CN103913493A - Keggin type heteropoly acid functionalized graphene loaded nano copper particle modified electrode and application thereof - Google Patents
Keggin type heteropoly acid functionalized graphene loaded nano copper particle modified electrode and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 83
- 239000010949 copper Substances 0.000 title claims abstract description 68
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 41
- 239000002245 particle Substances 0.000 title abstract 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 78
- 239000008103 glucose Substances 0.000 claims abstract description 78
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- 238000000034 method Methods 0.000 claims abstract description 27
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- 239000000243 solution Substances 0.000 claims description 49
- 238000007306 functionalization reaction Methods 0.000 claims description 44
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims description 15
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000002484 cyclic voltammetry Methods 0.000 claims description 8
- 230000002255 enzymatic effect Effects 0.000 claims description 8
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 8
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000004070 electrodeposition Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000011088 calibration curve Methods 0.000 claims description 5
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- 239000000203 mixture Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000012086 standard solution Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000001514 detection method Methods 0.000 abstract description 5
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- 239000010409 thin film Substances 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 8
- 235000019420 glucose oxidase Nutrition 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 238000001338 self-assembly Methods 0.000 description 7
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- 230000004044 response Effects 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- 108010015776 Glucose oxidase Proteins 0.000 description 5
- 239000004366 Glucose oxidase Substances 0.000 description 5
- 235000010323 ascorbic acid Nutrition 0.000 description 5
- 229960005070 ascorbic acid Drugs 0.000 description 5
- 239000011668 ascorbic acid Substances 0.000 description 5
- 229940088598 enzyme Drugs 0.000 description 5
- 229940116332 glucose oxidase Drugs 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
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- 238000002474 experimental method Methods 0.000 description 4
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- 239000002253 acid Substances 0.000 description 3
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- 239000003054 catalyst Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
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- -1 graphite alkene Chemical class 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000011896 sensitive detection Methods 0.000 description 2
- NHUFMXNVSAWNTO-OJUPNBFJSA-N (3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O.OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O NHUFMXNVSAWNTO-OJUPNBFJSA-N 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention discloses preparation and application of a Keggin type heteropoly acid functionalized graphene loaded nano copper particle modified electrode. The preparation comprises the following steps: preparing Keggin type heteropoly acid functionalized graphene; pre-treating a glassy carbon electrode; preparing a Keggin type heteropoly acid functionalized graphene thin film which is taken as an ideal platform for loading copper nano-particles by using a layer-by-layer self-assembling method; constructing a Cu/Keggin type heteropoly acid-GR biosensor; and carrying out flexible quantitative analysis and determination on glucose by using a current-time curve method. The preparation and the application have the beneficial effects that a novel sensor constructed by the method has a good catalytic performance on the glucose and has the advantages of good selectivity and stability, high sensitivity, wide detection range and the like.
Description
Technical field
The present invention relates to electrochemical analysis detection technique field, relate in particular to the preparation of Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode and in the application without in enzymatic determination glucose.
Background technology
The detection of glucose is caused people's broad research because of its clinical importance, particularly to diabetic.Detecting the classic method of glucose is spectral luminosity method, but lacks chromophoric group and fluorophor part cannot carry out quantitative and qualitative analysis detection because of glucose.Galvanochemistry is because equipment needed thereby and method of operating are simply to detect at present the effective method of glucose.Glucose amperometric sensor is divided into current mode glucose oxidase enzyme biologic sensor and without enzyme sensing, from Clark in 1962 and Lyons reported first about glucose oxidase electrode, in the past 50 years, glucose oxidase enzyme biologic sensor is subject to well international research personnel's favor because of its high sensitivity and selectivity, but glucose oxidase sensor is due to low some defects that still exist of instability, reappearance of native enzyme.In order to overcome the above problems, more research steering, without enzyme sensor, is developed rapidly without enzyme sensor, mostly produces direct current-responsive based on glucose oxidase thing at electrode surface without enzyme sensor cardinal principle.
Noble metal and transition metal are widely used in to be constructed without enzymatic determination glucose electrode.Pulsed electrochemical detection glucose is commonly used noble metal, although this method sensitivity and stability are higher, it is electroactive that electrode surface absorption intermediate product causes electrode surface easily to lose; Another kind method, transition metal, as copper, nickel, alloy, does electrode modified material and constructs amperometric sensor, and main reaction mechanism is that the electrode surface glucose of modifying at transition metal participates in the adjusting that oxidizing polyvalent metal reduction electron pair shifts.Because the electric catalyticing characteristic of copper, responding range is wide, detectability is low, and have than the better stability of other materials, the research that adopts at present copper nanometer material modified electrode to measure glucose has caused concern.
Nearest research shows, the size, quality, the surface topography that change catalyst granules can change its catalyst characteristics, and therefore nm-class catalyst is the focus of research at present.The copper nano-particle that at present report is devoted to prepare high degree of dispersion changes its catalytic performance to glucose, but seldom copper nano-particle is dispersed in the Graphene surface by heteropoly acid functionalization by bibliographical information.
Graphene (GR) is a kind of two-dimensional material, and two planes of Graphene can be metal nanoparticles loaded, is a kind of desirable carrier.The character of Graphene uniqueness is to embody by the form of its individual layer, but Graphene Van der Waals force is between layers easy to cause its irreversible reunion, therefore avoiding the irreversible reunion of Graphene is the key issue of utilizing Graphene property to solve.
Summary of the invention
For above-mentioned prior art, the invention provides a kind of Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode and as electrochemical glucose sensor in the using method without in enzymatic determination glucose.
The present invention is achieved by the following technical solutions:
A preparation method for Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode, step is as follows:
1) preparation of Keggin type heteropoly acid functionalization graphene: the Keggin type heteropoly acid solution of 10mg GR being put into 10ml0.05～0.1M, ultrasonic dispersion 24h, do not change through centrifuging to its color after adding Keggin type heteropoly acid, obtain Keggin type heteropoly acid functionalization graphene;
2) pre-service of glass-carbon electrode: with the alumina powder of 0.3 μ m, 0.05 μ m, naked glass-carbon electrode is polished to minute surface successively, then rinses with redistilled water, then use successively nitric acid, acetone, redistilled water supersound washing, finally at room temperature dry;
2) a kind of Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode: first pretreated glass-carbon electrode is placed in to PDDA solution 10～20min, after pole drying, be placed on 10～20min in Keggin type heteropoly acid functionalization graphene solution, repeat same process, prepare different number of plies graphene film modified electrodes; Keggin type heteropoly acid functionalization graphene is adsorbed onto glass-carbon electrode surface by the electrostatic attraction between Keggin type heteropoly acid and PDDA, obtains Keggin type heteropoly acid-GR/GCE modified electrode; Keggin type heteropoly acid-GR/GCE modified electrode, as working electrode, forms three-electrode system with saturated calomel electrode, platinum electrode, at the CuSO of 0.04M
4in solution, pass through N
2after 15min, electro-deposition 480s under-0.4V, can obtain Cu/Keggin type heteropoly acid-GR modified electrode; Cu/Keggin type heteropoly acid-GR modified electrode is immersed in 0.1M NaOH solution, utilizes under the electrochemical window of cyclic voltammetry – 0.50～+ 0.30V, arrange and sweep fast 100mV s
– 1, be repeatedly scanned up to stable.
Described Keggin type heteropoly acid is phosphomolybdic acid, phosphotungstic acid or silico-tungstic acid.
The present invention also provides a kind of Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode of preparing according to said method.
A kind of Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode as electrochemical glucose sensor in the application without in enzymatic determination glucose, using Cu/Keggin type heteropoly acid-GR modified glassy carbon electrode as working electrode, saturated calomel electrode as contrast electrode, platinum electrode as auxiliary electrode, composition three-electrode system; While measuring glucose, three-electrode system is placed in to the NaOH solution of the 0.1M of 10mL; Then on working electrode, apply certain anode potential, when background current reaches after stable state, under agitation in the NaOH solution of 0.1M, add certain density glucose standard solution successively with microsyringe, record electricity Liu – time curve; Be within the scope of 0.01～0.10mM at concentration of glucose, obtain the linear relationship curve of electric current and concentration of glucose, its linearly dependent coefficient r=0.998, utilizes calibration curve method quantitatively to detect glucose.
Beneficial effect of the present invention is, utilize layer by layer self-assembly method to prepare Keggin type heteropoly acid functionalization graphene film and built Cu/Keggin type heteropoly acid-GR/GCE biology sensor as the ideal platform of supported copper nano particle, and use it for the Sensitive Detection of glucose; Utilize Keggin type heteropoly acid dispersed graphite alkene obviously to improve stability and the dispersion degree of Graphene, and make its surface with negative charge, thereby be conducive to assemble PDDA, be adsorbed on electrode surface, supported copper nano particle, has effectively improved the catalytic performance of copper nano-particle to glucose; The novel sensor that the method builds has good catalytic performance to glucose, has the advantages such as selectivity and good stability, highly sensitive, sensing range is wide.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention 1PMo
12in the cyclic voltammetric behavior on the glass-carbon electrode surface of being modified by 4,6,8,10 layers of self assembly graphene film;
Fig. 2 is embodiment of the present invention 1Cu/PMo
12the SEM figure of-GR, wherein, the assembling number of plies of Graphene is 8 layers, the time of acid copper is 480s;
Fig. 3 be in the embodiment of the present invention 1 in the 0.1M NaOH solution that contains 0.1mM glucose solution at Cu/PMo
12-GR/GCE (a), Cu/GR/GCE (b), PMo
12cyclic voltammogram on-GR/GCE (c), and in not containing the solution of the 0.1M NaOH of glucose solution at Cu/PMo
12cyclic voltammogram on-GR/GCE (d);
Fig. 4 is the optimization that the embodiment of the present invention 1 is prepared sensor condition, the Cu/PMo (a) preparing under different sedimentation times
12the electrochemical behavior of-GR/GCE in the 0.1M of the glucose of 0.1M NaOH solution, the Cu/PMo (b) preparing under different sedimentation potentials
12the electrochemical behavior of-GR/GCE in the 0.1M of the glucose of 0.1M NaOH solution;
Fig. 5 is embodiment of the present invention 1Cu/PMo
12-GR/GCE measures glucose time current curve under different potentials;
Fig. 6 is embodiment of the present invention 1Cu/PMo
12-GR/GCE measures the time current curve of glucose, and wherein interior illustration is the linear relationship chart of glucose oxidase peak current and concentration;
Fig. 7 is embodiment of the present invention 1Cu/PMo
12the mensuration figure of-GR/GCE to glucose interference experiment.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1:
A preparation method for Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode, step is as follows:
1) preparation of Keggin type heteropoly acid functionalization graphene: the PMo that 10mg GR is put into 10ml0.05～0.1M
12in solution, ultrasonic dispersion 24h, through centrifuging to adding PMo
12rear its color does not change, and obtains phosphomolybdic acid functionalization graphene;
2) pre-service of glass-carbon electrode: with the alumina powder of 0.3 μ m, 0.05 μ m, naked glass-carbon electrode is polished to minute surface successively, then rinses with redistilled water, then use successively nitric acid, acetone, redistilled water supersound washing, finally at room temperature dry;
3) a kind of Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode: first pretreated glass-carbon electrode is placed in to PDDA solution 10～20min, after pole drying, be placed on 10～20min in phosphomolybdic acid functionalization graphene solution, repeat same process, prepare different number of plies graphene film modified electrodes; Phosphomolybdic acid functionalization graphene is adsorbed onto glass-carbon electrode surface by the electrostatic attraction between phosphomolybdic acid and PDDA, obtains PMo
12-GR/GCE modified electrode; PMo
12-GR/GCE modified electrode, as working electrode, forms three-electrode system with saturated calomel electrode, platinum electrode, at the CuSO of 0.04M
4in solution, pass through N
2after 15min, electro-deposition 480s under-0.4V, can obtain Cu/PMo
12-GR modified electrode; By Cu/PMo
12-GR modified electrode is immersed in 0.1M NaOH solution, utilizes under the electrochemical window of cyclic voltammetry – 0.50～+ 0.30V, arranges and sweeps fast 100mV
s – 1, be repeatedly scanned up to stable.
Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode as electrochemical glucose sensor in the application without in enzymatic determination glucose, by Cu/PMo
12-GR modified glassy carbon electrode as working electrode, saturated calomel electrode as contrast electrode, platinum electrode as auxiliary electrode, composition three-electrode system; While measuring glucose, three-electrode system is placed in to the NaOH solution of the 0.1M of 10mL; Then on working electrode, apply certain anode potential, when background current reaches after stable state, under agitation in the NaOH solution of 0.1M, add certain density glucose standard solution successively with microsyringe, record electricity Liu – time curve; Be within the scope of 0.01～0.10mM at concentration of glucose, obtain the linear relationship curve of electric current and concentration of glucose, its linearly dependent coefficient r=0.998, utilizes calibration curve method to carry out analyzing and testing to glucose.
(1) sign of self assembly graphene film modified electrode
By cyclic voltammetry at 0.1M H
2sO
4in solution, study graphene film in electrode surface feature, swept speed for 100mV/s, as shown in Figure 1, along with the increase of the assembling number of plies, PMo
12the three pairs of redox peak currents increase, this shows to be successfully adsorbed on electrode surface by the Graphene of phosphomolybdic acid functionalization, in the time being assembled into 8 layers, PMo
12electric current no longer increases, and is now the best number of plies.PMo
12be used for chemical modification Graphene, mainly based on Graphene surface and PMo
12between spontaneous strong chemisorption, electronegative individual layer PMo
12can make Graphene be uniformly dispersed and good stability, by PMo
12the Graphene of embedding utilizes electronegative PMo
12and the electrostatic attraction self assembly between the PDDA of positively charged forms orderly graphene film at electrode surface.
Through adopting JSM-7001F to carry out SEM scanning, result as shown in Figure 2, in top condition, (sedimentation potential is-0.4V on self assembly Graphene surface, sedimentation time is 480s) pattern of lower acid copper nano particle, diameter is approximately copper nano-particle that 100nm is spherical and is dispersed in uniformly the surface of self assembly Graphene.
(2) prepare Cu/PMo
12the condition optimizing of-GR modified electrode
In the process of acid copper nano particle, sedimentation potential and sedimentation time have a great impact the catalytic activity of copper nano-particle.From Fig. 4 (a), can draw, when sedimentation potential is-0.4V, in the time that electrodeposition time is 480s, now modified electrode is best to the catalytic performance of glucose, possible reason is grain size and the shape characteristic that sedimentation potential and sedimentation time have affected copper nano-particle, the optimal deposition current potential of copper nano-particle is-0.4V, along with the increase of sedimentation time, the oxidation peak current of glucose increases, in the time that sedimentation time is 480s, the oxidation peak current of glucose is maximal value, overlong time, film is blocked up, has slowed down the transfer rate of electronics.
(3) glucose is at Cu/PMo
12electro-catalysis on-GR/GCE
As shown in Figure 3, relatively find out, after adding glucose, (a) in curve, have an irreversible oxidation peak current by (a) with (d), this is the variation of modified electrode peak current that the catalytic oxidation of glucose is caused.And compare (a), (b), (c) can find out at Cu/PMo
12the oxidation peak current maximum of-GR/GCE surface glucose, main cause is GR, PMo
12with the synergy of PDDA, in the process of dispersed graphite alkene, PMo
12prevent that on the one hand the reunion of Graphene from increasing the specific surface area of Graphene, make on the other hand Graphene surface with negative ion, strengthen the electrostatic attraction between positively charged PDDA, make it more be adsorbed on electrode surface, graphene film prepared by this self-assembly method can immobilized more copper nano-particle, Graphene provides a stephanoporate framework to have larger specific surface area, and electronegative film can adsorb more copper nano-particles.
(4) optimization of testing conditions
Detecting current potential is the most important factor of impact ampere response, as shown in Figure 5, in 0.1M NaOH solution, add continuously the glucose of 40 μ M with the time interval of 50s, detect current potential between 0.3～0.55V, along with the increase of current potential, response current also increases sharply, in the time that current potential is 0.5V, response current reaches maximal value, and therefore 0.5V is best response current potential.
(5) Electrochemical Detection glucose
Under best experiment condition, ampere detects glucose, as shown in Figure 6, when glucose solution while adding continuously 0.03mM and 0.1mM, presents stable electric current-time response, and in 5s Cu/PMo
12-GR modified electrode reaches 95% of steady-state current, this explanation, and this modified electrode is fast to the catalytic rate of glucose, can Sensitive Detection glucose; Reflected Cu/PMo simultaneously
12the reappearance of-GR modified electrode and stability, in 0.1M NaOH solution, voltage is+0.5V condition under, 0.01mM and 0.10mM glucose solution are carried out to parallel experiment, relative standard deviation is respectively 5.2% and 3.6%.Interior illustration in Fig. 6 is the linear relationship chart of glucose oxidase peak current and concentration, and linear equation is I=0.57+0.21c (μ M), and R is 0.998, and detection can reach 3.0 × 10
-8m.
The antijamming capability of glucose biological sensor is that the interfering material by coexisting with glucose in research people's serum and other sample is assessed, in the blood of human body, the normal concentration of glucose is other interfering material, as 30 times of dopamine (DA), urea (UA) and ascorbic acid (AA) etc.As shown in Figure 7, when adding 30 μ M glucose in 0.1M NaOH solution, there is obvious current-responsive, in the time continuing to add DA, the UA of 100 μ M and AA, electrode current response does not almost have, but in the time again adding glucose solution, occur equally star's current-responsive, show that this sensor antijamming capability is strong, selectivity is good.
Wherein, glucose is purchased from Tianjin recovery development in science and technology company limited, phosphomolybdic acid is purchased from the special Chemical Co., Ltd. in Rui Jin, Tianjin, expanded graphite is provided by the Qingdao good fortune metal and stone China ink close friend of company limited, copper sulphate is purchased from Tianjin Kermel Chemical Reagent Co., Ltd., NaOH is purchased from Chinasun Specialty Products Co., Ltd, dopamine is purchased from Aldrich company, uric acid is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, ascorbic acid AA is purchased from Shanghai Ai Bi Chemical Co., Ltd., phthalic acid two hexanediyl PDDA are purchased from Aldrich company, all reagent is pure for analyzing, experimental water is redistilled water.The operation of the CHI660C of Hai Chenhua instrument company electrochemical workstation, glass-carbon electrode (GCE) is working electrode, and saturated calomel electrode (SCE) is contrast electrode, and platinum electrode is to electrode, and all electrochemistry experiments carry out at normal temperatures.
Embodiment 2:
A preparation method for Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode, step is as follows:
1) preparation of Keggin type heteropoly acid functionalization graphene: the Salkowski's solution of 10mg GR being put into 0.05～0.1M of 10ml, ultrasonic dispersion 24h, do not change through centrifuging to its color after adding phosphotungstic acid, obtain phosphotungstic acid functionalization graphene;
2) pre-service of glass-carbon electrode: with the alumina powder of 0.3 μ m, 0.05 μ m, naked glass-carbon electrode is polished to minute surface successively, then rinses with redistilled water, then use successively nitric acid, acetone, redistilled water supersound washing, finally at room temperature dry;
3) a kind of Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode: first pretreated glass-carbon electrode is placed in to PDDA solution 10～20min, after pole drying, be placed on 10～20min in phosphotungstic acid functionalization graphene solution, repeat same process, prepare different number of plies graphene film modified electrodes; Phosphotungstic acid functionalization graphene is adsorbed onto glass-carbon electrode surface by the electrostatic attraction between phosphotungstic acid and PDDA, obtains phosphotungstic acid-GR/GCE modified electrode; Phosphotungstic acid-GR/GCE modified electrode, as working electrode, forms three-electrode system with saturated calomel electrode, platinum electrode, at the CuSO of 0.04M
4in solution, pass through N
2after 15min, electro-deposition 480s under-0.4V, can obtain Cu/ phosphotungstic acid-GR modified electrode; Cu/ phosphotungstic acid-GR modified electrode is immersed in 0.1M NaOH solution, utilizes under the electrochemical window of cyclic voltammetry – 0.50～+ 0.30V, arrange and sweep fast 100mV
s – 1, be repeatedly scanned up to stable.
A kind of Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode as electrochemical glucose sensor in the application without in enzymatic determination glucose, using Cu/ phosphotungstic acid-GR modified glassy carbon electrode as working electrode, saturated calomel electrode as contrast electrode, platinum electrode as auxiliary electrode, composition three-electrode system; While measuring glucose, three-electrode system is placed in to the NaOH solution of the 0.1M of 10mL; Then on working electrode, apply certain anode potential, when background current reaches after stable state, under agitation in the NaOH solution of 0.1M, add certain density glucose standard solution successively with microsyringe, record electricity Liu – time curve; Be within the scope of 0.01～0.10mM at concentration of glucose, obtain the linear relationship curve of electric current and concentration of glucose, its linearly dependent coefficient r=0.998, utilizes calibration curve method to carry out analyzing and testing to glucose.
Embodiment 3:
A preparation method for Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode, step is as follows:
1) preparation of Keggin type heteropoly acid functionalization graphene: 10mg GR is put into the silico-tungstic acid solution of 10ml0.05～0.1M, ultrasonic dispersion 24h, does not change through centrifuging to its color after adding silico-tungstic acid, obtains silico-tungstic acid functionalization graphene;
2) pre-service of glass-carbon electrode: with the alumina powder of 0.3 μ m, 0.05 μ m, naked glass-carbon electrode is polished to minute surface successively, then rinses with redistilled water, then use successively nitric acid, acetone, redistilled water supersound washing, finally at room temperature dry;
3) a kind of Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode: first pretreated glass-carbon electrode is placed in to PDDA solution 10～20min, after pole drying, be placed on 10～20min in silico-tungstic acid functionalization graphene solution, repeat same process, prepare different number of plies graphene film modified electrodes; Silico-tungstic acid functionalization graphene is adsorbed onto glass-carbon electrode surface by the electrostatic attraction between silico-tungstic acid and PDDA, obtains silico-tungstic acid-GR/GCE modified electrode; Silico-tungstic acid-GR/GCE modified electrode, as working electrode, forms three-electrode system with saturated calomel electrode, platinum electrode, at the CuSO of 0.04M
4in solution, pass through N
2after 15min, electro-deposition 480s under-0.4V, can obtain Cu/ silico-tungstic acid-GR modified electrode; Cu/ silico-tungstic acid-GR modified electrode is immersed in 0.1M NaOH solution, utilizes under the electrochemical window of cyclic voltammetry – 0.50～+ 0.30V, arrange and sweep fast 100mV
s – 1, be repeatedly scanned up to stable.
A kind of Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode as electrochemical glucose sensor in the application without in enzymatic determination glucose, using Cu/ silico-tungstic acid-GR modified glassy carbon electrode as working electrode, saturated calomel electrode as contrast electrode, platinum electrode as auxiliary electrode, composition three-electrode system; While measuring glucose, three-electrode system is placed in to the NaOH solution of the 0.1M of 10mL; Then on working electrode, apply certain anode potential, when background current reaches after stable state, under agitation in the NaOH solution of 0.1M, add certain density glucose standard solution successively with microsyringe, record electricity Liu – time curve; Be within the scope of 0.01～0.10mM at concentration of glucose, obtain the linear relationship curve of electric current and concentration of glucose, its linearly dependent coefficient r=0.998, utilizes calibration curve method to carry out analyzing and testing to glucose.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various modifications that creative work can make or distortion still in protection scope of the present invention.
Claims (4)
1. a preparation method for Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode, is characterized in that, step is as follows:
1) preparation of Keggin type heteropoly acid functionalization graphene: the Keggin type heteropoly acid solution of 10mg GR being put into 10ml0.05～0.1M, ultrasonic dispersion 24h, do not change through centrifuging to its color after adding Keggin type heteropoly acid, obtain Keggin type heteropoly acid functionalization graphene;
2) pre-service of glass-carbon electrode: with the alumina powder of 0.3 μ m, 0.05 μ m, naked glass-carbon electrode is polished to minute surface successively, then rinses with redistilled water, then use successively nitric acid, acetone, redistilled water supersound washing, finally at room temperature dry;
3) a kind of Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode: first pretreated glass-carbon electrode is placed in to PDDA solution 10～20min, after pole drying, be placed on 10～20min in Keggin type heteropoly acid functionalization graphene solution, repeat same process, prepare different number of plies graphene film modified electrodes; Keggin type heteropoly acid functionalization graphene is adsorbed onto glass-carbon electrode surface by the electrostatic attraction between Keggin type heteropoly acid and PDDA, obtains Keggin type heteropoly acid-GR/GCE modified electrode; Keggin type heteropoly acid-GR/GCE modified electrode, as working electrode, forms three-electrode system with saturated calomel electrode, platinum electrode, at the CuSO of 0.04M
4in solution, pass through N
2after 15min, electro-deposition 480s under-0.4V, can obtain Cu/Keggin type heteropoly acid-GR modified electrode; Cu/Keggin type heteropoly acid-GR modified electrode is immersed in 0.1M NaOH solution, utilizes under the electrochemical window of cyclic voltammetry – 0.50～+ 0.30V, arrange and sweep fast 100mV s
– 1, be repeatedly scanned up to stable.
2. the preparation method of a kind of Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode as claimed in claim 1, is characterized in that, described Keggin type heteropoly acid is phosphomolybdic acid, phosphotungstic acid or silico-tungstic acid.
3. a kind of Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode that prepared by method as claimed in claim 1 or 2.
A kind of Keggin type heteropoly acid functionalization graphene supported copper Nanoparticle Modified electrode as claimed in claim 3 as electrochemical glucose sensor in the application without in enzymatic determination glucose, it is characterized in that, using Cu/Keggin type heteropoly acid-GR modified glassy carbon electrode as working electrode, saturated calomel electrode as contrast electrode, platinum electrode as auxiliary electrode, composition three-electrode system; While measuring glucose, three-electrode system is placed in to the NaOH solution of the 0.1M of 10mL; Then on working electrode, apply certain anode potential, when background current reaches after stable state, under agitation in the NaOH solution of 0.1M, add certain density glucose standard solution successively with microsyringe, record electricity Liu – time curve; Be within the scope of 0.01～0.10mM at concentration of glucose, obtain the linear relationship curve of electric current and concentration of glucose, its linearly dependent coefficient r=0.998, utilizes calibration curve method quantitatively to detect glucose.
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