CN113813945B - Three-dimensional space network graphene-based polyaniline/PtAg composite catalyst and preparation method thereof - Google Patents
Three-dimensional space network graphene-based polyaniline/PtAg composite catalyst and preparation method thereof Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 68
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 34
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 34
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 34
- 238000012360 testing method Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 16
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 60
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
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- 239000010439 graphite Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000000083 pulse voltammetry Methods 0.000 claims description 3
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- 238000007781 pre-processing Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 238000004832 voltammetry Methods 0.000 claims 1
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 36
- 230000003647 oxidation Effects 0.000 abstract description 20
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- 230000035945 sensitivity Effects 0.000 abstract description 8
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- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 52
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 52
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- 238000001514 detection method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 229910018949 PtAu Inorganic materials 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
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- 230000002195 synergetic effect Effects 0.000 description 3
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- NYHBQMYGNKIUIF-UHFFFAOYSA-N D-guanosine Natural products C1=2NC(N)=NC(=O)C=2N=CN1C1OC(CO)C(O)C1O NYHBQMYGNKIUIF-UHFFFAOYSA-N 0.000 description 1
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- MRWXACSTFXYYMV-FDDDBJFASA-N nebularine Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1N1C2=NC=NC=C2N=C1 MRWXACSTFXYYMV-FDDDBJFASA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 230000004962 physiological condition Effects 0.000 description 1
- 239000002212 purine nucleoside Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01J35/33—
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/50—Silver
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/393—
-
- B01J35/396—
-
- 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
-
- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a three-dimensional network graphene-based polyaniline/PtAg composite catalyst and a preparation method thereof, wherein a space-limited material (PANI@3D rGO) formed by wrapping Polyaniline (PANI) on the outer layer of reduced graphene oxide (3D rGO) with a three-dimensional network structure is used as a carrier to load PtAg bimetallic nano particles, and finally the three-dimensional network graphene-based polyaniline/PtAg composite catalyst (PANI@3D rGO/PtAg) is formed. The electrode modified by the catalyst effectively shields oxidation signals of dopamine and ascorbic acid in the UA test process, and effectively solves the problems of interference resistance and sensitivity.
Description
Technical Field
The invention relates to a three-dimensional network graphene-based polyaniline/PtAg composite catalyst and a preparation method thereof, and belongs to the technical field of metal catalysts.
Background
Uric Acid (UA) is the main end product of purine nucleoside, adenosine and guanosine metabolism in organisms. Under physiological conditions, it is a monosodium salt. Normal concentrations of uric acid vary due to age, exercise, diet, medication, and other factors. Uric acid abnormality may cause gout, hyperuricemia, leachi-Ninham syndrome, leukemia, pneumonia, and the like. Therefore, it is important to develop a highly sensitive and selective assay for UA in biological systems. Common detection methods are capillary electrophoresis, fluorescence, chromatography, spectrophotometry, chemiluminescence, etc., but these methods typically require extreme experimental conditions and complex equipment. In recent decades, electroanalytical sensors for detection of biomolecules have attracted considerable attention due to their advantages of simple operation, low cost, fast response, high sensitivity, etc. Unfortunately, however, solid electrode fouling tends to result from adsorption of biomolecular oxidation products, ultimately resulting in poor solid electrode stability and repeatability. Furthermore, dopamine (DA), ascorbic Acid (AA) and UA generally coexist, and their oxidation potentials are very similar and difficult to separate. Therefore, developing a highly selective, highly sensitive catalyst for detecting UA remains a challenge for researchers.
Multicomponent nanocomposites are a very effective source for finding new performance catalysts due to the complementary and synergistic effects between their components. In the novel materials, the composite material with a space-limited structure improves the overall performance of the material, such as catalytic performance, anti-interference performance, stability and the like due to a synergistic effect and a space effect, has unique advantages in solving the problems of pollution and performance attenuation of the catalyst under complex environmental conditions, and is applied to the fields of energy sources, environment, analysis and test and the like. Research shows that the noble metal nano material with the space-limited structure, especially the platinum group metal material with obvious environmental poisoning effect, has obvious performance advantages in solving the poisoning and activity degradation of the catalyst in the small molecule catalytic oxidation process. The multidimensional space structure of the graphene-based material and the plasticity of the polymer material on the space structure make the graphene-based material become a new material for space structure construction after molecular sieves and MOFs. The precious metal composite catalyst which is formed by constructing a space-limited layer by using graphene and a polymer material is applied to detection of biomolecules such as UA, so that oxidation signals of dopamine and ascorbic acid can be effectively shielded, the problems of interference resistance and sensitivity of the precious metal composite catalyst can be effectively solved, and the problems of catalyst pollution and poisoning caused by complex environments in actual sample detection in the development process of a biosensing technology can be hopefully solved. However, how to effectively construct a space-constrained composite structure has been a difficulty in current research.
Disclosure of Invention
The invention provides a three-dimensional network graphene-based polyaniline/PtAg composite catalyst and a preparation method thereof, which can effectively solve the problems.
The invention is realized in the following way:
a three-dimensional network graphene-based polyaniline/PtAg composite catalyst is a three-dimensional network graphene-based polyaniline/PtAg composite catalyst (PANI@3DrGO/PtAg) which is formed by taking a space limiting material (PANI@3D rGO) formed by wrapping Polyaniline (PANI) on the outer layer of reduced graphene oxide (3D rGO) with a three-dimensional network structure as a carrier and loading PtAg bimetallic nano particles.
As a further improvement, the total loading of Pt and Ag is 2-3wt%, wherein Pt: the mass ratio of Ag is 2.5-3.5:1.
as a further improvement, the metal nanoparticles have a particle diameter of 30-60nm.
The preparation method of the three-dimensional network graphene-based polyaniline/PtAg composite catalyst comprises the steps of dispersing graphene oxide in distilled water, and then adding FeCl 3 After carrying out ultrasonic dispersion mixing on the solution and the metal catalyst precursor solution containing Pt and Ag, respectively adding aniline monomer and concentrated phosphoric acid for mixing, then adding phosphoric acid solution dissolved with ammonium persulfate for reaction to obtain a solid product, filtering the solid product through a mixed membrane with a preset aperture, washing with distilled water and washing with ethanol, adding the obtained powder product into phosphoric acid solution containing Ascorbic Acid (AA) for stirring and mixing treatment, filtering, washing with water and washing with alcohol, and naturally airing to obtain the three-dimensional space network graphene-based polyaniline/PtAg composite catalyst.
As a further improvement, the preparation method of the three-dimensional space network graphene-based polyaniline/PtAg composite catalyst comprises the following steps:
s11, stirring and dispersing 45-55mg of graphene oxide in 45-55ml of distilled water to obtain graphene oxide dispersion liquid;
s12, 180-220. Mu.l of 0.1M FeCl 3 Adding the solution and a preset dose of metal catalyst precursor solution containing Pt and Ag into the graphene oxide dispersion liquid, performing ultrasonic dispersion for 8-12min, and continuously stirring for 0.8-1.2h;
s13, adding 190-210 mu l of aniline monomer into the solution prepared in the step S02, stirring for 8-12min, adding 1.8-2.2ml of concentrated phosphoric acid, and continuing stirring for 7.5-8.5h;
s14, adding 0.28-0.32g of ammonium persulfate into 5ml of 10wt% phosphoric acid solution, slowly dropwise adding the solution into the solution prepared in the step S03 after complete dissolution, and continuously stirring for reacting for 0.8-1.2h to prepare a solid product;
s15, filtering the solid product by using a mixed membrane with the aperture of 220nm, and cleaning the solid product by using distilled water and ethanol to obtain a powder product;
s06, adding the powder product into 45-55ml of 2wt% phosphoric acid solution containing 100mM ascorbic acid for stirring and mixing treatment for 22-26h, filtering, washing with water, washing with alcohol, naturally airing the obtained product, and obtaining the three-dimensional space network graphene-based polyaniline/PtAg composite catalyst.
The dosage of each reagent, various reaction conditions and environment in the preparation method of the three-dimensional space network graphene-based polyaniline/PtAg composite catalyst form a three-dimensional space network structure of the catalyst, and if the dosage is not in the range, the three-dimensional space network graphene-based polyaniline/PtAg composite catalyst is difficult to form.
As a further improvement, the preset dose of the metal catalyst precursor solution containing Pt and Ag is 0.5-0.7ml of 47.93mM silver acetate solution and 0.6-0.80ml of 8.228mM potassium chloroplatinate solution.
A preparation method of a modified electrode based on a three-dimensional network graphene-based polyaniline/PtAg composite catalyst comprises the steps of polishing a glassy carbon electrode, cleaning and airing for later use; dispersing the three-dimensional network graphene-based polyaniline/PtAg composite catalyst and Nafion in ethanol and performing ultrasonic treatment to form mixed suspension; dripping the mixed suspension on the surface of the glassy carbon electrode, and airing at room temperature; dispersing Nafion in ethanol to form Nafion diluted solution, then dripping the Nafion diluted solution on the surface of the glassy carbon electrode, and airing at room temperature to obtain a catalyst modified electrode; and finally, preprocessing the catalyst modified electrode to obtain the modified electrode based on the three-dimensional network graphene-based polyaniline/PtAg composite catalyst.
As a further improvement, the preparation method of the modified electrode based on the three-dimensional network graphene-based polyaniline/PtAg composite catalyst comprises the following steps:
s21, polishing the glassy carbon electrode with the diameter of 5mm on a polishing pad by using alumina slurry with the particle diameters of 3, 1, 0.3 and 0.05 mu m respectively, flushing by using distilled water, respectively ultrasonically cleaning in absolute ethyl alcohol and distilled water, and airing for later use.
S22, dispersing 2mg of graphene-based polyaniline/PtAg composite catalyst powder with a three-dimensional network and 8-12 mu l of 5wt% Nafion ethanol solution in 0.5ml of ethanol, and performing ultrasonic treatment for 25-35min to form a uniform mixed suspension; and (3) dripping 12-14 mu l of the mixed suspension on the surface of the cleaned glassy carbon electrode, and airing at room temperature.
S23, dispersing 8-12 mu l of 5wt% Nafion ethanol solution in 0.5ml of ethanol to form Nafion diluted solution, dripping 12-14 mu l of Nafion diluted solution on the surface of the glassy carbon electrode obtained in the step S22, and airing at room temperature to obtain the catalyst modified electrode.
S24, adopting a three-electrode system, taking a catalyst modified electrode as a working electrode, a graphite electrode as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrode, firstly carrying out Cyclic Voltammetry (CV) scanning in 0.2M NaOH solution for 1h under the condition of a potential range of-0.1V-0.9V (vs. SCE), then carrying out Cyclic Voltammetry (CV) scanning in 0.5M phosphoric acid solution for 1h, and finally carrying out Cyclic Voltammetry (CV) scanning in 0.1M PBS solution containing 10mM ascorbic acid for 2h so as to pretreat the catalyst modified electrode; the pretreatment is very critical to obtaining an electrochemical detection signal with good stability and repeatability, and can improve the detection sensitivity and the anti-interference capability of the electrode.
S25, immersing the modified electrode pretreated in the step S24 in a 0.1M PBS solution containing 1mM ascorbic acid for later use.
The modified electrode based on the three-dimensional network graphene-based polyaniline/PtAg composite catalyst prepared by the method.
According to the electrochemical testing method of the modified electrode based on the three-dimensional network graphene-based polyaniline/PtAg composite catalyst, a three-electrode system is adopted, the modified electrode based on the three-dimensional network graphene-based polyaniline/PtAg composite catalyst is used as a working electrode, a graphite electrode is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode, so that a pulse voltammetry test is performed; the pulsed voltammetric test was performed at a potential ranging from-0.1V to 0.9V (vs. sce), a sweep amplitude of 50mV, a pulse width of 50ms, in an environment of 0.1M, pH =6.8 in PBS solution.
The beneficial effects of the invention are as follows:
the three-dimensional network graphene-based polyaniline/PtAg composite catalyst provided by the invention takes a space limited domain material (PANI@3D rGO) formed by wrapping Polyaniline (PANI) on the outer layer of reduced graphene oxide (3D rGO) with a three-dimensional network structure as a carrier, loads PtAg bimetallic nano materials, and finally forms the three-dimensional space limited domain type PtAg bimetallic composite catalyst (PANI@3D rGO/PtAg). The three-dimensional space domain-limited structure enables the electrode modified by the catalyst to effectively shield oxidation signals of dopamine and ascorbic acid in the UA test process, and effectively solves the problems of interference resistance and sensitivity.
The three-dimensional space network graphene-based polyaniline/PtAg composite catalyst synthesized by the space-limited synthesis method can provide a new thought and method for effectively solving the poisoning and activity degradation of the metal catalyst.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is SEM images of the surface and internal structures of pani@3d rGO nanocatalyst carrier and pani@3d rGO/PtAg nanocatalyst provided in examples and comparative examples of the present invention. Pani@3drgo nanocatalyst carrier surface SEM image (a) and internal structure diagram (B); PANI@3DrGO/PtAg nano catalyst surface morphology graph (C) and internal structure graph (D).
FIG. 2 is a graph of DPV test of PANI-PtAg nanocatalyst modified electrodes provided in examples and comparative examples of the invention in 0.1M PBS (pH 6.8) solution containing 1mM UA, 2mM AA, 200. Mu.M DA.
FIG. 3 is a graph of DPV test of PANI@3D rGO/PtAg nanocatalyst modified electrodes provided in examples and comparative examples of the invention in 0.1M PBS (pH 6.8) solution containing 1mM UA, 2mM AA, 200. Mu.M DA.
FIG. 4 is a graph of DPV test of PANI@3D rGO-based series modified electrodes provided in examples and comparative examples of the present invention in a solution of 1mM UA in 0.1M PBS (pH 6.8).
FIG. 5 is a graph of DPV test of the PANI series bimetallic nano-modified electrode provided by examples and comparative examples of the present invention in 0.1M PBS (pH 6.8) solution containing 1mM UA.
FIG. 6 is a graph of DPV test of PANI@3D rGO/PtAg modified electrodes provided in examples and comparative examples of the present invention in 0.1M PBS (pH 6.8) solutions containing UA at different concentrations.
Fig. 7 is a standard curve of the DPV test of UA on pani@3d rGO/PtAg modified electrode provided in examples and comparative examples of the present invention.
FIG. 8 is a graph of DPV test of PANI@3D rGO/PtAu modified electrodes provided in examples and comparative examples of the present invention in 0.1M PBS (pH 6.8) solutions containing UA at different concentrations.
Fig. 9 is a standard curve of the DPV test of UA on pani@3d rGO/PtAu modified electrode provided in examples and comparative examples of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
In the description of the present invention, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
Example 1
Preparation of PANI@3D rGO/PtAg nano catalyst:
50mg of graphene oxide was put in a 250ml flat-bottomed flask, 50ml of distilled water was added thereto, and after stirring and dispersion, 200. Mu.l of 0.1M FeCl was added thereto 3 Solution and metal catalyst precursor solution (0.5625 ml of 47.93mM silver acetate solution and 0.675ml of 8.228mM potassium chloroplatinate solution), stirring was continued for 1 hour after ultrasonic dispersion for 10 minutes. 200. Mu.l of aniline monomer was added to the above solution, and after stirring for 10min, 2ml of concentrated phosphoric acid was added and stirred for 8h. 0.3g of ammonium persulfate is taken and added into 5ml of 10% phosphoric acid solution, and slowly added into the solution after complete dissolution, and stirring is continued for reaction for 1h after the completion of the addition. The solid product was filtered through a 220nm pore size mixed membrane, washed with distilled water and ethanol, and the resulting powder was stirred in 50ml of a 100mM AA-containing 2% phosphoric acid solution for 24 hours. Filtering the product, washing with water and ethanol, naturally airing to obtain PANI@3D rGO/PtAg nano catalystPowder.
Preparation of modified electrode:
the glassy carbon electrode with the diameter of 5mm is sequentially polished on a polishing pad by alumina slurry with the particle diameters of 3, 1, 0.3 and 0.05 mu m, washed by distilled water, ultrasonically cleaned in absolute ethyl alcohol and distilled water respectively and then dried for standby. 2mg of PANI@3D rGO/PtAg nanocatalyst powder and 10. Mu.l of a 5% Nafion ethanol solution were dispersed in 0.5ml of ethanol and sonicated for 30min to form a homogeneous mixed suspension. And (3) dropwise adding 13 μl of the mixed suspension onto the surface of the cleaned glassy carbon electrode, and airing at room temperature. Dispersing 10 mu l of 5% Nafion ethanol solution in 0.5ml of ethanol to form Nafion diluted solution, dripping 13 mu l of Nafion diluted solution on the surface of the glassy carbon electrode containing nano catalyst powder, and airing at room temperature to obtain the catalyst modified electrode. In order to obtain an electrochemical detection signal with good stability and repeatability, the prepared catalyst modified electrode is subjected to pretreatment, namely, cyclic Voltammetry (CV) scanning is carried out in a 0.2M NaOH solution under the condition of potential range of-0.1V-0.9V (vs. SCE) for 1h, CV (-0.1V-0.9V (vs. SCE)) scanning is carried out in a 0.5M phosphoric acid solution for 1h, and CV (-0.1V-0.9V (vs. SCE)) scanning is carried out in a 0.1M PBS solution containing 10mM AA for 2h. The pretreated modified electrode was immersed in a 0.1M PBS solution containing 1mM AA for use.
Electrochemical testing:
the electrochemical experiment adopts a three-electrode system, wherein a catalyst modified electrode is used as a working electrode, a graphite electrode is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode, so as to carry out a pulse voltammetry (DPV) test. The potential range of the DPV test is-0.1V-0.9V (vs. SCE), the scanning amplitude is 50mV, and the pulse width is 50ms. The whole experiment was performed in an environment of phosphate buffer (0.1M PBS solution, ph=6.8).
Comparative example 1
The procedure of example 1 was followed except that the metal catalyst precursor solution used was 1.35ml of 8.228mM potassium chloroplatinate solution, and the catalyst prepared was PANI@3D rGO/Pt metal nanocatalyst.
Comparative example 2
The difference from example 1 is that the metal catalyst precursor solution used was 1.125ml of a 47.93mM silver acetate solution, and the catalyst prepared was PANI@3D rGO/Ag metal nanocatalyst, otherwise the procedure was as in example 1.
Comparative example 3
The procedure of example 1 was followed except that the metal catalyst precursor solution used was 0.225ml of 10g/L palladium chloride solution and 0.675ml of 8.228mM potassium chloroplatinate solution, and the catalyst prepared was PANI@3D rGO/PtPd metal nanocatalyst.
Comparative example 4
The procedure of example 1 was followed except that the metal catalyst precursor solutions used were 0.225ml of 24.28mM chloroauric acid solution and 0.675ml of 8.228mM potassium chloroplatinate solution, and the catalyst prepared was PANI@3D rGO/PtAu metal nanocatalyst.
Comparative example 5
The preparation method of the PANI@3D rGO nano powder comprises the following steps:
50mg of graphene oxide was put in a 250ml flat-bottomed flask, 50ml of distilled water was added thereto, and after stirring and dispersion, 200. Mu.l of 0.1M FeCl was added thereto 3 The solution was dispersed by ultrasound for 10min and stirred for 1h. 200. Mu.l of aniline monomer was added to the above solution, and after stirring for 10min, 2ml of concentrated phosphoric acid was added and stirred for 8h. 0.3g of ammonium persulfate is taken and added into 5ml of 10% phosphoric acid solution, and slowly added into the solution after complete dissolution, and stirring is continued for reaction for 1h after the completion of the addition. The solid product was filtered through a 220nm pore size mixed membrane, washed with distilled water and ethanol, and the resulting powder was stirred in 50ml of a 100mM AA-containing 2% phosphoric acid solution for 24 hours. Filtering the product, washing with water and ethanol, and naturally airing to obtain PANI@3DrGO nano powder.
Comparative example 6
The preparation method of the PANI-PtAg nano catalyst comprises the following steps:
into a 250ml flat bottom flask was charged 50ml distilled water, 200. Mu.l 0.1M FeCl was added 3 After stirring for 10min, 200. Mu.l of aniline monomer was added to the solution, followed by stirring for 10min, 2ml of concentrated phosphoric acid was added, and stirring was continued for 8h. Taking 0.3g of persulfuric acidAmmonium is added into 5ml of 10% phosphoric acid solution, slowly added into the solution after complete dissolution, and stirred for reaction for 1h after the addition. The solid product was filtered through a 220nm pore size mixed membrane, washed with distilled water and ethanol, and the resulting powder was stirred in 50ml of a 100mM AA-containing 2% phosphoric acid solution for 24 hours. Filtering the product, washing with water and ethanol, and naturally airing to obtain the PANI-PtAg nano catalyst powder.
The experimental results are shown in fig. 1 to 9.
FIG. 1 is an SEM (scanning electron microscope) diagram of the surface and internal structure of a PANI@3D rGO nano catalyst carrier and a PANI@3D rGO/PtAg nano catalyst. As can be seen from fig. 1A and 1B, the pani@3d rGO nanocatalyst support has a relatively dense membrane structure on the surface and a spatial network structure consisting of rGO with a polyaniline membrane covered on the surface. The thickness of the polyaniline/rGO interlayer forming the space network structure is 20-40nm, the size of the internal space channel is larger, and most of the internal space channel is distributed at 200-500nm. As can be seen from fig. 1C and 1D, after the metal nanoparticles are loaded, the metal nanoparticles are simultaneously loaded on the polyaniline film layer on the outer layer and the polyaniline/rGO interlayer surface forming the space network structure, and many fine metal nanoparticles are aggregated to form round particles of 30-60nm. By EDS characterization, the metal nano particles loaded in the PANI@3D rGO/PtAg nano catalyst powder are PtAg bimetallic nano particles, and the PtAg total loading amount is 2.5%, wherein Pt: the mass ratio of Ag is 3:1.
FIG. 2 is a graph of DPV test of PANI-PtAg nanocatalyst modified electrodes in 0.1M PBS (pH 6.8) solution containing 1mM UA, 2mM AA, 200. Mu.M DA. As can be seen from the graph, the oxidation current potential of DA ranges from 0.12V to 0.51V, and the oxidation peak potential is 0.24V; the oxidation current potential of UA ranges from 0.29V to 0.77V, and the oxidation peak potential is 0.42V; AA has no significant electrochemical response signal under this test condition. Therefore, in the detection of a system in which DA, UA and AA coexist, the detection of DA and UA has better anti-interference capability. However, through detection limit test, the detection limit of the PANI-PtAg nano catalyst modified electrode to UA is only 200 μm, and the current requirement of UA in human body fluid is hardly met.
FIG. 3 is a graph of DPV test of PANI@3D rGO/PtAg nanocatalyst modified electrodes in 0.1M PBS (pH 6.8) solution containing 1mM UA, 2mM AA, 200. Mu.M DA. As can be seen from the graph, the oxidation current potential of UA ranges from 0.29V to 0.75V, and the oxidation peak potential is 0.48V; DA. AA has no significant electrochemical response signal under this test condition. Therefore, in the detection of a system in which DA, UA and AA coexist, the detection method completely avoids the test interference of DA and AA on the detection of UA. In addition, compared with PANI-PtAg, the PANI@3D rGO/PtAg nano catalyst modified electrode has higher sensitivity to UA detection.
FIG. 4 is a graph of DPV test of PANI@3D rGO-based modified electrode in 0.1M PBS (pH 6.8) solution containing 1mM UA. From the graph, the oxidation current potential range of UA on PANI@3D rGO base series modified electrodes is 0.29V-0.75V, and the oxidation peak potential is 0.46-0.49V. In UA test, the electrochemical response signal of the PANI@3D rGO/PtAg modified electrode is obviously larger than that of the PANI@3D rGO/Pt, PANI@3D rGO/Ag and PANI@3D rGO modified electrode, and excellent electrocatalytic performance is shown; compared with the PANI@3DrGO modified electrode, the electrocatalytic performance of the nano metal catalyst modified electrode taking the PANI@3D rGO as the carrier to UA is greatly enhanced.
FIG. 5 is a graph of DPV test of a PANI-based series of bimetallic nano-modified electrodes in 0.1M PBS (pH 6.8) solution containing 1mM UA. From the graph, the oxidation current potential of UA on the PANI-based series modified electrode ranges from 0.29V to 0.75V, and the oxidation peak potential is greatly different. In UA test, the electrochemical response signal of the PANI@3D rGO/PtAg modified electrode is obviously larger than that of the PANI@3D rGO/PtAu, PANI@3D rGO/PtPd and PANI-PtAg modified electrode, and the electrochemical response signal of the PANI@3D rGO/PtAg modified electrode shows excellent electrocatalytic performance; the bimetallic nano-catalyst modified electrode taking PANI@3D rGO as a carrier, PANI@3D rGO/PtAu and PANI@3D rGO/PtPd, and the electrocatalytic performance of UA is only enhanced to a certain extent compared with that of the PtAg modified electrode taking PANI as the carrier. It can be speculated that the synergistic catalysis of the pani@3d rGO support on the PtAg bimetal is significantly better than that of PtAu and PtPd bimetal.
FIG. 6 is a graph of DPV test of PANI@3D rGO/PtAg modified electrodes in 0.1M PBS (pH 6.8) solutions containing various concentrations of UA. In the graph, the oxidation current potential ranges of UA with different concentrations on the modified electrode are all 0.29V-0.75V, and oxidation peak potentials are all near 0.48V; as the concentration of UA increases, the electrochemical response signal of UA on the modified electrode increases, and the detection limit is 0.001. Mu.M. The UA concentration in the serum of healthy human body is generally 120-460 mu M, and the method provided by the invention has ultrahigh sensitivity, can be used for detecting UA in the serum of human body, and is not interfered by DA and AA.
Fig. 7 is a standard curve of the DPV test of UA on pani@3d rGO/PtAg modified electrode. As can be seen from the graph, the UA test method provided by the invention has a very wide linear detection concentration range of 0.001 mu M-1mM, and a bilinear relationship is shown between DA concentration and peak current in the test concentration range. The linear curve at high concentration (10. Mu.M-1000. Mu.M) is y=0.0417 x+8.5848, the correlation coefficient R 2 = 0.99857. The linear curve at low concentration (0.001. Mu.M-10. Mu.M) is y=0.697x+1.292, the correlation coefficient R 2 ＝0.98454。
FIG. 8 is a graph of DPV test of PANI@3D rGO/PtAu modified electrodes in 0.1M PBS (pH 6.8) solutions containing various concentrations of UA. In the graph, the oxidation current potential ranges of UA with different concentrations on the modified electrode are all 0.29V-0.72V, and oxidation peak potentials are all near 0.48V; as the UA concentration increases, the electrochemical response signal of UA on the modified electrode increases with the detection limit of 1 μm. The UA concentration in the serum of healthy human body is generally 120-460 mu M, so that the PtAu bimetal modified electrode taking PANI@3D rGO as a carrier has enough sensitivity, can be used for normal detection of UA in the serum of human body, and is not interfered by DA and AA.
FIG. 9 shows a standard curve of DPV test of UA on PANI@3D rGO/PtAu modified electrode, wherein the concentration of UA shows a linear relationship with peak current in the concentration range of 1 mu M-1mM detected by the invention, the linear curve is y=0.0185x+3.615, and the correlation coefficient is R 2 ＝0.99711。
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and various modifications and variations may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A three-dimensional network graphene-based polyaniline/PtAg composite catalyst is characterized in that a three-dimensional network graphene-based polyaniline/PtAg composite catalyst (PANI@3D rGO/PtAg) is formed by taking a space limiting material (PANI@3D rGO) formed by wrapping Polyaniline (PANI) on the outer layer of reduced graphene oxide (3D rGO) with a three-dimensional network structure as a carrier and loading PtAg bimetallic nano particles; the preparation method of the three-dimensional network graphene-based polyaniline/PtAg composite catalyst comprises the following steps: dispersing graphene oxide in distilled water, and adding FeCl 3 After carrying out ultrasonic dispersion mixing on the solution and a metal catalyst precursor solution containing Pt and Ag, respectively adding aniline monomers and concentrated phosphoric acid for mixing, then adding a phosphoric acid solution dissolved with ammonium persulfate for reaction to obtain a solid product, filtering the solid product through a mixed membrane with a preset aperture, washing with distilled water and washing with ethanol, adding the obtained powder product into a phosphoric acid solution containing Ascorbic Acid (AA) for stirring and mixing treatment, filtering, washing with water and washing with alcohol, and naturally airing to obtain the three-dimensional space network graphene-based polyaniline/PtAg composite catalyst; the total loading of Pt and Ag is 2-3wt%, wherein Pt: the mass ratio of Ag is 2.5-3.5:1, a step of; the preparation method comprises the following steps:
s11, stirring and dispersing 45-55mg graphene oxide in 45-55ml of distilled water to obtain graphene oxide dispersion liquid;
s12, 180-220. Mu.l FeCl 0.1. 0.1M 3 Adding the solution and a preset dose of metal catalyst precursor solution containing Pt and Ag into graphene oxide dispersion liquid, performing ultrasonic dispersion for 8-12min, and continuously stirring for 0.8-1.2h;
s13, adding 190-210 mu l of aniline monomer into the solution prepared in the step S12, stirring for 8-12min, adding 1.8-2.2. 2.2ml concentrated phosphoric acid, and continuing stirring for 7.5-8.5h;
s14, adding 0.28-0.32-g ammonium persulfate into 5ml of 10wt% phosphoric acid solution, slowly dropwise adding the solution into the solution prepared in the step S13 after complete dissolution, and continuously stirring for reaction to obtain a solid product, wherein the reaction is 0.8-1.2h;
s15, filtering the solid product by using a mixed membrane with the aperture of 220nm, and cleaning the solid product by using distilled water and ethanol to obtain a powder product;
s16, adding the powder product into a 2wt% phosphoric acid solution containing 100mM ascorbic acid of 45-55ml, stirring and mixing the powder product to obtain 22-26h, filtering, washing with water, washing with alcohol, naturally airing the product obtained by treatment, and obtaining the three-dimensional space network graphene-based polyaniline/PtAg composite catalyst.
2. The three-dimensional network graphene-based polyaniline/PtAg composite catalyst according to claim 1, wherein the metal nanoparticles have a particle size of 30-60nm.
3. The preparation method of the three-dimensional network graphene-based polyaniline/PtAg composite catalyst according to claim 1 or 2, wherein graphene oxide is dispersed in distilled water, and FeCl is added 3 After carrying out ultrasonic dispersion mixing on the solution and the metal catalyst precursor solution containing Pt and Ag, respectively adding aniline monomer and concentrated phosphoric acid for mixing, then adding phosphoric acid solution dissolved with ammonium persulfate for reaction to obtain a solid product, filtering the solid product through a mixed membrane with a preset aperture, washing with distilled water and washing with ethanol, adding the obtained powder product into phosphoric acid solution containing Ascorbic Acid (AA) for stirring and mixing treatment, filtering, washing with water and washing with alcohol, and naturally airing to obtain the three-dimensional space network graphene-based polyaniline/PtAg composite catalyst.
4. A method according to claim 3, comprising the steps of:
s11, stirring and dispersing 45-55mg graphene oxide in 45-55ml of distilled water to obtain graphene oxide dispersion liquid;
s12, 180-220. Mu.l FeCl 0.1. 0.1M 3 Adding the solution and a preset dose of metal catalyst precursor solution containing Pt and Ag into graphene oxide dispersion liquid, performing ultrasonic dispersion for 8-12min, and continuously stirring for 0.8-1.2h;
s13, adding 190-210 mu l of aniline monomer into the solution prepared in the step S12, stirring for 8-12min, adding 1.8-2.2. 2.2ml concentrated phosphoric acid, and continuing stirring for 7.5-8.5h;
s14, adding 0.28-0.32-g ammonium persulfate into 5ml of 10wt% phosphoric acid solution, slowly dropwise adding the solution into the solution prepared in the step S13 after complete dissolution, and continuously stirring for reaction to obtain a solid product, wherein the reaction is 0.8-1.2h;
s15, filtering the solid product by using a mixed membrane with the aperture of 220nm, and cleaning the solid product by using distilled water and ethanol to obtain a powder product;
s16, adding the powder product into a 2wt% phosphoric acid solution containing 100mM ascorbic acid of 45-55ml, stirring and mixing the powder product to obtain 22-26h, filtering, washing with water, washing with alcohol, naturally airing the product obtained by treatment, and obtaining the three-dimensional space network graphene-based polyaniline/PtAg composite catalyst.
5. The method of claim 4, wherein the predetermined amount of the Pt, ag containing metal catalyst precursor solution is 0.5-0.7ml silver 47.93mM acetate solution and 0.6-0.80ml potassium 8.228mM chloroplatinate solution.
6. A preparation method of a modified electrode based on a three-dimensional network graphene-based polyaniline/PtAg composite catalyst is characterized by polishing a glassy carbon electrode, cleaning and airing for later use; dispersing the three-dimensional network graphene-based polyaniline/PtAg composite catalyst according to claim 1 or 2 and Nafion in ethanol and performing ultrasonic treatment to form mixed suspension; dripping the mixed suspension on the surface of the glassy carbon electrode, and airing at room temperature; dispersing Nafion in ethanol to form Nafion diluted solution, then dripping the Nafion diluted solution on the surface of the glassy carbon electrode, and airing at room temperature to obtain a catalyst modified electrode; and finally, preprocessing the catalyst modified electrode to obtain the modified electrode based on the three-dimensional network graphene-based polyaniline/PtAg composite catalyst.
7. The method according to claim 6, comprising the steps of:
s21, sequentially polishing the glassy carbon electrode with the diameter of 5mm on a polishing pad by using alumina slurry with the particle diameters of 3, 1, 0.3 and 0.05 mu m, washing by using distilled water, respectively ultrasonically washing in absolute ethyl alcohol and distilled water, and airing for later use;
s22, dispersing 2mg three-dimensional space network graphene-based polyaniline/PtAg composite catalyst powder and 8-12 mu l of 5-wt% Nafion ethanol solution in 0.5ml ethanol and performing ultrasonic treatment for 25-35min to form uniform mixed suspension; dripping 12-14 mu l of the mixed suspension on the surface of the cleaned glassy carbon electrode, and airing at room temperature;
s23, dispersing 8-12 mu l of 5wt% Nafion ethanol solution in 0.5ml ethanol to form Nafion diluted solution, dripping 12-14 mu l of Nafion diluted solution on the surface of the glassy carbon electrode obtained in the step S22, and airing at room temperature to obtain a catalyst modified electrode;
s24, adopting a three-electrode system, taking a catalyst modified electrode as a working electrode, a graphite electrode as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrode, firstly carrying out Cyclic Voltammetry (CV) scanning for 1h in a 0.2M NaOH solution under the condition of a potential range of-0.1V-0.9V (vs. SCE), then carrying out Cyclic Voltammetry (CV) scanning for 1h in a 0.5M phosphoric acid solution, and finally carrying out Cyclic Voltammetry (CV) scanning for 2h in a 0.1M PBS solution containing 10mM ascorbic acid so as to pretreat the catalyst modified electrode;
s25, immersing the modified electrode pretreated in the step S24 in a 0.1M PBS solution containing 1mM ascorbic acid for later use.
8. A modified electrode based on a three-dimensional network graphene-based polyaniline/PtAg composite catalyst prepared by the method of claim 6 or 7.
9. The electrochemical testing method for the modified electrode based on the three-dimensional network graphene-based polyaniline/PtAg composite catalyst according to claim 8, which is characterized in that a three-electrode system is adopted, the modified electrode based on the three-dimensional network graphene-based polyaniline/PtAg composite catalyst is used as a working electrode, a graphite electrode is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode, so that a pulse voltammetry test is performed; the pulsed voltammetry was performed in an environment of 0.1M, ph=6.8 in PBS solution with a potential range of-0.1V to 0.9V (vs. sce), a scanning amplitude of 50mV, and a pulse width of 50ms.
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