CN116726908A - Bismuth-doped high-performance electrocatalytic composite material, preparation method and application - Google Patents
Bismuth-doped high-performance electrocatalytic composite material, preparation method and application Download PDFInfo
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- CN116726908A CN116726908A CN202311013874.6A CN202311013874A CN116726908A CN 116726908 A CN116726908 A CN 116726908A CN 202311013874 A CN202311013874 A CN 202311013874A CN 116726908 A CN116726908 A CN 116726908A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 150000002500 ions Chemical class 0.000 claims abstract description 93
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 76
- 238000001514 detection method Methods 0.000 claims abstract description 38
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 24
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 26
- 229910021645 metal ion Inorganic materials 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 230000007613 environmental effect Effects 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000003950 stripping voltammetry Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 5
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- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 238000002848 electrochemical method Methods 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 230000035945 sensitivity Effects 0.000 abstract description 13
- 229910052793 cadmium Inorganic materials 0.000 abstract description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
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- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
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- 230000002194 synthesizing effect Effects 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
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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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- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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Abstract
The invention relates to the technical field of electrochemical sensing materials and detection, and discloses a bismuth-doped high-performance electrocatalytic composite material, a preparation method and application thereof, wherein the bismuth-doped high-performance electrocatalytic composite material is bismuth-doped bismuth Bi/Bi with multiple petal-shaped microscopic bulge structures after film formation 2 WO 6 . The heavy metal ion electrochemical sensor provided by the invention comprises Bi/Bi 2 WO 6 The composite material is prepared into a working electrode after film formation and applicationThe surface modification of the working electrode in the three-electrode system and the composite electrode system realizes the simultaneous detection of cadmium and lead ions by dynamically optimizing the standing time/the dripping amount/the enrichment time, can realize the synchronous detection of cadmium and lead ions in the aqueous solution, and has excellent sensitivity and wider linear detection range. The modified material of the working electrode provided by the invention has the advantages of large electrochemical active area, fast electron transmission, high anti-interference performance, strong electrocatalytic capacity and the like, and can realize high-sensitivity simultaneous detection of cadmium and lead ions.
Description
Technical Field
The invention relates to the technical field of electrochemical sensing materials and detection, in particular to a bismuth-doped high-performance electrocatalytic composite material, a preparation method and application thereof.
Background
Heavy metal is a persistent pollutant, and heavy metal ions in environmental water bodies comprise lead ions (Pb) 2+ ) And cadmium ions (Cd) 2+ ) The method has great harm to the ecological environment and the human health, so that the establishment of a rapid, accurate and reliable heavy metal ion detection technology has great significance for the prevention and control of the environmental health risks of the heavy metal ions.
Currently, it is commonly used for simultaneous determination of Cd 2+ And Pb 2+ Including Atomic Absorption Spectroscopy (AAS), atomic Fluorescence Spectroscopy (AFS), inductively coupled plasma mass spectrometry (ICP-MS), and the like. However, these techniques have the disadvantages of expensive equipment, complex operation, long time consumption, and need of specialized personnel to operate.
The electrochemical analysis method has the advantages of simple operation, lower cost and the like. However, electrochemical detection faces the problem that targets in complex substrate samples often do not show peaks or show distorted peaks and it is difficult to simultaneously analyze multicomponent targets with similar reduction or oxidation potentials. In the prior art, the document of Chinese invention application No. CN 202111424888.8 discloses an electrochemical sensor electrode for rapidly and simultaneously detecting lead ions and cadmium ions, and a preparation method and application thereof; the preparation method of the electrochemical sensor electrode comprises the following steps: and (3) dripping a mixture of bovine serum albumin, aminated graphene oxide and glutaraldehyde on the surface of the screen printing carbon electrode in an in-situ crosslinking polymerization mode to perform polymerization reaction to obtain the BSA-GO crosslinked polymer modified electrode, and then dripping the flower-shaped bismuth tungstate suspension on the surface of the electrode. The Chinese patent document CN 113083287A discloses a nano-particle stacked lamellar structure bismuth and bismuth tungstate composite powder, wherein the composite powder comprises a central through three-dimensional cage-shaped structure assembled by bismuth tungstate nano-sheets, the diameter of the central through hole is 200-300nm, the outer diameter of the three-dimensional cage-shaped structure is 1-2 mu m, the size of nano-particles is 10-40nm, micropores with the size of <2nm and mesopores with the size of 2-12nm are contained in nano-particle stacked lamellar layers, and lamellar layers are further assembled to form lamellar overlapping macropores with the size of 100-150 nm; bismuth particles with the size of 40-65nm are attached to the nano sheet layer, the cross section morphology is regular hexagon, the photocatalytic activity can be improved, but the material is not described that the electrocatalytic performance can be improved, and the material can be applied to simultaneously and rapidly detecting various heavy metal ions.
Therefore, although the prior art can simultaneously measure the content of lead ions and cadmium ions in a sample or improve the photocatalytic activity, the prior art also has the defects of complex preparation method, low electrocatalytic performance, low anti-interference capability and the like of the electrode material of the electrochemical sensor.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a bismuth-doped high-performance electrocatalytic composite material, a preparation method and application thereofSynchronous improvement of components, proportion and process, design and synthesis of bismuth doped bismuth tungstate Bi/Bi with unique microcosmic film forming structure and high-efficiency electrocatalytic performance 2 WO 6 The composite material is used for modifying the traditional electrode after film formation, so that the electrode has high selectivity, high sensitivity, good anti-interference capability and capability of detecting various target components simultaneously, and further an excellent electrocatalytic material modified electrode is prepared, and the composite material and GCE are prepared into the heavy metal ion electrochemical sensor with high sensitivity and ultra-wide linear detection range, so that the heavy metal ion electrochemical sensor is used for simultaneously and rapidly detecting various heavy metal ions, and the problems in the prior art are solved.
The invention provides a technical scheme for solving the problems, which comprises the following steps:
the preparation method of the bismuth-doped high-performance electrocatalytic composite material is characterized by comprising the following steps of:
s1: will be 0.1 mmol Na 2 WO 4 ·2H 2 O and 0.1. 0.1 g hexadecyl trimethyl ammonium bromide (CTAB) are respectively added into 80 mL deionized water, and the solution is uniformly mixed by magnetic stirring for 30min to obtain a mixed solution;
s2: 0.4 mmol Bi (NO) 3 ) 3 ·5H 2 Adding O into the mixed solution, after fully stirring, transferring the mixed solution into a 100 mL polytetrafluoroethylene lining autoclave, and keeping the temperature at 120 ℃ for 24 h to obtain a reaction product;
s3: washing the reaction product with deionized water and ethanol for 3 times respectively, and drying in a 60 ℃ drying oven for 12 h to obtain bismuth doped bismuth tungstate Bi/Bi with petal-shaped microscopic bump structures with multiple dimensions, different orientations and irregular distribution after film formation 2 WO 6 A composite material.
The bismuth-doped high-performance electrocatalytic composite material is characterized in that the bismuth-doped bismuth tungstate Bi/Bi with multiple irregularly distributed petal-shaped microscopic convex structures is prepared by adopting the method and is formed into a film 2 WO 6 A composite material.
The heavy metal ion electrochemical sensor is characterized by comprising the bismuth doped high performanceElectrocatalytic composite Bi/Bi 2 WO 6 。
The preparation method of the heavy metal ion electrochemical sensor is characterized by comprising the following steps of:
A. Bi/Bi 2 WO 6 Adding the composite material into ethanol solution, and performing ultrasonic treatment for 30min to obtain Bi/Bi 2 WO 6 Dripping the coating liquid on the electrode;
B. Bi/Bi 2 WO 6 Dripping the electrode coating liquid on the surface of the prepared clean and dry glassy carbon electrode GCE, uniformly coating, drying, and obtaining the Bi/Bi with the outer surface covered by the multiple petal-shaped microscopic convex structures after the solvent is evaporated to form a film and the surface has no layering section 2 WO 6 Heavy metal ion electrochemical sensor of membrane.
The application of the heavy metal ion electrochemical sensor is characterized in that the sensor is used as a working electrode and applied to simultaneous determination of two or more heavy metal ion concentrations in an environmental water body by an electrochemical method, and the heavy metal ions comprise lead ions and cadmium ions, and the application comprises the following steps:
p1: preparing Bi/Bi with multiple petal-shaped microscopic bulge structures in advance 2 WO 6 The GCE of the membrane is used as a heavy metal ion electrochemical sensor and is used as a working electrode, and can be used as a working electrode in an independent electrode or a composite electrode;
p2: one end of a working electrode (namely a heavy metal ion electrochemical sensor), one end of a counter electrode and one end of a reference electrode are respectively connected to an electrochemical workstation, the other ends of the working electrode, the counter electrode and the reference electrode are respectively placed in metal ion-containing electrolyte with known concentration in an electrolytic cell, an electrochemical anode stripping voltammetry is used for detection, an enrichment potential is set to be-1.1V, while enrichment, a solution is stirred for a set enrichment duration (such as 50-150 s), stirring is stopped after the enrichment is finished, after standing for a set duration (such as 10 s), a set of forward scanning voltage with a voltage scanning range of-1V-0.3V is applied to a three-electrode system, a current-voltage curve is obtained by recording current-voltage change conditions by the electrochemical workstation, a standard curve corresponding to the metal ions is drawn by taking the concentration of the heavy metal ions as an abscissa, and peak current as an ordinate, a regression equation is obtained, and a linear or nonlinear relation between the concentration of the metal ions and the peak current is determined;
p3: and (3) placing a sample to be detected of the environmental water sample into an electrolytic cell, repeating the step (P2), detecting peak current corresponding to metal ions in the sample to be detected through an electrochemical workstation, substituting the peak current into a regression equation, and calculating to obtain the concentration content of the metal ions in the sample to be detected.
The electrolyte during detection comprises lead ions, cadmium ions, magnesium ions, potassium ions, manganese ions and the like.
When the concentration of heavy metal ions in the environmental water sample is 5 mu mol/L or more, the set enrichment time is 100 s.
The stirring speed of the enrichment process is 100-500 rpm.
The electrochemical anodic stripping voltammetry includes, but is not limited to, square wave pulse stripping voltammetry, differential pulse stripping voltammetry, linear stripping voltammetry, and cyclic voltammetry.
The invention has the advantages and beneficial effects that at least comprises:
(1) The Bi/Bi with unique microcosmic film forming structure is designed and synthesized through synchronous improvement of components, proportion and process 2 WO 6 The composite material has the advantages that the outer surface of the composite material after film formation is provided with multiple irregularly distributed petal-shaped micro-convex structures (outwards extending multi-layer, multi-scale, multi-directional and irregularly distributed heavy petal-shaped micro-convex structures are formed on the outer surface of the GCE), the traditional electrode is modified by the material with high-efficiency electrocatalytic performance based on the micro-convex structure characteristics of the film layer surface, so that the electrode has high selectivity, high sensitivity, better anti-interference capability and capability of simultaneously detecting various target components, and the composite material is further designed and synthesized into an excellent electrocatalytic material modified electrode, so that the electrode can be used for simultaneously and rapidly detecting various heavy metal ions and can better solve the existing problems of high selectivity, high sensitivity and ultra-wide linear detection range of the heavy metal ion electrochemical sensorThe technology has problems.
(2) The bismuth-doped high-performance electrocatalytic composite material Bi/Bi provided by the invention 2 WO 6 The electrode is modified by the electrocatalytic material with high electrocatalytic performance, excellent design and synthesis performance, and has the linear detection range (0.3-30 mu mol/L and 0.4-30 mu mol/L) of ultra-wide cadmium ions and lead ions in aqueous solution as an electrochemical sensor, and has the advantages of good selectivity, high sensitivity and good anti-interference performance.
(3) The invention adopts a hydrothermal synthesis method to prepare the high-performance electrocatalytic composite material Bi/Bi 2 WO 6 The composite material has few steps, and the preparation process is not complex, and is easy for mass preparation. In addition, the method of dripping and evaporating the solvent is utilized to quickly form the uniform electrode film on the surface of the electrode, and the process of preparing the film only needs a small amount of time (usually 30-60 s), so that the electrochemical sensor is easy to prepare in batches and has low cost.
(4) The electrochemical sensor prepared by the modified material of the working electrode has the advantages of large electrochemical active area, fast electron transmission, high anti-interference performance, high electrocatalytic capacity and the like, and can realize high-sensitivity simultaneous detection of cadmium and lead ions. The results show that the Bi/Bi 2 WO 6 The composite material film has higher electrocatalytic performance, can be used as an electrochemical sensor, and can be used for rapidly and simultaneously detecting trace heavy metal lead ions (Pb) in water samples of environmental water bodies 2+ ) And cadmium ions (Cd) 2+ ) The detection limits of the (C) are 0.11 mu mol/L and 0.14 mu mol/L, respectively.
(5) The electrochemical sensor provided by the invention has good selectivity and high sensitivity in the process of synchronously detecting heavy metal lead and cadmium ions, and can realize lead ion (Pb) 2+ ) And cadmium ions (Cd) 2+ ) The simultaneous determination of two heavy metals has high anti-interference performance;
(6) The invention provides a heavy metal ion electrochemical sensor and application thereof, which is characterized in that Bi/Bi is adopted in the electrochemical sensor 2 WO 6 The composite material film is formed to prepare a working electrode, and is applied to a three-electrode system and a composite electrode systemAs the surface modification of the electrode, the simultaneous detection of cadmium and lead ions is realized by dynamically optimizing the standing time/the dripping amount/the enrichment time, the synchronous detection of cadmium and lead ions in the aqueous solution can be realized, and the method has excellent sensitivity and wider linear detection range. The method has high analysis speed, can be directly measured, and can meet the requirement of on-site rapid detection. The modification material Bi/Bi of the working electrode provided by the invention 2 WO 6 The composite material has the advantages of large electrochemical active area, fast electron transmission, high anti-interference performance, strong electrocatalytic capacity and the like after film formation, and can realize high-sensitivity simultaneous detection of cadmium and lead ions.
(7) The electrochemical sensor provided by the invention is based on Bi/Bi 2 WO 6 The microstructure of the composite material and the film reproducibility are good, and 10 mu mol/L lead ion (Pb) 2+ ) And cadmium ions (Cd) 2+ ) The solution was subjected to 5 parallel experiments, and the repeated condition of the modified electrode peak was observed, and the result of the relative standard deviation RSD of less than 6.1% was obtained, which indicates that the reproducibility of the film was good.
Drawings
FIG. 1 shows Bi/Bi prepared in the embodiment of the present invention 2 WO 6 Surface SEM image of composite material after film formation; wherein a is an SEM image of 3 μm scale; b is an SEM image of 1 μm scale;
FIG. 2 is a schematic diagram of the working principle and structure of the heavy metal ion electrochemical sensor of the invention;
FIG. 3 shows the preparation of Bi according to the embodiment of the present invention 2 WO 6 Material and Bi/Bi 2 WO 6 XRD pattern of the composite material;
FIG. 4 shows cadmium ions and lead ions at the bare electrode and Bi/Bi according to an embodiment of the present invention 2 WO 6 Differential pulse voltammogram on composite film modified electrode and Bi/Bi 2 WO 6 Differential pulse voltammogram of the composite membrane modified electrode in a blank solution;
FIG. 5 is a graph showing differential pulse voltammograms of different concentrations of cadmium ions and lead ions on the electrochemical sensor in accordance with an embodiment of the present invention;
FIG. 6 is a graph showing the linear relationship between the concentration of cadmium ions and lead ions and the current, in which: a is a linear relation diagram of the concentration of cadmium ions and current, and B is a linear relation diagram of the concentration of lead ions and current;
FIG. 7 shows Bi/Bi prepared in the embodiment of the present invention 2 WO 6 Differential pulse voltammogram of 5 parallel tests of the composite membrane modified electrode in cadmium ion and lead ion solutions.
Reference numerals:
1. a detection pool; 2. a sample to be detected; 3. a computer; 4. an electrochemical workstation; 5. a counter electrode; 6. a working electrode; 7. a reference electrode.
The present invention will be described in detail with reference to the accompanying drawings and examples.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to the above, and the reagents and methods used in the examples, unless otherwise specified, all employ conventional reagents and methods.
Example 1
The bismuth-doped high-performance electrocatalytic composite material provided by the invention is bismuth-doped bismuth tungstate Bi/Bi 2 WO 6 A composite material.
The preparation method of the bismuth-doped high-performance electrocatalytic composite material comprises the following steps:
s1: na is mixed with 2 WO 4 ·2H 2 O and hexadecyl trimethyl ammonium bromide (CTAB) are respectively added into deionized water, and the solution is uniformly mixed by magnetic stirring to obtain a mixed solution;
s2: taking Bi (NO) in a set proportion 3 ) 3 ·5H 2 O addingAdding the mixture into the mixed solution, fully stirring, transferring the mixed solution into an autoclave, and maintaining the mixed solution for a set period of time under a high temperature condition to obtain a reaction product;
s3: washing the reaction product with deionized water and ethanol respectively, and drying to obtain bismuth-doped bismuth tungstate Bi/Bi 2 WO 6 A composite material.
An electrochemical sensor for heavy metal ions comprises the bismuth-doped high-performance electrocatalytic Bi/Bi 2 WO 6 A composite material.
The preparation method of the heavy metal ion electrochemical sensor comprises the following steps:
A. Bi/Bi 2 WO 6 Adding the composite material into ethanol solution, and performing ultrasonic treatment for 30min to obtain Bi/Bi 2 WO 6 Dripping the coating liquid on the electrode;
B. Bi/Bi 2 WO 6 Dripping the electrode coating liquid on the surface of the prepared clean and dry glassy carbon electrode GCE, uniformly coating, drying, and obtaining the Bi/Bi with the outer surface covered by the multiple petal-shaped microscopic convex structures after the solvent is evaporated to form a film and the surface has no layering section 2 WO 6 Heavy metal ion electrochemical sensor of membrane.
The ethanol solution in the step A is ethanol water solution with the mass concentration of 50 and wt percent.
The application of the heavy metal ion electrochemical sensor takes the heavy metal ion electrochemical sensor as a working electrode, and is applied to simultaneous determination of the concentration of two or more heavy metal ions in an environmental water body by an electrochemical method, wherein the heavy metal ions comprise lead ions (Pb) 2 + ) And cadmium ions (Cd) 2+ ) The method comprises the following steps:
p1: preparing Bi/Bi with multiple petal-shaped microscopic convex structures on the outer surface in advance 2 WO 6 A GCE in a film form as a heavy metal ion electrochemical sensor, and further prepared as a working electrode;
p2: one end of a working electrode (heavy metal ion electrochemical sensor), one end of a counter electrode and one end of a reference electrode are respectively connected to an electrochemical workstation, the other ends of the working electrode, the counter electrode and the reference electrode are respectively placed in metal ion-containing electrolyte with known concentration in an electrolytic cell, detection is carried out by using an electrochemical anode stripping voltammetry, an enrichment potential is set to be-1.1V, while enrichment, solution is stirred, stirring is stopped after the enrichment is finished for a set enrichment duration, after standing for a set duration (such as 10 s), a group of forward scanning voltages with a voltage scanning range of-1V to 0.3V are applied to a three-electrode system, the change condition of current-voltage is recorded by the electrochemical workstation, a current-voltage curve is obtained, the concentration of the heavy metal ions is taken as an abscissa, a peak current is taken as an ordinate, a standard curve corresponding to the metal ions is drawn, a regression equation is obtained, and a linear or nonlinear relation between the concentration of the metal ions and the peak current is determined;
p3: and (3) placing the sample to be detected of the environmental water body into an electrolytic cell, repeating the step (P2), detecting peak current corresponding to heavy metal ions in the sample to be detected through an electrochemical workstation, substituting the peak current into a regression equation, and calculating to obtain the concentration content of the metal ions in the sample to be detected (the water sample collected from the environmental water body).
The electrolyte during detection comprises lead ions, cadmium ions, magnesium ions, potassium ions, manganese ions and the like; the working electrode is an independent electrode or a working electrode in the composite electrode; when the concentration of heavy metal ions in an environmental water sample is 5 mu mol/L or more, the set enrichment time is not less than 80 s, the enrichment time can be generally set to be 80-120 s so as to fully enrich, and the enrichment effect is better when 100s are generally selected. When the concentration of heavy metal ions in the environmental water sample is below 5 mu mol/L, the set enrichment time can be less than 80 s.
The embodiment of the invention focuses on designing and synthesizing a material with a unique microstructure and high-efficiency electrocatalytic performance to modify a traditional electrode through synchronous improvement of components, proportions and processes of a composite material, so that the electrode has high selectivity, high sensitivity, better anti-interference capability and capability of detecting various target components at the same time, and further designs and synthesizes an excellent electrocatalytic material modified electrode to prepare a heavy metal ion electrochemical sensor with high sensitivity and ultra-wide linear detection range, which can be used for simultaneously and rapidly detecting various heavy metal ions to pointedly solve the problems existing in the prior art.
More specific examples are described below.
Example 2
Referring to fig. 1-7, the bismuth-doped high-performance electrocatalytic composite material, the preparation method and the application thereof provided by the invention are embodied on the basis of the embodiment 1.
The preparation method of the bismuth-doped high-performance electrocatalytic composite material provided by the embodiment comprises the following steps:
s1: will be 0.1 mmol Na 2 WO 4 ·2H 2 O and 0.1. 0.1 g hexadecyl trimethyl ammonium bromide (CTAB) are respectively added into 80 mL deionized water, and the solution is uniformly mixed by magnetic stirring for 30min to obtain a mixed solution;
s2: 0.4 mmol Bi (NO) 3 ) 3 ·5H 2 Adding O into the mixed solution, after fully stirring, transferring the mixed solution into a 100 mL polytetrafluoroethylene lining autoclave, and keeping the temperature at 120 ℃ for 24 h to obtain a reaction product;
s3: washing the reaction product with deionized water and ethanol for 3 times, and drying in a 60 deg.C drying oven for 12 h to obtain bismuth doped bismuth tungstate Bi/Bi 2 WO 6 The composite material has a multi-petal-shaped microscopic convex structure after film formation.
The bismuth-doped high-performance electrocatalytic composite material prepared by the embodiment of the invention is bismuth-doped bismuth tungstate Bi/Bi with multiple petal-shaped microscopic bulge structures after film formation 2 WO 6 The surface of the film layer of the composite material has a unique microstructure, and the SEM image of the surface of the composite material is shown in figure 1. As can be seen from FIG. 1, after the composite material is formed on the GCE surface, the film layer has a microstructure of a plurality of lamellar (multi-layer, multi-scale, freely-stretched heavy petal-shaped) bulges which extend outwards from the outer surface of the glassy carbon electrode GCE at the micron scale and are irregularly arranged, namely a structure of multiple irregularly distributed petal-shaped microscopic bulges, and the outwards extending direction, length, height, width, area and the like of each petal-shaped bulge are irregular, and the whole film layer is formedThe surface of the catalyst has staggered distribution and mutual position compensation, so that the catalyst has large electrochemical active area, fast electron transmission and higher electrocatalytic performance.
An electrochemical sensor for heavy metal ions, which comprises the bismuth-doped high-performance electrocatalytic Bi/Bi 2 WO 6 A composite material.
The preparation method of the heavy metal ion electrochemical sensor comprises the following steps:
A. Bi/Bi 2 WO 6 Adding the composite material into ethanol solution, and performing ultrasonic treatment for 30min to obtain Bi/Bi 2 WO 6 Dripping the coating liquid on the electrode; wherein the ethanol solution is ethanol water solution with the mass concentration of 50 and wt percent;
B. Bi/Bi 2 WO 6 Dripping the electrode coating liquid on the surface of the prepared clean and dry GCE, uniformly coating, drying under a heating lamp, and obtaining Bi/Bi with multiple petal-shaped microscopic convex structures after film formation after solvent evaporation to form a film and no layering section 2 WO 6 An electrochemical sensor.
The application of the heavy metal ion electrochemical sensor is that the sensor is applied to the simultaneous determination of the concentration of two or more heavy metal ions in an environmental water sample, wherein the two heavy metal ions are lead ions (Pb 2+ ) And cadmium ions (Cd) 2+ ) The method comprises the following steps:
p1: preparing Bi/Bi with multiple petal-shaped microscopic bulge structures in advance 2 WO 6 GCE of the membrane layer is used as a heavy metal ion electrochemical sensor and is used as a working electrode; can be used as a working electrode in a separate electrode or a composite electrode;
p2: one end of a working electrode (heavy metal ion electrochemical sensor) 6, one end of a counter electrode 5 and one end of a reference electrode 7 are respectively connected to an electrochemical workstation 4, the other ends of the working electrode 6, the counter electrode 5 and the reference electrode 7 are respectively placed in a metal ion-containing electrolyte (sample 2 to be detected) with known concentration in a detection tank (electrolytic tank) 1, detection is carried out by using an electrochemical anode stripping voltammetry, the enrichment potential is set to be-1.1V, the solution is stirred while enrichment is carried out, the solution is enriched for a set period (100 s in the embodiment), the stirring is stopped after the enrichment is finished, a set of forward scanning voltage with a voltage scanning range of-1V to 0.3V is applied to a three-electrode system after the standing for a set period of time of s, a current-voltage change condition is recorded by the electrochemical workstation, a current-voltage curve is obtained, the heavy metal ion concentration is taken as an abscissa, a standard curve corresponding to the metal ion is drawn, a regression equation is obtained, and a linear or nonlinear relation between the metal ion concentration and the peak current is determined;
p3: and (3) placing the sample to be detected of the environmental water body into an electrolytic cell, repeating the step S2, detecting peak current corresponding to the metal ions in the sample to be detected through an electrochemical workstation, substituting the peak current into a regression equation, and calculating to obtain the concentration content of each metal ion in the sample to be detected.
The electrolyte during detection comprises lead ions, cadmium ions, magnesium ions, potassium ions, manganese ions and the like.
The stirring speed of the enrichment process is 100-500 rpm.
The electrochemical anodic stripping voltammetry includes, but is not limited to, square wave pulse stripping voltammetry, differential pulse stripping voltammetry, linear stripping voltammetry, and cyclic voltammetry.
Referring to fig. 2, the application provided in this embodiment is that the detection of heavy metal ions in a sample to be detected in an environmental water body is performed in a three-electrode system, which comprises a detection cell 1, a sample to be detected 2, a computer 3, an electrochemical workstation 4, a working electrode 6, a reference electrode 7, and a counter electrode 5, wherein the working electrode 6 has a surface Bi/Bi 2 WO 6 GCE of the membrane is used as an electrochemical sensor of heavy metal ions.
In detection, the heavy metal ion electrochemical sensor (working electrode 6) is placed in a detection cell 1 containing a sample (target object) 2 to be detected, and is electrically connected with an electrochemical workstation 4, and the electrochemical workstation 4 is electrically connected with a computer 3. When the heavy metal ion electrochemical sensor prepared by the embodiment of the invention is used for analyzing the concentration of cadmium ions and lead ions, the computer 3 controls the working procedure of the electrochemical workstation 4, and the signal obtained by the heavy metal ion electrochemical sensor (the working electrode 6) is output to the computer 3 for processing by controlling the electrochemical workstation 4, and the concentration data of each heavy metal ion in the sample 2 to be detected is obtained through analysis.
Example 3
The bismuth-doped high-performance electrocatalytic composite material, the preparation method and the application thereof provided by the embodiment of the invention are based on the embodiment 2, and further provide an optimized preparation method and application of a heavy metal ion electrochemical sensor, wherein the preparation method of the heavy metal ion electrochemical sensor comprises the following steps:
s1: will be 0.1 mmol Na 2 WO 4 ·2H 2 O and 0.1. 0.1 g hexadecyl trimethyl ammonium bromide (CTAB) are respectively added into 80 mL deionized water, and the solution is uniformly mixed by magnetic stirring for 30min to obtain a mixed solution;
s2: 0.4 mmol Bi (NO) 3 ) 3 ·5H 2 Adding O into the mixed solution, after fully stirring, transferring the mixed solution into a 100 mL polytetrafluoroethylene lining autoclave, and keeping the temperature at 120 ℃ for 24 h to obtain a reaction product;
s3: washing the reaction product with deionized water and ethanol for 3 times, drying in a 60 deg.C drying oven for 12 h, and drying to obtain Bi/Bi 2 WO 6 A composite material;
s4: bi/Bi 2 WO 6 Adding the composite material into ethanol solution, and performing ultrasonic treatment for 30min to obtain Bi/Bi 2 WO 6 Dripping the coating liquid on the electrode;
s5: mu.L of Bi/Bi with concentration of 2mg/mL 2 WO 6 The electrode is dripped with the coating liquid, and is dripped on the prepared clean and dry GCE surface, and is uniformly coated, and is dried under a heating lamp, and the Bi/Bi-containing coating liquid is obtained after the solvent is evaporated to form a film without layering section 2 WO 6 GCE of the film to obtain a film having an outer surface uniformly coated with Bi/Bi 2 WO 6 Electrochemical sensor with membrane, and the surface of the sensor is completely covered with Bi/Bi with multiple petal-shaped microscopic convex structures 2 WO 6 The film has moderate thickness, is a heavy metal ion electrochemical sensor with optimal electrochemical sensing performance, and has good reproducibility.
The heavy metal ion electrochemical sensor of the embodiment is adopted to detect a sample to be detected, and measured data are shown in table 1.
TABLE 1
The embodiments of the invention have the following advantages:
(1) The electrochemical sensor has an ultra-wide linear detection range for cadmium ions and lead ions in the aqueous solution. The invention prepares the Bi/Bi with unique micro-membrane structure by utilizing a hydrothermal synthesis method 2 WO 6 A composite material; the synthesis method has the advantages of simple steps, uncomplicated operation and easy control of reaction conditions, thereby being easy for industrialization.
(2) The invention further utilizes the methods of dripping and evaporating solvent to form uniform Bi/Bi on the surface of the electrode 2 WO 6 The composite material film requires little time in the film preparation process; experimental results show that the Bi/Bi 2 WO 6 The composite material film can be used for an electrochemical sensor to detect heavy metal lead ions (Pb) 2+ ) And cadmium ions (Cd) 2+ ) The content is as follows.
(3) By Bi/Bi 2 WO 6 The electrochemical sensor prepared by film forming of the composite material has good selectivity and high sensitivity, and can realize lead ion (Pb) 2+ ) And cadmium ions (Cd) 2+ ) And simultaneously measuring two heavy metals.
(4) The invention has high analysis speed, can directly measure, and can meet the requirement of on-site rapid detection;
(5) The improved Bi/Bi of the present invention 2 WO 6 The reproducibility of the composite material film layer is good, and 10 mu mol/L lead ion (Pb) 2 + ) And cadmium ions (Cd) 2+ ) The solution was subjected to 5 parallel experiments, and the repeated condition of the modified electrode peak was observed, and the result of the relative standard deviation RSD of less than 6.1% was obtained, which indicates that the reproducibility of the film was good.
In summary, the bismuth-doped high-performance electrocatalytic composite material, the preparation method and the application provided by the embodiment of the invention modify the traditional electrode by designing and synthesizing the film material with a unique microstructure and high-efficiency electrocatalytic performance, so that the electrode has high selectivity, high sensitivity, better anti-interference capability and capability of detecting various target components simultaneously, and further the electrode modified by the electrocatalytic material with excellent design and synthesis is prepared into the heavy metal ion electrochemical sensor with high sensitivity and ultra-wide linear detection range, so that the electrochemical sensor is used for rapidly detecting various heavy metal ions, solves various defects in the prior art, and can be prepared and applied in a large scale with low cost and high efficiency.
The bismuth doped high-performance electrocatalytic composite material with the multi-petal-shaped microscopic bulge structure after film formation, the preparation method and the application thereof in electrochemical detection of heavy metal ions, provided by the embodiment of the invention, are characterized in that the electrochemical sensor is based on Bi/Bi with unique microstructure and high electrocatalytic performance 2 WO 6 The film layer of the composite material is applied to the surface modification of the working electrode in the traditional three-electrode system and the composite electrode system, and realizes the simultaneous detection of cadmium and lead ions by dynamically optimizing the standing time/the dripping amount/the enrichment time. The modified material of the working electrode provided by the invention has the advantages of easiness in preparation, low cost, strong electrocatalytic capacity and the like, can realize simultaneous detection of cadmium and lead ions, and is free from interference of other metal ions in the detection process and high in anti-interference performance.
In other embodiments of the present invention, the technical effects described in the present invention may be achieved by selecting different schemes in detail within the ranges of steps, components, proportions, instrument process parameters and conditions described in the present invention, so the present invention is not listed one by one.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or modifications to equivalent embodiments using the methods and technical contents disclosed above, without departing from the scope of the technical solution of the present invention. All equivalent changes of the components, proportions and processes according to the invention are covered in the protection scope of the invention.
Claims (10)
1. The preparation method of the bismuth-doped high-performance electrocatalytic composite material is characterized by comprising the following steps of:
s1: na is mixed with 2 WO 4 ·2H 2 O and hexadecyl trimethyl ammonium bromide (CTAB) are respectively added into deionized water, and the solution is uniformly mixed by magnetic stirring to obtain a mixed solution;
s2: taking Bi (NO) in a set proportion 3 ) 3 ·5H 2 Adding O into the mixed solution, after fully stirring, transferring the mixed solution into an autoclave, and keeping the mixed solution for a set period of time under a high temperature condition to obtain a reaction product;
s3: the reaction product is respectively washed by deionized water and ethanol, and is dried to obtain bismuth doped bismuth tungstate Bi/Bi with multiple irregularly distributed petal-shaped microscopic convex structures after film formation 2 WO 6 A composite material.
2. A bismuth-doped high-performance electrocatalytic composite material is characterized in that the bismuth-doped high-performance electrocatalytic composite material is prepared by adopting the method of claim 1, and the bismuth-doped bismuth tungstate Bi/Bi with multiple irregularly-distributed petal-shaped microscopic bulge structures after film formation 2 WO 6 A composite material.
3. An electrochemical sensor for heavy metal ions, characterized in that the sensor comprises the Bi/Bi composite material with bismuth doped and high performance and electrocatalytic effect as set forth in claim 2 2 WO 6 。
4. A method of manufacturing the heavy metal ion electrochemical sensor of claim 3, comprising the steps of:
A. doping bismuth with bismuth tungstate Bi/Bi 2 WO 6 Adding the composite material into ethanol solution for ultrasonic treatment to obtain Bi/Bi 2 WO 6 Dripping the coating liquid on the electrode;
B. Bi/Bi 2 WO 6 Dripping the electrode coating liquid on the surface of the prepared clean and dry glassy carbon electrode GCE, uniformly coating, drying, and obtaining the Bi/Bi with the outer surface covered by the multiple petal-shaped microscopic convex structures after the solvent is evaporated to form a film and the surface has no layering section 2 WO 6 Heavy metal ion electrochemical sensor of membrane.
5. The method for preparing an electrochemical sensor for heavy metal ions according to claim 4, wherein the step B comprises the following steps:
b1: bi/Bi at a concentration of 2mg/mL 2 WO 6 Dripping the electrode coating liquid on the surface of the glassy carbon electrode GCE, uniformly coating, and drying to obtain the GCE with the outer surface covered with Bi/Bi with multiple petal-shaped microscopic bulge structures 2 WO 6 The electrochemical sensor for heavy metal ions of the membrane has optimal electrochemical sensing performance.
6. The method for preparing the bismuth-doped high performance electrocatalytic composite according to claim 4, wherein the ethanol solution in the step A is an ethanol water solution with a mass concentration of 50 wt%.
7. The use of the electrochemical sensor for heavy metal ions according to claim 3, wherein the electrochemical sensor is used as a working electrode for simultaneous determination of the concentration of two or more heavy metal ions in an environmental water body by an electrochemical method, and the heavy metal ions comprise lead ions and cadmium ions.
8. The use according to claim 7, characterized in that it comprises the steps of:
p1: preparing Bi/Bi with multiple petal-shaped microscopic bulge structures in advance 2 WO 6 GCE of the membrane, as an electrochemical sensor of heavy metal ions, and prepared as a working electrode;
p2: one end of a working electrode, one end of a counter electrode and one end of a reference electrode are respectively connected to an electrochemical workstation, the other ends of the working electrode, the counter electrode and the reference electrode are respectively placed in electrolyte containing metal ions with known concentration in an electrolytic cell, detection is carried out by using an electrochemical anode stripping voltammetry, the enrichment potential is set to be-1.1V, the solution is stirred while enrichment, the stirring is stopped after the enrichment is finished for a set enrichment time period, after the enrichment is finished, the solution is left to stand for the set time period, a set of forward scanning voltages with the voltage scanning range of-1V to 0.3V are applied to a three-electrode system, the change condition of current-voltage is recorded by the electrochemical workstation, a current-voltage curve is obtained, the concentration of heavy metal ions is taken as an abscissa, the peak current is taken as an ordinate, a standard curve corresponding to the metal ions is drawn, a regression equation is obtained, and the linear or nonlinear relation between the concentration of the metal ions and the peak current is determined;
p3: and (3) placing a sample to be detected of the environmental water sample into an electrolytic cell, repeating the step (P2), detecting peak current corresponding to heavy metal ions in the sample to be detected through an electrochemical workstation, substituting the peak current into a regression equation, and calculating to obtain the concentration content of the metal ions in the sample to be detected.
9. The use according to claim 8, characterized in that: the electrolyte during detection comprises lead ions, cadmium ions, magnesium ions, potassium ions and manganese ions; the working electrode is an independent electrode or a working electrode in the composite electrode.
10. The use according to claim 8, characterized in that: when the concentration of heavy metal ions in the sample to be detected is 5 mu mol/L or more, the enrichment time is not less than 80 s.
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