CN108445065A - A kind of preparation method and its electrocatalysis characteristic research of black phosphorus alkene hemin modified electrode - Google Patents
A kind of preparation method and its electrocatalysis characteristic research of black phosphorus alkene hemin modified electrode Download PDFInfo
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Abstract
The invention discloses a kind of black phosphorus alkene（BP）Hemin（Hemin）The preparation method and its electrocatalysis characteristic of modified electrode are studied, and the preparation method comprises the following steps：According to mass ratio（1.5~2.5）:1 takes graphite powder and ionic liquid（1 hexyl pyridine hexafluorophosphate, HPPF6）Carbon paste is obtained after being ground uniformly in mortar, is then filled in vitreous electricity pole pipe and is compacted, interpolation copper wire obtains ionic liquid carbon paste electrode as conducting wire（CILE）；Full of nitrogen（N2）Glove box in, take BP and poly- (styrene sulfonate) the i.e. PEDOT of Polyglycolic acid fibre by certain mass ratio：After sonic oscillation, it is mixed with a concentration of 20 ~ 40 mg/mL Hemin by certain volume ratio by PSS；It takes 5 ~ 10 μ L mixed solution drop coatings to the surfaces CILE, can be obtained modified electrode (BP PEDOT after dry in the glove box full of nitrogen:PSS‑Hemin/CILE).Modified electrode produced by the present invention is to trichloroacetic acid（TCA）And sodium nitrite（NaNO2）Electro-catalysis reduction effect it is good, the range of linearity is wide, detection limit low, high sensitivity.
Description
Technical field
The present invention relates to chemically modified electrode sensor technical fields more particularly to a kind of black phosphorus alkene hemin to modify
The preparation method and its Study of electrocatalysis of electrode.
Background technology
Biosensor is that a kind of biological combination or the sensing element of biological derivative and the analysis of physics and chemistry energy converter fill
It sets, it has important practical value in environmental monitoring, Food Inspection, drugs analysis and biochemical analysis etc., and can carry out
Quickly detection.One good sensor should has the following advantages：High sensitivity and selectivity, response quickly, reproducibility and
Stability is good, has long service life etc..With being constantly progressive for current biological sensing technology, to performance of biosensor
It is required that stepping up, Development of Novel is easy, accurate and reliable, sensitive and durable biosensor is particularly important.
In two-dimensional material field, black phosphorus alkene（BP）It is a kind of novel direct band-gap semicondictor material, possesses cellular
Fold lamellar structure, have big surface area.The appearance of two-dimentional BP is greatly enriched two-dimensional material field, to being at present
Only, monolayer BP is successfully stripped out.Compared to two-dimentional transition-metal sulphides（TMDCs）, BP is with higher current-carrying
Transport factor and high leakage current modulation capability, have a wide range of applications in photoelectric field.Although BP has many advantages,
It is research shows that BP is very sensitive to oxygen and water, when being contacted with natural environment and under the synergy of visible light, BP is easily
It is oxidized to PxOy.Therefore during experimental implementation, in order to keep electrical stability energy of the BP devices under air conditions, lead to
Normal way is to be covered in the surfaces BP using inert material to protect it.
Poly- 3,4- ethylenedioxy thiophenes；Polystyrolsulfon acid（PEDOT:PSS）A kind of conducting polymer composite, have at
The advantages that film property is good, thin film stability is high, good conductivity, in radar absorbing, electrochromic material, electrode material, anti-corrosion
There is research to apply in terms of material and sensor material.
The present invention utilizes PEDOT:PSS carries out effective protection to BP, in N2In the presence of prepare a kind of modified electrode（BP-
PEDOT:PSS-Hemin/CILE）, the Direct Electrochemistry of Hemin is realized, and studied its electrochemical behavior.It utilizes
The sensor is to trichloroacetic acid（TCA）And sodium nitrite（NaNO2）Electrocatalysis characteristic studied.
Invention content
The present invention provides a kind of preparation methods of black phosphorus alkene hemin modified electrode and its electrocatalysis characteristic to study,
Modified electrode obtained is to trichloroacetic acid（TCA）And sodium nitrite（NaNO2）Electro-catalysis reduction effect is good, and the range of linearity is wide,
Detection limits low, high sensitivity.
The technological means that the present invention uses is as follows：A kind of preparation method of black phosphorus alkene hemin modified electrode, including
Following steps：
S1, according to mass ratio（1.5~2.5）:1 takes graphite powder and ionic liquid（1- hexyl pyridine hexafluorophosphates, HPPF6）In
In mortar, carbon paste is obtained after grinding uniformly, then carbon paste is inserted in vitreous electricity pole pipe and is compacted, interpolation copper wire is obtained as conducting wire
To CILE；
S2, full of N2Glove box in, take BP and PEDOT by certain mass ratio：PSS is in brown centrifuge tube, after mixing
It is mixed with 20 ~ 40 mg/mL Hemin according to certain volume ratio, takes 5 ~ 10 μ L solution drop coatings to CILE by sonic oscillation
Surface can be obtained electrode to be prepared after dry in glove box（BP-PEDOT:PSS-Hemin/CILE）.
Further, in the S1 steps, graphite powder and ionic liquid HPPF6Mass ratio be 2:1.
Further, in the S1 steps, the milling time is 2 ~ 3 h or more.
Further, in the S1 steps, the glass electrode bore is 4 mm.
Further, in the S2 steps, Hemin solution concentrations are 30 mg/mL.
Further, in the S2 steps, BP and PEDOT：The mass ratio of PSS is 1:5.
Further, in the S2 steps, Hemin and mixing suspension（BP and PEDOT：PSS）Volume ratio be 1:1.
Further, the preparation method of a kind of black phosphorus alkene hemin modified electrode, includes the following steps：
S1,1.6 g graphite powders, 0.8 g ionic liquids are taken（1- hexyl pyridine hexafluorophosphates, HPPF6）In mortar, grinding is equal
Carbon paste is obtained after even, and then carbon paste is inserted in vitreous electricity pole pipe and is compacted, interpolation copper wire obtains CILE as conducting wire；
S2, full of N2Glove box in, in mass ratio 1:5 take BP and PEDOT：PSS is ultrasonic after mixing in brown centrifuge tube
Oscillation, it is mixed in equal volume with 30 mg/mL Hemin, takes the 8 μ L solution drop coatings to the surfaces CILE, dry in glove box
After can be obtained electrode to be prepared（BP-PEDOT:PSS-Hemin/CILE）.
Any one of them black phosphorus alkene hemin modified electrode of the present invention is for electro-catalysis reduction trichloroacetic acid and Asia
Sodium nitrate.
The detection environment of black phosphorus alkene hemin modified electrode of the present invention is the phosphate-buffered in pH 2.0
In solution.
In the present invention, HPPF6For 1- hexyl pyridine hexafluorophosphates, CILE is ionic liquid carbon paste electrode, and BP is black phosphorus
Nanometer sheet dispersion liquid, PEDOT:PSS is that Polyglycolic acid fibre-is poly- (styrene sulfonate), and Hemin is hemin, TCA
For trichloroacetic acid, NaNO2For sodium nitrate, PBS buffer solution is phosphate buffer solution.
Compared with prior art, the beneficial effects of the invention are as follows：
The black phosphorus alkene that the present invention uses（BP）It is a kind of novel direct band gap two-dimensional material, BP has higher carrier mobility
Rate and high leakage current modulation capability.The BP-PEDOT that the present invention is prepared using mixing drop-coating:PSS-Hemin/CILE is in pH
Occur the good redox peaks of a pair of of peak shape in 2.0 PBS, to trichloroacetic acid（TCA）And sodium nitrite（NaNO2）Electricity is urged
Change reduction effect is good, and the range of linearity is respectively 2.0 ~ 170.0 mmol L-1, 1.0 ~ 10.5 mmol L-1, the range of linearity
Extensively, high sensitivity can be applied to detection trichloroacetic acid very well（TCA）And sodium nitrite（NaNO2）The content in object.
Description of the drawings
Fig. 1 is different modifying electrode in the PBS buffer solutions of pH 2.0,100 mV/s cyclic voltammograms of sweep speed,
Wherein
Curve d is the BP-PEDOT of embodiment 3:The cyclic voltammetry curve of PSS-Hemin/CILE modified electrodes,
Curve c is the PEDOT of comparative example 1:The cyclic voltammetry curve of PSS-Hemin/CILE modified electrodes,
Curve b is the PEDOT of comparative example 3:The cyclic voltammetry curve of PSS/CILE modified electrodes,
Curve a is the BP-PEDOT of comparative example 2:The cyclic voltammetry curve of PSS/CILE modified electrodes.
Fig. 2 is BP-PEDOT in different pH buffer solutions:Cyclic voltammogram (a to the g of PSS-Hemin/CILE： 2.0,
3.0, 4.0, 5.0, 6.0, 7.0, 8.0)；
Fig. 3 is Middle Eocene (E0′) with the linear relationship of pH；
Fig. 4 is cyclic voltammogram of modified electrode in the presence of various concentration TCA, and a to m is 2.0,10.0,20.0,30.0,
40.0, 50.0, 60.0, 70.0, 80.0, 90.0, 110, 140, 170 mmol L-1, wherein illustration is reduction peak electricity
Graph of relation between stream and the concentration of TCA；
Fig. 5 is modified electrode in various concentration NaNO2In the presence of cyclic voltammogram, a to i be 1.6,2.6,3.6,4.6,
5.6, 6.6, 7.6, 8.6, 9.6 mmol L-1, wherein illustration is reduction peak current and NaNO2Concentration between relationship it is bent
Line chart.
Specific implementation mode
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
Embodiment 1
A kind of preparation method of black phosphorus alkene hemin modified electrode, includes the following steps：
S1, according to mass ratio 1.5:1 takes 1.5 g graphite powders and 1.0 g ionic liquids（1- hexyl pyridine hexafluorophosphates,
HPPF6）In mortar, carbon paste is obtained after grinding 2 h, then carbon paste is inserted in 4 mm vitreous electricity pole pipes and is compacted, interpolation copper wire
As conducting wire, CILE is obtained；
It needs electrode surface being polishing to minute surface on polishing paper before carrying out electrode modification every time；
S2, full of N2Glove box in, in mass ratio 1:5 take BP and PEDOT：PSS is ultrasonic after mixing in brown centrifuge tube
Oscillation, it is mixed in equal volume with 40 mg/mL Hemin, takes the 5 μ L solution drop coatings to the surfaces CILE, dry in glove box
After can be obtained electrode to be prepared（BP-PEDOT:PSS-Hemin/CILE）.
Embodiment 2
A kind of preparation method of black phosphorus alkene hemin modified electrode, includes the following steps：
S1, according to mass ratio 2.5:1 takes 2.5 g graphite powders and 1.0 g ionic liquids（1- hexyl pyridine hexafluorophosphates,
HPPF6）In mortar, carbon paste is obtained after grinding 2.5 h, then carbon paste is inserted in 4 mm vitreous electricity pole pipes and is compacted, interpolation copper
Silk is used as conducting wire, obtains CILE；
It needs electrode surface being polishing to minute surface on polishing paper before carrying out electrode modification every time；
S2, full of N2Glove box in, in mass ratio 1:5 take BP and PEDOT：PSS is ultrasonic after mixing in brown centrifuge tube
Oscillation, it is mixed in equal volume with 20 mg/mL Hemin, takes the 10 μ L solution drop coatings to the surfaces CILE, is done in glove box
It can be obtained electrode to be prepared after dry（BP-PEDOT:PSS-Hemin/CILE）.
Embodiment 3
A kind of preparation method of black phosphorus alkene hemin modified electrode, includes the following steps：
S1, according to mass ratio 2:1 takes 1.6 g graphite powders and 0.8 g HPPF6Ionic liquid obtains in mortar after grinding 3 h
Then carbon paste is inserted in 4 mm vitreous electricity pole pipes and is compacted by carbon paste, interpolation copper wire obtains CILE as conducting wire；
It needs electrode surface being polishing to minute surface on polishing paper before carrying out electrode modification every time；
S2, full of N2Glove box in, in mass ratio 1:5 take BP and PEDOT：PSS is ultrasonic after mixing in brown centrifuge tube
Oscillation, it is mixed in equal volume with 30 mg/mL Hemin, takes the 8 μ L solution drop coatings to the surfaces CILE, dry in glove box
After can be obtained electrode to be prepared（BP-PEDOT:PSS-Hemin/CILE）.
Comparative example 1
A kind of preparation method of hemin modified electrode, includes the following steps：
S1, according to mass ratio 2:1 takes 1.6 g graphite powders and 0.8 g ionic liquids（1- hexyl pyridine hexafluorophosphates, HPPF6）
In mortar, carbon paste is obtained after grinding 3 h, then carbon paste is inserted in 4 mm vitreous electricity pole pipes and is compacted, interpolation copper wire is used as and leads
Line obtains CILE；
It needs electrode surface being polishing to minute surface on polishing paper before carrying out electrode modification every time；
S2, full of N2Glove box in, take PEDOT：PSS is in brown centrifuge tube, sonic oscillation, by itself and 30 mg/mL
Hemin is mixed in equal volume, is taken the 8 μ L solution drop coatings to the surfaces CILE, be can be obtained after dry in glove box to be prepared
Electrode（PEDOT:PSS-Hemin/CILE）.
Comparative example 2
A kind of preparation method of black phosphorus modified electrode, includes the following steps：
S1, according to mass ratio 2:1 takes 1.6 g graphite powders and 0.8 g HPPF6Ionic liquid obtains in mortar after grinding 3 h
Then carbon paste is inserted in 4 mm vitreous electricity pole pipes and is compacted by carbon paste, interpolation copper wire obtains CILE as conducting wire；
It needs electrode surface being polishing to minute surface on polishing paper before carrying out electrode modification every time；
S2, full of N2Glove box in, in mass ratio 1:5 take BP and PEDOT：PSS is ultrasonic after mixing in brown centrifuge tube
Oscillation takes the 8 μ L solution drop coatings to the surfaces CILE, can be obtained electrode to be prepared after dry in glove box（BP-
PEDOT:PSS/CILE）.
Comparative example 3
A kind of preparation method of modified electrode, includes the following steps：
S1, according to mass ratio 2:1 takes 1.6 g graphite powders and 0.8 g ionic liquids（1- hexyl pyridine hexafluorophosphates, HPPF6）
In mortar, carbon paste is obtained after grinding 3 h, then carbon paste is inserted in 4 mm vitreous electricity pole pipes and is compacted, interpolation copper wire is used as and leads
Line obtains CILE；
It needs electrode surface being polishing to minute surface on polishing paper before carrying out electrode modification every time；
S2, full of N2Glove box in, take PEDOT：PSS is in brown centrifuge tube, sonic oscillation, takes the 8 μ L solution drop coatings
To the surfaces CILE, electrode PEDOT to be prepared can be obtained after dry in glove box:PSS/CILE.
One, Direct Electrochemistry behaviors of the research Hemin in the PBS buffer solutions of pH=2
Hemin is had studied in the PBS buffer solutions of pH=2,100 mV s of sweep speed-1Direct Electrochemistry behavior, as a result
As shown in Figure 1, it can be seen from the figure that
In curve (a) BP-PEDOT:PSS/CILE（Comparative example 2）On, an almost smoothed curve occurs without any peak.
In curve (b) PEDOT:PSS/CILE（Comparative example 3）On, occur without any redox peaks, i.e., surface does not have
Electroactive material is present in electrode surface.
In curve (c) PEDOT:PSS-Hemin/CILE（Comparative example 1）On, there is a pair of of redox peaks, this explanation
There is electronics transfers between Hemin and CILE electrodes.
In curve (d) BP-PEDOT:PSS-Hemin/CILE（Embodiment 3）On, redox peak current significantly increases,
This illustrates that the presence of BP accelerates electron transfer rate between Hemin and CILE electrodes.BP used in the present invention possesses honeycomb
The fold lamellar structure of shape has big surface area, is conducive to adsorb a large amount of Hemin.
It can be seen directly that spike potential is respectively the V of Epa=0 and the V of Epc=- 0.3, the poor (△ of spike potential from curve d
Ep) it is 0.3 V, Middle Eocene E0'=-0.15 V, the ratio between redox peak current are 1.3, close to 1, show Hemin in BP-
PEDOT:Direct electron transfer on PSS modified electrodes is accelerated.
Two, influences of the research pH to Hemin electrochemical response signals
Electrodes of the pH of this experimental study phosphate buffer solution to embodiment 3（BP-PEDOT:PSS-Hemin/CILE）Directly
The influence of electrochemical behavior, as a result as shown in Fig. 2 ~ 3.When pH is in 2.0 ~ 8.0 ranges, the electrochemical behavior of Hemin is one
Quasi-reversible process, the Middle Eocene of reaction and the size of pH value can be in good linear relationship, obtained equation of linear regression：E0′
(V) = -0.0427 pH - 0.0445 (γ= 0.999).Redox peak current as pH=2.0 is maximum, that is, occurs
The best pH of Direct Electrochemistry is 2.0, has enough protons to participate in electrode reaction in solution at this time.
Three, black phosphorus alkene hemin modified electrode of the present invention is studied to TCA electro-catalysis behaviors
The BP-PEDOT of this experimental study embodiment of the present invention 3:PBS buffer solution of the PSS-Hemin/CILE electrodes in pH 2.0
The catalytic effect of middle electro-catalysis reduction TCA, the results are shown in Figure 4.1.0 mol L are gradually added dropwise-1TCA is to 10 mL PBS solutions
Afterwards, can be observed also therewith to increase as TCA concentration increases reduction peak current, and its corresponding oxidation peak current is gradually reduced very
To disappearance, this is a typical TCA reduction process.
The concentration of TCA is in 2.0 ~ 170.0 mmol L-1In the range of when, the concentration of reduction peak current and TCA at
Good linear relationship obtains equation of linear regression I (mA)=0.0150 C (mmol L-1) + 0.5749 (γ=
0.997), detection is limited to 0.67 mmol L-1 (3σ).Peak current can be more than 170.0 mmol L in the concentration of TCA-1When, occur
One platform current value remains unchanged, this is the characteristic feature of Michaelis-Menten dynamic processes.Apparent K_m
(K M app ) it is the investigation dynamic (dynamical) important indicator of enzyme-substrate reactions, Lineweaver-Burk equations in enzymic catalytic reaction：
Above in formula each parameter meaning：IssIt is steady-state current when forming good linear relationship after adding substrate, C is to be added
Concentration of the substrate in 10 mL PBS, ImaxBe TCA concentration be more than 170.0 mmol L-1When the saturation of substrates state that is formed
Lower measured maximum current.It can be according to double-reciprocal plot method (1/Iss~ 1/ [TCA]) calculate BP-PEDOT:PSS-Hemin/
CILE reacts the catalysis of TCAK M app For 4.31 mmol L-1, show BP-PEDOT:PSS-Hemin/CILE urges TCA
Change works well.This is because BP-PEDOT:PSS-Hemin has good biocompatibility so that Hemin and modified electrode
Between electron transfer rate reinforce, to strengthen the catalytic effect to TCA.
Four, black phosphorus alkene hemin modified electrode of the present invention is studied to NaNO2Electro-catalysis behavior
The BP-PEDOT of this experimental study embodiment of the present invention 3:PSS-Hemin/CILE electrode electro-catalysis restores NaNO2Catalysis
Effect, the results are shown in Figure 5.NaNO is added in the PBS buffer solutions of pH 2.02After record cyclic voltammetry curve, find-
There is new reduction peak in 0.592 V, and reduction peak current is with NaNO2The increase of concentration and increase.Work as NaNO2Concentration 1.0 ~
10.5 mmol L-1In the range of when, reduction peak current and NaNO2Concentration at good linear relationship, linear regression side
Journey is Iss (mA) = 0.0569 C( mmol L-1)+0.0698 (γ=0.993), detection is limited to 0.33 mmol L-1 (3σ).Peak current can be in NaNO2Concentration be more than 10.5 mmol L-1When there is a platform and current value and remain unchanged.It can basis
Double-reciprocal plot method (1/Iss~1/[NaNO2]) calculate BP-PEDOT:PSS-Hemin/CILE is to NaNO2Catalysis reactionK M app For 23.31 mmol L-1。
In conclusion the black phosphorus alkene that the present invention uses（BP）It is a kind of novel direct band-gap semicondictor material, possesses bee
The fold lamellar structure of nest shape has big surface area and higher carrier mobility, Hemin can be promoted in modified electrode
The Direct electron transfer on surface accelerates electron transfer rate.The electrode that the present invention is prepared using mixing drop coating method（BP-
PEDOT:PSS-Hemin/CILE）Occur the good redox peaks of a pair of of peak shape in 2.0 PBS of pH, to trichloroacetic acid
（TCA）And sodium nitrite（NaNO2）Electro-catalysis reduction effect is good, and the range of linearity is respectively 2.0 ~ 170.0 mmol L-1With
1.0~10.5 mmol L-1, detect and be limited to 0.67 mmol L-1With 0.33 mmol L-1, the range of linearity is wide, and detection limit is low, sensitive
Degree is high, can be applied to trichloroacetic acid very well（TCA）And sodium nitrite（NaNO2）Detection.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent substitution, improvement and etc. done should be included within the scope of protection of the invention god.
Claims (9)
1. a kind of preparation method of black phosphorus alkene hemin modified electrode, which is characterized in that include the following steps：
S1, according to mass ratio（1.5~2.5）:1 takes graphite powder and ionic liquid（1- hexyl pyridine hexafluorophosphates, HPPF6）Yu Yan
In alms bowl, carbon paste is obtained after grinding uniformly, then carbon paste is inserted in vitreous electricity pole pipe and is compacted, interpolation copper wire is obtained as conducting wire
Ionic liquid carbon paste electrode（CILE）；
S2, full of nitrogen（N2）Glove box in, take black phosphorus alkene by certain mass ratio（BP）It is poly- with Polyglycolic acid fibre-
(styrene sulfonate) i.e. PEDOT：PSS is in brown centrifuge tube, sonic oscillation after mixing, by itself and 20 ~ 40 mg/mL
Hemin, than mixing, takes 5 ~ 10 μ L solution drop coatings to the surfaces CILE, can be obtained after dry in glove box according to certain volume
To electrode to be prepared（BP-PEDOT:PSS-Hemin/CILE).
2. a kind of preparation method of black phosphorus alkene hemin modified electrode according to claim 1, which is characterized in that institute
It states in S1 steps, the milling time is 2 ~ 3 hours.
3. a kind of preparation method of black phosphorus alkene hemin modified electrode according to claim 1, which is characterized in that institute
It states in S1 steps, the glass electrode bore is 4 mm.
4. a kind of preparation method of black phosphorus alkene hemin modified electrode according to claim 1, which is characterized in that institute
It states in S2 steps, Hemin solution concentrations are 30 mg/mL.
5. a kind of preparation method of black phosphorus alkene hemin modified electrode according to claim 1 and its electro-catalysis are ground
Study carefully, which is characterized in that in the S2 steps, BP and PEDOT：The mass ratio of PSS is 1:5.
6. the preparation method and its Study of electrocatalysis of a kind of black phosphorus alkene hemin modified electrode according to claim 1
With application, which is characterized in that in the S2 steps, Hemin and mixing suspension（BP and PEDOT：PSS）Volume ratio be 1:1.
7. a kind of preparation method of black phosphorus alkene hemin modified electrode according to claim 1, which is characterized in that packet
Include following steps：
S1,1.6 g graphite powders, 0.8 g ionic liquids are taken（1- hexyl pyridine hexafluorophosphates, HPPF6）In mortar, grinding is equal
Carbon paste is obtained after even, and then carbon paste is inserted in vitreous electricity pole pipe and is compacted, interpolation copper wire obtains CILE as conducting wire；
S2, full of N2Glove box in, in mass ratio 1:5 take BP and PEDOT：PSS is ultrasonic after mixing in brown centrifuge tube
Oscillation, it is mixed in equal volume with 30 mg/mL Hemin, takes the 8 μ L solution drop coatings to the surfaces CILE, dry in glove box
After can be obtained electrode to be prepared（BP-PEDOT:PSS-Hemin/CILE）.
8. claim 1 ~ 7 any one of them black phosphorus alkene hemin modified electrode for electro-catalysis reduction trichloroacetic acid and
Sodium nitrite.
9. the detection environment of black phosphorus alkene hemin modified electrode according to any one of claims 8 is the phosphate-buffered in pH 2.0
In solution.
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Cited By (5)
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| CN109613088A (en) * | 2018-12-20 | 2019-04-12 | 温州大学 | A kind of phosphatase activity detection method that black phosphorus mediates the electrochemical signals of copper ion aggregation to convert |
| CN112162024A (en) * | 2020-09-18 | 2021-01-01 | 苏州科技大学 | Black phosphorus/hemin composite material, preparation method thereof and electrochemical biosensor |
| CN112630275A (en) * | 2020-11-04 | 2021-04-09 | 苏州科技大学 | Carbon fiber bracket assembled with hemin and preparation method and application thereof |
| CN114563453A (en) * | 2022-03-03 | 2022-05-31 | 桂林理工大学 | Preparation method and application of enzyme biosensor using PEDOT/LYH as carrier |
| CN114852995A (en) * | 2022-03-31 | 2022-08-05 | 海南师范大学 | Electrocatalysis application of black phosphorus-based composite material in construction of horseradish peroxidase sensor |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109613088A (en) * | 2018-12-20 | 2019-04-12 | 温州大学 | A kind of phosphatase activity detection method that black phosphorus mediates the electrochemical signals of copper ion aggregation to convert |
| CN112162024A (en) * | 2020-09-18 | 2021-01-01 | 苏州科技大学 | Black phosphorus/hemin composite material, preparation method thereof and electrochemical biosensor |
| CN112630275A (en) * | 2020-11-04 | 2021-04-09 | 苏州科技大学 | Carbon fiber bracket assembled with hemin and preparation method and application thereof |
| CN114563453A (en) * | 2022-03-03 | 2022-05-31 | 桂林理工大学 | Preparation method and application of enzyme biosensor using PEDOT/LYH as carrier |
| CN114563453B (en) * | 2022-03-03 | 2024-02-06 | 桂林理工大学 | Preparation method and application of enzyme biosensor using PEDOT/LYH as carrier |
| CN114852995A (en) * | 2022-03-31 | 2022-08-05 | 海南师范大学 | Electrocatalysis application of black phosphorus-based composite material in construction of horseradish peroxidase sensor |
| CN114852995B (en) * | 2022-03-31 | 2024-03-22 | 海南师范大学 | Electrocatalytic application of horseradish peroxidase sensor constructed by black phosphorus-based composite material |
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