CN108414591B - Electrode and application thereof - Google Patents
Electrode and application thereof Download PDFInfo
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- CN108414591B CN108414591B CN201810107177.XA CN201810107177A CN108414591B CN 108414591 B CN108414591 B CN 108414591B CN 201810107177 A CN201810107177 A CN 201810107177A CN 108414591 B CN108414591 B CN 108414591B
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Abstract
The invention discloses an electrode, wherein a noble metal composition is attached to an electrode carrier of the electrode, and comprises, by weight, 10-20% of a noble metal, 40-60% of a polylactic acid modified polycarbonate copolymer (PPC/P L A) and 20-50% of graphene oxide, wherein the noble metal composition comprises, by weight, one or more of gold, silver, platinum, palladium, osmium and iridium, the noble metal has a particle size of 10-500 nm, and the PPC/P L A has a weight-average molecular weight Mw of 10,000-800,000.
Description
The present application is a divisional application of patent with application number 201510567167.0, application date 2015 09/08, entitled "a noble metal composition and its application".
Technical Field
The invention relates to a noble metal composition and application thereof, and further relates to a noble metal composition for preparing an electrode of an electrochemical sensor, belonging to the field of electrochemistry.
Background
The electrocatalytic oxidation of small organic molecules on electrodes made of noble metal materials such as gold, silver, platinum and the like is obvious, so the noble metal electrodes are often used for detecting the small organic molecules. When the electrochemical sensor using the noble metal electrode as the working electrode is used for detecting trace organic micromolecules, the electrochemical sensor has the characteristics of high detection speed, low detection limit and the like, is more convenient than a liquid chromatography, and has consistent detection results.
Slow sensitivity in the research on surface properties and SERS of noble metal nano structures and electrodes indicates that nano noble metals have large specific surface area due to surface effect and can catalyze and accelerate chemical reaction. Therefore, when the nano noble metal is used as an electrode, the reaction efficiency is higher, but the melting point of the noble metal atomic cluster limited by small size is greatly reduced and sometimes even can not exist stably.
The nanometer noble metal can not be accurately and uniformly coated in the process of coating the nanometer noble metal on a carrier to manufacture an electrode, thereby causing huge waste of the noble metal and not better playing the roles of reducing resistance and improving the efficiency of the electrochemical sensor.
Disclosure of Invention
Based on the drawbacks of the prior art, a first object of the present invention is to provide a noble metal composition.
A noble metal composition comprises a noble metal, a polylactic acid modified polycarbonate copolymer (PPC/P L A) and graphene oxide.
The noble metal is one or more of gold, silver, platinum, palladium, osmium and iridium.
The particle size of the noble metal is 10-500 nm, preferably 50-250 nm, more preferably 100nm, in order to increase the conductive efficiency of the electrode, and the melting point of the nano-sized metal particles is reduced due to the too small particle size, so that the nano-sized metal particles are melted in the process of reducing the graphene oxide and the original particle size of the nano-sized metal particles cannot be maintained.
The weight average molecular weight of the PPC/P L A is 10,000-800,000, preferably 60,000-500,000, and more preferably 300,000, and PPC/P L A is added to uniformly disperse the noble metal through pyrolysis, thereby obtaining an electrode with low resistivity.
The thermal decomposition temperature of PPC/P L A is 90-320 ℃.
Graphene oxide is added into the composition, so that the graphene oxide is reduced into graphene, the conductive effect is enhanced by increasing the conductive specific surface area and combining with part of nano noble metal, and the complete decomposition of the incompletely decomposed PPC/P L A is promoted by a reduction reaction.
The invention also provides the percentage contents of the components in the precious metal composition, and the percentage contents of the components are 10-20% of precious metal, 40-60% of polylactic acid modified polycarbonate copolymer (PPC/P L A) and 20-50% of graphene oxide.
Preferably, the components comprise, by weight, 12-18% of noble metal, 45-55% of polylactic acid modified polycarbonate copolymer (PPC/P L A) and 27-43% of graphene oxide.
More preferably, the components comprise 16 wt% of noble metal, 50 wt% of polylactic acid modified polycarbonate copolymer (PPC/P L A) and 34 wt% of graphene oxide.
A second object of the present invention is to provide a method of using a noble metal composition that can be attached to an electrode support under specific conditions, thereby modifying and improving the electrode.
The preparation method comprises the steps of uniformly mixing noble metal particles with the average particle size of 10-500 nm and polylactic acid modified polycarbonate copolymer (PPC/P L A) with the weight average molecular weight (Mw) of 10,000-800,000 by using a V-shaped mixer, discharging the mixed powder into a plasma atmosphere under the argon atmosphere by using a high-frequency induction thermal plasma device, and recovering the generated micro powder by using a filter to obtain composite particles.
The dosage of the noble metal, the PPC/P L A and the graphene oxide is proportioned according to the weight percentage of the noble metal composition.
The preferable reaction temperature is 700-920 ℃, and the further preferable temperature is 850 ℃.
The preferable heating time is 1-2 h, and the further preferable heating time is 1.5 h.
A third object of the present invention is to provide an electrochemical sensor constructed with an electrode composed of the noble metal composition according to the present invention.
The invention reduces the using amount of noble metal in the preparation process of the electrode, improves the utilization efficiency of the noble metal, and fully exerts the advantages of high specific surface area, good conductivity and the like of the graphene by uniformly coating a part of noble metal on an electrode carrier and uniformly coating the other part of noble metal on the reduced graphene oxide (graphene) through pyrolysis of the polylactic acid modified polycarbonate copolymer (PPC/P L A) mixed with the nano noble metal and the graphene oxide.
The invention combines the advantages of the nano noble metal and the graphene, prepares the electrode with good conductivity and low resistance, and provides a development direction for further improving the precision of the electrochemical sensor.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the following examples are given by way of illustration only and are not to be construed as limiting the scope of the present invention, and that various changes and modifications apparent to those skilled in the art in light of the teachings herein are deemed to be within the scope of the present invention.
Example 1
The preparation method comprises the steps of uniformly mixing 10% of gold nanoparticles with the average particle size of 10nm and 40% of polylactic acid modified polycarbonate copolymer (PPC/P L A) with the weight average molecular weight (Mw) of 10,000 by using a V-shaped mixer, discharging the mixed powder into a plasma atmosphere under the argon atmosphere by using a high-frequency induction thermal plasma device, and recovering the generated micro powder by using a filter to obtain composite particles, adding 50% of graphene oxide into the composite particles, fully mixing by using a planetary mill to obtain mixed powder, drying the mixed powder, and heating at 900 ℃ for 0.8 hour.
Example 2
Uniformly mixing 12% of nano palladium particles with the average particle size of 50nm and 45% of polylactic acid modified polycarbonate copolymer (PPC/P L A) with the weight average molecular weight (Mw) of 60,000 by using a V-shaped mixer, discharging the mixed powder into a plasma atmosphere under the argon atmosphere by using a high-frequency induction thermal plasma device, and recovering the generated micro powder by using a filter to obtain composite particles, adding 43% of graphene oxide into the composite particles, fully mixing by using a planetary mill to obtain mixed powder, drying the mixed powder, and heating at 950 ℃ for 0.5 hour.
Example 3
Uniformly mixing 15% of nano silver particles with the average particle size of 170nm and 52% of polylactic acid modified polycarbonate copolymer (PPC/P L A) with the weight average molecular weight (Mw) of 100,000 by using a V-shaped mixer, discharging the mixed powder into a plasma atmosphere under the argon atmosphere by using a high-frequency induction thermal plasma device, and recovering the generated micro powder by using a filter to obtain composite particles, adding 33% of graphene oxide into the composite particles, fully mixing by using a planetary mill to obtain mixed powder, drying the mixed powder, and heating at 500 ℃ for 2.5 hours.
Example 4
The preparation method comprises the steps of uniformly mixing 16% of nano platinum particles with the average particle size of 100nm and 50% of polylactic acid modified polycarbonate copolymer (PPC/P L A) with the weight average molecular weight (Mw) of 300,0000 by using a V-shaped mixer, discharging the mixed powder into a plasma atmosphere under the argon atmosphere by using a high-frequency induction thermal plasma device, and recovering the generated micro powder by using a filter to obtain composite particles, wherein 34% of graphene oxide is added into the composite particles, and the mixture is fully mixed by using a planetary mill to obtain the mixed powder, and the mixed powder is dried and then heated at 850 ℃ for 1.5 hours.
Example 5
The preparation method comprises the steps of uniformly mixing 18% of nano gold/iridium alloy particles with the average particle size of 250nm and 55% of polylactic acid modified polycarbonate copolymer (PPC/P L A) with the weight average molecular weight (Mw) of 500,000 by using a V-shaped mixer, discharging the mixed powder into a plasma atmosphere under the argon atmosphere by using a high-frequency induction thermal plasma device, and recovering the generated micro powder by using a filter to obtain composite particles, adding 27% of graphene oxide into the composite particles, fully mixing by using a planetary mill to obtain mixed powder, drying the mixed powder, and heating at 920 ℃ for 1 hour.
Example 6
The preparation method comprises the steps of uniformly mixing 19% of nano platinum particles with the average particle size of 200nm and 47% of polylactic acid modified polycarbonate copolymer (PPC/P L A) with the weight average molecular weight (Mw) of 200,000 by using a V-shaped mixer, discharging the mixed powder into a plasma atmosphere under the argon atmosphere by using a high-frequency induction thermal plasma device, and recovering the generated micro powder by using a filter to obtain composite particles, adding 34% of graphene oxide into the composite particles, fully mixing by using a planetary mill to obtain mixed powder, drying the mixed powder, and heating at 700 ℃ for 2.3 hours.
Example 7
Uniformly mixing 20% of nano palladium particles with the average particle size of 500nm and 60% of polylactic acid modified polycarbonate copolymer (PPC/P L A) with the weight average molecular weight (Mw) of 800,000 by using a V-shaped mixer, discharging the mixed powder into a plasma atmosphere under the argon atmosphere by using a high-frequency induction thermal plasma device, and recovering the generated micro powder by using a filter to obtain composite particles, adding 20% of graphene oxide into the composite particles, fully mixing by using a planetary mill to obtain mixed powder, drying the mixed powder, and heating at 620 ℃ for 2 hours.
The volume resistivity measurements of examples 1 to 7 were carried out, and the results are shown in Table I.
[ TABLE ] A
Claims (2)
1. The electrode is characterized in that a noble metal composition is attached to an electrode carrier of the electrode, and the noble metal composition comprises, by weight, 10-20% of a noble metal, 10-60% of a polylactic acid modified polycarbonate copolymer PPC/P L A and 20-50% of graphene oxide, wherein the noble metal is one or more of gold, silver, platinum, palladium, osmium and iridium, the particle size of the noble metal is 10-500 nm, and the weight-average molecular weight of the PPC/P L A is 10,000-800,000;
and the noble metal composition is attached to the electrode support to prepare the electrode by:
(1) uniformly mixing noble metal particles with the average particle size of 10-500 nm and polylactic acid modified polycarbonate copolymer with the weight-average molecular weight of 10,000-800,000 by using a V-shaped mixer, discharging mixed powder into a plasma atmosphere under the atmosphere of argon by using a high-frequency induction thermal plasma device, and recovering generated micro powder by using a filter to obtain composite particles;
(2) adding graphene oxide into the composite particles, and fully mixing by using a planetary mill to obtain mixed powder;
(3) drying the mixed powder, and heating at 500-950 ℃ for 0.5-2.5 hours, wherein the specific mode is as follows: heating the muffle furnace to above 950 ℃, then cooling to a set temperature, adding graphene oxide under the protection of argon, continuously filling argon, and placing an electrode carrier at an outlet in the reaction process to obtain the electrode.
2. Use of an electrode according to claim 1 in an electrochemical sensor.
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| CN201810107177.XA CN108414591B (en) | 2015-09-08 | 2015-09-08 | Electrode and application thereof |
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| CN201510567167.0A CN105181773B (en) | 2015-09-08 | 2015-09-08 | A kind of precious metal composition and its application |
| CN201810107177.XA CN108414591B (en) | 2015-09-08 | 2015-09-08 | Electrode and application thereof |
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| CN103926278A (en) * | 2014-04-24 | 2014-07-16 | 电子科技大学 | Graphene-based ternary composite film gas sensor and preparation method thereof |
| CN104559101A (en) * | 2015-02-04 | 2015-04-29 | 山东科技大学 | High-strength high-toughness full-degradable polylactic acid composite material and preparation method thereof |
| WO2015084945A1 (en) * | 2013-12-04 | 2015-06-11 | Cornell University | Electrospun composite nanofiber comprising graphene nanoribbon or graphene oxide nanoribbon, methods for producing same, and applications of same |
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| SE534257C2 (en) * | 2009-10-28 | 2011-06-21 | Lunavation Ab | A light emitting electrochemical device, a system comprising such a device and the use of such a device |
| CN102623640A (en) * | 2012-04-09 | 2012-08-01 | 苏州大学 | Solar cell |
| WO2014145771A1 (en) * | 2013-03-15 | 2014-09-18 | Modumetal, Inc. | Electrodeposited compositions and nanolaminated alloys for articles prepared by additive manufacturing processes |
| KR101536627B1 (en) * | 2013-04-30 | 2015-07-14 | 한국교통대학교산학협력단 | METHOD OF MANUFACTURING HYBRID ELECTRODE USING Ag NANOWIRE AND GRAPHENE |
| CN104030280A (en) * | 2014-06-16 | 2014-09-10 | 上海交通大学 | Preparation method of graphene paper |
| CN104479456B (en) * | 2014-12-23 | 2016-06-01 | 中国科学院化学研究所 | The application of a kind of gold contracted payment-graphene-based water-base ink and the transparent pattern conductive electrode of spray ink Printing thereof |
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Patent Citations (3)
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| WO2015084945A1 (en) * | 2013-12-04 | 2015-06-11 | Cornell University | Electrospun composite nanofiber comprising graphene nanoribbon or graphene oxide nanoribbon, methods for producing same, and applications of same |
| CN103926278A (en) * | 2014-04-24 | 2014-07-16 | 电子科技大学 | Graphene-based ternary composite film gas sensor and preparation method thereof |
| CN104559101A (en) * | 2015-02-04 | 2015-04-29 | 山东科技大学 | High-strength high-toughness full-degradable polylactic acid composite material and preparation method thereof |
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| Synthesis and Characterization of Reduced Graphene Oxide Supported Gold Nanoparticles-Poly (Pyrrole-Co-Pyrrolepropylic Acid) Nanocomposite-Based Electrochemical Biosensor;Nidhi Puri et.al;《Appl Biochem Biotechnol》;20140614;第174卷;第911-925页 * |
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| CN105181773B (en) | 2018-09-11 |
| CN108414591A (en) | 2018-08-17 |
| CN105181773A (en) | 2015-12-23 |
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