CN102507692A - 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
- Publication number
- CN102507692A CN102507692A CN2011103216269A CN201110321626A CN102507692A CN 102507692 A CN102507692 A CN 102507692A CN 2011103216269 A CN2011103216269 A CN 2011103216269A CN 201110321626 A CN201110321626 A CN 201110321626A CN 102507692 A CN102507692 A CN 102507692A
- Authority
- CN
- China
- Prior art keywords
- nano
- electrode
- sensor electrode
- nickel
- titanium substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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 that nickel in a kind of titanium substrate-copper oxygen materialization nano particle overlaps and assembles.Belong to fields such as biology, medical science, analytical chemistry, electronic device, electronic information, be mainly used in the electrochemical analytical instrument of series products such as biology, clinical medicine, chemistry, chemical industry.
Background technology
On common electrochemical glucose exploring electrode, need be fixed on the electrode with the glucose oxidase that shitosan or Nafion will play the electrochemical reaction effect.Because glucose oxidase costs an arm and a leg, 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 the glucose oxidase that plays the electrochemical reaction effect will be slowly water-soluble along with shitosan or Nafion, promptly long-time or use repeatedly; It is fewer and feweri that glucose oxidase on the 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 that nickel in a kind of titanium substrate-Cu oxide nano particle overlaps and assembles.The major advantage of this glucose sensor electrode without enzyme is: one of which, because sensor electrode does not need glucose oxidase, so there is not the problem of " preserving difficulty " and " inactivation " in this sensor, its cost reduces greatly simultaneously.Its two, owing to do not need cementing agents such as shitosan or Nafion, so there is not problem less and less in detecting material, its nonexpondable stability is very high in electrode production process.Its three, the preparation method of this electrode is simple and convenient, be easy to produce in batches.Its four because 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; Have only respectively for its response current of ascorbic acid of the uric acid of 0.03mM and 0.01mM 0.1mM glucose solution 4.2% and 2.9%; In normal human's blood the ratio of glucose and uric acid and ascorbic acid content at 30: 1 following level, response fast, less than 5 seconds.
Summary of the invention
The objective of the invention is to realize NiO and CuO even, controlled and nanostructure growth in titanium substrate with electrochemical stability and biocompatibility through 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 and do not have the enzyme sensor electrode; Serve the detection quick and precisely of blood sugar for human body, simple, convenient, cheap.
Inventive principle of the present invention is: use hydrothermal method, with copper chloride dihydrate (CuCl
22H
2O), six water nickel chloride (NiCl
26H
2O) and urea be raw material, in titanium substrate with electrochemical stability and biocompatibility the preparation electrode material presoma (Ni, Cu)
2(OH)
2CO
3Nano-wire array; Then the presoma nano-wire array film is annealed in air (chemical equation is: (Ni, Cu)
2(OH)
2CO
3→ NiO+CuO+CO
2+ H
2O), obtaining having the NiO of glucose electrochemical detection ability and the porous nano linear array glucose of CuO nano particle assembling does not have the enzyme sensor electrode, and the formation of nano-pore is because CO
2Due to the volatilization of gas.The principle of work of this enzyme-free glucose sensor is; At first the nickelous among the NiO is oxidized to nickelic in alkaline solution; Again because the reducing action of the glucose that exists in the solution; Make nickelic reduction become nickelous, (chemical equation is: NiO+OH thereby can detect existence and the content thereof of glucose in the electrochemical process solution
-→ NiO (OH)+e
-, NiO (OH)+glucose → Ni (OH)
2+ glucose lactone).
Key of the present invention is, to the presoma nano-wire array in-situ annealing in air that in the titanium substrate with electrochemical stability and biocompatibility, obtains, can realize that NiO and CuO nano particle in the titanium substrate intersect the porous nano linear array film of assembling.The gordian technique of this in-situ annealing can reach the whole homogeneity that ensures sensor simultaneously, the formation of nano particle, the formation of nano aperture and big specific surface area and glucose and survey highly sensitive purpose.
Realize that the object of the invention scheme is:
A kind of glucose sensor electrode without enzyme; It is characterized in that; This electrode is the porous nano linear array formation that nickel in the titanium substrate-copper oxygen materialization nano particle overlaps and assembles, 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 by the cupric oxide of 5 ± 0.2 nanometers and nickel oxide nano particle and foldedly assembles, and the nano-pore that has 5 ± 0.2 nanometers in the nano wire evenly distributes.
A kind of glucose sensor electrode without enzyme preparation method of the present invention comprises: with size is 3 * 2 * 0.03cm
3Titanium with dilute hydrofluoric acid solution soak, sheet is inserted 0.32 gram copper chloride dihydrate (CuCl after the flushing with clean water cleaning
22H
2O), 0.24 gram, six water nickel chloride (NiCl
26H
2O) and 0.7 the gram urea 80 ml water solution in; Heated sealed to 120 ℃ in the autoclave of polytetrafluoroethylliner liner kept 24 hours then; Behind the natural cooling titanium metal plate is taken out, promptly get titanium substrate top electrode sample presoma (Ni, Cu)
2(OH)
2CO
3Nano-wire array film; Again with presoma in the titanium substrate (Ni, Cu)
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 the titanium substrate and intersects the porous nano linear array film like 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.
With the sample that obtains; (company of NEC produces with field emission scanning electron microscope; Model: JEOL 6700F) and transmission electron microscope (company of NEC produces, and model: JEOL-2100F 200kV) observes its epontic nano-wire array and particle and the hole distribution situation of forming nano wire; And do X ray diffractive crystal structure analysis (Aolong Ray Equipment Co., Ltd., Dandong city, model: Y2000).Test findings shows, presoma be (Ni, Cu)
2(OH)
2CO
3Nano-wire array.Sample in the air after the annealing is the porous nano linear array that NiO and CuO nano particle overlap and assemble, 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 assembled by the cupric oxide and the nickel oxide nano particle overlapping of 5 nanometers, and the nano-pore that has 5 ± 0.2 nanometers in the nano wire evenly distributes.
Serviceability Applied Electrochemistry workstation test (the Shanghai occasion China company of nickel porous-Cu oxide nano-wire array glucose sensor electrode without enzyme; Model: CHI660C; Nickel porous in the titanium substrate-Cu oxide nano-wire array electrode of working, platinum filament is done auxiliary electrode, saturated calomel electrode is a contrast electrode); The result shows, highly sensitive (the 1600 μ AmM of this working electrode
-1Cm
-2), strong, the response of detection limit 0.1 μ M, antijamming capability is less than 5 seconds, the range of linearity 0.1～1200 μ M, stable work in work, continuous one month use, its detection sensitivity remains on more than 90%.
The present invention has compared following advantage and good effect with existing correlation technique:
1, the titanium substrate is as nickel porous-Cu oxide nano-wire array carrier, the performance that its chemical stability and biocompatibility in electrochemical process has ensured the excellent serviceability of electrode.
2, because sensor electrode does not need glucose oxidase, so there is not the problem of " preserving difficulty " and " inactivation " in this sensor, its cost reduces greatly simultaneously; In electrode production process,,, guaranteed the nonexpondable stability of electrode so there is not problem less and less in material for detector owing to do not need cementing agents such as shitosan or Nafion, continuous one month use, its detection sensitivity remains on more than 90%; Since 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 big (0.1～1200 μ M), selectivity; Has only 4.2% and 2.9% of 0.1mM glucose solution respectively for the uric acid of 0.03mM and its response current of ascorbic acid of 0.01mM; In normal human's blood the ratio of glucose and uric acid and ascorbic acid content at 30: 1 following level), response was fast, less than 5 seconds.
3, because nickel porous-Cu oxide nano-wire array preparation method's simplicity in the titanium substrate, be prone to control property, energy consumption is low, cost is low and the homogeneity of material growing environment, very easily realizes the high-quality of electrode sample, low-cost industrialization volume production.
Description of drawings
The presoma of Fig. 1 embodiment 1 preparation (Ni, Cu)
2(OH)
2CO
3The sample electron scanning micrograph
The presoma of Fig. 2 embodiment 1 preparation (Ni, Cu)
2(OH)
2CO
3The sample 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) preparation sample NiO/CuOX x ray diffration pattern x
Fig. 8 embodiment 3 is 500 ℃ of annealing) preparation sample NiO/CuO transmission electron microscope photo
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 capabilities
Visible by figure, have only 4.2% and 2.9% of 0.1mM glucose solution respectively for the uric acid of 0.03mM and its response current of ascorbic acid of 0.01mM, in normal human's blood the ratio of glucose and uric acid and ascorbic acid content at 30: 1 following level.
Figure 14 embodiment 5 stability test figure
By provable continuous one month use of figure, its detection sensitivity remains on more than 90%.
Embodiment
Concrete prescription, technological parameter and performance test instance are following:
Embodiment 1
Presoma (Ni, Cu)
2(OH)
2CO
3The preparation of nano-wire array: with titanium metal plate (3 * 2 * 0.03cm of cleaning
3) insert 0.32 gram copper chloride dihydrate (CuCl
22H
2O), 0.24 gram, six water nickel chloride (NiCl
26H
2O) and 0.7 the gram urea 80 ml water solution in; Heated sealed to 120 ℃ in the autoclave of polytetrafluoroethylliner liner kept 24 hours then; Behind the natural cooling titanium metal plate is taken out, promptly get electrode sample presoma (Ni, Cu)
2(OH)
2CO
3Nano-wire array film.Sample is done scanning electron microscope and X-ray diffraction observation.The result shows, and presoma (Ni, Cu)
2(OH)
2CO
3Nano wire is distributed in the titanium metal plate surface vertically, evenly, densely, presents the nano-wire array structure, single nano-wire top end diameter 20 nanometers, 2 microns of length.Its as a result figure see Fig. 1 and Fig. 2.
Embodiment 2
With presoma in the titanium substrate (Ni, Cu)
2(OH)
2CO
3Nano-wire array film is inserted in the batch-type furnace 350 ℃ of annealing 60 minutes, obtains NiO/CuO nano particle in the titanium substrate and intersects the porous nano linear array film of assembling.Use the pattern and the crystal structure of scanning electron microscope, transmission electron microscope and X-ray diffractometer observation sample then.Its result is illustrated among Fig. 3, Fig. 4 and Fig. 5.As can be seen from the figure, the state before its nano-wire array keeps annealing basically, but single nano-wire has become porous structure.Nano wire is assembled by NiO and CuO nano particle intersection, and its nano particle and nano-pore size are all in 5 nanometers.The X-ray diffraction result of 350 ℃ of annealing specimens shows that its annealing temperature is lower, and the crystalline attitude of the one-tenth of sample is relatively poor.
Embodiment 3
With presoma in the titanium substrate (Ni, Cu)
2(OH)
2CO
3Nano-wire array film is inserted in the batch-type furnace 500 ℃ of annealing 60 minutes, obtains in the titanium substrate NiO and CuO nano particle and intersects the porous nano linear array film of assembling.Use the pattern and the crystal structure of scanning electron microscope, transmission electron microscope and X-ray diffractometer observation sample then.Its result is illustrated among Fig. 6, Fig. 7 and Fig. 8.As can be seen from the figure, the state before its nano-wire array keeps annealing basically, but single nano-wire has become porous structure.Nano wire is assembled by NiO and CuO nano particle intersection, and its nano particle and nano-pore size are all in 5 nanometers.The X-ray diffraction result of 500 ℃ of annealing specimens shows that its annealing temperature is higher, and the crystalline attitude of the one-tenth of sample is better.
Embodiment 4
Sample with 350 ℃ and 500 ℃ annealing carries out electrochemical property test respectively.Applied Electrochemistry workstation (nickel porous in the titanium substrate-Cu oxide nano-wire array electrode of working; Platinum filament is done auxiliary electrode; Saturated calomel electrode is a contrast electrode); The D/W of 10 μ M is dropwise joined in the sodium hydrate aqueous solution of 0.1M, and measuring current time curve (Fig. 9) under the electrochemical potential condition of 0.42V (cyclic voltammetric family curve per sample confirm) is 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 among Figure 11 and Figure 12.Test result shows that the properties of sample of 350 ℃ of annealing all is superior to the sample of 500 ℃ of annealing.
Sample with 350 ℃ and 500 ℃ annealing carries out anti-interference and stability test respectively.Applied Electrochemistry workstation (nickel porous in the titanium substrate-Cu oxide nano-wire array electrode of working; Platinum filament is done auxiliary electrode; Saturated calomel electrode is a contrast electrode); Test the uric acid of 0.03mM, the ascorbic acid of 0.01mM and the corresponding electric current of 0.1mM glucose solution respectively, in normal human's blood the ratio of glucose and uric acid and ascorbic acid content at 30: 1 following level, and experimental result is depicted as Figure 13.The result shows that the uric acid of 0.03mM and its response current of the ascorbic acid of 0.01mM have only 4.2% and 2.9% of 0.1mM glucose solution respectively.Therefore the antijamming capability of sample is very strong.The test of sample job stability is continuous one month use, and relatively more each detection sensitivity result who measures.Experimental result is illustrated among Figure 14, and its sensitivity remains on more than 90%.
Claims (3)
1. glucose sensor electrode without enzyme; It is characterized in that; This electrode is the porous nano linear array formation that nickel in the titanium substrate-copper oxygen materialization nano particle overlaps and assembles, 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 by the cupric oxide of 5 ± 0.2 nanometers and nickel oxide nano particle and foldedly assembles, and the nano-pore that has 5 ± 0.2 nanometers in the nano wire evenly distributes.
2. a glucose sensor electrode without enzyme preparation method is characterized in that, is 3 * 2 * 0.03cm with the size that cleans
3Titanium metal plate is inserted 0.32 gram copper chloride dihydrate, in the 80 ml water solution of 0.24 gram six water nickel chlorides and 0.7 gram urea; Heated sealed to 120 ℃ in the autoclave of polytetrafluoroethylliner liner kept 24 hours then; Behind the natural cooling titanium metal plate is taken out, promptly get titanium substrate top electrode sample presoma (Ni, Cu)
2(OH)
2CO
3Nano-wire array film; Again with presoma in the titanium substrate (Ni, Cu)
2(OH)
2CO
3Nano-wire array film is inserted batch-type furnace 350-500 ℃ of annealing 60 minutes in air, obtains in the titanium substrate NiO and CuO nano particle and intersects the folded porous nano linear array film like glucose sensor electrode without enzyme of assembling.
3. the described glucose sensor electrode without enzyme of claim 1 is used, and it is characterized in that, is used for biology, medical science, chemistry, chemical industry, electronic device and electronic information series products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110321626.9A CN102507692B (en) | 2011-10-21 | 2011-10-21 | Porous nickel-copper oxide nanowire array enzyme-free glucose sensor electrode on titanium substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110321626.9A CN102507692B (en) | 2011-10-21 | 2011-10-21 | Porous nickel-copper oxide nanowire array enzyme-free glucose sensor electrode on titanium substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102507692A true CN102507692A (en) | 2012-06-20 |
| CN102507692B CN102507692B (en) | 2014-01-22 |
Family
ID=46219799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110321626.9A Expired - Fee Related CN102507692B (en) | 2011-10-21 | 2011-10-21 | Porous nickel-copper oxide nanowire array enzyme-free glucose sensor electrode on titanium substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102507692B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103424446A (en) * | 2013-08-13 | 2013-12-04 | 常州大学 | High-sensitivity non-enzymatic glucose electrochemical sensor and production 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 |
| CN108996557A (en) * | 2018-06-22 | 2018-12-14 | 安徽师范大学 | A kind of hollow ball structure nickel oxide/copper oxide composite nano materials 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 |
| CN111307904A (en) * | 2020-03-27 | 2020-06-19 | 西安工程大学 | Preparation method and application of bamboo-shaped copper-nickel nanowire array glucose sensor electrode |
| CN113176315A (en) * | 2021-03-15 | 2021-07-27 | 杭州电子科技大学 | NiO/Au nanotube array flexible electrode with core-shell structure and application thereof |
| CN113244922A (en) * | 2021-04-01 | 2021-08-13 | 西安理工大学 | Non-enzymatic glucose sensor catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004034025A2 (en) * | 2002-10-10 | 2004-04-22 | Nanosys, Inc. | Nano-chem-fet based biosensors |
| 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 |
-
2011
- 2011-10-21 CN CN201110321626.9A patent/CN102507692B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004034025A2 (en) * | 2002-10-10 | 2004-04-22 | Nanosys, Inc. | Nano-chem-fet based biosensors |
| 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 |
Non-Patent Citations (9)
| Title |
|---|
| 《Catalysis Science & Technology》 20110923 Ruimin Ding,Jinping Liu等 Tailored Ni-Cu alloy hierarchical porous nanowire as a potential efficient catalyst for DMFCs 1406-1411 第1卷, * |
| 《Chem. Commun.》 20031107 Hui-Min Zhang, Yu-Guo Guo, Li-Jun Wan等 Novel electrocatalytic activity in layered Ni-Cu nanowire arrays 3022-3023 , * |
| 《Journal of alloys and compounds》 20061212 Mursel Alper等 Comparison of Ni-Cu alloy films electrodeposited at low and high pH levels 第453卷, * |
| 《Phys. Chem. Chem. Phys.》 20020605 Yu-Guo Guo等 Preparation and dispersion of Ni-Cu composite nanoparticles , * |
| HUI-MIN ZHANG, YU-GUO GUO, LI-JUN WAN等: "Novel electrocatalytic activity in layered Ni–Cu nanowire arrays", 《CHEM. COMMUN.》, 7 November 2003 (2003-11-07), pages 3022 - 3023 * |
| MOJTABA SHAMSIPUR等: "Highly improved electrooxidation of glucose at a nickel(II) oxide/multi-walled carbon nanotube modified glassy carbon electrode", 《BIOELECTROCHEMISTRY》, vol. 77, 21 July 2009 (2009-07-21) * |
| MURSEL ALPER等: "Comparison of Ni–Cu alloy films electrodeposited at low and high pH levels", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 453, 12 December 2006 (2006-12-12) * |
| RUIMIN DING,JINPING LIU等: "Tailored Ni–Cu alloy hierarchical porous nanowire as a potential efficient catalyst for DMFCs", 《CATALYSIS SCIENCE & TECHNOLOGY》, vol. 1, 23 September 2011 (2011-09-23), pages 1406 - 1411 * |
| YU-GUO GUO等: "Preparation and dispersion of Ni–Cu composite nanoparticles", 《PHYS. CHEM. CHEM. PHYS.》, 5 June 2002 (2002-06-05) * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103424446A (en) * | 2013-08-13 | 2013-12-04 | 常州大学 | High-sensitivity non-enzymatic glucose electrochemical sensor and production 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 |
| CN108996557A (en) * | 2018-06-22 | 2018-12-14 | 安徽师范大学 | A kind of hollow ball structure nickel oxide/copper oxide composite nano materials and preparation method thereof |
| 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 |
| CN111307904A (en) * | 2020-03-27 | 2020-06-19 | 西安工程大学 | Preparation method and application of bamboo-shaped copper-nickel nanowire array glucose sensor electrode |
| 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 |
| CN113176315A (en) * | 2021-03-15 | 2021-07-27 | 杭州电子科技大学 | NiO/Au nanotube array flexible electrode with core-shell structure and application thereof |
| CN113244922A (en) * | 2021-04-01 | 2021-08-13 | 西安理工大学 | Non-enzymatic glucose sensor catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102507692B (en) | 2014-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102507692B (en) | Porous nickel-copper oxide nanowire array enzyme-free glucose sensor electrode on titanium substrate | |
| Long et al. | Novel helical TiO2 nanotube arrays modified by Cu2O for enzyme-free glucose oxidation | |
| Manjakkal et al. | Metal oxides based electrochemical pH sensors: Current progress and future perspectives | |
| Li et al. | Nanoporous gold induced vertically standing 2D NiCo bimetal-organic framework nanosheets for non-enzymatic glucose biosensing | |
| Wang et al. | An ultrasensitive non-enzymatic glucose sensors based on controlled petal-like CuO nanostructure | |
| Ashok et al. | Highly efficient nonenzymatic glucose sensors based on CuO nanoparticles | |
| Liu et al. | Design and facile synthesis of mesoporous cobalt nitride nanosheets modified by pyrolytic carbon for the nonenzymatic glucose detection | |
| Zhong et al. | Ultrasensitive non-enzymatic glucose sensors based on different copper oxide nanostructures by in-situ growth | |
| Chen et al. | Synergistic coupling of NiCo2O4 nanorods onto porous Co3O4 nanosheet surface for tri-functional glucose, hydrogen-peroxide sensors and supercapacitor | |
| Khan et al. | Glucose-assisted synthesis of Cu2O shuriken-like nanostructures and their application as nonenzymatic glucose biosensors | |
| Zhao et al. | Highly sensitive nonenzymetic glucose sensing based on multicomponent hierarchical NiCo-LDH/CCCH/CuF nanostructures | |
| eun Kim et al. | Metal-organic framework–assisted bimetallic Ni@ Cu microsphere for enzyme-free electrochemical sensing of glucose | |
| Fang et al. | Flower-like MoS2 decorated with Cu2O nanoparticles for non-enzymatic amperometric sensing of glucose | |
| Lu et al. | CuO/Cu 2 O nanofibers as electrode materials for non-enzymatic glucose sensors with improved sensitivity | |
| Zhang et al. | Porous Cu–NiO modified glass carbon electrode enhanced nonenzymatic glucose electrochemical sensors | |
| Zhao et al. | Highly sensitive and portable electrochemical detection system based on AuNPs@ CuO NWs/Cu2O/CF hierarchical nanostructures for enzymeless glucose sensing | |
| Guo et al. | In situ formation of Co3O4 hollow nanocubes on carbon cloth-supported NiCo2O4 nanowires and their enhanced performance in non-enzymatic glucose sensing | |
| Ponnusamy et al. | Pd-doped WO3 nanostructures as potential glucose sensor with insight from electronic structure simulations | |
| Khan et al. | Engineered CuO nanofibers with boosted non-enzymatic glucose sensing performance | |
| Wang et al. | Rapid synthesis of rGO conjugated hierarchical NiCo2O4 hollow mesoporous nanospheres with enhanced glucose sensitivity | |
| Liu et al. | Cobalt phosphide nanowires: an efficient electrocatalyst for enzymeless hydrogen peroxide detection | |
| Du et al. | Vertical α-FeOOH nanowires grown on the carbon fiber paper as a free-standing electrode for sensitive H 2 O 2 detection | |
| Mondal et al. | Probing the shape-specific electrochemical properties of cobalt oxide nanostructures for their application as selective and sensitive non-enzymatic glucose sensors | |
| CN107478699B (en) | A kind of preparation method and its usage of foam transition metal phosphide carried noble metal | |
| Chakraborty et al. | Salivary glucose sensing using highly sensitive and selective non-enzymatic porous NiO nanostructured electrodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140122 Termination date: 20161021 |