CN103539227A - Preparation process of Ag-supported and MnO2-CeO2 doped activated alumina particle electrode containing CuO interlayer - Google Patents
Preparation process of Ag-supported and MnO2-CeO2 doped activated alumina particle electrode containing CuO interlayer Download PDFInfo
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- CN103539227A CN103539227A CN201310525735.1A CN201310525735A CN103539227A CN 103539227 A CN103539227 A CN 103539227A CN 201310525735 A CN201310525735 A CN 201310525735A CN 103539227 A CN103539227 A CN 103539227A
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Abstract
The invention discloses a preparation process of an Ag-supported and MnO2-CeO2 doped activated alumina particle electrode containing a CuO interlayer. The preparation process comprises the following steps of adding AgNO3 to isopropanol to obtain a solution A, adding treated Al2O3 to the solution A, filtering the solution to obtain a particle B and micro-emulsion X, and washing the particle B with ethanol, thus obtaining a particle D; adding the particle D to X to obtain a particle F after filtration; utilizing Ce(NO3)2, CuCl2 and MnCl2 to prepare solutions B1, B2, B3, B4, B5, C, D, E and F; treating the particle F with the solutions B1, B2, B3, B4, B5 in sequence, thus obtaining a particle I; adding the particle I to the solution C, filtering the solution, then washing the obtained particle with ethanol, and drying the particle, thus obtaining a particle K; adding the particle K to the solution D, filtering the solution, then washing the obtained particle with ethanol, and drying the particle, thus obtaining a particle M; adding M to the solution E, filtering the solution, then washing the obtained particle with ethanol, and drying the particle, thus obtaining a particle O; adding the particle O to the solution F, filtering the solution, then washing the obtained particle with ethanol, drying the particle, and roasting the obtained particle at 580 DEG C for four hours, thus obtaining the Ag-supported and MnO2-CeO2 doped activated alumina particle electrode containing the CuO interlayer.
Description
Technical field
The invention belongs to By Electrocatalytic Oxidation and process the chemically modified electrode technical field of waste water, particularly a kind of loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2the preparation technology of activated alumina granule electrode.
Background technology
Electro-catalytic oxidation technology carrys out the organic pollutant in degrading waste water by producing the active group of the strong oxidizing properties such as hydroxyl radical free radical, processing high density, bio-refractory waste water aspect has non-secondary pollution, cost is low, suitability is strong, efficiency high, three-dimensional electro-catalytic oxidation technology wherein, by adding the granule electrode with catalytic activity between the anode at two-dimensional electrode and negative electrode, by certain mode, make the granular electrode surface of filling charged, its useful area that has improved two-dimensional electrode is little, mass transfer effect is poor, the defects such as current efficiency is low, be applicable to the waste water of various concentration, even if the waste water very low to Pollutant levels also has good treatment effect, to study at present more a kind of catalytic oxidation water technology.Based on Three-dimensional Electrode Method is applied to wastewater treatment, and its treatment effect is not only closely related with main electrode performance, and has much relations with the performance of granule electrode, and the catalytic performance that therefore how to improve granule electrode becomes the focus of Recent study.
Conventional granule electrode material mainly contains metallic conductor, metal oxide, is coated with glass sphere or baton round, graphite particle, active oxidation aluminum particulate, carbon fibre material and the activated carbon granule etc. of metal level.The resistance of traditional electrode is large, electric conductivity is low is to make that its current efficiency in wastewater treatment is low, stability is inadequate, the life-span is short, electrode material cost is higher, and technology for preparing electrode is complicated, limited the development of granule electrode material, so the research of novel granule electrode material also needs further reinforcement.Adopt in recent years dipping-thermal decomposition method to prepare loading type granule electrode and be subject to increasing scholar and pay attention to, but exist, reused the shortcomings such as weak effect, electrode efficiency are low, the current research that also lacks granule electrode preparation technology aspect.
Summary of the invention
The object of this invention is to provide a kind of loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2the preparation technology of activated alumina granule electrode.Its concrete steps are as follows:
(1) γ-Al that is 3-5mm by 300g particle diameter
2o
3ball 500ml deionized water wash, repeated washing 3 times, then puts into 200ml dehydrated alcohol and soaks 10h, and with after 500ml washed with de-ionized water 1 time, under 80 ℃ of conditions, dry 10h, obtains particulate matter A;
(2) AgNO that is 0.5mol/L by 50ml concentration
3add in 150ml Virahol, obtain solution A;
(3) particulate matter A step (1) being obtained adds in the solution A that step (2) obtains, and in shaking table, shake 3h, filtration obtains particulate matter B and microemulsion X, the washing with alcohol particulate matter B that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter C;
(4) particulate matter C step (3) being obtained is placed in retort furnace roasting 4h under 500 ℃ of conditions, obtains particulate matter D;
(5) particulate matter D step (4) being obtained adds in the microemulsion X that step (3) obtains, and in shaking table, shake 3h, remove by filter liquid and obtain particulate matter E, the washing with alcohol particulate matter E that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, is then placed in retort furnace roasting 4h under 500 ℃ of conditions, obtains particulate matter F;
(6) Ce (NO that is 0.5mol/L by 10ml concentration
3)
2the CuCl that solution and 100ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 10ml concentration be the MnCl of 0.5mol/L
2solution, is divided into 5 parts of equivalent after shaking up, obtain solution B
1, solution B
2, solution B
3, solution B
4, solution B
5;
(7) solution B that particulate matter F step (5) being obtained adds step (6) to obtain
1in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G1, the washing with alcohol particulate matter G1 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
1;
(8) particulate matter H step (7) being obtained
1the solution B that adds step (6) to obtain
2in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G2, the washing with alcohol particulate matter G2 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
2;
(9) particulate matter H step (8) being obtained
2the solution B that adds step (6) to obtain
3in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G3, the washing with alcohol particulate matter G3 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
3;
(10) particulate matter H step (9) being obtained
3the solution B that adds step (6) to obtain
4in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G4, the washing with alcohol particulate matter G4 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
4;
(11) particulate matter H step (10) being obtained
4the solution B that adds step (6) to obtain
5in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G5, the washing with alcohol particulate matter G5 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
5; By H
5be placed in retort furnace roasting 4h under 580 ℃ of conditions, obtain particulate matter I;
(12) Ce (NO that is 0.5mol/L by 20ml concentration
3)
2the CuCl that solution and 80ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 20ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution C;
(13) particulate matter I step (11) being obtained adds in the solution C that step (12) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter J, the washing with alcohol particulate matter J that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter K;
(14) Ce (NO that is 0.5mol/L by 40ml concentration
3)
2the CuCl that solution and 40ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 40ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution D;
(15) particulate matter K step (13) being obtained adds in the solution D that step (14) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter L, the washing with alcohol particulate matter L that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter M;
(16) Ce (NO that is 0.5mol/L by 45ml concentration
3)
2the CuCl that solution and l5ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 60ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution E;
(17) particulate matter M step (15) being obtained adds in the solution E that step (16) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter N, the washing with alcohol particulate matter N that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter O;
(18) Ce (NO that is 0.5mol/L by 15ml concentration
3)
2the CuCl that solution and 5ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 100ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution F;
(19) particulate matter O step (17) being obtained adds in the solution F that step (18) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter P, the washing with alcohol particulate matter P that is 95% by 100mL mass concentration, repeated washing 2 times, then under 80 ℃ of conditions, be dried 10h, obtain particulate matter Q, Q is placed in to retort furnace roasting 4h under 580 ℃ of conditions, and the particulate matter obtaining is the loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2activated alumina granule electrode.
The invention has the beneficial effects as follows the loaded Ag doped with Mn O containing CuO middle layer making
2-CeO
2activated alumina granule electrode has the features such as current efficiency is high, stability is strong, electrode life is long.
Embodiment
The invention provides a kind of loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2the preparation technology of activated alumina granule electrode, illustrates below by an example process of in fact executing.
Embodiment 1.
γ-the Al that is 3-5mm by 300g particle diameter
2o
3ball 500ml deionized water wash, repeated washing 3 times, then puts into 200ml dehydrated alcohol and soaks 10h, and with after 500ml washed with de-ionized water 1 time, under 80 ℃ of conditions, dry 10h, obtains particulate matter A.
The AgNO that is 0.5mol/L by 50ml concentration
3add in 150ml Virahol, obtain solution A.Particulate matter A is joined in solution A, and shake 3h in shaking table, filter and obtain particulate matter B and microemulsion X, the washing with alcohol particulate matter B that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter C; Particulate matter C is placed in to retort furnace roasting 4h under 500 ℃ of conditions, obtains particulate matter D; Particulate matter D is joined in microemulsion X, and in shaking table, shake 3h, remove by filter liquid and obtain particulate matter E, the washing with alcohol E that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, is then placed in retort furnace roasting 4h under 500 ℃ of conditions, obtains particulate matter F.
Ce (the NO that is 0.5mol/L by 10ml concentration
3)
2the CuCl that solution and 100ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 10ml concentration be the MnCl of 0.5mol/L
2solution, is divided into 5 parts of equivalent after shaking up, obtain solution B
1, solution B
2, solution B
3, solution B
4, solution B
5;
Particulate matter F is joined in solution B 1, and in shaking table, shake 3h, remove by filter liquid and obtain particulate matter G1, the washing with alcohol particulate matter G1 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
1; By particulate matter H
1join solution B
2in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G2, the washing with alcohol particulate matter G2 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
2; By particulate matter H
2join solution B
3in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G3, the washing with alcohol particulate matter G3 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
3; By particulate matter H
3join solution B
4in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G4, the washing with alcohol particulate matter G4 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
4; By particulate matter H
4join solution B
5in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G5, the washing with alcohol particulate matter G5 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
5; By H
5be placed in retort furnace roasting 4h under 580 ℃ of conditions, obtain particulate matter I.
Ce (the NO that is 0.5mol/L by 20ml concentration
3)
2the CuCl that solution and 80ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 20ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution C.
Particulate matter I is joined in solution C, and shake 3h in shaking table; Remove by filter liquid and obtain particulate matter J, the washing with alcohol particulate matter J that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter K.
Ce (the NO that is 0.5mol/L by 40ml concentration
3)
2the CuCl that solution and 40ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 40ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution D.
Particulate matter K is joined in solution D, and shake 3h in shaking table; Remove by filter liquid and obtain particulate matter L, the washing with alcohol particulate matter L that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter M.
Ce (the NO that is 0.5mol/L by 45ml concentration
3)
2the CuCl that solution and 15ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 60ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution E.
Particulate matter M is joined in solution E, and shake 3h in shaking table; Remove by filter liquid and obtain particulate matter N, the washing with alcohol particulate matter N that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter O.
Ce (the NO that is 0.5mol/L by 15ml concentration
3)
2the CuCl that solution and 5ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 100ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution F.
Particulate matter O is joined in solution F, and in shaking table, shake 3h; Remove by filter liquid and obtain particulate matter P, the washing with alcohol particulate matter P that is 95% by 100mL mass concentration, repeated washing 2 times, then under 80 ℃ of conditions, be dried 10h, obtain particulate matter Q, Q is placed in to retort furnace roasting 4h under 580 ℃ of conditions, and the particulate matter obtaining is the loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2activated alumina granule electrode.
The loaded Ag doped with Mn O containing CuO middle layer that uses the inventive method to make below
2-CeO
2activated alumina granule electrode has carried out Degrading experiment to coal chemical industrial waste water in 3 D electrode reactor, further illustrates the present invention.
The loaded Ag doped with Mn O containing CuO middle layer that the inventive method is made
2-CeO
2activated alumina granule electrode is seated in 3 D electrode reactor, and coal chemical industrial waste water has been carried out to Degrading experiment, and result shows the efficiently COD in Treatment of Wastewater in Coking of this electrode, when influent COD is 512mg/L, with the loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2active oxidation aluminum particulate is the 3rd utmost point, and pH is 4.5, and voltage is 12V, and the treatment time is 60min, and the COD after processing in water outlet is reduced to 44mg/L, and processing efficiency reaches 91.41%.
Claims (1)
1. the loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2the preparation technology of activated alumina granule electrode, is characterized in that, the concrete steps of this technique are as follows:
(1) γ-Al that is 3-5mm by 300g particle diameter
2o
3ball 500ml deionized water wash, repeated washing 3 times, then puts into 200ml dehydrated alcohol and soaks 10h, and with after 500ml washed with de-ionized water 1 time, under 80 ℃ of conditions, dry 10h, obtains particulate matter A;
(2) AgNO that is 0.5mol/L by 50ml concentration
3add in 150ml Virahol, obtain solution A;
(3) particulate matter A step (1) being obtained adds in the solution A that step (2) obtains, and in shaking table, shake 3h, filtration obtains particulate matter B and microemulsion X, the washing with alcohol particulate matter B that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter C;
(4) particulate matter C step (3) being obtained is placed in retort furnace roasting 4h under 500 ℃ of conditions, obtains particulate matter D;
(5) particulate matter D step (4) being obtained adds in the microemulsion X that step (3) obtains, and in shaking table, shake 3h, remove by filter liquid and obtain particulate matter E, the washing with alcohol particulate matter E that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, is then placed in retort furnace roasting 4h under 500 ℃ of conditions, obtains particulate matter F;
(6) Ce (NO that is 0.5mol/L by 10ml concentration
3)
2the CuCl that solution and 100ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 10ml concentration be the MnCl of 0.5mol/L
2solution, is divided into 5 parts of equivalent after shaking up, obtain solution B
1, solution B
2, solution B
3, solution B
4, solution B
5;
(7) solution B that particulate matter F step (5) being obtained adds step (6) to obtain
1in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G1, the washing with alcohol particulate matter G1 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H1;
(8) particulate matter H step (7) being obtained
1the solution B that adds step (6) to obtain
2in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G2, the washing with alcohol particulate matter G2 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
2;
(9) particulate matter H step (8) being obtained
2add in the solution B 3 that step (6) obtains, and in shaking table, shake 3h, remove by filter liquid and obtain particulate matter G3, the washing with alcohol particulate matter G3 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
3;
(10) particulate matter H step (9) being obtained
3the solution B that adds step (6) to obtain
4in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G4, the washing with alcohol particulate matter G4 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H
4;
(11) particulate matter H step (10) being obtained
4the solution B that adds step (6) to obtain
5in, and in shaking table, shake 3h, and remove by filter liquid and obtain particulate matter G5, the washing with alcohol particulate matter G5 that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter H5; H5 is placed in to retort furnace roasting 4h under 580 ℃ of conditions, obtains particulate matter I;
(12) Ce (NO that is 0.5mol/L by 20ml concentration
3)
2the CuCl that solution and 80ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 20ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution C;
(13) particulate matter I step (11) being obtained adds in the solution C that step (12) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter J, the washing with alcohol particulate matter J that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter K;
(14) Ce (NO that is 0.5mol/L by 40ml concentration
3)
2the CuCl that solution and 40ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 40ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution D;
(15) particulate matter K step (13) being obtained adds in the solution D that step (14) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter L, the washing with alcohol particulate matter L that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter M;
(16) Ce (NO that is 0.5mol/L by 45ml concentration
3)
2the CuCl that solution and 15ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 60ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution E;
(17) particulate matter M step (15) being obtained adds in the solution E that step (16) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter N, the washing with alcohol particulate matter N that is 95% by 100mL mass concentration, repeated washing 2 times, then dry 10h under 80 ℃ of conditions, obtains particulate matter O;
(18) Ce (NO that is 0.5mol/L by 15ml concentration
3)
2the CuCl that solution and 5ml concentration are 0.5mol/L
2solution joins in 120ml Virahol and 5ml concentrated hydrochloric acid, and then to add 100ml concentration be the MnCl of 0.5mol/L
2solution, obtains solution F;
(19) particulate matter O step (17) being obtained adds in the solution F that step (18) obtains, and in shaking table, shakes 3h; Remove by filter liquid and obtain particulate matter P, the washing with alcohol particulate matter P that is 95% by 100mL mass concentration, repeated washing 2 times, then under 80 ℃ of conditions, be dried 10h, obtain particulate matter Q, Q is placed in to retort furnace roasting 4h under 580 ℃ of conditions, and the particulate matter obtaining is the loaded Ag doped with Mn O containing CuO middle layer
2-CeO
2the active oxidation aluminum particulate Shen utmost point.
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| CN108163931A (en) * | 2017-12-28 | 2018-06-15 | 光合强化（北京）生物科技有限公司 | The graphite electrode modified based on CeO-ZrO-NiO and pyrazine |
| CN108178247A (en) * | 2017-12-28 | 2018-06-19 | 光合强化（北京）生物科技有限公司 | The graphite electrode modified based on CrO-FeO-PbO and quinoline |
| CN108178248A (en) * | 2017-12-28 | 2018-06-19 | 光合强化（北京）生物科技有限公司 | The graphite electrode modified based on CuO-CoO-ZnO and pyridine |
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| CN106495287A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove modified carbon fiber granule electrode and the preparation method of chlorophenol function |
| CN106495286A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove modified titanium foam granule electrode and the preparation method of benzoquinone function |
| CN106495279A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove modified nickel foam granule electrode and the preparation method of chlorophenol function |
| CN106495281A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove modified activated carbon granule electrode and the preparation method of carbazole function |
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| CN106495282A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove modified activated carbon granule electrode and the preparation method of benzoquinones function |
| CN106495290A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove modified graphite granule electrode and the preparation method of benzoquinone function |
| CN106495280A (en) * | 2016-11-21 | 2017-03-15 | 北京益清源环保科技有限公司 | There is electro-catalysis to remove improved ferroferric oxide granule electrode and the preparation method of phenol function |
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| CN106517434A (en) * | 2016-11-21 | 2017-03-22 | 北京益清源环保科技有限公司 | Modified activated carbon particle electrode with function of removing pyridine through electro-catalysis, and preparation method of modified activated carbon particle electrode |
| CN106517429A (en) * | 2016-11-21 | 2017-03-22 | 北京益清源环保科技有限公司 | Modified ceramic particle electrode with function of removing furan through electro-catalysis and preparation method |
| CN106517431A (en) * | 2016-11-21 | 2017-03-22 | 北京益清源环保科技有限公司 | Modified ceramic particle electrode with electrocatalytic carbazole removing function and preparing method thereof |
| CN108083393A (en) * | 2017-12-28 | 2018-05-29 | 光合强化（北京）生物科技有限公司 | The graphite electrode modified based on PbO-NiO-MgO and thiophene |
| CN108163931A (en) * | 2017-12-28 | 2018-06-15 | 光合强化（北京）生物科技有限公司 | The graphite electrode modified based on CeO-ZrO-NiO and pyrazine |
| CN108178247A (en) * | 2017-12-28 | 2018-06-19 | 光合强化（北京）生物科技有限公司 | The graphite electrode modified based on CrO-FeO-PbO and quinoline |
| CN108178248A (en) * | 2017-12-28 | 2018-06-19 | 光合强化（北京）生物科技有限公司 | The graphite electrode modified based on CuO-CoO-ZnO and pyridine |
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