CN108786795A - A kind of effective catalyst of modified electrode and its preparation method and application - Google Patents
A kind of effective catalyst of modified electrode and its preparation method and application Download PDFInfo
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- CN108786795A CN108786795A CN201810203143.0A CN201810203143A CN108786795A CN 108786795 A CN108786795 A CN 108786795A CN 201810203143 A CN201810203143 A CN 201810203143A CN 108786795 A CN108786795 A CN 108786795A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 210000001124 body fluid Anatomy 0.000 claims abstract description 8
- 239000010839 body fluid Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 6
- 229910004042 HAuCl4 Inorganic materials 0.000 claims abstract description 5
- 239000001509 sodium citrate Substances 0.000 claims abstract description 5
- 239000005457 ice water Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000006396 nitration reaction Methods 0.000 claims abstract description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 3
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 3
- 235000018417 cysteine Nutrition 0.000 claims description 22
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 22
- 239000010931 gold Substances 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- -1 gold ion Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 2
- 239000006229 carbon black Substances 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 description 7
- 229960003067 cystine Drugs 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000000825 ultraviolet detection Methods 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002038 chemiluminescence detection Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 230000006806 disease prevention Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 230000003862 health status Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000004792 oxidative damage Effects 0.000 description 1
- 230000004962 physiological condition Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- BDJXVNRFAQSMAA-UHFFFAOYSA-N quinhydrone Chemical group OC1=CC=C(O)C=C1.O=C1C=CC(=O)C=C1 BDJXVNRFAQSMAA-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- 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
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- 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
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- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
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- G01N27/416—Systems
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Abstract
The invention discloses a kind of effective catalysts of modified electrode and its preparation method and application, and the preparation method of the catalyst includes the following steps：Preparation contains HAuCl4With the solution of trisodium citrate, the NaBH of ice-water bath is added4Solution stirs evenly, and 2h or more is stood after liquid colour stable to be mixed, obtains metal front body fluid；Conductive black is added in hydrochloric acid solution and is reacted, then puts into HNO3It is reacted in solution；Nitration mixture is taken treated conductive black, adds water, be uniformly dispersed, obtain carbon slurry；Metal front body fluid and carbon slurry mixs, the pH value of adjusting reaction system is to 2 after stirring evenly；Post-processing obtains catalyst.The present invention prepares the colloidal gold of small particle using sodium borohydride reduction, and reaction condition is mild, is swift in response, size tunable.The present invention has prepared grain size and has been the colloidal gold of 3nm or so, and is evenly distributed on carbon black interface, and forms difunctional interface, can be used as the purposes such as high-performance catalysis material and electrode material.
Description
Technical field
The invention belongs to electrochemistry effective catalyst fields, and in particular to one kind is supported on by gold nanoparticle on XC-72
Catalyst obtained and its application in detecting cysteine.
Background technology
Cysteine is amino acid important in organism, can effectively remove the excessive oxidation generated in metabolic process and live
Property substance, can avoid other functional biomolecules oxidative damage, as important antioxidant, in disease prevention and regulation and control
Aspect plays an important role.
Cysteine/cystine of normal physiological conditions lower body is able to maintain that in certain level, but disease
The accumulation that the consumption and cystine of cysteine are promoted with aging course causes the variation of the two content.Therefore, pass through measurement
The variation of cysteine/cystine amount can be used for the health status of measure of cell or even body, can also be widely used for commenting
In aging, medical diagnosis on disease and the research of micromechanism of damage of valence body.
It is existing a variety of including Capillary Electrophoresis, ion-exchange chromatography, gas-chromatography, liquid chromatogram and mass spectrum at present
Technology is used for the discriminating of cysteine/cystine.These technologies generally use ultraviolet-visible, fluorescence or chemiluminescence detection
Device.Since the spectral signal of cysteine plus cystine is weak, easily gasify, retention time is shorter, it is necessary to use corresponding derivatization
Technology is to improve sensitivity and selectivity.But derivatization process causes detection process to become cumbersome, while bringing a large amount of new
Environmental contaminants.The Instrument purchase needed for above-mentioned authentication technique and maintenance cost costly, are unfavorable for realizing batch simultaneously
Formula quickly measures.How to realize quick, inexpensive detection cysteine, has become the emphasis of current research work.
Invention content
In view of the deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of catalyst of modified glassy carbon electrode
Preparation method.
Another object of the present invention is to provide the catalyst made from the above method.
It is still another object of the present invention to provide application of the above-mentioned catalyst in detecting cysteine.
The purpose of the invention is achieved by the following technical solution：
A kind of preparation method of catalyst, includes the following steps：
(1) it prepares and contains HAuCl4With the solution of trisodium citrate, the NaBH of ice-water bath is added4Solution stirs evenly, and waits mixing
2h or more is stood after closing liquid colour stable, obtains metal front body fluid；
In step (1), HAuCl4With NaBH4Molar ratio preferably 1:12；
(2) conductive black is added in hydrochloric acid solution, 10h or more is reacted at 120 DEG C, is then filtered, washed, dries, and
Grinding；Conductive black after HCl treatment is put into HNO again3In solution, 10h or more is reacted at 120 DEG C, be then filtered, washed,
It is dry, and grind；Nitration mixture is taken treated conductive black, adds water, be uniformly dispersed, obtain carbon slurry；
The preferred XC-72 of conductive black described in step (2)；XC-72 good conductivities, large specific surface area are of low cost；
Being uniformly dispersed described in step (2), is preferably used alternatingly stirring and ultrasonication, until being uniformly dispersed；
HAuCl in step (1)4Mass ratio with conductive black in step (2) is 1:1942；
(3) metal front body fluid made from step (1) is mixed with carbon slurry made from step (2), reaction is adjusted after stirring evenly
The pH value of system is to 2；Then it is filtered, washed, dries, obtain catalyst；
The washing, it is colourless for washing to the color of cleaning solution, and cleaning solution through UV detect no colloidal gold and
Gold ion.
Aforesaid operations are divided into two-step reaction in principle, and the first step is with reducing agent sodium borohydride in aqueous solution of chloraurate
Gold ion be reduced into colloidal gold, wherein the sodium citrate being added as a kind of protective agent avoid reaction it is too strong.Second step is
Glue processing is carried out brokenly with acid solution, colloidal solution is become aqueous solution in acid condition so that gold nanoparticle releases.
Application of the above-mentioned catalyst in detecting cysteine, includes the following steps：
(1) basal electrode is polished to minute surface, be eluted with water；Then it is cleaned by ultrasonic in absolute ethyl alcohol and water successively, takes
It is eluted with water, dries after go out, be subsequently placed in progress electrode activation processing in potassium ferricyanide solution；
(2) how phenol (Nafion) solution and above-mentioned catalyst are uniformly mixed to obtain catalyst and be homogenized by neutral；
Preferably, in step (2), per 10mg catalyst corresponds to 1mL 0.84% (W/W) neutrality how phenol solution；
(3) homogenate of the catalyst of step (2) is added drop-wise to the treated basal electrode surface of step (1), after drying
The glass-carbon electrode sensor modified to catalyst, for detecting the cysteine content in solution.
By the conductive black that nitration mixture is handled, surface is rich in many oxygen-containing functional groups, these oxygen-containing functional groups are namely
Cysteine can be catalytically oxidized to cystine by quinhydrone functional group under certain potentials.In addition, cysteine is rich in sulfydryl
(SH), and gold can form golden sulfide linkage Au-S as catalyst and sulphur, further form cystine linkage, in this way by carbon material and
The synergistic effect of gold can more delicately be used for the detection of cysteine.
The present invention has the following advantages and effects with respect to the prior art：
1, the present invention prepares the colloidal gold of small particle using sodium borohydride reduction, with sodium citrate heating reduction method,
Ethyl alcohol heating reduction method compares mild condition with high temperature microwave reduction method, is swift in response, gold nanometer particle grain size is controllable.
2, the present invention has prepared grain size as the colloidal gold of 3nm or so, and is evenly distributed on the interfaces XC-72, and shape
Function interface in pairs can be used as the purposes such as high-performance catalysis material and electrode material.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of the catalyst of modified electrode made from embodiment 1.
Fig. 2 is the grain size distribution of the catalyst of modified electrode made from embodiment 1.
Fig. 3 is the uv-visible absorption spectroscopy figure of different solutions.
Fig. 4 is that glass-carbon electrode CV in potassium ferricyanide solution schemes.
Fig. 5 is the cyclic voltammogram of various concentration cysteine.
Fig. 6 is the Linear Fit Chart of various concentration cysteine.
Specific implementation mode
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
A kind of preparation method of electrode modification catalyst, includes the following steps：
(1) HAuCl of 24.3mM is taken4Aqueous solution 0.515mL adds water to 50mL in beaker, and the lemon of 34mM is then added
Lemon acid trisodium 0.368mL, and stir evenly.0.1M NaBH are prepared under conditions of ice-water bath4Solution (quickly weighs, now matches existing
With), take the NaBH of 1.5mL4It is quickly added to above-mentioned solution, 2h is stood after colour stable, obtains metal front body fluid.
(2) 12g XC-72 are weighed in round-bottomed flask, hydrochloric acid solution (HCl (37%) is added:Water=1:5(V:V))
200mL is filtered after reaction 10h at 120 DEG C, is washed, is dried in vacuo (150 DEG C, 8h) and grind for use.After grinding
200mL 5M HNO310h is reacted in solution at 120 DEG C, filters, washing, be dried in vacuo (150 DEG C, 8h) and grind for use, obtain mixed
Acid treated XC-72 materials.It takes the processed XC-72 of 20mg in small beaker, adds the water of 25mL, stirring 30min ultrasounds
30min is stirred for 30min to being uniformly dispersed, and obtains carbon slurry.
(3) metal front body fluid is mixed with carbon slurry, the broken glue tune pH value of 0.1M HCl is added dropwise to 2 after stirring 30min.
It is filtered with vacuum pump, neutrality is presented in distillation water washing to filtrate completely, and filtrate carries out UV detections, the lower 80 DEG C of dryings of vacuum condition
Sample is ground after dry, obtains electrode modification catalyst by 6h.
As shown in figure 3, the peak of ultraviolet detection gold ion is in 282nm, aqueous solution of chloraurate has UV testing results at 282nm
Peak, colloidal gold and Filtrate solutions do not have at 282nm, illustrate that gold ion reaction is thorough during preparing material, side is said
The bright sodium borohydride reduction can be used for the reduction of gold chloride.
Take a small amount of catalyst sample preparation to carry out transmission electron microscope, as a result as depicted in figs. 1 and 2, test gold nanoparticle grain
Diameter is 3nm or so, and is evenly distributed on the interfaces XC-72.
Embodiment 2
Application of the electrode modification catalyst made from embodiment in detecting cysteine, includes the following steps：
(1) surface preparation is carried out to basal electrode；The surface of basal electrode is successively with a diameter of 0.3 μm and 0.05 μm
Al2O3Powder is polished to minute surface, then is rinsed with water；Then it is cleaned by ultrasonic 1min in absolute ethyl alcohol and water successively, taking-up is washed with water
Only, it dries, is subsequently placed in potassium ferricyanide solution (5mM K3Fe(CN)6+ 0.2M KCl) in carry out electrode activation processing.
(2) 1mL 0.84%Nafion solution and the catalyst fines of 10mg embodiments 1 ultrasound 30min after mixing are taken
Obtain catalyst homogenate.
(3) electrode top after 4 μ L homogenate being added drop-wise to activation with microsyringe obtains catalyst modification after drying
Glass-carbon electrode sensor.
Electrolytic solution cell is the PBS buffer solutions of 0.2mM pH value 2, in N2It is molten that cysteine is added under conditions of deoxygenation
Solution, carries out the detection of cyclic voltammetry, sweep speed 50mV/s.
Fig. 4 be do not do catalyst modification glass-carbon electrode in potassium ferricyanide solution CV scheme, illustrate the electronics of glass-carbon electrode
Conductivity is fine, will not be interfered to the performance for having modified gold nanoparticle complex carbon material.
Fig. 5 and Fig. 6 is the cyclic voltammogram and Linear Fit Chart of various concentration cysteine respectively, it can be seen that response electricity
Good linear relationship is presented in stream and concentration, can be used for the detection of semicystinol concentration under the modified electrode.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of catalyst, it is characterised in that include the following steps：
(1) it prepares and contains HAuCl4With the solution of trisodium citrate, the NaBH of ice-water bath is added4Solution stirs evenly, liquid to be mixed
2h or more is stood after colour stable, obtains metal front body fluid；
(2) conductive black is added in hydrochloric acid solution, 10h or more is reacted at 120 DEG C, is then filtered, washed, dries, and grind；
Conductive black after HCl treatment is put into HNO again3In solution, 10h or more is reacted at 120 DEG C, is then filtered, washed, dries,
And it grinds；Nitration mixture is taken treated conductive black, adds water, be uniformly dispersed, obtain carbon slurry；
(3) metal front body fluid made from step (1) is mixed with carbon slurry made from step (2), reaction system is adjusted after stirring evenly
PH value to 2；Then it is filtered, washed, dries, obtain catalyst.
2. preparation method according to claim 1, it is characterised in that：In step (1), HAuCl4With NaBH4Molar ratio
It is 1:12.
3. preparation method according to claim 1, it is characterised in that：Conductive black described in step (2) is XC-72.
4. preparation method according to claim 1, it is characterised in that：Washing described in step (3), will wash to cleaning solution
Color be colourless, and cleaning solution detects no colloidal gold and gold ion through UV.
5. a kind of catalyst, it is characterised in that：It is to be made by claim 1-4 any one of them methods.
6. application of the catalyst in detecting cysteine content described in claim 5.
7. application of the catalyst according to claim 6 in detecting cysteine content, it is characterised in that including as follows
Step：
(1) basal electrode is polished to minute surface, be eluted with water；Then it is cleaned by ultrasonic in absolute ethyl alcohol and water successively, after taking-up
It is eluted with water, dries, be subsequently placed in progress electrode activation processing in potassium ferricyanide solution；
(2) how phenol solution and above-mentioned catalyst are uniformly mixed to obtain catalyst and be homogenized by neutral；
(3) homogenate of the catalyst of step (2) is added drop-wise to the treated basal electrode surface of step (1), is urged after drying
The glass-carbon electrode sensor of agent modification, for detecting the cysteine content in solution.
8. application according to claim 7, it is characterised in that：In step (2), 1mL 0.84% is corresponded to per 10mg catalyst
(W/W) it is neutral how phenol solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114828397A (en) * | 2022-04-21 | 2022-07-29 | 华南理工大学 | Preparation method and application of conductive metal carbon paste |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986047A (en) * | 2006-12-29 | 2007-06-27 | 华东理工大学 | Noble metal electrocatalyst based on nano carbon fiber and its preparing method |
| US20090202887A1 (en) * | 2005-03-15 | 2009-08-13 | Tomoko Eguchi | Catalyst, electrode, membrane electrode assembly and fuel cell |
| CN101890368A (en) * | 2010-06-18 | 2010-11-24 | 昆明理工大学 | Method for preparing carbon-supported high-activity gold or gold-platinum alloy or gold-core platinum-shell structural nano catalyst |
| CN102387984A (en) * | 2008-09-08 | 2012-03-21 | 新加坡南洋理工大学 | Nanoparticle decorated nanostructured material as electrode material and method for obtaining the same |
| US20140322823A1 (en) * | 2011-11-09 | 2014-10-30 | Board Of Trustees Of Michigan State University | Metallic Nanoparticle Synthesis with Carbohydrate Capping Agent |
-
2018
- 2018-03-13 CN CN201810203143.0A patent/CN108786795A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090202887A1 (en) * | 2005-03-15 | 2009-08-13 | Tomoko Eguchi | Catalyst, electrode, membrane electrode assembly and fuel cell |
| CN1986047A (en) * | 2006-12-29 | 2007-06-27 | 华东理工大学 | Noble metal electrocatalyst based on nano carbon fiber and its preparing method |
| CN102387984A (en) * | 2008-09-08 | 2012-03-21 | 新加坡南洋理工大学 | Nanoparticle decorated nanostructured material as electrode material and method for obtaining the same |
| CN101890368A (en) * | 2010-06-18 | 2010-11-24 | 昆明理工大学 | Method for preparing carbon-supported high-activity gold or gold-platinum alloy or gold-core platinum-shell structural nano catalyst |
| US20140322823A1 (en) * | 2011-11-09 | 2014-10-30 | Board Of Trustees Of Michigan State University | Metallic Nanoparticle Synthesis with Carbohydrate Capping Agent |
Non-Patent Citations (4)
| Title |
|---|
| F. ARDUINI等: "Effective electrochemical sensor based on screen-printed electrodes modified with a carbon black-Au nanoparticles composite", 《SENSORS AND ACTUATORS B》 * |
| SURIYAPHA JONGJINAKOOL等: "Gold nanoparticles-based colorimetric sensor for cysteine detection", 《ENERGY PROCEDIA》 * |
| 杨子芹等: "纳米级Au/C催化剂的制备及其DBFC单池性能", 《新型炭材料》 * |
| 王善花主编: "《高考新脉动.高中化学：新课程标准影响下高中总复习全解全析》", 30 June 2004 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114828397A (en) * | 2022-04-21 | 2022-07-29 | 华南理工大学 | Preparation method and application of conductive metal carbon paste |
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