CN115746296B - Three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material, and preparation method and application thereof - Google Patents
Three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material and a preparation method thereof, comprising the following steps: (1) Adding carboxylated carbon nanotubes into an acid solution containing aniline monomers, uniformly dispersing to form a dispersion liquid, and carrying out adsorption soaking for 1-12h; then adding absolute ethyl alcohol into the dispersion liquid; (2) Slowly adding an acid solution containing an oxidant and tetrachloro-gold acid into the absolute ethanol dispersion liquid obtained in the step (1) to carry out a polymerization reaction for 3-10h; (3) After the reaction is finished, separating, washing and drying to obtain the gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material. The composite material provided by the invention has a three-dimensional interconnected mesoporous structure and rich active sites, the uniform loading of gold nanoparticles improves the stability and electrocatalytic activity of the composite material, and the composite material can be used for electrochemical determination of heavy metal pollutants cadmium and lead ions in environmental water bodies, and has high sensitivity and stability.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material, and a preparation method and application thereof.
Background
Polyaniline (PANI) is used as a classical high-molecular conductive polymer, has the advantages of easily available raw materials, simple synthesis, proton acid doping and excellent electrochemical performance, and is widely used in the fields of electrode material preparation, electrochemical sensors, energy sources, catalysis and the like. However, due to the agglomeration characteristic of polyaniline in the polymerization process, bulk polyaniline prepared by the conventional chemical oxidation polymerization method has a disordered stacking structure, a limited surface area, insufficient exposure of active sites, and poor electron transport capability and analyte detection capability. Ordered polyaniline nanowire/nanotube array composites can provide more active sites than bulk polyaniline, allowing for rapid charge transfer and mass transport, which is extremely beneficial for adsorption-desorption and surface reactions involved in the sensing process [ Journal of Hazardous Materials,2020,392:122342,Electrochimica Acta,2021,384:138414]. In addition, polyaniline suffers from poor conductivity and electrochemical activity at pH > 4, which also limits its wide application [ Chemistry of Materials,2005 17 (18): 4600-4609]. Because of the reducibility of polyaniline, many noble metal ions (Au, ag, pt, pd, etc.) can spontaneously reduce to polyaniline, forming metallic nanoparticle decorated PANI. The size of the noble metal nanoparticles and the uniform distribution in the polyaniline are the main factors determining the properties of the composite.
At present, the noble metal nanoparticle@high polymer composite material is prepared by an electrochemical precipitation method, a chemical reduction method, an in-situ polymerization method, an autonomous packaging technology and the like. The Chinese patent with publication number of CN107840957A discloses a method for synthesizing dandelion-shaped gold nanoparticle@polyaniline nanocomposite by a one-pot method, wherein aniline monomers and chloroauric acid are adopted to react, gold nanoparticles are obtained through in-situ reduction, the structure of the composite is a polyaniline-coated gold nanoparticle composite film, however, the dandelion-shaped structure is poor in uniformity in a large range and only exists at one end of a rod, and the gold nanoparticles in the center of the rod are agglomerated and the size is more than 100nm. Chinese patent publication No. CN105461920a discloses a method for synthesizing echinaceous gold nanoparticles and spherical polyaniline in one pot, which requires additional addition of stabilizer polyvinylpyrrolidone, and is complicated in operation and long in reaction time (more than 10 hours). Qian Tang et al [ Journal of Electroanalytic ]al Chemistry,2020,873:114381]The method comprises the steps of taking iron-containing carbon nanofibers prepared by electrostatic spinning as a substrate, synthesizing polyaniline nanosheet arrays, and then depositing gold nanoparticles by self-reduction. However, the process involves multiple steps of synthesis (electrostatic spinning, pre-oxidation, carbonization and the like) of the iron-containing nanofiber, aniline polymerization, self-reduction of gold nanoparticles on polyaniline and the like, and is complex in operation. In addition, the original polyaniline nano-sheet array structure is destroyed by the load of the gold nano-particles, and the specific surface area is reduced. Tong Feng et al [ Sensors and Actuators B:chemical,2022,369:132625 ]]Report on in situ polymerization strategy based synthesis of loaded Ag@SiO 2 Polyaniline nanofiber composite material of core-shell nano-ions, but due to the disordered growth of polyaniline, ag is wrapped in SiO 2 The core-shell structure in the nano particles is directly not connected with polyaniline sodium, the specific surface area of polyaniline is small, and the electron transfer efficiency is low.
Therefore, it is of great importance to develop an effective strategy for composite materials with high specific surface area and uniform loading of gold nanoparticles.
Disclosure of Invention
The invention provides a three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material and a preparation method thereof.
The technical scheme of the invention is as follows:
the preparation method of the three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material comprises the following steps of:
(1) Adding carboxylated carbon nanotubes into an acid solution containing aniline monomers, uniformly dispersing to form a dispersion liquid, and carrying out adsorption soaking for 1-12h; then adding absolute ethyl alcohol into the dispersion liquid;
(2) Slowly adding an acid solution containing an oxidant and tetrachloro-gold acid into the absolute ethanol dispersion liquid obtained in the step (1) to carry out a polymerization reaction for 3-10h;
(3) After the reaction is finished, separating, washing and drying to obtain the gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material.
According to the preparation method, an in-situ redox and dilute solution polymerization method is adopted, tetrachloroauric acid is used as a gold source, the polyaniline nanowires modified by gold nano are controlled to orderly grow along carbon fibers by regulating and controlling polymerization parameters under the action of an oxidant, the prepared composite material has a mesoporous structure with three-dimensional interconnection and rich active sites, the stability and electrocatalytic activity of the composite material are improved due to uniform loading of gold nano particles, and the composite material has high specific surface area and excellent electron transmission capacity when being used as a modified electrode to construct an electrochemical sensing device, and can be used for electrochemical determination of heavy metal pollutants (cadmium and lead ions) in environmental water body, and high sensitivity and stability.
In the step (1), the acid solution is 0.1-1.0moL/L hydrochloric acid solution.
The concentration of the carbon nano tube in the dispersion liquid obtained in the step (1) is 0.5-2.0g/L; the concentration of the aniline monomer is 0.01-0.05moL/L.
In the step (1), the volume ratio of the dispersion liquid to the absolute ethyl alcohol is 0.5-1.5:1.
The concentration of the oxidant in the acid solution containing the oxidant and the tetrachloroauric acid in the step (2) is 0.01-0.05moL/L; the concentration of the tetrachloroauric acid is 0.005-0.02moL/L.
Further, in the step (2), the acid solution is 0.1-1.0moL/L hydrochloric acid solution; the oxidant is ammonium persulfate.
Preferably, in the step (2), the polymerization temperature is-30-10 ℃ and the polymerization time is 2-6h.
In the step (2), the volume ratio of the absolute ethyl alcohol dispersion liquid obtained in the step (1) to the acid solution containing the oxidant and the tetrachloroauric acid is 0.5-1.5:1.
In the step (2), an acid solution containing an oxidant and tetrachloroauric acid is added dropwise to the absolute ethanol dispersion obtained in the step (1) at a rate of 10-50 mL/h.
In the step (3), gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material is separated through centrifugation; the centrifugal speed is 8000-11000rpm, and the centrifugal time is 3-10min.
The invention also provides the three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material prepared by the preparation method.
Preferably, in the three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material, the diameter of the carbon nanotube is 20-1000nm; the length of the polyaniline nanowire is 20-50nm; the particle size of the gold nanoparticles is 0.2-5nm.
The three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material has a three-dimensional mesoporous-rich structure, and gold nanoparticles are uniformly distributed in the polyaniline nanowire array without aggregation. The polyaniline nanowire has rich active sites, can cooperate with gold nanoparticles with high electrocatalytic activity loaded on the surface, and can greatly improve the high-sensitivity response of analytes (such as heavy metal cadmium ions and lead ions) by using the composite material as a sensing interface.
The invention also provides application of the three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material in electrochemical determination of heavy metal pollutants in environmental water.
Further, the application includes: and constructing an electrochemical sensing device by adopting the three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material modified electrode, and measuring heavy metal pollutants in environmental water by adopting the constructed electrochemical sensing device.
Further, the electrochemical sensing device is constructed by adopting the three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material modified electrode, and the electrochemical sensing device comprises:
dispersing a three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material in water to form a composite material dispersion liquid, coating the composite material dispersion liquid on the surface of a glassy carbon electrode, and drying to obtain a composite material modified electrode;
the composite material modified electrode is used as a working electrode, ag/AgCl is used as a reference electrode, and a three-electrode system is formed by the composite material modified electrode and a counter electrode, so that an electrochemical sensing device is formed.
Further, the heavy metal pollutant is at least one of cadmium ions and lead ions.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts in-situ oxidation-reduction and dilute solution polymerization methods, takes tetrachloro-gold acid as a gold source, does not add any stabilizer or reducer, and can realize the ordered growth of the polyaniline nanowire array modified by gold nanoparticles on the surface of the carbon nanotube by simply regulating and controlling polymerization parameters.
2. The composite material prepared by the invention has a three-dimensional interconnected mesoporous-rich structure, and gold nanoparticles with smaller diameters of 0.2-5nm are uniformly dispersed in the polyaniline nanowire array, so that the specific surface area and electrochemical activity of the composite material are improved, and the application range of the noble metal@polyaniline composite material is widened.
3. The method is simple, efficient, green and environment-friendly, and can be used for large-scale production of the polyaniline nanowire array/carbon nanotube composite material modified by the three-dimensional mesoporous gold nanoparticles.
4. The three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material can be used for electrochemical analysis and determination of trace heavy metal ions in environmental water, and has high sensitivity and stability.
Drawings
FIG. 1 is a schematic diagram of a preparation process of a three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material (denoted as Au-PANI-array@CNT) of the invention;
FIG. 2 is a scanning electron microscope image of Au-PANI-array@CNT in example 1 of the present invention;
FIG. 3 is a transmission electron micrograph (A), a high resolution transmission electron micrograph (B), and a corresponding elemental profile (C) of Au-PANI-array@CNT according to example 1 of the present invention;
FIG. 4 is an XRD pattern for Au-PANI-array@CNT in inventive example 1;
FIG. 5 is a square wave stripping voltammogram of Au-PANI-array@CNT modified glassy carbon electrode measured on cadmium ions of different concentrations in inventive example 1; the curves of the lower left graph are square wave stripping voltammograms of lead ions of 0, 30, 50, 70 and 100 mug/L on the modified electrode from bottom to top in sequence; the upper right interpolation chart is 0,0.1,0.5,2,3,5,7.5 and the square wave stripping voltammogram of 10 mug/L lead ions on the modified electrode from bottom to top;
FIG. 6 is a plot of pore size simulations of BET adsorption curves for CNTs, PANI-array@CNTs in example 2, and Au-PANI-array@CNTs in example 3;
FIG. 7 is a stripping voltammogram of a CNT, PANI-array@CNT in example 2 and Au-PANI-array@CNT modified glassy carbon electrode in example 3 in 0.5M sulfuric acid;
FIG. 8 is a square wave stripping voltammogram of Au-PANI-array@CNT modified glassy carbon electrode in example 3 measured on different concentrations of cadmium ions and lead ions, the square wave stripping voltammogram of lead ions (0,3,5, 10, 15, 20, 25 μg/L) and lead ions (0,1,2,5,7, 10, 15 μg/L) on the modified electrode in order from bottom to top.
Detailed Description
Example 1
The method for preparing the three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material comprises the following specific steps of:
under normal temperature, uniformly dispersing 0.8mmoL aniline monomer in 40mL 1moL/L hydrochloric acid solution, adding 80mg carboxylated carbon nanotubes, uniformly dispersing by ultrasonic, and absorbing and soaking for 8 hours under a stirring state; adding 40mL of absolute ethyl alcohol solution into the solution, regulating the reaction temperature of the solution to be minus 20 ℃, adding an equal volume of hydrochloric acid solution (1 moL/L) containing ammonium persulfate (40 mmoL/L) and tetrachloro-gold acid (10 mmoL/L) into the solution at a sample adding speed of 20mL/h, carrying out polymerization reaction for 6h, centrifuging at a rotating speed of 10000rpm for 5min, washing with absolute ethyl alcohol and water in sequence, and freeze-drying to obtain the three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material.
Characterization of morphology structure: the morphology of the material was characterized by using a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM) (see fig. 2 and 3), and the results show that dendritic polyaniline nanowires grow orderly along the carbon nanotubes, the high-resolution TEM shows a (111) characteristic crystal plane of gold with d=0.23 nm, and the element distribution surface uniformly loads gold nanoparticles in the polyaniline nanowire array. The composite material was characterized by X-ray diffraction (XRD) (see fig. 4), and the peaks of 2θ between 20 and 30 ° were characteristic peaks of polyaniline, and further, the characteristic peaks of the composite material at 38.1,44.4,64.6,77.5 and 81.7 ° correspond to the (110), (200), (220), (311) and (222) crystal planes of gold, indicating that the composite material is composed of gold nanoparticles and polyaniline.
Electrochemical determination of heavy metal ions: the prepared three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material is used for measuring cadmium ions in lake water. The method specifically comprises the following steps:
1.0g/L of Au-PANI-array@CNT dispersion liquid is prepared in a water body, the dispersion is uniform by ultrasonic, 4 mu L of the dispersion liquid is taken to be dripped and modified on the surface of a polished glassy carbon electrode, and the dispersion liquid is naturally dried for standby. The heavy metal determination adopts a square wave stripping voltammetry (SWV), a modified glassy carbon electrode is used as a working electrode, ag/AgCl is used as a reference electrode, a platinum wire is used as a counter electrode to form a traditional three-electrode system, and the three electrodes are immersed in acetic acid-sodium acetate buffer solutions containing cadmium ions with different concentrations (pH=5.5). The parameters of the square wave stripping voltammetry are as follows: the enrichment potential is-1.2V, the enrichment time is 6min, the frequency is 150Hz, the amplitude is 50mV, and the potential increment is 4mV. Each electrode test is completed, the heavy metal deposited on the surface of the electrode is dissolved out for 60 seconds under the condition of +0.6V. According to the obtained stripping voltammogram (figure 5) of cadmium ions at different concentrations, the linear range of the cadmium ions is 0.1-100 mug/L, and the detection limit is 20ng/L. Groundwater (Hangzhou, zhejiang) was collected and filtered through a 0.45 μm microporous filter. 5mL of water sample is taken, 5mL of acetic acid-sodium acetate buffer solution is added, the square wave stripping voltammetry is adopted to measure cadmium ions in lake water, the average value of three repeated tests is 0.46 mug/L, and the water quality limit value (3.0 mug/L) of drinking water according to the proposal of the world and sanitation organization is met.
Example 2
The method for preparing the three-dimensional mesoporous polyaniline nanowire array/carbon nanotube composite material comprises the following specific steps:
under normal temperature, 0.8moL of aniline monomer is uniformly dispersed in 40mL of 1moL/L hydrochloric acid solution, 40mg of carboxylated carbon nano tubes are added, and the mixture is uniformly dispersed by ultrasonic, and is adsorbed and soaked for 8 hours under a stirring state; adding 40mL of absolute ethyl alcohol solution into the solution, regulating the reaction temperature of the solution to be minus 15 ℃, adding equal volumes of ammonium persulfate (20 mmoL/L) and hydrochloric acid solution (1 mmoL/L) into the solution at a sample adding speed of 20mL/h, carrying out polymerization reaction for 5h, centrifuging at a rotating speed of 10000rpm for 5min, washing with absolute ethyl alcohol and water in sequence, and freeze-drying to obtain the three-dimensional mesoporous polyaniline nanowire array/carbon nanotube composite material (PANI-array@CNT).
Example 3
The method for preparing the three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material comprises the following specific steps of:
under normal temperature, 0.8moL of aniline monomer is uniformly dispersed in 40mL of 1moL/L hydrochloric acid solution, 40mg of carboxylated carbon nano tubes are added, and the mixture is uniformly dispersed by ultrasonic, and is adsorbed and soaked for 8 hours under a stirring state; adding 40mL of absolute ethyl alcohol solution into the solution, regulating the reaction temperature of the solution to be minus 15 ℃, adding an equal volume of hydrochloric acid solution (1 moL/L) containing ammonium persulfate (20 mmoL/L) and tetrachloro-gold acid (10 mmoL/L) into the solution at a sample adding speed of 20mL/h, carrying out polymerization reaction for 5h, centrifuging at a rotating speed of 10000rpm for 5min, washing with absolute ethyl alcohol and water in sequence, and freeze-drying to obtain the three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material.
Specific surface area and pore size analysis: the nitrogen adsorption-desorption curves of three composite materials of Carbon Nanotube (CNT), PANI-array@cnt prepared in example 2 and Au-PANI-array@cnt prepared in example 3 were measured using a gas analyzer, the specific surface area (BET) of the materials was analyzed, and the pore diameters were fitted (fig. 6). The specific surface areas of the CNT, PANI-array@CNT and Au-PANI-array@CNT are 36.44,55.64 and 50.03m respectively 2 g -1 The growth of PANI nanowires on the CNT surface results in a composite material with a larger specific surface area. Compared with the CNT, the PANI nanowire grows to enrich the mesopores of the composite material, and the average pore diameter is increased from 14nm to 20nm.
Analysis of electrical activity of PANI: the stripping voltammogram of the different modified electrodes in 0.5M sulfuric acid was analyzed using CV with CNT, PANI-array@CNT and Au-PANI-array@CNT modified glassy carbon electrodes (FIG. 7). In addition to CNT, PANI-array@cnt and Au-PANI-array@cnt both present distinct three pairs of redox peaks, ascribed to PANI in different redox states. The results indicate that PANI nanowire arrays have high electrochemical activity and successfully load on CNT surfaces.
Example 4
The simultaneous detection of cadmium ions and lead ions by the Au-PANI-array@CNT modified glassy carbon electrode specifically comprises the following steps:
1.0g/L of Au-PANI-array@CNT dispersion liquid is prepared in a water body, the dispersion is uniform by ultrasonic, 4 mu L of the dispersion liquid is taken to be dripped and modified on the surface of a polished glassy carbon electrode, and the dispersion liquid is naturally dried for standby. The heavy metal determination adopts a square wave stripping voltammetry (SWV), a modified glassy carbon electrode is used as a working electrode, ag/AgCl is used as a reference electrode, a platinum wire is used as a counter electrode to form a traditional three-electrode system, and the three electrodes are immersed in acetic acid-sodium acetate buffer solutions containing cadmium ions and lead ions in different concentrations (pH=5.5). The parameters of the square wave stripping voltammetry are as follows: the enrichment potential is-1.2V, the enrichment time is 6min, the frequency is 150Hz, the amplitude is 50mV, and the potential increment is 4mV. Each electrode test is completed, the heavy metal deposited on the surface of the electrode is dissolved out for 60 seconds under the condition of +0.6V. According to the obtained stripping voltammogram of cadmium ions and lead ions at different concentrations (fig. 8), two oxidation peaks around-0.76 and-0.54V correspond to the oxidation of cadmium and lead. The peak-to-peak distance of the oxidation peaks is wider, and mutual interference does not exist. In addition, the Au-PANI-array@CNT modified electrode is stored for 60 days at room temperature, and the response current of cadmium ions and lead ions is found to be kept at about 95% and 97% of the initial value, which shows that the modified electrode has higher stability, can be used for simultaneous determination of cadmium ions and lead ions, and has high sensitivity and stability.
The foregoing embodiments have described the technical solutions and advantages of the present invention in detail, and it should be understood that the foregoing embodiments are merely illustrative of the present invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like that fall within the principles of the present invention should be included in the scope of the invention.
Claims (7)
1. The application of the three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material in electrochemical determination of cadmium and/or lead ion pollutants in environmental water is characterized in that the diameter of a carbon nanotube in the three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material is 20-1000nm; the length of the polyaniline nanowire is 20-50nm; the particle size of the gold nano particles is 0.2-5nm;
the preparation method of the three-dimensional mesoporous gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material comprises the following steps:
(1) Adding carboxylated carbon nanotubes into an acid solution containing aniline monomers, uniformly dispersing to form a dispersion liquid, and carrying out adsorption soaking for 1-12h; then adding absolute ethyl alcohol into the dispersion liquid;
(2) Slowly adding an acid solution containing an oxidant and tetrachloro-gold acid into the absolute ethanol dispersion liquid obtained in the step (1) to carry out a polymerization reaction for 3-10h;
(3) After the reaction is finished, separating, washing and drying to obtain the gold nanoparticle modified polyaniline nanowire array/carbon nanotube composite material.
2. The use according to claim 1, wherein the concentration of carbon nanotubes in the dispersion obtained in step (1) is 0.5-2.0g/L; the concentration of the aniline monomer is 0.01-0.05moL/L.
3. The use according to claim 1, wherein in step (1) the volume ratio of dispersion to absolute ethanol is 0.5-1.5:1.
4. The use according to claim 1, wherein the concentration of the oxidizing agent in the acid solution comprising the oxidizing agent and the tetrachloroauric acid of step (2) is 0.01-0.05moL/L; the concentration of the tetrachloroauric acid is 0.005-0.02moL/L.
5. The use according to claim 1, wherein in step (2), the polymerization temperature is from-30 to 10 ℃ and the polymerization time is from 3 to 6 hours.
6. The use according to claim 1, wherein in step (2), the volume ratio of the anhydrous ethanol dispersion obtained in step (1) to the acid solution comprising the oxidizing agent and the tetrachloroauric acid is 0.5-1.5:1.
7. The use according to claim 1, wherein in step (2) the acid solution comprising the oxidizing agent and the tetrachloroauric acid is added dropwise to the anhydrous ethanol dispersion obtained in step (1) at a rate of 10-50 mL/h.
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| CN102051047A (en) * | 2010-11-19 | 2011-05-11 | 南京邮电大学 | Method for preparing carbon nitride tube-polyaniline-gold composite material and application method thereof |
| CN107840957A (en) * | 2017-11-23 | 2018-03-27 | 华南理工大学 | The gold nano grain@polyaniline nano-composite materials of dandelion shape prepared by one kettle way and its preparation method and application |
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