CN103586024B - A kind of hollow ball or spherical Ag 2znGeO 4the preparation method of photochemical catalyst - Google Patents
A kind of hollow ball or spherical Ag 2znGeO 4the preparation method of photochemical catalyst Download PDFInfo
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- CN103586024B CN103586024B CN201310591746.XA CN201310591746A CN103586024B CN 103586024 B CN103586024 B CN 103586024B CN 201310591746 A CN201310591746 A CN 201310591746A CN 103586024 B CN103586024 B CN 103586024B
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- hollow ball
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Abstract
The present invention relates to a kind of hollow ball or spherical Ag
2znGeO
4the preparation method of photochemical catalyst, comprise the steps: to adopt germanium oxide, basic zinc carbonate and silver nitrate to be raw material, be mixed in deionized water, and the ammoniacal liquor slowly added again, then at constant temperature Keep agitation 3 ~ 6h, obtained yellow mercury oxide is washed, is separated, hollow ball or spherical Ag can be obtained
2znGeO
4photochemical catalyst.The invention has the advantages that preparation method is simple, less energy consumption, pollution be little, the purity of prepared product is high, better crystallinity degree, has a good application prospect in photocatalysis field.
Description
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, be also subject to people's attention in photocatalysis field, as ZnO, TiO
2, Bi
2wO
6deng.General synthesis hollow ball or chondritic method for semiconductor mainly contain ion-exchange, template and without template etc., but also there is many difficulties for the many hollow balls of synthesis or chondritic ternary metal oxide, hinder 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 to study further for the photocatalysis effect how improving argentum-based catalyzer.Ag
2znGeO
4semiconductor, as the typical money base photochemical catalyst of one, has good visible light photocatalysis active, water pollutant of can effectively degrading.Ag
2znGeO
4crystal is by ZnO
4, GeO
4and AgO
4tetrahedron forms, wherein AgO
4tetrahedron effectively can suppress the compound in light induced electron and hole, improves photon utilization rate.At present, about Ag
2znGeO
4the pattern control research of photochemical catalyst is very limited, especially has the Ag of hollow ball or chondritic
2znGeO
4photochemical catalyst.Therefore, the present invention have studied hollow ball or chondritic Ag
2znGeO
4the preparation method of photochemical catalyst, and prepare hollow ball or chondritic Ag about the easy method of employing research at present
2znGeO photochemical catalyst there is not yet relevant report.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists for above-mentioned prior art and provides a kind of hollow ball or spherical Ag
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 technical scheme that the problem that the present invention is 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) be 1:0.2:3 by the mol ratio of germanium oxide, basic zinc carbonate and silver nitrate, take germanium oxide, basic zinc carbonate and silver nitrate and be mixed in deionized water, obtaining presoma suspension;
(2) under the state stirred, the ammoniacal liquor dripped in presoma suspension, make its pH be 6.5 ~ 7.5, after being uniformly mixed, isothermal reaction 3 ~ 6h at temperature 60 ~ 80 DEG C, isolates yellow mercury oxide after cooling;
(3) by after yellow mercury oxide washing and drying, hollow ball or spherical Ag is namely obtained
2znGeO
4photochemical catalyst.
By such scheme, be 1:0.2:3 by the mol ratio of germanium oxide, basic zinc carbonate and silver nitrate, take 0.21gGeO
2, 0.22g3Zn (OH)
22ZnCO
3and 1.02gAgNO
3time, the amount of described deionized water is that 30mL is more suitable.
By such scheme, the concentration of described ammoniacal liquor is 12 ~ 14wt%.
By such scheme, the temperature of described step (3) drying is 50 ~ 60 DEG C, and the dry time is 8 ~ 10h.
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, the sample prepared when the isothermal reaction time is 3 ~ 4h is hollow ball Ag
2znGeO
4photochemical catalyst; The sample prepared when the isothermal reaction time is 4 ~ 6h is spherical Ag
2znGeO
4photochemical catalyst
.
Compared with prior art, the invention has the beneficial effects as follows:
(1) hollow ball that obtains of the present invention or spherical Ag
2znGeO
4photochemical catalyst catalytic activity is high, has a good application prospect in photocatalysis field;
(2) Ag prepared by 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, and can control Ag
2znGeO
4the pattern of photochemical catalyst;
(3) the inventive method prepares hollow ball or spherical Ag
2znGeO
4photochemical catalyst process is simple, with low cost.
Accompanying drawing explanation
In Fig. 1, a is hollow ball Ag prepared by embodiment 1
2znGeO
4the XRD collection of illustrative plates of photochemical catalyst, b is spherical Ag prepared by embodiment 2
2znGeO
4the XRD collection of illustrative plates of photochemical catalyst.Ag in figure
2znGeO
4the XRD diffraction maximum position of photochemical catalyst and Ag
2znGeO
4(JCPDS86-0630) base peak position is identical, shows that sample is pure Ag
2znGeO
4.
In Fig. 2, a and b is hollow ball Ag prepared by embodiment 1
2znGeO
4the SEM figure of photochemical catalyst, c and d is spherical Ag prepared by embodiment 2
2znGeO
4the SEM figure of photochemical catalyst.
Fig. 3 is hollow ball Ag prepared by embodiment 1
2znGeO
4the TEM figure of photochemical catalyst.
Fig. 4 is hollow ball Ag prepared by embodiment 1
2znGeO
4spherical Ag prepared by photochemical catalyst and embodiment 2
2znGeO
4to the degradation effect figure of Acid Red G under photochemical catalyst radiation of visible light.
Detailed description of the invention
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, 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 Flied emission transmission electron microscope (JEM-2100F) and characterize the Ag obtained
2znGeO
4the thing phase of sample and pattern.
Hollow ball prepared by the present invention or spherical Ag
2znGeO
4the photocatalytic activity of sample is assessed by photocatalytic degradation Acid Red G solution, and concrete operations are as follows:
With 300W dysprosium lamp for light source provides radiation of visible light, filter out the ultraviolet light of below wavelength 420nm with optical filter, the wavelength irradiating light is more than or equal to 420nm; Take 0.1g hollow ball or spherical Ag
2znGeO
4sample is in the beaker of 500mL in volume, adds volume and is 100mL and concentration is 30mg/L Acid Red G solution stimulated dye wastewater, under lucifuge condition, first stir 30min with the Ag in abundant dispersion soln
2znGeO
4photochemical catalyst; Then open visible light source, sample about 6mL every certain hour, detect the concentration of wherein 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) be 1:0.2:3 by the mol ratio of germanium oxide, basic zinc carbonate and silver nitrate, take 0.21g germanium oxide, 0.22g basic zinc carbonate and 1.02g silver nitrate and be mixed in 30mL deionized water, obtaining presoma suspension;
(2) under the state stirred, in presoma suspension, slowly drip the ammoniacal liquor that concentration is about 12wt%, make its pH be 6.5, continue to stir 20min; Above-mentioned suspension being transferred to volume is in the container of 50mL, is placed in 60 DEG C of thermostat water bath 3h; After naturally cooling, centrifugation goes out the yellow mercury oxide in container;
(3) adopted by yellow mercury oxide deionized water to wash 5 times, dry 10h at 50 DEG C of temperature, namely obtains 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 of this embodiment synthesis
2znGeO
4photochemical catalyst is in the experiment of degraded Acid Red G, and dosage is 1.0g/L, and the initial concentration of Acid Red G is 30mg/L, and irradiating the degradation rate of Acid Red G after the wavelength X>=420nm, 120min of light 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) be 1:0.2:3 by the mol ratio of germanium oxide, basic zinc carbonate and silver nitrate, take 0.21g germanium oxide, 0.22g basic zinc carbonate and 1.02g silver nitrate and be mixed in 30mL deionized water, obtaining presoma suspension;
(2) under the state stirred, in presoma suspension, slowly drip the ammoniacal liquor that concentration is about 14wt%, make its pH be 7.5, continue to stir 20min; Above-mentioned suspension being transferred to volume is in the container of 50mL, is placed in 60 DEG C of thermostat water bath 6h; After naturally cooling, centrifugation goes out the yellow mercury oxide in container;
(3) adopted by yellow mercury oxide deionized water to wash 5 times, dry 8h at 60 DEG C of temperature, namely obtains spherical Ag
2znGeO
4photochemical catalyst, Fig. 1 is shown in by its XRD collection of illustrative plates, and SEM figure is shown in Fig. 2, prepared Ag
2znGeO
4sample purity is high, better crystallinity degree, and pattern is spherical.
The spherical Ag of this embodiment synthesis
2znGeO
4photochemical catalyst is in the experiment of degraded Acid Red G, and dosage is 1.0g/L, and the initial concentration of Acid Red G is 30mg/L, and irradiating the degradation rate of Acid Red G after the wavelength X>=420nm, 120min of light 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 (3)
1. a hollow ball or spherical Ag
2znGeO
4the preparation method of photochemical catalyst, is characterized in that it comprises the following steps:
(1) be 1:0.2:3 by the mol ratio of germanium oxide, basic zinc carbonate and silver nitrate, take germanium oxide, basic zinc carbonate and silver nitrate and be mixed in deionized water, obtaining presoma suspension; Described basic zinc carbonate is 3Zn (OH)
22ZnCO
3;
(2) under the state stirred, in presoma suspension, drip ammoniacal liquor, make its pH be 6.5 ~ 7.5, after being uniformly mixed, isothermal reaction 3 ~ 6h at temperature 60 ~ 80 DEG C, isolates yellow mercury oxide after cooling;
(3), after yellow mercury oxide being washed drying, hollow ball or spherical Ag is namely obtained
2znGeO
4.
2. a kind of hollow ball according to claim 1 or spherical Ag
2znGeO
4the preparation method of photochemical catalyst, is characterized in that the concentration of 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, it is characterized in that the temperature of described step (3) drying is 50 ~ 60 DEG C, the dry time is 8 ~ 10h.
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Citations (4)
| 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 |
-
2013
- 2013-11-22 CN CN201310591746.XA patent/CN103586024B/en active Active
Patent Citations (4)
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of hierarchical Ag2ZnGeO4 hollow spheres for enhanced photocatalytic property;Ning Zhang et al.;《chemical communications》;20121231;第48卷(第79期);electronic supplementary information 第2页第1段，第9894页第2栏第1段，第9895页第1栏第1段，第1栏第3段，第2栏第1段 * |
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Effective date of registration: 20180621 Address after: 430065 3098, 3 floor, office building, 522 embankment street, Baisha Chau, Wuchang, Wuhan, Hubei, China (395) Patentee after: Wuhan Da Shu Environmental Protection Technology Co., Ltd. Address before: 430070 Hubei Province, Wuhan city Hongshan District Luoshi Road No. 122 Patentee before: Wuhan University of Technology |