CN112823885B - Gold nanoparticle/cerium dioxide quantum dot co-modified graphite phase carbon nitride nanosheet composite material and preparation method and application thereof - Google Patents
Gold nanoparticle/cerium dioxide quantum dot co-modified graphite phase carbon nitride nanosheet composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a graphite phase carbon nitride nanosheet composite material jointly modified by gold nanoparticles/cerium dioxide quantum dots, and a preparation method and application thereof, wherein the composite material comprises graphite phase carbon nitride nanosheets loaded with cerium dioxide quantum dots and gold nanoparticles modified on the graphite phase carbon nitride nanosheets; the graphite phase carbon nitride nanosheet loaded with the cerium dioxide quantum dots takes the graphite phase carbon nitride nanosheet as a carrier, and the cerium dioxide quantum dots are loaded on the graphite phase carbon nitride nanosheet. The preparation method comprises the step of modifying the gold nanoparticles on a carrier. The composite material has the advantages of strong photoelectric capacity, high light energy utilization rate, good dispersion performance, high stability and the like, can be widely used for detecting and degrading pollutants in the environment as a functional material, and has high use value and application prospect. The preparation method of the composite material has the advantages of simple process, convenient operation, low cost, no need of adding additional chemical auxiliary solvent and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
Description
Technical Field
The invention belongs to the technical field of materials, relates to a functional nano material for detecting and degrading pollutants in the environment, and particularly relates to a graphite phase carbon nitride nanosheet composite material jointly modified by gold nanoparticles/cerium dioxide quantum dots, and a preparation method and application thereof.
Background
In recent years, facing the serious challenges of energy crisis and environmental deterioration, more and more researchers are looking at renewable energy sources such as solar energy, and the semiconductor photoelectric material can convert low-density solar energy into storable high-density energy, can also fully utilize the pollutants in the solar energy degradation and mineralization environment, has the characteristics of low cost, environmental friendliness and the like, and has important application prospects in the aspect of solving energy and environmental problems. Generally, the action of the photoelectrochemical reaction is accelerated by selecting a semiconductor material and/or changing its surface state (surface treatment or modification catalyst). However, the semiconductor photoelectric material generally has the problems of low light energy conversion efficiency, low catalyst selectivity, easy recombination of photogenerated carriers and the like. In order to avoid these disadvantages and to further improve the conversion efficiency of solar energy, it is very important to develop a semiconductor material having high photoelectric properties.
Graphite phase carbon nitride (g-C) as a semiconductor photoelectric material widely used in the fields of photocatalytic degradation of organic pollutants, photocatalytic decomposition of water and the like3N4) Low cost, easy obtaining, and good thermal stability and chemical stability. However, g-C is due to its higher rate of photogenerated electron-hole recombination3N4The method is limited in practical application. The solution currently studied is to construct a heterojunction; the thickness of the carbon nitride is reduced through stripping and hot corrosion to increase high-activity sites and shorten a carrier transmission path; preparing a 2D conjugated layer structure of a nanoporous structure or a destructive material; the band structure and carrier separation efficiency are optimized by utilizing heteroatom doping and defects. Wherein g-C3N4Can be effectively inhibited by compounding with other semiconductor materialsElectron hole recombination efficiency. However, the existing g-C3N4Although the semiconductor nano composite material can enhance the electron conversion efficiency to a certain extent, the simple II-type structure enables the valence band position to move upwards and the conduction band position to move downwards, so that the redox capability of a photoproduction electron hole is reduced, and the g-C is greatly limited3N4The composite material is widely applied. Therefore, the obtained gold nanoparticle/cerium dioxide quantum dot co-modified graphite phase carbon nitride nanosheet composite material has strong photoelectric capacity, high light energy utilization rate, good dispersion performance and high stability, and has very important significance for improving the application range of the graphite phase carbon nitride composite material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a gold nanoparticle/cerium dioxide quantum dot jointly-modified graphite phase carbon nitride nanosheet composite material with strong photoelectric capacity, high light energy utilization rate, good dispersion performance and high stability and a preparation method thereof, and also provides application of the gold nanoparticle/cerium dioxide quantum dot jointly-modified graphite phase carbon nitride nanosheet composite material as a functional material in detecting or degrading pollutants in the environment.
In order to solve the technical problem, the invention adopts the following technical scheme:
a gold nanoparticle/ceria quantum dot co-modified graphite phase carbon nitride nanosheet composite comprises graphite phase carbon nitride nanosheets loaded with ceria quantum dots; gold nanoparticles are modified on the graphite phase carbon nitride nanosheets loaded with the cerium dioxide quantum dots; the graphite phase carbon nitride nanosheet loaded with the cerium dioxide quantum dots is characterized in that the graphite phase carbon nitride nanosheet is used as a carrier, and the graphite phase carbon nitride nanosheet is loaded with the cerium dioxide quantum dots.
According to the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles and the cerium dioxide quantum dots, the mass percentage of the gold nanoparticles in the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles and the cerium dioxide quantum dots is 1-20%; the mass percentage content of the cerium dioxide quantum dots in the graphite phase carbon nitride nanosheet loaded with the cerium dioxide quantum dots is 5-25%; the particle size of the cerium dioxide quantum dots is less than or equal to 20 nm; the particle size of the gold nanoparticles is 8 nm-10 nm.
As a general technical concept, the invention also provides a preparation method of the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles/cerium dioxide quantum dots, which comprises the following steps:
s1, dispersing the graphite phase carbon nitride nanosheets loaded with the cerium dioxide quantum dots in a methanol/water mixed solution to obtain graphite phase carbon nitride nanosheet dispersion liquid loaded with the cerium dioxide quantum dots;
and S2, mixing the cerium dioxide quantum dot-loaded graphite-phase carbon nitride nanosheet dispersion liquid obtained in the step S1 with a chloroauric acid solution under a dark condition, stirring, and carrying out a photoreduction reaction on the obtained mixed liquid under an illumination condition to obtain the gold nanoparticle/cerium dioxide quantum dot co-modified graphite-phase carbon nitride nanosheet composite material.
In step S1, the ceria quantum dot-supported graphite-phase carbon nitride nanosheet is prepared by the following method:
(1) mixing graphite phase carbon nitride nanosheets, cerous nitrate hexahydrate and water, performing ultrasonic treatment, and adding NH under stirring3·H2O, obtaining a mixed solution;
(2) and (2) carrying out hydrothermal reaction on the mixed solution obtained in the step (1), centrifuging and drying to obtain the cerium dioxide quantum dot-loaded graphite-phase carbon nitride nanosheet.
In the above preparation method, the mass ratio of the graphite-phase carbon nitride nanosheet to the cerous nitrate hexahydrate in step (1) is further improved to be 1: 0.1-0.5; the mass ratio of the graphite-phase carbon nitride nanosheets to the water is 1: 150-250; the NH3·H2The volume ratio of O to the sum of the volumes of the graphite-phase carbon nitride nanosheets, the cerous nitrate hexahydrate and the waterThe ratio of the components is 1: 30-50; the ultrasonic time is 30-40 min.
In a further improvement of the above preparation method, in the step (1), the graphite-phase carbon nitride nanosheet is prepared by the following method: heating melamine to 500-550 ℃, calcining for 2h, continuously heating to 550-600 ℃, calcining for 2h, and cooling to obtain a yellow product; and heating the yellow product to 550-600 ℃ and calcining for 4h to obtain the graphite-phase carbon nitride nanosheet.
In the preparation method, the temperature of the hydrothermal reaction in the step (2) is 160-180 ℃; the time of the hydrothermal reaction is 12-16 h; the rotation speed of the centrifugation is 2500 rpm-3500 rpm; the drying is carried out at a temperature of 60 ℃.
In the step S1, the mass-to-volume ratio of the ceria quantum dot-loaded graphite-phase carbon nitride nanosheet to the methanol/water mixed solution is 1 mg: 2mL to 4 mL; the methanol/water mixed solution is prepared by mixing methanol and ultrapure water; the volume ratio of the methanol to the ultrapure water is 1: 5-6.
In the step S2, the volume ratio of the ceria quantum dot-loaded graphite-phase carbon nitride nanosheet dispersion to the chloroauric acid solution is 1: 0.0008-0.004; the chloroauric acid solution is prepared by mixing chloroauric acid and ultrapure water; the mass volume ratio of the chloroauric acid to the ultrapure water is 1 g: 60 mL-120 mL; the stirring time is 1-1.5 h; the photoreduction reaction time is 1-1.5 h.
As a general technical concept, the invention also provides an application of the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles and the cerium dioxide quantum dots or the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles and the cerium dioxide quantum dots prepared by the preparation method as a functional material in detecting or degrading pollutants in the environment.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides gold nanoparticles/cerium dioxideThe quantum dot jointly modified graphite phase carbon nitride nanosheet composite material comprises graphite phase carbon nitride nanosheets loaded with cerium dioxide quantum dots, and the graphite phase carbon nitride nanosheets loaded with the cerium dioxide quantum dots are modified with gold nanoparticles, wherein the graphite phase carbon nitride nanosheets loaded with the cerium dioxide quantum dots are carried by the graphite phase carbon nitride nanosheets which are used as carriers, and the graphite phase carbon nitride nanosheets are loaded with the cerium dioxide quantum dots. In the cerium dioxide quantum dot-loaded graphite-phase carbon nitride nanosheet, the graphite-phase carbon nitride nanosheet has the advantages of simplicity in preparation, environmental friendliness, high controllability, high stability and the like, the cerium dioxide quantum dots are modified on the graphite-phase carbon nitride nanosheet, the absorption capacity of the graphite-phase carbon nitride nanosheet on visible light can be improved, the photocatalytic effect of the material of the graphite-phase carbon nitride nanosheet is further improved, the cerium dioxide quantum dots have a cubic fluorite structure and have a large number of oxygen vacancies, and the formation of the oxygen vacancies is accompanied with the formation of Ce4+And Ce3+The material has unique oxidation-reduction performance due to conversion, and the photoelectric performance of the material can be improved due to the existence of oxygen vacancies, so that the recombination rate of photo-generated electron-hole pairs is further inhibited. In the invention, the gold nanoparticles are an excellent electronic conductor, have a plasma resonance effect (SPR), and are modified on the surface of the graphite-phase carbon nitride nanosheet loaded with cerium dioxide quantum dots, so that the response degree of the material in near-infrared light can be fully improved, and the light energy utilization rate of the material is enhanced; meanwhile, the gold nanoparticles are used as an electronic bridge between the graphite phase carbon nitride nanosheets and the cerium dioxide quantum dots, and an original electron transfer path is changed to form a Z-type heterojunction, so that the gathering position of an electron hole in the traditional II-type heterojunction is changed, photo-generated electrons and holes are gathered on a high-potential energy band respectively, the redox capability of the electron hole is improved, and the composite material has stronger photoelectric capability 2The quantum dots are uniformly distributed in g-C3N4On the nano-chip, the combination skillfully avoids the aggregation effect of quantum dots, ensures the catalytic capability of the composite material, and simultaneously, CeO2Presence of oxygen defects in quantum dots and Ce4+Synergy with Au nanoparticlesThe redox capability of the composite material is further improved under the action of the composite material, so that the photoelectrochemical property of the material is greatly improved. In the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles and the cerium dioxide quantum dots, the gold nanoparticles and the cerium dioxide quantum dots are jointly modified on the surface of the graphite phase carbon nitride nanosheets, so that the material has high visible light absorption capacity and a good photocatalytic effect, has the advantages of high photoelectric capacity, high light energy utilization rate, good dispersion performance, high stability and the like, is widely used for detecting and degrading pollutants in the environment as a functional material, and has high use value and application prospect.
(2) The invention also provides a preparation method of the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles/cerium dioxide quantum dots, the graphite phase carbon nitride nanosheets loaded with the cerium dioxide quantum dots are dispersed in a methanol/water mixed solution, and a chloroauric acid solution is added for carrying out a photoreduction reaction, so that the gold nanoparticles are in-situ modified on the surfaces of the graphite phase carbon nitride nanosheets, and the composite material with strong photoelectric capacity and high stability is prepared. The gold nanoparticles prepared by the preparation method are uniformly dispersed and uniform in size, so that the formed graphite-phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles and cerium dioxide quantum dots is good in stability and strong in photoelectrochemical property, has the advantages of simple process, convenience in operation, low cost, no need of adding an additional chemical auxiliary solvent and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
(3) The invention also provides application of the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles and the cerium dioxide quantum dots as a functional material in detecting or degrading pollutants in the environment, such as application of the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles and the cerium dioxide quantum dots in detecting pollutants in the environment, and specifically, the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles and the cerium dioxide quantum dots is used for preparing a working electrode of the photoelectrochemical aptamer sensor, so that the preparation steps of the working electrode can be reduced, and the detection sensitivity of the photoelectrochemical aptamer sensor can be improved; the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles and the cerium dioxide quantum dots has the advantages of good dispersion performance, high biocompatibility and the like, can improve more active sites and load sites of the aptamer, minimizes the electron diffusion distance, and greatly promotes the separation of electrons and holes, so that the photoelectrochemical analysis performance of the photoelectrochemical aptamer sensor is improved, meanwhile, the synergistic amplification effect of the cerium dioxide quantum dots and the gold nanoparticles, higher conductivity and good thermal stability of the cerium dioxide quantum dots and the gold nanoparticles are benefited, the light energy utilization rate is improved, the separation of the electrons and the holes is promoted, the sensitivity of the photoelectrochemical aptamer sensor is greatly improved, and the signal to noise ratio is reduced, so that the photoelectrochemical aptamer sensor has a wide detection range and a low detection limit. Therefore, the graphite-phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles and the cerium dioxide quantum dots is used as a functional material to prepare the working electrode of the photoelectrochemical aptamer sensor, the electrode can be used for detecting pollutants (such as microcystins) in the environment, can obtain a better detection range and detection limit for detecting the pollutants, has the advantages of high stability, long service life, wide detection range, low detection limit, strong anti-interference capability and the like, and has high use value and good application prospect.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 shows a graphite-phase carbon nitride nanosheet composite (CeO) jointly modified by gold nanoparticles/cerium dioxide quantum dots, prepared in example 1 of the present invention2 QDs/Au/g-C3N4) Graphite phase carbon nitride nanosheet (g-C)3N4) Graphite phase carbon nitride nanosheet (CeO) loaded with cerium dioxide quantum dots2 QDs/g-C3N4) In which (a) is g-C3N4And (b) is CeO2 QDs/g-C3N4And (c) is CeO2 QDs/Au/g-C3N4。
FIG. 2 shows a graphite-phase carbon nitride nanosheet composite (CeO) jointly modified by gold nanoparticles/cerium dioxide quantum dots, prepared in example 1 of the present invention2 QDs/Au/g-C3N4) Graphite phase carbon nitride nanosheet (g-C)3N4) Cerium oxide quantum dots (CeO)2QDs) in which (a) is g-C3N4And (b) is CeO2QDs, (c) is CeO2 QDs/Au/g-C3N4。
FIG. 3 shows a graphite-phase carbon nitride nanosheet composite (CeO) jointly modified by gold nanoparticles and cerium dioxide quantum dots, prepared in example 1 of the present invention2 QDs/Au/g-C3N4) Graphite phase carbon nitride nanosheet composite material (CeO) loaded with cerium dioxide quantum dots2 QDs/g-C3N4) Graphite phase carbon nitride nanosheet (g-C)3N4) Cerium oxide quantum dots (CeO) 2QDs) in a uv-vis diffuse reflectance pattern.
Fig. 4 is a graph of photocurrent generated after light excitation of the graphite-phase carbon nitride nanosheet composite material jointly modified with gold nanoparticles/cerium dioxide quantum dots with different gold nanoparticle contents, prepared in embodiments 1 to 4 of the present invention.
Fig. 5 is a graph of photocurrent curves generated by graphite-phase carbon nitride nanosheets loaded with cerium dioxide quantum dots after being excited by light according to different cerium dioxide quantum dot contents prepared in the present invention.
Fig. 6 is a photo current response diagram corresponding to the photo-electrochemical aptamer sensor detecting MC-LR solutions with different concentrations in example 5 of the present invention.
FIG. 7 is a linear regression graph of the photo current variation versus MC-LR at different concentrations in example 5 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
In the following examples, unless otherwise specified, the raw materials and equipment used were commercially available, the process used was a conventional one, the equipment used was conventional, and the data obtained were average values of three or more repeated experiments.
The light source is taken from a high-brightness xenon lamp parallel light source system instrument, and a 300W xenon lamp (Beijing Pofely) is taken as a visible light source. The visible light of the xenon lamp was filtered off with a 420nm filter. Electrochemical experiments used the CHI660B electrochemical workstation (Shanghai Chenghua instruments, Inc.) and utilized a conventional three-electrode system, modified conductive glass electrode as the working electrode, platinum wire electrode as the counter electrode, and Saturated Calomel Electrode (SCE) as the reference electrode (all potentials relative to SCE).
Example 1
Graphite phase carbon nitride nanosheet composite material (CeO) jointly modified by gold nanoparticles/cerium dioxide quantum dots2QDs/Au/g-C3N4) The cerium dioxide quantum dot-loaded graphite-phase carbon nitride nanosheet is characterized by comprising a cerium dioxide quantum dot-loaded graphite-phase carbon nitride nanosheet, wherein gold nanoparticles are modified on the cerium dioxide quantum dot-loaded graphite-phase carbon nitride nanosheet, the cerium dioxide quantum dot-loaded graphite-phase carbon nitride nanosheet takes the graphite-phase carbon nitride nanosheet as a carrier, and the graphite-phase carbon nitride nanosheet is loaded with the cerium dioxide quantum dot.
In the embodiment, the mass percentage of gold nanoparticles in the graphite-phase carbon nitride nanosheet composite material jointly modified by gold nanoparticles/cerium dioxide quantum dots is 5%; the mass percentage of the cerium dioxide quantum dots in the graphite phase carbon nitride nanosheet loaded with the cerium dioxide quantum dots is 10%.
In the embodiment, the particle size of the cerium dioxide quantum dots is less than or equal to 20 nm; the particle size of the gold nanoparticles was 10 nm.
In this embodiment, ceria quantum dots are modified on the surface of the graphite-phase carbon nitride nanosheets by a hydrothermal reaction method, and further, gold nanoparticles are uniformly dispersed on the surface of the graphite-phase carbon nitride nanosheets by a photo-reduction method.
The graphite phase carbon nitride nanosheet composite material (CeO) jointly modified by gold nanoparticles/cerium dioxide quantum dots in the embodiment 2 QDs/Au/g-C3N4) The preparation method comprises the following steps:
(1) 6.0g of melamine is addedSpreading amine powder in a crucible, placing in a muffle furnace, heating from room temperature to 520 ℃ for calcining for 2h, continuing heating to 550 ℃ for calcining for 2h, and cooling to obtain a yellow product, which is recorded as B-g-C3N4。
(2) Weighing 3.0g of the yellow product obtained in the step (1), paving the yellow product in a crucible, putting the crucible into a muffle furnace, heating to 550 ℃, and calcining for 4h to obtain graphite-phase carbon nitride nanosheets marked as g-C3N4。
(3) Weighing 0.3g of graphite-phase carbon nitride nanosheet obtained in step (2), mixing with 0.04g of cerous nitrate hexahydrate, dissolving in 60mL of water, performing ultrasonic treatment for 30min, and adding 2mL of NH under stirring3·H2And O, obtaining a mixed solution. Pouring the mixed solution into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a matched steel sleeve, putting the polytetrafluoroethylene lining into an oven, raising the temperature from room temperature to 170 ℃, keeping the temperature for 12 hours, cooling to room temperature, centrifuging the obtained light yellow mixed solution at the speed of 2500rpm, drying the product obtained by centrifuging at the temperature of 60 ℃ to obtain the graphite-phase carbon nitride nanosheet loaded with cerium dioxide quantum dots, and marking the graphite-phase carbon nitride nanosheet as CeO2QDs/g-C3N4。
(4) Weighing 10mg of the ceria quantum dot-loaded graphite-phase carbon nitride nanosheet prepared in the step (3), placing the graphite-phase carbon nitride nanosheet into 20mL of methanol/water mixed solution (the methanol/water mixed solution is prepared by mixing methanol and ultrapure water, wherein the volume ratio of the methanol to the ultrapure water is 1: 5), and uniformly mixing to obtain ceria quantum dot-loaded graphite-phase carbon nitride nanosheet dispersion liquid. Adding 25 mu L of chloroauric acid solution (the mass-volume ratio of chloroauric acid to ultrapure water in the chloroauric acid solution is 1 g: 120mL) into the graphite-phase carbon nitride nanosheet dispersion liquid loaded with cerium dioxide quantum dots, stirring for 1h under the condition of keeping out of the sun, carrying out photoreduction reaction for 1h under the irradiation of a xenon lamp to generate gold nanoparticles, enabling the gold nanoparticles to be modified on the surface of the graphite-phase carbon nitride nanosheets, centrifuging, drying, and obtaining the graphite-phase carbon nitride nanosheet composite material modified by the gold nanoparticles/cerium dioxide quantum dots together, which is recorded as CeO 2 QDs/Au/g-C3N4。
Monomer cerium dioxide quantum dot (CeO)2QDs) preparationThe preparation method comprises the following steps:
weighing 0.04g cerous nitrate hexahydrate, dissolving in 60mL water, performing ultrasonic treatment for 30min, and adding 2mL NH under stirring3·H2And O, obtaining a mixed solution. Pouring the mixed solution into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a matched steel sleeve, putting the polytetrafluoroethylene lining into an oven, heating the temperature from room temperature to 170 ℃, keeping the temperature for 12 hours, cooling the mixture to room temperature, centrifuging the obtained mixed solution at the speed of 2500rpm, drying the product obtained by centrifugation at the temperature of 60 ℃ to obtain cerium dioxide quantum dot monomers, and marking the cerium dioxide quantum dot monomers as CeO2QDs。
Graphite phase carbon nitride nanosheet composite (CeO) jointly modified by gold nanoparticles/cerium dioxide quantum dots prepared in embodiment 1 of the invention2 QDs/Au/g-C3N4) Graphite phase carbon nitride nanosheet (g-C)3N4) Graphite phase carbon nitride nanosheet (CeO) loaded with cerium dioxide quantum dots2 QDs/g-C3N4) And (5) carrying out transmission electron microscope imaging analysis. The results are shown in FIG. 1. FIG. 1 shows a graphite-phase carbon nitride nanosheet composite (CeO) jointly modified by gold nanoparticles/cerium dioxide quantum dots, prepared in example 1 of the present invention2 QDs/Au/g-C3N4) Graphite phase carbon nitride nanosheet (g-C)3N4) Graphite phase carbon nitride nanosheet (CeO) loaded with cerium dioxide quantum dots 2 QDs/g-C3N4) In the transmission electron micrograph of (a), wherein (a) is g-C3N4And (b) is CeO2 QDs/g-C3N4And (c) is CeO2 QDs/Au/g-C3N4. As can be seen from fig. 1(a), the graphite phase carbon nitride exhibits a typical lamellar structure, and the surface is not smooth. As can be seen from the graph (b), the ceria quantum dots are uniformly distributed on the surface of the graphite phase carbon nitride nanosheets, have extremely small and uniform sizes, and are well combined with the graphite phase carbon nitride nanosheets. As can be seen from the graph (c), the gold nanoparticles are uniformly dispersed on the surface of the graphite phase carbon nitride nanosheets, the particle size is uniform, the particle diameter is 10nm, the successful preparation of the gold nanoparticles is illustrated, and the gold nanoparticles and the graphite phase carbon nitride nanosheets loaded with the cerium dioxide quantum dots are well compoundedTogether.
Graphite phase carbon nitride nanosheet composite (CeO) jointly modified by gold nanoparticles/cerium dioxide quantum dots prepared in embodiment 1 of the invention2 QDs/Au/g-C3N4) Graphite phase carbon nitride nanosheet (g-C)3N4) Cerium oxide quantum dots (CeO)2QDs) were subjected to X-ray diffraction analysis. The results are shown in FIG. 2. FIG. 2 shows a graphite-phase carbon nitride nanosheet composite (CeO) jointly modified by gold nanoparticles/cerium dioxide quantum dots, prepared in example 1 of the present invention2 QDs/Au/g-C3N4) Graphite phase carbon nitride nanosheet (g-C) 3N4) Cerium oxide quantum dots (CeO)2QDs) in which (a) is g-C3N4And (b) is CeO2QDs, (c) is CeO2 QDs/Au/g-C3N4. As can be seen from FIG. 2(a), g-C3N4Shows two characteristic peaks of graphite phase carbon nitride nano-sheets (100) and (002), CeO2QDs exhibit eight characteristic peaks for ceria quantum dots (111), (200), (220), (311), (222), (400), (420), (331), while gold nanoparticles/ceria quantum dots co-modified graphitic phase carbon nitride nanosheet composites (CeO)2 QDs/Au/g-C3N4) The gold nanoparticle (022) and the characteristic peaks of the graphite phase carbon nitride and cerium dioxide quantum dots are included, which indicates that the gold nanoparticle/cerium dioxide quantum dot co-modified graphite phase carbon nitride nanosheet composite material is successfully prepared.
Graphite phase carbon nitride nanosheet composite (CeO) jointly modified by gold nanoparticles/cerium dioxide quantum dots prepared in embodiment 1 of the invention2 QDs/Au/g-C3N4) Graphite phase carbon nitride nanosheet (g-C)3N4) Cerium oxide quantum dots (CeO)2QDs) was subjected to ultraviolet-visible (UV-vis) diffuse reflectance analysis. The results are shown in FIG. 3. FIG. 3 shows a graphite-phase carbon nitride nanosheet composite (CeO) jointly modified by gold nanoparticles and cerium dioxide quantum dots, prepared in example 1 of the present invention2 QDs/Au/g-C3N4) And graphite phase carbon nitride nanosheet composite loaded with cerium dioxide quantum dots Composite material (CeO)2 QDs/g-C3N4) Graphite phase carbon nitride nanosheet (g-C)3N4) Cerium oxide quantum dots (CeO)2QDs) ultraviolet-visible diffuse reflectance pattern. As can be seen from FIG. 3, CeO2QDs/Au/g-C3N4Relative to the simple g-C3N4And CeO2QDs are red-shifted to a certain extent, and the absorbance of light is relative to that of CeO2 QDs/g-C3N4A great lift occurs. Thus, it is found that in g-C3N4Upper modification of CeO2QDs and Au can improve the photoresponse range of the composite material and further improve the photoelectric conversion capability of the material.
From the results of fig. 1 to 3, it can be seen that the gold nanoparticle/ceria quantum dot co-modified graphite phase carbon nitride nanosheet composite (CeO) of the present invention2 QDs/Au/g-C3N4) The cerium dioxide nano-particles are of a regular sheet structure, the cerium dioxide quantum dots are extremely small in size and are uniformly distributed, the size of the gold nano-particles is 10nm, and the gold nano-particles are uniformly dispersed on the surface of the graphite phase carbon nitride nano-sheet.
The graphite phase carbon nitride nanosheet composite material (CeO) jointly modified by gold nanoparticles/cerium dioxide quantum dots in the embodiment2 QDs/Au/g-C3N4) The functional nano material can be used for detecting the microcystin, wherein the microcystin is microcystin (MC-LR).
The graphite phase carbon nitride nanosheet composite material (CeO) jointly modified by gold nanoparticles/cerium dioxide quantum dots in the embodiment 2 QDs/Au/g-C3N4) The functional nano material can be used for degrading microcystin, wherein the microcystin is microcystin (MC-LR).
Example 2
A gold nanoparticle/ceria quantum dot co-modified graphite phase carbon nitride nanosheet composite material (CeO) and the gold nanoparticle/ceria quantum dot co-modified graphite phase carbon nitride nanosheet composite material in example 12QDs/Au/g-C3N4) Essentially the same, differing only in that: gold nanoparticles of example 2The mass percentage of gold nanoparticles in the graphite-phase carbon nitride nanosheet composite material jointly modified by the cerium dioxide quantum dots is 10%.
Example 3
A gold nanoparticle/ceria quantum dot co-modified graphite phase carbon nitride nanosheet composite material (CeO) and the gold nanoparticle/ceria quantum dot co-modified graphite phase carbon nitride nanosheet composite material in example 12QDs/Au/g-C3N4) Essentially the same, differing only in that: the mass percentage of gold nanoparticles in the gold nanoparticle/ceria quantum dot co-modified graphite-phase carbon nitride nanosheet composite material of example 3 was 15%.
Example 4
A gold nanoparticle/ceria quantum dot co-modified graphite phase carbon nitride nanosheet composite material (CeO) and the gold nanoparticle/ceria quantum dot co-modified graphite phase carbon nitride nanosheet composite material in example 1 2QDs/Au/g-C3N4) Essentially the same, differing only in that: the mass percentage of gold nanoparticles in the gold nanoparticle/ceria quantum dot co-modified graphite phase carbon nitride nanosheet composite of example 4 was 20%.
Fig. 4 is a graph of photocurrent generated after light excitation of the graphite-phase carbon nitride nanosheet composite material jointly modified with gold nanoparticles/cerium dioxide quantum dots with different gold nanoparticle contents, prepared in embodiments 1 to 4 of the present invention. As can be seen from fig. 4, the graphite-phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles and the cerium dioxide quantum dots with different gold nanoparticle contents, prepared by the method disclosed by the invention, can generate a relatively high photocurrent after being excited by light, wherein when the mass percentage of the gold nanoparticles is 5 wt%, the generated photocurrent is maximum, which indicates that the photoelectric conversion efficiency is highest at the moment, which indicates that the construction of a Z-type system is more ideal due to the addition of the gold nanoparticles, and the absorption of the composite material on visible light is promoted, so that the transfer rate of a photon-generated carrier is increased. And because the size of the gold nanoparticles is small, excessive gold nanoparticles are also easy to gather on the surface of the graphite carbon nitride carbon nanosheet, and the photoelectric effect of the graphite carbon nitride carbon nanosheet is influenced, so that when the mass percentage of the gold nanoparticles is 1-20%, the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles/cerium dioxide quantum dots has high photoelectric capacity and stability, and particularly when the mass percentage of the gold nanoparticles is 5%, the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles/cerium dioxide quantum dots obtains the optimal photoelectric capacity and stability.
Furthermore, the influence of different cerium dioxide quantum dot contents on the photocurrent of the graphite phase carbon nitride nanosheet loaded with cerium dioxide quantum dots is also examined, and the structure is shown in fig. 5. Fig. 5 is a graph of photocurrent curves generated by graphite-phase carbon nitride nanosheets loaded with cerium dioxide quantum dots after being excited by light according to different cerium dioxide quantum dot contents prepared in the present invention. From fig. 5, it can be seen that when the mass percentage of the ceria quantum dots is 5. wt% to 10. wt%, the generated photocurrent is gradually increased, which indicates that the introduction of the ceria quantum dots can promote the transfer of the photogenerated carriers in the composite material. When the mass fraction of the cerium oxide quantum dots is 10-25. wt%, the generated photocurrent is gradually reduced, which is presumed to be because excessive cerium oxide quantum dots are easily accumulated on the surface of the graphite carbon nitride carbon nanosheet, so that the photoelectric effect is influenced, and the photoelectric conversion capability is weakened. Therefore, the mass percentage of the cerium dioxide quantum dots in the graphite phase carbon nitride nanosheets loaded with the cerium dioxide quantum dots is 5% -25%, the material obtains high photocurrent and high photoelectric capacity, and particularly, when the mass percentage of the cerium dioxide quantum dots is 10%, the graphite phase carbon nitride nanosheets loaded with the cerium dioxide quantum dots obtain the maximum photocurrent, and the optimal photoelectric capacity is obtained.
Example 5
Graphite phase carbon nitride nanosheet composite material (CeO) jointly modified by gold nanoparticles/cerium dioxide quantum dots2QDs/Au/g-C3N4) The functional nano material is applied to the detection of the phycotoxin, and particularly a graphite phase jointly modified by gold nano particles/cerium dioxide quantum dots is consideredCarbon nitride nanosheet composite (CeO)2 QDs/Au/g-C3N4) The application of the prepared photoelectrochemical aptamer sensor in detecting microcystin (MC-LR) comprises the following steps:
(1) 4mg of the gold nanoparticle/ceria quantum dot co-modified graphite phase carbon nitride nanosheet composite (CeO) prepared in example 12 QDs/Au/g-C3N4) Adding into 1mL of perfluorosulfonic acid/ethanol mixed solution (the volume ratio of perfluorosulfonic acid to ethanol in the mixed solution is 1: 1), mixing uniformly, and performing ultrasonic treatment for 35min to obtain the graphite-phase carbon nitride nanosheet composite material (CeO) modified by gold nanoparticles/cerium dioxide quantum dots together2 QDs/Au/g-C3N4) (ii) a suspension.
(2) The graphite phase carbon nitride nanosheet composite (CeO) jointly modified by the gold nanoparticles/cerium dioxide quantum dots obtained in the step (1)2 QDs/Au/g-C3N4) Uniformly coating the suspension on the reaction end surface of a cleaned Indium Tin Oxide (ITO) conductive glass electrode to form a graphite phase carbon nitride nanosheet composite (CeO) jointly modified by gold nanoparticles/cerium dioxide quantum dots 2 QDs/Au/g-C3N4) Composite film formed, after drying, CeO is obtained2 QDs/Au/g-C3N4A modified indium tin oxide conductive glass electrode.
(3) An MC-LR specific probe solution (commercially available, in which the MC-LR specific probe has the sequence 5 '-SH-GGC GCC AAA CAG GAC CAC CAT GAC AAT TAC CCA TAC CAC CTCATT ATG CCC CAT CTC CGC-3') was added dropwise to the CeO obtained in step (2) at a concentration of 1.5. mu.M2 QDs/Au/g-C3N4Incubating the reaction end surface of the modified indium tin oxide conductive glass electrode for 12h at 4 ℃, cleaning, adding the incubated end surface into a 6-mercaptoethanol solution with the concentration of 1mM, and keeping the incubation for 35min to obtain a solution in which an aptamer and CeO are combined on the reaction end surface2 QDs/Au/g-C3N4The indium tin oxide conductive glass electrode completes the preparation of the photoelectric aptamer sensor.
(4) Mixing MC-LR solutions of different concentrations (MC-LR concentration of 0.05pM, 0.1pM, 1pM, 10pM, 1 pM)02pM，103pM，104pM，105pM，106pM) is dripped on the surface of the indium tin oxide conductive glass electrode reaction end of the photoelectrochemical aptamer sensor, and the photoelectrochemical aptamer sensor is incubated for 20min at the temperature of 60 ℃ so that the aptamer probe on the photoelectrochemical aptamer sensor can carry out specific recognition and capture on MC-LR.
(5) And (4) establishing a three-electrode system by taking the indium tin oxide conductive glass electrode for capturing the MC-LR in the step (4) as a working electrode, taking a saturated calomel electrode as a reference electrode and taking a platinum electrode as a counter electrode. And connecting the three-electrode system with an electrochemical workstation, and testing under intermittent illumination by adopting a chronoamperometry method.
(6) And constructing a detection linear regression equation according to the relation between the MC-LR concentration and the photocurrent change, and calculating the concentration of the MC-LR in the solution to be detected according to the detection linear regression equation.
FIG. 6 is a photo-current response diagram of the photo-electrochemical aptamer sensor in detecting MC-LR solutions with different concentrations in example 5 of the present invention. As can be seen from fig. 6, the photocurrent increased with increasing concentration of MC-LR.
FIG. 7 is a linear regression graph of the detection of the variation of the photocurrent versus MC-LR at different concentrations in example 5 of the present invention. As can be seen from FIG. 7, the linear regression equation for the MC-LR versus the change of the photocurrent is as follows:
I(μA)＝0.6767lg(CMC-LR)+1.8008 (1)
in formula (1), I represents the difference between the peak current and the background peak current, and the unit is muA; cMC-LRThe concentration of MC-LR in the solution to be tested is expressed in pM; correlation coefficient R of formula (1)2The MC-LR detection linearity range is 0.05nM to 100pM with a lower limit of 0.01pM at 0.997.
From this, it can be seen that the graphite phase carbon nitride nanosheet composite (CeO) co-modified with the gold nanoparticles/ceria quantum dots of example 12 QDs/Au/g-C3N4) The prepared photoelectrochemistry aptamer sensor can be used for detecting MC-LR, and the concentration of the MC-LR to be detected can be calculated according to a detection linear regression equation.
Example 6
Investigation of gold nanoparticles Particle/cerium dioxide quantum dot co-modified graphite phase carbon nitride nanosheet composite material (CeO)2QDs/Au/g-C3N4) The detection accuracy of the functional nano material for detecting the phycotoxin is specifically considered to be the graphite phase carbon nitride nanosheet composite material (CeO) jointly modified by the gold nanoparticles/cerium dioxide quantum dots2 QDs/Au/g-C3N4) The detection accuracy of the prepared photoelectrochemical aptamer sensor is high.
(1) The photoelectrochemical aptamer sensors in example 5 are used for respectively detecting the concentration of MC-LR in peach lake water, Dongting lake water and laboratory tap water, and the specific steps are that after the water samples are pretreated by filtration and the like, the supernatant is taken and the pH value of the supernatant is adjusted to 7.5 by using a phosphate buffer solution. The concentration of the target substance in the sample (containing MC-LR) was referred to table 1, and the photoelectrochemical aptamer sensor was finally used for target detection in an actual sample (the measurement method was referred to example 5), and a recovery rate test was performed. The measurement results are shown in Table 1.
TABLE 1 results of the verification of the recovery of the test solutions
As can be seen from Table 1, the photoelectrochemical aptamer sensor has the advantages that the recovery rate is basically between 98.8% and 102.2% within the measurable concentration range, the measurement result is ideal, and compared with the traditional detection technology, the detection method adopting the photoelectrochemical aptamer sensor is simple and rapid to operate.
As can be seen from table 1, the graphite phase carbon nitride nanosheet composite (CeO) co-modified with the gold nanoparticles/ceria quantum dots of example 12 QDs/Au/g-C3N4) The prepared photoelectrochemistry aptamer sensor can be used for detecting MC-LR in a water body and can obtain better detection precision.
Graphite phase carbon nitride nanosheet composite material (CeO) jointly modified by gold nanoparticles/cerium dioxide quantum dots2QDs/Au/g-C3N4) The prepared photoelectrochemical aptamerThe sensor has the advantages of wide detection range, low detection limit, strong anti-interference capability and the like.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (8)
1. The application of the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles and the cerium dioxide quantum dots as a functional material in detecting pollutants in the environment is characterized in that the graphite phase carbon nitride nanosheet composite material jointly modified by the gold nanoparticles and the cerium dioxide quantum dots comprises graphite phase carbon nitride nanosheets loaded with the cerium dioxide quantum dots; gold nanoparticles are modified on the graphite-phase carbon nitride nanosheets loaded with cerium dioxide quantum dots; the graphite phase carbon nitride nanosheet loaded with the cerium dioxide quantum dots takes the graphite phase carbon nitride nanosheet as a carrier, and the graphite phase carbon nitride nanosheet is loaded with the cerium dioxide quantum dots; the graphite phase carbon nitride nanosheet is prepared by the following method: heating melamine to 500-520 ℃ for calcining for 2h, continuing heating to 550 ℃ for calcining for 2h, and cooling to obtain a yellow product; heating the yellow product to 550 ℃ and calcining for 4h to obtain graphite-phase carbon nitride nanosheets; the mass percentage of the cerium dioxide quantum dots in the graphite-phase carbon nitride nanosheet loaded with the cerium dioxide quantum dots is 10%; the pollutant is microcystin.
2. The use of claim 1, wherein the gold nanoparticles are present in an amount of 1-20% by weight of the co-modified gold nanoparticle/ceria quantum dots graphitic carbon nitride nanosheet composite; the particle size of the cerium dioxide quantum dots is less than or equal to 20 nm; the particle size of the gold nanoparticles is 8-10 nm.
3. The application of the gold nanoparticle/cerium dioxide quantum dot co-modified graphite phase carbon nitride nanosheet composite material as claimed in claim 2, wherein the preparation method comprises the following steps:
s1, dispersing the graphite phase carbon nitride nanosheets loaded with the cerium dioxide quantum dots in a methanol/water mixed solution to obtain graphite phase carbon nitride nanosheet dispersion liquid loaded with the cerium dioxide quantum dots;
and S2, mixing the cerium dioxide quantum dot-loaded graphite-phase carbon nitride nanosheet dispersion liquid obtained in the step S1 with a chloroauric acid solution under a dark condition, stirring, and carrying out a photoreduction reaction on the obtained mixed liquid under an illumination condition to obtain the gold nanoparticle/cerium dioxide quantum dot co-modified graphite-phase carbon nitride nanosheet composite material.
4. The use according to claim 3, wherein in step S1, the ceria quantum dot-supported graphite-phase carbon nitride nanosheets are prepared by:
(1) Mixing graphite-phase carbon nitride nanosheets, cerous nitrate hexahydrate and water, performing ultrasonic treatment, and adding NH under the stirring condition3·H2O, obtaining a mixed solution;
(2) and (2) carrying out hydrothermal reaction on the mixed solution obtained in the step (1), centrifuging and drying to obtain the cerium dioxide quantum dot-loaded graphite-phase carbon nitride nanosheet.
5. The use according to claim 4, wherein in the step (1), the mass ratio of the graphite-phase carbon nitride nanosheets to the cerous nitrate hexahydrate is 1: 0.1-0.5; the mass ratio of the graphite-phase carbon nitride nanosheets to the water is 1: 150-250; the NH3·H2The ratio of the volume of O to the sum of the volumes of the graphite-phase carbon nitride nanosheets, the cerous nitrate hexahydrate and the water is 1: 30-50; the ultrasonic time is 30-40 min.
6. The use according to claim 4, wherein in the step (2), the temperature of the hydrothermal reaction is 160-180 ℃; the time of the hydrothermal reaction is 12-16 h; the rotation speed of the centrifugation is 2500 rpm-3500 rpm; the drying is carried out at a temperature of 60 ℃.
7. The use according to any one of claims 3 to 6, wherein in the step S1, the mass-to-volume ratio of the ceria quantum dot-loaded graphite-phase carbon nitride nanosheet to the methanol/water mixed solution is 1 mg: 2 mL-4 mL; the methanol/water mixed solution is prepared by mixing methanol and ultrapure water; the volume ratio of the methanol to the ultrapure water is 1: 5-6.
8. The use according to any one of claims 3 to 6, wherein in the step S2, the volume ratio of the ceria quantum dot-supported graphite-phase carbon nitride nanosheet dispersion to the chloroauric acid solution is 1: 0.0008-0.004; the chloroauric acid solution is prepared by mixing chloroauric acid and ultrapure water; the mass volume ratio of the chloroauric acid to the ultrapure water is 1 g: 60 mL-120 mL; the stirring time is 1-1.5 h; the photoreduction reaction time is 1-1.5 h.
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