CN113522291A - Fe3O4@ BC nano composite material and preparation method and application thereof - Google Patents
Fe3O4@ BC nano composite material and preparation method and application thereof Download PDFInfo
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- CN113522291A CN113522291A CN202110626256.3A CN202110626256A CN113522291A CN 113522291 A CN113522291 A CN 113522291A CN 202110626256 A CN202110626256 A CN 202110626256A CN 113522291 A CN113522291 A CN 113522291A
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000000463 material Substances 0.000 title claims abstract description 51
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002028 Biomass Substances 0.000 claims abstract description 46
- 239000003610 charcoal Substances 0.000 claims abstract description 30
- 238000000498 ball milling Methods 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000987 azo dye Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000010935 stainless steel Substances 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 16
- 241000219000 Populus Species 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000002023 wood Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
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- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000008188 pellet Substances 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 20
- 230000015556 catabolic process Effects 0.000 abstract description 19
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- 239000002245 particle Substances 0.000 abstract description 4
- 238000000053 physical method Methods 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- CQPFMGBJSMSXLP-ZAGWXBKKSA-M Acid orange 7 Chemical group OC1=C(C2=CC=CC=C2C=C1)/N=N/C1=CC=C(C=C1)S(=O)(=O)[O-].[Na+] CQPFMGBJSMSXLP-ZAGWXBKKSA-M 0.000 description 17
- 239000000975 dye Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 238000001994 activation Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 239000012190 activator Substances 0.000 description 5
- 238000009303 advanced oxidation process reaction Methods 0.000 description 5
- 238000007872 degassing Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- -1 aromatic amine compounds Chemical class 0.000 description 3
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- 238000001819 mass spectrum Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 229950000244 sulfanilic acid Drugs 0.000 description 3
- FHMMQQXRSYSWCM-UHFFFAOYSA-N 1-aminonaphthalen-2-ol Chemical compound C1=CC=C2C(N)=C(O)C=CC2=C1 FHMMQQXRSYSWCM-UHFFFAOYSA-N 0.000 description 2
- 229910017135 Fe—O Inorganic materials 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 1
- 229940105324 1,2-naphthoquinone Drugs 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 206010005003 Bladder cancer Diseases 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 208000007097 Urinary Bladder Neoplasms Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
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- 230000006652 catabolic pathway Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
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- 235000019253 formic acid Nutrition 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000004047 hole gas Substances 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 201000005112 urinary bladder cancer Diseases 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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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
- B01J35/60—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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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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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
- C02F2101/38—Organic compounds containing nitrogen
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Abstract
The invention discloses Fe3O4A @ BC nano composite material and a preparation method and application thereof, belonging to the technical field of composite materials. The preparation method comprises the steps of putting natural magnetite and biomass charcoal in a high-energy ball millPreparation of Fe by ball milling3O4@ BC nanocomposites. The mechanochemical method is a simple physical method, has simple process, high efficiency and low cost, and utilizes a ball milling mode to mix the materials and reduce the particle size of the materials to be nano-scale so as to synthesize various metal @ carbon nano-composite catalytic materials. The degradation rate of azo dye AO7 can reach 100% within 2h of reaction of the composite material.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to Fe3O4@ BC nanocomposite and preparation method and application thereof.
Background
Azo dyes are widely used in various industries such as textile, paper making, medicine and food, and are the most widely used dyes at present. Because the application range is wide, a large amount of dye wastewater is generated to pollute the environment. The azo dye wastewater is nontoxic and harmless, but aromatic amine substances can be generated in the degradation process and harm human health, and the aromatic amine compounds have carcinogenicity and are easy to induce bladder cancer and the like after long-term contact. The presence of azo dyes has been found in various environments, the conditions of the traditional physical methods are difficult to control and difficult to recover, the biological methods are time-consuming and the culture process of the strains is complex, so that new technologies need to be developed to degrade the azo dyes.
Advanced Oxidation Processes (AOPs) are widely used for degrading persistent organic pollutants in water environment, and the commonly used metal @ carbon nano-composite catalytic material has a complex preparation method and higher cost, and causes secondary pollution to the environment under the conditions of addition of other chemical reagents and leaching of metals. Therefore, the method for synthesizing the composite catalyst with high efficiency, economy, environmental protection needs to be developed, and the method has important significance for the research and development of the catalyst based on the persulfate advanced oxidation process. The PS-based advanced oxidation process can also generate sulfate radicals (. SO)4-) The oxidation-reduction potential and the half-life period are both higher than that of hydroxyl radical (. OH), and the application prospect is wideAnd 4. preparing the compound. However, PS needs to be activated to function, and currently, the main activation modes include thermal activation, ultraviolet light activation, alkali activation, transition metal activation, and the like.
Transition metals or transition metal oxides have been used as common activators for activating PS, wherein iron-based activators are used most frequently, and the activation principle is mainly based on Fe2+PS is activated to generate highly reactive radicals to degrade contaminants. The research on the tetracycline degradation of the material prepared from pyrite (FeS) shows that the degradation rate can reach 87.4% in 30 min. Magnetite (Fe)3O4) Is a mineral which is widely existed in the environment and is nontoxic, and similar to FeS, magnetite can also be used as Fe2+Activates the PS for contaminant degradation. However, magnetic nanomaterials are very unstable and prone to agglomeration, which may reduce their degradation efficiency and limit their environmental applications
Biomass Carbon (BC) is generally selected as the carbon-based material for preparing nanocomposites due to its abundant porous structure and large specific surface area. The biomass carbon can also activate PS, and the PS can be used as a good electron transport carrier to participate in the activation reaction. It is found that the combination of FeS and biochar can significantly reduce FeS agglomeration and improve trichloroethylene removal rate. To date, the use of magnetite (Fe) has not been reported3O4) And BC to prepare a composite catalytic material as a PS activator to remove azo dyes.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide Fe3O4A preparation method of the @ BC nano composite material. Another technical problem to be solved by the present invention is to provide Fe3O4@ BC nanocomposites. The invention also provides a Fe alloy3O4Application of the @ BC nanocomposite in activating PB to degrade azo dyes.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
fe3O4Preparation method of @ BC nano composite materialPreparing Fe by ball milling natural magnetite and Biomass Carbon (BC) in a high-energy ball mill3O4@ BC nanocomposites.
Said Fe3O4The preparation method of the @ BC nanocomposite comprises the following steps of 1: 1-1: 7 by mass of magnetite and biomass carbon; the ball-material ratio is 8: 1-12: 1, and the ball-material ratio refers to the mass ratio of the mass of the stainless steel ball to the mass of the mixture (the mixture is the mixture of magnetite and biomass charcoal).
Said Fe3O4The preparation method of the @ BC nanocomposite comprises the steps of adding a mixture of stainless steel pellets and magnetite and biomass charcoal into a planetary ball mill, changing the direction of the ball mill every 1-3 hours, and stopping the ball mill for cooling; obtaining Fe after ball milling3O4@ BC nanocomposite; the rotating speed of the ball mill is 100-500 rpm, and the ball milling time is 10-14 h; the stainless steel pellets had diameters of 5mm and 10 mm.
Said Fe3O4The preparation method of the @ BC nanocomposite comprises the following steps of 1:5 mass ratio of magnetite to biomass charcoal; the ball material ratio is 10: 1; the ball mill was run at 300rpm for a ball milling time of 12 h.
Said Fe3O4The preparation method of the @ BC nanocomposite comprises the steps of placing the biomass fiber raw material in a tubular furnace for firing, heating the tubular furnace to 600-800 ℃ at a heating rate of 5-10 ℃/min, keeping the temperature for 3 hours, cooling to room temperature after firing, taking out the biomass fiber raw material, alternately cleaning with KOH and HCl, washing with deionized water to be neutral, placing the biomass fiber raw material in a dryer for drying for 10-12 hours at 60-80 ℃, taking out the biomass fiber raw material, and placing the biomass fiber raw material in the dryer for storage for later use.
Said Fe3O4The preparation method of the @ BC nanocomposite material comprises the step of preparing the biomass fiber raw material, namely poplar wood powder.
Said Fe3O4The preparation method of the @ BC nanocomposite comprises the following steps:
(1) firstly, placing poplar wood powder in a tubular furnace for burning, heating the poplar wood powder to 700 ℃ at a heating rate of 10 ℃/min in the tubular furnace, keeping the temperature for 3h, cooling to room temperature after burning, taking out, alternately cleaning with 1M KOH and 1M HCl, washing with deionized water to be neutral, placing at 80 ℃ for drying for 12h, taking out, and placing in a dryer for storage for later use;
(2) adding a mixture of stainless steel balls, magnetite and biomass charcoal into a planetary ball mill, wherein the diameter of the stainless steel balls is 5mm and 10mm, the ball mill runs at the speed of 300rpm, the ball milling time is 12 hours, and the ball mill changes direction once every 3 hours and stops to cool; obtaining Fe after ball milling3O4@ BC nanocomposite; the mass ratio of the magnetite to the biomass charcoal is 1: 5; the ball-material ratio is 10: 1.
Fe prepared by the method3O4@ BC nanocomposites.
Fe as described above3O4Application of @ BC nano composite material in degrading azo dye by activating PS (persulfate).
Said Fe3O4Application of @ BC nanocomposite in activating PS (persulfate) to degrade azo dye, wherein the azo dye is AO7 (acid orange 7).
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) the mechanochemical method is a simple physical method, has simple process, high efficiency and low cost, and utilizes a ball milling mode to mix the materials and reduce the particle size of the materials to be nano-scale so as to synthesize various metal @ carbon nano-composite catalytic materials.
(2) Fe of the invention3O4Within 2h of reaction of the @ BC nano composite material, the degradation rate of the azo dye AO7 can reach 100%.
Drawings
FIG. 1 is a scanning electron micrograph of different materials;
FIG. 2 is a graph of the distribution of elements for different materials;
FIG. 3 is a graph of FTIR spectra for different materials;
FIG. 4 is a Raman spectrum of different materials;
FIG. 5 is a graph of the degradation effect of different materials on AO 7;
FIG. 6 is a radical scavenger vs. Fe3O4The influence graph of @ BC activated PMS degrading AO 7;
FIG. 7 is Fe3O4Graph of the degradation result of @ BC 5 on AO 7;
FIG. 8 is a mass spectrum of the product of AO7 degradation.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Example 1
Fe3O4The preparation method of the @ BC nanocomposite comprises the following steps:
(1) firstly, placing poplar wood powder in a tubular furnace for burning, heating the poplar wood powder to 700 ℃ at a heating rate of 10 ℃/min in the tubular furnace, keeping the temperature for 3h, cooling to room temperature after burning, taking out, alternately cleaning with 1M KOH and 1M HCl, washing with deionized water to be neutral, placing at 80 ℃ for drying for 12h, taking out, and placing in a dryer for storage for later use;
(2) adding a mixture of 120g of stainless steel balls, 0.6g of magnetite and 0.6g of biomass charcoal into a planetary ball mill, wherein the diameter of the stainless steel balls is 5mm and 10mm, the ball mill runs at the speed of 300rpm, the ball milling time is 12h, and the ball mill changes direction once every 3h and stops to cool for 5 min; obtaining Fe after ball milling3O4@ BC nanocomposite, noted as Fe3O4@BC 1。
Example 2
Fe3O4The preparation method of the @ BC nanocomposite comprises the following steps:
(1) firstly, placing poplar wood powder in a tubular furnace for burning, heating the poplar wood powder to 700 ℃ at a heating rate of 10 ℃/min in the tubular furnace, keeping the temperature for 3h, cooling to room temperature after burning, taking out, alternately cleaning with 1M KOH and 1M HCl, washing with deionized water to be neutral, placing at 80 ℃ for drying for 12h, taking out, and placing in a dryer for storage for later use;
(2) adding a mixture of 120g of stainless steel balls with the diameter of 5mm and 10mm, 0.2g of magnetite and 1.0g of biomass charcoal into a planetary ball mill, operating the ball mill at the speed of 300rpm for 12h, changing the direction of the ball mill every 3h and stopping the ball millCooling for 5 min; obtaining Fe after ball milling3O4@ BC nanocomposite, noted as Fe3O4@BC 5。
Example 3
Fe3O4The preparation method of the @ BC nanocomposite comprises the following steps:
(1) firstly, placing poplar wood powder in a tubular furnace for burning, heating the poplar wood powder to 700 ℃ at a heating rate of 10 ℃/min in the tubular furnace, keeping the temperature for 3h, cooling to room temperature after burning, taking out, alternately cleaning with 1M KOH and 1M HCl, washing with deionized water to be neutral, placing at 80 ℃ for drying for 12h, taking out, and placing in a dryer for storage for later use;
(2) adding a mixture of 120g of stainless steel balls, 0.15g of magnetite and 1.05g of biomass charcoal into a planetary ball mill, wherein the diameter of the stainless steel balls is 5mm and 10mm, the ball mill runs at the speed of 300rpm, the ball milling time is 12h, and the ball mill changes direction once every 3h and stops to cool for 5 min; obtaining Fe after ball milling3O4@ BC nanocomposite, noted as Fe3O4@BC 7。
Magnetite, BC, Fe by projection electron microscope3O4@BC 1、Fe3O4@ BC 5 and Fe3O4The results of the analysis are shown in FIG. 1 at @ BC 7. Measuring and calculating the specific surface area and the pore diameter of the material by a polymolecular layer adsorption formula (BET), putting the dried sample into a sample tube, weighing, degassing the sample, heating to 250 ℃ from 10 ℃, wherein the heating rate is 10 ℃/min, and keeping at 250 ℃ for 8h, the gas used for degassing is liquid nitrogen, and the degassing rate is 2 mmHg/s. And after the degassing is finished and the sample tube is cooled, transferring the sample tube to an analysis station, and selecting a corresponding degassing file for sample analysis. The results are shown in Table 1.
TABLE 1 Fe3O4BET result of @ BC
| SBET(m2/g) | Pore volume(cm3/g) | Pore width(nm) | |
| BC | 198.3218 | 0.103 | 9.13 |
| Fe3O4 | 5.85 | ＜0.001 | / |
| Fe3O4@BC 1 | 92.4341 | 0.070 | 4.46 |
| Fe3O4@BC 5 | 98.0441 | 0.075 | 4.15 |
| Fe3O4@BC 7 | 96.9741 | 0.073 | 4.30 |
FIG. 1 shows magnetite, BC, Fe3O4@BC 1、Fe3O4@ BC 5 and Fe3O4SEM image of @ BC 7. Before ball milling, the structures and sizes of magnetite and biomass charcoal are large. Through ball milling, the material and stainless steel grinding balls generate friction and collision, and the material is broken, welded and deformed. Fe prepared by ball milling3O4@ BC produces a significant change in morphology, and the composite becomes an irregular particulate mass and contains many nanoscale particles, thereby enhancing their reactivity. As can also be seen from FIG. 1, Fe3O4@ BC 5 surface generated defect ratio Fe3O4More than @ BC 1, and the inside or surface of the biomass charcoal is covered with a large amount of Fe3O4The particles are agglomerated, and the surface roughness of the material is increased. As can be seen from FIG. 1(e), although Fe3O4The particles on the surface of the @ BC 7 are aggregated, but excessive biomass charcoal can agglomerate, so that the defects on the surface of the material are reduced, and the specific surface area is reduced (as shown in Table 1).
As can be seen from the energy dispersion spectrogram, the material elements are wide, comprise C, N, O, Si, Cr, Fe, Ni and other elements, and are uniformly distributed (figure 2). Thus, it can be concluded that ball milling promotes a gradual refinement of the particle size reduction and also ensures the heterogeneous combination of magnetite and biomass charcoal, while Fe3O4The material @ BC contains oxides of various metals in addition to iron oxide, for example, Ni element may be present in the form of Ni2+，Ni2+Can promote Fe3+To Fe2+Leading to an increase in the active sites of the reaction, thereby enhancing Fe3O4Catalysis of @ BC.
The molecular structure and functional groups of Biomass Carbon (BC), natural magnetite and mixed ball milled samples of different proportions were determined by FTIR spectroscopy. As shown in FIG. 3, at 3420cm-1The peak of stretching vibration of O-H appears at 1630cm-1The characteristic absorption peak of C ═ O appears at 1083cm-1And the position is a C-O-C asymmetric stretching vibration peak. And the peaks are reduced along with the increase of the biomass charcoal ratio, because higher instantaneous temperature is generated in the ball milling processDehydration of the lignin and cellulose components of the biomass char reduces some of the surface functional groups. Furthermore, at 568cm-1The peaks at (a) are due to the inherent Fe-O/Ni-O stretching, which indicates the formation of Fe-O clusters between the inorganic metal and the organic linker.
FIG. 4 is a Raman spectrum of a sample in the "D band" (1330-1380 cm)-1) And "G band" (1540-1580 cm)-1) Two peaks appear, corresponding to typical raman spectra of amorphous and graphitic carbon, respectively, indicating that graphitic carbon may be produced by pyrolysis during the preparation and ball milling of biomass carbon. The ratio of the D band to the G band (ID/IG) represents the degree of disorder in the structure of the graphitic carbon material and the average size of the sp2 domains. After the biomass charcoal and the magnetite are mixed and ball-milled, the ID/IG of the magnetite and biomass charcoal materials with the ratio of 1:1, 1:5 and 1:7 are respectively 1.09, 1.11 and 1.14, and with the addition of the biomass charcoal, the defects of C atom crystals increase and the graphitization degree increases. According to the SEM results (FIG. 1), internal ferroferric oxide (Fe) was observed as the ball milling reaction proceeded3O4) The nano particles gradually diffuse to the outer layer and are doped in the biomass charcoal. This results in Fe3O4@BC 1、Fe3O4@ BC 5 and Fe3O4More defects and disorganization of the graphitized structure in @ BC 7.
Example 4
To test the application of the composite material of the invention in degrading AO7, BC, magnetite and Fe were performed3O4@BC 1、Fe3O4@BC 5、Fe3O4The @ BC 7 material was separately subjected to the following test experiments: preparing a 250ml conical flask, weighing 50ml of dye with adjusted pH, pouring the dye into the 250ml conical flask, adding the materials, performing ultrasonic dispersion for 1min, then adding PS (single PS set as a control group), placing the whole culture system in a shaking table, operating at 25 ℃ at 180rpm/min, taking a sample every 15 min, and measuring the absorbance of the solution by using an ultraviolet spectrophotometer to obtain the degradation effect of the dye. In the above reaction, the pH of the dye was 3, the concentration of the catalyst was 200mg/L, PS, and the concentration was 200mg/L, AO7, and the concentration was 50 mg/L. The above experiment was repeated three times to obtain an average, and the results are shown in FIG. 5.
As can be seen from FIG. 5, PS alone had little effect on AO7, while Fe3O4The @ BC material has obvious degradation effect on AO7, which proves that the prepared Fe3O4The @ BC material is an effective activator for PS. Comparing magnetite and biomass charcoal with different proportioning ratios, the ratio of magnetite to biomass charcoal is 1:5, namely Fe3O4The material of @ BC 5 has the best degradation effect when used as a catalyst, and is nearly completely degraded after 3 hours. When the mass ratio of magnetite to BC is increased from 1:5 to 1:7, the degradation rate is reduced, which shows that the ratio of magnetite to biomass charcoal has a great influence on the degradation effect of the material, but the biomass charcoal accounts for more and better, and the reason for the phenomenon is probably that the biomass charcoal gradually agglomerates along with the increase of the biomass charcoal amount, so that Fe is reduced3O4The specific surface area of the @ BC material further reduces the reaction rate, so the optimal combination ratio of the magnetite to the biomass charcoal is 1:5 in combination with the experimental phenomenon and the experimental cost.
Fe (II) is due to Fe in the process of PS-based advanced oxidation3O4Reduction and conversion of Fe (III) by direct electron transfer to the surface (formula 1), and then Fe2+Activate S2O8 2Produce SO4-(formula 2). At the same time, electrons are driven from contaminants or H2O is transferred to PS (formula 4) via the active site of BC, further generating SO4-(formula 5). BC, as a catalyst for SR-AOPs, generally has a major mechanism of action, electron conduction, acting as both an adsorbent and a PS activator, and thus, part of the SO4-Can be directly at Fe3O4The active site provided by BC in the @ BC complex is directly oxidized to form OH (formula 6 and formula 7).
To study Fe3O4In the @ BC-PS system SO4-And OH in p-benzoquinone (BQ, quenching O), respectively2-) tert-Butanol (TBA, Special purge SO)4-And. OH), ethanol (EtOH, effective to quench. SO4-And. OH) were subjected to radical quenching experiments. Such asFIG. 6 shows that after 120min of reaction in a reaction system with excess EtOH and excess TBA, the removal efficiency of AO7 decreased from 100% to 73.05% and 95.89%, respectively, the degradation rate decreased significantly, and the degradation rate slowed, indicating SO4-And OH is inhibited during oxidative degradation of AO7,. SO4-OH and OH are involved in the oxidative degradation process, but SO4-Is the primary free radical that degrades AO 7. Adding excessive BQ, reacting for 3h, and then Fe3O4The degradation rate of the @ BC-PS system to AO7 is reduced by 10 percent than that of the system without adding, which indicates that O2 ·-The catalyst also has a certain effect on the degradation of AO7 in a reaction system.
Fe2++e-→Fe3+(formula 1)
Fe2++S2O8 2-→·SO4 -+SO4 2-+Fe3+(formula 2)
Fe3++S2O8 2-→·SO4 -+SO4 2-+Fe2+(formula 3)
2H2O+S2O8 2-→HO2 -+2SO4 2-+3H+(formula 4)
HO2 -+S2O8 2-→·SO4 -+SO4 2-+O2 ·-+3H (formula 5)
·SO4 -+H2O→SO4 2-+3H+OH (formula 6)
·SO4 -+OH-→SO4 2-OH (formula 7)
Example 5
A250 ml Erlenmeyer flask was prepared, 50ml of the pH adjusted dye was weighed into the 250ml Erlenmeyer flask, and Fe was added3O4@ BC 5 composite material, adding PS activation reaction (setting a control group of single PS) after ultrasonic dispersion for 1min, placing the whole culture system in a shaking table at 25 ℃ and 180rpm/miAnd n, running, taking a sample every 15 minutes, and measuring the absorbance of the solution by using an ultraviolet spectrophotometer to obtain the degradation effect of the dye. In the above reaction, the pH of the dye was 3, the catalyst concentration was 400mg/L, PS, the concentration was 400mg/L, AO7, and the concentration was 50 mg/L. The above experiment was repeated three times to obtain an average, and the results are shown in FIG. 7. As can be seen from FIG. 7, Fe was present within 2h of the reaction3O4The removal rate of the @ BC 5 composite material to AO7 can reach 100%, which indicates that the composite material has good application prospect for degrading AO 7.
The degradation products of AO7 were qualitatively determined by liquid phase mass spectrometry (LC-MS). The column temperature is 25 ℃, the sample injection amount: 5 μ L. By using 10mmol/L ammonium acetate in water and acetonitrile (50:50, v/v), at 0.3mL min-1The ion source is an ESI negative ion source, scanning is carried out in a positive ion mode, and the mass spectrum scanning range is as follows: 100-. The detection mode is a multi-reaction monitoring mode; capillary voltage: 2.5kV, ion source temperature: 120 ℃, desolventizing gas temperature: 450 ℃, desolventizing gas flow: 600L/h, taper hole gas flow: 50L/h.
The degradation pathway of AO7 is shown by the following formula, and fig. 8 is a corresponding mass spectrum of the degradation product of AO 7. SO produced by the reaction4-The first attack of the free radicals such as OH and the like is the cleavage of azo bonds in AO7 molecule to produce 1-amino-2-naphthol and 4-aminobenzenesulfonic acid, and the oxidation of 1-amino-2-naphthol by the active free radicals generates fused heterocyclic substances such as coumarin and 1, 2-naphthoquinone. Then, the intermediate products are further oxidized to generate aromatic hydrocarbons such as salicylic acid, the active groups attack C ═ C bonds in salicylic acid molecules to open the rings to generate small-molecular organic acids such as oxalic acid, acetic acid and formic acid, and finally the small-molecular organic acids are mineralized to be CO2And H2And O. In addition, free radicals act on 4-aminobenzenesulfonic acid, the sulfanilic acid is further desulfonated to form hydroquinone, and then the benzoquinone is formed, and nitrogen is mainly converted into N2. Finally, C ═ C bonds of the benzene ring are broken and gradually converted into small molecular substances until the substances are completely mineralized.
Claims (9)
1. Fe3O4Preparation of @ BC nanocompositeThe method is characterized in that natural magnetite and biomass carbon are subjected to ball milling in a high-energy ball mill to prepare Fe3O4@ BC nanocomposites.
2. Fe according to claim 13O4The preparation method of the @ BC nanocomposite is characterized in that the mass ratio of the magnetite to the biomass charcoal is 1: 1-1: 7; the ball-material ratio is 8: 1-12: 1, and the ball-material ratio refers to the mass ratio of the stainless steel balls to the mixture.
3. Fe according to claim 13O4The preparation method of the @ BC nanocomposite is characterized in that a mixture of stainless steel pellets and magnetite and biomass charcoal is added into a planetary ball mill, and the ball mill changes direction once every 1-3 hours and stops to cool; obtaining Fe after ball milling3O4@ BC nanocomposite; the rotating speed of the ball mill is 100-500 rpm, and the ball milling time is 10-14 h; the stainless steel pellets had diameters of 5mm and 10 mm.
4. Fe according to claim 13O4The preparation method of the @ BC nanocomposite is characterized in that the mass ratio of the magnetite to the biomass charcoal is 1: 5; the ball material ratio is 10: 1; the ball mill was run at 300rpm for a ball milling time of 12 h.
5. Fe according to claim 13O4The preparation method of the @ BC nanocomposite is characterized by comprising the steps of placing the biomass fiber raw material in a tubular furnace for firing, heating the tubular furnace to 600-800 ℃ at a heating rate of 5-10 ℃/min, keeping the temperature for 3 hours, cooling the fired material to room temperature, taking the cooled material out, alternately cleaning the material with KOH and HCl, washing the material to be neutral with deionized water, placing the material in a dryer for drying at 60-80 ℃ for 10-12 hours, taking the material out, and storing the material in the dryer for later use.
6. Fe according to claim 13O4A method for preparing a @ BC nanocomposite material, characterized in thatThe biomass fiber raw material is poplar wood powder.
7. Fe according to claim 13O4The preparation method of the @ BC nanocomposite is characterized by comprising the following steps of:
(1) firstly, placing poplar wood powder in a tubular furnace for burning, heating the poplar wood powder to 700 ℃ at a heating rate of 10 ℃/min in the tubular furnace, keeping the temperature for 3h, cooling to room temperature after burning, taking out, alternately cleaning with 1M KOH and 1M HCl, washing with deionized water to be neutral, placing at 80 ℃ for drying for 12h, taking out, and placing in a dryer for storage for later use;
(2) adding a mixture of stainless steel balls, magnetite and biomass charcoal into a planetary ball mill, wherein the diameter of the stainless steel balls is 5mm and 10mm, the ball mill runs at the speed of 300rpm, the ball milling time is 12 hours, and the ball mill changes direction once every 3 hours and stops to cool; obtaining Fe after ball milling3O4@ BC nanocomposite; the mass ratio of the magnetite to the biomass charcoal is 1: 5; the ball-material ratio is 10: 1.
8. Fe prepared by the method of any one of claims 1 to 73O4@ BC nanocomposites.
9. Fe as recited in claim 83O4Application of @ BC nanocomposite in activating PS to degrade azo dyes.
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