration is 50%, obtains
Ethanol alkali liquor；2. the ITO electro-conductive glass cleaned up is put in water heating kettle, be subsequently adding the ethanol that 1. 20mL obtains
Alkali liquor, tightens kettle cover, reacts 0.5h at temperature is 100 DEG C, after having reacted, takes out ITO electro-conductive glass, with steaming
Distilled water drip washing 1min, then dries up with nitrogen, obtains electronegative ITO electro-conductive glass, is subsequently placed in strong aqua ammonia guarantor
Deposit standby；
Four, the preparation of cation nickel phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole: 1. step 3 obtained is electronegative
ITO electro-conductive glass immerse in the cation nickel phthalocyanine aqueous solution that concentration is 2mg/mL that obtains of step one, stand 10min,
Then taking out ITO electro-conductive glass and use deionized water rinsing 30s, then drying up with nitrogen, must arrive surface has positively charged sun
The ITO electro-conductive glass of ion nickel phthalocyanine layer；The concentration the most first step 2 obtained is that Carboxylation many walls carbon of 1mg/mL is received
Mitron dispersion liquid ultrasonic disperse 1h, then has the ITO of positively charged cation nickel phthalocyanine layer to conduct electricity by the surface 1. obtained
In the Carboxylation multi-walled carbon nano-tubes dispersion liquid that concentration is 1mg/mL that step 2 after glass immersion ultrasonic disperse obtains, quiet
Putting 10min, then taking out surface has the ITO electro-conductive glass of positively charged cation nickel phthalocyanine layer and uses deionized water rinsing
30s, then dry up with nitrogen, obtain being had positively charged by the surface of electronegative Carboxylation multi-wall carbon nano-tube tube layer parcel
The ITO electro-conductive glass of cation nickel phthalocyanine layer；3. 1. circulation repeats～step 14 2. time, forms cation nickel phthalocyanine layer
With multi-wall carbon nano-tube tube layer Multilayer Film Electrode alternately, i.e. obtain cation nickel phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole.
Cation nickel phthalocyanine described in this test procedure one be with reference to existing document (T.T.Tasso etc., Inorg.Chem.,
52 (2013) 9206-9215) disclosed in method synthesis.
Cation nickel phthalocyanine described in this test procedure one has a below general formula:
Wherein M is Ni2+。
(3) cation nickel phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole that test two obtains is carried out ultraviolet-visible light inspection
Surveying, obtain uv-visible absorption spectroscopy figure as shown in Figure 6, wherein in figure, curve is corresponding in turn to membrane electrode from top to bottom
In from the curve of the 1st layer to the 14th layer.Cation nickel phthalocyanine/multi-walled carbon nano-tubes that test two obtains as can be seen from Fig. 6 is certainly
Assembling film electrode is provided with the characteristic absorption peak of cation nickel phthalocyanine and functionalized multi-wall carbonnanotubes simultaneously, and cation nickel is described
Phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole is successfully prepared, and it is uniform sequential from the 1st layer to the 14th layer every tunic
Growth.
Test three, the preparation method of a kind of cationic metal phthalocyanine/CNT self-assemble film pole of this test press following step
Suddenly carry out:
One, the preparation of cation cobalt phthalocyanine aqueous solution: be 2mg/mL by the concentration that is configured to soluble in water for cation cobalt phthalocyanine
Cation cobalt phthalocyanine aqueous solution；
Two, the preparation of Carboxylation single-walled carbon nanotube dispersion liquid: Carboxylation SWCN is joined in deionized water super
Sound is uniformly dispersed, and prepared concentration is the Carboxylation single-walled carbon nanotube dispersion liquid of 1mg/mL；
Three, substrate pretreatment: 1. 5g sodium hydroxide is dissolved in the ethanol solution that 200mL mass concentration is 50%, obtains
Ethanol alkali liquor；2. the FTO electro-conductive glass cleaned up is put in water heating kettle, be subsequently adding the ethanol that 1. 20mL obtains
Alkali liquor, tightens kettle cover, reacts 0.5h at temperature is 100 DEG C, after having reacted, takes out FTO electro-conductive glass, with steaming
Distilled water drip washing 1min, then dries up with nitrogen, obtains electronegative FTO electro-conductive glass, is subsequently placed in strong aqua ammonia
Save backup；
Four, the preparation of cation cobalt phthalocyanine/SWCN self-assemble film pole: 1. step 3 obtained is electronegative
FTO electro-conductive glass immerse in the cation cobalt phthalocyanine aqueous solution that concentration is 2mg/mL that obtains of step one, stand
10min, then takes out FTO electro-conductive glass and uses deionized water rinsing 30s, then drying up with nitrogen, and must arrive surface has band just
The FTO electro-conductive glass of the cation cobalt phthalocyanine layer of electric charge；The concentration the most first step 2 obtained is the Carboxylation of 1mg/mL
Single-walled carbon nanotube dispersion liquid ultrasonic disperse 1h, then has positively charged cation cobalt phthalocyanine layer by the surface 1. obtained
The Carboxylation SWCN that concentration is 1mg/mL that step 2 after FTO electro-conductive glass immersion ultrasonic disperse obtains divides
Dissipating in liquid, stand 10min, then taking out surface has the FTO electro-conductive glass of positively charged cation cobalt phthalocyanine layer and uses
Deionized water rinsing 30s, then dry up with nitrogen, obtain by the surface of electronegative Carboxylation single tube layer parcel
There is the FTO electro-conductive glass of positively charged cation cobalt phthalocyanine layer；3. 1. circulation repeats～step 10 2. time, forms sun
Ionic cobalt phthalocyanine layer and single tube layer Multilayer Film Electrode alternately, i.e. obtain cation cobalt phthalocyanine/SWCN
Self-assemble film pole.
Cation cobalt phthalocyanine described in this test procedure one be with reference to existing document (T.T.Tasso etc., Inorg.Chem.,
52 (2013) 9206-9215) disclosed in method synthesis.
Cation cobalt phthalocyanine described in this test procedure one has a below general formula:
Wherein M is Co2+。
Test four, the preparation method of a kind of cationic metal phthalocyanine/CNT self-assemble film pole of this test press following step
Suddenly carry out:
One, the preparation of cation nickel phthalocyanine aqueous solution: be 2mg/mL by the concentration that is configured to soluble in water for cation nickel phthalocyanine
Cation nickel phthalocyanine aqueous solution；
Two, the preparation of Carboxylation multi-walled carbon nano-tubes dispersion liquid: Carboxylation multi-walled carbon nano-tubes is joined in deionized water super
Sound is uniformly dispersed, and prepared concentration is the Carboxylation multi-walled carbon nano-tubes dispersion liquid of 1mg/mL；
Three, substrate pretreatment: 1. 5g sodium hydroxide is dissolved in the ethanol solution that 200mL mass concentration is 50%, obtains
Ethanol alkali liquor；2. the ITO electro-conductive glass cleaned up is put in water heating kettle, be subsequently adding the ethanol that 1. 20mL obtains
Alkali liquor, tightens kettle cover, reacts 0.5h at temperature is 100 DEG C, after having reacted, takes out ITO electro-conductive glass, with steaming
Distilled water drip washing 1min, then dries up with nitrogen, obtains electronegative ITO electro-conductive glass, is subsequently placed in strong aqua ammonia guarantor
Deposit standby；
Four, the preparation of cation nickel phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole: 1. step 3 obtained is electronegative
ITO electro-conductive glass immerse in the cation nickel phthalocyanine aqueous solution that concentration is 2mg/mL that obtains of step one, stand 10min,
Then taking out ITO electro-conductive glass and use deionized water rinsing 30s, then drying up with nitrogen, must arrive surface has positively charged sun
The ITO electro-conductive glass of ion nickel phthalocyanine layer；The concentration the most first step 2 obtained is that Carboxylation many walls carbon of 1mg/mL is received
Mitron dispersion liquid ultrasonic disperse 1h, then has the ITO of positively charged cation nickel phthalocyanine layer to conduct electricity by the surface 1. obtained
In the Carboxylation multi-walled carbon nano-tubes dispersion liquid that concentration is 1mg/mL that step 2 after glass immersion ultrasonic disperse obtains, quiet
Putting 10min, then taking out surface has the ITO electro-conductive glass of positively charged cation nickel phthalocyanine layer and uses deionized water rinsing
30s, then dry up with nitrogen, obtain being had positively charged by the surface of electronegative Carboxylation multi-wall carbon nano-tube tube layer parcel
The ITO electro-conductive glass of cation nickel phthalocyanine layer；3. 1. circulation repeats～step 20 2. time, forms cation nickel phthalocyanine layer
With multi-wall carbon nano-tube tube layer Multilayer Film Electrode alternately, i.e. obtain cation nickel phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole.
Cation nickel phthalocyanine described in this test procedure one be with reference to existing document (T.T.Tasso etc., Inorg.Chem.,
52 (2013) 9206-9215) disclosed in method synthesis.
Cation nickel phthalocyanine described in this test procedure one has a below general formula:
Wherein M is Ni2+。
Test five, the preparation method of a kind of cationic metal phthalocyanine/CNT self-assemble film pole of this test press following step
Suddenly carry out:
One, the preparation of cation cobalt phthalocyanine aqueous solution: be 2mg/mL by the concentration that is configured to soluble in water for cation cobalt phthalocyanine
Cation cobalt phthalocyanine aqueous solution；
Two, the preparation of Carboxylation single-walled carbon nanotube dispersion liquid: Carboxylation SWCN is joined in deionized water super
Sound is uniformly dispersed, and prepared concentration is the Carboxylation single-walled carbon nanotube dispersion liquid of 1mg/mL；
Three, substrate pretreatment: 1. 5g sodium hydroxide is dissolved in the ethanol solution that 200mL mass concentration is 50%, obtains
Ethanol alkali liquor；2. the ITO electro-conductive glass cleaned up is put in water heating kettle, be subsequently adding the ethanol that 1. 20mL obtains
Alkali liquor, tightens kettle cover, reacts 0.5h at temperature is 100 DEG C, after having reacted, takes out ITO electro-conductive glass, with steaming
Distilled water drip washing 1min, then dries up with nitrogen, obtains electronegative ITO electro-conductive glass, is subsequently placed in strong aqua ammonia guarantor
Deposit standby；
Four, the preparation of cation cobalt phthalocyanine/SWCN self-assemble film pole: 1. step 3 obtained is electronegative
ITO electro-conductive glass immerse in the cation cobalt phthalocyanine aqueous solution that concentration is 2mg/mL that obtains of step one, stand 10min,
Then taking out ITO electro-conductive glass and use deionized water rinsing 30s, then drying up with nitrogen, must arrive surface has positively charged sun
The ITO electro-conductive glass of ionic cobalt phthalocyanine layer；The concentration the most first step 2 obtained is that the Carboxylation single wall carbon of 1mg/mL is received
Mitron dispersion liquid ultrasonic disperse 1h, then has the ITO of positively charged cation cobalt phthalocyanine layer to conduct electricity by the surface 1. obtained
In the Carboxylation single-walled carbon nanotube dispersion liquid that concentration is 1mg/mL that step 2 after glass immersion ultrasonic disperse obtains, quiet
Putting 10min, then taking out surface has the ITO electro-conductive glass of positively charged cation cobalt phthalocyanine layer and uses deionized water rinsing
30s, then dry up with nitrogen, obtain being had positively charged by the surface of electronegative Carboxylation single tube layer parcel
The ITO electro-conductive glass of cation cobalt phthalocyanine layer；3. 1. circulation repeats～step 14 2. time, forms cation cobalt phthalocyanine layer
With single tube layer Multilayer Film Electrode alternately, i.e. obtain cation cobalt phthalocyanine/SWCN self-assemble film pole.
Cation cobalt phthalocyanine described in this test procedure one be with reference to existing document (T.T.Tasso etc., Inorg.Chem.,
52 (2013) 9206-9215) disclosed in method synthesis.
Cation cobalt phthalocyanine described in this test procedure one has a below general formula:
Wherein M is Co2+。
Claims (9)
1. cationic metal phthalocyanine/CNT self-assemble film pole, it is characterised in that a kind of cationic metal phthalocyanine/carbon
Nanotubes self-assemble membrane electrode is the cationic metal phthalocyanine layer of alternately assembled belt positive charge in electronegative substrate and carries negative
The carbon nanotube layer of electric charge, forms cationic metal phthalocyanine layer and carbon nanotube layer Multilayer Film Electrode alternately；
The general structure of described positively charged cationic metal phthalocyanine layer cationic metal phthalocyanine is as follows:
Wherein M is Co2+、Fe2+、Ni2+、Cu2+、Zn2+、
Pd2+、Pb2+Or Mn2+。
A kind of cationic metal phthalocyanine/CNT self-assemble film pole the most according to claim 1, it is characterised in that
Cationic metal phthalocyanine layer positively charged in described cationic metal phthalocyanine/CNT self-assemble film pole is with electronegative
The number of plies of the carbon nanotube layer of lotus is identical, is 4～30 layers.
A kind of cationic metal phthalocyanine/CNT self-assemble film pole the most according to claim 1, it is characterised in that
In described electronegative carbon nanotube layer CNT be Carboxylation SWCN, Carboxylation multi-walled carbon nano-tubes,
Hydroxyl SWCN or hydroxyl multi-walled carbon nano-tubes.
A kind of cationic metal phthalocyanine/CNT self-assemble film pole the most according to claim 1, it is characterised in that
The described substrate in electronegative substrate is glass-carbon electrode, ito glass, FTO glass, piezoid, sheet glass or silicon
Sheet.
5. the preparation method of cationic metal phthalocyanine/CNT self-assemble film pole, it is characterised in that a kind of cation
The preparation method of metal phthalocyanine/carbon nano-tube self-assemble film pole sequentially includes the following steps:
One, the preparation of cationic metal phthalocyanine aqueous solution: be by the concentration that is configured to soluble in water for cationic metal phthalocyanine
0.5mg/mL～2mg/mL cationic metal phthalocyanine aqueous solution；
Two, the preparation of carbon nano tube dispersion liquid: CNT is joined ultrasonic disperse in deionized water uniform, prepare concentration
Carbon nano tube dispersion liquid for 0.5mg/mL～2mg/mL；
Three, substrate pretreatment: be 1. dissolved in ethanol solution by sodium hydroxide, obtains ethanol alkali liquor；Described ethanol solution
Mass concentration is 40%～60%, and the quality of described sodium hydroxide is 5g:(150～250 with the ratio of the volume of ethanol solution)
mL；2. the substrate cleaned up is put in water heating kettle, be subsequently adding the ethanol alkali liquor 1. obtained, tighten kettle cover, in temperature
Degree is reaction 0.5h～2h at 80～160 DEG C, and after react, taking-up substrate, with distilled water drip washing 1min～2min, then
Dry up with nitrogen, obtain electronegative substrate, be subsequently placed in strong aqua ammonia and save backup；The volume of described ethanol alkali liquor
It is 20mL:(0.9～10 with the ratio of the quality of substrate) g；
Four, the preparation of cationic metal phthalocyanine/CNT self-assemble film pole: the electronegative base 1. step 3 obtained
The end, is immersed in the cationic metal phthalocyanine aqueous solution that concentration is 0.5mg/mL～2mg/mL that step one obtains, and stands
5min～30min, then takes out substrate and with deionized water rinsing 15s～60s, then dries up with nitrogen, and must arrive surface has band just
The substrate of the cationic metal phthalocyanine layer of electric charge；The concentration the most first step 2 obtained is that the carbon of 0.5mg/mL～2mg/mL is received
Mitron dispersion liquid ultrasonic disperse 1h～4h, then has the substrate of positively charged cationic metal phthalocyanine layer by the surface 1. obtained
Immerse in the carbon nano tube dispersion liquid that concentration is 0.5mg/mL～2mg/mL that the step 2 after ultrasonic disperse obtains, stand
5min～30min, then taking out surface has the substrate of positively charged cationic metal phthalocyanine layer and uses deionized water rinsing
15s～60s, then dry up with nitrogen, obtain there is positively charged cationic gold by the surface of electronegative carbon nanotube layer parcel
Belong to the substrate of phthalocyanine layer；3. 1. circulation repeats～step 4 2.～30 times, forms cationic metal phthalocyanine layer and carbon nanotube layer
Multilayer Film Electrode alternately, i.e. obtains cationic metal phthalocyanine/CNT self-assemble film pole.
The preparation method of a kind of cationic metal phthalocyanine/CNT self-assemble film pole the most according to claim 5,
It is characterized in that the cationic metal phthalocyanine described in step one has a below general formula:
Wherein M is Co2+、Fe2+、Ni2+、Cu2+、Zn2+、
Pd2+、Pb2+Or Mn2+。
The preparation method of a kind of cationic metal phthalocyanine/CNT self-assemble film pole the most according to claim 5,
It is characterized in that the CNT described in step 2 is Carboxylation SWCN, Carboxylation multi-walled carbon nano-tubes, hydroxyl
SWCN or hydroxyl multi-walled carbon nano-tubes.
The preparation method of a kind of cationic metal phthalocyanine/CNT self-assemble film pole the most according to claim 5,
It is characterized in that the substrate described in step 3 is after pretreatment and electronegative glass-carbon electrode, ito glass, FTO glass
Glass, piezoid, sheet glass or silicon chip.
The preparation method of a kind of cationic metal phthalocyanine/CNT self-assemble film pole the most according to claim 5,
It is characterized in that the quality of the sodium hydroxide described in step 3 is 5g:200mL with the ratio of the volume of ethanol solution；Described
The volume of ethanol alkali liquor is 20mL:9g with the ratio of the quality of substrate.
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