CN102507692B - Porous nickel-copper oxide nanowire array enzyme-free glucose sensor electrode on titanium substrate - Google Patents
Porous nickel-copper oxide nanowire array enzyme-free glucose sensor electrode on titanium substrate Download PDFInfo
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- CN102507692B CN102507692B CN201110321626.9A CN201110321626A CN102507692B CN 102507692 B CN102507692 B CN 102507692B CN 201110321626 A CN201110321626 A CN 201110321626A CN 102507692 B CN102507692 B CN 102507692B
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Abstract
The invention relates to a porous nickel-copper oxide nanowire array enzyme-free glucose sensor electrode on a titanium substrate. The electrode is of a porous nanowire array structure formed by alternately assembling nickel-copper oxide nanoparticles on the titanium substrate, wherein single nanowire has the top-end diameter of 20+/-1 nm and the length of 2+/-0.2 mu m; the nanowires are vertically, uniformly and compactly distributed on the surface of titanium metal so as to form an array; the single nanowire is formed by alternately assembling copper oxide and nickel oxide nanoparticles with particle size of 5+/-0.2 nm; and nanopores with size of 5+/-0.2 nm are uniformly distributed in the nanowires. The preparation method comprises the steps of: placing a clean titanium metal sheet in an aqueous solution of copper chloride dihydrate, nickel chloride hexahydrate and urea, sealing and heating in an autoclave with polytetrafluoroethylene inner lining to 120 DEG C and maintaining for 24 hours; naturally cooling, and taking out the titanium metal sheet to obtain a precursor (Ni,Cu)2(OH)2CO3 nanowire array film of an electrode sample; and respectively annealing the precursor sample in air at 350 DEG C and 500 DEG C to obtain the sensor electrode. The obtained electrode can be applied to biological, medical, electronic instruments and other products.
Description
Technical field
The present invention relates to glucose sensor electrode without enzyme, be specially the porous nano linear array glucose sensor electrode without enzyme of the overlapping assembling of nickel-copper oxygen materialization nano particle in a kind of titanium substrate.Belong to the fields such as biology, medical science, analytical chemistry, electronic device, electronic information, be mainly used in the electrochemical analytical instrument of the series products such as biology, clinical medicine, chemistry, chemical industry.
Background technology
On common electrochemical glucose exploring electrode, need to the glucose oxidase that play electrochemical reaction effect be fixed on electrode with shitosan or Nafion.Because glucose oxidase is expensive, be difficult for preserving, necessary deepfreeze, easy inactivation, if it is improper to preserve, glucose oxidase will lose catalytic activity, loses the effect that concentration of glucose is surveyed, therefore, the cheapness of kind electrode, convenience and universal use just exist the difficulty that is difficult to overcome; Simultaneously, the shitosan of fixing glucose oxidase or Nafion have the character that is slightly soluble in water, so, play electrochemical reaction effect glucose oxidase will along with shitosan or Nafion slowly water-soluble, i.e. use for a long time or repeatedly, it is fewer and feweri that glucose oxidase on electrode will become, and its chemical property will be worse and worse.In order to overcome these difficulties, the present invention proposes the porous nano linear array glucose sensor electrode without enzyme of the overlapping assembling of nickel-Cu oxide nano particle in a kind of titanium substrate.The major advantage of this glucose sensor electrode without enzyme is: one, because sensor electrode does not need glucose oxidase, so this sensor does not exist the problem of " preserving difficulty " and " inactivation ", its cost reduces greatly simultaneously.Its two, in electrode production process, owing to not needing the cementing agents such as shitosan or Nafion, so detecting material does not exist problem less and less, its nonexpondable stability is very high.Its three, the preparation method of this electrode is simple and convenient, be easy to batch production.Its four, due to the porous nano linear array structure of electrode material, the limit 0.1 μ M, highly sensitive (1600 μ AmM that its glucose is surveyed
-1cm
-2), the range of linearity 0.1～1200 μ M, selectivity be good, antijamming capability is strong, for the uric acid of 0.03mM and its response current of the ascorbic acid of 0.01mM, only have respectively 0.1mM glucose solution 4.2% and 2.9%, the ratio of normal human's glucose in blood and uric acid and ascorbic acid content at 30: 1 following level, response fast, be less than 5 seconds.
Summary of the invention
The object of the invention is to realize NiO and CuO even, controlled and nanostructure growth in the titanium substrate with electrochemical stability and biocompatibility by nanometer technology, obtain the NiO of a kind of cost performance height and highly versatile and the porous nano linear array glucose of CuO nano particle assembling without enzyme sensor electrode, serve the quick and precisely detection of blood sugar for human body, simple, convenient, cheap.
Inventive principle of the present invention is: application hydrothermal method, and with copper chloride dihydrate (CuCl
22H
2o), six water nickel chloride (NiCl
26H
2o) and urea be raw material, in the titanium substrate with electrochemical stability and biocompatibility, prepare the presoma (Ni, Cu) of electrode material
2(OH)
2cO
3nano-wire array; Then presoma nano-wire array film being annealed in air, (chemical equation is: (Ni, Cu)
2(OH)
2cO
3→ NiO+CuO+CO
2+ H
2o), obtain having the NiO of glucose electrochemical detection ability and the porous nano linear array glucose of CuO nano particle assembling without enzyme sensor electrode, the formation of nano-pore is due to CO
2due to the volatilization of gas.The principle of work of this enzyme-free glucose sensor is, first the nickelous in NiO is oxidized to nickelic in alkaline solution, again due to the reducing action of the glucose existing in solution, make nickelic reduction become nickelous, thereby can detect the existence of electrochemical process glucose in solutions and content thereof, (chemical equation is: NiO+OH
-→ NiO (OH)+e
-, NiO (OH)+glucose → Ni (OH)
2+ gluconolactone).
Key of the present invention is, to the presoma nano-wire array obtaining in the titanium substrate having electrochemical stability and biocompatibility, in the annealing of air situ, can realize NiO and CuO nano particle in titanium substrate and intersect the porous nano nanowire array film of assembling.The gordian technique of this in-situ annealing, can reach the whole homogeneity, the formation of nano particle, the formation of nano aperture and large specific surface area and the glucose that ensure sensor simultaneously and survey highly sensitive object.
Realizing object scheme of the present invention is:
A kind of glucose sensor electrode without enzyme, it is characterized in that, this electrode is that the porous nano linear array of the overlapping assembling of nickel-copper oxygen materialization nano particle in titanium substrate forms, its single nano-wire top end diameter 20 ± 1 nanometers, 2 ± 0.2 microns of length, be distributed in surface of metal titanium vertically, evenly, densely, present array; Single nano-wire is intersected and is foldedly assembled by the cupric oxide of 5 ± 0.2 nanometers and nickel oxide nanoparticle, and the nano-pore in nano wire with 5 ± 0.2 nanometers is uniformly distributed.
A kind of glucose sensor electrode without enzyme preparation method of the present invention comprises: by size, be 3 * 2 * 0.03cm
3dilute hydrofluoric acid solution immersion for titanium, clear water rinse clean rear panel and insert 0.32 gram of copper chloride dihydrate (CuCl
22H
2o), 0.24 gram of six water nickel chloride (NiCl
26H
2in 80 ml water solution of O) and 0.7 gram of urea; Then in the autoclave of polytetrafluoroethylliner liner, be heated to seal to 120 ℃, keep 24 hours; Naturally after cooling, titanium metal plate is taken out, obtain the presoma (Ni, Cu) of titanium substrate top electrode sample
2(OH)
2cO
3nano-wire array film; Again by presoma (Ni, Cu) in titanium substrate
2(OH)
2cO
3nano-wire array film is inserted batch-type furnace 350-500 ℃ of annealing 60 minutes in air, obtains NiO and CuO nano particle in titanium substrate and intersects the porous nano nanowire array film shape glucose sensor electrode without enzyme of stacked assembling.
Glucose sensor electrode without enzyme of the present invention is applied to biology, medical science, chemistry, chemical industry, electronic device and electronic information series products.
By the sample obtaining, with field emission scanning electron microscope, (NEC company produces, model: JEOL 6700F) and transmission electron microscope (NEC company produces, model: JEOL-2100F, 200kV) observe particle and the hole distribution situation of its epontic nano-wire array and composition nano wire, and do X ray diffractive crystal structure analysis (Aolong Ray Equipment Co., Ltd., Dandong city, model: Y2000).Test findings shows, presoma is (Ni, Cu)
2(OH)
2cO
3nano-wire array.Sample in air after annealing is the porous nano linear array of NiO and the overlapping assembling of CuO nano particle, its single nano-wire top end diameter 20 ± 1 nanometers, and 2 ± 0.2 microns of length, are distributed in surface of metal titanium vertically, evenly, densely, present array; Single nano-wire is by the cupric oxide of 5 nanometers and nickel oxide nanoparticle is overlapping assembles, and the nano-pore in nano wire with 5 ± 0.2 nanometers is uniformly distributed.
Serviceability Applied Electrochemistry workstation test (the Shanghai Chen Hua company of porous nickel-copper oxide nanowire array enzyme-free glucose sensor electrode, model: CHI660C, nickel porous-Cu oxide nano-wire array electrode of working in titanium substrate, platinum filament is done auxiliary electrode, saturated calomel electrode is contrast electrode), result shows, highly sensitive (the 1600 μ AmM of this working electrode
-1cm
-2), detection limit 0.1 μ M, antijamming capability are strong, response is less than 5 seconds, the range of linearity 0.1～1200 μ M, stable work in work, the use of continuous month, its detection sensitivity remains on more than 90%.
The present invention compares and has the following advantages and good effect with existing correlation technique:
1, titanium substrate is as nickel porous-Cu oxide nano-wire array carrier, the performance that its chemical stability in electrochemical process and biocompatibility have ensured the excellent serviceability of electrode.
2,, because sensor electrode does not need glucose oxidase, so this sensor does not exist the problem of " preserving difficulty " and " inactivation ", its cost reduces greatly simultaneously; In electrode production process, owing to not needing the cementing agents such as shitosan or Nafion, so material for detector does not exist problem less and less, guaranteed the nonexpondable stability of electrode, the use of continuous month, its detection sensitivity remains on more than 90%; Due to the porous nano linear array structure of electrode material, the limit low (0.1 μ M), highly sensitive (1600 μ Am M that its glucose is surveyed
-1cm
-2), good (antijamming capability is strong for the range of linearity large (0.1～1200 μ M), selectivity, for the uric acid of 0.03mM and its response current of the ascorbic acid of 0.01mM, only has respectively 4.2% and 2.9% of 0.1mM glucose solution, the ratio of normal human's glucose in blood and uric acid and ascorbic acid content is following level at 30: 1), response is fast, is less than 5 seconds.
3, due to the simplicity of nickel porous-Cu oxide nano-wire array preparation method in titanium substrate, easily the property controlled, energy consumption is low, cost is low and the homogeneity of Material growth environment, very easily realizes high-quality, the low-cost industrial volume production of electrode sample.
Accompanying drawing explanation
The presoma (Ni, Cu) of Fig. 1 embodiment 1 preparation
2(OH)
2cO
3sample Scan electron micrograph
The presoma (Ni, Cu) of Fig. 2 embodiment 1 preparation
2(OH)
2cO
3sample X-ray diffractogram
Fig. 3 embodiment 2 is at the sample NiO/CuO electron scanning micrograph of 350 ℃ of annealing preparations
Fig. 4 embodiment 2 is at the sample NiO/CuOX x ray diffration pattern x of 350 ℃ of annealing preparations
Fig. 5 embodiment 2 is at the sample NiO/CuO transmission electron microscope photo of 350 ℃ of annealing preparations
Fig. 6 embodiment 3 is at the sample NiO/CuO electron scanning micrograph of 500 ℃ of annealing preparations
Fig. 7 embodiment 3 is 500 ℃ of annealing) the sample NiO/CuOX x ray diffration pattern x prepared
Fig. 8 embodiment 3 is 500 ℃ of annealing) the sample NiO/CuO transmission electron microscope photo prepared
Fig. 9 embodiment 4 is at the current time response curve of 350 ℃ and 500 ℃ annealing specimens
The calibration curve of Figure 10 embodiment 4 glucose contents
Figure 11 embodiment 4 measures curve in the detection limit of 350 ℃ of annealing specimens
Figure 12 embodiment 4 measures curve in the detection limit of 500 ℃ of annealing specimens
The strong test pattern of Figure 13 embodiment 5 antijamming capability
As seen from the figure, for the uric acid of 0.03mM and its response current of the ascorbic acid of 0.01mM, only have respectively 4.2% and 2.9% of 0.1mM glucose solution, the ratio of normal human's glucose in blood and uric acid and ascorbic acid content is following level at 30: 1.
Figure 14 embodiment 5 stability test figure
By the figure use of provable continuous month, its detection sensitivity remains on more than 90%.
Embodiment
Concrete formula, technological parameter and performance test example are as follows:
Embodiment 1
Presoma (Ni, Cu)
2(OH)
2cO
3the preparation of nano-wire array: by clean titanium metal plate (3 * 2 * 0.03cm
3) insert 0.32 gram of copper chloride dihydrate (CuCl
22H
2o), 0.24 gram of six water nickel chloride (NiCl
26H
2in 80 ml water solution of O) and 0.7 gram of urea; Then in the autoclave of polytetrafluoroethylliner liner, be heated to seal to 120 ℃, keep 24 hours; Naturally after cooling, titanium metal plate is taken out, obtain the presoma (Ni, Cu) of electrode sample
2(OH)
2cO
3nano-wire array film.Sample is done to scanning electron microscope and X-ray diffraction observation.Result shows, presoma (Ni, Cu)
2(OH)
2cO
3nano wire is distributed in titanium metal plate surface vertically, evenly, densely, presents nanowire array structure, single nano-wire top end diameter 20 nanometers, 2 microns of length.Its result figure is shown in Fig. 1 and Fig. 2.
Embodiment 2
By presoma (Ni, Cu) in titanium substrate
2(OH)
2cO
3nano-wire array film is inserted in batch-type furnace 350 ℃ of annealing 60 minutes, obtains NiO/CuO nano particle in titanium substrate and intersects the porous nano nanowire array film of assembling.Then with scanning electron microscope, transmission electron microscope and X-ray diffractometer, observe pattern and the crystal structure of sample.Its result is illustrated in Fig. 3, Fig. 4 and Fig. 5.As can be seen from the figure, its nano-wire array keeps the state before annealing substantially, but single nano-wire has become porous structure.Nano wire is intersected and is assembled by NiO and CuO nano particle, and its nano particle and nano-pore size are all in 5 nanometers.The X-ray diffraction result of 350 ℃ of annealing specimens shows, its annealing temperature is lower, and the crystalline state of one-tenth of sample is poor.
Embodiment 3
By presoma (Ni, Cu) in titanium substrate
2(OH)
2cO
3nano-wire array film is inserted in batch-type furnace 500 ℃ of annealing 60 minutes, obtains NiO and CuO nano particle in titanium substrate and intersects the porous nano nanowire array film of assembling.Then with scanning electron microscope, transmission electron microscope and X-ray diffractometer, observe pattern and the crystal structure of sample.Its result is illustrated in Fig. 6, Fig. 7 and Fig. 8.As can be seen from the figure, its nano-wire array keeps the state before annealing substantially, but single nano-wire has become porous structure.Nano wire is intersected and is assembled by NiO and CuO nano particle, and its nano particle and nano-pore size are all in 5 nanometers.The X-ray diffraction result of 500 ℃ of annealing specimens shows, its annealing temperature is higher, and the crystalline state of one-tenth of sample is better.
Embodiment 4
Respectively the sample of 350 ℃ and 500 ℃ annealing is carried out to electrochemical property test.Applied Electrochemistry workstation (nickel porous-Cu oxide nano-wire array electrode of working in titanium substrate, platinum filament is done auxiliary electrode, saturated calomel electrode is contrast electrode), the D/W of 10 μ M is dropwise joined in the sodium hydrate aqueous solution of 0.1M, measuring current time curve (Fig. 9) under the electrochemical potential condition of 0.42V (cyclic voltammetric family curve is per sample determined), then according to the calibration curve (Figure 10) of current-time curvel decision sample.The detection limit test result of the sample of 350 ℃ and 500 ℃ annealing is illustrated respectively in Figure 11 and Figure 12.Test result shows that the properties of sample of 350 ℃ of annealing is all better than the sample of 500 ℃ of annealing.
Respectively the sample of 350 ℃ and 500 ℃ annealing is carried out to anti-interference and stability test.Applied Electrochemistry workstation (nickel porous-Cu oxide nano-wire array electrode of working in titanium substrate, platinum filament is done auxiliary electrode, saturated calomel electrode is contrast electrode), test respectively the uric acid of 0.03mM, the corresponding electric current of the ascorbic acid of 0.01mM and 0.1mM glucose solution, the ratio of normal human's glucose in blood and uric acid and ascorbic acid content is following level at 30: 1, and experimental result is depicted as to Figure 13.Result shows, the uric acid of 0.03mM and its response current of the ascorbic acid of 0.01mM only have respectively 4.2% and 2.9% of 0.1mM glucose solution.Therefore the antijamming capability of sample is very strong.The test of sample job stability is the use of continuous month, and relatively more each detection sensitivity result of measuring.Experimental result is illustrated in Figure 14, and its sensitivity remains on more than 90%.
Claims (3)
1. a glucose sensor electrode without enzyme, it is characterized in that, this electrode is that the porous nano linear array of the overlapping assembling of nickel-copper oxygen materialization nano particle in titanium substrate forms, its single nano-wire top end diameter 20 ± 1 nanometers, 2 ± 0.2 microns of length, be distributed in surface of metal titanium vertically, evenly, thick and fast, present array; Single nano-wire is folded and is assembled by the cupric oxide of 5 ± 0.2 nanometers and the nickel oxide nanoparticle of 5 ± 0.2 nanometers intersection, and the nano-pore in nano wire with 5 ± 0.2 nanometers is uniformly distributed.
2. a glucose sensor electrode without enzyme preparation method, is characterized in that, by clean size, is 3 * 2 * 0.03cm
3titanium metal plate is inserted 0.32 gram of copper chloride dihydrate, in 80 ml water solution of 0.24 gram of six water nickel chloride and 0.7 gram of urea; Then in the autoclave of polytetrafluoroethylliner liner, be heated to seal to 120 ℃, keep 24 hours; Naturally after cooling, titanium metal plate is taken out, obtain the presoma (Ni, Cu) of titanium substrate top electrode sample
2(OH)
2cO
3nano-wire array film; Again by presoma (Ni, Cu) in titanium substrate
2(OH)
2cO
3nano-wire array film is inserted batch-type furnace 350-500 ℃ of annealing 60 minutes in air, obtains NiO and CuO nano particle in titanium substrate and intersects the porous nano nanowire array film shape glucose sensor electrode without enzyme of stacked group dress.
3. glucose sensor electrode without enzyme application claimed in claim 1, is characterized in that, for detection of the application of glucose aspect.
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| CN103265061A (en) * | 2013-04-23 | 2013-08-28 | 北京化工大学 | One-dimensional copper oxide nano-array glucose sensor electrode material and preparation method thereof |
| CN103424446B (en) * | 2013-08-13 | 2015-09-16 | 常州大学 | A kind of highly sensitive enzyme-free glucose electrochemical sensor and preparation method thereof |
| CN104076076A (en) * | 2013-12-19 | 2014-10-01 | 浙江工商大学 | Preparation method of non-enzyme glucose sensor foamy copper modified carbon working electrode |
| CN104713927A (en) * | 2015-03-16 | 2015-06-17 | 常州大学 | Electrochemical method for detecting sucralose in food |
| CN106525927A (en) * | 2016-12-13 | 2017-03-22 | 中驭(北京)生物工程有限公司 | Automatic detection apparatus and method for glucose in peritoneal dialysis machine |
| CN108996557B (en) * | 2018-06-22 | 2020-11-13 | 安徽师范大学 | Hollow sphere structured nickel oxide/copper oxide composite nano material and preparation method thereof |
| CN110550649A (en) * | 2019-08-23 | 2019-12-10 | 安徽大学 | Porous copper oxide nanobelt assembled film, electrode plate, preparation method and application thereof |
| CN110872704A (en) * | 2019-11-22 | 2020-03-10 | 山东理工大学 | Copper oxide nano film, preparation method, electrode and gas sensor |
| CN111307904B (en) * | 2020-03-27 | 2023-03-24 | 西安工程大学 | Preparation method and application of bamboo-shaped copper-nickel nanowire array glucose sensor electrode |
| CN113176315B (en) * | 2021-03-15 | 2023-01-17 | 杭州电子科技大学 | NiO/Au nanotube array flexible electrode with core-shell structure and application thereof |
| CN113244922B (en) * | 2021-04-01 | 2022-09-30 | 西安理工大学 | Non-enzymatic glucose sensor catalyst and preparation method thereof |
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| KR20090093639A (en) * | 2008-02-29 | 2009-09-02 | 고려대학교 산학협력단 | Method of Fabricating ZnO Nanowire and Glucose Sensor Using The Same |
| CN101603941A (en) * | 2009-07-16 | 2009-12-16 | 中国科学院长春应用化学研究所 | Nano nickel particles/carbon nano-fiber composite material prepares the method for non-enzymatic glucose sensor |
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