CN106770547A - A kind of synthetic method of cobalt acid nickel hollow ball non-enzymatic biological sensor sensing material - Google Patents
A kind of synthetic method of cobalt acid nickel hollow ball non-enzymatic biological sensor sensing material Download PDFInfo
- Publication number
- CN106770547A CN106770547A CN201611112566.9A CN201611112566A CN106770547A CN 106770547 A CN106770547 A CN 106770547A CN 201611112566 A CN201611112566 A CN 201611112566A CN 106770547 A CN106770547 A CN 106770547A
- Authority
- CN
- China
- Prior art keywords
- nico
- beads
- solution
- parts
- ascorbic acid
- 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.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention belongs to field of chemical material synthesizing technology, it is related to a kind of synthetic method of cobalt acid nickel hollow ball non-enzymatic biological sensor sensing material, is at ambient temperature, with CuCl2·5H2O、SDS、NH2OHHCl and NaOH are that raw material prepares Cu2O beads；Take Cu2O beads are scattered in the mixed solution containing PVP, and ultrasonic agitation uniformly adds NiCl afterwards2·6H2O and CoCl2·6H2O, is subsequently added Na2S2O3, centrifuge washing, drying, calcining, collect and obtain NiCo after stable reaction2O4Powder.Present invention process is simple, and reaction condition is gentle, with Cu2O beads are that template, nickel chloride and cobalt chloride are nickel source and cobalt source, and hollow NiCo is prepared using quick etching method2O4Presoma, NiCo is obtained through calcination2O4Hollow nano-sphere, resulting materials not only maintain the pattern of cuprous oxide, and also with polycrystalline feature, the electrode modified using the material shows excellent detection performance, and Ascorbic Acid has good selectivity.
Description
Technical field
The invention belongs to field of chemical material synthesizing technology, it is related to a kind of synthetic method of sensitive material, it is specifically a kind of to use
In the synthetic method of the cobalt acid nickel hollow ball non-enzymatic biological sensor sensing material of Ascorbic Acid detection.
Background technology
Ascorbic acid (AA) is a kind of important water soluble vitamin for maintaining body normal physiological function, and it participates in human body
A series of interior metabolic activities and redox reaction.Ascorbic acid content is too high in vivo can cause stomach convulsion, otherwise in vivo
Shortage can then cause the various disease conditions such as scurvy, soft tissue bleeding and hypoimmunity.Therefore, Ascorbic Acid Determination method
Research has important theoretical and practical significance.Now, the method for determining ascorbic acid is a lot, including titrimetry method, fluorescence
Agent method, voltammetry, flow injection analysis, spectrophotometry de termination, ultra-performance liquid chromatography and electrochemical sensor etc., its
In, electrochemical sensor method has analyze speed fast, and reagent dosage is few, and detection sensitivity it is high the advantages of, so anti-in detection
There is preferable prospect in the detection of bad hematic acid.Electrochemical sensor is based primarily upon the redox of target detection thing and material surface
Effect, it is easy to operation, paid close attention to by more and more researchers.
So far, based on nickel oxide (NiO), cobalt oxide (Co3O4), cuprous oxide (Cu2O), zinc oxide (ZnO), dioxy
Change manganese (MnO2) and cobalt acid nickel (NiCo2O4) etc. transition metal oxide for modified electrode sensitive material sensor lead
Domain has carried out certain research.Wherein in these oxides, due to ternary transition oxide NiCo2O4Contain different prices
Nickel ion and cobalt ions, show the electron conduction and excellent electro catalytic activity of superelevation.According to research reports, with NiO, Co3O4
Compare, hybrid transition metal NiCo2O4Electron conduction be at least more than their twice, these characteristics to test high-performance
Electrochemical sensor electrodes material it is highly beneficial.
The pattern of material plays an important role with structure on performance, hollow-core construction due to have surface area higher,
Permeability and the shorter diffusion path of electronic and ionic, are widely used in electric photonic propulsion, catalyst, insoluble drug release and biology
In sensor.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of cobalt acid nickel hollow ball non-enzymatic biological sensor sensing material, with
Cu2O beads are template, and nickel chloride and cobalt chloride are nickel source and cobalt source, obtain hollow by quick etching method in a mild condition
NiCo2O4Presoma, NiCo is obtained through calcination2O4Hollow nano-sphere, cobalt acid nickel hollow ball maintains the pattern of cuprous oxide,
With polycrystalline feature, in the application of electrode that the material is modified to ascorbic acid non-enzymatic electrochemical sensor, it is to Vitamin C
Acid has preferable detectable limit, linear correlation system, linear detection range, and sensitivity is high, shows excellent detection performance,
And Ascorbic Acid has good selectivity.
The technical solution adopted in the present invention：
A kind of synthetic method of cobalt acid nickel hollow ball non-enzymatic biological sensor sensing material, it is comprised the following steps that：
1、Cu2The preparation of O beads
At ambient temperature, by 2~4 parts of CuCl of 0.1M of volume parts2·5H2O solution is added to 180~200 parts and goes
In ionized water, and SDS (lauryl sodium sulfate) is added in deionized water, stirring is completely dissolved to SDS, makes its ultimate density
It is 9.0~12.0mg/mL, then by the NH of 8~12 volume parts 0.2M2OHHCl (hydroxylamine hydrochloride) is added in mixed solution, most
The NaOH of 4~6 volume parts 1M is rapidly joined afterwards, is mixed, until solution colour is changed into yellow from green.Treat colour stable
Afterwards, reaction solution is allowed to be aged 40~50min at room temperature.Clean with distilled water centrifuge washing afterwards, vacuum is dried at 55~65 DEG C
Dry 22~26h, finally collects powder sample and is Cu2O beads.
2nd, the preparation of metallic oxide hollow sphere
It is by volume 1 to take second alcohol and water:1 ratio is mixed to get mixed liquor, weighs 1~3 part respectively by weight
Cu2, first be dissolved in PVP in 500~550 portions of mixed liquors by O beads, 28~32 parts of PVP (poly- acetyl pyrrole alkanone, Mw ≈ 55000),
Again by Cu2O beads are scattered in mixed liquor, and ultrasonic agitation uniformly adds NiCl afterwards2·6H2O and CoCl2·6H2O, stirring makes it
Ultimate density is respectively 0.001~0.003mg/L, 0.002~0.004mg/L；Then by volume in above-mentioned solution dropwise
Add 0.004 part of 1M Na2S2O3.After colour stable immediately use distilled water and ethanol centrifuge washing, at 40~50 DEG C dry after
280~320 DEG C of 2~3h of calcining in air, collection obtains NiCo2O4Powder.
Present invention process is simple, and reaction condition is gentle, with Cu2O beads are that template, nickel chloride and cobalt chloride are nickel source and cobalt
Source, hollow NiCo is prepared using quick etching method2O4Presoma, NiCo is obtained through calcination2O4Hollow nano-sphere, gained material
Material not only maintains the pattern of cuprous oxide, also with polycrystalline feature, has preferably detection using the material modified electrode
The limit, linear correlation system, linear detection range, sensitivity are high, show excellent detection performance, and Ascorbic Acid has
Good selectivity.
Brief description of the drawings
Fig. 1 is Cu2O beads and NiCo2O4The stereoscan photograph figure of hollow ball：(a)Cu2O；(b)NiCo2O4。
Fig. 2 is NiCo2O4The XPS collection of illustrative plates of hollow ball：(a) full spectrogram；(b)Co 2p；(c)Ni 2p；(d)O 1s.
Fig. 3 is the EIS curves of the glass-carbon electrode of different sensitive material modifications：(a)NiO；(b)Co3O4；(c)NiCo2O4。
Fig. 4 is NiCo2O4The CV curves of/GCE in with/without the 0.1M NaOH solutions containing 1mM ascorbic acid：A () has
Ascorbic acid；B () is without ascorbic acid；CV curve of (c) bare electrode in the 0.1M NaOH solutions containing 1mM ascorbic acid.
Fig. 5 is that difference sweeps NiCo under speed2O4(illustration is peak current and scanning to CV curves of/the GCE in ascorbic acid solution
The fitted figure of speed).
Fig. 6 is NiCo in 0.1M NaOH solutions2O4(illustration is corresponding fitting to chrono-amperometric detection (+0.54V) of/GCE
Curve).
Fig. 7 is containing UA, and the relative value of electric current is tested in the ascorbic acid solution of DA, sucrose.
Specific embodiment
With reference to embodiment, specific embodiment of the invention is described in further detail.Following examples are used for
The present invention is illustrated, but is not limited to the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally
According to normal condition, or according to the condition proposed by manufacturer.
First, NiCo2O4The preparation of powder
1st, by 2mL 0.1M CuCl under the conditions of room temperature (25 DEG C)2·5H2O and 1.74g SDS (lauryl sodium sulfate)
In sequentially adding 180mL deionized waters, stirring to SDS is completely dissolved, then by the NH of 10mL 0.2M2OHHCl (hydroxylamine hydrochloride)
Add above-mentioned mixed solution.The NaOH for being then quickly added into 5mL 1M shakes up manually, until solution colour is changed into from green
Yellow.40min is aged at room temperature after reaction solution after colour stable, is allowed.It is clean with distilled water centrifuge washing afterwards, at 60 DEG C
Vacuum drying 24h, finally collects powder sample and is Cu2O beads.
2nd, it is by volume 1 to take second alcohol and water:1 ratio is mixed to get mixed liquor, and 10mg Cu are weighed respectively2O beads,
, first be dissolved in PVP in 500mL mixed liquors by 30mg PVP (poly- acetyl pyrrole alkanone, Mw ≈ 55000), then by Cu2O beads disperse
In mixed liquor, ultrasonic agitation uniformly adds 0.57mg NiCl afterwards2·6H2O and 1.13mg CoCl2·6H2O, is followed by stirring for
10min.Then to being added dropwise over 4mL 1M Na in above-mentioned solution2S2O3.It is centrifuged with distilled water and ethanol immediately after colour stable
Washing, at 40 DEG C dry after in atmosphere 300 DEG C calcining 2h, collection obtain NiCo2O4Powder.
2nd, the sign of material
X-ray powder diffraction (XRD) collection of illustrative plates use Germany Bruker AXS D8 diffractometers (Cu K α,
) determine, scanned under tube voltage 40kV, tube current 30mA.SEM (FE-SEM) photo is in Japanese Hitachi
Completed on S-4800 type ESEMs.X-ray photoelectron power spectrum (XPS) atlas analysis are tested in U.S. Thermo
Scientific ESCALAB250 types x-ray photoelectron spectroscopies are carried out, with Al K α as x-ray radiation source.
Cu2O beads and NiCo2O4The stereoscan photograph of hollow ball is as shown in figure 1, Fig. 1 a are Cu2The scanning electricity of O beads
Mirror photo.It can be seen that sample is uniform bead in figure, average diameter is about 300nm.Illustration is the XRD of sample powder
Spectrum, the diffracting spectrum (JCPDS with standard:05-0667) compare, 29.6 °, 36.4 °, 42.3 °, 61.3 °, 73.5 °, 77.3 °
Diffraction maximum corresponds to (110), (111), (200), (220), (311), (222) crystal face.But the width at peak is significantly increased, it may be possible to
Due to made Cu2The crystallization degree of O samples declines, crystallite dimension it is smaller caused by, this shows that the powder sample of gained is polycrystalline
Cu2O beads.Fig. 1 b are with above-mentioned Cu2O beads are hard template, and the ESEM for obtaining product by calcining after chemical etching shines
Piece.From electromicroscopic photograph it can be seen that particle diameter is about the spheric granules of 350nm.From in terms of the breakage of partial particulate, can speculate
Product is hollow-core construction.Be probably due under the conditions of high-temperature calcination, product be heated it is uneven there occurs caving in for structure, and
Cause the phenomenon of part reunion.Upper right corner illustration is the XRD spectrum of sample, the diffracting spectrum (JCPDS with standard:73-
1702) compare, 19.3 °, 31.2 °, 36.8 °, 44.8 °, 59.3 ° and 65 ° correspond respectively to NiCo in figure2O4(111),
(220), (311), (400), (511), (440) crystal face.With Cu2The situation of O is similar to, and diffraction maximum is weaker, and peak width is significantly increased, this
Show that the gained sample is NiCo2O4Polycrystalline structure.In building-up process, NiCo2O4The pattern of hard template is maintained, also one
Determine to present its polycrystalline feature in degree.
In order to further determine that gained sample (NiCo2O4) in contained element species and valence state, X-ray has been carried out to it
The sign of photoelectron spectroscopy, its XPS spectrum figure and its matched curve are as shown in Figure 2.Mainly contained in sample obtained by figure (a) expression
Tri- kinds of elements of Co, Ni and O, this is consistent with the result of XRD analysis.Additionally, also containing a small amount of C element in sample, this may
It is PVP no completely cleared caused.Figure (b) is the XPS collection of illustrative plates of Co2p, it can be seen that there is 2p at Co2p peaks3/2With
2p1/2Two peaks, and have its corresponding satellite peak near each main peak, show Co2+, Co3+While exist.Figure (c) is Ni2p
XPS collection of illustrative plates, Ni2p peaks are similar with Co2p peaks in figure, show NiCo2O4In simultaneously there is Ni2+And Ni3+.This is reported with above
The spinelle NiCo in road2O4The characteristic of the XPS of middle Ni, Co element matches.High power XPS collection of illustrative plates and its fitting of the figure (d) for O1s
Curve, three kinds of different oxygen components, are represented with O1, O2, O3 respectively as can be observed from Figure.Wherein, positioned at the O1 of 529.5ev
Peak correspondence is the associative key in typical oxide between metal and oxygen；Positioned at the O3 peaks correspondence metal oxide table of 531.1ev
The defect in face；The absorption water in metal oxide is then corresponded to positioned at the O3 peaks of 532.6ev.XPS pattern analysis results show gained
NiCo2O4Material surface includes abundant Co2+、Co3+、Ni2+、Ni3+.The nickel ion and cobalt ions of these different prices be
NiCo2O4The electric conductivity and electro catalytic activity of sample provide favourable condition[7]。
3rd, the preparation of working electrode and electro-chemical test
All electrochemical measurements are carried out on CHI660E electrochemical workstations (Shanghai Chen Hua, China), using three electricity
Polar body system：Glass-carbon electrode (diameter 3mm) is working electrode, and Ag/AgCl electrodes are reference electrode, and Pt electrodes are to electrode.Glass carbon
Electrode is thoroughly clear with ethanol and deionized water after polishing every time with 1.0 μm, 0.3 μm, 0.05 μm of alumina powder polishing grinding successively
Wash, dry in atmosphere.The NiCo that will be prepared2O4Hollow ball is dispersed in absolute ethyl alcohol (5mg/mL), takes a certain amount of gained dispersion
Drop-coated is in the glassy carbon electrode surface handled well.The certain density NaOH of 5mL is standby as electrolyte solution.
Electrochemical impedance spectroscopy (EIS) is usually used in analyzing the charge transfer resistance of modified electrode, with the electrochemistry of assessment material
Performance.Fig. 3 provides NiO, Co3O4, NiCo2O4The electrode of modification EIS collection of illustrative plates in 10mmol/L potassium ferricyanide solutions.Three in figure
Bar curve has obvious semi arch in high frequency region, and semi arch is handed over the lewis' acid in electrolyte with the electric charge of electrode surface
Throw-over rate is relevant, and the size of arc radius represents the size of charge transfer resistance.Shown in figure, compared to NiO, Co3O4, NiCo2O4Repair
The electrode of decorations has less high frequency region semi arch, illustrates that it has smaller charge transfer resistance, embodies its good conductive
Performance, thus NiCo2O4The electrode surface of modification is easier catalytic oxidation.
Fig. 4 is Different electrodes cyclic voltammetric (CV) curve in the solution, wherein, (a), (b) are respectively NiCo2O4/GCE
CV curves in with/without the 0.1M NaOH solutions containing 1mM ascorbic acid；C () is containing 1mM ascorbic acid for bare electrode
0.1M NaOH solutions in CV curves.Curve a and curve c can be seen that electrode by active material NiCo in comparison diagram2O4
After modification, a pair obvious redox peaks are occurred in that on its CV curve, illustrate NiCo2O4With preferable electro-chemical activity, together
When larger response current show NiCo2O4With less charge transfer resistance, the electric conductivity of electrode is improved, may advantageously facilitate
It is redox to carry out；Correlation curve a and curve b understands, after adding ascorbic acid in the solution, the oxidation peak current of CV curves
Obvious enhancing is obtained, has shown NiCo2O4The electrode Ascorbic Acid of modification has preferable electro catalytic activity.Therefore,
NiCo2O4Can be as the sensor sensing material of ascorbic acid.
In order to further study the rate-determining steps of electrode interface reaction, we to its oxidation peak current and corresponding will sweep
The relation retouched between speed is analyzed.Fig. 5 is shown NiCo2O4Modified electrode is in the 0.1M containing 1mM ascorbic acid
In NaOH solution, the CV curves of different scanning rates.Experiment shows：With the increase of sweep speed, oxidation peak and reduction peak are electric
Stream is also with enhancing.Corresponding sweep speed and peak current intensity fitting result as is shown in said inset, in 10~100mV/s scopes
It is interior, its linearly dependent coefficient R2Respectively 0.9931,0.9968, both this explanations have good linear relationship, therefore electrode
The rate-determining steps of process are reaction controlling.
In order to determine by the quantitative relationship between different ascorbic acid concentrations and electric current, the electrode is used for current-vs-time
Curve tests (test of i-t curves), and the electrolyte of test is 0.1M NaOH solutions.Fig. 6 is be continuously added to various concentrations anti-bad
The i-t curves of hematic acid, illustration is corresponding concentration-current strength Linear Fit Chart.As can be seen from the figure it is molten in 0.1M NaOH
In liquid, under the conditions of the operating potential of+0.54mV, the quick response of Ascorbic Acid is successfully realized.From the fitting result of illustration
It has been shown that, its detection is limited to 3 × 10-7M (S/N=3), linearly dependent coefficient is 0.9993, and linear detection range is 0.1mM~3mM,
Sensitivity is up to 1148.7 μ AmM-1·cm-2.Additionally, NiCo2O4The detection of the electrode Ascorbic Acid of modification is limited to 0.3 μM.
In sum, NiCo2O4The electrode of modification shows Ascorbic Acid and shows good detection performance.The electrode has good
Ascorbic acid detection performance possible cause be：NiCo2O4With preferable electric conductivity and electro-chemical activity, while hollow knot
Structure has larger specific surface area, and the electroactive site that increased electrode surface further increases the detection of its Ascorbic Acid
Performance.
Antijamming capability is another important indicator for characterizing sensor performance.Therefore, from uric acid (UA), dopamine
(DA), sucrose carries out anti-interference test, the antijamming capability of detecting electrode as chaff interference.Testing result is as shown in Figure 7.From
As can be seen that the response current influence of the addition Ascorbic Acid of chaff interference is smaller in figure, NiCo is illustrated2O4The electrode pair of modification
The response of ascorbic acid has certain selectivity.Stability test shows, the relative standard deviation RSD=of the test of the electrode
3.93% (n=5), illustrates that electrode stability is preferable.
The present invention prepares NiCo using simple gentle synthetic method2O4Hollow material, shows from the result of XRD and SEM
Show, obtained the NiCo of a diameter of 350nm2O4Hollow ball, with polycrystalline feature.By simple on glass-carbon electrode (GCE) surface
The method of drop coating is made non-enzymatic electrochemical sensor, for the direct measure of ascorbic acid concentrations.Shown by electro-chemical test,
The detectable limit of its Ascorbic Acid is 3 × 10-7M (S/N=3), linear detection range is 0.1mM~3mM, and sensitivity is up to
1148.7μA·mM-1·cm-2, Ascorbic Acid detected representation goes out excellent detection performance, and with good selectivity.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, on the premise of the technology of the present invention principle is not departed from, some improvements and modifications can also be made, these improvements and modifications
Also should be regarded as protection scope of the present invention.
Claims (1)
1. the synthetic method of a kind of cobalt acid nickel hollow ball non-enzymatic biological sensor sensing material, it is comprised the following steps that：
1)、Cu2The preparation of O beads
At ambient temperature, by 2~4 parts of CuCl of 0.1M of volume parts2·5H2O solution is added to 180~200 parts of deionization
In water, and SDS is added in deionized water, stirring is completely dissolved to SDS, make its ultimate density for 9.0~12.0mg/mL, then
By the NH of 8~12 volume parts 0.2M2OHHCl is added in mixed solution, finally rapidly joins the hydrogen of 4~6 volume parts 1M
Sodium oxide molybdena, mixes, until solution colour is changed into yellow from green；After after colour stable, allow reaction solution be aged 40 at room temperature~
50min；It is clean with distilled water centrifuge washing afterwards, 22~26h of vacuum drying at 55~65 DEG C, finally collecting powder sample is
It is Cu2O beads；
2), the preparation of metallic oxide hollow sphere
It is by volume 1 to take second alcohol and water:1 ratio is mixed to get mixed liquor, weighs 1~3 part of Cu respectively by weight2O is small
Ball, 28~32 parts of PVP, the Mw ≈ 55000 of wherein PVP；First PVP is dissolved in 500~550 portions of mixed liquors, then by Cu2O beads
It is scattered in mixed liquor, ultrasonic agitation uniformly adds NiCl afterwards2·6H2O and CoCl2·6H2O, stirring distinguishes its ultimate density
It is 0.001~0.003mg/L, 0.002~0.004mg/L；Then by volume to being added dropwise over 0.004 part of 1M in above-mentioned solution
Na2S2O3；Distilled water and ethanol centrifuge washing are used after colour stable immediately, in atmosphere 280~320 after being dried at 40~50 DEG C
DEG C calcining 2~3h, collection obtain NiCo2O4Powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611112566.9A CN106770547A (en) | 2016-12-07 | 2016-12-07 | A kind of synthetic method of cobalt acid nickel hollow ball non-enzymatic biological sensor sensing material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611112566.9A CN106770547A (en) | 2016-12-07 | 2016-12-07 | A kind of synthetic method of cobalt acid nickel hollow ball non-enzymatic biological sensor sensing material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106770547A true CN106770547A (en) | 2017-05-31 |
Family
ID=58878437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611112566.9A Pending CN106770547A (en) | 2016-12-07 | 2016-12-07 | A kind of synthetic method of cobalt acid nickel hollow ball non-enzymatic biological sensor sensing material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106770547A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108318556A (en) * | 2017-12-24 | 2018-07-24 | 苏州南尔材料科技有限公司 | A kind of preparation method of graphene cobalt acid nickel sensor material |
| CN108333242A (en) * | 2017-12-31 | 2018-07-27 | 苏州南尔材料科技有限公司 | A kind of preparation method of nano-cellulose cobalt acid nickel sensor material |
| CN109580737A (en) * | 2018-11-13 | 2019-04-05 | 云南大学 | A kind of preparation method of non-enzymatic glucose electrolytic catalysis material |
| CN110182858A (en) * | 2019-07-09 | 2019-08-30 | 南京林业大学 | The hollow NiCo of high-sequential2O4The preparation method of electrode material |
| WO2021104087A1 (en) * | 2019-11-28 | 2021-06-03 | 深圳先进技术研究院 | Metal oxide nanoparticles, and preparation method therefor and application thereof |
| CN115246659A (en) * | 2021-10-18 | 2022-10-28 | 齐齐哈尔大学 | Preparation method of defective hollow nickel cobaltate nanocube |
| CN115372435A (en) * | 2022-08-15 | 2022-11-22 | 金陵科技学院 | Snow cake-shaped NiCo 2 O 4 Electrode material modified by nano material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103928676A (en) * | 2014-04-25 | 2014-07-16 | 云南大学 | Hollow nano cubic NiCo2O4 dual-metal oxide material and preparation method thereof |
| CN104129818A (en) * | 2014-07-09 | 2014-11-05 | 奇瑞汽车股份有限公司 | Nickel-cobalt oxide material and preparation method thereof |
| CN104979551A (en) * | 2015-07-17 | 2015-10-14 | 武汉大学 | Carbon nano-sphere/NiCo2O4 composite material as well as preparation method and application thereof |
| CN105651836A (en) * | 2016-02-26 | 2016-06-08 | 浙江大学 | Self-driven all-solid-state glucose biosensor and preparation method thereof |
-
2016
- 2016-12-07 CN CN201611112566.9A patent/CN106770547A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103928676A (en) * | 2014-04-25 | 2014-07-16 | 云南大学 | Hollow nano cubic NiCo2O4 dual-metal oxide material and preparation method thereof |
| CN104129818A (en) * | 2014-07-09 | 2014-11-05 | 奇瑞汽车股份有限公司 | Nickel-cobalt oxide material and preparation method thereof |
| CN104979551A (en) * | 2015-07-17 | 2015-10-14 | 武汉大学 | Carbon nano-sphere/NiCo2O4 composite material as well as preparation method and application thereof |
| CN105651836A (en) * | 2016-02-26 | 2016-06-08 | 浙江大学 | Self-driven all-solid-state glucose biosensor and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| WEI HUANG 等: "Fast synthesis of porous NiCo2O4 hollow nanospheres for a high-sensitivity non-enzymatic glucose sensor", 《APPLIED SURFACE SCIENCE》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108318556A (en) * | 2017-12-24 | 2018-07-24 | 苏州南尔材料科技有限公司 | A kind of preparation method of graphene cobalt acid nickel sensor material |
| CN108333242A (en) * | 2017-12-31 | 2018-07-27 | 苏州南尔材料科技有限公司 | A kind of preparation method of nano-cellulose cobalt acid nickel sensor material |
| CN109580737A (en) * | 2018-11-13 | 2019-04-05 | 云南大学 | A kind of preparation method of non-enzymatic glucose electrolytic catalysis material |
| CN110182858A (en) * | 2019-07-09 | 2019-08-30 | 南京林业大学 | The hollow NiCo of high-sequential2O4The preparation method of electrode material |
| WO2021104087A1 (en) * | 2019-11-28 | 2021-06-03 | 深圳先进技术研究院 | Metal oxide nanoparticles, and preparation method therefor and application thereof |
| CN115246659A (en) * | 2021-10-18 | 2022-10-28 | 齐齐哈尔大学 | Preparation method of defective hollow nickel cobaltate nanocube |
| CN115246659B (en) * | 2021-10-18 | 2024-05-03 | 齐齐哈尔大学 | Preparation method of defect type hollow nickel cobalt oxide nanocube |
| CN115372435A (en) * | 2022-08-15 | 2022-11-22 | 金陵科技学院 | Snow cake-shaped NiCo 2 O 4 Electrode material modified by nano material and preparation method and application thereof |
| CN115372435B (en) * | 2022-08-15 | 2024-08-02 | 金陵科技学院 | Snow cake-shaped NiCo2O4Nano material modified electrode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106770547A (en) | A kind of synthetic method of cobalt acid nickel hollow ball non-enzymatic biological sensor sensing material | |
| Lavanya et al. | Electrochemical sensor for simultaneous determination of ascorbic acid, uric acid and folic acid based on Mn-SnO2 nanoparticles modified glassy carbon electrode | |
| Wu et al. | A novel nonenzymatic electrochemical sensor based on 3D flower-like Ni7S6 for hydrogen peroxide and glucose | |
| Gopal et al. | MXene-based composite electrodes for efficient electrochemical sensing of glucose by non-enzymatic method | |
| Moarefdoust et al. | An electrochemical sensor based on hierarchical nickel oxide nanostructures doped with indium ions for voltammetric simultaneous determination of sunset yellow and tartrazine colorants in soft drink powders | |
| Jia et al. | A novel nonenzymatic ECL glucose sensor based on perovskite LaTiO3-Ag0. 1 nanomaterials | |
| Hosseini et al. | Nonenzymatic glucose and hydrogen peroxide sensors based on catalytic properties of palladium nanoparticles/poly (3, 4-ethylenedioxythiophene) nanofibers | |
| CN107991371B (en) | Copper oxide non-enzymatic glucose electrochemical sensor | |
| Chen et al. | Facile synthesis of copper (II) oxide nanospheres covered on functionalized multiwalled carbon nanotubes modified electrode as rapid electrochemical sensing platform for super-sensitive detection of antibiotic | |
| Zhang et al. | A vertically aligned CuO nanosheet film prepared by electrochemical conversion on Cu-based metal-organic framework for non-enzymatic glucose sensors | |
| CN110082416A (en) | A kind of l-tyrosine and dopamine Simultaneous Detection and sensor based on complex film modified electrode | |
| Lv et al. | Zinc ion mediated synthesis of cuprous oxide crystals for non-enzymatic glucose detection | |
| Zhang et al. | Screen-printing of core-shell Mn3O4@ C nanocubes based sensing microchip performing ultrasensitive recognition of allura red | |
| Hao et al. | Monodisperse copper selenide nanoparticles for ultrasensitive and selective non-enzymatic glucose biosensor | |
| Yang et al. | Facile preparation of MnO2–TiO2 nanotube arrays composite electrode for electrochemical detection of hydrogen peroxide | |
| Jia et al. | Facile in-situ synthesis of Ti3C2Tx/TiO2 nanowires toward simultaneous determination of ascorbic acid, dopamine and uric acid | |
| Rohani et al. | A novel and sensitive electrochemical sensor, MgONP/MWCNT/CCE, for the concurrent detection of biotin and dopamine | |
| Manjula et al. | Electrochemical sensors for β-adrenoceptor agonist isoprenaline analysis in human urine and serum samples using manganese cobalt oxide-modified glassy carbon electrode | |
| Zhao et al. | Self-supported loofah-like Co (OH) F@ NiMn-LDH hierarchical core–shell nanosheet arrays as efficient electrocatalyst for hydrazine sensing | |
| Rajab et al. | Selective determination of nitrite in water and food samples using zirconium oxide (ZrO 2)@ MWCNTs modified screen printed electrode | |
| CN112362712B (en) | Electrochemical sensor electrode capable of simultaneously detecting heavy metal lead and cadmium ions in grains | |
| Phung et al. | Copper molybdenum sulfide (Cu 2 MoS 4) nanoplates as a proficient electrocatalytic interface for enhancing the electrochemical redox signals of ofloxacin for detection in pharmaceutical samples | |
| Lin et al. | Nano-composite of Co 3 O 4 and Cu with enhanced stability and catalytic performance for non-enzymatic electrochemical glucose sensors | |
| Zou et al. | The facile synthesis of a Co 3 O 4–NiNP composite as an electrochemical non-enzymatic sensing platform for small chemical molecules | |
| Cheng et al. | A 3D reduced graphene oxide and flower-like ZnO crystal composite for electrochemical detection of reducing small biomolecules |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170531 |