CN113083302B - Heterostructure nano-composite and preparation method and application thereof - Google Patents

Heterostructure nano-composite and preparation method and application thereof Download PDF

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CN113083302B
CN113083302B CN202110449960.6A CN202110449960A CN113083302B CN 113083302 B CN113083302 B CN 113083302B CN 202110449960 A CN202110449960 A CN 202110449960A CN 113083302 B CN113083302 B CN 113083302B
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CN113083302A (en
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徐�明
李靖
张秋平
袁欢
刘禹彤
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Southwest Minzu University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • B01J35/23—
    • B01J35/39—
    • B01J35/40—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

The invention belongs to the technical field of material synthesis. The invention provides a heterostructure nano-composite and a preparation method and application thereof. The invention adopts silver nitrate, zinc nitrate, tartaric acid, glucose, acrylamide, methylene bisacrylamide and water to prepare a nanocomposite, and prepares the heterostructure nanocomposite from the nanocomposite, manganese trioxide, glucose, tartaric acid, acrylamide, methylene bisacrylamide and water. The heterostructure nano-composite provided by the application comprises a metal-semiconductor and semiconductor-semiconductor multi-heterojunction nano-composite photocatalyst, has uniform particle size distribution, and has excellent visible light absorption capacity and effective photon-generated carrier separation. The preparation method provided by the invention is simple, the reaction condition is mild, the environment is protected, the product is solid nano powder, and the storage and the further utilization are facilitated.

Description

Heterostructure nano-composite and preparation method and application thereof
Technical Field
The invention relates to the technical field of material synthesis, in particular to a heterostructure nanocomposite and a preparation method and application thereof.
Background
Through designing and constructing a multi-heterostructure, the specific performances of a plurality of components are organically combined, so that the high efficiency and the multifunction of the material are realized, and the material is a research hot spot in the fields of sensors, photoelectric materials, catalysis and the like in recent years. The loading of noble metal Ag on ZnO is considered as a means for effectively improving the performance of ZnO catalysts, a unique metal-semiconductor heterojunction structure can form a Schottky barrier, and the plasma resonance effect on the surface of Ag can promote the separation of photogenerated carriers, so that the light absorption of ZnO is expanded to a visible light region.
The synthesis of ternary and higher nanocomposite materials is very demanding in terms of preparation method and reaction conditions, and there are several methods in the prior art to prepare ternary and higher nanocomposite materialsThe nanocomposite material: and (3) thermal decomposition: mixing a certain amount of zinc acetate, manganese acetate and silver acetate, grinding with mortar and pestle for 3 hr, and calcining to obtain ZnO/Ag/Mn 2 O 3 Nanocomposite, but the structure prepared by thermal decomposition method is amorphous. High molecular network gel method: the method adopts a polymer network gel method to prepare the silver/zinc oxide composite nano powder, the initiator is ammonium persulfate, and nitric acid is used for adjusting the pH value of the solution, but the method is not beneficial to environmental protection and safe production.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a heterostructure nanocomposite and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a heterostructure nanocomposite, which comprises the following steps:
(1) Mixing silver nitrate, zinc nitrate, tartaric acid, glucose, acrylamide, methylene bisacrylamide and water to obtain wet gel;
(2) Sequentially drying, grinding and calcining the wet gel to obtain a nanocomposite;
(3) Mixing the nanocomposite, manganese trioxide, glucose, tartaric acid, acrylamide, methylene bisacrylamide and water to obtain wet gel;
(4) And sequentially drying, grinding and calcining the wet gel to obtain the heterostructure nanocomposite.
Preferably, in the step (1), the molar ratio of the silver nitrate to the zinc nitrate is 1 to 5: 95-100;
the molar ratio of zinc nitrate to glucose is 1:6.10 to 6.85;
the molar sum of the silver nitrate and zinc nitrate cations and the molar ratio of tartaric acid is 1:1.45 to 1.55;
the molar sum of the silver nitrate and zinc nitrate cations and the molar ratio of the acrylamide are 1:7.45 to 7.55;
the molar ratio of the silver nitrate to the zinc nitrate cations to the methylene bisacrylamide is 1:1.45 to 1.55;
the mass ratio of the zinc nitrate to the water is 1:10.5 to 11.5.
Preferably, the mixing in the step (1) is performed under stirring conditions, the temperature of the mixing is 85-90 ℃, the rotation speed of the stirring is 500-600 rpm, and the stirring time is 30-60 min.
Preferably, the temperature of the drying in the step (2) is 110-130 ℃, and the drying time is 22-24 hours;
the calcination temperature in the step (2) is 600-700 ℃, and the calcination time is 200-300 min.
Preferably, in the step (3), the molar ratio of the manganese trioxide to the nanocomposite is 1-10: 90-100;
the molar ratio of the nanocomposite to glucose is 1:6.10 to 6.85;
the molar ratio of the manganese trioxide to the tartaric acid is 1:1.45 to 1.55;
the mole ratio of the manganese trioxide to the acrylamide is 1:7.45 to 7.55;
the molar ratio of the manganese trioxide to the methylenebisacrylamide is 1:1.45 to 1.55;
the mass ratio of the nanocomposite to water is 1:5.5 to 6.5.
Preferably, the mixing in the step (3) is performed under stirring conditions, the temperature of the mixing is 85-90 ℃, the rotation speed of the stirring is 500-600 rpm, and the stirring time is 120-150 min.
Preferably, the initial temperature of the drying in the step (4) is 75-85 ℃, the heating rate of the drying is 10-20 ℃/4h, the target temperature of the drying is 120-130 ℃, and the drying time is 10-12 h.
Preferably, the calcination temperature in the step (4) is 600 to 700 ℃, and the calcination time is 200 to 300min.
The invention also provides the heterostructure nano-composite obtained by the preparation method.
The invention also provides application of the heterostructure nanocomposite in preparation of a photocatalyst and a gas-sensitive sensing material.
The invention provides a preparation method of a heterostructure nanocomposite, which is characterized in that silver nitrate, zinc nitrate, tartaric acid, glucose, acrylamide, methylene bisacrylamide and water are adopted to prepare a nanocomposite, and the nanocomposite, manganese trioxide, glucose, tartaric acid, acrylamide, methylene bisacrylamide and water are adopted to prepare the heterostructure nanocomposite. The heterostructure nano-composite provided by the application comprises a metal-semiconductor and semiconductor-semiconductor multi-heterojunction nano-composite photocatalyst, has uniform particle size distribution, and has excellent visible light absorption capacity and effective photon-generated carrier separation. The preparation method provided by the invention is simple, the reaction condition is mild, the environment is protected, the product is solid nano powder, and the storage and the further utilization are facilitated.
Drawings
FIG. 1 is an XRD diffraction pattern of the nanocomposite prepared in examples and comparative examples;
FIG. 2 is an electron microscope image of the nanocomposite prepared in example 1;
FIG. 3 is a TEM image of the nanocomposite prepared in example 1;
FIG. 4 is a TEM image of the nanocomposite prepared in example 1;
FIG. 5 is XPS full spectrum spectra of nanocomposites prepared in example 1, example 2, example 5 and comparative example;
FIG. 6 is XPS full spectrum spectra of nanocomposites prepared in example 1, example 2, example 5 and comparative example;
FIG. 7 is an ultraviolet-visible absorption spectrum of the nanocomposites prepared in examples and comparative examples;
FIG. 8 is a graph of the surface photovoltage of nanocomposites prepared in examples and comparative examples;
FIG. 9 is a graph showing fluorescence emission spectra of nanocomposites prepared in examples and comparative examples;
FIG. 10 shows the degradation efficiency of the nanocomposite prepared in examples and comparative examples on methyl orange;
FIG. 11 shows the degradation efficiency of the nanocomposite prepared in examples and comparative examples on methylene blue;
FIG. 12 is the degradation efficiency of the nanocomposites prepared in examples and comparative examples on rhodamine B;
FIG. 13 is a graph of the photodegradation of methylene blue for example 1, comparative example, and blank group;
FIG. 14 is a log plot of the photodegradation curves for methylene blue for example 1, comparative example, and blank group;
FIG. 15 is NO under ultraviolet light for nanocomposites prepared in example 1, example 5 and comparative example 2 A gas-sensitive activity curve comparison graph of the gas;
FIG. 16 is NO under visible light of the nanocomposites prepared in example 5 and comparative example 2 A gas-sensitive activity curve comparison graph of the gas;
FIG. 17 is an electron microscope image of the nanocomposite prepared in example 5;
FIG. 18 is an electron micrograph of the nanocomposite prepared in the comparative example.
Detailed Description
The invention provides a preparation method of a heterostructure nanocomposite, which comprises the following steps:
(1) Mixing silver nitrate, zinc nitrate, tartaric acid, glucose, acrylamide, methylene bisacrylamide and water to obtain wet gel;
(2) Sequentially drying, grinding and calcining the wet gel to obtain a nanocomposite;
(3) Mixing the nanocomposite, manganese trioxide, glucose, tartaric acid, acrylamide, methylene bisacrylamide and water to obtain wet gel;
(4) And sequentially drying, grinding and calcining the wet gel to obtain the heterostructure nanocomposite.
In the present invention, the molar ratio of silver nitrate to zinc nitrate in the step (1) is preferably 1 to 5:95 to 100, more preferably 2 to 4:96 to 99, more preferably 2.5 to 3.5: 97-98.
In the present invention, the molar ratio of zinc nitrate to glucose is preferably 1:6.10 to 6.85, more preferably 1:6.20 to 6.75, more preferably 1:6.30 to 6.65.
In the present invention, the molar sum of the silver nitrate and zinc nitrate cations to tartaric acid molar ratio is preferably 1:1.45 to 1.55, more preferably 1:1.46 to 1.54, more preferably 1:1.48 to 1.52.
In the present invention, the molar sum of the silver nitrate and zinc nitrate cations to acrylamide molar ratio is preferably 1:7.45 to 7.55, more preferably 1:7.46 to 7.54, more preferably 1:7.48 to 7.52.
In the present invention, the molar sum of the silver nitrate and zinc nitrate cations to methylene bisacrylamide molar ratio is preferably 1:1.45 to 1.55, more preferably 1:1.46 to 1.54, more preferably 1:1.48 to 1.52.
In the invention, the mass ratio of the zinc nitrate to the water is preferably 1:10.5 to 11.5, more preferably 1:10.7 to 11.3, more preferably 1:10.9 to 11.1.
In the present invention, silver nitrate, zinc nitrate, tartaric acid, glucose, acrylamide and methylenebisacrylamide are sequentially dispersed in water, wherein the dispersion is preferably performed in a stirring state, the temperature of the dispersion is preferably room temperature, and the rotation speed of the stirring is preferably 500 to 600rpm, more preferably 520 to 580rpm, and even more preferably 540 to 560rpm; after the addition of the raw materials, a colorless transparent sol is obtained, and the next mixing is performed.
In the present invention, the mixing in the step (1) is preferably performed under water bath and stirring conditions, and the temperature of the water bath is preferably 85 to 90 ℃, more preferably 86 to 89 ℃, and even more preferably 87 to 88 ℃; the rotation speed of the stirring is preferably 500 to 600rpm, more preferably 520 to 580rpm, and still more preferably 540 to 560rpm; the stirring time is preferably 30 to 60 minutes, more preferably 40 to 50 minutes, and still more preferably 43 to 47 minutes; and obtaining wet gel after the stirring is finished.
In the present invention, the drying temperature in the step (2) is preferably 110 to 130 ℃, more preferably 113 to 127 ℃, still more preferably 116 to 124 ℃; the drying time is preferably 22 to 24 hours, more preferably 22.2 to 23.8 hours, and still more preferably 22.6 to 23.4 hours; and obtaining xerogel after the drying is finished.
In the invention, the xerogel is ground in the step (2) to obtain fine and uniform powder without agglomeration or caking.
In the present invention, the temperature of calcination in the step (2) is preferably 600 to 700 ℃, more preferably 620 to 680 ℃, and even more preferably 640 to 660 ℃; the calcination time is preferably 200 to 300 minutes, more preferably 220 to 280 minutes, and even more preferably 240 to 260 minutes.
In the invention, the nanocomposite is obtained after the calcination in the step (2), and the nanocomposite is Ag/ZnO nanocomposite.
In the present invention, the molar ratio of the manganese sesquioxide to the nanocomposite in the step (3) is preferably 1 to 10:90 to 100, more preferably 2 to 9:92 to 98, more preferably 4 to 7: 94-96.
In the present invention, the molar ratio of the nanocomposite to glucose is preferably 1:6.10 to 6.85, more preferably 1:6.20 to 6.75, more preferably 1:6.30 to 6.65.
In the present invention, the molar ratio of manganese trioxide to tartaric acid is preferably 1:1.45 to 1.55, more preferably 1:1.46 to 1.54, more preferably 1:1.48 to 1.52.
In the present invention, the molar ratio of manganese trioxide to acrylamide is preferably 1:7.45 to 7.55, more preferably 1:7.46 to 7.54, more preferably 1:7.48 to 7.52.
In the present invention, the molar ratio of manganese trioxide to methylenebisacrylamide is preferably 1:1.45 to 1.55, more preferably 1:1.46 to 1.54, more preferably 1:1.48 to 1.52.
In the present invention, the mass ratio of the nanocomposite to water is preferably 1:5.5 to 6.5, more preferably 1:5.6 to 6.4, more preferably 1:5.8 to 6.2.
In the present invention, the nanocomposite, manganese sesquioxide, glucose, tartaric acid, acrylamide and methylene bisacrylamide are sequentially dispersed in water, wherein the dispersion is preferably performed in a stirring state, the temperature of the dispersion is preferably room temperature, and the stirring speed is preferably 500-600 rpm, more preferably 520-580 rpm, and even more preferably 540-560 rpm; after the raw materials are added, a brown suspension is obtained, and the next step of mixing is carried out.
In the present invention, the mixing in the step (3) is preferably performed under water bath and stirring conditions, and the temperature of the water bath is preferably 85 to 90 ℃, more preferably 86 to 89 ℃, and even more preferably 87 to 88 ℃; the rotation speed of the stirring is preferably 500 to 600rpm, more preferably 520 to 580rpm, and still more preferably 540 to 560rpm; the stirring time is preferably 120 to 150 minutes, more preferably 130 to 140 minutes, and even more preferably 133 to 137 minutes; and obtaining brown wet gel after the stirring is finished.
In the present invention, the initial temperature of the drying in the step (4) is preferably 75 to 85 ℃, more preferably 77 to 83 ℃, still more preferably 79 to 81 ℃; the heating rate of the drying is preferably 10-20 ℃/4h, more preferably 12-18 ℃/4h, and even more preferably 14-16 ℃/4h; the target temperature for drying is preferably 120 to 130 ℃, more preferably 122 to 128 ℃, and even more preferably 124 to 126 ℃; the drying time is preferably 10 to 12 hours, more preferably 10.3 to 11.7 hours, and still more preferably 10.6 to 11.4 hours; and after the drying is finished, obtaining the honeycomb xerogel.
In the invention, the xerogel is ground in the step (4) to obtain fine and uniform powder without agglomeration or caking phenomenon.
In the present invention, the temperature of calcination in the step (4) is preferably 600 to 700 ℃, more preferably 620 to 680 ℃, and even more preferably 640 to 660 ℃; the calcination time is preferably 200 to 300 minutes, more preferably 220 to 280 minutes, and even more preferably 240 to 260 minutes.
In the invention, the (Ag, mn) is obtained after the calcination in the step (4) 2 O 3 ) Co-modified ZnO multi-heterostructure nanocomposites.
The invention also provides the heterostructure nano-composite obtained by the preparation method.
The invention also provides application of the heterostructure nanocomposite in preparation of a photocatalyst and a gas-sensitive sensing material.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The purity of each raw material adopted in the embodiment of the invention is as follows:
Figure BDA0003038283520000071
example 1
0.3mol of silver nitrate, 9.5mol of zinc nitrate, 14.7mol of tartaric acid, 60mol of glucose, 73.5mol of acrylamide and 14.7mol of methylenebisacrylamide are sequentially dispersed in 31036g of water at a stirring speed of 550rpm to obtain colorless transparent sol;
stirring the colorless transparent sol at 88 ℃ and 550rpm for 60min to obtain wet gel;
drying the wet gel at 120 ℃ for 23 hours to obtain xerogel, grinding the xerogel to a particle size smaller than 100nm, and calcining the ground powder at 650 ℃ for 250 minutes to obtain an Ag/ZnO nanocomposite;
taking 0.95mol of the Ag/ZnO nanocomposite material prepared by the preparation method, and dispersing 0.03mol of manganese sesquioxide, 6.08mol of glucose, 0.045mol of tartaric acid, 0.225mol of acrylamide and 0.045mol of methylenebisacrylamide in 1077.3g of water sequentially at a stirring speed of 550rpm to obtain a tan suspension;
stirring the brown suspension at 88 ℃ and 550rpm for 130min to obtain brown wet gel;
drying the tan wet gel at an initial temperature of 75 ℃, heating to 15 ℃ every 4 hours, heating to 125 ℃, and drying for 12 hours to obtain honeycomb xerogel;
grinding the honeycomb xerogel to particle size smaller than 100nm, and calcining the powder at 650deg.C for 300min to obtain (Ag, mn) 2 O 3 ) Co-modified ZnO multi-heterostructure nanocomposites.
The nanocomposite prepared in the application is denoted as AZM3, the XRD diffraction patterns of which are shown in figure 1, and the main diffraction peaks of (101), (002) and (100) are characteristic diffraction peaks of ZnO (JCDF 5-664), and the characteristic diffraction peaks are indicated by "#". Diffraction peaks at 2θ= 38.03 °, 44.09 °, and 64.45 ° correspond to characteristic peaks of metallic Ag, denoted by "×". Whereas diffraction peaks at 2θ=30.03 °, 35.40 °, 43.04 °, 53.39 ° and 56.97 ° correspond to Mn 2 O 3 Is used for the characteristic diffraction peak of (1)
Figure BDA0003038283520000081
And (3) representing. Indicating that the prepared (Ag, mn 2 O 3 ) Ag and Mn exist in co-modified ZnO nano-composite 2 O 3 And ZnO.
As a result of observing the (Ag, mn2O 3) co-modified ZnO nanocomposite (AZM 3) prepared in this example by using a Scanning Electron Microscope (SEM), as shown in FIG. 2, it was observed that the particle size distribution of the sample was more uniform, the clusters were fewer, and the average particle size was in the range of 57.1nm to 62.5 nm.
The microstructure of the AZM3 nanocomposite prepared in this example was analyzed by transmission electron microscope TEM. As shown in FIGS. 3 and 4, ag, znO and Mn can be clearly seen 2 O 3 The nanoparticles form well-defined (Ag, mn 2 O 3 ) Co-modified ZnO nanostructures. The lattice spacing of about 0.281nm, 0.172nm, 0.14nm in FIG. 4 corresponds to ZnO, mn, respectively 2 O 3 And the (100), (521) and (111) crystal planes of Ag, indicating the formation of a multi-heterojunction structure of metal-semiconductor, semiconductor-semiconductor.
The XPS spectrum of the AZM3 nanocomposite prepared in this example is shown in fig. 5: the main peak of 367.65eV corresponds to Ag3d 5/2 Two characteristic peaks with binding energy of 641.7eV and 653.4eV correspond to Mn 2p respectively 3/2 And Mn 2p 1/2 The spin orbital state, which has a split energy between the two peaks of 11.7eV, was confirmed to be in (Ag, mn 2 O 3 ) Mn in co-modified ZnO nano composite powder 3 + Is present. FIG. 6 shows the peak separation of O1s with binding energy position 529.8eV, 530.5eV and 531.95eV, respectively correspond to lattice oxygen (O) L ) Oxygen of vacancy (O) V ) Chemisorbed oxygen (O) C ). As can be seen from the figure, the AZM3 sample was taken as O V The highest content of O in the catalyst V Can generally serve as a capture site for photo-generated carriers, and is beneficial to the progress of photocatalytic reaction.
The UV-vis UV-visible absorption spectrum of the AZM3 compound prepared in this example is shown in FIG. 7: mn (Mn) 2 O 3 The introduction of (3) further significantly improves the visible light absorption of Ag/ZnO, which can be attributed to (Ag, mn) 2 O 3 ) The formation of multiple heterojunction structures in co-modified ZnO.
The AZM3 nanocomposite prepared in this example was tested for photo-generated carrier separation efficiency and carrier recombination using a Surface Photovoltage (SPV) technique and fluorescence emission spectroscopy (PL), and the results are shown in fig. 8 and 9: AZM3 has the lowest PL emission intensity and the highest SPV intensity, and the SPV intensity is 10 times that of Ag/ZnO, which indicates that it has efficient photogenerated carrier separation.
(Ag, mn) prepared in this example 2 O 3 ) The co-modified ZnO nano composite powder (AZM 3) is subjected to a catalytic activity test experiment under simulated sunlight and visible light irradiation. Photocatalytic degradation was performed on three typical organic dyes (chengdou koku chemical company, inc.) Methylene Blue (MB), methyl Orange (MO) and rhodamine b (RhB). All experiments were performed under the same conditions (room temperature 30 ℃, ph=7). The characteristic wavelengths of the three contaminants were 664nm, 554nm and 464nm, respectively, and the initial absorbance (A0) of each contaminant solution was measured at the characteristic wavelengths using a spectrophotometer (V-1100D, beijing Porphy technology Co., ltd.). The specific photocatalysis steps are as follows: 50mg of the catalyst was dispersed in 100mL of an aqueous MB/MO/RhB (4 mg/L) solution containing 4mL of a dye, magnetically stirred at room temperature for 5min, sonicated (KQ-3200 DE, kunshan ultrasonic instruments Co., ltd.) for 5min, and then allowed to stand in a dark environment for 30min to reach adsorption-desorption equilibrium. The solution was subjected to irradiation under a xenon lamp (PLS-SXE 300C, beijing light technology Co., ltd.) with simulated sunlight having a power of 300W, and the irradiation intensity and distance were divided0.17W cm-2 and 20cm, respectively). By providing a 420nm cut-off filter, the light source is used as a visible light source with the wavelength of 420 nm-720 nm. 5ml of liquid were taken out at regular intervals into test tubes and centrifuged in a centrifuge (rotation speed 6000 r/min). The supernatant of the centrifuged solution was collected by a dropper, and the absorbance (At) was measured by a spectrophotometer, and the relationship between the absorbance and the concentration was determined by the lambert-beer formula. Finally, the degradation rate is calculated according to the following formula as shown in formula (1):
Figure BDA0003038283520000091
wherein A0 and At are the absorbance of MB/MO/RhB solution before and after light irradiation, and C0 and Ct are the corresponding pollutant concentrations after light irradiation t time.
The irradiation intensity of the light source in the photocatalytic activity test experiment is shown in table 1;
TABLE 1
Figure BDA0003038283520000092
Fig. 10 shows the degradation rate of methyl orange, fig. 11 shows the degradation rate of methylene blue, and fig. 12 shows the degradation rate of rhodamine B; as can be seen from FIGS. 10, 11 and 12, the (Ag, mn) obtained by the present invention 2 O 3 ) The co-modified ZnO nano composite powder has better photocatalytic degradation activity on various organic dyes under the irradiation of simulated sunlight or visible light, and obviously improves the degradation efficiency under the visible light compared with Ag/ZnO.
Comparison of AZM3 prepared in this example with methylene blue dye without any catalyst shows the photodegradation curves as shown in fig. 13 and 14, from which it can be seen that: the degradation rate of the organic dye without catalyst is almost always zero. The nano composite powder prepared by the method has excellent photocatalytic activity.
NO on the nanocomposite (AZM 3) prepared in this example 2 Gas-sensitive Activity test experiment
For the preparation of the nitrogen dioxide gas sensor, an ethanol suspension of the prepared sample (3.0 mg/ml) was spun at 500 rpm while dropping on fork electrodes (IDEs) on a silicon (Si) substrate with a dropper, and then spin-coated at 3000 rpm for another 15 seconds. The relevant process was repeated 80 times and then dried in a constant temperature oven at 80 ℃ for 8 hours to stabilize the gas sensitive coating.
As can be seen from FIG. 15, under 365nm ultraviolet light irradiation (NO 2 The concentration was changed from 1ppm to 40 ppm). As can be seen from the corresponding dynamic response curve and response concentration curve, compared with the Ag/ZnO sample, (Ag, mn 2 O 3 ) Co-modified ZnO nano composite powder pair NO 2 The gas is more sensitive to different NO 2 The response of the concentration shows stronger performance. Furthermore, as can be seen from the response-concentration curves shown in the figures, the gas response of the sensor is compared with NO 2 The concentration is proportional and shows good linear relation.
Example 2
0.1mol of silver nitrate, 2mol of zinc nitrate, 3.1mol of tartaric acid, 12.6mol of glucose, 15mol of acrylamide and 3mol of methylenebisacrylamide are sequentially dispersed in 6534g of water at a stirring speed of 540rpm to obtain colorless transparent sol;
stirring the colorless transparent sol at 85deg.C and 560rpm for 50min to obtain wet gel;
drying the wet gel at 130 ℃ for 24 hours to obtain xerogel, grinding the xerogel to a particle size smaller than 100nm, and calcining the ground powder at 700 ℃ for 230 minutes to obtain an Ag/ZnO nanocomposite;
taking 0.99mol of the Ag/ZnO nanocomposite material prepared by the preparation method, 0.01mol of manganese sesquioxide, 6.435mol of glucose, 0.0148mol of tartaric acid, 0.0747mol of acrylamide and 0.0145mol of methylenebisacrylamide, and dispersing the materials in 1122g of water at a stirring speed of 580rpm to obtain a tan suspension;
stirring the brown suspension at 90 ℃ and 540rpm for 140min to obtain brown wet gel;
drying the tan wet gel at an initial temperature of 75 ℃, heating to 15 ℃ every 4 hours, heating to 125 ℃, and drying for 12 hours to obtain honeycomb xerogel;
grinding the honeycomb xerogel to particle size smaller than 100nm, calcining the ground powder at 700deg.C for 210min to obtain (Ag, mn) 2 O 3 ) Co-modified ZnO multi-heterostructure nanocomposites.
The nanocomposite prepared in this example was denoted as AZM1, the XRD diffractogram thereof was shown in fig. 1, the XPS full spectrum spectra were shown in fig. 5 and 6, the ultraviolet visible absorption spectrum was shown in fig. 7, the Surface Photovoltage (SPV) was shown in fig. 8, the fluorescence emission spectrum (PL) was shown in fig. 9, the degradation rate of methyl orange was shown in fig. 10, the degradation rate of methylene blue was shown in fig. 11, and the degradation rate of rhodamine B was shown in fig. 12.
Example 3
0.5mol of silver nitrate, 10mol of zinc nitrate, 15mol of tartaric acid, 67mol of glucose, 75.6mol of acrylamide and 15mol of methylenebisacrylamide are sequentially dispersed in 32076g of water at a stirring speed of 580rpm to obtain colorless transparent sol;
stirring the colorless transparent sol at 85deg.C and 580rpm for 40min to obtain wet gel;
drying the wet gel at 130 ℃ for 24 hours to obtain xerogel, grinding the xerogel to less than 100nm, and calcining the ground powder at 700 ℃ for 300 minutes to obtain an Ag/ZnO nanocomposite;
taking 0.95mol of the Ag/ZnO nanocomposite material prepared by the preparation method, 0.05mol of manganese sesquioxide, 6.27mol of glucose, 0.074mol of tartaric acid, 0.373mol of acrylamide and 0.076mol of methylenebisacrylamide, and dispersing the materials in 1113g of water at a stirring speed of 560rpm to obtain a tan suspension;
stirring the brown suspension at 86 ℃ and 520rpm for 140min to obtain brown wet gel;
drying the tan wet gel at an initial temperature of 75 ℃, heating to 15 ℃ every 4 hours, heating to 125 ℃, and drying for 12 hours to obtain honeycomb xerogel;
grinding the cellular xerogel to a particle size of less than 100nm, and grindingCalcining the powder at 700deg.C for 280min to obtain (Ag, mn) 2 O 3 ) Co-modified ZnO multi-heterostructure nanocomposites.
The nanocomposite prepared in this example was denoted as AZM5, whose XRD diffractogram is shown in fig. 1, uv-visible absorption spectrum is shown in fig. 7, surface Photovoltage (SPV) pattern is shown in fig. 8, fluorescence emission spectrum (PL) pattern is shown in fig. 9, degradation rate of methyl orange is shown in fig. 10, degradation rate of methylene blue is shown in fig. 11, and degradation rate of rhodamine B is shown in fig. 12.
Example 4
0.1mol of silver nitrate, 9mol of zinc nitrate, 13mol of tartaric acid, 55.8mol of glucose, 67.8mol of acrylamide and 13.8mol of methylenebisacrylamide are sequentially dispersed in 28868g of water at a stirring speed of 540rpm to obtain colorless transparent sol;
stirring the colorless transparent sol at 90 ℃ and 600rpm for 55min to obtain wet gel;
drying the wet gel at 130 ℃ for 24 hours to obtain xerogel, grinding the xerogel to a particle size smaller than 100nm, and calcining the ground powder at 700 ℃ for 230 minutes to obtain an Ag/ZnO nanocomposite;
taking 0.93mol of the prepared Ag/ZnO nanocomposite, 0.07mol of manganese sesquioxide, 6.13mol of glucose, 0.1mol of tartaric acid, 0.52mol of acrylamide and 0.1mol of methylenebisacrylamide, and dispersing the materials in 1019g of water in sequence at a stirring speed of 600rpm to obtain a tan suspension;
stirring the brown suspension at 90 ℃ and 580rpm for 140min to obtain brown wet gel;
drying the tan wet gel at an initial temperature of 75 ℃, heating to 15 ℃ every 4 hours, heating to 125 ℃, and drying for 12 hours to obtain honeycomb xerogel;
grinding the honeycomb xerogel to particle size smaller than 100nm, and calcining the ground powder at 700deg.C for 280min to obtain (Ag, mn) 2 O 3 ) Co-modified ZnO multi-heterostructure nanocomposites.
The nanocomposite prepared in this example was denoted as AZM7, the XRD diffractogram thereof was shown in fig. 1, the uv-vis absorption spectrum was shown in fig. 7, the Surface Photovoltage (SPV) pattern was shown in fig. 8, the fluorescence emission spectrum (PL) pattern was shown in fig. 9, the degradation rate of methyl orange was shown in fig. 10, the degradation rate of methylene blue was shown in fig. 11, and the degradation rate of rhodamine B was shown in fig. 12.
Example 5
0.1mol of silver nitrate, 9.6mol of zinc nitrate, 14.7mol of tartaric acid, 63.36mol of glucose, 72.75mol of acrylamide and 14.16mol of methylenebisacrylamide are sequentially dispersed in 31363g of water at a stirring speed of 540rpm to obtain colorless transparent sol;
stirring the colorless transparent sol at 89 ℃ and 540rpm for 45min to obtain wet gel;
drying the wet gel at 130 ℃ for 24 hours to obtain xerogel, grinding the xerogel to a particle size smaller than 100nm, and calcining the ground powder at 700 ℃ for 260 minutes to obtain an Ag/ZnO nanocomposite;
taking 0.9mol of the prepared Ag/ZnO nanocomposite, 0.1mol of manganese sesquioxide, 5.76mol of glucose, 0.148mol of tartaric acid, 0.75mol of acrylamide and 0.15mol of methylenebisacrylamide, and dispersing the materials in 1020g of water in sequence at a stirring speed of 600rpm to obtain a tan suspension;
stirring the brown suspension at 90 ℃ and 530rpm for 140min to obtain brown wet gel;
drying the tan wet gel at an initial temperature of 75 ℃, heating to 15 ℃ every 4 hours, heating to 125 ℃, and drying for 12 hours to obtain honeycomb xerogel;
grinding the honeycomb xerogel to particle size smaller than 100nm, calcining the ground powder at 700deg.C for 230min to obtain (Ag, mn) 2 O 3 ) Co-modified ZnO multi-heterostructure nanocomposites.
The same NO as in example 1 was used 2 Gas sensitive test method, when the excitation wavelength is increased to 470nm visible light (NO 2 The concentration varies from 10ppm to 50 ppm). As shown in fig. 16, when NO 2 At a concentration of less than 10ppm, the resistance response is relatively insignificant, but (Ag, mn) 2 O 3 ) The response intensity of the co-modified ZnO nano composite powder is obviously stronger than that of Ag/ZnO. And when NO 2 When the injection amount exceeds 20ppm, (Ag, mn) 2 O 3 ) The response intensity of the co-modified ZnO nano composite powder exceeds the measuring range of a universal meter, and the response intensity of the co-modified ZnO nano composite powder exceeds more than 5 times of that of Ag/ZnO. This indicates (Ag, mn 2 O 3 ) Co-modified ZnO nano composite powder has excellent NO under visible light 2 Gas sensitive detection performance.
The nanocomposite prepared in this example was denoted as AZM10, whose XRD diffraction patterns are shown in FIG. 1, XPS full spectrum patterns are shown in FIG. 5 and FIG. 6, ultraviolet visible absorption spectrum patterns are shown in FIG. 7, surface Photovoltage (SPV) patterns are shown in FIG. 8, fluorescence emission spectrum (PL) patterns are shown in FIG. 9, methyl orange degradation rate is shown in FIG. 10, methylene blue degradation rate is shown in FIG. 11, rhodamine B degradation rate is shown in FIG. 12, and NO under ultraviolet light 2 The gas-sensitive activity graph of the gas is shown in FIG. 15, NO under visible light 2 The gas-sensitive activity profile of the gas is shown in figure 16.
As shown in FIG. 17, the electron microscope images of AZM10 prepared in this example show a relatively uniform particle size distribution, fewer clusters, and average particle sizes in the range of 57.1nm to 62.5 nm.
Comparative example
In this comparative example, mn was not added 2 O 3 The remaining parameters were the same as in example 1, and the (Ag) -modified ZnO multi-heterostructure nanocomposite was prepared.
The nanocomposite prepared in this comparative example was designated as AZM0, and its XRD diffraction pattern was as shown in FIG. 1, and it was observed that following Mn 2 O 3 The content exceeds 3mol%, the XRD main diffraction peak intensity is obviously reduced, indicating excessive Mn 2 O 3 The crystalline quality of ZnO is reduced.
XPS spectrum spectra are shown in FIGS. 5 and 6, with Mn 2 O 3 When the content is increased to more than 3mol%, the OL ratio thereof is significantly decreased, indicating an excessive Mn 2 O 3 This results in a decrease in the crystalline quality of ZnO, which is consistent with the analysis results in XRD. Meanwhile, the OV content of the sample surface is along with Mn 2 O 3 The content is increased firstly and then is increasedDecrease in Mn 2 O 3 The molar fraction reaches a maximum at 3 mol%.
The ultraviolet-visible absorption spectrum is shown in FIG. 7, which shows that with Mn 2 O 3 The visible light absorption of Ag/ZnO with increased content is gradually enhanced.
The Surface Photovoltage (SPV) graph is shown in FIG. 8, the fluorescence emission spectrum (PL) graph is shown in FIG. 9, and the result shows that with Mn 2 O 3 The SPV strength is firstly increased and then decreased when the content is increased, the PL change trend is consistent with the SPV result, and the strength change is opposite. Indicating that a proper amount of AZM3 has the highest efficiency of photo-generated carrier separation.
The degradation rate of methyl orange is shown in fig. 10, the degradation rate of methylene blue is shown in fig. 11, the degradation rate of rhodamine B is shown in fig. 12, and the photodegradation curve of methylene blue is shown in fig. 13; a log plot of the photodegradation curve for methylene blue is shown in fig. 14; NO under ultraviolet light 2 The gas-sensitive activity graph of the gas is shown in FIG. 15, NO under visible light 2 The gas-sensitive activity profile of the gas is shown in figure 16.
As shown in FIG. 18, the electron microscope images of AZM0 prepared in this comparative example show a relatively uniform particle size distribution of the samples, fewer clusters, and an average particle size in the range of 57.1nm to 62.5 nm.
From the above examples, the present invention provides a heterostructure nanocomposite, which is further optimized for Ag/ZnO by intentionally designing and constructing a multi-heterostructure including metal-semiconductor, semiconductor-semiconductor, and has a unique structure capable of achieving excellent visible light absorption while having significantly enhanced efficient carrier separation; high-efficiency degradation activity of organic pollutants under simulated sunlight or visible light is realized, and the high-efficiency organic pollutant-degrading agent has remarkably enhanced good gas-sensitive performance. The preparation steps and experimental equipment of the invention are simple, the reaction condition is mild, the yield is high, the cost of the required chemical reagent raw materials is low, and the invention is green and environment-friendly and does not cause pollution.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (6)

1. A method of preparing a heterostructure nanocomposite, comprising the steps of:
(1) Mixing silver nitrate, zinc nitrate, tartaric acid, glucose, acrylamide, methylene bisacrylamide and water to obtain wet gel;
(2) Sequentially drying, grinding and calcining the wet gel to obtain a nanocomposite;
(3) Mixing the nanocomposite, manganese trioxide, glucose, tartaric acid, acrylamide, methylene bisacrylamide and water to obtain wet gel;
(4) Sequentially drying, grinding and calcining the wet gel to obtain the heterostructure nanocomposite;
in the step (1), the molar ratio of the silver nitrate to the zinc nitrate is 1-5: 95-100;
the molar ratio of zinc nitrate to glucose is 1:6.10 to 6.85;
the molar sum of the silver nitrate and zinc nitrate cations and the molar ratio of tartaric acid is 1:1.45 to 1.55;
the molar sum of the silver nitrate and zinc nitrate cations and the molar ratio of the acrylamide are 1:7.45 to 7.55;
the molar ratio of the silver nitrate to the zinc nitrate cations to the methylene bisacrylamide is 1:1.45 to 1.55;
the mass ratio of the zinc nitrate to the water is 1:10.5 to 11.5;
the molar ratio of the manganese trioxide to the nanocomposite in the step (3) is 1-10: 90-100;
the molar ratio of the nanocomposite to glucose is 1:6.10 to 6.85;
the molar ratio of the manganese trioxide to the tartaric acid is 1:1.45 to 1.55;
the mole ratio of the manganese trioxide to the acrylamide is 1:7.45 to 7.55;
the molar ratio of the manganese trioxide to the methylenebisacrylamide is 1:1.45 to 1.55;
the mass ratio of the nanocomposite to water is 1:5.5 to 6.5;
the initial temperature of the drying in the step (4) is 75-85 ℃, the heating rate of the drying is 10-20 ℃/4h, the target temperature of the drying is 125 ℃, and the drying time is 10-12 h;
the calcining temperature in the step (4) is 700 ℃, and the calcining time is 230-300 min.
2. The method according to claim 1, wherein the mixing in the step (1) is performed under stirring conditions, the temperature of the mixing is 85 to 90 ℃, the rotation speed of the stirring is 500 to 600rpm, and the stirring time is 30 to 60 minutes.
3. The method according to claim 2, wherein the drying temperature in the step (2) is 110 to 130 ℃, and the drying time is 22 to 24 hours;
the calcination temperature in the step (2) is 600-700 ℃, and the calcination time is 200-300 min.
4. The method according to claim 1, wherein the mixing in the step (3) is performed under stirring conditions, the temperature of the mixing is 85 to 90 ℃, the rotation speed of the stirring is 500 to 600rpm, and the stirring time is 120 to 150 minutes.
5. Heterostructure nanocomposite obtained by the process according to any one of claims 1 to 4.
6. Use of the heterostructure nanocomposite of claim 5 in the preparation of photocatalysts and gas sensitive sensing materials.
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