Preparation method and application of poly-sulfosalicylic acid / titanium dioxide / carbon nanotube nanocomposite with electrode as substrate

The technical field of

[0001] the invention claims a composite material preparation method especially relates to a electrode is substrate the polymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material preparation method which belongs to the electrode material technology field.

Background technology

[0002] titanium dioxide nanometre material it has large specific surface area light absorbing property good dispersivity is good without poison high chemical stability and high optical electronic air cavity to oxidation reduction electric potential and so on it is widely used as photoelectric catalytic agent is applied in organic dye and poison material photocatalysis and degradation of light construction biological sensor and preparation method new energy material etc. Only of the titanium dioxide catalytic capability the particle aggregate and fast the light generating electron hole the complex limitation of.

[0003] zhou such as human kenneth f zhu zhou yan h x y z l c yang jiang li preparat1nof graphene t12 composites with enhanced photocatalytic activity new j chem 35 353 359 the graphite alkene carbon nanometer pipe and so on as support material for preparing titanium dioxide nanometre composite material it can effectively avoid the titanium dioxide nanometre particle aggregate so as to increase the catalyzing performance the optical electron hole pair of fast composite still can not be avoided. In existing technology the invention claims a method and it reduces the light generating electron hole pair of composite is prepared by the surface deposition cds and so on semiconductor nanometer granule titanium dioxide nanometre composite material the composite material electron transporting property always with the reducing. The composite material preparation in the process or directly introduced into the titanium dioxide or adopting the mechanical grinding method to obtain nanometer composite material applied to the electrode material the preparation method complex.

The content of invention

[0004] aiming at the present technology of titanium dioxide nanometre composite material of synthesizing process can not avoid the titanium dioxide is fast the light generating electron hole composite overcomes the defects of the invention claims a method of using electrode as the base polymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material preparation method the method of preparing titanium dioxide or carbon nanometer pipe compound material the surface of the depositing a layer of the ammonia benzene sulfonic acid polymer film electron transporting property is good and it can effectively avoid the titanium dioxide is fast the light generating electron hole compound has high selectivity and sensitivity.

[0005] this invention in order to realize said purpose the technical plan is as follows:

The invention claims a method of using electrode as the base polymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material preparation method comprises the following steps:

To 0.5 mg/l ml of carbon nano-tube suspension liquid and 0.074mm 2mmol/ ml of nanometer titanium dioxide gel according to volume ratio 3.5: 1-5: 1 after mixing evenly obtained mixed liquid to 5-8 mu l mixed solution evenly coated on the drop of blank space of the surface of electrode is set on the infrared ray drying the;

The dried the electrode is set on than 2mmol/ the ammonia of the l benzene sulfonic acid water solution carrying out circulation volt-ampere radial polymerization condition is: Level zone is 1.5-2.5 v scanning speed is 100 scott mv and sensitivity is 100 mu a waiting time 2s polymer coil number is 8 ring polymerization after drying to obtain the electrode is substrate the polymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material.

[0006] further comprises the steps of the carbon nano-tube suspension liquid of preparation method is as follows: Weighing 0.02 g carbon nanometer pipe is set in 40ml absolute ethyl alcohol in ultrasonic vibration apparatus ultrasonic treatment for 4 h at can be.

[0007] further comprises the steps of the nanometer titanium dioxide of the colloid the preparing method is as follows: The magnetic force stirring is filled with anhydrous alcohol 20ml of the beaker adding iml titanic acid tetra-n-butyl ester stirring 15_30 s; By burette and then be dripped slowly into 20ml 0.2 mol/l of dilute nitric acid dripping speed is i or drop s; After dripping continue to stir for 30 min then to put in beaker 25-40° c in constant temperature oven for 24 hours after being aged.

[0008] is further step of the blank of the electrode preparation method is as follows: The glass carbon electrode after polished by secondary water flushing and the secondary water in the ultrasonic vibration 3min then in the anhydrous ethanol to ultrasonic vibration 3min and finally placed in secondary water in the vibration ultrasonic 3min drying to obtain blank electrode.

[0009] said blank electrode of the activating condition is: The blank of the electrode is set on lmol g/l sulphuric acid in the electricity level area is set between the scanning speed v 0.6-1.2 surface as 100 / mv s under the condition of adopting the cyclic volt-ampere scanning method of ring 10.

[0010] this invention prepares a polymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material as the electrode is substrate and the ammonia benzene sulfonic acid are equally deposited on titanium dioxide or carbon nanometre tube nanometre composite material surface.

[0011] this invention also claims a poly the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material is biological molecule separation and measurement to be used in the.

[0012] further the ammonia said poly benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material is ascorbic acid aa dopamine da uric acid ua ingredient separating and determining.

[0013] the invention claims a titanium dioxide and carbon nanometer pipe compound material preparation on the basis of firstly by sol-gel method for preparing nanometre titanium dioxide gel by drip coating method of the titanium dioxide and carbon nanotube hybrid drop in the surface of glassy carbon electrode finally through electrochemical method of the titanium dioxide or carbon nanometer pipe compound material the surface of the depositing a layer of the ammonia benzene sulfonic acid polymer film is prepared by the ammonia on the benzene sulfonic acid is set with ion exchange property of the conducting polymer with amino on its contrapuntal with sulfonic acid group in the presence of a steric effect and strong absorbing electricity effect which can effectively inhibit titanium dioxide electron hole the reset of the extended cavity of the electric stored in the time. Other amino benzene sulfonic acid dipolymer- with the carbon nanometre tube side wall in the presence of a large amount of the height of the separation of pi electronic system through key pi pi conjugated to form the conjugation system of the polymer in the inner part of the electron transfer. The polymerization of the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material of the bottom of the catalyzing effect of showing good synergistic effect on ascorbic acid aa dopamine da uric acid such as ua ingredient separating and measuring analysis shows it has high selectivity and sensitivity.

[0014] this invention has the advantages and beneficial effect is as follows:

1 uses sol gel method and electric polymer through polymerization in the way of the ammonia benzene sulfonic acid coating carbon nanometre tube nanometre titanium dioxide to form the nanometre composite material of the mutual association of the electric high catalytic activity it can effectively avoid the titanium dioxide is fast the light generating electron hole composite.

[0015] 2 the preparation of the invention and the electrode is substrate the polymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material has high selectivity and sensitivity the invention has the ability of the invention claims a biological molecule separation and measurement to.

Specification attached drawing

[0016] 1 is an embodiment of the preparation of carbon nanometer pipe material film of the scanning electron microscope image.

[0017] 2 is an embodiment of the preparation of t12 or carbon nanometer pipe compound material of the film scanning electron microscope image.

[0018] 3 is an embodiment of the preparation of the copolymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometer pipe compound material of the scanning electron microscope image.

[0019] 4 is an effect of the example of 1 the different material modified electrode of the uric acid ua solution circulation volt-ampere image.

[0020] a blank electrode b carbon nanotube modified electrode c of the example of preparing the poly amino benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material modified electrode.

[0021] 5 is an effect of the example of 2 the different material modified electrode of the i mmol per l of the potassium ferricyanide and potassium ferrocyanide solution circulation volt-ampere image.

[0022] a blank electrode b carbon nanotube modified electrode c the ammonia polymerization benzene sulfonic acid modified electrode d nanometer titanium dioxide or carbon nanotube modified electrode e the ammonia poly benzene sulfonic acid or nanometer titanium dioxide or carbon nanotube modified electrode.

[0023] 6 as an effect of the example of 3 the nanometre composite material of the change of aa and ua concentration of solution of difference pulse curved line map.

[0024] the aa concentration is 0.25 xl t3mol g/l 0.50 xl t3mol g/l 0.75 x l t3mol g/l 1.00 x l t3mol g/l 1.25 x l t3mol 1.5 g/l x l t3mol g/l; Ua the concentration of 1 x is 0.5 mol/l t5 1.5 x 10 5 mol/l x 10 5 2.5 mol/l 4.0 x 10 5 mol/l 5.0 x 10 5 mol/l 6.0 x 10 5 mol/l.

[0025] graph 7 the effect of the embodiment of the nanometer composite material on the fixed aa ua change da concentration of solution of difference pulse curved line map.

[0026] 6 6 wherein the concentration of the inside of 1 0.4 10-311101 or; * concentration is 1 / or 10-511101 1.0; Da concentration in order to be 1.0 xl t5mol g/l to 2.0 1 5 *** 3.0 mol/l x l t5mol g/l 4.0 x t5mol 5.0 x and l l l l l t5mol / 6.0 x t5mol 7.0 g/l x l t5mol g/l.

Specific implementing manner

[0027] a lower surface of the embodiment of this invention is further describes. The used raw materials are reagent ltd purchase analysis pure more.

[0028] of the reagent preparation method and electrode material pre-treatment:

1 phosphate buffer solution of making irradiation

To respectively weigh 11.4 g potassium dihydrogen phosphate g 6.8 potassium dihydrogen phosphate are separately set on two beaker by secondary water to dissolve respectively set the volume of the two 500 ml of the measuring bottle in certain proportion and putting the two solution prepared by mixing the ph value of the different pbs buffer solution.

[0029] 2.1 mol/l of vitriol solution for preparation of

Measuring 5.4 to 98% concentration sulfuric acid slowly poured into filled with certain quantity of secondary water of the beaker aside to wait for the diluted solution after cooling moved into 100 ml in volumetric flask containing the spare;

3 potassium ferricyanide and potassium ferrocyanide solution preparation of

To respectively weigh 0.165 g potassium ferricyanide 0.211 g potassium ferro cyanide and 3.73 g potassium chloride is set in the beaker for ph value is 7.00 of pbs solution contained in the 500 ml of the measuring bottle to prepare i mmol per l of k3fe 6a 4fe cn cn 6 solution.

[0030] 1 x a t3 mol/l the ammonia benzene sulfonic acid solution preparing

Weighing 0.0866 g without water the ammonia benzene sulfonic acid for secondary water solution diluting to fix the capacitance to 250 ml in volumetric flask so as to obtain an 10_3 mol/l the ammonia benzene sulfonic acid solution.

[0031] 5 electrode pre-treating

Blank electrode preparation method is as follows: The glass carbon electrode after polished by secondary water flushing and the secondary water in the ultrasonic vibration 3min then in the anhydrous ethanol to ultrasonic vibration 3min and finally placed in secondary water in the vibration ultrasonic * 3min to dry to obtain blank electrode.

[0032] embodiment 1 carbon nano-tube suspension liquid of preparing: Weighing 0.02 g carbon nanometer pipe is set in 40 to absolute ethyl alcohol in ultrasonic vibration apparatus ultrasonic treatment for 4 h to make it be dispersed evenly the thickness is 0.5 mg/ml carbon nano-tube suspension liquid micro appearances picture 1o

[0033] 2 titanium dioxide gel the preparation of: Is adopted by sol-gel method of sol gel preparing titanium dioxide colloidal. Moving fetch 20 ml ethanol without water for small beaker the magnetic force under the condition of stirring and dry moving the pipette to 1.00 titanic acid tetra-n-butyl ester drip it into the beaker 20s the stirring evenly mixing; By burette and then be dripped slowly into 20.00 to 0.2 mol/l of dilute nitric acid dripping speed is about one droplet of each seconds; After dripping then stir for 30 min then to put in beaker 25-40° c constant temperature oven in aging 24 h and can obtain good stability of the colloid titanium dioxide concentration is 0.074 mmol per ml.

[0034] 3 by electrode is substrate the polymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material preparation:

The pretreatment to obtain blank space of the electrode is set in the i mol/l sulphuric acid solution in the electric level area of the v 0.6 1.2 v scanning speed is 100 scott mv or under the condition of adopting the cyclic volt-ampere scanning method for activating the ring 10 6 yl dispersed carbon nano-tube suspension liquid and nanometer titanium dioxide according to volume ratio 4: 1 mixing to obtain mixed solution the mixed solution equably drop coated on the blank surface of electrode is set on the infrared ray drying the injection: Drying the electrode distance infrared light can not be too near to or it is easy to be damaged electrode on the surface of the carbon nanometer tube film to obtain titanium dioxide or carbon nanometer pipe compound material micro appearances picture 2.

[0035] after drying then the ammonia benzene sulfonic acid in carrying out circulation volt-ampere radial polymerization condition is: Electric potential between 1.5 v v 2.5 scanning speed is 100 scott mv and the sensitivity is 100 mu *** selecting the waiting time 2 s polymer coil number is 8 ring after polymerizing drying. Through said two steps to obtain the electrode is substrate the polymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometer pipe compound material micro appearances picture 3 from the pattern 3 can be seen titanium dioxide or carbon nanometer pipe compound material the surface of the uniformly depositing a layer of the ammonia benzene sulfonic acid polymer film.

[0036] embodiment using electrode as the base polymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material preparation:

The pretreatment to obtain blank space of the electrode is set in the i mol/l sulphuric acid solution in the electric level area of the v 0.6 1.2 v scanning speed is 100 scott mv or under the condition of adopting the cyclic volt-ampere scanning 10 ring method for activating and yl 5 dispersed carbon nano-tube suspension liquid and nanometer titanium dioxide according to volume ratio 3.5: 1 mixing to obtain mixed solution the mixed solution equably drop coated on the blank surface of electrode is set on the infrared ray drying the injection: Drying the electrode distance infrared light can not be too near to or it is easy to be damaged electrode on the surface of the carbon nanometer tube film to obtain titanium dioxide or carbon nanometer pipe compound material micro appearances picture

After drying then the ammonia benzene sulfonic acid in carrying out circulation volt-ampere radial polymerization condition is: Electric potential between 1.5 v v 2.5 scanning speed is 100 scott mv and the sensitivity is 100 mu *** selecting the waiting time 2 s polymer coil number is 8 ring after polymerizing drying. Through said two steps to obtain the electrode is substrate the polymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometer pipe compound material to prepare the nanometer composite material is titanium dioxide or carbon nanometer pipe compound material the surface of the uniformly depositing a layer of the ammonia benzene sulfonic acid polymer film.

[0037] the carbon nano-tube suspension liquid and titanium dioxide gel preparation method of the embodiment of 1.

[0038] 3 embodiment of the electrode is substrate the polymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material preparation:

The pretreatment to obtain blank space of the electrode is set in the i mol/l sulphuric acid solution in the electric level area of the v 0.6 1.2 v scanning speed is 100 scott mv or under the condition of adopting the cyclic volt-ampere scanning method for activating to 8 ring 10 mu l dispersed carbon nano-tube suspension liquid and nanometer titanium dioxide according to volume ratio of 5: 1 mixing to obtain mixed solution the mixed solution equably drop coated on the blank surface of electrode is set on the infrared ray drying the injection: Drying the electrode distance infrared light can not be too near to or it is easy to be damaged electrode on the surface of the carbon nanometer tube film to obtain titanium dioxide or carbon nanometer pipe compound material micro appearances picture

After drying then the ammonia benzene sulfonic acid in carrying out circulation volt-ampere radial polymerization condition is: Electric potential between 1.5 v v 2.5 scanning speed is 100 scott mv and the sensitivity is 100 mu *** selecting the waiting time 2 s polymer coil number is 8 ring after polymerizing drying. Through said two steps to obtain the electrode is substrate the polymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometer pipe compound material to prepare the nanometer composite material is titanium dioxide or carbon nanometer pipe compound material the surface of the uniformly depositing a layer of the ammonia benzene sulfonic acid polymer film.

[0039] the carbon nano-tube suspension liquid and titanium dioxide gel preparation method of the embodiment of 1.

[0040] effect embodiment it is not at the same electrode to the concentration is 5 1***1 *** mol/l the uric acid catalysis of ua

Different electrode the concentration is 5 1***1 *** mol/l the uric acid ua the catalyzing effect of gap electrode a carbon nanotube modified electrode b embodiment of the preparation of the copolymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material modified electrode if the displaying picture 4. It is comprised of an 4 it can be known that the ua solution composite film modified electrode is blank electrode peak potential obviously negative shift peak current obviously improves the invention composite film modified electrode the ua solution of the catalytic action it can effectively reduce the reaction of the electric potential of promoting the electronic mobile the reaction is easy to be carried out; Peak current to the increase of the invention also indicates composite film modified electrode the sensitivity of the blank of the electrode is more sensitive.

[0041] effect embodiment two different materials and decoration of the electrode circulation volt-ampere detecting characteristic

The ph value is 7.00 of pbs solution into buffer solution to concentration is 0.1 mol/l the kcl solution as the liquid in the concentration of the i mmol per liter of solution k3fe cn 6 are respectively and gap electrode a carbon nanotube modified electrode b of the poly amino benzene sulfonic acid modified electrode c of carbon nanometer pipe or titanium dioxide modified electrode d of the example of the preparation of the poly amino benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material modified electrode e carrying out circulation volt-ampere scanning region is set between the electric potential v 0.2-0.6 scan rate is 100 mv s 1 to characteristic of each material an electrochemical activity the result picture 5. 5 can be known it is comprised of an empty electrode a current response is not good and the peak potential difference very large surface will show reversible electrochemical behaviour. And through the modified electrode b e ~ ratio of empty electrode of the peak of the peak potential difference value is less the invention the ammonia benzene sulfonic acid film of carbon nanometre tube film and nanometer titanium dioxide and it can promote the electronic transmission. Further analysis it can be known that the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material modified electrode peak current the highest peak potential difference value of minimum surface the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material has the functions of promoting stronger electron transfer effect the utility model is with high efficiency electrochemical active.

[0042] effect of the example of ua 3 uric acid and ascorbic acid solution mixing aa concentration at the same time is changed to carry out difference of pulse method for scanning

The embodiment of the preparation of the copolymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material changing the concentration of uric acid ua and ascorbic acid solution mixing aa are carried out at the same time difference of pulse method for scanning such as the picture 6. It is comprised of an 6 can be seen output measurement of the base is not affected by the ua the influence of ua the measuring of the base will not be aa the influence of the two materials can be measured to. Respectively according to output of the oxygen current hua-feng jp the concentrations c of the working curve the obtained linear fitting process is respectively: Or pi = 10.338 *** mu l c t3 mol/l 15.507 and relative parameter r = 0.9997; Or pi = mu *** 6.799 c 10_5 mol/l 9.861 and relative parameter r = 0.9991. From the working curve can be proved composite material modified electrode can be used in aa and the ua in mixed solution to measure the mutual non-interference at the same time the eaa ua and a peak current is connected with the concentration of the proportional relationship so as to improve the working curve according to the practical application the measuring.

[0043] effect embodiment 4 ascorbic acid uric acid aa ua at the same time when the presence of hydrochloric acid dopamine da concentration change when the difference of pulse method for scanning

The embodiment of the preparation of the copolymer the ammonia benzene sulfonic acid and titanium dioxide or carbon nanometre tube nanometre composite material the certain concentration of ascorbic acid uric acid aa ua change of the concentration of hydrochloric acid dopamine da mixed solution to carry out difference of pulse method for scanning such as the picture 7. It is comprised of an 7 can be seen of dna of measuring the base will not be aa ua the influence of. Da according to the oxidation of peak power flow iv to the concentrations c of the working curve the obtained linear equation for fitting: Or pi = mu *** 5.235 *** 5 mol/l 14.137 and relative parameter r = 0.9998. From the working curve can be proved composite film modified electrode can be fixed on the aa ua the da concentration measuring the concentration of the same time to get the dna of the peak current with the concentration of the proportional relationship so as to improve the working curve according to the practical application the measuring.