CN102764652A - Preparation method of flower-like tin oxide/silver heterojunction material - Google Patents

Abstract

The invention discloses a preparation method of a flower-like tin oxide/silver heterojunction material. The method is used for solving the technical problem that the preparation period of preparation of the metal silver doped with stannic oxide is long. The technical scheme includes that a mixed solution of SnC12.2H20 and Na3C6H5O7.2H2O is prepared firstly, flaky NaOH is added, the mixture is mixed uniformly, the prepared AgNO3 solution is added to the mixed solution, the mixed solution is transferred to a reaction tank and added into a microwave reactor for heating, the temperature is lowered to a room temperature after the reaction, the solution in a reaction container is poured out, performing repeat washing with deionized water and absolute ethyl alcohol and drying after filtering, the temperature is raised to 450-600 DEG C with the speed of 1-3 DEG C min-1, 1-2.5 h heat preservation is achieved, and the flower-like tin oxide/silver heterojunction material is obtained. Microwave water heating is performed, and a heat processing method is supplemented, so that flower-like tin oxide/silver heterojunction which is in good crystallinity is obtained, the preparation period is shortened, and the technological parameter can be controlled accurately.

Description

The preparation method of flower-shaped tin oxide/silver-colored heterojunction material

Technical field

The present invention relates to the preparation method of a kind of tin oxide/silver-colored heterojunction material, particularly relate to the preparation method of a kind of flower-shaped tin oxide/silver-colored heterojunction material.

Background technology

Document " Ceng Wen, Lin Zhidong, high person of outstanding talent, metallic ion doped nano SnO ₂The air-sensitive performance of material and Doping Mechanism, nanometer technology and precision engineering, 6 (2008) 174-179 " a kind of preparation method of metal ion mixing tin ash disclosed; wherein relate to the preparation of metal-silver-doped tin ash; this method adopts sol-gel process to obtain to carry out the doping of metallic again after tin ash particle, calcines at last; the gained particle diameter is all in nanometer range, the Size Distribution narrow range.

This method belongs to two step synthetic methods, and technology is miscellaneous, uneconomical practicality in large-scale production; In the preparation of solution, make pH through dropping ammonia>7, in concrete operation, be difficult to precisely control, poor repeatability; Simultaneously, the crystallinity of gained nano particle is bad, and this can make some performance such as the photocatalysis performance of tin ash, air-sensitive performance be restricted.

Summary of the invention

Prepare the long deficiency of metal-silver-doped tin ash manufacturing cycle in order to overcome existing method, the present invention provides the preparation method of a kind of flower-shaped tin oxide/silver-colored heterojunction material.This method adopts microwave hydrothermal, is aided with heat-treating methods simultaneously, can obtain the good flower-shaped tin oxide of crystallinity/silver-colored hetero-junctions, and manufacturing cycle is short, and technological parameter can accurately be controlled.

The technical solution adopted for the present invention to solve the technical problems is: the preparation method of a kind of flower-shaped tin oxide/silver-colored heterojunction material is characterized in may further comprise the steps:

(a) preparation SnCl ₂2H ₂O and Na ₃C ₆H ₅O ₇2H ₂The mixed solution of O, wherein SnCl ₂Molar concentration be 0.1～0.2mol/L, Na ₃C ₆H ₅O ₇Molar concentration be 0.25～0.4mol/L, magnetic agitation 10～20min makes it to mix;

(b) add sheet NaOH, controlling its molar concentration is 0.05～0.1mol/L, and magnetic agitation 10～20min makes it to mix;

(c) prepare the AgNO that molar concentration is 0.06～0.35mol/L simultaneously ₃Solution, magnetic agitation 10～20min joins after mixing in the mixed solution that step (b) prepares, and continues magnetic agitation 10～20min;

(d) mixed solution that step (c) is prepared is transferred in the retort that polytetrafluoroethylene (PTFE) processes, and container is screwed, and in the microwave reaction appearance of packing into, is heated to 150～250 ℃, insulation 0.5～1.5h;

(e) after question response finishes to be cooled to room temperature, the solution in the reaction vessel is poured out, filtered with deionized water and absolute ethyl alcohol cyclic washing, the pH value of the deionized water after filtering is that 7 backs are dry;

(d) with 1～3 ℃ of min ^-1Speed be warming up to 450～600 ℃, the insulation 1～2.5h, obtain flower-shaped tin oxide/silver-colored heterojunction material.

The invention has the beneficial effects as follows: owing to adopt microwave hydrothermal, be aided with heat-treating methods simultaneously, obtained the good flower-shaped tin oxide/silver-colored hetero-junctions of crystallinity, it is short to have shortened manufacturing cycle, and technological parameter can accurately be controlled.

Below in conjunction with accompanying drawing and embodiment the present invention is elaborated.

Description of drawings

Fig. 1 is the XRD figure spectrum of the inventive method embodiment 1, embodiment 2 prepared flower-shaped tin oxide/silver-colored heterojunction materials; (a) is embodiment 1 prepared flower-shaped tin oxide/silver-colored heterojunction material among the figure; (b) embodiment 2 prepared flower-shaped tin oxide/silver-colored heterojunction materials.

Fig. 2 (a) is the SEM photo of the prepared flower-shaped tin oxide/silver-colored heterojunction material of the inventive method embodiment 3, and Fig. 2 (b) is the SEM photo of the flower-shaped tin oxide/silver-colored heterojunction material of the inventive method embodiment 4 preparations.

Fig. 3 is the flower-shaped tin oxide/silver-colored heterojunction material of the inventive method preparation and the photocatalysis performance correlation curve of commercially available tin ash.

The specific embodiment

Following examples are with reference to Fig. 1～3.

Embodiment 1, with 0.9026gSnCl ₂2H ₂O and 0.2941gNa ₃C ₆H ₅O ₇2H ₂O adds in the 30ml deionized water, and magnetic agitation 10min makes it to mix; Add 0.06g sheet NaOH, magnetic agitation 10min mixes; Simultaneously with 0.1019g AgNO ₃Join in the 10ml deionized water, after magnetic agitation 10min is mixed with homogeneous solution, join in the aforementioned mixed solution, continue magnetic agitation 10min; Mixed solution is transferred in the retort that polytetrafluoroethylene (PTFE) processes, container is screwed, in the microwave reaction appearance of packing into, be heated to 150 ℃, insulation 1.5h; Question response after finishing to be cooled to room temperature is poured out the solution in the reaction vessel, filters with deionized water and absolute ethyl alcohol cyclic washing, and the pH value of the deionized water after filtering is 7,60 ℃ of dryings; With 1 ℃ of min ^-1Speed be warming up to 450 ℃, insulation 2.5h collects the gained sample and carries out various tests and characterize.

As can beappreciated from fig. 1, be 26.6 ° in 2 θ values, 33.9 °; 39.0 ° and 51.8 ° locate all to exist the obvious diffraction peak, in conjunction with some other more weak peak, corresponding the tin ash of rutile-type; Explanation is under the reaction condition of present embodiment, and the material of generation is tin ash really.In addition, also there is the peak a little of faint silver to occur.

Embodiment 2, with 0.9477gSnCl ₂2H ₂O and 3.088gNa ₃C ₆H ₅O ₇2H ₂O adds in the 35ml deionized water, and magnetic agitation 15min makes it to mix; Add 0.084g sheet NaOH, magnetic agitation 15min mixes; Simultaneously with 0.1698g AgNO ₃Join in the 10ml deionized water, after magnetic agitation 15min is mixed with homogeneous solution, join in the aforementioned mixed solution, continue magnetic agitation 15min; Mixed solution is transferred in the retort that polytetrafluoroethylene (PTFE) processes, container is screwed, in the microwave reaction appearance of packing into, be heated to 180 ℃, insulation 1.3h; Question response after finishing to be cooled to room temperature is poured out the solution in the reaction vessel, filters with deionized water and absolute ethyl alcohol cyclic washing, and the pH value of the deionized water after filtering is 7,60 ℃ of dryings; With 2 ℃ of min ^-1Speed be warming up to 500 ℃, insulation 2h collects the gained sample and carries out various tests and characterize.

As can beappreciated from fig. 1, still can obtain the compound crystalline phase of tin ash and silver under this reaction condition.Because the content of silver increases, it also has enhancing in the peak a little.The tin ash diffraction maximum is explained the certain compound entering tin ash lattice of silver slightly to the low angle skew simultaneously.

Embodiment 3, with 1.0831gSnCl ₂2H ₂O and 3.5292gNa ₃C ₆H ₅O ₇2H ₂O adds in the 40ml deionized water, and magnetic agitation 20min makes it to mix; Add 0.096g sheet NaOH, magnetic agitation 20min mixes; Simultaneously with 0.3396gAgNO ₃Join in the 10ml deionized water, after magnetic agitation 20min is mixed with homogeneous solution, join in the aforementioned mixed solution, continue magnetic agitation 20min; Mixed solution is transferred in the retort that polytetrafluoroethylene (PTFE) processes, container is screwed, in the microwave reaction appearance of packing into, be heated to 200 ℃, insulation 1h; Question response after finishing to be cooled to room temperature is poured out the solution in the reaction vessel, filters with deionized water and absolute ethyl alcohol cyclic washing, and the pH value of the deionized water after filtering is 7,60 ℃ of dryings; With 2 ℃ of min ^-1Speed be warming up to 550 ℃, insulation 1.5h collects the gained sample and carries out various tests and characterize.

As can beappreciated from fig. 2, tin oxide/silver composite material pattern that this embodiment generates is flower-shaped, and diameter is in 0.8～1 mu m range, and it is comparatively even to distribute.

Embodiment 4, with 1.1283gSnCl ₂2H ₂O and 3.6704gNa ₃C ₆H ₅O ₇2H ₂O adds in the 40ml deionized water, and magnetic agitation 20min makes it to mix; Add 0.1g sheet NaOH, magnetic agitation 20min mixes; Simultaneously with 0.5943g AgNO ₃Join in the 10ml deionized water, after magnetic agitation 20min is mixed with homogeneous solution, join in the aforementioned mixed solution, continue magnetic agitation 20min; Mixed solution is transferred in the retort that polytetrafluoroethylene (PTFE) processes, container is screwed, in the microwave reaction appearance of packing into, be heated to 250 ℃, insulation 0.5h; Question response after finishing to be cooled to room temperature is poured out the solution in the reaction vessel, filters with deionized water and absolute ethyl alcohol cyclic washing, and the pH value of the deionized water after filtering is 7,60 ℃ of dryings; With 3 ℃ of min ^-1Speed be warming up to 600 ℃, insulation 1h collects the gained sample and carries out various tests and characterize.

As can beappreciated from fig. 3, compare with the tin ash that is purchased, the material that present embodiment synthesized has excellent more photocatalysis performance.Simultaneously, along with the increase of silver-colored doping in the preparation system, the photocatalytic of material descends.

The method that the present invention combines photoactivation and heat treatment phase has prepared the coralliform tin oxide nano particles.Particle grain size distribution is even, and photocatalysis performance is high.Method of operating is simple, cleaning, be prone to repetition, helps in commercial production, applying.

Claims (1)

1. the preparation method of flower-shaped tin oxide/silver-colored heterojunction material is characterized in that may further comprise the steps:

(a) preparation SnCl ₂2H ₂O and Na ₃C ₆H ₅O ₇2H ₂The mixed solution of O, wherein SnCl ₂Molar concentration be 0.1～0.2mol/L, Na ₃C ₆H ₅O ₇Molar concentration be 0.25～0.4mol/L, magnetic agitation 10～20min makes it to mix;

(b) add sheet NaOH, controlling its molar concentration is 0.05～0.1mol/L, and magnetic agitation 10～20min makes it to mix;

(c) prepare the AgNO that molar concentration is 0.06～0.35mol/L simultaneously ₃Solution, magnetic agitation 10～20min joins after mixing in the mixed solution that step (b) prepares, and continues magnetic agitation 10～20min;

(d) mixed solution that step (c) is prepared is transferred in the retort that polytetrafluoroethylene (PTFE) processes, and container is screwed, and in the microwave reaction appearance of packing into, is heated to 150～250 ℃, insulation 0.5～1.5h;

(e) after question response finishes to be cooled to room temperature, the solution in the reaction vessel is poured out, filtered with deionized water and absolute ethyl alcohol cyclic washing, the pH value of the deionized water after filtering is that 7 backs are dry;

(d) with 1～3 ℃ of min ^-1Speed be warming up to 450～600 ℃, the insulation 1～2.5h, obtain flower-shaped tin oxide/silver-colored heterojunction material.

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