CN114392754A - Modified activated carbon fiber composite material, preparation method thereof, heterogeneous electro-Fenton catalytic composite material and application thereof - Google Patents
Modified activated carbon fiber composite material, preparation method thereof, heterogeneous electro-Fenton catalytic composite material and application thereof Download PDFInfo
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- CN114392754A CN114392754A CN202210115832.2A CN202210115832A CN114392754A CN 114392754 A CN114392754 A CN 114392754A CN 202210115832 A CN202210115832 A CN 202210115832A CN 114392754 A CN114392754 A CN 114392754A
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- activated carbon
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- 239000002131 composite material Substances 0.000 title claims abstract description 109
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 68
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000015556 catabolic process Effects 0.000 claims abstract description 17
- 238000006731 degradation reaction Methods 0.000 claims abstract description 17
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 17
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229910001868 water Inorganic materials 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims description 40
- 239000004332 silver Substances 0.000 claims description 38
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 35
- 239000000126 substance Substances 0.000 claims description 34
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- -1 silver ions Chemical class 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 9
- 229910001448 ferrous ion Inorganic materials 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 229910001447 ferric ion Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XSNQEMWVLMRPFR-UHFFFAOYSA-N silver nitride Chemical compound [N-3].[Ag+].[Ag+].[Ag+] XSNQEMWVLMRPFR-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 229910052598 goethite Inorganic materials 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
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- 238000000975 co-precipitation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
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- 238000002791 soaking Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J35/20—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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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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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
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
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Abstract
The invention provides a modified activated carbon fiber composite material and a preparation method thereof, a heterogeneous electro-Fenton catalytic composite material and application thereof. The preparation method comprises the steps of pretreating the activated carbon fiber by using an acid solution to obtain a pre-acidified activated carbon fiber; mixing ferrous salt and silver salt in water to carry out a first reaction, then adding pre-acidified activated carbon fiber and alkali to form a reaction system, and carrying out a second reaction to obtain the modified activated carbon fiber composite material. The invention also provides the modified activated carbon fiber composite material prepared by the preparation method. The invention further provides a heterogeneous electro-Fenton catalytic composite material comprising the modified activated carbon fiber composite material and application of the heterogeneous electro-Fenton catalytic composite material in the heterogeneous electro-Fenton catalytic degradation of organic pollutants. The modified activated carbon fiber composite material provided by the invention has high catalytic activity and cycling stability.
Description
Technical Field
The invention relates to the technical field of heterogeneous electro-Fenton catalytic materials, in particular to a modified activated carbon fiber composite material and a preparation method thereof, a heterogeneous electro-Fenton catalytic composite material and application thereof.
Background
Activated Carbon Fiber (ACF) is considered to be an excellent adsorbent for environmental pollution treatment by virtue of its developed pore structure, large specific surface area, abundant surface functional groups, relatively high mechanical strength, etc., and has been widely used for the treatment of harmful substances and pollutants in water, but since adsorption only achieves the process of transferring pollutant molecules to the surface of activated carbon fiber, the activated carbon fiber itself becomes a harmful substance after adsorption, and the molecular structure of organic substances cannot be destroyed. Although the modification methods of the active carbon fiber are numerous at present: oxidation, reduction modification, high-temperature heat treatment modification, microwave modification and the like, but the preparation process is complex, the energy consumption is high, secondary pollution is easy to cause and the like, and the wide application is greatly limited.
Most of transition metals contained in the prior heterogeneous electro-Fenton solid catalyst have biotoxicity, and the iron-containing nano-particle/transition metal loaded particle type catalyst is difficult to recycle after reaction, so that secondary pollution is easily caused, and further the operation cost is greatly increased. In addition, in the actual water treatment process, the nanoparticles are easily lost due to the action of water flow and are not easy to separate, so that secondary pollution is caused.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a modified activated carbon fiber composite material, a preparation method thereof, a heterogeneous electro-Fenton catalytic composite material and application thereof. The modified activated carbon fiber composite material comprises magnetite Fe3O4And silver simple substance Ag, has higher catalytic activity and stability, and can be used as a catalyst and a functionalized cathode.
In order to achieve the above object, the present invention provides a method for preparing a modified activated carbon fiber composite material, comprising: immersing the activated carbon fiber into an acid solution to obtain a pre-acidified activated carbon fiber; mixing ferrous salt and silver salt in water to carry out a first reaction, then adding pre-acidified activated carbon fiber and alkali to form a reaction system, carrying out a second reaction, and heating to obtain the modified activated carbon fiber composite material, wherein the modified activated carbon fiber composite material comprises activated carbon fiber, and silver simple substance and ferroferric oxide loaded in the activated carbon fiber; wherein the mass ratio of the pre-acidified activated carbon fiber to the ferrous salt to the silver salt is (0.04-0.06): (2-3.5): (2-2.5).
According to the preparation method, simultaneous deposition of magnetite (ferroferric oxide) and silver particles on the activated carbon fiber is realized by optimizing a coprecipitation method, modification of the activated carbon fiber is realized, and the obtained modified activated carbon fiber composite material can be used as a heterogeneous electro-Fenton catalytic composite material and has high H2O2Yield and Fenton catalytic activity. Compared with the conventional modification method for gradually and sequentially depositing metal and oxide on the activated carbon, the preparation method provided by the invention loads the simple substance silver and the ferroferric oxide in the activated carbon fiber by a one-step method, and the obtained composite material can keep the porous characteristic of the activated carbon fiber, has larger specific surface area and reaction space, and has a large number of defects and active sites on the surface of the fiber. When the composite material is applied to electro-Fenton catalysis, the mass transfer path of the composite material is shorter, and the reaction efficiency and the reaction activity are higher.
In the above preparation method, the operation of immersing the activated carbon fiber in an acid solution has the following advantages: 1. the activated carbon fiber is acidic, which is beneficial to the subsequent reaction of silver ions and ferrous ions; 2. the activated carbon fiber is made into a porous active surface, and generates a large amount of defects and H after Fenton reaction2O2The active site of (a); 3. rich pore structure is introduced into the activated carbon fiber, and more reactive active sites and more defects and sp are exposed on the surface of the activated carbon fiber3C, increasing O2Adsorption and O2To H2O2The number of the active sites of the electrochemical reduction is increased, the pH application range of the reaction system is widened, the reaction efficiency of the heterogeneous electro-Fenton system with the composite material is improved, the process cost is reduced, and the energy is saved.
In the preparation method, the loading amounts of the silver simple substance and the ferroferric oxide in the modified activated carbon fiber composite material and the catalytic activity of the modified activated carbon fiber composite material can be effectively regulated and controlled by controlling the proportion of the activated carbon fiber, the ferrous salt and the silver salt.
In the above preparation method, the impregnation time of the activated carbon fiber in the acid solution is generally controlled to be 6h to 8h, for example, 8 h.
In the above preparation method, the acid solution may include hydrochloric acid, sulfuric acid, and the like. The concentration of the acid solution is generally controlled to be 0.1M to 0.5M.
In a specific embodiment of the present invention, the specific process of obtaining pre-acidified activated carbon fibers may comprise: and immersing the washed activated carbon fiber into an acid solution, standing, washing with water, and drying to obtain the pre-acidified activated carbon fiber.
In the preparation method, the pre-acidified activated carbon fiber is simultaneously mixed with silver salt and ferrous salt, so that ferric ions and ferrous ions can be simultaneously loaded in the activated carbon fiber structure, and the one-step synthesis of the modified material is realized. Specifically, silver ions in the silver salt and ferrous ions in the ferrous salt undergo an oxidation-reduction reaction (i.e., the first reaction) to generate a silver simple substance and ferric ions, and by controlling the degree of reaction between the silver ions and the ferrous ions, a part of the ferrous ions undergo an oxidation-reduction reaction, while the other part of the ferrous ions do not participate in the reaction, so that the ferric ions and the unreacted ferrous ions generate ferroferric oxide. Silver simple substance and ferroferric oxide are embedded into the activated carbon fiber to cause a great amount of tiny cracks, and the cracks can provide reaction space for three-phase reaction, thereby shortening the mass transfer path.
In a specific embodiment of the present invention, a generation process of the ferroferric oxide loaded in the modified activated carbon fiber composite material may specifically be: ferric ions generated by the first reaction and ferrous ions which do not participate in the first reaction form ferric hydroxide and ferrous hydroxide precipitates in an alkali solution, and then the ferric hydroxide and ferrous hydroxide precipitates are heated to form a mixture of ferrous oxide and ferric oxide, namely the ferroferric oxide.
In a specific embodiment of the present invention, the generation process of the silver elementary substance particles loaded in the modified activated carbon fiber composite material may be: most of silver ions generate a silver simple substance through a first reaction, the rest silver ions which do not participate in the first reaction and alkaline solutions such as ammonia water form a silver-ammonia solution, the silver-ammonia solution is decomposed into unstable silver nitride, the silver nitride is finally decomposed into a silver simple substance and nitrogen, and the simple substance silver formed through the first reaction and the simple substance silver formed by decomposing the silver nitride are the simple substance silver loaded in the composite material.
In the above preparation method, the ferrous salt generally includes a soluble ferrous salt, and may include, for example, ferrous sulfate, ferrous chloride, and the like.
In the above preparation method, the silver salt generally includes a soluble silver salt, and may include, for example, silver nitrate or the like.
In the above preparation method, the aspect ratio of the activated carbon fiber is generally 80 to 110.
In the preparation method, the reaction efficiency of the first reaction can be improved by heating the reaction system of the first reaction formed by the ferrous salt and the silver salt and violently stirring the reaction system. In a particular embodiment, the reaction temperature of the first reaction is typically 55 to 65 ℃, e.g., 60 ℃, and the reaction time of the first reaction is typically 17min to 23min, e.g., 20 min.
In the above production method, the reaction temperature of the second reaction is generally 58 to 62 ℃, for example, 60 ℃, and the reaction time of the second reaction is generally 55 to 65min, for example, 60 min.
In the above production method, the base can provide an alkaline environment to the reaction system of the second reaction, control the pH of the reaction system to about 9 to 11 (e.g., about 10), and can serve as a catalyst for the second reaction. In some embodiments, the base may comprise aqueous ammonia. In a specific embodiment, the actual amount of the ammonia water can be adjusted according to the specific concentration of the ammonia water, for example, when the mass concentration of the ammonia water is 25% to 30% (preferably 28%), the amount of the ammonia water can be controlled to be 6mL to 8 mL.
According to a specific embodiment of the present invention, the above preparation method may comprise:
1. immersing the washed activated carbon fiber into an acid solution, standing for 6-8h, washing the activated carbon fiber with water, and drying to obtain pre-acidified activated carbon fiber;
2. mixing ferrous salt and silver salt, stirring vigorously, carrying out a first reaction for 17-23min at 55-65 ℃, then adding pre-acidified activated carbon fiber and alkali, carrying out a second reaction for 55-65min at 58-62 ℃, and heating a reaction product to 70-80 ℃ to obtain the modified activated carbon fiber composite material; wherein the mass ratio of the pre-acidified activated carbon fiber to the ferrous salt to the silver salt is controlled to be (0.04-0.06): (2-3.5): (2-2.5).
The invention further provides a modified activated carbon fiber composite material, which is obtained by the preparation method.
According to a specific embodiment of the invention, the modified activated carbon fiber composite material comprises activated carbon fiber, a silver simple substance and ferroferric oxide, wherein the silver simple substance and the ferroferric oxide are loaded in the activated carbon fiber. Specifically, the modified activated carbon fiber contains silver in an elemental form, divalent iron ions and trivalent iron ions.
According to a specific embodiment of the invention, in the modified activated carbon fiber composite material, the mass ratio of the activated carbon fiber to the ferroferric oxide to the elemental silver is generally 63-67: 5-8: 25-32, for example, may be 64.64: 7.06: 28.3.
In a specific embodiment of the invention, the Fe is obtained by using activated carbon fibers as magnetite3O4And the load carrier of the simple substance Ag can effectively solve the problem that the metal and the metal oxide particles are difficult to recycle after the catalytic reaction. And by reacting Fe3O4And simple substance Ag particles are loaded into the activated carbon fiber with a porous structure, and Fe can be carried out by utilizing the steric hindrance and the porous framework of the activated carbon fiber3O4And the nanoparticles of the simple substance Ag are dispersed on the surface of the fiber material and in the pore channel, so that the integral specific surface area of the activated carbon fiber composite material is improved, and the problems of load loss, secondary pollution, reduction of catalytic activity caused by nanoparticle aggregation and the like can be effectively avoided. Meanwhile, the particle size of the silver simple substance is about 5 microns generally, the particle size of the ferroferric oxide particles is smaller than that of the silver simple substance, the small-size silver simple substance and the ferroferric oxide particles cannot change the self property of the activated carbon fiber, the porous activity of the activated carbon fiber is reserved in the modification process, and a large number of defects are further caused on the surface of the activated carbon fiber and H is generated after Fenton reaction2O2The active site of (1). Generally, the modified activated carbon fiber has micropores with a diameter of 1.7nm-2.0nm and mesopores with a diameter of 2.0nm-5.5nm (preferably including 2.6nm, 4.5nm, etc.), and the specific surface area can reach 540m2More than g, the total pore volume can reach 0.24cm2More than g. In the process of electro-Fenton catalytic reaction, the porous structure on the surface of the activated carbon fiber can reduce concentration polarization in the mass transfer process and enhance the three-phase interface catalytic dynamics on the active site.
The invention further provides a heterogeneous electro-Fenton catalytic composite material which comprises the modified activated carbon fiber composite material. When the modified activated carbon fiber composite material is applied to catalytic reaction, Fe3O4As a host of catalytic degradation, compared to other iron oxides such as goethite (FeOOH), hematite (Fe)2O3) Better catalytic activity and easier separation backRecycling; the silver mainly has the function of enhancing the conductivity and the catalytic activity, and the simple substance silver particles prepared by the method have the particle size of about 5 mu m and have higher conductivity and catalytic activity. Fe (II) in a partially oxidized porous structure in the modified activated carbon fiber composite material can be used as a catalyst to participate in Fenton reaction so as to promote H2O2Decomposition of (2); meanwhile, Fe ions (including ferrous ions and ferric ions) leached from the modified activated carbon fiber composite material can be directly used as an Fe source for Fenton reaction, so that the reaction process is simplified, and the cost of external Fe feeding is avoided. The structural specificity can ensure that the modified activated carbon fiber composite material can be applied to a heterogeneous electro-Fenton oxidation system and simultaneously has a system catalyst source (Fe)2+，H2O2) And a functionalized cathode.
The invention also provides application of the heterogeneous electro-Fenton catalytic composite material in the heterogeneous electro-Fenton catalytic degradation of organic pollutants, such as the electro-Fenton catalytic degradation of methyl blue. The modified activated carbon fiber composite material can be widely applied to the treatment of organic pollutants in wastewater and air, and has the advantages of high oxidation treatment efficiency, stable property, easy recycling, low energy consumption, safety and environmental protection. In a heterogeneous-electric Fenton oxidation system, the catalytic composite material is used as a functional cathode to effectively adsorb pollutant molecules and improve H2O2Yield and Fe (II), thereby showing excellent activity and stability of the electro-Fenton catalyzing and degrading the organic dye methyl blue. Specifically, when the catalytic composite material is used as a cathode for catalyzing advanced oxidative degradation of organic matters through electric Fenton, ferroferric oxide loaded in the activated carbon fiber is used as a Fe source for Fenton reaction, and is subjected to two-electron reduction with the surface of the cathode material to generate H2O2The reaction generates hydroxyl radical (. OH) having strong oxidizing property, and further oxidizes most organic substances to CO2And water.
The invention has the beneficial effects that:
1. the invention combines the adsorption characteristic of the activated carbon with a heterogeneous electro-Fenton advanced oxidation technology, and loads metal and metal oxide in the activated carbon, so that the obtained modified composite material has the performance of adsorbing pollutants on one hand, and can degrade pollutants adsorbed on the surface of the material through a heterogeneous electro-Fenton reaction on the other hand.
2. Compared with other iron oxides such as goethite (FeOOH), hematite (Fe)2O3) Etc. the magnetite (Fe) loaded in the activated carbon fiber of the present invention3O4) Has higher catalytic activity and thermal stability, is easy to separate, recycle and reuse, has excellent catalytic performance of simple substance Ag particles, and can simultaneously have a system catalyst source (Fe) when being applied to a heterogeneous electro-Fenton oxidation system2+，H2O2) And a functionalized cathode.
3. In the invention, nano Fe is embedded into the activated carbon fiber3O4And Ag particles, the cracks can provide reaction space for three-phase reaction, so that a mass transfer path is shortened, and Fe (II) in a partially oxidized porous structure can participate in Fenton reaction as a catalyst to promote H2O2Decomposition of (3).
4. In the invention, Fe (II) ions leached from the composite material can be directly used as an Fe source for Fenton reaction, thereby simplifying the reaction process and avoiding the cost of external Fe feeding; at the same time, double electron reduction O can be generated at the cathode2In situ generation of H2O2The cost of synthesis, transportation and storage is reduced; and the modified activated carbon fiber composite material has a porous active surface, further causes a large number of defects and generates H after Fenton reaction2O2The active site of (1). The Fe (III) ions leached from the composite material can promote the catalyst process to be carried out and improve the catalytic efficiency.
5. The preparation method provided by the invention can realize simultaneous deposition of magnetite and simple substance silver particles in the activated carbon fiber, and has the advantages of simple preparation process and low operation cost.
6. The heterogeneous electro-Fenton catalytic composite material prepared by the invention can be widely applied to the treatment of organic pollutants in wastewater and air, and has the advantages of high oxidation treatment efficiency, stable property, easy recovery and reuse, low energy consumption, safety and environmental protection. Particularly for methyl blue, the composite material provided by the invention can show excellent activity and stability for catalyzing and degrading the organic dye methyl blue by the electro-Fenton.
Drawings
Fig. 1 is an XRD pattern of the modified activated carbon fiber composite of example 1.
Fig. 2 is an XPS broad spectrum scanning spectrum of the modified activated carbon fiber composite of example 1.
Fig. 3a to 3d are XPS fine scanning spectra of the modified activated carbon fiber composite of example 1. Fig. 3a is a fine scan of C element, fig. 3b is a fine scan of O element, fig. 3C is a fine scan of Fe element, and fig. 3d is a fine scan of Ag element.
Fig. 4a is a TEM image of the modified activated carbon fiber composite of example 1, and fig. 4b to 4f are element distribution diagrams of the modified activated carbon fiber composite of example 1.
Fig. 5a is an SEM photograph of the modified activated carbon fiber composite of example 1, and fig. 5b is an EDS energy spectrum of the regions of spectrum 1 and spectrum 2 in fig. 5 a.
Fig. 6a is an SEM photograph of the modified activated carbon fiber composite of example 1, and fig. 6b is an EDS energy spectrum of the regions of spectrum 1 and spectrum 2 in fig. 6 a.
Fig. 7 is a BET data graph of the modified activated carbon fiber composite of example 1.
Fig. 8 is a BJH data plot for the modified activated carbon fiber composite of example 1.
Fig. 9 is a graph of EIS results for the modified activated carbon fiber composite of example 1 and the pre-acidified carbon fiber of comparative example 1.
Fig. 10 is a graph of heterogeneous electro-Fenton catalytic degradation performance of the modified activated carbon fiber composite of example 1 and the pre-acidified carbon fiber of comparative example 1.
Fig. 11 is a heterogeneous electro-Fenton catalytic degradation performance stability curve of the modified activated carbon fiber composite of example 1.
FIG. 12 is a graph of the stability of the performance of heterogeneous electro-Fenton catalytic degradation of COD for pre-acidified carbon fibers of comparative example 1.
FIG. 13 is n-Fe of comparative example 23O4XPS result graph of/ACF sample.
FIG. 14 is n-Fe of comparative example 23O4ACF samples with Ag @ n-Fe from example 13O4The performance curve of heterogeneous electro-Fenton catalytic degradation COD of ACF.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
The embodiment provides an activated carbon fiber composite material with magnetite and elemental silver surface modified, and the preparation method comprises the following steps:
1. pretreatment of activated carbon fiber: putting pure activated carbon fiber (length multiplied by width multiplied by thickness: 2cm multiplied by 2mm, purity 99.8%) into a 250mL beaker filled with deionized water, putting the beaker into an ultrasonic cleaning instrument for ultrasonic cleaning for 10min, taking out the beaker, repeating the ultrasonic cleaning for 2 to 3 times to remove residual impurities and ash on the surface, and drying the beaker for later use; and then adding a certain amount of 0.1M HCl solution until the carbon fiber is completely immersed, soaking for 6-8h, filtering, washing by deionized water to remove residual acid, and drying at 80 ℃ to obtain the pre-acidified activated carbon fiber.
2. Nano Fe3O4And deposition of Ag particles: 3g of iron sulfate heptahydrate (FeSO)4·7H2O) and 2.5g silver nitrate (AgNO)3) Dissolved in 60mL of distilled water to form a mixed solution, reacted for 20min, and vigorously stirred at 60 ℃ for 20 min. Then, 0.05g of pre-acidified activated carbon fiber and 6mL of ammonium hydroxide solution (NH) were added to the mixed solution3·H2O, 28% by mass), and holding at 60 deg.C for 60 min. Washing the activated carbon fiber with deionized water, and drying at 80 ℃ in a preheated vacuum drying oven to obtain the activated carbon fiber composite material with magnetite and simple substance silver surface modification, which is marked as Ag @ nFe3O4/ACF。
Comparative example 1
This comparative example provides a pre-acidified activated carbon fiber material. The activated carbon fiber was pre-treated according to the method of step 1 of example 1, and then dried at 80 ℃ for 10min in the same air atmosphere to obtain a pre-acidified activated carbon fiber, which was designated pure-ACF.
Comparative example 2
The comparative example provides a modified activated carbon fiber material, and the preparation method comprises the following steps:
1. putting the activated carbon fiber into a beaker, adding deionized water, ultrasonically cleaning for 2-3 times, washing with the deionized water, and drying at 80 ℃ to obtain the pretreated activated carbon fiber;
2. dissolving 7g of ferrous sulfate heptahydrate and 13g of ferric chloride hexahydrate in ethanol water solution, fully reacting, stirring at 70 ℃, then adding 0.05g of pretreated activated carbon fiber (stirring at a fixed temperature for 30min, then adding 2M sodium hydroxide solution, stirring at 75 ℃ for 30min, standing and aging, washing the surface of the activated carbon fiber with deionized water after 24h, and finally drying to obtain the modified activated carbon fiber composite material (also called n-Fe)3O4/ACF heterogeneous electro-Fenton catalytic material).
Test example 1 structural characterization
The composite material obtained in example 1 was subjected to structural characterization. Fig. 1 is an XRD pattern of the composite material. By comparing the XRD pattern of the sample with nFe3O4The comparison of the spectrogram standard card and the Ag simple substance spectrogram standard card can prove that the composite material has Ag simple substance and Fe in a face-centered cubic crystal phase3O4A crystalline phase.
Figure 2 is an XPS broad spectrum scan spectrum of the composite of example 1. As can be seen from FIG. 2, the surface of the test sample mainly contains four elements of C, O, Fe and Ag, and the spectrogram contains a C1s peak, an O1s peak, an Fe2p peak and an Ag3d peak. FIGS. 3a to 3d are fine XPS structure of FIG. 2 and a graph fitted thereto, and it can be seen that in FIG. 3c, Fe2p3/2And Fe2p1/2Are located at 711.2eV and 724.9eV, respectively, and are close to Fe3O4Standard XPS data of (3). In addition, the presence of Fe (II) and Fe (III) in the composite material is determined by the values of 710.80eV, 712.9eV, 724.3eV and 726.2 eVPeak at 7 eV. In the Ag3d spectrum (FIG. 3d), Ag3d3/2And Ag3d5/2The binding energy peaks of (a) were 374.2eV and 368.2eV, respectively, which are 6.0eV apart, matching the standard XPS spectrum of metallic Ag. From the above results, it was confirmed that the product obtained in example 1 was an activated carbon fiber composite material modified with magnetite and elemental silver.
Fig. 4a to 4f are TEM pictures and elemental distribution maps (mapping) of the composite material of example 1. Wherein, fig. 4a is a TEM image of the composite material, fig. 4b is an EDS layered image (EDS layered image) of the composite catalytic material, and fig. 4C is a C element distribution diagram; FIG. 4d is a diagram of the distribution of O elements; FIG. 4e is a distribution diagram of Fe element; FIG. 4f is a distribution diagram of Ag element. As can be seen, the sample surface mainly contains four elements of C, O, Fe and Ag (the S element is polluted by the surface of the instrument), and the distribution is very uniform, so that the sample can be proved to contain Fe3O4And Ag exists, namely the magnetite and elemental silver modified activated carbon fiber composite material is obtained. According to the calculation of the EDS result, the mass content of the activated carbon fiber in the composite material is 64.64%, the mass content of ferroferric oxide is 7.06%, and the mass content of the silver simple substance is 28.3%.
Fig. 5a and 6a are SEM photographs of the composite material of example 1. Fig. 5b is an EDS spectrum of the region of spectrum 1 and spectrum 2 in fig. 5a, and fig. 6b is an EDS spectrum of the region of spectrum 1 and spectrum 2 in fig. 6 a. As can be seen from fig. 5a and 5b, nanoparticles having a diameter of about 5 μm are distributed on the surface of the activated carbon fiber (for example, corresponding to the region of spectrogram 1 in fig. 5 a), and the nanoparticles are elemental silver. As can be seen from fig. 6a and 6b, small-sized ferroferric oxide nanoparticles are distributed on the surface of the activated carbon fiber.
The composite of example 1 was subjected to a nitrogen adsorption test, and fig. 7 is a BET data graph of the composite, and fig. 7 is a BJH data graph of the composite. As can be seen from the analysis of FIGS. 7 and 8, N in the composite material2The surface area of the adsorption isotherm (SBET) may be up to about 543.16m2(ii) in terms of/g. The total pore volume of the single-point adsorption of the pores is 0.24cm2(ii) in terms of/g. In addition, the adsorption and desorption isotherms of the samples in fig. 7 do not coincide with each other, forming hysteresis loops, indicating that a large amount of carbon is present in the composite material. According to IUPAC classification, the sample isThe sample was characterized by a hysteresis loop of type II adsorption isotherm H3, demonstrating that the channel structure of the sample is generally formed by loose packing of plate-like particles into wedge-shaped pores.
N of FIG. 7 analyzed by using BJH method2The isotherms, the pore size distributions obtained are shown in fig. 8. As can be seen from FIG. 8, the pore structure of the sample is mainly based on the micropore with the diameter of 1.7nm-2.0nm and the mesopore distribution of about 2.0nm-4.5nm, which is very similar to the pore size distribution of the activated carbon fiber itself. The above results indicate that the magnetite and silver loading in the activated carbon fiber does not significantly change the structural characteristics of the activated carbon.
Test example 2EIS test
EIS testing was performed on the composite of example 1 and the pre-acidified activated carbon fiber of comparative example 1. The test method comprises the following steps: electrochemical performance studies of the electrodes were performed using a CHI660E electrochemical workstation (CH Instruments Co., usa). An electrochemical cell is provided with a three electrode arrangement. At 0.1mol of L-1Na2SO4Electrochemical Impedance Spectroscopy (EIS) was performed at open circuit potential in solution. Amplitude of 5mV and frequency range of 1 × 106To 1X 10-2Hz. The test results are shown in fig. 9.
As can be seen from FIG. 9, the composite material (Ag @ nFe) of example 13O4/ACF) arc span in the middle frequency region was significantly reduced compared to the pre-acidified activated carbon fiber of comparative example 1 (pure-ACF), indicating that charge is transported in its channels and its diffusion resistance is less; the intersection point of the high-frequency area and the real axis shows the same trend, which shows that the equivalent resistance of the modified ACF is smaller and the conductivity is stronger.
Test example 3 test of catalytic degradation Performance
Catalytic performance tests were conducted using the composite of example 1 and the pre-acidified activated carbon fiber of comparative example 1 as samples.
Heterogeneous electro-Fenton catalytic performance tests were performed on the two samples. The test method comprises the following steps:
a beaker with the effective volume of 250mL is used as a reactor, a Pt sheet electrode is used as a reaction anode, a sample to be detected is used as a functionalized cathode, and the size of the cathode is 20mm multiplied by 20 mm. A heterogeneous electro-Fenton oxidation system was constructed by adding 200mL of 100mg/L methyl blue solution (pH about 5.73) to a reactor beaker while pumping air into the solution at a flow rate of 200 mL/min. And (3) taking 200mL of methyl blue solution with the concentration of 100mg/L as a target degradation product, testing the heterogeneous electro-Fenton catalytic performance of the obtained material, wherein the degradation time is 120min, placing the supernatant into a cuvette every 30min, measuring the concentration of the supernatant by using an ultraviolet-visible spectrophotometer, and drawing a photocatalytic degradation rate curve. The results of the experiment are shown in FIG. 9.
As can be seen from FIG. 10, the degradation rate of the pre-acidified activated carbon fiber of comparative example 1 (pure-ACF composite in FIG. 10) after 120min was only 59.14%, compared to the composite of example 1 (Ag @ nFe in FIG. 10)3O4the/ACF composite material) has a heterogeneous electro-Fenton catalytic degradation efficiency of 95.25%, which shows that the catalytic degradation efficiency of the activated carbon fiber can be obviously improved after magnetite and silver are loaded.
Test example 4 stability test
Pre-acidified activated carbon fiber prepared in comparative example 1 and composite (Ag @ nFe) prepared in example 13O4/ACF composite) were subjected to repeated catalytic testing.
The specific test method comprises the following steps: the sample tested in test example 2 was rinsed 2-3 times with deionized water, washed of adsorbed organic contaminants and then placed in a vacuum oven at 80 ℃ for thorough drying, followed by the next cycle test: the experiment was carried out in a beaker with an effective volume of 250mL, which was used as a reactor. The Pt sheet electrode is used as a reaction anode, and pre-acidified activated carbon fiber and a composite material are respectively used as functional cathodes, wherein the size of each cathode is 20mm multiplied by 20 mm. 200mL of 100mg/L methyl blue solution (pH about 5.73) was added to a beaker while air was pumped into the solution at a flow rate of 200mL/min to form a heterogeneous electro-Fenton oxidation system, and the solution was stirred and homogenized with a magnetic stirrer throughout the electro-Fenton reaction period, with current supplied by a regulated constant voltage DC power supply. Taking out supernatant at the room temperature every 30min, measuring the absorbance of the supernatant in an ultraviolet-visible spectrophotometer, calculating the concentration of the supernatant according to the F factor, and drawing a degradation rate curve, wherein the result is shown in FIG. 11; meanwhile, Chemical Oxygen Demand (COD) is measured, a COD removal rate curve is drawn by adopting a rapid digestion spectrophotometry (COD tester: Chinese DR1010), and the result is shown in figure 12.
As can be seen from fig. 11 and 12: the heterogeneous electro-Fenton system in which the composite material provided by the invention is located has a very stable treatment effect, the final COD removal rates are respectively 96.5%, 95.8%, 93.0% and 91.3%, the removal rate reduction is still kept within 5% after four times of repeated utilization, and the reduction range of the UV-vis degradation rate is kept about 10%, so that the composite material prepared by the invention has good stability and excellent electrochemical performance when being used as a heterogeneous electro-Fenton catalytic composite material.
Fig. 13 is an XPS spectrum of the catalytic material prepared in comparative example 2, and it can be seen that there are only a C peak, an O peak and an Fe peak in the material, and no Ag peak exists, demonstrating that there is no loading of elemental Ag in the material. FIG. 14 shows the catalytic material (Ag @ n-Fe) of example 13O4ACF) and catalytic material of comparative example 2 (n-Fe)3O4/ACF), the same as fig. 11. As can be seen from FIG. 14, the catalytic material (Ag @ n-Fe) obtained by the preparation method provided by the invention3O4/ACF) has a higher rate of electrocatalytic degradation.
Claims (10)
1. A preparation method of a modified activated carbon fiber composite material comprises the following steps:
immersing the activated carbon fiber into an acid solution to obtain a pre-acidified activated carbon fiber;
mixing ferrous salt and silver salt in water to carry out a first reaction, then adding pre-acidified activated carbon fiber and alkali to carry out a second reaction, and heating to obtain the modified activated carbon fiber composite material, wherein the modified activated carbon fiber composite material comprises activated carbon fiber, silver simple substance loaded in the activated carbon fiber and ferroferric oxide;
wherein the mass ratio of the pre-acidified activated carbon fiber to the ferrous salt to the silver salt is (0.04-0.06): (2-3.5): (2-2.5).
2. The method for preparing a modified activated carbon fiber composite according to claim 1, wherein the acid solution comprises hydrochloric acid and/or sulfuric acid; preferably, the concentration of the acid solution is 0.1M to 0.5M;
preferably, the dipping time of the activated carbon fiber in the acid solution is 6-8 h;
preferably, the process of obtaining pre-acidified activated carbon fibers comprises: and immersing the washed activated carbon fiber into an acid solution, washing with water, and drying to obtain the pre-acidified activated carbon fiber.
3. The method of claim 1, wherein the ferrous salt comprises a soluble ferrous salt;
preferably, the ferrous salt comprises ferrous sulfate and/or ferrous chloride.
4. The method for preparing a modified activated carbon fiber composite according to claim 1 or 3, wherein the silver salt comprises a soluble silver salt;
preferably, the silver salt comprises silver nitrate.
5. The method for preparing a modified activated carbon fiber composite material according to claim 1, wherein the aspect ratio of the activated carbon fiber is 80-110.
6. The method for preparing a modified activated carbon fiber composite according to claim 1, wherein the pH of the reaction system of the second reaction is 9 to 11;
preferably, the base comprises aqueous ammonia;
more preferably, the ammonia water is used in an amount of 6-8mL, wherein the mass concentration of the ammonia water is 25-30%.
7. The preparation method of the modified activated carbon fiber composite material according to claim 1 or 6, wherein the reaction temperature of the first reaction is 55-65 ℃, and the reaction time of the first reaction is 17-23 min;
the reaction temperature of the second reaction is 58-62 ℃, and the reaction time of the second reaction is 55-65 min;
the heating temperature is 70-80 ℃.
8. A modified activated carbon fiber composite material obtained by the production method according to any one of claims 1 to 7;
preferably, the modified activated carbon fiber composite material comprises the following components in a mass ratio of 63-67: 5-8: 25-32 parts of activated carbon fiber, ferroferric oxide and simple substance silver;
preferably, the specific surface area of the modified activated carbon fiber is 540m2More than g, the total pore volume of the modified activated carbon fiber is 0.24cm2More than g;
preferably, the modified activated carbon fiber has micropores with a diameter of 1.7nm to 2.0nm and mesopores with a diameter of 2.0nm to 5.5 nm.
9. A heterogeneous electro-Fenton catalytic composite comprising the modified activated carbon fiber composite of claim 8.
10. Use of the heterogeneous electro-Fenton catalytic composite of claim 9 in the heterogeneous electro-Fenton catalytic degradation of organic pollutants; preferably, the organic contaminant comprises methyl blue.
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| CN115382530A (en) * | 2022-08-23 | 2022-11-25 | 南京工业大学 | Catalyst for strengthening homogeneous Fenton oxidation synergistic adsorption and preparation method thereof |
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