CN106908498B - A kind of Co4S3The preparation method and applications of/nitrogen-doped graphene composite material - Google Patents
A kind of Co4S3The preparation method and applications of/nitrogen-doped graphene composite material Download PDFInfo
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Abstract
The invention discloses a kind of Co4S3The preparation method and applications of/nitrogen-doped graphene composite material belong to inorganic material synthesis and analysis field.The composite material uses ammonium hydroxide to be modulated into alkaline environment first, is converted into nitrogen-doped graphene using hydrazine hydrate and graphite oxide alkene reaction, then adds cobalt acetate and thiocarbamide and is made by solvent thermal process.Synthesis technology of the present invention is simple, it is at low cost, it is carried out in main body reaction water phase, reaction condition is mild, while the electrochemical sensor constructed using the composite material is because played bigger serface, the nitrogen-doped graphene of high conductivity and strong biocompatibility and the good Co of electron transfer characteristic4S3Synergistic effect between nano material and stronger catalytic action is shown to the electrochemical reduction of hydrogen peroxide, and detect that the range of linearity is wide, detection limit is low, high sensitivity is selectively good, be successfully used for the analysis detection of hydrogen peroxide in actual sample.
Description
Technical field
The invention belongs to inorganic material synthesis and analysis fields, and in particular to a kind of easy preparation Co4S3/ N doping graphite
The method and its application of alkene composite material.
Background technique
Hydrogen peroxide is widely used in weaving, chemical industry, papermaking, electronics, food are defended as a kind of important chemical products
Raw and other fields, at the same in hydrogen peroxide or human body in addition to oxidizing ferment all enzymes activated product, its too high levels
Human body cell damage or aging can be directly resulted in, and then is lacked of proper care.Toxicologic study also demonstrates that a certain amount of hydrogen peroxide is to people
Body mucous membrane has strong impulse damaging action.Therefore, rapid quantitative detection hydrogen peroxide is of great significance.The inspection of hydrogen peroxide
Survey method has fluorescence method, chromatography, photometry and capillary electrophoresis etc., wherein solid phase electrochemical sensing method because it is swift to operate,
Without expensive instrument, reagent loss is few, pre-treatment is simple the advantages that extensive concern by researcher.
In general, hydrogen peroxide overpotential on bare electrode is higher and recovering signal is caused to be difficult to be captured, therefore section
Worker is ground to attempt to modify using different electronic media materials to basal electrode surface to be fabricated to sense film to detect peroxide
Change hydrogen.In recent years, many materials such as large specific surface area, good conductivity, two-dimentional carbon nanomaterial-graphene is employed successfully in
The measurement of hydrogen peroxide.On the other hand, different binary cobalt sulfide (CoSx, such as Co9S8、CoS、Co4S3、Co2S3、CoS2Deng)
Because preparation is simple, raw material is cheap, less toxic, function Modulatory character and become catalyst star's material of industrially desulfurized reaction.It will
Part carbon atom is substituted for the original distribution of charges of nitrogen-atoms change and spin density in graphene, enhances adsorptivity and biofacies
After capacitive again with the compound electron-transport efficiency and stability that would be possible to further improve graphene of cobalt sulfide, thus
Construct the electrochemical sensor to hydrogen peroxide high sensitivity and highly selective response.So far, nitrogen-doped graphene base
Co4S3The preparation of composite material and electrochemical process detection hydrogen peroxide have not been reported, compared with existing modification agent material,
Co4S3/ nitrogen-doped graphene composite material and preparation method thereof is more simple, and reaction condition is mild, carries out in main body reaction water phase, right
It is environmental-friendly, and the good dispersion of composite material, it effectively compensates for the electrochemical sensor that other dressing agents are constructed and is measuring
Background current is big in hydrogen peroxide process, and poorly conductive, sensitivity and selective low defect, practicability are stronger.
Summary of the invention
It is an object of the invention to overcome the synthesis of dressing agent in existing electrochemical sensor measurement hydrogen peroxide technology
Process complexity, raw material expend excessive, severe reaction conditions, electrochemical sensing sensitivity and the low, linear response range of selectivity
The defects of narrow, by simple reaction process, more mild reaction condition, green reaction environment, efficient separation method
It prepares novel electro-catalytic and acts on stronger Co4S3/ nitrogen-doped graphene composite material, and make full use of the graphite of unique properties
Alkene is the Co that excellent carrier doping can significantly improve electronically active and electron transmission performance4S3Nano material is realized to peroxide
Change the high sensitivity and highly selective measurement of hydrogen.
In order to achieve the above-mentioned object of the invention, the present invention is achieved by the following technical programs.
A kind of Co of the present invention4S3The preparation method of/nitrogen-doped graphene composite material, specifically includes following steps：
(1) disperse active oxidation graphene：
It weighs 30~80mg graphene oxide and is scattered in ultrasonic disperse 2~5 hours in distilled water.
(2) nitrogen-doped graphene is prepared：
The pH value of the graphene dispersing solution of step (1) is transferred to 9~11 using ammonium hydroxide, it is 85% that mass concentration, which is then added,
0.8~1.6mL of hydrazine hydrate, reaction temperature be 40~60 DEG C, 18~36h of reaction time；Product is centrifugated and is washed later
It washs, obtained nitrogen-doped graphene powder after vacuum dried.
(3) Co is synthesized4S3/ nitrogen-doped graphene：
The nitrogen-doped graphene powder of a certain amount of step (2) preparation is weighed in the mixed solution of secondary water and ethyl alcohol, is surpassed
Four acetate hydrate cobalts and thiocarbamide is added in sound after being uniformly dispersed, continue ultrasound and stir to dissolve it all；Solution is shifted later
Hydro-thermal reaction is carried out into reaction kettle, reaction temperature is 150~170 DEG C, and the reaction time is 20~30h；After reaction, by institute
It obtains precipitating secondary water and ethanol washing and is centrifugated, it is finally vacuum dried to obtain Co4S3/ nitrogen-doped graphene composite material.
In the mixed solution of the secondary water and ethyl alcohol：Secondary water and the volume ratio of ethyl alcohol are 1~1.5:1.The nitrogen is mixed
The mass ratio of miscellaneous graphene, four acetate hydrate cobalts and thiocarbamide is 1:35~45:10~20.
Optimum reaction condition is in above-mentioned reaction：In the mixed solution of the secondary water and ethyl alcohol, secondary water and ethyl alcohol
Volume ratio is 1:1；The mass ratio of the nitrogen-doped graphene, four acetate hydrate cobalts and thiocarbamide is 15: 560:170.
The Co of above-mentioned preparation4S3/ nitrogen-doped graphene composite material can construct electrochemical sensor in hydrogen peroxide electrification
It is applied in credit analysis.
Compared with prior art, the present invention has the following technical effects：
1, the preparation method of composite material is simple, without complicated instrument and equipment；Raw material dosage is less, at low cost；Main body
Reaction carries out in water phase, environmentally friendly；
2, reaction condition is milder, energy-saving consumption-reducing；It is simple to prepare last handling process, it is easy to separate and purify；
3, the electrochemical sensor constructed using the composite material is because played bigger serface, high conductivity and strong
The good Co of the nitrogen-doped graphene and electron transfer characteristic of biocompatibility4S3Synergistic effect between nano material and to peroxide
The electrochemical reduction for changing hydrogen shows stronger catalytic action, and it is wide to detect the range of linearity, and detection limit is low, high sensitivity selection
Property is good, is successfully used for the analysis detection of hydrogen peroxide in actual sample；
4, it is other can compatible substance it is noiseless to the measurement of hydrogen peroxide, Co4S3/ nitrogen-doped graphene composite material
The electrochemical sensor stability and favorable reproducibility constructed.
Detailed description of the invention
Fig. 1 is Co4S3The preparation of/nitrogen-doped graphene composite material and catalytic action to hydrogen peroxide electrochemical reduction
Schematic diagram.
Fig. 2 is nitrogen-doped graphene (A), Co4S3(B) and Co4S3The scanning of/nitrogen-doped graphene composite material (C)
Electron microscope.
Fig. 3 is nitrogen-doped graphene, Co4S3And Co4S3The X-ray powder diffraction of/nitrogen-doped graphene composite material
Figure.
Fig. 4 is at Fe containing 5mM (CN)6 -4/-30.1M KCl solution in (working frequency is from the naked glass of 0.01~100 kHz)
Carbon electrode (a), Co4S3Modified glassy carbon electrode (b) and Co4S3The AC impedance figure of/nitrogen-doped graphene modified glassy carbon electrode (c).
Fig. 5 is bare glassy carbon electrode (a), Co in the phosphate buffer solution of 0.1M pH=7.04S3Modified glassy carbon electrode
(b), nitrogen-doped graphene modified glassy carbon electrode (c) and Co4S3/ nitrogen-doped graphene modified glassy carbon electrode (d) is containing 2mM
Voltammogram in hydrogenperoxide steam generator.
Fig. 6 is Co in the phosphate buffer solution of 0.1M pH=7.04S3/ nitrogen-doped graphene modified electrode is to different dense
Spend the linear relationship chart between the ampere response diagram (A) and resulting catalytic current and concentration of hydrogen peroxide of hydrogen oxide
(B)。
Fig. 7 is various possible coexisting substances in system to the interference figure of hydrogen peroxide electrochemical gaging.
Specific embodiment
Substantive features and remarkable result of the invention can be emerged from from following embodiments, but they not to this
Invention imposes any restrictions, and those skilled in the art's content according to the present invention makes some nonessential modifications and adaptations,
It belongs to the scope of protection of the present invention.Below by the drawings and specific embodiments, the present invention is further illustrated, wherein implementing
Co in example4S3/ nitrogen-doped graphene composite material using Holland's Philips X ' Pert type X-ray powder diffraction instrument (XRD) and
Hitachi, Japan F-4800 electron scanning Electronic Speculum (SEM) characterizes pattern；Electrochemistry experiment is all in Shanghai Chen Hua instrument company
It is completed on the CHI660E electrochemical workstation of assembling, experiment uses three-electrode system (i.e. glass-carbon electrode or Co4S3// N doping stone
Black alkene composite material modified glassy carbon electrode is working electrode, and saturated calomel electrode is reference electrode, and platinum electrode is to electrode).
Using relative to graphene there is the nitrogen of bigger specific surface area, stronger electric conductivity and biocompatibility to mix herein
Miscellaneous graphene is host material, and the Co of excellent electron transmission characteristic is doped with by simple hydro-thermal reaction4S3Nano material,
Electro catalytic activity and the catalytic stability more preferably composite material than homogenous material are produced, and the composite material is constructed
Modified electrode stronger reducing power shown to hydrogen peroxide, and sensitivity and selectivity are high, and linear detection range is wide,
Therefore nitrogen-doped graphene and Co in composite material are made full use of4S3Synergistic effect between nano material can develop for peroxide
Change hydrogen trace detection electrochemical sensor.Co4S3The preparation of/nitrogen-doped graphene composite material and to hydrogen peroxide electrochemistry also
Former catalytic action is as shown in Figure 1.
One, Co of the present invention4S3The preparation method of/nitrogen-doped graphene composite material
Embodiment 1
(1) 50mg graphene oxide powder is weighed in 50mL secondary distilled water, and it is uniform that ultrasound is dispersed into it in 2 hours
Solution.
(2) graphene dispersing solution is adjusted to pH with the ammonium hydroxide that mass concentration is 30% is about 9, and mass concentration is then added
For 85% hydrazine hydrate 0.8mL and stir 15 minutes, resulting mixed solution is heated to reflux 36 hours at 40 DEG C.
(3) after reaction, multiple with secondary water and ethanol washing after centrifuge separation, finally centrifugation product is done in vacuum
18 hours obtained nitrogen-doped graphene powder are dried in dry case at 15 DEG C.
(4) 15mg nitrogen-doped graphene powder is weighed in the secondary water and ethyl alcohol (1.0 of 70mL:1.0) in mixed solution,
Tetra- acetate hydrate cobalt of 525mg and 140mg thiocarbamide is added after keeping its evenly dispersed in ultrasound 30 minutes, continues ultrasound 15 minutes and stirs
Mixing dissolves it all, is transferred the solution into 100mL reaction kettle later, and set temperature is 150 DEG C, hydro-thermal reaction 30 hours.
After reaction, gained precipitating secondary water and ethyl alcohol are repeatedly washed and is centrifugated, crude product is put into vacuum oven
15 hours are dried at 15 DEG C up to Co4S3/ nitrogen-doped graphene composite material.
Embodiment 2
(1) 50mg graphene oxide powder is weighed in 50mL secondary distilled water, and it is uniform that ultrasound is dispersed into it in 3 hours
Solution.
(2) graphene dispersing solution is adjusted to pH with the ammonium hydroxide that mass concentration is 30% is about 10, and matter is then added
It measures the hydrazine hydrate 1.0mL that concentration is 85% and stirs 8 minutes, resulting mixed solution is heated to reflux 24 hours at 50 DEG C.
(3) after reaction, multiple with secondary water and ethanol washing after centrifuge separation, finally centrifugation product is done in vacuum
15 hours obtained nitrogen-doped graphene powder are dried in dry case at 20 DEG C.
It is centrifugated after the reaction was completed, product is washed three times with dehydrated alcohol, and product is dried in vacuo 12h at 50 DEG C
(4) 15mg nitrogen-doped graphene powder is weighed in the secondary water and ethyl alcohol (1.2 of 70mL:1.0) in mixed solution,
Tetra- acetate hydrate cobalt of 540mg and 150mg thiocarbamide is added after keeping its evenly dispersed in ultrasound 25 minutes, continues ultrasound 15 minutes and stirs
Mixing dissolves it all, is transferred the solution into 100mL reaction kettle later, and set temperature is 160 DEG C, hydro-thermal reaction 24 hours.
After reaction, gained precipitating secondary water and ethyl alcohol are repeatedly washed and is centrifugated, crude product is put into vacuum oven
14 hours are dried at 20 DEG C up to Co4S3/ nitrogen-doped graphene composite material.
Embodiment 3
(1) 50mg graphene oxide powder is weighed in 50mL secondary distilled water, and it is uniform that ultrasound is dispersed into it in 4 hours
Solution.
(2) graphene dispersing solution is adjusted to pH with the ammonium hydroxide that mass concentration is 30% is about 10, and matter is then added
It measures the hydrazine hydrate 1.2mL that concentration is 85% and stirs 10 minutes, resulting mixed solution is heated to reflux 24 hours at 50 DEG C.
(3) after reaction, multiple with secondary water and ethanol washing after centrifuge separation, finally centrifugation product is done in vacuum
12 hours obtained nitrogen-doped graphene powder are dried in dry case at 30 DEG C.
(4) 15mg nitrogen-doped graphene powder is weighed in the secondary water and ethyl alcohol (1.0 of 70mL:1.0) in mixed solution,
Tetra- acetate hydrate cobalt of 560mg and 170mg thiocarbamide is added after keeping its evenly dispersed in ultrasound 30 minutes, continues ultrasound 15 minutes and stirs
Mixing dissolves it all, is transferred the solution into 100mL reaction kettle later, and set temperature is 160 DEG C, hydro-thermal reaction 24 hours.
After reaction, gained precipitating secondary water and ethyl alcohol are repeatedly washed and is centrifugated, crude product is put into vacuum oven
12 hours are dried at 20 DEG C up to Co4S3/ nitrogen-doped graphene composite material.
Embodiment 4
(1) 50mg graphene oxide powder is weighed in 50mL secondary distilled water, and it is uniform that ultrasound is dispersed into it in 5 hours
Solution.
(2) graphene dispersing solution is adjusted to pH with the ammonium hydroxide that mass concentration is 30% is about 11, and matter is then added
It measures the hydrazine hydrate 1.4mL that concentration is 85% and stirs 15 minutes, resulting mixed solution is heated to reflux 18 hours at 60 DEG C.
(3) after reaction, multiple with secondary water and ethanol washing after centrifuge separation, finally centrifugation product is done in vacuum
15 hours obtained nitrogen-doped graphene powder are dried in dry case at 25 DEG C.
(4) 15mg nitrogen-doped graphene powder is weighed in the secondary water and ethyl alcohol (1.5 of 70mL:1.0) in mixed solution,
Tetra- acetate hydrate cobalt of 570mg and 180mg thiocarbamide is added after keeping its evenly dispersed in ultrasound 40 minutes, continues ultrasound 15 minutes and stirs
Mixing dissolves it all, is transferred the solution into 100mL reaction kettle later, and set temperature is 170 DEG C, hydro-thermal reaction 20 hours.
After reaction, gained precipitating secondary water and ethyl alcohol are repeatedly washed and is centrifugated, crude product is put into vacuum oven
12 hours are dried at 30 DEG C up to Co4S3/ nitrogen-doped graphene composite material.
Embodiment 5
(1) 50mg graphene oxide powder is weighed in 50mL secondary distilled water, and it is uniform that ultrasound is dispersed into it in 3 hours
Solution.
(2) graphene dispersing solution is adjusted to pH with the ammonium hydroxide that mass concentration is 30% is about 10, and it is dense that quality is then added
It spends the hydrazine hydrate 1.6mL for 85% and stirs 15 minutes, resulting mixed solution is heated to reflux 28 hours at 50 DEG C.
(3) after reaction, multiple with secondary water and ethanol washing after centrifuge separation, finally centrifugation product is done in vacuum
10 hours obtained nitrogen-doped graphene powder are dried in dry case at 30 DEG C.
(4) 15mg nitrogen-doped graphene powder is weighed in the secondary water and ethyl alcohol (1.2 of 70mL:1.0) in mixed solution,
Tetra- acetate hydrate cobalt of 550mg and 160mg thiocarbamide is added after keeping its evenly dispersed in ultrasound 30 minutes, continues ultrasound 15 minutes and stirs
Mixing dissolves it all, is transferred the solution into 100mL reaction kettle later, and set temperature is 150 DEG C, hydro-thermal reaction 30 hours.
After reaction, gained precipitating secondary water and ethyl alcohol are repeatedly washed and is centrifugated, crude product is put into vacuum oven
15 hours are dried at 20 DEG C up to Co4S3/ nitrogen-doped graphene composite material.
Embodiment 6
(1) 50mg graphene oxide powder is weighed in 50mL secondary distilled water, and it is uniform that ultrasound is dispersed into it in 4 hours
Solution.
(2) graphene dispersing solution is adjusted to pH with the ammonium hydroxide that mass concentration is 30% is about 10, and matter is then added
It measures the hydrazine hydrate 1.2mL that concentration is 85% and stirs 10 minutes, resulting mixed solution is heated to reflux 20 hours at 60 DEG C.
(3) after reaction, multiple with secondary water and ethanol washing after centrifuge separation, finally centrifugation product is done in vacuum
15 hours obtained nitrogen-doped graphene powder are dried in dry case at 25 DEG C.
(4) 15mg nitrogen-doped graphene powder is weighed in the secondary water and ethyl alcohol (1.0 of 70mL:1.0) in mixed solution,
Tetra- acetate hydrate cobalt of 590mg and 190mg thiocarbamide is added after keeping its evenly dispersed in ultrasound 30 minutes, continues ultrasound 15 minutes and stirs
Mixing dissolves it all, is transferred the solution into 100mL reaction kettle later, and set temperature is 170 DEG C, hydro-thermal reaction 22 hours.
After reaction, gained precipitating secondary water and ethyl alcohol are repeatedly washed and is centrifugated, crude product is put into vacuum oven
15 hours are dried at 20 DEG C up to Co4S3/ nitrogen-doped graphene composite material.
Two, Co of the present invention4S3The electrochemical catalysis effect assessment of/nitrogen-doped graphene composite material to glucose
Target product is coated on the carbon-based hearth electrode of glass and is fabricated to modified electrode, studies the electrochemical credit to hydrogen peroxide
Analyse effect.
(1) using electron scanning Electronic Speculum respectively to nitrogen-doped graphene, Co4S3And Co4S3/ nitrogen-doped graphene is compound
The pattern of material, which has been done, characterizes (as shown in Figure 2), and nitrogen-doped graphene is (Fig. 2A) wave-shaped as seen from the figure, and surface has very
Mostly such as the folded structure of paper-like.Co4S3The granular size of nano material (Fig. 2 B) is more uniform, and most of particle size is 50
Between~70nm, work as Co4S3With nitrogen-doped graphene it is compound after, can clearly observe Co4S3Nano particle is distributed in N doping stone
Black alkene wrinkled surface (Fig. 2 C).
(2) using x-ray powder diffraction instrument to nitrogen-doped graphene, Co4S3And Co4S3/ nitrogen-doped graphene composite wood
Material carries out material phase analysis, and as a result as shown in figure 3, nitrogen-doped graphene has a broad peak at 24 ° or so, which corresponds to N doping
(002) diffraction maximum of graphene.Co4S3/ nitrogen-doped graphene composite material 2 θ be followed successively by 29.86 °, 31.14 °, 39.49 °,
47.57 °, 51.91 ° and 61.80 ° respectively correspond Co4S3(JCPDS No.02-1338) standard spectrogram 311,222,331,
211,440 and 622 crystallographic plane diffraction peak.In addition, not detecting other impurity peaks in X-ray powder diffraction pattern, show Co4S3/
The purity of nitrogen-doped graphene composite material is higher.
(3) this experiment also further has studied the electrical conductance of composite material with AC impedence method, as shown in figure 4, naked glass
Carbon electrode (Fig. 4 a) is almost straight line in entire high frequency region, this shows that the resistance of bare glassy carbon electrode is smaller.It repairs on the electrode
Adorn Co4S3It is shown in high frequency region than single Co after/nitrogen-doped graphene composite material (Fig. 4 c)4S3Modified electrode (Fig. 4 b)
Much smaller semi arch, or even close to bare glassy carbon electrode, show Co4S3/ nitrogen-doped graphene composite material is mixed because being added to nitrogen
Miscellaneous graphene makes it than single Co4S3Nano material has smaller solid-state interface layer resistance and electron transport rate is faster.
(4) experiment has studied bare glassy carbon electrode, Co using voltammetry respectively4S3Modified glassy carbon electrode, nitrogen-doped graphene are repaired
Adorn glass-carbon electrode and Co4S3/ nitrogen-doped graphene composite material modified glassy carbon electrode urges the electrochemical reduction of hydrogen peroxide
Change response effect, as shown in Figure 5.It can observe and almost be observed not in bare glassy carbon electrode after hydrogen peroxide is added in system
To reduction peak (Fig. 5 a), after modifying nitrogen-doped graphene on glass-carbon electrode, background current increases, to the electrochemistry of hydrogen peroxide
Reduction catalysts effect also unobvious (Fig. 5 b), in Co4S3Response (the figure of hydrogen peroxide can be observed on modified glassy carbon electrode
5c), show Co4S3Also original certain catalytic action of the nano material to hydrogen peroxide.However in Co4S3/ nitrogen-doped graphene
On composite material modified glassy carbon electrode (Fig. 5 d), the reduction peak current of hydrogen peroxide is maximum, and peak shape is best, and reduction spike potential is obvious
It shuffles.It is above-mentioned the experimental results showed that nitrogen-doped graphene and Co4S3The specific surface of homogenous material is improved after nano material is compound
Product, electric conductivity and interface electron transport rate, to show catalytic effect more stronger than homogenous material.
(5) after optimizing the test conditions such as medium, scanning speed, dressing agent load capacity, operating potential, using timing electricity
Stream method has studied response of the composite material modified electrode to hydrogen peroxide.The result shows that the composite material modified electrode is in 2s
Stationary value is reached to the catalytic current of hydrogen peroxide, shows that the modified electrode is rapid (Fig. 6 A) to the response of hydrogen peroxide.In addition
It has also been found that when concentration of hydrogen peroxide is within the scope of 1.0 μM~2.18mM, in Co4S3The modification of/nitrogen-doped graphene composite material
Response current and its concentration on glass-carbon electrode are in good linear relationship (Fig. 6 B), and equation of linear regression is respectively：I (μ A)=
6.0220+65.6270C Hydrogen peroxide(r=0.9918), detection limit is most down to 0.29 μM (S/N=3).
(6) interference--free experiments are continuously to add 0.1mM using during Ampere currents method measures 0.1mM hydrogen peroxide
Uric acid (UA), 0.1mM ascorbic acid (AA), 0.1mM dopamine (DA), 0.1 mM glucose (Glu), 0.1mM fructose (Fru) with
And carried out in the case where 0.5mM NaCl.Experimental result is as shown in fig. 7, the electric current that the above interfering substance generates modified electrode
Disturbance is respectively less than 2%, shows that modified electrode has good Anti-Jamming to the above substance.By Co4S3/ nitrogen-doped graphene
Composite material modified glassy carbon electrode is measured in parallel hydrogen peroxide 11 times of same concentration, and standard deviation 3.86% shows this
The repeatability of modified electrode is higher.Then by Co4S3/ nitrogen-doped graphene composite material modified glassy carbon electrode is stored in 4 DEG C of ice
In case, the hydrogen peroxide of same concentration is detected two days later, and current-responsive is the 91% of legacy data, shows that the modified electrode has
There are preferable reproducibility and stability.
(7) in order to detect Co4S3/ nitrogen-doped graphene composite material modified glassy carbon electrode authentic sample application power,
Under optimum experimental condition, the concentration of hydrogen peroxide in three kinds of milk samples is had detected using standard addition method, every kind of sample is flat
Row detection 6 times, experimental result is as shown in table 1.For the rate of recovery within zone of reasonableness (between 95%~105%), relative standard is inclined
Poor (RSD) is less than 5%, it was demonstrated that the modified electrode can be used for actual sample analysis detection.
The detection (n=6) of hydrogen peroxide in 1 milk sample of table
Claims (3)
1. a kind of Co4S3The preparation method of/nitrogen-doped graphene composite material, it is characterised in that include the following steps：
(1) disperse active oxidation graphene：
It weighs 30~80mg graphene oxide and is scattered in ultrasonic disperse 2~5 hours in distilled water；
(2) nitrogen-doped graphene is prepared：
The pH value of the graphene dispersing solution of step (1) is transferred to 9~11 using ammonium hydroxide, the water that mass concentration is 85% is then added
0.8~1.6mL of hydrazine is closed, reaction temperature is 40~60 DEG C, 18~36h of reaction time；Product is centrifugated and is washed later, is passed through
Nitrogen-doped graphene powder is made after vacuum drying；
(3) Co is synthesized4S3/ nitrogen-doped graphene：
The nitrogen-doped graphene powder of a certain amount of step (2) preparation is weighed in the mixed solution of secondary water and ethyl alcohol, ultrasound point
Four acetate hydrate cobalts and thiocarbamide is added after dissipating uniformly, continues ultrasound and stir to dissolve it all；It transfers the solution into later anti-
It answers and carries out hydro-thermal reaction in kettle, reaction temperature is 150~170 DEG C, and the reaction time is 20~30h；After reaction, gained is sunk
Shallow lake secondary water and ethanol washing are simultaneously centrifugated, finally vacuum dried to obtain Co4S3/ nitrogen-doped graphene composite material；
In the mixed solution of the secondary water and ethyl alcohol：Secondary water and the volume ratio of ethyl alcohol are 1~1.5:1；
The mass ratio of the nitrogen-doped graphene, four acetate hydrate cobalts and thiocarbamide is 1:35~45:10~20.
2. Co as described in claim 14S3The preparation method of/nitrogen-doped graphene composite material, which is characterized in that described two
In the mixed solution of secondary water and ethyl alcohol：Secondary water and the volume ratio of ethyl alcohol are 1:1；The nitrogen-doped graphene, four acetate hydrates
The mass ratio of cobalt and thiocarbamide is 15:560:170.
3. the Co that preparation method as described in claim 1 obtains4S3/ nitrogen-doped graphene composite material constructs electrochemical sensor
Application in hydrogen peroxide electrochemical analysis.
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| CN107356643B (en) * | 2017-07-06 | 2019-10-25 | 衡阳师范学院 | A kind of quick detection hydrogen peroxide without enzyme electrochemical sensor and its preparation method and application |
| CN109529885B (en) * | 2018-11-19 | 2020-06-26 | 中南大学 | Cobalt sulfide/biomass charcoal composite material, preparation method thereof and application of cobalt sulfide/biomass charcoal composite material as elemental mercury oxidation catalyst |
| CN109342473A (en) * | 2018-12-21 | 2019-02-15 | 四川聚创石墨烯科技有限公司 | A kind of graphite material method for comprehensive detection |
| CN109696463A (en) * | 2019-02-21 | 2019-04-30 | 三峡大学 | A kind of Co4S3With the preparation method of nitrogen-doped carbon composite array electrode |
| CN116203088A (en) * | 2023-03-09 | 2023-06-02 | 南通大学 | Preparation method for ultra-sensitively detecting metalloenzyme by hydrogen peroxide |
| CN117535677A (en) * | 2023-09-27 | 2024-02-09 | 暨南大学 | N, P Co-doped Co 9 S 8 Integrated water decomposition electrocatalyst and preparation method and application thereof |
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| CN104681823B (en) * | 2015-01-23 | 2017-10-03 | 西华师范大学 | A kind of nitrogen-doped graphene and Co3O4 hollow nano-sphere composites and its preparation method and application |
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