CN103586024A - Preparation method for hollow ball or spheroidal Ag2ZnGeO4 photocatalyst - Google Patents

Preparation method for hollow ball or spheroidal Ag2ZnGeO4 photocatalyst Download PDF

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CN103586024A
CN103586024A CN201310591746.XA CN201310591746A CN103586024A CN 103586024 A CN103586024 A CN 103586024A CN 201310591746 A CN201310591746 A CN 201310591746A CN 103586024 A CN103586024 A CN 103586024A
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zngeo
hollow ball
preparation
photochemical catalyst
spherical
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CN103586024B (en
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张高科
刘进
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Wuhan Da Shu Environmental Protection Technology Co., Ltd.
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Wuhan University of Technology WUT
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Abstract

The invention relates to a preparation method for a hollow ball or spheroidal Ag2ZnGeO4 photocatalyst. The preparation method comprises the following steps: adopting germanium oxide, basic zinc carbonate and silver nitrate as raw materials and mixing the raw materials in deionized water, adding ammonia water slowly, continuously stirring for 3 to 6 h under the condition of constant temperature, washing with water and separating obtained yellow precipitation so as to obtain the hollow ball or spheroidal Ag2ZnGeO4 photocatalyst. The preparation method has the advantages of simplicity, feasibility, less energy consumption and little pollution; a prepared product is high in purity and good in crystallinity; the preparation method has a good application prospect in the field of photocatalysis.

Description

A kind of hollow ball or spherical Ag 2znGeO 4the preparation method of photochemical catalyst
Technical field
The present invention relates to a kind of hollow ball or spherical Ag 2znGeO 4the preparation method of photochemical catalyst, belongs to new material technology field.
Background technology
The semiconductor of hollow ball or chondritic has a wide range of applications in fields such as battery, sensor, catalysis.Because the semiconductor of hollow ball-shape structure has high absorptivity to light, in photocatalysis field, be also subject to people's attention, as ZnO, TiO 2, Bi 2wO 6deng.General synthetic hollow ball or chondritic method for semiconductor mainly contain ion-exchange, template and without template etc., but also have many difficulties for synthetic many hollow balls or chondritic ternary metal oxide, have hindered its photocatalytic applications research.
Many argentum-based catalyzers had good visible light photocatalysis effect and were subject to extensive concern in recent years, but needed further to study for the photocatalysis effect that how to improve argentum-based catalyzer.Ag 2znGeO 4semiconductor, as a kind of typical money base photochemical catalyst, has good visible light photocatalysis active, the water pollutant of can effectively degrading.Ag 2znGeO 4crystal is by ZnO 4, GeO 4and AgO 4tetrahedron forms, wherein AgO 4tetrahedron can effectively suppress the compound of light induced electron and hole, improves photon utilization rate.At present, about Ag 2znGeO 4it is very limited that the pattern of photochemical catalyst is controlled research, especially has the Ag of hollow ball or chondritic 2znGeO 4photochemical catalyst.Therefore, the present invention has studied hollow ball or chondritic Ag 2znGeO 4the preparation method of photochemical catalyst, and about the method that adopts research easily to go, prepare hollow ball or chondritic Ag at present 2znGeO photochemical catalyst there is not yet relevant report.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of hollow ball or spherical Ag for the deficiency of above-mentioned prior art existence 2znGeO 4the preparation method of photochemical catalyst, prepared Ag 2znGeO 4photochemical catalyst purity is high, better crystallinity degree, and pattern is hollow ball or spherical, and properties of catalyst is good.
The present invention is that the technical scheme that the problem of the above-mentioned proposition of solution adopts is:
A kind of hollow ball or spherical Ag 2znGeO 4the preparation method of photochemical catalyst, it comprises the following steps:
(1) by the mol ratio of germanium oxide, basic zinc carbonate and silver nitrate, be 1:0.2:3, take germanium oxide, basic zinc carbonate and silver nitrate and be mixed in deionized water, obtain presoma suspension;
(2) under the state stirring, to the ammoniacal liquor dripping in presoma suspension, making its pH is 6.5～7.5, and after being uniformly mixed, isothermal reaction 3～6 h at 60～80 ℃ of temperature, isolate yellow mercury oxide after cooling;
(3), by after yellow mercury oxide washing and drying, obtain hollow ball or spherical Ag 2znGeO 4photochemical catalyst.
Pressing such scheme, is 1:0.2:3 by the mol ratio of germanium oxide, basic zinc carbonate and silver nitrate, takes 0.21 g GeO 2, 0.22 g 3Zn (OH) 22ZnCO 3with 1.02 g AgNO 3time, the amount of described deionized water is that 30 mL are more suitable.
Press such scheme, the concentration of described ammoniacal liquor is 12～14wt%.
Press such scheme, the dry temperature of described step (3) is 50～60 ℃, and the dry time is 8～10 h.
The preparation-obtained hollow ball of said method or spherical Ag 2znGeO 4photochemical catalyst, by controlling the time of isothermal reaction, can control Ag 2znGeO 4the pattern of photochemical catalyst, when the isothermal reaction time is 3～4 h, prepared sample is hollow ball Ag 2znGeO 4photochemical catalyst; When the isothermal reaction time is 4～6 h, prepared sample is spherical Ag 2znGeO 4photochemical catalyst .
Compared with prior art, the invention has the beneficial effects as follows:
(1) hollow ball that the present invention obtains or spherical Ag 2znGeO 4photochemical catalyst catalytic activity is high, in photocatalysis field, has a good application prospect;
(2) the prepared Ag of the inventive method 2znGeO 4photochemical catalyst purity is high, better crystallinity degree, and pattern is hollow ball or spherical, by controlling the time of isothermal reaction, can control Ag 2znGeO 4the pattern of photochemical catalyst;
(3) the inventive method is prepared hollow ball or spherical Ag 2znGeO 4photochemical catalyst process is simple, with low cost.
Accompanying drawing explanation
In Fig. 1, a is the hollow ball Ag of embodiment 1 preparation 2znGeO 4the XRD collection of illustrative plates of photochemical catalyst, b is the spherical Ag of embodiment 2 preparations 2znGeO 4the XRD collection of illustrative plates of photochemical catalyst.Ag in figure 2znGeO 4xRD diffraction maximum position and the Ag of photochemical catalyst 2znGeO 4(JCPDS 86-0630) base peak position is identical, shows that sample is pure Ag 2znGeO 4.
In Fig. 2, a and b are the hollow ball Ag of embodiment 1 preparation 2znGeO 4the SEM figure of photochemical catalyst, c and d are the spherical Ag of embodiment 2 preparations 2znGeO 4the SEM figure of photochemical catalyst.
Fig. 3 is the hollow ball Ag of embodiment 1 preparation 2znGeO 4the TEM figure of photochemical catalyst.
Fig. 4 is the hollow ball Ag of embodiment 1 preparation 2znGeO 4the spherical Ag of photochemical catalyst and embodiment 2 preparations 2znGeO 4degradation effect figure to Acid Red G under photochemical catalyst radiation of visible light.
The specific embodiment
In order to understand better the present invention, below in conjunction with embodiment, further illustrate content of the present invention, but content of the present invention is not only confined to the following examples.
Employings of the present invention etc. turn target X-ray diffractometer (D/MAX-RB), SEM (JSM-5610LV) and a transmission electron microscope (JEM-2100F) and characterize the Ag obtaining 2znGeO 4the phase of sample and pattern.
The hollow ball that the present invention is prepared or spherical Ag 2znGeO 4the photocatalytic activity of sample is assessed by photocatalytic degradation Acid Red G solution, and concrete operations are as follows:
Take 300 W dysprosium lamps as light source provides radiation of visible light, with optical filter, filter out the ultraviolet light below wavelength 420 nm, irradiate light wavelength and be more than or equal to 420 nm; Take 0.1 g hollow ball or spherical Ag 2znGeO 4sample is in the beaker of 500 mL in volume, and adding volume is that 100 mL and concentration are 30 mg/L Acid Red G solutions simulate dyeing waste waters, first under lucifuge condition, stirs 30 min with the Ag in abundant dispersion soln 2znGeO 4photochemical catalyst; Then open visible light source, every certain hour, sample approximately 6 mL, detect the wherein concentration of Acid Red G solution.
embodiment 1
A kind of hollow ball Ag 2znGeO 4the preparation method of photochemical catalyst, it comprises the following steps:
(1) by the mol ratio of germanium oxide, basic zinc carbonate and silver nitrate, be 1:0.2:3, take 0.21 g germanium oxide, 0.22 g basic zinc carbonate and 1.02 g silver nitrates and be mixed in 30 mL deionized waters, obtain presoma suspension;
(2) under the state stirring, in presoma suspension, slowly drip the ammoniacal liquor that concentration is about 12wt%, making its pH is 6.5, continues to stir 20 min; Above-mentioned suspension is transferred in the container that volume is 50 mL, is placed in 60 ℃ of thermostat water bath 3 h; After naturally cooling, centrifugation goes out the yellow mercury oxide in container;
(3) yellow mercury oxide is adopted to deionized water washing 5 times, at 50 ℃ of temperature, dry 10 h, obtain hollow ball Ag 2znGeO 4photochemical catalyst, Fig. 1 is shown in by its XRD collection of illustrative plates, and SEM figure is shown in Fig. 2, and TEM figure is shown in Fig. 3, prepared Ag 2znGeO 4sample purity is high, better crystallinity degree, and pattern is hollow ball.
The hollow ball Ag that this embodiment is synthetic 2znGeO 4photochemical catalyst is in the experiment of degraded Acid Red G, dosage is 1.0 g/L, and the initial concentration of Acid Red G is 30 mg/L, irradiates light wavelength λ>=420 nm, after 120 min, the degradation rate of Acid Red G is that 93.5%(is shown in Fig. 4), hollow ball Ag prepared by the method is described 2znGeO 4photochemical catalyst has good visible light photocatalysis active.
embodiment 2
A kind of spherical Ag 2znGeO 4the preparation method of photochemical catalyst, it comprises the following steps:
(1) by the mol ratio of germanium oxide, basic zinc carbonate and silver nitrate, be 1:0.2:3, take 0.21 g germanium oxide, 0.22 g basic zinc carbonate and 1.02 g silver nitrates and be mixed in 30 mL deionized waters, obtain presoma suspension;
(2) under the state stirring, in presoma suspension, slowly drip the ammoniacal liquor that concentration is about 14wt%, making its pH is 7.5, continues to stir 20 min; Above-mentioned suspension is transferred in the container that volume is 50 mL, is placed in 60 ℃ of thermostat water bath 6 h; After naturally cooling, centrifugation goes out the yellow mercury oxide in container;
(3) yellow mercury oxide is adopted to deionized water washing 5 times, at 60 ℃ of temperature, dry 8 h, obtain spherical Ag 2znGeO 4photochemical catalyst, Fig. 1 is shown in by its XRD collection of illustrative plates, SEM figure is shown in Fig. 2,, prepared Ag 2znGeO 4sample purity is high, better crystallinity degree, and pattern is spherical.
The spherical Ag that this embodiment synthesizes 2znGeO 4photochemical catalyst is in the experiment of degraded Acid Red G, and dosage is 1.0 g/L, and the initial concentration of Acid Red G is 30 mg/L, irradiates light wavelength λ>=420 nm, and after 120 min, the degradation rate of Acid Red G is that 90.2%(is shown in Fig. 4), spherical Ag prepared by the method is described 2znGeO 4there is good visible light photocatalysis active.

Claims (4)

1. a hollow ball or spherical Ag 2znGeO 4the preparation method of photochemical catalyst, is characterized in that it comprises the following steps:
(1) by the mol ratio of germanium oxide, basic zinc carbonate and silver nitrate, be 1:0.2:3, take germanium oxide, basic zinc carbonate and silver nitrate and be mixed in deionized water, obtain presoma suspension;
(2) under the state stirring, in presoma suspension, drip ammoniacal liquor, making its pH is 6.5～7.5, and after being uniformly mixed, isothermal reaction 3～6 h at 60～80 ℃ of temperature, isolate yellow mercury oxide after cooling;
(3) after yellow mercury oxide washing is dry, obtain hollow ball or spherical Ag 2znGeO 4.
2. a kind of hollow ball according to claim 1 or spherical Ag 2znGeO 4the preparation method of photochemical catalyst, the concentration that it is characterized in that described ammoniacal liquor is 12～14wt%.
3. a kind of hollow ball according to claim 1 or spherical Ag 2znGeO 4the preparation method of photochemical catalyst, is characterized in that the dry temperature of described step (3) is 50～60 ℃, and the dry time is 8～10 h.
4. the preparation-obtained hollow ball of any one method or the spherical Ag in claim 1～4 2znGeO 4photochemical catalyst.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107020091A (en) * 2017-03-27 2017-08-08 山东大学 It is a kind of that there is visible light-responded Ag4(GeO4) photochemical catalyst and its preparation method and application

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WO2006119134A1 (en) * 2005-05-04 2006-11-09 Ceramphysics, Inc. High temperature superconducting dielectric ceramic insulation
CN102962049A (en) * 2012-11-26 2013-03-13 南京大学 Method for preparing nanometer photocatalytic material via hydrothermal reaction
CN103073052A (en) * 2012-12-19 2013-05-01 东华大学 Preparation method of zinc germanate longitudinal twin crystal nano-wire
CN103349976A (en) * 2013-07-20 2013-10-16 湖州师范学院 Preparation method for two-dimensional ultrathin mesh-shaped ZnO nano photocatalyst

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006119134A1 (en) * 2005-05-04 2006-11-09 Ceramphysics, Inc. High temperature superconducting dielectric ceramic insulation
CN102962049A (en) * 2012-11-26 2013-03-13 南京大学 Method for preparing nanometer photocatalytic material via hydrothermal reaction
CN103073052A (en) * 2012-12-19 2013-05-01 东华大学 Preparation method of zinc germanate longitudinal twin crystal nano-wire
CN103349976A (en) * 2013-07-20 2013-10-16 湖州师范学院 Preparation method for two-dimensional ultrathin mesh-shaped ZnO nano photocatalyst

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107020091A (en) * 2017-03-27 2017-08-08 山东大学 It is a kind of that there is visible light-responded Ag4(GeO4) photochemical catalyst and its preparation method and application
CN107020091B (en) * 2017-03-27 2020-03-17 山东大学 Ag with visible light response4(GeO4) Photocatalyst and preparation method and application thereof

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