CN116371446B - Iron-nitrogen compound-carbon nano tube composite material, preparation method and application - Google Patents
Iron-nitrogen compound-carbon nano tube composite material, preparation method and application Download PDFInfo
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- CN116371446B CN116371446B CN202310417490.4A CN202310417490A CN116371446B CN 116371446 B CN116371446 B CN 116371446B CN 202310417490 A CN202310417490 A CN 202310417490A CN 116371446 B CN116371446 B CN 116371446B
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- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 102
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 101
- 239000002131 composite material Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910017464 nitrogen compound Inorganic materials 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000011241 protective layer Substances 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 239000002351 wastewater Substances 0.000 claims description 62
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- 238000006731 degradation reaction Methods 0.000 claims description 17
- 230000015556 catabolic process Effects 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- 230000000593 degrading effect Effects 0.000 claims description 11
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 11
- -1 sodium fatty alcohol Chemical class 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229910002547 FeII Inorganic materials 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229920006221 acetate fiber Polymers 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 238000005121 nitriding Methods 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- 150000003456 sulfonamides Chemical class 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 3
- 239000000057 synthetic resin Substances 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- 150000003460 sulfonic acids Chemical class 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 40
- 230000000694 effects Effects 0.000 description 19
- 238000005516 engineering process Methods 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 13
- 239000002957 persistent organic pollutant Substances 0.000 description 12
- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 description 11
- 229960001544 sulfathiazole Drugs 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000013543 active substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910001337 iron nitride Inorganic materials 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000010815 organic waste Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229940075397 calomel Drugs 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 241001274216 Naso Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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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
- C02F1/72—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
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
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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
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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
- C02F2101/38—Organic compounds containing nitrogen
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/20—Total organic carbon [TOC]
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- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The present disclosure provides an iron-nitrogen compound-carbon nanotube composite material, a preparation method and applications thereof. The preparation method of the iron-nitrogen compound-carbon nano tube composite material comprises the following steps: grinding a mixture of an iron-nitrogen compound and a carbon nano tube, adding the mixture into a dispersion solution, and loading the mixture onto a filter membrane through ultrasonic suction filtration to obtain a composite filter membrane; and dripping perfluorinated sulfonic acid polymer-ethanol solution on the composite filter membrane, and drying to form a protective layer to obtain the iron-nitrogen compound-carbon nano tube composite material.
Description
Technical Field
The present disclosure relates to the technical field of environmental protection, and in particular, to an iron-nitrogen compound-carbon nanotube composite material, a preparation method and applications thereof.
Background
With the rapid development of industry, the discharge of a large amount of organic wastewater difficult to degrade causes serious environmental health and ecological safety problems. At present, the electro-Fenton technology is an emerging technology in the field of environmental remediation as an environment-friendly electrochemical technology, and has a wide application prospect in the aspect of degrading organic wastewater. The cathode electro-Fenton technology utilizes oxygen dissolved in the wastewater to produce H 2O2 on the surface of a cathode in situ, and H 2O2 is further decomposed to generate hydroxyl radicals and other active oxygen substances under the catalysis of Fe 2+, so that the difficult-to-degrade organic pollutants in the wastewater are removed. The technology eliminates the potential safety hazard in the storage and transportation processes of the traditional Fenton technology H 2O2, greatly reduces the treatment cost and improves the pollutant treatment efficiency. However, the cathode electro-Fenton technology still has the defects of poor two-electron reduction activity on the cathode surface, low selective generation efficiency of H 2O2, poor pH adaptability, low electrode reusability, easy inactivation and the like, thereby limiting the popularization of the method in the field of industrial wastewater treatment.
Therefore, it is necessary to develop a novel efficient composite material for use as an electrode to improve stability, durability and reactivity of the electrode, so as to overcome limitations and disadvantages of the prior art, thereby improving efficiency and applicability of the electro-Fenton technology.
Disclosure of Invention
In view of the above, the present disclosure provides an iron-nitrogen compound-carbon nanotube composite material, a preparation method and applications thereof, so as to at least partially solve the above technical problems.
In order to solve the above technical problems, as one aspect of the present disclosure, there is provided a method for preparing an iron nitrogen compound-carbon nanotube composite material, including:
Grinding a mixture of an iron-nitrogen compound and a carbon nano tube, adding the mixture into a dispersion solution, and loading the mixture onto a filter membrane through ultrasonic suction filtration to obtain a composite filter membrane;
And dripping perfluorinated sulfonic acid polymer-ethanol solution on the composite filter membrane, and drying to form a protective layer to obtain the iron-nitrogen compound-carbon nano tube composite material.
In one embodiment, the mixing ratio of the iron nitrogen compound to the carbon nanotubes is 10:1 to 1:10;
The concentration of the mixture added into the dispersion solution is 0.5-2 g/L.
In one embodiment, the carbon nanotubes are single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
In one embodiment, the dispersion solution is a dispersion solution comprising any one of a sodium dodecyl sulfate solution, a sodium dodecyl sulfonate solution and a sodium fatty alcohol polyoxyethylene ether sulfate solution;
the mass fraction of the dispersion solution is 1-10%;
The filter membrane comprises any one of hydrophilic polytetrafluoroethylene membrane, nylon fiber membrane, acetate fiber membrane and glass fiber membrane.
In one embodiment, the volume ratio of the perfluorosulfonic acid polymer solution to the ethanol solution in the perfluorosulfonic acid polymer-ethanol solution is 1:14 to 1:2;
wherein the concentration of the perfluorosulfonic acid-based polymer solution is 5wt%.
As another aspect of the present disclosure, there is provided an iron-nitrogen compound-carbon nanotube composite material prepared by the above-described method of preparing an iron-nitrogen compound-carbon nanotube composite material.
In one embodiment, the iron-nitrogen compound-carbon nanotube composite material is a sphere with a diameter of 1-4 mu m, and the surface of the sphere is rugged.
As a final aspect of the present disclosure, there is provided a method for removing organic matter from wastewater in an electro-Fenton system using an iron-nitrogen compound-carbon nanotube composite as an electrode, comprising:
Taking the iron-nitrogen compound-carbon nano tube composite material as a cathode, and taking a graphite plate as an anode to be connected into an electrolytic cell containing organic wastewater to form an electro-Fenton system;
Regulating the pH value of the organic wastewater, introducing oxygen, applying constant current to an electro-Fenton system, and degrading the organic wastewater;
The iron-nitrogen compound-carbon nano tube composite material after organic wastewater degradation can be repeatedly used after being cleaned.
In one embodiment, the organic wastewater includes any one or more of sulfonamide wastewater, synthetic resin wastewater, halogenated compound wastewater, high-salt organic wastewater, and alkaline organic wastewater.
In one embodiment, oxygen is introduced 30 minutes ahead of time;
the flow rate of oxygen is 150-250 mL/min;
the density of the constant current is 1-7 mA/cm 2.
Based on the technical scheme, the iron-nitrogen compound-carbon nano tube composite material, the preparation method and the application provided by the disclosure have one of the following beneficial effects:
(1) The method prepares the composite material by mixing the iron nitrogen compound and the carbon nano tube for the first time, and the surface layer of the iron nitrogen compound is oxidized in the grinding process, so that the iron nitrogen compound is prevented from being further oxidized in the aqueous solution, the iron nitrogen compound-carbon nano tube composite material is favorable for keeping higher activity, and the service life of the iron nitrogen compound-carbon nano tube composite material is prolonged. In addition, the carbon nano tube has excellent conductivity and rich pore structure, and is favorable for improving the conductivity and the electrocatalytic performance of the iron-nitrogen compound-carbon nano tube composite material.
(2) The iron-nitrogen compound-carbon nanotube composite material has higher stability, can realize continuous and efficient degradation of organic pollutants through a two-electron approach and electro-Fenton catalysis, overcomes the defects of easy inactivation and shorter catalytic life of other materials in the prior art in the use process, and has wide application prospect.
(3) The iron-nitrogen compound-carbon nano tube composite material is used as a cathode material in an electrolytic cell, an electro-Fenton system is formed in the electrolytic cell, oxygen is reduced through a two-electron way to generate hydrogen peroxide, and ferrous ions (Fe 2+) generated on the surface of the iron-nitrogen compound (Fe x N) decompose the hydrogen peroxide into hydroxyl free radicals (OH), so that the hydrogen peroxide has higher activity. Meanwhile, the cathode of the electrolytic cell provides an electron-rich environment for the iron-nitrogen compound-carbon nano tube composite material, so that iron elements in the catalytic process can be mutually converted between three valence states of Fe 0、FeⅡ and Fe Ⅲ, and the stability of the rechecking material is ensured.
(4) According to embodiments of the present disclosure, the use of iron nitrogen compound-carbon nanotube composites as electrodes in electro-Fenton systems can be used for efficient degradation of organic pollutants in wastewater. The special structure of the iron-nitrogen compound can ensure that iron components are not easy to lose, is favorable for maintaining Fenton catalytic activity, improves the pH tolerance range of the electro-Fenton technology, and avoids the generation of red mud in the wastewater treatment process.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of an iron-nitrogen compound-carbon nanotube composite material prepared in example 1 of the present disclosure;
FIG. 2 is a comparative graph of different types of composite filters in an embodiment of the disclosure;
FIG. 3 is a graph showing the electrode test of the ring-disk for the iron-nitrogen compound-carbon nanotube composite material in example 3 of the present disclosure;
FIG. 4 is a graph showing the effect of iron-nitrogen compound-carbon nanotube composites of different filters on electrode degradation simulated wastewater in an embodiment of the disclosure;
FIG. 5 is a graph showing the effect of the iron nitrogen compound-carbon nanotube composite material of example 5 of the present disclosure as an electrode to degrade simulated wastewater under different pH conditions;
FIG. 6 is a graph showing the effect of recycling the iron-nitrogen compound-carbon nanotube composite material to degrade organic wastewater in example 6 of the present disclosure;
Fig. 7 is a graph showing the effect of Total Organic Carbon (TOC) removal for degrading different types of organic wastewater in example 7 of the present disclosure.
Detailed Description
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made in detail to the embodiments.
At present, nano zero-valent iron (nZVI) has been widely used in removing pollutants in groundwater, soil and sewage due to the advantages of higher activity, low toxicity, even no toxicity, easily available raw materials, easy preparation and the like. However, the high activity of nano zero-valent iron causes that the nano zero-valent iron is easily corroded by environmental media (such as water molecules, dissolved oxygen, cl -、NO3-、PO4 3-、CO3 2- and other anions) in the environment, and precipitates are generated on the surface of the nZVI, so that mass transfer of the zero-valent iron and other active substances is hindered, and the activity of the zero-valent iron is reduced or even deactivated. In the prior art, the zero-valent iron stability is improved through zero-valent iron vulcanization, and the hydrophobicity of the zero-valent iron is improved by utilizing an iron sulfide coating layer on the surface of the zero-valent iron, so that the adsorption capacity to organic pollutants is enhanced. However, under aerobic conditions, iron sulfide is easily oxidized, gradually converted into iron oxide or iron hydroxide, etc., and finally, zero-valent iron is deactivated.
In practicing the present disclosure, steel nitriding has been found to improve steel wear resistance, fatigue, and corrosion resistance, and nitriding of nano zero-valent iron forms iron nitrogen compounds (Fe X N) throughout the entire particle volume. When the iron nitrogen compound nanoparticles are dispersed in an aqueous solution and/or exposed to oxygen, an ultra-thin (3 nm) but stable Fe 3+ oxide (hydroxide) surface layer is produced, resulting in an increase in corrosion potential, thereby improving the corrosion resistance of the material. Compared with a hydroxyl oxidation coating layer on the surface of the nano zero-valent iron, the hydroxide layer on the surface of the Fe X N has higher hydrophobicity, so that the adsorption capacity to pollutants is enhanced; a thinner oxide (hydroxide) surface layer may promote faster transfer of electrons from the zero-valent iron core to the surface. Fe X N (including gamma' -Fe 4N、ε-Fe2-3 N and the like) and N-doped Fe 0 containing Fe X N components can reduce chlorinated hydrocarbon pollutants more efficiently, and the reduction dechlorination efficiency of trichloroethylene is 20 times that of zero-valent iron after the chlorinated hydrocarbon pollutants are aged in water for three months. The iron nitride technology overcomes the disadvantages of the nZVI technology as a novel and potential method.
In the process of realizing the present disclosure, it is found that iron nitrogen compounds are also a class of electrocatalysts with application prospects, which can catalyze ammonia and hydrazine decomposition, amine synthesis, persulfate oxidation reaction, oxygen reduction, and CO 2 reduction. At present, no report of using ferric nitride as a cathode material to activate dissolved oxygen to generate active substances so as to degrade organic pollutants exists. The multi-valence iron ions in the iron nitride coexist, the stability is superior, and the iron-based material with longer effective catalytic activity and higher stability is established for degrading organic pollutants in an electro-Fenton system by regulating and controlling reaction conditions or compounding with carbon materials and the like.
In the process of realizing the present disclosure, it is found that the development of a heterogeneous electro-Fenton cathode currently has some challenges, such as stability of a catalyst, cost and the like. In the reaction process, the catalyst is easy to be deactivated, corroded, peeled off and other problems due to the interaction between the catalyst and other substances in water. The cathode electro-Fenton technology has the defects of poor electron reduction activity on the cathode surface, low selective generation efficiency of H 2O2, poor pH adaptability, low electrode recycling property, easy deactivation and the like. Therefore, there is a need to develop new and efficient composite materials to improve the stability, durability, and activity of cathode materials to overcome these limitations and deficiencies to improve the efficiency and applicability of the electro-Fenton technology.
To achieve the above technical object, as one aspect of the present disclosure, there is provided a method for preparing an iron nitrogen compound-carbon nanotube composite material, comprising:
Grinding a mixture of an iron-nitrogen compound (Fe X N) and Carbon Nanotubes (CNTs), adding the mixture into a dispersion solution, and carrying out ultrasonic suction filtration on the mixture to obtain a composite filter membrane;
And dripping perfluorinated sulfonic acid polymer-ethanol solution on the composite filter membrane, and drying to form a protective layer to obtain the iron-nitrogen compound-carbon nano tube composite material.
In the embodiment of the disclosure, the prepared iron-nitrogen compound-carbon nanotube composite material is shown in fig. 1, and it can be seen from the figure that the carbon nanotubes in the iron-nitrogen compound-carbon nanotube composite material have a large number of pore structures, and the iron-nitrogen compound nanoparticles form an ultrathin oxide surface layer. The carbon nano tube has better conductivity, is favorable for improving the conductivity and electrocatalytic performance of the iron-nitrogen compound-carbon nano tube composite material, has better adsorption capacity on organic pollutants by a carbon skeleton of the carbon nano tube, and improves the utilization rate of active substances; the iron-nitrogen compound nano particles are dispersed in the aqueous solution or exposed to oxygen to generate an ultrathin stable ferric ion oxide surface layer, so that the iron-nitrogen compound nano particles have higher hydrophobicity, can enhance the adsorption capacity to pollutants, promote electron transfer, and overcome the defects of easy inactivation and short catalytic life of zero-valent iron in the prior art.
According to the embodiments of the present disclosure, the mixing ratio of the iron nitrogen compound to the carbon nanotube is 10:1 to 1:10, for example, may be 10:1, 10:5, 5:10, 1:10, etc.
In the embodiment of the disclosure, the iron nitrogen compound and the carbon nano tube are ground for more than 5 minutes in an agate grinding pot, so that the iron nitrogen compound and the carbon nano tube are fully and uniformly mixed. The reduction of nitrogen (N) and the oxidation of iron (Fe) occur during the grinding and mixing process of the iron-nitrogen compound and the carbon nano tube, so that the surface of the material contains three valence states of iron (Fe 0、FeⅡ and Fe Ⅲ).
According to embodiments of the present disclosure, the mixture is added to the dispersion solution at a concentration of 0.5 to 2g/L, which may be, for example, 0.5g/L, 1g/L, 1.5g/L, 2g/L, etc.
According to embodiments of the present disclosure, the carbon nanotubes are single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
According to an embodiment of the present disclosure, the dispersion solution is a dispersion solution including any one of a sodium dodecyl sulfate solution, a sodium dodecyl sulfonate solution, and a sodium fatty alcohol-polyoxyethylene ether sulfate solution.
According to the embodiment of the disclosure, the filter membrane comprises any one of a hydrophilic polytetrafluoroethylene membrane, a nylon fiber membrane, an acetate fiber membrane and a glass fiber membrane, the mixture of the iron-nitrogen compound and the carbon nano tube is ground and then added into a dispersion solution to prevent the filler particles from mutually gathering, and the mixture is uniformly loaded on the filter membrane by suction filtration after ultrasonic treatment for 30 minutes, so that the composite filter membrane prepared by adopting the nanofiber membrane made of the materials has good permeability to oxygen.
According to embodiments of the present disclosure, the volume ratio of the perfluorosulfonic acid-based polymer solution to the ethanol solution in the perfluorosulfonic acid-based polymer-ethanol solution is 1:14 to 1:2, for example, may be 1: 14. 1: 7. 1:5. 1:2, etc.
Wherein the concentration of the perfluorosulfonic acid-based polymer solution is 5wt%.
In the embodiment of the disclosure, 5wt% of fluorosulfonic acid-based polymer-ethanol solution (5% of Nafion-ethanol solution) is dropwise added on the composite filter membrane layer by layer, 1-10 layers are dropwise added, and the composite filter membrane is dried at room temperature to form a high polymer membrane which is used as a protective layer, so that the conductivity of the composite material is enhanced, the electrode is protected from oxidation, and meanwhile, the bonding effect is achieved, so that the iron-nitrogen compound and the carbon nanotube material are more firmly bonded on the filter membrane.
As another aspect of the present disclosure, there is provided an iron-nitrogen compound-carbon nanotube composite material prepared by the above-described method of preparing an iron-nitrogen compound-carbon nanotube composite material.
According to the embodiment of the disclosure, the iron-nitrogen compound in the iron-nitrogen compound-carbon nano tube composite material is a sphere with the diameter of 1-4 mu m, and the surface of the sphere is rugged.
As yet another aspect of the present disclosure, there is provided a method for removing organic matter from wastewater in an electro-Fenton system using an iron-nitrogen compound-carbon nanotube composite as an electrode, comprising:
Taking the iron-nitrogen compound-carbon nano tube composite material as a cathode, and taking a graphite plate as an anode to be connected into an electrolytic cell containing organic wastewater to form an electro-Fenton system;
Regulating the pH value of the organic wastewater, introducing oxygen, applying constant current to an electro-Fenton system, and degrading the organic wastewater;
The iron-nitrogen compound-carbon nano tube composite material after organic wastewater degradation can be repeatedly used after being cleaned.
In embodiments of the present disclosure, an iron-nitrogen compound-carbon nanotube composite is used as a cathode to construct an electro-Fenton system, wherein carbon nanotubes increase the adsorption capacity of an electrode surface to organic matter and oxygen, hydrogen peroxide is generated by reducing oxygen via a two-electron pathway, and the hydrogen peroxide is catalytically decomposed into hydroxyl radicals (OH) by ferrous iron generated on the surface of the iron-nitrogen compound, which is beneficial to degrading and mineralizing organic pollutants.
The electron-rich environment provided by the cathode enables the iron in the catalytic process to be converted between three valence states, meanwhile, the extremely strong stability of the iron-nitrogen compound is ensured, and the selectivity and the removal efficiency of organic matters in the wastewater degradation process are improved.
According to embodiments of the present disclosure, the organic wastewater includes any one or more of sulfonamide wastewater, synthetic resin wastewater, halogenated compound wastewater, high-salt organic wastewater, alkaline organic wastewater.
In the embodiment of the disclosure, the iron-nitrogen compound-carbon nanotube composite material used as an electrode has higher di-electron oxygen reduction selectivity and hydrogen peroxide generation efficiency, and in addition, has high-efficiency Fenton catalytic activity, can generate a large amount of hydroxyl free radicals, does not need to add chemical reagents such as H 2O2, fe 2+ and the like, improves the pH tolerance range of the electro-Fenton technology, avoids the generation of red mud in the wastewater treatment process, and is suitable for removing organic pollutants in a wider pH range.
According to embodiments of the present disclosure, oxygen may be introduced 30 minutes in advance;
according to embodiments of the present disclosure, the flow rate of the oxygen gas is 150 to 250mL/min, for example, 150mL/min, 200mL/min, 250mL/min, etc.
According to an embodiment of the present disclosure, the constant current has a density of 1 to 7mA/cm 2, for example, 1mA/cm 2、3mA/cm2、5mA/cm2、7mA/cm2, or the like.
In order to make the objects, technical solutions and advantages of the present disclosure clearer, the technical solutions and principles of the present disclosure are further described below by specific embodiments with reference to the accompanying drawings. It should be noted that the following specific examples are given by way of illustration only and the scope of the present disclosure is not limited thereto.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. The examples are not intended to identify specific techniques or conditions, but are conventional and may be carried out according to techniques or conditions described in the literature in this field or according to product specifications.
Example 1
A method of preparing an iron nitrogen compound-carbon nanotube composite comprising:
Weighing 0.04g of iron nitride and 0.02g of single-walled carbon nanotube, mixing, putting into an agate bowl, grinding for 5 minutes to fully and uniformly mix, then dispersing into 50mL of 5wt% sodium dodecyl sulfate solution, carrying out ultrasonic vibration treatment for 30 minutes, and carrying out suction filtration to uniformly plug the mixture on a hydrophilic polytetrafluoroethylene membrane to obtain a composite filter membrane; preparing 5wt% of perfluorosulfonic acid polymer and ethanol with a volume ratio of 13:127 (5% Nafion-ethanol solution), dropwise adding 1.5ml of 5% Nafion-ethanol solution layer by layer on the composite filter membrane, and drying at room temperature to form a protective layer to obtain the iron-nitrogen compound-carbon nano tubes (Fe x N/CNTs) composite material.
The structure of the iron-nitrogen compound-carbon nanotube composite material prepared in example 1 was subjected to Scanning Electron Microscope (SEM) characterization by using a field emission scanning electron microscope (FES) with the model of Hitachi S-8020, and the particle size and morphology structure of the material were analyzed.
Fig. 1 is a Scanning Electron Microscope (SEM) image of the iron-nitrogen compound-carbon nanotube composite material prepared in example 1 of the present disclosure, and it can be seen that the iron-nitrogen compound is a sphere with a diameter of 1-4 μm, and the surface of the sphere is rugged, which is beneficial for the tight adhesion and winding of carbon nanotubes. The iron-nitrogen compound microsphere is tightly connected with the carbon nano tube, the iron-nitrogen compound microsphere is attached to the carbon nano tube through hydrogen bonds and van der Waals force kinks, and abundant pore spaces are reserved, so that the adsorption of oxygen is facilitated.
Example 2
The iron-nitrogen compound-carbon nanotube composite material was prepared by the same preparation method as in example 1, except that the hydrophilic polytetrafluoroethylene membrane was replaced with a nylon fiber membrane, a glass fiber membrane and a plain filter paper, respectively, to obtain a corresponding composite filter membrane.
Fig. 2 is a comparative diagram of different types of composite filters according to an embodiment of the present disclosure, and as shown in fig. 2, a mixture of an iron-nitrogen compound and carbon nanotubes may be well loaded onto different filters.
Example 3
The activity of the two electron oxygen reduction process and the hydrogen peroxide (H 2O2) selectivity of the iron nitrogen compound-carbon nanotube composite material obtained in example 1 were tested by using a rotating ring plate electrode (RRDE) test, using a rotating ring plate electrode instrument model RRDE-3A Ver2.0 of BAS Co., ltd., connected to a CHI760E electrochemical analyzer, using a Linear Sweep Voltammetry (LSV) set up at a sweep rate of 10mV/s in a sweep range of-0.6 to 0.1V vs. SCE (relative to a calomel electrode), applying a constant potential of 0.2V to a platinum ring, and performing RRDE test on an oxygen-saturated 50mM Na 2SO4 solution.
Preparing 5% wt of perfluorosulfonic acid polymer to ethanol in a volume ratio of 1:9 (Nafion-ethanol solution), weighing 10mg of iron nitrogen compound-carbon nano tube composite material into 2.5mL of 5% Nafion-ethanol solution, carrying out ultrasonic treatment for 1 hour to obtain a uniformly dispersed suspension, taking 12 mu L of suspension liquid to drop on a glass carbon plate of RRDE electrode, standing under a mercury lamp, and drying to obtain a uniformly distributed film electrode, wherein the diameter of the glass carbon plate of RRDE electrode is 4mm, and the load capacity of the iron nitrogen compound-carbon nano tube composite material is 381.9 mu g/cm 2.
FIG. 3 is a graph showing the electrode test of the ring-plate of the iron-nitrogen compound-carbon nanotube composite material in example 3 of the present disclosure, wherein the electron transfer number of the thin film electrode of the iron-nitrogen compound-carbon nanotube composite material is 2.21 and the H 2O2 selectivity is 89.2% at a potential of-0.2V vs. SCE (vs. calomel electrode); in the range of-0.4V to-0.2V vs. SCE, the average value of the electron transfer number is 2.9, and the average value of H 2O2 selectivity is 55.3%. It can be seen that the iron-nitrogen compound-carbon nanotube composite material film electrode mainly performs oxygen reduction (ORR) reaction through a two-electron approach, and has stronger H 2O2 selectivity.
Example 4
The iron-nitrogen compound-carbon nano tube composite materials prepared in the example 1 and the example 2 are used as electrodes, and sulfathiazole in organic wastewater is degraded under different pH conditions in an electro-Fenton system;
The initial concentration of Sulfathiazole (STZ) is 10mg/L as a simulated pollutant, the electrolyte is 50mM NaSO 4 solution, the degradation experiment is carried out in a 100ml single-chamber electrolytic cell, the cathode is an iron-nitrogen compound-carbon nano tube composite material with the working area of 13.8cm 2, the anode adopts a commercial graphite plate with the same working area, and the electrode spacing is adjusted to be 1cm. The pH value of the simulated polluted wastewater solution is regulated by adopting dilute sulfuric acid and dilute sodium hydroxide solution, the initial pH value is regulated to 3, high-purity oxygen with the flow rate of 150-250 mL/min is continuously introduced in the process of electric degradation, a direct current power supply with the model DH1766A is adopted to provide constant current, 68mA of constant current is applied, and the reaction time is 60 minutes.
FIG. 4 is a graph showing the effect of iron nitrogen compound-carbon nanotube composites of different filters on simulating wastewater degradation by electrodes in the disclosed example, wherein C/C 0 represents the effect of simulating the degradation of sulfathiazole in wastewater. As shown in figure 4, the iron-nitrogen compound-carbon nano tube composite material prepared by loading four different filter membranes can completely degrade the sulfathiazole simulated wastewater within 60 minutes.
Example 5
The same procedure as in example 4 was employed, except that the iron nitrogen compound-carbon nanotube composite material prepared in example 1 was used as an electrode, the initial pH of the simulated contaminated wastewater was adjusted to 1,3, 5, 7, 9, and sulfathiazole in organic wastewater was degraded under different pH conditions in an electro-Fenton system.
FIG. 5 is a graph showing the effect of the iron nitrogen compound-carbon nanotube composite material of example 5 of the present disclosure on degrading simulated wastewater under different pH conditions, wherein C/C 0 represents the effect of degrading sulfathiazole in the simulated wastewater. As shown in fig. 5, when ph=3, the degradation rate of the iron nitrogen compound-carbon nanotube composite material electrode to sulfathiazole is highest, which can reach 99.8%. When ph=1, the iron nitrogen compound is excessively corroded, reducing the activation efficiency of O 2, whereas hydroxide precipitation may be generated on the electrode surface at pH >5, reducing the active sites of the electrode, and impeding mass transfer of electrons and active substances. At ph=1, 5, 7, 9, the sulfathiazole degradation rates were 84.6%, 88.4%, 82.7% and 87.6%, respectively. Therefore, the iron-nitrogen compound-carbon nano tube composite material used as an electrode has higher electrocatalytic activity in a wider pH range, and can adapt to a complex pH environment in the actual wastewater treatment process.
Example 6
The pH of the simulated contaminated wastewater was adjusted to 3 by the same method as in example 5, and the iron-nitrogen compound-carbon nanotube composite material prepared in example 1 was used as an electrode to degrade organic wastewater in an electro-Fenton system; and (3) flushing the iron-nitrogen compound-carbon nano tube composite material subjected to organic wastewater degradation with deionized water, using the method to be used as electrode degradation organic wastewater again, and repeating the steps to recycle the iron-nitrogen compound-carbon nano tube composite material.
Fig. 6 is a graph showing the effect of recycling the iron nitrogen compound-carbon nanotube composite material to degrade organic wastewater in example 6 of the present disclosure, and as shown in fig. 6, the removal rate of the contaminant Sulfathiazole (STZ) can still reach 94.5% after the iron nitrogen compound-carbon nanotube composite material is used as an electrode for 5 times of repeated use, which indicates that the iron nitrogen compound-carbon nanotube composite material can be recycled under the electro-Fenton system, still has reactivity, and has excellent stability.
Example 7
The same method as in example 4 was used, except that only the iron nitrogen compound-carbon nanotube composite material prepared in example 1 was used as an electrode, degrading three different types of organic wastewater, respectively. Wherein, organic waste water is respectively: the chemical oxygen demand (COD content) of the resin-containing and halogenated compound waste water of Yue Yangmou factory, the high-salt organic waste water of the god factory and the caustic soda organic waste water of the Tianjin factory is 99.1-217.8 mg/L, and the initial pH value is 6-8 without adjustment.
Fig. 7 is a graph showing the effect of Total Organic Carbon (TOC) removal rate of degrading different types of organic wastewater in example 7 of the present disclosure, and as can be seen from fig. 7, organic wastewater produced by three different industries does not need to be pH-adjusted or other chemical reagents added, and after the method provided by the present disclosure is used for reacting for two hours, the total organic carbon removal rate in the organic wastewater can reach 46.8-75.7%, and efficient degradation of organic pollutants can be achieved.
Based on the experimental analysis, the iron-nitrogen compound-carbon nano tube composite material, the preparation method and the application provided by the disclosure are characterized in that the iron-nitrogen compound and the carbon nano tube are ground and mixed and then are loaded on a filter membrane, and then Nafion-ethanol solution is dripped to form a protective film, so that the iron-nitrogen compound-carbon nano tube composite material with high stability, oxygen permeability and catalytic activity is obtained. The excellent conductivity and rich pore structure of the carbon nano tube are beneficial to improving the electrocatalytic performance of the iron-nitrogen compound and the carbon nano tube, and the oxide layer on the surface of the iron-nitrogen compound can effectively prevent corrosion in the electrocatalytic process. The iron-nitrogen compound-carbon nanotube composite material is used as a cathode in an electro-Fenton system, has strong stability and high pH adaptability, can realize continuous and high-efficiency rapid degradation of organic pollutants through a two-electron approach and Fenton catalysis, still keeps the removal rate of the organic pollutants above 94% after being recycled for a plurality of times, overcomes the defects of easy inactivation and short catalytic life of zero-valent iron technology, and has wide application prospect.
While the foregoing is directed to embodiments of the present disclosure, other and further details of the invention may be had by the present application, it is to be understood that the foregoing description is merely exemplary of the present disclosure and that no limitations are intended to the scope of the disclosure, except insofar as modifications, equivalents, improvements or modifications may be made without departing from the spirit and principles of the present disclosure.
Claims (9)
1. A method for removing organic matters in wastewater in an electro-Fenton system by using an iron-nitrogen compound-carbon nano tube composite material as an electrode, comprising the following steps:
Taking an iron-nitrogen compound-carbon nano tube composite material as a cathode, taking a graphite plate as an anode, and connecting the graphite plate into an electrolytic cell containing organic wastewater to form an electro-Fenton system, applying constant current to the electro-Fenton system, degrading the organic wastewater, and interconverting iron elements between three valence states of Fe 0、FeⅡ and Fe Ⅲ in the process of removing organic matters, wherein:
The preparation method of the iron-nitrogen compound-carbon nano tube composite material comprises the following steps:
Nitriding nano zero-valent iron to form an iron-nitrogen compound, grinding a mixture of the iron-nitrogen compound and the carbon nano tube, adding the mixture into a dispersion solution, and loading the mixture onto a filter membrane through ultrasonic suction filtration to obtain a composite filter membrane;
And dripping perfluorinated sulfonic polymer-ethanol solution on the composite filter membrane, and drying to form a protective layer to obtain the iron-nitrogen compound-carbon nano tube composite material, wherein the surface of the composite material contains Fe 0、FeⅡ and Fe Ⅲ in three valence states.
2. The method of claim 1, wherein,
The mass ratio of the iron-nitrogen compound to the carbon nano tube is 10: 1-1: 10;
The concentration of the mixture added into the dispersion solution is 0.5-2 g/L.
3. The method of claim 1, wherein,
The carbon nanotubes are single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
4. The method of claim 1, wherein,
The dispersion solution comprises any one of a sodium dodecyl sulfate solution, a sodium dodecyl sulfonate solution and a sodium fatty alcohol polyoxyethylene ether sulfate solution;
the mass fraction of the dispersion solution is 1-10%;
The filter membrane comprises any one of a hydrophilic polytetrafluoroethylene membrane, a nylon fiber membrane, an acetate fiber membrane and a glass fiber membrane.
5. The method of claim 1, wherein,
The volume ratio of the perfluorosulfonic acid polymer solution to the ethanol solution in the perfluorosulfonic acid polymer-ethanol solution is 1: 14-1: 2;
Wherein the concentration of the perfluorinated sulfonic acid group polymer solution is 5 wt percent.
6. The method of claim 5, wherein,
The iron-nitrogen compound in the iron-nitrogen compound-carbon nanotube composite material is a sphere with the diameter of 1-4 mu m, and the surface of the sphere is rugged.
7. The method of claim 1, further comprising:
Adjusting the pH value of the organic wastewater and introducing oxygen; and
The iron-nitrogen compound-carbon nano tube composite material after organic wastewater degradation can be repeatedly used after being cleaned.
8. The method according to claim 1 or 7, wherein,
The organic wastewater comprises any one or more of sulfonamide wastewater, synthetic resin wastewater, halogenated compound wastewater, high-salt organic wastewater and alkaline organic wastewater.
9. The method of claim 7, wherein,
Introducing the oxygen in advance for 30 minutes;
the flow rate of the oxygen is 150-250 mL/min;
the density of the constant current is 1-7 mA/cm 2.
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| CN113083272A (en) * | 2021-03-31 | 2021-07-09 | 合肥工业大学 | FeNxPreparation method of nano-particle doped bamboo-like carbon nano-tube |
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