CN113716657A - Preparation method and application of green recyclable metal oxide embedded ordered mesoporous carbon particle electrode - Google Patents
Preparation method and application of green recyclable metal oxide embedded ordered mesoporous carbon particle electrode Download PDFInfo
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- CN113716657A CN113716657A CN202111108021.1A CN202111108021A CN113716657A CN 113716657 A CN113716657 A CN 113716657A CN 202111108021 A CN202111108021 A CN 202111108021A CN 113716657 A CN113716657 A CN 113716657A
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- 239000002245 particle Substances 0.000 title claims abstract description 66
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 38
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 18
- 231100000719 pollutant Toxicity 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- -1 NiO Chemical class 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
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- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000009396 hybridization Methods 0.000 claims description 3
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005580 one pot reaction Methods 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940043267 rhodamine b Drugs 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000137 annealing Methods 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000010170 biological method Methods 0.000 claims description 2
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 claims description 2
- 229960000623 carbamazepine Drugs 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 2
- 229960001180 norfloxacin Drugs 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 claims description 2
- 229960005404 sulfamethoxazole Drugs 0.000 claims description 2
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 1
- 230000027756 respiratory electron transport chain Effects 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 238000003487 electrochemical reaction Methods 0.000 abstract description 2
- 239000006181 electrochemical material Substances 0.000 abstract 1
- 150000002989 phenols Chemical class 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HJPBEXZMTWFZHY-UHFFFAOYSA-N [Ti].[Ru].[Ir] Chemical compound [Ti].[Ru].[Ir] HJPBEXZMTWFZHY-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 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 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
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- 239000012265 solid product Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910006287 γ-MnO2 Inorganic materials 0.000 description 1
Images
Classifications
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46176—Galvanic cells
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- 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 preparation method and application of a green recyclable low-cost metal oxide embedded pore channel framework hybrid modified ordered mesoporous carbon particle electrode. With cheap metal oxide (such as NiO, CeO)2、MnO2、FeO、MgO、Al2O3And CaO), and the like, and the particle electrodes are prepared by the binder, can be applied to various three-dimensional electrochemical reactors, and belong to the application field of electrocatalysis materials. The particle electrode prepared by the method has high treatment efficiency, is not easy to block the aperture, and can be circulated for many times and run for a long time. Particle electrode bonding using the inventionThe three-dimensional electrochemical reaction device is used for treating high-salt/high-concentration organic wastewater such as benzene and phenols, the removal rate of pollutants is 100%, the removal rate of COD is 96%, and the degradation efficiency of the pollutants can still reach more than 98% after the pollutants are recycled for 1000 times. The particle electrode has the advantages of simple preparation method, wide application range and strong processing capacity, and is an electrochemical material which can be applied in scale and has a prospect.
Description
Technical Field
The invention relates to a preparation method of green recyclable metal oxide inlaid ordered mesoporous carbon, in particular to one or more cheap metal oxides (NiO, CeO)2、MnO2、FeO、MgO、Al2O3CaO, etc.) and the research of eliminating pollutant in three-dimensional electrochemical reactor, and belongs to the field of electric catalytic material application.
Background
In the field of water treatment, two-dimensional electrochemical reactors are generally used, however, due to the disadvantages of small electrode surface area, low current efficiency, limited mass transfer, and short electrode life of two-dimensional electrode reactors. Three-dimensional electrochemical reactors have come into use, in which particle electrodes are applied between a cathode and an anode, and in an electrostatic field, the particles are polarized to form individual charged microelectrodes, i.e. each electrode corresponds to a micro-electrolytic cell. Due to the existence of the particle electrode, the electrochemical area and the catalytic active sites of the electrode are obviously increased, the mass transfer distance is reduced, the conductivity is increased, and the organic matter degradation efficiency is increased. It can be seen that the core of the three-dimensional electrochemical reactor is the particle electrode.
The particle electrodes of the three-dimensional electrochemical reaction device for wastewater treatment at present are as follows: activated carbon particles, carbon nanotubes, carbon aerogels and the like, all of which belong to porous structures with non-adjustable pore diameters. The invention relates to a three-dimensional particle electrode taking metal oxide modified by F doping as a catalyst, which adopts columnar active carbon as a carrier and doped F-Can enter the crystal lattice of the metal oxide to replace O2-Thus improving the electrocatalytic activity of the particle electrode and increasing the pollutant removal efficiency, but the preparation method takes long time, and the mass transfer efficiency is affected by the blockage of the activated carbon micropores, thus increasing the cost in the practical application process (patent No. 109967097A); limei et al invented Mn-GAC particle electrode uses single cheap metal oxide MnO2The catalyst is loaded on the surface of the granular activated carbon, the preparation method is simple, the removal rate of 4-chlorophenol reaches 99%, but the impregnation loading on the surface of the granular activated carbon can cause the loss of metal oxide, thereby influencing the degradation efficiency of the particle electrode (patent No. 107930618A); the ordered mesoporous carbon/Ni nano particle blocky electrode of Lujiaxing and the like is prepared by synthesizing an ordered mesoporous carbon material by adopting a one-step method, forming a polymer film by evaporating a solvent and mixing polymersThe material is obtained by carbonization after the membrane is pressed into a block, although the mesoporous structure solves the problem of pore channel blockage, the pore channel can be damaged to a certain extent by pressing into particles by external force, so that the long-term recycling of the particle electrode is influenced (patent No. 106011921A).
In summary, the current methods for preparing and using particle electrodes have the following disadvantages: (1) the traditional granular carbon material has the defects that the self microporous structure is blocked in the using process, the mass transfer efficiency is influenced, and the actual application cost is increased to a certain extent; (2) the metal oxide loaded on the surface of the carbon material is easy to run off in the reaction process, so that the degradation efficiency of pollutants is reduced; (3) the pore channels of the particle electrodes can be damaged by adopting methods such as external force fixation or tabletting and the like, and certain influence is generated on the long-term stable circulation use of the particle electrodes.
Disclosure of Invention
The invention provides a preparation method and application of a low-cost metal oxide embedded ordered mesoporous carbon particle electrode, aiming at solving the defects of high practical application cost, limited pollutant removal efficiency, short electrode service life and the like of the existing particle electrode. Adopting one-pot framework hybridization method to mix low-cost metal oxides NiO and CeO2、MnO2、FeO、MgO、Al2O3One or more of CaO and the like are embedded in the pore channels of the ordered mesoporous carbon, and the bipolar particle electrode is prepared by a binder, so that the loss of metal oxides in the reaction process is reduced while the pore channel structure of the ordered mesoporous carbon is completely reserved. The service life of the particle electrode is prolonged by supplementing electrons to the cathode and the anode, and the method can be applied to various three-dimensional electrochemical reactors.
In order to solve the problems and achieve the purpose of the invention, the following technical scheme is adopted:
the preparation method and the application of the green recyclable low-cost metal oxide inlaid ordered mesoporous carbon particle electrode are characterized in that:
s1 adopts a one-pot framework hybridization method to embed cheap metal oxide into the pore canal of the ordered mesoporous carbon.
And (3) stirring and washing in water bath by using S2, and carbonizing the obtained mixture in protective gas to obtain the modified ordered mesoporous carbon.
S3 preparing a binder from polyvinyl alcohol and citric acid, and preparing the modified ordered mesoporous carbon into a particle electrode.
The cheap metal oxide inlaid ordered mesoporous carbon particle electrode prepared by the S4 can be applied to various three-dimensional electrochemical reactors to degrade common or difficultly-degraded pollutants.
According to the scheme, the green recyclable low-cost metal oxide inlaid ordered mesoporous carbon particle electrode is characterized in that: the template precursor is one of F127, P123, MCM-41, SBA15, F108 or KIT-6 and the like; the metal precursor can be one or more of nitrate, acetate and carbonate of iron, nickel, manganese, cerium, copper, zinc, calcium and magnesium; the solvent for dissolving the metal precursor is water, ethyl acetate or ethanol and the like.
According to the preparation method of the low-cost metal oxide inlaid ordered mesoporous carbon, the ratio of metal oxide to carbon element is 1: 1-1: 10, the protective gas is one of nitrogen or argon, the first stage of calcination temperature is 200-300 ℃, the second stage of calcination temperature is 600-900 ℃, the heating rate is 1-5 ℃, and the annealing time is 6-8 hours.
The specific preparation steps of the modified ordered mesoporous carbon particle electrode are as follows: mixing polyvinyl alcohol and citric acid according to a certain proportion, adding 10-20 mL of concentrated hydrochloric acid, and stirring at 60 ℃ for 1h to obtain the binder. Mixing the ordered mesoporous carbon powder and the binder according to the proportion of 0.1-1, binding the ordered mesoporous carbon powder and the binder into particles with the particle size of 3-5 mm, and naturally drying the particles.
The application of the electrode with the cheap metal oxide inlaid with the ordered mesoporous carbon particles is characterized in that: the prepared electrode inlaid with ordered mesoporous carbon particles can be applied to the technical fields of electrochemical technologies such as photocatalysis, electrocatalysis, electroreduction and the like or combined use with ozone, biological methods and the like. The removal rate of common pollutants in the field such as phenol, bisphenol A, methylene blue, aniline, rhodamine B, acetone and the like or refractory pollutants such as carbamazepine, norfloxacin, hexachloro, sulfamethoxazole and the like can reach 100 percent.
Compared with the prior art, the invention has the advantages that:
(1) the method adopts cheap metal oxide to inlay the ordered mesoporous carbon, has low cost and high treatment efficiency up to 100 percent, and can be applied in large-scale practical application.
(2) The particle electrode disclosed by the invention is simple in preparation method and high in performance, not only retains the complete pore channel structure of the ordered mesoporous carbon, but also embeds the metal oxide in the pore channel and pores, so that a large amount of active species such as hydroxyl radicals, superoxide radicals and the like are rapidly generated by catalyzing ozone and a cathode in the reaction process, and the degradation efficiency of more than 98% can be achieved after the reaction is cycled for 1000 times.
(3) The particle electrode can be applied to various three-dimensional electrochemical reactors, has high reaction efficiency and long service life, can not selectively treat common or difficultly degraded organic matters in the three-dimensional electrochemical reactors, and has wide application range. The method can be used for treating high-salt organic wastewater of benzene and phenol, can also be applied to the treatment of other organic wastewater, and has a removal rate of 100% for common or difficultly-degradable pollutants.
Drawings
FIG. 1 shows that different cheap metal oxides are inlaid with ordered mesoporous carbon particles, and electrodes degrade high-salt phenol wastewater.
FIG. 2 shows the removal of pollutants and COD after 500 cycles of Ni/Ce/Mn-NOMC particle electrode use.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
A preparation method of an electrode with cheap metal oxide inlaid with ordered mesoporous carbon particles comprises the following steps:
to 100mL of deionized water were added 4.0g of F127, 3.0g of o-aminophenol, 3.4g of hexamethylenetetramine, 2.8g of ammonia water, and a low-cost metal oxide (nickel nitrate, cerium nitrate, manganese nitrate, calcium nitrate, etc.) and stirred under magnetic stirring for 1 hour, after which the mixture solution was heated in a water bath to 80 ℃ and kept stirring for 24 hours. The solid product was collected by centrifugation, washed with water and ethanol and dried for 12 h. Keeping the temperature for 1h under the protection of nitrogen flow at 350 ℃, and heating to 800 ℃ for 3 h.
Example 2
The application of the modified ordered mesoporous carbon particle electrode in degrading high-salt phenol wastewater comprises the following specific steps:
the water quality condition is as follows: the phenol concentration was 300mg/L, the pH was 8, and the CON was 26.8mS/cm2DO is 5.6 mg/L. The main process parameters are as follows: the treated water amount is 150mL, the particle electrode prepared by the method of the application example 1 is adopted, the anode is a ruthenium iridium titanium plate, the cathode is a titanium plate, the distance between the polar plates is 2.5cm, and the current density is 10mA/cm2The voltage is 2.8V, the ozone flow is 0.2L/min, the ozone concentration is 6mg/L, and the reaction time is 60 min.
As shown in figure 1, the efficiency of degrading phenol by using electrodes with different cheap metal oxides inlaid with ordered mesoporous carbon particles is 100% when the electrodes with Ni/Ce/Mn-NOMC particles are used for 60 min. Wherein, the removal efficiency of the single metal oxide to the phenol is lower, and the combined action of the three metal oxides promotes the reaction system to generate more active species, thereby greatly improving the degradation efficiency of the phenol.
The removal rate of phenol is shown in figure 2 after the Ni/Ce/Mn-NOMC particle electrode is recycled for 500 times, and the better degradation efficiency can still reach 99% after the electrode is recycled for 500 times. This is because MnO synthesized by this method2Belonging to gamma-MnO2Irreversible formation of beta-MnO during the oxidation process2And carbon corrosion can be relieved while ozone is catalyzed. Therefore, the prepared metal oxide is better embedded in the pore channel, and the metal oxide is not greatly lost along with the increase of the cycle number.
Example 3
The application of the electrodes of different modified ordered mesoporous carbon particles in degrading various organic waste water comprises the following specific steps:
the water quality condition is as follows: pH of 7 and CON of 25.6mS/cm2DO is 5.6 mg/L. The main process parameters are as follows: the treated water amount is 500mL, different cheap metal oxides prepared by the method of the application example 1 are inlaid with ordered mesoporous carbon particle electrodes, the anode is a ruthenium iridium titanium plate, the cathode is a titanium plate, the distance between the plates is 2.5cm, and the current density is 10mA/cm2The voltage is 2.8V, the ozone flow is 0.2L/min, the ozone concentration is 6mg/L, and the reaction time is 60 min.
TABLE 1 removal of various organic pollutants from water by different particle electrodes
Table 2 removal of COD for 500 cycles of different particle electrodes
It can be found from tables 1 and 2 that the modified ordered mesoporous carbon particle electrode prepared by the method can effectively remove common pollutants in organic wastewater, such as phenol, bisphenol a, methylene blue, aniline, rhodamine B, acetone and the like. Comparing different particle electrodes, the Mg/Fe/Al-NOMC and the Ni/Ce/Mn-NOMC with the ordered mesoporous carbon particle electrodes inlaid with the trimetal oxides can remove various pollutants to the highest extent, and reach 100 percent, which shows that the electrocatalysis and ozone catalysis capability of the particle electrodes can be improved under the combined action of various metal oxides; after multiple cycles, the removal rate of pollutants of the ordered mesoporous carbon particle electrode prepared by the method can still reach 98% after 1000 cycles, the actual requirement is met, and the method is an invention technology with a very good application prospect.
The above-described embodiments should be construed broadly within the scope as defined in the appended claims, and therefore all changes that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the claims. The above description is not intended to limit the present invention, but rather, the present invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention.
Claims (8)
1. A preparation method and application of a green recyclable low-cost metal oxide inlaid ordered mesoporous carbon particle electrode are characterized in that:
s1, embedding cheap metal oxide into the pore canal of the ordered mesoporous carbon by adopting a one-pot framework hybridization method;
s2 stirring and washing in water bath, and carbonizing the obtained mixture in protective gas to obtain modified ordered mesoporous carbon;
s3, preparing a binder from polyvinyl alcohol and citric acid, and preparing the modified ordered mesoporous carbon into a particle electrode;
the cheap metal oxide inlaid ordered mesoporous carbon particle electrode prepared by the S4 can be applied to various three-dimensional electrochemical reactors to degrade common or difficultly-degraded pollutants.
2. The method for preparing an inexpensive metal oxide-inlaid ordered mesoporous carbon particle electrode according to claim 1, wherein: the cheap metal oxide can be NiO or CeO2、MnO2、FeO、MgO、Al2O3And CaO and the like.
3. The method for preparing an inexpensive metal oxide-inlaid ordered mesoporous carbon particle electrode according to claim 1, wherein: the template precursor of the S1 ordered mesoporous carbon is as follows: f127, P123, MCM-41, SBA15, F108, KIT-6 and the like.
4. The method for preparing an inexpensive metal oxide-inlaid ordered mesoporous carbon particle electrode according to claim 1, wherein: the protective gas of S1 is one of nitrogen or argon, the first section of the calcining temperature is 200-300 ℃, the second section is 600-900 ℃, the heating rate is 1-5 ℃, and the annealing time is 6-8 h.
5. The method for preparing an inexpensive metal oxide-inlaid ordered mesoporous carbon particle electrode according to claim 1, wherein: the ratio of the S3 ordered mesoporous carbon powder to the binder is 0.1-1, the powder is bound into particles of 3-5 mm, and the particles are naturally dried.
6. The inexpensive electrode of claim 1, wherein the metal oxide is uniformly and stably dispersed in the pores and pores of the ordered mesoporous carbon, and the specific surface area is 300-500 m2Per g, poreThe diameter is 2-7 nm, the electron transfer capability is strong, and the electrochemical activity is high.
7. The use of the inexpensive metal oxide-inlaid ordered mesoporous carbon particle electrode as claimed in claim 1, wherein: the prepared modified ordered mesoporous carbon particle electrode can be applied to the process fields of electrochemical technologies such as photocatalysis, electrocatalysis, electro-reduction and the like or combined use with ozone, biological methods and the like.
8. Use according to claim 7, characterized in that: the removal rate of common pollutants in the process field such as phenol, bisphenol A, methylene blue, aniline, rhodamine B, acetone and the like or refractory pollutants such as carbamazepine, norfloxacin, hexachloro, sulfamethoxazole and the like can reach 100 percent.
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