CN105396619A - MIL-100(Fe) silver phosphate composite photocatalyst, preparation and applications - Google Patents
MIL-100(Fe) silver phosphate composite photocatalyst, preparation and applications Download PDFInfo
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- CN105396619A CN105396619A CN201510930469.XA CN201510930469A CN105396619A CN 105396619 A CN105396619 A CN 105396619A CN 201510930469 A CN201510930469 A CN 201510930469A CN 105396619 A CN105396619 A CN 105396619A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention belongs to the photocatalysis material technology field, and discloses an MIL-100(Fe) silver phosphate composite photocatalyst, preparation and applications. The preparation method is as follows: firstly, MIL-100(Fe) is prepared through a hydrothermal method and silver phosphate is prepared through a precipitation method; then the prepared silver phosphate is dispersed in a solvent, MIL-100(Fe) is added, and the mixture is mixed uniformly; finally, the solvent is removed through evaporation, and an MIL-100(Fe) silver phosphate composite photocatalyst is prepared. The preparation technology is simple, environmentally friendly, and is easy for large-scale production. The prepared MIL-100(Fe) silver phosphate composite photocatalyst has good stability and high catalytic activity, and can be used for catalysis degradation of organic pollutants such as rhodamine B or the like.
Description
Technical field
The invention belongs to catalysis material technical field, be specifically related to a kind of MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst and preparation and application.
Background technology
Study and Development has the important subject that visible light-responded photochemical catalyst is current photocatalysis field efficiently.Silver orthophosphate is a kind of catalyst under visible light illumination with photocatalytic activity, but its photocatalytic activity and stability still need to improve and improve.In recent years, metal-organic framework materials (MOFs) as a kind of novel porous multifunctional polymeric material, because it has high-specific surface area, regulatable hole dimension, structure diversity and surface be the advantage such as modification easily, in catalysis etc., show potential application prospect.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, primary and foremost purpose of the present invention is the preparation method providing a kind of MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst.
Another object of the present invention is to provide a kind of MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst prepared by said method.This catalyst with metallic organic framework MIL-100 (Fe) compound phosphoric acid silver, thus improves the stability of silver phosphate photocatalyst, improves its catalytic activity, promotes the degradation efficiency to organic pollution.
Another object of the present invention is to provide above-mentioned MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst at catalyze and degrade organic pollutants, as the application in the materials such as rhodamine B.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst, comprises following preparation process:
(1) hydro-thermal method prepares MIL-100 (Fe);
(2) precipitation method prepare silver orthophosphate;
(3) step (2) gained silver orthophosphate is scattered in solvent, then adds step (1) gained MIL-100 (Fe), be uniformly mixed;
(4) evaporation of solvent, obtains MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst.
The process that hydro-thermal method described in step (1) prepares MIL-100 (Fe) is as follows:
Take iron powder and 1,3,5-benzenetricarboxylic acid (H
3bTC) in reactor, then add nitric acid, hydrofluoric acid and water and react, reaction gained pressed powder product, through centrifugal, washing, dry, obtains MIL-100 (Fe).
The process that the precipitation method described in step (2) prepare silver orthophosphate is as follows:
By AgNO
3soluble in water, obtain liquor argenti nitratis ophthalmicus; By Na
2hPO
4soluble in water, obtain disodium phosphate soln; Disodium phosphate soln is added drop-wise in liquor argenti nitratis ophthalmicus, stirring reaction under room temperature condition; Gained yellow mercury oxide, through centrifugal, washing, drying, obtains silver orthophosphate.
Preferably, the solvent described in step (3) refers to absolute ethyl alcohol.
Preferably, described in step (3), the addition of MIL-100 (Fe) is 1% ~ 9% of silver orthophosphate quality; More preferably the addition of MIL-100 (Fe) is 1% ~ 5% of silver orthophosphate quality.
A kind of MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst, is prepared by above method.
The application of above-mentioned MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst in catalyze and degrade organic pollutants; The preferred rhodamine B of described organic pollution.
Preparation method of the present invention and the product tool obtained have the following advantages and beneficial effect:
(1) simple, the environmental protection of preparation technology of the present invention, is easy to comparatively produce in enormous quantities;
(2) MIL-100 (Fe)/Ag of preparing of the present invention
3pO
4photochemical catalyst, the ratio that can add MIL-100 (Fe) by adjustment makes its catalytic performance reach optimum;
(3) MIL-100 (Fe)/Ag of preparing of the present invention
3pO
4photochemical catalyst has good degradation effect to rhodamine B, has very large development & application prospect under visible light conditions in organic dye pollutant of degrading;
(4) the present invention is Ag
3pO
4composite catalyst preparation extends new direction.
Accompanying drawing explanation
Fig. 1 is embodiment 1 ~ 3 gained MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst and Ag
3pO
4the photocatalytic activity test result figure of catalyst rhodamine B degradation under visible radiation.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) hydro-thermal method prepares MIL-100 (Fe): take iron powder 0.2775g, 1,3,5-benzenetricarboxylic acid (H
3bTC) 0.6875g is in 25mL polytetrafluoroethylene (PTFE) reactor, then adds nitric acid (HNO
3, 65%) 190 μ L, hydrofluoric acid (HF, 35%) 200 μ L, H
2o20mL, is then placed in 150 DEG C of baking ovens and reacts 24h by reactor, gained pressed powder is through centrifugal, and the alternately washing of absolute ethyl alcohol and distilled water, finally dry 12h in 60 DEG C of vacuum drying chambers, obtains MIL-100 (Fe).
(2) precipitation method prepare silver orthophosphate: take 1.02gAgNO
3be dissolved in 20mL water, prepare liquor argenti nitratis ophthalmicus; Take 0.716gNa
2hPO
4be dissolved in 10mL water, prepare disodium phosphate soln; Disodium phosphate soln is dropwise added in liquor argenti nitratis ophthalmicus, under room temperature condition, stirs 1h with 500r/min rotating speed; Gained yellow mercury oxide, through centrifugal, after absolute ethyl alcohol and distilled water alternately wash, be placed in 60 DEG C of dry 12h of vacuum drying chamber, obtain silver phosphate photocatalyst.
(3) getting 0.15g step (2) gained silver orthophosphate is scattered in 10mL absolute ethyl alcohol, add 0.0015g (1%) step (1) gained MIL-100 (Fe) again, with 400r/min rotating speed Keep agitation 8h under room temperature condition;
(4) step (3) products therefrom is placed in 60 DEG C of dry 5h evaporation of solvent of baking oven, obtains Powdered MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst.
Embodiment 2
(1) hydro-thermal method prepares MIL-100 (Fe): take iron powder 0.2775g, 1,3,5-benzenetricarboxylic acid (H
3bTC) 0.6875g is in 25mL polytetrafluoroethylene (PTFE) reactor, then adds nitric acid (HNO
3, 65%) 190 μ L, hydrofluoric acid (HF, 35%) 200 μ L, H
2o20mL, is then placed in 150 DEG C of baking ovens and reacts 24h by reactor, gained pressed powder is through centrifugal, and the alternately washing of absolute ethyl alcohol and distilled water, finally dry 12h in 60 DEG C of vacuum drying chambers, obtains MIL-100 (Fe).
(2) precipitation method prepare silver orthophosphate: take 1.02gAgNO
3be dissolved in 20mL water, prepare liquor argenti nitratis ophthalmicus; Take 0.716gNa
2hPO
4be dissolved in 10mL water, prepare disodium phosphate soln; Disodium phosphate soln is dropwise added in liquor argenti nitratis ophthalmicus, under room temperature condition, stirs 1h with 500r/min rotating speed; Gained yellow mercury oxide, through centrifugal, after absolute ethyl alcohol and distilled water alternately wash, be placed in 60 DEG C of dry 12h of vacuum drying chamber, obtain silver phosphate photocatalyst.
(3) getting 0.15g step (2) gained silver orthophosphate is scattered in 10mL absolute ethyl alcohol, add 0.0045g (3%) step (1) gained MIL-100 (Fe) again, with 400r/min rotating speed Keep agitation 8h under room temperature condition;
(4) step (3) products therefrom is placed in 60 DEG C of dry 5h evaporation of solvent of baking oven, obtains Powdered MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst.
Embodiment 3
(1) hydro-thermal method prepares MIL-100 (Fe): take iron powder 0.2775g, 1,3,5-benzenetricarboxylic acid (H
3bTC) 0.6875g is in 25mL polytetrafluoroethylene (PTFE) reactor, then adds nitric acid (HNO
3, 65%) 190 μ L, hydrofluoric acid (HF, 35%) 200 μ L, H
2o20mL, is then placed in 150 DEG C of baking ovens and reacts 24h by reactor, gained pressed powder is through centrifugal, and the alternately washing of absolute ethyl alcohol and distilled water, finally dry 12h in 60 DEG C of vacuum drying chambers, obtains MIL-100 (Fe).
(2) precipitation method prepare silver orthophosphate: take 1.02gAgNO
3be dissolved in 20mL water, prepare liquor argenti nitratis ophthalmicus; Take 0.716gNa
2hPO
4be dissolved in 10mL water, prepare disodium phosphate soln; Disodium phosphate soln is dropwise added in liquor argenti nitratis ophthalmicus, under room temperature condition, stirs 1h with 500r/min rotating speed; Gained yellow mercury oxide, through centrifugal, after absolute ethyl alcohol and distilled water alternately wash, be placed in 60 DEG C of dry 12h of vacuum drying chamber, obtain silver phosphate photocatalyst.
(3) getting 0.15g step (2) gained silver orthophosphate is scattered in 10mL absolute ethyl alcohol, add 0.0075g (5%) step (1) gained MIL-100 (Fe) again, with 400r/min rotating speed Keep agitation 8h under room temperature condition;
(4) step (3) products therefrom is placed in 60 DEG C of dry 5h evaporation of solvent of baking oven, obtains Powdered MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst.
The photocatalytic activity test of embodiment 1 ~ 3 gained MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst rhodamine B degradation under visible radiation, concrete grammar and condition as follows:
Active testing carries out in 100mL quartz reactor.Adopt 500W xenon lamp (being provided with optical filter λ>=420nm) to be radiating light source, reactant liquor is the 100mL10mg/L rhodamine B aqueous solution, adds 0.1g embodiment 1 ~ 3 gained catalyst, and uses Ag
3pO
4catalyst as a comparison.Under magnetic agitation condition, first dark reaction 30min, makes it reach adsorption equilibrium, then reacts 1h under light illumination.Extract 4mL reactant liquor every 15min centrifugal, get supernatant and measure its absorbance at 554nm place.Record is curve plotting also, and result as shown in Figure 1.As can be seen from Figure, the Ag of non-compound MIL-100 (Fe) is compared
3pO
4catalyst, the effect of MIL-100 of the present invention (Fe) compound phosphoric acid silver photocatalyst for degrading rhodamine B obtains and promotes significantly.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. a preparation method for MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst, is characterized in that, comprise following preparation process:
(1) hydro-thermal method prepares MIL-100 (Fe);
(2) precipitation method prepare silver orthophosphate;
(3) step (2) gained silver orthophosphate is scattered in solvent, then adds step (1) gained MIL-100 (Fe), be uniformly mixed;
(4) evaporation of solvent, obtains MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst.
2. the preparation method of a kind of MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst according to claim 1, is characterized in that: the process that hydro-thermal method described in step (1) prepares MIL-100 (Fe) is as follows:
Take iron powder and 1,3,5-benzenetricarboxylic acid in reactor, then add nitric acid, hydrofluoric acid and water and react, reaction gained pressed powder product, through centrifugal, washing, dry, obtains MIL-100 (Fe).
3. the preparation method of a kind of MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst according to claim 1, is characterized in that: the process that the precipitation method described in step (2) prepare silver orthophosphate is as follows:
By AgNO
3soluble in water, obtain liquor argenti nitratis ophthalmicus; By Na
2hPO
4soluble in water, obtain disodium phosphate soln; Disodium phosphate soln is added drop-wise in liquor argenti nitratis ophthalmicus, stirring reaction under room temperature condition; Gained precipitation, through centrifugal, washing, drying, obtains silver orthophosphate.
4. the preparation method of a kind of MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst according to claim 1, is characterized in that: the solvent described in step (3) refers to absolute ethyl alcohol.
5. the preparation method of a kind of MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst according to claim 1, is characterized in that: described in step (3), the addition of MIL-100 (Fe) is 1% ~ 9% of silver orthophosphate quality.
6. the preparation method of a kind of MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst according to claim 5, is characterized in that: described in step (3), the addition of MIL-100 (Fe) is 1% ~ 5% of silver orthophosphate quality.
7. MIL-100 (Fe) compound phosphoric acid silver photochemical catalyst, be is characterized in that: prepared by the method described in any one of claim 1 ~ 6.
8. the application of MIL-100 according to claim 7 (Fe) compound phosphoric acid silver photochemical catalyst in catalyze and degrade organic pollutants.
9. the application of MIL-100 according to claim 8 (Fe) compound phosphoric acid silver photochemical catalyst in catalyze and degrade organic pollutants, is characterized in that: described organic pollution refers to rhodamine B.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106215979A (en) * | 2016-07-07 | 2016-12-14 | 中国科学院福建物质结构研究所 | The preparation of load-type iron-based metallic organic framework oxidation-desulfurizing catalyst and application thereof |
| CN107008507A (en) * | 2017-06-08 | 2017-08-04 | 合肥工业大学 | A kind of mesoporous Fe bases MOF@AgI high efficiency composition visible-light photocatalysis materials and its preparation method and application |
| CN109174198A (en) * | 2018-09-25 | 2019-01-11 | 吉林化工学院 | A kind of magnetic metal organogel load silver phosphate composite photocatalyst and its preparation method and application |
| CN111410749A (en) * | 2020-03-17 | 2020-07-14 | 广西民族大学 | Application of nano carrier MI L-100 (Fe) in loading of nitidine chloride |
| CN114797990A (en) * | 2022-04-11 | 2022-07-29 | 扬州大学 | Improve Ag 3 PO 4 Material with photocatalytic oxygen production activity and stability and preparation method thereof |
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| CN102000594A (en) * | 2010-11-26 | 2011-04-06 | 大连理工大学 | Preparation method of visible light photo catalyst silver and silver phosphate and application thereof |
| CN102580714A (en) * | 2012-02-09 | 2012-07-18 | 江苏大学 | Graphene oxide/silver phosphate composite visible light catalyst and preparation method thereof |
| CN102626647A (en) * | 2012-03-30 | 2012-08-08 | 常州大学 | Synthesizing method of playgouskite-loaded silver orthophosphate photochemical catalyst |
| CN104624211A (en) * | 2015-01-19 | 2015-05-20 | 江苏大学 | Preparation method of complex photocatalyst responsive to visible light and application of complex photocatalyst |
| CN104707658A (en) * | 2015-02-27 | 2015-06-17 | 福州大学 | Pd/metal-organic framework compound catalyst as well as preparation method and application thereof |
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2015
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| CN102000594A (en) * | 2010-11-26 | 2011-04-06 | 大连理工大学 | Preparation method of visible light photo catalyst silver and silver phosphate and application thereof |
| CN102580714A (en) * | 2012-02-09 | 2012-07-18 | 江苏大学 | Graphene oxide/silver phosphate composite visible light catalyst and preparation method thereof |
| CN102626647A (en) * | 2012-03-30 | 2012-08-08 | 常州大学 | Synthesizing method of playgouskite-loaded silver orthophosphate photochemical catalyst |
| CN104624211A (en) * | 2015-01-19 | 2015-05-20 | 江苏大学 | Preparation method of complex photocatalyst responsive to visible light and application of complex photocatalyst |
| CN104707658A (en) * | 2015-02-27 | 2015-06-17 | 福州大学 | Pd/metal-organic framework compound catalyst as well as preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106215979A (en) * | 2016-07-07 | 2016-12-14 | 中国科学院福建物质结构研究所 | The preparation of load-type iron-based metallic organic framework oxidation-desulfurizing catalyst and application thereof |
| CN107008507A (en) * | 2017-06-08 | 2017-08-04 | 合肥工业大学 | A kind of mesoporous Fe bases MOF@AgI high efficiency composition visible-light photocatalysis materials and its preparation method and application |
| CN109174198A (en) * | 2018-09-25 | 2019-01-11 | 吉林化工学院 | A kind of magnetic metal organogel load silver phosphate composite photocatalyst and its preparation method and application |
| CN111410749A (en) * | 2020-03-17 | 2020-07-14 | 广西民族大学 | Application of nano carrier MI L-100 (Fe) in loading of nitidine chloride |
| CN114797990A (en) * | 2022-04-11 | 2022-07-29 | 扬州大学 | Improve Ag 3 PO 4 Material with photocatalytic oxygen production activity and stability and preparation method thereof |
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