AU2021100148A4 - 3D Graphene-Based Nanosized Zero-Valent Iron Material, Preparation Method Thereof and Use Thereof - Google Patents
3D Graphene-Based Nanosized Zero-Valent Iron Material, Preparation Method Thereof and Use Thereof Download PDFInfo
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- AU2021100148A4 AU2021100148A4 AU2021100148A AU2021100148A AU2021100148A4 AU 2021100148 A4 AU2021100148 A4 AU 2021100148A4 AU 2021100148 A AU2021100148 A AU 2021100148A AU 2021100148 A AU2021100148 A AU 2021100148A AU 2021100148 A4 AU2021100148 A4 AU 2021100148A4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 126
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 113
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims abstract description 35
- 229910052742 iron Inorganic materials 0.000 claims abstract description 31
- 239000004964 aerogel Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 32
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000003344 environmental pollutant Substances 0.000 claims description 10
- 231100000719 pollutant Toxicity 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000006731 degradation reaction Methods 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 12
- BULVZWIRKLYCBC-UHFFFAOYSA-N phorate Chemical compound CCOP(=S)(OCC)SCSCC BULVZWIRKLYCBC-UHFFFAOYSA-N 0.000 description 12
- 239000002131 composite material Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- XLNZEKHULJKQBA-UHFFFAOYSA-N terbufos Chemical compound CCOP(=S)(OCC)SCSC(C)(C)C XLNZEKHULJKQBA-UHFFFAOYSA-N 0.000 description 8
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical class NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 7
- -1 biochar Chemical compound 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 235000000396 iron Nutrition 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 4
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 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 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
-
- 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
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Disclosed is a preparation method of a 3D graphene-based nanosized zero-valent iron
material. The method comprises the steps of: step 1. preparing a 3D graphene aerogel; and step
2. loading nanosized zero-valent iron; 2.1. mixing the 3D graphene aerogel with a ferrous or
ferric iron solution in nitrogen atmosphere to obtain a mixed solution A, wherein the mass ratio
of the 3D graphene to the iron is 1: 1-1: 10; 2.2. adding sodium borohydride into the mixed
solution A, allowing to react for 20-40 min, and filtering to obtain a product B, wherein the
molar ratio of iron to sodium borohydride is 1: 1-1: 10; and 2.3. washing the product B with
absolute ethyl alcohol, freeze-drying for 12-36 h to obtain a 3D graphene-based nanosized
zero-valent iron material. This method provides more mild reaction conditions than the
previous one-step hydrothermal synthesis method, and the resulting 3D graphene-based
nanosized zero-valent iron materials are morphologically controllable with high iron loading,
easy to recycle after use, and avoid secondary pollution, which are simple, economical, and
highly operable.
Description
3D Graphene-Based Nanosized Zero-Valent Iron Material, Preparation Method
Thereof and Use Thereof
[01] The present invention relates to the field of functional composite materials, in particular to a 3D graphene-based nanosized zero-valent iron material, a preparation method thereof and a use thereof.
[02] The advanced oxidation technology is based on a series of physical and chemical interactions (including the synergistic effect of oxidant and catalyst) to generate highly active free radicals in the system, which oxidize and decompose refractory organic pollutants into small molecule substances. In contrast to the incomplete reduction technology, the advanced oxidation technology converts organic pollutants into carbon dioxide, water and inorganic substances, or into biodegradable or harmless products. The common oxidation agents mainly include Fenton reagent, potassium permanganate, hydrogen peroxide, persulfate, percarbonate and ozone. Different from other oxidants, persulfate reveals relatively stable properties at room temperature, and is highly operable in the process of pollution remediation. The sulfate radical generated by the activation technology reveals high redox potential, and thus can oxidize and degrade refractory organic matter at wide pH range.
[03] Iron materials represented by zero-valent iron have been used in industrial water treatment or groundwater remediation as important persulfate activation technology due to their characteristics of environmental friendliness, low price, strong oxidation effect and wide range of applications. Among them, the nanosized zero-valent iron has an improved activation effect because of its larger specific surface area, which can make oxidation reaction more efficient. However, the zero-valent iron will passivate on its surface during the catalytic process, reducing the reaction rate, and how to improve the utilization of iron has become one of the main trends of current research. Moreover, the nano-catalysts, especially nanosized zero-valent iron, tend to aggregate and settle in the environment due to their high surface activity and magnetic properties, which reduce their reactivity.
[04] In response to the above problems, some solutions have been proposed by scholars at home and abroad. The nanosized zero-valent iron is mainly immobilized on activated carbon, biochar, silica, bentonite and organic polymer carriers with large specific surface area, strong mechanical properties, adsorption properties and thermal stability to make a loaded nanosized zero-valent iron, which can effectively prevent the agglomeration of nanoparticles and thus improve the reaction activity.
[05] Carbon-based materials can be a good choice for zero-valent iron carriers due to their unique properties. Graphene is a new type of carbon allotrope with two dimensional structure, which is a planar structure with hexagonal honeycomb lattice formed by a single layer of carbon atoms hybridized by sp2 electron orbit and closely stacked, and with great theoretical specific surface area, making graphene a good adsorption material or catalyst carrier. New property is explored from graphene during its functionalization with inorganic materials. The magnetic iron material modified graphene is used to treat pollutants as the most important material, which can remove pollutants efficiently and quickly, and allow them to be recycled by the magnetic separation method. However, in the actual preparation and application process, 7-n stacking interactions and van der Waals forces between two-dimensional graphene sheets always tend to form irreversible agglomerates, resulting in poor dispersion of graphene in the polymer matrix, which greatly limits its intrinsic properties and application potential. Therefore, three-dimensional (3D) porous graphene-based materials (e.g., aerogel and hydrogel) and their preparation methods have been studied and reported successively, and their unique 3D porous-like structure provides high diffusion rate and adsorption rate of pollutants.
[06] The preparation method of graphene/iron-based composites and their use in advanced oxidation technology have been reported. For example, Zhang Yagang et al. invented a graphene/iron-based magnetic composite for activation of hydrogen peroxide for phenol oxidation and removal (preparation method of graphene-loaded magnetic iron-based non-homogeneous Fenton-like catalyst and use thereof [P]. Xinjiang Uygur Autonomous Region: CN106669677A, 2017-05-17). Yang Chunping et al. invented a method for atrazine removal from water through activation of persulfate with nanosized zero-valent iron/graphene complex (method for atrazine removal from water through activation of persulfate with nanosized zero-valent iron/graphene complex [P]. Hunan Province: CN108176400A, 2018-06-19), comprising the steps of: uniformly mixing persulfate and wastewater containing atrazine, adjusting the pH of the solution to 3-9, adding nanosized zero-valent iron/graphene complex, between which the interaction produces strongly oxidizing sulfate radicals and hydroxyl radicals to oxidize and remove atrazine from the aqueous body.
[07] The above two patents have solved the problems that the traditional Fenton catalyst is difficult to recover and produces a large amount of chemical sludge, thus avoiding secondary pollution, and providing a way of thinking for the development of iron-based catalysts suitable for advanced oxidation technology. However, the graphene in the above patents has a two-dimensional structure, which has not solved the problem of its poor dispersion in the matrix of composite materials, and the stability and pH application range of composite materials need to be improved. In addition, the spatial structure of graphene/iron-based composites, the uniformity of distribution and loading of iron-based particulate matter will directly affect the ability of oxidants such as persulfate to remove pollutants.
[08] Graphene oxide (GO) has become a suitable precursor for preparing 3D graphene components by virtue of its high dispersibility in aqueous medium and its functionality, and also provides a carrier with high specific area, high stability and strong conductivity for zero-valent iron and iron oxides. For example, Zhang Hui et al. invented a preparation method of reduced graphene oxide/ferroferric oxide composite hydrogel based on a liquid phase reduction method of ascorbic acid (preparation method of reduced graphene oxide/ferroferric oxide composite wave-absorbing hydrogel with 3D structure [P]. Anhui Province: CN103450843A, 2013-12-18), in which the content of ferroferric oxide was 10%-40%. Chen Wenjin et al. invented a preparation method of a recyclable, 3D graphene macrobody supported nanosized zero-valent iron composite based on an impregnation method combined with a liquid-phase reduction method (3D graphene macrobody supported nanosized zero-valent iron composite and preparation method thereof [P]. Sichuan Province: CN109173989A, 2019-01-11), in which the loading of nanosized zero-valent iron was 10%-30%. Ge Hongshan et al. invented a preparation method of reduced graphene oxide/nanosized ferroferric oxide composite magnetic material by a water/ethylene glycol co-pyrolysis method (preparation method of reduced graphene oxide/nanosized ferroferric oxide composite magnetic adsorbent [P]. Jiangsu Province: CN107081128A, 2017-08-22), in which the material has excellent adsorption performance and magnetism, and is convenient to recycle.
[09] However, the maximum loading of iron-based materials in graphene-based composites prepared by the above patents is only 30%-40% by weight, and there is still much room for improvement. Meanwhile, the application of 3D graphene/iron-based composites in advanced oxidation technology has not been reported. The above defects and shortcomings seriously hinder the application of graphene/zero-valent iron composites in advanced oxidation and need to be addressed urgently.
[010] The present invention aims to provide a 3D graphene-based nanosized zero valent iron material, a preparation method thereof and a use thereof to overcome the deficiencies in the prior art.
[011] To solve the above technical problems, the technical solution of the present invention is as follows:
[012] a preparation method of a 3D graphene-based nanosized zero-valent iron material, includes the steps of:
[013] step 1: preparing a 3D graphene aerogel;
[014] step 2: loading nanosized zero-valent iron;
[015] 2.1 mixing the 3D graphene aerogel with a ferrous or ferric iron solution in nitrogen atmosphere to obtain a mixed solution A, wherein the mass ratio of the 3D graphene to the iron is 1: 1-1: 10;
[016] 2.2 adding sodium borohydride into the mixed solution A, allowing to react for 20-40 min, and filtering to obtain a product B, wherein the molar ratio of iron to sodium borohydride is 1: 1-1: 10;
[017] 2.3 washing the product B with absolute ethyl alcohol, freeze-drying for 12 36 h to obtain a 3D graphene-based nanosized zero-valent iron material.
[018] Preferably, the 3D graphene-based nanosized zero-valent iron material is sealed and stored in nitrogen atmosphere.
[019] Preferably, the molar ratio of iron to sodium borohydride is 1:1-1:5.
[020] Preferably, the ferrous or ferric iron solution is ferrous sulfate heptahydrate solution, ferrous chloride solution or ferric chloride solution.
[021] Preferably, the preparation of the 3D graphene aerogel comprises the steps of:
[022] 1.1 mixing graphite powder and sodium nitrate, adding concentrated sulfuric acid and placing in an ice bath; adding potassium permanganate while stirring to obtain a mixture C, with the mass ratio of graphite powder to sodium nitrate being 2:1; adding 23 mL of concentrated sulfuric acid for every 1 g of graphite powder, with the mass ratio of graphite powder to potassium permanganate being 1:1-1:5; controlling the temperature of the reaction solution below 20 °C, and the reaction time of 1.5-3 h;
[023] 1.2 transferring the mixture C from the ice bath into a water bath at 30 °C to continue the reaction for 30-50 min;
[024] 1.3 after the reaction in step 1.2, placing the mixture C in an oil bath and adding 80-100 mL of deionized water to control the temperature of the reaction solution at 95-100 °C; stirring for 20-40 min, diluting with 400-500 mL of deionized water and then adding 10-50 mL of hydrogen peroxide to obtain a mixture D;
[025] 1.4 centrifuging and washing the mixture D with 5% hydrochloric acid until no white precipitate is detected by barium chloride, and freeze-drying for 12-36 h to obtain graphene oxide.
[026] Preferably, the preparation of the 3D graphene aerogel comprises the steps of:
[027] 1.5 ultrasonically separating graphene oxide obtained in step 1.4 in ultrapure water for 30-120 min, and then mixing with a reducing agent to obtain a mixture E, wherein the mass ratio of the reducing agent to graphene oxide is 1: 1-15: 1;
[028] 1.6 sonicating the mixture E for 30-120 min and heating in a water bath at -100 °C for 30-120 min;
[029] 1.7 obtaining 3D graphene aerogel through washing, filtering and freeze drying of the mixture E treated by step 1.6 for 12-36 h.
[030] Preferably, the reducing agent is sodium borohydride, ascorbic acid or hydrazine hydrate.
[031] Preferably, the mass ratio of the reducing agent to graphene oxide is 5:1 :1.
[032] Preferably, the mass ratio of the reducing agent to graphene oxide is 1:1 :1.
[033] The present invention further discloses a 3D graphene-based nanosized zero-valent iron material.
[034] The present invention further discloses a use of the 3D graphene-based nanosized zero-valent iron material in advanced oxidation technology.
[035] The present invention further discloses a use of the 3D graphene-based nanosized zero-valent iron material in catalytic oxidative degradation of organophosphorus pollutants by persulfate.
[036] Preferably, the molar ratio of iron in the 3D graphene-based nanosized zero valent iron material to persulfate is 1:1-1:20.
[037] Preferably, the catalytic degradation reaction system has a pH value of 1-9.
[038] Preferably, the molar ratio of a loading of the 3D graphene-based nanosized zero-valent iron material to persulfate is 1:0.5-1:10.
[039] Preferably, the reaction time of the catalytic degradation reaction system is 1-10 min.
[040] Compared with the prior art, the advantageous effect of the present invention is as follows:
[041] (1) The preparation method of the present invention has milder reaction conditions than the previous one-step hydrothermal synthesis method, and the prepared 3D graphene-based nanosized zero-valent iron material has a 3D spatial structure, which overcomes the problems of stacking and agglomeration of graphene sheets, and improves the uniformity of distribution, loading and catalytic activity of nanosized zero-valent iron material with a loading of more than 50 wt%.
[042] (2) The 3D graphene-based nanosized zero-valent iron material prepared according to the present invention is highly reactive. Firstly, zero-valent iron reacts with hydrogen ions to form divalent ions that react with persulfate to form trivalent irons. Then, zero-valent irons can react with trivalent irons to form divalent irons, thus continuing to activate persulfate to generate sulfate radicals and hydroxyl radicals, and then further oxidizing and degrading organic phosphorus pollutants. The reaction is terminated until the zero-valent irons are completely consumed. In addition to its own role in activating persulfate, the 3D graphene can improve the effect of electron transfer and enhance the reactivity of the composite material and the removal rate of organic pollutants.
[043] (3) The 3D graphene-based nanosized zero-valent iron material prepared according to the present invention is highly stable and magnetic before and after the reaction, and can be magnetically recycled and reused without secondary pollution.
[044] (4) The 3D graphene-based nanosized zero-valent iron material of the present invention provides a high reaction rate, degrading more than 99.9% of organic pollutants at 10 minutes when combined with advanced oxidation to remove organic pollutants.
[045] Fig. 1 is a scanning electron micrograph (SEM) of the 3D graphene aerogel of Example 1;
[046] Fig. 2 is a scanning electron micrograph (SEM) of the 3D graphene-based nanosized zero-valent iron material according to Example 1;
[047] Fig. 3 is a broken line graph showing the degradation effect of the 3D graphene-based nanosized zero-valent iron material and nanosized zero-valent iron activated sodium persulfate on phorate according to Example 3;
[048] Fig. 4 is a broken line graph showing the degradation effect of the 3D graphene-based nanosized zero-valent iron material activated sodium persulfate on phorate at different pH conditions according to Example 4;
[049] Fig. 5 is a broken line graph showing the catalytic degradation effect of the 3D graphene-based nanosized zero-valent iron material activated sodium persulfate on three organophosphorus mixed pollutants (phorate, terbufos and parathion) according to Example 5.
[050] The present invention may be understood more readily by reference to the following detailed description of the preferred embodiments of the present invention and the examples included herein. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event of a conflict, the definitions in this specification shall prevail. For example, the term "prepared from" as used herein is synonymous with "comprising". The terms "comprising" "including" "having" "containing" or any other variation thereof, as used herein, are intended to cover non exclusive inclusion, such that a composition, step, method, article or device that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, step, method, article or device.
[051] The conjunction "consisting of..." excludes any unspecified element, step or component. If used in a claim, this phrase will make the claim closed so that it does not include materials other than those described, except for conventional impurities associated therewith. When this phrase appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
[052] When an equivalent, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and4 to 5", "1 to 3 and 5", etc. Where arange of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
[053] The singular form includes the plural object of discussion, unless the context clearly indicates otherwise. "Optional" or "any one" means that the matter or event described thereafter may or may not occur, and that the description includes both the circumstances in which the event occurs and the circumstances in which it does not occur.
[054] The approximate terms in the specification and claims are used to modify the quantity, indicating that the present invention is not limited to that specific quantity, but also includes a portion of the modification that is close to that quantity that is acceptable and does not result in a change in the underlying functionality. Accordingly, modifying a numerical value with "approximately", "about", etc. means that the present invention is not limited to that precise value. In some examples, the approximate term may correspond to the precision of the instrument measuring the value. In the specification and claims of this application, the range limitations may be combined and/or interchanged, unless otherwise stated, these ranges include all sub-ranges contained therein.
[055] Furthermore, the indefinite articles "a" and "an" before the elements or components of the present invention are not restrictive as to the number of elements or components required (i.e., the number of occurrences). Thus, "a" and "an" should be read as including one or at least one, and elements or components in the singular form also include the plural form, unless the number stated is clearly intended to refer to the singular form.
[056] Example 1
[057] Mix 2 g of graphite powder and 1 g of NaNO3, add 46 mL of concentrated H2SO4 and place in an ice bath. Add 6 g of KMnO4 while rapidly stirring to obtain a mixture C. KMnO4 must be added to the reaction solution slowly to prevent the temperature of the reaction system from increasing sharply, while the reaction solution was controlled below 20 °C. After 2 h of reaction, transfer the mixture C to a warm water bath at 35 °C for 40 min. Then, add 92 mL of deionized water while stirring. The reaction solution was controlled at about 98 °C. Continue stirring for 30 min, dilute with 440 mL of deionized water, and slowly add a certain amount of H202 for a high temperature reaction. The reaction solution turned golden yellow (10- 50mL of general hydrogen peroxide) to obtain a mixture D. Considering that unreacted concentrated sulfuric acid could generate a lot of heat at the presence of water, deionized water must be slowly added for twice. The reaction solution was 98 °C and could not exceed 100 °C, and the reaction was carried out in an oil bath. The resulting solution, i.e., mixture D, was centrifugally washed with 5% HCl for many times in a centrifuge until no white precipitate was detected by BaCl2. Then, the sample was freeze-dried for 24 h to obtain graphene oxide.
[058] Ultrasonically separate graphene oxide solution (1 g/300 mL) for 1 h, and add sodium borohydride powder (10 g) to obtain a mixture E. Ultrasonicate the mixture E for 1 h, heat in a 95 °C water bath for1 h, and wash with deionized water. Filter and freeze-dry for 24 h to obtain the 3D graphene aerogel.
[059] Place 1g/300mL of 3D graphene solution in a three-neck flask, fill with nitrogen, add 15g of FeSO4 -7H20 (the mass ratio of 3D graphene to iron was 1:3) to the 3D graphene aerogel solution while stirring for 12 h to obtain a mixed solution A. Then place the mixed solution A at room temperature and add 7.9g/5OmL of NaBH4. Allowing to react for 30 min to obtain a product B. Wash the product B three times with anhydrous ethanol and then freeze-dry for 24 h to obtain 3D graphene-based nanosized zero-valent iron materials. Finally, seal and store in nitrogen atmosphere. The product B can be washed by anhydrous ethanol only instead of deionized water in the washing step; otherwise the nanosized zero-valent iron will be oxidized and affect the performance of the final product.
[060] The scanning electron micrographs of the 3D graphene aerogel and the 3D graphene-based nanosized zero-valent iron materials prepared in this example are shown in Figs. 1-2, and the iron content of the prepared materials was 52.77% as determined by inductively coupled atomic emission spectrometry.
[061] Example 2
[062] Mix 2g of graphite powder and Ig of NaNO3, add 46 mL of concentrated H2SO4, and place in an ice bath. Add 8 g of KMnO4 while rapidly stirring to obtain a mixture C. KMnO4 must be added to the reaction solution slowly to prevent the temperature of the reaction system from increasing sharply, while the reaction solution was controlled below 20 °C. After 2 h of reaction, transfer the mixture C to a warm water bath at 35 °C for 45 min. Then, add 92 mL of deionized water while stirring. The reaction solution was controlled at about 98 °C. Continue stirring for 35 min, dilute with 440 mL of deionized water, and slowly add a certain amount of H202 for a high temperature reaction. The reaction solution turned golden yellow to obtain a mixture D. Considering that unreacted concentrated sulfuric acid could generate a lot of heat at the presence of water, deionized water must be slowly added for twice. The reaction solution was 98 °C and could not exceed 100 °C, and the reaction was carried out in an oil bath. The resulting solution, i.e., mixture D, was centrifugally washed with 5% HCl for many times in a centrifuge until no white precipitate was detected by BaC2. Then, the sample was freeze-dried for 30 h to obtain graphene oxide.
[063] Ultrasonically separate graphene oxide solution (1g/300mL) for 1.5 h, and add ascorbic acid powder (20 g) to obtain a mixture E. Ultrasonicate the mixture E for 1.5 h, heat in a 95 °C water bath for1 h, and wash with deionized water. Filter and freeze-dry for 30 h to obtain the 3D graphene aerogel.
[064] Place 1g/300mL of 3D graphene solution in a three-neck flask, fill with nitrogen, add 15g of FeSO4 -7H20 (the mass ratio of 3D graphene to iron was 1:8) to the 3D graphene aerogel solution while stirring for 14 h to obtain a mixed solution A. Then place the mixed solution A at room temperature and add 8.5g/5OmL of NaBH4. Allowing to react for 35 min to obtain a product B. Wash the product B four times with anhydrous ethanol and then freeze-dry for 30 h to obtain 3D graphene-based nanosized zero-valent iron materials. Finally, seal and store in nitrogen atmosphere.
[065] Example 3
[066] To a 40 mL EPA bottle, add 6 mg of 3D graphene-based nanosized zero valent iron material (the mass ratio of 3D graphene to iron was 1:3, and the same mass of nanosized zero-valent iron was used as the control). Then, add an appropriate amount of distilled water, followed by 40 L of phorate having a concentration of 10,000 ppm, and finally 62 L of sodium persulfate solution having a concentration of 800mM, so that the molar ratio of iron to the 3D graphene-based nanosized zero-valent iron material is 1:1. Immediately react in a shaking table, with the oscillation frequency of 150 rpm/min. Take 0.5 mL of each sample in a 2 mL centrifuge tube at 0, 0.5, 1, 1.5, 2, 3, 4, 5, 7 and 10 min after the reaction started, and add 1 mL of hexane immediately for extraction (30 min in the shaking table), followed by 0.7 mL in the injection vial for gas chromatography-mass spectrometry.
[067] The experimental results are shown in Table 1 and Fig. 3, indicating that the reaction of sodium persulfate catalyzed by 3D graphene-based nanosized zero valent iron materials for the removal of phorate basically reached equilibrium (99.94%) at 5 min, and the removal rate and efficiency were significantly better than that of nanosized zero-valent iron materials (79.55%). When the reaction time was 10 min, the reaction of nanosized zero-valent iron also basically reached equilibrium (88.96%), and the removal rate was also lower than that of 3D graphene-based nanosized zero-valent iron material (99.99%).
[068] Table 1 Degradation effects of 3D graphene-based nanosized zero-valent iron materials and nanosized zero-valent iron activated sodium persulfate prepared by the present invention on phorate
[069] Example 4
[070] To a 40 mL EPA bottle, add 6 mg of 3D graphene-based nanosized zero valent iron material (the mass ratio of 3D graphene to iron is 1:3). Then, add an appropriate amount of distilled water and adjust the pH value to 1.0, 3.0, 5.0, 7.0 and 9.0 with 1 M of sulfuric acid or sodium hydroxide, followed by 40 L of phorate having a concentration of 10,000 ppm, and finally 62 L of sodium persulfate solution having a concentration of 800 mM, so that the molar ratio of iron to the 3D graphene-based nanosized zero-valent iron material is 1:1. Immediately react in a shaking table, with the oscillation frequency of 150 rpm/min. Take 0.5 mL of each sample in a 2 mL centrifuge tube at 0, 0.5, 1, 1.5, 2, 3, 4, 5, 7 and 10 min after the reaction started, and add 1 mL of hexane immediately for extraction (30 min in the shaking table), followed by 0.7 mL in the injection vial for gas chromatography-mass spectrometry.
[071] The experimental results are shown in Table 2 and Fig. 4, indicating that the removal rate of phorate by the 3D graphene-based nanosized zero-valent iron materials at pH = 5 basically reached equilibrium (99.98%) when the reaction time was 3 min, which was better than the removal rates at other pH conditions, such as pH = 1 (78.92%), pH = 3 (79.17%), pH = 7 (86.91%), pH = 9 (81.91 %).
[072] Table 2 Degradation effects of 3D graphene-based nanosized zero-valent iron materials and nanosized zero-valent iron activated sodium persulfate prepared by the present invention on phorate at different pH conditions
[073] Example 5
[074] To a 40 mL EPA bottle, add 6 mg of 3D graphene-based nanosized zero valent iron material (the mass ratio of 3D graphene to iron is 1:3). Then, add an appropriate amount of distilled water, followed by 40 L of three organophosphorus mixed pollutants (phorate, terbufos and parathion) having a concentration of 10,000 ppm, and finally 62 L of sodium persulfate solution having a concentration of 800 mM, so that the molar ratio of iron to the 3D graphene-based nanosized zero-valent iron material is 1:1. Immediately react in a shaking table, with the oscillation frequency of 150 rpm/min. Take 0.5 mL of each sample in a 2 mL centrifuge tube at 0, 0.5, 1, 1.5, 2, 3, 4, 5, 7 and 10 min after the reaction started, and add 1 mL of hexane immediately for extraction (30 min in the shaking table), followed by 0.7 mL in the injection vial for gas chromatography-mass spectrometry.
[075] The experimental results are shown in Table 3 and Fig. 5, indicating that the 3D graphene-based nanosized zero-valent iron material revealed the maximum removal rate of phorate, followed by terbufos and finally parathion.
[076] Table 3 Degradation effects of 3D graphene-based nanosized zero-valent iron material activated sodium persulfate on three organophosphorus mixed pollutants (phorate, terbufos and parathion)
[077] To sum up, the present invention combines a liquid-phase reduction chemical method to prepare the 3D reduced graphene oxide aerogel with large specific surface area and uniform and stable structure; and further combines a liquid-phase reduction method to prepare the 3D graphene-based nanosized zero-valent iron materials. This method provides more mild reaction conditions than the previous one step hydrothermal synthesis method, and the resulting 3D graphene-based nanosized zero-valent iron materials are morphologically controllable with high iron loading, easy to recycle after use, and avoid secondary pollution, which are simple, economical, and highly operable.
[078] Although the invention has been described with reference to specific examples, it will be appreciated by those skilled in the art that the invention may be embodied in many other forms, in keeping with the broad principles and the spirit of the invention described herein.
[079] The present invention and the described embodiments specifically include the best method known to the applicant of performing the invention. The present invention and the described preferred embodiments specifically include at least one feature that is industrially applicable
Claims (10)
1. A preparation method of a 3D graphene-based nanosized zero-valent iron material, characterized by comprising the steps of:
step 1: preparing a 3D graphene aerogel;
step 2: loading nanosized zero-valent iron;
2.1 mixing the 3D graphene aerogel with a ferrous or ferric iron solution in nitrogen atmosphere to obtain a mixed solution A, wherein the mass ratio of the 3D graphene to the iron is 1: 1-1: 10;
2.2 adding sodium borohydride into the mixed solution A, allowing to react for 20-40 min, and filtering to obtain a product B, wherein the molar ratio of iron to sodium borohydride is 1: 1-1: 10;
2.3 washing the product B with absolute ethyl alcohol, freeze-drying for 12 36 h to obtain a 3D graphene-based nanosized zero-valent iron material.
2. The preparation method of a 3D graphene-based nanosized zero-valent iron material according to claim 1, characterized in that the 3D graphene-based nanosized zero-valent iron material is sealed and stored in nitrogen atmosphere.
3. The preparation method of a 3D graphene-based nanosized zero-valent iron material according to claim 1, characterized in that the molar ratio of iron to sodium borohydride is 1:1-1:5.
4. The preparation method of a 3D graphene-based nanosized zero-valent iron material according to claim 1, characterized in that the preparation of the 3D graphene aerogel comprises the steps of:
1.1 mixing graphite powder and sodium nitrate, adding concentrated sulfuric acid and placing in an ice bath; adding potassium permanganate while stirring to obtain a mixture C, with the mass ratio of graphite powder to sodium nitrate being 2:1; adding 23 mL of concentrated sulfuric acid for every 1 g of graphite powder, with the mass ratio of graphite powder to potassium permanganate being 1:1-1:5; controlling the temperature of the reaction solution below 20 °C, and the reaction time of 1.5-3 h;
1.2 transferring the mixture C from the ice bath into a water bath at 30-40 °C to continue the reaction for 30-50 min;
1.3 after the reaction in step 1.2, placing the mixture C in an oil bath and adding -100 mL of deionized water to control the temperature of the reaction solution at 95 100 °C; stirring for 20-40 min, diluting with 400-500 mL of deionized water and then adding 10-50 mL of hydrogen peroxide to obtain a mixture D;
1.4 centrifuging and washing the mixture D with 5% hydrochloric acid until no white precipitate is detected by barium chloride, and freeze-drying for 12-36 h to obtain graphene oxide.
5. The preparation method of a 3D graphene-based nanosized zero-valent iron material according to claim 4, characterized in that the preparation of the 3D graphene aerogel comprises the steps of:
1.5 ultrasonically separating graphene oxide obtained in step 1.4 in ultrapure water for 30-120 min, and then mixing with a reducing agent to obtain a mixture E, wherein the mass ratio of the reducing agent to graphene oxide is 1: 1-15: 1;
1.6 sonicating the mixture E for 30-120 min and heating in a water bath at 90 100 °C for 30-120 min; and
1.7 obtaining 3D graphene aerogel through washing, filtering and freeze drying of the mixture E treated by step 1.6 for 12-36 h.
6. A 3D graphene-based nanosized zero-valent iron material prepared by the method according to any one of claims I to 5.
7. A use of the 3D graphene-based nanosized zero-valent iron material according to claim 6 in advanced oxidation technology.
8. A use of the 3D graphene-based nanosized zero-valent iron material according to claim 6 in catalytic oxidative degradation of organophosphorus pollutants by persulfate.
9. The use according to claim 8, characterized in that the molar ratio of iron in the 3D graphene-based nanosized zero-valent iron material to persulfate is 1:1-1:20.
10. The use according to claim 8, characterized in that the catalytic degradation reaction system has a pH value of 1-9.
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| CN115108632A (en) * | 2022-05-27 | 2022-09-27 | 广州大学 | Rapid construction method of aerobic granular sludge culture system |
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| CN113777195B (en) * | 2021-09-09 | 2023-10-31 | 公安部物证鉴定中心 | Analysis method of amphetamine drugs in environmental water sample and special graphene-based three-dimensional macroscopic material and solid phase extraction device thereof |
| CN115108632A (en) * | 2022-05-27 | 2022-09-27 | 广州大学 | Rapid construction method of aerobic granular sludge culture system |
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