CN105478102A - Method for preparing catalyst for electrical catalytic degradation of organic wastewater - Google Patents
Method for preparing catalyst for electrical catalytic degradation of organic wastewater Download PDFInfo
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- CN105478102A CN105478102A CN201610079959.8A CN201610079959A CN105478102A CN 105478102 A CN105478102 A CN 105478102A CN 201610079959 A CN201610079959 A CN 201610079959A CN 105478102 A CN105478102 A CN 105478102A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000015556 catabolic process Effects 0.000 title claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 title abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 21
- 238000009987 spinning Methods 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 150000004706 metal oxides Chemical class 0.000 claims description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 5
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 235000011837 pasties Nutrition 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 6
- 238000001523 electrospinning Methods 0.000 abstract description 6
- 239000000835 fiber Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000010411 electrocatalyst Substances 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 238000009475 tablet pressing Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000002121 nanofiber Substances 0.000 description 12
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 6
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/58—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a method for preparing a catalyst for electrical catalytic degradation of organic wastewater and relates to the technique for preparing a one-dimensional metallic oxide electrode catalyst for electrical catalytic degradation of organic wastewater. Metal salt, high-molecular polymer and organic solvent are mixed and stirred to form a spinning solution, electrostatic spinning is conducted to generate M/PVP composite fiber yarn, the yarn is subjected to heat treatment in the air to prepare a one-dimensional metallic oxide catalyst, and the prepared catalyst is made into an electrode through tablet pressing to serve as the positive pole for electrical catalysis of organic wastewater. The one-dimensional continuous filament-shaped metallic oxide can be prepared with the electrospinning method to be used as the electrode catalyst, has higher stability and conductivity compared with granules, and has a good catalysis effect in wastewater electro-catalysis as an electrocatalyst electrode.
Description
Technical field
The present invention is the preparation field belonging to electrode catalyst, is specifically related to the preparation method of the one-dimensional metal oxide electrode catalyst for Electrocatalysis Degradation organic wastewater.
Technical background
Along with socioeconomic fast-developing simultaneously also with a series of environmental problem, particularly the pollution of water resource is directly threaten to the existence of the mankind.Therefore, the process for organic wastewater is subject to people's attention gradually.At present, both at home and abroad for the process tertiary treatment processes of organic wastewater, designed treatment technology mainly comprises Physical, bioanalysis, absorption method, chemical oxidization method etc.Wherein, chemical oxidization method mainly contains wet oxidation, wet method catalytic oxidation, catalytic oxidation etc.Catalytic oxidation is the method for the process organic wastewater with difficult degradation thereby grown up gradually in recent years.It can carry out at normal temperatures and pressures, mild condition, equipment are simple, floor space is little, operation and maintenance expense is lower, do not need to add reductant-oxidant in addition, avoids secondary pollution.
The position residing in electrocatalysis device according to eelctro-catalyst, can be divided into two types: one is that eelctro-catalyst is arranged in solution; Another kind of to be coupling on base electrode material (matrix) for eelctro-catalyst, thus the catalyst electrode made is for electro-catalysis process, eelctro-catalyst wherein also can be called electrode catalyst.The Chinese invention patent of the patent No. 201410675982.4 discloses the metal oxide that utilized Electrospinning to prepare as eelctro-catalyst for Water oxidize catalyst.And for the preparation of catalyst electrode, mainly comprise electrodeposition process, thermal decomposition method, dipping or brushing method etc.But the anode material pattern prepared by this several method is restive, and catalytic effect is not very desirable.As F.Montilla(JournalofPhysicalChemistryB, 108:5036-5043) etc. prepared Ti/SnO by thermal decomposition method
2-Sb electrode, there is crack performance in various degree on SEM picture show electrode surface, and this structure makes coating shedding, and matrix is easy to passivation, thus reduces the effect of catalytic degradation.And utilize Electrospinning to prepare one-dimensional metal oxide as electrode catalyst for Electrocatalysis Degradation organic wastewater, up to now, there is not been reported up to now.
Summary of the invention
The present invention seeks to propose the preparation method of the catalyst for Electrocatalysis Degradation organic wastewater of a kind of non-secondary pollution, excellent catalytic effect.
The present invention includes following steps:
1) polymer is first dissolved in organic solvent, then dissolves in soluble metallic salt, form spinning solution;
2) spinning solution is carried out electrostatic spinning, obtain precursor;
3) precursor is calcined, obtain metal oxide nanofibres;
4) by compressing tablet after metal oxide nanofibres and auxiliary material mixing, electrode catalyst is obtained.
The present invention utilizes electrostatic spinning technique to prepare the electrodeless fibrous material of continuous print one-dimensional metal oxide and is used as electrode catalyst, to be then coupled with basic electrode by compressing tablet and to prepare catalyst electrode, as anode for electric electro-catalysis process organic wastewater.
The present invention compared with prior art, has the following advantages:
1, compared with the existing method preparing electrode, one-dimensional metal oxide prepared by the present invention mainly utilizes electrostatic spinning technique as electrode catalyst, wherein Electrospinning has simple to operate, controllability is strong, Cheap highly effective, utilize electrostatic spinning technique to prepare its pattern of metal oxide for one dimension continuous print comparatively stable relative to granular.
2, can well reach by changing temperature and programming rate and temperature retention time the effect wanted on the one-dimensional metal oxide utilizing Electrospinning to prepare changes as its pattern of electrode catalyst, it is simple to operate.
3, the one-dimensional metal oxide utilizing Electrospinning to prepare can prepare composite metal oxide by the interpolation of the slaine changing presoma.
Further, polymer of the present invention is polyvinylpyrrolidone (PVP).PVP is amphiphilic macromolecular, and spinnability is strong.
Described organic solvent be in ethanol or N-N dimethyl formamide (DMF) at least any one.Above-mentioned solvent all has suitable volatility, and low cost.
Described polymer is 10 ~ 15: 100 with the mixing quality ratio of organic solvent.The spinning solution moderate viscosity of this proportions, is easy to spinning.
Described soluble metallic salt is stannic chloride pentahydrate, Schweinfurt green, acetylacetone cobalt, ferric acetyl acetonade or manganese acetate.These five kinds of slaine presomas are soluble in spinning solution system, and the metal oxide catalyst obtained has higher catalytic activity.
Described soluble metallic salt is 0.5 ~ 1: 1 with the mixing quality ratio of polymer.Mass ratio is excessive, and slaine can not be well dispersed in PVP, there will be serious agglomeration; Otherwise then the yield of metal oxide is too low.
Accompanying drawing explanation
Fig. 1 calcines with the programming rate of 3 DEG C/min the SnO that 3h obtains in example 1 under air at 500 DEG C
2the SEM photo of fiber.
For calcining with the programming rate of 3 DEG C/min the SnO that 3h obtains at 500 DEG C under air in Fig. 2 example 1
2the x-ray diffraction pattern (XRD) of nanofiber.
Detailed description of the invention
Example 1: the polyvinylpyrrolidone (PVP) taking 2g adds in the solvent be made up of the mixing of 9g ethanol and 9gN-N dimethyl formamide (DMF), stirs 12h until solution is clear shape, then takes the SnCl of 2g
45H
2o adds in above-mentioned solution, is stirred to solution and becomes clear, namely obtain spinning solution.
Loaded by spinning solution in the syringe of 10mL and carry out spinning control spinning condition, spinning voltage is 24kv, and temperature is 35 DEG C, and humidity is 30%, and receiving range is 15cm, and spinning speed is 0.2mm/min, obtains SnCl
45H
2the composite nano fiber of O/PVP=1, calcines 3h with the programming rate of 3 DEG C/min in atmosphere by composite nano fiber at 500 DEG C, can obtain inorganic SnO
2nanofiber.
Be stir 24h, through ultrasonic process 40min after the ratio mixing of 80:10:5:5 with mass ratio by metal oxide nanofibres and acetylene black, polytetrafluoroethylene (PTFE), ethanol.Make it mix, then be dried to pasty state, be then coated on electrode matrix, vacuum drying 24h, then use tablet press machine at 10MPa tableting under pressure, obtain SnO
2h
2o nanofiber makes electrode material by compressing tablet.
By obtained SnO
2h
2o electrode material is used for electrode electro-catalysis waste water: with fibrous SnO
2as anode, copper coin is the NaNO of negative electrode, 0.25mol/L
3for electrolyte, interelectrode distance is 2cm, and current density is 20mA/cm
2, the concentration of organic wastewater is 200mg/L, and organic wastewater is phenolic waste water, methylene blue waste water, Congo red waste water, and the electro-catalysis time is 5h.
Wherein the removal efficiency of electro-catalysis phenolic waste water is 85.78%, COD clearance is 62.79%; The removal efficiency of methylene blue is 94.46%, COD clearance is 66.33%; Congo red removal efficiency is 88.79%, COD clearance is 10.39%.
Obtained fiber is carried out electron-microscope scanning, and obtain surface sweeping Electronic Speculum figure as shown in Figure 1, its fibre structure is continuously uniform and stable as seen.
Obtained fiber is carried out X-ray powder diffraction (XRD), obtain XRD figure as shown in Figure 2, its metal oxide is SnO2 as seen, and diffraction maximum is relatively more sharp-pointed, and degree of crystallinity is better.
Example 2: similar with the step in example 1, the polyvinylpyrrolidone (PVP) taking 2.5g joins in 18gN-N solvent dimethylformamide, stirs 12h until solution is the SnCl of clear shape
45H
2o changes the ferric acetyl acetonade of 2g into.Obtained Fe
2o
3nanofiber, the removal efficiency of electro-catalysis phenolic waste water is 84.64%, COD clearance is 66.11%; The removal efficiency of methylene blue is 89.23%, COD clearance is 69.43%; The removal efficiency of Congo red waste water is 91.21%, COD clearance is 10.11%.
Example 3: similar with the step in example 1, the polyvinylpyrrolidone (PVP) taking 2g joins in 18g alcohol solvent, stirs 12h until solution is clear shape, by the SnCl of 2g
45H
2o changes the manganese acetate of 2g into.Obtained MnOx nanofiber, the removal efficiency of electro-catalysis phenolic waste water is the clearance of 84.23%, COD is 42.23%; The removal efficiency of methylene blue is 83.47%, COD clearance is 57.93%; The removal efficiency of Congo red waste water is 80.93%, COD clearance is 7.02%.
Example 4: identical with the step in example 1, by the SnCl of 2g
45H
2o changes the Schweinfurt green of 2g into.Obtained CuO nanofiber, the removal efficiency of electro-catalysis phenolic waste water is the clearance of 79.26%, COD is 34.21%; The removal efficiency of methylene blue is 82.46%, COD clearance is 36.38%; The removal efficiency of Congo red waste water is 77.83%, COD clearance is 6.88%.
Example 5: the polyvinylpyrrolidone (PVP) taking 2.5g joins in the solvent of 18gN-N dimethyl formamide (DMF), stir until solution clear, the acetylacetone cobalt taking 2g joins in the solution dissolved, and is stirred to solution and mixes, and can obtain spinning solution.The spinning of having dissolved also is loaded in the syringe of 10mL and carry out spinning control spinning condition, spinning voltage is 16kV, temperature is 40 DEG C, humidity is 35%, receiving range is 20cm, and spinning speed is 0.1mm/min, obtains the composite nano fiber of acetylacetone cobalt/PVP=0.8/1, composite nano fiber is calcined 3h with the programming rate of 3 DEG C/min in atmosphere at 500 DEG C, Co3O4 inorganic nano-fiber can be obtained.
By the Co made
3o
4nanofiber is prepared into electrode, and the removal efficiency of electro-catalysis phenolic waste water is 91.79%, COD clearance is 74.32%; The removal efficiency of methylene blue is 85.61%, COD clearance is 68.37%; The removal efficiency of Congo red waste water is 90.43%, COD clearance is 11.12%.
Claims (8)
1., for the preparation method of the catalyst of Electrocatalysis Degradation organic wastewater, it is characterized in that comprising the following steps:
1) polymer is first dissolved in organic solvent, then dissolves in soluble metallic salt, form spinning solution;
2) spinning solution is carried out electrostatic spinning, obtain precursor;
3) precursor is calcined, obtain metal oxide nanofibres;
4) by compressing tablet after metal oxide nanofibres and auxiliary material mixing, electrode catalyst is obtained.
2. preparation method according to claim 1, is characterized in that: described polymer is polyvinylpyrrolidone.
3. preparation method according to claim 1, is characterized in that: described organic solvent be in ethanol or N-N dimethyl formamide at least any one.
4. the preparation method according to claim 1 or 2 or 3, is characterized in that: described polymer is 10 ~ 15: 100 with the mixing quality ratio of organic solvent.
5. preparation method according to claim 1, is characterized in that: described soluble metallic salt is stannic chloride pentahydrate, Schweinfurt green, acetylacetone cobalt, ferric acetyl acetonade or manganese acetate.
6. preparation method according to claim 1 or 5, is characterized in that: described soluble metallic salt is 0.5 ~ 1: 1 with the mixing quality ratio of polymer.
7. preparation method according to claim 1 or 5, is characterized in that: the temperature conditions of described precursor calcining is 500 DEG C, and calcination time is 3h, and heating rate is 3 DEG C/min.
8. preparation method according to claim 1, it is characterized in that: after metal oxide nanofibres and acetylene black, polytetrafluoroethylene (PTFE), ethanol being mixed, through ultrasonic process 40min, then be dried to pasty state, then be coated on electrode matrix, after vacuum drying, use tabletting machine.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107055701A (en) * | 2017-05-25 | 2017-08-18 | 扬州大学 | A kind of Fe (Co) SnO2The preparation method of combination electrode |
| CN107082462A (en) * | 2017-05-22 | 2017-08-22 | 中国人民解放军后勤工程学院 | A kind of modified and reinforced tubular type fresh-water generator in surface |
| CN108914249A (en) * | 2018-06-26 | 2018-11-30 | 合肥萃励新材料科技有限公司 | A kind of synthetic method of fluorine-doped tin oxide fiber |
| CN111841602A (en) * | 2020-07-03 | 2020-10-30 | 江南大学 | CuCoMn multi-level structure electrolytic water catalytic material and preparation method thereof |
| CN112803030A (en) * | 2020-12-29 | 2021-05-14 | 河北工业大学 | Preparation method and application method of electro-Fenton composite membrane cathode |
| CN113461140A (en) * | 2021-06-28 | 2021-10-01 | 烟台大学 | Cobalt-based molybdenum-manganese catalytic electrode and preparation method thereof |
| CN115155661A (en) * | 2022-06-21 | 2022-10-11 | 苏州凯清碳中和科技有限公司 | Polyurethane catalytic membrane and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082462A (en) * | 2017-05-22 | 2017-08-22 | 中国人民解放军后勤工程学院 | A kind of modified and reinforced tubular type fresh-water generator in surface |
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| CN111841602B (en) * | 2020-07-03 | 2021-10-22 | 江南大学 | CuCoMn multi-level structure electrolytic water catalytic material and preparation method thereof |
| CN112803030A (en) * | 2020-12-29 | 2021-05-14 | 河北工业大学 | Preparation method and application method of electro-Fenton composite membrane cathode |
| CN112803030B (en) * | 2020-12-29 | 2022-06-10 | 河北工业大学 | Preparation method and application method of electro-Fenton composite membrane cathode |
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| CN113461140B (en) * | 2021-06-28 | 2022-11-22 | 烟台大学 | Cobalt-based molybdenum-manganese catalytic electrode and preparation method thereof |
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Application publication date: 20160413 |