CN104198561A - Cationic metal phthalocyanine/carbon nano-tube self-assembled membrane electrode and preparation method thereof - Google Patents
Cationic metal phthalocyanine/carbon nano-tube self-assembled membrane electrode and preparation method thereof Download PDFInfo
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- CN104198561A CN104198561A CN201410431790.9A CN201410431790A CN104198561A CN 104198561 A CN104198561 A CN 104198561A CN 201410431790 A CN201410431790 A CN 201410431790A CN 104198561 A CN104198561 A CN 104198561A
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Abstract
The invention belongs to the field of electrochemical/biological sensors, and in particular relates to a cationic metal phthalocyanine/carbon nano-tube self-assembled membrane electrode and a preparation method thereof, aiming to solve the problems that an existing membrane electrode is non-uniform in surface coverage, low in surface coverage rate and non-steady in electrochemical property, and an existing preparation method is complex in process and high in cost and pollutes the environment. The cationic metal phthalocyanine/carbon nano-tube self-assembled membrane electrode is obtained by alternatively assembling a cationic metal phthalocyanine layer with positive charge and a carbon nano-tube layer with negative charge on a substrate with negative charge and forming a multi-layer membrane electrode with the cationic metal phthalocyanine layer and the carbon nano-tube layer which are alternative. The preparation method disclosed by the invention comprises the following steps: (1), preparing a cationic metal phthalocyanine aqueous solution; (2), preparing carbon nano-tube dispersion liquid; (3), pre-processing the substrate; and (4), preparing the cationic metal phthalocyanine/carbon nano-tube self-assembled membrane electrode.
Description
Technical field
The invention belongs to galvanochemistry/field of biosensors, be specifically related to a kind of positive in metal phthalocyanine/carbon nano-tube self-assemble film pole and preparation method thereof.
Background technology
It is legal etc. that conventional method for preparing membrane electrode is divided into drop-coating, absorption method, electrochemical process, doping method and covalent bond.Drop-coating is because the consumption of filmogen is difficult to accurate control, non-uniform film thickness is even, so electrode reappearance is poor, and surface coverage is subject to the physical property of decorating liquid to affect large (Yin H.S. etc., Food Chem, 125 (2011) 1097-1103).The membrane electrode stable chemical performance that covalent bonding legal system is standby, can complete according to design proposal in advance the formation of electrode surface microstructure.But this method is because process is loaded down with trivial details, the dressing agent molecule coverage rate of final surface bond is low, has restricted the performance (K.Sanusi etc., J.Phys.Chem.C, 118 (2014) 7057-7069) of membrane electrode.Electrochemical process is generally used for the electrochemical deposition of inolrganic chemicals or complex material.And absorption method can obtain the double-deck characteristic of good stability and high-sequential.This stable chemical nature of self-assembled film layer by layer, molecules align rule.Because generally only having several monolayers thick, the transmission of electronics or material is very easily carried out on electrode, shows extremely strong electrochemical response.The high-sequential of kind electrode finishing molecules align can produce the effect that other modified electrode does not reach, and is widely used at aspects such as electrochemical sensor, surface electrical catalysis.
Polyelectrolyte has all adulterated in existing phthalocyanine/carbon nano-tube membrane electrode, as polydiene base the third alkyl dimethyl ammonium chloride (PDDA), polystyrolsulfon acid (PSS), poly-(3,4-ethene dioxythiophene), (J.B.Han etc. such as polyetherimide (PEI), 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's complexity, in addition because the introducing of the materials such as polyelectrolyte has not only increased preparation cost, and has reduced the chemical property of membrane electrode.Though the people such as H.Z.Zhao have prepared phthalocyanine/carbon nano-tube compound film, but substrate still needs first modifying polyethyleneimine, and phthalocyanine and carbon nano-tube are to be all dispersed in N, in the organic solvents such as dinethylformamide, organic solvent cost is high and large to human body and environmental hazard, (Environ.Sci.Technol., 46 (2012) 5198 – 5204).Therefore, preparation technology is simple, cost is low, phthalocyanine/carbon nano-tube membrane electrode uniform sequential, good stability is problem demanding prompt solution.
Summary of the invention
The present invention shows to cover the problems such as the high and contaminated environment of complex technical process, cost inhomogeneous, that surface coverage is low, electrochemical properties is unstable and preparation method exists in order to solve existing membrane electrode, and a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole and preparation method thereof is provided.
A kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole of the present invention is in electronegative substrate, alternately to assemble positively charged cationic metal phthalocyanine layer and electronegative carbon nanotube layer, forms the Multilayer Film Electrode that cationic metal phthalocyanine layer and carbon nanotube layer replace.
The preparation method of a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole of the present invention carries out according to the following steps:
One, the preparation of cationic metal phthalocyanine aqueous solution: be 0.5mg/mL～2mg/mL cationic metal phthalocyanine aqueous solution by the concentration that is mixed with soluble in water cationic metal phthalocyanine;
Two, the preparation of carbon nano tube dispersion liquid: carbon nano-tube is joined to deionized water for ultrasonic and be uniformly dispersed, make the carbon nano tube dispersion liquid that concentration is 0.5mg/mL～2mg/mL;
Three, substrate pretreatment: 1. NaOH is dissolved in ethanolic solution, obtains ethanol alkali lye; The mass concentration of described ethanolic solution is 40%～60%, and the quality of described NaOH is 5g:(150～250 with the ratio of the volume of ethanolic solution) mL; 2. the substrate cleaning up is put into water heating kettle, then add the ethanol alkali lye 1. obtaining, tighten kettle cover, be to react 0.5h～2h at 80～160 DEG C in temperature, after having reacted, take out substrate, with distilled water drip washing 1min～2min, then dry up with nitrogen, obtain electronegative substrate, be then placed in strong aqua and save backup; The described volume of ethanol alkali lye and the ratio of the quality of substrate are 20mL:(0.9～10) g;
Four, the preparation of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole: in the cationic metal phthalocyanine aqueous solution that the concentration that the electronegative substrate immersion step 1 1. step 3 being obtained obtains is 0.5mg/mL～2mg/mL, leave standstill 5min～30min, then take out substrate and use deionized water rinsing 15s～60s, dry up with nitrogen, obtaining surface has the substrate of positively charged cationic metal phthalocyanine layer again, 2. the concentration first step 2 being obtained is the ultrasonic dispersion of the carbon nano tube dispersion liquid of 0.5mg/mL～2mg/mL 1h～4h, then the surface 1. obtaining there is is the substrate of positively charged cationic metal phthalocyanine layer to immerse in the carbon nano tube dispersion liquid that concentration that the step 2 after ultrasonic dispersion obtains is 0.5mg/mL～2mg/mL, leave standstill 5min～30min, then taking out surface has the substrate of positively charged cationic metal phthalocyanine layer and uses deionized water rinsing 15s～60s, dry up with nitrogen again, obtain being had by the surface of electronegative carbon nanotube layer parcel the substrate of positively charged cationic metal phthalocyanine layer, 3. be cycled to repeat 1.～step 4 2.～30 time, form the Multilayer Film Electrode that cationic metal phthalocyanine layer and carbon nanotube layer replace, obtain cationic metal phthalocyanine/carbon nano-tube self-assemble film pole.
Beneficial effect of the present invention:
1. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole surface molecular that the present invention makes is arranged uniform sequential, successively increases with equal thickness.
2. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole that the present invention makes has good electrocatalysis characteristic, and its range of linearity is wide to 0.1mmolL
-1～10mmolL
-1, detection limit is low to moderate 10 μ molL
-1, sensitivity is 0.051mALmol
-1.
3. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole that the present invention makes, because every layer of unimolecular film all attracts each other with electrostatic force, so this membrane electrode also has outstanding stability.
4. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole that the present invention makes, membrane material is more firm, is difficult for coming off from substrate surface, long service life, the life-span reaches more than 2 months.
5. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole that the present invention makes does not use any polyelectrolyte as coupling agent, accelerates the transmission of electronics, has improved the electro catalytic activity of electrode.
6. preparation method of the present invention, simple to operate, do not need to introduce the materials such as polyelectrolyte in preparation process, ensured the chemical property of membrane electrode when reducing preparation cost.
Brief description of the drawings
Fig. 1 is the structural representation of kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole of test one preparation; Wherein a is glass-carbon electrode, and b is kation cobalt phthalocyanine layer, and c is multi-walled carbon nano-tubes layer;
Fig. 2 is that kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole of test one preparation is 1.5mmolL in concentration
-1cyclic voltammetry curve figure in the phosphate buffer solution (pH=7.0) of sodium nitrite; Wherein dotted line is glass-carbon electrode, and solid line is kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole of test one preparation;
Fig. 3 is that kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole of test one preparation is 1.0mmolL in concentration
-1cyclic voltammetry curve figure in the phosphate buffer solution (pH=7.0) of sodium nitrite after scanning 100 circles; Wherein solid line is kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole of test one preparation;
Fig. 4 is that kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole of test one preparation is 0.1mmolL in concentration
-1～10mmolL-
1the phosphate buffer solution (pH=7.0) of sodium nitrite in cyclic voltammetry curve figure; Wherein the concentration of the phosphate buffer solution of corresponding sodium nitrite is 0mmolL successively from the bottom to top
-1, 0.1mmolL
-1, 0.2mmolL
-1, 0.4mmolL
-1, 0.6mmolL
-1, 1.0mmolL
-1, 1.4mmolL
-1, 1.8mmolL
-1, 2.2mmolL
-1, 2.6mmolL
-1, 3.0mmolL
-1, 3.4mmolL
-1, 3.8mmolL
-1, 4.2mmolL
-1, 5.0mmolL
-1, 5.8mmolL
-1, 6.6mmolL
-1, 7.4mmolL
-1, 8.2mmolL
-1and 10.0mmolL
-1;
Fig. 5 is the linear relationship chart of the relation of test one kation cobalt phthalocyanine/multi-walled carbon nano-tubes its response current of self-assemble film pole of preparation and the concentration of sodium nitrite;
Fig. 6 is the ultraviolet spectrogram of kation nickel phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole of test two preparations; Wherein curve from bottom to up successively the 1st, 2,3 of corresponding membrane electrode in Fig. 6 ... 14 layers.
Embodiment
Embodiment one: a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole of present embodiment is alternately to assemble positively charged cationic metal phthalocyanine layer and electronegative carbon nanotube layer in electronegative substrate, forms the Multilayer Film Electrode that cationic metal phthalocyanine layer and carbon nanotube layer replace.
1. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole surface molecular that present embodiment makes is arranged uniform sequential, successively increases with equal thickness.
2. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole that present embodiment makes has good electrocatalysis characteristic, and its range of linearity is wide to 0.1～10mmolL
-1, detection limit is low to moderate 10 μ molL
-1, sensitivity is 0.051mALmol
-1.
3. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole that present embodiment makes, because every layer of unimolecular film all attracts each other with electrostatic force, so this membrane electrode also has outstanding stability.
4. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole that present embodiment makes, membrane material is more firm, is difficult for coming off from substrate surface, long service life, the life-span reaches more than 2 months.
5. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole that present embodiment makes does not use any polyelectrolyte as coupling agent, accelerates the transmission of electronics, has improved the electro catalytic activity of electrode.
Embodiment two: present embodiment is different from embodiment one: in described cationic metal phthalocyanine/carbon nano-tube self-assemble film pole, the number of plies of positively charged cationic metal phthalocyanine layer and electronegative carbon nanotube layer is identical, is 4～30 layers.Other steps and parameter are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two: in described positively charged cationic metal phthalocyanine layer, the general structure of cationic metal phthalocyanine is as follows:
wherein M is Co
2+, Fe
2+, Ni
2+, Cu
2+, Zn
2+, Pd
2+, Pb
2+or Mn
2+.Other steps and parameter are identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: in described electronegative carbon nanotube layer, carbon nano-tube is carboxylic acid Single Walled Carbon Nanotube, carboxylic acid multi-walled carbon nano-tube, hydroxyl Single Walled Carbon Nanotube or hydroxyl multi-walled carbon nano-tubes.Other steps and parameter are identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: the substrate in described electronegative substrate is glass-carbon electrode, ito glass, FTO glass, piezoid, glass sheet or silicon chip.Other steps and parameter are identical with one of embodiment one to four.
Embodiment six: the preparation method of a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole of present embodiment carries out according to the following steps:
One, the preparation of cationic metal phthalocyanine aqueous solution: be 0.5mg/mL～2mg/mL cationic metal phthalocyanine aqueous solution by the concentration that is mixed with soluble in water cationic metal phthalocyanine;
Two, the preparation of carbon nano tube dispersion liquid: carbon nano-tube is joined to deionized water for ultrasonic and be uniformly dispersed, make the carbon nano tube dispersion liquid that concentration is 0.5mg/mL～2mg/mL;
Three, substrate pretreatment: 1. NaOH is dissolved in ethanolic solution, obtains ethanol alkali lye; The mass concentration of described ethanolic solution is 40%～60%, and the quality of described NaOH is 5g:(150～250 with the ratio of the volume of ethanolic solution) mL; 2. the substrate cleaning up is put into water heating kettle, then add the ethanol alkali lye 1. obtaining, tighten kettle cover, be to react 0.5h～2h at 80～160 DEG C in temperature, after having reacted, take out substrate, with distilled water drip washing 1min～2min, then dry up with nitrogen, obtain electronegative substrate, be then placed in strong aqua and save backup; The described volume of ethanol alkali lye and the ratio of the quality of substrate are 20mL:(0.9～10) g;
Four, the preparation of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole: in the cationic metal phthalocyanine aqueous solution that the concentration that the electronegative substrate immersion step 1 1. step 3 being obtained obtains is 0.5mg/mL～2mg/mL, leave standstill 5min～30min, then take out substrate and use deionized water rinsing 15s～60s, dry up with nitrogen, obtaining surface has the substrate of positively charged cationic metal phthalocyanine layer again; 2. the concentration first step 2 being obtained is the ultrasonic dispersion of the carbon nano tube dispersion liquid of 0.5mg/mL～2mg/mL 1h～4h, then the surface 1. obtaining there is is the substrate of positively charged cationic metal phthalocyanine layer to immerse in the carbon nano tube dispersion liquid that concentration that the step 2 after ultrasonic dispersion obtains is 0.5mg/mL～2mg/mL, leave standstill 5min～30min, then taking out surface has the substrate of positively charged cationic metal phthalocyanine layer and uses deionized water rinsing 15
s～60
s, then dry up with nitrogen, obtain being had by the surface of electronegative carbon nanotube layer parcel the substrate of positively charged cationic metal phthalocyanine layer; 3. be cycled to repeat 1.～step 4 2.～30 time, form the Multilayer Film Electrode that cationic metal phthalocyanine layer and carbon nanotube layer replace, obtain cationic metal phthalocyanine/carbon nano-tube self-assemble film pole.
1. the preparation method of present embodiment, simple to operate, do not need to introduce the materials such as polyelectrolyte in preparation process, ensured the chemical property of membrane electrode when reducing preparation cost.
2. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole surface molecular that present embodiment makes is arranged uniform sequential, successively increases with equal thickness.
3. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole that present embodiment makes has good electrocatalysis characteristic, and its range of linearity is wide to 0.1～10mmolL
-1, detection limit is low to moderate 10 μ molL
-1, sensitivity is 0.051mALmol
-1.
4. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole that present embodiment makes, because every layer of unimolecular film all attracts each other with electrostatic force, so this membrane electrode also has outstanding stability.
5. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole that present embodiment makes, membrane material is more firm, is difficult for coming off from substrate surface, long service life, the life-span reaches more than 2 months.
6. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole that present embodiment makes does not use any polyelectrolyte as coupling agent, accelerates the transmission of electronics, has improved the electro catalytic activity of electrode.
Embodiment seven: present embodiment is different from embodiment six: the general structure of the cationic metal phthalocyanine described in step 1 is as follows:
Wherein M is Co
2+, Fe
2+, Ni
2+, Cu
2+, Zn
2+, Pd
2+, Pb
2+or Mn
2+.Other steps and parameter are identical with embodiment six.
Embodiment eight: present embodiment is different from embodiment six or seven: the carbon nano-tube described in step 2 is carboxylic acid Single Walled Carbon Nanotube, carboxylic acid multi-walled carbon nano-tube, hydroxyl Single Walled Carbon Nanotube or hydroxyl multi-walled carbon nano-tubes.Other steps and parameter are identical with embodiment six or seven.
Embodiment nine: present embodiment is different from one of embodiment six to eight: the substrate described in step 3 is after pretreatment and electronegative glass-carbon electrode, ito glass, FTO glass, piezoid, glass sheet or silicon chip.Other steps and parameter are identical with one of embodiment six to eight.
Embodiment ten: present embodiment is different from one of embodiment six to nine: the quality of the NaOH described in step 3 is 5g:200mL with the ratio of the volume of ethanolic solution; The described volume of ethanol alkali lye and the ratio of the quality of substrate are 20mL:9g.Other steps and parameter are identical with one of embodiment six to nine.
With following verification experimental verification beneficial effect of the present invention:
The preparation method of a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole of test one, this test carries out according to the following steps:
One, the preparation of kation cobalt phthalocyanine aqueous solution: be 2mg/mL kation cobalt phthalocyanine aqueous solution by the concentration that is mixed with soluble in water kation cobalt phthalocyanine;
Two, the preparation of carboxylic acid multi-walled carbon nano-tube dispersion liquid: carboxylic acid multi-walled carbon nano-tube is joined to deionized water for ultrasonic and be uniformly dispersed, making concentration is the carboxylic acid multi-walled carbon nano-tube dispersion liquid of 1mg/mL;
Three, substrate pretreatment: 1. 5g NaOH is dissolved in to 200mL mass concentration and is in 50% ethanolic solution, obtain ethanol alkali lye; 2. the glass-carbon electrode cleaning up is put into water heating kettle, then the ethanol alkali lye that adds 20mL 1. to obtain, tighten kettle cover, be to react 0.5h at 100 DEG C in temperature, after having reacted, take out glass-carbon electrode, with distilled water drip washing 1min, then dry up with nitrogen, obtain electronegative glass-carbon electrode, be then placed in strong aqua and save backup;
Four, the preparation of kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole: in the kation cobalt phthalocyanine aqueous solution that the concentration that the electronegative glass-carbon electrode immersion step 1 1. step 3 being obtained obtains is 2mg/mL, leave standstill 10min, then take out glass-carbon electrode and use deionized water rinsing 30s, dry up with nitrogen, obtaining surface has the glass-carbon electrode of positively charged kation cobalt phthalocyanine layer again, 2. the concentration first step 2 being obtained is the ultrasonic dispersion of the carboxylic acid multi-walled carbon nano-tube dispersion liquid 1h of 1mg/mL, then the surface 1. obtaining there is is the glass-carbon electrode of positively charged kation cobalt phthalocyanine layer to immerse in the carboxylic acid multi-walled carbon nano-tube dispersion liquid that concentration that the step 2 after ultrasonic dispersion obtains is 1mg/mL, leave standstill 10min, then taking out surface has the glass-carbon electrode of positively charged kation cobalt phthalocyanine layer and uses deionized water rinsing 30s, dry up with nitrogen again, obtain being had by the surface of electronegative carboxylic acid multi-walled carbon nano-tube layer parcel the glass-carbon electrode of positively charged kation cobalt phthalocyanine layer, 3. be cycled to repeat 1.～step 20 2. time, form the Multilayer Film Electrode that kation cobalt phthalocyanine layer and multi-walled carbon nano-tubes layer replace, obtain kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole.
Kation cobalt phthalocyanine described in this test procedure one is synthetic with reference to the existing disclosed method of document (T.T.Tasso etc., Inorg.Chem., 52 (2013) 9206-9215).
Kation cobalt phthalocyanine described in this test procedure one has following general formula:
wherein M is Co
2+.
The structural representation of kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole that this test obtains as shown in Figure 1.
(1) be 1.5mmolL by the test one kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole preparing in concentration
-1the phosphate buffer solution (pH=7.0) of sodium nitrite in detect, scanning the 20th circle obtains cyclic voltammetry curve figure as shown in Figure 2.Test as can be seen from Fig. 2 a kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole preparing to 1.5mmolL
-1sodium nitrite show obvious response at 0.75 volt
Conclusion: the test one kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole preparing can be used for detecting the nitrite in solution.
(2) be 1.0mmolL by the test one kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole preparing in concentration
-1the phosphate buffer solution (pH=7.0) of sodium nitrite in detect, after scanning 100 circles, obtain cyclic voltammetry curve figure as shown in Figure 3.Test as can be seen from Fig. 3 a kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole preparing after scanning 100 circles, the current-responsive of its 0.75 Fu Chu declines 3%.
Conclusion: the test one kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole preparing has outstanding stability, and stability is compared and existingly improved 2.1%.
(3) be 0.1mmolL by the test one kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole preparing in concentration
-1～10mmolL
-1the phosphate buffer solution (pH=7.0) of sodium nitrite in detect, obtain cyclic voltammetry curve figure as shown in Figure 4.Test as can be seen from Fig. 4 a kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole preparing and have excellent electrocatalysis characteristic for sodium nitrite.
Concentration at 0.75 Fu Chu test one kation cobalt phthalocyanine/multi-walled carbon nano-tubes its response current of self-assemble film pole preparing and sodium nitrite is linear, and its existing graph of a relation as shown in Figure 5.Obtain linear equation by Fig. 5: Y=3.9778E-5+5.07696E-5*X, can be calculated its range of linearity by equation is 0.1～10mmolL
-1, detection limit is low to moderate 10 μ molL
-1, sensitivity is 0.051mALmol
-1.
Conclusion: the test one kation cobalt phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole preparing has outstanding electrocatalysis characteristic for sodium nitrite.
The preparation method of a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole of test two, this test carries out according to the following steps:
One, the preparation of kation nickel phthalocyanine aqueous solution: be 2mg/mL kation nickel phthalocyanine aqueous solution by the concentration that is mixed with soluble in water kation nickel phthalocyanine;
Two, the preparation of carboxylic acid multi-walled carbon nano-tube dispersion liquid: carboxylic acid multi-walled carbon nano-tube is joined to deionized water for ultrasonic and be uniformly dispersed, making concentration is the carboxylic acid multi-walled carbon nano-tube dispersion liquid of 1mg/mL;
Three, substrate pretreatment: 1. 5g NaOH is dissolved in to 200mL mass concentration and is in 50% ethanolic solution, obtain ethanol alkali lye; 2. the ITO electro-conductive glass cleaning up is put into water heating kettle, then the ethanol alkali lye that adds 20mL 1. to obtain, tighten kettle cover, be to react 0.5h at 100 DEG C in temperature, after having reacted, take out ITO electro-conductive glass, with distilled water drip washing 1min, then dry up with nitrogen, obtain electronegative ITO electro-conductive glass, be then placed in strong aqua and save backup;
Four, the preparation of kation nickel phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole: in the kation nickel phthalocyanine aqueous solution that the concentration that the electronegative ITO electro-conductive glass immersion step 1 1. step 3 being obtained obtains is 2mg/mL, leave standstill 10min, then take out ITO electro-conductive glass and use deionized water rinsing 30s, dry up with nitrogen, obtaining surface has the ITO electro-conductive glass of positively charged kation nickel phthalocyanine layer again, 2. the concentration first step 2 being obtained is the ultrasonic dispersion of the carboxylic acid multi-walled carbon nano-tube dispersion liquid 1h of 1mg/mL, then the surface 1. obtaining there is is the ITO electro-conductive glass of positively charged kation nickel phthalocyanine layer to immerse in the carboxylic acid multi-walled carbon nano-tube dispersion liquid that concentration that the step 2 after ultrasonic dispersion obtains is 1mg/mL, leave standstill 10min, then taking out surface has the ITO electro-conductive glass of positively charged kation nickel phthalocyanine layer and uses deionized water rinsing 30s, dry up with nitrogen again, obtain being had by the surface of electronegative carboxylic acid multi-walled carbon nano-tube layer parcel the ITO electro-conductive glass of positively charged kation nickel phthalocyanine layer, 3. be cycled to repeat 1.～step 14 2. time, form the Multilayer Film Electrode that kation nickel phthalocyanine layer and multi-walled carbon nano-tubes layer replace, obtain kation nickel phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole.
Kation nickel phthalocyanine described in this test procedure one is synthetic with reference to the existing disclosed method of document (T.T.Tasso etc., Inorg.Chem., 52 (2013) 9206-9215).
Kation nickel phthalocyanine described in this test procedure one has following general formula:
wherein M is Ni
2+.
(3) the test two kation nickel phthalocyanine/multi-walled carbon nano-tubes self-assemble film poles that obtain are carried out to ultraviolet-visible light detection, obtain uv-visible absorption spectroscopy figure as shown in Figure 6, wherein in figure curve from top to bottom successively in corresponding membrane electrode from the curve of the 1st layer to the 14th layer.Test as can be seen from Fig. 6 the characteristic absorption peak that the two kation nickel phthalocyanine/multi-walled carbon nano-tubes self-assemble film poles that obtain have had kation nickel phthalocyanine and carboxylated multi-walled carbon nano-tubes simultaneously, illustrate that kation nickel phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole is successfully prepared, and its uniform sequential growth of every tunic from the 1st layer to the 14th layer.
The preparation method of a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole of test three, this test carries out according to the following steps:
One, the preparation of kation cobalt phthalocyanine aqueous solution: be 2mg/mL kation cobalt phthalocyanine aqueous solution by the concentration that is mixed with soluble in water kation cobalt phthalocyanine;
Two, the preparation of carboxylic acid single-walled carbon nanotube dispersion liquid: carboxylic acid Single Walled Carbon Nanotube is joined to deionized water for ultrasonic and be uniformly dispersed, making concentration is the carboxylic acid single-walled carbon nanotube dispersion liquid of 1mg/mL;
Three, substrate pretreatment: 1. 5g NaOH is dissolved in to 200mL mass concentration and is in 50% ethanolic solution, obtain ethanol alkali lye; 2. the FTO electro-conductive glass cleaning up is put into water heating kettle, then the ethanol alkali lye that adds 20mL 1. to obtain, tighten kettle cover, be to react 0.5h at 100 DEG C in temperature, after having reacted, take out FTO electro-conductive glass, with distilled water drip washing 1min, then dry up with nitrogen, obtain electronegative FTO electro-conductive glass, be then placed in strong aqua and save backup;
Four, the preparation of kation cobalt phthalocyanine/Single Walled Carbon Nanotube self-assemble film pole: in the kation cobalt phthalocyanine aqueous solution that the concentration that the electronegative FTO electro-conductive glass immersion step 1 1. step 3 being obtained obtains is 2mg/mL, leave standstill 10min, then take out FTO electro-conductive glass and use deionized water rinsing 30s, dry up with nitrogen, obtaining surface has the FTO electro-conductive glass of positively charged kation cobalt phthalocyanine layer again, 2. the concentration first step 2 being obtained is the ultrasonic dispersion of the carboxylic acid single-walled carbon nanotube dispersion liquid 1h of 1mg/mL, then the surface 1. obtaining there is is the FTO electro-conductive glass of positively charged kation cobalt phthalocyanine layer to immerse in the carboxylic acid single-walled carbon nanotube dispersion liquid that concentration that the step 2 after ultrasonic dispersion obtains is 1mg/mL, leave standstill 10min, then taking out surface has the FTO electro-conductive glass of positively charged kation cobalt phthalocyanine layer and uses deionized water rinsing 30s, dry up with nitrogen again, obtain being had by the surface of electronegative carboxylic acid Single Walled Carbon Nanotube layer parcel the FTO electro-conductive glass of positively charged kation cobalt phthalocyanine layer, 3. be cycled to repeat 1.～step 10 2. time, form the Multilayer Film Electrode that kation cobalt phthalocyanine layer and Single Walled Carbon Nanotube layer replace, obtain kation cobalt phthalocyanine/Single Walled Carbon Nanotube self-assemble film pole.
Kation cobalt phthalocyanine described in this test procedure one is synthetic with reference to the existing disclosed method of document (T.T.Tasso etc., Inorg.Chem., 52 (2013) 9206-9215).
Kation cobalt phthalocyanine described in this test procedure one has following general formula:
wherein M is Co
2+.
The preparation method of a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole of test four, this test carries out according to the following steps:
One, the preparation of kation nickel phthalocyanine aqueous solution: be 2mg/mL kation nickel phthalocyanine aqueous solution by the concentration that is mixed with soluble in water kation nickel phthalocyanine;
Two, the preparation of carboxylic acid multi-walled carbon nano-tube dispersion liquid: carboxylic acid multi-walled carbon nano-tube is joined to deionized water for ultrasonic and be uniformly dispersed, making concentration is the carboxylic acid multi-walled carbon nano-tube dispersion liquid of 1mg/mL;
Three, substrate pretreatment: 1. 5g NaOH is dissolved in to 200mL mass concentration and is in 50% ethanolic solution, obtain ethanol alkali lye; 2. the ITO electro-conductive glass cleaning up is put into water heating kettle, then the ethanol alkali lye that adds 20mL 1. to obtain, tighten kettle cover, be to react 0.5h at 100 DEG C in temperature, after having reacted, take out ITO electro-conductive glass, with distilled water drip washing 1min, then dry up with nitrogen, obtain electronegative ITO electro-conductive glass, be then placed in strong aqua and save backup;
Four, the preparation of kation nickel phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole: in the kation nickel phthalocyanine aqueous solution that the concentration that the electronegative ITO electro-conductive glass immersion step 1 1. step 3 being obtained obtains is 2mg/mL, leave standstill 10min, then take out ITO electro-conductive glass and use deionized water rinsing 30s, dry up with nitrogen, obtaining surface has the ITO electro-conductive glass of positively charged kation nickel phthalocyanine layer again; 2. the concentration first step 2 being obtained is the ultrasonic dispersion of the carboxylic acid multi-walled carbon nano-tube dispersion liquid 1h of 1mg/mL, then the surface 1. obtaining there is is the ITO electro-conductive glass of positively charged kation nickel phthalocyanine layer to immerse in the carboxylic acid multi-walled carbon nano-tube dispersion liquid that concentration that the step 2 after ultrasonic dispersion obtains is 1mg/mL, leave standstill 10min, the ITO electro-conductive glass that then taking out surface has positively charged kation nickel phthalocyanine layer is also used deionized water rinsing 30
s, then dry up with nitrogen, obtain being had by the surface of electronegative carboxylic acid multi-walled carbon nano-tube layer parcel the ITO electro-conductive glass of positively charged kation nickel phthalocyanine layer; 3. be cycled to repeat 1.～step 20 2. time, form the Multilayer Film Electrode that kation nickel phthalocyanine layer and multi-walled carbon nano-tubes layer replace, obtain kation nickel phthalocyanine/multi-walled carbon nano-tubes self-assemble film pole.
Kation nickel phthalocyanine described in this test procedure one is synthetic with reference to the existing disclosed method of document (T.T.Tasso etc., Inorg.Chem., 52 (2013) 9206-9215).
Kation nickel phthalocyanine described in this test procedure one has following general formula:
wherein M is Ni
2+.
The preparation method of a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole of test five, this test carries out according to the following steps:
One, the preparation of kation cobalt phthalocyanine aqueous solution: be 2mg/mL kation cobalt phthalocyanine aqueous solution by the concentration that is mixed with soluble in water kation cobalt phthalocyanine;
Two, the preparation of carboxylic acid single-walled carbon nanotube dispersion liquid: carboxylic acid Single Walled Carbon Nanotube is joined to deionized water for ultrasonic and be uniformly dispersed, making concentration is the carboxylic acid single-walled carbon nanotube dispersion liquid of 1mg/mL;
Three, substrate pretreatment: 1. 5g NaOH is dissolved in to 200mL mass concentration and is in 50% ethanolic solution, obtain ethanol alkali lye; 2. the ITO electro-conductive glass cleaning up is put into water heating kettle, then the ethanol alkali lye that adds 20mL 1. to obtain, tighten kettle cover, be to react 0.5h at 100 DEG C in temperature, after having reacted, take out ITO electro-conductive glass, with distilled water drip washing 1min, then dry up with nitrogen, obtain electronegative ITO electro-conductive glass, be then placed in strong aqua and save backup;
Four, the preparation of kation cobalt phthalocyanine/Single Walled Carbon Nanotube self-assemble film pole: in the kation cobalt phthalocyanine aqueous solution that the concentration that the electronegative ITO electro-conductive glass immersion step 1 1. step 3 being obtained obtains is 2mg/mL, leave standstill 10min, then take out ITO electro-conductive glass and use deionized water rinsing 30s, dry up with nitrogen, obtaining surface has the ITO electro-conductive glass of positively charged kation cobalt phthalocyanine layer again, 2. the concentration first step 2 being obtained is the ultrasonic dispersion of the carboxylic acid single-walled carbon nanotube dispersion liquid 1h of 1mg/mL, then the surface 1. obtaining there is is the ITO electro-conductive glass of positively charged kation cobalt phthalocyanine layer to immerse in the carboxylic acid single-walled carbon nanotube dispersion liquid that concentration that the step 2 after ultrasonic dispersion obtains is 1mg/mL, leave standstill 10min, then taking out surface has the ITO electro-conductive glass of positively charged kation cobalt phthalocyanine layer and uses deionized water rinsing 30s, dry up with nitrogen again, obtain being had by the surface of electronegative carboxylic acid Single Walled Carbon Nanotube layer parcel the ITO electro-conductive glass of positively charged kation cobalt phthalocyanine layer, 3. be cycled to repeat 1.～step 14 2. time, form the Multilayer Film Electrode that kation cobalt phthalocyanine layer and Single Walled Carbon Nanotube layer replace, obtain kation cobalt phthalocyanine/Single Walled Carbon Nanotube self-assemble film pole.
Kation cobalt phthalocyanine described in this test procedure one is synthetic with reference to the existing disclosed method of document (T.T.Tasso etc., Inorg.Chem., 52 (2013) 9206-9215).
Kation cobalt phthalocyanine described in this test procedure one has following general formula:
wherein M is Co
2+.
Claims (10)
1. cationic metal phthalocyanine/carbon nano-tube self-assemble film pole, it is characterized in that a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole is in electronegative substrate, alternately to assemble positively charged cationic metal phthalocyanine layer and electronegative carbon nanotube layer, form the Multilayer Film Electrode that cationic metal phthalocyanine layer and carbon nanotube layer replace.
2. a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole according to claim 1, it is characterized in that cationic metal phthalocyanine layer positively charged in described cationic metal phthalocyanine/carbon nano-tube self-assemble film pole is identical with the number of plies of electronegative carbon nanotube layer, is 4～30 layers.
3. a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole according to claim 1, is characterized in that the general structure of cationic metal phthalocyanine in described positively charged cationic metal phthalocyanine layer is as follows:
wherein M is Co
2+, Fe
2+, Ni
2+, Cu
2+, Zn
2+, Pd
2+, Pb
2+or Mn
2+.
4. a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole according to claim 1, is characterized in that in described electronegative carbon nanotube layer, carbon nano-tube is carboxylic acid Single Walled Carbon Nanotube, carboxylic acid multi-walled carbon nano-tube, hydroxyl Single Walled Carbon Nanotube or hydroxyl multi-walled carbon nano-tubes.
5. a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole according to claim 1, is characterized in that the substrate in described electronegative substrate is glass-carbon electrode, ito glass, FTO glass, piezoid, glass sheet or silicon chip.
6. a preparation method for cationic metal phthalocyanine/carbon nano-tube self-assemble film pole, is characterized in that a kind of preparation method of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole carries out according to the following steps:
One, the preparation of cationic metal phthalocyanine aqueous solution: be 0.5mg/mL～2mg/mL cationic metal phthalocyanine aqueous solution by the concentration that is mixed with soluble in water cationic metal phthalocyanine;
Two, the preparation of carbon nano tube dispersion liquid: carbon nano-tube is joined to deionized water for ultrasonic and be uniformly dispersed, make the carbon nano tube dispersion liquid that concentration is 0.5mg/mL～2mg/mL;
Three, substrate pretreatment: 1. NaOH is dissolved in ethanolic solution, obtains ethanol alkali lye; The mass concentration of described ethanolic solution is 40%～60%, and the quality of described NaOH is 5g:(150～250 with the ratio of the volume of ethanolic solution) mL; 2. the substrate cleaning up is put into water heating kettle, then add the ethanol alkali lye 1. obtaining, tighten kettle cover, be to react 0.5h～2h at 80～160 DEG C in temperature, after having reacted, take out substrate, with distilled water drip washing 1min～2min, then dry up with nitrogen, obtain electronegative substrate, be then placed in strong aqua and save backup; The described volume of ethanol alkali lye and the ratio of the quality of substrate are 20mL:(0.9～10) g;
Four, the preparation of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole: in the cationic metal phthalocyanine aqueous solution that the concentration that the electronegative substrate immersion step 1 1. step 3 being obtained obtains is 0.5mg/mL～2mg/mL, leave standstill 5min～30min, then take out substrate and use deionized water rinsing 15s～60s, dry up with nitrogen, obtaining surface has the substrate of positively charged cationic metal phthalocyanine layer again, 2. the concentration first step 2 being obtained is the ultrasonic dispersion of the carbon nano tube dispersion liquid of 0.5mg/mL～2mg/mL 1h～4h, then the surface 1. obtaining there is is the substrate of positively charged cationic metal phthalocyanine layer to immerse in the carbon nano tube dispersion liquid that concentration that the step 2 after ultrasonic dispersion obtains is 0.5mg/mL～2mg/mL, leave standstill 5min～30min, then taking out surface has the substrate of positively charged cationic metal phthalocyanine layer and uses deionized water rinsing 15s～60s, dry up with nitrogen again, obtain being had by the surface of electronegative carbon nanotube layer parcel the substrate of positively charged cationic metal phthalocyanine layer, 3. be cycled to repeat 1.～step 4 2.～30 time, form the Multilayer Film Electrode that cationic metal phthalocyanine layer and carbon nanotube layer replace, obtain cationic metal phthalocyanine/carbon nano-tube self-assemble film pole.
7. a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole according to claim 6, is characterized in that the cationic metal phthalocyanine described in step 1 has following general formula:
wherein M is Co
2+, Fe
2+, Ni
2+, Cu
2+, Zn
2+, Pd
2+, Pb
2+or Mn
2+.
8. a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole according to claim 6, is characterized in that the carbon nano-tube described in step 2 is carboxylic acid Single Walled Carbon Nanotube, carboxylic acid multi-walled carbon nano-tube, hydroxyl Single Walled Carbon Nanotube or hydroxyl multi-walled carbon nano-tubes.
9. a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole according to claim 6, is characterized in that the substrate described in step 3 is after pretreatment and electronegative glass-carbon electrode, ito glass, FTO glass, piezoid, glass sheet or silicon chip.
10. a kind of cationic metal phthalocyanine/carbon nano-tube self-assemble film pole according to claim 6, the ratio that it is characterized in that the quality of the NaOH described in step 3 and the volume of ethanolic solution is 5g:200mL; The described volume of ethanol alkali lye and the ratio of the quality of substrate are 20mL:9g.
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