CN107774264A - Load composite oxides magnetic nanometer and the electrode of CNT and its preparation and application - Google Patents
Load composite oxides magnetic nanometer and the electrode of CNT and its preparation and application Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 26
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 15
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 14
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- 230000007704 transition Effects 0.000 claims abstract description 5
- 238000005202 decontamination Methods 0.000 claims abstract description 4
- 230000003588 decontaminative effect Effects 0.000 claims abstract description 4
- 239000002070 nanowire Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000009938 salting Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 19
- 150000004706 metal oxides Chemical class 0.000 abstract description 19
- 239000002041 carbon nanotube Substances 0.000 abstract description 17
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 15
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 5
- 229910003119 ZnCo2O4 Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- -1 Oxalic acid forms oxalates Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 239000004064 cosurfactant Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- PMKQSEYPLQIEAY-YWNRKNDBSA-N Phaseolic acid Chemical compound OC(=O)C[C@@H](C(O)=O)OC(=O)\C=C\C1=CC=C(O)C(O)=C1 PMKQSEYPLQIEAY-YWNRKNDBSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000003851 corona treatment Methods 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
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical class CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- PMKQSEYPLQIEAY-UHFFFAOYSA-N trans-caffeoyl-L-malic acid Natural products OC(=O)CC(C(O)=O)OC(=O)C=CC1=CC=C(O)C(O)=C1 PMKQSEYPLQIEAY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
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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
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- 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
- C02F2101/34—Organic compounds containing oxygen
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Abstract
The invention discloses a kind of load composite oxides magnetic nanometer and the electrode of CNT and its preparation and application, preparation to include：(1) cetyl trimethylammonium bromide, hexamethylene and n-amyl alcohol are well mixed, then add oxalic acid solution, the mixed solution of transition-containing metal ion and cobalt ions is added after being well mixed, persistently stirring reaction obtains microemulsion at room temperature；(2) powder is dried to obtain in atmosphere after centrifuging decontamination, then calcines to obtain transition metal/cobalt composite oxide magnetic nanometer in atmosphere；(3) gained transition metal/cobalt composite oxide magnetic nanometer and multi-walled carbon nanotube and neopelex are dissolved in ethylene glycol, sponge or carbon felt electrode are immersed after being uniformly dispersed, sponge or carbon felt electrode take out drying, then immerse, and are produced after being repeated several times.Practical application effect stability and high efficiency of the present invention, appendix metal oxide/carbon nano-tube electrode can further be prepared, carry out the plasma degradation of organic pollution.
Description
Technical field
The invention belongs to the preparation of catalysis material nano line electrode and environmental pollution purification applications technical field, and in particular to
A kind of preparation method of appendix metal oxide/carbon nano-tube electrode.
Background technology
In recent years, plasma-catalytic technology is considered as a kind of advanced oxidation skill of efficient degradation organic pollution always
Art, but the problems such as voltage is high, and export license is larger be present in discharge in water technology.In order to solve, electrode material loss is big, bloom is electric
Press the shortcomings of high, researchers improve electric discharge as electrode using porous reticulated vitreous carbon electrodes or stainless steel wire mesh and led to
Road, or in plate electrode surface distributed aperture, discharge channel can be formed in electrode perimeter and bore edges area, pass through macroscopic electrode
The change energy enhanced discharge passage of material structure and form.And produce nano effect by changing microcosmic nano structure electrode material
Also increasingly it attract attention, suitable nano structure electrode material is more beneficial for the generation of corona discharge.
The content of the invention
The present invention provides a kind of simple transition metal/cobalt composite oxide magnetic nanometer synthetic method easily made, actual
Application effect stability and high efficiency, appendix metal oxide/carbon nano-tube electrode can further be prepared, carry out organic pollution
Plasma degradation.
A kind of preparation method for loading composite oxides magnetic nanometer and carbon nanotube electrode, comprises the following steps：
(1) cetyl trimethylammonium bromide, hexamethylene and n-amyl alcohol are well mixed, then add oxalic acid solution, mixed
The mixed solution of transition-containing metal ion and cobalt ions is added after closing uniformly, persistently stirring reaction obtains microemulsion at room temperature；
(2) powder is dried to obtain in atmosphere after microemulsion being centrifuged into decontamination, then gained powder is calcined in atmosphere
Transition metal/cobalt composite oxide magnetic nanometer；
(3) by gained transition metal/cobalt composite oxide magnetic nanometer and multi-walled carbon nanotube and detergent alkylate sulphur
Sour sodium is dissolved in ethylene glycol, sponge or carbon felt electrode is immersed after being uniformly dispersed, sponge or carbon felt electrode take out drying, then soak
Enter, produced after being repeated several times.
Metal oxide nano-wire/carbon nanotube electrode is applied to corona discharge pulse system by the present invention, utilizes CNTs
As metal oxide nano-wire carrier, by CNTs surface enrichments, improve pollutant and fully connect with metal oxide catalyst
Touch, the metal oxide nano-wire of electrode surface greatly improves electrode conductivuty, forms that nanowire tip is micro- puts in electrode surface
Electricity, discharge electric field intensity is improved, realize that metal oxide oxidation catalyst acts on, multiple advantage is provided to improve degradation efficiency.
Preparation method of the present invention prepares method using microemulsion.Microemulsion generally by surfactant, cosurfactant, have
Solvent and water (or aqueous solution) composition.Particle diameter and stability to nano material are accurately controlled, and limit nano-particle
Nucleation, growth, coalescence, the process such as reunion, so as to which the nano-particle formed is enclosed with layer of surface activating agent, and have certain
Condensed state structure.
Preferably, cetyl trimethylammonium bromide, hexamethylene, n-amyl alcohol, oxalic acid mixing.Wherein cetyl trimethyl
Ammonium bromide (CTAB), is a kind of surfactant, plays increase surface-active, reduces oil water interfacial tension and prevents liquid level from gathering
Collection, stability is improved, form the effect for the organized assembles that oil/water interface is formed.N-amyl alcohol is then a kind of cosurfactant.
Primarily serve following effect：(1) interfacial tension is reduced；(2) interface membrane fluidity is increased；(3) surfactant activity value is adjusted.
Hexamethylene is oil phase, and oxalic acid solution then forms aqueous phase.Oxalic acid forms oxalates with metal ion, further formed as template
Template can be sacrificed, microemulsion and oxalic acid template are decomposed removal after high-temperature calcination, ultimately form metal oxide nano-wire.Two kinds
Immiscible continuous media is divided into short space to form microreactor by surfactant parents' molecule, and its size is controllable
For system in nano-scale range, reactant reacts generation solid phase particles in system.Preferably, cetyl trimethylammonium bromide, ring
Hexane, n-amyl alcohol, the mixed proportion of oxalic acid and mixed solution are 1g：25~35mL：0.8~1.2mL：1.2~1.8mL：0.4~
0.6mL, the concentration of the oxalic acid solution are 0.1M, and the concentration of transition metal ions is 0.05M~0.1M in mixed solution, cobalt from
The concentration of son is 0.05M~0.1M.
Further preferably, the mixed proportion of the cetyl trimethylammonium bromide, hexamethylene, n-amyl alcohol and oxalic acid is
1g：30mL：1mL：1.5mL：0.5mL.
Preferably, by the salting liquid of the salting liquid of transition metal and cobalt mix described in step (1) containing transition metal from
The mixed solution of son and cobalt ions, the salting liquid of the transition metal is Zn (NO3)2、FeSO4Mn(NO3)2、Ni(NO3)2Solution
In one kind；The salting liquid of the cobalt is Co (NO3)2Solution.
Preferably, continue 20~25h of stirring reaction in step (1) and obtain microemulsion.
The method of decontamination is to be centrifuged using alcohol in step (2).
Preferably, drying temperature is 75~85 DEG C in step (2)；Calcining heat is 500 DEG C~700 DEG C；Further preferably
Ground, calcining heat are 500 DEG C, and calcination time is 2~4 hours.
Preferably, electrode each immersion time is 15~25min in step (3)；Dry every time in 65~75 DEG C of baking ovens
Dry 0.8~1.2h.
Preferably, transition metal/concentration of the cobalt composite oxide magnetic nanometer in ethylene glycol is in step (4)
0.05mg/mL~0.15mg/mL；Concentration of the multi-walled carbon nanotube in ethylene glycol is 3mg/mL~5mg/mL；Detergent alkylate
Concentration of the sodium sulfonate in ethylene glycol is 35mg/mL~45mg/mL.
It is further preferred that transition metal/concentration of the cobalt composite oxide magnetic nanometer in ethylene glycol in step (4)
For 0.1mg/mL；Concentration of the multi-walled carbon nanotube in ethylene glycol is 4mg/mL；Neopelex is in ethylene glycol
Concentration is 40mg/mL.
Microemulsion system mixes at room temperature can occur good reaction, save the energy and preparation flow is simple；
Secondly, powder has obtained bimetallic oxide nano wire after high-temperature calcination, nano wire is had stronger stability, is not easy
It is high-temperature denatured.
There is the characteristics of moderate length, even thickness, and double gold by the nano-material prepared by above preferred steps
Category oxide nano thread has higher stability compared to monometallic nano wire, not mutability under high temperature, compared to nonmetallic
Nano wire has more preferable electric conductivity, and preparation cost is more cheap, and process is more simple.Substrate is using sponge, carbon felt, carbon cloth
Deng specific surface area is big, and load capacity is strong, can adsorb a large amount of polluters and catalyst material.
Material will be prepared further to be supported in substrate, obtain good conductive material.It is placed in high-pressure reactor to dirt
Water is handled, and removal efficiency is high, and degraded is thorough, has the characteristics of efficient, quick compared to traditional water treatment technology.It is a kind of
Most preferred preparation method, comprises the following steps：
(1) 2.59g cetyl trimethylammonium bromides (CTAB), 75mL hexamethylenes and 2.5mL n-amyl alcohols are mixed, are placed on
Stir 20 minutes and formed on magnetic stirring apparatus, the oxalic acid solution that 3.75mL concentration is 0.1M is added into above-mentioned solution system, and
It is sufficiently stirred 30 minutes；
(2) toward the Zn (NO of addition 1.25ml 0.05M~0.1M in step (1)3)2、FeSO4Mn(NO3)2Or Ni (NO3)2
Solution and 0.05M~0.1M Co (NO3)2Mixed solution, and be stirred at room temperature 24 hours, whole operation process is kept stirring for；
(3) microemulsion for obtaining step (2) removes unnecessary foreign ion, the sample finally given by alcohol centrifugation
80 DEG C of drying in atmosphere, obtain powder, and powder difference is calcined 3 hours for (500 DEG C/700 DEG C) in atmosphere, finally produced
Thing transition metals cobalt oxide magnetic nano wire；
(4) step (3) 0.01g magnetic couplings metal oxide nano-wire, 0.4g multi-walled carbon nanotubes and 4g dodecanes are taken
Base benzene sulfonic acid sodium salt is dissolved in 100mL ethylene glycol, prepares rear ultrasonic 30min；Sponge/carbon felt electrode is compound molten what is configured
20min is steeped in liquid leaching, 70 DEG C of oven for drying (about 1h), this process are repeated 3 times after taking-up, are obtained appendix metal oxide/carbon and are received
Mitron electrode.
The present invention also provides a kind of load composite oxides magnetic nanometer and carbon being prepared such as the preparation method
The electrode of nanotube.
The present invention also provides a kind of method of plasma processing of organic polluting water, it is characterised in that including following step
Suddenly：
It is high using the electrode of the load composite oxides magnetic nanometer and CNT as grounding electrode, quartz glass
Piezoelectricity pole, corona treatment is carried out to organic polluting water, is biased 10~30V, 0.5~1h of discharge process.
The organic pollution is phenyl ring class organic pollution (phenol, chlorophenol, Polychlorinated biphenyls etc.).
Preferably, input voltage 20V in plasma treatment process, discharge process time are 0.5h.
The beneficial effects of the invention are as follows：
Using the strong sponge of stable adsorptivity or carbon felt as carrier, while CNT is as metal oxide nano-wire
Carrier, by surface enrichment, improves pollutant and is fully contacted with metal oxide catalyst, and nano wire point is formed in electrode surface
Micro discharge is held, improves discharge electric field intensity, realizes that metal oxide oxidation catalyst acts on, multiple advantage is provided to improve degradation efficiency.
By simple thermal decomposition method synthesis of metal oxide/cobalt/cobalt oxide composite nano-line, preparation process condition is easy to control, prepared
Composite catalyst excellent catalytic effect, and circulate repeatedly still be able to keep excellent catalytic activity, have a extensive future.
Brief description of the drawings
Fig. 1 is ZnCo in embodiment 12O4Nano wire/carbon nanotube electrode SEM figures.
Fig. 2 is CoFe2O4Nano wire/carbon nanotube electrode SEM figures.
Fig. 3 is ZnCo2O4Nano wire/carbon nanotube electrode or CoFe2O4Nano wire/carbon nanotube electrode gas-liquid interface is micro-
Discharge degradation of phenol design sketch.
Embodiment
Embodiment 1
ZnCo2O4The preparation of nano wire/carbon nanotube electrode
2.5g cetyl trimethylammonium bromides (CTAB), 75mL hexamethylenes and 2.5mL n-amyl alcohols are mixed, are placed on magnetic force
Stir 20 minutes and formed on agitator.The oxalic acid solution that 3.75mL concentration is 0.1M is added into above-mentioned solution system, and fully
Stirring 30 minutes.1.25ml 0.05M Zn (NO are added into above-mentioned system3)2Solution and 0.1M Co (NO3)2The mixing of solution
Solution, and be stirred at room temperature 24 hours, whole operation process is kept stirring for.After question response terminates, the yellow micro emulsion that will obtain
Liquid removes unnecessary foreign ion by alcohol centrifugation, the sample finally given 80 DEG C of drying in atmosphere, obtains pink
Powder.By yellow powder respectively in O2It is heat-treated 3 hours at 500 DEG C, obtains final product ZnCo2O4Nano wire.
0.01g metal oxides, 0.4g multi-walled carbon nanotubes and 4g neopelexes is taken to be dissolved in 100ml second two
In alcohol, rear ultrasonic 30min is prepared；Length × wide=7cm × 1.5cm sponge electrode is steeped in the composite solution leaching configured
20min, 70 DEG C of oven for drying (about 1h), this process are repeated 3 times after taking-up, obtain appendix metal oxide/carbon nano-tube sponge
Electrode, it is as shown in Figure 1 ZnCo2O4Nano wire/carbon nanotube electrode SEM figures.
Embodiment 2
CoFe2O4The preparation of nano wire/carbon nanotube electrode
2.5g cetyl trimethylammonium bromides (CTAB), 75mL hexamethylenes and 2.5mL n-amyl alcohols are mixed, are placed on magnetic force
Stir 20 minutes and formed on agitator.The oxalic acid solution that 3.75mL concentration is 0.1M is added into above-mentioned solution system, and fully
Stirring 30 minutes.1.25ml 0.05M Co (NO are added into above-mentioned system3)2Solution and 0.1M FeSO4Solution, and in room temperature
Lower stirring 24 hours, whole operation process is kept stirring for.After question response terminates, obtained yellow microemulsion is centrifuged by alcohol
Unnecessary foreign ion is removed, the sample finally given 80 DEG C of drying in atmosphere, obtains the powder of yellow.By yellow powder point
Not in O2It is heat-treated 3 hours at 500 DEG C, obtains final product CoFe2O4Nano wire.
0.01g metal oxides, 0.4g multi-walled carbon nanotubes and 4g neopelexes is taken to be dissolved in 100ml second two
In alcohol, rear ultrasonic 30min is prepared；Length × wide=7cm × 1.5cm sponge electrode is steeped in the composite solution leaching configured
20min, 70 DEG C of oven for drying (about 1h), this process are repeated 3 times after taking-up, obtain appendix metal oxide/carbon nano-tube sponge
Electrode, it is illustrated in figure 2 CoFe2O4Nano wire/carbon nanotube electrode SEM figures.
Embodiment 3
Carry out gas-liquid interface micro discharge experiment.Using quartz glass as high-field electrode, dielectric barrier discharge is carried out, is used
The transition metal being prepared in embodiment (1) or (2)/cobalt composite oxide nano wire/CNT sponge electrode is as ground
Pole, the electrode that whole reactor is exactly embodiment (1) or prepared by (2).At the combination electrode prepared using embodiment (1) or (2)
10mg/L phenol solutions are managed, the wherein size of combination electrode is 6 × 7cm, adds the phenol solution that 100mL has been configured, and sets electricity
The distance between pole and liquid level 2mm, close reactor door.Reactor is opened, adjusts response voltage 30V and at this voltage most
Big kinetic current.Phenol degrading process time is set as 60min, and a sample is gathered per 5min-10min, and sampling amount is about
1mL or so, the content of phenol when determining different degradation times using high performance liquid chromatography.Experimental result is as shown in Figure 3, it is seen that
After 60min, the clearance of methylene blue is more than 99%.
The specific implementation case of patent of the present invention is the foregoing is only, but the technical characteristic of patent of the present invention is not limited to
This, any those skilled in the relevant art in the field of the invention, all cover in the special of the present invention by the change or modification made
Among sharp scope.
Claims (9)
- A kind of 1. preparation method for the electrode for loading composite oxides magnetic nanometer and CNT, it is characterised in that including Following steps：(1) cetyl trimethylammonium bromide, hexamethylene and n-amyl alcohol are well mixed, then add oxalic acid solution, mixing is equal The mixed solution of transition-containing metal ion and cobalt ions is added after even, persistently stirring reaction obtains microemulsion at room temperature；(2) powder is dried to obtain in atmosphere after microemulsion being centrifuged into decontamination, then gained powder is calcined into obtain transition in atmosphere Metal/cobalt composite oxide magnetic nanometer；(3) by gained transition metal/cobalt composite oxide magnetic nanometer and multi-walled carbon nanotube and neopelex It is dissolved in ethylene glycol, sponge or carbon felt electrode is immersed after being uniformly dispersed, sponge or carbon felt electrode take out drying, then immerse, weight Produced after plural time.
- 2. preparation method according to claim 1, it is characterised in that cetyl trimethylammonium bromide, hexamethylene, positive penta The mixed proportion of alcohol, oxalic acid and mixed solution is 1g：25~35mL：0.8~1.2mL：1.2~1.8mL：0.4~0.6mL, institute The concentration for stating oxalic acid solution is 0.1M, and the concentration of transition metal ions is 0.05M~0.1M in mixed solution, the concentration of cobalt ions For 0.05M~0.1M.
- 3. preparation method according to claim 1, it is characterised in that mix the salting liquid of the salting liquid of transition metal and cobalt The mixed solution of transition-containing metal ion and cobalt ions described in step (1) is obtained, the salting liquid of the transition metal is Zn (NO3)2、FeSO4Mn(NO3)2、Ni(NO3)2One kind in solution；The salting liquid of the cobalt is Co (NO3)2Solution.
- 4. preparation method according to claim 1, it is characterised in that continue 20~25h of stirring reaction in step (1) and obtain micro emulsion Liquid.
- 5. preparation method according to claim 1, it is characterised in that drying temperature is 75~85 DEG C in step (2)；Calcining temperature Spend for 500 DEG C~700 DEG C.
- 6. preparation method according to claim 1, it is characterised in that in step (3) electrode each immersion time be 15~ 25min；Dry every time in 65~75 DEG C of 0.8~1.2h of oven for drying.
- 7. preparation method according to claim 1, it is characterised in that transition metal/cobalt composite oxide magnetic in step (4) Concentration of the nano wire in ethylene glycol is 0.05mg/mL~0.15mg/mL；Concentration of the multi-walled carbon nanotube in ethylene glycol is 3mg/mL~5mg/mL；Concentration of the neopelex in ethylene glycol is 35mg/mL~45mg/mL.
- A kind of 8. load composite oxides magnetic that preparation method as described in claim 1~7 any claim is prepared The electrode of nano wire and CNT.
- 9. a kind of method of plasma processing of organic polluting water, it is characterised in that comprise the following steps：To load the electrode of composite oxides magnetic nanometer and CNT as claimed in claim 8 as grounding electrode, quartz Glass is high-field electrode, is biased 10~30V, and electrolysis handles 0.5~1h.
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