CN103043710A - Method for heterogeneously growing nano SnO2 on surface of alpha-Fe2O3 nanocrystalline - Google Patents

Method for heterogeneously growing nano SnO2 on surface of alpha-Fe2O3 nanocrystalline Download PDF

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CN103043710A
CN103043710A CN2011103158507A CN201110315850A CN103043710A CN 103043710 A CN103043710 A CN 103043710A CN 2011103158507 A CN2011103158507 A CN 2011103158507A CN 201110315850 A CN201110315850 A CN 201110315850A CN 103043710 A CN103043710 A CN 103043710A
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fe2o3
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CN103043710B (en
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王元生
牛牧童
黄烽
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

The invention provides a method for heterogeneously growing nano SnO2 on the surface of alpha-Fe2O3 nanocrystallines. The alpha-Fe2O3 nanocrystallines obtained in advance are dispersed in Sn(OH)6<2-> ethanol solution, and nano SnO2 is heterogeneously grown on the alpha-Fe2O3 nanocrystallines by virtue of solvothermal reaction, so that a semiconductor heterogeneous junction is formed. The preparation method provided by the invention is simple and convenient in process and high in yield, adopts cheap raw materials, is applicable to alpha-Fe2O3 crystallines with various morphologies and exposed surfaces, reported in literatures at present, and is not affected by residual surfactant on the surfaces of the nanocrystallines.

Description

A kind of at α-Fe 2O 3Nanocrystal surface Heteroepitaxy nano SnO 2Method
Technical field the present invention relates to the field of chemical synthesis.
Background technology α-Fe 2O 3And SnO 2Two kinds of widely used semiconductor materials, wherein α-Fe 2O 3Band gap is 2.2eV, is a kind of narrow bandgap semiconductor material; And SnO 2The band gap length reach 3.8eV, be a kind of wide bandgap semiconductor materials.The nanocrystalline of this bi-material all has respectively separately superiority in Application Areass such as photochemical catalysis, air-sensitive, solar cells.Bibliographical information is arranged in recent years, with the nanocrystalline Heterogeneous Composite formation SnO of this bi-material 2/ α-Fe 2O 3Nano heterojunction, its photoelectric properties will be better than single-phase nano crystalline.For example, on the magazine " nanotechnology " (Nanotechnology, 19 (2008) 205603) of physical society of Britain imperial family, once there was one piece of article report to synthesize SnO in 2008 2/ α-Fe 2O 3Nano heterojunction, this heterojunction powder has very strong selective gas effect for ethanol; And 2011 Britain's imperial family chemistry can magazine " crystal engineering design " (Crystengcomm, 13 (2011) 4486) on also have one piece of reported in literature to synthesize SnO 2/ α-Fe 2O 3Nano junction, this nano material visible light according under the effective organic pollutant in the degradation water solution.In addition, at the magazine of American Chemical Society " crystal growth design " (Crystal Growth﹠amp; Design) and on the internationally famous magazine such as " nanometer " (ACS Nano) all occurred about SnO in recent years 2/ α-Fe 2O 3The report of nano heterojunction.
The SnO that present document is reported 2/ α-Fe 2O 3The synthetic method of nano heterogeneous mixture all is two-step approach, namely synthesizes first Fe 2O 3Or SnO 2Single-phase nano crystalline, and then Heteroepitaxy to go out second-phase nanocrystalline.Yet the synthetic nanocrystalline pattern of first-phase and exposure are different and surperficial usually residually to have certain tensio-active agent, and whether these factors all can affect second-phase can successful Heteroepitaxy.At present, the method for reporting can only for specific pattern and exposure or specific tensio-active agent, synthesize the SnO of specific microstructure and pattern 2/ α-Fe 2O 3Nano heterojunction, some in addition can only synthesize simple two-phase mixture (SnO 2And Fe 2O 3Do not form heterogeneous interface between nanocrystalline).What in addition, these synthetic methods had need to be by high-temperature heat treatment; What have then need to by specific solvent or tensio-active agent, not yet have synthetic method appearance easy, efficient and that have certain universality at present.
As everyone knows, the microscopic appearance of nano material has a great impact its physical and chemical performance, if can develop a kind of efficiently, easy and have certain universality synthetic method of (can synthesize a series of patterns), will help performance optimization and the application and development of this nano material.This patent proposes a kind of efficient, easy at various Fe 2O 3Nanocrystalline upper Heteroepitaxy nano SnO 2, form SnO 2/ α-Fe 2O 3The synthetic method of nano heterojunction.The method is applicable to the Fe of various patterns and exposure 2O 3Nanocrystalline, and be not subjected to the impact of the residual tensio-active agent of nanocrystal surface.
Summary of the invention
The present invention proposes a kind of efficient, easy at α-Fe 2O 3Nanocrystal surface Heteroepitaxy nano SnO 2, the method for formation semiconductor nano heterojunction.The present invention proposes synthetic method:
At first, obtain α-Fe by the mode of synthesizing voluntarily or buy 2O 3Nanocrystalline (according to the obtainable α-Fe of present reported in literature 2O 3Nanocrystalline nanometer pseudo-cubic, spindle body, rhombohedron, nano-rings etc. arranged); Take by weighing mol ratio and be 1: 6～60 SnCl 4Be dissolved in the ethanol with NaOH, form Sn (OH) 6 2-Ethanolic soln; With α-Fe 2O 3The nanocrystalline Sn (OH) that is scattered in 6 2-In the solution, α-Fe 2O 3With Sn (OH) 6 2-Mol ratio be 1: 1～50; The gained mixed solution is transferred in the stainless steel cauldron, carries out solvent thermal reaction under 180～240 ℃ temperature, the reaction times is more than 2 hours; Then, by the high speed centrifugation collecting reaction product, namely obtain SnO 2/ α-Fe 2O 3The nano heterojunction powder.
The synthetic method that the present invention proposes has realized SnO 2Nanocrystalline at α-Fe 2O 3The heteroepitaxial growth of forerunner's nanocrystal surface has obtained the SnO of various patterns 2/ α-Fe 2O 3Nano heterojunction.Shown in embodiment 1-5, the present invention is applicable to the α-Fe of various patterns 2O 3Nanocrystalline, comprise the α-Fe of present reported in literature 2O 3Nanometer pseudo-cubic, spindle body, rhombohedron, nano-rings etc.The residual different tensio-active agent of these nanocrystal surface, for example, nanometer pseudo-cubic remained on surface be polyvinylpyrrolidone; The spindle body remained on surface be phosphoric acid salt; The rhombohedron remained on surface be hexadecyl trimethyl ammonium bromide etc., and method of the present invention is not subjected to the impact of these residual tensio-active agents.Preparation method's process of the present invention is easy, raw material is cheap, productive rate is high and suitability is strong.
Description of drawings
Fig. 1 pseudo-cubic shape α-Fe 2O 3The SnO nanocrystalline and example 1 prepares 2/ α-Fe 2O 3The photo of (pseudo-cubic) nano heterojunction powder under electron microscope: (a) α-Fe 2O 3Nanocrystal, (b) nano heterojunction, illustration are the enlarged photograph of heterogeneous interface;
Fig. 2 spindle body shape α-Fe 2O 3The SnO nanocrystalline and example 2 prepares 2/ α-Fe 2O 3The Photomicrograph of (spindle body) nano heterojunction powder: (a) α-Fe 2O 3Nanocrystal, (b) nano heterojunction;
Fig. 3 rhombohedron shape α-Fe 2O 3The SnO nanocrystalline and example 3 prepares 2/ α-Fe 2O 3The Photomicrograph of (rhombohedron) nano heterojunction powder: (a) α-Fe 2O 3Nanocrystal, the rhombohedron nanocrystalline photo of illustration for amplifying, (b) nano heterojunction;
Fig. 4 hollow ellipsoid shape α-Fe 2O 3The SnO nanocrystalline and example 4 prepares 2/ α-Fe 2O 3The Photomicrograph of (hollow ellipsoid) nano heterojunction powder: (a) α-Fe 2O 3Nanocrystal, (b) nano heterojunction;
Fig. 5 ring-type α-Fe 2O 3The SnO nanocrystalline and example 5 prepares 2/ α-Fe 2O 3The Photomicrograph of (ring bodies) nano heterojunction powder: (a) α-Fe 2O 3Nanocrystal, (b) nano heterojunction, illustration are the enlarged photograph of single heterojunction.
Embodiment
Example 1:SnO 2/ α-Fe 2O 3The preparation of (pseudo-cubic) nano heterojunction powder, appearance structure characterize
Nanometer pseudo-cubic shape α-Fe that this example is selected 2O 3The manocrystalline powders pattern is seen Fig. 1 a, and its remained on surface has the tensio-active agent polyvinylpyrrolidone.Take by weighing 0.087g SnCl 45H 2O and 0.267g NaOH are dissolved in (SnCl in the 15mL ethanol 4With the NaOH mole be 1: 6), obtain Sn (OH) 6 2-Solution; Take by weighing 0.010g pseudo-cubic shape α-Fe 2O 3The forerunner is nanocrystalline, and ultra-sonic dispersion is in prefabricated Sn (OH) 6 2-In the solution, α-Fe 2O 3With Sn (OH) 6 2-Mol ratio is 1: 1; The suspension liquid of gained is transferred in the stainless steel cauldron of 25mL, in retort furnace, under 220 ℃, carried out solvent thermal reaction 2 hours; Collect product by high speed centrifugation; Product is used respectively deionized water and washing with alcohol 3 times, and 50 ℃ of inner dryings are 4 hours under vacuum drying oven, namely obtain SnO 2/ α-Fe 2O 3(pseudo-cubic) nano heterojunction powder.
X-ray diffraction, transmission electron microscope and sem test result show, gained SnO 2/ α-Fe 2O 3The nano heterogeneous SnO that becomes 2The nanometer rod heteroepitaxial growth is in α-Fe 2O 3The pseudo-cubic surface forms multistage SnO 2/ α-Fe 2O 3Composite structure (seeing Fig. 1 b).Can find out SnO from figure b illustration 2Nanocrystalline and α-Fe 2O 3Between the connection of lattice fringe is arranged, illustrate that these two kinds of semi-conductors have formed the Nano semiconductor heterojunction, rather than simple mixture.
Following instance will change the material rate in the prescription, at different α-Fe 2O 3Nanocrystalline upper Heteroepitaxy SnO 2Nanocrystalline.
Example 2:SnO 2/ α-Fe 2O 3The preparation of (spindle body) nano heterojunction powder, appearance structure characterize
Nano-spun hammer body shape α-Fe that this example is selected 2O 3The manocrystalline powders pattern is seen Fig. 2 a, and its remained on surface has tensio-active agent phosphoric acid salt.Take by weighing 0.870g SnCl 45H 2O and 26.700g NaOH are dissolved in (SnCl in the 150mL ethanol 4With the NaOH mole be 1: 60), obtain Sn (OH) 6 2-Solution; Take by weighing 0.010g spindle shaped alpha-Fe 2O 3The forerunner is nanocrystalline, and ultra-sonic dispersion is in prefabricated Sn (OH) 6 2-(α-Fe in the solution 2O 3With Sn (OH) 6 2-Mol ratio is 1: 8); The suspension liquid of gained is transferred in the stainless steel cauldron of 25mL, in retort furnace, carried out solvent thermal reaction 2 hours in 200 ℃; Collect product by high speed centrifugation; Product is used respectively deionized water and washing with alcohol 3 times, in vacuum drying oven, in 50 ℃ of dryings 4 hours, namely get SnO 2/ α-Fe 2O 3(spindle body) nano heterojunction powder.
X-ray diffraction, transmission electron microscope and sem test result show, gained SnO 2/ α-Fe 2O 3The nano heterogeneous SnO that becomes 2Nanocrystalline heteroepitaxial growth is in α-Fe 2O 3The spindle body surface is with α-Fe 2O 3Spindle body forerunner plane of crystal covers (seeing Fig. 2 b) fully.
Example 3:SnO 2/ α-Fe 2O 3The preparation of (rhombohedron) nano heterojunction powder, appearance structure characterize
Nanometer rhombohedron shape α-Fe that this example is selected 2O 3The manocrystalline powders pattern is seen Fig. 3 a, and its remained on surface has the tensio-active agent hexadecyl trimethyl ammonium bromide.Take by weighing 0.870g SnCl 45H 2O and 26.700g NaOH are dissolved in (SnCl in the 75mL ethanol 4With the NaOH mole be 1: 60); Take by weighing 0.010g rhombohedron shape α-Fe 2O 3Nanocrystalline, ultra-sonic dispersion is in prefabricated Sn (OH) 6 2-(α-Fe in the dilute solution 2O 3With Sn (OH) 6 2-Mol ratio is 1: 20); The suspension liquid of gained is transferred in the stainless steel reaction of 25mL, in retort furnace, carried out solvent thermal reaction 3 hours in 240 ℃; Collect product by high speed centrifugation; Product is used respectively deionized water and washing with alcohol 3 times, in vacuum drying oven, in 50 ℃ of dryings 4 hours, namely obtain SnO 2/ α-Fe 2O 3(rhombohedron) nano heterojunction powder.
X-ray diffraction, transmission electron microscope and sem test result show, gained SnO 2/ α-Fe 2O 3The nano heterogeneous SnO that becomes 2Nanometer stub heteroepitaxial growth is in α-Fe 2O 3Rhombohedron surface (such as Fig. 3 b).
Example 4:SnO 2/ α-Fe 2O 3The preparation of (hollow ellipsoid) nano heterojunction powder, appearance structure characterize
Hollow ellipsoid shape α-Fe that this example is selected 2O 3The manocrystalline powders pattern is seen Fig. 4 a, and its remained on surface has phosphoric acid salt.Take by weighing 0.870g SnCl 45H 2O and 13.300g NaOH are dissolved in (SnCl in the 50mL ethanol 4With the NaOH mole be 1: 30); Take by weighing 0.010g spindle shaped alpha-Fe 2O 3The forerunner is nanocrystalline, and ultra-sonic dispersion is in prefabricated Sn (OH) 6 2-In the solution, α-Fe 2O 3With Sn (OH) 6 2-Mol ratio is 1: 50; The suspension liquid of gained is transferred in the stainless steel reaction of 25mL, in retort furnace, carried out solvent thermal reaction 2 hours in 180 ℃; Collect product by high speed centrifugation; Product is used respectively deionized water and washing with alcohol 3 times, in vacuum drying oven, in 50 ℃ of dryings 4 hours, namely get SnO 2/ α-Fe 2O 3(hollow ellipsoid) nano heterojunction powder.
X-ray diffraction, transmission electron microscope and sem test show, gained SnO 2/ α-Fe 2O 3The nano heterogeneous SnO that becomes 2Nanometer stub hetero epitaxy is born in α-Fe 2O 3The surfaces externally and internally of nano hollow ellipsoid (such as Fig. 4 b).
Example 5:SnO 2/ α-Fe 2O 3The preparation of (ring-type) nano heterojunction powder, appearance structure characterize
The selected ring-type α of this example-Fe 2O 3The manocrystalline powders pattern is seen Fig. 5 a, and its remained on surface has phosphoric acid salt and vitriol.Take by weighing 0.087g SnCl 45H 2O and 0.267g NaOH are dissolved in (SnCl in the 15mL ethanol 4With the NaOH mole be 1: 6), obtain Sn (OH) 6 2-Solution; Take by weighing 0.010g pseudo-cubic shape α-Fe 2O 3The forerunner is nanocrystalline, and ultra-sonic dispersion is in prefabricated Sn (OH) 6 2-In the solution, α-Fe 2O 3With Sn (OH) 6 2-Mol ratio is 1: 1; The suspension liquid of gained is transferred in the stainless steel cauldron of 25mL, in retort furnace, under 220 ℃, carried out solvent thermal reaction 2 hours; Collect product by high speed centrifugation; Product is used respectively deionized water and washing with alcohol 3 times, and 50 ℃ of inner dryings are 4 hours under vacuum drying oven, namely obtain SnO 2/ α-Fe 2O 3(ring-type) nano heterojunction powder.
X-ray diffraction, transmission electron microscope and sem test show, gained SnO 2/ α-Fe 2O 3The nano heterogeneous SnO that becomes 2Nanometer stub heteroepitaxial growth is in α-Fe 2O 3The interior outer side of nano-rings (such as Fig. 4 b).
Example 6: change the reaction times to synthetic SnO 2/ α-Fe 2O 3The impact of nano heterojunction powder
According to the prescription of example 1, change the solvent thermal reaction time (extending to 5 hours from 1 hour), find in conjunction with the XRD test by the electron microscope sem observation, when the reaction times less than 2 hours, do not have SnO 2Nanocrystalline generation.Therefore utilize method of the present invention to synthesize SnO 2/ α-Fe 2O 3Nano heterojunction, the Heteroepitaxy nano SnO 2Reaction times should be above 2 hours.

Claims (1)

1. one kind at α-Fe 2O 3Nanocrystal surface Heteroepitaxy nano SnO 2Method, it is characterized by: be 1: 6～60 SnCl with molar ratio 4Mix in ethanol with NaOH, form Sn (OH) 6 2-Ethanolic soln; With the α-Fe that obtains in advance 2O 3Nanocrystal is dispersed in Sn (OH) 6 2-In the solution, α-Fe 2O 3Nanocrystalline and Sn (OH) 6 2-Mol ratio be 1: 1～50; The mixed solution of gained is carried out solvent thermal reaction, and temperature is 180～240 ℃, and the reaction times is more than 2 hours.
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