CN111744474B - Nano composite material, preparation method and application thereof - Google Patents

Nano composite material, preparation method and application thereof Download PDF

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CN111744474B
CN111744474B CN202010566516.8A CN202010566516A CN111744474B CN 111744474 B CN111744474 B CN 111744474B CN 202010566516 A CN202010566516 A CN 202010566516A CN 111744474 B CN111744474 B CN 111744474B
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hollow
nanocomposite
particles
sesame
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CN111744474A (en
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刘浩梅
郝喜海
刘跃军
张宁
颜爱国
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Central South University
Hunan University of Technology
Xiamen University of Technology
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Hunan University of Technology
Xiamen University of Technology
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Abstract

The invention discloses a nano composite material, which comprises Ag nano particles and Ag 1.7 Sb 2 O 6.25 Nanoparticles of Ag, wherein 1.7 Sb 2 O 6.25 The nano particles are hollow spherical, and the Ag nano particles are embedded into the Ag 1.7 Sb 2 O 6.25 Hollow sesame ball-shaped particles are formed in the nano particles. The invention also discloses a preparation method and application of the nano composite material. The nano composite material has excellent photocatalytic performance.

Description

Nano composite material, preparation method and application thereof
Technical Field
The invention relates to the field of composite materials, in particular to a nano composite material containing Ag nano particles and Ag1.7Sb2O6.25 nano particles, a preparation method and application thereof.
Background
In recent years, due to the high electron mobility and photocatalytic activity of silver antimonate nanoparticles and the technical application of silver antimonate nanoparticles in visible light-sensitive photocatalysts, people have conducted extensive research on the preparation of silver antimonate nanoparticles. As a silver and pentavalent p-block Sb-containing metal composite oxide, the minimum Conduction Band (CBM) of silver antimonate consists of a hybrid orbital of Ag 5s and Sb 5s and results in its hybridization to other Ag-d-block metal composite oxides such as AgNbO 3 And AgVO 3 ) Has higher visible light sensitivity. However, single-phase silver antimonate has a relatively low reduction potential and recombination of photo-generated electrons and holes readily occurs. Construction of silver antimonate-based heterostructure photocatalysts (e.g., AgSbO) in conjunction with two semiconductors 3 /NaNbO 3 ，AgSbO 3 /AgNbO 3 ) Or designing "Z solutions" (e.g., AgSbO) 3 /Ag/CN) can improve the photocatalytic activity.
In contrast to the above process, visible light triggered plasmonic photocatalysts are considered as another promising alternative to traditional photocatalysts. In these metal-semiconductor composites, metal Nanoparticles (NPS) can strongly absorb visible light due to the Surface Plasmon Resonance (SPR) effect and help to separate eCB-and hVB-generated on the semiconductor. Recently, many semiconductors modified with nanoscale noble metals (e.g., Au) have been reported to improve the overall photocatalytic efficiency due to their unique Surface Plasmon Resonance (SPR) characteristics resulting from the collective vibration of electrons on the surface of NPs. For example, Haruta and co-workers demonstrated exceptionally high catalytic activity for gold nanoparticles in the 2-5nm range. As an inexpensive noble metal, some studies on the selection of silver as a mediator to shuttle electrons between two semiconductor components in the Z scheme have been reported, but there are very few reports on Ag-based metal semiconductors, particularly Ag/silver antimonate composites.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a nanocomposite comprising Ag nanoparticles and Ag1.7sb2o6.25 nanoparticles, a preparation method and use thereof.
The technical scheme of the invention is as follows:
in one aspect, the present invention provides a nanocomposite material comprising Ag nanoparticles and Ag 1.7 Sb 2 O 6.25 Nanoparticles, wherein the Ag 1.7 Sb 2 O 6.25 The nano particles are hollow spheres, and the Ag nano particles are embedded into the Ag 1.7 Sb 2 O 6.25 Hollow sesame spherical particles are formed in the nano particles.
In one embodiment, the particle size of the hollow sesame ball-shaped particles is 80-180 nm; preferably, the particle size of the hollow sesame ball-shaped particles is about 170 nm.
In one embodiment, the Ag nanoparticles have a particle size of 15-25 nm.
In one embodiment, the Ag 1.7 Sb 2 O 6.25 Obtained by the following reaction:
KSbO 6 H 6 ＝SbO 6 H 6 - +K + (1)
AgNO 3 ＝NO 3 - +Ag + (2)
2SbO 6 H 6 - +1.7Ag + →Ag 1.7 Sb 2 O 6.25 ↓ (3)。
in another aspect, the present invention also provides a method for preparing the nanocomposite described above, comprising the steps of:
(1) mixing potassium pyroantimonate and silver nitrate in an aqueous solution state for reaction to obtain a product; the method for preparing the nano composite material is characterized in that a silver simple substance exists;
(2) and heating the reactant to obtain the composite material.
In one embodiment, the molar ratio of potassium pyroantimonate to silver nitrate is 0.8-2.0: 1; preferably, the molar ratio of potassium pyroantimonate to silver nitrate is 3.88: 4.
in one embodiment, the heating temperature in step (ii) is 105-; preferably, the heating temperature is 127 ℃.
In one embodiment, in step (i), the reaction temperature is 70-120 ℃; preferably, the reaction temperature is 80 ℃.
In one embodiment, the heating is performed under sealed conditions.
In one embodiment, in the step (2), after the mixture is heated, a washing and drying step is further included.
In a further aspect, the present invention also provides the use of the nanocomposite described above as a photocatalyst.
Drawings
FIG. 1 shows hollow sesame ball-type Ag prepared in example 1 1.7 Sb 2 O 6.25 X-ray diffraction (XRD) of the nanocomposite.
FIG. 2 shows hollow sesame ball-shaped Ag/Ag 1.7 Sb 2 O 6.25 SEM images of the nanocomposite; wherein FIG. 2a shows Ag/Ag 1.7 Sb 2 O 6.25 Typical SEM images of the nanocomposites show a large number of spherical particles with an average size of about 170nm, with many broken spheres present in the SEM image, indicating that the interior of the spherical particles is hollow. Fig. 2b is a higher magnification SEM image obtained from the selected area of fig. 2a, where a large number of uniformly dense smaller particles can be clearly observed on the surface of the hollow nanospheres, and the overall shape of the nanocomposite material looks like a chinese delicious hollow sesame-based sphere. The fine structure and composition of the sesame spherical hollow particles were further studied using HRTEM, and fig. 2c shows the following formulaHRTEM images of local regions of individual hollow spheres, in which two smaller spheres, labeled "a" and "b", were embedded in the particles, with an average size of 18.3 nm; the lattice of the "a" sphere was measured to be 0.23nm, which corresponds to the (111) crystal plane of metallic Ag. Apart from silver, a interplanar distance of 0.3nm was observed on each hollow sphere, which was the same as the (222) plane of silver antimonate. As shown in fig. 2d, the elemental distribution of silver/silver antimonate was verified by EDS elemental mapping, indicating that these broken hollow spheres contain Sb, O, Ag elements, but only Ag in all smaller nanospheres does not contain Sb, O, indicating that Ag nanoparticles are embedded in Ag 1.7 Sb 2 O 6.25 The hollow sesame ball is formed in the hollow ball.
Fig. 3 shows 3 XPS plots of Ag/Ag1.7sb2o6.25 hollow sesame-spherical nanocomposites, wherein: (a) ag 3 d; (b) o1 s; (c) and (5) antimony 3 d.
FIG. 4 shows Ag/Ag 1.7 Sb 2 O 6.25 And a calculated band gap and absorption spectrum of the UV-visible light of the precursor.
FIG. 5 shows hollow sesame ball type Ag/Ag 1.7 Sb 2 O 6.25 A process for forming a nanocomposite.
Detailed Description
In the invention, the sesame hollow sphere type Ag/Ag1.7Sb2O6.25 nano composite material is prepared by a simple one-step hydrothermal method, and Ag in a hydrometallurgy system is researched + Mechanism of reduction to Ag. This work has been directed to providing a versatile and economical synthesis strategy for obtaining a variety of silver-based semiconductors and to better understand their mechanism of formation.
In one embodiment, the present invention provides a nanocomposite material comprising Ag nanoparticles and Ag 1.7 Sb 2 O 6.25 Nanoparticles, wherein the Ag 1.7 Sb 2 O 6.25 The nano particles are hollow spherical, and the Ag nano particles are embedded into the Ag 1.7 Sb 2 O 6.25 Hollow sesame ball-shaped particles are formed in the nano particles.
In some embodiments, the hollow sesame sphere-type particles have a particle size of 80 to 180 nm; in a preferred embodiment, the particle size of the hollow sesame ball-type particles is about 170nm, and the photocatalytic performance of the nanocomposite material is optimal.
In some embodiments, the Ag nanoparticles have a particle size of 15-25 nm. In a preferred embodiment, the particle size of the hollow sesame sphere-shaped particles is about 17 nm.
In one embodiment, the Ag 1.7 Sb 2 O 6.25 Obtained by the following reaction:
KSbO 6 H 6 ＝SbO 6 H 6 - +K + (1)
AgNO 3 ＝NO 3 - +Ag + (2)
2SbO 6 H 6 - +1.7Ag + →Ag 1.7 Sb 2 O 6.25 ↓ (3)。
in one embodiment, the present invention also provides a method of preparing the nanocomposite described above, comprising the steps of:
(1) mixing potassium pyroantimonate and silver nitrate in an aqueous solution state for reaction to obtain a product; the method for preparing the nano composite material is characterized in that a silver simple substance exists;
(2) and heating the reactant to obtain the composite material.
In one embodiment, the molar ratio of potassium pyroantimonate to silver nitrate is from 0.8 to 2.0: 1; preferably, the molar ratio of potassium pyroantimonate to silver nitrate is 3.88: 4.
in one embodiment, the heating temperature in step (ii) is 105-180 ℃; preferably, the heating temperature is 127 ℃.
In one embodiment, in step (i), the reaction temperature is 70-120 ℃; preferably, the reaction temperature is 80 ℃.
In one embodiment, the heating is performed under sealed conditions.
In one embodiment, in the step (2), after the mixture is heated, a washing and drying step is further included.
In one embodiment, the present invention also provides the use of the nanocomposite described above as a photocatalyst.
The following includes definitions of various terms and phrases used in the specification.
"nanoparticles" include particles having an average diameter size of 1nm to 1000nm, preferably 1nm to 100 nm.
The use of "including," comprising, "" containing, "or" having "when used in conjunction with any term in the claims or specification, the absence of a quantity preceding an element may mean" one, "but it is also consistent with the meaning of" one or more, "" at least one, "and" one or more than one.
The term "about" is defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the term is defined as being within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.
The words "comprising," "having," "including," or "containing" are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
Other objects, features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating specific embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
Example 1 1.7 2 6.25 Preparation of sesame ball-type Ag/AgSbO hollow nano composite material
And (3) synthesizing a powdery nano composite material. All chemical reagents were analytically pure without further purification. First, 1.0192g (3.88m mol) of potassium pyroantimonate (KSbO) 6 H 6 ) Dispersed in 50mL of deionized water and stirred at 80 ℃ for 0.5 hour (h). Secondly, 0 is added6796g (4.0mmol) of AgNO 3 Dissolved in 5mL of deionized water and added slowly to the above mixture, followed by stirring for 5 minutes. Again, the mixture (pH 6.8 measured using a pH meter) was sealed in a stainless steel autoclave lined with polytetrafluoroethylene (capacity 100ml) and heated at 127 ℃ (400K) for 24 hours. After the reaction, the autoclave was naturally cooled to room temperature. Finally, the product was washed (with deionized water and 99.5% ethanol) and dried (at 70 ℃ for 3 hours) to obtain a powdery nanocomposite.
Example 2 1.7 2 6.25 Preparation of sesame ball-type Ag/AgSbO hollow nano composite material
The same as example 1 except that the heating temperature of the mixture in the stainless steel autoclave was 100 deg.C (373K).
Example 3 1.7 2 6.25 Preparation of sesame ball-type Ag/AgSbO hollow nano composite material
The same procedure as in example 1 was repeated, except that the heating temperature of the mixture in the stainless steel autoclave was 200 ℃ C. (473K).
Example 4Material characterization
The sample obtained in example 1 was irradiated with CuK alpha radiation
Figure BDA0002548021850000051
Characterized on a Bruker D8 advanced X-ray powder diffractometer (XRD). The size and morphology of the synthesized product was determined by Zeiss Gemini500 Scanning Electron Microscope (SEM). The JEOL JEM2010 collects High Resolution Transmission Electron Microscope (HRTEM) images.
Sesame ball type Ag/Ag 1.7 Sb 2 O 6.25 A hollow nanocomposite. The crystal structure of the prepared sample was checked by X-ray diffraction (XRD) (see fig. 1). All diffraction peaks are related to Ag 1.69 Sb 2.27 O 6.25 JCPDS card numbers 89-6552 are identical and no XRD peak for metallic Ag was observed, probably due to the too small number of silver bar particles to be detected by XRD.
FIG. 2a shows Ag/Ag 1.7 Sb 2 O 6.25 A typical SEM image of the composite material and shows a large number of spherical particles with an average size of about 170nm and the presence of many broken spheres, showing that they are hollow inside. Fig. 2b is a higher magnification SEM image obtained from the selected area of fig. 2a, where a large number of uniformly dense smaller particles can be clearly observed on the surface of the hollow nanospheres, and the overall shape of the nanocomposite material looks like a chinese delicious hollow sesame-based sphere. HRTEM further investigated the fine structure and composition of the sesame-type spherical hollow particles, and figure 2c shows HRTEM images obtained from a localized area of a single hollow sphere, with two smaller spheres embedded in the particle, identified as "a" and "b", respectively, and an average size of 18.3 nm. The lattice of the "a" sphere was measured to be 0.23nm, which corresponds to the (111) crystal plane of metallic Ag. Apart from silver, a interplanar distance of 0.3nm was observed on each hollow sphere, which was the same as the (222) plane of silver antimonate. As shown in fig. 2d, the elemental distribution of silver/silver antimonate was verified by EDS elemental mapping and showed that there were Sb, O, Ag elements in these broken hollow spheres, but only Ag in all smaller nanospheres did not contain Sb and O, indicating that Ag nanoparticles are embedded in Ag 1.7 Sb 2 O 6.25 The hollow sesame ball is formed in the hollow ball.
The surface chemistry of Ag/Ag1.7Sb2O6.25 was studied by XPS. The detailed XPS spectra for Ag 3d in FIG. 3(a) show the assignment to Ag respectively + And Ag 0 Four peaks. The Ag 3d peaks at 373.9eV and 368.0eV correspond to Ag 3d3/2 and Ag 3d5/2 for Ag, respectively + Whereas the Ag0 peaks at 373.3eV and 367.9eV correspond to Ag0, indicating the presence of metallic Ag. The O1s XPS spectrum in fig. 3(b) shows two peaks at 530.4eV and 530.8 eV. The first peak 530.4eV is derived from the lattice oxygen of Ag/Ag1.7Sb2O6.25 and the latter peak is derived from hydroxyl groups. Fig. 3(c) shows Sb 3d XPS spectra, which consists of three fitted peaks. Peaks at 530.4eV and 530.5eV are represented by Sb 3+ And Sb 5+ Is assigned to oxygen, and the peak at 539.8eV corresponds to antimony-bonded silver. All peaks of Ag 3d, O1s and Sb 3d show different chemical states, revealing the mechanism of the hydrothermal synthesis of Ag/Ag 1.7sb2o6.25.
In this process, the formation of Ag/Ag results 1.7 Sb 2 O 6.25 The mechanism of the sesame ball type hollow nano composite material is not clear. However, our own experimental evidence led us to believe that Ag/Ag 1.7 Sb 2 O 6.25 The formation process of (a) is shown in fig. 3. First, potassium pyroantimonate and silver nitrate were decomposed into SbO in warm aqueous solution, respectively 6 H 6 - And K + (equation 1) and Ag + And NO 3 - (equation 2). When SbO is formed 6 H 6 - And Ag + When mixed together and preferentially adsorbed at the gas-liquid interface of the bubbles generated by the boiling aqueous solution in the concealed reactor at a temperature of 400k, many minute Ag forms 1.7 Sb 2 O 6.25 And (3) a crystal nucleus. Due to the presence of K + And NO 3 - Such inorganic ions increase the surface tension of the gas-liquid interface layer. The equation is as follows:
KSbO 6 H 6 ＝SbO 6 H 6 - +K + (1)
AgNO 3 ＝NO 3 - +Ag + (2)
2SbO 6 H 6 - +1.7Ag + →Ag 1.7 Sb 2 O 6.25 ↓ (3)。
then, Ag produced 1.7 Sb 2 O 6.25 The core grows on the spherical interface of the bubble and forms Ag with a hollow sphere structure 1.7 Sb 2 O 6.25 Nanoparticles. From Ag in hydrothermal reaction systems + The Ag aggregates with reduced Ag nanoparticles of 18.3nm average size 1.7 Sb 2 O 6.25 On the surface of the hollow nanospheres.
Example 5 optical Properties
FIG. 4 shows Ag/Ag prepared in example 1 1.7 Sb 2 O 6.25 And a calculated band gap and absorption spectrum of the UV-visible light of the precursor. The energy band gap (Eg) can be estimated according to the following formula:
αhυ＝A(hυ-E g ) 1/2
wherein the content of the first and second substances,E g h, α, v and a are the band gap, the plank constant, the absorption coefficient, the optical frequency and the constant, respectively. Precursor and Ag/Ag 1.7 Sb 2 O 6.25 E of (A) g 2.55eV and 2.65 eV.
Example 6Photocatalytic performance of nanocomposites
The Ag/Ag used in examples 1 to 3 1.7 Sb 2 O 6.25 The powder is used for carrying out catalytic degradation experiments on tetracycline hydrochloride respectively, and the photocatalytic activity of the powder material is researched. 1g of photocatalyst was added to 100mL of a tetracycline hydrochloride aqueous solution having a concentration of 16mg/L, and stirred for 30min in the absence of light to reach adsorption equilibrium. Subsequently, photocatalysis was performed with a 300W xenon lamp with a 420nm filter. In the experiment, samples are taken every 10min, and the absorbance of the samples is measured by an ultraviolet-visible diffuse reflection spectrophotometer, so that the concentration change of the tetracycline hydrochloride in the photocatalytic degradation process is judged.
The results show that, at 180min, Ag/Ag in examples 1, 2 and 3 1.7 Sb 2 O 6.25 The TC-HCl degradation rates of the powders were 97%, 78% and 85%, respectively, of Ag/Ag in example 1 1.7 Sb 2 O 6.25 The photocatalytic properties of the powder are optimal.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

1. A process for preparing a nanocomposite material comprising Ag nanoparticles and Ag 1.7 Sb 2 O 6.25 Nanoparticles, wherein the Ag 1.7 Sb 2 O 6.25 The nano particles are hollow spheres, and the Ag nano particles are embedded into the Ag 1.7 Sb 2 O 6.25 Hollow sesame spherical particles are formed in the nano particles, and the hollow sesame spherical particles are characterized in that:
the method comprises the following steps:
(i) mixing potassium pyroantimonate and silver nitrate in an aqueous solution state for reaction to obtain a product; wherein the addition amount of the silver nitrate can enable the product to contain a silver simple substance;
(ii) heating the reactant to obtain the composite material, wherein the heating is carried out under a sealed condition;
in the step (ii), the heating temperature is 105-180 ℃.
2. The method for preparing a nanocomposite material as claimed in claim 1, wherein the hollow sesame ball-type particles have a particle size of 80 to 180 nm.
3. The method for preparing a nanocomposite material as claimed in claim 1, wherein the hollow sesame sphere-shaped particles have a particle size of about 170 nm.
4. A process for the preparation of a nanocomposite as claimed in claim 1, characterized in that said ag1.7sb2o6.25 is obtained by the reaction:
Figure 180798DEST_PATH_IMAGE001
。
5. the method for preparing a nanocomposite as claimed in claim 1, wherein the molar ratio of potassium pyroantimonate to silver nitrate is from 0.8 to 2.0: 1.
6. the method for preparing a nanocomposite as claimed in claim 1, wherein the reaction temperature in the step (i) is 70 to 120 ℃.
7. The method according to claim 1, wherein in the step (ii), after heating the mixture, the method further comprises washing and drying steps.
8. Use of the nanocomposite obtained by the preparation method according to any one of claims 1 to 7 as a photocatalyst.
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