CN110270358A - A kind of preparation method of the graphene-supported CuO catalyst of N, S codope - Google Patents
A kind of preparation method of the graphene-supported CuO catalyst of N, S codope Download PDFInfo
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
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- B01J35/61—
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Abstract
The present invention relates to the synthesis technical fields of catalyst, specifically provide a kind of preparation method of graphene-supported CuO composite catalyst of N, S codope, the composite material can be used for non-enzymatic glucose sensor, belong to a kind of high activated catalyst to promote electro-catalysis grape glycoxidative.Graphite oxide (GO) is obtained using Hummers method is improved, thiocarbamide is then added and continues to be ultrasonically treated, mixture is finally transferred to reaction in autoclave and obtains NSG.NSG suspension is dispersed in n,N-Dimethylformamide, Cu (Ac) is added after heating2Solution, reaction obtain product CuO/NSG.CuO/NSG is prepared by two step solvent-thermal methods, efficient, controllable and easy-operating process characteristic is played, CuO/NSG has big surface area and hole abundant, and this not only adds the exposures of active site, and promote diffusion of reactant during electro-catalysis, both contribute to enhancing EGO activity.NSG can provide improved electric conductivity as CuO carrier, and accelerated charge transfer is to be used for effective electro-catalysis.It is glycoxidative to be applied to electro-catalysis grape in non-enzymatic glucose sensor as catalyst by prepared CuO/NSG.
Description
[technical field]
The present invention relates to the synthesis technical fields of catalyst, and it is multiple to specifically provide a kind of graphene-supported CuO of N, S codope
The preparation method of condensation material catalyst, the composite material can be used for non-enzymatic glucose sensor, belong to a kind of high activated catalyst
To promote electro-catalysis grape glycoxidative.
[background technique]
Sense organ organ of the sensor for people just as him is the same, is their extension, it is also assumed that being the mankind
" face ".Wherein mostly important with the research of biosensor, this is related to the happiness of the mankind, is to cease manner of breathing the most with the mankind
It closes.So said for we are daily, most it is proper we health no more than glucose sensor use, many people are
Perplexed by this disease.Glucose sensor can be divided into enzyme type and non-enzyme type.Non-enzyme type is exactly using electrochemical reaction come mould
The effect of quasi- enzyme, so it is mobile to achieve the effect that oxidizing glucose by electronics, then shown by sensing system.It is non-
For the glucose sensor of enzyme type without the concern for the factor of enzyme, this just greatly expands its use scope, no matter environment or
Limit, it is all accurate with respect to enzyme type glucose sensor, stablize.
Exploitation high-performance non-enzyme type glucose sensor will develop high activated catalyst to promote electro-catalysis grape glycosyloxy
Change (EGO), this is the key point of non-enzymatic glucose sensing.Pt and other noble metals are most active EGO catalyst, but its is dilute
It lacks property and high cost significantly limits practical application.In recent years, developed various effective metal oxides (CuO, NiO,
Co3O4Deng) most promising substitute as the catalyst based on noble metal.In all these alternative solutions, CuO nanometers
Structure is due to its high electrochemical activity, oxidation-reduction potential appropriate, and excellent stability and environment are benign and attracted extensively
Concern.However, undesirable electric conductivity and aggregation tendency significantly reduce the electro catalytic activity of CuO nanostructure.These are solved to ask
The most efficient method of topic is directly grown on the conducting carbon-based material for including carbon nano-fiber, carbon nanotube and graphene
CuO nanostructure forms nanocomposite.Graphene two dimensional crystal structure, have unique calorifics, mechanics, electric property with
And superelevation specific surface area and become the research hotspot of current major subject.Using graphene and its composite material as carrier
Biosensor is constructed, this is to take the course of its own, and is especially expected.
Foreign atom (N, B, P, S), which has been disclosed, in nearest research can greatly improve urging for graphene into carbon skeleton
Change activity, this is attributed to the polarisation distribution of spin and charge density.In addition, there are two types of different hetero atoms (such as N and S) for codope
The graphene counterpart than monatomic doping that has been reported show even higher electro catalytic activity.This is because opposite
Synergistic effect between single doping, hetero atom can induce the enhancing of asymmetric spin and charge density, this greatly enhances
Electro catalytic activity.It is recently reported N, S codope graphene (NSG), which has, is used for while detecting the excellent of glucose and hydrogen peroxide
Sensing performance.Although the hetero atom of doped graphene has been widely studied for the relevant electro-catalysis application of energy, seldom
It is considered for electrochemical sensor.Meanwhile hetero atom codope graphene is used as and is used for metal/metal oxide nanostructure
The substrate of hybridization still do not developed largely.As far as we know, the CuO nano junction on NSG (CuO/NSG) is supported
Structure be not produced previously and had sensed for glucose.
In order to solve the scarcity of electro-catalysis glucose oxidation catalyst in non-enzymatic glucose sensor, Gao Chengben, bad
Electric conductivity and aggregation tendency, the present invention provides graphene-supported CuO composite material and its preparation side of a kind of doping of diatomic
Method can adjust its conduction type and (realize p-type and N by doping because the elements such as N, S can effectively open the band gap of graphene
Conversion between type semiconductor), change its electronic structure, to improve its free carrier density, increases its electric conductivity and steady
Qualitative, the present invention selection graphene-supported CuO of N, S codope, experimental result obtains high activated catalyst of good performance, i.e.,
N, the graphene-supported CuO composite material (CuO/NSG) of S codope.
Tradition is mainly adulterated with vapour deposition process (CVD) preparation N, S and its N and S codope graphene, but its preparation process
It is very cumbersome, not only need the templates such as metallic catalyst and silicon wafer, it is also necessary to which complicated vacuum systems are mass produced at high cost
It is high, it is difficult to realize its commercialization.In addition to this, direct high-temperature calcination is containing macromolecules and its polymer precursor melamines such as N, S
The mixture of amine, ammonium hydroxide etc. and graphene graphene oxide, and by graphene-based derivative in the (NH of gas containing hetero atom3、
H2S, HCN) etc. be heat-treated under atmosphere, monatomic doping or diatomic doped graphene also can be obtained.But both methods
The graphene specific surface area of preparation is not generally high, and preparation process is complex, needs first to prepare graphene oxide and be mixed again
It closes, or needs complicated organic gas environment, this is all unfavorable for its popularization, and polymer precursor and how toxic organic gas is has
Evil, seriously threatens human health.
[summary of the invention]
The object of the present invention is to provide a kind of graphene-supported CuO composite material (CuO/NSG) of N, S codope and its systems
Preparation Method is prepared by two step solvent-thermal methods with big specific surface area, the CuO/NSG of excellent chemical property, can
To be applied in non-enzymatic glucose sensor as high activated catalyst to promote electro-catalysis grape glycoxidative.
[specific process step]
A, graphite oxide (GO) is obtained using Hummers method is improved, after powdered graphite and sodium nitrate are mixed in proportion,
The addition concentrated sulfuric acid, potassium permanganate are aoxidized, and hydrogen peroxide oxidation is added after low temperature, medium temperature, the reaction of high temperature three phases,
Then by centrifugation, precipitating, washing, drying, GO is obtained.
B, it is ultrasonically treated after dissolving obtained GO in water, thiocarbamide is then added and continues to be ultrasonically treated, finally will
Mixture, which is transferred in autoclave, to react, and is cooled to room temperature after reaction, obtains NSG using centrifugation, washing, vacuum drying.
C, NSG suspension is dispersed in n,N-Dimethylformamide, Cu (Ac) is added after heating2Solution, after reaction
Sediment is dispersed in deionized water and is transferred in autoclave to be kept for a period of time, passes through centrifugation after cooling by centrifugation
Product CuO/NSG is collected, and by repeatedly washing, is then dried in a vacuum.
The major advantage of this reality is:
1, easily operated, controllability is good, and the control of many conditions has very big section.
2, cost is relatively low, also more friendly to environment.
3, synthetic product is relatively stable, is easy to large-scale production.
[specific embodiment]
Embodiment 1: pressing NSG: CuO=4: 3, prepares CuO/NSG
1. natural graphite powder 2g, sodium nitrate 1g are added in flask, while mechanical stirring, it is placed in ice-water bath, then
It is slowly added to 98% concentrated sulfuric acid 50mL；It weighs 3g potassium permanganate and is slowly added in beaker several times, completed in 30 minutes；
50mL distilled water is added into flask, puts it into 37 DEG C of thermostat water baths and reacts, while strong stirring 4 hours；In solution
Middle addition 50ml deionized water makes temperature be heated to 97 DEG C and keeps this thermotonus 30 minutes, is kept stirring during this together；
After liquid is transferred in conical flask and 100mL distilled water is added, 200mL30% hydrogen peroxide is then slowly added dropwise, until
Bubble-free generates；It is centrifuged with the centrifugal device of 2000r/min, then places on one side precipitating；Supernatant is taken out after being layered thoroughly,
It is repeatedly washed with a small amount of deionized water and distilled water to remove extra acid and excess ions, until solution ph is in 5-7, vacuum
It filters；Gained filter cake is placed in 60 DEG C of electric drying oven with forced convections and dries 12 hours as graphite oxide GO, takes out and saves for use.
2. the graphite oxide GO of 0.1g is dispersed in 100mL deionized water and be ultrasonically treated within 30 minutes；By 0.2g
Thiocarbamide is slowly added into graphite oxide GO suspension, and mixture is ultrasonically treated again 1 hour.Mixture is transferred to height
It presses in kettle and keeps reaction 24 hours at 180 DEG C；Reaction solution is cooled to room temperature, and production is collected by centrifugation by centrifugal device
Object (NSG)；Then it is washed with distilled water several times and filters, be then dried in a vacuum 12 hours.
3. 2ml NSG suspension (2.0mg/mL) is dispersed in 15ml n,N-Dimethylformamide (0.1mg/ml)；?
NSG suspension is heated to 90 DEG C in round-bottomed flask with magnetic agitation, is then slowly added to 1.5ml in NSG suspension
Cu(Ac)2Solution (0.2mol/L), and stir 1 hour；By centrifuge centrifugal sediment, then deionized water is removed more
Remaining foreign ion；Sediment is dispersed in 30mL deionized water and suspension is transferred in autoclave, is kept at 180 DEG C
12 hours；After being cooled to room temperature, by the way that product (CuO/NSG) is collected by centrifugation, and it is washed with distilled water repeatedly, filters and in vacuum
High activated catalyst of good performance (CuO/NSG) can be obtained in middle drying 24 hours.
Embodiment 2: pressing NSG: CuO=2: 1, prepares CuO/NSG
1. preparing GO with method in example 1；
2. preparing NSG with method in example 1；
3. 2ml NSG suspension (2.0mg/mL) is dispersed in 15ml n,N-Dimethylformamide (0.1mg/ml)；?
NSG suspension is heated to 90 DEG C in round-bottomed flask with magnetic agitation, 1ml Cu is then slowly added in NSG suspension
(Ac)2Solution (0.2mol/L), and stir 1 hour；By centrifuge centrifugal sediment, then deionized water is removed extra
Foreign ion；Sediment is dispersed in 20mL deionized water and suspension is transferred in autoclave, keeps 12 at 180 DEG C
Hour；After being cooled to room temperature, by the way that product (CuO/NSG) is collected by centrifugation, and be washed with distilled water repeatedly, filter and in a vacuum
It is 24 hours dry, high activated catalyst of good performance (CuO/NSG) can be obtained.
Embodiment 3: pressing NSG: CuO=1: 1, prepares CuO/NSG
1. preparing GO with method in example 1；
2. preparing NSG with method in example 1；
3. 3ml NSG suspension (2.0mg/mL) is dispersed in 15ml n,N-Dimethylformamide (0.1mg/ml)；?
NSG suspension is heated to 90 DEG C in round-bottomed flask with magnetic agitation, is then slowly added to 1.5ml in NSG suspension
Cu(Ac)2Solution (0.2mol/L), and stir 30 minutes；By centrifuge centrifugal sediment, then deionized water is removed
Undesired impurities ion；Sediment is dispersed in 15mL deionized water and suspension is transferred in autoclave, is protected at 180 DEG C
It holds 12 hours；After being cooled to room temperature, by the way that product (CuO/NSG) is collected by centrifugation, and it is washed with distilled water repeatedly, filters and true
It is aerial 24 hours dry, high activated catalyst of good performance (CuO/NSG) can be obtained.
Embodiment 4: pressing NSG: CuO=1: 2, prepares CuO/NSG
1. preparing GO with method in example 1；
2. preparing NSG with method in example 1；
3. 4ml NSG suspension (2.0mg/mL) is dispersed in 15ml n,N-Dimethylformamide (0.1mg/ml)；?
NSG suspension is heated to 90 DEG C in round-bottomed flask with magnetic agitation, 2ml Cu is then slowly added in NSG suspension
(Ac)2Solution (0.2mol/L), and stir 1 hour；By centrifuge centrifugal sediment, then deionized water is removed extra
Foreign ion；Sediment is dispersed in 20mL deionized water and suspension is transferred in autoclave, keeps 12 at 180 DEG C
Hour；After being cooled to room temperature, by the way that product (CuO/NSG) is collected by centrifugation, and be washed with distilled water repeatedly, filter and in a vacuum
It is 24 hours dry, high activated catalyst of good performance (CuO/NSG) can be obtained.
Finally, it should be noted that obviously, examples detailed above is only to clearly illustrate example of the present invention, and not to be
Restriction to embodiment.For those of ordinary skill in the art, it can also be made on the basis of the above description
His various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.And it thus amplifies out
Obvious changes or variations be still in the protection scope of this invention.
Claims (1)
1. a kind of preparation method of the graphene-supported CuO catalyst of N, S codope, specific process step are as follows:
Step 1: obtaining graphite oxide (GO) using Hummers method is improved, powdered graphite and sodium nitrate are pressed 1.5-3.5: 1
After (mass ratio) mixing, the addition concentrated sulfuric acid, potassium permanganate are aoxidized, by low temperature, medium temperature, high temperature three phases (35-98
DEG C) reaction after hydrogen peroxide oxidation is added, then by centrifugation, precipitating, washing, drying, obtain GO.
Step 2: being ultrasonically treated after obtained GO is dissolved in water, thiocarbamide is then added and continues to be ultrasonically treated, finally will
Mixture, which is transferred in autoclave, to react, and 160-200 DEG C of reaction temperature, is cooled to room temperature after reaction, using centrifugation, washing,
Vacuum drying obtains NSG.
Step 3: dispersing NSG suspension in n,N-Dimethylformamide, adjusting NSG concentration is 0.002-0.007mol/L,
The concentration of n,N-Dimethylformamide is 0.001-0.002mol/L, and Cu (Ac) is added after heating2Solution is adjusted Cu (Ac)2It is dense
Degree is 0.011-0.019mol/L, and sediment is dispersed in deionized water and is transferred to autoclave by centrifugation after reaction
Middle holding a period of time (10-14h), by the way that product CuO/NSG is collected by centrifugation after cooling, and is passed through by 160-200 DEG C of reaction temperature
Repeatedly washing, is then dried in a vacuum.
The above method, which is characterized in that N, S are as hetero atom codope graphene and carrier material is CuO；Dopant selection N,
S, one of P, B, Cl., F, amino acid or a variety of, carrier material select CuO, NiO, Co3O4One of or it is a variety of.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113097470A (en) * | 2021-03-29 | 2021-07-09 | 长春理工大学 | Nitrogen-sulfur-containing co-doped graphene cobalt-copper-silicon hydrogen storage composite material and preparation method thereof |
| CN113731467A (en) * | 2021-09-06 | 2021-12-03 | 湘潭大学 | Nitrogen-modified graphene-loaded copper oxide composite material and preparation method and application thereof |
| CN114345346A (en) * | 2022-01-11 | 2022-04-15 | 上海师范大学 | Method for preparing metal monatomic catalyst by hydrothermal method |
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