CN106167912A - The preparation method of Pt nanoparticle/Nano tube array of titanium dioxide, electrode, non-enzymatic glucose sensor and composite - Google Patents
The preparation method of Pt nanoparticle/Nano tube array of titanium dioxide, electrode, non-enzymatic glucose sensor and composite 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, comprising: S1. titanium sheet pretreatment；S2. anodizing prepares TiO2Nano-tube array；S3. use the method for electropolymerization at TiO2Bionical poly-dopamine coating is constructed on nanotube；S4. based on poly-dopamine coating, utilize the reproducibility of himself, Pt nanoparticle is loaded in titania nanotube surface；S5. the working electrode prepared is utilized to carry out the performance test of non-enzymatic glucose sensor.The Pt nanoparticle of the present invention/Nano tube array of titanium dioxide uses the method reduction of the poly-dopamine of electropolymerization to prepare Pt nanoparticle and the complex of titania nanotube, finally can be applicable to make non-enzymatic glucose sensor.The method using electropolymerization to load bionical poly-dopamine reduction Pt nanoparticle, solves in dopamine tradition infusion process autohemagglutination the problems such as operation time-consumingly length, lack of homogeneity.
Description
Technical field
The present invention relates to Material Field, particularly relate to the preparation method of Pt nanoparticle/Nano tube array of titanium dioxide, electricity
Pole, non-enzymatic glucose sensor and composite.
Background technology
Titanium dioxide (TiO2) as a kind of novel n-type semiconductor, there is prominent chemical stability, photoelectricity special
Property, the feature such as biocompatibility, corrosion resistance, have been widely used for photocatalytic pollutant degradation, fuel sensitization solar electricity
The aspects such as pond, bio-medical material, gas sensor and photolysis water hydrogen.Nano-TiO2Except 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 character,
Especially catalytic performance.
Relatively TiO2Nano-particle, TiO2Nano-tube array has that specific surface area is big, surface can be high, easy to be recycled and electric
The advantages such as sub and hole rate of load condensate is relatively low, receive people and more pay close attention to and study.But, TiO2Nano-tube array is still deposited
In some shortcomings, limit it in the most many application.As, (1) TiO2Energy gap wider (anatase is 3.2eV,
Rutile is 3.0eV), the solar energy (λ ＜ 387nm) of 3～5% can only be absorbed, utilization rate is low；(2)TiO2The light of nanotube
The recombination rate of raw electron hole pair is the highest, and photocatalytic activity is low.
For the problems referred to above, doping metals, nonmetal and semi-conductor nano particles and TiO by all means2Nanometer
Pipe array combines, to improve TiO2The PhotoelectrocatalytiPerformance Performance of nano-tube array becomes the focus of research at present.On the one hand, noble metal
Nano-particle is dispersed in TiO2Nanotube surface can assist to capture light induced electron, accelerates the separation of electron hole, and then suppression light
Raw electronics and hole-recombination.On the other hand, noble metal granule can improve TiO by surface resonance effect2The visible ray of nanotube
Absorbability.Compared to other precious metals ag, Cu etc., Pt is at detection glucose, hydrogen peroxide, degraded methanol, formic acid, methyl ester etc.
Aspect is applied, and 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.Additionally, Pt nano-particle has ion surface resonance effect
Should, it is carried on TiO2It is equally applicable on nanotube being strengthened by Raman, amplifies organic Raman signal, reach detection dirt
The effect of dye thing.
In recent years, multiple matrix (such as metal, glass, Organic substance etc.) is had good viscous because of it by poly-dopamine (PDA)
The features such as attached property and good biocompatibility and be widely used in biomaterial surface modify；Additionally, PDA utilizes going back of self
Originality can realize material surface electroless metallising.Appropriate dopamine is dissolved in buffer, under aerobic conditions, DOPA
It is deposited on the various substrate surfaces from inorganic (metal, metal-oxide) to organic (polymer), at base after amine oxidation auto polymerization
Material surface forms one layer of PDA coating with permanent Adhering capacity.Further investigation shows: the catechol group of dopamine and ammonia
Main Function plays in the adhesion process of poly-dopamine in base functional group.Utilize the catechol group can be expensive to gold, silver and platinum etc.
Heavy metallic salt shows reducing power, derives precious metal particles in poly-DOPA amine layer；Can with containing mercaptan, amino hydrophilic
Or hydrophobic organic molecules or polymer etc. occur Michael addition reaction and schiff base reaction, and functional Organic substance is introduced
To material surface, material surface is made to have special nature, such as: corrosion resistance, rub resistance, biological activity and biocompatibility etc.
Functional characteristic.With other surface modification method comparatively, PDA to modify this method of base material simple and convenient, and be modified base material
Geometry unrelated, and modify after surface there is good chemical reactivity.But, realize many by tradition infusion process
The course of reaction that bar amine oxidation autohemagglutination obtains poly-dopamine is the longest, and consumption is big and modification evenness of membranous layer is poor.Therefore, find
A kind of quicker, simple, economic method realizes the surface bionical poly-dopamine coating of modification and is particularly important.
Therefore, for the problems referred to above, it is necessary to propose further solution.
Summary of the invention
Present invention solves the technical problem that the preparation side being to provide a kind of Pt nanoparticle/Nano tube array of titanium dioxide
Method, to overcome the problems of the prior art.
The technical solution adopted for the present invention to solve the technical problems is:
The preparation method of Pt nanoparticle/Nano tube array of titanium dioxide, including:
On matrix, TiO is prepared by anodizing2Nano-tube array, then matrix is calcined；
Preparation dopamine solution is as electrolyte, and with above-mentioned matrix as working electrode, platinum electrode is as to electrode, silver electricity
Electrode and reference electrode, as reference electrode, by described working electrode, are put into described dopamine solution by pole or silver chloride electrode
In, electrochemical workstation utilize cyclic voltammetry obtain being loaded with the TiO of bionical poly-dopamine coating on the matrix2
Nano-tube array；
Preparation platinum acid chloride solution, by the TiO loading bionical poly-dopamine coating on above-mentioned matrix2Nano-tube array impregnates
After platinum acid chloride solution certain time, obtain Pt nanoparticle/Nano tube array of titanium dioxide.
Further: dopamine solution concentration is 0.2-0.8mg/ml, dopamine solution pH value is 6.5-8.0, circulation
The voltage range of voltammetry is enclosed at 15-35 in-1V to 1V, the scanning number of turns, and sweep speed is at 50-200mV/S.
Further: the concentration of described platinum acid chloride solution is 0.1-0.8mg/ml, the dioxy of bionical poly-dopamine is loaded
Changing titanium nano-tube array dip time in chloroplatinic acid is 1-5h, utilizes Induced by Dopamine reduction platinum in dipping process, above-mentioned
Reaction condition: 60-100 DEG C of water-bath vibration.
Present invention also offers electrode, described electrode is provided with Pt nanoparticle/titanium dioxide that above-mentioned preparation method prepares
Titanium nano-tube array.
Present invention also offers non-enzymatic glucose sensor, described non-enzymatic glucose sensor is provided with above-mentioned preparation method
Pt nanoparticle/the Nano tube array of titanium dioxide prepared.
Present invention also offers composite, described composite is provided with the platinum nanometer that above-mentioned preparation method prepares
Grain/Nano tube array of titanium dioxide.
The invention has the beneficial effects as follows: the present invention uses electropolymerization to load bionical poly-dopamine and realizes the method solution of reduction platinum
Determine the problem such as operation time-consumingly length, lack of homogeneity in dopamine tradition infusion process autohemagglutination.The present invention has simple process and easily grasps
Making, poly-dopamine film layer can control, and can control the advantage such as dispersion and size of Pt nanoparticle simultaneously.Pt nanoparticle is repaiied
On the one hand the Nano tube array of titanium dioxide of decorations can improve the photoelectric effect of Nano tube array of titanium dioxide；On the other hand two are improved
The catalytic capability of titania nanotube array, to reach methanol, formic acid, the electrochemical degradation of mercaptan and for making non-enzymatic
Glucose sensor.With pure TiO2Relatively, the TiO of supported platinum nano granule2Nano-tube array photoelectric properties significantly improve,
It is provided simultaneously with good chemical stability and reusing, can be by Pt nanoparticle/Nano tube array of titanium dioxide application
In aspects such as photocatalytic pollutant degradation, non-enzymatic glucose sensor, fuel cell and Raman enhancings, possesses precision height, stream
The superioritys such as journey is simple, fast, economical.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
In having technology to describe, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is only this
Some embodiments described in invention, for those of ordinary skill in the art, on the premise of not paying creative work,
Other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the schematic flow sheet of the preparation method of the Pt nanoparticle/Nano tube array of titanium dioxide of the present invention.
Fig. 2 is to use electropolymerization by poly-many in embodiment 1 in the Pt nanoparticle/Nano tube array of titanium dioxide of preparation
Bar amine coating modifying is to the cyclic voltammetry curve figure on titania nanotube.
The SEM figure of platinum/Nano tube array of titanium dioxide that Fig. 3-1 prepares for the present invention, four width are all front elevation.Wherein,
A (), (b), (c), (d) respectively dipping chloroplatinic acid concentration is the platinum of 0.1mg/ml, 0.2mg/ml, 0.4mg/ml, 0.8mg/ml
The SEM figure of nano-particle carried titanium dioxide nano-tube array.
The SEM figure of platinum/Nano tube array of titanium dioxide that Fig. 3-2 prepares for the present invention, four width are all chamfer map.Wherein,
A (), (b), (c), (d) respectively dipping chloroplatinic acid concentration is the platinum of 0.1mg/ml, 0.2mg/ml, 0.4mg/ml, 0.8mg/ml
The SEM figure of nano-particle carried titanium dioxide nano-tube array.
Fig. 4 is for tradition dipping autohemagglutination is legal and electrochemical polymerization method prepares poly-dopamine on Nano tube array of titanium dioxide
The SEM figure of supported platinum nano granule, in figure (a), the preparation method of platinum/Nano tube array of titanium dioxide is poly-many for tradition auto polymerization
Bar amine, in figure (b), the preparation method of platinum/Nano tube array of titanium dioxide is electrochemical polymerization method.
Fig. 5 is EDS and the Elemental redistribution collection of illustrative plates of the Pt nanoparticle/Nano tube array of titanium dioxide of preparation in embodiment 1；
Fig. 6 is the most modified TiO of the Pt nanoparticle/Nano tube array of titanium dioxide of preparation in embodiment 12Nanometer
The TiO that pipe array and Pt nanoparticle are modified2The XRD figure of nano-tube array.
Fig. 7 is TEM, HRTEM and the constituency electricity of the Pt nanoparticle/Nano tube array of titanium dioxide of preparation in embodiment 1
Sub-diffraction pattern.View (a), (b) are the TEM of Pt nanoparticle/Nano tube array of titanium dioxide, view (c) be Pt nanoparticle/
The HRTEM of Nano tube array of titanium dioxide, view (d) is the SEAD figure (SAED) of view (c).
Fig. 8 is the most modified TiO of the silver Nano granule/titanium dioxide nano-tube array of preparation in embodiment 22Nanometer
The TiO that pipe array and Pt nanoparticle are modified2The XPS figure of nano-tube array, wherein figure (a) is full spectrogram, and figure (b) is the narrow of platinum
Spectrogram.
Fig. 9 is TiO the most modified in embodiment 32The TiO that nano-tube array and variable concentrations Pt nanoparticle are modified2Receive
The uv absorption spectra of mitron array.
Figure 10 is TiO the most modified in embodiment 42The TiO that nano-tube array and variable concentrations Pt nanoparticle are modified2
The photocurrent response figure of nano-tube array.
Figure 11 is in embodiment 1 under having non-illuminated conditions, the most modified TiO2Nano-tube array and Pt nanoparticle
The TiO modified2The impedance spectrogram 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.Embed the partial enlarged drawing that figure is glucose oxidation curve.
Figure 13 is TiO the most modified in embodiment 22The TiO that nano-tube array and platinum are modified2Nano-tube array is to Fructus Vitis viniferae
The response staircase curve figure of sugar juice, embedding figure is the matched curve that electric current density changes with concentration of glucose.
Figure 14 is the TiO that in embodiment 2, platinum is modified2Ascorbic Acid when nano-tube array does non-enzymatic glucose sensor,
The interference effect staircase curve figure of uric acid etc..
Detailed description of the invention
For the technical scheme making those skilled in the art be more fully understood that in the present invention, real below in conjunction with the present invention
Execute the accompanying drawing in example, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described enforcement
Example is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under not making creative work premise, all should belong to present invention protection
Scope.
As it is shown in figure 1, be the flow process signal of the preparation method of the 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. matrix can be selected for titanium sheet, first to titanium sheet pretreatment.
Specifically, titanium sheet is carried out.Wherein, described titanium sheet is pure titanium or titanium alloy, its a size of 1.5cm ×
3.0cm.Use dust technology, acetone, ethanol and deionized water to titanium sheet ultrasonic cleaning 20-40min successively.
S2. anodizing prepares TiO2Nano-tube array.
Specifically, make as in the ethylene glycol solution of negative electrode, ammonium fluoride and water using the titanium sheet after cleaning as anode, platinized platinum
For electrolyte, applying certain voltage, carry out twice anodic oxidation, anodic oxidation prepares TiO2Nano-tube array, then calcine to obtain
Obtain crystal formation more preferable Detitanium-ore-type TiO2Nano-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
Concentration is 2.0-4.0v%.Carrying out anodised voltage for the first time is 40-60V, and the time is 1-3h, for the second time anodic oxidation
Voltage be 40-60V, the time is 3-10min.Prepared TiO2 nano-tube array is calcined in atmosphere, the temperature of calcining
Degree is for 400-500 DEG C, and the time of calcination is 1-3h, and the liter gentleness rate of temperature fall of calcining is 3-8 DEG C/min.By calcining,
To crystal formation more preferable Detitanium-ore-type TiO2Nano-tube array.
S3. use the method for electropolymerization at TiO2Bionical poly-dopamine coating is constructed on nanotube.
Specifically, preparation dopamine solution as electrolyte, the TiO that step S2 obtains2Nano-tube array makees working electrode,
Platinized platinum is made electrode, and reference electrode made by silver/silver chloride, utilizes electrochemical workstation scan cycle volt-ampere curve, is loaded with
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 at-1V-1V, the scanning number of turns is enclosed at 15-35, and sweep speed is at 50-200mV/S.To TiO2Nano-tube array enters
When row cleans, utilizing deionized water to be carried out, drying condition is 80 DEG C, 6h.
S4. based on poly-dopamine coating, utilize the reproducibility of himself, Pt nanoparticle is loaded in titania nanotube
Surface.
Specifically, the concentration of platinum acid chloride solution is 0.1-0.8mM, 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 use as electrode, can be used widely in non-enzymatic glucose sensor field.
The working electrode prepared is utilized to carry out the performance test of non-enzymatic glucose sensor.
Specifically, cyclical voltage is-1V-0.8V, and the scanning number of turns is enclosed at 5-15, and sweep speed is at 20-100mV/S.Oxidation
In curve, concentration of glucose is 0-0.05M, and in interference curve, glucose dropping concentration is 0-10mM, ascorbic acid and uric acid
Dropping concentration is 2mM.
Further, definition is by the TiO in step S42Nano-tube array immerses platinum acid chloride solution, and precursor chloroplatinic acid is molten
The concentration of liquid is 0.1-0.8mg/ml, it is illustrated that middle 0.1Pt/TiO2NTs represents that the concentration of precursor chloroplatinic acid is 0.1mg/ml,
0.2Pt/TiO2NTs represents that the concentration of precursor chloroplatinic acid is 0.2mg/ml, 0.4Pt/TiO2NTs represents precursor chloroplatinic acid
Concentration is 0.4mg/ml, 0.8Pt/TiO2NTs represents that the concentration of precursor chloroplatinic acid is 0.8mg/ml.
As shown in Fig. 3-1,3-2, for the SEM figure of Pt nanoparticle/Nano tube array of titanium dioxide that the present invention prepares.By
Figure understands, nanotube a length of 2-4 μm in Pt nanoparticle/Nano tube array of titanium dioxide, and nanotube caliber is 80-100nm, pipe
Wall thickness is 10-20nm.
Understandable for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from, below in conjunction with the accompanying drawings and embodiment
Further illustrate technical scheme.But the invention is not restricted to listed embodiment, also should be included in institute of the present invention
Other any known changes in the interest field required.
First, " embodiment " or " embodiment " referred to herein refers to may be included at least one realization side of the present invention
Special characteristic, structure or characteristic in formula.Different in this manual local " in one embodiment " occurred not refer both to
Same embodiment, is not single or the most mutually exclusive with other embodiments embodiment.
Secondly, the present invention utilizes structural representation etc. to be described in detail, when describing the embodiment of the present invention in detail, for ease of saying
Bright, schematic diagram can be disobeyed general ratio and be made partial enlargement, and described schematic diagram is example, and it should not limit the present invention at this
The scope of protection.
It addition, the letter abbreviation said in the present invention, being the fixing abbreviation in this area, wherein subalphbet literary composition 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: SEAD figure；EDS schemes: can spectrogram；XRD figure: X-ray diffractogram；XPS spectrum figure: x-ray photoelectron
Energy spectrum analysis spectrogram.
Embodiment 1
(1) pretreatment and the two-step electrochemical anodizing method of titanium sheet prepares TiO2Nano-tube array.To the pure dilute nitre of titanium sheet substrate
Acid, acetone, dehydrated alcohol, deionized water ultrasonic cleaning 15min successively.With platinum plate electrode as negative electrode, it is inserted simultaneously into containing 98v%
In ethylene glycol (ammonium fluoride 0.3wt%) and the electrolyte solution of 2v% water, apply 40V ultor oxidation 1.5h, ultrasonic come off
After film layer, continue to 40V ultor oxidation 8min, prepare TiO2Nano-tube array, then 450 DEG C of calcining 2h so that it is from nothing
Stabilized condition is transformed into anatase.
(2) method using the reduction of electropolymerization poly-Induced by Dopamine, prepares the dioxy titanium nanotube that Pt nanoparticle is compound
Array.The Tris of the 1.5mg/ml of preparation 50ml, regulates pH to 7.0, makes buffer, adds 0.1g dopamine hydrochloride, obtains
Dopamine solution, after solution is uniformly dispersed, by the TiO in step S22Nano-tube array is as working electrode, and platinized platinum is as to electricity
Pole, silver/silver chloride, as reference electrode, utilizes electrochemical workstation to make cyclic voltammetry scan curve, scanning voltage scope-1V-
1V, speed 80mV/S, the scanning number of turns is 15 circles, to TiO2Nano-tube array is carried out, dries, and obtains loading bionical poly-DOPA
The Nano tube array of titanium dioxide of amine.
(3) utilize Induced by Dopamine reduction noble metal platinum nano-particle, the platinum acid chloride solution of differently configured concentration, be respectively
0.1mg/ml, 0.2mg/ml, 0.3mg/ml and 0.4mg/ml, divide the titania nanotube loading poly-dopamine prepared
Not impregnated in the chloroplatinic acid of variable concentrations, condition is 60 DEG C of water-bath vibrations, and dip time is 2h, then takes out washing, is dried,
Obtain Pt nanoparticle/Nano tube array of titanium dioxide.
(5) Pt nanoparticle/Nano tube array of titanium dioxide prepared is made non-enzymatic glucose sensor application: configure
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, reference electrode made by silver/silver chloride, utilizes cyclic voltammetry curve detection glucose, the wherein Fructus Vitis viniferae of electrochemical workstation
Sugar adds concentration 5mM successively, and further, electrode performance interference detects, test prepare electrode Ascorbic Acid, uric acid dry
Immunity, wherein glucose adds concentration is 2-10mM, and it is 2mM that uric acid, ascorbic acid add concentration.
As in figure 2 it is shown, Fig. 2 is to use electropolymerization by the circulation in poly-dopamine coating modifying to titania nanotube
Volt-ampere curve figure, from the beginning of scanning the second circle, curve progressively tends towards stability.
As shown in Fig. 3-1,3-2, Fig. 3-1,3-2 are the Pt nanoparticle/titania nanotube battle array of preparation in embodiment 1
The SEM shape appearance figure 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, respectively tradition autohemagglutination is legal and electrochemical polymerization method obtains poly-dopamine coating for figure (a), (b),
And then obtain the SEM figure of platinum/Nano tube array of titanium dioxide.Wherein, two kinds of methods all use the hydrochloric acid listed in embodiment 1 many
The concentration of bar amine, all impregnated in the platinum acid chloride solution of same concentrations, and reaction condition is the most identical, wherein, uses tradition infusion process
The autohemagglutination time be 24h, use electrochemical polymerization method time be about 6 minutes.From SEM shape appearance figure, use electrochemistry
The load capacity of the Pt nanoparticle in platinum/Nano tube array of titanium dioxide prepared by infusion process is significantly greater than and uses tradition dipping certainly
Pt nanoparticle in platinum/Nano tube array of titanium dioxide prepared by polymerization, Pt nanoparticle dispersibility is more preferable simultaneously, and then
Illustrate that there is the most uniform poly-dopamine coating.Therefore it follows that use electropolymerization to load bionical poly-dopamine reduction platinum
The method of nano-particle, solves the problem such as operation time-consumingly length, lack of homogeneity in tradition infusion process autohemagglutination.
Fig. 5 is constituency EDS and the Elemental redistribution of the Pt nanoparticle/Nano tube array of titanium dioxide of preparation 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 up of anatase and Ti substrate, 25.3 °, 37.9 °, 48.0 °
With (101) of 53.9 ° of peak values occurred corresponding anatase respectively, (004), (200) and (105) crystal face (JCPDS no.21-
1272).At TiO2After nano-tube array deposition Pt nano-particle, occur in that peak value, (111) crystal face of corresponding Pt at 39.8 °
(JCPDS no.04-0802), thus, it is consistent with TEM result in Fig. 7.
As shown in Figure 7, TEM result further demonstrates that Pt nanoparticle is evenly distributed on TiO2Nanotube surface and inside,
Particle size is about 10nm；HRTEM and SAED figure shows TiO2Detitanium-ore-type (101) crystal face spacing of lattice is 0.352nm, Pt
(111) interplanar distance is 0.217nm, matches with the XRD test result of Fig. 6.
Fig. 8 is the TiO of unmodified2The full spectrum of the TiO2 nanotube that nanotube and platinum are modified and narrow spectrum, except O 1s
(532.4eV), Ti 2p (458.9eV) and C 1s (284.5eV) peak, the existence at Pt 4f (72.6eV) peak demonstrates what Pt modified
TiO2Nano-tube array.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 Pt0Existence
Further as shown in Fig. 9,10,11, Fig. 9 is the most modified TiO2Nano-tube array and variable concentrations are modified
The uv absorption spectra of platinum/Nano tube array of titanium dioxide；Figure 10 is the most modified TiO2Nano-tube array is with the denseest
The photoelectric current collection of illustrative plates of platinum/Nano tube array of titanium dioxide that degree is modified；Figure 11 is under having non-illuminated conditions, the most modified
TiO2Nano-tube array and platinum/Nano tube array of titanium dioxide AC impedance curve.
As shown in Figure 9, the most modified TiO2The absworption peak of nanotube is less than 390nm, after modifying Pt nano-particle, at 400-
At 700nm, absorption intensity increases, and absorptivity improves.
In Fig. 10, with the anhydrous sodium sulfate of 0.1M as electrolyte, xenon lamp (filters the wavelength of below 400nm) with optical filter
Simulated visible light, the distance of light source to beaker is 15cm, and intensity of illumination is 60mW/cm2, at CHI660D electrochemical workstation three
Test through row photoelectric current under electrode system.It is shown in the most modified TiO under visible-range2Nanotube and different deposited concentration
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, represent that TiO2 nano-tube array is modified after Pt nano-particle and improve electricity
The separation efficiency in sub-hole pair.
In fig. 11, with the anhydrous sodium sulfate of 0.1M as electrolyte, xenon lamp (filters the wavelength of below 400nm) with optical filter
Simulated visible light, the distance of light source to beaker is 15cm, and intensity of illumination is 60mW/cm2, at CHI660D electrochemical workstation three
Test through row photoelectric current under electrode system.It is illustrated as respectively under conditions of shining with or without visible ray, unmodified TiO2Nanotube battle array
Row and the ac impedance spectroscopy of platinum/Nano tube array of titanium dioxide, wherein, the arc diameter of high frequency region characterizes electron transmission mistake
Journey, diameter is the least, and resistance is the least.The resistance value of platinum/Nano tube array of titanium dioxide is significantly less than the titanium dioxide of unmodified and receives
The resistance value of mitron array；Under visible light illumination, the array of platinum/titania nanotube substantially diminishes, and shows more excellent
Photoelectric properties more.
In fig. 12, with 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 about-0.8V is that electrode surface adsorbs glucose
Electrochemical oxidation, the peak of about-0.4V is the entering of intermediate produced in electrode surface absorption glucose electrochemical oxidation process
Oxidation step.The peak of about 0.2V be solution body mutually in glucose diffuse on electrode, carry out direct oxidation and cause.Along with
The continuous increase of concentration of glucose, peak value is also gradually increased.
Figure 13 is glucose responding staircase curve, and embedding figure is that the linear fit that electric current density changes with concentration of glucose is bent
Line, equation is y=0.01518x+0.7326, R2=0.9765.
Figure 14 is that electrode interference of Ascorbic Acid, uric acid etc. during detection glucose is investigated, wherein glucose
Contributive rate to electric current density is 100%, and ascorbic acid is about 4% to the contributive rate of electric current density, and uric acid is to electric current density
Contributive rate be about 0.3%.
Embodiment 2
(1) pretreatment and the two-step electrochemical anodizing method of titanium sheet prepares TiO2Nano-tube array.To the pure dilute nitre of titanium sheet substrate
Acid, acetone, dehydrated alcohol, deionized water ultrasonic cleaning 10min successively.With platinum plate electrode as negative electrode, it is inserted simultaneously into containing 97v%
In ethylene glycol (ammonium fluoride 0.4wt%) and the electrolyte solution of 3v% water, apply 50V ultor oxidation 2h, ultrasonic dezidua
After Ceng, continue to 50V ultor oxidation 6min, prepare TiO2Nano-tube array, then 450 DEG C of calcining 1.5h so that it is from nothing
Stabilized condition is transformed into anatase.
(2) method using the reduction of electropolymerization poly-Induced by Dopamine, prepares the dioxy titanium nanotube that Pt nanoparticle is compound
Array.The Tris of the 1.2mg/ml of preparation 50ml, regulates pH to 7.5, makes buffer, adds 0.2g dopamine hydrochloride, obtains
Dopamine solution, after solution is uniformly dispersed, by the TiO in step S22Nano-tube array is as working electrode, and platinized platinum is as to electricity
Pole, silver/silver chloride, as reference electrode, utilizes electrochemical workstation to make cyclic voltammetry scan curve, scanning voltage scope-1～
1V, speed 100mV/S, the scanning number of turns is 20 circles, to TiO2Nano-tube array is carried out, dries, and obtains loading bionical poly-many
The Nano tube array of titanium dioxide of bar amine.
(3) Induced by Dopamine reduction noble metal platinum, the platinum acid chloride solution of differently configured concentration, respectively 0.05mg/ are utilized
Ml, 0.1mg/ml, 0.2mg/ml and 0.4mg/ml, impregnate respectively by the titania nanotube loading poly-dopamine prepared
In the chloroplatinic acid of variable concentrations, condition is 70 DEG C of water-bath vibrations, and dip time is 3h, then takes out washing, is dried, obtains platinum
Nano granule/titanium dioxide nano-tube array.
(5) Pt nanoparticle/Nano tube array of titanium dioxide prepared is made non-enzymatic glucose sensor application: configure
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, reference electrode made by silver/silver chloride, utilizes cyclic voltammetry curve detection glucose, the wherein Fructus Vitis viniferae of electrochemical workstation
Sugar adds concentration 10mM successively, further, electrode performance interference detects, and electrode Ascorbic Acid, uric acid are prepared in test
Interference, wherein glucose adds concentration is 5-10mM, and it is 5mM that uric acid, ascorbic acid add concentration.
Embodiment 3
(1) pretreatment and the two-step electrochemical anodizing method of titanium sheet prepares TiO2Nano-tube array.To the pure dilute nitre of titanium sheet substrate
Acid, acetone, dehydrated alcohol, deionized water ultrasonic cleaning 25min successively.With platinum plate electrode as negative electrode, it is inserted simultaneously into containing 99v%
In ethylene glycol (ammonium fluoride 0.1wt%) and the electrolyte solution of 1v% water, apply 60V ultor oxidation 1h, ultrasonic dezidua
After Ceng, continue to 60V ultor oxidation 5min, prepare TiO2Nano-tube array, then 450 DEG C of calcining 1h so that it is from without fixed
Type state is transformed into anatase.
(2) method using the reduction of electropolymerization poly-Induced by Dopamine, prepares the dioxy titanium nanotube that Pt nanoparticle is compound
Array.The Tris of the 1.0mg/ml of preparation 50ml, regulates pH to 7.5, makes buffer, adds 0.3g dopamine hydrochloride, obtains
Dopamine solution, after solution is uniformly dispersed, by the TiO in step S22Nano-tube array is as working electrode, and platinized platinum is as to electricity
Pole, silver/silver chloride, as reference electrode, utilizes electrochemical workstation to make cyclic voltammetry scan curve, scanning voltage scope-1～
1V, speed 150mV/S, the scanning number of turns is 25 circles, to TiO2Nano-tube array is carried out, dries, and obtains loading bionical poly-many
The Nano tube array of titanium dioxide of bar amine.
(3) Induced by Dopamine reduction noble metal platinum, the platinum acid chloride solution of differently configured concentration, respectively 0.1mg/ are utilized
Ml, 0.2mg/ml, 0.4mg/ml and 0.8mg/ml, impregnate respectively by the titania nanotube loading poly-dopamine prepared
In the chloroplatinic acid of variable concentrations, condition is 80 DEG C of water-bath vibrations, and dip time is 2.5h, then takes out washing, is dried, obtains
Pt nanoparticle/Nano tube array of titanium dioxide.
(5) Pt nanoparticle/Nano tube array of titanium dioxide prepared is made non-enzymatic glucose sensor application: configure
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, reference electrode made by silver/silver chloride, utilizes cyclic voltammetry curve detection glucose, the wherein Fructus Vitis viniferae of electrochemical workstation
Sugar adds concentration 3mM successively, and further, electrode performance interference detects, test prepare electrode Ascorbic Acid, uric acid dry
Immunity, wherein glucose adds concentration is 1-5mM, and it is 1mM that uric acid, ascorbic acid add concentration.
Embodiment 4
(1) pretreatment and the two-step electrochemical anodizing method of titanium sheet prepares TiO2Nano-tube array.To the pure dilute nitre of titanium sheet substrate
Acid, acetone, dehydrated alcohol, deionized water ultrasonic cleaning 15min successively.With platinum plate electrode as negative electrode, it is inserted simultaneously into containing 98v%
In ethylene glycol (ammonium fluoride 0.3wt%) and the electrolyte solution of 2v% water, apply 50V ultor oxidation 2.5h, ultrasonic come off
After film layer, continue to 50V ultor oxidation 10min, prepare TiO2Nano-tube array, then 450 DEG C of calcining 2h so that it is from nothing
Stabilized condition is transformed into anatase.
(2) method using the reduction of electropolymerization poly-Induced by Dopamine, prepares the dioxy titanium nanotube that Pt nanoparticle is compound
Array.The Tris of the 1.2mg/ml of preparation 50ml, regulates pH to 7.0, makes buffer, adds 0.4g dopamine hydrochloride, obtains
Dopamine solution, after solution is uniformly dispersed, by the TiO in step S22Nano-tube array is as working electrode, and platinized platinum is as to electricity
Pole, silver/silver chloride, as reference electrode, utilizes electrochemical workstation to make cyclic voltammetry scan curve, scanning voltage scope-1V-
1V, speed 50mV/S, the scanning number of turns is 20 circles, to TiO2Nano-tube array is carried out, dries, and obtains loading bionical poly-DOPA
The Nano tube array of titanium dioxide of amine.
(3) Induced by Dopamine reduction noble metal platinum, the platinum acid chloride solution of differently configured concentration, respectively 0.1mg/ are utilized
Ml, 0.2mg/ml, 0.3mg/ml and 0.4mg/ml, impregnate respectively by the titania nanotube loading poly-dopamine prepared
In the chloroplatinic acid of variable concentrations, condition is 90 DEG C of water-bath vibrations, and dip time is 2h, then takes out washing, is dried, obtains platinum
Nano granule/titanium dioxide nano-tube array.
(5) Pt nanoparticle/Nano tube array of titanium dioxide prepared is made non-enzymatic glucose sensor application: configure
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, reference electrode made by silver/silver chloride, utilizes cyclic voltammetry curve detection glucose, the wherein Fructus Vitis viniferae of electrochemical workstation
Sugar adds concentration 4mM successively, and further, electrode performance interference detects, test prepare electrode Ascorbic Acid, uric acid dry
Immunity, wherein glucose adds concentration is 2-10mM, and it is 2mM that uric acid, ascorbic acid add concentration.
Compared with prior art, the invention has the beneficial effects as follows: the Pt nanoparticle of the present invention/titania nanotube battle array
Arrange and use electropolymerization to load the method that bionical poly-dopamine realizes reduction Pt nanoparticle, solve dopamine tradition infusion process certainly
The problems such as poly-middle operation time-consumingly length, lack of homogeneity, having simple process easily operates, and poly-dopamine film layer can control, and controls simultaneously
The advantages such as the dispersion of Pt nanoparticle and size.The TiO that Pt nanoparticle is modified2On the one hand nano-tube array can improve
TiO2The photoelectric effect of nano-tube array；On the other hand TiO is improved2The catalytic capability of nano-tube array, to reach methanol, first
Acid, the electrochemical degradation of mercaptan and be used for making non-enzymatic glucose sensor.With pure TiO2Relatively, 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
The aspects such as battery and Raman enhancing, possess the superioritys such as high, simple, the fast, economical of flow process of precision.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of the spirit or essential attributes of the present invention, it is possible to realize the present invention in other specific forms.Therefore, no matter
From the point of view of which point, all should regard embodiment as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all by fall in the implication of equivalency and scope of claim
Change is included in the present invention.Should not be considered as limiting involved claim by any reference in claim.
Although moreover, it will be appreciated that this specification is been described by according to embodiment, but the most each embodiment only wraps
Containing an independent technical scheme, this narrating mode of description is only that for clarity sake those skilled in the art should
Description can also be formed those skilled in the art through appropriately combined as an entirety, the technical scheme in each embodiment
May be appreciated other embodiments.
Claims (6)
1. the preparation method of Pt nanoparticle/Nano tube array of titanium dioxide, it is characterised in that including:
On matrix, TiO is prepared by anodizing2Nano-tube array, then matrix is calcined；
Preparation dopamine solution is as electrolyte, with above-mentioned matrix as working electrode, platinum electrode as to electrode, silver electrode or
Electrode and reference electrode, as reference electrode, by described working electrode, are put in described dopamine solution by silver chloride electrode,
Cyclic voltammetry is utilized to obtain being loaded with the TiO of bionical poly-dopamine coating on the matrix on electrochemical workstation2Nanometer
Pipe array；
Preparation platinum acid chloride solution, by the TiO loading bionical poly-dopamine coating on above-mentioned matrix2Nano-tube array impregnated in chlorine
After platinic acid solution certain time, obtain Pt nanoparticle/Nano tube array of titanium dioxide.
The preparation method of Pt nanoparticle/Nano tube array of titanium dioxide the most according to claim 1, it is characterised in that:
Dopamine solution concentration is 0.2-0.8mg/ml, and dopamine solution pH value is 6.5-8.0, the voltage range of cyclic voltammetry
At-1V to 1V, the scanning number of turns is enclosed at 15-35, and sweep speed is at 50-200mV/S.
The preparation method of Pt nanoparticle/Nano tube array of titanium dioxide the most according to claim 1, it is characterised in that:
The concentration of described platinum acid chloride solution is 0.1-0.8mg/ml, and the Nano tube array of titanium dioxide loading bionical poly-dopamine exists
Dip time in chloroplatinic acid is 1-5 hour, utilizes Induced by Dopamine reduction platinum, above-mentioned reaction condition: 60-in dipping process
100 DEG C of water-bath vibrations.
4. electrode, it is characterised in that: described electrode is provided with the platinum nanometer prepared by the preparation method of claim 1,2 or 3
Grain/Nano tube array of titanium dioxide.
5. non-enzymatic glucose sensor, it is characterised in that: described non-enzymatic glucose sensor is provided with by claim 1,2 or 3
Preparation method prepare Pt nanoparticle/Nano tube array of titanium dioxide.
6. composite, it is characterised in that: described composite be provided with by the preparation method of claim 1,2 or 3 prepare
Pt nanoparticle/Nano tube array of titanium dioxide.
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| CN111990994A (en) * | 2020-09-02 | 2020-11-27 | 天津理工大学 | EEG flexible dry electrode and preparation method and application 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 |
| CN113846342A (en) * | 2021-10-13 | 2021-12-28 | 浙江工业大学 | Inorganic-organic core-shell framework loaded low-dose noble metal palladium material, preparation thereof and application thereof in electrocatalytic dechlorination and hydrogenation reaction |
| 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 |
| CN114182263A (en) * | 2021-11-01 | 2022-03-15 | 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 |
| CN114887862A (en) * | 2022-05-10 | 2022-08-12 | 华南农业大学 | nanoparticle-hPDA-TDNT material and preparation method and application thereof |
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| Publication number | Publication date |
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| WO2017219608A1 (en) | 2017-12-28 |
| CN106167912B (en) | 2018-07-17 |
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