CN1562776A - Method of preparing electrode in photoelectrocatalysis for treating oxygen in organic water - Google Patents
Method of preparing electrode in photoelectrocatalysis for treating oxygen in organic water Download PDFInfo
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- CN1562776A CN1562776A CN 200410012198 CN200410012198A CN1562776A CN 1562776 A CN1562776 A CN 1562776A CN 200410012198 CN200410012198 CN 200410012198 CN 200410012198 A CN200410012198 A CN 200410012198A CN 1562776 A CN1562776 A CN 1562776A
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- oxygen electrode
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Abstract
The characteristics are: oxygen electrode is composed of catalyzing layer plus catalyzing layer, the catalyzing layer is composed of active carbon, catalytic agent, graphite powder and binder, the electric conduction frame is made by silver-plated net and copper net. The prepn. method of oxygen electrode is to uniform mix active carbon, catalytic agent graphite powder and binder according to a proper ratio at first, to roll it into catalytic layer with a fixed thick by grinder machine, then to press the catalytic layer with the electric conduction frame together by hydraulic oil presser, which is fired on a proper temp. to be shaped to required oxygen electrode. This electrode is used as negative electrode in photo-electric catalytic process to create active perssads (H2O2, OH++ etc.) in acting of electric field, the active perssad can create OH with very strong oxidability to remove organic substances in water quickly and completely.
Description
Technical field
The present invention relates to a kind of oxygen electrode that is used for the organic water treatment of photoelectrocatalysis and preparation method thereof, belong to photoelectrochemistry reaction engineering advanced oxidation AOP (Advanced Oxidation Processes) water-treatment technology field.
Background technology
Gas diffusion electrode (claiming oxygen electrode again, air electrode) is the thin three-phase porous electrode that is interwoven by " pore ", " liquid hole " and " solid phase " three kinds of networks, is found by Grove1839 the earliest, is used for the experiment of hydrogen-air fuel cell; Thereafter, along with the exploitation of fuel cell, the gas diffusion electrode technology is constantly progressive, and steady running has become possibility under the high current density, and the eighties year in last century begins to be applied among the salt electrolysis technology.
Recently, both at home and abroad the investigator gas diffusion electrode is applied in the processing of organic water (Cai Naicai, Wang Yaping, Wang Efeng etc. applied chemistry, 1999,16 (2): 87-89; Tomas Harrington, Derek Pletcher.J.of the Electrochem.Society, 1999,146 (8): 2983-2989), utilize its reduction oxygen to generate H
2O
2, at Fe
2+Under the existence of ion or light, hydrogen peroxide decomposition produces the extremely strong OH free radical (Standard Electrode Potentials 2.80eV) of oxidation capacity, with organism generation oxidizing reaction and radical chain reaction in the water, makes organic matter degradation, and H
2O
2Controlled, the newborn H of output and organic degradation rate
2O
2Oxidation capacity is stronger.But the amount of hydrogen peroxide that this process produces is few, and speed of reaction is low, and reaction needs to carry out under strong acid or highly basic condition, and water treatment procedure has been introduced chemical reagent.
Photochemical catalysis is the advanced oxidation AOP water technology that development in recent years is got up, and utilizes it to produce the extremely strong OH free radical of oxidation capacity (Standard Electrode Potentials 2.80eV) (Fujishima A, Honda K, Nature, 1972,238:37～38 in water; Matthews R.W.J.Catal.1988,111:264-272; Ollis D F, Al-Ekabi H.Amsterdam:Elsevier, 1993), can make and be difficult to the organic pollutant permineralization of degrading in the water, and to Substrate non-selectivity almost, degradation process can be carried out at normal temperatures and pressures, and this method needn't be added chemical reagent in addition, non-secondary pollution is so become the research forward position and the exploitation focus of current domestic and international water treatment technology.But up to now, one of subject matter that big quantity research discloses this process is that quantum yield is too low, and speed of reaction is not high.
The auxiliary photocatalysis method of electrochemistry in recent years, or claim the photoelectrocatalysis method can stop light induced electron and hole simple composite to take place to improve quantum yield (Vinodgopal K, Hotchandani S and Kamat P V.J.Phys.Chem., 1993,97 (26): 9040-9044; Kesselman J M, Lewis N S and Hoffmann.Environ.Sci.Technol., 1997,31 (8): 2298-2305; Fan Caimei, Sun Yanping. Institutes Of Technology Of Taiyuan's journal, 2000,31 (5): 525-527,531).People pay attention to TiO more in research in the past
2The promoter action that the light anode improves the process quantum yield, and the contribution of photoelectrochemistry process negative electrode is not caused enough attention, cause the total speed of reaction of process to can not get improving.
The present invention introduces the photoelectrocatalysis water treatment system with oxygen electrode, and it not only utilizes the H of its generation
2O
2, the more important thing is the OH that utilizes its generation
-With TiO
2Light anode or TiO
2The combined action of photocatalytic particle, to disclose the essence of photochemical catalysis and electrochemistry associating, this is a kind of new approaches, yet there are no report so far.
Summary of the invention
The preparation method who the purpose of this invention is to provide the oxygen electrode of the organic water treatment of photoelectrocatalysis, this electrode is made negative electrode at the photoelectrocatalysis water treatment procedure, can with the semiconductor optical anode combined action, effectively stop the compound of photohole and electronics, remove organism in the water, improve the photocatalytic process speed of reaction.
The preparation method of the oxygen electrode of the organic water treatment of photoelectrocatalysis of the present invention, it is characterized in that oxygen electrode is made up of for three layers Catalytic Layer+conducting matrix grain+Catalytic Layer, the preparation method is divided into three steps and carries out: the conducting matrix grain that at first prepares oxygen electrode, the Catalytic Layer of second step preparation oxygen electrode, at last three layers of the Catalytic Layer, conducting matrix grain, the Catalytic Layer that prepare stack combinations are successively obtained the oxygen electrode of the organic water treatment of photoelectrocatalysis of a kind of Catalytic Layer+conducting matrix grain+three layers of formation of Catalytic Layer, its concrete preparation technology's method is:
The preparation of I conducting matrix grain: conducting matrix grain is for crossing silver-bearing copper net or nickel screen, to cross silver-bearing copper net or nickel screen and cut out shaping according to the required area of electrode, through acetone and washed with de-ionized water, be placed in the oxalic acid solution and flood, and be heated 85-95 ℃, keep about 1-3h after, take out and to cross silver-bearing copper net or nickel screen, rinse well with deionized water, room temperature is dried stand-by again;
The preparation of II Catalytic Layer: the component of Catalytic Layer is gac, metal oxide catalyst, Graphite Powder 99 and binding agent, gac, metal oxide catalyst, Graphite Powder 99 are mixed by the proportioning of mass ratio 8: 0.5-1.5: 0.5-2.0, not stopping to add the binding agent emulsion under the stirring condition, its each component is bonded together.When stirring into when being similar to heavy-gravity and having suitable flexible dough, being put in membrane milling machine, to be rolled into certain thickness catalytic film stand-by;
The preparation of III oxygen electrode: the Catalytic Layer, conducting matrix grain, the Catalytic Layer that prepare are folded for three layers successively, be positioned on the oil press, compression moulding under 100-160kg pressure, then at 200-300 ℃ of following sintering 1-4 hour, naturally cooling.
Among the above-mentioned preparation method of the present invention, the concentration of the used oxalic acid solution of described processing conducting matrix grain is 10-20%; Gac is the hydrophilic active charcoal, and the aperture is 2nm-50nm; Used binding agent is tetrafluoroethylene or resin; Used metal oxide catalyst is TiO
2, MnO
2, SnO
2Or ZnO; The film thickness of Catalytic Layer is 0.1-1.0mm.
Advantage of the present invention is: oxygen electrode is introduced the photoelectrocatalysis water treatment system, at TiO
2Light anode or TiO
2When photocatalytic particle played a role, oxygen electrode can play a role simultaneously, light, electrocatalytic reaction is organically combined, thereby realize organism in the efficient degradation water.Concrete advantage is: 1. oxygen electrode has two effects greatly: one, synthetic H
2O
2Its two, produce OH
-2. oxygen electrode and TiO
2OH is produced in the combined action of light anode; 3. OH is produced in oxygen electrode and light combined action; 4. TiO
2Light anodic effect: catch light induced electron, suppress it and high energy holes is compound, produce OH; Its two, organic pollutant in the Direct Electrochemistry oxidizing water.
Therefore, the present invention can thoroughly remove organism in the water fast, and needn't add chemical reagent, non-secondary pollution, processing efficiency height.
Embodiment
Embodiment 1
With gac 4g, MnO
2Catalyzer 0.5g, Graphite Powder 99 0.5g mix by 8: 1: 1 proportioning of mass ratio, not stopping to add the binding agent emulsion under the stirring condition, its each component are bonded together.When stirring into when being similar to heavy-gravity and having suitable flexible dough, be put in membrane milling machine and roll into about the thick catalytic film of 0.1mm stand-by; To cross the silver-bearing copper net and cut out shaping, and, be placed in 10% oxalic acid solution and flood, and be heated 90 ℃ through acetone and washed with de-ionized water, keep about 3h after, take out and to cross the silver-bearing copper net, rinse well with deionized water, room temperature is dried stand-by; Then, Catalytic Layer, conducting matrix grain, Catalytic Layer three is stacked good, be positioned on the oil press, compression moulding under 150kg pressure, then 250 ℃ of following sintering 1 hour, naturally cooling.
Embodiment 2
Gac 4g, catalyzer 0.75g, Graphite Powder 99 0.25g are mixed by 8: 1.5: 0.5 proportioning of mass ratio, and wherein catalyzer is that mass ratio is 1: 1 TiO
2And MnO
2,, its each component is bonded together not stopping to add the binding agent emulsion under the stirring condition.When stirring into when being similar to heavy-gravity and having suitable flexible dough, be put in membrane milling machine and roll into about the thick catalytic film of 0.1mm stand-by; Nickel screen is cut out shaping,, is placed in 20% oxalic acid solution and floods, and be heated 95 ℃ through acetone and washed with de-ionized water, keep about 1h after, take out nickel screen, rinse well with deionized water, room temperature is dried stand-by; Then, Catalytic Layer, conducting matrix grain, Catalytic Layer three is stacked good, be positioned on the oil press, compression moulding under 160kg pressure, then 200 ℃ of following sintering 2 hours, naturally cooling.
Embodiment 3
Gac 4g, catalyzer 0.5g, Graphite Powder 99 0.75g are mixed by 8: 1: 2 proportioning of mass ratio, and wherein catalyzer is that mass ratio is 1: 1 SnO
2And ZnO, not stopping to add the binding agent emulsion under the stirring condition, its each component is bonded together.When stirring into when being similar to heavy-gravity and having suitable flexible dough, be put in membrane milling machine and roll into about the thick catalytic film of 1.0mm stand-by; To cross the silver-bearing copper net and cut out shaping, and, be placed in 15% oxalic acid solution and flood, and be heated 85 ℃ through acetone and washed with de-ionized water, keep about 3h after, take out and to cross the silver-bearing copper net, rinse well with deionized water, room temperature is dried stand-by; Then, Catalytic Layer, conducting matrix grain, Catalytic Layer three is stacked good, be positioned on the oil press, compression moulding under 100kg pressure, then 360 ℃ of following sintering 4 hours, naturally cooling.
Carry out the experiment of photoelectric catalysis degrading phenol with the oxygen electrode in the embodiment of the invention 1,2,3, the experiment of photoelectric catalysis degrading phenol is carried out in the glass three-electrode system, wherein initial phenol concentration is 20ppm, and oxygen electrode, copper sheet, platinum filament among the embodiment 1,2,3 are respectively research electrode, TiO
2/ Ti is the light anode, and saturated calomel electrode is made reference electrode, at 0-15mA/cm
2Current density and illumination certain hour, analysis of Phenol change in concentration and TOC (total organic carbon) change in concentration.The result shows that phenol in the oxygen electrode removal water and the speed of reaction of TOC are much larger than platinum electrode and copper electrode.
Claims (6)
1. the preparation method of the oxygen electrode of the organic water treatment of photoelectrocatalysis, it is characterized in that oxygen electrode is made up of for three layers Catalytic Layer+conducting matrix grain+Catalytic Layer, the preparation method is divided into three steps and carries out: the conducting matrix grain that at first prepares oxygen electrode, the Catalytic Layer of second step preparation oxygen electrode, at last three layers of the Catalytic Layer, conducting matrix grain, the Catalytic Layer that prepare stack combinations are successively obtained the oxygen electrode of the organic water treatment of photoelectrocatalysis of a kind of Catalytic Layer+conducting matrix grain+three layers of formation of Catalytic Layer, its concrete preparation technology's method is:
The preparation of I conducting matrix grain: conducting matrix grain is for crossing silver-bearing copper net or nickel screen, to cross silver-bearing copper net or nickel screen and cut out shaping according to the required area of electrode, through acetone and washed with de-ionized water, be placed in the oxalic acid solution and flood, and be heated 85-95 ℃, keep about 1-3h after, take out and to cross silver-bearing copper net or nickel screen, rinse well with deionized water, room temperature is dried stand-by again;
The preparation of II Catalytic Layer: the component of Catalytic Layer is gac, metal oxide catalyst, Graphite Powder 99 and binding agent, gac, metal oxide catalyst, Graphite Powder 99 are mixed by the proportioning of mass ratio 8: 0.5-1.5: 0.5-2.0, not stopping to add the binding agent emulsion under the stirring condition, its each component is bonded together.When stirring into when being similar to heavy-gravity and having suitable flexible dough, being put in membrane milling machine, to be rolled into certain thickness catalytic film stand-by;
The preparation of III oxygen electrode: the Catalytic Layer, conducting matrix grain, the Catalytic Layer that prepare are folded for three layers successively, be positioned on the oil press, compression moulding under 100-160kg pressure, then at 200-300 ℃ of following sintering 1-4 hour, naturally cooling.
2. press the preparation method of the oxygen electrode of the organic water treatment of the described photoelectrocatalysis of claim 1, it is characterized in that the concentration 10-20% of oxalic acid solution.
3. press the preparation method of the oxygen electrode of the organic water treatment of the described photoelectrocatalysis of claim 1, it is characterized in that used gac is the hydrophilic active charcoal, the aperture is 2nm-50nm.
4. press the preparation method of the oxygen electrode of the organic water treatment of the described photoelectrocatalysis of claim 1, it is characterized in that used metal oxide catalyst is TiO
2, MnO
2, SnO
2Or ZnO.
5. press the preparation method of the oxygen electrode of the organic water treatment of the described photoelectrocatalysis of claim 1, it is characterized in that used binding agent is tetrafluoroethylene or resin.
6. press the preparation method of the oxygen electrode of the organic water treatment of the described photoelectrocatalysis of claim 1, the film thickness that it is characterized in that Catalytic Layer is 0.1-1.0mm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102596823A (en) * | 2009-05-20 | 2012-07-18 | 湖首大学 | Method and system for combined photocatalytic and electrochemical wastewater remediation |
| CN102677093A (en) * | 2012-05-30 | 2012-09-19 | 合肥工业大学 | Lead dioxide powder porous electrode and preparation method thereof |
| CN106542619A (en) * | 2016-10-31 | 2017-03-29 | 上海电力学院 | A kind of electrode for efficient fast degradation refractory organic and preparation method thereof |
| CN108579717A (en) * | 2018-04-08 | 2018-09-28 | 南京工业大学 | A kind of sludge carbon photocatalysis hydrogen phosphide oxidation catalyst and its preparation and application |
| CN112723486A (en) * | 2020-11-30 | 2021-04-30 | 河南开炭新材料设计研究院有限公司 | Preparation method of three-dimensional porous carbon-based material for wastewater treatment |
-
2004
- 2004-03-19 CN CN 200410012198 patent/CN1230384C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102596823A (en) * | 2009-05-20 | 2012-07-18 | 湖首大学 | Method and system for combined photocatalytic and electrochemical wastewater remediation |
| CN102677093A (en) * | 2012-05-30 | 2012-09-19 | 合肥工业大学 | Lead dioxide powder porous electrode and preparation method thereof |
| CN106542619A (en) * | 2016-10-31 | 2017-03-29 | 上海电力学院 | A kind of electrode for efficient fast degradation refractory organic and preparation method thereof |
| CN106542619B (en) * | 2016-10-31 | 2019-06-28 | 上海电力学院 | A kind of electrode and preparation method thereof for efficient fast degradation refractory organic |
| CN108579717A (en) * | 2018-04-08 | 2018-09-28 | 南京工业大学 | A kind of sludge carbon photocatalysis hydrogen phosphide oxidation catalyst and its preparation and application |
| CN112723486A (en) * | 2020-11-30 | 2021-04-30 | 河南开炭新材料设计研究院有限公司 | Preparation method of three-dimensional porous carbon-based material for wastewater treatment |
| CN112723486B (en) * | 2020-11-30 | 2023-09-29 | 开封平煤新型炭材料科技有限公司 | Preparation method of three-dimensional porous carbon-based material for wastewater treatment |
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