CN106908498A - A kind of Co4S3The preparation method and applications of/nitrogen-doped graphene composite - Google Patents
A kind of Co4S3The preparation method and applications of/nitrogen-doped graphene composite Download PDFInfo
- Publication number
- CN106908498A CN106908498A CN201710222414.2A CN201710222414A CN106908498A CN 106908498 A CN106908498 A CN 106908498A CN 201710222414 A CN201710222414 A CN 201710222414A CN 106908498 A CN106908498 A CN 106908498A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- doped graphene
- ethanol
- composite
- secondary water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
-
- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention discloses a kind of Co4S3The preparation method and applications of/nitrogen-doped graphene composite, belong to inorganic material synthesis and analysis field.The composite is modulated into alkaline environment using ammoniacal liquor first, and nitrogen-doped graphene is converted into using hydrazine hydrate and graphite oxide alkene reaction, then adds cobalt acetate and thiocarbamide and is obtained by solvent thermal process.Synthesis technique of the present invention is simple, low cost, carried out in main body reaction water phase, reaction condition is gentle, while the electrochemical sensor constructed using the composite is because the good Co of the nitrogen-doped graphene and electron transfer characteristic that have played bigger serface, high conductivity and strong biocompatibility4S3Synergy between nano material and stronger catalytic action is shown to the electrochemical reduction of hydrogen peroxide, and detect that linear wide ranges, test limit are low, sensitivity high selectivity is 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 field, and in particular to a kind of easy preparation Co4S3/ N doping graphite
The method of alkene composite and its application.
Background technology
Used as a kind of important chemical products, it is widely used in weaving, chemical industry, papermaking, electronics, food and defends hydrogen peroxide
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 can be directly resulted in damage or aging, and then 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, Quantitative detection hydrogen peroxide is significant.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 of by researcher extensive concern.
In general, hydrogen peroxide overpotential on bare electrode is higher and cause recovering signal to be difficult to be captured, therefore section
Grind worker and attempt modifying to basal electrode surface using different electronic media materials and be fabricated to sense film and detect peroxide
Change hydrogen.In recent years, many materials such as specific surface area is big, good conductivity, two-dimentional carbon nanomaterial-Graphene be employed successfully in
The measure of hydrogen peroxide.On the other hand, different binary cobalt sulfide (CoSx, such as Co9S8、CoS、Co4S3、Co2S3、CoS2Deng)
Because preparing simple, raw material is cheap, low toxicity, function Modulatory character and turn into catalyst star's material of industrially desulfurized reaction.Will
Part carbon atom is substituted for the original distribution of charges of nitrogen-atoms change and spin density in Graphene, strengthens adsorptivity and biofacies
It is combined with cobalt sulfide again after capacitive and would be possible to the electric transmission efficiency for further improving Graphene and stability, so that
Construct the electrochemical sensor responded to hydrogen peroxide high sensitivity and high selectivity.So far, nitrogen-doped graphene base
Co4S3The preparation of composite and electrochemical process detection hydrogen peroxide have no report, compared with existing modification agent material,
Co4S3/ nitrogen-doped graphene composite material and preparation method thereof is more simple, and reaction condition is gentle, is carried out in main body reaction water phase, right
It is environment-friendly, and composite good dispersion, effectively compensate for the electrochemical sensor that other dressing agents construct and determining
Background current is big in hydrogen peroxide process, and poorly conductive, sensitivity and the low defect of selectivity, practicality are stronger.
The content of the invention
It is an object of the invention to overcome existing electrochemical sensor to determine the synthesis of dressing agent in hydrogen peroxide technology
Process complexity, raw material expend excessive, severe reaction conditions, electrochemical sensing sensitivity and the low, linear response range of selectivity
The defect such as narrow, by simple reaction process, more gentle reaction condition, the reaction environment of green, efficient separation method
Prepare novel electro-catalytic and act on stronger Co4S3/ nitrogen-doped graphene composite, 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
The high sensitivity and high selectivity for changing hydrogen are determined.
In order to realize foregoing invention purpose, 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, specifically includes following steps：
(1) active oxidation Graphene is disperseed：
Weigh 30~80mg graphene oxides and be 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 ammoniacal liquor, it is 85% to be subsequently adding mass concentration
0.8~1.6mL of hydrazine hydrate, reaction temperature be 40~60 DEG C, 18~36h of reaction time；By product centrifugation and wash afterwards
Wash, vacuum dried rear prepared nitrogen-doped graphene powder.
(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 ethanol, is surpassed
Sound adds four acetate hydrate cobalts and thiocarbamide after being uniformly dispersed, continue ultrasound and stir to make it all dissolve；Solution is shifted afterwards
Hydro-thermal reaction is carried out in reactor, reaction temperature is 150~170 DEG C, and the reaction time is 20~30h；After reaction terminates, by institute
Must precipitate and be washed with secondary water and ethanol and centrifugation, it is finally vacuum dried to obtain Co4S3/ nitrogen-doped graphene composite.
In the mixed solution of the secondary water and ethanol：Secondary water is 1~1.5 with the volume ratio of ethanol: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 ethanol, secondary water and ethanol
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 can construct electrochemical sensor in hydrogen peroxide electrification
It is applied in credit analysis.
Compared with prior art, the present invention has following technique effect：
1st, the preparation method of composite is simple, without complicated instrument and equipment；Raw material dosage is less, low cost；Main body
Reaction is carried out in water phase, environmentally friendly；
2nd, reaction condition is gentleer, energy-saving consumption-reducing；Prepare last handling process simple, it is easy to separating-purifying；
3rd, the electrochemical sensor constructed using the composite is because played bigger serface, high conductivity and strong
The good Co of the nitrogen-doped graphene and electron transfer characteristic of biocompatibility4S3Synergy between nano material and to peroxide
The electrochemical reduction for changing hydrogen shows stronger catalytic action, and detects linear wide ranges, and test limit is low, sensitivity high selection
Property it is good, be successfully used for hydrogen peroxide in actual sample analysis detection；
4th, other can compatible material it is noiseless to the measure of hydrogen peroxide, Co4S3/ nitrogen-doped graphene composite
The electrochemical sensor stability and favorable reproducibility constructed.
Brief description of the drawings
Fig. 1 is Co4S3The preparation of/nitrogen-doped graphene composite and the catalytic action to hydrogen peroxide electrochemical reduction
Schematic diagram.
Fig. 2 is nitrogen-doped graphene (A), Co4S3And Co (B)4S3The scanning electricity of/nitrogen-doped graphene composite (C)
Mirror figure.
Fig. 3 is nitrogen-doped graphene, Co4S3And Co4S3The X-ray powder diffraction of/nitrogen-doped graphene composite
Figure.
Fig. 4 is at Fe containing 5mM (CN)6 -4/-30.1M KCl solution in (working frequency from 0.01~100kHz) naked glass carbon
Electrode (a), Co4S3Modified glassy carbon electrode (b) and Co4S3The AC impedance figure of/nitrogen-doped graphene modified glassy carbon electrode (c).
Fig. 5 for 0.1M pH=7.0 PBS in, bare glassy carbon electrode (a), Co4S3Modified 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 for 0.1M pH=7.0 PBS in, Co4S3/ nitrogen-doped graphene modified electrode is dense to difference
Spend the ampere response diagram (A) and the linear relationship chart between resulting catalytic current and concentration of hydrogen peroxide of hydrogen oxide
(B)。
Fig. 7 is interference figure of the various possible coexisting substances to hydrogen peroxide electrochemical gaging in system.
Specific embodiment
Substantive features of the invention and remarkable result can be emerged from from following embodiments, but they are not to this
Invention is imposed any restrictions, and those skilled in the art's content of the invention makes some nonessential modifications and adaptations,
Belong to protection scope 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 using Holland Philips X ' Pert type X-ray powder diffractions instrument (XRD) and
HIT F-4800 electron scannings Electronic Speculum (SEM) characterize pattern；Electrochemistry experiment is all in Shanghai Chen Hua instrument company
Completed on the CHI660E electrochemical workstations of assembling, experiment is using three-electrode system (i.e. glass-carbon electrode or Co4S3// N doping stone
Black alkene composite modified glassy carbon electrode is working electrode, and saturated calomel electrode is reference electrode, and platinum electrode is to electrode).
Mixed using the nitrogen that there is bigger specific surface area, stronger electric conductivity and biocompatibility relative to Graphene 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 than homogenous material are produced, and causes that the composite is constructed
Modified electrode show stronger reducing power to hydrogen peroxide, and sensitivity and selectivity are high, and linear detection range is wide,
Therefore nitrogen-doped graphene and Co in composite are made full use of4S3Synergy between nano material can develop for peroxide
Change hydrogen trace detection electrochemical sensor.Co4S3The preparation of/nitrogen-doped graphene composite and to hydrogen peroxide electrochemistry also
Former catalytic action is as shown in Figure 1.
First, Co of the present invention4S3The preparation method of/nitrogen-doped graphene composite
Embodiment 1
(1) 50mg graphene oxide powders are weighed in 50mL redistilled waters, it is homogeneous that ultrasound is dispersed into it in 2 hours
Solution.
(2) graphene dispersing solution is adjusted to pH with the ammoniacal liquor that mass concentration is 30% and is about 9, be subsequently adding mass concentration
For 85% hydrazine hydrate 0.8mL and stir 15 minutes, by the mixed solution of gained in being heated to reflux at 40 DEG C 36 hours.
(3) after reaction terminates, washed repeatedly with secondary water and ethanol after centrifugation, finally centrifugation product is done in vacuum
In dry 18 hours prepared nitrogen-doped graphene powder at 15 DEG C in dry case.
(4) 15mg nitrogen-doped graphenes powder is weighed in the secondary water and ethanol (1.0 of 70mL:1.0) in mixed solution,
Ultrasound 30 minutes, the acetate hydrate cobalts of 525mg tetra- and 140mg thiocarbamides are added after making its dispersed, are continued ultrasound 15 minutes and are stirred
Mixing makes it all dissolve, and transfers the solution into afterwards in 100mL reactors, and design temperature is 150 DEG C, hydro-thermal reaction 30 hours.
After reaction terminates, by repeatedly washing and the centrifugation of gained precipitation secondary water and ethanol, crude product is put into vacuum drying chamber
Co is obtained final product in drying at 15 DEG C within 15 hours4S3/ nitrogen-doped graphene composite.
Embodiment 2
(1) 50mg graphene oxide powders are weighed in 50mL redistilled waters, it is homogeneous that ultrasound is dispersed into it in 3 hours
Solution.
(2) graphene dispersing solution is adjusted to pH with the ammoniacal liquor that mass concentration is 30% and is about 10, be subsequently adding addition matter
Amount concentration is 85% hydrazine hydrate 1.0mL and stirring 8 minutes, by the mixed solution of gained in being heated to reflux at 50 DEG C 24 hours.
(3) after reaction terminates, washed repeatedly with secondary water and ethanol after centrifugation, finally centrifugation product is done in vacuum
In dry 15 hours prepared nitrogen-doped graphene powder at 20 DEG C in dry case.
Centrifugation after the completion of reaction, product absolute ethanol washing three times, product at 50 DEG C in being vacuum dried 12h
(4) 15mg nitrogen-doped graphenes powder is weighed in the secondary water and ethanol (1.2 of 70mL:1.0) in mixed solution,
Ultrasound 25 minutes, the acetate hydrate cobalts of 540mg tetra- and 150mg thiocarbamides are added after making its dispersed, are continued ultrasound 15 minutes and are stirred
Mixing makes it all dissolve, and transfers the solution into afterwards in 100mL reactors, and design temperature is 160 DEG C, hydro-thermal reaction 24 hours.
After reaction terminates, by repeatedly washing and the centrifugation of gained precipitation secondary water and ethanol, crude product is put into vacuum drying chamber
Co is obtained final product in drying at 20 DEG C within 14 hours4S3/ nitrogen-doped graphene composite.
Embodiment 3
(1) 50mg graphene oxide powders are weighed in 50mL redistilled waters, it is homogeneous that ultrasound is dispersed into it in 4 hours
Solution.
(2) graphene dispersing solution is adjusted to pH with the ammoniacal liquor that mass concentration is 30% and is about 10, be subsequently adding addition matter
Amount concentration is 85% hydrazine hydrate 1.2mL and stirring 10 minutes, by the mixed solution of gained in being heated to reflux at 50 DEG C 24 hours.
(3) after reaction terminates, washed repeatedly with secondary water and ethanol after centrifugation, finally centrifugation product is done in vacuum
In dry 12 hours prepared nitrogen-doped graphene powder at 30 DEG C in dry case.
(4) 15mg nitrogen-doped graphenes powder is weighed in the secondary water and ethanol (1.0 of 70mL:1.0) in mixed solution,
Ultrasound 30 minutes, the acetate hydrate cobalts of 560mg tetra- and 170mg thiocarbamides are added after making its dispersed, are continued ultrasound 15 minutes and are stirred
Mixing makes it all dissolve, and transfers the solution into afterwards in 100mL reactors, and design temperature is 160 DEG C, hydro-thermal reaction 24 hours.
After reaction terminates, by repeatedly washing and the centrifugation of gained precipitation secondary water and ethanol, crude product is put into vacuum drying chamber
Co is obtained final product in drying at 20 DEG C within 12 hours4S3/ nitrogen-doped graphene composite.
Embodiment 4
(1) 50mg graphene oxide powders are weighed in 50mL redistilled waters, it is homogeneous that ultrasound is dispersed into it in 5 hours
Solution.
(2) graphene dispersing solution is adjusted to pH with the ammoniacal liquor that mass concentration is 30% and is about 11, be subsequently adding addition matter
Amount concentration is 85% hydrazine hydrate 1.4mL and stirring 15 minutes, by the mixed solution of gained in being heated to reflux at 60 DEG C 18 hours.
(3) after reaction terminates, washed repeatedly with secondary water and ethanol after centrifugation, finally centrifugation product is done in vacuum
In dry 15 hours prepared nitrogen-doped graphene powder at 25 DEG C in dry case.
(4) 15mg nitrogen-doped graphenes powder is weighed in the secondary water and ethanol (1.5 of 70mL:1.0) in mixed solution,
Ultrasound 40 minutes, the acetate hydrate cobalts of 570mg tetra- and 180mg thiocarbamides are added after making its dispersed, are continued ultrasound 15 minutes and are stirred
Mixing makes it all dissolve, and transfers the solution into afterwards in 100mL reactors, and design temperature is 170 DEG C, hydro-thermal reaction 20 hours.
After reaction terminates, by repeatedly washing and the centrifugation of gained precipitation secondary water and ethanol, crude product is put into vacuum drying chamber
Co is obtained final product in drying at 30 DEG C within 12 hours4S3/ nitrogen-doped graphene composite.
Embodiment 5
(1) 50mg graphene oxide powders are weighed in 50mL redistilled waters, it is homogeneous that ultrasound is dispersed into it in 3 hours
Solution.
(2) graphene dispersing solution is adjusted to pH with the ammoniacal liquor that mass concentration is 30% and is about 10, be subsequently adding quality dense
Spend the hydrazine hydrate 1.6mL for 85% and stir 15 minutes, by the mixed solution of gained in being heated to reflux at 50 DEG C 28 hours.
(3) after reaction terminates, washed repeatedly with secondary water and ethanol after centrifugation, finally centrifugation product is done in vacuum
In dry 10 hours prepared nitrogen-doped graphene powder at 30 DEG C in dry case.
(4) 15mg nitrogen-doped graphenes powder is weighed in the secondary water and ethanol (1.2 of 70mL:1.0) in mixed solution,
Ultrasound 30 minutes, the acetate hydrate cobalts of 550mg tetra- and 160mg thiocarbamides are added after making its dispersed, are continued ultrasound 15 minutes and are stirred
Mixing makes it all dissolve, and transfers the solution into afterwards in 100mL reactors, and design temperature is 150 DEG C, hydro-thermal reaction 30 hours.
After reaction terminates, by repeatedly washing and the centrifugation of gained precipitation secondary water and ethanol, crude product is put into vacuum drying chamber
Co is obtained final product in drying at 20 DEG C within 15 hours4S3/ nitrogen-doped graphene composite.
Embodiment 6
(1) 50mg graphene oxide powders are weighed in 50mL redistilled waters, it is homogeneous that ultrasound is dispersed into it in 4 hours
Solution.
(2) graphene dispersing solution is adjusted to pH with the ammoniacal liquor that mass concentration is 30% and is about 10, be subsequently adding addition matter
Amount concentration is 85% hydrazine hydrate 1.2mL and stirring 10 minutes, by the mixed solution of gained in being heated to reflux at 60 DEG C 20 hours.
(3) after reaction terminates, washed repeatedly with secondary water and ethanol after centrifugation, finally centrifugation product is done in vacuum
In dry 15 hours prepared nitrogen-doped graphene powder at 25 DEG C in dry case.
(4) 15mg nitrogen-doped graphenes powder is weighed in the secondary water and ethanol (1.0 of 70mL:1.0) in mixed solution,
Ultrasound 30 minutes, the acetate hydrate cobalts of 590mg tetra- and 190mg thiocarbamides are added after making its dispersed, are continued ultrasound 15 minutes and are stirred
Mixing makes it all dissolve, and transfers the solution into afterwards in 100mL reactors, and design temperature is 170 DEG C, hydro-thermal reaction 22 hours.
After reaction terminates, by repeatedly washing and the centrifugation of gained precipitation secondary water and ethanol, crude product is put into vacuum drying chamber
Co is obtained final product in drying at 20 DEG C within 15 hours4S3/ nitrogen-doped graphene composite.
2nd, Co of the present invention4S3The electrochemical catalysis effect assessment of/nitrogen-doped graphene composite to glucose
Target product is coated in modified electrode is fabricated on the carbon-based hearth electrode of glass, study the electrochemical credit to hydrogen peroxide
Analysis effect.
(1) using electron scanning Electronic Speculum respectively to nitrogen-doped graphene, Co4S3And Co4S3/ nitrogen-doped graphene is combined
The pattern of material has done and has characterized (as shown in Figure 2), and nitrogen-doped graphene has much in wavy (Fig. 2A), and surface as seen from the figure
Such as the folded structure of paper-like.Co4S3The granular size of nano material (Fig. 2 B) is more uniform, most of particle size 50~
Between 70nm, work as Co4S3After compound with nitrogen-doped graphene, Co can be clearly observed4S3Nano particle is distributed in N doping graphite
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, the peak correspond to N doping
(002) diffraction maximum of Graphene.Co4S3/ nitrogen-doped graphene composite 2 θ be followed successively by 29.86 °, 31.14 °, 39.49 °,
47.57 °, 51.91 ° and 61.80 ° correspond to Co respectively4S3(JCPDS No.02-1338) standard spectrogram 311,222,331,
211st, 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 is higher.
(3) this experiment also further have studied the electrical conductance of composite with AC impedence method, as shown in figure 4, naked glass
Carbon electrode (Fig. 4 a) is almost straight line in whole high frequency region, and this shows that the resistance of bare glassy carbon electrode is smaller.Repaiied on electrode
Decorations Co4S3/ nitrogen-doped graphene composite (Fig. 4 c) is shown than single Co after high frequency region4S3Modified electrode (Fig. 4 b)
Much smaller semi arch, or even close to bare glassy carbon electrode, show Co4S3/ nitrogen-doped graphene composite is mixed because with the addition of nitrogen
Miscellaneous Graphene causes it than single Co4S3Nano material has smaller solid-state interface layer resistance and electron transport rate faster.
(4) experiment have studied bare glassy carbon electrode, Co using voltammetry respectively4S3Modified glassy carbon electrode, nitrogen-doped graphene are repaiied
Decorations glass-carbon electrode and Co4S3/ nitrogen-doped graphene composite modified glassy carbon electrode is urged the electrochemical reduction of hydrogen peroxide
Change response effect, as shown in Figure 5.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 nitrogen-doped graphene is modified on glass-carbon electrode, background current increase, to the electrochemistry of hydrogen peroxide
Reduction catalystses effect is not also obvious (Fig. 5 b), in Co4S3Response (the figure of hydrogen peroxide can be observed on modified glassy carbon electrode
5c), Co is shown4S3Also original certain catalytic action of the nano material to hydrogen peroxide.But in Co4S3/ nitrogen-doped graphene
On composite modified glassy carbon electrode (Fig. 5 d), the reduction peak current of hydrogen peroxide is maximum, and preferably, reduction spike potential is obvious for peak shape
Shuffle.It is above-mentioned test result indicate 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, so as to show the catalytic effect more stronger than homogenous material.
(5) after the test conditions such as medium, sweep speed, dressing agent load capacity, operating potential are optimized, using timing electricity
Stream method have studied response of the composite modified electrode to hydrogen peroxide.Result shows that the composite modified electrode is in 2s
Catalytic current to hydrogen peroxide reaches stationary value, shows that response of the modified electrode to hydrogen peroxide is rapid (Fig. 6 A).In addition
It has also been found that when concentration of hydrogen peroxide is in the range of 1.0 μM~2.18mM, it is in Co4S3/ nitrogen-doped graphene composite modifies glass
Response current and its concentration on carbon electrode are in good linear relationship (Fig. 6 B), and equation of linear regression is respectively：I (μ A)=
6.0220+65.6270CHydrogen peroxide(r=0.9918), test limit is minimum up to 0.29 μM (S/N=3).
(6) interference--free experiments are to utilize the continuous addition 0.1mM during Ampere currents method determines 0.1mM hydrogen peroxide
Uric acid (UA), 0.1mM ascorbic acid (AA), 0.1mM dopamines (DA), 0.1mM glucose (Glu), 0.1mM fructose (Fru) with
And carried out in the case of 0.5mM NaCl.Experimental result is as shown in fig. 7, the electric current that is produced to modified electrode of above interfering material
Disturbance is respectively less than 2%, shows that modified electrode has good Anti-Jamming to above material.By Co4S3/ nitrogen-doped graphene
The hydrogen peroxide of composite modified glassy carbon electrode parallel determination same concentration 11 times, its standard deviation is 3.86%, shows this
The repeatability of modified electrode is higher.Then by Co4S3/ nitrogen-doped graphene composite 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, current-responsive is the 91% of legacy data, shows that the modified electrode has
Preferable repeatability and stability.
(7) in order to detect Co4S3/ nitrogen-doped graphene composite modified glassy carbon electrode authentic sample application power,
Under optimum experimental condition, the concentration of hydrogen peroxide in three kinds of milk samples have detected using standard addition method, every kind of sample is put down
Row detection 6 times, experimental result is as shown in table 1.The rate of recovery is within zone of reasonableness (between 95%~105%), and relative standard is inclined
Difference (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 the milk sample of table 1
Claims (3)
1. a kind of Co4S3The preparation method of/nitrogen-doped graphene composite, it is characterised in that comprise the following steps：
(1) active oxidation Graphene is disperseed：
Weigh 30~80mg graphene oxides and be 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 ammoniacal liquor, the water that mass concentration is 85% is subsequently adding
0.8~1.6mL of hydrazine is closed, reaction temperature is 40~60 DEG C, 18~36h of reaction time；By product centrifugation and wash afterwards, pass through
Nitrogen-doped graphene powder is obtained 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 ethanol, ultrasound is divided
Uniform rear addition four acetate hydrate cobalts and thiocarbamide are dissipated, continues ultrasound and stir to make its whole dissolving；Transfer the solution into afterwards anti-
Answer and carry out in kettle hydro-thermal reaction, reaction temperature is 150~170 DEG C, the reaction time is 20~30h；After reaction terminates, gained is sunk
Shallow lake is washed and centrifugation with secondary water and ethanol, finally vacuum dried to obtain Co4S3/ nitrogen-doped graphene composite；
In the mixed solution of the secondary water and ethanol：Secondary water is 1~1.5 with the volume ratio of ethanol:1；
The mass ratio of the nitrogen-doped graphene, four acetate hydrate cobalts and thiocarbamide is 1:35~45:10~20.
2. Co as claimed in claim 14S3The preparation method of/nitrogen-doped graphene composite, it is characterised in that described two
In the mixed solution of secondary water and ethanol：Secondary water is 1 with the volume ratio of ethanol:1；The nitrogen-doped graphene, four acetate hydrates
The mass ratio of cobalt and thiocarbamide is 15:560:170.
3. Co as claimed in claim 14S3/ nitrogen-doped graphene composite constructs electrochemical sensor in hydrogen peroxide electricity
Application in chemical analysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710222414.2A CN106908498B (en) | 2017-04-07 | 2017-04-07 | A kind of Co4S3The preparation method and applications of/nitrogen-doped graphene composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710222414.2A CN106908498B (en) | 2017-04-07 | 2017-04-07 | A kind of Co4S3The preparation method and applications of/nitrogen-doped graphene composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106908498A true CN106908498A (en) | 2017-06-30 |
| CN106908498B CN106908498B (en) | 2018-11-27 |
Family
ID=59195021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710222414.2A Active CN106908498B (en) | 2017-04-07 | 2017-04-07 | A kind of Co4S3The preparation method and applications of/nitrogen-doped graphene composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106908498B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107213908A (en) * | 2017-07-04 | 2017-09-29 | 安徽师范大学 | A kind of trisulfides four cobalts nano-hollow pipe@nickel foam composite arrays material, preparation method and applications |
| CN107356643A (en) * | 2017-07-06 | 2017-11-17 | 衡阳师范学院 | A kind of quick detection hydrogen peroxide without enzyme electrochemical sensor and its preparation method and application |
| 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 |
| CN109529885A (en) * | 2018-11-19 | 2019-03-29 | 中南大学 | A kind of cobalt sulfide/biomass carbon composite material and preparation method and as elemental mercury oxidation catalyst application |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409706A (en) * | 2014-12-22 | 2015-03-11 | 湖南大学 | Molybdenum disulfide/sulfur-and-nitrogen-doped graphene nanosheet composite material as well as preparation method and application thereof |
| CN104681823A (en) * | 2015-01-23 | 2015-06-03 | 西华师范大学 | Nitrogen-doped graphene and Co3O4 hollow nanosphere composite material as well as preparation method and application of composite material |
| CN105225844A (en) * | 2015-09-09 | 2016-01-06 | 南京航空航天大学 | The preparation method of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobalt acid zinc composite material and application |
| CN105244175A (en) * | 2015-09-21 | 2016-01-13 | 福州大学 | N-doped graphene/cobaltosic oxide nanocomposite |
| CN105540682A (en) * | 2015-12-30 | 2016-05-04 | 哈尔滨理工大学 | Method for preparing ferroferric oxide loaded nitrogen-doped graphene composite material by taking urea iron as iron source |
| CN106328387A (en) * | 2016-08-31 | 2017-01-11 | 江苏大学 | Nitrogen-doped carbon nanotube/molybdenum disulfide nanosphere composite material and preparation method thereof |
-
2017
- 2017-04-07 CN CN201710222414.2A patent/CN106908498B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409706A (en) * | 2014-12-22 | 2015-03-11 | 湖南大学 | Molybdenum disulfide/sulfur-and-nitrogen-doped graphene nanosheet composite material as well as preparation method and application thereof |
| CN104681823A (en) * | 2015-01-23 | 2015-06-03 | 西华师范大学 | Nitrogen-doped graphene and Co3O4 hollow nanosphere composite material as well as preparation method and application of composite material |
| CN105225844A (en) * | 2015-09-09 | 2016-01-06 | 南京航空航天大学 | The preparation method of nitrogen-doped graphene/nitrogen-doped carbon nanometer pipe/cobalt acid zinc composite material and application |
| CN105244175A (en) * | 2015-09-21 | 2016-01-13 | 福州大学 | N-doped graphene/cobaltosic oxide nanocomposite |
| CN105540682A (en) * | 2015-12-30 | 2016-05-04 | 哈尔滨理工大学 | Method for preparing ferroferric oxide loaded nitrogen-doped graphene composite material by taking urea iron as iron source |
| CN106328387A (en) * | 2016-08-31 | 2017-01-11 | 江苏大学 | Nitrogen-doped carbon nanotube/molybdenum disulfide nanosphere composite material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107213908A (en) * | 2017-07-04 | 2017-09-29 | 安徽师范大学 | A kind of trisulfides four cobalts nano-hollow pipe@nickel foam composite arrays material, preparation method and applications |
| CN107356643A (en) * | 2017-07-06 | 2017-11-17 | 衡阳师范学院 | A kind of quick detection hydrogen peroxide without enzyme electrochemical sensor and its preparation method and application |
| CN109529885A (en) * | 2018-11-19 | 2019-03-29 | 中南大学 | A kind of cobalt sulfide/biomass carbon composite material and preparation method and as elemental mercury oxidation catalyst 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106908498B (en) | 2018-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106908498A (en) | A kind of Co4S3The preparation method and applications of/nitrogen-doped graphene composite | |
| Li et al. | Ag/N-doped reduced graphene oxide incorporated with molecularly imprinted polymer: an advanced electrochemical sensing platform for salbutamol determination | |
| Ensafi et al. | A novel enzyme-free amperometric sensor for hydrogen peroxide based on Nafion/exfoliated graphene oxide–Co3O4 nanocomposite | |
| Kilele et al. | Ultra-sensitive electrochemical sensor for fenitrothion pesticide residues in fruit samples using IL@ CoFe2O4NPs@ MWCNTs nanocomposite | |
| Li et al. | Electrodeposition of cobalt oxide nanoparticles on reduced graphene oxide: a two-dimensional hybrid for enzyme-free glucose sensing | |
| CN108007998B (en) | Nickel oxide non-enzymatic glucose electrochemical sensor | |
| CN106770562B (en) | A kind of CoS2/ nitrogen-doped graphene composite material constructs application of the electrochemical sensor in glucose electrochemical analysis | |
| Xia et al. | Hollow Fe2O3 polyhedrons: one-pot synthesis and their use as electrochemical material for nitrite sensing | |
| CN112285174B (en) | Enzyme-free glucose sensor and preparation method and application thereof | |
| CN106383158B (en) | A kind of hydrogen peroxide based on silver-graphene nano-complex is without enzyme sensor and preparation method thereof | |
| CN105929007A (en) | Method of construction for photoelectrochemical glucose oxidase sensor with graphite like g-C3N4-TiO2 nanosheet composite as enzymatic molecule immobilization scaffold | |
| Cui et al. | Electro-oxidation nitrite based on copper calcined layered double hydroxide and gold nanoparticles modified glassy carbon electrode | |
| Kokulnathan et al. | Hexammine cobalt (iii) coordination complex grafted reduced graphene oxide composite for sensitive and selective electrochemical determination of morin in fruit samples | |
| Salimi et al. | Electrooxidation of insulin at silicon carbide nanoparticles modified glassy carbon electrode | |
| CN104614425B (en) | A kind of functionalized carbon nano-tube carries Cu2The preparation and application of O hexagram crystallite composites | |
| Zhang et al. | Bimetal-organic frameworks MnCo-MOF-74 derived Co/MnO@ HC for the construction of a novel enzyme-free glucose sensor | |
| CN104777157A (en) | Non-enzyme electrogenerated chemiluminescence (ECL) glucose sensor | |
| Khairy et al. | Copper oxide microstructures with hemisphere pineapple morphology for selective amperometric determination of vitamin C (L‐ascorbic acid) in human fluids | |
| CN103852512A (en) | Electrochemical sensor for detecting hydrogen peroxide, and preparation method of electrochemical sensor | |
| Asadpour‐Zeynali et al. | Nanostructured hexacyanoferrate intercalated Ni/Al layered double hydroxide modified electrode as a sensitive electrochemical sensor for paracetamol determination | |
| CN107500264A (en) | The preparation method of a kind of smallfruit fig leaf based biomass porous carbon and its in protein（Enzyme）Applied in sensor | |
| Zhao et al. | Reduced graphene oxide-modified screen-printed carbon (rGO-SPCE)-based disposable electrochemical sensor for sensitive and selective determination of ethyl carbamate | |
| Derakhshi et al. | Synthesis and characterization of NiO nanoparticle as a high sensitive voltammetric sensor for vitamin C determination in food samples | |
| CN106053564B (en) | A kind of method that graphite-phase nitrogen carbide-chitosan-modified electrode detects protocatechuic acid as working electrode | |
| Adeniyi et al. | High-performance non-enzymatic glucose sensing on nanocomposite electrocatalysts of nickel phthalocyanine nanorods and nitrogen doped-reduced graphene oxide nanosheets |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |