CN105699454A - Preparing method for graphene-nanogold hydrogel electrode - Google Patents
Preparing method for graphene-nanogold hydrogel electrode Download PDFInfo
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- CN105699454A CN105699454A CN201610107638.4A CN201610107638A CN105699454A CN 105699454 A CN105699454 A CN 105699454A CN 201610107638 A CN201610107638 A CN 201610107638A CN 105699454 A CN105699454 A CN 105699454A
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Abstract
The invention discloses a preparing method for a graphene-nanogold hydrogel electrode. The preparing method includes the following steps that 1, a graphene oxide water solution is prepared; 2, a shell of the graphene-nanogold hydrogel electrode is manufactured; 3, the graphene oxide water solution, chloroauric acid and sodium borohydride are added into the shell to prepare the graphene-nanogold hydrogel electrode. According to the preparing method, nanogold particles are introduced into graphene oxide gel, so that the conductivity of the prepared graphene-nanogold hydrogel electrode is improved substantially, meanwhile, binding sites of a sulfhydrylated bioprobe can be provided by nanogold, and the probe is fixed to the hydrogel electrode, which is beneficial for biological detection of the electrode.
Description
Technical field
The invention belongs to technical field of electrochemistry, the preparation method being specifically related to a kind of Graphene-nanometer gold hydrogel electrode。
Background technology
The electric charge that Graphene, graphene oxide and reduzate thereof are with makes it have good dispersibility, simultaneously can also as function construction unit, pass through noncovalent interaction, such as Van der Waals force, hydrogen bond, π-π effect, electrostatic interaction etc., self assembly or assemble formation hydrogel altogether with other function construction units；Also have by solid liquid interface effect strong between Woelm Alumina and graphene oxide water solution, promote graphene oxide to be enriched with rapidly at alumina surface, form graphene oxide hydrogel (Chem.Commun., 2011,47:5771-5773)。It addition, utilize the noncovalent interaction between DNA and graphene oxide, in-situ cross-linked graphene oxide, the graphene oxide of preparation/DNA hydrogel mechanical strength height, good stability, absorption affinity strong (J.Phys.Chem.C., 2011,115:5545-5551)。Graphene oxide hydrogel electrode may be used for biomacromolecule, and such as the super sensitivity detection (Adv.Funct.Mater.2014,24,6,905 6913) of DNA, but the electric conductivity of graphene oxide hydrogel electrode of the prior art is still not satisfactory。
Summary of the invention
It is an object of the invention to overcome prior art defect, it is provided that the preparation method of a kind of Graphene-nanometer gold hydrogel electrode。
Principles of the invention is as follows:
The concrete technical scheme of the present invention is as follows:
The preparation method of a kind of Graphene-nanometer gold hydrogel electrode, comprises the steps:
(1) graphene oxide water solution is prepared:
A, natural graphite powder and sodium nitrate are mixed homogeneously with concentrated sulphuric acid under condition of ice bath；
B, potassium permanganate is gradually slowly added in the material of above-mentioned steps a, the temperature keeping material lower than 20 DEG C and stirs 2～3h, then reaction 30～35min is continued in 35 DEG C, then in material, gradually it is slowly added to deionized water, temperature is risen to 95 DEG C and continues reaction 3～4h, add pure water and terminate reaction, be simultaneously introduced 30%H2O2, it is cooled to room temperature；
C, step b gained material is carried out sucking filtration, obtain filter cake；
D, successively with aqueous hydrochloric acid solution and the above-mentioned filter cake of pure water, to remove metal ion and the hydrochloric acid of residual, then the filter cake after washing is dispersed in water again, the graphite that 1800～2500rpm centrifugal segregation is not oxidized, obtains clear liquid；
E, clear liquid carrying out supersound process to realize being completely dispersed, 3800～4200rpm is centrifuged off unstripped graphite oxide, then 7500～8500rpm is centrifuged, and collects precipitation；
F, above-mentioned precipitation is dispersed in again in pure water dialyse, with removes remain salt, obtain finely dispersed graphene oxide water solution；
(2) making the shell of Graphene-nanometer gold hydrogel electrode, this shell has a through hole run through for conductive filament this through hole of temporarily sealing；
(3) in above-mentioned shell implantation step (1) prepare graphene oxide solution, 4～6mg/mL HAuCl4The NaBH of solution and 1.8～2.2mM/L4Solution, mix homogeneously also avoids bubble to produce, then in 93～95 DEG C, 450～520rpm heat vortex 8～11min, it is cooled to room temperature, conductive filament is inserted in shell by described through hole, obtains described Graphene-nanometer gold hydrogel electrode, above-mentioned graphene oxide solution, HAuCl4Solution and NaBH4The volume ratio of solution is 3～7:0.3～0.6:0.1～0.2。
In a preferred embodiment of the invention, natural graphite powder, sodium nitrate, concentrated sulphuric acid, potassium permanganate, deionized water and 30%H in described step (1)2O2Ratio be 1.5～2.5g:0.8～1.2g:44～47mL:5～7g:90～95mL:5～7mL。
It is further preferred that natural graphite powder, sodium nitrate, concentrated sulphuric acid, potassium permanganate, deionized water and 30%H in described step (1)2O2Ratio be 2g:1g:46mL:6g:92mL:6mL。
In a preferred embodiment of the invention, described step d is centrifuged as 2000rpm, and the time is 10min。
In a preferred embodiment of the invention, described step e is: clear liquid carries out supersound process to realize being completely dispersed, and the centrifugal 20min of 4000rpm removes unstripped graphite oxide the more centrifugal 20min of 8000rpm, collects precipitation。
In a preferred embodiment of the invention, the material of described conductive filament is copper。
In a preferred embodiment of the invention, described step (3) is: in above-mentioned shell implantation step (1) prepare graphene oxide solution, 5mg/mL HAuCl4The NaBH of solution and 2mM/L4Solution, mix homogeneously also avoids bubble to produce, then in 95 DEG C, 500rpm heat vortex 10min, be cooled to room temperature, obtain described Graphene-nanometer gold hydrogel electrode。
In a preferred embodiment of the invention, described graphene oxide solution, HAuCl4Solution and NaBH4The volume ratio of solution is 5:0.5:0.1。
The invention has the beneficial effects as follows: the preparation method of the present invention introduces nanogold particle in graphene oxide gel, the electric conductivity making obtained Graphene-nanometer gold hydrogel electrode significantly improves, nanometer gold may be provided for the binding site of sulfhydrylation bioprobe simultaneously, probe is fixed in hydrogel electrode, is conducive to the biological detection of electrode。
Accompanying drawing explanation
Fig. 1 is the photo of the Graphene-nanometer gold hydrogel electrode of the embodiment of the present invention 1 preparation。
Fig. 2 is the stereoscan photograph of the hydrogel of the second comparison electrode。
Fig. 3 is the stereoscan photograph of the hydrogel of the Graphene-nanometer gold hydrogel electrode of the embodiment of the present invention 1 preparation。
The EIS that Fig. 4 is the Graphene-nanometer gold hydrogel electrode of the embodiment of the present invention 1 preparation, the first comparison electrode and the second comparison electrode contrasts collection of illustrative plates。
Detailed description of the invention
In conjunction with accompanying drawing technical scheme it is further detailed below by way of detailed description of the invention and describes。
Embodiment 1
(1) graphene oxide water solution is prepared:
A, 2g natural graphite powder and 1g sodium nitrate are added flask, mix homogeneously with 46mL concentrated sulphuric acid under condition of ice bath；
B, 6g potassium permanganate is gradually slowly added in the material of above-mentioned steps a, the temperature keeping material lower than 20 DEG C and stirs 2h, then reaction 30min is continued in 35 DEG C, then in material, gradually it is slowly added to 92mL deionized water, temperature is risen to 95 DEG C and continues reaction 3h, add 400mL pure water and terminate reaction, be simultaneously introduced 6mL30%H2O2, it is cooled to room temperature；
C, step b gained material is carried out sucking filtration, obtain filter cake；
D, successively with 100mL aqueous hydrochloric acid solution (hydrochloric acid: water=1:10) and a large amount of above-mentioned filter cake of pure water cyclic washing, to remove metal ion and the hydrochloric acid of residual, again being dispersed in water by filter cake after washing, the centrifugal 10min of 2000rpm removes not oxidized graphite, obtains clear liquid again；
E, clear liquid carrying out supersound process 8h to realize being completely dispersed, the centrifugal 20min of 4000rpm removes unstripped graphite oxide the more centrifugal 20min of 8000rpm, collects precipitation；
F, above-mentioned precipitation is dispersed in again in pure water dialyse, with removes remain salt, obtain finely dispersed graphene oxide water solution；
(2) making the shell of Graphene-nanometer gold hydrogel electrode, this shell has a through hole run through for conductive filament, specific as follows: to make a hole with copper wire bottom the centrifuge tube of 2mL, then encases with preservative film, then pinions with rubber band；
(3) graphene oxide solution 0.5mL, the HAuCl of 5mg/mL that implantation step (1) prepares in above-mentioned centrifuge tube4The NaBH of solution 0.05mL and 2mM/L4Solution 0.01mL, prevent from splashing on tube wall, with pipettor gentleness mix homogeneously, bubble is avoided to produce, then in 95 DEG C, 500rpm heat vortex 10min, be cooled to room temperature, take off rubber band and preservative film, bottom pipe, inject copper wire, obtain described Graphene-nanometer gold hydrogel electrode (as shown in Figure 1)。
Prepare the first comparison electrode and the second comparison electrode by above-mentioned steps, difference is in that: the first comparison electrode does not add gold chloride and sodium borohydride, and the second comparison electrode does not add sodium borohydride。
The hydrogel of the Graphene in above-mentioned electrode-nanometer gold hydrogel and the second comparison electrode is placed on-80 DEG C of refrigerator pre-freezes, put lyophilization in freezer dryer again into, the powder scanning electron microscope obtained characterizes, as shown in Figures 2 and 3, the nanometer gold (GNPs) that in the lamellar structure of the graphene oxide fold of the hydrogel of visible second comparison electrode, in-situ reducing goes out, density is 32/μm2, particle diameter 100 ± 10.5nm, and visible nanometer gold quantity showed increased on electrode prepared by the present embodiment, density 63/μm2, particle diameter 200 ± 12.5nm。
The EIS of the hydrogel of electrode, the first comparison electrode and the second comparison electrode prepared by the present embodiment contrasts as shown in Figure 4, the impedance of the hydrogel of the first comparison electrode is about 90.36k Ω (curve a), and the hydrogel impedance of the second comparison electrode is reduced to 50.47k Ω (curve b)；And the hydrogel impedance of electrode prepared by the present embodiment is further reduced to 18.25k Ω (curve c), illustrate that electric conductivity is remarkably reinforced；
Nanometer gold may be provided for the binding site of sulfhydrylation bioprobe simultaneously, probe is fixed in hydrogel electrode, is conducive to the biological detection of electrode。
Those of ordinary skill in the art are it can be seen that when technical scheme changes in following ranges, remain able to obtain same as the previously described embodiments or close technique effect, still fall within protection scope of the present invention:
The preparation method of a kind of Graphene-nanometer gold hydrogel electrode, comprises the steps:
(1) graphene oxide water solution is prepared:
A, natural graphite powder and sodium nitrate are mixed homogeneously with concentrated sulphuric acid under condition of ice bath；
B, potassium permanganate is gradually slowly added in the material of above-mentioned steps a, the temperature keeping material lower than 20 DEG C and stirs 2～3h, then reaction 30～35min is continued in 35 DEG C, then in material, gradually it is slowly added to deionized water, temperature is risen to 95 DEG C and continues reaction 3～4h, add pure water and terminate reaction, be simultaneously introduced 30%H2O2, it is cooled to room temperature；
C, step b gained material is carried out sucking filtration, obtain filter cake；
D, successively with aqueous hydrochloric acid solution and the above-mentioned filter cake of pure water, to remove metal ion and the hydrochloric acid of residual, then the filter cake after washing is dispersed in water again, the graphite that 1800～2500rpm centrifugal segregation is not oxidized, obtains clear liquid；
E, clear liquid carrying out supersound process to realize being completely dispersed, 3800～4200rpm is centrifuged off unstripped graphite oxide, then 7500～8500rpm is centrifuged, and collects precipitation；
F, above-mentioned precipitation is dispersed in again in pure water dialyse, with removes remain salt, obtain finely dispersed graphene oxide water solution；
Above-mentioned natural graphite powder, sodium nitrate, concentrated sulphuric acid, potassium permanganate, deionized water and 30%H2O2Ratio be 1.5～2.5g:0.8～1.2g:44～47mL:5～7g:90～95mL:5～7mL；
(2) making the shell of Graphene-nanometer gold hydrogel electrode, this shell has a through hole run through for conductive filament this through hole of temporarily sealing；
(3) in above-mentioned shell implantation step (1) prepare graphene oxide solution, 4～6mg/mL HAuCl4The NaBH of solution and 1.8～2.2mM/L4Solution, mix homogeneously also avoids bubble to produce, then in 93～95 DEG C, 450～520rpm heat vortex 8～11min, it is cooled to room temperature, conductive filament is inserted in shell by described through hole, obtains described Graphene-nanometer gold hydrogel electrode, above-mentioned graphene oxide solution, HAuCl4Solution and NaBH4The volume ratio of solution is 3～7:0.3～0.6:0.1～0.2。
The above, be only presently preferred embodiments of the present invention, therefore can not limit scope of the invention process according to this, and the equivalence namely made according to the scope of the claims of the present invention and description changes and modifies, and all should still belong in the scope that the present invention contains。
Claims (8)
1. the preparation method of Graphene-nanometer gold hydrogel electrode, it is characterised in that: comprise the steps:
(1) graphene oxide water solution is prepared:
A, natural graphite powder and sodium nitrate are mixed homogeneously with concentrated sulphuric acid under condition of ice bath；
B, potassium permanganate is gradually slowly added in the material of above-mentioned steps a, the temperature keeping material lower than 20 DEG C and stirs 2～3h, then reaction 30～35min is continued in 35 DEG C, then in material, gradually it is slowly added to deionized water, temperature is risen to 95 DEG C and continues reaction 3～4h, add pure water and terminate reaction, be simultaneously introduced 30%H2O2, it is cooled to room temperature；
C, step b gained material is carried out sucking filtration, obtain filter cake；
D, successively with aqueous hydrochloric acid solution and the above-mentioned filter cake of pure water, to remove metal ion and the hydrochloric acid of residual, then the filter cake after washing is dispersed in water again, the graphite that 1800～2500rpm centrifugal segregation is not oxidized, obtains clear liquid；
E, clear liquid carrying out supersound process to realize being completely dispersed, 3800～4200rpm is centrifuged off unstripped graphite oxide, then 7500～8500rpm is centrifuged, and collects precipitation；
F, above-mentioned precipitation is dispersed in again in pure water dialyse, with removes remain salt, obtain finely dispersed graphene oxide water solution；
(2) making the shell of Graphene-nanometer gold hydrogel electrode, this shell has a through hole run through for conductive filament this through hole of temporarily sealing；
(3) in above-mentioned shell implantation step (1) prepare graphene oxide solution, 4～6mg/mL HAuCl4The NaBH of solution and 1.8～2.2mM/L4Solution, mix homogeneously also avoids bubble to produce, then in 93～95 DEG C, 450～520rpm heat vortex 8～11min, it is cooled to room temperature, conductive filament is inserted in shell by described through hole, obtains described Graphene-nanometer gold hydrogel electrode, above-mentioned graphene oxide solution, HAuCl4Solution and NaBH4The volume ratio of solution is 3～7:0.3～0.6:0.1～0.2。
2. preparation method as claimed in claim 1, it is characterised in that: natural graphite powder, sodium nitrate, concentrated sulphuric acid, potassium permanganate, deionized water and 30%H in described step (1)2O2Ratio be 1.5～2.5g:0.8～1.2g:44～47mL:5～7g:90～95mL:5～7mL。
3. preparation method as claimed in claim 2, it is characterised in that: natural graphite powder, sodium nitrate, concentrated sulphuric acid, potassium permanganate, deionized water and 30%H in described step (1)2O2Ratio be 2g:1g:46mL:6g:92mL:6mL。
4. preparation method as claimed in claim 1, it is characterised in that: described step d is centrifuged as 2000rpm, and the time is 10min。
5. preparation method as claimed in claim 1, it is characterised in that: described step e is: clear liquid carries out supersound process to realize being completely dispersed, and the centrifugal 20min of 4000rpm removes unstripped graphite oxide the more centrifugal 20min of 8000rpm, collects precipitation。
6. preparation method as claimed in claim 1, it is characterised in that: the material of described conductive filament is copper。
7. preparation method as claimed in claim 1, it is characterised in that: described step (3) is: implantation step (1) prepares in above-mentioned shell graphene oxide solution, the HAuCl of 5mg/mL4The NaBH of solution and 2mM/L4Solution, mix homogeneously also avoids bubble to produce, then in 95 DEG C, 500rpm heat vortex 10min, be cooled to room temperature, obtain described Graphene-nanometer gold hydrogel electrode。
8. preparation method as claimed in claim 7, it is characterised in that: described graphene oxide solution, HAuCl4Solution and NaBH4The volume ratio of solution is 5:0.5:0.1。
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| CN108132289A (en) * | 2017-12-25 | 2018-06-08 | 信利光电股份有限公司 | A kind of preparation method of graphene-nano-silver water gel electrode |
| CN108380177A (en) * | 2018-03-09 | 2018-08-10 | 浙江农林大学 | A kind of preparation method of magnetism modified graphene oxide hydrogel |
| CN109521072A (en) * | 2018-12-31 | 2019-03-26 | 合肥工业大学 | Detect heteroauxin and salicylic method and its electrochemical sensor used |
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