CN106167912B - Preparation method, electrode, non-enzymatic glucose sensor and the composite material of Pt nanoparticle/Nano tube array of titanium dioxide - Google Patents
Preparation method, electrode, non-enzymatic glucose sensor and the composite material of Pt nanoparticle/Nano tube array of titanium dioxide Download PDFInfo
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Abstract
The invention discloses the preparation method of Pt nanoparticle/Nano tube array of titanium dioxide, electrode, non-enzymatic glucose sensor and composite materials comprising：S1. titanium sheet pre-processes；S2. anodizing prepares TiO2Nano-tube array；S3. use the method for electropolymerization in TiO2Bionical poly-dopamine coating is constructed on nanotube；S4. Pt nanoparticle is loaded in by titania nanotube surface using the reproducibility of its own based on poly-dopamine coating；S5. the performance test of non-enzymatic glucose sensor is carried out using the working electrode prepared.The compound of Pt nanoparticle and titania nanotube is made using the method reduction of electropolymerization poly-dopamine for Pt nanoparticle/Nano tube array of titanium dioxide of the present invention, finally can be applied to make non-enzymatic glucose sensor.The method that bionical poly-dopamine restores Pt nanoparticle is loaded using electropolymerization, the problems such as solving process in dopamine tradition infusion process autohemagglutination time-consuming, lack of homogeneity.
Description
Technical field
The present invention relates to the preparation method of Material Field more particularly to Pt nanoparticle/Nano tube array of titanium dioxide, electricity
Pole, non-enzymatic glucose sensor and composite material.
Background technology
Titanium dioxide (TiO2) as a kind of novel n-type semiconductor, have chemical stability outstanding, photoelectricity special
Property, biocompatibility, corrosion resistance the features such as, have been widely used for photocatalytic pollutant degradation, fuel sensitization solar electricity
Pond, bio-medical material, gas sensor and photolysis water hydrogen etc..Nano-TiO2In addition to having and common nano material one
Outside the skin effect of sample, low dimensional effect, quantum size effect and macro quanta tunnel effect, also there is its special property,
Especially catalytic performance.
Compared with TiO2Nano particle, TiO2Nano-tube array has large specific surface area, surface energy high, easy to be recycled and electric
The advantages that rate of load condensate in son and hole is relatively low receives people more concern and research.But TiO2Nano-tube array is still deposited
In some disadvantages, it is limited in very various applications.Such as, (1) TiO2Energy gap it is wider (anatase 3.2eV,
Rutile is 3.0eV), 3~5% solar energy (λ ＜ 387nm) can only be absorbed, utilization rate is low；(2)TiO2The light of nanotube
The recombination rate of raw electron hole pair is still higher, and photocatalytic activity is low.
In view of the above-mentioned problems, doping metals, nonmetallic and semi-conductor nano particles and TiO by all means2Nanometer
Pipe array combines, to improve TiO2The PhotoelectrocatalytiPerformance Performance of nano-tube array becomes the hot spot studied at present.On the one hand, noble metal
Nano particle is dispersed in TiO2Nanotube surface can assist capture light induced electron, accelerate the separation of electron hole, and then inhibit light
Raw electrons and holes are compound.On the other hand, TiO can be improved by surface resonance effect in noble metal granule2The visible light of nanotube
Absorbability.Compared to other precious metals ags, Cu etc., Pt is in detection glucose, hydrogen peroxide, degradation methanol, formic acid, methyl esters etc.
Aspect application has more superior catalytic performance so that Pt loads TiO2Nanotube has been widely used for non-enzymatic glucose detection
The fields such as electrode, light degradation pollutant, photolysis water hydrogen, fuel cell.In addition, Pt nano particles have ion surface resonance effect
It answers, is carried on TiO2It is equally applicable for enhancing by Raman on nanotube, to amplify the Raman signal of organic matter, it is dirty to reach detection
Contaminate the effect of object.
In recent years, poly-dopamine (PDA) because its have to a variety of matrixes (such as metal, glass, organic matter etc.) it is good viscous
The features such as attached property and good biocompatibility and be widely used in biomaterial surface modification；In addition, PDA going back using itself
Material surface electroless metallising may be implemented in originality.Suitable dopamine is dissolved in buffer solution, under aerobic conditions, DOPA
The various substrate surfaces from inorganic (metal, metal oxide) to organic (polymer) are deposited on after amine oxidation auto polymerization, in base
Material surface forms one layer of PDA coating with permanent Adhering capacity.Further investigation shows：The catechol group and ammonia of dopamine
Main function plays in the adhesion process of poly-dopamine in base functional group.It can be expensive to gold, silver and platinum etc. using catechol group
Heavy metallic salt shows reducing power, is going out precious metal particles derived from poly-dopamine layer；Can with containing mercaptan, amino it is hydrophilic
Or Michael addition reaction and schiff base reaction occur for hydrophobic organic molecules or polymer etc., and functional organic matter is introduced into
Material surface makes material surface have special nature, such as：The work(such as corrosion resistance, rub resistance, bioactivity and biocompatibility
It can characteristic.With other surface modification methods comparatively, PDA modifications base material this method is simple and convenient, and it is modified base material
Geometry is unrelated, and the surface after modification has good chemical reactivity.But DOPA is realized by traditional infusion process
Amine oxidation autohemagglutination obtains the reaction process of poly-dopamine, and time-consuming, and dosage is big and modification evenness of membranous layer is poor.Therefore, one is found
The method of kind more quickly, simple, economic realizes that the bionical poly-dopamine coating of surface modification is particularly important.
Therefore, in view of the above-mentioned problems, it is necessary to propose further solution.
Invention content
The technical problem to be solved by the present invention is to provide a kind of preparation sides of Pt nanoparticle/Nano tube array of titanium dioxide
Method, to overcome the problems of the prior art.
The technical solution adopted by the present invention to solve the technical problems is：
The preparation method of Pt nanoparticle/Nano tube array of titanium dioxide, including：
TiO is prepared on matrix by anodizing2Nano-tube array, then matrix is calcined；
Dopamine solution is prepared as electrolyte, uses above-mentioned matrix as working electrode, platinum electrode is used as to electrode, silver electricity
Pole or silver chloride electrode are put into the dopamine solution as reference electrode by the working electrode, to electrode and reference electrode
In, on electrochemical workstation obtaining load on the matrix using cyclic voltammetry has the TiO of bionical poly-dopamine coating2
Nano-tube array；
Platinum acid chloride solution is prepared, by the TiO of the bionical poly-dopamine coating of load on above-mentioned matrix2Nano-tube array impregnates
After a certain period of time in platinum acid chloride solution, Pt nanoparticle/Nano tube array of titanium dioxide is obtained.
It is further：A concentration of 0.2-0.8mg/ml of dopamine solution, dopamine solution pH value are 6.5-8.0, cycle
The voltage range of voltammetry is enclosed in -1V to 1V, the scanning number of turns in 15-35, and sweep speed is in 50-200mV/S.
It is further：A concentration of 0.1-0.8mg/ml of the platinum acid chloride solution, loads the dioxy of bionical poly-dopamine
It is 1-5h to change dip time of the titanium nano-tube array in chloroplatinic acid, and Induced by Dopamine is utilized to restore platinum in dipping process, above-mentioned
Reaction condition：60-100 DEG C of water-bath oscillation.
The present invention also provides electrode, the electrode is provided with Pt nanoparticle/titanium dioxide made from above-mentioned preparation method
Titanium nano-tube array.
The present invention also provides non-enzymatic glucose sensor, the non-enzymatic glucose sensor is provided with above-mentioned preparation method
Pt nanoparticle/Nano tube array of titanium dioxide obtained.
The present invention also provides composite material, the composite material is provided with platinum nanometer made from above-mentioned preparation method
Grain/Nano tube array of titanium dioxide.
The beneficial effects of the invention are as follows：The present invention loads the method solution that bionical poly-dopamine realizes reduction platinum using electropolymerization
Process in dopamine tradition infusion process autohemagglutination of having determined the problems such as time-consuming, lack of homogeneity.The present invention has simple process easy to operate,
Poly-dopamine film layer is controllable, while the advantages that dispersion and the size of controllable Pt nanoparticle.Pt nanoparticle is modified
Nano tube array of titanium dioxide the photoelectric effect of Nano tube array of titanium dioxide on the one hand can be improved；On the other hand dioxy is improved
The catalytic capability for changing titanium nano-tube array, to reach to methanol, formic acid, the electrochemical degradation of mercaptan and for making non-enzymatic Portugal
Grape sugar sensor.With pure TiO2Compare, the TiO of supported platinum nano particle2Nano-tube array photoelectric properties significantly improve, together
When have good chemical stability and reusing, Pt nanoparticle/Nano tube array of titanium dioxide can be applied to
Photocatalytic pollutant degradation, non-enzymatic glucose sensor, fuel cell and Raman enhancing etc., have precision height, flow
Simply, the superiority such as fast, economical.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments described in invention, for those of ordinary skill in the art, without creative efforts,
Other drawings may also be obtained based on these drawings.
Fig. 1 is the flow diagram of the preparation method of Pt nanoparticle/Nano tube array of titanium dioxide of the present invention.
Fig. 2 is will be poly- more using electropolymerization in the Pt nanoparticle/Nano tube array of titanium dioxide prepared in embodiment 1
The modification of bar amine coating is to the cyclic voltammetry curve figure on titania nanotube.
Fig. 3-1 is that the SEM of platinum/Nano tube array of titanium dioxide produced by the present invention schemes, and four width are all front elevation.Wherein,
(a), (b), (c), (d) are respectively the platinum for impregnating chloroplatinic acid a concentration of 0.1mg/ml, 0.2mg/ml, 0.4mg/ml, 0.8mg/ml
The SEM of nano particle carried titanium dioxide nano-tube array schemes.
Fig. 3-2 is that the SEM of platinum/Nano tube array of titanium dioxide produced by the present invention schemes, and four width are all chamfer map.Wherein,
(a), (b), (c), (d) are respectively the platinum for impregnating chloroplatinic acid a concentration of 0.1mg/ml, 0.2mg/ml, 0.4mg/ml, 0.8mg/ml
The SEM of nano particle carried titanium dioxide nano-tube array schemes.
Fig. 4 is that tradition dipping autohemagglutination is legal and electrochemical polymerization method prepares poly-dopamine on Nano tube array of titanium dioxide
The SEM of supported platinum nano particle schemes, and in figure (a), the preparation method of platinum/Nano tube array of titanium dioxide is that traditional auto polymerization is poly- more
Bar amine, in figure (b), the preparation method of platinum/Nano tube array of titanium dioxide is electrochemical polymerization method.
Fig. 5 is the EDS and Elemental redistribution collection of illustrative plates of the Pt nanoparticle/Nano tube array of titanium dioxide prepared in embodiment 1；
Fig. 6 is the unmodified TiO of the Pt nanoparticle/Nano tube array of titanium dioxide prepared in embodiment 12Nanometer
The TiO of pipe array and Pt nanoparticle modification2The XRD diagram of nano-tube array.
Fig. 7 is TEM, HRTEM and constituency electricity of the Pt nanoparticle/Nano tube array of titanium dioxide prepared in embodiment 1
Sub- diffraction pattern.View (a), (b) be Pt nanoparticle/Nano tube array of titanium dioxide TEM, view (c) be Pt nanoparticle/
The HRTEM of Nano tube array of titanium dioxide, view (d) are the selective electron diffraction figure (SAED) of view (c).
Fig. 8 is the unmodified TiO of the silver Nano granule/titanium dioxide nano-tube array prepared in embodiment 22Nanometer
The TiO of pipe array and Pt nanoparticle modification2The XPS of nano-tube array schemes, wherein figure (a) is full spectrogram, figure (b) is the narrow of platinum
Spectrogram.
Fig. 9 is unmodified TiO in embodiment 32The TiO of nano-tube array and the modification of various concentration Pt nanoparticle2It receives
The uv absorption spectra of mitron array.
Figure 10 is unmodified TiO in embodiment 42The TiO of nano-tube array and the modification of various concentration Pt nanoparticle2
The photocurrent response figure of nano-tube array.
Figure 11 is the unmodified TiO in embodiment 1 in the case where there is non-illuminated conditions2Nano-tube array and Pt nanoparticle
The TiO of modification2The impedance spectra of nano-tube array.
Figure 12 is the TiO modified through platinum in embodiment 22Nano-tube array is bent to the oxidation of different glucose solution
Line.Embedded figure is the partial enlarged view of the glycoxidative curve of grape.
Figure 13 is unmodified TiO in embodiment 22The TiO of nano-tube array and platinum modification2Nano-tube array is to grape
The response staircase curve figure of sugar juice, embedded figure are the matched curve that current density changes with concentration of glucose.
Figure 14 is the TiO that platinum is modified in embodiment 22Ascorbic Acid when nano-tube array does non-enzymatic glucose sensor,
The interference effect staircase curve figure of uric acid etc..
Specific implementation mode
In order to make those skilled in the art more fully understand the technical solution in the present invention, below in conjunction with of the invention real
The attached drawing in example is applied, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
The every other embodiment that technical staff is obtained without making creative work, should all belong to protection of the present invention
Range.
As shown in Figure 1, the flow signal of the preparation method for Pt nanoparticle/Nano tube array of titanium dioxide of the present invention
Figure.
A kind of preparation method of Pt nanoparticle/Nano tube array of titanium dioxide, including：
S1. titanium sheet can be selected in matrix, is first pre-processed to titanium sheet.
Specifically, titanium sheet is cleaned.Wherein, the titanium sheet be pure titanium or titanium alloy, size be 1.5cm ×
3.0cm.Dust technology, acetone, ethyl alcohol and deionized water is used to be cleaned by ultrasonic 20-40min to titanium sheet successively.
S2. anodizing prepares TiO2Nano-tube array.
Specifically, using the titanium sheet after cleaning as anode, platinized platinum is made in the ethylene glycol solution of ammonium fluoride and water as cathode
For electrolyte, apply certain voltage, carry out anodic oxidation twice, TiO is made in anodic oxidation2Nano-tube array, then calcine to obtain
Obtain the better Detitanium-ore-type TiO of crystal form2Nano-tube array.
Wherein, in ethylene glycol solution, the mass percent concentration of ammonium fluoride is 0.2-0.8wt%, the percent by volume of water
A concentration of 2.0-4.0v%.Carry out first time anodic oxidation voltage be 40-60V, time 1-3h, second of anodic oxidation
Voltage is 40-60V, time 3-10min.TiO2 nano-tube arrays obtained are calcined in air, the temperature of calcining
It it is 400-500 DEG C, the time of calcination is 1-3h, and the heating of calcining and rate of temperature fall are 3-8 DEG C/min.By calcining, obtain
The better Detitanium-ore-type TiO of crystal form2Nano-tube array.
S3. use the method for electropolymerization in TiO2Bionical poly-dopamine coating is constructed on nanotube.
Specifically, the TiO that dopamine solution is obtained as electrolyte, step S2 is prepared2Nano-tube array makees working electrode,
Platinized platinum is made to electrode, and silver/silver chlorate makees reference electrode, and using electrochemical workstation scan cycle volt-ampere curve, obtaining load has
The Nano tube array of titanium dioxide of bionical poly-dopamine coating.
Specifically, dopamine solubility is 0.2-0.8mg/ml, and solution ph is 6.5-8.0 (acid on the weak side).Cyclic voltammetry
Voltage range in -1V-1V, the scanning number of turns is enclosed in 15-35, and sweep speed is in 50-200mV/S.To TiO2Nano-tube array into
It when row cleaning, is cleaned using deionized water, drying condition is 80 DEG C, 6h.
S4. Pt nanoparticle is loaded in by titania nanotube using the reproducibility of its own based on poly-dopamine coating
Surface.
Specifically, a concentration of 0.1-0.8mM of platinum acid chloride solution loads the titania nanotube battle array of bionical poly-dopamine
The dip time being listed in chloroplatinic acid is 1-5h, and reaction condition is：Temperature (60-100 DEG C), low-speed oscillation.
The above-mentioned matrix prepared can be used as electrode use, can be used widely in non-enzymatic glucose sensor field.
The performance test of non-enzymatic glucose sensor is carried out using the working electrode prepared.
Specifically, cyclical voltage is -1V-0.8V, and the scanning number of turns is enclosed in 5-15, and sweep speed is in 20-100mV/S.Oxidation
In curve, concentration of glucose 0-0.05M is interfered in linearity curve, and a concentration of 0-10mM, ascorbic acid and uric acid is added dropwise in glucose
A concentration of 2mM is added dropwise.
Further, it defines the TiO in step S42Nano-tube array immerses platinum acid chloride solution, and precursor chloroplatinic acid is molten
A concentration of 0.1-0.8mg/ml of liquid, it is illustrated that middle 0.1Pt/TiO2NTs indicates a concentration of 0.1mg/ml of precursor chloroplatinic acid,
0.2Pt/TiO2NTs indicates a concentration of 0.2mg/ml, 0.4Pt/TiO of precursor chloroplatinic acid2NTs indicates precursor chloroplatinic acid
A concentration of 0.4mg/ml, 0.8Pt/TiO2NTs indicates a concentration of 0.8mg/ml of precursor chloroplatinic acid.
It is that the SEM of Pt nanoparticle/Nano tube array of titanium dioxide produced by the present invention schemes as shown in Fig. 3-1,3-2.By
Figure is it is found that a length of 2-4 μm of nanotube, nanotube caliber are 80-100nm, pipe in Pt nanoparticle/Nano tube array of titanium dioxide
Wall thickness is 10-20nm.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawings and examples
The technical solution further illustrated the present invention.But the present invention is not limited to listed embodiments, should also be included in institute of the present invention
It is required that interest field in other any well known change.
First, " one embodiment " or " embodiment " referred to herein refers to that may be included at least one realization side of the present invention
A particular feature, structure, or characteristic in formula." in one embodiment " that different places occur in the present specification not refers both to
The same embodiment, nor the individual or selective embodiment mutually exclusive with other embodiment.
Secondly, the present invention is described in detail using structural schematic diagram etc., when describing the embodiments of the present invention, for ease of saying
Bright, schematic diagram can disobey general proportion and make partial enlargement, and the schematic diagram is example, should not limit the present invention herein
The range of protection.
In addition, the letter said in the present invention is referred to as, it is that this field is fixed referred to as, which part letter text is explained such as
Under：SEM schemes：Electron scanning imaging figure；TEM schemes：Transmitted electron surface sweeping imaging figure；HRTEM schemes：High-resolution transmitted electron surface sweeping
Imaging figure；SAED：Selective electron diffraction figure；EDS schemes：Energy spectrum diagram；XRD diagram：X-ray diffractogram；XPS spectrum figure：X-ray photoelectron
Energy spectrum analysis spectrogram.
Embodiment 1
(1) pretreatment of titanium sheet and two-step electrochemical anodizing method prepare TiO2Nano-tube array.To the dilute nitre of pure titanium sheet substrate
Acid, acetone, absolute ethyl alcohol, deionized water are cleaned by ultrasonic 15min successively.Using platinum plate electrode as cathode, while being inserted into and containing 98v%
In the electrolyte solution of ethylene glycol (ammonium fluoride 0.3wt%) and 2v% water, applies 40V ultors and aoxidize 1.5h, ultrasound falls off
After film layer, 40V ultors oxidation 8min is continued to, TiO is made2Nano-tube array, then 450 DEG C of calcining 2h, make it from nothing
Stabilized condition is transformed into anatase.
(2) method for using the induction reduction of electropolymerization poly-dopamine, prepares the compound dioxy titanium nanotube of Pt nanoparticle
Array.The Tris of the 1.5mg/ml of 50ml is prepared, pH to 7.0 is adjusted, buffer solution is made, 0.1g Dopamine hydrochlorides are added, obtain
Dopamine solution, after solution is uniformly dispersed, by the TiO in step S22Nano-tube array is used as working electrode, platinized platinum to electricity
Pole, silver/silver chlorate make cyclic voltammetry scan curve, scanning voltage range -1V- as reference electrode, using electrochemical workstation
1V, rate 80mV/S, the scanning number of turns is 15 circles, to TiO2Nano-tube array is cleaned, is dried, and obtains loading bionical poly- DOPA
The Nano tube array of titanium dioxide of amine.
(3) it utilizes Induced by Dopamine to restore noble metal Pt nanoparticle, configures the platinum acid chloride solution of various concentration, respectively
0.1mg/ml, 0.2mg/ml, 0.3mg/ml and 0.4mg/ml, by the titania nanotube of the load poly-dopamine prepared point
It not being impregnated in the chloroplatinic acid of various concentration, condition is that 60 DEG C of water-baths are vibrated, and dip time 2h then takes out washing, drying,
Obtain Pt nanoparticle/Nano tube array of titanium dioxide.
(5) non-enzymatic glucose sensor application is made to the Pt nanoparticle/Nano tube array of titanium dioxide prepared：Configuration
The sodium hydroxide solution of 0.1M does supporting electrolyte, and Pt nanoparticle/Nano tube array of titanium dioxide makees working electrode, and platinized platinum is made
To electrode, silver/silver chlorate makees reference electrode, and glucose, wherein grape are detected using the cyclic voltammetry curve of electrochemical workstation
Sugar adds concentration 5mM successively, further, the detection of electrode performance interference, test prepare electrode Ascorbic Acid, uric acid it is dry
Immunity, wherein glucose add a concentration of 2-10mM, and uric acid, ascorbic acid add a concentration of 2mM.
As shown in Fig. 2, Fig. 2 is to be modified poly-dopamine coating to the cycle on titania nanotube using electropolymerization
Volt-ampere curve figure, since the second circle of scanning, curve gradually tends towards stability.
As shown in Fig. 3-1,3-2, Fig. 3-1,3-2 are the Pt nanoparticle/titania nanotube battle array prepared in embodiment 1
The SEM shape appearance figures of row, it is known that, the Pt nanoparticle of 10-30nm is uniformly deposited on nanotube surface and inside.
As shown in figure 4, figure (a), (b) they are respectively that traditional autohemagglutination is legal and electrochemical polymerization method obtains poly-dopamine coating,
And then obtain the SEM figures of platinum/Nano tube array of titanium dioxide.Wherein, it is more to be all made of the hydrochloric acid listed in embodiment 1 for two methods
The concentration of bar amine, is impregnated in the platinum acid chloride solution of same concentrations, reaction condition all same, wherein using traditional infusion process
The autohemagglutination time be for 24 hours, use the time of electrochemical polymerization method for 6 minutes or so.By SEM shape appearance figures it is found that using electrochemistry
The load capacity of Pt nanoparticle in platinum/Nano tube array of titanium dioxide of infusion process preparation is significantly greater than using tradition dipping certainly
Pt nanoparticle in platinum/Nano tube array of titanium dioxide prepared by polymerization, while Pt nanoparticle dispersibility is more preferable, in turn
Illustrate that there is more uniform poly-dopamine coating.Therefore it can obtain：Bionical poly-dopamine is loaded using electropolymerization and restores platinum
The method of nano particle, the problems such as solving process in traditional infusion process autohemagglutination time-consuming, lack of homogeneity.
Fig. 5 is the constituency EDS and Elemental redistribution of the Pt nanoparticle/Nano tube array of titanium dioxide prepared in embodiment 1
Figure, shows that Pt nanoparticle/Nano tube array of titanium dioxide mainly contains C, Ti, O, Pt element.
It will be appreciated from fig. 6 that unmodified TiO2Nanotube is mainly made of anatase and Ti substrates, 25.3 °, 37.9 °, 48.0 °
The peak value occurred with 53.9 ° corresponds to (101) of anatase, (004), (200) and (105) crystal face (JCPDS no.21- respectively
1272).In TiO2After nano-tube array deposits Pt nano particles, occur peak value, (111) crystal face of corresponding Pt at 39.8 °
(JCPDS no.04-0802), to be consistent with TEM results in Fig. 7.
As shown in Figure 7, TEM results further demonstrate that Pt nanoparticle is evenly distributed on TiO2Nanotube surface and inside,
Particle size is about 10nm；HRTEM and SAED figures show TiO2Detitanium-ore-type (101) crystal face spacing of lattice is 0.352nm, Pt
(111) interplanar distance is 0.217nm, is matched with the XRD test results of Fig. 6.
Fig. 8 is unmodified TiO2The full spectrum and narrow spectrum of nanotube and the TiO2 nanotubes of platinum modification, in addition to O 1s
The presence at (532.4eV), Ti 2p (458.9eV) and the peak C 1s (284.5eV), the peak Pt 4f (72.6eV) demonstrates Pt modifications
TiO2Nano-tube array.It can be seen that from Pt 4f high-resolution XPS collection of illustrative plates (b), Pt 4f7/2 (71.0eV) and Pt 4f5/2
(74.4eV) peak separation is 3.4eV, it was demonstrated that Pt0Presence
Further as shown in Fig. 9,10,11, Fig. 9 is unmodified TiO2What nano-tube array and various concentration were modified
The uv absorption spectra of platinum/Nano tube array of titanium dioxide；Figure 10 is unmodified TiO2Nano-tube array with it is difference dense
Spend the photoelectric current collection of illustrative plates of platinum/Nano tube array of titanium dioxide of modification；Figure 11 be in the case where there is non-illuminated conditions, it is unmodified
TiO2The AC impedance curve of nano-tube array and platinum/Nano tube array of titanium dioxide.
As shown in Figure 9, unmodified TiO2The absorption peak of nanotube is less than 390nm, after modifying Pt nano particles, in 400-
Absorption intensity increases at 700nm, and absorptivity improves.
In Fig. 10, using the anhydrous sodium sulfate of 0.1M as electrolyte, xenon lamp (filters 400nm wavelength below) with optical filter
The distance of simulated visible light, light source to beaker is 15cm, intensity of illumination 60mW/cm2, in CHI660D electrochemical workstations three
Through row photoelectricity current test under electrode system.Illustrate unmodified TiO under visible-range2Nanotube and different deposited concentrations
The photocurrent curve of Pt nanoparticle/titania nanotube.The Pt/TiO of 0.1-0.8mg/ml2The photoelectric current of nano-tube array
For 0.050mA/cm2, 0.056mA/cm2, 0.072mA/cm2, 0.042mA/cm2It is unmodified TiO respectively2The photoelectric current of nanotube
(0.004mA/cm2) 13 times, 14 times, 18 times, 11 times, indicate TiO2 nano-tube arrays modification Pt nano particles after improve electricity
The separative efficiency in sub- hole pair.
In fig. 11, using the anhydrous sodium sulfate of 0.1M as electrolyte, xenon lamp (filters 400nm wavelength below) with optical filter
The distance of simulated visible light, light source to beaker is 15cm, intensity of illumination 60mW/cm2, in CHI660D electrochemical workstations three
Through row photoelectricity current test under electrode system.It is illustrated as respectively under conditions of being shone whether there is or not visible light, unmodified TiO2Nanotube battle array
The ac impedance spectroscopy of row and platinum/Nano tube array of titanium dioxide, wherein the arc diameter of high frequency region characterizes electron transmission mistake
Journey, diameter is smaller, and resistance value is smaller.The impedance value of platinum/Nano tube array of titanium dioxide is significantly less than unmodified titanium dioxide and receives
The impedance value of mitron array；Under visible light illumination, the array of platinum/titania nanotube obviously becomes smaller, and shows more excellent
Photoelectric properties more.
In fig. 12, using the sodium hydroxide solution of 0.1M as supporting electrolyte, platinum/Nano tube array of titanium dioxide is in difference
Oxidation curve in the sodium hydroxide solution of concentration of glucose, wherein the peak of -0.8V or so, which is electrode surface, adsorbs glucose
Electrochemical oxidation, the peak of -0.4V or so be the intermediate generated in electrode surface absorption glucose electrochemical oxidation process into
One step aoxidizes.The peak of 0.2V or so is that the glucose in solution body phase diffuses on electrode caused by progress direct oxidation.With
The continuous increase of concentration of glucose, peak value also gradually increase.
Figure 13 is glucose responding staircase curve, and embedded figure is that the linear fit that current density changes with concentration of glucose is bent
Line, equation y=0.01518x+0.7326, R2=0.9765.
Figure 14 is that the interference of electrode Ascorbic Acid, uric acid etc. during detecting glucose is investigated, wherein glucose
Contributive rate to current density is 100%, and ascorbic acid is 4% or so to the contributive rate of current density, and uric acid is to current density
Contributive rate be 0.3% or so.
Embodiment 2
(1) pretreatment of titanium sheet and two-step electrochemical anodizing method prepare TiO2Nano-tube array.To the dilute nitre of pure titanium sheet substrate
Acid, acetone, absolute ethyl alcohol, deionized water are cleaned by ultrasonic 10min successively.Using platinum plate electrode as cathode, while being inserted into and containing 97v%
In the electrolyte solution of ethylene glycol (ammonium fluoride 0.4wt%) and 3v% water, applies 50V ultors and aoxidize 2h, ultrasonic dezidua
After layer, 50V ultors oxidation 6min is continued to, TiO is made2Nano-tube array, then 450 DEG C of calcining 1.5h, make it from nothing
Stabilized condition is transformed into anatase.
(2) method for using the induction reduction of electropolymerization poly-dopamine, prepares the compound dioxy titanium nanotube of Pt nanoparticle
Array.The Tris of the 1.2mg/ml of 50ml is prepared, pH to 7.5 is adjusted, buffer solution is made, 0.2g Dopamine hydrochlorides are added, obtain
Dopamine solution, after solution is uniformly dispersed, by the TiO in step S22Nano-tube array is used as working electrode, platinized platinum to electricity
Pole, silver/silver chlorate make cyclic voltammetry scan curve as reference electrode, using electrochemical workstation, and scanning voltage range -1~
1V, rate 100mV/S, the scanning number of turns is 20 circles, to TiO2Nano-tube array is cleaned, is dried, and obtains loading bionical poly- more
The Nano tube array of titanium dioxide of bar amine.
(3) it utilizes Induced by Dopamine to restore noble metal platinum, configures the platinum acid chloride solution of various concentration, respectively 0.05mg/
Ml, 0.1mg/ml, 0.2mg/ml and 0.4mg/ml impregnate the titania nanotube of the load poly-dopamine prepared respectively
In the chloroplatinic acid of various concentration, condition is that 70 DEG C of water-baths are vibrated, and dip time 3h then takes out washing, drying, obtains platinum
Nano granule/titanium dioxide nano-tube array.
(5) non-enzymatic glucose sensor application is made to the Pt nanoparticle/Nano tube array of titanium dioxide prepared：Configuration
The sodium hydroxide solution of 0.1M does supporting electrolyte, and Pt nanoparticle/Nano tube array of titanium dioxide makees working electrode, and platinized platinum is made
To electrode, silver/silver chlorate makees reference electrode, and glucose, wherein grape are detected using the cyclic voltammetry curve of electrochemical workstation
Sugar adds concentration 10mM successively, and further, electrode performance interference detection, test prepares electrode Ascorbic Acid, uric acid
Interference, wherein glucose add a concentration of 5-10mM, and uric acid, ascorbic acid add a concentration of 5mM.
Embodiment 3
(1) pretreatment of titanium sheet and two-step electrochemical anodizing method prepare TiO2Nano-tube array.To the dilute nitre of pure titanium sheet substrate
Acid, acetone, absolute ethyl alcohol, deionized water are cleaned by ultrasonic 25min successively.Using platinum plate electrode as cathode, while being inserted into and containing 99v%
In the electrolyte solution of ethylene glycol (ammonium fluoride 0.1wt%) and 1v% water, applies 60V ultors and aoxidize 1h, ultrasonic dezidua
After layer, 60V ultors oxidation 5min is continued to, TiO is made2Nano-tube array, then 450 DEG C of calcining 1h, make it from without fixed
Type state is transformed into anatase.
(2) method for using the induction reduction of electropolymerization poly-dopamine, prepares the compound dioxy titanium nanotube of Pt nanoparticle
Array.The Tris of the 1.0mg/ml of 50ml is prepared, pH to 7.5 is adjusted, buffer solution is made, 0.3g Dopamine hydrochlorides are added, obtain
Dopamine solution, after solution is uniformly dispersed, by the TiO in step S22Nano-tube array is used as working electrode, platinized platinum to electricity
Pole, silver/silver chlorate make cyclic voltammetry scan curve as reference electrode, using electrochemical workstation, and scanning voltage range -1~
1V, rate 150mV/S, the scanning number of turns is 25 circles, to TiO2Nano-tube array is cleaned, is dried, and obtains loading bionical poly- more
The Nano tube array of titanium dioxide of bar amine.
(3) it utilizes Induced by Dopamine to restore noble metal platinum, configures the platinum acid chloride solution of various concentration, respectively 0.1mg/
Ml, 0.2mg/ml, 0.4mg/ml and 0.8mg/ml impregnate the titania nanotube of the load poly-dopamine prepared respectively
In the chloroplatinic acid of various concentration, condition is that 80 DEG C of water-baths are vibrated, and dip time 2.5h then takes out washing, drying, obtains
Pt nanoparticle/Nano tube array of titanium dioxide.
(5) non-enzymatic glucose sensor application is made to the Pt nanoparticle/Nano tube array of titanium dioxide prepared：Configuration
The sodium hydroxide solution of 0.1M does supporting electrolyte, and Pt nanoparticle/Nano tube array of titanium dioxide makees working electrode, and platinized platinum is made
To electrode, silver/silver chlorate makees reference electrode, and glucose, wherein grape are detected using the cyclic voltammetry curve of electrochemical workstation
Sugar adds concentration 3mM successively, further, the detection of electrode performance interference, test prepare electrode Ascorbic Acid, uric acid it is dry
Immunity, wherein glucose add a concentration of 1-5mM, and uric acid, ascorbic acid add a concentration of 1mM.
Embodiment 4
(1) pretreatment of titanium sheet and two-step electrochemical anodizing method prepare TiO2Nano-tube array.To the dilute nitre of pure titanium sheet substrate
Acid, acetone, absolute ethyl alcohol, deionized water are cleaned by ultrasonic 15min successively.Using platinum plate electrode as cathode, while being inserted into and containing 98v%
In the electrolyte solution of ethylene glycol (ammonium fluoride 0.3wt%) and 2v% water, applies 50V ultors and aoxidize 2.5h, ultrasound falls off
After film layer, 50V ultors oxidation 10min is continued to, TiO is made2Nano-tube array, then 450 DEG C of calcining 2h, make it from nothing
Stabilized condition is transformed into anatase.
(2) method for using the induction reduction of electropolymerization poly-dopamine, prepares the compound dioxy titanium nanotube of Pt nanoparticle
Array.The Tris of the 1.2mg/ml of 50ml is prepared, pH to 7.0 is adjusted, buffer solution is made, 0.4g Dopamine hydrochlorides are added, obtain
Dopamine solution, after solution is uniformly dispersed, by the TiO in step S22Nano-tube array is used as working electrode, platinized platinum to electricity
Pole, silver/silver chlorate make cyclic voltammetry scan curve, scanning voltage range -1V- as reference electrode, using electrochemical workstation
1V, rate 50mV/S, the scanning number of turns is 20 circles, to TiO2Nano-tube array is cleaned, is dried, and obtains loading bionical poly- DOPA
The Nano tube array of titanium dioxide of amine.
(3) it utilizes Induced by Dopamine to restore noble metal platinum, configures the platinum acid chloride solution of various concentration, respectively 0.1mg/
Ml, 0.2mg/ml, 0.3mg/ml and 0.4mg/ml impregnate the titania nanotube of the load poly-dopamine prepared respectively
In the chloroplatinic acid of various concentration, condition is that 90 DEG C of water-baths are vibrated, and dip time 2h then takes out washing, drying, obtains platinum
Nano granule/titanium dioxide nano-tube array.
(5) non-enzymatic glucose sensor application is made to the Pt nanoparticle/Nano tube array of titanium dioxide prepared：Configuration
The sodium hydroxide solution of 0.1M does supporting electrolyte, and Pt nanoparticle/Nano tube array of titanium dioxide makees working electrode, and platinized platinum is made
To electrode, silver/silver chlorate makees reference electrode, and glucose, wherein grape are detected using the cyclic voltammetry curve of electrochemical workstation
Sugar adds concentration 4mM successively, further, the detection of electrode performance interference, test prepare electrode Ascorbic Acid, uric acid it is dry
Immunity, wherein glucose add a concentration of 2-10mM, and uric acid, ascorbic acid add a concentration of 2mM.
Compared with prior art, the beneficial effects of the invention are as follows：Pt nanoparticle/titania nanotube battle array of the present invention
Row load the method that bionical poly-dopamine realizes reduction Pt nanoparticle using electropolymerization, solve dopamine tradition infusion process certainly
Process the problems such as time-consuming, lack of homogeneity, have simple process easy to operate, poly-dopamine film layer is controllable, controls simultaneously in poly-
The advantages that dispersion of Pt nanoparticle and size.The TiO of Pt nanoparticle modification2On the one hand nano-tube array can be improved
TiO2The photoelectric effect of nano-tube array；On the other hand TiO is improved2The catalytic capability of nano-tube array, to reach to methanol, first
Acid, the electrochemical degradation of mercaptan and for making non-enzymatic glucose sensor.With pure TiO2Compare, supported platinum nano
The TiO of grain2Nano-tube array photoelectric properties significantly improve, and are provided simultaneously with good chemical stability and reusing, can
Pt nanoparticle/Nano tube array of titanium dioxide is applied to photocatalytic pollutant degradation, non-enzymatic glucose sensor, fuel electricity
Pond and Raman enhancing etc. have the superiority such as high, the simple, fast, economical of flow of precision.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Profit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent requirements of the claims
Variation is included within the present invention.Any reference signs in the claims should not be construed as limiting the involved claims.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiment being appreciated that.
Claims (6)
1. the preparation method of Pt nanoparticle/Nano tube array of titanium dioxide, it is characterised in that including：
TiO is prepared on matrix by anodizing2Nano-tube array, then matrix is calcined；
Prepare dopamine solution and be used as electrolyte, use above-mentioned matrix as working electrode, platinum electrode as to electrode, silver electrode or
Silver chloride electrode is put by the working electrode, to electrode and reference electrode in the dopamine solution, institute as reference electrode
A concentration of 0.2-0.8mg/ml of dopamine solution is stated, is obtained on the matrix using cyclic voltammetry on electrochemical workstation
Load has the TiO of bionical poly-dopamine coating2Nano-tube array；
Platinum acid chloride solution is prepared, by the TiO of the bionical poly-dopamine coating of load on above-mentioned matrix2Nano-tube array is impregnated in chlorine
Platinic acid solution after a certain period of time, obtains Pt nanoparticle/Nano tube array of titanium dioxide.
2. the preparation method of Pt nanoparticle/Nano tube array of titanium dioxide according to claim 1, it is characterised in that：
Dopamine solution pH value is 6.5-8.0, and the voltage range of cyclic voltammetry in -1V to 1V, in 15-35 enclose by the scanning number of turns,
Sweep speed is in 50-200mV/S.
3. the preparation method of Pt nanoparticle/Nano tube array of titanium dioxide according to claim 1, it is characterised in that：
A concentration of 0.1-0.8mg/ml of the platinum acid chloride solution, the Nano tube array of titanium dioxide for loading bionical poly-dopamine exist
Dip time in chloroplatinic acid is 1-5 hours, and platinum, above-mentioned reaction condition are restored using Induced by Dopamine in dipping process：60-
100 DEG C of water-bath oscillations.
4. electrode, it is characterised in that：The electrode is provided with platinum nanometer made from the preparation method by claim 1,2 or 3
Grain/Nano tube array of titanium dioxide.
5. non-enzymatic glucose sensor, it is characterised in that：The non-enzymatic glucose sensor is provided with by claim 1,2 or 3
Preparation method made from Pt nanoparticle/Nano tube array of titanium dioxide.
6. composite material, it is characterised in that：The composite material is provided with made from the preparation method by claim 1,2 or 3
Pt nanoparticle/Nano tube array of titanium dioxide.
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| CN106645350B (en) * | 2016-12-29 | 2019-03-08 | 西南大学 | Poly-dopamine modifies application of the n-type semiconductor in building photoelectricity immunosensor |
| CN107096068A (en) * | 2017-03-15 | 2017-08-29 | 北京科技大学 | A kind of preparation method of dentistry implant and its bioactivity antimicrobial surface |
| US10040948B1 (en) | 2017-11-21 | 2018-08-07 | Uxn Co., Ltd. | Method of making a colloid and nanoporous layer |
| KR102608737B1 (en) * | 2017-12-15 | 2023-12-01 | 주식회사 유엑스엔 | Nanoporous structure and enzyme-free glucose sensing device and system |
| CN108456909A (en) * | 2018-03-12 | 2018-08-28 | 武汉科技大学 | A kind of titanium substrate nano surface pipe carried noble metal nano particle composite material and preparation method thereof |
| CN111146459B (en) * | 2019-12-10 | 2021-05-25 | 一汽解放汽车有限公司 | Fuel cell cathode catalyst, preparation method thereof and application thereof in fuel cell |
| WO2021114287A1 (en) | 2019-12-13 | 2021-06-17 | 深圳先进技术研究院 | Flexible electrode and preparation method therefor |
| CN111017870B (en) * | 2019-12-13 | 2023-08-08 | 深圳市中科先见医疗科技有限公司 | Flexible electrode and preparation method thereof |
| CN111358963B (en) * | 2020-05-18 | 2023-10-24 | 青岛科技大学 | Doped MoO 2 Poly-dopamine platinum particle nano material and preparation method thereof |
| CN111505078B (en) * | 2020-05-20 | 2021-04-23 | 郑州轻工业大学 | Ni/Au composite nanowire array enzyme-free glucose sensor electrode and preparation method thereof |
| CN111990994B (en) * | 2020-09-02 | 2023-10-10 | 天津理工大学 | EEG flexible dry electrode and preparation method and application thereof |
| PL436218A1 (en) * | 2020-12-02 | 2021-12-20 | Uniwersytet Wrocławski | Method of obtaining an aliphatic polydopamine layer |
| CN113121859B (en) * | 2021-04-22 | 2022-09-02 | 哈尔滨工业大学 | Preparation method of electropolymerized polydopamine-carbon nanotube composite membrane |
| CN113846342B (en) * | 2021-10-13 | 2023-09-05 | 浙江工业大学 | Inorganic-organic core-shell skeleton loaded low-dose noble metal palladium material, preparation thereof and application thereof in electrocatalytic dechlorination hydrogenation reaction |
| CN114182263B (en) * | 2021-11-01 | 2023-04-07 | 中国科学院海洋研究所 | Polydopamine-sensitized spacing type titanium dioxide composite membrane photo-anode and preparation method and application thereof |
| CN114432500B (en) * | 2022-01-20 | 2022-09-16 | 南京医科大学附属口腔医院 | CeO (CeO) 2 Modified TiO 2 2 Bionic porous titanium stent of variable nanotube array and preparation method thereof |
| CN114887862B (en) * | 2022-05-10 | 2023-04-18 | 华南农业大学 | nanoparticle-hPDA-TDNT material and preparation method and application thereof |
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