CN101879443B - Novel high-efficiency strontium borate-like photocatalyst - Google Patents
Novel high-efficiency strontium borate-like photocatalyst Download PDFInfo
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- CN101879443B CN101879443B CN 201010219274 CN201010219274A CN101879443B CN 101879443 B CN101879443 B CN 101879443B CN 201010219274 CN201010219274 CN 201010219274 CN 201010219274 A CN201010219274 A CN 201010219274A CN 101879443 B CN101879443 B CN 101879443B
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- strontium
- borate
- citrate
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Abstract
The invention discloses a high-efficiency strontium borate-like photocatalyst and a preparation method thereof and aims to prepare methane by reducing carbon dioxide and water through photocatalysis technology. In the photocatalyst, strontium salt, a boron-containing compound, citric acid or citrate and alcohols are used as precursors. The photocatalysis efficiency of reducing the carbon dioxide and water to prepare the methane of the high-activity strontium borate-like photocatalyst prepared by a sol-gel method is superior to that of a TiO2 photocatalyst (P25, which is known as the photocatalyst with higher photocatalysis efficiency at present). The novel high-efficiency strontium borate-like photocatalyst has the advantages of simple preparation process, easy operation, low requirements on equipment and the like and has wide application prospect and development potential in the fields of emission reduction of carbon dioxide, recycling of energy, environmental science and the like.
Description
[technical field]
The present invention develops a kind of high efficiency class strontium borate photochemical catalyst, and the efficient that the photocatalytic reduction of carbon oxide of this catalyst and water prepare methane has surpassed TiO
2(P25) photochemical catalyst.The invention belongs to the photocatalysis technology field, provide a kind of high efficiency photochemical catalyst for utilizing photocatalysis technology reducing carbon dioxide and water methane processed.
[background technology]
The new method that world today's energy crisis and ecological deterioration impel people to seek cleaning, reproducible new forms of energy and administer environment.In recent years, the research to catalysis material has obtained remarkable progress.1972, Fujishima and Honda utilized titanium dioxide (TiO
2) experiment of monocrystalline electrode photolysis water hydrogen, started the heterogeneous light-catalysed research field of semiconductor.TiO
2Have the high characteristics of good stability and photocatalysis efficiency, but utilize TiO
2Photocatalytic reduction of carbon oxide and water prepare methane, still exist photocatalysis efficiency than problems such as low and depollution of environment effect differences, do not reach requirement of actual application as yet.
The present invention develops a kind of high efficiency class strontium borate photochemical catalyst, utilizes this catalyst photocatalytic reduction of carbon oxide and water to prepare methane, and its photocatalysis efficiency surpasses TiO
2(P25).At present, the class strontium borate does not appear in the newspapers in the research work of photocatalytic reduction of carbon oxide and water methane processed, and this achievement in research will be for designing, prepare the high efficiency photochemical catalyst and opening up new direction in the application in energy environment field.
[summary of the invention]
The present invention is presoma with strontium salt, boron-containing compound, citric acid or citrate and many alcohol, adopts a kind of high efficiency class strontium borate of Prepared by Sol Gel Method photochemical catalyst.The invention has the advantages that this photochemical catalyst has very high photocatalysis efficiency, its photocatalysis efficiency far surpasses TiO
2(P25).
[description of drawings]
Fig. 1 embodiment 1,2,3 X ray diffracting spectrum;
Class strontium borate and P25 photochemical catalyst photocatalytic reduction of carbon oxide and water prepare the concentration time curve of methane among Fig. 2 embodiment 1,2,3;
Below in conjunction with specific embodiments and the drawings the present invention is described further, and specifies photocatalysis effect of the present invention.
[specific embodiment]
Concrete preparation method of the present invention is as follows: at normal temperatures, citric acid or citrate are joined diluent, the mass ratio of citric acid or citrate and diluent is 1: 5～1: 15; Under vigorous stirring, added strontium salt and boron-containing compound successively every 5～10 minutes, the mol ratio of citric acid or citrate and strontium salt is 4: 0.5～4: 2, the mol ratio of citric acid or citrate and boron-containing compound is 4: 1～4: 3; Stir, how pure add then, citric acid or citrate and how pure mol ratio are 4: 4～4: 8, last 80 ℃～100 ℃ water-baths 4～10 hours, obtain mixed sols, with mixed sols at 90 ℃～150 ℃ oven dry, grind into powder, in air atmosphere, calcined 3.0～5.0 hours for 500 ℃～800 ℃, make high efficiency class strontium borate photochemical catalyst.
In the above preparation process, described strontium salt can be one or more mixing in strontium chloride, strontium nitrate or the strontium acetate.
Described many alcohol can be any in ethylene glycol, the polyethylene glycol.
Described boron-containing compound can be any in boric acid, borax, Boratex, potassium borate, ammonium borate, metaboric acid, kodalk, potassium metaborate, tetraboric acid, sodium tetraborate or the dipotassium tetraborate.
Described diluent is any or several mixing in high purity water, absolute ethyl alcohol, absolute methanol, glacial acetic acid or the formic acid.
The evaluation method of photocatalysis efficiency is: the mercury lamp with 35W is light source, and radiation wavelength is＞253.7nm; The aqueous solution is 125ml; Catalyst amount is 125mg; Naoh concentration is 0.2mol/L; Feed CO in the solution before the reaction
2Gas 45min, flow is 0.3L/min, and solution is reached capacity; Solution concentration in the magnetic agitation maintenance system; Water-bath keeps the temperature balance of system; Extract 0.4ml gas every 2h, analyze the end product methane concentration with gas chromatograph, demarcate the photocatalysis efficiency of catalyst.End product methane content height shows catalyst photocatalysis efficiency height.
For a better understanding of the present invention, be described in further detail below in conjunction with the present invention of embodiment, but the scope of protection of present invention is not limited to the represented scope of embodiment.
Embodiment 1
Get a certain amount of Sr (NO
3)
2Solid as solvent, is mixed with the Sr (NO of 1mol/L with high purity water
3)
2Solution.Get the 85ml high purity water, at room temperature stir, add 7.6856g citric acid (0.04mol) successively and (analyze pure and mild 10ml Sr (NO
3)
2Solution stirred 5 minutes; With 1.2366g boric acid (0.02mol) adding system, fully stir and it was dissolved fully in 10 minutes; Add 3.3ml ethylene glycol (0.06mol), fully stir and it was dissolved fully in 10 minutes; 90 ℃ of water-bath evaporations 4 hours, up to becoming colloidal sol fully; Colloidal sol 120 ℃ of oven dry in baking oven were become gel in 10 hours; Grind into powder is calcined 4.5h in 500 ℃ of air, makes nanometer class strontium borate photochemical catalyst (sample A).With the evaluation method of above-mentioned photocatalysis efficiency, 10 hours methane-generated quantities of photocatalysis are 2.44 * 10
-5Mol/L, and under the equal conditions, TiO
2(P25) methane-generated quantity is 2.42 * 10
-5Mol/L.
Embodiment 2
Experiment condition, step are with embodiment 1, and changing calcining heat is 600 ℃, the nanoscale strontium borate photochemical catalyst (sample B) that makes, and with above-mentioned photocatalytic activity evaluation method, 10 hours methane-generated quantities of photocatalysis are 5.63 * 10
-5Mol/L is TiO
2(P25) 2.33 times.
Embodiment 3
Experiment condition, step are with embodiment 1, and changing calcining heat is 700 ℃, makes nanometer class strontium borate photochemical catalyst (sample C), and with above-mentioned photocatalytic activity evaluation method, under UV-irradiation, 10 hours methane-generated quantities of photocatalysis are 3.77 * 10
-5Mol/L is TiO
2(P25) 1.56 times.
Above example shows that class strontium borate photochemical catalyst photocatalytic reduction of carbon oxide and water methane processed have high photocatalysis efficiency.
Claims (5)
1. high efficiency class strontium borate photochemical catalyst, it is characterized in that with strontium salt, boron-containing compound, citric acid or citrate, with many alcohol be presoma, adopt Prepared by Sol Gel Method, described preparation comprises the steps: at normal temperatures, citric acid or citrate are joined diluent, and the mass ratio of citric acid or citrate and diluent is 1: 5～1: 15; Under vigorous stirring, every 5～10 minutes, add strontium salt and boron-containing compound successively, the mol ratio of citric acid or citrate and strontium salt is 4: 0.5～4: 2, citric acid or citrate and boron-containing compound mol ratio are 4: 1～4: 3; Stir, how pure add then, citric acid or citrate and how pure mol ratio are 4: 4～4: 8, at last 80 ℃～100 ℃ water-baths 4～10 hours, obtain mixed sols, mixed sols is dried into gel, grind into powder through 90 ℃～150 ℃, in air atmosphere, calcined 3.0～5.0 hours for 500 ℃～800 ℃, make high efficiency class strontium borate photochemical catalyst.
2. a kind of high efficiency class strontium borate photochemical catalyst according to claim 1 is characterized in that: described strontium salt is any in strontium chloride, strontium nitrate or the strontium acetate.
3. a kind of high efficiency class strontium borate photochemical catalyst according to claim 1 is characterized in that: described boron-containing compound is any in boric acid, borax, Boratex, potassium borate, ammonium borate, metaboric acid, kodalk, potassium metaborate, tetraboric acid, sodium tetraborate or the dipotassium tetraborate.
4. a kind of high efficiency class strontium borate photochemical catalyst according to claim 1 is characterized in that: described many alcohol are any in ethylene glycol, the polyethylene glycol.
5. a kind of high efficiency class strontium borate photochemical catalyst according to claim 1, it is characterized in that: described diluent is any or several mixing in high purity water, absolute ethyl alcohol, absolute methanol, glacial acetic acid or the formic acid.
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| CN102921423A (en) * | 2012-04-26 | 2013-02-13 | 南开大学 | Efficient nickel/nickel oxide/nickel borate composite photocatalyst |
| CN104649364B (en) * | 2013-11-22 | 2016-03-16 | 中国科学院新疆理化技术研究所 | The method of vanadium Sodium Tetraborate photocatalytic oxidation degradation chlorophenol pollutant |
| CN104645992B (en) * | 2014-11-30 | 2016-08-24 | 桂林理工大学 | Visible light-responded photocatalyst Li3cu2bO5and preparation method thereof |
| CN104492419B (en) * | 2014-12-28 | 2016-08-17 | 桂林理工大学 | Visible light-responded photocatalyst Li Bi3b4o11and preparation method thereof |
| CN104525208B (en) * | 2014-12-28 | 2016-08-24 | 桂林理工大学 | Visible light-responded photocatalyst Li Fe2b3o8and preparation method thereof |
| CN104437505B (en) * | 2014-12-28 | 2016-08-24 | 桂林理工大学 | Visible light-responded photocatalyst Li FeB2o5and preparation method thereof |
| CN108946751B (en) * | 2018-07-13 | 2021-04-13 | 湘潭大学 | Preparation method and application of boron hexa-oxygen |
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| CN101301619A (en) * | 2008-07-03 | 2008-11-12 | 南开大学 | Method for preparing high efficiency metallic, non-metallic ion co-doped nano-TiO2 visible-light responsive photocatalyst |
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| CN101301619A (en) * | 2008-07-03 | 2008-11-12 | 南开大学 | Method for preparing high efficiency metallic, non-metallic ion co-doped nano-TiO2 visible-light responsive photocatalyst |
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| 张林进等.水合硼酸锶的制备及脱水热分解动力学.《应用化学》.2009,第26卷(第6期),第697页. * |
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