CN113697844B - Fe doped ZnO nano-particle with dodecahedron structure - Google Patents
Fe doped ZnO nano-particle with dodecahedron structure Download PDFInfo
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Abstract
The invention discloses a Fe doped ZnO nano particle with a dodecahedron structure, which is prepared by the following steps: (1) Dissolving a zinc source and an iron source in deionized water to obtain zinc-iron source liquid; dissolving 2-methylimidazole to deionizedObtaining 2-methylimidazole solution in water; (2) Mixing zinc-iron source solution and 2-methylimidazole solution, homogenizing by stirring, standing at room temperature in dark to react, centrifuging, washing and drying precipitate after the reaction is finished to obtain ZnFe-ZIF precursor; (3) Annealing ZnFe-ZIF precursor at high temperature, cooling to obtain Zn with dodecahedron structure 1‑x Fe x O nanoparticles. The MOF precursor is adopted to simplify the doping step, the internal structure of the material is easy to control, and the material can be in a solid, single-shell or double-shell dodecahedron structure, and has the advantages of uniform appearance, good dispersibility and crystallinity, high surface chemical activity and large specific surface area.
Description
Technical Field
The invention relates to the technical field of nano material production, in particular to Fe doped ZnO nano particles with a dodecahedron structure.
Background
Zinc oxide (ZnO), which is an n-type semiconductor material having a wide band gap of 3.37 and eV, is widely used in various fields such as solar energy, gas sensors, spintronics, photonics, photocatalysis, etc., because of its advantages of no toxicity, excellent chemical stability, high electron mobility, structural adjustability, etc. In addition, it has been reported that doping ZnO with various elements such as noble metals, rare metals, transition metals, etc. is a useful method for improving conductivity when used in a gas sensing device. Iron (Fe) is one of the most common elements in nature; and the d-orbital electrons of Fe easily overlap with the ZnO valence band. When Fe is doped with ZnO, the number of active sites of the material is increased, so that the adsorption of gas elements is facilitated. Therefore, the synthesis of Fe doped ZnO material to improve the gas-sensitive performance of ZnO has important significance.
The Metal Oxide Framework (MOF) is a novel porous material assembled by inorganic metal nodes and organic ligand molecules, and has good application prospect in the field of sensing due to high porosity, specific surface area and morphological stability. However, high electrical resistance limits the immediate use of MOFs as sensing materials. Thermal annealing of the MOF precursor can maintain the morphology and porous structure of the MOF for metal oxide semiconductors, and the high specific surface area allows MOF-derived oxide semiconductor materials to exhibit better gas-sensitive properties. Among these MOF derivatives of metal oxide semiconductors, hollow multishell structures (HoMS) have attracted considerable attention. This is because MOFs have extremely strong flexibility, and their organic ligands and metal components can be separated by fine secondary treatments. The MOF-derived oxide-based shell structure has great research potential, but few research reports exist, and the structure is relatively simple.
Disclosure of Invention
The invention aims to provide Fe doped ZnO nano particles with a dodecahedron structure, which adopts MOF precursors to simplify the doping steps, and the internal structure of the material is easy to control, and can be a solid, single-shell or double-shell dodecahedron structure, and the Fe doped ZnO nano particles have the advantages of uniform morphology, good dispersibility and crystallinity, high surface chemical activity and large specific surface area.
The technical scheme adopted for solving the technical problems is as follows:
zn with dodecahedron structure 1-x Fe x O nanoparticles prepared by the steps of:
(1) Dissolving a zinc source and an iron source in deionized water, and uniformly stirring and mixing to obtain zinc-iron source liquid; simultaneously, dissolving 2-methylimidazole into deionized water, and stirring until the 2-methylimidazole is completely dissolved to obtain a 2-methylimidazole solution;
(2) Mixing zinc-iron source solution and 2-methylimidazole solution, homogenizing by stirring, standing at room temperature in dark for 12-96 hours, centrifuging to obtain precipitate after the reaction, washing the precipitate with methanol for multiple times, and drying to obtain ZnFe-ZIF precursor with a solid dodecahedral structure;
(3) High-temperature annealing the ZnFe-ZIF precursor with the solid dodecahedron structure at the annealing temperature of 350-450 ℃ for 1-4 hours, and cooling to obtain Zn with the dodecahedron structure 1-x Fe x O nanoparticles.
Annealing the ZnFe-ZIF precursor with the solid dodecahedron structure in the air atmosphere at the temperature of 2-20 ℃/min to be increased to 350 ℃ for 2 hours, and cooling to obtain the Zn with the solid dodecahedron structure 1-x Fe x O nanoparticles.
ZnFe-ZIF precursor with solid dodecahedron structure is carried out at 2 ℃ in air atmosphereHeating to 400 ℃ per min, annealing for 2 hours, and cooling to obtain Zn with a single-shell dodecahedron structure 1-x Fe x O nanoparticles.
Annealing the ZnFe-ZIF precursor with the solid dodecahedron structure for 2 hours in an air atmosphere at the temperature of 2 ℃/min to 400 ℃, then annealing for 1 hour at the temperature of 20 ℃/min to 450 ℃, and cooling to obtain the Zn with the double-shell dodecahedron structure 1- x Fe x O nanoparticles. Zn of double-shell dodecahedron structure as the most preferable structure 1-x Fe x Compared with solid and single-shell structures, the O nano particles have larger specific surface area and more pores, fe is doped in ZnO in a +2 valence form, the O nano particles have a hollow dodecahedron structure with uniform morphology and the diameter of about 1.0-1.2 mu m, and as a gas sensor, the more active sites on the surface of a material are, the more defects are, the more pores are, the more reaction between the material and gas molecules is facilitated, and compared with the solid and single-shell structures, the ZnO with the double-shell dodecahedron structure has the advantages of more active sites, the more defects and the more pores on the surface of the material, and the Fe with catalytic activity is doped 2+ The valence ions improve the conductivity, and are particularly suitable for being used as a gas sensor material. Ferric iron can not be synthesized into a dodecahedron hollow structure, and only ferrous iron can be doped into ZnO of the structure.
2-methylimidazole is an organic linker which forms a zeolitic imidazolate framework with metallic Zn/Fe. Zn with single shell dodecahedron structure 1-x Fe x The O nanoparticles are hollow structures. Zn (zinc) 1-x Fe x O is 0.1 +.x +.0.5.
The zinc source is zinc acetate and the iron source is ferrous sulfate heptahydrate.
The molar ratio of the zinc source to the iron source is 9:1-1:1. Preferably, the molar ratio of the zinc source to the iron source is 9:1.
In the zinc-iron source liquid, the total concentration of the zinc source and the iron source is 0.2-0.35mol/L.
The concentration of the 2-methylimidazole solution is 2.2-3.2mol/L.
The zinc-iron source solution and the 2-methylimidazole solution are mixed according to the volume ratio of 1:1.
Fe doped with the preparation methodThe mixed ZnO sample has a hexagonal wurtzite structure. The invention takes zinc acetate and ferrous sulfate heptahydrate as metal sources, wherein the ferrous sulfate heptahydrate is taken as doping agent, and adopts simple normal temperature stirring combined annealing method to prepare Zn 1-x Fe x Nanoparticles of the Ododecahedron structure. Adjustment of annealing conditions to form Zn with different internal structures 1-x Fe x The Ododecahedron nanoparticles play an important role.
The beneficial effects of the invention are as follows:
1. zn of the invention 1-x Fe x The O dodecahedron nano particles are of a hierarchical structure, MOF precursors are adopted to simplify doping steps, the internal structure of the material is easy to control, the O dodecahedron nano particles can be of solid, single-shell and double-shell dodecahedron structures, the O dodecahedron nano particles are uniform in appearance, good in dispersibility and crystallinity, high in surface chemical activity and large in specific surface area, and meanwhile, the doping can improve the conductivity, so that the O dodecahedron nano particles have potential application values in the field of gas sensors.
2. The Fe-doped ZnO double-shell dodecahedron nanoparticle prepared by the method has the advantages of low-cost and easily-obtained raw materials, simple preparation process, low cost, controllable morphology and structure, good repeatability and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern of the ZnFe-ZIF precursor prepared in example 1;
FIG. 2 is a scanning electron microscope and transmission diagram of a ZnFe-ZIF precursor prepared in example 1; wherein: (a) scanning electron microscope images; (b) transmitting the picture;
FIG. 3 is a Zn of a double shell dodecahedron structure prepared in example 1 1-x Fe x X-ray diffraction pattern of O nanoparticles;
FIG. 4 is a Zn of a double shell dodecahedron structure prepared in example 1 1-x Fe x Scanning electron microscope images of O nano particles;
FIG. 5 is Zn of a double shell dodecahedron structure prepared in example 1 1-x Fe x A transmission map of O nanoparticles;
FIG. 6 is a Zn solid dodecahedron structure prepared in example 2 1-x Fe x A transmission map of O nanoparticles;
FIG. 7 is a real worldExample 3 preparation of Zn of monocoque structure 1-x Fe x Transmission diagram of O nanoparticles.
Detailed Description
The technical scheme of the invention is further specifically described by the following specific examples.
In the present invention, the materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Zn with dodecahedron structure 1-x Fe x O nanoparticles prepared by the steps of:
(1) Dissolving a zinc source and an iron source in deionized water, and uniformly stirring and mixing to obtain zinc-iron source liquid; simultaneously, dissolving 2-methylimidazole into deionized water, and stirring until the 2-methylimidazole is completely dissolved to obtain a 2-methylimidazole solution;
(2) Mixing zinc-iron source solution and 2-methylimidazole solution, homogenizing by stirring, standing at room temperature in dark for 12-96 hr, centrifuging to obtain precipitate, washing the precipitate with methanol for 2-5 times, and drying to obtain ZnFe-ZIF precursor with solid dodecahedron structure
(3) High-temperature annealing the ZnFe-ZIF precursor with the solid dodecahedron structure at the annealing temperature of 350-450 ℃ for 1-4 hours, and cooling to obtain Zn with the dodecahedron structure 1-x Fe x O nanoparticles.
Annealing the ZnFe-ZIF precursor with the solid dodecahedron structure for 2 hours at the temperature of 350 ℃ at the temperature rising rate of 2-20 ℃/min in the air atmosphere, and cooling to obtain the Zn with the solid dodecahedron structure 1-x Fe x O nanoparticles.
Annealing the ZnFe-ZIF precursor with the solid dodecahedron structure in the air atmosphere at the temperature of 2 ℃/min to 400 ℃ for 2 hours, and cooling to obtain the Zn with the single-shell dodecahedron structure 1-x Fe x O nanoparticles.
The ZnFe-ZIF precursor with the solid dodecahedron structure is annealed for 2 hours in the air atmosphere at the temperature of 2 ℃/min to 400 ℃ and then at the temperature of 20 ℃/minAnnealing for 1 hour at the temperature of 450 ℃, and cooling to obtain Zn with a double-shell dodecahedron structure 1- x Fe x O nanoparticles.
The zinc source is zinc acetate and the iron source is ferrous sulfate heptahydrate.
The molar ratio of the zinc source to the iron source is 9:1-1:1; in the zinc-iron source liquid, the total concentration of the zinc source and the iron source is 0.2-0.35mol/L. The concentration of the 2-methylimidazole solution is 2.2-3.2mol/L. The zinc-iron source solution and the 2-methylimidazole solution are mixed according to the volume ratio of 1:1.
Example 1:
zn with double-shell dodecahedron structure 1-x Fe x The preparation of the O nano-particles comprises the following steps:
(1) 0.26g of C 4 H 6 O 4 Zn·2H 2 O was dissolved in 5mL of deionized water, then 0.04g of FeSO was added 4 ·7H 2 Adding O into the solution, and vigorously stirring until the O is completely dissolved; simultaneously, 1.12g of 2-methylimidazole was dissolved in 5mL of deionized water, and stirred until completely dissolved. Then, rapidly mix C 4 H 6 O 4 Zn·2H 2 O and FeSO 4 ·7H 2 The mixed solution of O was poured into a 2-methylimidazole solution and stirred for 60 seconds for homogenization. Finally, the mixture was left to stand at room temperature under a dark condition for 48 h to carry out a reaction, after the reaction was completed, the product was centrifugally separated and washed with methanol for 3 times, and dried to obtain a ZnFe-ZIF precursor with a solid dodecahedral structure, the XRD of which is shown in FIG. 1, and the SEM and TEM patterns of which are shown in FIG. 2.
(2) Annealing the ZnFe-ZIF precursor with the solid dodecahedron structure prepared in the step (1) for 2 hours at the temperature of 400 ℃ in an air environment, wherein the heating rate is 2 ℃/min; secondly, the temperature is increased to 450 ℃ at a speed of 20 ℃/min, and then the temperature is kept for 1h, so as to obtain the Zn with a double-shell dodecahedron structure 0.9 Fe 0.1 The XRD, SEM and TEM of the O nanoparticles are shown in figures 3-5.
As can be seen from FIG. 1, the obtained ZnFe-ZIF precursor with the solid dodecahedron structure has the same structure as ZIF-8, and the morphological characterization result shows that the ZnFe-ZIF precursor has smooth surface, uniform size and average particle sizeA solid dodecahedron structure of about 1.2 μm. XRD results after annealing showed Zn 1-x Fe x The O sample is a hexagonal wurtzite structure, has a space group of P63mc (JCPDS 36-1451), has no redundant impurity peak, and has stronger peak intensity, thus indicating the Zn of the invention 0.9 Fe 0.1 The crystallinity of the O sample is good; the appearance and the size of the sample are not obviously changed, the surface is roughened, the sample is assembled by primary nano particles, and the size is about 1.0-1.2 mu m.
Example 2:
zn with solid dodecahedron structure 1-x Fe x The preparation of the O nano-particles comprises the following steps:
(1) 0.26g of C 4 H 6 O 4 Zn·2H 2 O was dissolved in 5mL of deionized water, then 0.04g of FeSO was added 4 ·7H 2 Adding O into the solution, and vigorously stirring until the O is completely dissolved; simultaneously, 1.12g of 2-methylimidazole was dissolved in 5mL of deionized water, and stirred until completely dissolved. Then, rapidly mix C 4 H 6 O 4 Zn·2H 2 O and FeSO 4 ·7H 2 The mixed solution of O was poured into a 2-methylimidazole solution and stirred for 60 seconds for homogenization. Finally, the mixture was left to stand at room temperature under a dark condition for 48 h to carry out a reaction, after the reaction was completed, the product was centrifugally separated and washed with methanol for 3 times, and dried to obtain a ZnFe-ZIF precursor with a solid dodecahedral structure, the XRD of which is shown in FIG. 1, and the SEM and TEM patterns of which are shown in FIG. 2.
(2) Annealing the ZnFe-ZIF precursor with the solid dodecahedron structure prepared in the step (1) for 2 hours at the temperature of 350 ℃ in an air environment to obtain the Zn with the solid dodecahedron structure 0.9 Fe 0.1 The TEM image of the O nano particles is shown in figure 6.
Example 3:
zn with single shell dodecahedron structure 1-x Fe x The preparation of the O nano-particles comprises the following steps:
(1) 0.26g of C 4 H 6 O 4 Zn·2H 2 O was dissolved in 5mL of deionized water, then 0.04g of FeSO was added 4 ·7H 2 Adding O into the above solutionStirring vigorously to dissolve completely; simultaneously, 1.12g of 2-methylimidazole was dissolved in 5mL of deionized water, and stirred until completely dissolved. Then, rapidly mix C 4 H 6 O 4 Zn·2H 2 O and FeSO 4 ·7H 2 The mixed solution of O was poured into a 2-methylimidazole solution and stirred for 60 seconds for homogenization. Finally, the mixture was left to stand at room temperature under a dark condition for 48 h to carry out a reaction, after the reaction was completed, the product was centrifugally separated and washed with methanol for 3 times, and dried to obtain a ZnFe-ZIF precursor with a solid dodecahedral structure, the XRD of which is shown in FIG. 1, and the SEM and TEM patterns of which are shown in FIG. 2.
(2) Annealing the ZnFe-ZIF precursor with the solid dodecahedron structure prepared in the step (1) for 2 hours at the temperature of 400 ℃ in an air environment, wherein the heating rate is 2 ℃/min, and obtaining the Zn with the single-shell dodecahedron structure 0.9 Fe 0.1 The TEM image of the O nano particles is shown in figure 7.
Comparative example 1
This example differs from example 1 in that FeSO 4 ·7H 2 O is replaced by ferric sulfate, otherwise the same as in example 1. Finally, zn with a double-shell dodecahedron structure cannot be prepared 1-x Fe x O nanoparticles.
The above-described embodiment is only a preferred embodiment of the present invention, and is not limited in any way, and other variations and modifications may be made without departing from the technical aspects set forth in the claims.
Claims (1)
1. Zn with dodecahedron structure 1-x Fe x The O nano-particles are characterized by being prepared by the following steps:
(1) Dissolving a zinc source and an iron source in deionized water, and uniformly stirring and mixing to obtain zinc-iron source liquid; simultaneously, dissolving 2-methylimidazole into deionized water, and stirring until the 2-methylimidazole is completely dissolved to obtain a 2-methylimidazole solution;
(2) Mixing zinc-iron source solution and 2-methylimidazole solution, homogenizing by stirring, standing at room temperature in dark for 12-96 hours, centrifuging to obtain precipitate after the reaction, washing the precipitate with methanol for multiple times, and drying to obtain ZnFe-ZIF precursor with a solid dodecahedral structure;
(3) Annealing the ZnFe-ZIF precursor with the solid dodecahedron structure for 2 hours in an air atmosphere at the temperature of 2 ℃/min to 400 ℃, then annealing for 1 hour at the temperature of 20 ℃/min to 450 ℃, and cooling to obtain the Zn with the double-shell dodecahedron structure 1- x Fe x O nanoparticles;
the zinc source is zinc acetate, and the iron source is ferrous sulfate heptahydrate; the molar ratio of the zinc source to the iron source is 9:1-1:1; in the zinc-iron source liquid, the total concentration of the zinc source and the iron source is 0.2-0.35mol/L; the concentration of the 2-methylimidazole solution is 2.2-3.2mol/L; the zinc-iron source solution and the 2-methylimidazole solution are mixed according to the volume ratio of 1:1.
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