CN102507681A - Surface functional double-heterostructural material for titanium dioxide nanobelt and application thereof - Google Patents
Surface functional double-heterostructural material for titanium dioxide nanobelt and application thereof Download PDFInfo
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- CN102507681A CN102507681A CN2011103238164A CN201110323816A CN102507681A CN 102507681 A CN102507681 A CN 102507681A CN 2011103238164 A CN2011103238164 A CN 2011103238164A CN 201110323816 A CN201110323816 A CN 201110323816A CN 102507681 A CN102507681 A CN 102507681A
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Abstract
The invention discloses a surface functional double-heterostructural material for a titanium dioxide nanobelt. A monocrystal titanate nanobelt and a commercialized precious metal chlorine complex or a metal nitrate are added into ethyl alcohol to be evenly dispersed, then, a dispersion is subjected to heating, decomposition and corrosion in a muffle furnace under normal pressure, and a double-heterostructural material which contains nanoparticles of titanium dioxide and nanoparticles of precious metal or precious metal oxide is one-step formed on the surface of a product, i.e. the titanium dioxide nanobelt, namely, the surface functional double-heterostructural material for the titanium dioxide nanobelt is formed. The invention further discloses the application of the surface functional double-heterostructural material for the titanium dioxide nanobelt to the preparation of an electrochemical sensing electrode. Proved by experiments, the prepared electrochemical sensing electrode has the characteristics of fastness in load transfer, excellent sensing performance, easiness for functional modification and the like and has good application prospects in the aspects of electrochemical biosensing detection.
Description
Technical field
The invention belongs to microelectronics biosensor technique field, relate in particular to the surface-functionalized double-heterostructure material of a kind of titanium dioxide nano-belts and in chemically modified electrode that electrochemica biological detects or the application in the biological sensor electrode preparation.
Background technology
The electrochemica biological sensing detection is the focus of current concern, also is the key areas that electro-chemical test is used.But biomolecule such as protein (amino acid), nucleic acid (DNA/RNA) and carbohydrate (glucose) etc. all are organic molecules, and electric conductivity is very poor; And very easily be adsorbed on electrode surface (incrustation), the sensitivity of biomolecule test system is reduced, even cause electrochemica biological sensor to lose efficacy.
Because having big surface area, unique physical characteristics, sensitive sensing characteristics, monodimension nanometer material, particularly oxidate nano band make it demonstrate tempting application prospect at aspects such as numerous areas such as catalysis, sensor, galvanochemistry.Compare with nano wire with nano particle; Because nano belt can reach sub-micron and micron-scale at width and thickness direction; Make the may observe and the navigability of nano belt can be far longer than nano particle and nano wire, so some are that the senser element of construction material arises at the historic moment with the nano belt.The maximum nano belt of research is a zinc oxide nano-belt at present, and the various sensors that utilize zinc oxide nano-belt to make have demonstrated good characteristic.Yet zinc oxide nano-belt has a fatal weakness, is exactly that it is acid even very high dissolubility is all arranged in water, in air, also can absorb the variation of moisture generation shape and character.The strong effect of zinc paste and water makes the practicality of its device be very limited.So research will become the research direction of nano belt device as the nano-device of basic material with the titanium dioxide nano-belts of ambient stable.Although titanium dioxide nano-belts has good photoelectricity, air-sensitive, catalysis, photovoltaic property and environmental stability,, be difficult to obtain higher performance because the signal of output is too little.Through retrieval, the surface-functionalized double-heterostructure material of exploitation titanium dioxide nano-belts does not also appear in the newspapers at the chemically modified electrode of electrochemica biological detection or the application in the biological sensor electrode preparation.
Summary of the invention
To the deficiency of prior art, the present invention proposes the surface-functionalized double-heterostructure material of a kind of titanium dioxide nano-belts and detect the application in the sensing electrode preparation at electrochemica biological.
The surface-functionalized double-heterostructure material of titanium dioxide nano-belts of the present invention; It is characterized in that; Said material is made by following method: is to mix in 12: 1～15: 1 monocrystalline metatitanic acid nano belt and commercialization noble metal chlorine complex or commercialization metal nitrate by mass ratio; Add then in the absolute ethyl alcohol of submergence amount and evenly disperse; Again in the normal pressure underlying muffle furnace with 200～500 ℃ of heated at constant temperature 1～3h, a step forms the surface-functionalized double-heterostructure material of titanium dioxide nano-belts, promptly forms the double-heterostructure material that contains titania nanoparticles and noble metal or metal oxide containing precious metals nano particle.
In the surface-functionalized double-heterostructure material of above-mentioned titanium dioxide nano-belts, said monocrystalline metatitanic acid nano belt is meant that with commerical grade P-25 be raw material, and 10M NaOH solution is the solvent of reaction, adopts the synthetic metatitanic acid (H of hydro-thermal method
2Ti
3O
7) nano belt, concrete preparation method is referring to 200710017081.6 1 kinds of titanium dioxide nano papers of patent and preparation method thereof.
In the surface-functionalized double-heterostructure material of above-mentioned titanium dioxide nano-belts, said commercialization noble metal chlorine complex is meant gold chloride, chloroplatinic acid or chloro-iridic acid; Said commercialization metal nitrate is meant nickel nitrate, bismuth nitrate, indium nitrate or nitric acid tin.
Further, the preferred gold chloride of said commercialization noble metal chlorine complex; Preferred nickel nitrate of said commercialization metal nitrate or bismuth nitrate.
In the surface-functionalized double-heterostructure material of above-mentioned titanium dioxide nano-belts, preferred 500 ℃ of the temperature of said heated at constant temperature; Preferred 1-2h of the time of heated at constant temperature.
The application of the surface-functionalized double-heterostructure material of titanium dioxide nano-belts according to the invention in preparation electrochemical sensing electrode.
Wherein, The said method for preparing the electrochemical sensing electrode is: with the consumption of following unit ratio; The surface-functionalized double-heterostructure material of 0.5～1mg titanium dioxide nano-belts is dispersed in 1.3～3mL absolute ethyl alcohol; Take out the even mixed solution of 3～6 μ L then as active sensing material, drop on the basal electrode that scribbles cementing agent, make the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of titanium dioxide nano-belts is modified; Wherein said cementing agent is 1wt% naphthols, conduction carbon paste or 10wt% teflon; Said basal electrode is meant platinum electrode, glass-carbon electrode or graphite electrode.
Further, the preferred 1wt% naphthols of above-mentioned cementing agent; Preferred platinum electrode of said basal electrode or graphite electrode.
The application of electrochemical sensing electrode in the electrochemica biological sensing detection of the surface-functionalized double-heterostructure material preparation of titanium dioxide nano-belts according to the invention.
Wherein, the electrochemical sensing electrode of using the surface-functionalized double-heterostructure material preparation of titanium dioxide nano-belts according to the invention is implemented biomolecule is carried out sensing detection in the simulated body fluid phosphate buffer solution (PBS) of pH=7.4.
The present invention mixes monocrystalline metatitanic acid nano belt with commercialization noble metal chlorine complex or commercialization metal nitrate; Disperse with absolute ethyl alcohol then; Heat in the normal pressure underlying muffle furnace again; In the heating process, monocrystalline metatitanic acid nano belt resolves into titanium dioxide nano-belts, and noble metal chlorine complex or metal nitrate resolve into metal simple-substance or metal oxide nanoparticles; The steam and corrosive gas such as the hydrogen chloride that generate in the decomposable process simultaneously; Potpourris such as nitrogen dioxide make the surface corrosion of monocrystalline metatitanic acid nano belt form titania nanoparticles, form the double-heterostructure material that contains titania nanoparticles and noble metal or metal oxide containing precious metals nano particle, and promptly a step forms the surface-functionalized double-heterostructure material of titanium dioxide nano-belts.
Can regulate its band structure at titanium dioxide nano-belts surface-assembled heterojunction structure; Produce the quantum coupling effect; Improve the interfacial charge transferring power, double-heterostructure can also further increase titanium dioxide nano-belts specific surface area and (110) active crystal face except that above-mentioned advantage; For external functional group provides more how active connection site, help improving the titanium dioxide nano-belts surfactivity and improve its function application.The sensitive material that the special semiconductor oxygenatedchemicals of burning compound is light, electricity, gas, ion even protein and enzyme, the titanium dioxide nano-belts of surface-functionalized double-heterostructure represent excellent performance at aspects such as opto-electronic conversion, environment measuring, biology sensors; The electric conductivity that metal simple-substance is good helps accelerating semiconductor-metal-biomolecule interface electron transport dynamics, the sensitivity that helps improving sensing electrode; In addition,, can utilize different organic molecule such as amido, hydroxyl, carboxyl to connect, process various modification function nano belt electrode sensing material because there are abundant hydroxyl and metallic ion in these nano belt surfaces.
To sum up, the application in surface-functionalized double-heterostructure material of the titanium dioxide nano-belts that the present invention relates to and the electrochemica biological sensing modified electrode thereof has following characteristics: (1) is responsive to biomolecule such as nucleic acid, protein and enzymes.(2) electrode is easy to functional modification.(3) the electrode load transfer is rapid, and is highly sensitive.
Description of drawings
The different nano belt microphotos of Fig. 1, wherein the single heterojunction titanium dioxide nano-belts of (a) acid corrosion; (b) gold/titania double heterojunction nano belt.
The different nano belt sensing electrodes of Fig. 2 volt-ampere scanning curve, wherein (a) blank solution in containing the pH=7.4 simulated body fluid phosphate buffer solution of adenine phosphoric acid (0.08mM); (b) gold/titania double heterojunction nano belt; (c) the single heterojunction titanium dioxide nano-belts of acid corrosion.
The different nano belt sensing electrodes of Fig. 3 volt-ampere scanning curve, wherein (a) blank solution in containing the pH=7.4 simulated body fluid phosphate buffer solution of O-6-benzyl guanine (0.08mM); (b) gold/titania double heterojunction nano belt; (c) the single heterojunction titanium dioxide nano-belts of acid corrosion.
Embodiment
Below in conjunction with instance the present invention is further specified, but the present invention protects content to be not limited only to this.
Embodiment 1:
0.1g after evenly disperseing in monocrystalline metatitanic acid nano belt and the 1.8mL0.01M commercialization chlorauric acid solution adding ethanol; Under normal pressure; 500 ℃ of heated at constant temperature 1h in the muffle furnace form the surface-functionalized double-heterostructure material of gold/titanium dioxide nano-belts (shown in accompanying drawing 1b).
The surface-functionalized double-heterostructure material of 0.5mg gold/titanium dioxide nano-belts is dispersed in the 1.3mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 3 μ L then, drop on the glass-carbon electrode that scribbles the 1wt% naphthols; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of gold/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, result such as accompanying drawing 2 with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, gold/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Above-mentioned monocrystalline metatitanic acid nano belt is meant that with commerical grade P-25 be raw material, and 10M NaOH solution is the solvent of reaction, adopts the synthetic metatitanic acid (H of hydro-thermal method
2Ti
3O
7) nano belt, concrete preparation method is referring to 200710017081.6 1 kinds of titanium dioxide nano papers of patent and preparation method thereof.
Embodiment 2:
0.1g after evenly disperseing in monocrystalline metatitanic acid nano belt and the 2mL0.01M commercialization chlorauric acid solution adding ethanol; Under normal pressure; 500 ℃ of heated at constant temperature 2h in the muffle furnace form the surface-functionalized double-heterostructure material of gold/titanium dioxide nano-belts (shown in the similar accompanying drawing 1b).
The surface-functionalized double-heterostructure material of 0.8mg gold/titanium dioxide nano-belts is dispersed in the 2mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 4 μ L then, drop on the platinum electrode that scribbles the conduction carbon paste; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of gold/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, gold/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 3:
0.1g after evenly disperseing in monocrystalline metatitanic acid nano belt and the 1.6mL0.01M commercialization chlorauric acid solution adding ethanol; Under normal pressure; 300 ℃ of heated at constant temperature 2h in the muffle furnace form the surface-functionalized double-heterostructure material of gold/titanium dioxide nano-belts (shown in the similar accompanying drawing 1b).
The surface-functionalized double-heterostructure material of 1mg gold/titanium dioxide nano-belts is dispersed in the 3mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 6 μ L then, drop on the graphite electrode that scribbles the 10wt% teflon; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of gold/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, gold/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 4:
0.1g after evenly disperseing in monocrystalline metatitanic acid nano belt and the 22mg37wt% commercialization platinum acid chloride solution adding ethanol, under normal pressure, 200 ℃ of heated at constant temperature 3h in the muffle furnace form the surface-functionalized double-heterostructure material of platinum/titanium dioxide nano-belts.
The surface-functionalized double-heterostructure material of 0.5mg platinum/titanium dioxide nano-belts is dispersed in the 1.3mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 3 μ L then, drop on the glass-carbon electrode that scribbles the 10wt% teflon; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of platinum/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, platinum/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 5:
0.1g after evenly disperseing in monocrystalline metatitanic acid nano belt and the 20mg37wt% commercialization platinum acid chloride solution adding ethanol, under normal pressure, 400 ℃ of heated at constant temperature 2h in the muffle furnace form the surface-functionalized double-heterostructure material of platinum/titanium dioxide nano-belts.
The surface-functionalized double-heterostructure material of 0.8mg platinum/titanium dioxide nano-belts is dispersed in the 2mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 4 μ L then, drop on the platinum electrode that scribbles the conduction carbon paste; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of platinum/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, platinum/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 6:
0.1g after evenly disperseing in monocrystalline metatitanic acid nano belt and the 18mg37wt% commercialization platinum acid chloride solution adding ethanol, under normal pressure, 500 ℃ of heated at constant temperature 1h in the muffle furnace form the surface-functionalized double-heterostructure material of platinum/titanium dioxide nano-belts.
The surface-functionalized double-heterostructure material of 1mg platinum/titanium dioxide nano-belts is dispersed in the 3mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 6 μ L then, drop on the graphite electrode that scribbles the 1wt% naphthols; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of platinum/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, platinum/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 7:
0.1g after evenly disperseing in monocrystalline metatitanic acid nano belt and the 23.8mg35wt% commercialization chloro-iridic acid adding ethanol, under normal pressure, 500 ℃ of heated at constant temperature 3h in the muffle furnace form the surface-functionalized double-heterostructure material of iridium/titanium dioxide nano-belts.
The surface-functionalized double-heterostructure material of 0.5mg iridium/titanium dioxide nano-belts is dispersed in the 1.3mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 3 μ L then, drop on the glass-carbon electrode that scribbles the 1wt% naphthols; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of iridium/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, iridium/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 8:
0.1g after evenly disperseing in monocrystalline metatitanic acid nano belt and the 20mg35wt% commercialization chloro-iridic acid adding ethanol, under normal pressure, 500 ℃ of heated at constant temperature 2h in the muffle furnace form the surface-functionalized double-heterostructure material of iridium/titanium dioxide nano-belts.
The surface-functionalized double-heterostructure material of 0.8mg iridium/titanium dioxide nano-belts is dispersed in the 2mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 4 μ L then, drop on the platinum electrode that scribbles the conduction carbon paste; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of iridium/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, iridium/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 9:
0.1g after evenly disperseing in monocrystalline metatitanic acid nano belt and the 19mg35wt% commercialization chloro-iridic acid adding ethanol; Under normal pressure; 500 ℃ of heated at constant temperature 1h in the muffle furnace form the surface-functionalized double-heterostructure material of iridium/titanium dioxide nano-belts (shown in the similar accompanying drawing 1b of pattern).
The surface-functionalized double-heterostructure material of 1mg iridium/titanium dioxide nano-belts is dispersed in the 3mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 6 μ L then, drop on the graphite electrode that scribbles the 10wt% teflon; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of iridium/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, iridium/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 10:
0.1g after evenly disperseing in monocrystalline metatitanic acid nano belt and the 8.3mg commercialization nickel nitrate adding ethanol, under normal pressure, 500 ℃ of heated at constant temperature 3h in the muffle furnace form the surface-functionalized double-heterostructure material of nickel oxide/titanium dioxide nano-belts.
The surface-functionalized double-heterostructure material of 0.5mg nickel oxide/titanium dioxide nano-belts is dispersed in the 1.3mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 3 μ L then, drop on the glass-carbon electrode that scribbles the 10wt% teflon; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of nickel oxide/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, oxidation nickel/titanium dioxide double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 11:
0.1g after evenly disperseing in monocrystalline metatitanic acid nano belt and the 7mg commercialization nickel nitrate adding ethanol; Under normal pressure; 500 ℃ of heated at constant temperature 2h in the muffle furnace form the surface-functionalized double-heterostructure material of nickel oxide/titanium dioxide nano-belts (shown in the similar accompanying drawing 1b of pattern).
The surface-functionalized double-heterostructure material of 0.8mg nickel oxide/titanium dioxide nano-belts is dispersed in the 2mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 4 μ L then, drop on the platinum electrode that scribbles the conduction carbon paste; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of nickel oxide/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Fig. 3; Compare with titania single heterojunction nanometer band electrode, oxidation nickel/titanium dioxide double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 12:
0.1g after evenly disperseing in the monocrystalline metatitanic acid nano belt of Hydrothermal Preparation and the 6.6mg commercialization nickel nitrate adding ethanol; Under normal pressure; 500 ℃ of heated at constant temperature 1h in the muffle furnace form the surface-functionalized double-heterostructure material of nickel oxide/titanium dioxide nano-belts (shown in the similar accompanying drawing 1b of pattern).
The surface-functionalized double-heterostructure material of 1mg nickel oxide/titanium dioxide nano-belts is dispersed in the 3mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 6 μ L then, drop on the graphite electrode that scribbles the 1wt% naphthols; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of nickel oxide/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, oxidation nickel/titanium dioxide double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 13:
0.1g after evenly disperseing in the monocrystalline metatitanic acid nano belt of Hydrothermal Preparation and the 8.3mg commercialization metal bismuth nitrate adding ethanol; Under normal pressure; 300 ℃ of heated at constant temperature 3h in the muffle furnace form the surface-functionalized double-heterostructure material of bismuth oxide/titanium dioxide nano-belts.
The surface-functionalized double-heterostructure material of 0.5mg bismuth oxide/titanium dioxide nano-belts is dispersed in the 1.3mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 3 μ L then, drop on the glass-carbon electrode that scribbles the 1wt% naphthols; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of bismuth oxide/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, bismuth oxide/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 14:
0.1g after evenly disperseing in the monocrystalline metatitanic acid nano belt of Hydrothermal Preparation and the 7mg commercialization metal bismuth nitrate adding ethanol; Under normal pressure; 500 ℃ of heated at constant temperature 2h in the muffle furnace form the surface-functionalized double-heterostructure material of bismuth oxide/titanium dioxide nano-belts (shown in the similar accompanying drawing 1b of pattern).
The surface-functionalized double-heterostructure material of 0.8mg bismuth oxide/titanium dioxide nano-belts is dispersed in the 2mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 4 μ L then, drop on the platinum electrode that scribbles the conduction carbon paste; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of bismuth oxide/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, bismuth oxide/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 15:
0.1g after evenly disperseing in the monocrystalline metatitanic acid nano belt of Hydrothermal Preparation and the 6.6mg commercialization metal bismuth nitrate adding ethanol; Under normal pressure; 500 ℃ of heated at constant temperature 1h in the muffle furnace form the surface-functionalized double-heterostructure material of bismuth oxide/titanium dioxide nano-belts (shown in the similar accompanying drawing 1b of pattern).
The surface-functionalized double-heterostructure material of 1mg bismuth oxide/titanium dioxide nano-belts is dispersed in the 3mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 6 μ L then, drop on the graphite electrode that scribbles the 10wt% teflon; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of bismuth oxide/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, bismuth oxide/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 16:
0.1g after evenly disperseing in the monocrystalline metatitanic acid nano belt of Hydrothermal Preparation and the 8.3mg commercialization metal indium nitrate adding ethanol; Under normal pressure; 200 ℃ of heated at constant temperature 3h in the muffle furnace form the surface-functionalized double-heterostructure material of indium sesquioxide/titanium dioxide nano-belts.
The surface-functionalized double-heterostructure material of 0.5mg indium sesquioxide/titanium dioxide nano-belts is dispersed in the 1.3mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 3 μ L then, drop on the glass-carbon electrode that scribbles the 10wt% teflon; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of indium sesquioxide/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, indium sesquioxide/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 17:
0.1g after evenly disperseing in the monocrystalline metatitanic acid nano belt of Hydrothermal Preparation and the 7mg commercialization metal indium nitrate adding ethanol; Under normal pressure; 500 ℃ of heated at constant temperature 2h in the muffle furnace form the surface-functionalized double-heterostructure material of indium sesquioxide/titanium dioxide nano-belts (shown in the similar accompanying drawing 1b of pattern).
The surface-functionalized double-heterostructure material of 0.8mg indium sesquioxide/titanium dioxide nano-belts is dispersed in the 2mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 4 μ L then, drop on the platinum electrode that scribbles the conduction carbon paste; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of indium sesquioxide/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, indium sesquioxide/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 18:
0.1g after evenly disperseing in the monocrystalline metatitanic acid nano belt of Hydrothermal Preparation and the 6.6mg commercialization metal indium nitrate adding ethanol; Under normal pressure; 400 ℃ of heated at constant temperature 2h in the muffle furnace form the surface-functionalized double-heterostructure material of indium sesquioxide/titanium dioxide nano-belts.
The surface-functionalized double-heterostructure material of 1mg indium sesquioxide/titanium dioxide nano-belts is dispersed in the 3mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 6 μ L then, drop on the graphite electrode that scribbles the 1wt% naphthols; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of indium sesquioxide/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, indium sesquioxide/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 19:
0.1g after evenly disperseing in the monocrystalline metatitanic acid nano belt of Hydrothermal Preparation and the 8.3mg commercialization metal nitric acid tin adding ethanol; Under normal pressure; 300 ℃ of heated at constant temperature 3h in the muffle furnace form the surface-functionalized double-heterostructure material of tin ash/titanium dioxide nano-belts.
The surface-functionalized double-heterostructure material of 0.5mg tin ash/titanium dioxide nano-belts is dispersed in the 1.3mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 3 μ L then, drop on the glass-carbon electrode that scribbles the 1wt% naphthols; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of tin ash/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, tin ash/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 20:
0.1g after evenly disperseing in the monocrystalline metatitanic acid nano belt of Hydrothermal Preparation and the 7mg commercialization metal nitric acid tin adding ethanol; Under normal pressure; 500 ℃ of heated at constant temperature 2h in the muffle furnace form the surface-functionalized double-heterostructure material of tin ash/titanium dioxide nano-belts (shown in the similar accompanying drawing 1b of pattern).
The surface-functionalized double-heterostructure material of 0.8mg tin ash/titanium dioxide nano-belts is dispersed in the 2mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 4 μ L then, drop on the platinum electrode that scribbles the conduction carbon paste; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of tin ash/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, tin ash/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
Embodiment 21:
0.1g after evenly disperseing in the monocrystalline metatitanic acid nano belt of Hydrothermal Preparation and the 6.6mg commercialization metal nitric acid tin adding ethanol; Under normal pressure; 500 ℃ of heated at constant temperature 1h in the muffle furnace form the surface-functionalized double-heterostructure material of tin ash/titanium dioxide nano-belts (shown in the similar accompanying drawing 1b of pattern).
The surface-functionalized double-heterostructure material of 1mg tin ash/titanium dioxide nano-belts is dispersed in the 3mL absolute ethyl alcohol, takes out the above-mentioned even mixed liquor of 6 μ L then, drop on the graphite electrode that scribbles the 10wt% teflon; Process the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of tin ash/titanium dioxide nano-belts is modified; Be electrolyte solution at simulated body fluid phosphate buffer solution (PBS) then, carry out the electrochemica biological sensing detection, the similar accompanying drawing 2 of result with pH=7.4; Shown in Figure 3; Compare with titania single heterojunction nanometer band electrode, tin ash/titania double-heterostructure nanometer band electrode shows more high sensitivity in adenine phosphoric acid and the O-6-benzyl guanine biomolecule sensing detection; Littler electrode polarization, and electron transport ability faster.
The metatitanic acid of monocrystalline described in the foregoing description nano belt is meant that with commerical grade P-25 be raw material, and 10M NaOH solution is the solvent of reaction, adopts the synthetic metatitanic acid (H of hydro-thermal method
2Ti
3O
7) nano belt, concrete preparation method is referring to 200710017081.6 1 kinds of titanium dioxide nano papers of patent and preparation method thereof.
Claims (7)
1. surface-functionalized double-heterostructure material of titanium dioxide nano-belts; It is characterized in that; Said material is made by following method: is to mix in 12: 1～15: 1 monocrystalline metatitanic acid nano belt and commercialization noble metal chlorine complex or commercialization metal nitrate by mass ratio; Add then in the absolute ethyl alcohol of submergence amount and evenly disperse; Again in the normal pressure underlying muffle furnace with 200～500 ℃ of heated at constant temperature 1～3h, a step forms the surface-functionalized double-heterostructure material of titanium dioxide nano-belts, promptly forms the double-heterostructure material that contains titania nanoparticles and noble metal or metal oxide containing precious metals nano particle.
2. the surface-functionalized double-heterostructure material of titanium dioxide nano-belts as claimed in claim 1 is characterized in that, said commercialization noble metal chlorine complex is meant gold chloride, chloroplatinic acid or chloro-iridic acid; Said commercialization metal nitrate is meant nickel nitrate, bismuth nitrate, indium nitrate or nitric acid tin.
3. the surface-functionalized double-heterostructure material of titanium dioxide nano-belts as claimed in claim 2 is characterized in that, said commercialization noble metal chlorine complex is meant gold chloride; Said commercialization metal nitrate is meant nickel nitrate or bismuth nitrate.
4. the surface-functionalized double-heterostructure material of titanium dioxide nano-belts as claimed in claim 1 is characterized in that the temperature of said heated at constant temperature is 500 ℃; The time of heated at constant temperature is 1-2h.
5. the application of the surface-functionalized double-heterostructure material of the said titanium dioxide nano-belts of claim 1 in preparation electrochemical sensing electrode.
6. application as claimed in claim 5; It is characterized in that; The said method for preparing the electrochemical sensing electrode is: with the consumption of following unit ratio; The surface-functionalized double-heterostructure material of 0.5～1mg titanium dioxide nano-belts is dispersed in 1.3～3mL absolute ethyl alcohol; Take out the even mixed solution of 3～6 μ L then as active sensing material, drop on the basal electrode that scribbles cementing agent, make the electrochemical sensing electrode that the surface-functionalized double-heterostructure material of titanium dioxide nano-belts is modified; Wherein said cementing agent is 1wt% naphthols, conduction carbon paste or 10wt% teflon; Said basal electrode is meant platinum electrode, glass-carbon electrode or graphite electrode.
7. application as claimed in claim 6 is characterized in that, said cementing agent is the 1wt% naphthols; Said basal electrode is meant platinum electrode or graphite electrode.
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| CN106525914A (en) * | 2016-09-29 | 2017-03-22 | 湖北大学 | Preparation method of barium strontium titanate nanoparticle modified titanium dioxide thin film hydrogen sensor |
| CN108264239A (en) * | 2018-04-24 | 2018-07-10 | 合肥工业大学 | A kind of TiO with concentration gradient2Base heterojunction nano crystal array and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105664974A (en) * | 2016-02-29 | 2016-06-15 | 山东科技大学 | Silver sulfide/titanium dioxide nanobelt photocatalyst and preparation method thereof |
| CN105688940A (en) * | 2016-02-29 | 2016-06-22 | 山东科技大学 | Tungsten sulfide nanosheet/titanium dioxide nanobelt composite and preparation method thereof |
| CN106525914A (en) * | 2016-09-29 | 2017-03-22 | 湖北大学 | Preparation method of barium strontium titanate nanoparticle modified titanium dioxide thin film hydrogen sensor |
| CN106525914B (en) * | 2016-09-29 | 2019-04-05 | 湖北大学 | A kind of preparation method of barium strontium titanate modifying titanium dioxide film hydrogen gas sensor |
| CN108264239A (en) * | 2018-04-24 | 2018-07-10 | 合肥工业大学 | A kind of TiO with concentration gradient2Base heterojunction nano crystal array and preparation method thereof |
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