CN113304749A - Graphene hollow nanosphere zero-valent iron-loaded nanomaterial and preparation method thereof - Google Patents
Graphene hollow nanosphere zero-valent iron-loaded nanomaterial and preparation method thereof Download PDFInfo
- Publication number
- CN113304749A CN113304749A CN202110427636.4A CN202110427636A CN113304749A CN 113304749 A CN113304749 A CN 113304749A CN 202110427636 A CN202110427636 A CN 202110427636A CN 113304749 A CN113304749 A CN 113304749A
- Authority
- CN
- China
- Prior art keywords
- zero
- valent iron
- sio
- nanospheres
- loaded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002077 nanosphere Substances 0.000 title claims abstract description 166
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 111
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 119
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 62
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 62
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 62
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 62
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000005119 centrifugation Methods 0.000 claims description 40
- 239000006185 dispersion Substances 0.000 claims description 34
- 238000002604 ultrasonography Methods 0.000 claims description 29
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 24
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 22
- 238000001291 vacuum drying Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 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 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 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 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 2
- UMFJAHHVKNCGLG-UHFFFAOYSA-N n-Nitrosodimethylamine Chemical compound CN(C)N=O UMFJAHHVKNCGLG-UHFFFAOYSA-N 0.000 abstract description 81
- 238000006731 degradation reaction Methods 0.000 abstract description 27
- 230000015556 catabolic process Effects 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 10
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 8
- 230000000593 degrading effect Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract 1
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 31
- 239000012425 OXONE® Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003651 drinking water Substances 0.000 description 4
- 235000020188 drinking water Nutrition 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 125000003916 ethylene diamine group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011807 nanoball Substances 0.000 description 2
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- -1 sulfate radical Chemical class 0.000 description 2
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
Images
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/23—
-
- B01J35/40—
-
- B01J35/50—
-
- B01J35/61—
-
- 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
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- 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
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention provides a graphene hollow nanosphere zero-valent iron-loaded nano material and a preparation method thereof. The method comprises the following steps: preparation of SiO2@ GO nanosphere and preparation of SiO2The method comprises the following steps of @ rGO/nZVI nanospheres and preparation of the zero-valent iron-loaded nano material of the graphene hollow nanospheres. The preparation method of the zero-valent iron-loaded graphene hollow nanosphere nano material has a large specific surface area and high electronic conductivity, and is beneficial to exerting the catalytic degradation activity of the zero-valent iron nano material on N-nitrosodimethylamine serving as a disinfection by-product. In addition, the zero-valent iron nano material is loaded on the stable graphene hollow nanospheres, so that the zero-valent iron nano material can be effectively prevented from agglomerating and being corroded in the process of catalyzing and degrading N-nitrosodimethylamine, and the repeatable degradation efficiency of the zero-valent iron loaded nano material of the graphene hollow nanospheres is improved.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a graphene hollow nanosphere zero-valent iron-loaded nano material and a preparation method of the graphene hollow nanosphere zero-valent iron-loaded nano material.
Background
N-Nitrosodimethylamine (NDMA) is a N-nitrosamine which is carcinogenic and mutagenic. Since the first time NDMA was detected as a disinfection by-product in drinking water from Ontario, Canada in 1989, researchers found that nitrosamine-based disinfection by-products, mainly NDMA, were ubiquitous in drinking water plants and sewage treatment plants around the world for over thirty years. NDMA is an emerging disinfection byproduct, which can be generated during chlorine disinfection or chloramine disinfection of drinking water and wastewater, and the detected highest concentration of NDMA in drinking water and wastewater treatment systems can reach 630ng/L and 1000ng/L respectively. At present, the indirect reuse of urban wastewater is receiving more and more attention, and highly treated urban wastewater is increasingly being regarded as a substitute water source for domestic and ecological applications. However, the wastewater from wastewater treatment plants (WWTPs) contains potential trace contaminants, such as NDMA, that may affect the quality of the received water. Therefore, in the advanced wastewater treatment process, the effective removal of trace pollutant residues including NDMA is of great significance.
Because NDMA has the characteristics of high water solubility, semi-volatility and biological accumulation, the traditional wastewater treatment technology, such as air stripping, adsorption and biodegradation, has poor removal effect. Advanced Oxidation Processes (AOPs) are known as an effective NDMA elimination method. Among the AOPs, the most widely used are UV, ozone and fenton reactions. Ultraviolet radiation is effective for NDMA removal. However, the cost of the UV treatment system to achieve acceptable NDMA levels is quite high. In addition, fenton oxidation usually needs ultraviolet rays, visible light irradiation or ultrasonic waves to accelerate the degradation rate, extra energy consumption is needed, namely, a corresponding energy supply link is implanted in a water treatment process, on one hand, light energy hardly and thoroughly acts on a water body, on the other hand, the existing equipment needs to be integrally redesigned and reformed, and the cost is high. Therefore, a catalyst capable of efficiently degrading N-nitrosodimethylamine in water is urgently needed to be developed, and the stable degradation performance and the reusability of the catalyst can be ensured.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a zero-valent iron-loaded graphene hollow nanosphere nanomaterial, and the invention also provides a zero-valent iron-loaded graphene hollow nanosphere nanomaterial prepared based on the preparation method of the zero-valent iron-loaded graphene hollow nanosphere nanomaterial, so as to overcome the defects of low efficiency, high cost, incomplete degradation, additional energy supply and the like of the existing process for degrading a nitrogen-containing disinfection by-product N-nitrosodimethylamine in a water body.
In a first aspect, the invention provides a preparation method of a zero-valent iron-loaded graphene hollow nanosphere nano material, which comprises the following steps:
preparation of SiO2@ GO nanosphere: providing SiO2Nanospheres and graphene oxide, SiO2Mixing the nanospheres and graphene oxide in deionized water, and mixing SiO2Transferring the mixed solution of the nanospheres and the graphene oxide into water bath ultrasound for 6-48 h, centrifuging after the ultrasound is finished, and drying in vacuum to obtain SiO2@ GO nanospheres;
preparation of SiO2@ rGO/nZVI nanospheres: providing nano zero-valent iron and dispersing in deionized water to obtain a first dispersion system, and adding SiO into the first dispersion system2Stirring the @ GO nanospheres and a reducing agent to obtain a second dispersion system, transferring the second dispersion system to water bath ultrasound for 6-48 hours, and centrifuging and vacuum drying after ultrasound to obtain SiO2@ rGO/nZVI nanospheres;
preparing the zero-valent iron-loaded graphene hollow nanosphere nano material: in N2Under the atmosphere, SiO2The @ rGO/nZVI nanospheres are transferred to the condition of 300-400 ℃ for curing treatment for 6-24 h, and then the cured SiO nanospheres are subjected to curing treatment2And (3) transferring the @ rGO/nZVI nanospheres into a silicon oxide etching agent to etch a silicon oxide template, centrifuging, and drying in vacuum to obtain the zero-valent iron-loaded graphene hollow nanosphere nanomaterial.
The preparation method of the graphene hollow nanosphere zero-valent iron-loaded nanomaterial provided by the invention is realized by means of SiO2Preparing the graphene oxide hollow sphere by the template action of the nanosphere, specifically by using SiO2Adsorbing graphene oxide on the surface of the nanosphere to form a graphene oxide shell to obtain SiO2@ GO nanospheres. And doping a zero-valent iron nano material in the graphene oxide shell structure. The graphene oxide sheet structure contains a large number of oxygen-containing functional groups including hydroxyl groups, carboxyl groups, ketone groups, etc., and these oxygen-containing functional groups can adsorb to SiO by van der waals' forces2Surface of nanospheres to form graphite oxideThe olefinic shell, on the other hand, these oxygen-containing functional groups are also capable of adsorbing zero-valent iron nanomaterials by van der waals forces. And reducing the graphene oxide into reduced graphene oxide by using a reducing agent, so as to play a role in stabilizing the graphene lamellar structure, thereby obtaining the composite nano material of the zero-valent iron nano material doped in the reduced graphene oxide lamellar structure. Finally, the graphene oxide hollow nanospheres and the connection between the zero-valent iron nano material and the graphene shell are reduced through high-temperature curing, and SiO inside the graphene oxide hollow nanospheres and the connection between the zero-valent iron nano material and the graphene shell are etched through a silicon oxide etching agent2And (4) carrying out nano ball core to obtain the zero-valent iron loaded nano material of the graphene hollow nano ball.
The zero-valent iron-loaded graphene hollow nanosphere nano material has a large specific surface area and a high electronic conductivity, and contributes to exerting the catalytic degradation activity of the zero-valent iron nano material on a disinfection by-product N-nitrosodimethylamine. In addition, the zero-valent iron nano material is loaded on the stable graphene hollow nanospheres, so that the zero-valent iron nano material can be effectively prevented from agglomerating and being corroded in the process of catalyzing and degrading N-nitrosodimethylamine, and the repeatable degradation efficiency of the zero-valent iron loaded nano material of the graphene hollow nanospheres is improved.
Preferably, the SiO2The preparation method of the nanosphere comprises the following steps: providing an ethanol aqueous solution, ammonia water, a silicon dioxide precursor and a regulator, adding the ammonia water and the regulator into the ethanol aqueous solution, uniformly mixing, adding the silicon dioxide precursor into the ethanol aqueous solution, stirring and mixing at 100-500 rpm for 3-10 h, centrifuging, and drying to obtain SiO2Nanospheres.
Preferably, the concentration of the silicon dioxide precursor in the mixed system is 0.01-0.5 mg/L;
the silicon dioxide precursor is at least one of tetraethyl orthosilicate, tetramethyl orthosilicate and sodium silicate.
Preferably, the regulator is ethylenediamine.
Preferably, in the preparation of SiO2@ GO nanosphere step, the SiO2The mass ratio of the nanospheres to the graphene oxide is 10-1: 1, and the power of the water bath ultrasound is 250 ℃; E-350W。
Preferably, in the preparation of SiO2In the step of @ GO nanospheres, the centrifugal rotating speed is 10000-18000 rpm, the centrifugal time is 10-40 min, and the vacuum drying temperature is 60-80 ℃.
Preferably, in the preparation of SiO2In the step of @ rGO/nZVI nanosphere, the concentration of zero-valent iron in the first dispersion system is 0.2-2 mg/mL, and SiO in the second dispersion system2The concentration of the @ GO nanosphere is 0.5-4 mg/mL, and the concentration of the reducing agent in the second dispersion system is 0.1-1 mg/mL;
the reducing agent is at least one of hydrazine hydrate, ascorbic acid and sodium borohydride.
Preferably, in the preparation of SiO2In the step of @ rGO/nZVI nanosphere, the power of water bath ultrasound is 250-350W, the centrifugal rotating speed is 10000-15000 rpm, the centrifugal time is 10-40 min, and the temperature of vacuum drying is 50-60 ℃.
Preferably, in the step of preparing the graphene hollow nanosphere zero-valent iron-loaded nanomaterial, the silicon oxide etchant is sodium hydroxide or potassium hydroxide, and the concentration of the silicon oxide etchant is 1-4 mol/L.
Preferably, in the step of preparing the graphene hollow nanosphere zero-valent iron-loaded nanomaterial, the centrifugation comprises primary centrifugation and secondary centrifugation;
the primary centrifugation is to contain SiO2Centrifuging the silicon oxide etching agent of the @ rGO/nZVI nanosphere for 10-40 min at 5000-8000 rpm, and collecting primary precipitates;
the secondary centrifugation is as follows: dispersing the precipitate in deionized water to obtain an rGO/nZVI aqueous dispersion, centrifuging the rGO/nZVI aqueous dispersion at 12000-18000 rpm for 20-40 min, and collecting secondary precipitate to obtain the graphene hollow nanosphere zero-valent iron-loaded nanomaterial.
In a second aspect, the invention further provides a zero-valent iron-loaded graphene hollow nanosphere nanomaterial, which is prepared by adopting the preparation method of the zero-valent iron-loaded graphene hollow nanosphere nanomaterial of any one of the first aspects.
The zero-valent iron loaded nano material of the graphene hollow nanosphere comprises the graphene hollow nanosphere and a zero-valent iron nano material loaded on the graphene hollow nanosphere. The graphene hollow nanosphere zero-valent iron-loaded nanomaterial disclosed by the invention can efficiently catalyze Potassium Monopersulfate (PMS) to generate sulfate radical (SO) free radical by virtue of the catalytic activity of zero-valent iron4 -). The applicant discovers that OH and SO formed in the rGO/nZVI nano material/PMS system through discussing the degradation mechanism of the rGO/nZVI nano material/PMS system4 -Plays a key role in the oxidative degradation of the difficultly degradable disinfection by-product N-nitrosodimethylamine through OH and SO in the form of active free radicals4 -The combined action on N-nitrosodimethylamine promotes the high-efficiency degradation of N-nitrosodimethylamine, and the recycling efficiency is high.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
In order to more clearly illustrate the contents of the present invention, a detailed description thereof will be given below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a TEM characterization result of a zero-valent iron-loaded graphene hollow nanosphere nanomaterial prepared in example 3 of the present invention;
FIG. 2 is a graph showing the NDMA degradation effect of the present invention;
FIG. 3 is a graph showing the degradation stability of NDMA according to the present invention.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
In a first aspect, the invention provides a preparation method of a zero-valent iron-loaded graphene hollow nanosphere nano material, which comprises the following steps:
preparation of SiO2@ GO nanosphere:providing SiO2Nanospheres and graphene oxide, SiO2Mixing the nanospheres and graphene oxide in deionized water, and mixing SiO2Transferring the mixed solution of the nanospheres and the graphene oxide into water bath ultrasound for 6-48 h, centrifuging after the ultrasound is finished, and drying in vacuum to obtain SiO2@ GO nanospheres;
preparation of SiO2@ rGO/nZVI nanospheres: providing nano zero-valent iron and dispersing in deionized water to obtain a first dispersion system, and adding SiO into the first dispersion system2Stirring the @ GO nanospheres and a reducing agent to obtain a second dispersion system, transferring the second dispersion system to water bath ultrasound for 6-48 hours, and centrifuging and vacuum drying after ultrasound to obtain SiO2@ rGO/nZVI nanospheres;
preparing the zero-valent iron-loaded graphene hollow nanosphere nano material: in N2Under the atmosphere, SiO2The @ rGO/nZVI nanospheres are transferred to the condition of 300-400 ℃ for curing treatment for 6-24 h, and then the cured SiO nanospheres are subjected to curing treatment2And (3) transferring the @ rGO/nZVI nanospheres into a silicon oxide etching agent to etch a silicon oxide template, centrifuging, and drying in vacuum to obtain the zero-valent iron-loaded graphene hollow nanosphere nanomaterial.
As a preferred embodiment, the SiO2The preparation method of the nanosphere comprises the following steps: providing an ethanol aqueous solution, ammonia water, a silicon dioxide precursor and a regulator, adding the ammonia water and the regulator into the ethanol aqueous solution, uniformly mixing, adding the silicon dioxide precursor into the ethanol aqueous solution, stirring and mixing at 100-500 rpm for 3-10 h, centrifuging, and drying to obtain SiO2Nanospheres. Improvement by addition of no surfactant
Method for synthesizing SiO2Nanospheres, both to reduce SiO2The synthesis cost of the nanospheres is reduced, and SiO is reduced2The difficulty of the synthesis process of the nanospheres is improved, and the SiO is improved2The stability of the synthesis of the nanospheres also ensures the safety of the subsequently prepared graphene hollow nanosphere zero-valent iron-loaded nanomaterial applied to the degradation of the water disinfection byproducts.
In a preferred embodiment, the concentration of the silicon dioxide precursor in the mixed system is 0.01-0.5 mg/L;
the silicon dioxide precursor is at least one of tetraethyl orthosilicate, tetramethyl orthosilicate and sodium silicate. The specific concentration may be 0.01mg/L, 0.02mg/L, 0.05mg/L, 0.1mg/L, 0.2mg/L, 0.3mg/L or 0.5 mg/L. The concentration of the silicon dioxide precursor is improved, and the synthesized SiO can be improved2The diameter of the nanosphere is adjusted, and the size of the zero-valent iron-loaded nanomaterial of the subsequent graphene hollow nanosphere is further adjusted.
As a preferred embodiment, the modulator is ethylenediamine. The ethylene diamine regulator can regulate SiO2The synthesis progress and the diameter of the nanospheres, and then the SiO with the size meeting the requirement is obtained2Nanospheres.
As a preferred embodiment, in the preparation of SiO2@ GO nanosphere step, the SiO2The mass ratio of the nanospheres to the graphene oxide is 10-1: 1, and the power of the water bath ultrasound is 250-350W. SiO 22The dosage ratio of the nanospheres and the graphene oxide can be regulated and controlled by regulating and controlling SiO2The thickness of the graphene oxide adsorbed on the surface of the nano-spheres is further controlled, and the thickness of the zero-valent iron loaded nano-material of the graphene hollow nano-spheres is further controlled. In a specific embodiment, SiO2The mass ratio of the nanospheres to graphene oxide may be 10:1, 8:1, 5:1, 2:1, or 1: 1.
As a preferred embodiment, in the preparation of SiO2In the step of @ GO nanospheres, the centrifugal rotating speed is 10000-18000 rpm, the centrifugal time is 10-40 min, and the vacuum drying temperature is 60-80 ℃. Collecting the precipitate by means of a centrifugation step, thereby precipitating the SiO2@ GO nanospheres are separated from graphene oxide in the supernatant, and SiO is dried through a drying step2@ GO nanospheres. The specific centrifugation parameter can be 10000rpm centrifugation for 40min, or 12000rpm centrifugation for 30min, or 15000rpm centrifugation for 20min, or 18000rpm centrifugation for 10 min. The vacuum drying may be 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C or 80 deg.C.
As a preferred embodiment, in the preparation of SiO2@rGO/nZVIn the step of nanosphere I, the concentration of zero-valent iron in the first dispersion system is 0.2-2 mg/mL, and SiO in the second dispersion system2The concentration of the @ GO nanosphere is 0.5-4 mg/mL. Regulating and controlling the concentration of zero-valent iron and SiO2The concentration of the @ GO nanosphere can control the doping amount of the zero-valent iron nanomaterial, so that the zero-valent iron nanomaterial is prevented from being doped too little to reduce the catalytic activity of the zero-valent iron loaded nanomaterial of the graphene hollow nanosphere, and the zero-valent iron nanomaterial is also prevented from being doped too much to reduce the specific surface area of the zero-valent iron loaded nanomaterial of the graphene hollow nanosphere.
In a preferred embodiment, the concentration of the reducing agent in the second dispersion system is 0.1 to 1mg/mL, and the reducing agent is at least one of hydrazine hydrate, ascorbic acid and sodium borohydride. By means of the reducing agent, GO can be effectively reduced into rGO, and the structure of the graphene hollow sphere is stabilized, and meanwhile, the connection between the zero-valent iron nano material and the graphene hollow sphere can also be stabilized.
As a preferred embodiment, in the preparation of SiO2In the step of @ rGO/nZVI nanosphere, the power of water bath ultrasound is 250-350W, the centrifugal rotating speed is 10000-15000 rpm, the centrifugal time is 10-40 min, and the temperature of vacuum drying is 50-60 ℃. By means of water bath ultrasound, SiO can be guaranteed2The @ GO nanospheres and the nano zero-valent iron are fully dispersed, so that the nano zero-valent iron is promoted to be uniformly doped into SiO2@ GO nanosphere surface. The centrifugation and collection process enables the purification of the SiO produced2The @ rGO/nZVI nanosphere is convenient for the subsequent preparation of the zero-valent iron-loaded nanomaterial of the graphene hollow nanosphere. Specifically, the ultrasonic power may be 250W, 280W, 300W, 320W, or 350W. The specific centrifugation parameter can be 10000rpm centrifugation for 40min, or 12000rpm centrifugation for 30min, or 13000rpm centrifugation for 20min, or 15000rpm centrifugation for 10 min.
In a preferred embodiment, in the step of preparing the graphene hollow nanosphere zero-valent iron-loaded nanomaterial, the silicon oxide etchant is sodium hydroxide or potassium hydroxide, and the concentration of the silicon oxide etchant is 1-4 mol/L. Etching of internal SiO by a silicon oxide etchant2Nano-sphere core to obtain grapheneThe hollow nanospheres are loaded with the zero-valent iron nano material, so that the zero-valent iron nano material is completely loaded on the graphene hollow nanospheres, and the catalytic degradation activity and stability of the graphene hollow nanospheres are improved. Specifically, the concentration of the silicon oxide etchant may be 1mol/L, 2mol/L, 3mol/L, or 4 mol/L.
As a preferred embodiment, in the step of preparing the graphene hollow nanosphere zero-valent iron-loaded nanomaterial, the centrifugation includes primary centrifugation and secondary centrifugation;
the primary centrifugation is to contain SiO2Centrifuging the silicon oxide etching agent of the @ rGO/nZVI nanosphere for 10-40 min at 5000-8000 rpm, and collecting primary precipitates;
the secondary centrifugation is as follows: dispersing the precipitate in deionized water to obtain an rGO/nZVI aqueous dispersion, centrifuging the rGO/nZVI aqueous dispersion at 12000-18000 rpm for 20-40 min, and collecting secondary precipitate to obtain the graphene hollow nanosphere zero-valent iron-loaded nanomaterial. The precipitation is collected through primary centrifugation, so that the unreacted zero-valent iron nano material, the reduced graphene oxide, the etching agent and the silicate can be effectively removed, and the purpose of concentrating the graphene hollow nanosphere zero-valent iron-loaded nano material is realized. Collecting the precipitate by secondary centrifugation can further remove the residual etchant as well as the silicate. Specifically, the parameter of the primary centrifugation can be 5000rpm centrifugation for 40min, or 6000rpm centrifugation for 60min, or 8000rpm centrifugation for 10 min. The parameters of the secondary centrifugation may be 12000rpm for 40min, or 15000rpm for 30min, or 18000rpm for 20 min.
In a second aspect, the invention further provides a zero-valent iron-loaded graphene hollow nanosphere nanomaterial, which is prepared by adopting the preparation method of the zero-valent iron-loaded graphene hollow nanosphere nanomaterial of any one of the first aspects.
The following describes in detail a method for preparing a zero-valent iron-loaded graphene hollow nanosphere nanomaterial and the prepared zero-valent iron-loaded graphene hollow nanosphere nanomaterial by using specific examples.
(1) Preparation of SiO2@ GO nanosphere: providing SiO2Nanospheres and graphene oxide, SiO2Mixing the nanospheres and graphene oxide in deionized water, and mixing SiO2Transferring the mixed solution of the nanospheres and the graphene oxide into water bath ultrasound for ultrasound, centrifuging and drying in vacuum after ultrasound is finished to obtain SiO2@ GO nanospheres. Wherein, SiO in deionized water2The concentrations of nanospheres and Graphene Oxide (GO), the power of the water bath ultrasound, the time of the water bath ultrasound, the centrifugal speed, the centrifugal time, and the vacuum drying temperature are shown in table 1.
TABLE 1 preparation of SiO2Parameter table in @ GO nanosphere process
(2) Preparation of SiO2@ rGO/nZVI nanospheres: providing nano zero-valent iron and dispersing in deionized water to obtain a first dispersion system, and adding SiO into the first dispersion system2Stirring the @ GO nanospheres and a reducing agent to obtain a second dispersion system, transferring the second dispersion system into water bath ultrasound for ultrasound, and centrifuging and vacuum drying after ultrasound to obtain SiO2@ rGO/nZVI nanospheres. Wherein the concentration of zero-valent iron in the first dispersion and SiO in the second dispersion2The concentration of the @ GO nanosphere, the concentration of the reducing agent in the second dispersion system, the power of the water bath ultrasound, the time of the water bath ultrasound, the centrifugal speed, the centrifugal time and the vacuum drying temperature are shown in Table 2.
TABLE 2 preparation of SiO2Parameter table in @ rGO/nZVI nanosphere process
(3) Preparing the zero-valent iron-loaded graphene hollow nanosphere nano material: in N2Under the atmosphere, SiO2The @ rGO/nZVI nanospheres are transferred to the condition of 300-400 ℃ for curing treatment, and then the curing treatment is carried outSiO of (2)2And transferring the @ rGO/nZVI nanospheres to a silicon oxide etching agent to etch a silicon oxide template, carrying out primary centrifugation on the reacted mixed system, collecting precipitates, dispersing in deionized water, carrying out secondary centrifugation, collecting secondary precipitates, and carrying out vacuum drying to obtain the zero-valent iron-loaded graphene hollow nanosphere nanomaterial. Wherein the curing temperature and time, the type of silicon oxide etchant, the silicon oxide etchant concentration, the primary centrifugation rate, the primary centrifugation time, the secondary centrifugation rate, the secondary centrifugation time, and the vacuum drying temperature are shown in Table 3.
Table 3 parameter table in the process of preparing graphene hollow nanosphere zero-valent iron-loaded nanomaterial
Effect example 1: characterization results
The graphene hollow nanosphere zero-valent iron-loaded nanomaterial prepared in example 3 is characterized by TEM. The characterization result is shown in fig. 1, the prepared graphene hollow nanosphere zero-valent iron-loaded nanomaterial is spherical, and the diameter range is 150-200 nm.
Effect example 2: NDMA degradation Effect test
NDMA degradation experiments were performed in 500ml Erlenmeyer flasks and the degradation method was as follows: first, zero-valent iron nanomaterial (nZVl group) was added to make its concentration 56 mg/L; a second group, PMS was added so that the concentration thereof became 0.5mmol/L (PMS group); in the third group, a zero-valent iron nano material and PMS (an nZVl + PMS group) are added, so that the concentration of the zero-valent iron nano material is 56mg/L, and the concentration of the PMS is 0.5 mmol/L; fourthly, adding the zero-valent iron-loaded nano material of the graphene hollow nanospheres prepared in the embodiment 3 and PMS (rGO/nZVl-3+ PMS group) so that the concentration of rGO/nZVl-3 is 78mg/L and the concentration of PMS is 0.5 mmol/L; and in the fifth group, the zero-valent iron-loaded nanomaterial of the graphene hollow nanospheres prepared in the example 4 and PMS (rGO/nZVl-4+ PMS group) are added, so that the concentration of rGO/nZVl-4 is 78mg/L and the concentration of PMS is 0.5 mmol/L. The volume of NDMA solution in each group was 250ml, and after adding catalyst and PMS, the flask was capped and placed on a rotary shaker under dark conditions (temperature 25 ℃, speed 200 rpm). The NDMA solution had an initial concentration of 0.5mg/mL and an initial pH of 7. 1ml of water sample was taken from the flask at different sampling times and methanol was added to stop the radical mediated reaction, after 0.22 μm filtration for NDMA analysis. The NDMA concentration was quantitatively determined by HPLC, using a C18 column (250 mm. times.4.6 mm, filler diameter 5 μm, Supelco), a methanol/water (10/90) mobile phase volume ratio, a total flow rate of 1mL/min, an ultraviolet detection wavelength of 228nm, and a sample introduction of 20 μ L.
The NDMA measurement results are shown in FIG. 2 (in five broken lines, 60min corresponds to an nZVI group, a PMS group, an nZVI/PMS group, an rGO/nZVl-4+ PMS group and an rGO/nZVl-3+ PMS group from top to bottom in sequence), when PMS is used alone, 4% of NDMA is degraded within 60 minutes, when nZVI is used alone, the NDMA is not degraded, and when nZVI/PMS is used alone, NDMA is completely removed within 60 minutes. Compared with the nZVl + PMS group, the graphene hollow nanosphere zero-valent iron-loaded nanomaterial prepared in example 3 (rGO/nZVl-3) and the graphene hollow nanosphere zero-valent iron-loaded nanomaterial prepared in example 4 (rGO/nZVl-4) are combined with PMS to degrade NDMA, NDMA can be almost completely removed within 45min, and the degradation efficiency is higher.
Effect example 3: NDMA degradation stability test
Referring to the above effect example 2, the NDMA degradation experiment was repeated 5 times for the aforementioned nZVl + PMS group, rGO/nZVl-3+ PMS group, and rGO/nZVl-4+ PMS group, and the change in the concentration of NDMA during the fifth NDMA degradation was detected, as shown in fig. 3. Compared with the 1 st NDMA degradation process, in the 5 th repeated NDMA degradation process, the catalytic degradation efficiency of the nZVl + PMS group is obviously reduced, although the catalytic degradation efficiency of the rGO/nZVl-3+ PMS group and the catalytic degradation efficiency of the rGO/nZVl-4+ PMS group are also reduced to a certain degree, the reduction range of the catalytic degradation activity is obviously smaller compared with the nZVl + PMS group, and the nano material of the graphene hollow nanosphere loaded with zero-valent iron is shown to have better stability in the repeated NDMA catalytic degradation process.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a zero-valent iron-loaded graphene hollow nanosphere nano material is characterized by comprising the following steps:
preparation of SiO2@ GO nanosphere: providing SiO2Nanospheres and graphene oxide, SiO2Mixing the nanospheres and graphene oxide in deionized water, and mixing SiO2Transferring the mixed solution of the nanospheres and the graphene oxide into water bath ultrasound for 6-48 h, centrifuging after the ultrasound is finished, and drying in vacuum to obtain SiO2@ GO nanospheres;
preparation of SiO2@ rGO/nZVI nanospheres: providing nano zero-valent iron and dispersing in deionized water to obtain a first dispersion system, and adding SiO into the first dispersion system2Stirring the @ GO nanospheres and a reducing agent to obtain a second dispersion system, transferring the second dispersion system to water bath ultrasound for 6-48 hours, and centrifuging and vacuum drying after ultrasound to obtain SiO2@ rGO/nZVI nanospheres;
preparing the zero-valent iron-loaded graphene hollow nanosphere nano material: in N2Under the atmosphere, SiO2The @ rGO/nZVI nanospheres are transferred to the condition of 300-400 ℃ for curing treatment for 6-24 h, and then the cured SiO nanospheres are subjected to curing treatment2And (3) transferring the @ rGO/nZVI nanospheres into a silicon oxide etching agent to etch a silicon oxide template, centrifuging, and drying in vacuum to obtain the zero-valent iron-loaded graphene hollow nanosphere nanomaterial.
2. The method for preparing zero-valent iron-loaded nanomaterial of graphene hollow nanospheres according to claim 1, wherein the SiO is2The preparation method of the nanosphere comprises the following steps: providing ethanol water solution, ammonia water, silicon dioxide precursor and regulator, adding the ammonia water and the regulator into the ethanol water solutionAdding and mixing the solution, adding a silicon dioxide precursor into the ethanol aqueous solution, stirring and mixing the solution at 100-500 rpm for 3-10 h, centrifuging and drying to obtain SiO2Nanospheres.
3. The preparation method of the zero-valent iron-loaded nano-material of the graphene hollow nanospheres of claim 2, wherein the concentration of the silicon dioxide precursor in the mixed system is 0.01-0.5 mg/L;
the silicon dioxide precursor is at least one of tetraethyl orthosilicate, tetramethyl orthosilicate and sodium silicate.
4. The method for preparing the zero-valent iron-loaded nanomaterial of graphene hollow nanospheres as claimed in claim 1, wherein the method is used for preparing SiO2@ GO nanosphere step, the SiO2The mass ratio of the nanospheres to the graphene oxide is 10-1: 1, and the power of the water bath ultrasound is 250-350W.
5. The method for preparing the zero-valent iron-loaded nanomaterial of graphene hollow nanospheres as claimed in claim 1, wherein the method is used for preparing SiO2In the step of @ GO nanospheres, the centrifugal rotating speed is 10000-18000 rpm, the centrifugal time is 10-40 min, and the vacuum drying temperature is 60-80 ℃.
6. The method for preparing the zero-valent iron-loaded nanomaterial of graphene hollow nanospheres as claimed in claim 1, wherein the method is used for preparing SiO2In the step of @ rGO/nZVI nanosphere, the concentration of zero-valent iron in the first dispersion system is 0.2-2 mg/mL, and SiO in the second dispersion system2The concentration of the @ GO nanosphere is 0.5-4 mg/mL, and the concentration of the reducing agent in the second dispersion system is 0.1-1 mg/mL;
the reducing agent is at least one of hydrazine hydrate, ascorbic acid and sodium borohydride.
7. The graphene hollow nanosphere zero-valent iron-loaded nanomaterial of claim 6Is characterized in that in the preparation of SiO2In the step of @ rGO/nZVI nanosphere, the power of water bath ultrasound is 250-350W, the centrifugal rotating speed is 10000-15000 rpm, the centrifugal time is 10-40 min, and the temperature of vacuum drying is 50-60 ℃.
8. The method for preparing the zero-valent iron-loaded graphene hollow nanosphere nanomaterial according to claim 1, wherein in the step of preparing the zero-valent iron-loaded graphene hollow nanosphere nanomaterial, the silicon oxide etchant is sodium hydroxide or potassium hydroxide, and the concentration of the silicon oxide etchant is 1-4 mol/L.
9. The method for preparing the zero-valent iron-loaded nanomaterial of graphene hollow nanospheres according to claim 8, wherein in the step of preparing the zero-valent iron-loaded nanomaterial of graphene hollow nanospheres, the centrifugation comprises primary centrifugation and secondary centrifugation;
the primary centrifugation is to contain SiO2Centrifuging the silicon oxide etching agent of the @ rGO/nZVI nanosphere for 10-40 min at 5000-8000 rpm, and collecting primary precipitates;
the secondary centrifugation is as follows: dispersing the precipitate in deionized water to obtain an rGO/nZVI aqueous dispersion, centrifuging the rGO/nZVI aqueous dispersion at 12000-18000 rpm for 20-40 min, and collecting secondary precipitate to obtain the graphene hollow nanosphere zero-valent iron-loaded nanomaterial.
10. A zero-valent iron-loaded graphene hollow nanosphere nanomaterial characterized by being prepared by the preparation method of the zero-valent iron-loaded graphene hollow nanosphere nanomaterial of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110427636.4A CN113304749A (en) | 2021-04-21 | 2021-04-21 | Graphene hollow nanosphere zero-valent iron-loaded nanomaterial and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110427636.4A CN113304749A (en) | 2021-04-21 | 2021-04-21 | Graphene hollow nanosphere zero-valent iron-loaded nanomaterial and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113304749A true CN113304749A (en) | 2021-08-27 |
Family
ID=77372544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110427636.4A Pending CN113304749A (en) | 2021-04-21 | 2021-04-21 | Graphene hollow nanosphere zero-valent iron-loaded nanomaterial and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113304749A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105056929A (en) * | 2015-07-20 | 2015-11-18 | 重庆文理学院 | Graphene/titanium dioxide composite adopting hollow microspherical structure and preparation method of composite |
| CN105944667A (en) * | 2016-05-09 | 2016-09-21 | 吉林大学 | Graphene oxide loaded nano-iron material with magnetic separation characteristics in underground medium and preparation method thereof |
| US20170369333A1 (en) * | 2016-06-23 | 2017-12-28 | Southern Methodist University | Graphene Oxide/Magnesium Oxide Nanocomposites as Superior Sorbents for Methylene Blue Removal from Aqueous Solutions |
| CN108176400A (en) * | 2017-12-20 | 2018-06-19 | 湖南大学 | The method of Atrazine in a kind of nano zero valence iron/graphene complex activation persulfate removal water body |
| CN108545721A (en) * | 2018-05-18 | 2018-09-18 | 南京师范大学 | The preparation method and its resulting materials of a kind of three-dimensional grapheme hollow ball of high stable state and application |
| CN108584923A (en) * | 2018-05-03 | 2018-09-28 | *** | A kind of preparation method of ultra-thin shell graphene hollow ball |
| CN110841639A (en) * | 2019-11-21 | 2020-02-28 | 南开大学 | Three-dimensional graphene-based nano zero-valent iron material and preparation method and application thereof |
-
2021
- 2021-04-21 CN CN202110427636.4A patent/CN113304749A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105056929A (en) * | 2015-07-20 | 2015-11-18 | 重庆文理学院 | Graphene/titanium dioxide composite adopting hollow microspherical structure and preparation method of composite |
| CN105944667A (en) * | 2016-05-09 | 2016-09-21 | 吉林大学 | Graphene oxide loaded nano-iron material with magnetic separation characteristics in underground medium and preparation method thereof |
| US20170369333A1 (en) * | 2016-06-23 | 2017-12-28 | Southern Methodist University | Graphene Oxide/Magnesium Oxide Nanocomposites as Superior Sorbents for Methylene Blue Removal from Aqueous Solutions |
| CN108176400A (en) * | 2017-12-20 | 2018-06-19 | 湖南大学 | The method of Atrazine in a kind of nano zero valence iron/graphene complex activation persulfate removal water body |
| CN108584923A (en) * | 2018-05-03 | 2018-09-28 | *** | A kind of preparation method of ultra-thin shell graphene hollow ball |
| CN108545721A (en) * | 2018-05-18 | 2018-09-18 | 南京师范大学 | The preparation method and its resulting materials of a kind of three-dimensional grapheme hollow ball of high stable state and application |
| CN110841639A (en) * | 2019-11-21 | 2020-02-28 | 南开大学 | Three-dimensional graphene-based nano zero-valent iron material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 杨娟等: "纳米零价铁去除水中微量N-亚硝基二甲胺的研究", 《中国环境科学》 * |
| 陈砚田等: "还原氧化石墨烯负载零价铁的合成及对TNT废水处理", 《高等学校化学学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Oxygen vacancies-enriched Cu/Co bimetallic oxides catalysts for high-efficiency peroxymonosulfate activation to degrade TC: Insight into the increase of Cu+ triggered by Co doping | |
| Zhang et al. | Photocatalytic removal of chromium (VI) and sulfite using transition metal (Cu, Fe, Zn) doped TiO2 driven by visible light: Feasibility, mechanism and kinetics | |
| Xiang et al. | Nanoscale zero-valent iron/cobalt@ mesoporous hydrated silica core–shell particles as a highly active heterogeneous Fenton catalyst for the degradation of tetrabromobisphenol A | |
| US11713256B2 (en) | Composite material for water treatment | |
| Li et al. | N, P co-doped core/shell porous carbon as a highly efficient peroxymonosulfate activator for phenol degradation | |
| Liu et al. | Catalytic activation of O2 by Al0-CNTs-Cu2O composite for Fenton-like degradation of sulfamerazine antibiotic at wide pH range | |
| CN108786893B (en) | Copper-doped carbon nitrogen polymer multiphase Fenton catalyst and synthesis and application thereof | |
| Wang et al. | Selective reduction of nitrate into nitrogen at neutral pH range by iron/copper bimetal coupled with formate/ferric ion and ultraviolet radiation | |
| de Sousa et al. | Environmental remediation processes by zero valence copper: reaction mechanisms | |
| CN112827511A (en) | Cyclodextrin modified magnetic CuO-Fe3O4-biochar heterogeneous nano-catalyst and method for repairing organic pollution by using same | |
| CN111790386A (en) | Method for preparing catalyst by utilizing coagulated sludge of waterworks and application | |
| CN111825168B (en) | Copper-modified carbon fiber electrode and preparation method and application thereof | |
| Zhou et al. | Efficient removal of roxarsone and emerging organic contaminants by a solar light-driven in-situ Fenton system | |
| Liang et al. | Activation of persulfate by mesoporous silica spheres-doping CuO for bisphenol A removal | |
| Liu et al. | Emerging investigator series: 3D graphene anchored zerovalent Fe/Cu aerogel activating persulfate for efficiently 2, 4 dichlorophenol degradation over a broad pH range | |
| CN113304749A (en) | Graphene hollow nanosphere zero-valent iron-loaded nanomaterial and preparation method thereof | |
| CN110548519B (en) | Porous nano cobalt-doped zinc manganate spinel catalyst and preparation method and application thereof | |
| Huang et al. | In-situ synthesis of well-dispersed Cu/Cu2O nanoparticles supported on petaloid SiO2 for efficient degradation of high concentration tetracycline hydrochloride | |
| CN108862538B (en) | Method for degrading bisphenol A by activating sodium percarbonate with nano zero-valent iron | |
| Tu et al. | Preparation and application of green calcium-based catalyst for advanced treatment of salty wastewater with ozone | |
| JPH05115B2 (en) | ||
| CN113200592A (en) | Method for degrading N-nitrosodimethylamine in water body and application | |
| CN115228476A (en) | Metal-loaded lignin carbon material and preparation method and application thereof | |
| Dang et al. | Tannin-functionalized Mn3O4 as support for FeNiB alloy to construct sono-Fenton-like reaction for the degradation of antibiotic pollutants in water | |
| CN112960796A (en) | Method for removing sulfadimidine in wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210827 |